EP0689584A1 - Detergent synthetique en pain et fabrication de celui-ci - Google Patents

Detergent synthetique en pain et fabrication de celui-ci

Info

Publication number
EP0689584A1
EP0689584A1 EP94911169A EP94911169A EP0689584A1 EP 0689584 A1 EP0689584 A1 EP 0689584A1 EP 94911169 A EP94911169 A EP 94911169A EP 94911169 A EP94911169 A EP 94911169A EP 0689584 A1 EP0689584 A1 EP 0689584A1
Authority
EP
European Patent Office
Prior art keywords
soap
detergent
water
bars
synthetic
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
EP94911169A
Other languages
German (de)
English (en)
Other versions
EP0689584B1 (fr
Inventor
John George Chambers
Bryan Stuart Joy
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
Publication of EP0689584A1 publication Critical patent/EP0689584A1/fr
Application granted granted Critical
Publication of EP0689584B1 publication Critical patent/EP0689584B1/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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides

Definitions

  • This invention relates to synthetic detergent bars and detergent compositions which can be shaped into bars.
  • Washing bars can be classified into soap bars, mixed active bars containing a significant proportion of soap and thirdly synthetic detergent bars containing only a small proportion of soap or none at all.
  • Conventional soap bars comprise a large proportion, typically 60-80% by weight, of fatty acid soap.
  • Fatty acid soaps are selected to provide a balance of soluble and insoluble soaps which provide the required functional properties as regards lather formation and bar structure.
  • Conventional soap bars are manufactured by milling, plodding and stamping a semi-solid mass of soap and other components.
  • Bars which contain a mixture of soap and synthetic detergent where the amount of soap may be less than the amount of synthetic detergent but is nevertheless still a significant contributor to the content of the bar.
  • the content of soap especially the insoluble soap contributes to the structure and physical properties of the bar.
  • the third category is synthetic detergent bars, often known as "Syndet” bars, in which there is no soap or only a small amount and the detergent active is mostly or wholly a synthetic, non-soap, detergent.
  • Such bars contain a substantial proportion of material which is not a detergent and which serves to give structure to the bar.
  • Such "structurants” are normally water- insoluble and include such materials as starch and kaolin.
  • the bars frequently also contain a plasticiser: known plasticisers include stearic acid and cetyl alcohol.
  • known surfactants for Syndet bars include primary alkyl sulphates, alkyl ether sulphates, betaines, sarcosinates, sulphosuccinates and isethionates. These syndet bars containing no soap or only a small proportion of soap are traditionally produced by energetic working of a physical mix of structurant, plasticiser and surfactant, i.e. both the soluble and insoluble components, in a high shear mixer to an end point at which the product is not gritty. The mix is then formed into 'syndet' bars.
  • the known process has several disadvantages in that the physical mixing step is performed batchwise and requires an energetic mixer.
  • syndet bars may be produced by a process which dispenses with the known energetic working step.
  • the invention relies on ingredients which are molten at conveniently accessible temperatures but which are above the temperatures normally encountered during use of "Syndet" bars.
  • the necessary intimate mixing of the ingredients of the bar can be accomplished by simple mixing while the bar composition is liquid rather than by relying on energetic working to achieve intimate mixing of a mixture of solids.
  • the present invention provides a detergent composition which is, or can be shaped into, a synthetic detergent bar, the composition comprising:
  • the content (if any) of material other than said synthetic non-soap detergent (a) which does not melt below 100°C is less than 20% by weight of the composition.
  • the content of the synthetic detergent (a) will lie in the range 10 to 50% by weight.
  • the composition will contain some water, in an amount from 3% or 5% to 20% better at most 15% by weight of the composition.
  • a significant constituent of a composition according to this invention is a water-soluble material which melts at a temperature in the range 40-100°C and serves as a bar structurant.
  • Such a material assists in giving the desired properties notably that the bar has a rigid solid form.
  • the composition of the bar can tolerate the presence of some material which does not melt at temperatures below 100°C.
  • Such material can also serve as a structurant.
  • Such material is not an essential requirement and it may be entirely absent. If such material is present, the molten composition will not be fully liquid at temperatures of up to 100°C unless the non-melting material dissolves in the other materials present.
  • a moderate amount of material which does not melt can be dispersed in the molten composition while it remains sufficiently liquid to be stirred without requiring energetic working.
  • this material which disperses but does not melt may be at least part of the non-soap synthetic detergent (a) and/or material other than this category.
  • Suitable synthetic detergents are: alkyl ether sulphates; alkylethoxylates; alkyl glyceryl ether sulphonates; alpha olefin sulphonates; acyl taurides; methyl acyl taurates; N- acyl glutamates; acyl isethionates; anionic acyl sarcosinates; alkyl phosphates; methyl glucose esters; protein condensates,- ethoxylated alkyl sulphates; alkyl polyglucosides; alkyl amine oxides; betaines; sultaines,- alkyl sulphosuccinates, dialkyl sulphosuccinates, acyl lactylates and mixtures thereof.
