JPH02502804A - Novel polymer/metal laminates and their manufacturing methods - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Novel polymer/metal laminates and their manufacturing methods Field of the invention The present invention relates generally to novel polymer/metal laminates and methods of making the same: More specifically, smooth, untreated, @kneaded 1il (rough-meta) l) and characterized by the cohesive and adhesive strength of the laminate layer. Regarding such laminate layers.

Background of the invention The production of polymer/metal laminates for use in microcircuits is rapidly evolving. This is a technological field that In this field, copper is used to impart St properties to the circuit. It is the metal of choice. In general, the prior art Polymer prior to laminate formation to increase physical adhesion between metals and/or pretreatment of the metal has been considered necessary. Typically, super Electrodeposited metal foils treated in the production of laminates for small circuits (generally referred to as “treated E”) D-foil) or treated wrought metal foil is used. these are For ED foil, 0.0002-0.0005inch depth, and wrought copper In the case of foil, the surface roughness is applied to the metal foil at a depth of o, oooi ~ 0, OOO 31 nch. It is formed from a treated metal foil that has been etched or etched. Inventor of the invention The adhesion efficiency for these various foils is It is believed to be based on the formation of slits and/or nodules on the surface.

In the past, adhesive strength and cohesive strength in polymer/metal laminates To increase this, attempts have been made to use separate adhesive layers or adhesion promoters. Examples and In the application GB2162124A published on January 29, 1986, , to improve the adhesion strength of fluoropolymer-coated polyimide to gold foil. The use of a robolimer/microglass adhesive film is disclosed. Konori, to.

P, gold li used for application! 4rA10 of the same specification, although the foil is not specified. ~ “Mechanical entanglement I J (IleChaniCal)” assumed in line 12 According to the theory of 1nter-10Ck), the metal surface at the polymer/metal interface is Pre-treatment to obtain roughness, which results in mechanical entanglement of the metal foil and polymer. It is suggested that it will be useful as II.

As an alternative or supplement to adhesion promoters or metal surface treatments, the prior art The bondability of the polymer that forms the Electrical discharge treatment of the surface of PEGI polymer could be used to bond to increase .

For example, 3,676.566 for U, S, P, has a laminate in column 5, lines 42-67. Electricity combined with polyalkyleneimine adhesion promoter to promote adhesion to The use of electrical discharge is disclosed.

All of the above treatments of metals and/or polymers are expensive and Laminate production time increases. Additionally, the use of adhesion promoters throughout the laminate Additional costs and separate costly processing steps in laminate production join. Therefore, there is no need to pre-treat the polymeric or polymeric surfaces, and separate adhesion Novel polymer/metal laminates and methods of making them that do not require accelerators are commercially available. This would be extremely desirable from a commercial standpoint.

Summary of the invention The present invention provides at least one layer of smooth, untreated, wrought metal and fluoroalkoko Sivinyl ether copolymer (E, 1. du Pont de Nemour It is a product of s & Co@pany, Inc. and has TEFLON PF eight. commercially available), perfluorinated poly(ethylene-copolyethylene) (E, 1. duPont de Nemours & Company, Inc., commercially available as TEFLON FEP), Polymer (Ethylene-cochdolafluoroethylene) (E, 1. (ILI Pon It is a product of T deNelOurS & co+1pany, Inc. commercially available as EFZEL), liquid crystal polyacrylic ester, Syndiota Cutic 1.2-polybutadiene, polyenamine, polycyanoarylethe RA, polyaryl sulfone (a product of Amoeo Chemical, RA commercially available as DEL), polynorbornene (cdr CheliB) It is a product of S, ^, and commercially available as N0RSOREX) and poly Polymer comprising at least one layer of a polymer selected from the group consisting of aryl ketones. Regarding metal/metal laminates.

In other embodiments, the invention provides smooth, untreated, wrought metal surfaces and bar-fluorinated metal surfaces. Acukoxy ether copolymer, perfluorinated poly(ethylene-copropylene) ), poly(ethylene-coated tetrafluoroethylene), liquid crystal polyarylene Stell, syndiotactic 1,2-polybutadiene, polyenamine, polysil Anoaryl ethers, polyarylsulfones, polynorbornenes and polyas to form a laminate with a polymer selected from the group consisting of Production of polymer/metal laminates consisting of contact under suitable lamination conditions Regarding the method.

