EP0873393A1 - Bloc detergent solide - Google Patents

Bloc detergent solide

Info

Publication number
EP0873393A1
EP0873393A1 EP96937246A EP96937246A EP0873393A1 EP 0873393 A1 EP0873393 A1 EP 0873393A1 EP 96937246 A EP96937246 A EP 96937246A EP 96937246 A EP96937246 A EP 96937246A EP 0873393 A1 EP0873393 A1 EP 0873393A1
Authority
EP
European Patent Office
Prior art keywords
weight
block
solid detergent
detergent composition
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96937246A
Other languages
German (de)
English (en)
Other versions
EP0873393B1 (fr
Inventor
Guido Clemens Van Den Brom
Hendrik Johannes J. Connotte
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
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP96937246A priority Critical patent/EP0873393B1/fr
Publication of EP0873393A1 publication Critical patent/EP0873393A1/fr
Application granted granted Critical
Publication of EP0873393B1 publication Critical patent/EP0873393B1/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
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • 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
    • C11D3/06—Phosphates, including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/06—Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/16—Phosphates including polyphosphates

Definitions

  • the present invention relates to a solid detergent block for obtaining an aqueous chemical solution having a substantially constant concentration.
  • the invention also relates to a process for preparing such a block.
  • Such detergent blocks are suitable for use in an industrial cleaning process, particularly a mechanical warewashing process, and generally comprise alkaline agents and detergency builders.
  • Industrial warewashing machines generally comprise a wash tank which contains the cleaning solution for the wash process.
  • the soiled wash load is doused with the cleaning solution and subsequently with rinse water which falls into the wash tank.
  • the cleaning power of the cleaning liquor is reduced, first because some is exhausted by the soil-removing process and, secondly, because it is diluted with rinse water.
  • the cleaning solution is therefore recharged from time to time by adding fresh cleaning product from a dispenser system, which usually provides liquid product or a concentrated aqueous solution of a composition including solid chemicals.
  • a number of techniques are known for converting solid chemicals into a concentrated aqueous solution, dependent on the nature of the solid.
  • a solid powdered chemical can be dissolved by placing it on a sieve and spraying water on to said sieve from below.
  • the powdered material can be dissolved in a dispenser of the "water-in-reservoir" type. In this type of dispenser, the powdered material is submerged under water, which therefore becomes loaded or even saturated with the powder. When more water is added, the excess solution flows into an overflow pipe leading to the washing machine.
  • a well-known type of solid detergent is the cast block form, whereby a solid detergent block having a weight of several kilograms is formed by pouring a concentrated aqueous slurry into a container, in which it solidifies upon cooling as a result of the hydration of the salts in the composition.
  • Such cast solid blocks are, for example, described in European patent 3,769.
  • Solid detergent blocks have won a certain degree of popularity in the area of industrial warewashing because they constitute a non-dusty and therefore relatively safe product form for the often aggressive chemicals used. Furthermore, hydrated solid blocks are economical in use because they can be manufactured and transported as concentrated products. However, elevated temperatures are required in the manufacturing process of these hydrated solid detergent blocks and these temperatures have an adverse effect on the stability of hea -labile components of the blocks.
  • EP-A-375, 022 an alternative type of detergent block is disclosed, namely a block of compressed granular material. This block constitutes an even more concentrated product and enables the incorporation of heat-labile components such as bleach compounds .
  • a good quality block is defined as a block having a bulk density of 1200- 2100 kg/m 3 , preferably 1700-2000 kg/m 3 , and showing neither cracks in the block (lamination) nor at the top or bottom surface of the block (capping) .
  • the present invention provides a solid detergent composition suitable for use in an industrial warewashing process and in the form of a block of compressed granular material, said block having a weight of 0.2-10 kg and comprising:
  • an alkalimetal hydroxide selected from sodium- and potassium hydroxide
  • a phosphate builder 1 - 3 % by weight of a compressing aid selected from low foaming nonionic surfactants, metal soaps, paraffins, talcum powder, polyethylene glycol, sodium benzoate, mixtures of long chain ketones having more than 25 carbon atoms and fatty alcohols, and mixtures thereof; and up to 6% by weight of free water.
  • the detergent block according to the present invention has a weight of 1-5 kg.
  • the present invention provides a process for manufacturing a solid detergent block of the invention, whereby a powder having a corresponding composition is compressed in a mould under a pressure of 3- 30 kN/cm 2 to form a solid block.
  • a third aspect of the present invention is the use of a solid detergent block according to the invention in an industrial warewashing process.
  • the solid detergent blocks of the invention generally contain detergent components usually found in detergent material suitable for use in a machine warewashing process. As shown above, these components comprise an alkalimetal hydroxide, a phosphate builder, and one or more types of compressing aid.
