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WO2002081604A1 - Hydraulische flüssigkeiten mit verbessertem korrosionsschutz - Google Patents

Hydraulische flüssigkeiten mit verbessertem korrosionsschutz Download PDF

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Publication number
WO2002081604A1
WO2002081604A1 PCT/EP2002/003671 EP0203671W WO02081604A1 WO 2002081604 A1 WO2002081604 A1 WO 2002081604A1 EP 0203671 W EP0203671 W EP 0203671W WO 02081604 A1 WO02081604 A1 WO 02081604A1
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WO
WIPO (PCT)
Prior art keywords
weight
fluids
triazole
motor vehicles
corrosion
Prior art date
Application number
PCT/EP2002/003671
Other languages
German (de)
English (en)
French (fr)
Inventor
Bernd Wenderoth
Michael Roida
Bayram Aydin
Uwe Fidorra
Original Assignee
Basf Aktiengesellschaft
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
Priority to PL367159A priority Critical patent/PL197796B1/pl
Priority to MXPA03007944A priority patent/MXPA03007944A/es
Priority to BR0208415-5A priority patent/BR0208415A/pt
Priority to KR1020037013131A priority patent/KR100861969B1/ko
Priority to EP02759789A priority patent/EP1379615B1/de
Priority to AT02759789T priority patent/ATE286112T1/de
Priority to SK1192-2003A priority patent/SK286828B6/sk
Priority to CA2442697A priority patent/CA2442697C/en
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to JP2002579971A priority patent/JP4116445B2/ja
Priority to AU2002308121A priority patent/AU2002308121B2/en
Priority to DE50201902T priority patent/DE50201902D1/de
Priority to US10/469,770 priority patent/US20040116306A1/en
Priority to HU0303757A priority patent/HUP0303757A2/hu
Publication of WO2002081604A1 publication Critical patent/WO2002081604A1/de
Priority to NO20034495A priority patent/NO325635B1/no

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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/10—Phosphatides, e.g. lecithin, cephalin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • C10M2227/0615—Esters derived from boron used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • C10M2227/062—Cyclic esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • C10M2227/062—Cyclic esters
    • C10M2227/0625—Cyclic esters used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