In other embodiments, the invention provides a smooth, untreated, wrought steel surface and a layer of polymer. The polymer is thermoplastic and the polymer is thermoplastic. , and does not contain an adhesion promoter, and the method does not contain a polymer before or after lamination. Any electrical discharge (e.g. plasma, flame, corona or other electrical discharge) on the surface of the ) for polymer/copper laminates produced by the above method without pretreatment. do.

In yet other embodiments, the method provides a smooth, untreated, wrought steel surface and a surface electrical A single layer of polymer without pre-discharge treatment can be laminated with sufficient laminating strips to form a laminate. The present invention relates to a method of manufacturing a polymer/copper laminate by contacting under conditions.

These and other aspects will become apparent from reading the following detailed description of the invention. There will be.

Detailed description of the invention Akira A novel polymer characterized by excellent cohesion and adhesive strength of the polymer in /metal laminates. bound by any theory However, the inventors of the present invention have found that At least some of the polymer's excellent cohesive and adhesive strength in untreated wrought metal We speculate that this is due to the chemical adhesion efficiency of this selected group of polymers to the genus 1 Ru. Polymers generally have a double-layered toothpick between the copper/copper oxide surface and the polymer. It is well known that guiding dipole, hydrogen, coordination, ionic or covalent valence bonds can be used. be. The inventors believe that polymers useful in the present invention include epoxy compounds and polyimides. Assume that it does not depend primarily on hydrogen bonding. That is, these are Adhesives are less susceptible to moisture degradation, and their adhesive strength is higher than that of epoxy and polyamide resins. Bigger than fat.

Polymers useful in the present invention generally include crystalline metals, metal oxides or metals. Can form chemical bonds with the hydroxide surface layer. Preferably these chemical bonds In the case of dispersion, Van de Waals, hydrogen bond, ion, FMffl/key region, or covalent bond. More preferably, the bond is dipole- dipstick, ionic, coordination/chelation or covalent, most preferably These are ionic, covalent or coordination/chelation type bonds. Therefore, Preferred polymers have low hydroxyl content but high local dipole efficiency. do. These include functional groups capable of forming chelating, coordinating or ionic or covalent bonds. Functional groups or pendants can be incorporated.

In addition to this, the polymer is stable against oxidation or thermal degradation in the presence of metal ions. must be fixed.

This laminate ensures sufficient contact between the metal and polymer interfaces in the laminate. and bonding temperature, pressure and time to contact the polymer layer with the gold iam. Manufactured by

As is well known, adhesives are heat compressed at temperatures much higher than the TO or Tm of the polymer. obtained by The peel strength of the resulting adhesive layer depends on the lamination temperature and pressure. and the time of exposure to this pressure/temperature. Preferably the lamination temperature is The temperature is 5° to 50° C. higher than the glass transition temperature or melting point of the remer. even better Preferably 1, only the surface layer of the polymer melts, but the main body of the polymer remains solid or remains porous. Just below the glass transition temperature or melting point of the rimer. Most preferably during lamination About 5° to about 50°C below TQ or Tm until the polymer surface reaches a depth of about 1 to about 10μ while the body of the polymer substrate is maintained at an elevated temperature of about 5° below Tg or Tm. ~50°C lower temperature. Preferably, the lamination mixture is about 350T to about 800T. more preferably between about 500'F and about 800F. Lamination used The lamination pressure depends on the melt viscosity of the particular polymer selected and the lamination temperature used. Between about 1 and about 10° psig, more preferably between about 100 and about 5.0 psig. 000 psio, most preferably between about 300 and about 2.000 psig. be. The lamination time is preferably between about 0.01 and about 2.00 minutes. preferably between about 0.1 and about 0.5 minutes, most preferably between about 0.1 and about 0.2 minutes. Ru. To laminate, a single layer of copper and polymer is applied to the laminate as described herein. Contact is made under conditions, typically in a hot press. Alternatively, this pasting This can also be done by melt lamination using calender rolls or continuous belt lamination. can.

The metal used in the invention is generally steel, copper or aluminum, preferably Copper is a smooth, untreated, wrought metal. For example, smooth A4 foil generally has 1 It has a surface smoothness up to a depth of between ×10 and 50×1Q’Jnch.

