EP0822012B1 - Revêtement de surfaces métalliques son application aux tubes et aux câbles - Google Patents
Revêtement de surfaces métalliques son application aux tubes et aux câbles Download PDFInfo
- Publication number
- EP0822012B1 EP0822012B1 EP97401839A EP97401839A EP0822012B1 EP 0822012 B1 EP0822012 B1 EP 0822012B1 EP 97401839 A EP97401839 A EP 97401839A EP 97401839 A EP97401839 A EP 97401839A EP 0822012 B1 EP0822012 B1 EP 0822012B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyurethane
- cables
- layer
- metal surface
- polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B1/00—Constructional features of ropes or cables
- D07B1/16—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics
- D07B1/162—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics characterised by a plastic or rubber enveloping sheathing
-
- 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
- B05D7/16—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 synthetic lacquers or varnishes
-
- 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
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
-
- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01D—CONSTRUCTION OF BRIDGES, ELEVATED ROADWAYS OR VIADUCTS; ASSEMBLY OF BRIDGES
- E01D19/00—Structural or constructional details of bridges
- E01D19/16—Suspension cables; Cable clamps for suspension cables ; Pre- or post-stressed cables
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2201/00—Ropes or cables
- D07B2201/20—Rope or cable components
- D07B2201/2083—Jackets or coverings
- D07B2201/2087—Jackets or coverings being of the coated type
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2201/00—Ropes or cables
- D07B2201/20—Rope or cable components
- D07B2201/2083—Jackets or coverings
- D07B2201/2088—Jackets or coverings having multiple layers
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2205/00—Rope or cable materials
- D07B2205/20—Organic high polymers
- D07B2205/2003—Thermoplastics
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2205/00—Rope or cable materials
- D07B2205/20—Organic high polymers
- D07B2205/2064—Polyurethane resins
-
- 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
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
- Y10T428/1393—Multilayer [continuous 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2938—Coating on discrete and individual rods, strands or filaments
-
- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2973—Particular cross section
- Y10T428/2975—Tubular or cellular
-
- 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]
- Y10T428/3154—Of fluorinated 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]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31562—Next to polyamide [nylon, etc.]
-
- 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]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
-
- 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]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
-
- 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]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
- Y10T428/31576—Ester monomer type [polyvinylacetate, etc.]
-
- 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]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
- Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
-
- 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]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31605—Next to free metal
Definitions
- the present invention relates to a metal surface coating and its application to tubes and cables, it relates more particularly to a coating successively comprising, starting from the metal, a layer of polyurethane and a layer of thermoplastic polymer, an adhesion binder can be placed between the polyurethane and the thermoplastic polymer.
- the present invention is useful for example for coating the surface outside of pipes, to coat electrical or telephone cables or metal cables such as guy wires.
- DE 3,422,920 describes coatings for steel pipes successively comprising a layer of epoxy resin, a layer of grafted polypropylene and finally an outer layer of a mixture of polypropylene and a polypropylene / polyethylene block copolymer.
- the glass transition temperature (T g ) of the epoxy resin is between 80 and 94 ° C. These coatings are suitable for hot water at 90 ° C.
- Re 30 006 describes coatings of steel pipes comprising successively an epoxy resin and a polyethylene modified by grafting or copolymerization with maleic anhydride.
- Epoxy resins are not flexible enough and are not perfect for protection against humidity.
- EP 185,058 describes telecommunication cables coated by polyurethanes for protection against humidity, but these cables have no thermoplastic coating.
- the coatings of the invention thanks to this shear strength have a very high cohesion, thus for an electric cable which must resist the efforts of its own weight or support the weight of boxes of connection or other instruments, it is necessary that the forces transmitted by through the thermoplastic polymer layer can be spread throughout the cable including the metallic core. It also helps that when connection of two electric cables, the connection box can lean on the external coverings of the two cables to be connected without that this results in a decohesion inside the cable and thus the forces such as the tensile forces on the cables can be transmitted. It is then possible make the connection by stripping the cable only to the minimum. Cables must also withstand winding, which is why it is important that the coating according to the present invention has good flexibility.
- the invention is useful for strands that are individually protected from suspended civil engineering works.
- the protective material used in these individually protected strands of the prior art is generally constituted by wax or fat, so these individually protected strands cannot effectively transmit significant axial forces from their outer sheath towards their twisted steel wires.