  • the above-mentioned detergents are preferably those based upon C 8 to C 24 , more preferably those based upon C 10 to C 18 , alkyl and acyl moieties.
  • the amount of synthetic detergent (a) may lie in the range from 10 to 50% wt . Further preferences are at least 20% and not more than 40%.
  • acyl isethionates are less water-soluble than others. If a detergent of low solubility is used, it is preferably mixed with another synthetic detergent.
  • detergent compositions of this invention may possibly exclude acyl isethionate from the synthetic detergent (a) or may possibly include it jointly with other synthetic detergent.
  • acyl isethionate is not more than 10% by weight of the composition e.g. 5% to 9.5%.
  • further embodiments of the invention include larger quantities of acyl isethionate, e.g. up to 30% by weight of the composition.
  • the water-soluble structurant (b) is required to melt in the temperature range from 40°C to 100°C so that it can be melted to form the bar composition but will be in a solid state at temperatures at which the bar will be used.
  • it has a melting point of at least 50°C, notably in the narrower range from 50°C to 90°C.
  • water-soluble structurant (b) Materials which are envisaged as the water-soluble structurant (b) are moderately high molecular weight polyalkylene oxides of appropriate melting point and in particular polyethylene glycols or mixtures thereof.
  • Polyethylene glycols which are used may have a molecular weight in the range 1500-10,000. However, in some embodiments of this invention it is preferred to include a fairly small quantity of polyethylene glycol with a molecular weight in the range from 50,000 to 500,000, especially molecular weights of around 100,000. Such polyethylene glycols have been found to improve the wear rate of the bars. It is believed that this is because their long polymer chains remain entangled even when the bar composition is wetted during use.
  • the quantity is preferably from 1% to 5%, more preferably from 1% or 1.5% to 4% or 4.5% by weight of the composition.
  • these materials will generally be used jointly with a larger quantity of other water-soluble structurant (b) such as the abovementioned polyethylene glycol of molecular weight 1500 to 10,000.
  • polyethylene oxide-polypropylene oxide block copolymers melt at temperatures in the required range of 40 to 100°C and may be used as part or all of the water- soluble structurant (b) .
  • block copolymers in which polyethylene oxide provides at least 40% by weight of the block copolymer.
  • Such block copolymers may be used, in mixtures with polyethylene glycol or other water-soluble structurant.
  • the total quantity of water-soluble structurant (b) is from 20% to 50% by weight of the composition.
  • the water-insoluble structurants (c) are also required to have a melting point in the range 40-100°C, more preferably at least 50°C, notably 50°C to 90°C.
  • Suitable materials which are particularly envisaged are fatty acids, particularly those having a carbon chain of 12 to 24 carbon atoms. Examples are lauric, myristic, palmitic, stearic, arachidic and behenic acids and mixtures thereof. Sources of these fatty acids are coconut, topped coconut, palm, palm kernel, babassu and tallow fatty acids and partially or fully hardened fatty acids or distilled fatty acids.
  • Other suitable water- insoluble structurants include alkanols of 8 to 20 carbon atoms, particularly cetyl alcohol. These materials generally have a water-solubility of less than 5g/litre at 20°C.
  • the relative proportions of the water-soluble structurants (b) and water-insoluble structurants (c) govern the rate at which the bar wears during use.
  • the presence of the water-insoluble structurant tends to delay dissolution of the bar when exposed to water during use and hence retard the rate of wear.
  • the total quantity of component (c) is from 10% to 40% by weight of the composition.
  • a water-insoluble material which does not melt below 100°C can function as an additional bar structurant. It may be stipulated as a requirement that the content (if any) of water-insoluble material which does not melt below 100°C is less than 20% by weight of the composition.
  • a water-insoluble structurant (c) which does not melt below 100°C may well be selected from plant materials or minerals. Starches, including corn starch, are preferred amongst the plant materials while kaolin and calcite are preferred mineral materials.
  • the ratio of water-soluble structurant (b) to the total of water- insoluble structurants may possibly lie in a range from 2:3 or 1:1 up to 3:1 or 5:1.
  • Some soap that is to say salts of monocarboxylic fatty acids having chain lengths of 8 to 22 carbon atoms may be included in the bar compositions of this invention.
  • the amount is desirably not greater than 10% by weight of the composition.
  • water-insoluble soaps are salts of saturated fatty acids having chain lengths of 16 to 22 carbon atoms, especially 16 and 18.
  • these salts are sodium salts. They melt at temperatures above 100°C and therefore come within a category (e) which is material, other than synthetic detergent, melting above 100°C.
  • water-insoluble soap is present in the composition, the amount of it desirably does not exceed 10% by weight of the composition, for example lying in a range from 3% to 9.5% by weight, more preferably 5% to 9%.
  • soluble structurant a combination of polyethylene glycol with molecular weight 50,000 to 500,000 as at least part of the soluble structurant (b) and water- insoluble soap as at least part of the insoluble material (c) .
  • Use of these materials in combination has been found to improve wear rate of the bars, while also giving them a good feel when handled during use.
  • the preferred amounts, by weight of the composition are: 4 to 9.5% of water-insoluble soap and 1.5 to 4.5% polyethylene glycol with molecular weight in the range from 50,000 to 500,000.
