EP1023423B1 - Alkoxylated amines and their use in cleaning compositions - Google Patents

Alkoxylated amines and their use in cleaning compositions Download PDF

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Publication number
EP1023423B1
EP1023423B1 EP98955491A EP98955491A EP1023423B1 EP 1023423 B1 EP1023423 B1 EP 1023423B1 EP 98955491 A EP98955491 A EP 98955491A EP 98955491 A EP98955491 A EP 98955491A EP 1023423 B1 EP1023423 B1 EP 1023423B1
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EP
European Patent Office
Prior art keywords
composition according
anionic surfactant
amine
viscosity
hydrotrope
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
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EP98955491A
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German (de)
English (en)
French (fr)
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EP1023423A1 (en
Inventor
Marcella M. L. nilever Italia S.p.a. BARTOLETTI
Giuseppe Vincenzo Unilever Italia S.p.A. BOLZONI
Emanuela Unilever Italia S.p.A. FERRO
Marco Unilever Italia S.p.A. GALLI
Ronald Meredith Morris
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
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Publication of EP1023423A1 publication Critical patent/EP1023423A1/en
Application granted granted Critical
Publication of EP1023423B1 publication Critical patent/EP1023423B1/en
Anticipated expiration legal-status Critical
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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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D3/042—Acids
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to acidic cleaning compositions, and in particular to acidic antimicrobial cleaning composition suitable for use on hard surfaces.
  • compositions generally comprise sufficient acid to give a low pH and may comprise a thickening agent to as to cause the composition to be retained on sloping surfaces, such as the inside of toilet bowls.
  • thickeners include both ethoxylated and unethoxylated tertiary amines, either alone or in combination with a hydrotrope.
  • acids for use in such compositions include sulphamic and phosphoric acids.
  • GB 1443244 relates to acid cleaners and descalers which comprise as a thickening agent an ethoxylated tertiary amine of which ETHOMEEN S12 (N,N-dihydroxyethyl-oleylamine) is given as an example.
  • the composition also comprises acids which are selected from mineral acids and acid salts of strong inorganic acids such as sulphamic acid.
  • Bacteriocides are an additional, optional component.
  • FR 2459830 discloses compositions which comprise non-ethoxylated and ethoxylated amines together with sulphamic acid.
  • the composition may also comprise disinfectants.
  • AU-A-57022/86 relates to cleaning systems which comprise a mixture of sulphamic and phosphoric acids and an acid stable surfactant.
  • Bacteriocides are optional and formalin is disclosed as a bacteriocide which improves the antibacterial effect of the acids.
  • EP-B-0276501 discloses thickened aqueous cleaning compositions which comprise 0.1-50%wt of a weak acid having a pK >2 (of which sulphamic acid is given as an example), 0.1-20%wt of an amine which can include 2% of oleyl-bis(2-hydroxyethyl)amine and 0.01%-5%wt hydrotrope (sodium xylene-sulphonate is given as an example). Disinfecting agents are optional.
  • EP-A-0314232 relates to compositions which undergo a viscosity increase on dilution and discloses that thickened liquid detergent compositions can be prepared with an amine oxide, amine (such as ETHOMEEN S12), betaine or quaternary ammonium compound and hydrotrope (sodium xylene-sulphonate). It is stated in the specification that amine oxides and quaternary ammonium compounds are known to have biocidal properties and that further microbiocides including organic peracids are optional. These compositions can be of acidic, neutral or alkaline pH.
  • compositions which comprise a specific mixture of both saturated and unsaturated alkoxylated aliphatic amines in the presence of an anionic surfactant show an improved stability of viscosity on storage.
  • anionic surfactant hydrotrope to these formulations has the additional benefit that the surface energy of surfaces treated with the composition is reduced and the subsequent deposition of limescale is retarded.
  • a cleaning composition which comprises
  • a process for retarding the deposition of limescale on a surface which comprises the step of treating said surface with a cleaning composition as defined above, said composition having a pH of less than 1.
  • the alkoxylated aliphatic amine is an ethoxylated tertiary amine of the general formula: H(A) x -N(R)-(A) y H wherein R is an alkyl or alkenyl group comprising 8-18 carbon atoms, A is an ethoxy or propoxy group and x and y may be the same or different and are integers from 1-3.