- the prior art FR 2739113 has proposed coating the strand and filling the spaces between the metal wires with polybutadiene then coat the strand a polyethylene sheath by placing a grafted polyethylene to reinforce the bond between polybutadiene and the polyethylene sheath.
- the axial forces are effectively transmitted from the outer sheath of the strand to its twisted steel wires, both by surface adhesion and shape adhesion of polybutadiene to the sheath exterior and on twisted steel wires, and by resistance of polybutadiene to shear.
- polybutadiene must be vulcanized to present good resistance to aging and keep an elastomeric character to avoid penetration of water into the strands while continuing to provide the connection mechanical with polyethylene sheath.
- the present invention also relates to the device comprising these bundles of strands or strands of coated steel forming a cable and surrounded by a metal collar made of two substantially hemicylindrical shells which are tightened around the cable at the by means of bolts, said collar is provided with at least one hook.
- the present invention is therefore a coated metal surface comprising successively starting from the metal at least one layer of polyurethane, and at least a single layer of polymer thermoplastic, a binder that can be placed between the polyurethane and the thermoplastic polymer, said polyurethane resulting from the reaction of at least one polyol with at least one polyisocyanate and optionally at least a chain extender, said polyol being chosen from polydienepolyols.
- the metal surface can for example be an electric cable, telephone, the outside surface of a pipe, or a guy wire.
- the metal part can be of circular section or be a set of cables with circular cross-section as usual in cables cables or guy lines.
- shroud metallic cables used for their tensile strength and generally formed of several cross-section elements which are twisted. Their diameter can be from a few millimeters to several centimeters. Several cables formed of twisted elements can themselves be brought together to form a single shroud.
- the metal can be steel, copper, aluminum, zinc, stainless steel or their alloys or even galvanized steel.
- the surface can therefore be either a simple surface like the surface outside of a pipe either the result of several twisted elements or the assembly of cables formed themselves from several twisted elements. This surface is therefore covered with at least one layer of polyurethane.
- the polyurethane is placed so as to cover the whole surface or surfaces of the different elements and that we obtain essentially a cylinder whose outer surface is polyurethane.
- the advantage of polyurethane is that it covers metals well and that in the case complex surfaces like twisted elements, it penetrates the heart of cable or guy line.
- Hydrophobic polyurethanes are preferably used. These polyurethanes are resistant to aqueous acidic, basic or saline and hydrolysis. They have good electrical insulation, adhere to metals and retain a certain flexibility between - 65 ° C and + 100 ° C. polyurethanes result from the reaction of at least one polyol with at least one polyisocyanate and possibly a chain extender.
- the polyols which can be used according to the present invention can be chosen among the polyester polyols, the polyether polyols, the polythioether polyols, the polyacetals-polyols, polycarbonates-polyols, polyestamides-polyols, polyamide polyols, polydien polyols and the mixture of at least two of the aforementioned polyols.
- polyesters bearing hydroxy groups By way of polyesters bearing hydroxy groups, mention will be made of the products reaction of polyvalent alcohols, preferably divalent, accompanied optionally trivalent alcohols, and polyvalent carboxylic acids, and preferably divalent. Instead of free polycarboxylic acids, one can also use in the preparation of polyesters the acid anhydrides corresponding polycarboxylic acids or esters of polycarboxylic acids and corresponding lower alcohols or mixtures thereof. Acids polycarboxylics can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic and optionally substituted, for example by halogen atoms, and / or saturated.
- carboxylic acids and derivatives By way of illustration of such carboxylic acids and derivatives, mention will be made of: succinic, adipic, suberic, azelaic, sebacic, phthalic acids, trimellitic, phthalic, tetrahydrophthalic, hexahydrophthalic anhydrides, tetrachtorophthalic, endomethylene-tetrahydrophthalic, glutaric, acid maleic, maleic anhydride, fumaric acid, unsaturated fatty acids dimerized and trimerized optionally as a mixture with fatty acids unsaturated monomers such as oleic acid; dimethyl terephthalate and bis-glycol terephthalate.
