EP0379514A1 - Nouveau lamine de polymere/metal et son procede de fabrication - Google Patents

Nouveau lamine de polymere/metal et son procede de fabrication

Info

Publication number
EP0379514A1
EP0379514A1 EP88907970A EP88907970A EP0379514A1 EP 0379514 A1 EP0379514 A1 EP 0379514A1 EP 88907970 A EP88907970 A EP 88907970A EP 88907970 A EP88907970 A EP 88907970A EP 0379514 A1 EP0379514 A1 EP 0379514A1
Authority
EP
European Patent Office
Prior art keywords
polymer
laminate
layer
wrought
smooth
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Withdrawn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
EP88907970A
Other languages
German (de)
English (en)
Other versions
EP0379514A4 (en
Inventor
William G. Bridges
Thomas A. Armer
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.)
Olin Corp
Original Assignee
Olin Corp
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
Priority claimed from US07/087,195 external-priority patent/US4833022A/en
Application filed by Olin Corp filed Critical Olin Corp
Publication of EP0379514A1 publication Critical patent/EP0379514A1/fr
Publication of EP0379514A4 publication Critical patent/EP0379514A4/en
Withdrawn legal-status Critical Current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
    • 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
    • B32B15/06—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 natural rubber or synthetic rubber
    • 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
    • B32B15/085—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 polyolefins
    • 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
    • B32B15/09—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 polyesters
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—Copper
    • 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
    • B32B2319/00—Synthetic rubber
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene
    • 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
    • B32B2327/00—Polyvinylhalogenides
    • B32B2327/12—Polyvinylhalogenides containing fluorine
    • B32B2327/18—PTFE, i.e. polytetrafluoroethylene
    • 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
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • 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
    • B32B2371/00—Polyethers, e.g. PEEK, i.e. polyether-etherketone; PEK, i.e. polyetherketone
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/034—Organic insulating material consisting of one material containing halogen
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0133—Elastomeric or compliant polymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0141—Liquid crystal polymer [LCP]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/015—Fluoropolymer, e.g. polytetrafluoroethylene [PTFE]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0158—Polyalkene or polyolefin, e.g. polyethylene [PE], polypropylene [PP]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0242—Shape of an individual particle
    • H05K2201/0251—Non-conductive microfibers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0275—Fibers and reinforcement materials
    • H05K2201/0278—Polymeric fibers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils

Definitions

  • This invention relates generally to novel polymer/metal laminates and a method for their manufacture; and, more particularly, to such laminates made from smooth, untreated, wrought-metal and characterized by cohesive and adhesive strength of the laminate layers.
  • the present invention relates to polymer/metal laminates comprising at least one layer of smooth, untreated, wrought-metal and at least one layer of polymer selected from the group consisting of: perfluoroalkoxyvinyl ether copolymer (commercially available as TEFLON PFA, a product of E. I. du Pont de Nemours & Company, Inc.), perfluorinated poly(ethylene- co-propylene) (commercially available as TEFLON FEP, a product of E. I. du Pont de Nemours & Company, Inc.), poly(ethylene-co-tetrafluoroethylene) (commercially available as TEFZEL, a product of E. I.
  • liquid crystal polyarylesters syndiotactic 1,2-polybutadiene, polyenamine, polycyanoarylethers, polyarylsulfones (commercially available as RADEL, a product of Amoco Chemical), polynorbornene (commercially available as NORSOREX, a product of CdF Chemie S.A.) and polyarylketones.
  • the present invention relates to a method for fabricating a polymer/metal laminate by contacting a surface of smooth, untreated, wrought-metal with a polymer selected from the group consisting of: perfluoroalkoxyvinyl ether copolymer, perfluorinated poly(ethylene-co-propylene), poly(ethylene-co-tetrafluoroethylene), liquid crystal polyarylester, syndiotactic 1,2-polybutadiene, polyenamine, polycyanoarylethers, polyarylsulfones, polynorbornene and polyarylketones under lamination conditions sufficient to effect formation of said laminate.
  • a polymer selected from the group consisting of: perfluoroalkoxyvinyl ether copolymer, perfluorinated poly(ethylene-co-propylene), poly(ethylene-co-tetrafluoroethylene), liquid crystal polyarylester, syndiotactic 1,2-polybutadiene, polyenamine, polycyan
  • the present invention relates to a polymer/copper laminate produced by a method comprising contacting a surface of smooth, untreated, wrought-copper with a surface of a layer of polymer under lamination conditions, said polymer being thermoplastic and free of an adhesion promoter, said method, being free of any discharge (e.g. plasma, flame, corona or other electrical discharge) pretreatment of said surface of said layer of polymer prior to or during the lamination.
  • any discharge e.g. plasma, flame, corona or other electrical discharge
  • the present invention relates to a method for fabricating a polymer/copper laminate by contacting a surface of smooth, untreated, wrought-copper with a polymer layer free of surface electrical discharge pretreatment under lamination conditions sufficient to effect formation of said laminate.
  • a select group of polymers have been found to produce novel polymer/metal laminates characterized by excellent cohesive and adhesive strength of the polymer in the laminate.
  • the present inventors hypothesize that the excellent cohesive and adhesive strengths of the polymers in the laminates made by the method of the present invention are attributable, at least in part, to the chemical bonding efficacy of this select group of polymers to untreated wrought-metal.
  • polymers generally can utilize dipole-dipole, induced dipole, hydrogen, coordination, ionic or covalent bonding between the copper/copper oxide surface and the polymer.
  • the polymers useful in the present invention are generally capable of forming chemical bonds with the crystalline metal, metal oxide or metal hydroxyl surface layers.
  • these chemical bonds are dispersive. Van de Waals, hydrogen bonds, ionic, coordination/chelation or covalent-type bonds. More preferably, the bonds are dipole-dipole, ionic, coordination/chelation or covalent, and most preferably, they are an ionic, covalent or coordination/chelation type of bond.
  • the preferred polymers have low hydroxyl content but high local dipole moments. They can incorporate functional groups on the backbone or pendant to the backbone which can chelate, coordinate, or form ionic or covalent bonds.
  • the polymers should be stable to oxidative or thermal degradation in the presence of metal ions.
  • the laminate is fabricated by contacting the polymer layer (s) with the metal layer (s) at a temperature and pressure and for a time sufficient to allow contact and bonding of the metal and polymer interface(s) in the laminate.
  • the lamination temperature is between 5° and 50°C above the glass transition temperature or the melting point of the polymer. More preferably, only the surface layers of the polymer are melted while the bulk of the polymer remains solidified or just below the glass transition or melting point temperature. Most preferably, the polymer surface layer to a depth of between about 1 and about 10 microns is maintained at a temperature of between about 5 and about 50°C higher than the