  • the preferred materials are ethoxylated amines wherein A is -OCH 2 CH 2 -.
  • R is mixed saturated and unsaturated C14-C18 alkyl and is most preferably derived from fatty acids residues of which the majority correspond to oleic and/or stearic acids.
  • the mole ratio of saturated to unsaturated fatty acids falls into the range 50:50 to 66:33.
  • a particularly suitable alkoxylated aliphatic amine is a material known as ETHOMEEN BTB/12TM, available from AKZO.
  • BTB/12 is believed to be a mixture of material derived from fully hardened tallow and the oleyl derivative in a 65/35 ratio.
  • Such a mixed material can be prepared by synethesis using an appropriate ratio of mixed starting materials or obtained by mixing an alkoxylated aliphatic amine such as ETHOMEEN HT12TM (ex AKZO) with an unsaturated material such as ETHOMEEN S12.
  • ETHOMEEN S12TM is N,N-(dihydroxyethyl)-oleylamine.
  • the preferred levels of the alkoxylated aliphatic amine are 1-10%wt on product with levels of 2-6%wt on product being particularly preferred.
  • the alkoxylated aliphatic amine is present together with an anionic surfactant hydrotrope.
  • the levels of these materials are such that they interact so as to thicken the composition.
  • Suitable anionic surfactant hydrotropes include the sulphonate hydrotropes.
  • Preferred surfactant hydrotropes are alkylarylsulphonates such as salts, particularly alkali metal salts, of toluene, cumene or xylene sulphonate.
  • the preferred anionic surfactant is sodium cumenesulphonate.
  • a suitable material is ELTESOL SC 40TM (ex. Albright and Wilson). Typical levels of anionic surfactant range from 0.05-2%wt on product.
  • formulations comprising the alkylaryl sulphonates are formulated at a pH below 1.
  • the ethoxylated amine behaves as a cationic surfactant and interacts with the alkylaryl sulphonate to form a water-insoluble gel which deposits as a monolayer on surfaces. It is believed that this monolayer lowers the surface energy of the surface and retards or prevents the deposition of further limescale.
  • the preferred mole ratio of the ethoxylated amine and the anionic surfactant is 3.25-3.5.
  • the preferred viscosity of the cleaning compositions according to the present invention is between 50 mPas and 1000 mPas when measured at 11.7 sec -1 shear and at 25°C using Haake RV2 rotoviscometer (RTM) and an MV1 bob
  • cleaning compositions which embody the present invention comprise 0.01-15%wt of a limescale removing acid, preferably an organic acid and more preferably sulphamic acid.
  • a limescale removing acid preferably an organic acid and more preferably sulphamic acid.
  • typical levels of the acid range from 1-10%wt on product with levels of 2-6% on product being particularly preferred.
  • the pH of the compositions according to the invention should have a pH of ⁇ 2.0, more preferably a pH ⁇ 1.0.
  • Preferred embodiments of the invention are cleaning and/or hygiene compositions which comprises a peroxygen compound.
  • typical sources of peroxygen species include one or more of hydrogen peroxide, peracetic acid and/or other organic or inorganic peroxygen sources.
  • Hydrogen peroxide is a preferred source of peroxygen species.
  • Typical levels of hydrogen peroxide range from 1-10%wt on product with levels of 3-8% being particularly preferred.
  • compositions according to the invention additionally comprise nonionic surfactant.
  • Suitable nonionic surfactants include alkoxylated alcohols, preferably ethoxylated alcohols.
  • Suitable nonionic detergent active compounds can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • the preferred alkoxylated alcohols are selected from the group comprising ethoxylated alcohols of the general formula: R 1 -(OCH 2 CH 2 ) m -OH wherein R 1 is straight or branched, C 8 to C 18 alkyl or hydroxyalkyl and m is, on average, 1-14.
  • Ethoxylated alcohols suitable for use in the present invention include LIAL 111.10EO [TM] available in the marketplace from DAC. Typical levels of nonionic surfactant in products according to the present invention range from 0-5%.
  • compositions according to the present invention comprise:
  • xanthan gums are suitable thickeners.
  • Preferred xanthan gums are the KelzanTM series (available from Kelco Corp). Typical levels of xanthan gum range from 0.05-1wt%.
  • the resulting viscosity of the composition is preferably in the range 10-200 mPas at 20 sec -1 shear and 25°C, using an MV1 bob. More preferably the viscosity is 10-100 mPas under the conditions mentioned above.
  • Metal ion sequestrants such as ethylene diamine tetraacetates, amino-poly phosphonates (such as those in the DEQUESTTM range ex. Monsanto) and phosphates and a wide variety of other poly-functional organic acids and salts, can also optionally be employed.
