Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
  • C08K5/42—Sulfonic acids; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/062—Copolymers with monomers not covered by C09D133/06
  • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
  • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
  • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine

Definitions

• Coating composition based on an addition polymer containing hydroxyl groups and an aminoplast resin crosslinking agent, containing acid catalysts with hydroxyl groups
• the invention relates to a coating composition containing
• a and B being 100% by weight, as well as suitable auxiliaries and additives, optionally pigments, optionally fillers, organic solvent and an acid catalyst.
• the present invention also relates to processes for the production of this coating composition and the use of this coating composition for automotive refinishing and as a stoving enamel.
• EP-B-64 338 discloses a coating composition 15 based on linear addition polymers containing hydroxyl groups and an essentially fully alkylated melamine-formaldehyde crosslinking agent, a mixture of alkylated arylsulfonic acids being used as the acid catalyst.
• the mixture contains 20 differently alkylated arylsulfonic acids.
• EP-A-158161 acid-curing coating compositions which, in addition to melamine-formaldehyde crosslinking agents, contain hydroxyl group-containing binders.
• the present invention was therefore based on the object
• the addition polymers and aminoplast resin crosslinking agents which cure quickly at low temperatures, in particular room temperature, but nevertheless have a pot life as long as possible (at least approx. H).
• the resulting coatings should have the least possible glossy haze and show good hardness and resistance to solvents.
• a and B being 100% by weight, as well as suitable auxiliaries and additives, optionally pigments, optionally fillers, organic solvent and an acid catalyst.
• This coating composition is characterized in that the acidic catalysts 1.) at least one hydroxyl group-containing succinic acid diestersulfonic acids and / or sulfonium salts are used which correspond to the following formulas (I) or (II):
• R linear or branched alkyl or alkoxyalkyl radical having 2 to 12 carbon atoms and having 1, 2 or 3 hydroxyl groups
• R alkyl, hydroxyalkyl, aryl, hydroxiaryl, where R can be the same or different, or aliphatic or aromatic N-heterocycle
• the present invention also relates to a process for the production of these coating compositions and their use as a car refinish paint or as a stoving paint.
• succinic acid ester sulfonic acids or sulfonium salts used as acid catalysts with hydroxyl groups and their preparation are known and have been described for the preparation of detergents, wetting agents, emulsifiers and the like (cf., for example, Stache, Tensid-Taschenbuch, Hanser-Verlag, Kunststoff, Vienna 1981; U.S. Patent 2,761,795; U.S. Patent 2,454,546; GB-B-652,128).
• succinic acid ester sulfonium salts or sulfonic acids as catalysts in acid-curing coating compositions.
• Suitable addition polymers A containing hydroxyl groups are prepared by copolymerizing hydroxyalkyl esters of acrylic acid or methacrylic acid with alkyl esters acrylic acid or methacrylic acid and / or other copolymerizable monomers.
• Preferred OH functional monomers are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate,
• reaction products of acrylic acid and / or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary e (carbon atom or of the glycidyl ester of a, ethylenically unsaturated carboxylic acid with one tertiary aliphatic carboxylic acid can also be used, in some cases reaction products of one mole of hydroxyethyl acrylate and / or hydroxyethyl methacrylate with an average of 2 moles of ⁇ -caprolactone.
• P-ethylenically unsaturated carboxylic acids can contain up to 75% by weight, preferably up to 50% by weight, based on the total weight of the hydroxyalkyl esters, hydroxyl-containing esters of acrylic acid and / or methacrylic acid with a secondary hydroxyl group be used.
• ethylenically unsaturated monomers which can be used to prepare component A are monomers with a carboxyl group, such as, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic and fumaric acid.
• alkyl esters of acrylic and methacrylic acid such as, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, t-butyl acrylate, isopropyl acrylate, isobutyl acrylate, pentyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate Trimethylhexyl acrylate, decyl acrylate, dodecyl acrylate, hexadecyl acrylate, octadecyl acrylate, octadecenyl acrylate and the corresponding methacrylates.
• Suitable polymerizable monomers are styrene, vinyltoluene, alkoxyethyl acrylates and aryloxyethyl acrylates and corresponding methacrylates, esters of maleic and fumaric acid, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride. Further monomers can be used, provided that these do not lead to undesirable properties of the copolymer.
• a branched acrylate copolymer which is obtainable by copolymerization of
• hydroxyl numbers of component A are preferably in the range from about 70 to 200 mg KOH / g.
• component a and a examples are the monomers already mentioned on pages 6 and 7 of this description, Compounds of the general formula can advantageously be used as component a
• Examples of such compounds are hexanediol diacrylate, hexanediol dimethacrylate, glycol diacrylate, glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate and similar compounds.
