EP0966519B1 - Geformte syndetmasse - Google Patents
Geformte syndetmasse Download PDFInfo
- Publication number
- EP0966519B1 EP0966519B1 EP98913574A EP98913574A EP0966519B1 EP 0966519 B1 EP0966519 B1 EP 0966519B1 EP 98913574 A EP98913574 A EP 98913574A EP 98913574 A EP98913574 A EP 98913574A EP 0966519 B1 EP0966519 B1 EP 0966519B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- syndet
- surfactants
- molded
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- 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
- C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
-
- 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
- C11D1/126—Acylisethionates
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
Definitions
- the invention relates to a shaped composition based on synthetic surfactants, Plasticizers and fillers, preferably in piece form, by the addition of Talc is improved in the foam quality.
- the well-known high-foaming anionic surfactants are used for this purpose usually mixed with plasticizers, fillers and extenders, which is a lighter Make deformation possible and bring about better dimensional stability.
- the invention therefore relates to a shaped syndet mass with a content of at least 25% by weight of synthetic surfactants and at least 30% by weight of non-surfactants organic plasticizers and fillers used to improve foam properties and the formability contains 5-30% by weight talc.
- Ionic and nonionic surfactants can be included as synthetic surfactants, however, preference should predominantly, i.e. more than 15% by weight of highly foaming anionic surfactants are used.
- ampholytic, zwitterionic and nonionic surfactants can be contained in amounts of up to 10% by weight.
- Anionic surfactants with a linear alkyl or acyl group with 12-18 C atoms and a sulfonate or sulfate group in the form of their alkali, magnesium, ammonium or alkanolammonium salts in an amount of 25-50% by weight are preferred as strongly foaming synthetic surfactants. -% used.
- Suitable anionic surfactants can be, for example, by the following general formulas I to IV R 1 - SO 3 (-) M (+) R 2 O - (EO) x - SO 3 (-) M (+) R 3 CO (A) - CH 2 - CH 2 - SO 3 (-) M R 4 O CO (B) - SO 3 (-) M (+) being represented.
- R 1 , R 2 and R 4 are linear alkyl or alkenyl groups with 10 - 18 C atoms and R 3 CO is a linear acyl group with 12 - 18 C atoms
- (EO) means a (C 2 H 4 O) or (C 3 H 6 O) group
- x is 0 or a number from 1 to 6
- (A) is oxygen or a CH 3 N group
- Suitable surfactants of the formula I are alkane sulfonates and olefin sulfonates; suitable Surfactants of the formula II are the alkyl sulfates and the alkyl ether sulfates; Surfactants of Formula III are the acyl isethionates and acyl taurides; suitable surfactants of the formula IV are the sulfocarboxylic acid esters, e.g. the sulfoacetates, sulfopropionates or Sulfosuccinates. Suitable anionic surfactants are especially preferred Acyl isethionates, the sulfosuccinates and their mixtures.
- amphoteric or zwitterionic surfactants can also be present in minor amounts in the compositions of up to 10% by weight.
- Suitable amphoteric surfactants are, for example, the C 12 -C 18 alkylaminopropionic acid or the C 12 -C 18 alkylaminoacetic acid.
- Suitable zwitterionic surfactants are, for example, the C 12 -C 18 alkyl-dimethyl-carboxymethyl-acetobetaine and the C 12 -C 13 -acylamide propyl-dimethyl-acetobetaine.
- Non-ionic surfactants can also be present in the syndet compositions according to the invention in smaller amounts of 1-10% by weight.
- Suitable non-ionic surfactants are the addition products of ethylene oxide with C 10 -C 22 fatty alcohols, on C 10 - C 22 fatty acids, on fatty acid monoglycerides, sorbitan fatty acid monoester to FettTexretri glycerides or methyl glucoside Fen yarnremonoester.
- Particularly preferred nonionic surfactants are the alkyl (oligo) glycosides of the formula R 5 O (C 6 H 10 O 5 ) y - H, in which R 5 is an alkyl group with 8 to 18 C atoms, (C 6 H 10 O) y is a glucoside residue and y whose average degree of oligomerization is 1 to 5.
