EP2951258A1 - Procédé de fabrication d'un element composite metal-plastique - Google Patents

Procédé de fabrication d'un element composite metal-plastique

Info

Publication number
EP2951258A1
EP2951258A1 EP14702233.9A EP14702233A EP2951258A1 EP 2951258 A1 EP2951258 A1 EP 2951258A1 EP 14702233 A EP14702233 A EP 14702233A EP 2951258 A1 EP2951258 A1 EP 2951258A1
Authority
EP
European Patent Office
Prior art keywords
metal
plastic
layer
conversion
halides
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.)
Withdrawn
Application number
EP14702233.9A
Other languages
German (de)
English (en)
Inventor
Maximilian Gruhn
Karl Kuhmann
Martin Risthaus
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of EP2951258A1 publication Critical patent/EP2951258A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/16—Making multilayered or multicoloured articles
    • B29C45/1671—Making multilayered or multicoloured articles with an insert
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/08—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/10—Next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C09J177/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C2045/1486—Details, accessories and auxiliary operations
    • B29C2045/14868—Pretreatment of the insert, e.g. etching, cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1207—Heat-activated adhesive
    • B32B2037/1215—Hot-melt adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/18—Aircraft
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2607/00—Walls, panels
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2477/00—Presence of polyamide
    • 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