  • T GLASS or T MELT during lamination while the bulk of the polymer substrate has a temperature of between about 5 and about 50°C below T g or T m.
  • the lamination temperature is between about 350°F and about 800°F, more preferably between about 500°F and about 800°F.
  • the lamination pressure employed is between about 1 psig and about 10,000 psig, more preferably between about 100 psig and about 5,000 psig, most preferably between about 300 psig and about 2,000 psig depending on the melt viscosity of the particular polymer selected and the lamination temperature utilized.
  • the lamination time preferably is between about 0.01 and about 2.00 minutes, more preferably between about 0.1 and about 0.5 minutes, most preferably between about 0.1 and about 0.2 minutes.
  • the copper and polymer layers are typically contacted in a hot press under the lamination conditions described herein. Alternately, this lamination can be carried out by fusion lamination between calendar rolls, or by continuous belt lamination.
  • the metal utilized in the present invention is generally smooth, untreated, wrought-metal, such as steel, copper or aluminum, preferably copper.
  • a smooth copper foil for example, generally has a surface smoothness to a depth of between 1x10 -6 and 50x10 -6 inches.
  • One advantage to using smooth copper foil in accordance with the present invention is that it is relatively inexpensive as compared to the cost of providing foils treated to provide a roughened metal surface.
  • An additional advantage is that smooth foils improve the electrical performance of the laminates.
  • the preferred metal, namely copper, utilized in the present invention is generally smooth, untreated, wrought-copper, and can include copper foil (generally having a thickness of less than 20 mils, preferably between about 25 and about 50 microns), copper strip (generally having a thickness of between about 10 and about 20 mils), and copper sheet
  • the term "untreated” is intended to designate that the copper foil surface is not subjected to surface roughening treatment prior to lamination (although it may be subjected to a surface cleaning treatment or wash).
  • This type of copper when in the form of a foil, generally has a surface smoothness to a depth of between 1x10 -6 and 10x10 -6 inches.
  • One advantage to using this type of foil in accordance with the present invention is that it is relatively inexpensive as compared to the cost of providing foils treated to provide a roughened copper surface.
  • peel strengths of laminates increased 40 percent to 100 percent when the smooth, untreated wrought-copper foils were washed by immersion in MeCl 2 (methylene chloride) for five seconds and then air dried prior to lamination of the copper to the polymer films.
  • MeCl 2 methylene chloride
  • This solvent rinse probably removes the trace amounts of machine oils/greases in the surface grain structure of the "rolled" (wrought) copper foil and thereby prevents these oils from migrating to the laminate layer interface and interfering with the formation of an adhesive bond, ultrasonic washing in methylene chloride improved adhesion by another 30 percent over washing (light agitation) by hand.
  • the copper foil layer (s) if used in the laminate can have a wide range of foil thickness of between about 0.1 and about 20.0 mils, more preferably between about 0.5 and about 10.0 mils, most preferably between about 1.0 and about 2.0 mils in thickness for each layer.
  • the polymer layer(s) utilized in the present invention generally provide the following desirable functional characteristics of: (a) binding the copper layers together preferably by chemical bonds, (b) providing an insulating dielectric barrier between the copper layers, and (c) maintaining a constant support and separation of the two copper layers. Additionally, the polymer layer can protect the copper surface from attack by corrosive agents, especially water and air.
  • the preferred polymers for use in this invention are, in decreasing order of preference: perfluoroalkoxyvinyl ether copolymer (commercially available as TEFLON PFA, a product of E. I. du Pont de Nemours & Company, Inc.), perfluorinated poly(ethylene-co-propylene)
  • copolymers can be made from a wide range of monomer ratios, generally a weight ratio of between 90 to 10 and 10 to 90 parts of one monomer to the other.
  • the polymer layer (s) in the laminate can have a wide range of thicknesses, preferably between about 0.5 and about 125 mils, more preferably between about 0.5 and about 10.0 mils, most preferably between about 1.0 and about 5.0 mils.
  • a particularly suitable range of polymer layer thicknesses for electronics applications is between about 50 and about 150 microns.
  • an intermediate layer of unfilled polymer be used at the polymer/copper interface.