• component a can advantageously be a reaction product of a carboxylic acid with a polymerizable, olefinically unsaturated double bond and glycidyl acrylate and / or glycidyl methacrylate or a polycarboxylic acid or unsaturated monocarboxylic acid esterified with an unsaturated alcohol.
• polyvinyl compounds such as e.g. Divinylbenzene suitable.
• a reaction product of a polyisocyanate and an unsaturated alcohol or amine can be used as component a ?
• An example of this is the reaction product of one mole of hexamethylene diisocyanate and 2 moles of allyl alcohol.
• Another advantageous component a_ is a diester of polyethylene glycol and / or polypropylene glycol with an average molecular weight of less than 1500, preferably less than 1000, and acrylic acid and / or methacrylic acid.
• acrylates with more than 2 ethylenically unsaturated double bonds such as, for example, trimethylolpropane, can also be used as component a_.
• Suitable aminoplast resins are known urea, carbamide, melamine, benzoguanamine and glycoluril resins. The latter are e.g. available on the market under the trade name Cymel 1171 (cyanamide).
• Amine resins of the melamine type are preferably used as crosslinker component B in the coating compositions according to the invention.
• the melamine-formaldehyde crosslinking agents used have an average degree of methylolation of at least 0.65, preferably 0.9 to 1.0, and are mixed with monoalcohols in an amount of at least 80 mol%, preferably 90 to 100 mol. %, based on the maximum possible etherification, etherified.
• Suitable etherification alcohols are methanol, ethanol, propanol, iso-propanol, n-butanol, iso-butanol, tert-butanol, hexanols, heptanols and ethyl hexanol.
• Hexamethoxymethylmelamine which is available on the market under the trademark Cymel 301 (cyanamide), is particularly preferably used.
• hydroxifunctional succinic acid diestersulfonic acids and succinic acid polyester sulfonic acids or the respective sulfonium salts used as acid catalysts in the coating compositions according to the invention or the respective sulfonium salts are known (cf. for example US Pat. No. 2, 761, 795; US Pat. No.
• these sulfonic acids are accessible by sulfonation using gaseous sulfur dioxide from et, ⁇ -unsaturated dicarboxylic acids and esterification of the resulting sulfosuccinic acid , as described in DE-OS 1803 881.
• Hydroxy-functional succinic acid ester sulfonic acids or sulfonium salts which are suitable as acidic catalysts can be prepared particularly easily and without great expenditure on apparatus by the following process:
• Maleic anhydride is first reacted with an alcohol component in a molar ratio of 1 ol anhydride: 1 ol polyol at temperatures between 70 and 100 ° C. in the presence of a conventional esterification catalyst until the monoester has formed completely (check by determining the acid number ). Thereafter, further polyol in the molar ratio of 1 mol of polyol: 1 mol of monoester is added together with organic solvent and further esterification catalyst and the reaction mixture is slowly (ie at a " heating rate of approx. 2 ° C./min) to temperatures between heated to 130 and 230 ° C.
• the resulting reaction water is continuously removed from the reaction mixture by distillation and the esterification reaction is continued until an acid number of the reaction product of less than 5 mg KOH / g, preferably less than 3 mg KOH / g is reached the solvent is distilled off, if appropriate under a slight reduced pressure.
• the maleic acid ester thus obtained is then reacted at temperatures which are generally between 80 and 110 ° C. with an aqueous hydrogen sulfite solution in a molar ratio between 1: 0.9 and 1: 1.1.
• the sulfonation reaction is continued up to a degree of sulfonation of the maleic acid ester of 50 to 100%, preferably 80 to 100%. If appropriate, the sulfonation reaction can, however, also only be carried out up to lower degrees of sulfonation of less than 50%. In this case, the amount of acid catalyst used in the coating compositions must be increased accordingly.
• the excess sulfur dioxide is then removed, for example by passing a nitrogen stream through the solution.
• Hydrogen sulfite residues are removed by oxidation, for example by adding aqueous Hydrogen peroxide solution removed. Then solvent is added and the water contained in the reaction mixture is distilled off azeotropically. To release the sulfonic acid, it is acidified, for example with sulfuric acid.
• Alcohol components suitable for the preparation of the acidic catalysts are linear or branched polyols with 2 to 4 hydroxyl groups and 2 to 12 C atoms in the molecule. They can also be used in a mixture with monoalcohols.
• suitable alcohols are ethylene glycol, propylene glycol, butylene glycol, hexamethylene-1,6-diol, neopentyl glycol, pentanediol, 2-methylpentanediol, 2-ethylbutanediol, dimethylolcyclohexanediol, glycerol, timethylolethane, trimethylolpropane, trimethylol butane, pentiterythritol methylolpropane and monoalcohols such as ethanol, propanol, butanol etc.
• ether alcohols for example diethylene glycol and triethylene glycol. Trimethylolpropane, propylene glycol
• the acidic catalysts can be used both as free sulfonic acids or in the form of their amine or ammonium salts.
• the sulfonium salts correspond to the general formula R - SO, Z, where R represents the succinic acid ester residue.
• the remainder Z can e.g. H or N H R 14-n
• Alkyl, hydroxyalkyl, aryl or hydroxyaryl radicals can mean.
• R can mean, for example: methyl, ethyl, propyl, i-propyl, n-butyl, t-butyl, i-butyl, pentyl, iso-amyl, hexyl, hydroxiethyl, hydroxypropyl, hydroxibutyl, hydroxylhexyl, phenyl, toluyl, naphthyl , Hydroxyphenyl.