- alkyl (oligo) glycosides are commercially available, for example under the Plantaren® 2000 CSUP or Plantacare® 2000 CSUP trademark.
- Talc is a hydrated magnesium silicate with the theoretical composition 3MgO ⁇ 4SiO 2 ⁇ H 2 O and Mg 3 (Si 4 O 10) ⁇ (OH) 2, but which may contain fractions of hydrated magnesium aluminum silicate in an amount that an Al 2 O 3 Content of up to 12% by weight.
- the particle diameter (equivalent spherical diameter) of the talc should be in the range from 0.5 to 50 ⁇ m. In general, such talc qualities have proven themselves not more than 5% by weight of particles less than 1 ⁇ m and not more than 5% by weight Contain particles larger than 50 ⁇ m. Preferably the proportion of particles is larger than 40 ⁇ m in diameter (sieve residue), at most 2% by weight, the middle Particle diameter is preferably 5 to 15 microns.
- the content of accompanying substances should not exceed 1.6% by weight of Fe 2 O 3 , 1% by weight of CaO and 1% by weight of unbound water (loss of drying at 105 ° C.).
- the hydrated magnesium aluminum silicate content can be up to 60% by weight (calculated as Al 2 O 3 up to 12% by weight).
- the syndet composition according to the invention is preferably free of fatty acid soaps. Amounts of however, less than 10% by weight of fatty acids in the form of soap can be tolerated.
- Suitable organic fillers are e.g. Carbohydrates (starch, dextrins, sugar), Sorbitol, mannitol, urea, proteins and protein hydrolyzates and polyethylene glycols (Carbowax®).
- syndet compositions according to the invention are 30-50% by weight of non-surfactant organic plasticizers and fillers from the group of the C 12 -C 22 fatty alcohols, the free C 16 -C 22 fatty acids, the fatty acid esters, the paraffins and the carbohydrates or their Mixtures included.
- Water can also be present in the syndet compositions according to the invention, its proportion however, should remain below 10% by weight of the syndet mass. About 5-10 are preferred % By weight of water contained in the syndet mass.
- the production of the shaped syndet masses according to the invention can be done for such Products take place in the usual way, the combination of synthetic surfactants and talc are particularly easy to form in the heat plastic and hard mass after cooling.
- the molded products have a smooth surface that dries again even after wetting with water to become soft.
- the meltable components for example the fatty acid, the fatty alcohol, the alkyl (oligo) glucoside and the meltable or liquid plasticizers, are melted and mixed at a temperature in the range from 60 to 90 ° C. in a heatable kneader or mixer.
- the anionic surfactant for example the C 12 -C 18 -acyl isethionate salt, optionally the sulfosuccinate and the starch and other components which cannot be melted at 60-90 ° C. and, if appropriate, the water, are added, and the mixture is mixed or kneaded at a temperature of approx. 70 ° C.
- a further homogenization can be achieved in that the mass is repeated pressed through sieves and finally at a head temperature of 40 to 70 ° C Strand is pressed, which is cut into uniform pieces. The pieces can are finally brought into the final shape in a molding press.
- extrusion through a perforated plate can also take place noodles or needles are obtained or if the perforated plate is followed by a knife are formed, granules.
- the Syndet soaps were produced in a heatable kneader.
- the components were heated to 90 ° C and mixed intensively. After cooling to 40 ° C the fragrances were added. After a short mixing, the mass was turned into a Extruded press transferred.
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)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
- Inorganic Insulating Materials (AREA)
- Permanent Field Magnets Of Synchronous Machinery (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Thermistors And Varistors (AREA)
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
- Micromachines (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
- freie Fettsäuren mit 16 - 22 C-Atomen
- Fettalkohole mit 16 - 22 C-Atomen und
- Fettsäureester, wie z.B. gehärtete Fette (Triglyceride), Wachse, Glycerinmonostearat, Glycoldistearat
- Paraffine.