  • the present invention relates to hydraulic fluids, in particular brake fluids for motor vehicles, with improved corrosion protection, which
  • Hydraulic fluids and especially brake fluids for motor vehicles are subject to very high requirements with regard to their chemical and physical properties.
  • modern brake fluids are said to have high dry boiling points (reflux boiling points, dry [ERBP "]) and high wet boiling points (reflux boiling points, moist [" wet ERBP "]) , but on the other hand also have a viscosity that changes only slightly within a wide temperature range.
  • Corrosion inhibitors in brake fluids have the task of preventing the destruction of metallic materials caused by corrosion.
  • 1H-1, 2, 3-triazoles such as 1H-1, 2, 3-benzotriazole or 1H-1, 2,3-tolutriazole as corrosion inhibitors in hydraulic fluids or brake fluids has long been known, for example from EP-A 028 789 (1) and EP-A 454 110 (2).
  • hydraulic fluids which contain a combination of 1H-1,2, 3-benzotriazole or its derivatives such as 1H-1,2, 3-tolutriazuol and 1H-1, 2,4-triazole or whose Derivatives in a weight ratio of 1: 4 to 4: 1 contained as a corrosion inhibitor system.
  • hydraulic fluids are also given in Tables 1 to 4 of (3), which contain 1H-1,2,4-triazole alone in concentrations of 0.15% by weight; however, their corrosion-preventing effect is only acceptable for copper.
  • the hydraulic fluids and brake fluids for motor vehicles known in the prior art are, however, in need of improvement with regard to their properties and in particular corrosion protection.
  • the object was therefore to provide hydraulic liquids which, in particular, meet the above-mentioned requirements for improved corrosion protection in metals and non-ferrous metals.
  • the hydraulic fluids according to the invention in particular brake fluids for motor vehicles, preferably contain 0.005 to 0.10% by weight, preferably 0.005 to 0.08% by weight, in particular 0.005 to 0.06% by weight, of component (a) ,
  • the hydraulic fluids according to the invention in particular brake fluids for motor vehicles, contain component (a) as the sole corrosion inhibitor based on triazole.
  • component (a) as the sole corrosion inhibitor based on triazole.
  • triazoles such as 1H-1, 2,3-benzotriazole, 1H-1,2, 3-tolutriazole or hydrogenated 1H-1, 2,3-tolutriazole are excluded here, inorganic and / or organic corrosion inhibitors of a different structure can however be present.
  • hydraulic fluids according to the invention in particular motor vehicle brake, even up to 10 wt .-%, in particular up to 5 wt .-% of one or more further Korro ⁇ sion inhibitors (b), wherein in the concomitant use of 1H -1, 2, 3-benzotriazole and / or 1H-1, 2, 3-tolutriazole and / or their derivatives the weight ratio of 1H-1, 2, 4-triazole to the mentioned 1H-1,2 , 3-triazoles must be greater than 4: 1.
  • alkali metal salts of phosphoric acid and phosphorous acid fatty acids such as caprylic, auric, palitinic, stearic or oleic acid and their alkali metal salts, esters of phosphoric acid and phosphorous acid such as ethyl phosphate, dimethyl phosphate , Isopropyl phosphate, diisopropyl phosphate, butyl phosphite or dimethyl phosphite, optionally ethoxylated mono- and dialkylamines and their salts with mineral and fatty acids, for example butylamine, hexylamine, octylamine, isononylamine, oleylamine, dipropylamine, diisopropylamine or dibutylamine, optionally ethoxylated alkanolamines, for example mono-, di- or triethanolamine, N, N'-di-n-butyla
  • the corrosion inhibitors (b) mentioned are preferably present in amounts of 0.001 to 10% by weight, in particular 0.001 to 5% by weight, in the hydraulic fluids according to the invention, in particular brake fluids for motor vehicles.
  • the hydraulic fluids according to the invention in particular brake fluids for motor vehicles, contain 0.001 to 5% by weight, in particular 0.001 to 0.5% by weight, in addition to 1H-1, 2, 4-triazole (a) as additional corrosion inhibitors (b) .-%, one or more compounds from the group benzimidazole, hydrogenated 1H-1, 2, 3-tolutriazole, purine, adenine, 6-chloropurine, 2, 6-dichloropurine, 6-methoxypurine, 1H-1, 2, 3-triazolo (4, 5B) pyridine, 6-histaminopurine and 6-furfurylaminopurine and optionally other corrosion inhibitors other than (a).
  • the purine derivatives mentioned are described as non-ferrous metal corrosion inhibitors for hydraulic fluids or brake fluids in German patent application Az. P 100 26 010.1.
  • the present invention relates in particular to brake fluids for motor vehicles which contain the components (a) and optionally (b) mentioned as corrosion inhibitors.
  • the brake fluids for motor vehicles according to the invention contain, in addition to components (a) and optionally (b), 0.1 to 97% by weight, in particular 30 to 97% by weight, especially 50 to 97% by weight , one or more polyglycol ethers and / or their boric acid esters.
  • Suitable polyglycol ethers are above all ethylene glycol monoalkyl ethers with up to 6 ethylene oxide units and with up to 4 carbon atoms in the alkyl radical, such as, for example, methyldiglycol, methyltriglycol, butyltriglycol or methyltetraglycol.