- polyvalent alcohols there may be mentioned, for example, 1,2-ethanediol, 1,2-and1,3-propanediol, 1,4-and 2,3-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bis-hydroxymethylcyclohexane, 2-methyl-1,3-propanediol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butane-triol, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, formitol, methylglucoside, and also diethylene glycol, triethylene glycol, tetra-ethylene glycol and higher polyethylene glycols, dipropylene glycol and higher propylene glycols and dibutylene glycol and higher polybutylene glycol and higher
- the polyether polyols which can be used according to the invention carrying at least 2, in general 2 to 8, preferably 2 to 3 hydroxy groups are those of the type known per se which are obtained for example by polymerization of epoxides such as oxide ethylene, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin on themselves, for example in the presence of Lewis catalysts such as BF 3 , or by addition of these epoxides, preferably ethylene oxide and propylene oxide, optionally as a mixture or successively, on starting components carrying reactive hydrogen atoms such as water, alcohols, ammonia or amines, for example 1,2-ethanediol, 1,3 or 1,2 propaneediol, trimethylolpropane, glycerol, sorbitol, 4,4'-dihydroxydiphenylpropane, aniline, ethanolamine or ethylene- diamine.
- epoxides such as oxide
- Polyethers of sucrose or polyethers condensed on formitol or on formose can also be used in accordance with the invention.
- polyethers containing preponderant proportions (up to 90% by weight, relative to all the OH groups present in the polyether) of primary OH groups are preferred.
- polythioters-polyols By way of polythioters-polyols, mention will be made in particular of the products of condensation of thiodiglycol on itself and / or on other glycols, acids dicarboxylics, formaldehyde, and aminocarboxylic acids or amino alcohols. Depending on the nature of the second component, the products obtained are for example mixed polythioethers, polythioether esters or polythioether ester amides.
- polyacetal polyols By way of illustration of polyacetal polyols, mention will be made, for example, of those which can be prepared from glycols such as diethylene glycol, triethylene glycol, 4,4'-dihydroxyethoxydiphenyldimethylmethane, hexane-diol and formaldehyde. Polyacetals can also be used in the invention obtained by polymerization of cylindrical halves such as, for example, trioxane.
- polycarbonates carrying hydroxy groups we cite those of known type which are obtained for example by reaction of diols such as propane-diol-1,3, butane-diol-1,4 and / or hexane-diol-1,6, diethylene glycol, triethylene glycol, tetraethylene glycol or thiodiglycol, with diaryl carbonates, for example diphenyl carbonate, or phosgene;
- diols such as propane-diol-1,3, butane-diol-1,4 and / or hexane-diol-1,6, diethylene glycol, triethylene glycol, tetraethylene glycol or thiodiglycol
- diaryl carbonates for example diphenyl carbonate, or phosgene
- polyesteramides-polyols and polyamides-polyols we cite for example the mainly linear condensates obtained from saturated or unsaturated polyvalent carboxylic acids and their anhydrides and saturated or unsaturated polyvalent amino alcohols, diamines, polyamines and their mixtures.
- polydien-polyols which can be used according to the present invention
- hydroxytelechelic conjugated diene oligomers which can be obtained by different processes such as polymerization conjugated diene radical having 4 to 20 carbon atoms in the presence a polymerization initiator such as hydrogen peroxide or a compound azo such as azobis-2,2 '[methyl-2, N- (hydroxy-2ethyl) propionamide] or anionic polymerization of conjugated diene having 4 to 20 carbon atoms in the presence of a catalyst such as naphthalene dilithium.
- the conjugated diene of the polydiene-polyol is chosen from the group comprising butadiene, isoprene, chloroprene, 1,3-pentadiene, cyclopentadiene.
- the number-average molar mass of polyols which can be used can vary from 500 to 15,000 and preferably from 1000 to 3000.
- a polydiene polyol based on butadiene is preferably used.
- the polydiene glycol comprises 70 to 85% by mole, preferably 80% of units and 15 to 30% preferably 20% of patterns
- copolymers of conjugated dienes and vinyl and acrylic monomers such as styrene, acrylonitrile.
- the polydien-polyols can have number average molecular weights at most equal to 7000 and preferably between 1000 and 3000.
- the OH index expressed in mlq / g is between 0.5 and 5, their viscosity is between 1000 and 10 000 M.Pa.s.
- polystyrene-polyols By way of illustration of polydien-polyols, mention will be made of polybutadienes with hydroxylated terminations marketed by the company ELF ATOCHEM S.A. under the names Poly Bd®R45 HT and Poly Bd®R20 LM.