Definitions

  • the present invention relates to a method for producing a hybrid component comprising metal and plastic, a coating for hybrid components and their
  • Hybrid components are composites of the two materials metal and plastic. They can be produced by the injection molding process. Hybrid components are components that are used, inter alia, in vehicle construction and in the automotive industry
  • the disadvantage of these hybrid components lies in the lack of or insufficient adhesion between metal and plastic. In this respect, mechanical anchoring of the plastic to the metal has hitherto been carried out.
  • adhesion between metal and plastic can be improved by adhesion promoters.
  • adhesion promoters From EP-A-1808468 and EP-A-2435246 hybrid components are known, wherein metal and plastic are connected by hot melt adhesives as adhesion promoters on copolyamide base, which additionally contain isocyanate and epoxide groups.
  • hot melt adhesives as adhesion promoters on copolyamide base, which additionally contain isocyanate and epoxide groups.
  • Especially in the automotive industry metal substrates are known which
  • Conversion layers include, which are used for surface treatment.
  • the layers are formed, for example, by phosphating or
  • the hybrid components obtainable from the process should have an improved or increased adhesion between metal and plastic compared with the prior art.
  • the hybrid components obtained should meet the requirements of vehicle and aircraft construction as well as the electronics and electrical engineering industry.
  • a good weather resistance, in particular corrosion protection resistance should be given.
  • Metal and plastic of the hybrid component should be materially bonded
  • the method according to the invention comprises the steps a. Pretreatment of the metal surface by applying at least one conversion layer,
  • the primer composition contains at least one copolyamide-based hot melt adhesive.
  • the metal surface is first pretreated over the whole area or partially.
  • the metal can be cleaned before pretreatment or already have metallic protective coatings.
  • the metal cleaning is known in the art.
  • the pretreatment can be done with conversion means.
  • the conversion agents are usually used as aqueous solutions. Conversion agents are commercially available passivants and products for the
  • Conversion treatment in question such as zinc phosphating agents, iron phosphating and phosphoric acid solutions containing titanates or zirconates.
  • Chromating agents are also technically possible, but they are less preferred because of their health-endangering properties.
  • Conversion agents preferably contain halides.
  • halides salt-like, covalent and complex compounds of the halogens fluorine, chlorine, bromine and iodine with more electropositive elements are considered, with salt-like halides, complex halides or mixtures of these halides are preferred.
  • Halogens are salt-like substances of alkali and alkaline earth salts and ammonium salts of hydrohalic acids.
  • halogen ions occur as monodentate anionic ligands.
  • fluorine-containing halides Particularly preferred salt-like fluorine-containing halides are fluoride anions or hydrogen fluoride anions, for example hydrogendifluoride.
  • complex halides preferably subgroup elements, preferably titanium or zirconium, form the central atom.
  • Complex halides are included, for example, hexafluorotitanate anions, hexafluorozirconate anions or
  • the complex halides are preferably in a proportion of 0.2 to 10 wt .-%, preferably 0.5 to 8 wt .-%, based on the total weight of the aqueous
  • Conversion agent solution included. Suitable conversion agents are sold, for example, by the company Henkel, Germany, under the name Granodine.
  • the salt-like halides are preferably contained in a proportion of 10 to 300 ppm, preferably 20 to 200 ppm and particularly preferably 30 to 100 ppm, each based on the total weight of the conversion agent solution.
  • Fluoride-containing solutions containing fluoride and hydrogen difluoride are
  • Grano Toner 38 offered by Henkel.
  • the metal can be immersed in the conversion agent.
  • the conversion agent can be applied by means of spraying, knife coating, rolling, pressing, dipping, rolling, pouring or laminating.
  • Post-passivation can be carried out after the pretreatment. This is understood to mean a passivating rinse with acidic solutions, preference being given to using the abovementioned halides. Furthermore, the conversion layer can be obtained by a
  • the surface to be treated is passed through the oxidizing region of a gas flame into which a silicon-containing substance, the precursor, is metered. This burns and the residue separates as an amorphous silicate as firmly adherent
  • a plasma jet is generated from a working gas or a flame jet is swept out of a fuel gas, wherein at least one precursor material is supplied to the working gas and / or the plasma jet or the fuel gas and / or the flame jet and in the plasma jet or flame jet is reacted, wherein at least one reaction product of at least one of the precursors on the surface and / or deposited on at least one disposed on the surface layer.
  • a plasma jet is generated from a working gas or a flame jet is swept out of a fuel gas, wherein at least one precursor material is supplied to the working gas and / or the plasma jet or the fuel gas and / or the flame jet and in the plasma jet or flame jet is reacted, wherein at least one reaction product of at least one of the precursors on the surface and / or deposited on at least one disposed on the surface layer.
  • the treatment of the surface can be done at atmospheric pressure.
  • optical emissions of the plasma jet or flame jet can be measured by means of a spectrometer, on the basis of which the characteristics of the plasma jet or flame jet are determined.
  • the treatment of the surface may consist in an activation or in a coating of the surface by means of the plasma jet or flame jet.
  • Reflection behavior transmission behavior, refractive index, transparency,
  • Light scattering electrical conductivity, antibacterial behavior, friction, adhesion, hydrophilicity, hydrophobicity, oleophobicity, surface tension, surface energy, anti-corrosive effect, dirt-repellent effect, self-cleaning ability, photocatalytic behavior, anti-stress behavior, wear behavior, chemical resistance, biocidal behavior, biocompatible behavior, electrostatic behavior, electrochromic Activity, photochromic activity, gasochromic activity.
  • the generation of the plasma can be done in a free-jet plasma source.
  • a high-frequency discharge between two concentric electrodes is ignited, which is formed by an introduced gas flow
  • Hollow cathode plasma as Plasmajet from the electrode assembly usually several centimeters in the free space and is led out to be coated surface.
  • the precursor can be introduced both before the excitation in the working gas (direct plasma processing) and then in the already formed plasma or in the vicinity (remote plasma processing).
  • Another possibility of plasma generation is the exploitation of a dielectrically impeded discharge.
  • the precursor is preferably introduced in the gaseous state or as an aerosol into the working gas or the plasma stream.
  • Liquid or solid, in particular pulverulent precursors can also be used, but are preferably converted into the gaseous state before introduction, for example by evaporation.
  • the precursor can first be introduced into a carrier gas, entrained therefrom, and introduced together with it into the working gas or the plasma stream.
  • the deposited layer preferably comprises at least one of silicon, silver, gold, copper, iron, nickel, cobalt, selenium, tin, aluminum, titanium, zinc, zirconium, tantalum, chromium, manganese, molybdenum, tungsten, bismuth, germanium, niobium , Vanadium, gallium, indium, magnesium, calcium, strontium, barium, lithium,
  • the layers contain oxidic or / and nitridic compounds of silicon, titanium, tin, aluminum, zinc, tungsten and zirconium.
  • the precursor used is preferably an organosilicon and / or an organo-titanium compound, for example hexamethyldisiloxane, tetramethylsilane,
  • Tetramethoxysilane, tetraethoxysilane, titanium tetraisopropylate or titanium tetraisobutylate Tetramethoxysilane, tetraethoxysilane, titanium tetraisopropylate or titanium tetraisobutylate.
  • barrier layers can be realized that the
  • air, steam or other gas can be used, for example, oxygen, nitrogen, noble gases, hydrogen, carbon dioxide, gaseous hydrocarbons or a mixture thereof.
  • propane can be used as the fuel gas for the flame treatment, air or oxygen being supplied for combustion.
  • the fuel gas can be premixed with air or oxygen.
  • the mixing ratio between fuel gas and oxygen or air can be used as a parameter based on the determined
  • Characteristics are controlled and / or regulated.
  • the generation of the plasma can take place in a free-jet plasma source or by means of dielectrically impeded discharge.
  • the precursor is preferably introduced in the gaseous state or as an aerosol into the working gas or the plasma stream.
  • Liquid or solid, in particular pulverulent precursors can also be used, but are preferably converted into the gaseous state before introduction, for example by evaporation.