  • the additives, fillers, lubricants, plasticizers, stabilizers, and coupling agents which are added to the bonding layer are contained by the polymer matrix and kept sufficiently immobile so as not to migrate to the metal-polymer interface and cause a weakening of the metal-polymer adhesive bond or form a weak boundary layer in the polymer adjacent to the interface.
  • Multilayer A-B-A type polymer films may be employed to enhance physical properties such as dimensional stability or coefficient of thermal expansion or to minimize cost by using a less costly "B” layer and using an "A" layer for its adhesive properties to smooth, untreated, wrought foils.
  • the following examples are intended to illustrate, but in no way limit the scope of, the present invention.
  • sheets of polymeric resin core were prepared from resin granules using well-known compression molding techniques on a sheet extruder.
  • Laminates made using various commercial polymers and methylene chloride-washed (as described above) smooth, untreated, wrought-copper were fabricated in a thermocompression molder at a temperature and pressure and for a time as specified in the examples. Peel strength tests on the laminates fabricated as disclosed in these examples were conducted in accordance with the Institute for Interconnecting and Packaging Electronic Circuits (IPC) Test Method No. 2.4.9, Revision A, dated December 1982, the contents of which are incorporated herein by reference. In short, this test involves masking the foil with 1/8 inch wide strips, then etching away the unmasked, exposed metal.
  • IPC Institute for Interconnecting and Packaging Electronic Circuits
  • the remaining, 1/8 inch wide metal/polymer laminate strips are mounted into an Instron test jig and peeled apart at a 90° angle. The force required to peel the sample apart is recorded and the lowest value is reported as a force per inch of strip width.
  • the resulting assembly was placed in a molding press and was soaked at a temperature of 650 F for a period of 300 seconds under a pressure of 235 psig. The pressure in the mold was then increased to 2500 psig and held for 30 seconds.
  • the press was opened, the laminated assembly removed and allowed to cool to room temperature.
  • the laminate was masked, etched, and peeled according to the IPC test method referenced above. The resulting peel strength was greater than 5 pounds per inch.
  • the resulting assembly was placed in a molding press and was soaked at a temperature of 675°F for a period of 300 seconds under a pressure of 235 PSI. The pressure in the mold was then increased to 1875 PSI and held for 30 seconds.
  • the press was opened, the laminated assembly removed and allowed to cool to room temperature.
  • the resulting laminate was masked, etched, and peeled according to the above-referenced IPC test, yielding a peel strength of greater than 5 pounds per inch.
  • the resulting assembly was placed in a molding press and was soaked at a temperature of 650°F for a period of 100 seconds under a pressure of 80 PSI. The pressure in the mold was then increased to 560 PSI and held for 30 seconds. The press was opened, the laminated assembly removed and allowed to cool to room temperature.
  • the resulting laminate was masked, etched, and peeled according to the above-referenced IPC test, yielding a peel strength of greater than 5 pounds per inch.
  • Sheets of pure liquid crystalline polyester (VECTRA A900 series from Celanese Corporation) were formed by well-known compression molding techniques. A sheet of this material, approximately 5 mils thick, was placed between two skin layer s of " 1-ounce " smooth, untreated, wrought-copper foil. The resulting assembly was placed in a molding press and soaked at a temperature of 640°F for 300 seconds at a pressure of 30 psig. The pressure in the mold was then increased to 2100 psig and held for 30 seconds. The press was then opened, the laminated assembly was removed and allowed to cool to room temperature. The resulting laminate was masked, etched, and peeled according to the above-referenced IPC test, yielding a peel strength of greater than 5 pounds per inch.
  • Sheets of pure syndiotactic 1,2-polybutadiene (RB 830 from Japan Synthetic Rubber Company) were prepared from resin granules using well-known compression molding or cast-film extrusion techniques. A sheet of this material approximately 5 mils thick was positioned between two "1-ounce" copper skin layers of smooth, untreated, wrought-copper foil. The resulting assembly was placed in a molding press and was soaked at a temperature of 500°F for a period of 100 seconds under a pressure of 60 PSI. The pressure in the mold was then increased to 1250 PSI and held for 30 seconds. The press was opened, the laminated assembly was removed and allowed to cool to room temperature. The resulting laminate was masked, etched, and peeled according to the above-referenced IPC test, yielding a peel strength of greater than 2.0 pounds per inch.
