EP0639632B1 - Utilisation d'un additif pour combustibles sans plomb pour moteurs à combustion interne à allumage commandé pour réduire l'érosion du siège de soupape. - Google Patents

Utilisation d'un additif pour combustibles sans plomb pour moteurs à combustion interne à allumage commandé pour réduire l'érosion du siège de soupape. Download PDF

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Publication number
EP0639632B1
EP0639632B1 EP94890107A EP94890107A EP0639632B1 EP 0639632 B1 EP0639632 B1 EP 0639632B1 EP 94890107 A EP94890107 A EP 94890107A EP 94890107 A EP94890107 A EP 94890107A EP 0639632 B1 EP0639632 B1 EP 0639632B1
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EP
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Prior art keywords
mentioned
formula
ash
combined
sulphosuccinic acid
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Expired - Lifetime
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EP94890107A
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German (de)
English (en)
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EP0639632A1 (fr
Inventor
Alexander Dr. Buchsbaum
Werner Dr. Koliander
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OMV Downstream GmbH
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OMV AG
OEMV AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)

Definitions

  • the invention relates to the use of an additive for unleaded Gasoline fuels to prevent or reduce Valve seat wear, which is essentially at least one Alkali metal or alkaline earth metal salt of an organic Sulfonic acid and at least one ashless detergent as well optionally contains other known additives.
  • U.S. Patent 3,955,938 describes (Exxon) Compositions based on inorganic and organic sodium salts that work together with ashless Dispersants as additives in unleaded fuels to protect the valve seats.
  • EP 0 288 296 (BP Chemicals) uses as an additive a fine-particle metal salt dispersion against valve seat wear, especially a dispersion of potassium borate, Sodium borate, potassium carbonate and potassium bicarbonate.
  • the fuels contain to prevent or reduce wear and tear on the valves and for simultaneous reduction of corrosion phenomena alkali metal or alkaline earth metal salts of monoamides of dicarboxylic acids with 2 up to 4 carbon atoms between the carboxyl groups or of amides of tri- or tetracarboxylic acids, the amino nitrogen at least one hydrocarbon group, optionally is oxygen or amine substituted.
  • these additives are said to work simultaneously through their detergent action also keep the motors clean.
  • EP-A1-0 307 815 (BASF) relates to fuels, in which small amounts of copolymers of olefins and / or cycloolefins with maleic anhydride and / or copolymers of alkyl vinyl ethers and / or cycloalkyl vinyl ethers with maleic anhydride and / or copolymers of alkyl vinyl ethers and / or cycloalkyl vinyl ethers and olefins and / or contain cycloolefins with maleic anhydride are, the carboxyl groups entirely or partially under Formation of alkali metal or alkaline earth metal salts and the Rest of the carboxyl groups with alcohols and / or amines corresponding ester and / or amide groups and / or ammonium groups are implemented.
  • EP 0 342 497 also describes Purpose of preventing wear and tear on the wearer Valves and the simultaneous reduction of corrosion the addition of copolymers Alkyl (meth) acrylates and / or vinyl esters from optionally monoethylenically unsaturated carboxylic acids, the All or part of the carboxyl groups of the copolymers Alkali are implemented to form the alkali metal salts and the rest of the acid groups with ammonia and / or amines to the corresponding amide groups and / or ammonium salts is implemented.
  • EP-A1-0 207 560 (Shell) alkali metal and alkaline earth metal salts of hydrocarbon-substituted Succinic acid as wear protection additives described.
  • hydrocarbon-substituted succinic acid derivatives are the subject of an extensive older and newer patent literature. Also the imide derivatives of these substances are used alone or in because of their dispersing action Combination with other additives used.
  • EP-A-233 250 (Lubrizol) is used as an additive against the valve seat wear a combination of alkaline or compositions containing alkaline earth metals and ashless dispersants proposed.
  • alkali metals Concretely, only the compositions Salts of organic alkyl aryl sulfonic acids; both Dispersants are those already mentioned, known alkenyl succinimides, which are usually at least contain about 30 aliphatic carbon atoms.
  • the PCT application WO 91/07477 deals deal with the improvement of the ignition behavior of fuels and as an addition to this discloses alkali metal and alkaline earth metal salts of mono- or diesters of Sulfosuccinic acid.
  • These compounds are succinic acid derivatives are in which the carboxylic acid group (s) with Hydrocarbon residues are esterified and an alpha carbon atom of succinic acid through a sulfonic acid group is substituted.
