EP0802970B1 - Composition detergente comprenant la zeolite map et des enzymes amylases - Google Patents

Composition detergente comprenant la zeolite map et des enzymes amylases Download PDF

Info

Publication number
EP0802970B1
EP0802970B1 EP96905128A EP96905128A EP0802970B1 EP 0802970 B1 EP0802970 B1 EP 0802970B1 EP 96905128 A EP96905128 A EP 96905128A EP 96905128 A EP96905128 A EP 96905128A EP 0802970 B1 EP0802970 B1 EP 0802970B1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
composition according
zeolite
enzyme
amylase
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
EP96905128A
Other languages
German (de)
English (en)
Other versions
EP0802970A4 (fr
EP0802970A1 (fr
Inventor
Carolyn Jayne Brown
Jonathan Richard Clare
Johan Juliaan Serafin Wauben
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
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0802970A1 publication Critical patent/EP0802970A1/fr
Publication of EP0802970A4 publication Critical patent/EP0802970A4/fr
Application granted granted Critical
Publication of EP0802970B1 publication Critical patent/EP0802970B1/fr
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
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only

Definitions

  • the present invention relates to a detergent composition
  • a detergent composition comprising an amylase enzyme and a zeolite component as a sequestering agent for water hardness.
  • water soluble inorganic phosphates such as sodium tripolyphosphate
  • sodium tripolyphosphate have been used as builders for laundry detergents.
  • alkali metal aluminosilicate ion-exchangers particularly crystalline water insoluble sodium aluminosilicate zeolites, have been proposed as replacements for the inorganic phosphates.
  • EP 21 491A (Procter & Gamble) discloses detergent compositions containing a builder system which includes zeolite A, X or P (B) or a mixture thereof.
  • EP 384070A (Unilever) discloses specific zeolite P materials having an especially low silicon to aluminium ratio not greater than 1.33 (hereinafter referred to as zeolite MAP) and describes their use as detergency builders.
  • the problem relates to the formation of white residues, which adhere to the fabrics and remain thereon at the end of a laundry washing process.
  • the degree of residue formation may vary. On coloured fabrics the appearance of the white residues tends to be visually more apparent than on white fabrics. White residues frequently form on areas of fabric where there is a stain present, interfering with and preventing the complete removal of the stain. As a result of the visible contrast between the white residues and the coloured fabric, the stained area on which white deposits have formed may be more noticeable that the original stain.
  • a detergent composition selected from liquid compositions and granular compositions having a bulk density of at least 550 g/l and containing
  • the first essential component of the present invention is a zeolite MAP builder, optionally in conjunction with one or more supplementary builders.
  • the zeolite MAP is typically present at a level of from 1% to 80%, more preferably from 15% to 40% by weight of the compositions.
  • Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
  • zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
  • Zeolite P having a Si:Al ratio of 1.33 or less may be prepared by the following steps:
  • Preferred drying methods are spray-drying and flash drying. It appears that oven drying at too high a temperature may adversely affect the calcium binding capacity of the product under certain circumstances.
  • Zeolite MAP generally has a calcium binding capacity of at least 150 mg CaO per g of anhydrous aluminosilcate, as measured by the standard method described in GB 1473201 (Henkel).
  • the calcium binding capacity is normally 160 mg CaO/g and may be as high 170 mg CaO/g.
  • zeolite MAP like other zeolites contains water of hydration, for the purposes of the present invention amounts and percentages of zeolite are expressed in terms of the notional anhydrous material.
  • the amount of water present in hydrated zeolite MAP at ambient temperature and humidity is generally about 20 wt.%.
  • the zeolite MAP detergent builder has a particle size, expressed as a d 50 value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
  • the d 50 value indicates that 50% by weight of the particles have a diameter smaller than that figure.
  • the particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d 50 values are disclosed in EP 384070A.
  • the second essential component of the compositions is an amylase enzyme, that is to say an enzyme having amylolytic activity.
  • the amylase enzyme is typically incorporated into the compositions in accordance with the invention at a level of from 0.01% to 5%, preferably from 0.1 % to 3%, more preferably from 0.2% to 2%, most preferably from 0.3% to 1.5% active enzyme by weight of the composition, on a 60KNU/g (Kilo Novo Units/gram) activity basis.
  • KNU/g The units of 'Kilo Novo Units/gram (KNU/g)' are a well known means of defining amylolytic enzyme activity and are described in GB-1,269,839 A (Novo).