One of the advantages of using smooth copper foil according to the present invention is that it imparts a roughened metal surface. Therefore, it is relatively inexpensive compared to the cost of obtaining treated foil. Additional benefits are , the smooth foil improves the electrical performance of the laminate.

The preferred metal utilized in the present invention, namely copper, is generally smooth, untreated, wrought steel and copper foil (generally less than 2Qmi1, preferably from about 25 to about 5 copper strip (generally having a thickness between about 10 and about 2011 ) and copper sheets (generally having a thickness of 1011 or more). Ru. As used herein, the term "untreated" means that the copper foil surface is Not subjected to roughening treatment (this has not been subjected to surface cleaning treatment or cleaning) ) used to mean something. This type of copper, when in foil form, is generally 1X10 It has a surface smoothness to a depth of between ~10 x 10-6 inches. present invention One of the advantages of using this type of foil is that it is treated to give it a rough surface. It is relatively inexpensive compared to the cost of obtaining foil.

The smooth, untreated, wrought copper foil was coated with MoCl3 ( methylene chloride) for 5 seconds and then air-dried. It has been found by the present invention that the peel strength of the laminate increases by 40 to 100% when Therefore, this treatment is considered significant. Cleaning with this solvent Traces of machine oil/grease in the surface particle structure of “rolled” (wrought) copper foil , thereby migrating these oils to the laminate layer interface and forming an adhesive layer. It is thought to prevent interference with Ultrasound in methylene chloride Cleaning improves adhesion by 30 layers more than cleaning by hand (gently stirring) .

Copper foil when used for lamination is between about 0.1 and about 20, O■11, and even Preferably between about 0.5 and about 10.0 ml, most preferably between about 1.0 and about 2.0 ml. A wide range of foil thicknesses between .011 and .011 can be had in each layer.

The polymer layer used in the present invention generally has the following functional properties: ( b) bonding the tA layers together, preferably by chemical bonding; (c) discontinuing between the copper layers; provide an edge dielectric barrier and maintain constant support and separation between the copper layers of the (02) layer. do. In addition to this, polymer layers are susceptible to attack by corrosive agents, especially water and air. It can protect the copper surface from scratches. Preferred polymers for use in the present invention - in order of decreasing degree of preference; perfluoroalkoxy vinyl ethers; Copolymer (E, 1.du Pont deNemours & Compa ny, Inc. and is commercially available as TEFLON PFA. ), perfluorinated poly(ethylene-fupropylene) (E, 1.du P ont deNelOurS & C01pan17. It is a product of Inc. , TEFLOI4 (commercially available as FEP), poly(ethylene-coated) Fluoroethylene) (E, 1. du Pont de Hemour It is a product of S&Compay, Inc. and is commercially available as TEFZEL. ), liquid crystal polyarylester (VECT, a product of Ce1anese) (commercially available as RA or XYDAR, a product of oartco), Syndiotactic 1,2-polybutadiene, polyenamine, polycyanoantide polyether, boaryaryl sulfone (＾■oco Chemical products) (commercially available as RADEL), polynorbornene (CdF It is a product of Cheiie S, A, and is commercially available as N03OREX. ), and boriyal ketones.

The above polymers have a wide range of monomer ratios, generally from 90 to 10 to 10 to 90 parts. It can be produced from a weight ratio of one monomer to another monomer.

The single layer of polymer in the laminate has a wide thickness range, preferably from about 0.5 to about 1 25 ml, more preferably about 0.5 to about 10.0 ml, most preferably Approximately 1.0 to approximately 5. It is possible to have a Quit period. Points for electronic industrial applications A particularly preferred range of reamer layer thickness is between about 50 and about 150 microns.

According to the present invention, good adhesion of the above polymers to smooth wrought copper is achieved in a separate manner. Achieved without the need for adhesive layers or polymer or metal processing steps .

Various additives can be incorporated into the polymers useful in the present invention. For example, additives Solid as described above and without damaging the polymer/copper adhesion properties relevant to this invention. Fillers, pigments, lubricants, antioxidants, etc. can be incorporated into the polymer. From this point of view , solid fillers are generally expected to interfere with the desired adhesion properties to copper foils. Therefore, it is preferable not to use it on the polymer surface that will come into contact with copper foil. for example If it is desired to use a filled polymer to provide dimensional stability, the polymer/ Preferably, an unfilled interlayer is used at the copper interface. From this point of view, it is added to the adhesive diagram. Additives, fillers, lubricants, plasticizers, stabilizers and coupling agents that are contained by the matrix and migrated to the metal-polymer interface, where the metal-polymer Remer weakens the adhesion layer or forms a weak boundary layer in the polymer adjacent to the interface. It is preferable to maintain sufficient immobility so that it does not occur.