- Komplexbildner
- antimikrobielle Stoffe, Konservierungsmittel
- Farbstoffe. Pigmente (TiO2), Trübungs- und Mattierungsmittel
- Duftstoffe
- Salze. z.B. Na2SO4, NaH2PO4, Na5P3O10
- Antioxidantien
- dermatologische oder kosmetische Wirkstoffe (z.B. Hautfeuchthaltemittel wie z.B. Na-Lactat, Pyrrolindoncarbonsäure, Glycerin).
- Isethionat :
- Natrium-C12-C18-acylisethionat (sodium cocoyl isethionate)
- Sulfosuccinat :
- Sulfobernsteinsäure-mono-C12-C18-alkylester-Dinatriumsalz
- Texapon® K12 :
- Na-Lauryl-(C12-C18)-sulfat
- Plantacare® 2000 UP :
- C8-C16-Alkyl-(oligo)-glucosid, DP-Grad x = 1,4 (50 %ig in H2O)
- Steasilk® 5 AE :
- Talkum (hydrous magnesium silicate)
SiO2: 63 % MgO : 31,4 % Al2O3 : 0,1 %
Fe2O3 : 0,2 %, CaO : 0,4 %
Teilchengrößenverteilung: 5 Gew.-% kleiner als 0,9 µm
5 Gew.-% größer als 10 µm
Siebrückstand 45 µm : max. 0,1 % - Vitamin F (wasserlöslich) :
- Linolensäure mit Polysorbat 20
Rezepturen: | 1 | 2 | 3 |
Isethionat | 17 | 14 | 20 |
Sulfosuccinat | 17 | 14 | - |
Texapon® K12 | 2 | 1,5 | 20 |
Plantacare® 2000 UP | 5 | 4 | - |
Stearinsäure | 5 | 4 | - |
Cetyl-/Stearylalkohol (1:1) | 12 | 10 | 11 |
hydriertes Rizinusöl | 5 | 4 | - |
Glycerin | 6 | 5 | 5 |
Weizen-Stärkemehl | 10 | 8 | 15 |
Steasilk® 5 AE | 10 | 25 | 15 |
Paraffinwachs | - | - | 7 |
Paraffinöl | 2 | 1,5 | - |
Squalan | 0,1 | 0,1 | 0,1 |
Vitamin F (wasserlöslich) | - | - | 0,1 |
Panthenol | 0,1 | 0,1 | 0,1 |
Zitronensäure | - | - | 1,0 |
Milchsäure (80 % in H2O) | - | - | 0,5 |
Na-Lactat (50 % in H2O) | 0,2 | 0,2 | 0,2 |
Titandioxid | 1,2 | 1,2 | 1 |
Wasser | 6,2 | 6,2 | 3 |
Parfümöl | 1,2 | 1,2 | 1 |
Texapon® K12 | Kokosfettalkohol-(C12-C18)-sulfat, Na-Salz |
Plantacare® 2000 UP | Alkyl-(C8-C16)-oligo-(1,4)-glucosid |
Steasil® 5 AE | Talkum-Pulver |
Vitamin F (wasserlöslich) | Linolensäure mit POE 20 Sorbitanmonolaurat |
Claims (6)
- Geformte Syndetmasse mit einem Gehalt von wenigstens 25 Gew..-% synthetischer Tenside und wenigstens 30 Gew.-% nichttensidischer, organischer Plastifikatoren und Füllstoffe, dadurch gekennzeichnet, daß zur Verbesserung der Schäumeigenschaften und der Formbarkeit 5 - 30 Gew.-% Talkum enthalten ist.
- Geformte Syndetmasse nach Anspruch 1, dadurch gekennzeichnet, daß als synthetische Tenside Sulfat- oder Sulfonattenside mit einer linearen Alkyl- oder Acylgruppe mit 12 bis 22 C-Atomen in Form ihrer Alkali-, Magnesium-, Ammonium- oder Alkanolammoniumsalze in einer Menge von 25 bis 50 Gew.-% enthalten sind.