  • Non-soap synthetic detergent which does not completely liquify at temperatures below 100°C, for example acyl isethionates; soap, especially water-insoluble soap, which does not melt below 100°C; other water-insoluble materials which do not melt below 100°C.
  • Materials, other than synthetic detergent, which are water-soluble but do not melt below 100°C are preferably absent, or present only in quantities which are small such as not more than 10% better not more than 5% by weight of the composition.
  • the total quantity of material in the second and third of these categories is not more than 20% by weight of the composition.
  • the total quantity of material which does not melt below 100°C should not exceed 50% by weight of the composition, preferably less, such as not more than 40% or not more than 30%, or even 20% and should not be so much that the molten composition ceases to be stirrable.
  • Bar compositions of this invention will usually contain water, but the amount of water is only a fairly small proportion of the bar. Larger quantities of water reduce the hardness of the bars. Preferred is that the quantity of water is not over 15% by weight of the bars, e.g. lying in a range from 3% or 5% to 14.9% by weight.
  • Bars of this invention may optionally include so-called benefit agents - materials included in relatively small proportions which confer some benefit additional to the basic cleansing action of the bars.
  • benefit agents include emollients such as fatty alcohols and vegetable oils, essential oils, waxes, phospholipids, lanolin, anti-bacterial agents and sanitisers, opacifiers, pearlescers, electrolytes, perfumes, suncreens, fluorescers and colouring agents.
  • Preferred skin conditioning agents comprise silicone oils, mineral oils and/or glycerol .
  • a process for the manufacture of synthetic detergents bars rfhich comprises the steps of :
  • step (ii) cooling the product of step (i) to a temperature at which it solidifies
  • step (iii) forming the product of step (i) into bars.
  • the liquid mixture can be a single or multiple phase system.
  • the single phase can be an isotropic mixture whereas the multiple phase system can comprise either an emulsion or liquid crystal dispersion.
  • the mixture can be prepared by mixing of the components followed by heating of the mixture to the molten state when further mixing will occur, or by heating of the components followed by mixing of the components.
  • Step (i) may be carried out in a stirred, heated vessel.
  • a useful procedure begins with melting the fatty acid in a heated vessel with a stirrer. The stirrer is started, and the polyalkylene oxide is added. At this stage any soap is made in situ by partial neutralisation of the fatty acid.
  • the end result is a macroscopically homogenous molten mixture, with not more than 50% solids present.
  • step (ii) is carried out on a chilled, scraped roller which may be part of a chilled mill.
  • Step (iii) can comprise milling, plodding and stamping, or optional milling followed by compression of the material into a bar shape.
  • the liquid mixture from step (i) is cast into moulds.
  • the casting step can be employed to form a log which is further processed into bars or to form bars directly.
  • the process steps (ii) and (iii) are combined; the moulds which are used can form the final packaging of the bars or the bars can be extracted from the moulds and re-packaged.
  • compositions (A) and (B) were melted together at 80°C to produce a material consisting predominantly of a liquid phase. All amounts are given in percentages by weight .
  • solid, generally cuboid bars were formed from compositions (A) and (B) using a single bar press. Identical compositions were also formed into bars by using a casting process from the hot melt.
  • SLES 3EO denotes sodium lauryl ether sulphate with average 3 ethylene oxide residues.
  • PEG 4000 denotes polyethylene glycol with mean molecular weight 4000.
  • Aerosol OT is dioctylsulphosuccinate
  • a quantity of each melt was processed into bars by a different route.
  • the melt was cooled by passing over a chilled three-roll mill. Small quantities of perfume, opacifier and fluorescer were added, totalling less than 2% by weight of the composition.
  • the resulting composition was re-milled, passed through a vacuum plodder and stamped into the desired bar shape using a manual press .
  • the materials listed in Table 5 below were made into bars by the procedure of Example 2. All amounts are given in percentages by weight.
  • the water-soluble structurant was a mixture of polyethylene glycol and a block copolymer of polyethylene oxideand polypropylene oxide, available as Pluronic F87, ex BASF Germany.
  • the PEG 4000 and stearic acid were the first materials to be heated and melted. When these were molten, a small quantity of sodium hydroxide was added to neutralise a little of the stearic acid to sodium stearate. After this the remaining materials were added and stirred to produce a pumpable, homogeneous liquid.
  • Each melt was cooled by passing over a chilled three- roll mill. 1% of perfume, and 0.3% of titanium dioxide as opacifier were then added, followed by milling and plodding the resulting composition and stamped into the desired bar shape using a manual press.
  • compositions 7C and 7F gave compositions which were too soft to process whereas the remaining compositions could be processed into firm bars .
  • Example 8
  • compositions from the preceding examples were assessed for mildness using a zein test generally as described by Gotte, Proc. Int. Cong. Surface Active Subs., 4th, Brussels, 3., 89-90 (1964) .
  • the test determines the amount of amino acid solubilised from zein under specified conditions.
  • the solubilised material is determined by a nitrogen assay. The results were as follows.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