In the case of filled laminates, if the filler amount is approximately up to the critical filling volume part of the filler, A minimum of 30 to 40% by weight is generally the size that does not adversely affect adhesion. It is expected that this is necessary for imparting stability.

Dosage stability or increase physical properties such as thermal I8 tensile modulus, or rBJ layer is used, and rA is used for its adhesion to smooth, untreated wrought foil. To minimize cost by using JB, a multi-IIA-B-A type polymer can be used.

The following examples are presented for illustrative purposes and do not limit the invention in any way. It's not something you do. In these examples, the polymer resin core is sheet extruded. The granules were manufactured from S+ fat granules using the well-known compression molding process. Various commercial polymers and methylene chloride cleaned (as described above) smooth, untreated, wrought copper. The laminate used was molded using a heat compression molding machine at the temperature, pressure, and time described in the example. Manufactured inside. with laminates manufactured as disclosed in these examples. The peel strength test conducted by orInterconnecting and Packaging Elec tronic C1rcuit (IPC) test method! 1Q2.4.9,Revis ion A, December 1982. In summary, this test is 1 ・ Shield the foil with a /8+nch wide strip, then etch the unshielded, exposed metal. consists of ching. Residual 1/8 inch wide metal/polymer laminate Attach the strip to the In5trOn test jig and peel off at a 90° angle. sample Record the force required to peel off the strip and calculate the lowest value per inch of strip width. Report as a force.

Examples 1-7 Manufacturing and Testing Example 1 of Various Polymer/Copper Laminates E.1. du Pont de He5ours and Company? Can be purchased from Le 0.005' FJg (7) 14+7) TEFLON PFA 340 full sheet of tO polymer film with two sheets of smooth, untreated wrought copper foil '1-0LInCe was placed between the J steel skin layers.The resulting assembly was Place in a mold press and infiltrate for 300 seconds at a temperature below 650 psio under a pressure of 235 psio (soak) The pressure in the mold was then increased to 2500 psio and 3 It was maintained for 0 seconds. Open the press, remove the laminated assembly, and empty Cooled to warm temperature. IPCH mentioned above! Shielding, etching and stripping according to I let go.

The peel strength obtained was 5 pounds per inch or more.

Example 2 E.1. du Pont de Nemours and Company? 0,005" thick pure TEFLON 100N fluoropolymer available from A sheet of rimmer film is rolled into two sheets of smooth, untreated wrought copper foil. e placed between the copper skin layers of J. Place the resulting assembly in a forming press , 235. Infiltrated for 300 seconds at a temperature of 675″F under a pressure of psig. The pressure in the mold was then increased to 1875 psio and held for 30 seconds. press was opened and the laminated assembly was removed and allowed to cool to air temperature. Obtained The laminate was shielded, etched and peeled according to the above IPC test, and 1i A peel strength of 5 pounds or more per nch was obtained.

Example 3 E.1. du Pont de Nemours and Company? Pure TEFZEL PE-TFE 500 with 0,005″ thickness available from LZ poly(ethylene-cochidrafluoroethylene) fluoropolymer film Smooth, untreated, forged sheet of II! Two pieces of copper foil "i-0unce J steel Placed between the layers. Place the resulting assembly in a forming press and press at 80 psi. Infiltration was carried out for 100 seconds at a temperature of below 650°C under a pressure of . Then the pressure in the mold was increased to 5 Increased to 60 psi and held for 30 seconds. Open the press and laminated The assembly was removed and allowed to cool to room temperature. , the resulting laminate was Shielded, etched and peeled according to PC test, 5 po per i nch A peel strength greater than or equal to und was obtained.

11■A Pure liquid crystal polyester (Ce1anese corp, Garano VECrRA) A 900 series) sheet was formed by a well-known compression molding method. Approximately 5 A sheet of this material with a thickness of -11 r of smooth, untreated, wrought foil It was placed between two skin layers of ounce J. The resulting assembly is molded in a press and soak for 300 seconds at a temperature of 640″F under a pressure of 30 psig. I let it see through. The pressure in the mold was then increased to 2100 pSig and held for 30 seconds. Ta. The press is then opened and the laminated assembly is removed and allowed to come to room temperature. Allowed to cool. The resulting laminate was screened and etched according to the above IPC test. After peeling, a peel strength of 5 pounds or more per inch was obtained.