  • Preferred metal ion complexing agents are selected from dipicolinic acid, ethylene diamine tetra acetic acid (EDTA) and its salts, hydroxy-ethylidene diphosphonic acid (Dequest 2010), ethylenediamine-tetra(methylene phosphonic acid) (Dequest 2040), diethylene-triamine-penta(methylene phosphonic acid) (Dequest 2060).
  • minor components also include those typically found in cleaning compositions and are selected from opacifiers, colours perfumes and fluorescers. Preferred levels of perfume range from 0.05-2%wt. Acid stable perfumes are available from a variety of sources.
  • a particularly preferred composition according to the present invention comprises: ETHOMEEN BTB/12 ex AKZO 2-5% Ethoxylated amine SULPHAMIC ACID 4% HYDROGEN PEROXIDE 5% LIAL 111.10EO ex DAC 0.1% Nonionic surfactant ELTESOL SC40 ex Albright 0.4-1.1% Sodium Cumene Sulphonate BRILLIANT BLUE 9 ex WJE 0.0021% CI 307047/colour PERFUME ex IFF 0.12% Othello 39 DEQUEST 2066 ex Monsanto 0-0.3% WATER to 100%
  • Typical products having the above formulation made with 3.0%wt of the amine and around 0.56%wt of the SCS are preferably clear, have a specific gravity of 1.040 g/ml, an initial viscosity at 106 sec -1 (at 25°C) of 120mPas, an initial viscosity at 11.7 sec -1 (at 25°C) of 300-600 mPas and pH 0.9 (at 25°C).
  • a composition was prepared as follows: ETHOMEEN BTB/12 ex AKZO 3% Ethoxylated amine SULPHAMIC ACID 4% HYDROGEN PEROXIDE 5% LIAL 111.10EO ex DAC 0.1% Nonionic surfactant ELTESOL SC 40 ex Albright 0.4-1.1%* Sodium Cumene Sulphonate BRILLIANT BLUE ex WJE 0.0021% CI 307047/colour PERFUME ex IFF 0.12% Othello 39 DEQUEST 2066 ex Monsanto 0.15% WATER to 100%
  • the molar ratio of the ethoxylated amine / anionic surfactant can be modified to give thickening at a range of viscosities.
  • a finished product similar to that described above was used. (all with 3.0% Ethomeen BTB12) % Sodium Cumene Molar Ratio Viscosity mMas (11.7 sec -1 shear, 25°C) 0.69% 2.89 1500(non-flowing gel) 0.63% 3.03 1000 0.60% 3.18 700 0.59% 3.24 400 0.57% 3.35 300 0.56% 3.42 200 0.54% 3.51 75 0.50% 3.83 -10(water thin)
  • compositions having a viscosity between 50 mPas and 1000 mPas were flowable compositions which were suitable for use as toilet cleaners. Compositions with a lower viscosity were too thin to stay on sloping surfaces, while those with a higher viscosity could not be dispensed with ease. Compositions with a viscosity of from 200-700 mPas were particularly suited to this purpose.
  • compositions of the type described above were prepared with differing degrees of saturation in the ethoxylated amine.
  • the materials used were:
  • Figure 1 shows the viscosity of materials according to the present invention and comparative examples in mPas at 11.7 sec -1 , as measured using on a Haake RV2 rotoviscometer and an MV1 bob after storage at room temperature. It can be seen that the viscosity of the 'HT12' sample rose with time until the product became a non-flowing gel. The viscosity of the 'S12' sample fell, such that the product eventually became too thin to be retained on sloping surfaces. The viscosities of the products containing a mixture of hardened and unhardened tallow remained in the acceptable range on storage.
  • Figure 2 shows the viscosity of materials according to the present invention and comparative examples in mPas at 106 sec -1 , as measured using on a Haake RV2 rotoviscometer and an MV1 bob after storage at room temperature. It can be seen that the viscosity of the 'HT12' sample first fell and then rose. The viscosity of the 'S12' sample fell, such that the product eventually became too thin to be retained on sloping surfaces. The viscosities of the products containing a mixture of hardened and unhardened materials remained in the acceptable range on storage.
  • Figure 3 shows the viscosity of materials according to the present invention and comparative examples in mPas at 106 sec -1 , as measured using on a Haake RV2 rotoviscometer and an MV1 bob after storage at 37°C. It can be seen that the viscosity of the 'HT12' sample again first fell and then rose. The viscosity of the 'S12' sample fell, such that the product eventually became too thin to be retained on sloping surfaces. The viscosities of the products containing a mixture of hardened and unhardened materials remained in the acceptable range on storage.
  • Figure 4 shows the viscosity of materials according to the present invention and comparative examples in mPas at 11.7 sec -1 , as measured using on a Haake RV2 rotoviscometer and an MV1 bob after storage at 37°C. It can be seen that the viscosity of the 'HT12' sample again rose. The viscosity of the 'S12' sample fell, such that the product eventually became too thin to be retained on sloping surfaces. The viscosities of the products containing a mixture of hardened and unhardened materials remained in the acceptable range on storage.