- Mixtures of the above-mentioned compounds can be used such as, for example, mixtures of polyether polyols and of polydienes polyols.
- chain extender we currently designate compounds bearing at least two reactive functions with the isocyanate functions.
- the chain extender can be chosen from polyols. Their molecular mass can be between 62 and 500.
- Polyamines can also be used as chain extenders. Their molecular mass can be between 60 and 500.
- At least part by weight of one or more extenders of aforementioned chain for 100 parts by weight of polyol used and, from preferably 5 to 30 parts by weight.
- a catalyst which can be chosen from the group including tertiary amines, imidazoles and compounds organometallics.
- DABCO 1,4-diaza bicyclo [2.2.2] octane
- organometallic compounds By way of illustration of organometallic compounds, mention may be made of tin dibutyldilaurate, tin dibutyldiacetate.
- the amounts of catalyst can be between 0.01 and 5 parts by weight per 100 parts by weight of polyol.
- composition according to the invention may also contain fillers inert and various additives such as antioxidants, anti U-V.
- the polyisocyanate used can be a aromatic, aliphatic or cycloaliphatic polyisocyanate having at least two isocyanate functions in its molecule.
- MDI 4,4'-diphenyl-methane diisocyanate
- TDI liquid modified MDI
- XDI xylylene diisocyanate
- TMXDI triphenylmethane triisocyanate
- PPDI paraphenylene diisacyanate
- NDI naphthalene diisocyanate
- the invention relates to preferably 4,4'-diphenylmethane diisocyanate and especially MDI modified liquids.
- HMDI hexamethylene diisocyanate
- IPDI isophorone diisocyanate
- CHDI cyclohexyl diisocyanate
- isocyanate prepolymers obtained by reaction of a mentioned polyisocyanate previously with a polyol such as in particular polyether-polyol, polyester-polyol and polydiene-polyol or with a polyamine.
- a polyol such as in particular polyether-polyol, polyester-polyol and polydiene-polyol or with a polyamine.
- the isocyanates are used in such amounts that the NCO / OH molar ratio is between 0.3 and 2 and, preferably, between 0.5 and 1.2.
- the NCO / OH molar ratio must be calculated taking into account the presence of reactive functions with isocyanate functions, such as hydroxyl and / or amine functions, of the chain extender.
- adhesion promoters such as functional silanes. ie products having a trialcoxysilane end and an organic function such as amine, epoxy or vinyl, coupling agents such as acids or unsaturated carboxylic acid anhydrides and mineral fillers such as calcium carbonate, anti-bubble agents, anti U.V., sieves molecules, anti-corrosion pigments and flame retardants.
- the possible binder is any product which makes it possible to adhere the layer of polyurethane and the thermoplastic polymer layer while giving a cohesion to the whole as explained above unless the polymer has good adhesion to polyurethane.
- Polyolefins grafted with anhydride are advantageously used maleic.
- the thickness of this binder layer can be between 15 and 500 ⁇ m.
- thermoplastic polymer it may be by example of a polyamide, a polyolefin, a fluoropolymer, a resin styrenic or polyester.
- the polyamide can be PA-6, PA-6.6, PA-11, PA-12.
- the polyolefin can be a polyethylene, a copolymer of ethylene and of an alpha olefin, a homo or copolymer polypropylene, a copolymer of ethylene and a vinyl ester of saturated carboxylic acid.
- the fluoropolymer can be PVDF.
- the styrenic resin can be polystyrene.
- the polyester can be PET or PBT.
- high density and medium polyethylenes are used density.
- thermoplastic polymer may also contain a product which facilitates adhesion to polyurethane.
- This product can be the thermoplastic polymer grafted or the binder mentioned above.
- thermoplastic polymer is a function of desired properties, they can be between 1 and 30 mm.
- the present invention also relates to a method for manufacturing these coated surfaces in which the polyurethane is deposited, before the end of the polymerization, on the metal surface then the polymerization is completed optionally by heating, the outer surface of the layer of polyurethane then we cover it with the thermoplastic polymer and then we cools.
- the deposition of the polyurethane layer depends on the nature of the metal surface. If this is the outside surface of a steel pipe, we will advantageously proceed to a degreasing then a sandblasting unless the surface is not already galvanized. The same is true for cables such as wire.