  • These sulfosuccinic acid esters are in Form of alkali metal or alkaline earth metal salts.
  • the aim of the present invention was now to Inexpensive wear protection additive for unleaded petrol to provide the valve seat wear on the engine output side Completely prevented and at the same time for keeping the engine clean worries.
  • a neutral alkali metal and / or alkaline earth metal salt of a mono- or diester of sulfosuccinic acid of the general formula I is thus used in which R 1 and R 2 independently of one another are hydrogen or an aliphatic hydrocarbon group, with the proviso that at most one of the radicals R 1 or R 2 is hydrogen, M is an alkali metal or alkaline earth metal ion and n corresponds to the valence of M. , used in combination with an ash-free detergent as a wear protection additive to reduce or prevent valve seat closures.
  • the aliphatic groups can be saturated or be unsaturated groups, optionally also substituents can wear.
  • substituents are: Hydroxy, ether, ketone, phenyl or ester groups in Question that's the same on the two hydrocarbon groups or can be different.
  • Mono- or diesters of sulfosuccinic acid can be used, it being possible for the carboxyl group in the ⁇ -position to the SO 3 group, the ⁇ -position carboxyl group or both carboxyl groups to be esterified with the same or different radicals.
  • the salts of the diesters of sulfosuccinic acid are preferred. They have proven to be soluble in gasoline to an extent which allows the desired amount of the alkali metal or alkaline earth metal additive to be adjusted without difficulty.
  • the chain length of the aliphatic hydrocarbon group in the ester radical is preferably 4 to 20 carbon atoms. Hydrocarbon radicals with a chain length of 6 to 13 carbon atoms, in particular with a chain length of about 8 carbon atoms, are particularly preferred.
  • alkali metal salts of the sulfosuccinic acid esters are preferred, being for the purpose of protecting the Exhaust valves the potassium salts proved to be particularly cheap to have.
  • the salts of the sulfosuccinic acid esters also work as a surfactant, what the formulation of additive packages for high demands on engine cleanliness.
  • They are all different ash-free detergents, such as long-chain amide-imide compounds, long chain amines, polyethers or polyether amines suitable.
  • the polybutenamines have been particularly advantageous in combination with the salts of sulfosuccinic acid esters proven.
  • the detergents preferably have one average molecular weight from 2000 to 3000.
  • the additives used according to the invention can also contain other known additives. Frequently e.g. Corrosion protection is desirable or necessary.
  • carrier oils are also used. These either exist from mineral oil fractions or they are synthetic products, such as. Poly alpha olefins. Usually it's the detergents which are formulated as a solution in a carrier oil and therefore bring this component into the additive package. In addition, the alkali metal component can also be added a carrier oil to be easier to handle.
  • Aromatic are preferred Kerosene can be used for this purpose.
  • Such diluents can have viscosity limits of about 800 cP at -20 ° C are observed for European Ratios are favorable.
  • the proportions of alkali metal component for detergents are preferably in the range of 1: (8-15), these details refer to detergents, which if necessary contain a carrier oil.
  • additive 15 % By mass to 40% by mass, preferably 30% by mass to 40 % By mass, of an aromatic kerosene as a diluent contain.
  • a fuel for gasoline engines the one according to the invention contains used additive, corresponds to the put to it Requirements if it is 0.01 milligram atom (mVal) to 2.5 milligram atom (mVal) of alkali metal per kg of fuel contains.
  • the preferred range is between 0.02 mVal and 1.0 mVal, in particular between 0.07 mVal and 0.25 mVal Alkali metal per kg of fuel.
  • the ranges 1 mg to 30 mg are preferred, in particular 3 mg to 10 mg of potassium per kg of fuel.
  • the alkali metal component consists of a Potassium sulfosuccinic acid dioctyl ester. If this component is present without carrier oil, it contains about 8.5% by mass Potassium.
  • the detergent is based on Polybutenamine.
  • Carrier oil including the potassium sulfosuccinate with carrier oil can be formulated.
  • the product contains an aromatic for dilution Kerosene.
  • This additive is added in an amount of 1100 ml 1000 liters of fuel added, so that per kg of fuel about 4 mg of potassium are included.
  • Test fuel Deposits: Gasoline (Eurosuper) without additives 350 to 700 mg / valve Gasoline (Eurosuper) + addition less than 100 mg / valve (1 g / 1000 g petrol)

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Powder Metallurgy (AREA)
  • Fuel-Injection Apparatus (AREA)
  • Lift Valve (AREA)
  • Safety Valves (AREA)

Claims (13)