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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)
EP98955491A 1997-10-13 1998-10-09 Alkoxylated amines and their use in cleaning compositions Expired - Lifetime EP1023423B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9721691.5A GB9721691D0 (en) 1997-10-13 1997-10-13 Improvements relating to acidic cleaning compositions
GB9721691 1997-10-13
PCT/EP1998/006633 WO1999019431A1 (en) 1997-10-13 1998-10-09 Alkoxylated amines and their use in cleaning compositions

Publications (2)

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EP1023423A1 EP1023423A1 (en) 2000-08-02
EP1023423B1 true EP1023423B1 (en) 2004-02-11

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EP98955491A Expired - Lifetime EP1023423B1 (en) 1997-10-13 1998-10-09 Alkoxylated amines and their use in cleaning compositions

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EP (1) EP1023423B1 (enrdf_load_stackoverflow)
JP (1) JP4323093B2 (enrdf_load_stackoverflow)
KR (1) KR20010015748A (enrdf_load_stackoverflow)
AR (1) AR017315A1 (enrdf_load_stackoverflow)
AU (1) AU735924B2 (enrdf_load_stackoverflow)
BR (1) BR9813044A (enrdf_load_stackoverflow)
CA (1) CA2305193C (enrdf_load_stackoverflow)
DE (1) DE69821636T2 (enrdf_load_stackoverflow)
ES (1) ES2214747T3 (enrdf_load_stackoverflow)
GB (1) GB9721691D0 (enrdf_load_stackoverflow)
HU (1) HU224521B1 (enrdf_load_stackoverflow)
ID (1) ID24420A (enrdf_load_stackoverflow)
IN (1) IN185797B (enrdf_load_stackoverflow)
MY (1) MY123176A (enrdf_load_stackoverflow)
PL (1) PL188434B1 (enrdf_load_stackoverflow)
SK (1) SK5302000A3 (enrdf_load_stackoverflow)
TR (1) TR200000972T2 (enrdf_load_stackoverflow)
WO (1) WO1999019431A1 (enrdf_load_stackoverflow)
ZA (1) ZA989144B (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012153270A3 (en) * 2011-05-10 2013-04-04 Ecolab Usa Inc. Couplers for medium-chain fatty acids and disinfecting compositions
WO2024012732A1 (de) * 2022-07-13 2024-01-18 Henkel Ag & Co. Kgaa "waschaktive verbindungen auf basis einer kombination von anionen und kationentensid"

