Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
  • B01J31/226—Sulfur, e.g. thiocarbamates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
  • B01J31/2208—Oxygen, e.g. acetylacetonates
  • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
  • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
  • B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
  • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
  • B01J2231/14—Other (co) polymerisation, e.g. of lactides, epoxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
  • B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
  • B01J2531/31—Aluminium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
  • B01J2531/46—Titanium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
  • B01J2531/48—Zirconium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
  • B01J2531/49—Hafnium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0201—Oxygen-containing compounds
  • B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
  • B01J31/0212—Alkoxylates

Definitions

• This invention relates to catalysts and in particular to catalysts for use in the preparation of polyurethanes.
• Polyurethane coatings, films, sealants and foams are made by reacting hydroxyl containing polymers and polyisocyanates according to the isocyanate addition 5 polymerisation process.
• the reaction between the isocyanate groups and the active hydrogen atoms of the hydroxyl containing polymer is usually accelerated by the means of catalysts.
• catalysts Tertiary amines and metal compounds have been used as catalysts, examples being triethylene diamine, tin(ll) octoate and di-n-butyl tin dilaurate.
• the prior art catalysts have disadvantages. In the case of amines, this is manifested by lower catalytic o activity mol per mol than metal based catalysts, odour and toxicity. Many of the traditional metal catalysts also demonstrate an activity that is high but difficult to control appropriately for some applications.
• a catalyst comprising the reaction product of: 5 (a) the reaction product of a titanium, zirconium, hafnium or aluminium orthoester and a ⁇ -diketone or ⁇ -ketoester having the general formula
• R ⁇ R 2 and R 3 may be independently selected from the group consisting of hydrogen and alkyl, aryl, cycloalkyl, alkoxy, aryloxy, hydroxyalkyl, alkoxyalkyl and o hydroxyalkoxyalkyl groups containing up to eight carbon atoms; and (b) a complexing agent selected from a mercapto compound or an oxazolidine or a tetrahydro-oxazine having the general formula (A) or (B) respectively,
• R 10 is hydrogen or an alkyl group and X is a hydroxyalkyl group, or mixtures thereof.
• the orthoester has the formula M(OR) 4 in which M is titanium or zirconium and R is an alkyl group, a cycloalkyl group or an aryl group. More preferably R contains 1 to 8 carbon atoms and particularly suitable orthoesters include tetra/sopropoxy titanium, tetra-n-butoxy titanium, tetra-n-propoxy zirconium and tetra-n-butoxy zirconium.
• the ⁇ -diketone or ⁇ -ketoester is selected from acetylacetone, methylacetoacetate, ethylacetoacetate or te/ ⁇ -butylacetoacetate and the molar ratio of titanium, zirconium, hafnium or aluminium orthoester to the ⁇ -diketone or ⁇ -ketoester is from 1 :0.5 to 1 :4. Reaction products of mixtures of both types of ligand and of titanium, zirconium, hafnium or aluminium orthoesters containing more than one alkoxy group are within the scope of the invention.
• the ⁇ -diketone or ⁇ -ketoester is acetylacetone or ethylacetoacetate and the molar ratio of titanium, zirconium, hafnium or aluminium orthoester to acetylacetone or ethylacetoacetate is from 1 :1 to 1 :4.
• a variety of mono-functional or poly-functional mercaptans can be used to advantage.
• Representative mercaptans include, for example, trimethylol propane trithioglycolate, pentaerythritol tefrat ⁇ s-(3-mercapto propionate), ethylene glycol b/s-(3-mercapto propionate), ethylene glycol di-mercapto acetate, mercapto propionic acid and esters thereof, trimethylol propane fr/s-(3-mercaptopropionate), toluene-3,4-dithiol, ⁇ , ⁇ '-dimercapto-p-xylene, dodecane dithiol, didodecane dithiol, 3,4-dimercaptotoluene, dimercapto benzothiazole, allyl mercaptan, methylthioglycolate, benzyl mercaptan, 1 -octane thio
• 6-ethoxy-2-mercaptobenzothiazole 1 ,6-hexane dithiol, -limonene dimercaptan, and the like and mixtures thereof.
• monomer or oligomer compounds can be synthesised or modified to contain pendant mercaptan or thiol groups.
• the mercapto compound is selected from trimethylolpropane fris-(3-mercaptopropionate), pentaerythritol tefra/ « ' s-(3-mercaptopropionate), ethylene glycol b/s-(3-mercaptopropionate) and pentaerythritol tefra/ «s-(2-mercaptoacetate) and mixtures thereof.
