EP0816485B1 - Process for making detergent compositions - Google Patents

Process for making detergent compositions Download PDF

Info

Publication number
EP0816485B1
EP0816485B1 EP96201854A EP96201854A EP0816485B1 EP 0816485 B1 EP0816485 B1 EP 0816485B1 EP 96201854 A EP96201854 A EP 96201854A EP 96201854 A EP96201854 A EP 96201854A EP 0816485 B1 EP0816485 B1 EP 0816485B1
Authority
EP
European Patent Office
Prior art keywords
surfactant
particle size
parts
micrometers
zeolite
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
EP96201854A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0816485A1 (en
Inventor
Scott John Donoghue
Marcel Karel Nelis Liplijn
Carole Patricia Denise Wilkinson
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
Priority to EP96201854A priority Critical patent/EP0816485B1/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to DE69635575T priority patent/DE69635575T2/de
Priority to ES96201854T priority patent/ES2253747T3/es
Priority to AT96201854T priority patent/ATE312901T1/de
Priority to US09/214,327 priority patent/US6156718A/en
Priority to BR9710199-0A priority patent/BR9710199A/pt
Priority to CNB971973946A priority patent/CN1195834C/zh
Priority to JP10505241A priority patent/JPH11514033A/ja
Priority to PCT/US1997/011281 priority patent/WO1998001520A2/en
Priority to CA002259535A priority patent/CA2259535C/en
Priority to ARP970102992A priority patent/AR008062A1/es
Publication of EP0816485A1 publication Critical patent/EP0816485A1/en
Application granted granted Critical
Publication of EP0816485B1 publication Critical patent/EP0816485B1/en
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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles

Definitions

  • the present invention relates to a process for making detergent compositions
  • JP-A-61 089 300 and US 4 136 051 relate to processes for preparing surfactant-containing detergent compositions.
  • WO94/05761 published on 17th March 1994, describes a final product densification step wherein substantially all of the product is sprayed with nonionic surfactant and coated with zeolite. Good dispensing and dissolving properties are claimed.
  • the object of the invention is to provide an improved process for making a detergent composition comprising anionic surfactant, nonionic surfactant and non-surfactant additives.
  • the object of the present invention is achieved by a process comprising the steps of:
  • the first intermediate particle is formed by :
  • the first intermediate particle is formed by :
  • the process of the invention results in a narrow particle size distribution with a sharply defined mean.
  • the mean particle size is from 900 to 1100 micrometers, and the particle size distribution has a standard deviation of less than 50 micrometers.
  • Non-surfactant additives may include any detergent additives such as bleach, especially perborate or percarbonate; inorganic salts, especially carbonate, bicarbonate, silicate, sulphate, or citrate; chelants, enzymes.
  • detergent additives such as bleach, especially perborate or percarbonate
  • inorganic salts especially carbonate, bicarbonate, silicate, sulphate, or citrate
  • chelants especially enzymes.
  • Finely divided particulate materials useful herein include aluminosilicates having the empirical formula: M z (zAlO 2 ) y ] ⁇ x H 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
  • Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived.
  • aluminosilicate ion exchange materials A method for producing aluminosilicate ion exchange materials is disclosed in US-A-3 985 669, Krummel et al, issued October 12, 1976.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations zeolite A, zeolite P(B), zeolite MAP, zeolite X and zeolite Y.
  • the crystalline aluminosilicate ion exchange material has the formula : Na 12 [(AlO 2 ) 12 (SiO2) 12 ] ⁇ x H 2 O wherein x is from about 20 to about 30, especially about 27. This material is known as zeolite A.
  • the "overdried" zeolites are particularly useful when a low moisture environment is required, for example to improve stability of detergent bleaches such as perborate and percarbonate.
  • the aluminosilicate has a particle size of about 0.1-10 micrometers in diameter.
  • Preferred ion exchange materials have a particle size diameter of from about 0.2 micrometers to about 4 micrometers.
  • the term "particle size diameter” herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
  • the crystalline zeolite A materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg equivalent of CaCO 3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg eq./g to about 352 mg eq./g.
  • the zeolite A materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /gallon/minute/gram/gallon (0.13g Ca ++ /litre/minute/gram/litre) of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon(0.13g Ca ++ /litre/minute/gram/litre) to about 6 grains/gallon/minute/gram/gallon (0.39g Ca ++ /litre/minute/gram/litre), based on calcium ion hardness.
  • Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon (0.26g Ca ++ /litre/minute/gram/litre).
  • nonionic surfactant While any nonionic surfactant may be usefully employed in the present invention, two families of nonionics have been found to be particularly useful. These are nonionic surfactants based on alkoxylated (especially ethoxylated) alcohols, and those nonionic surfactants based on amidation products of fatty acid esters and N-alkyl polyhydroxy amine. The amidation products of the esters and the amines are generally referred to herein as polyhydroxy fatty acid amides. Particularly useful in the present invention are mixtures comprising two or more nonionic surfactants wherein at least one nonionic surfactant is selected from each of the groups of alkoxylated alcohols and the polyhydroxy fatty acid amides.
  • Suitable nonionic surfactants include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
  • the length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • nonionic surfactants such as the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from about 4 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with an average of up to 25 moles of ethylene oxide per more of alcohol.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 2 to 10 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide.
  • the nonionic surfactant system also includes a polyhydroxy fatty acid amide component.
  • Polyhydroxy fatty acid amides may be produced by reacting a fatty acid ester and an N-alkyl polyhydroxy amine.
  • the preferred amine for use in the present invention is N-(R1)-CH2(CH2OH)4-CH2-OH, where R1 is typically a alkyl, e.g. methyl group; and the preferred ester is a C12-C20 fatty acid methyl ester.
  • nonionic surfactants which may be used as components of the surfactant systems herein include ethoxylated nonionic surfactants, glycerol ethers, glucosamides, glycerol amides, glycerol esters, fatty acids, fatty acid esters, fatty amides, alkyl polyglucosides, alkyl polyglycol ethers, polyethylene glycols, ethoxylated alkyl phenols and mixtures thereof.
  • ethoxylated nonionic surfactants include ethoxylated nonionic surfactants, glycerol ethers, glucosamides, glycerol amides, glycerol esters, fatty acids, fatty acid esters, fatty amides, alkyl polyglucosides, alkyl polyglycol ethers, polyethylene glycols, ethoxylated alkyl phenols and mixtures thereof.
  • the second intermediate particle of the present invention comprises anionic surfactant.
  • the second intermediate particle may be made by any process including spray drying, flaking, prilling, extruding, pastillating, and agglomeration.
  • Agglomeration processes for making anionic surfactant particles have been disclosed in the prior art in, for example, EP-A-0 508 543, EP-A-0 510 746, EP-A-0 618 289 and EP-A-0 663 439.
  • An essential feature of the invention is that no nonionic surfactant is sprayed on to the surfactant agglomerate stream.
  • Non-limiting examples of anionic surfactants useful herein include the conventional C11-C18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulfates (“AS”), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOSO 3 - M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3 - M + ) CH 2 CH 3 where x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C10-C18 alkyl alkoxy sulfates ("AE x S", especially EO 1-7 ethoxy sulfates), C10-C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxy
  • surfactant agglomerates and layered granular additives are mixed, optionally with additional additives to form a finished detergent composition.
  • the various mixing steps of the present invention may be carried out in any suitable mixer such as the Eirich®, series RV, manufactured by Gustau Eirich Hardheim, Germany; Lödige®, series FM for batch mixing, series Baud KM for continuous mixing/agglomeration, manufactured by Lödige Machinenbau GmbH, Paderborn Germany; Drais® T160 series, manufactured by Drais Werke GmbH, Mannheim Germany; and Winkworth® RT 25 series, manufactured by Winkworth Machinery Ltd., Berkshire, England; the Littleford Mixer, Model #FM-130-D-12, with internal chopping blades and the Cuisinart® Food Processor, Model #DCX-Plus, with 7.75 inch (19.7 cm) blades.
  • Many other mixers are commercially available for both batch and continuous mixing.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Sodium carbonate 3 2 2 7.8 - Sodium citrate - - - - 10 Sodium bicarbonate - - - - 10 Percarbonate 20 16 16 - - Perborate - - - 18 - Enzymes 1.7 2.2 2.2 1 2 Nonionic surfactant particles 4 13 19 20 20 Hydroxy ethylene diphosphonic acid 1 1 1 - - Tetraacetyl ethylene diamine 6 4.7 4.7 4 - Antifoam particle 2.8 1 1 - - Layered silicate 15 12 12 - - Sodium silicate (2.0R) - - - 2 3 Sodium sulphate - - - - 5 Cationic surfactant particles 5 - - - - Brightener - - - 0.2 - 58.5 51.9 57.9 53 50
  • Nonionic surfactant particles contained 15 parts alcohol ethoxylate with an average of 5 EO groups per mole, AE5, 15 parts of polyhydroxy fatty acid amide, 60 parts zeolite, 5 parts fatty acid and 5 parts water, and were made according to the process disclosed in EP-A-0 643 130.
  • Antifoam particles contained 12 parts silicone oil, 70 parts starch and 12 parts hydrogenated fatty acid / tallow alcohol ethoxylate (TAE80), and were made according to the process disclosed in EP-A-0 495 345.
  • Layered silicate is SKS-6® supplied by Hoechst Cationic surfactant particles contained 30 parts alkyl dimethyl ethoxy ammonium chloride, 60 parts sodium sulphate, 5 parts alkyl sulphate and 5 parts water and were made according to the process disclosed in EP-A-0 714 976.
  • Brightener is Tinopal CDX® supplied by Ciba-Geigy.
  • Example 1 The additives shown under Example 1 in the previous table were mixed together and found to have an average particle size of 440 micrometers.
  • the product in the concrete mixer had an average particle size of 1020 micrometers.
  • the anionic surfactant particle was then added to the concrete mixer at a level of 22%.
  • the anionic surfactant particle contained 28 parts linear alkyl benzene sulphonate, 12 parts tallow alkyl sulphate, 30 parts zeolite, 20 parts carbonate and 10 parts water, and had an average particle size of 850 micrometers.
  • the finished product had an average particle size of 960 micrometers.
  • nonionic surfactant (AE5) at 35°C was sprayed onto the additive mixture in a concrete mixer using a two-fluid spray nozzle.
  • 4% of zeolite A was added into the concrete mixer over a period of 1 minute.
  • the mixer then continued to operate without further addition of zeolite for a further one minute.
  • Finally a further 9% of zeolite was added over a period of 2 minutes.
  • the product in the concrete mixer had an average particle size of 1080 micrometers.
  • the anionic surfactant particle was then added to the concrete mixer at a level of 28.6%.
  • the anionic surfactant particle contained 28 parts linear alkyl benzene sulphonate, 12 parts tallow alkyl sulphate, 30 parts zeolite, 20 parts carbonate and 10 parts water, and had an average particle size of 850 micrometers.
  • the finished product had an average particle size of 1030 micrometers.
  • the product in the concrete mixer had an average particle size of 555 micrometers.
  • the anionic surfactant particle was then added to the concrete mixer at a level of 28.6%.
  • the anionic surfactant particle contained 28 parts linear alkyl benzene sulphonate, 12 parts tallow alkyl sulphate, 30 parts zeolite, 20 parts carbonate and 10 parts water, and had an average particle size of 410 micrometers.
  • the finished product had an average particle size of 520 micrometers.
  • nonionic surfactant AE5
  • zeolite A 6% were added into the concrete mixer in discrete portions, 1% at a time.
  • the product in the concrete mixer had an average particle size of 1000 micrometers.
  • a spray dried powder was then added to the concrete mixer at a level of 28%.
  • the spray dried particle contained 20 parts linear alkyl benzene sulphonate, 5 parts polyacrylate polymer, 5 parts of chelant, 30 parts zeolite, 30 parts sulphate and 10 parts water, and had an average particle size of 1000 micrometers.
  • the finished product had an average particle size of 1000 micrometers.
  • Example 5 not in accordance with the present invention
  • nonionic surfactant AE5
  • zeolite A 7% were added into the concrete mixer in discrete portions, 1% at a time.
  • the product in the concrete mixer had an average particle size of 1050 micrometers.
  • a spray-dried granule was then added to the concrete mixer at a level of 30%.
  • the spray dried particle contained 20 parts linear alkyl benzene sulphonate, 5 parts polyacrylate polymer, 5 parts of chelant, 30 parts zeolite, 30 parts sulphate and 10 parts water, and had an average particle size of 1000 micrometers.
  • the finished product had an average particle size of 1020 micrometers.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP96201854A 1996-07-04 1996-07-04 Process for making detergent compositions Expired - Lifetime EP0816485B1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
DE69635575T DE69635575T2 (de) 1996-07-04 1996-07-04 Verfahren zur Herstellung von Reinigungsmittelzusammensetzungen
ES96201854T ES2253747T3 (es) 1996-07-04 1996-07-04 Proceso para la fabricar composiciones detergentes.
AT96201854T ATE312901T1 (de) 1996-07-04 1996-07-04 Verfahren zur herstellung von reinigungsmittelzusammensetzungen
EP96201854A EP0816485B1 (en) 1996-07-04 1996-07-04 Process for making detergent compositions
BR9710199-0A BR9710199A (pt) 1996-07-04 1997-06-27 Processo para fabricação de composições detergentes
CNB971973946A CN1195834C (zh) 1996-07-04 1997-06-27 制备洗涤剂组合物的方法
US09/214,327 US6156718A (en) 1996-07-04 1997-06-27 Process for making detergent compositions
JP10505241A JPH11514033A (ja) 1996-07-04 1997-06-27 洗剤組成物を製造する方法
PCT/US1997/011281 WO1998001520A2 (en) 1996-07-04 1997-06-27 Process for making detergent compositions
CA002259535A CA2259535C (en) 1996-07-04 1997-06-27 Process for making detergent compositions
ARP970102992A AR008062A1 (es) 1996-07-04 1997-07-03 Proceso para fabricar composiciones detergentes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP96201854A EP0816485B1 (en) 1996-07-04 1996-07-04 Process for making detergent compositions