  • the precursor can first be introduced into a carrier gas, entrained therefrom, and introduced together with it into the working gas or the plasma stream.
  • the precursor used is preferably an organosilicon and / or an organo-titanium compound, for example hexamethyldisiloxane, tetramethylsilane,
  • Tetramethoxysilane, tetraethoxysilane, titanium tetraisopropylate or titanium tetraisobutylate Tetramethoxysilane, tetraethoxysilane, titanium tetraisopropylate or titanium tetraisobutylate.
  • the adhesion promoter composition is then applied over the entire surface or partially to the metal or the conversion layer.
  • the metal with the applied primer composition is thermally crosslinked or dried, with object temperatures of 120 ° C to 240 ° C, preferably 150 ° C to 225 ° C, preferably 175 ° C to 200 ° C, for a period of 0, 5 min to 30 min, preferably from 1 min to 20 min, preferably 3 min to 10 min, are advantageous.
  • object temperatures of 120 ° C to 240 ° C, preferably 150 ° C to 225 ° C, preferably 175 ° C to 200 ° C, for a period of 0, 5 min to 30 min, preferably from 1 min to 20 min, preferably 3 min to 10 min, are advantageous.
  • the person skilled in the art can determine suitable time / temperature conditions by means of preliminary tests. In rolling processes, peak metal temperatures (PMT) of 180 ° C to 230 °
  • compositions are thus thermally cured.
  • compositions can be continuous or discontinuous by means of
  • compositions according to the invention can be applied on one or both sides, locally or over the entire surface.
  • the baked layer thicknesses (dry layer thicknesses) of the adhesion promoter compositions may be from 10 to 1000 ⁇ m, preferably from 20 to 250 ⁇ m and preferably from 30 to 150 ⁇ m. in the
  • Roller processes are layer thicknesses of 5 ⁇ to 250 ⁇ , in particular 10 ⁇ to 50 ⁇ , preferably.
  • the plastic is applied, for example, by an injection molding process or by hot pressing on the metal and the metal physically and / or chemically connected to the plastic.
  • the plastic is by means of
  • Injection molding technology injected.
  • the coated metal part is inserted into the injection mold and back-injected after closing the tool with the plastic.
  • Upon contact of the plastic melt with the coated metal surface forms a cohesive bond or the adhesion between the components.
  • the cohesively connected hybrid component can then be removed from the injection mold and further processed or processed.
  • Bonding adhesion and degree of crosslinking are subjected to a heat treatment.
  • Hybrid components produced in this way have a permanent connection between the pretreated and coated metal and the plastic and show a high mechanical and dynamic load capacity.
  • Suitable metals are, for example, iron-containing alloys such as steel, aluminum, copper, magnesium, titanium and alloys of the aforementioned metals.
  • Preferred metals are steel, titanium, aluminum and alloys of the aforementioned metals, more preferably steel and aluminum and aluminum alloys.
  • Preferred steels are unalloyed steels or stainless steels. Steels with a protective coating are particularly preferred.
  • Suitable coatings are, for example, coatings of zinc, aluminum-silicon, aluminum-zinc, zinc-aluminum, zinc-iron or zinc-magnesium, aluminum-silicon, zinc-aluminum and zinc being preferred.
  • composition of the coatings is defined, for example, in the brochure "Schmelztauchveredelt.es Band and Blech" of the Stahl-Informations-Zentrum in the Stahl-Zentrum, Düsseldorf, Germany, 2010 edition.
  • the coated metal Before the application of the plastic, the coated metal can be trimmed, reshaped or deformed The deformation or deformation can take place before or after the application of the abovementioned compositions.
  • the application of the plastic to the coated metal can in a known manner, for. Example, by injection molding, pressing, laminating, injection molding or (co) extruding done.
  • the plastic is injected by means of injection molding technology.
  • the metal provided with the coatings according to the invention may be preheated in a range from 50 ° C to 250 ° C in order to maintain the temperature in the contact area with the plastic, e.g. when over-molding or coextruding for a good bond between primer and plastic.
  • Suitable plastics contain e.g. Polybutylene terephthalates, polyolefins,
  • the plastics are preferably reinforced (Reinforcing), for example, fiber-reinforced, with glass fiber (GF) or
  • Plastics contain fillers such as talc or chalk.
  • the plastics may further contain additives such as stabilizers, impact modifiers, flow aids and pigments.
  • Preferred polyamides (PA) are selected from the group consisting of
  • Particularly preferred polyamides are selected from polyamide 6, polyamide 6.6, polyamide 610, polyamide 1010 and mixtures thereof.
  • the polyamides preferably contain reinforcing agents.
  • Another object of the invention is a coating for hybrid components, comprising at least one conversion layer and at least one layer of the aforementioned adhesion promoter composition (adhesion promoter layer).
  • the coating is obtainable by the method according to the invention.
  • the coatings according to the invention can be used as adhesion promoters between metal and plastic of a hybrid component.
  • hybrid components wherein the metal is connected to the plastic at least by a coating according to the invention.
  • the hybrid components according to the invention are used, for example, in mechanical and plant engineering, vehicle construction, in the aerospace industry, in rail construction, in electronics or in electrical engineering. Typical applications are in the area of
  • Another object of the invention is a metal substrate which is coated with at least one coating according to the invention.
  • the substrate may, for. B. be a metallic semi-finished or a metallic molding.
  • the substrate is
  • Primer composition preferably a metal band, a metal panel, a metal profile, a metal casting or a metal wire.
  • the primer composition contains at least one copolyamide-based hot melt adhesive.
  • the primer composition may be in solution, in dispersion or as a solid.
  • the hotmelt adhesive contains at least one copolyamide.
  • the copolyamide can be prepared from amide monomers and comonomers. The comonomers preferably give copolyamides which have a melting point between 95 ° C. and 175 ° C.
  • the amide monomers are preferably selected from the group consisting of laurolactam, amionoundecanoic acid or mixtures thereof. Copolyamides based on laurolactam are particularly preferred.
  • the comonomers are preferably selected from aliphatic or
  • cycloaliphatic diamines aliphatic or cycloaliphatic dicarboxylic acids, lactams and mixtures thereof.
  • the comonomers contain, independently of each other, preferably 4 to 18 C atoms.
  • Suitable dicarboxylic acids are, for example, adipic acid, sebacic acid or dodecanedioic acid.
  • suitable diamines are hexamethylenediamine, decamethylenediamine or
  • Lactams such as caprolactam can also be used as Comonomer can be used.
  • Preferred comonomers are caprolactam and a polymer of adipic acid and hexamethylenediamine, preferably in a mass ratio of 1: 1.
  • the copolyamides preferably have amine numbers of 75 to 400 mmol / kg.
  • the weight-average molecular weight of the copolyamides is preferably found in a range of 15,000 to 70,000 g / mol (measured by means of
  • the relative solution viscosity is preferably 1.2 to 1.8 (determination according to ISO 307).
  • copolyamides or the hotmelt adhesive can be used in the inventive
  • compositions can be used in solution, in dispersion or in powder form, with the powder form being preferred.
  • a suitable solvent is, for example, m-cresol.
  • the powder form can be obtained for example by grinding, wherein the grain diameter is preferably ⁇ 200 ⁇ , preferably ⁇ 100 ⁇ and particularly preferably ⁇ 70 ⁇ (sieve analysis).
  • the grain diameter is preferably ⁇ 200 ⁇ , preferably ⁇ 100 ⁇ and particularly preferably ⁇ 70 ⁇ (sieve analysis).
  • at least one epoxide component and at least one blocked polyisocyanate are added to the copolyamide as further constituents of the hot-melt adhesive.
  • the epoxy component has an epoxy index of 1-2 Eq / kg.
  • the epoxide equivalent weight of the epoxy resins used may be between 400 to 4000 g / mol, preferably 700 to 3000 g / mol and preferably between 875 and 1000 g / mol lie (determined by SMS 2026).
  • the proportion of OH groups of suitable epoxy resins is preferably from 2000 to 4500 mmol / kg, preferably from 2300 to 4000 mmol / kg (method SMS 2367).
  • epoxide component compounds based on diols, polyols or dicarboxylic acids can be used as the epoxide component, diols being preferred and corresponding phenol-diol derivatives being particularly preferred.
  • Very particularly preferred phenol-diol derivatives are bisphenols, in particular bisphenol A.
  • the epoxide component is usually obtained by reaction with epichlorohydrin.
  • Suitable epoxy resins have a density of 1 to 1.3 kg / L, preferably 1.15 to 1.25 kg / L (25 ° C, determined according to ASTM D792).
