Classifications

• • 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
  • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
• • 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
  • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
• • 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
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
  • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
  • C10M145/14—Acrylate; Methacrylate
• • 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
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
• • 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
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
• • 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
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
• • 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/084—Acrylate; Methacrylate
• • 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
  • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
• • 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
  • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
• • 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
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
  • C10M2217/023—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group the amino group containing an ester bond
• • 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
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
• • 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
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
• • 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
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
• • 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
  • C10N2040/25—Internal-combustion engines
• • 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
  • C10N2040/25—Internal-combustion engines
  • C10N2040/251—Alcohol-fuelled engines
• • 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
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines
• • 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
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines
  • C10N2040/253—Small diesel engines
• • 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
  • C10N2040/25—Internal-combustion engines
  • C10N2040/255—Gasoline engines
• • 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
  • C10N2040/25—Internal-combustion engines
  • C10N2040/255—Gasoline engines
  • C10N2040/28—Rotary engines
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
  • F02B1/00—Engines characterised by fuel-air mixture compression
  • F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
  • F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
  • F02B3/00—Engines characterised by air compression and subsequent fuel addition
  • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
  • F02F7/00—Casings, e.g. crankcases or frames
  • F02F7/006—Camshaft or pushrod housings

Definitions

• the invention relates to viscosity index (VI) improvers with good shear stability and good dispersing detergent action in lubricating oils, in particular for diesel and gasoline engines.
• VI viscosity index
• N-vinylpyrrolidone is particularly suitable as a dispersing monomer in addition to N-vinylimidazole.
• graft products based on OCP or PAMA as base polymers or as constituents of concentrated polymer emulsions which are composed of both polymer classes have gained practical importance.
• the object was therefore to provide polyalkyl (meth) acrylates, in particular in the form of highly concentrated polymer emulsions with sufficient dispersing action and detergent action, the other properties of which, in particular the ratio "thickening action to shear stability", meet modern requirements. It has now been found that the additives according to the present invention meet the requirements of technology to an outstanding degree.
• the poly (meth) acrylates are in combination with olefin copolymers (OCP) and / or hydrogenated isoprene or butadiene-styrene copolymers (HSD) and / or hydrogenated polyisoprene or polybutadiene in the form of concentrated polymer emulsions.
• OCP olefin copolymers
• HSD hydrogenated isoprene or butadiene-styrene copolymers
• polyisoprene or polybutadiene in the form of concentrated polymer emulsions.
• the present application furthermore relates to a process for the preparation of concentrated polymer emulsions from poly (meth) acrylates and olefin copolymers suitable for improving the viscosity index in liquid carrier media for use as oil additives with improved dispersing and detergent action in diesel and gasoline engines, with monomers 80 to 99.5 parts by weight of alkyl (meth) acrylates of the formula I.
• the polymerization of the monomers I, II, IIA, IIB and III can be carried out with the addition of 0.1 to 2.0% by weight of radical initiator and with the simultaneous presence of 0.05 up to 0.5% by weight of molecular weight regulators, in each case based on the total of the monomers.
• the usual sulfur regulators cf. Th.Völker, H.Rauch-Puntigam, acrylic and methacrylic compounds, Springer-Verlag 1968
• the concentrations of the monomers and polymers are preferably such that the total of the monomers and polymers present in the liquid carrier medium TM is 40 to 75% by weight, preferably 55 to 70% by weight, based on the overall system.
• the polymerization batch is followed by At the end of the polymerization, further olefin copolymers were added in amounts such that the olefin copolymer content in the total polymer present was 31 to 80% by weight.
• the olefin copolymer can advantageously be added tel quel, ie in undiluted form, it being advantageously emulsified using shear forces.
• the additional olefin copolymer can also be added in the form of a solution, for example a 10-20% solution in the liquid carrier medium.
• VI improvers namely olefin copolymers (OCP), polyalkyl (meth) acrylates (PAMA) and the aforementioned “mixed polymers” serve e.g. according to EP 14 746 as base polymers for the process according to the invention.
• the polyalkyl (meth) acrylates are primarily those with alkyl radicals with 6-24 carbon atoms, which lead to solubility in mineral oil. Shorter alkyl residues and those with polar substituents that do not impart solubility in the mineral oil can be present to a certain extent.
• the molecular weights M w are between 5,000 and 1,000,000, preferably between 50,000 and 500,000. Such products are described in GB-C 1 068 938, US Pat. No. 3,732,334, US Pat. No. 4,149,984, US Pat.
• the monomers to be used in the process according to the invention are illustrated below.
• alkyl (meth) acrylates of the formula I are copolymerized in proportions of 80 to 99.5, preferably 90 to 98.5, parts by weight.