• Z can also be an aliphatic or aromatic N-heterocycle which is derived, for example, from pyridine, oxazolidine, hydropyridine, morpholine, pyrrole, imidazole, picoline and piperidine.
• the hydroxyl-functional sulfonic acid catalysts are used in a proportion of 0.1 to 10, preferably 0.1 to 5% by weight, based on the binder solids.
• Binder solid is by definition the sum of the solids of components A and B.
• the acidic catalyst is used in a proportion of more than 1 to 10% by weight, preferably 2 to 5% by weight, based on the Binder solids used.
• the sulfonic acid catalysts are also preferably used in the form of their free acids. If the coating composition is used as a stoving enamel, a proportion of 0.1 to 2% by weight, preferably 0.1 to 1% by weight, based on the binder solid, is quite sufficient.
• hydroxy-functional catalysts can also be used together with non-hydroxy-functional organic sulfonic acids in the coating compositions according to the invention. Care should be taken to ensure that the proportion of the non-hydroxifunctional organic sulfonic acids is not more than 50% by weight, based on the total weight of the catalysts used.
• Suitable non-hydroxifunctional sulfonic acids are para-toluenesulfonic acid, xylenesulfonic acids, ethylbenzenesulfonic acids, methylnaphthalenesulfonic acids, p-octylbenzenesulfonic acid, p-dodecylbenzenesulfonic acid, branched-chain C ._- alkylbenzenesulfonic acid and di- (C) to call naphthalenedisulfonic acid,
• the coating compositions according to the invention also contain organic solvents, optionally pigments, fillers and suitable auxiliaries and additives in the usual amounts.
• Suitable organic solvents which are preferably used in an amount of 30 to 90% by weight, based on the total composition of the coating composition, are aliphatic, cycloaliphatic and aromatic hydrocarbons, esters, ethers and ketones.
• xan ethylene glycol dibutyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, dibutyl ether, cyclohexanone, methyl ethyl ketone, acetone, isophorone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, ethyl butyl ketone, ethylacetyl ethyl, diisopropyl ketone, diisopropyl ketone, diisobethyl acetate, called acetate, amylacetate, methylglycol acetate and ethylglycol acetate.
• customary auxiliaries and additives which are preferably used in amounts of 0 to 10% by weight, based on the total composition of the coating composition, are leveling agents, silicone oils, plasticizers such as phosphoric acid esters and phthalic acid esters, viscosity control agents. additives, matting agents, UV absorbers and light protection agents.
• optionally added pigments are metal pigments, such as, for example, aluminum flake pigments and mica flakes coated with metal oxides (for example mica) as effect pigments, which are preferably used in amounts of 0 to 20% by weight, based on the overall composition. Color pigments may also be used, if appropriate also in combination with the effect or metal pigments, preferably in amounts of 0 up to 40% by weight, based on the total composition of the coating composition.
• metal pigments such as, for example, aluminum flake pigments and mica flakes coated with metal oxides (for example mica) as effect pigments, which are preferably used in amounts of 0 to 20% by weight, based on the overall composition.
• Color pigments may also be used, if appropriate also in combination with the effect or metal pigments, preferably in amounts of 0 up to 40% by weight, based on the total composition of the coating composition.
• inorganic and organic pigments such as various types of iron oxide, titanium dioxide, graphite, carbon black, zinc, strontium, barium and lead bleach, lead cyanamide, lead silicochromate, zinc oxide, cadmium sulfide, chromium oxide, zinc sulfide, nickel titanium yellow, chromium titanium yellow, Ultramarine blue, phthalocyanine complexes, naphthol red, quinaridones, halogenated thioindigo pigments or the like.
• Suitable fillers are e.g. Talc, mica, kaolin, chalk, quartz flour, asbestos flour, slate flour, barium sulfate, various silicas, silicates, glass fibers, organic fibers and the like. They are preferably used in amounts of 0 to 50% by weight, based on the total composition of the coating composition.
• the coating compositions according to the invention are formulated as two- and three-component systems, but preferably as three-component systems.
• the ammonium salts of the hydroxifunctional sulfonic acids are used as acid analyzers, one- or two-component systems can be produced from the coating compositions according to the invention. In this case, the sulfonic acids are only released when elevated temperatures are used.
• the paint component I contains the hydroxyl group-containing addition polymer A, the paint component II the amino resin and the paint component III the acidic curing catalyst.
• the paint components I, II and III are mixed shortly before the application of the coating composition.
• the duration of the processability ("pot life") of the mixture is generally over 5 hours, while the varnish components I, II and III are stable for several months separately.
• the lacquer components I, II and III are produced in a conventional manner by mixing the components contained in each case. Sometimes it is advisable to first dissolve a component in a solvent if it is not in liquid form and to mix the solution with the other components.
• the coating composition contains pigments, they are preferably incorporated into the lacquer component I, which contains the addition polymer containing hydroxyl groups. This can be done, for example, by milling the pigments with the binder or addition polymer or by incorporating a pigment paste.