- Polyurethane is in the form of at least two parts liquids which are mixed at the time of application on the metal surface.
- One part contains the polyol, the other isocyanate, the third possibly the catalyst.
- the other ingredients are divided between parts, depending on their responsiveness and compatibility. We operate advantageously at room temperature for example between 10 and 50 ° C. But we would not get out of the framework of the invention if one operated at 60 or 80 ° C. Generally, the reaction between polyol, polyisocyanate and chain extender takes place between 50 and 80 ° C in a few minutes. It would not go beyond the scope of the invention to use a monocomponent polyurethane powder system with thermal activation.
- the polyurethane for the outer surface of a pipe, we deposit the polyurethane (before polymerization) by coating or rolling, or by a flat die producing a continuous ribbon which is wrapped around the tube by the rotation of the tube on himself.
- a flat die For an electric cable or a shroud, one can proceed by a annular die which deposits the mixture of the two parts around the cable or the guy. If it is several twisted elements, we proceed in the same way making sure to fill all the gaps between the different elements.
- Layer polyurethane being deposited and polymerized we then proceed to deposit the optional layer of binder and thermoplastic polymer.
- the binder and the polymer are deposited thermoplastic, either by coextrusion in annular dies for small tube diameters or for cables and shrouds either by flat dies producing ribbons that are rolled up. Then cooling is carried out. the water.
- Example 1 the following polyurethane formulation is prepared.
- the first part is homogenized and degassed under vacuum (1 hour, 80 ° C at 1,360 Pa absolute pressure). Then we mix the two solutions and the mixture is placed at room temperature (20 ° C) on the exterior surface a galvanized steel pipe with an outside diameter of 115, a thickness of 6.5 mm, length. 3 m.
- the thickness of the polyurethane layer is 0.5 to 1 mm.
- the tube thus coated is heated polyurethane at 180 ° C-190 ° C then covered with a layer of binder (OREVAC 1) 200 to 300 ⁇ m thick then a layer of 2.50 to 3 mm of HDPE.
- the binder and HDPE are each deposited by a flat die producing a ribbon continuous that is wrapped around the tube by the rotation of the tube on itself.
- the tube coated is then cooled with water for 5 minutes.
Landscapes
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Ropes Or Cables (AREA)
- Manufacturing Of Electric Cables (AREA)
- Paints Or Removers (AREA)
- Organic Insulating Materials (AREA)
- Adhesives Or Adhesive Processes (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9609559 | 1996-07-30 | ||
FR9609559 | 1996-07-30 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0822012A1 EP0822012A1 (fr) | 1998-02-04 |
EP0822012B1 true EP0822012B1 (fr) | 2003-12-03 |
Family
ID=9494617
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97401839A Expired - Lifetime EP0822012B1 (fr) | 1996-07-30 | 1997-07-23 | Revêtement de surfaces métalliques son application aux tubes et aux câbles |
Country Status (13)
Country | Link |
---|---|
US (2) | US5993924A (ja) |
EP (1) | EP0822012B1 (ja) |
JP (1) | JP2934217B2 (ja) |
KR (1) | KR100297042B1 (ja) |
AT (1) | ATE255471T1 (ja) |
AU (1) | AU719791B2 (ja) |
BR (1) | BR9704137A (ja) |
CA (1) | CA2210844C (ja) |
DE (1) | DE69726502T2 (ja) |
DK (1) | DK0822012T3 (ja) |
ES (1) | ES2212061T3 (ja) |
NO (1) | NO973469L (ja) |
PT (1) | PT822012E (ja) |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3846757B2 (ja) * | 1997-08-06 | 2006-11-15 | 古河電気工業株式会社 | ケーブル |
US7874404B1 (en) | 1998-09-29 | 2011-01-25 | Otis Elevator Company | Elevator system having drive motor located between elevator car and hoistway sidewall |
