Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
  • B05D7/148—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using epoxy-polyolefin systems in mono- or multilayers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
  • B05D7/146—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies to metallic pipes or tubes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/56—Three layers or more
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2202/00—Metallic substrate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2254/00—Tubes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2350/00—Pretreatment of the substrate
  • B05D2350/60—Adding a layer before coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2504/00—Epoxy polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2507/00—Polyolefins
  • B05D2507/01—Polyethylene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2507/00—Polyolefins
  • B05D2507/02—Polypropylene
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31511—Of epoxy ether
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31511—Of epoxy ether
  • Y10T428/31515—As intermediate layer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31511—Of epoxy ether
  • Y10T428/31529—Next to metal
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31909—Next to second addition polymer from unsaturated monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31909—Next to second addition polymer from unsaturated monomers
  • Y10T428/31913—Monoolefin polymer

Definitions

• the subject of the present invention is a new coating of metal surfaces and its method of implementation.
• the invention particularly relates to a three-layer coating of metal surfaces, composed of a layer of epoxy primer, a layer of adhesive and a layer of polyolefin.
• the invention also relates to the method of coating metal surfaces.
• Tri-layer metallic surface coatings are already known in the prior art, in particular for coating metal tubes.
• the first layer consists of an epoxy primer, which initially forms a gel and then crosslinks.
• the second layer consists of a polymer adhesive, this layer being generally placed on the primer before gelling thereof.
• the third layer generally consists of a thermoplastic polymer, most often a polyolefin.
• patents EP-A-0 057 823, EP-A-0 205 395, FR-A-2 184 321, FR-A-2 529 829 describe such tri-layer systems, which makes it possible to combine the advantages epoxy resins and polyolefins, namely high adhesion and good resistance to impact and to cathodic delamination.
• problems related to the epoxy / adhesive reactivity and to the time which elapses between the application of the epoxy layer and that of the adhesive are no mention of the problems related to the epoxy / adhesive reactivity and to the time which elapses between the application of the epoxy layer and that of the adhesive.
• Patent WO-92/03234 describes a method of coating metal tubes, in which the adhesive is applied to the partially crosslinked epoxy resin so as to promote the epoxy / adhesive reactions and therefore the adhesion. It is also recommended to apply the adhesive before crosslinking, but after gelation of the epoxy. However, there are no examples or numerical values.
• Coatings are therefore sought which have both good adhesion and good water resistance.
• Adhesive compositions are therefore sought which exhibit high adhesion, regardless of the nature and origin of the primer and / or of the thermoplastic polymer, but also of the conditions of application at the time level between epoxy-adhesive primer layers. .
• said adhesive is an ethylene / C1-C4 alkyl (meth) acrylate / maleic anhydride terpolymer.
• said adhesive is a polyethylene or a polypropylene grafted with maleic anhydride.
• said catalyst is present in an amount of 0.005% to 2.5% by weight relative to the weight of the adhesive.
• said catalyst is 1,4-diazabicyclo (2,2,2) octane (DABCO) or methyl-2-imidazole (M2ID).
• said primer is an epoxy primer.
• thermoplastic polymer is polyethylene or polypropylene.
• the primer is any primer conventionally used in the art of three-layer coating. Mention may be made of epoxy resins, polyesters, or acrylics. An epoxy resin is conventionally used with advantage.
• the epoxy resins used in the present invention can be crosslinkable resins at high temperature, typically from 160 to 250 ° C, conventionally from 180 to 220 ° C.
• the epoxy resins could also be resins which can be crosslinked at room temperature, with, for example, amines or amides.
• the gel time of these primers or epoxy resins can be between 15 and 45 s, for example between 20 and 30 s, at the temperature at which said epoxy resin is applied.
• the gel time is determined in accordance with Afnor NFA 49-706 standard; it is the time necessary to cause a rapid increase in viscosity at a determined temperature.
• the glass transition temperature, Tg, when this is defined, is conventionally between 80 ° C. and 120 ° C.
• primers typically epoxy resins
• the grafted polyethylenes and polypropylenes on the one hand, and the ethylene / alkyl (meth) acrylate / maleic anhydride terpolymers on the other hand are the preferred adhesives in the present invention.
• the adhesives can be mixed with each other or with polyethylenes (VLDPE, etc.).
• catalyst designates any compound capable of accelerating the reaction at the epoxy / adhesive interface between the remaining epoxy functions and the functional groups present on the adhesive.
• catalysts examples include: 1,4-diazabicyclo [2,2,2] octane (DABCO), methyl-2-imidazole (M2ID), H3BO3, stearic acid, calcium stearate, B4Na2O7 (Borax ), NaH2PO4, Sb2O3, TNPP, APTS, DLBBE, etc.