  • ethylene glycol or propylene glycol dialkyl ethers with up to 6 alkylene oxide units and each with up to 4 carbon atoms in the alkyl radicals, such as, for example, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol di-tert.- butyl ether, diethylene glycol dibutyl ether, butyl diglycol tert-butyl ether or dipropylene glycol dimethyl ether.
  • Suitable boric acid esters of said polyglycol ethers or of other polyglycol ethers are described in particular in documents EP-B 013 925 (cyclic bis-boric acid esters), DE-C 28 04 535 (nitrogen-containing boric acid esters), DE-A 24 38 038 (boric acid-alkylene glycol) Monoalkyl ether esters) and DE-B 17 68 933 (tris-alkoxyalkyl borate).
  • the brake fluids according to the invention for motor vehicles can also contain, as the main component, those based on carboxylic acid esters, mineral oils or silicone oils.
  • the brake fluids for motor vehicles according to the invention contain, in addition to components (a) and optionally (b), 0.1 to 50% by weight, in particular 1 to 40% by weight, especially 5 to 30% by weight. %, one or more polyglycols.
  • Suitable polyglycols are, above all, higher-boiling reaction products of ethylene oxide and / or propylene oxide and / or butylene oxide with water or diols; in particular, corresponding reaction products of mixtures of ethylene oxide and propylene oxide with water are used.
  • the number of alkylene oxide units in such polyglycols is usually 2 to 10.
  • the effect of these high-boiling polyglycols is that of a lubricant, which is essentially due to an improvement in the temperature-viscosity behavior.
  • the polyglycols give the thin-bodied polyglycols sufficient viscosity at high temperatures and thus ensure adequate lubrication. Sufficient lubrication is therefore necessary in the components of the motor vehicle brake system, since rubber or elastomers on metal have to slide as wear-free as possible.
  • Further components and auxiliaries in the brake fluids for motor vehicles according to the invention can be customary antioxidants, such as phenothiazine and / or those based on phenol, and customary defoamers.
  • the brake fluids according to the invention can contain the cyclic carboxylic acid derivatives listed in WO 00/65001, which are suitable as components for lowering the low-temperature viscosity in the presence of water.
  • hydraulic fluids or brake fluids for motor vehicles are their favorable low-temperature viscosity, good water compatibility, a gentle pH value, good low-temperature, high-temperature and oxidation stability as well as good chemical stability, favorable behavior (ie good behavior) Compatibility) with materials such as rubbers, plastics, glue joints, fiber, elastomer and rubber seals and similar materials as well as good lubrication behavior.
  • brake fluids BF 1 (ERBP: 267 ° C, wet ERBP: 173 ° C, kinematic viscosity at -40 ° C: 676 cSt) and BF 2 (ERBP: 263 ° C, wet ERBP: 181 ° C, kinematic viscosity at -40 ° C: 850 cSt) with 0.05 wt .-% lH-l, 2,3-tolutriazole as a non-ferrous metal corrosion inhibitor
  • the brake fluids BF la, BF lb, BF lc and BF 2a tested according to the invention.
  • the motor vehicle brake fluids used had the following compositions:
  • methyltriglycol-borate 43.44% by weight of a mixture of methyltriglycol, methyltetraglycol, butyltriglycol and methyldiglycol, 1.51% by weight of a mixture of 1,1'-iminodipropan-2-ol, Phenothiazine and a phosphoric acid ester 0.05 wt .-% lH-l, 2,3-tolutriazole
  • the brake fluids BF la and BF 2a according to the invention differ from BF 1 and BF 2 only in that instead of 0.05% by weight 1H-l, 2,3-tolutriazole they contain the same amount of 1H-1, 2,4 -Triazole contained;
  • the brake fluid BF 1b according to the invention contained 0.04% by weight of 1H-1, 2, 4-triazole and 0.01% by weight of adenine instead of 0.05% by weight of 1H-1, 2, 3-tolutriazole;
  • the brake fluid BF 1c according to the invention contained 0.07% by weight of 1H-1, 2, 4-triazole instead of 0.05% by weight of 1H-l, 2,3-tolutriazole (but only 54.98% by weight for this) % Methyl triglycol borate).
  • the application tests were carried out in accordance with the copper corrosion test PSA D 53 5387 in the version of the year 2000 from the company PSA Ober-Citroen.
  • a copper sheet with a total area of 1000 cm2 (dimensions: 71.4 cm x 7 cm x 0.05 cm) previously cleaned in acetone is rolled up in a spiral shape in the form of a round cylinder so that the metal surface inside does not touch.
  • the copper sheet is placed in a mixture of 294 ml of brake fluid with 6 ml of distilled water and heated to 100 ° C. for 100 hours; 10 liters of air are passed through the liquid per hour, which was previously passed through distilled water cooled to 2 ° C.
  • the formulations according to the invention not only offer very good copper corrosion protection with a low Cu content in the test fluid, but also additionally cause a deposit-free metal surface and no sediment formation in the brake fluid.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Braking Arrangements (AREA)
PCT/EP2002/003671 2001-04-09 2002-04-03 Hydraulische flüssigkeiten mit verbessertem korrosionsschutz WO2002081604A1 (de)