  • the moisture sensitivity is reduced during manufacturing of said blocks. This is of importance since it was found that the free water content of the detergent blocks must be below 6% by weight in order to obtain good quality blocks. A free water content above this level was found to result in lamination and capping phenomena, and or in considerable block expansion by which the lifetime and the block density are dramatically reduced. A high block density of at least 1700 kg/m 3 is preferred since transport cost and amount of packaging material are generally reduced with blocks of higher density.
  • Control of the free water level during manufacture of the detergent blocks of the invention was found to be essential to obtain good quality blocks.
  • the free water level of the detergent blocks is below 4% by weight.
  • free water level is defined as the weight loss observed when heating the granular material used for producing the block concerned, during 4 hours at a temperature of 130°C.
  • alkalimetal hydroxide preferably used in the blocks of the invention, is sodium hydroxide.
  • the blocks of the invention may contain up to 20% by weight of other types of alkaline agent, preferably sodium- or potassium- metasilicate, or -carbonate.
  • Phosphate builder Generally, the detergent blocks of the invention contain 40-55% by weight of phosphate builder. This relatively high concentration range of phosphate builder, in combination with the relatively low level of alkalimetal hydroxide, makes the blocks extremely suitable for use with hard water.
  • the phosphate builder material present in the blocks of the invention is generally defined to be phosphate containing material which is capable of reducing the level of free calcium and magnesium ions in the wash liquor, and, preferably, provides the composition with other beneficial properties such as the generation of an alkaline pH and the suspension of soil removed from the substrate to be removed.
  • Preferred phophate builders are pyrophosphate, orthophosphate and tripolyphosphate. Sodium tripolyphosphate is most preferred.
  • the compressing aid present in the blocks of the invention is selected from low foaming nonionic surfactants,such as C 8 -C 20 alkoxylated fatty alcohols, metal soaps, paraffins, talcum powder, polyethylene glycol, sodium benzoate, mixtures of long chain ketones having more than 25 carbon atoms and fatty alcohols, and mixtures thereof.
  • This compressing aid is an essential ingredient of the detergent block of the invention since it is needed during the compaction process for obtaining strong blocks of good quality. However, only moderate levels of compressing aid, being in the range of 1-3% by weight, are required since levels above said range would result in weaker blocks.
  • Preferred compressing aids are mixtures of long chain ketones having more than 25 carbon atoms and fatty alcohols, since such mixtures are highly effective both as a lubricant during the manufacturing process of the block and as an anti-foaming agent when using the block in a machine warewashing process .
  • These mixtures are preferably in the form of a dispersion of the long chain ketone in the liquid-form fatty alcohol which is preferably a branched fatty alcohol having 8 to 24 carbon atoms.
  • Such compositions are commercially available, for instance from Henkel as Dehypon 2429.
  • the detergent block of the invention may also comprise a bleach component, encapsulated or not, in an amount of up to 20% by weight.
  • Said bleach component may be a hypohaiite bleach such as NaDCCA, or a peroxygen compound, i.e. a compound capable of yielding hydrogen peroxide in aqueous solution.
  • a peroxygen compound selected from alkali metal peroxides, organix peroxides, such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates, is preferably used. Mixtures of two or more of such compounds may also be suitable.
  • sodium perborate tetrahydrate and, especially, sodium perborate monohydrate.
  • Sodium perborate monohydrate is preferred because of its high active oxygen content.
  • Sodium percarbonate may also be preferred for environmental reasons.
  • the peroxygen bleach compound is suitably present in the detergent block of the invention at a level of up to 20% by weight, preferably of from 5 to 10% by weight.
  • the hypohaiite bleach if present, may be suitably used in an amount of up to 5%, preferably 1-4% by weight, as active chlorine.
  • Organic peroxyacids may also be suitable as peroxygen bleaching agent.
  • Such materials normally have the general formula:
  • R is an alkylene or substituted alkylene group containing from 1 to about 20 carbon atoms, optionally having an internal amide linkage; or a phenylene or substituted phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imido-aromatic or non-aromatic group, a COOH or 0 C OOH group or a quaternary ammonium group.
  • Typical monoperoxy acids useful herein include, for example:
  • peroxybenzoic acid and ring-substituted peroxybenzoic acids e.g. peroxy- a-naphthoic acid
  • aliphatic, substituted aliphatic and arylalkyl monoperoxyacids e.g. peroxylauric acid, peroxystearic acid and N,N-phthaloylaminoperoxy caproic acid (PAP)
  • PAP N,N-phthaloylaminoperoxy caproic acid
  • 6-octylamino-6-oxo-peroxyhexanoic acid 6-octylamino-6-oxo-peroxyhexanoic acid
  • diperoxyacids useful herein include, for example: (iv) 1, 12-diperoxydodecanedioic acid (DPDA) ; (v) 1, -diperoxyazelaic acid;
  • inorganic peroxyacid compounds are suitable, such as for example potassium monopersulphate (MPS) .
  • MPS potassium monopersulphate
  • organic or inorganic peroxyacids are used as the peroxygen compound, the amount thereof will normally be within the range of about 2-10 % by weight, preferably from 4-8 % by weight.
  • All these peroxide compounds may be utilized alone or in conjunction with a peroxyacid bleach precursor and/or an organic bleach catalyst not containing a transition metal.