  • 1 KNU is the amount of enzyme which breaks down 5.25 grams of starch (Merck, Amylum Solubile Erg. B.6, Batch 9947275) per hour in the method described in GB-1,269,839 A, which has the following standard conditions: Substrate Soluble starch Calcium content in solvent 0.0043 M Reaction time 7-20 minutes Temperature 37°C pH 5.6
  • the amylase enzyme may be fungal or bacterial in origin. Amylases obtained by chemical or genetic manipulation of fungal or bacterial derived strains are also useful herein.
  • the amylase enzyme is preferably an ⁇ -amylase.
  • Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B. licheniformis, described in more detail in GB-1,269,839 A.
  • Reported deposit numbers for B. licheniformis strains capable of producing ⁇ -amylases include NCIB 8061, NCIB 8059, ATCC 6634, ATCC 6598, ATCC 11945, ATCC 8480 and ATCC 9945a.
  • Preferred commercially available ⁇ -amylases include for example, those sold under the tradename Rapidase and Maxamyl by Gist-Brocades; those sold under the tradename Taka-Therm L-340 by Miles Laboratories, Elkhart, Indiana; those sold under the tradename Rohalase AT by Rohm and Haas, West Philadelphia, PA; and those sold under the tradenames Termamyl 60T and 120T, Fungamyl and BAN by Novo Industries A/S.
  • the amylases have been designed to have improved stability, particularly having improved stability to oxidation, for example in a bleaching environment, and improved thermal stability. Stability can be measured using any of the technical tests known in the art including those referred to in WO 94/02597 A. Stability-enhanced amylases are commercially available from Novo Industries A/S or from Genencor International.
  • Highly preferred amylases with enhanced oxidative stability are derived using site-directed mutagenesis from one or more of the Baccillus amylases, especialy the Bacillus ⁇ -amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors.
  • Preferred amylases of this type are described in WO 94/02597 A, and comprise a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of the B. licheniformis ⁇ -amylase, sold under the tradename Termamyl, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B.subtilis, or B.stearothermophilus.
  • amylases having enhanced oxidative stability include those described in WO 94/18314 A (Genencor International) and WO 94/02597 A (Novo). Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other enzyme modifications are acceptable including those described in WO 95/09909 A (Novo).
  • enzymes for incorporation into solid detergent compositions are generally sold commercially as enzyme prills containing active enzyme supported on a variety of inert host materials, which for example, can include alkali metal sulfates, carbonates and silicates.
  • organic binder materials are also incorporated.
  • the calcium content of these enzyme prills is minimzed to ensure good in-product storage stability of the enzyme.
  • the detergent composition according to the invention may contain other detergent components such as surfactants, cobuilders, bleaches, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, other enzymes, lather control agents, fabric softening agents, pigments, coloured speckles and perfumes.
  • other detergent components such as surfactants, cobuilders, bleaches, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, other enzymes, lather control agents, fabric softening agents, pigments, coloured speckles and perfumes.
  • the detergent composition according to the invention preferably includes a surfactant selected from anionics, nonionics, zwitterionics, ampholytics and cationics.
  • the surfactant is preferably present in the detergent compositions at a level of from 1% to 50%, preferably from 3% to 30%, most preferably from 5% to 20% by weight of the compositions.
  • Suitable additional anionic surfactants include anionic sulfates, olefin sulphonates, alkyl xylene sulphonates, dialkylsulphosuccinates, and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C 5 -C 17 acyl-N-(C 1 -C 4 alkyl) and -N-(C 1 -C 2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C 6 -C 18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C 6 -C 18 alkyl sulfate which has been ethoxylated with from 0.5 to 20, preferably from 0.5 to 5, moles of ethylene oxide per molecule.
  • Anionic sulfonate surfactant Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include the salts of C 5 -C 20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C 6 -C 22 primary or secondary alkane sulfonates, C 6 -C 24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • the nonionic surfactant is preferably a hydrophobic nonionic surfactant, particularly an alkoxylated nonionic surfactant, having a hydrophilic lipophilic balance (hlb) value of ⁇ 9.5, more preferably ⁇ 10.5.
  • hlb hydrophilic lipophilic balance
  • hydrophobic alkoxylated nonionic surfactants include alkoxylated adducts of fatty alcohols containing an average of less than 5 alkylene oxide groups per molecule.
  • the alkylene oxide residues may, for example, be ethylene oxide residues or mixtures thereof with propylene oxide residues.