Priority Applications (14)

Application Number Priority Date Filing Date Title
SK1192-2003A SK286828B6 (sk) 2001-04-09 2002-04-03 Brzdová kvapalina pre motorové vozidlá so zlepšenou ochranou proti korózii
BR0208415-5A BR0208415A (pt) 2001-04-09 2002-04-03 fluido de freio para automóveis
KR1020037013131A KR100861969B1 (ko) 2001-04-09 2002-04-03 방식성이 개선된 유압 작동액
EP02759789A EP1379615B1 (de) 2001-04-09 2002-04-03 Hydraulische flüssigkeiten mit verbessertem korrosionsschutz
AT02759789T ATE286112T1 (de) 2001-04-09 2002-04-03 Hydraulische flüssigkeiten mit verbessertem korrosionsschutz
CA2442697A CA2442697C (en) 2001-04-09 2002-04-03 Hydraulic fluids having improved corrosion protection
JP2002579971A JP4116445B2 (ja) 2001-04-09 2002-04-03 改善された腐食防止を有する圧媒液
PL367159A PL197796B1 (pl) 2001-04-09 2002-04-03 Płyn hamulcowy do pojazdów mechanicznych
MXPA03007944A MXPA03007944A (es) 2001-04-09 2002-04-03 Liquidos hidraulicos con proteccion anticorrosiva mejorada.
AU2002308121A AU2002308121B2 (en) 2001-04-09 2002-04-03 Hydraulic fluids with improved anti-corrosion properties
DE50201902T DE50201902D1 (de) 2001-04-09 2002-04-03 Hydraulische flüssigkeiten mit verbessertem korrosionsschutz
US10/469,770 US20040116306A1 (en) 2001-04-09 2002-04-03 Hydraulic fluids with improved anti-corrosion properties
HU0303757A HUP0303757A2 (hu) 2001-04-09 2002-04-03 Javított antikorrozitív tulajdonságokkal rendelkező hidraulikus folyadékok
NO20034495A NO325635B1 (no) 2001-04-09 2003-10-08 Bremsevaeske for motorkjoretoyer

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10117647.3 2001-04-09
DE10117647A DE10117647A1 (de) 2001-04-09 2001-04-09 Hydraulische Flüssigkeiten mit verbessertem Korrosionsschutz

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WO2002081604A1 true WO2002081604A1 (de) 2002-10-17

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JP (1) JP4116445B2 (pt)
KR (1) KR100861969B1 (pt)
CN (1) CN1312261C (pt)
AR (1) AR033453A1 (pt)
AT (1) ATE286112T1 (pt)
AU (1) AU2002308121B2 (pt)
BR (1) BR0208415A (pt)
CA (1) CA2442697C (pt)
CZ (1) CZ299651B6 (pt)
DE (2) DE10117647A1 (pt)
ES (1) ES2235077T3 (pt)
HU (1) HUP0303757A2 (pt)
MX (1) MXPA03007944A (pt)
NO (1) NO325635B1 (pt)
PL (1) PL197796B1 (pt)
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Cited By (2)

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EP3111194A4 (en) * 2014-02-25 2018-03-14 Jon A. Petty Corrosion inhibiting hydraulic fluid additive
US10669503B2 (en) 2014-02-25 2020-06-02 Jon A. Petty Corrosion inhibiting hydraulic fluid additive