AU2001250425A1 (en) * | 2000-05-08 | 2001-11-20 | N V. Bekaert S.A. | Zinc-coated steel cord with improved fatigue resistance |
JP4043856B2 (ja) * | 2002-06-11 | 2008-02-06 | 矢崎化工株式会社 | 摺動性等の機械的強度に優れた樹脂被覆鋼管 |
GB2399305B (en) * | 2003-06-09 | 2006-02-22 | Wood Ltd E | Pipe renovating method |
GB0313275D0 (en) * | 2003-06-09 | 2003-07-16 | Wood Ltd E | Renovating water pipelines |
US8344410B2 (en) * | 2004-10-14 | 2013-01-01 | Daktronics, Inc. | Flexible pixel element and signal distribution means |
US7868903B2 (en) * | 2004-10-14 | 2011-01-11 | Daktronics, Inc. | Flexible pixel element fabrication and sealing method |
US7893948B1 (en) | 2004-10-14 | 2011-02-22 | Daktronics, Inc. | Flexible pixel hardware and method |
EP2225313B1 (en) * | 2007-12-20 | 2016-04-13 | Coatings Foreign IP Co. LLC | Process for producing a multilayer coating |
AU2008343024B2 (en) * | 2007-12-20 | 2013-10-24 | Coatings Foreign Ip Co. Llc | Process for producing a multilayer coating |
JP5202048B2 (ja) * | 2008-03-13 | 2013-06-05 | 富士フイルム株式会社 | インクジェット記録方法 |
US20100282400A1 (en) * | 2009-05-05 | 2010-11-11 | Chandra Sekar | Methods for manufacturing a paint roller and component parts thereof |
US8142599B2 (en) * | 2009-01-08 | 2012-03-27 | Chandra Sekar | Methods for manufacturing a paint roller and component parts thereof |
US20120238685A1 (en) * | 2009-12-01 | 2012-09-20 | Nv Bekaert Sa | Reinforced polymer composite |
US8795832B2 (en) * | 2010-07-30 | 2014-08-05 | Fyfe Co., Llc | Systems and methods for protecting a cable or cable bundle |
KR101273931B1 (ko) | 2011-01-21 | 2013-06-11 | 이영술 | 천공홀 코팅 금속판 및 그 제조방법 |
EP3031862B1 (de) | 2014-12-11 | 2018-08-29 | Ems-Patent Ag | Mehrschichtstruktur mit mindestens einer metallschicht und mindestens einer polyamidschicht |
EP3297001B1 (en) | 2015-05-11 | 2021-04-14 | LS Cable & System Ltd. | Power cable |
WO2016182254A1 (ko) * | 2015-05-11 | 2016-11-17 | 엘에스전선 주식회사 | 전력 케이블 |
CN112725711B (zh) * | 2020-12-21 | 2022-02-18 | 山东大学 | 一种提高高强铝合金疲劳性能的方法 |
CN114164984B (zh) * | 2021-12-09 | 2023-03-10 | 广州市亚丹柜业有限公司 | 一种由复合板材组成的墙面板及其制备方法 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US30006A (en) * | 1860-09-11 | Safety-gtjakd fob | ||
FR790494A (fr) * | 1935-05-24 | 1935-11-21 | Baudin B | Dispositif d'immobilisation des têtes de suspentes dans les ponts suspendus |
AT320718B (de) * | 1969-07-30 | 1975-02-25 | Unitecta Oberflaechenschutz | Verfahren zur Herstellung von Kabeln und Vorrichtung hierzu |
JPS528253B1 (ja) * | 1970-05-15 | 1977-03-08 | ||
US3671622A (en) * | 1970-11-13 | 1972-06-20 | Bethlehem Steel Corp | Method of forming seal for multi-wire strand |
USRE30006E (en) | 1973-11-22 | 1979-05-22 | Mitsui Petrochemical Industries Ltd. | Process for the formation of a polyolefin coating layer onto a metal surface |
DE3046264C2 (de) * | 1980-12-09 | 1982-12-09 | Basf Farben + Fasern Ag, 2000 Hamburg | Verfahren zum Ummanteln eines Metallrohres |
DE3046263C2 (de) * | 1980-12-09 | 1982-12-09 | Basf Farben + Fasern Ag, 2000 Hamburg | Verfahren zum Ummanteln eines Metallrohres |
US4379807A (en) * | 1981-03-13 | 1983-04-12 | Rea Magnet Wire Co., Inc. | Magnet wire for hermetic motors |
US4606953A (en) * | 1983-06-23 | 1986-08-19 | Nippon Steel Corporation | Polypropylene coated steel pipe |
US4533598A (en) * | 1983-11-18 | 1985-08-06 | Caschem, Inc. | Extended polyurethanes |
EP0185058B1 (en) * | 1984-06-15 | 1991-10-09 | AT&T Corp. | Encapsulating compound and articles comprising same |
DE3619032A1 (de) * | 1986-06-06 | 1987-12-10 | Bayer Ag | Verfahren zur herstellung eines metall-kunststoff-laminates |
US4692383A (en) * | 1986-07-21 | 1987-09-08 | Ppg Industries, Inc. | Polycarbonate based elastomeric coating compositions |
US4734545A (en) * | 1986-11-26 | 1988-03-29 | The Furukawa Electric Co., Ltd. | Insulated conductor for a wire harness |