• monomers of the formula I are (meth) acrylic acid esters of tallow fatty alcohols (for example in the C number range 14-20, on average approx. 17.3), of coconut fatty alcohols (C number range 10 -16, on average approx. 12.6) ) or of synthetic alcohols such as Dobanol 25 R (C number range 11 - 16, on average 13.5).
• Examples of functionalized monomers of the formula II are those with an OH group in the alkyl radical, in particular in the u-position of the alkyl radical, for example the 2-hydroxyethyl methacrylate and the -acrylate, the 3-hydroxypropyl methacrylate and -acrylate, and also the 2-position or double methyl-substituted derivatives, 4-hydroxybutyl methacrylate and acrylate, but also the 2-hydroxypropyl methacrylate and acrylate.
• the monomers of the formula II in which R 2 stands for a frequently alkoxylated, in particular ethoxylated radical, for example 2- (2-ethoxyethoxy) ethyl methacrylate and - are of particular interest because of their low other aggressiveness under practical conditions in motor testing.
• R 7 represents an alkylene dialkylamino group
• R 7 represents an alkylene dialkylamino group
• the corresponding amides especially the N- (3-dimethylaminopropyl) methacrylamide.
• These comonomers can be copolymerized, for example by copolymerization, together with compounds of the formula II, but also at a later point in time.
• the formula IIA also includes heterocyclically substituted monomers, such as, for example, the 2- (1-imidazolyl) ethyl methacrylate and acrylate, the 2- (4-morpholinyl) ethyl methacrylate and acrylate and the 1- (2-methylacryloyloxyethyl) -2-pyrrolidone, as well as the corresponding amides.
• heterocyclically substituted monomers such as, for example, the 2- (1-imidazolyl) ethyl methacrylate and acrylate, the 2- (4-morpholinyl) ethyl methacrylate and acrylate and the 1- (2-methylacryloyloxyethyl) -2-pyrrolidone, as well as the corresponding amides.
• the monomers of the formula IIB are of particular importance, especially N-vinylpyrrolidone-2.
• the olefin copolymers to be used according to the invention are known per se. It is primarily composed of ethylene, propylene, butylene and / or other ⁇ -olefins with 5 to 200 carbon atoms built-up polymers, as have already been recommended as VI improvers.
• the molecular weight M w is in general from 10,000 to 300,000, preferably between 50,000 and 150,000.
• Such olefin copolymers are described, for example, in German Offenlegungsschriften DE-A 16 44 941, DE-A 17 69 834, DE-A 19 39 037 , DE-A 19 63 039 and DE-A 20 59 981.
• the base copolymer consists of a hydrogenated polyisoprene or copolymer with styrene
• commercially available hydrogenated products for example commercial products SHELLVIS 50, 200 or 250 @ are preferred.
• Ethylene-propylene copolymers are particularly useful, and terpolymers with the known tercomponents, such as ethylidene Norbornen (cf. Macromolecular Reviews, Vol. 10 (1975)) is possible, but their tendency to cross-link during the aging process must be taken into account.
• the distribution can be largely statistical, but sequence polymers with ethylene blocks can also be used with advantage
• the ratio of the monomers ethylene-propylene is variable within certain limits, which can be set as the upper limit at around 75% for ethylene and around 80% for propylene.As a result of its reduced tendency to solubility in oil, polypropylene is already less suitable than ethylene-propylene copolymers .
• the solvents therefore fall e.g. in the group of hydrocarbons such as kerosene (boiling range 180-210 degrees C), the naphthenic oils, the paraffin-based oils or the gas oils. (Cf. Ullmanns Enzyklopadie der Techn. Chemie, 4th edition, vol. 10, pp. 641-714.
• carrier media are advantageously used which only solve OCP to a limited extent or are only swelling agents, as described in detail in "USP 4,677,151 and US Pat. No. 4,622,358.
• phthalic esters such as dibutyl phthalate and esters of 2,2,4-trimethyladipic acid, for example with a mixture of octanol / decanol.
• the mono- or multifunctional alcohols themselves are also suitable.
• *** for example hexadecanol, octadecanol, diethylene glycol, tetraethylene glycol and methoxypolyethylene glycols with degrees of ethoxylation of approx. 2-50.
• the polymerization of the alkyl (meth) acrylates is generally carried out as a monomer feed polymerization at 80-100 ° C. in a liquid carrier medium with the addition of peroxidic initiators such as t-butyl peroctoate. In the case of the production of concentrated polymer emulsions, this is done in the presence of a small amount of dissolved OCP. The polymerization is usually complete after about 8 hours. Subsequently, further monomers can be graft-polymerized at 130 ° C. with the addition of t-butyl perbenzoate. Finally, the desired final composition is then set by adding further OCP and, if appropriate, solvent or carrier medium.
• the VI-improving additives according to the invention with dispersing / detergent action are generally available as relatively concentrated polymer solutions in the carrier media.
• the polymer content in the concentrates is 30 to 75% by weight, preferably 40 to 70%.
• oils or fractions are advantageously added to the oils or fractions, the viscosity indices of which are to be improved, in such amounts that they preferably contain 1 to 10% by weight of the polymeric additives according to the present invention.
• the advantage of the additives according to the invention is an excellent dispersing and detergent effect in Otto and diesel engines with completely neutral behavior against sealing materials such as e.g. Viton ®.
• Polymer content 60% by weight
• Table 2 shows results of the M-102-E black sludge test.
• Additive 4 (example 5) containing OH groups is rated significantly better than additive 5 with vinylpyrrolidone (example 6). Both additives are present as a concentrated polymer emulsion.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Detergent Compositions (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 1989
  • 1989-09-09 DE DE3930142A patent/DE3930142A1/de not_active Withdrawn
• 1990
  • 1990-08-30 ES ES90116624T patent/ES2062234T3/es not_active Expired - Lifetime
  • 1990-08-30 DE DE90116624T patent/DE59004308D1/de not_active Expired - Lifetime
  • 1990-08-30 AT AT90116624T patent/ATE100489T1/de not_active IP Right Cessation
  • 1990-08-30 DK DK90116624.9T patent/DK0418610T3/da active
  • 1990-08-30 EP EP90116624A patent/EP0418610B1/fr not_active Expired - Lifetime
  • 1990-08-31 US US07/576,670 patent/US5188770A/en not_active Expired - Lifetime
  • 1990-09-10 JP JP2237310A patent/JP2941392B2/ja not_active Expired - Fee Related
• 1996
  • 1996-08-15 HK HK155396A patent/HK155396A/xx not_active IP Right Cessation

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