  • Preferred alkylene oxide adducts of fatty alcohols useful in the present invention can suitably be chosen from those of the general formula: R-O-(C n H 2n O)yH wherein R is an alkyl or alkenyl group having at least 10 carbon atoms, most preferably from 10 to 22 carbon atoms, y is from 0.5 to 3.5 and n is 2 or 3.
  • Preferred nonionic surfactants include primary C 11 -C 15 aliphatic alcohols condensed with an average of no more than five ethylene oxide groups per mole of alcohol, having an ethylene oxide content of less than 50% by weight, preferably from 25% to less than 50% by weight.
  • a particularly preferred aliphatic alcohol ethoxylated is a primary alcohol having an average of 12 to 15 carbon atoms in the alkyl chain condensed with an average of three ethoxy groups per mole of alcohol.
  • alkoxylated adducts of fatty alcohols are Synperonic A3 (ex ICI), which is a C 13 -C 15 alcohol with about three ethylene oxide groups per molecule and Empilan KB3 (ex Marchon), which is lauric alcohol 3EO.
  • Another class of nonionic sufactants comprises alkyl polyglucoside compounds of general formula RO(C n H 2n O) t Z x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 0094118.
  • the builder system may contain an organic or inorganic cobuilder.
  • Suitable organic cobuilders can be monomeric or polymeric carboxylates such as citrates or polymers of acrylic, methacrylic and/or maleic acids in neutralised form.
  • Suitable inorganic cobuilders include carbonates and amorphous and crystalline layered silicates.
  • Suitable crystalline layered silicates have the composition: NaMSi x O 2x +1 . y H 2 0 where M is sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20.
  • M sodium or hydrogen, preferably sodium
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20.
  • Such materials are described in US Patents No. 4664839; No. 4728443 and No. 4820439 (Hoechst AG).
  • the synthetic material is commercially available from Hoechst AG as ⁇ - Na 2 Si 2 O 5 (SKS6) and is described in US Patent No. 4664830.
  • the total amount of detergency builder in the granular composition typically ranges from 10 to 80 wt. %, more preferably from 15 to 60 wt% and most preferably from 10 to 45 wt.%.
  • Detergent compositions according to the invention may also suitably contain a bleach system.
  • a bleach system preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with bleach precursors to improve bleaching action at low temperatures.
  • the bleach system preferably comprises a peroxy bleach compound, preferably an inorganic persalt, optionally in conjunction with a peroxyacid bleach precursor.
  • Suitable persalts include sodium perborate monohydrate and tetrahydrate and sodium percarbonate, with sodium percarbonate being most preferred.
  • Preferred bleach precursors are peracetic acid precursors, such as tetraacetylethylene diamine (TAED); peroxybenzoic acid precursors.
  • TAED tetraacetylethylene diamine
  • the detergent composition according to the invention may be of any physical type, for example powders, liquids and gels. However, granular and liquid compositions are preferred.
  • the detergent compositions of the invention may be prepared by any suitable method.
  • the particulate detergent compositions are suitably prepared by any tower (spray-drying) or non-tower process.
  • a base powder is first prepared by spray-drying a slurry and then other components unsuitable for processing via the slurry can be sprayed on or admixed (postdosed).
  • the zeolite MAP is suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the zeolite MAP to be incorporated post-tower.
  • the crystalline layered silicate, where this is employed, is also incorporated via a non-tower process and is preferably postdosed.
  • particulate detergent compositions in accordance with the invention may be prepared by wholly non-tower processes such as granulation.
  • the granular detergent compositions of the invention may be prepared to any suitable bulk density.
  • the compositions preferably have a bulk density of at least 400 g/l preferably at least 550 g/l, most preferably at least 700 g/l and, with particular preference at least 800 g/l.
  • powders of high bulk density for example, of 700 g/l or above.
  • Such powders may be prepared either by post-tower densification of spraydried powder, or by wholly non-tower methods such as dry mixing and granulation; in both cases a high-speed mixer/granulator may advantageously be used.
  • Processes using high-speed mixer/granulators are disclosed, for example, in EP340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).
  • the detergent composition of the invention may be formulated as a liquid detergent composition which may be aqueous or anhydrous.
  • liquid used herein includes pasty viscous formulations such as gels.
  • the liquid detergent composition generally has a pH of from 6.5 to 10.5.
  • the total amount of detergency builder in the liquid composition is preferably from 5 to 70% of the total liquid composition.
  • compositions according to the present invention are presented in the following Examples.