- Geformte Syndetmasse nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß nichtionische Tenside in einer Menge von 1 bis 10 Gew.-% enthalten sind.
- Geformte Syndetmasse nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß 30 bis 50 Gew.-% nichttensidischer, organischer Plastifikatoren und Füllstoffe aus der Gruppe der C12-C22-Fettalkohole, der freien C16-C22-Fettsäuren, der Fettsäureester, der Paraffine, der Kohlenhydrate oder deren Gemische enthalten sind.
- Geformte Syndetmasse nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß 5 bis 10 Gew.-% Wasser darin enthalten ist.
- Geformte Syndetmasse nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß30 - 40 Gew.-% anionischer Tenside aus der Gruppe der Acylisethionat-Salze, der Sulfobemsteinsäuremonoalkylester-Salze und deren Gemische30-50 Gew.-% organischer Plastifikatoren und Füllstoffe aus der Gruppe der Fettalkohole, der freien Fettsäuren, der Fettsäureester, der Paraffine und der Stärke10 - 30 Gew.-% Talkum und5 - 10 Gew.-% Wasser
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19708605A DE19708605A1 (de) | 1997-03-03 | 1997-03-03 | Geformte Syndetmasse |
DE19708605 | 1997-03-03 | ||
PCT/EP1998/001011 WO1998039408A1 (de) | 1997-03-03 | 1998-02-21 | Geformte syndetmasse |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0966519A1 EP0966519A1 (de) | 1999-12-29 |
EP0966519B1 true EP0966519B1 (de) | 2001-06-20 |
Family
ID=7822086
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98913574A Expired - Lifetime EP0966519B1 (de) | 1997-03-03 | 1998-02-21 | Geformte syndetmasse |
Country Status (15)
Country | Link |
---|---|
US (1) | US6376440B1 (de) |
EP (1) | EP0966519B1 (de) |
AT (1) | ATE202379T1 (de) |
CA (1) | CA2282465C (de) |
CZ (1) | CZ291966B6 (de) |
DE (2) | DE19708605A1 (de) |
DK (1) | DK0966519T3 (de) |
ES (1) | ES2160411T3 (de) |
GR (1) | GR3036400T3 (de) |
HU (1) | HUP0002150A3 (de) |
NO (1) | NO994253D0 (de) |
PL (1) | PL191146B1 (de) |
PT (1) | PT966519E (de) |
SK (1) | SK285136B6 (de) |
WO (1) | WO1998039408A1 (de) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002527532A (ja) * | 1998-10-13 | 2002-08-27 | ジョンソン・アンド・ジョンソン・コンシューマー・カンパニーズ・インコーポレイテッド | 高濃度のエモリエントおよびグリセリンを含有するクリーム・クレンザー |
DE10046251A1 (de) * | 2000-09-19 | 2002-03-28 | Cognis Deutschland Gmbh | Wasch- und Reinigungsmittel auf Basis von Alkyl- und/oder Alkenyloligoglycosiden und Fettalkoholen |
US6458751B1 (en) * | 2001-07-23 | 2002-10-01 | Unilever Home & Personal Care Usa | Skin cleansing bar comprising a fatty alcohol with low mush |
US20060003908A1 (en) * | 2004-07-01 | 2006-01-05 | Brennan Michael A | Mild synthetic detergent toilet bar composition |
RU2527522C2 (ru) | 2009-12-23 | 2014-09-10 | Колгейт-Палмолив Компани | Очищающий брусок |
US8822403B2 (en) | 2011-01-20 | 2014-09-02 | Ecolab Usa Inc. | Detergent composition including a saccharide or sugar alcohol |
GB2502339B (en) | 2012-05-25 | 2018-02-07 | Cosmetic Warriors Ltd | Solid cosmetic composition |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2678921A (en) * | 1948-08-04 | 1954-05-18 | Colgate Palmolive Co | Process of producing a milled nonsoap detergent in bar form |