• the catalyst is added in an amount which is sufficient to catalyze the reaction at the interface.
• the catalyst is effective at very low concentrations, for example 0.005% by weight, based on the weight of the adhesive.
• concentration which can be used in the present invention is from 0.005 to 2.5% by weight, advantageously from 0.01 to 1% by weight, for example between 0.05 and 0.5% by weight, relative the weight of the adhesive.
• the catalyst is added to the adhesive by any means known in the art, such as for example compounding, carried out at an appropriate temperature depending on the components.
• thermoplastic polymer used in the present invention is any thermoplastic conventionally used in the art.
• thermoplastic polymer mention may be made of: polyamides, polyolefins, polyamide alloys, their mixtures.
• thermoplastic polymer layer may also contain conventional fillers, such as glass fibers.
• the polyamide is PA6 or PA6.6.
• Polyolefin is understood to mean homopolymers or copolymers of alpha-olefins or of diolefins.
• olefins are, for example, ethylene, propylene, butene-1, octene-1, butadiene.
• the molecular weight of polyolefins can vary widely, which one skilled in the art will appreciate.
• thermoplastic is polyethylene
• an ethylene-based adhesive is used, for example, while when the thermoplastic is polypropylene, a propylene-based adhesive is used, for example.
• alloy By alloy is meant the products comprising a polyamide, as described above; a polyolefin, as described above, and when the latter does not contain sufficient functionality to ensure compatibilization with the polyamide a compatibilizing agent; the polyolefin being present in the form of a phase dispersed in the polyamide phase, which is thus called polyamide matrix.
• the polyamide represents from 25 to 75% by weight of the weight of the alloy.
• the compatibilizing agent is present in an amount sufficient to ensure compatibility, namely the dispersion of the polyolefin in the polyamide matrix in the form of nodules, for example, up to 25% by weight of the polyolefin.
• the diameter of the nodules can be from 0.1 to 5 ⁇ m.
• the compatibilizing agent is a product known per se for compatibilizing polyamides and polyolefins, for example as described in applications FR-A-2 291 225, EP-A-0 342 066 and EP-A-0 218 665 of which the content is incorporated into this application.
• the thickness of the primer layer can be between 20 and 400 ⁇ m, for example between 50 and 150 ⁇ m.
• the thickness of the adhesive layer can be between 100 and 500 ⁇ m, for example between 200 and 350 ⁇ m.
• the thickness of the thermoplastic layer can be between 0.5 and 5mm, for example between 1.5 and 3mm.
• additives and / or fillers such as CaCO3, talc or mica, silicones, anti-UV, pigments, were added to the primer, the adhesive or the thermoplastic.
• additives and / or fillers such as CaCO3, talc or mica, silicones, anti-UV, pigments, were added to the primer, the adhesive or the thermoplastic.
• the metal surface Prior to the application of the primer, the metal surface is conventionally degreased, possibly shot-blasted or sanded, and heated.
• the purpose of the pretreatment is to increase the surface roughness and to promote bonding of the primer.
• Step (i) is the implementation by depositing the primer in liquid form, or if it is in powder form by spraying, for example by electrostatic spraying, the deposit taking place on the heated metal surface.
• Step (ii) is the implementation by depositing the adhesive in the molten state on the primer layer, for example after hardening, or before hardening and after gelation or before gelation.
• the adhesive is extruded and applied in the form of a film, or sprayed if it is in the form of a powder.
• Step (iii) is the implementation by depositing the thermoplastic on the adhesive. Conventionally, the thermoplastic is extruded which is then applied in the form of a film by wrapping.
• the tube thus coated can then be subjected to pressing, for example using rollers.
• the tube can then be cooled in a cooling chamber, for example by spraying water.
• the time between the application of the primer and the cooling must be sufficient to ensure complete crosslinking of the epoxy primer, guaranteeing good anti-corrosion resistance (control ⁇ Tg ⁇ 5 ° C according to standards NFA 49710 or NFA 49711).
• the adhesive is applied before hardening of the primer, but after gelling of the primer.
• the term "after gelation” includes very short times, namely immediately after gelation, at least partially, but also longer times, which can for example be of the order of the gel time of the primary.
• the present invention also relates to a metal object whose surface is coated with a coating according to the invention, and in particular a metal tube.
• This metal tube has a diameter up to 0.8, even 2.5m, and a thickness of 2 to 50mm.
• the metal tubes with the coating according to the invention are entirely suitable for transporting hydrocarbons, gas or water, these tubes being able to be buried and / or submerged.
• the coating is applied according to the following method: heating the tube; electrostatic spraying of epoxy; extrusion of the adhesive; thermoplastic extrusion; pressing between rollers; water spray cooling.
• the peel strength is measured by peeling at 180 ° at room temperature and at 100 m / min over 5 cm in width. We do 5 tests and we take the average value.
• the adhesive does not contain a catalyst