• the coating compositions according to the invention cure in the temperature range from room temperature to about 100 ° C., but can also be used at higher temperatures.
• the low curing temperatures make them particularly suitable for automotive refinishing.
• These coating compositions can be applied by spraying, flooding, dipping, rolling, knife coating or brushing onto a substrate in the form of a film, the film then being cured to form a firmly adhering coating.
• the coating compositions according to the invention are particularly notable for high reactivity with a simultaneous pot life of several hours.
• the resulting coatings have a low gloss haze with good hardness and resistance to solvents.
• the invention is explained in more detail below with the aid of exemplary embodiments. All information on parts and percentages are weight data unless expressly stated otherwise.
• polyester A 980 g of maleic anhydride, 760 g of propylene glycol and 2 g of dibutyltin oxide are reacted at a maximum of 80 ° C. up to the acid number 316. Then 760 g of propylene glycol, 125 g of toluene and 2.5 g of p-benzoquinone are added and the mixture is boiled at 144 ° C. until an acid number of 2 is reached. The solvent is then distilled off and the polyester B is thus obtained.
• Polyester B heated to 100 ° C., 557 g of a 50% aqueous ammonium bisulfite solution were added dropwise within 1 hour and then the temperature for 6 hours kept at 100 ° C. Then an N ? -Current passed through the solution to remove excess sulfur dioxide. 45 ml of 30% hydrogen peroxide solution and then 300 g of n-butanol are then added at 70 ° C. and the water of reaction is distilled off azeotropically in analogy to 1. An intermediate 2A is obtained.
• polyester A In the apparatus described for the production of polyester A, 784 g of maleic anhydride, 1,072 g of trimethylolpropane and 1.84 g of di-butyltin oxide are reacted at 80 ° C. to an acid number of 219. Then 1,072 g of trimethylolpropane, 146.4 g of toluene and 2.96 g of p-benzoquinone are added and the mixture is boiled at 200 ° C. until an acid number of 1.3 is reached. The solvent is then distilled off and the polyester C is thus obtained.
• the sulfonic acid 3 is prepared analogously to the preparation of the sulfonic acid 1, but using the following amounts of the individual reagents: For the production of intermediate 3A:
• p-TSA X * 14.0 DBSA 2) 6.0 sulfonic acid 1 33.5 sulfonic acid 2 26.0 sulfonic acid 3 30.7 butanol 66.5 74.0 69.3 56.0 isopropanol 24.0 1)
• p-TSA para-toluenesulfonic acid (technical) 'dodecylbenzenesulfonic acid (technical)
• the content of the monomer tank is metered in in 3 h, the content in the initiator tank is metered in 3.5 h.
• the inlets are started at the same time.
• the temperature is kept at 110 ° C. during the polymerization.
• polymerization is continued for 3 h.
• the acrylic resin solution I thus obtained has a viscosity of 1.8 dPa.s and a solids content of 50% (130 ° C., 60 min).
• the components specified in Table 2 are ground in a laboratory sand mill to a Hegman fineness of 10 ⁇ m.
• a green or red topcoat is prepared from the components shown in Table 3 in a known manner by mixing, to which the amount of various acid solutions 1-3 given in Table 4 is added with stirring.
• the coating composition obtained is now knotted on glass sheets and dried as follows:
• the glass sheets are kept at room temperature for 6 days and the König pendulum hardness is then determined. The results of these tests are shown in Table 5.
• the pot life was determined from the coating compositions obtained, by which is meant the time in which the viscosity of the coating compositions rose to twice the initial viscosity.
• the coating composition obtained is also applied to steel sheets which are coated with a commercially available filler based on a polyamino amide, a dimer fatty acid and an epoxy resin based on bisphenol A with an epoxy equivalent weight of 450-500. These sheets are dried for 30 minutes at 60 ° C and the gloss after Load of 240 h in a constant condensation water climate tested according to DIN 50017.
• the solvent resistance of the resulting coatings was investigated by spraying the coating composition onto glass panels and then curing it by storage at room temperature for 7 days. The results of these tests are shown in Table 6.
• the glossy haze of the coatings was investigated by spraying the coating compositions onto glass panels and drying them for 30 minutes to 60 ° C. The results of these tests are also shown in Table 6.
• Table 3 Composition of the ⁇ rüne or red topcoat
• Hexamethoxymethylmelamine resin Cymel '301 commercial product of cyanamide.
• the glossiness metric g is defined as:
• I diff 45 ° radiation, intensity at 0 ° with ideally diffuse surface
• Table 7 Determination of the run-out times in the DIN4 cup at 23 ° C. of the topcoats of Examples 2, 5, VI and
• Examples 1 to 6 and comparative examples 1 and 2 show that the coating compositions according to the invention cure rapidly at low temperatures, but in comparison to systems based on branched acrylates, in which mixtures of differently alkylated arylsulfonic acids are used as acid catalysts - be set, have significantly longer pot lives.
• the gloss haze index is also improved compared to such coating compositions, while hardness and gloss have comparable values.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Paints Or Removers (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=6374932