Composition détergente que l'on peut transformer en pains utilisables pour les soins personnels. Elle comporte (a) de 10 à 60 % en poids d'un détergent synthétique non savonneux; (b) de 10 à 60 % en poids d'une matière hydrosoluble qui est ni un savon ni un détergent non savonneux et qui présente un point de fusion compris entre 40 et 100 °C; et (c) de 5 à 50 % en poids d'une matière non hydrosoluble qui est ni un savon ni un détergent non savonneux et qui présente un point de fusion compris entre 40 et 100°C. Le cas échéant, la teneur en eau est égale ou inférieure à 20 % en poids de la composition, et de préférence inférieure à 15 % en poids. Les matières (b) et (c) servent à conférer une structure aux pains. On peut préparer les compositions en mélangeant les constituants précités à l'état fondu, à une température comprise entre 50 et 100 °C, et sans le malaxage vigoureux traditionnel. De préférence, le mélange en fusion renferme moins de 20 % en poids de matière, mis à part le détergent synthétique non savonneux, qui n'entre pas dans la phase liquide. On peut transformer le mélange en fusion en pains par coulée, ou le refroidir, le broyer, le boudiner et le découper afin d'obtenir des pains.
EP94911169A 1993-03-16 1994-03-14 Detergent synthetique en pain et fabrication de celui-ci Expired - Lifetime EP0689584B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9305377 1993-03-16
GB939305377A GB9305377D0 (en) 1993-03-16 1993-03-16 Synthetic detergent bar and manufacture thereof
PCT/EP1994/000792 WO1994021778A1 (fr) 1993-03-16 1994-03-14 Detergent synthetique en pain et fabrication de celui-ci

