EP0802969B1 - Composition detergente comprenant de la zeolite et une enzyme amylase - Google Patents
Composition detergente comprenant de la zeolite et une enzyme amylase Download PDFInfo
- Publication number
- EP0802969B1 EP0802969B1 EP96903400A EP96903400A EP0802969B1 EP 0802969 B1 EP0802969 B1 EP 0802969B1 EP 96903400 A EP96903400 A EP 96903400A EP 96903400 A EP96903400 A EP 96903400A EP 0802969 B1 EP0802969 B1 EP 0802969B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- detergent composition
- zeolite
- composition according
- surfactant
- enzyme
- 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
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
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
-
- 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
Definitions
- the present invention relates to a particulate laundry detergent composition
- a particulate laundry detergent composition comprising an amylase enzyme and a small particle size 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-exchanges particularly crystalline water insoluble sodium aluminosilicate zeolites, have been proposed as replacements for the inorganic phosphates.
- EP 21491A Patent & 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.
- EP-A-580245 proposes a range of 0.005 ⁇ m to 20 ⁇ m
- W094/00545 proposes sizes of below 6 ⁇ m
- DE-A-2656009 proposes a range of 0.5 to 12 ⁇ m
- EP-A-0384070 proposes a zeolite MAP having a d 50 size of 0.1 to 5 ⁇ m, with 0.1 to 1 ⁇ m being preferred when the composition is to be a stable liquid.
- the invention is based in part on the discovery that a problem may occur when a water insoluble zeolite, having a small particle size, is used as a detergency builder in a composition formulated for use in the laundering of fabrics.
- the problem has been found to be particularly pronounced when the zeolite is zeolite MAP.
- 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 than the original stain.
- the invention is based also on the surprising discovery that this problem of white residue formation when the zeolite has a defined small particle size can be reduced by including amylase enzyme in the laundry detergent.
- a particulate laundry detergent composition according to the invention comprises
- the invention also includes use of an amylase enzyme in a particulate laundry composition for reducing white residues on fabrics subjected to laundry washing using the composition, wherein the composition contains surfactant comprising anionic surfactant, zeolite builder having a particle size, expressed as a d 50 value, of less than 1.0 micrometres, and organic or inorganic cobuilder.
- surfactant comprising anionic surfactant, zeolite builder having a particle size, expressed as a d 50 value, of less than 1.0 micrometres, and organic or inorganic cobuilder.
- the zeolite builder comprises zeolite P having a silicon to aluminium ratio of not greater than 1.33 (zeolite MAP).
- the first essential component of the present invention is an aluminosilicate zeolite builder, optionally in conjunction with one or more supplementary builders.
- the zeolite builder is typically present at a level of from 1% to 80%, more preferably from 15% to 40% by weight of the compositions.
- the zeolite detergent builder has a particle size, expressed as a d 50 value of less than 1.0 micrometres, more preferably from 0.05 to 0.9 micrometres, most preferably from 0.2 to 0.7 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.
- Suitable aluminosilicate zeolites have the unit cell formula Na z [(AlO 2 ) z (SiO 2 )y]. XH 2 O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
- the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
- the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP, Zeolite HS and mixtures thereof.
- Zeolite A has the formula Na 12 [AlO 2 ) 12 (SiO 2 ) 12 ]. xH 2 O wherein x is from 20 to 30, especially 27.
- Zeolite X has the formula Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ].276 H 2 O.
- 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 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.
- 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.stearothemiophilus.
- 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 contains surfactant and cobuilder and may contain other detergent components such as 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 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 akyl 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 polygiucosides.
- Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 0094118.
- the builder system includes 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 O 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 8 -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 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 builder is suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the zeolite builder 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 be prepared to any suitable bulk density.
- the composition 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).
- compositions according to the present invention are presented in the following Examples.
Claims (13)
- Composition détergente de blanchissage particulaire comprenant(a) un tensioactif comprenant un tensioactif anionique,(b) un adjuvant zéolite et(c) un co-adjuvant organique ou minéral,
l'adjuvant zéolite a une taille particulaire, exprimée comme une valeur d50, inférieure à 1,0 micromètre et la composition comprend une enzyme amylase. - Composition détergente selon la revendication 1, dans laquelle ledit adjuvant zéolite a une taille particulaire, exprimée comme une valeur d50, de 0,05 à 0,9 micromètre.
- Composition détergente selon l'une quelconque des revendications 1 ou 2, dans laquelle ledit adjuvant zéolite comprend la zéolite P ayant un rapport du silicium à l'aluminium non supérieur à 1,33 (zéolite MAP).
- Composition détergente selon l'une quelconque des revendications 1 à 3, dans laquelle ledit adjuvant zéolite est cristallin et comprend 10-28 % d'eau liée et est présent en une quantité de 15 % à 40 % en poids de la composition.
- Composition détergente selon l'une quelconque des revendications 1 à 4, dans laquelle ladite enzyme amylase est une α-amylase.
- Composition détergente selon l'une quelconque des revendications 1 à 6, dans laquelle ladite enzyme amylase est présente en une quantité de 0,1 % à 5 %, d'enzyme active en poids de la composition, sur une base d'activité de 60 KNU/g.
- Composition détergente selon l'une quelconque des revendications 1 à 6, contenant un tensioactif en une quantité de 5 % à 50 % en poids de la composition.