  • TEFLON PFA 350 or TEFLON PFA 340 perfluoroalkoxyvinyl ether copolymer from E. I. du Pont de Nemours and Company was compounded with fumed silica in the weight ratio 30 parts silica to 70 parts polymer, using a twin screw extruder operating at 680°F, and practicing well-known compounding extrusion techniques. The extrudate was pelletized then dried in a hopper dryer for 24 hours at 350°F. Sheets of the silica filled TEFLON PFA were formed by using well-known compression molding techniques. A sheet of this material, approximately 5 mils thick, was placed between two sheets of "1-ounce" smooth, untreated, wrought-copper foil.
  • the resulting assembly was placed in a molding press and soaked at a temperature of 680°F for 300 seconds at a pressure of 30 psig. The pressure in the mold was then increased to 1875 psig and held for 30 seconds. The press was then opened, the laminated assembly was removed and allowed to cool to room temperature. The resulting laminate was masked, etched, and peeled according to the above-referenced IPC test, yielding a peel strength of greater than 3 pounds per inch.
  • TEFLON PFA 350 or TEFLON PFA 340 perfluoroalkoxyvinyl ether copolymer from E. I. du Pont de Nemours and Company was compounded with fumed silica in the weight ratio of 30 parts silica to 70 parts polymer, using a twin screw extruder operating at 680°F, and practicing well-known compounding extrusion techniques. The extrudate was pelletized then dried in a hopper dryer for 24 hours at 350°F. Sheets of the silica filled PFA were formed by using well-known compression molding techniques. A sheet of this material, approximately 3 mils thick was placed between two 1.0 mil thick sheets of pure TEFLON PFA 340 or 350.
  • This three layer assembly was placed between two sheets of "1-ounce" smooth, untreated wrought-copper foil.
  • the resulting five layer assembly was placed in a molding press and soaked at a temperature of 680°F for 600 seconds at a pressure of 30 psig. The pressure in the mold was then increased to 1875 psig and held for 60 seconds. The press was then opened, the laminated assembly was removed, and allowed to cool to room temperature. The resulting laminate was masked, etched, and peeled according to the above-referenced IPC test, yielding a peel strength greater than 5 pounds per inch.
  • poly(phenylene sulfide) does not adhere to smooth, washed, wrought-copper foil, it does adhere to PFA, as shown in this example. Therefore, the poly(phenylene sulfide) can be used as the "B" inner layer in an A-B-A type multilayer film, with PFA as the "A" layer providing good adhesion to smooth, washed, wrought-copper.
  • PFA as the "A” layer providing good adhesion to smooth, washed, wrought-copper.
  • the use of materials such as poly(phenylene sulfide) is expected to greatly reduce material cost (due to the cheapness of these materials) without significantly adversely affecting the electrical performance or mechanical strength of the finished laminate.
  • FEP or filled FEP can be utilized as the "B" layer in an A-B-A type multilayer polymer film.
  • TEFZEL 500LZ poly(ethylene-co- tetrafluoroethylene) from E. I. du Pont de Nemours and Company was compounded with fumed silica in the weight ratio 30 parts silica to 70 parts polymer, using a twin screw extruder operating at 680°F, and practicing well-known compounding extrusion techniques. The extrudate was pelletized then dried in a hopper dryer for 24 hours at 350°F. Sheets of the silica filled TEFZEL were formed by using well-known compression molding techniques. A sheet of this material, approximately 3 mils thick was placed between two 1.0 mil thick sheets of pure TEFLON PFA 340 or 350.
  • This three layer assembly was placed between two sheets of "1-ounce" smooth, untreated, wrought-copper foil.
  • the resulting five layer assembly was placed in a molding press and soaked at a temperature of 680°F for 600 seconds at a pressure of 30 psig. The pressure in the mold was then increased to 2100 psig and held for 60 seconds. The press was then opened, and the laminated assembly was removed and allowed to cool to room temperature. The resulting laminate was masked, etched, and peeled according to the above-referenced IPC test, yielding a peel strength of greater than 5 pounds per inch.
  • Sheets of pure polynorbornene (NORSOREX N from CdF Chemie S.A.) were formed by using well-known compression molding or cast-film extrusion techniques. A sheet of this material, approximately 5 mils thick, was placed between two sheets of "1-ounce", smooth, untreated, wrought-copper foil. The resulting assembly was placed in a molding press and soaked at a temperature of 520°F for 300 seconds at a pressure of 30 psig. The pressure in the mold was then increased to 2100 psig and held for 30 seconds. The press was then opened, the laminated assembly was removed and allowed to cool to room temperature. The resulting laminate was masked, etched, and peeled according to the above-referenced IPC test, yielding a peel strength of greater than 2 pounds per inch.
