EP0972009A1 - Compositions de nettoyage pour w.c. - Google Patents

Compositions de nettoyage pour w.c.

Info

Publication number
EP0972009A1
EP0972009A1 EP98912449A EP98912449A EP0972009A1 EP 0972009 A1 EP0972009 A1 EP 0972009A1 EP 98912449 A EP98912449 A EP 98912449A EP 98912449 A EP98912449 A EP 98912449A EP 0972009 A1 EP0972009 A1 EP 0972009A1
Authority
EP
European Patent Office
Prior art keywords
block according
polymer
water
block
ethylenically unsaturated
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
EP98912449A
Other languages
German (de)
English (en)
Other versions
EP0972009B1 (fr
Inventor
Marcella M. L. Unilever Italia S.p.A BARTOLETTI
Ronald Meredith Morris
Roberto Unilever Italia S.p.A. TUMMIOLO
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 EP0972009A1 publication Critical patent/EP0972009A1/fr
Application granted granted Critical
Publication of EP0972009B1 publication Critical patent/EP0972009B1/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
    • C11D17/0056—Lavatory cleansing blocks
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D3/18—Hydrocarbons
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3955—Organic bleaching agents
    • 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
    • C11D3/50—Perfumes
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

Definitions

  • This invention is concerned with improvements in and relating to lavatory cleansing compositions. More particularly, the invention is concerned with solid lavatory cleansing compositions which may be used to impart cleansing and/or other components to the flush water of a lavatory or urinal by placement of the composition in the cistern of the lavatory or urinal .
  • compositions to impart cleansing and/or other components to the flush water of a lavatory or urinal are well known.
  • Such compositions may, for example, be immersed in the water of a lavatory cistern either in free-standing form or in containerised form (i.e. in a dispensing container which allows for release of components of the solid composition in solution in water in a moie or less metered fashion, on flushing of the cistern) .
  • the solid composition may be held under the rim of a toilet, in a suitable holder, for intermittent contact of the solid material with flush water.
  • a suitable holder for intermittent contact of the solid material with flush water.
  • Solid lavatory cleansing compositions typically comprise a surfactant component, generally together with one or more fillers or builders (e.g. inorganic salts such as sodium sulphate, sodium chloride etc.). Commonly, such compositions also contain a dyestuff and, frequently, a dissolution retardant material.
  • a surfactant component generally together with one or more fillers or builders (e.g. inorganic salts such as sodium sulphate, sodium chloride etc.).
  • fillers or builders e.g. inorganic salts such as sodium sulphate, sodium chloride etc.
  • such compositions also contain a dyestuff and, frequently, a dissolution retardant material.
  • GB1364459 and GB1364460 disclose that the incorporation of a hydrophobic material such as a wax, stearin, long chain alcohol (up to 6EO) , paradichlorobenzene or ethylene glycol monostearate in a lavatory block enables the solubility rate of the block to be controlled.
  • a hydrophobic material such as a wax, stearin, long chain alcohol (up to 6EO) , paradichlorobenzene or ethylene glycol monostearate in a lavatory block enables the solubility rate of the block to be controlled.
  • EP0167210 is concerned with a lavatory rim-block which is free of the solid perfume component para-dichlorobenzene (PDCB) .
  • the block contains as essential ingredients anionic surfactant (40-90%wt) an inert or electrolyte filler (5- 55%wt) and an oily liquid perfume (5-55%wt) .
  • the block may also contain non-surfactant nonionic polymeric materials such as polyethylene glycols and minor ingredients such as dyes, germicides, fungicides, bleaches, opacifiers and the like.
  • EP 0 073 542 describes a lavatory cleansing block comprising a partially esterified copolymer of vinyl methyl ether and maleic anhydride.
  • compositions having mineralisation prevention properties is disclosed in US4861511.
  • the compositions disclosed therein contains from 2% to 15% by weight of a polyacrylate having a molecular weight in the range 500 - 50,000.
  • any reference to an average molecular weight means the weight average molecular weight, unless specifically recited to the contrary.
  • W096/28536 which relates to a slow release lavatory block which comprises a water soluble polymer derived from one or more ethylenically unsaturated carboxyl group- containing monomers and having an average molecular weight greater than 50,000.
  • Polymers of acrylic acid with molecular weights of about 90,000 are preferred.
  • halogen release agents are, by their nature, powerful chemically reactive species, serving as halogenating or oxidising agents.
  • halogen release agents tend to react with surface active materials and/or tend, when moistened, to evolve gas destroying the physical integrity of the cleaning composition, particularly in the case of free standing blocks for immersion in the cistern of a lavatory.
  • improved in-cistern blocks can be formulated which comprise: a bleaching agent (or its precursor) , an oily liquid perfume and a water-insoluble polymer derived from one or more ethylenically unsaturated carboxyl group-containing monomers.