Claims (9)

  1. Composition détergente choisie parmi des compositions liquides et des compositions granulaires ayant une masse volumique apparente d'au moins 550 g/l et contenant
    (a) un adjuvant zéolite comprenant une zéolite P ayant un rapport silicium à l'aluminium non supérieur à 1,33 (zéolite MAP) et ayant une taille particulaire, exprimée comme une valeur d50, de 1 à 5 micromètres, et
    (b) une enzyme amylase présente en une quantité de 0,1 % à 2 % d'enzyme active en poids de la composition sur une base d'activité de 60 KNU/g.
  2. Composition selon l'une quelconque des revendications précédentes qui est une composition détergente de blanchissage particulaire comprenant un tensioactif non ionique, adjuvant zéolite, un co-adjuvant organique ou minéral et l'enzyme amylase.
  3. Composition détergente selon l'une quelconque des revendications précédentes, dans laquelle ledit adjuvant zéolite est cristallin et est présent en une quantité de 15 % à 40 % en poids de la composition.
  4. Composition détergente selon l'une quelconque des revendications précédentes, dans laquelle ladite enzyme amylase est une α-amylase.
  5. Composition détergente selon l'une quelconque des revendications précédentes, dans laquelle ladite enzyme amylase a été modifiée afin d'augmenter sa stabilité d'oxydation.
  6. Composition détergente selon l'une quelconque des revendications précédentes contenant un tensioactif en une quantité de 5 % à 50 % en poids de la composition.
  7. Composition détergente selon l'une quelconque des revendications précédentes et comprenant un co-adjuvant qui est un phyllosilicate cristallin.
  8. Composition détergente selon l'une quelconque des revendications précédentes contenant un système de blanchiment comprenant un composé de blanchiment peroxy et un précurseur de blanchiment peroxyacide.
  9. Composition détergente selon la revendication 8, dans laquelle le composé de blanchiment peroxy est le percarbonate de sodium.
EP96905128A 1995-01-14 1996-01-05 Composition detergente comprenant la zeolite map et des enzymes amylases Expired - Lifetime EP0802970B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9500737.3A GB9500737D0 (en) 1995-01-14 1995-01-14 Detergent composition
GB9500737 1995-01-14
PCT/US1996/000284 WO1996021718A1 (fr) 1995-01-14 1996-01-05 Composition detergente comprenant la zeolite map et des enzymes amylases

Publications (3)

Publication Number Publication Date
EP0802970A1 EP0802970A1 (fr) 1997-10-29
EP0802970A4 EP0802970A4 (fr) 1999-01-07
EP0802970B1 true EP0802970B1 (fr) 2004-03-17

Family

ID=10768052

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96905128A Expired - Lifetime EP0802970B1 (fr) 1995-01-14 1996-01-05 Composition detergente comprenant la zeolite map et des enzymes amylases

Country Status (8)

Country Link
EP (1) EP0802970B1 (fr)
AR (1) AR000716A1 (fr)
AT (1) ATE262025T1 (fr)
BR (1) BR9606759A (fr)
CA (1) CA2210646C (fr)
DE (1) DE69631873T2 (fr)
GB (1) GB9500737D0 (fr)
WO (1) WO1996021718A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004007468A1 (de) * 2004-02-13 2005-09-01 De-Sta-Co Metallerzeugnisse Gmbh Spannvorrichtung

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0753043A1 (fr) * 1994-03-31 1997-01-15 The Procter & Gamble Company Compositions detergentes