  • Sheets of pure polyarylsulfone (RADEL A-400 from Amoco Chemical) were formed by using well-known compression molding or cast-film extrusion techniques. A sheet of this material, approximately 5 mils thick, was placed between two sheets of "1-ounce", smooth, untreated, wrought-copper foil. The resulting assembly was placed in a molding press and soaked at a temperature of 700°F for 300 seconds at a pressure of 30 psig. The pressure in the mold was then increased to 1860 psig and held for 30 seconds. The press was then opened, the laminated assembly was removed and allowed to cool to room temperature. The resulting laminate was masked, etched, and peeled according to the above-referenced IPC test, yielding a peel strength of greater than 2 pounds per inch.
  • RADEL A-400 from Amoco Chemical
  • TEFLON PFA, TEFLON FEP, TEFZEL, polynorbornene, syndiotactic 1,2-polybutadiene, and liquid crystal polyarylesters are thermoplastics with excellent adhesion to untreated copper-wrought foil. Since there is essentially no surface roughness on the copper foil, the present inventors speculate that the adhesion mechanism must be chemical in nature and not merely a mechanical bonding.
  • thermosetting resins such as epoxy and bismaleimide
  • PTFE and conventional high performance thermosetting resins exhibit poorer adhesion to smooth, wrought-copper, see COMPARATIVE EXAMPLES A through C which follow.
  • Skived sheets of pure TEFLON-PTFE (a product of E. I. du Pont de Nemours and Company) were purchased from a commercial supplier. A sheet of this material, approximately 3 mils thick, was placed between two sheets of "1-ounce" smooth, untreated, wrought-copper foil. The resulting assembly was placed in a molding press and soaked at a temperature of 700°F for 300 seconds at a pressure of 30 psig. The pressure in the mold was then increased to 2100 psig and held for 30 seconds. The press was then opened, the laminated assembly was removed and allowed to cool to room temperature. The resulting laminate was masked, etched, and peeled according to the above-referenced IPC test, yielding a peel strength of less than 1 pound per inch .
  • Skived sheets of pure TEFLON-PTFE (a product of E. I. du Pont de Nemours and Company) were purchased from a commercial supplier. A sheet of this material, approximately 3 mils thick, was placed between two sheets of "1-ounce" smooth, untreated, wrought-copper foil. The resulting assembly was placed in a molding press and soaked at a temperature of 700°F for 300 seconds at a pressure of 30 psig. The pressure in the mold was then increased to 2100 psig and held for 30 seconds. The press was then opened, the laminated assembly was removed and allowed to cool to room temperature. The resulting laminate was masked, etched, and peeled according to the above-referenced IPC test, yielding a peel strength of less than 1 pound per inch. COMPARATIVE EXAMPLE B
  • EPON 828 diglycidalether bisphenolacetone epoxy resin from Shell Oil Company was mixed with TETA (triethylenetetraamine in the ratio of 11 parts epoxy to 1 part TETA). This mixture was applied in a thickness of 0.005" to a sheet of "1-ounce" smooth, untreated, wrought-copper foil, using a doctor blade applicator. A second sheet of copper foil was laid on top of the epoxy mixture and the whole assembly was cured in a press at 160°C for 3 hours under 5 psig pressure. The press was then opened, the laminated assembly was removed and allowed to cool to room temperature. The resulting laminate was masked, etched and peeled according to the above-referenced IPC test, yielding a peel strength of less than 0.8 pounds per inch.
  • KERIMIDE 1050 bismaleimide resin from Rhone-Poulenc was mixed with Curethane (methylenedianiline) in the ratio of 2 parts Kerimide to 1 part Curethane.
  • the mixture was dissolved in N-methylpyrrolidone to make a 50 weight percent solution.
  • the solution was applied in a thickness of 0.005" to a sheet of "1-ounce" smooth, untreated, wrought-copper foil, using a doctor blade applicator and heated in a vacuum oven at 60°C for 12 hours to flash the solvent.
  • a second sheet of copper foil was laid on top of the resin mixture and the whole assembly was cured in a press at 270°C for 4 hours under 5 Psig pressure. The press was then opened, the laminated assembly was removed and allowed to cool to room temperature.
  • the resulting laminate was masked, etched, and peeled according to the above-referenced IPC test, yielding a peel strength less than 0.6 pounds per inch.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)