  • the glass transition temperature (Tg) may be 20 ° C to 100 ° C, preferably 25 ° C to 90 ° C, preferably 40 ° C to 60 ° C and more preferably 45 to 55 ° C (determined according to ASTM D3418).
  • EPIKOTE Resin such as EPIKOTE Resin 1001 or 1009 from Hexion Specialty Chemicals, Inc.
  • the hotmelt adhesive preferably contains the epoxide component in a proportion of 2.5 to 10% by weight, preferably 4 to 6% by weight, in each case based on the total weight of the hotmelt adhesive.
  • the hot-melt adhesive furthermore comprises hardeners such as dicyandiamide (DCD), preferably in proportions of from 3 to 6% by weight, based on the total weight of epoxy resin. Hardening derivatives such as monuron or fenuron can be added for curing acceleration, whereby the curing temperatures can be lowered or the curing times can be shortened.
  • the proportion of blocked polyisocyanate is preferably 2.5 to 15 wt .-%, preferably 4 to 6 wt .-%, each based on the total weight of
  • the blocked polyisocyanate component may be aromatic, aliphatic or
  • Blocking agent for isocyanates such as oximes, phenols or
  • Caprolactam are known in the art. Preferably lies the
  • Polyisocyanate component as uretdione to be blocked are sold under the name VESTAGON by Evonik Industries, Germany.
  • the adhesion promoter composition may contain self-crosslinking or externally crosslinking binders (for the term "binder”, see Rompp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, Binders, pages 73 and 74)
  • self-crosslinking refers to the property of a binder to undergo crosslinking reactions with itself, provided that the binders contain complementary reactive functional groups that react with each other to crosslink, or that the binders contain a reactive functional group
  • such binder systems are referred to as externally crosslinking, in which one type of the complementary reactive functional groups is present in the binder, and the other type in a hardener or crosslinking agent Printing inks, Georg Thieme Ve rlag, Stuttgart, New York, 1998, Hardening, pages 274 to 276, especially page 275, below.
  • the primer composition may further include electrically conductive materials selected from graphite, carbon black, zinc dust, or mixtures of these materials, thereby forming electrically conductive primer compositions.
  • the hybrid components comprising coatings of electrically conductive adhesion promoter compositions can be provided with a cathodic dip coating (KTL).
  • the primer composition may further contain organic solvents. Accordingly, the hot melt adhesive may be in solution or as a dispersion. Suitable solvents are polar or non-polar organic solvents.
  • Mixtures of polar and nonpolar solvents can also be used.
  • the primer compositions may further contain colorants, preferably pigments.
  • colorants preferably pigments.
  • functional pigments such as
  • Suitable hotmelt adhesives are available, for example, from Evonik Industries, Germany, under the name VESTAMELT.
  • the types X1027-P1, X1038-P1, X1316-P1 and X1333-P1 may be mentioned.
  • graft copolymers of polyamine and polamide-forming monomers such as lactams or co-aminocarboxylic acids may also be present, as described in EP1065236A2:
  • the amino group concentration is preferably in the range of 100 to 2,500 mmol / kg.
  • polyamine for example, the following classes of substances can be used:
  • Tris (2-aminoethyl) amine N, N-bis (2-aminoethyl) -N ', N'-bis [2- [bis (2-aminoethyl) amino] ethyl] -1, 2-ethanediamine,
  • Linear polyethyleneimines which can be prepared by polymerization of 4,5-dihydro-1, 3-oxazoles and subsequent hydrolysis (Houben-Weyl, Methods of Organic Chemistry, Volume E20, pages 1482-1487, Georg Thieme Verlag Stuttgart, 1987) ;
  • branched polyethyleneimines which are obtainable by polymerization of aziridines (Houben-Weyl, Methods of Organic Chemistry, Volume E20, pages 1482-1487, Georg Thieme Verlag Stuttgart, 1987) and which generally have the following amino group distribution:
  • the polyamine in the preferred case has a number average molecular weight M n of at most 20,000 g / mol, more preferably of at most 10,000 g / mol and
  • Lactams or ⁇ -aminocarboxylic acids which are used as polyamide-forming monomers contain 4 to 19 and in particular 6 to 12 carbon atoms. Particular preference is given to using ⁇ -caprolactam and laurolactam or the associated co-aminocarboxylic acids.
  • the molar ratio C12 / C6 building block is preferably between 4: 1 to 1: 4.
  • the mass ratio of hot melt adhesive to graft copolymer is preferably between 19: 1 and 1: 1.
  • the functionalized polyolefin is in the simplest case polypropylene-based. But are also suitable Etylen / C3 to Ci2- ⁇ -olefin copolymers. For example, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-dodecene are used as C 3 - to C 12 -alpha-olefin. Furthermore, the ethylene / C3 to C12 ⁇ -olefin copolymers may also contain up to about 10 wt .-% maximum of olefin loci such as ethylidenenorbornene or 1, 4-hexadiene. As functionalization serve preferably
  • Dicarboxylic anhydride or an unsaturated dicarboxylic acid are introduced.
  • Suitable reagents are, for example, maleic anhydride or
  • maleic acid-grafted polyolefins has become widely used in industrial applications, particularly for impact modifiers or as compatibilizers in blends and mechanically reinforced systems
  • a typical representative of a functionalized polyolefin is the
  • Another functionalization option is the melt blend of unfunctionalized polyolefins with reactive compatibilizers containing epoxide or carboxylic acid anhydride moieties.
  • Copolymers consisting of ethylene, one or more non-reactive
  • Lotader AX8900 (Arkema) represents a typical representative with glycidyl methacrylate units.
  • the ratio of polyamide component to polyolefin component is between 9 to 1 and 2 to 3.
  • Granodine 958 A from Henkel, Germany, containing, inter alia, phosphoric acid and zinc bis (dihydrogen phosphate),
  • Granodine 958 A from Henkel, Germany, additionally containing 170 ppm of Grano Toner 38 from Henkel, Germany (component comprising fluoride and hydrogendifluoride anions),
  • Granodine 1455 T from Henkel, Germany, containing, inter alia, phosphoric acid and dihydrogen hexafluorotitanate and
  • HDG EA sheet thickness 0.6mm
  • the metal samples were coated with a primer composition. As composition were applied
  • Solvent-containing spray paint A containing 29% by weight of a copolyamide-based hot melt adhesive containing an epoxy component and a blocked polyisocyanate, and
  • Solvent-containing spray paint B containing 30 wt .-% of a A copolyamide-based hot melt adhesive containing an epoxy component and a blocked polyisocyanate.
  • compositions I to IV contain the same hot melt adhesives.
  • the paint system was applied by spraying with a layer thickness of 50 to 70 ⁇ m and the powder coating was applied electrostatically with a layer thickness of 50 to 100 ⁇ m.
  • the spray paint and powder coating were baked at 150 ° C for 5 minutes.
  • the coated sheets were placed in a preheated autoclave (oven). After the baking process, the metal sheets were cut with shearing shears into metal strips measuring 24.9 mm x 59.8 mm which were suitable for the injection molding cavity
  • the metal strips were then inserted into a tempered injection mold for the production of the final hybrid components and overmoulded with a thermoplastic.
  • the following molding compositions were used as the plastic component:
  • K4 PA12GF30 VESTAMID L-GF30 from Evonik Industries AG.
  • the plastics were processed on a type Allrounder 420
  • Tool temperature 80 ° C or 120 ° C and at an injection rate of about 30 cc / s.
  • tool temperatures of 120 ° C and 70 ° C and melt temperatures of 335 ° C and 270 ° C were used.
  • test specimens used had the following design features:
  • the specimens thus produced were stored at 50% relative humidity for at least 24 hours at 23 ° C to a uniform conditioning state
  • KV conversion agent
  • HV adhesion promoter composition
  • Temp
  • the results show that the coating of the conversion layer and the adhesion promoter layer can achieve an increased adhesion strength between metal and plastic in hybrid components compared to systems without a conversion layer.
  • the adhesive strength is increased in particular with conversion agents used which halide-containing, preferably fluoride-containing, are (converters B and C).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Materials Engineering (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un élément composite à base de métal et de plastique. Le procédé comprend les étapes suivantes: a) prétraitement de la surface métallique par application d'au moins une couche de conversion, b) application d'au moins une couche d'une composition de promoteur d'adhésion et c) liaison du métal et du plastique. La couche de composition de promoteur d'adhésion contient au moins une colle thermofusible à base de copolyamide.
EP14702233.9A 2013-01-29 2014-01-29 Procédé de fabrication d'un element composite metal-plastique Withdrawn EP2951258A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201310201388 DE102013201388A1 (de) 2013-01-29 2013-01-29 Verfahren zur Herstellung eines Metall-Kunststoff-Hybridbauteils
PCT/EP2014/051693 WO2014118211A1 (fr) 2013-01-29 2014-01-29 Procédé de fabrication d'un element composite metal-plastique