  • Peroxyacid bleach precursors are known and amply described in literature, such as in the British Patents 836988; 864,798; 907,356; 1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522; EP-A-0174132 ; EP-A-0120591; and US Patents 1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.
  • Another useful class of peroxyacid bleach precursors is that of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US Patent 4,751,015 and 4,397,757, in EP-A0284292 and EP-A-331,229. Examples of peroxyacid bleach precursors of this class are:
  • a further special class of bleach precursors is formed by the cationic nitriles as disclosed in EP-A-303,520 and in European Patent Specification No.'s 458,396 and 464,880.
  • any one of these peroxyacid bleach precursors can be used in the present invention, though some may be more preferred than others.
  • the preferred classes are the esters, including acyl phenol sulphonates and acyl alkyl phenol sulphonates; the acyl-amides; and the quaternary ammonium substituted peroxyacid precursors including the cationic nitriles.
  • Examples of said preferred peroxyacid bleach precursors or activators are sodium-4-benzoyloxy benzene sulphonate (SBOBS) ; N,N, 'N' -tetraacetyl ethylene diamine (TAED) ; sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate; sodium- 4-methyl-3-benzoloxy benzoate; SPCC; trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3, 5, 5-trimethyl hexanoyloxyben- zene sulphonate (STHOBS) ; and the substituted cationic nitriles.
  • SBOBS sodium-4-benzoyloxy benzene sulphonate
  • TAED N,N, 'N' -tetraacetyl ethylene diamine
  • TAED sodium-1-methyl-2-benzoyl
  • the precursors may be used in an amount of up to 12 %, preferably from 2-10 % by weight, of the composition.
  • Organic bleach catalyst most suitable for being utilized here are the so-called sulphonimides as disclosed in EP-A- 0453,003 and EP-A-0446, 82.
  • the detergent block of the invention preferably also comprises 0-10% by weight of a polycarboxylated polymer.
  • Suitable polymers are for instance polyacrylates such as Norasol LMW45D, ex Norsohaas.
  • a polycarboxylate polymer on a suitable carrier material for instance a polyacrylate polymer on a carbonate and/or silicate carrier, such as Norasol WL2-Si, ex NorsoHaas, is more preferred.
  • a polycarboxylate polymer on carrier in the detergent block desirably at a level up to 25% by weight, results in a higher density and improved stability of the block.
  • the detergent block of the invention may further comprise suitable minor ingredients, such as bleach stabilizers, enzymes, etc.
  • all solid starting materials should be dry and (in the case of hydratable salts) in a low hydration state.
  • anhydrous phosphate builder is preferably used as constituent of the detergent block.
  • a suitable granular detergent powder corresponding to the desired chemical composition is formed and subsequently compressed in a mould under a pressure of 3-30 kN/cm 2 .
  • all constituents of the detergent block are homogeneously distributed through the powder before compression of said powder is carried out.
  • This process can be carried out in any suitable press, preferably a hydraulic press containing two movable punches, for instance a LAEIS Hydraulische Doppelbuchpresse, TYP HPF 630 as manufactured by LAEIS, West Germany.
  • a hydraulic press preferably a hydraulic press containing two movable punches, for instance a LAEIS Hydraulische Doppelbuchpresse, TYP HPF 630 as manufactured by LAEIS, West Germany.
  • the relative humidity of the air that is contact with the powder to be compacted during the manufacturing process is preferably kept below 35%, more preferably below 10% .
  • Preheating of the powder to be compacted or heating of the punches of the hydraulic press generally results in reduced stickyness of said powder, which in turn leads to less wall friction of the detergent block in the mould, and, consequently, a reduced risk of damage when ejecting said block out of the mould.
  • the powder temperature is preferably kept below 40°C, more preferably below 35°C.
  • the compaction is carried out at such moderate temperatures, considerable levels of heat sensitive components, such as bleach compounds, may be incorporated in the detergent block of the invention. This is regarded as an additional advantage of this manufacturing process .
  • a deaeration step is preferably applied during the compaction process.
  • the detergent block of the invention is desirably packaged as soon as possible, owing to its hygroscopic nature.
  • Another aspect of the invention is the use of the solid detergent block of the invention in an industrial warewashing process. Owing to the relatively high phosphate builder content of the block of the invention, said block is very suitable for use with hard water.
  • the detergent block may be placed inside a suitable dispenser, in which it is sprayed upon with water in order to obtain an aqueous solution of the solid detergent material.
  • the water may also form a slurry or suspension of the chemical material contained therein.
  • Thermphos NW sodium tripolyphophate, ex Hoechst; Dehypon 2429 : mixture of ketones in fatty alcohol, ex
  • Lodige-type mixer Example no. 1 A
  • the free water content of the resulting powder was measured to be 3.4% by weight (for the mixture of Example 1) respectively 6.6% by weight (for the mixture of Example A) .
  • the resulting powder was compressed to 3 kg blocks in a mould under a pressure of 14 kN/cm 2 using a double punch press. During this compaction process, the temperature and relative humidity of the air that was in contact with the powder to be compacted, were respectively
  • the block according to the invention has a significantly better quality than the block of the comparative Example having a free water content in excess of 6% by weight.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