Publications (2)

Publication Number Publication Date
EP0689584A1 true EP0689584A1 (fr) 1996-01-03
EP0689584B1 EP0689584B1 (fr) 1999-10-13

Family

ID=10732138

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94911169A Expired - Lifetime EP0689584B1 (fr) 1993-03-16 1994-03-14 Detergent synthetique en pain et fabrication de celui-ci

Country Status (16)

Country Link
EP (1) EP0689584B1 (fr)
JP (1) JP2740355B2 (fr)
KR (1) KR100200456B1 (fr)
AU (1) AU694728B2 (fr)
BR (1) BR9406008A (fr)
CA (1) CA2157773C (fr)
CZ (1) CZ287044B6 (fr)
DE (1) DE69421172T2 (fr)
ES (1) ES2139738T3 (fr)
GB (1) GB9305377D0 (fr)
HU (1) HU217658B (fr)
IN (1) IN181612B (fr)
PL (1) PL177068B1 (fr)
SK (1) SK113995A3 (fr)
WO (1) WO1994021778A1 (fr)
ZA (1) ZA941813B (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5520840A (en) * 1995-03-22 1996-05-28 Lever Brothers Company Detergent bars comprising water soluble starches
US5540854A (en) * 1995-04-28 1996-07-30 Lever Brothers Company, Division Of Conopco, Inc. Polyalkylene structured detergent bars comprising organic amide
EP0781838A1 (fr) * 1995-12-29 1997-07-02 Colgate-Palmolive Company Composition détergente ayant un pouvoir nettoyant amélioré
US5683973A (en) * 1996-02-15 1997-11-04 Lever Brothers Company, Division Of Conopco, Inc. Mild bar compositions comprising blends of higher melting point polyalkylene glycol(s) and lower melting point polyalkylene glycol(s) as processing aids
US5780405A (en) * 1996-03-18 1998-07-14 Lever Brothers Company, Division Of Conopco, Inc. Bar composition comprising copolymer mildness actives
CA2248099A1 (fr) * 1996-04-24 1997-10-30 Michael Massaro Composition synthetique se presentant sous forme de pain et comprenant des tensioactifs alcoxyles
US5795852A (en) * 1996-04-24 1998-08-18 Lever Brothers Company, Division Of Conopco, Inc. Bar composition comprising nonionic polymeric surfacing as mildness enhancement agents
US5786312A (en) * 1996-06-12 1998-07-28 Lever Brothers Company, Division Of Conopco, Inc. Bar composition comprising copolymer mildness actives
GB2316088A (en) * 1996-08-06 1998-02-18 Cussons Int Ltd Lotion Bar
US5916856A (en) * 1996-10-16 1999-06-29 Lever Brothers Company Pourable cast melt bar compositions comprising low levels of water and minimum ratios of polyol to water
ES2227900T3 (es) * 1997-11-26 2005-04-01 THE PROCTER & GAMBLE COMPANY Procedimiento para fabricar una pastilla detergente.
ATE287944T1 (de) * 1997-11-26 2005-02-15 Procter & Gamble Waschmitteltablette
DE69805758T2 (de) * 1997-11-26 2003-01-30 Procter & Gamble Geschirrspülverfahren
CA2340706A1 (fr) * 1998-08-26 2000-03-09 Unilever Plc Batons cosmetiques comprenant un agent traitant et un polymere cationique
DE102016116112A1 (de) * 2016-06-29 2018-01-04 Buck-Chemie Gmbh Stückförmiges Reinigungsmittel für den WC-Bereich

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BE541084A (fr) * 1954-09-06
US2987484A (en) * 1959-05-29 1961-06-06 Procter & Gamble Closed die molding a detergent bar
US3376229A (en) * 1964-12-11 1968-04-02 Lever Brothers Ltd Synthetic detergent bar
US3687855A (en) * 1969-05-05 1972-08-29 Synergistics Inc Solid iodophor cleansing compositions
GB1294754A (en) * 1969-12-01 1972-11-01 Unilever Ltd Synthetic detergent toilet bars
WO1992013060A2 (fr) * 1991-01-28 1992-08-06 The Procter & Gamble Company Systemes de liants utilises dans des savons en barres

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Also Published As

Publication number Publication date
CA2157773C (fr) 2000-07-18
KR100200456B1 (ko) 1999-06-15
JP2740355B2 (ja) 1998-04-15
CA2157773A1 (fr) 1994-09-29
CZ287044B6 (en) 2000-08-16
DE69421172T2 (de) 2000-01-20
ES2139738T3 (es) 2000-02-16
CZ235995A3 (en) 1996-01-17
PL177068B1 (pl) 1999-09-30
DE69421172D1 (de) 1999-11-18
HUT73042A (en) 1996-06-28
ZA941813B (en) 1995-09-15
IN181612B (fr) 1998-07-25
HU217658B (hu) 2000-03-28
HU9501988D0 (en) 1995-09-28
GB9305377D0 (en) 1993-05-05
AU6377194A (en) 1994-10-11
PL310619A1 (en) 1995-12-27
JPH08507816A (ja) 1996-08-20
SK113995A3 (en) 1997-07-09
WO1994021778A1 (fr) 1994-09-29
EP0689584B1 (fr) 1999-10-13
AU694728B2 (en) 1998-07-30
BR9406008A (pt) 1995-12-26

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