K1■1 Pure syndiotactic 1,2-polybutadiene (Japan 5ynthe RB830 sheet from tic RLlbtler C0IIDanl/ Manufactured from granular resin using well-known compression molding or cast-film extrusion methods did. A sheet of this material with a thickness of about 5-11 mm is made of smooth, untreated, wrought steel foil. There was a W between the two r1-ounce JvA skin layers. 4+! The assets that were The assembly was placed in a molding press and heated at a temperature of 500°F under a pressure of 60 psi. It was allowed to penetrate for 00 seconds. The pressure in the entire mold was then increased to 1250 psi, and It was held for 30 seconds. Open the press, remove the laminated assembly, Allowed to cool to room temperature. The resulting laminate was screened according to the IPC test described above. , etching and peeling 2 per 11 nch, Peeling strength greater than Opound Sasa was obtained.

Example 6 E.1. From du pont de Ne1OurS and couany TEFLON PF＾350 or TEFLON PFA 340, purfle The oloalkoxyvinyl ether copolymer was run under 680 Using a single-screw extruder, 30 parts of silica 0 It was blended with fumed silica at a polymer fit ratio of 50%. Pelletize the extrudate , then dried in a hopper dryer under 350°C for 24 hours. well known A sheet of silica-filled TEFLON PFA was formed using a compression molding method. about A sheet of this material having a thickness of - Placed between Hnce J sheets. The resulting assembly was placed in a molding press. It was then infiltrated for 300 seconds at a temperature of 680°C under a pressure of 30pSig. in the mold Pressure was then increased to 1875 psio and held for 30 seconds. then The press was opened and the laminated assembly was removed and allowed to cool to room temperature. . The resulting laminate was screened, etched and stripped according to the IPc test described above. When separated, a peel strength of 3 points or more per inch was obtained.

Example 7 E.1. du Pont de Nemours and Company? TEFLON PF^350 or TEFLON PFA 340, perf fluoroalkoxyvinyl ether copolymer operated under 680 Using a twin-screw extruder, 30 parts of silicania was added by a well-known compound extrusion method. It was formulated with fumed silica at an ff1fi ratio of 0 parts of polymer. Pellet the extrudate and then dried in a hopper dryer under 350°C for 24 hours. well known A compression molding method was used to form sheets of silica-filled PFA. Thickness of about 311 A sheet of this material with pure TEFLON PFA 340 or 35 I placed it between the two sheets of 0 "l, 0 + il".

This 3-layer assembly with a thickness of approximately 511" , placed between two sheets of wrought copper foil.

The resulting 5-layer assembly was placed in a molding press and compressed under a pressure of 30 psig at 68 Infiltration was carried out for 600 seconds at a temperature below zero.

The pressure in the mold was then increased to 1875 psiO and held for 60 seconds.

Open the press, remove the laminated assembly and allow to cool to 'Jl. Ta. The resulting laminate was screened, etched and etched according to the above IPC test. A peel strength of 5 pounds or more per 1 nch was obtained.

Manufacturing and testing Poly(phenylene sulfide) will not adhere to smooth, cleaned wrought copper foil. However, as demonstrated in this example, it is in contact with the PFA. Therefore, smooth, PFA is used as the rAJ layer because it has good adhesion to cleaned i-wrought copper. Poly(phenylene sulfate) as rBJ inner layer in A-B-A type multilayer film ) can be used. Use of substances such as poly(phenylene sulfide) has a significant adverse effect on the electrical performance or mechanical strength of the finished laminate. Significant reductions in material costs (due to the low cost of these materials) are expected without any problems.

Consisting of approximately 30 parts glass to 70 parts polymer, Ph1llips Ch RYTON R3 obtained from chemical, glass-filled poly(phenylene resin) ruphide) was formed into sheets using well-known compression molding techniques. Thickness of about 311 The sheet of material is made of pure TEFLON 340 or 350 i,Q placed between mil thick sheets. This 3m is about 511 thick! assembly , r 1-0LlnCe J smooth, untreated, wrought - between two sheets of copper foil I placed it on.