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9108136D0 (en) * 1991-04-17 1991-06-05 Unilever Plc Concentrated detergent powder compositions
GB9113674D0 (en) * 1991-06-25 1991-08-14 Unilever Plc Detergent compositions
SK278834B6 (sk) * 1992-01-17 1998-03-04 Unilever Nv Časticová bieliaca detergentná zmes
CZ280524B6 (cs) * 1992-01-17 1996-02-14 Unilever Nv Částicové detergenční směsi
GB9305599D0 (en) * 1993-03-18 1993-05-05 Unilever Plc Detergent compositions
GB2287948B (en) * 1994-03-31 1998-04-08 Procter & Gamble Detergent composition
USH1468H (en) * 1994-04-28 1995-08-01 Costa Jill B Detergent compositions containing cellulase enzyme and selected perfumes for improved odor and stability

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0753043A1 (fr) * 1994-03-31 1997-01-15 The Procter & Gamble Company Compositions detergentes

Also Published As

Publication number Publication date
ATE262025T1 (de) 2004-04-15
AR000716A1 (es) 1997-08-06
BR9606759A (pt) 1998-01-06
GB9500737D0 (en) 1995-03-08
WO1996021718A1 (fr) 1996-07-18
DE69631873D1 (de) 2004-04-22
CA2210646A1 (fr) 1996-07-18
EP0802970A4 (fr) 1999-01-07
MX9705326A (es) 1997-10-31
EP0802970A1 (fr) 1997-10-29
DE69631873T2 (de) 2005-03-03
CA2210646C (fr) 2001-07-31

Similar Documents

Publication Publication Date Title
EP0802970B1 (fr) Composition detergente comprenant la zeolite map et des enzymes amylases
US6440922B1 (en) Detergent composition comprising zeolite and amylase enzyme
EP0802969B1 (fr) Composition detergente comprenant de la zeolite et une enzyme amylase
US5958871A (en) Detergent composition based on zeolite-bicarbonate builder mixture
GB2287948A (en) Laundry detergent composition
GB2303858A (en) Detergent composition
GB2297977A (en) Detergent composition containing Zeolite MAP
GB2296919A (en) Detergent composition
EP0754216B1 (fr) Compositions detergentes contenant des aldobionamides
MXPA97005326A (en) Detergent composition that comprises zeolite map and amil enzymes
WO1997012023A1 (fr) Composition detergente
WO1997012025A1 (fr) Composition detergente comprenant un melange d'adjuvant bicarbonate-zeolite
EP0880578A1 (fr) Composition detergente comportant de la zeolite et une enzyme proteolytique
GB2288187A (en) Detergent composition
EP0964907A1 (fr) Composition detergente contenant un adjuvant de zeolite particulaire et un agent lubrifiant
MXPA98002408A (en) Deterge composition
EP0759463A2 (fr) Composition de détergent
MXPA98002410A (es) Composicion detergente a base de una mezcla mejoradora de detergencia de zeolita y bicarbonato
MXPA98002501A (en) Detergent composition containing a zeolite detergent improvement and a lubricant for elmi
MXPA98002409A (en) Detergent composition comprising zeolite and enzyme proteolit
GB2294269A (en) Detergent composition
MXPA97005327A (en) Detergent composition comprising zeolite and enzyme amil
GB2287950A (en) Detergent composition
MXPA97005330A (en) Deterge composition
EP0733699A2 (fr) Composition détergente

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

17P Request for examination filed

Effective date: 19970701

AK Designated contracting states

Kind code of ref document: A1

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

A4 Supplementary search report drawn up and despatched

Effective date: 19981120

AK Designated contracting states

Kind code of ref document: A4

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

17Q First examination report despatched

Effective date: 20020411

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

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 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: 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: 20040317

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: 20040317

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 20040317

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: 20040317

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: 20040317

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: 20040317

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: 20040317

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: 69631873

Country of ref document: DE

Date of ref document: 20040422

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: 20040617

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: 20040617

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: 20040617

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

ET Fr: translation filed
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: 20050105

Ref country code: IE

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

Effective date: 20050105

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: 20041220

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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 NON-PAYMENT OF DUE FEES

Effective date: 20040817

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

Ref country code: FR

Payment date: 20100125

Year of fee payment: 15

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

Ref country code: DE

Payment date: 20100129

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20110930

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: 20110131

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69631873

Country of ref document: DE

Effective date: 20110802

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

Ref country code: DE

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

Effective date: 20110802

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

Ref country code: GB

Payment date: 20141230

Year of fee payment: 20

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20160104

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 EXPIRATION OF PROTECTION

Effective date: 20160104