  • a slow-release lavatory cleansing block comprising:
  • the water-insoluble, gelling polymers used in the composition of the invention are polycarboxylic acids derived from one or more ethylenically unsaturated carboxyl group-containing monomers, especially ethylenically unsaturated carboxylic acids such as acrylic acid or maleic acid.
  • the carboxyl group-containing monomers may be polymerized alone or in combination with other ethylenically unsaturated monomers.
  • the preferred polymers in embodiments of the present invention are those which are readily available in the marketplace. These are polymers of acrylic or methacrylic acid or maleic anhydride, or a co-polymer of one or more of the same either together or with other monomers. In general, polymers derived largely or wholly from the acidic monomers are preferred.
  • Suitable polymers include polyacrylic acid, polymaleic anhydride and copolymers of either of the aformentioned with ethylene, styrene and methyl vinyl ether.
  • Typical polymers are polyacrylic acid and acrylic acid/ aleic acid copolymers .
  • the polymers are employed in the form of acids, but can also be employed as salts e.g. alkali metal salts such as the sodium salt.
  • the use of the polymer salts is advantageous if it is required to reduce dust production during formulation and manufacture.
  • the cross-linked polyacrylate polymers of the present invention are generally characterised as resins in the form of acrylic acid polymers. Such materials are available from a number of sources including materials available under the tradename CARBOPOL (TM) from B. F. Goodrich Company, the tradename SOKOLAN (TM) from the BASF Corporation and under the tradename POLYGEL (TM) from 3V Sigma.
  • the cross-linked polyacrylate polymers are generally characterised as acrylic acid polymers which are cross-linked with an additional monomer or monomers in order to exhibit an effective molecular weight of one to seven million g/mole.
  • the average formula weight for a polymer sub-unit is preferably of the order of 60-120 g/mole.
  • the polymer is suitably present in an amount of from 0.5 to 20% by weight, more preferably from 1 to 5% by weight, most preferably around 2-3% by weight thereof.
  • Polygel DB (TM) ex 3V Sigma a cross-linked high molecular weight polyacrylate, has been found to be a suitable material at an inclusion level of around 2-3%wt.
  • the composition will also contain a surfactant component which may be anionic or nonionic in nature.
  • the surfactant serves to provide a cleansing and foaming effect and may, also act synergistically with the polymer component.
  • surfactant comprises up to 50%wt of the composition.
  • the surfactant component comprises one or more anionic surface active agents, optionally in combination with one or more nonionic surface active agents.
  • Suitable anionic surface active agents include alkali metal or ammonium alkylaryl sulphonates (especially alkyl benzene sulphonates), alkane sulphonates, alkyl sulphates and sarcosinates .
  • a surfactant system which comprises primary alkyl sulphate (PAS) together with other anionic surfactants.
  • PAS primary alkyl sulphate
  • the present invention provides a lavatory block comprising l-15%wt (more preferably l-5%wt) of a primary alkyl sulphate and 15-50%wt (more preferably 30-50%wt) of other anionic surfactants.
  • this mixed surfactant system is advantageous in that it reduces the stickiness of the block during manufacture.
  • the blocks with 1-5% PAS show improved wear characteristics .
  • said other anionic surfactants is a sulphonate.
  • Suitable sulphonates include alkyl benzene sulphonate (ABS) . It is believed that the combination of relatively low levels of PAS together with higher levels of ABS promotes the foaming and the perfume delivery from the block. PAS is also believed to be environmentally more acceptable than alkyl benzene sulphonate.
  • ABS alkyl benzene sulphonate
  • Suitable nonionic surfactants include polyethoxylated fatty alcohols, polyethoxylated fatty acids, polyethoxylated alkyl phenols, amine oxides and ethylene oxide/propylene oxide block copolymers .
  • the total amount of surfactant when present may lie within wide limits.
  • the surfactant will generally for 10 to 70% by weight of the composition, but more preferable that surfactant comprises from 20 to 50% by weight thereof.
  • the blocks according to the invention further comprise a processing aid to assist in extrusion.
  • processing aids include oils (including both mineral and silicone oils), esters (other than those derived from ethylenically unsaturated carboxyl group-containing monomers) and polybutene.
  • One particularly suitable processing aid is an alkoxylated alcohol. It is preferred that the alkoxylated alcohol is an ethoxylated alcohol. The preferred level of alkoxylated alcohol is 0.75-2%wt. The preferred ethoxy chain length is 40-60 with an average ethoxy chain length of around 50 being preferred. Suitable materials include Empilan KM 50/KF (TM) ex. Albright & Wilson. Another suitable process aid is a PEG monostearate. PEG 4000 Monostearate (100%) ex DAC is a suitable raw material. It is believed that an effect of the process aid is to make the block harder and easier to cut from an extruded billet.
  • blocks according to the present invention comprise 0 to 50% by weight of an inert non-polymeric and/or electrolyte filler.