Publications (1)

Publication Number Publication Date
EP2951258A1 true EP2951258A1 (fr) 2015-12-09

Family

ID=48578744

Family Applications (3)

Application Number Title Priority Date Filing Date
EP20130002778 Withdrawn EP2759580A1 (fr) 2013-01-29 2013-05-29 Composants hybrides de matériau en fibres composites
EP14702529.0A Active EP2951259B1 (fr) 2013-01-29 2014-01-29 Composants hybrides de matériau en fibres composites
EP14702233.9A Withdrawn EP2951258A1 (fr) 2013-01-29 2014-01-29 Procédé de fabrication d'un element composite metal-plastique

Family Applications Before (2)

Application Number Title Priority Date Filing Date
EP20130002778 Withdrawn EP2759580A1 (fr) 2013-01-29 2013-05-29 Composants hybrides de matériau en fibres composites
EP14702529.0A Active EP2951259B1 (fr) 2013-01-29 2014-01-29 Composants hybrides de matériau en fibres composites

Country Status (8)

Country Link
US (2) US20150375478A1 (fr)
EP (3) EP2759580A1 (fr)
JP (2) JP2016510270A (fr)
KR (2) KR20150113967A (fr)
CN (2) CN105308144A (fr)
BR (4) BR122021018633B1 (fr)
DE (1) DE102013201388A1 (fr)
WO (2) WO2014118211A1 (fr)