CA2125551A1 (en) * | 1994-06-08 | 1995-12-09 | Mark Gibson | Pipe treatment process |
FR2739113B1 (fr) * | 1995-09-26 | 1997-12-05 | Freyssinet Int Stup | Toron individuellement protege pour ouvrage de genie civil suspendu, ouvrage incluant de tels torons, et procede de fabrication |
-
1997
- 1997-07-23 EP EP97401839A patent/EP0822012B1/fr not_active Expired - Lifetime
- 1997-07-23 AT AT97401839T patent/ATE255471T1/de not_active IP Right Cessation
- 1997-07-23 DK DK97401839T patent/DK0822012T3/da active
- 1997-07-23 PT PT97401839T patent/PT822012E/pt unknown
- 1997-07-23 DE DE69726502T patent/DE69726502T2/de not_active Expired - Lifetime
- 1997-07-23 ES ES97401839T patent/ES2212061T3/es not_active Expired - Lifetime
- 1997-07-28 US US08/901,412 patent/US5993924A/en not_active Expired - Lifetime
- 1997-07-28 NO NO973469A patent/NO973469L/no not_active Application Discontinuation
- 1997-07-29 AU AU32372/97A patent/AU719791B2/en not_active Expired
- 1997-07-29 CA CA002210844A patent/CA2210844C/fr not_active Expired - Fee Related
- 1997-07-30 KR KR1019970036205A patent/KR100297042B1/ko not_active IP Right Cessation
- 1997-07-30 JP JP9219224A patent/JP2934217B2/ja not_active Expired - Lifetime
- 1997-07-30 BR BR9704137A patent/BR9704137A/pt not_active Application Discontinuation
-
1999
- 1999-09-02 US US09/389,087 patent/US6291024B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
NO973469L (no) | 1998-02-02 |
ES2212061T3 (es) | 2004-07-16 |
AU719791B2 (en) | 2000-05-18 |
US5993924A (en) | 1999-11-30 |
PT822012E (pt) | 2004-04-30 |
ATE255471T1 (de) | 2003-12-15 |
NO973469D0 (no) | 1997-07-28 |
DK0822012T3 (da) | 2004-04-13 |
BR9704137A (pt) | 1998-12-15 |
CA2210844C (fr) | 2001-04-17 |
AU3237297A (en) | 1998-02-05 |
KR980009520A (ko) | 1998-04-30 |
US6291024B1 (en) | 2001-09-18 |
EP0822012A1 (fr) | 1998-02-04 |
DE69726502T2 (de) | 2004-12-30 |
DE69726502D1 (de) | 2004-01-15 |
CA2210844A1 (fr) | 1998-01-30 |
KR100297042B1 (ko) | 2002-11-18 |
JPH10114015A (ja) | 1998-05-06 |
JP2934217B2 (ja) | 1999-08-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0822012B1 (fr) | Revêtement de surfaces métalliques son application aux tubes et aux câbles | |
EP2399058B1 (de) | Verwendung eines leitungsrohrs zur herstellung einer im wasser verlegten rohrleitung | |
EP1877467B1 (fr) | Utilisation de compositions thermoplastiques pour la protection thermique de substrats | |
CA1098080A (en) | Zinc coated wire | |
WO2007062812A1 (en) | Process for preparing a metal wire with a non-isocyanate polyurethane coating | |
KR101072616B1 (ko) | 저온 피이 상도막 | |
US5939145A (en) | Coated pipes and methods of making them | |
JPH0629889B2 (ja) | 海底光ケーブル | |
EP1485433A1 (fr) | Compositions a base de dispersions aqueuses de bitume et de polyurethane, procede de preparation et utilisations | |
CA2231070A1 (fr) | Composition thermoplastique pour conduites de carburant | |
JPH10226973A (ja) | 防錆被覆の低リラクセーションpcストランドとその製造方法 | |
CN1178842A (zh) | 金属表面的涂料,该涂料在管子和电缆上的应用 | |
EP4165133A1 (fr) | Compositions de moulage à base de polyamide, de fibres de carbone et de billes de verre creuses et leur utilisation | |
TW381272B (en) | Coating of metal surface, its application to tubes and to cables | |
EP3433303B1 (fr) | Copolymère à blocs pour la protection de pièces à base de métaux | |
AU6073590A (en) | Steel substrate for reinforcement of elastomers | |
US5792388A (en) | Chemically-modified silyl-terminated polythioether-diisocyanate polymers, compositions and processes | |
RU2186082C1 (ru) | Адгезионная композиция | |
EP1095084B1 (fr) | Procede pour remplir et etancher des connecteurs electriques | |
FR2554114A1 (fr) | Materiaux d'isolation elastomeres exempts d'amiante pour les parois internes des moteurs-fusees | |
CN116606541A (zh) | 一种高强度耐脏污tpu材料及其制备方法 | |