• the adhesive contains a catalyst.
• the catalyst is DABCO, added in an amount of 0.25% by weight relative to the weight of adhesive.
• the adhesive / catalyst mixture is obtained by compounding at 130-140 ° C of the components.
• Adhesion is then determined, for variable epoxy / adhesive times.
• Table 1a epoxy / adhesive time 22-25 seconds: temperature nature thickness time tube 180 ° C - - - layer 1 180 ° C epoxy 1 70 ⁇ m - layer 2 225 ° C adhesive 1 250-300 ⁇ m - layer 3 210 ° C top coat 1 2.5mm - 180 ° C epoxy gel 45 s epoxy / adhesive - - - 22-25 s epoxy / cooling - - - 90s
• the adhesive does not contain a catalyst
• the adhesive contains a catalyst.
• the catalyst is DABCO, added in an amount of 0.25% by weight relative to the weight of adhesive.
• the adhesive / catalyst mixture is obtained by compounding at 130-140 ° C the components.
• Adhesion is then determined, for variable epoxy / adhesive times.
• Table 4a epoxy / adhesive time 22-25 seconds: temperature nature thickness time tube 200 ° C - - - layer 1 200 ° C epoxy 1 70 ⁇ m - layer 2 225 ° C adhesive 1 250-300 ⁇ m - layer 3 210 ° C top coat 1 2.5mm - epoxy gel at 200 ° C 45 s epoxy / adhesive - - - 22-25 s epoxy / cooling - - - 90s
• Adhesion is then determined, for variable epoxy / adhesive times.
• Table 7a epoxy / adhesive time 22-25 seconds: temperature nature thickness time tube 200 ° C - - - layer 1 200 ° C epoxy 2 70 ⁇ m - layer 2 225 ° C adhesive 1 250-300 ⁇ m - layer 3 210 ° C top coat 1 2.5mm - epoxy gel at 200 ° C 45 s epoxy / adhesive - - - 22-25 s epoxy / cooling - - - 90s
• the adhesive does not contain a catalyst
• the adhesive contains a catalyst.
• the catalyst is DABCO, added in an amount of 0.25% by weight relative to the weight of adhesive.
• the adhesive / catalyst mixture is obtained by compounding at 130-140 ° C the components. Adhesion is then determined.
• Table 9a epoxy / adhesive time 22-25 seconds: temperature nature thickness time tube 180 ° C - - - layer 1 180 ° C epoxy 3 70 ⁇ m - layer 2 230 ° C adhesive 1 250-300 ⁇ m - layer 3 215 ° C top coat 1 2.5mm - 180 ° C epoxy gel 40s epoxy / adhesive - - - 22-25 s epoxy / cooling - - - 90s
• the adhesive does not contain a catalyst
• the adhesive contains a catalyst.
• the catalyst is DABCO, added in an amount of 0.25% by weight relative to the weight of adhesive.
• the adhesive / catalyst mixture is obtained by compounding at 130-140 ° C the components. Adhesion is then determined.
• Table 10a epoxy / adhesive time 22-25 seconds: temperature nature thickness time tube 180 ° C - - - layer 1 180 ° C epoxy 1 70 ⁇ m - layer 2 225 ° C adhesive 2 250-300 ⁇ m - layer 3 210 ° C top coat 2 2.5mm - 180 ° C epoxy gel 45 s epoxy / adhesive - - - 22-25 s epoxy / cooling - - - 90s
• the adhesive does not contain a catalyst
• the adhesive contains a catalyst.
• the catalyst is DABCO, added in an amount of 0.25% by weight relative to the weight of adhesive.
• the adhesive / catalyst mixture is obtained by compounding at 130-140 ° C of the components. Adhesion is then determined.
• Table 11a (epoxy / adhesive time 22-25 seconds): temperature nature thickness time tube 180 ° C - - - layer 1 185 ° C epoxy 4 70 ⁇ m - layer 2 225 ° C adhesive 2 250-300 ⁇ m - layer 3 250 ° C top coat 3 2.5mm - 180 ° C epoxy gel 38s epoxy / adhesive - - - 22-25 s epoxy / cooling - - - 3 mins
• the adhesive does not contain a catalyst
• the adhesive contains a catalyst.
• the catalyst is DABCO, added in an amount of 0.25% by weight relative to the weight of adhesive.
• the adhesive / catalyst mixture is obtained by compounding at 130-140 ° C the components. Adhesion is then determined.
• Table 12a (epoxy / adhesive time 22-25 seconds): temperature nature thickness time tube 180 ° C - - - layer 1 185 ° C ° C epoxy 5 70 ⁇ m - layer 2 230 ° C adhesive 2 250-300 ⁇ m - layer 3 250 ° C top coat 3 2.5mm - 180 ° C epoxy gel 25s epoxy / adhesive - - - 22-25 s epoxy / cooling - - - 3 mins
• the adhesive does not contain a catalyst
• the adhesive contains a catalyst.
• the catalyst is M2ID, added at a rate of 0.25% by weight relative to the weight of adhesive.
• the adhesive / catalyst mixture is obtained by compounding at 130-140 ° C the components. Adhesion is then determined.
• Table 13a (epoxy / adhesive time 22-25 seconds): temperature nature thickness time tube 200 ° C - - - layer 1 200 ° C epoxy 2 70 ⁇ m - layer 2 235 ° C adhesive 3 250-300 ⁇ m - layer 3 250 ° C top coat 4 2.5mm - epoxy gel at 200 ° C 45 s epoxy / adhesive - - - 22-25 s epoxy / cooling - - - 3 mins
• Table 13b Temperature Peel strength in N / 5 cm without catalyst with catalyst 80 ° C 825 1056 110 ° C 726 713
• Table 14a epoxy / adhesive time 45 seconds: temperature nature thickness time tube 200 ° C - - - layer 1 200 ° C epoxy 2 70 ⁇ m - layer 2 235 ° C adhesive 3 250-300 ⁇ m - layer 3 250 ° C top coat 4 2.5mm - epoxy gel at 200 ° C 45 s epoxy / adhesive - - - 45 s epoxy / cooling - - - 3 mins
• the water resistance improves when the epoxy / adhesive time increases (adhesive applied after freezing time); for systems without catalyst the adhesion decreases while for systems with catalyst, the adhesion remains high.
• the present tri-layer coatings therefore allow good water resistance at the same time as high adhesion.
• the invention also covers the embodiment in which the layers of adhesive and of thermoplastic form only one and the same layer.
• the adhesive and the thermoplastic are substantially of the same nature, only the layer of adhesive comprising the catalyst.
• the adhesive can be mixed with the thermoplastic and form only a single layer.