Families Citing this family (58)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013109616A1 (de) 2013-09-03 2015-03-05 Thyssenkrupp Steel Europe Ag Halbzeug und Verfahren zur Herstellung eines dreidimensional geformten Hybridbauteils im Metall/Kunststoffverbund sowie Verwendung eines solchen Halbzeuges
DE102014206022A1 (de) 2014-03-31 2015-10-01 Evonik Degussa Gmbh Metall-Kunststoff-Hybridbauteil
MX2017004139A (es) 2014-10-02 2018-08-15 Lewit Scott Panel estructural compuesto y metodo de fabricacion.
DE102014016329B4 (de) * 2014-11-05 2018-12-27 Audi Ag Verbundbauteil
US12454759B2 (en) 2014-11-10 2025-10-28 Superior Industries International, Inc. Method of coating alloy wheels using inter-coat plasma
EP3218207B8 (fr) * 2014-11-10 2019-08-14 Superior Industries International, Inc. Procédé de revêtement de roues d'alliage
US10137675B1 (en) * 2015-01-01 2018-11-27 Midmark Corporation Application of polymer thermofoil to metal substrate
EP3078475B2 (fr) 2015-04-07 2025-01-22 Ems-Chemie Ag Corps de moulage renforcé par un élément de renfort, son procédé de fabrication et d'utilisation
JP2017030311A (ja) * 2015-08-05 2017-02-09 住友林業株式会社 木質材の製造方法
DE102015117201A1 (de) 2015-10-08 2017-04-13 Bwg Bergwerk- Und Walzwerk-Maschinenbau Gmbh Verfahren und Anlage zum kontinuierlichen Herstellen von Verbundbändern oder -blechen
DE102015118597A1 (de) * 2015-10-30 2017-05-04 Salzgitter Flachstahl Gmbh Metall/Kunststoff-Verbundbauteil und Verfahren zur Herstellung eines solchen Verbundbauteils
US20190047191A1 (en) * 2016-01-27 2019-02-14 Plasmatreat Gmbh Injection-Molded Component with Insert Part, Method for Producing Same, and Uses Thereof
DE102016101456A1 (de) * 2016-01-27 2017-07-27 Plasmatreat Gmbh Spritzgussbauteil mit Einlegeteil, Verfahren zu dessen Herstellung und Verwendungen dafür
US10329763B2 (en) 2016-02-24 2019-06-25 Wabash National, L.P. Composite floor structure and method of making the same
JP2017205920A (ja) * 2016-05-17 2017-11-24 株式会社ジェイテクト 歯車の製造方法
US10597559B2 (en) * 2016-06-06 2020-03-24 Crane Composites, Inc. Method of manufacturing a composite panel containing lauan or other moisture-carrying or moisture-absorbing material using adhesion promoter and panel made using the method
EP3257893B1 (fr) * 2016-06-15 2018-12-26 LANXESS Deutschland GmbH Demi-produit matrice/fibre
US11491766B2 (en) 2016-08-29 2022-11-08 Northrop Grumman Systems Corporation Hybrid metal composite structures, rocket motors and multi stage rocket motor assemblies including hybrid metal composite structures, and related methods
US10603873B2 (en) * 2016-08-29 2020-03-31 Northrop Grumman Innovation Systems, Inc. Hybrid metal composite structures, rocket cases, and related methods
FR3056144B1 (fr) 2016-09-16 2018-10-12 Plastic Omnium Cie Procede de fabrication ameliore d'une piece de structure hybride de vehicule automobile et piece de structure hybride correspondante
WO2018106989A1 (fr) * 2016-12-09 2018-06-14 Magna Exteriors Inc. Procédé de fabrication de poutre hybride et poutre hybride
CN106853692A (zh) * 2016-12-30 2017-06-16 北京天恒长鹰科技股份有限公司 实现复合材料快速固化粘接的加热方法及桁架装配方法
JP6751041B2 (ja) * 2017-03-17 2020-09-02 株式会社神戸製鋼所 ポリオレフィン接着用表面処理金属板、及び複合部材
EP3600880B1 (fr) * 2017-03-20 2021-01-27 Basf Se Stratifié contenant un métal et une composition de polyamide
EP3378884A1 (fr) * 2017-03-21 2018-09-26 Solvay Specialty Polymers USA, LLC. Compositions thermoplastiques et procédé de traitement et des articles
CN108570303A (zh) * 2017-05-02 2018-09-25 浙江星月安防科技有限公司 一种新型金属塑料胶粘剂及其制备方法和应用
DE202017003886U1 (de) * 2017-07-21 2017-08-17 Lanxess Deutschland Gmbh Türmodul
TWI638712B (zh) * 2017-07-28 2018-10-21 雪曼電漿科技有限公司 Metal nano plastic injection molding method using atmospheric plasma surface treatment
WO2019112008A1 (fr) 2017-12-08 2019-06-13 本田技研工業株式会社 Structure de châssis de carrosserie de véhicule
DE102018204407A1 (de) 2018-03-22 2019-09-26 Thyssenkrupp Ag Funktionsintegrierte Temperierung in Stahl-Kunststoff-Hybriden durch wärmeleitfähige Füllstoffe
DE102018207205A1 (de) * 2018-05-09 2019-11-14 Thyssenkrupp Ag Hybrides Stahl-Kunststoffgehäuse für Leistungselektronik
EP3808557B1 (fr) * 2018-06-14 2024-03-20 Nippon Steel Corporation Composite de matière plastique renforcé de fibres de métal-carbone et procédé de production d'un composite de matière plastique renforcé de fibres de métal-carbone
DE102018120623A1 (de) 2018-08-23 2020-02-27 ACO Severin Ahlmann GmbH & Co Kommanditgesellschaft Rahmensystem und Schachtabdeckung
US10926002B2 (en) * 2018-12-21 2021-02-23 Toyota Motor Engineering & Manufacturing North America, Inc. Metal matrix composite orthopedic replacements
US10988243B2 (en) * 2019-03-15 2021-04-27 Bell Textron Inc. Tension-torsion strap
JP7245190B2 (ja) 2019-03-21 2023-03-23 トヨタ モーター エンジニアリング アンド マニュファクチャリング ノース アメリカ，インコーポレイティド 非強化領域を有する織物カーボン繊維強化鋼マトリックス複合材料
US11788175B2 (en) 2019-03-21 2023-10-17 Toyota Motor Engineering & Manufacturing North America, Inc. Chemically bonded amorphous interface between phases in carbon fiber and steel composite
CN112238562A (zh) * 2019-07-17 2021-01-19 精元电脑股份有限公司 键盘用基板装置的制造方法
CN112297544A (zh) * 2019-07-23 2021-02-02 Oppo广东移动通信有限公司 陶瓷壳体的制备方法、陶瓷壳体及电子设备
CN110524744A (zh) * 2019-08-19 2019-12-03 大同新成新材料股份有限公司 一种回收利用碳纤维热塑性复合材料的方法
US11207801B2 (en) 2019-09-06 2021-12-28 Eagle Technology Systems and methods for making and/or using composite tube structures formed of hybrid laminates
CN110884009B (zh) * 2019-10-22 2021-05-25 厦门迈勒滚塑有限公司 一种塑料油箱外接口的成型工艺
DE102020117925A1 (de) 2020-07-07 2022-01-13 Salzgitter Flachstahl Gmbh Blech mit Haftvermittlerbeschichtung als Halbzeug zur Fertigung von Metall-Thermoplastverbundbauteilen und Verfahren zur Herstellung eines solchen Bleches
CN110893690A (zh) * 2020-01-02 2020-03-20 沈阳航空航天大学 一种增强合金和复合材料电阻焊接混合接头强度的方法
DE102020202818A1 (de) 2020-03-05 2021-09-09 Thyssenkrupp Steel Europe Ag Hybrides Metall-Kunststoffhalbzeug mit verbessertem Wärmedurchgang
DE102020204360A1 (de) 2020-04-03 2021-10-07 Volkswagen Aktiengesellschaft Verfahren zur Herstellung eines Verbundbauteils, eine das Verbundbauteil umfassende Baugruppe sowie ein Kraftfahrzeug
US11686947B2 (en) * 2020-05-27 2023-06-27 Microsoft Technology Licensing, Llc Structural fiber component for injection molding in head mounted displays
CN111844954A (zh) * 2020-07-31 2020-10-30 深圳市跃洋光学有限公司 金属与塑胶料一到多层的眼镜复合材料及制备工艺和镜架
CN112859652B (zh) * 2021-01-20 2022-03-29 青岛海尔空调器有限总公司 室内抽烟监控方法及监控装置
US12337903B2 (en) 2021-03-12 2025-06-24 Wabash National, L.P. Reinforced preforms for optimized composite structures
DE102021115422A1 (de) 2021-06-15 2022-12-15 Dr. Ing. H.C. F. Porsche Aktiengesellschaft Holz-Kunststoff-Hybridbauteil zur Verwendung in einem Kraftfahrzeug
DE102021208630A1 (de) 2021-08-09 2023-02-09 Mahle International Gmbh Verfahren zur Herstellung eines Hybridbauteils
US12539802B2 (en) 2021-12-07 2026-02-03 Wabash National, L.P. Embedded mounting inserts
US12145731B2 (en) 2021-12-07 2024-11-19 B/E Aerospace, Inc. Aircraft seat base assembly
EP4286455A1 (fr) 2022-06-03 2023-12-06 Evonik Operations GmbH Filament continu renforcé par des fibres en matière thermoplastique destiné à être utilisé dans des processus de fabrication additive et procédé correspondant
CN116376464A (zh) * 2023-04-10 2023-07-04 杭州师范大学 一种高粘接强度、高耐热性的热熔胶膜及其制备方法和应用
ES1310122Y (es) * 2024-01-22 2024-11-19 Martin Portugues Muniz Jaime Montura para gafas y molde para obtencion de frontal para dicha montura
US20250313956A1 (en) * 2024-04-09 2025-10-09 The Boeing Company Systems and methods for preparing metal matrix composite substrates for subsequent treatment