Abstract

Laminés de polymère/métal ainsi qu'un procédé de fabrication utilisant un métal ouvré, lisse, non traité conférant au laminé obtenu des caractéristiques de résistance à la cohésion et à l'adhésion.
EP19880907970 1987-08-20 1988-08-18 Novel polymer/metal laminate and method for fabrication thereof Withdrawn EP0379514A4 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US87195 1979-10-22
US07/087,195 US4833022A (en) 1987-08-20 1987-08-20 Polymer/copper laminate and method for fabrication thereof
US8792587A 1987-08-21 1987-08-21
US87925 1987-08-21

Publications (2)

Publication Number Publication Date
EP0379514A1 true EP0379514A1 (fr) 1990-08-01
EP0379514A4 EP0379514A4 (en) 1991-01-30

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EP (1) EP0379514A4 (fr)
JP (1) JPH02502804A (fr)
WO (1) WO1989001407A1 (fr)

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NL9002406A (nl) * 1990-06-27 1992-01-16 Ferro Tech Werkwijze voor het verbinden van geemailleerde voorwerpen en het verkregen samenstel.
NL9002022A (nl) * 1990-09-14 1992-04-01 Hoogovens Groep Bv Werkwijze en inrichting voor het vervaardigen van een metaal-thermoplast-metaal laminaat, alsmede het aldus verkregen laminaat.
JP2939477B2 (ja) * 1994-08-16 1999-08-25 エイチエヌエイ・ホールディングス・インコーポレーテッド 液晶重合体−金属積層品および該積層品の製造法
JP4187270B2 (ja) * 1996-10-29 2008-11-26 日本ゼオン株式会社 変性熱可塑性ノルボルネン系重合体と架橋剤とを含んでなる架橋性重合体組成物
US6472082B2 (en) 1996-10-29 2002-10-29 Nippon Zeon Co., Ltd. Modified thermoplastic norbornene polymer and process for the production thereof
JP5286669B2 (ja) 2004-12-09 2013-09-11 旭硝子株式会社 プリント配線板用積層体
KR101214419B1 (ko) * 2004-12-20 2012-12-21 아사히 가라스 가부시키가이샤 플렉시블 프린트 배선판용 적층체
JP5084722B2 (ja) * 2005-04-27 2012-11-28 ワールド・プロパティーズ・インコーポレイテッド 回路材料、回路およびこれらの作製方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3702788A (en) * 1971-03-05 1972-11-14 Minnesota Mining & Mfg Insulated electrical conductors coated with polyimide-amide modified polyimide
US4634631A (en) * 1985-07-15 1987-01-06 Rogers Corporation Flexible circuit laminate and method of making the same

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3676566A (en) * 1967-08-18 1972-07-11 Du Pont Laminar structures of polyimide and fluorocarbon polymers
JPS55123626A (en) * 1979-03-19 1980-09-24 Fujitsu Ltd Production of copper-plated laminate
US4313996A (en) * 1979-05-21 1982-02-02 The Dow Chemical Company Formable metal-plastic-metal structural laminates
JPS6037855B2 (ja) * 1981-09-30 1985-08-28 住友金属工業株式会社 スキツドマ−ク軽減装置
DE3221785C2 (de) * 1982-06-09 1986-10-23 Glyco-Metall-Werke Daelen & Loos Gmbh, 6200 Wiesbaden Schichtverbundwerkstoff mit metallischer Trägerschicht und Gleit- bzw. Reibschicht, sowie Verfahren zu seiner Herstellung
KR910009491B1 (en) * 1984-07-09 1991-11-19 Rogers Corp Flexible circuit lamination
JPS61199689A (ja) * 1985-03-01 1986-09-04 出光興産株式会社 プリント回路用基板

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3702788A (en) * 1971-03-05 1972-11-14 Minnesota Mining & Mfg Insulated electrical conductors coated with polyimide-amide modified polyimide
US4634631A (en) * 1985-07-15 1987-01-06 Rogers Corporation Flexible circuit laminate and method of making the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO8901407A1 *

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WO1989001407A1 (fr) 1989-02-23
EP0379514A4 (en) 1991-01-30
JPH02502804A (ja) 1990-09-06

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