  • blocks Preferably contain 5-50%wt, more preferably 10-30% of filler.
  • Suitable fillers include one or more of urea, sodium, magnesium and calcium carbonates, sodium chloride, borax, talc and sodium, magnesium and calcium sulphates.
  • Preferred ionic fillers include sodium sulphate.
  • Preferred inert, non-polymeric fillers include calcium carbonate.
  • Typical levels of total filler range from 10-40%wt on product in total .
  • the blocks comprise up to 50% by weight of an at least sparingly water soluble bleaching agent.
  • Typical levels of bleaching agents are 2-30%wt on product.
  • bleaching agent is used to mean both a bleaching agent and a precursor which produces a bleaching agent unless the context demands otherwise .
  • Suitable bleaching agents active-halide and active-oxygen bleaching agents particularly the so-called 'halogen release agents' .
  • Chlorine bleaching agents are preferred. Suitable water- soluble, active chlorine, bleaching agents used in accordance with the invention include chlorinated cyanurates, phthalimides , p- oluene sulphonamides , azodicarbonamides, hydantoins, glycoluracils , amines and melamines. The alkali metal salts of cyanurates are preferred.
  • a particularly preferred bleaching agent is sodium dichlorocyanurate (NaDCCA) .
  • the bleaching agent is typically present in an amount of 10-30% and most preferably at around 25%.
  • Oxidan DCN/WSG (TM) ex Sigma has been found to be a suitable bleaching agent.
  • the blocks comprise 2-15%wt of a hydrophobic oily liquid perfume.
  • the blocks more preferably comprise, 2-10%, more preferably 3-6%wt of the perfume. Levels of around 4%wt perfume are particularly preferred.
  • This oily perfume is typically of the kind described in the European patent application EP 167,210. It will be understood that the liquid oily perfume must be stable in the presence of the water-soluble, active chlorine, bleaching agent. Suitable oily perfumes can be easily selected by testing them in combination with the water-soluble, active chlorine, bleaching agent.
  • bleach-stable perfumes examples include Verdeo 898, Bonanza 048 and Ponderosa 431 all ex IFF, and LB 132 ex.
  • perfumes are Icebreaker Super Mod, Oxygen Supra Mod, Motebianco Supra and le onfit Supra (all TM) ex Givaudan Roure.
  • the most preferred perfume is Green Tank Harder (TM) ex. Givaudan Roure.
  • Minor components will generally be present but are optional. These include colouring agents, and/or whiteners. These materials should be chosen such that they are compatible with the bleaching agent and do not react therewith to a significant extent.
  • TM Sudangelb 150'
  • Sandoz is an acceptable colouring agent as are Colanyl Green (TM) ex Hoechst and Dispers Blue (TM) ex BASF.
  • a particularly preferred colouring agent is P. Green (CI 74260 ) .
  • Titanium dioxide is an acceptable whitener.
  • Levels of colouring agents and/or whiteners as typically below 5%wt. For colouring agents levels are typically in the range 0.0001-0. l%wt.
  • chelating agent such as ethylene diamine tetra-acetic acid or a derivative thereof, nitrolotriacetic acid, phosphonates of polyphosphates, metasilicates, boroheptonates, s.s- thylene-diamino disuccinate, dipicolinic acid, 2- phosphonobutane-1, 2 , 4-tricarboxylic acid, or lower molecular weight polymeric materials capable of inhibiting crystal growth.
  • Further reducing agents such as alkali metal metabisulphates may be present to assist in the reduction of staining due to metals such as iron.
  • An optional minor component is a foam-boosting surfactant.
  • Suitable surfactants include amine oxides.
  • compositions in accordance with the invention may be produced by a variety of routes. For example, they may be prepared by a so-called "hot-melt” process comprising melting the fusible constituents of the block either alone and then adding other components in admixture with non- fusible components, and subsequently casting the melt into moulds. More preferably, however, compositions in accordance with the invention are formed into the desired final shape by a compression technique, i.e. a technique involving the steps of forming a mixture of the ingredients of the composition and then compressing that mixture into the desired shape.
  • a compression technique i.e. a technique involving the steps of forming a mixture of the ingredients of the composition and then compressing that mixture into the desired shape.
  • An especially preferred process is an extrusion process in which the mixture of the components is extruded into a solid bar or rod which is subsequently cut into pieces of the desired size.
  • these suitably have a weight from 30 to 150gms.
  • some lubricant component or process aid be present to facilitate extrusion.
  • compositions in accordance with the invention may also be formed into the final desired shape by a tabletting technique .
  • block is not intended to limit the shape of the eventual product.
  • the rod is cut into lengths which are short relative to their diameter .
  • compositions are:
  • the invention also provides a method of cleaning a lavatory or urinal using a block of a composition in accordance with the invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Materials For Medical Uses (AREA)
  • Bidet-Like Cleaning Device And Other Flush Toilet Accessories (AREA)