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4053682A (en) * 1976-06-21 1977-10-11 Monsanto Company Process for improving the adhesion of hot melts to metal substrates
US4252712A (en) * 1978-10-04 1981-02-24 Monsanto Company Block copolymer hot melt adhesive composition
EP1808468A2 (fr) * 2006-01-17 2007-07-18 Degussa AG Composants hybrides contenant des matières adhésives à fondre réactives
DE102007025152A1 (de) * 2007-05-29 2008-12-04 Innovent E.V. Verfahren zum Beschichten eines Substrats
DE102008061166A1 (de) * 2008-12-09 2010-07-08 Daimler Ag Verbundbauteil und Verfahren zum Herstellen eines Verbundbauteils
DE102010011914A1 (de) * 2010-03-18 2010-10-21 Daimler Ag Verfahren zur Herstellung eines Metall-Kunststoffhybridbauteils
WO2010136241A1 (fr) * 2009-05-27 2010-12-02 Evonik Degussa Gmbh Composants hybrides dotés de colles fusibles réactives
DE102009042103A1 (de) * 2009-09-21 2011-03-24 Innovent E.V. Verfahren zur Behandlung einer Oberfläche
WO2013104397A2 (fr) * 2012-01-14 2013-07-18 Daimler Ag Pièce métallique de support pourvue d'une surface d'adhérence, pièce hybride et procédé de fabrication associé

Family Cites Families (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2836529A (en) * 1954-05-03 1958-05-27 Hugh Adam Kirk Reinforced plastic
US4219458A (en) * 1978-10-02 1980-08-26 Monsanto Company Block copolymer hot melt adhesive compositions
US4222976A (en) * 1978-10-02 1980-09-16 Monsanto Company Cavity filling with a hot melt adhesive composition
US4215159A (en) * 1978-10-04 1980-07-29 Monsanto Company Cavity filling with a hot melt adhesive composition
US4214019A (en) * 1978-10-04 1980-07-22 Monsanto Company Cavity filling with a hot melt adhesive composition
US4219459A (en) * 1978-10-04 1980-08-26 Monsanto Company Block copolymer hot melt adhesive compositions
EP0009951B1 (fr) * 1978-10-04 1984-03-21 Monsanto Company Composition adhésive fusible à chaud et procédé pour remplir une cavité dans un substrat avec cet adhésif
DE2966919D1 (en) * 1978-10-04 1984-05-24 Monsanto Co Block copolymer hot melt adhesive composition and method of filling a cavity
US4217376A (en) * 1978-10-04 1980-08-12 Monsanto Company Cavity filling with a hot melt adhesive composition
US4701481A (en) * 1985-08-26 1987-10-20 The Dow Chemical Company Durable epoxy resin
DE3730504C1 (en) * 1987-09-11 1989-03-16 Atochem Werke Gmbh Copolyamides containing caprolactam and laurolactam, process for the preparation thereof and use thereof for heat-sealing textiles
JP3123761B2 (ja) * 1991-02-18 2001-01-15 三井化学株式会社 表面改良された繊維補強樹脂成形品及びその成形方法
EP0535214A4 (en) * 1991-04-04 1993-09-08 James D. Lincoln Unidirectional carbon/phenolic prepreg material and method of manufacture
US5321120A (en) * 1993-01-26 1994-06-14 Bostik, Inc. Copolyamide adhesive compositions containing asymmetric aliphatic residues
US5773042A (en) * 1994-10-14 1998-06-30 Kabushiki Kaisha Kobe Seiko Sho Injection molding unit for long fiber-reinforced thermoplastic resin
JP3076780B2 (ja) * 1996-11-22 2000-08-14 東洋錫鈑株式会社 溶接缶用樹脂フィルム被覆金属板の製造方法
DE19654179A1 (de) 1996-12-23 1998-06-25 Basf Ag H-förmige Polyamide
DE19654058A1 (de) 1996-12-23 1998-06-25 Basf Ag Polymere Polyamine aus alternierenden Polyketonen
US6156396A (en) * 1998-08-11 2000-12-05 Florian; Raymond Golf practice mat
EP1065236B1 (fr) 1999-06-29 2003-09-24 Degussa AG Copolyamides greffés hautement ramifiés
JP4023515B2 (ja) * 2002-12-27 2007-12-19 東レ株式会社 熱接着用基材が用いられてなるプリフォーム、および積層体の製造方法
DE10312817A1 (de) * 2003-03-22 2004-10-07 Carl Freudenberg Kg Abdeckschicht für Motorraumauskleidung
JP4300861B2 (ja) * 2003-04-25 2009-07-22 東レ株式会社 発泡樹脂製コア内蔵ｆｒｐおよびその製造方法
US20060137799A1 (en) * 2004-12-29 2006-06-29 Enamul Haque Thermoplastic composites with improved sound absorbing capabilities
DE102005015295A1 (de) * 2005-04-01 2006-10-19 Billhöfer Maschinenfabrik GmbH & Co. KG Vorrichtung und Verfahren zum Beschichten eines metallischen Trägermaterials
DE102006041138A1 (de) 2006-09-01 2008-03-06 Evonik Degussa Gmbh Verbund aus einer Folie und einem Substrat auf Basis eines amorphen Polyamids
JP5151535B2 (ja) * 2007-02-22 2013-02-27 東レ株式会社 サンドイッチ構造体、およびそれを用いた成形体、電子機器筐体
EP2167338B1 (fr) * 2007-07-09 2011-12-28 ThyssenKrupp System Engineering GmbH Porte de vehicule automobile
US20090162544A1 (en) * 2007-12-20 2009-06-25 Garesche Carl E Method of surface coating to enhance durability of aesthetics and substrate component fatigue
DE102007062063A1 (de) 2007-12-21 2009-06-25 Ems-Patent Ag Transparente Polyamidformmasse
JP5651911B2 (ja) * 2008-03-03 2015-01-14 Ｊｆｅスチール株式会社 樹脂被覆鋼材の製造方法
JP5123052B2 (ja) * 2008-05-26 2013-01-16 日本パーカライジング株式会社 表面化成処理液、化成処理金属板およびその製造方法、ならびに上層被覆金属板およびその製造方法
DE102008058224A1 (de) * 2008-11-19 2010-05-20 Lanxess Deutschland Gmbh Leichtbauteil in Hybridbauweise
DE102009006593A1 (de) * 2009-01-29 2010-08-05 Tesa Se Verfahren zur Korrosionsschutzbehandlung von Metalloberflächen
JP2012007095A (ja) * 2010-06-25 2012-01-12 Teijin Ltd 複合材料の接着方法
US9409329B2 (en) * 2012-06-21 2016-08-09 Toyota Motor Engineering & Manufacturing North America, Inc. Method and application for controlling alignment of fibers during injection molding process