• the mercapto compound is selected from pentaerythritol tefra/V/s-(3-mercaptopropionate), ethylene glycol b;s-(3-mercapto propionate) and pentaerythritol fefra/c/s-(2-mercaptoacetate) and mixtures thereof.
• the complexing agent is an oxazolidine or a tetrahydro-oxazine having the formula (A) or (B) respectively as hereinbefore defined.
• Preferred complexing agents of thi ⁇ embodiment are oxazolidines having formula (A).
• R 10 is hydrogen or an alkyl group preferably containing up to 8 carbon atoms. Suitable alkyl groups include methyl, ethyl, propyl, isopropyl and butyl groups.
• X is a hydroxyalkyl group preferably containing up to ⁇ and more preferably up to 4 carbon atoms. Particularly preferred complexing agents are compounds in which X is a hydroxyethyl or a hydroxypropyl group.
• Sufficient complexing agent must be present relative to the reaction product of a titanium, zirconium, hafnium or aluminium orthoester and a ⁇ -diketone or ⁇ -ketoester in order that the hydroxyl containing polymer/ polyisocyanate reaction mixture containing the catalyst has a pot life suitable for the particular application.
• the pot life of a reaction mixture is normally defined as the time required for the viscosity of the mixture in an open pot to double from its initial viscosity.
• the catalyst of the present invention provides the ability to formulate a catalysed reaction mixture which has a very long and useful pot life without the need for formulating specifically designed resins, curing agents, or the like.
• a further advantage is that the catalysed reaction mixture need not be heated to achieve cure, although it can be heat cured if desired. Furthermore it is often found that utilisation of the catalyst of this invention will allow lower cure temperatures or shorter cure times when compared to standard catalyst technology. Yet another advantage is the ability to form harder and more corrosion resistant films than allowed by previous catalyst technology.
• the catalyst of the invention is usually added to the reaction mixture in an amount in the range 0.005 per cent to 0.5 per cent by weight with respect to weight of o reaction mixture.
• urethane coatings may be provided as two separate packages (a two-pack system).
• One component (Part 1 ) typically, is the hydroxyl containing polymer while the second component (Part 2) is the polyisocyanate.
• Solvents and other conventional paint additives may be added to each component in accordance 5 with conventional teachings.
• the catalyst is often included in the hydroxyl containing polymer to avoid premature gelation of the polyisocyanate. Occasionally, the catalyst package is not added to either Part 1 or Part 2 until just prior to application of the coating composition.
• Application of conventional two-pack coating compositions typically takes place by the admixture of the two components just before application which may be by conventional roll coat, reverse rollcoat, or other conventional tactile means; or can be by spray techniques.
• the two components are kept separate in order to prevent premature reaction with attendant viscosity increase which prevents effective application.
• the applied coatings are often baked in order to speed the cure and ensure expulsion of solvent and gases from the applied film.
• the invention also provides for the use of the catalyst as hereinbefore defined in the reaction between a hydroxyl containing polymer or mixture of hyuroxyl containing polymers and an isocyanate containing compound or a mixture of isocyanate containing compounds.
• the hydroxyl containing polymers for use in the present invention include 5 in particular polyesters, polyesteramides, polyethers, siloxanes and/or silicones and copolymers of such materials having hydroxyl functionality within their structure.
• polyesters examples include those predominately hydroxyl terminated polyesters prepared from dicarboxylic acids including, but not restricted to, succinic, glutaric, adipic, pimelic, azeiaic and sebacic acids.
• Polybasic acids obtained by the o polymerisation of unsaturated long-chain fatty acids obtained from naturally occurring oils may be used. Mixtures of acids may also be used.
• Suitable glycols for use in the preparation of polyesters include but are not restricted to ethylene glycol, 1 ,2-propyleneglycol, 1 ,3-butylene glycol, diethylene glycol, triethylene glycol and decamethylene glycol. Mixtures of glycols may be used.
• Branching groups containing 5 more than two isocyanate reactive groups may also be used.
• Suitable branching components include polyhydric alcohols such as glycerol, pentaerythritol, sorbitol and polycarboxylic acids such as tricarballylic acid and pyromellitic acid and compounds containing mixed functional groups such as diethanolamine and dihydroxystearic acid.