Abstract

L'invention concerne un bloc de nettoyage pour W.C à libération lente, comprenant: (a) un agent de blanchiment ou précurseur pour ce dernier, (b) un parfum liquide huileux, et (c) un polymère de gélification, insoluble à l'eau, dérivé d'un ou de plusieurs monomères contenant des groupes carboxyle non saturés en éthylène.
EP98912449A 1997-03-14 1998-03-02 Compositions de nettoyage pour w.c. Expired - Lifetime EP0972009B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9705346 1997-03-14
GBGB9705346.6A GB9705346D0 (en) 1997-03-14 1997-03-14 Lavatory cleansing compositions
PCT/EP1998/001289 WO1998041608A1 (fr) 1997-03-14 1998-03-02 Compositions de nettoyage pour w.c.

Publications (2)

Publication Number Publication Date
EP0972009A1 true EP0972009A1 (fr) 2000-01-19
EP0972009B1 EP0972009B1 (fr) 2002-06-26

Family

ID=10809259

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98912449A Expired - Lifetime EP0972009B1 (fr) 1997-03-14 1998-03-02 Compositions de nettoyage pour w.c.

Country Status (12)

Country Link
EP (1) EP0972009B1 (fr)
AR (1) AR011966A1 (fr)
AU (1) AU725381B2 (fr)
BR (1) BR9808021A (fr)
CA (1) CA2282295C (fr)
DE (1) DE69806234T2 (fr)
ES (1) ES2176992T3 (fr)
GB (1) GB9705346D0 (fr)
HU (1) HU226080B1 (fr)
PL (1) PL186733B1 (fr)
WO (1) WO1998041608A1 (fr)
ZA (1) ZA982101B (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020046762A (ko) * 2000-12-15 2002-06-21 박성기 용기형 겔타입 변기세정제 및 이의 제조방법
GB2410031A (en) * 2003-11-21 2005-07-20 Reckitt Benckiser Inc Solid treatment blocks containing hydrocarbon solvent

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1538857A (en) * 1976-09-08 1979-01-24 Ciba Geigy Cleaning compositions
DE2750528A1 (de) * 1976-11-15 1978-05-24 Procter & Gamble Verfahren zum sauberhalten eines toilettenbeckens
DE2907029A1 (de) * 1979-02-23 1980-09-04 Henkel Kgaa Verfahren zur herstellung von abspuelbloecken fuer die toilettenhygiene
GB2061996B (en) * 1979-09-21 1983-06-22 Jeyes Group Ltd Lavatory cleansing blocks
GB2169612B (en) * 1984-11-30 1989-01-11 Jeyes Group Ltd Lavatory cleansing
GB9225338D0 (en) * 1992-12-03 1993-01-27 Jeyes Group Plc Lavatory cleansing blocks
GB9505203D0 (en) * 1995-03-15 1995-05-03 Jeyes Group Plc Lavatory cleansing compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9841608A1 *

Also Published As

Publication number Publication date
PL186733B1 (pl) 2004-02-27
HUP0001500A2 (hu) 2000-09-28
AR011966A1 (es) 2000-09-13
DE69806234D1 (de) 2002-08-01
ES2176992T3 (es) 2002-12-01
PL335638A1 (en) 2000-05-08
WO1998041608A1 (fr) 1998-09-24
HUP0001500A3 (en) 2003-02-28
CA2282295A1 (fr) 1998-09-24
AU725381B2 (en) 2000-10-12
BR9808021A (pt) 2000-03-08
AU6728398A (en) 1998-10-12
GB9705346D0 (en) 1997-04-30
DE69806234T2 (de) 2002-11-07
CA2282295C (fr) 2008-01-08
HU226080B1 (en) 2008-04-28
ZA982101B (en) 1999-09-13
EP0972009B1 (fr) 2002-06-26

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