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4053682A (en) * 1976-06-21 1977-10-11 Monsanto Company Process for improving the adhesion of hot melts to metal substrates
US4252712A (en) * 1978-10-04 1981-02-24 Monsanto Company Block copolymer hot melt adhesive composition
EP1808468A2 (fr) * 2006-01-17 2007-07-18 Degussa AG Composants hybrides contenant des matières adhésives à fondre réactives
DE102007025152A1 (de) * 2007-05-29 2008-12-04 Innovent E.V. Verfahren zum Beschichten eines Substrats
DE102008061166A1 (de) * 2008-12-09 2010-07-08 Daimler Ag Verbundbauteil und Verfahren zum Herstellen eines Verbundbauteils
WO2010136241A1 (fr) * 2009-05-27 2010-12-02 Evonik Degussa Gmbh Composants hybrides dotés de colles fusibles réactives
DE102009042103A1 (de) * 2009-09-21 2011-03-24 Innovent E.V. Verfahren zur Behandlung einer Oberfläche
DE102010011914A1 (de) * 2010-03-18 2010-10-21 Daimler Ag Verfahren zur Herstellung eines Metall-Kunststoffhybridbauteils
WO2013104397A2 (fr) * 2012-01-14 2013-07-18 Daimler Ag Pièce métallique de support pourvue d'une surface d'adhérence, pièce hybride et procédé de fabrication associé

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2014118211A1 *

Also Published As

Publication number Publication date
JP2016506882A (ja) 2016-03-07
EP2951259A1 (fr) 2015-12-09
US20150361304A1 (en) 2015-12-17
BR122021018679B1 (pt) 2022-05-17
US10603872B2 (en) 2020-03-31
CN105229107A (zh) 2016-01-06
EP2951259B1 (fr) 2020-03-04
DE102013201388A1 (de) 2014-07-31
KR20150113966A (ko) 2015-10-08
JP6133440B2 (ja) 2017-05-24
WO2014118210A1 (fr) 2014-08-07
CN105229107B (zh) 2018-02-27
CN105308144A (zh) 2016-02-03
BR112015017978A2 (pt) 2017-07-11
BR122021018633B1 (pt) 2022-08-02
US20150375478A1 (en) 2015-12-31
JP2016510270A (ja) 2016-04-07
EP2759580A1 (fr) 2014-07-30
WO2014118211A1 (fr) 2014-08-07
KR101840099B1 (ko) 2018-03-19
KR20150113967A (ko) 2015-10-08
BR112015017991A2 (pt) 2017-07-11

Similar Documents

Publication Publication Date Title
EP2951258A1 (fr) Procédé de fabrication d'un element composite metal-plastique
EP2951255B1 (fr) Compositions de promoteurs d'adhésion et d'amorces pour éléments structuraux hybrides métal-plastique
EP3149224B1 (fr) Procédé de fabrication d'une structure sandwich, structure sandwich fabriquée par ledit procédé, et utilisation de ladite structure
DE102009026988A1 (de) Hybridbauteile mit reaktiven Schmelzklebstoffen
EP3010971B1 (fr) Promoteurs d'adhésion pour élément hybride métal-plastique
DE102006002125A1 (de) Reaktive Schmelzklebstoffe enthaltende Hybridbauteile
EP2863768B1 (fr) Chaussure de sport comportant des crampons ou des logements de crampons
DE102013213579A1 (de) Sehhilfe
US20080087377A1 (en) Method for Coating a Substrate Using a Paint Intensifier and Method for Bonding Coated Parts
EP3368272A1 (fr) Pièce composite en métal et matière plastique et procédé de fabrication de ladite pièce composite

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: 20150722

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20170201

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK OPERATIONS GMBH

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20210209