Publications (2)

Publication Number Publication Date
EP0816485A1 EP0816485A1 (en) 1998-01-07
EP0816485B1 true EP0816485B1 (en) 2005-12-14

Family

ID=8224140

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96201854A Expired - Lifetime EP0816485B1 (en) 1996-07-04 1996-07-04 Process for making detergent compositions

Country Status (10)

Country Link
EP (1) EP0816485B1 (ja)
JP (1) JPH11514033A (ja)
CN (1) CN1195834C (ja)
AR (1) AR008062A1 (ja)
AT (1) ATE312901T1 (ja)
BR (1) BR9710199A (ja)
CA (1) CA2259535C (ja)
DE (1) DE69635575T2 (ja)
ES (1) ES2253747T3 (ja)
WO (1) WO1998001520A2 (ja)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6156718A (en) * 1996-07-04 2000-12-05 The Procter & Gamble Company Process for making detergent compositions
US6906022B1 (en) * 1998-09-25 2005-06-14 The Procter & Gamble Company Granular detergent compositions having homogenous particles and process for producing same
AU9585098A (en) * 1998-09-25 2000-04-17 Procter & Gamble Company, The Granular detergent composition having improved appearance and solubility
CA2343810A1 (en) * 1998-09-25 2000-04-06 Jacqueline Westfield Granular detergent composition having improved appearance and solubility
US6964945B1 (en) 1998-09-25 2005-11-15 The Procter & Gamble Company Solid detergent compositions
US6673766B1 (en) * 1998-09-25 2004-01-06 The Procter & Gamble Company Solid detergent compositions containing mixtures of surfactant/builder particles
JP2003527455A (ja) * 1998-09-25 2003-09-16 ザ、プロクター、エンド、ギャンブル、カンパニー 改善された溶解度特性を有する粒状洗剤組成物
JP2002528600A (ja) 1998-10-26 2002-09-03 ザ、プロクター、エンド、ギャンブル、カンパニー 外観と溶解性の改良された粒状洗剤組成物の製造方法
EP1104804B1 (en) * 1999-06-14 2005-04-20 Kao Corporation Method for producing single nucleus detergent particles
CN1200999C (zh) * 1999-06-21 2005-05-11 宝洁公司 制造粒状洗涤剂组合物的方法
US6833346B1 (en) * 1999-06-21 2004-12-21 The Procter & Gamble Company Process for making detergent particulates
US6951837B1 (en) 1999-06-21 2005-10-04 The Procter & Gamble Company Process for making a granular detergent composition
GB0111863D0 (en) * 2001-05-15 2001-07-04 Unilever Plc Granular composition
DE102006029007A1 (de) * 2006-06-24 2008-01-03 Cognis Ip Management Gmbh Feste Tenside in granularer Form