  1. Utilisation d'un sel neutre d'un métal alcalin et/ou d'un métal alcalino-terreux d'un mono- ou d'un diester de l'acide sulfosuccinique de formule générale (I)
    Figure 00160001
       dans laquelle R1 et R2, indépendamment l'un de l'autre, représentent chacun un atome d'hydrogène ou un groupe hydrocarboné aliphatique, à la condition qu'au moins l'un des radicaux R1 ou R2 soit un atome d'hydrogène, M est un ion d'un métal alcalin ou alcalino-terreux, et n correspond à la valence de M, en combinaison avec au moins un détergent sans cendres, et éventuellement d'autres additifs connus, en tant qu'additif pour des essences sans plomb pour moteur à allumage commandé, pour empêcher ou réduire l'usure des sièges de soupape.
  2. Utilisation d'un sel d'un diester de l'acide sulfosuccinique ayant la formule I donnée dans la revendication 1, en combinaison avec un détergent sans cendres, pour l'application mentionnée dans la revendication 1.
  3. Utilisation d'un sel d'un ester de l'acide sulfosuccinique ayant la formule I donnée dans la revendication 1, dans lequel les groupes esters sont constitués de résidus hydrocarbonés ayant de 4 à 20 atomes de carbone, en combinaison avec un détergent sans cendres pour l'application mentionnée dans la revendication 1.
  4. Utilisation d'un sel d'un ester de l'acide sulfosuccinique ayant la formule I donnée dans la revendication 1, dans lequel les groupes esters sont constitués de résidus hydrocarbonés ayant de 6 à 13 atomes de carbone, en combinaison avec un détergent sans cendres, pour l'application mentionnée dans la revendication 1.
  5. Utilisation d'un sel d'un ester de l'acide sulfosuccinique ayant la formule I donnée dans la revendication 1, dans lequel les groupes esters sont constitués de résidus hydrocarbonés ayant 8 atomes de carbone, en combinaison avec un détergent sans cendres, pour l'application mentionnée dans la revendication 1.
  6. Utilisation d'un sel d'un métal alcalin d'un ester de l'acide sulfosuccinique ayant la formule I donnée dans la revendication 1, en combinaison avec un détergent sans cendres, pour l'application mentionnée dans la revendication 1.
  7. Utilisation d'un sel de potassium d'un ester de l'acide sulfosuccinique ayant la formule I donnée dans la revendication 1, en combinaison avec un détergent sans cendres, pour l'application mentionnée dans la revendication 1.
  8. Utilisation d'un sel d'un métal alcalin ou d'un métal alcalino-terreux d'un ester de l'acide sulfosuccinique ayant la formule I donnée dans la revendication 1, en combinaison avec un détergent à base de polybuténamine, pour l'application mentionnée dans la revendication 1.
  9. Utilisation d'un sel d'un métal alcalin ou d'un métal alcalino-terreux d'un ester de l'acide sulfosuccinique ayant la formule I donnée dans la revendication 1, en combinaison avec un détergent à base de polyétheramine, pour l'application mentionnée dans la revendication 1.
  10. Utilisation d'un sel d'un métal alcalin et/ou d'un métal alcalino-terreux d'un ester de l'acide sulfosuccinique ayant la formule I donnée dans la revendication 1, en combinaison avec un détergent sans cendres, ayant une masse moléculaire de 2000 à 3000, pour l'application mentionnée dans la revendication 1.
  11. Utilisation d'un sel de potassium d'un ester de l'acide sulfosuccinique ayant la formule I donnée dans la revendication 1, en combinaison avec un détergent sans cendres, selon un rapport en masse de 1:(8-15), pour l'application mentionnée dans la revendication 1.
  12. Utilisation d'un mélange de 4 % en masse à 9 % en masse du sel d'un métal alcalin d'un ester de l'acide sulfosuccinique ayant la formule I donnée dans la revendication 1, et de 60 % en masse à 80 % en masse d'un détergent sans cendres, le complément à 100 % en masse étant constitué d'une huile support et/ou d'un diluant, pour l'application mentionnée dans la revendication 1.
  13. Utilisation d'un mélange contenant un sel de potassium d'un ester de l'acide sulfosuccinique ayant la formule I mentionnée ci-dessus et un détergent sans cendres, où le potassium est présent en une quantité de 0,2 % en masse à 0,7 % en masse, pour l'application mentionnée dans la revendication 1.
EP94890107A 1993-08-17 1994-06-21 Utilisation d'un additif pour combustibles sans plomb pour moteurs à combustion interne à allumage commandé pour réduire l'érosion du siège de soupape. Expired - Lifetime EP0639632B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0163693A AT400149B (de) 1993-08-17 1993-08-17 Additiv für unverbleite ottokraftstoffe sowie dieses enthaltender kraftstoff
AT1636/93 1993-08-17

Publications (2)

Publication Number Publication Date
EP0639632A1 EP0639632A1 (fr) 1995-02-22
EP0639632B1 true EP0639632B1 (fr) 1998-04-22

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EP94890107A Expired - Lifetime EP0639632B1 (fr) 1993-08-17 1994-06-21 Utilisation d'un additif pour combustibles sans plomb pour moteurs à combustion interne à allumage commandé pour réduire l'érosion du siège de soupape.