- Composition détergente selon l'une quelconque des revendications précédentes, dans laquelle ledit co-adjuvant comprend un silicate lamellaire cristallin ou un carboxylate monomère ou polymère.
- 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.
- Composition détergente selon la revendication 9, dans laquelle ledit composé de blanchiment peroxy est le percarbonate de sodium.
- Composition détergente particulaire selon l'une quelconque des revendications précédentes, qui est une composition granulaire qui a une masse volumique apparente d'au moins 550 g/l.
- Composition détergente particulaire selon l'une quelconque des revendications précédentes, ayant une masse volumique apparente d'au moins 700 g/l et préparée par densification postérieure en tour ou par pulvérisation d'une poudre sèche ou par mélange à sec et granulation.
- Utilisation d'une enzyme amylase dans une composition de blanchissage particulaire pour réduire les résidus blancs sur des tissus soumis au lavage par blanchissage utilisant la composition, dans laquelle la composition contient un tensioactif comprenant un tensioactif anionique, un adjuvant zéolite ayant une taille particulaire, exprimée comme une valeur d50, inférieure à 1,0 micromètre, et un co-adjuvant organique ou minéral.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9500738.1A GB9500738D0 (en) | 1995-01-14 | 1995-01-14 | Detergent composition |
GB9500738 | 1995-03-31 | ||
PCT/US1996/000281 WO1996021717A1 (fr) | 1995-01-14 | 1996-01-05 | Composition detergente comprenant de la zeolite et une enzyme amylase |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0802969A1 EP0802969A1 (fr) | 1997-10-29 |
EP0802969A4 EP0802969A4 (fr) | 1999-12-01 |
EP0802969B1 true EP0802969B1 (fr) | 2003-10-08 |
Family
ID=10768053
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96903400A Expired - Lifetime EP0802969B1 (fr) | 1995-01-14 | 1996-01-05 | Composition detergente comprenant de la zeolite et une enzyme amylase |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0802969B1 (fr) |
AR (1) | AR000717A1 (fr) |
AT (1) | ATE251664T1 (fr) |
BR (1) | BR9606758A (fr) |
CA (1) | CA2210293C (fr) |
DE (1) | DE69630279T2 (fr) |
ES (1) | ES2206559T3 (fr) |
GB (1) | GB9500738D0 (fr) |
WO (1) | WO1996021717A1 (fr) |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ZA767170B (en) * | 1975-12-15 | 1978-07-26 | Colgate Palmolive Co | Detergent composition and method for use |
US4900475A (en) * | 1985-07-26 | 1990-02-13 | Colgate-Palmolive Co. | Stabilized built liquid detergent composition containing enzyme |
CA2001927C (fr) * | 1988-11-03 | 1999-12-21 | Graham Thomas Brown | Aluminosilicates et detergents |
US5030377A (en) * | 1988-11-11 | 1991-07-09 | Kao Corporation | Detergent compositions containing starch debranching enzymes |
DE4034131C2 (de) * | 1990-10-26 | 1999-08-26 | Henkel Kgaa | Gerüststoff für Waschmittel |
CA2083331C (fr) * | 1991-11-26 | 1998-08-11 | Johannes H. M. Akkermans | Compositions pour detergent |
CZ280524B6 (cs) * | 1992-01-17 | 1996-02-14 | Unilever Nv | Částicové detergenční směsi |
AU4326193A (en) * | 1992-06-25 | 1994-01-24 | Unilever Plc | Machine dishwashing composition |
AU669900B2 (en) * | 1992-07-20 | 1996-06-27 | Colgate-Palmolive Company, The | Stabilized built aqueous liquid softergent compositions |
-
1995
- 1995-01-14 GB GBGB9500738.1A patent/GB9500738D0/en active Pending
-
1996
- 1996-01-05 DE DE69630279T patent/DE69630279T2/de not_active Expired - Fee Related
- 1996-01-05 EP EP96903400A patent/EP0802969B1/fr not_active Expired - Lifetime
- 1996-01-05 ES ES96903400T patent/ES2206559T3/es not_active Expired - Lifetime
- 1996-01-05 WO PCT/US1996/000281 patent/WO1996021717A1/fr active IP Right Grant
- 1996-01-05 BR BR9606758A patent/BR9606758A/pt not_active Application Discontinuation
- 1996-01-05 AT AT96903400T patent/ATE251664T1/de not_active IP Right Cessation
- 1996-01-05 CA CA002210293A patent/CA2210293C/fr not_active Expired - Fee Related
- 1996-01-12 AR ARP960101000A patent/AR000717A1/es unknown
Also Published As
Publication number | Publication date |
---|---|
AR000717A1 (es) | 1997-08-06 |
EP0802969A4 (fr) | 1999-12-01 |
MX9705327A (es) | 1997-10-31 |
EP0802969A1 (fr) | 1997-10-29 |
ES2206559T3 (es) | 2004-05-16 |
WO1996021717A1 (fr) | 1996-07-18 |
DE69630279D1 (de) | 2003-11-13 |
GB9500738D0 (en) | 1995-03-08 |
ATE251664T1 (de) | 2003-10-15 |
BR9606758A (pt) | 1998-01-06 |
CA2210293C (fr) | 2001-07-24 |
DE69630279T2 (de) | 2004-07-22 |
CA2210293A1 (fr) | 1996-07-18 |
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