Family Applications (2)

Family Applications After (1)

Country Status (10)

Families Citing this family (10)

Family Cites Families (5)

• 1989
  • 1989-02-25 DE DE3905915A patent/DE3905915A1/de not_active Withdrawn
• 1990
  • 1990-02-08 EP EP19900902251 patent/EP0461120A1/de active Pending
  • 1990-02-08 WO PCT/EP1990/000201 patent/WO1990010039A1/de not_active Application Discontinuation
  • 1990-02-08 EP EP90200344A patent/EP0385527B1/de not_active Expired - Lifetime
  • 1990-02-08 DK DK90200344.1T patent/DK0385527T3/da active
  • 1990-02-08 CA CA002046866A patent/CA2046866C/en not_active Expired - Fee Related
  • 1990-02-08 AT AT90200344T patent/ATE96157T1/de not_active IP Right Cessation
  • 1990-02-08 DE DE90200344T patent/DE59003107D1/de not_active Expired - Fee Related
  • 1990-02-08 JP JP2502605A patent/JPH0757855B2/ja not_active Expired - Lifetime
  • 1990-02-08 US US07/752,651 patent/US5212242A/en not_active Expired - Lifetime
  • 1990-02-08 ES ES90200344T patent/ES2060924T3/es not_active Expired - Lifetime
  • 1990-02-08 BR BR909007169A patent/BR9007169A/pt not_active IP Right Cessation

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events