CA1114546A (en) | Asphalt and rubber comprising composition | |
JPH01148544A (ja) | 有機被覆防錆鋼板 | |
JPH0358828A (ja) | コントロールケーブル | |
JPS61171784A (ja) | 固体推進薬の接着剤 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19970807 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FI FR GB IE IT LI NL PT SE |
|
AKX | Designation fees paid |
Free format text: AT BE CH DE DK ES FI FR GB IE IT LI NL PT SE |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AT BE CH DE DK ES FI FR GB IE IT LI NL PT SE |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: ATOFINA |
|
17Q | First examination report despatched |
Effective date: 20021206 |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK ES FI FR GB IE IT LI NL PT SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20031203 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20031203 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: FRENCH |
|
REF | Corresponds to: |
Ref document number: 69726502 Country of ref document: DE Date of ref document: 20040115 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20040310 |
|
RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: FREYSSINET INTERNATIONAL (STUP) |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20040213 Ref country code: CH Ref legal event code: PUE Owner name: FREYSSINET INTERNATIONAL (STUP) Free format text: ATOFINA#4/8 COURS MICHELET#92800 PUTEAUX (FR) -TRANSFER TO- FREYSSINET INTERNATIONAL (STUP)#1BIS, RUE DU PETIT CLAMART#78140 VELIZY VILLACOUBLAY (FR) Ref country code: PT Ref legal event code: PC4A Free format text: FREYSSINET INTERNATIONAL (STUP) FR Effective date: 20040303 Ref country code: CH Ref legal event code: NV Representative=s name: KELLER & PARTNER PATENTANWAELTE AG |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
NLT2 | Nl: modifications (of names), taken from the european patent patent bulletin |
Owner name: FREYSSINET INTERNATIONAL (STUP) |
|
NLS | Nl: assignments of ep-patents |
Owner name: FREYSSINET INTERNATIONAL STUP |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2212061 Country of ref document: ES Kind code of ref document: T3 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20040906 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IE Payment date: 20110622 Year of fee payment: 15 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120723 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PCAR Free format text: NEW ADDRESS: EIGERSTRASSE 2 POSTFACH, 3000 BERN 14 (CH) |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20160627 Year of fee payment: 20 Ref country code: CH Payment date: 20160621 Year of fee payment: 20 Ref country code: ES Payment date: 20160623 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20160623 Year of fee payment: 20 Ref country code: SE Payment date: 20160627 Year of fee payment: 20 Ref country code: PT Payment date: 20160630 Year of fee payment: 20 Ref country code: FR Payment date: 20160622 Year of fee payment: 20 Ref country code: DK Payment date: 20160622 Year of fee payment: 20 Ref country code: BE Payment date: 20160622 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20160627 Year of fee payment: 20 Ref country code: DE Payment date: 20160622 Year of fee payment: 20 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 69726502 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: EUP Effective date: 20170723 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MK Effective date: 20170722 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20170722 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MK Effective date: 20170723 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20170801 Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20170722 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20180508 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20170724 |