Landscapes

• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Laminated Bodies (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Catalysts (AREA)
• Lining Or Joining Of Plastics Or The Like (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=9489880

Family Applications (1)

Country Status (14)

Families Citing this family (6)

Citations (1)

Family Cites Families (2)

• 1996
  • 1996-03-05 FR FR9602766A patent/FR2745733A1/fr active Pending
• 1997
  • 1997-02-23 IL IL12029397A patent/IL120293A/xx not_active IP Right Cessation
  • 1997-02-26 SG SG1997000488A patent/SG60045A1/en unknown
  • 1997-03-03 NO NO970960A patent/NO970960L/no unknown
  • 1997-03-04 BR BR9701172A patent/BR9701172A/pt not_active Application Discontinuation
  • 1997-03-04 CA CA002199168A patent/CA2199168A1/fr not_active Abandoned
  • 1997-03-04 CN CN97109667A patent/CN1170746A/zh active Pending
  • 1997-03-04 US US08/810,579 patent/US5939196A/en not_active Expired - Fee Related
  • 1997-03-04 ID IDP970664A patent/ID16119A/id unknown
  • 1997-03-04 EP EP97400490A patent/EP0794019A1/fr not_active Withdrawn
  • 1997-03-05 AR ARP970100878A patent/AR006110A1/es unknown
  • 1997-03-05 MX MX9701672A patent/MX9701672A/es not_active Application Discontinuation
  • 1997-03-05 JP JP9067318A patent/JPH1030080A/ja active Pending
  • 1997-03-05 KR KR1019970007246A patent/KR970064742A/ko not_active Application Discontinuation

Patent Citations (1)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events