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2495400A (en) * 1999-01-11 2000-08-01 Huntsman Petrochemical Corporation Surfactant compositions containing alkoxylated amines
WO2003076559A1 (de) * 2002-03-13 2003-09-18 Cognis Iberia, S.L. Verdickte peroxidlösungen
DE102004055492A1 (de) * 2004-11-17 2006-07-13 Chemische Fabrik Dr. Weigert Gmbh & Co. Kg Klarspüler für Kunststoffteile
GB0804727D0 (en) * 2008-03-14 2008-04-16 Reckitt Benckiser Inc Thickened hard surface cleaning compositions comprising fatty amine alkoxylate compounds

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2459830A1 (fr) * 1979-06-26 1981-01-16 Voreppe Ind Chimiques Compositions nettoyantes et detartrantes a base d'acide sulfamique, ayant une viscosite stable
DE3603579A1 (de) * 1986-02-06 1987-08-13 Henkel Kgaa Verwendung ethoxylierter fettamine als loesungsvermittler
NO170944C (no) * 1987-01-24 1992-12-30 Akzo Nv Fortykkede, vandige preparater, samt anvendelse av slike

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012153270A3 (en) * 2011-05-10 2013-04-04 Ecolab Usa Inc. Couplers for medium-chain fatty acids and disinfecting compositions
CN103501606A (zh) * 2011-05-10 2014-01-08 艺康美国股份有限公司 用于中链脂肪酸的偶联剂和灭菌组合物
US9006286B2 (en) 2011-05-10 2015-04-14 Ecolab Usa Inc. Couplers for medium-chain fatty acids and disinfecting compositions
CN103501606B (zh) * 2011-05-10 2015-10-21 艺康美国股份有限公司 用于中链脂肪酸的偶联剂和灭菌组合物
WO2024012732A1 (de) * 2022-07-13 2024-01-18 Henkel Ag & Co. Kgaa "waschaktive verbindungen auf basis einer kombination von anionen und kationentensid"

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JP2001520259A (ja) 2001-10-30
ES2214747T3 (es) 2004-09-16
WO1999019431A1 (en) 1999-04-22
BR9813044A (pt) 2000-08-15
IN185797B (enrdf_load_stackoverflow) 2001-05-05
PL339808A1 (en) 2001-01-02
SK5302000A3 (en) 2000-09-12
HUP0004913A3 (en) 2005-06-28
ID24420A (id) 2000-07-20
AR017315A1 (es) 2001-09-05
DE69821636D1 (de) 2004-03-18
JP4323093B2 (ja) 2009-09-02
ZA989144B (en) 2000-04-07
MY123176A (en) 2006-05-31
GB9721691D0 (en) 1997-12-10
CA2305193A1 (en) 1999-04-22
HU224521B1 (hu) 2005-10-28
EP1023423A1 (en) 2000-08-02
CA2305193C (en) 2010-03-23
TR200000972T2 (tr) 2000-11-21
KR20010015748A (ko) 2001-02-26
AU735924B2 (en) 2001-07-19
HUP0004913A2 (hu) 2001-05-28
DE69821636T2 (de) 2004-07-29
AU1229899A (en) 1999-05-03
PL188434B1 (pl) 2005-01-31

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