• the polyethers may be any hydroxyl containing polymers or co-polymers o made by the polymerisation or co-polymerisation of cyclic ethers such as epichlorohydrin, tetrahydrofuran, oxacyclobutane and substituted oxacyclobutanes and 1 ,2-alkylene oxides, for example, ethylene oxide and 1 ,2-propylene oxide.
• cyclic ethers such as epichlorohydrin, tetrahydrofuran, oxacyclobutane and substituted oxacyclobutanes and 1 ,2-alkylene oxides, for example, ethylene oxide and 1 ,2-propylene oxide.
• branched polyethers prepared, for example, by polymerising an alkylene oxide in the presence of a substance having more than two active hydrogen atoms, for example, glycerol, pentaerythritol and ethylene diamine. Mixtures of linear and branched poly
• Siloxanes may also be referred to as polyoxysilanes, and are sometimes simply referred to as polysilanes.
• siloxane refers to compositions having the formula
• R 4 , R 5 and R 6 is independently selected from the group consisting of hydrogen and alkyl, aryl, cycloalkyl, alkoxy, aryloxy, hydroxyalkyi, alkoxyalkyl and hydroxyaikoxyalkyi groups containing up to six carbons.
• R 7 is selected from the group consisting of hydrogen and alkyl and aryl groups. In most cases, at least two of the R 4 , R 5 and R 6 groups are hydrolysable oxy substituents which can form polymers by hydrolysis.
• Silicone refers to compositions having the formula
• each R 9 is independently selected from the group consisting of the hydroxyl group and alkyl, aryl and alkoxy groups having up to six carbons
• each R 8 is independently selected from the group consisting of hydrogen and alkyl and aryl groups having up to twelve carbons and n is from 1 to 10 when no solvents are present in the composition. o When solvents are included in the composition , n may be higher than 10.
• Isocyanate containing compounds crosslink with the hydroxyl groups of the resin or polymer under the influence of the metal catalyst to cure the coating.
• Aromatic, aliphatic, or mixed aromatic/aliphatic isocyanates may be used. Further, alcohol-modified and alternatively modified isocyanate compositions can be used.
• Poly-isocyanates 5 preferably will have from about 2 to 4 isocyanate groups per molecule.
• Suitable poly-isocyanates include, for example, hexamethylene diisocyanate, polymethyl polyphenyl isocyanate (Polymeric MDI or PAPI), 4,4'-toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), m- and p-phenylene diisocyanates, fris-(4-isocyanatophenyl) thiophosphate, triphenylmethane triisocyanate, dicyclohexylmethane diisocyanate (H 12 MDI), cyclohexane diisocyanate (CHDI), bis-isocyanatomethyl cyclohexane (H 6 XDI), trimethylhexane diisocyanate, dimer acid diisocyanate (DDI), trimethyl hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and dimethyl derivatives thereof, lysine diis
• Aromatic and aliphatic polyisocyanate dimers, trimers, oligomers, polymers (including biuret and isocyanurate derivatives) and isocyanate functional prepolymers are often available as preformed packages and such packages are also suitable for use.
• the ratio of isocyanate equivalents of the polyisocyanate cross-linking agents to the hydroxyl groups of the hydroxy materials preferably should be greater than 1 :1 and can range from 1 :2 up to 2:1. The precise intended application of the coating composition will often dictate this ratio which is known as the isocyanate index.
• a solvent or vehicle may be included as part of the coating composition.
• Volatile organic solvents may include ketones and esters for minimising viscosity, though some aromatic solvent may be used and typically such solvents are part of the volatiles contained in commercial isocyanate polymers.
• Representative volatile organic solvents include, for example, methyl ethyl ketone, acetone, butyl acetate, methyl amyl ketone, methyl isobutyl ketone, ethylene glycol monoethyl ether acetate (sold under the Trademark Cellosolve acetate) and the like.
• Organic solvents commercially utilised in polyisocyanate polymers include, for example, toluene, xylene and the like.
• the effective non-volatile solids content of the coating composition can be increased by incorporation of a plasticiser ester which is non-volatile or has a relatively low volatility (high boiling point) and which is retained for the most part in the cured film.
• suitable plasticiser esters include, for example, di-(2-ethylhexyl) phthalate (DOP) and the like. If used, the proportion of plasticiser ester should not exceed 10% by weight; otherwise loss of mar o resistance can occur. Typically, the proportion of plasticiser ester, when used, is in the range 5 to 10% by weight.