NL82428C (de) * | 1952-07-02 | |||
GB1333042A (en) * | 1969-08-22 | 1973-10-10 | Unilever Ltd | Detergent bars |
US4150001A (en) | 1977-05-26 | 1979-04-17 | Lever Brothers Company | Detergent bars containing alkaline earth metal hydrogen orthophosphate |
US4557853A (en) | 1984-08-24 | 1985-12-10 | The Procter & Gamble Company | Skin cleansing compositions containing alkaline earth metal carbonates as skin feel agents |
GB8626080D0 (en) * | 1986-10-31 | 1986-12-03 | Unilever Plc | Detergent composition |
DE3939579A1 (de) * | 1989-11-30 | 1991-06-06 | Henkel Kgaa | Geformte koerperreinigungsmittel |
JP3628327B2 (ja) * | 1993-11-08 | 2005-03-09 | ザ プロクター アンド ギャンブル カンパニー | トップド蒸留ココイルイセチオネート固形スキンクレンジング製品 |
US5496493A (en) | 1994-05-10 | 1996-03-05 | The Procter & Gamble Company | Ultra mild personal cleansing bar containing smaller-sized particulate wax |
DE19544453A1 (de) * | 1995-11-29 | 1997-06-05 | Henkel Kgaa | Syndet-Seifenmassen |
-
1997
- 1997-03-03 DE DE19708605A patent/DE19708605A1/de not_active Withdrawn
-
1998
- 1998-02-21 HU HU0002150A patent/HUP0002150A3/hu unknown
- 1998-02-21 AT AT98913574T patent/ATE202379T1/de not_active IP Right Cessation
- 1998-02-21 DE DE59800891T patent/DE59800891D1/de not_active Expired - Fee Related
- 1998-02-21 PT PT98913574T patent/PT966519E/pt unknown
- 1998-02-21 WO PCT/EP1998/001011 patent/WO1998039408A1/de active IP Right Grant
- 1998-02-21 PL PL335281A patent/PL191146B1/pl not_active IP Right Cessation
- 1998-02-21 US US09/380,697 patent/US6376440B1/en not_active Expired - Fee Related
- 1998-02-21 CZ CZ19993144A patent/CZ291966B6/cs not_active IP Right Cessation
- 1998-02-21 CA CA002282465A patent/CA2282465C/en not_active Expired - Fee Related
- 1998-02-21 ES ES98913574T patent/ES2160411T3/es not_active Expired - Lifetime
- 1998-02-21 EP EP98913574A patent/EP0966519B1/de not_active Expired - Lifetime
- 1998-02-21 DK DK98913574T patent/DK0966519T3/da active
- 1998-02-21 SK SK1198-99A patent/SK285136B6/sk not_active IP Right Cessation
-
1999
- 1999-09-02 NO NO994253A patent/NO994253D0/no not_active Application Discontinuation
-
2001
- 2001-08-16 GR GR20010401257T patent/GR3036400T3/el not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
DE19708605A1 (de) | 1998-09-10 |
SK119899A3 (en) | 2000-05-16 |
PL191146B1 (pl) | 2006-03-31 |
SK285136B6 (sk) | 2006-07-07 |
CZ9903144A3 (cs) | 2000-12-13 |
HUP0002150A2 (hu) | 2000-10-28 |
WO1998039408A1 (de) | 1998-09-11 |
PT966519E (pt) | 2001-12-28 |
CA2282465C (en) | 2007-06-26 |
NO994253L (no) | 1999-09-02 |
US6376440B1 (en) | 2002-04-23 |
EP0966519A1 (de) | 1999-12-29 |
CZ291966B6 (cs) | 2003-06-18 |
GR3036400T3 (en) | 2001-11-30 |
DE59800891D1 (de) | 2001-07-26 |
HUP0002150A3 (en) | 2001-08-28 |
NO994253D0 (no) | 1999-09-02 |
ES2160411T3 (es) | 2001-11-01 |
CA2282465A1 (en) | 1998-09-11 |
PL335281A1 (en) | 2000-04-10 |
DK0966519T3 (da) | 2001-10-15 |
ATE202379T1 (de) | 2001-07-15 |
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