Country Status (8)

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EP (1) EP0639632B1 (fr)
AT (2) AT400149B (fr)
CZ (1) CZ285397B6 (fr)
DE (1) DE59405767D1 (fr)
DK (1) DK0639632T3 (fr)
HU (1) HU214907B (fr)
SI (1) SI0639632T1 (fr)
SK (1) SK280988B6 (fr)

Cited By (1)

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US7850744B2 (en) 2004-08-05 2010-12-14 Basf Aktiengesellschaft Heterocyclic compounds containing nitrogen as a fuel additive in order to reduce abrasion

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WO2018007445A1 (fr) 2016-07-07 2018-01-11 Basf Se Inhibiteurs de corrosion pour carburants et lubrifiants
CN109312242A (zh) 2016-07-07 2019-02-05 巴斯夫欧洲公司 作为用于燃料和润滑剂的添加剂的共聚物
WO2018007486A1 (fr) 2016-07-07 2018-01-11 Basf Se Polymères utilisés en tant qu'additifs pour carburants et lubrifiants
WO2018108534A1 (fr) 2016-12-15 2018-06-21 Basf Se Polymères comme additifs pour carburants
EP3555242B1 (fr) 2016-12-19 2020-11-25 Basf Se Additif destiné à améliorer la stabilité thermique de carburants
EP3559173A1 (fr) 2016-12-20 2019-10-30 Basf Se Utilisation d'un mélange d'un ester complexe avec un acide monocarboxylique pour réduire un frottement
SG11201909437RA (en) 2017-04-11 2019-11-28 Basf Se Alkoxylated amines as fuel additives
EP3609990B1 (fr) 2017-04-13 2021-10-27 Basf Se Polymères utilisés en tant qu'additifs pour carburants et lubrifiants
WO2020260062A1 (fr) 2019-06-26 2020-12-30 Basf Se Nouveaux packages d'additifs pour carburants à base d'essence
EP3933014A1 (fr) 2020-06-30 2022-01-05 Basf Se Additivation de carburants permettant de réduire les allumages non contrôlés dans des moteurs à combustion interne
PL3940043T3 (pl) 2020-07-14 2024-02-19 Basf Se Inhibitory korozji do paliw silnikowych i smarów
DE102022131356A1 (de) 2022-11-28 2023-01-12 Basf Se Formamidine als Kraftstoffadditive
DE102022131890A1 (de) 2022-12-01 2023-01-26 Basf Se Guanidinderivate als Kraftstoffadditive
DE102022132342A1 (de) 2022-12-06 2023-01-26 Basf Se Guanidiniumsalze als Kraftstoffadditive
EP4382588A1 (fr) 2022-12-06 2024-06-12 Basf Se Additifs pour améliorer la stabilité thermique de carburants

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FR2421958A1 (fr) * 1978-04-04 1979-11-02 Raffinage Cie Francaise Nouveaux agents anti-salissures et application desdits agents
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Publication number Priority date Publication date Assignee Title
US7850744B2 (en) 2004-08-05 2010-12-14 Basf Aktiengesellschaft Heterocyclic compounds containing nitrogen as a fuel additive in order to reduce abrasion
US8814957B2 (en) 2004-08-05 2014-08-26 Basf Aktiengesellschaft Heterocyclic compounds containing nitrogen as a fuel additive in order to reduce abrasion

Also Published As

Publication number Publication date
ATE165389T1 (de) 1998-05-15
CZ285397B6 (cs) 1999-08-11
SK97094A3 (en) 1995-03-08
AT400149B (de) 1995-10-25
SI0639632T1 (en) 1998-08-31
EP0639632A1 (fr) 1995-02-22
DK0639632T3 (da) 1999-02-15
HUT69325A (en) 1995-09-28
HU214907B (hu) 1998-07-28
SK280988B6 (sk) 2000-10-09
CZ198594A3 (en) 1995-03-15
DE59405767D1 (de) 1998-05-28
HU9402368D0 (en) 1994-11-28
ATA163693A (de) 1995-02-15

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