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WO2007005593A2 (en) * 2005-07-01 2007-01-11 Dow Global Technologies, Inc. Low viscosity functional fluid
US20070093395A1 (en) * 2005-10-21 2007-04-26 Habeeb Jacob J Antiwear inhibiting and load enhancing additive combinations for lubricating oils
US7535673B2 (en) * 2006-01-23 2009-05-19 Hitachi Global Storage Technologies Netherlands B.V. Fluid dynamic bearing comprising a lubricating fluid having tolutriazole
WO2008142795A1 (ja) 2007-05-24 2008-11-27 Chiyoda Chemical Co., Ltd. 機能性流体
CN107557121A (zh) * 2017-08-15 2018-01-09 杭州天汇精细化工有限公司 一种汽车制动液及其生产方法
CN111676082A (zh) * 2020-05-11 2020-09-18 江苏龙蟠科技股份有限公司 一种用于esp汽车控制系统的制动液及其制备方法
US11788026B2 (en) 2021-07-28 2023-10-17 Afton Chemical Corporation Hydraulic fluid
US12018224B2 (en) 2021-07-28 2024-06-25 Afton Chemical Corporation Hydraulic fluid

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EP0028789A1 (de) * 1979-11-08 1981-05-20 Hoechst Aktiengesellschaft Hydraulische Flüssigkeit mit verbesserten Eigenschaften
EP0454110A1 (de) * 1990-04-26 1991-10-30 Hoechst Aktiengesellschaft Gegen Metallkorrosion inhibierte Bremsflüssigkeiten auf der Basis von Glykolverbindungen
WO2000046325A1 (en) * 1999-02-02 2000-08-10 Union Carbide Chemicals & Plastics Technology Corporation Hydraulic fluid compositions
DE10026010A1 (de) * 2000-05-25 2001-11-29 Basf Ag Hydraulische Flüssigkeiten mit verbessertem Korrosionsschutz für Buntmetalle

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FR2733509B1 (fr) * 1995-04-28 1997-07-04 Bp Chemicals Snc Composition d'antigel et fluide aqueux comprenant la composition
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EP0028789A1 (de) * 1979-11-08 1981-05-20 Hoechst Aktiengesellschaft Hydraulische Flüssigkeit mit verbesserten Eigenschaften
EP0454110A1 (de) * 1990-04-26 1991-10-30 Hoechst Aktiengesellschaft Gegen Metallkorrosion inhibierte Bremsflüssigkeiten auf der Basis von Glykolverbindungen
WO2000046325A1 (en) * 1999-02-02 2000-08-10 Union Carbide Chemicals & Plastics Technology Corporation Hydraulic fluid compositions
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3111194A4 (en) * 2014-02-25 2018-03-14 Jon A. Petty Corrosion inhibiting hydraulic fluid additive
US10669503B2 (en) 2014-02-25 2020-06-02 Jon A. Petty Corrosion inhibiting hydraulic fluid additive

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PT1379615E (pt) 2005-04-29
EP1379615B1 (de) 2004-12-29
CZ299651B6 (cs) 2008-10-01
ZA200308690B (en) 2004-11-08
PL197796B1 (pl) 2008-04-30
KR100861969B1 (ko) 2008-10-08
AR033453A1 (es) 2003-12-17
ATE286112T1 (de) 2005-01-15
DE50201902D1 (de) 2005-02-03
NO20034495D0 (no) 2003-10-08
SK286828B6 (sk) 2009-06-05
PL367159A1 (en) 2005-02-21
KR20030087063A (ko) 2003-11-12
ES2235077T3 (es) 2005-07-01
MXPA03007944A (es) 2004-04-02
CZ20032736A3 (cs) 2003-12-17
JP4116445B2 (ja) 2008-07-09
CA2442697A1 (en) 2002-10-17
NO325635B1 (no) 2008-06-30
SK11922003A3 (sk) 2004-02-03
EP1379615A1 (de) 2004-01-14
CN1312261C (zh) 2007-04-25
CN1501971A (zh) 2004-06-02
US20040116306A1 (en) 2004-06-17
NO20034495L (no) 2003-10-08
AU2002308121B2 (en) 2007-08-09
BR0208415A (pt) 2004-03-30
CA2442697C (en) 2011-03-15
HUP0303757A2 (hu) 2004-03-01
JP2004523641A (ja) 2004-08-05
DE10117647A1 (de) 2002-10-17

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