• the coating composition can additionally contain opacifying pigments and inert extenders such as, for example, titanium dioxide, zinc oxide, clays such as kaolinite clays, silica, talc, carbon or graphite (e.g. for conductive coatings) and the like. Additionally, the coating compositions can contain tinctorial pigments, 5 corrosion-inhibiting pigments, and a variety of agents typically found in coating compositions. Such additional additives include, for example, surfactants, flow or levelling agents, pigment dispersants and moisture scavengers based on systems such as oxazolidines and the like.
• a coating composition can be formulated to have a minimum pot life of at least 2 hours in an open pot and generally the coating can be formulated to have a pot life which is in the range 2 to 8 hours. Such extended pot life is desirable and means that refilling the pot at the plant during shifts is not usually required.
• the stored composition can be modified to application viscosity with suitable solvent (if required) and such a composition retains all the excellent performance characteristics which it initially possessed.
• Heat curing of coatings generally involves baking the applied coating composition at temperatures ranging from 50°C to 150°C or higher for time periods ranging from 1 to 30 minutes. Heating of the coated substrate can be beneficial for solvent expulsion from the film as well as ensuring that the film is non-blocking for rapid handling of the coated substrate.
• the heating schedules needed for the catalyst of this invention tend to be rather mild in terms of temperature and time compared to conventional heat-cured urethane systems.
• a variety of substrates can be coated with the coating compositions prepared according to the present invention.
• Substrates include metal, such as, for example, iron, steel, aluminium, copper, galvanised steel, zinc, and the like.
• the coating composition can be applied to wood, glass, concrete, fibreboard, RIM (reaction injection moulded urethanes), SMC (sheet moulding compound), vinyl, acrylic, polyolefine and other polymeric or plastic material, paper and the like. Since the coating 5 compositions can be cured at room temperature, thermal damage to thermally-sensitive substrates is not a limitation on use of the coating compositions. Further, with the ability to use the vaporous amine catalyst spray method, the flexibility in use of the coating compositions is enhanced even further. It should be understood, however, that heating of the coating composition following application (e.g. to a temperature between about 50°C o and 150°C) is often recommended for enhancing solvent expulsion.
• the coatings which are made available by this invention can be used as primers, intermediate coats, and top coats and the cure is substantially independent of film thickness.
• the invention will be more readily understood from the following examples in which all percentages and proportions are by weight, unless otherwise expressly indicated.
• Dibutyl tin dilaurate (source Aldrich Chemicals) was used as the comparative catalyst. 5 Testing of the Catalysts in Film Formation (at an addition level to give molar% Zr equal to molar% Sn)
• Dibutyl tin dilaurate (source Aldrich Chemicals) was used as the comparative catalyst.
• Cure schedule 168 hrs, ambient.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Inorganic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Polyurethanes Or Polyureas (AREA)
• Paints Or Removers (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

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Citations (8)

• 1997
  • 1997-09-19 KR KR1019990702949A patent/KR20000048918A/ko not_active Application Discontinuation
  • 1997-09-19 JP JP10517274A patent/JP2001501534A/ja active Pending
  • 1997-09-19 CN CN97180286A patent/CN1239484A/zh active Pending
  • 1997-09-19 TR TR1999/01203T patent/TR199901203T2/xx unknown
  • 1997-09-19 WO PCT/GB1997/002565 patent/WO1998015585A1/en not_active Application Discontinuation
  • 1997-09-19 CZ CZ991180A patent/CZ118099A3/cs unknown
  • 1997-09-19 PL PL97332641A patent/PL332641A1/xx unknown
  • 1997-09-19 BR BR9711862-1A patent/BR9711862A/pt not_active Application Discontinuation
  • 1997-09-19 CA CA002267773A patent/CA2267773A1/en not_active Abandoned
  • 1997-09-19 IL IL12930397A patent/IL129303A0/xx unknown
  • 1997-09-19 HU HU0000438A patent/HUP0000438A2/hu unknown
  • 1997-09-19 AU AU43126/97A patent/AU735671B2/en not_active Ceased
  • 1997-09-19 NZ NZ335210A patent/NZ335210A/en unknown
  • 1997-09-19 EP EP97941101A patent/EP0929585A1/en not_active Withdrawn
  • 1997-10-01 AR ARP970104522A patent/AR008869A1/es not_active Application Discontinuation
  • 1997-10-03 ID IDP973356A patent/ID17410A/id unknown
  • 1997-10-04 TW TW086114514A patent/TW394782B/zh not_active IP Right Cessation
• 1999
  • 1999-04-06 NO NO991616A patent/NO991616L/no not_active Application Discontinuation

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