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4136051A (en) * 1974-02-25 1979-01-23 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Pourable washing compositions containing a luminosilicates and non-ionics and method for their preparation
JPS6189300A (ja) * 1984-10-09 1986-05-07 ライオン株式会社 非イオン界面活性剤を含む粒状洗剤組成物の製造方法
TW240243B (ja) * 1992-03-12 1995-02-11 Kao Corp
DE4209435A1 (de) * 1992-03-24 1993-09-30 Henkel Kgaa Granulares, nichtionische Tenside enthaltendes, phosphatfreies Additiv für Wasch- und Reinigungsmittel
TR27586A (tr) * 1992-09-01 1995-06-13 Procter & Gamble Yüksek yogunlukla zerre deterjanin yapilmasi icin islem ve islem ile yapilan bilesimler.

Also Published As

Publication number Publication date
WO1998001520A2 (en) 1998-01-15
BR9710199A (pt) 1999-11-23
CA2259535C (en) 2002-10-01
ES2253747T3 (es) 2006-06-01
DE69635575T2 (de) 2006-09-14
AR008062A1 (es) 1999-12-09
CN1332790A (zh) 2002-01-23
CN1195834C (zh) 2005-04-06
DE69635575D1 (de) 2006-01-19
ATE312901T1 (de) 2005-12-15
EP0816485A1 (en) 1998-01-07
JPH11514033A (ja) 1999-11-30
CA2259535A1 (en) 1998-01-15

Similar Documents

Publication Publication Date Title
EP0390251B1 (en) Detergent compositions and process for preparing them
EP0451894B2 (en) High bulk density granular detergent compositions and process for preparing them
EP0349201B1 (en) Detergent granules from cold dough using fine dispersion granulation
EP0816485B1 (en) Process for making detergent compositions
EP0656825B2 (en) Process for making compact detergent compositions
EP0040091A1 (en) Suds suppressing granules for use in detergent compositions
CA2028204A1 (en) Detergent compositions
SK32098A3 (en) Method for preparing an amorphous alkali silicate with impregnation
EP0882126B1 (en) Process for the production of a detergent composition
EP0578871B1 (en) Process and compositions for compact detergents
CA2083332C (en) Detergent compositions and process for preparing them
EP0643129A1 (en) Process for preparing detergent compositions
US5610131A (en) Structuring liquid nonionic surfactants prior to granulation process
US6156718A (en) Process for making detergent compositions
EP0870008B1 (en) Process for producing granular detergent components or compositions
JPH0762160B2 (ja) 粘土を含有する高嵩密度の洗剤粉末の製造方法
US5998356A (en) Process for making granular detergents
CA2231577C (en) Process for making granular detergents
US5990073A (en) Process for the production of a detergent composition
AU739651B2 (en) Process for the production of a detergent composition

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE

17P Request for examination filed

Effective date: 19980706

AKX Designation fees paid

Free format text: AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE

RBV Designated contracting states (corrected)

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE

17Q First examination report despatched

Effective date: 20040517

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE

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

Ref country code: LI

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: 20051214

Ref country code: FI

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: 20051214

Ref country code: CH

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: 20051214

Ref country code: BE

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: 20051214

Ref country code: AT

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: 20051214

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69635575

Country of ref document: DE

Date of ref document: 20060119

Kind code of ref document: P

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

Ref country code: SE

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: 20060314

Ref country code: GR

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: 20060314

Ref country code: DK

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: 20060314

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

Ref country code: PT

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: 20060515

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2253747

Country of ref document: ES

Kind code of ref document: T3

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

Ref country code: GB

Payment date: 20060614

Year of fee payment: 11

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

Ref country code: NL

Payment date: 20060616

Year of fee payment: 11

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: IE

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

Effective date: 20060704

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

Ref country code: FR

Payment date: 20060705

Year of fee payment: 11

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

Ref country code: IT

Payment date: 20060731

Year of fee payment: 11

Ref country code: DE

Payment date: 20060731

Year of fee payment: 11

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20060915

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

Effective date: 20070704

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20080201

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 NON-PAYMENT OF DUE FEES

Effective date: 20080201

Ref country code: DE

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

Effective date: 20080201

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: 20070704

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20080331

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

Ref country code: LU

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

Effective date: 20060704

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: 20070731

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20070705

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

Ref country code: ES

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

Effective date: 20070705

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: 20070704