On décrit une composition détergente solide, apte à être utilisée dans un procédé industriel de lavage d'ustensiles et de vaisselle, et se présentant sous la forme d'un bloc de matériel granulaire comprimée, lequel bloc possède un poids compris entre 0,2 et 10 kg et comprend: 25 à 35 % en poids d'un hydroxyde de métal alcalin choisi entre l'hydroxyde de sodium et de potassium, 40 à 55 % en poids d'un adjuvant à base de phosphate, 1 à 3 % en poids d'un agent de compression choisi parmi des tensioactifs non ioniques et faiblement moussants, des savons métalliques, des paraffines, de la poudre de talc, du polyéthylèneglycol, du benzoate de sodium, des mélanges de cétones à chaîne longue comportant plus de 25 atomes de carbone et des alcools gras, ainsi que des mélanges de ces substances, et jusqu'à 6 % en poids d'eau libre. Ce bloc possède des caractéristiques qualitatives optimales.
EP96937246A 1995-11-13 1996-10-23 Bloc detergent solide Expired - Lifetime EP0873393B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP96937246A EP0873393B1 (fr) 1995-11-13 1996-10-23 Bloc detergent solide

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP95203080 1995-11-13
EP95203080 1995-11-13
PCT/EP1996/004658 WO1997018292A1 (fr) 1995-11-13 1996-10-23 Bloc detergent solide
EP96937246A EP0873393B1 (fr) 1995-11-13 1996-10-23 Bloc detergent solide

Publications (2)

Publication Number Publication Date
EP0873393A1 true EP0873393A1 (fr) 1998-10-28
EP0873393B1 EP0873393B1 (fr) 2000-03-29

Family

ID=8220825

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96937246A Expired - Lifetime EP0873393B1 (fr) 1995-11-13 1996-10-23 Bloc detergent solide

Country Status (11)

Country Link
EP (1) EP0873393B1 (fr)
JP (1) JP2000500178A (fr)
AU (1) AU700879B2 (fr)
BR (1) BR9611281A (fr)
CA (1) CA2236210A1 (fr)
DE (1) DE69607490T2 (fr)
ES (1) ES2146027T3 (fr)
TR (1) TR199600896A2 (fr)
TW (1) TW341599B (fr)
WO (1) WO1997018292A1 (fr)
ZA (1) ZA969316B (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19627986A1 (de) * 1996-07-11 1998-01-15 Henkel Kgaa Verfahren zur Herstellung von alkalischen Reinigunsmittel(komponente)n, so erhaltene Reinigungsmittel sowie deren Verwendung

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3721461A1 (de) * 1987-06-30 1989-01-12 Hoechst Ag Formstabile und spezifisch leichte alkalische reinigungsmittel sowie ein verfahren zu ihrer herstellung
GB8830010D0 (en) * 1988-12-22 1989-02-15 Unilever Plc Detergent composition
US5209864A (en) * 1991-07-03 1993-05-11 Winbro Group, Ltd. Cake-like detergent and method of manufacture
DE4229650C1 (de) * 1992-09-04 1994-01-05 Henkel Kgaa Verfahren zur Herstellung von Reinigungstabletten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9718292A1 *

Also Published As

Publication number Publication date
ES2146027T3 (es) 2000-07-16
AU7493096A (en) 1997-06-05
EP0873393B1 (fr) 2000-03-29
BR9611281A (pt) 1999-01-26
DE69607490T2 (de) 2000-08-24
DE69607490D1 (de) 2000-05-04
AU700879B2 (en) 1999-01-14
ZA969316B (en) 1998-05-06
JP2000500178A (ja) 2000-01-11
TR199600896A2 (tr) 1997-05-21
TW341599B (en) 1998-10-01
CA2236210A1 (fr) 1997-05-22
WO1997018292A1 (fr) 1997-05-22

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