The resulting 5-layer assembly was placed in a molding press and heated at 68° C. under a pressure of 3° psig. Infiltration was carried out for 600 seconds at a temperature below zero.

The pressure in the mold was then increased to 1875+) Sill and held for 60 seconds. I held it. Open the press, remove the laminated assembly and cool to room temperature. I let it happen. The resulting laminate was screened, etched and etched according to the above IPC test. A peel strength of 5 points or more per 11 nch was obtained.

As a particular example (see Example 9), PFA adheres to FEP and thus or [rBJ in A-B-A type multilayer polymer film filled with FEPJ 1 Prove that it can be used as m.

E.1. Du Pant de Ne1ours and Company? TEFZEL500 LZ, poly(ethylene-cochidrafluoroethylene) using a twin-screw extruder operated at 680 °C and using well-known compounding methods. and blended with fumed silica in a 1 m ratio of 30 parts of silicania and 0 parts of polymer. . The extrudate was pelletized and then dried in a hopper dryer under 350 Let dry for an hour. By using well-known compression molding techniques, silica-filled [TEF] A ZEL sheet was formed. A sheet of this material approximately 311 mm thick is made of pure TE It was placed between two 1.011 thick sheets of FLON 340 or 350.

This 31 is about 511 thick! The assembly is "i-QnuCe J's plain, Placed between two sheets of untreated, wrought copper foil. The resulting five-layer assembly was Place in a mold press and infiltrate for 600 seconds at a temperature below 680°C under a pressure of 30 psig. I let it happen. The pressure in the mold was then increased to 2100 Dsig and held for 60 seconds. . The press is then opened and the laminated assembly is removed and allowed to cool to room temperature. I made him reject it. The resulting laminate was subjected to side L etching according to the IPc test described. After peeling, a peel strength of 5 DOounds or more per 1 nch was obtained.

Examples 10-11 Other polymers/Ii! Laminate 1 Example 10 By using well-known compression molding or cast-film extrusion techniques, pure N0R3OREX from polynorbornene (CdFChemie S, A, A sheet of 14) was manufactured.

A sheet of this material approximately 511 mm thick was cut into a smooth, untreated, It was placed between two sheets of wrought steel foil.

The resulting assembly was placed in a forming press at 30 psi.

Infiltration was carried out for 300 seconds at a pressure of 520°C and a temperature of 520°C. The pressure in the mold was then increased to 2 Increased to 100 psia and held for 30 seconds. Then open the press and laminate The heated assembly was removed and allowed to cool to room temperature. The resulting laminate , per 11 nCh after shielding, etching and peeling according to the above IPC test. A peel strength of 2 pounds or more was obtained.

Example 11 pure by using well-known compression molding or cast-film extrusion methods. Polyaryl sulfone (RADEL A from Ag+oco Chemical -400) sheet was formed. A sheet of this material approximately 511 mm thick is called "1-o placed between two sheets of smooth, untreated, wrought-copper foil. Obtained The assembled assembly was placed in a molding press and subjected to 700 psig under a pressure of 30 psig. Infiltration was carried out for 300 seconds at temperature. The pressure in the mold was then increased to 1860 psi.

and held for 30 seconds. Then the press is opened and the laminated The assembled assembly was removed and allowed to cool to room temperature. The resulting laminate was According to IPC test, shielded, etched and peeled to 2po per 1nch. A peel strength greater than or equal to und was obtained.

Thus, according to the present invention, TEFLON PFA, TEFLON FEP , TEFZEL, polynorbornene, syndiotactic 1,2-polybutadiene Polyester and liquid crystalline boary aryl esters exhibit excellent adhesion to untreated wrought copper foil. It is a thermoplastic material with strength. There is essentially no surface roughness on copper foil. , the inventors believe that the contact mechanism is of chemical nature and is not simply a mechanical bond. I'm guessing that.

In contrast, conventional materials such as PTFE and epoxies and bismaleimides High Performance Thermoset Resins Show Poor Adhesion to Smooth Wrought Copper, Following Comparison See Examples AC.

Example 12 Pure (DTEFLON-PTFE (E, 1 du Pont de Nemo urs and (oa+pany product) skived sheet was purchased from a commercial supplier. A sheet of this material with a thickness of about 311 r ounce J of smooth, untreated, wrought-copper foil. profit The assembled assembly was placed in a forming press and under a pressure of 30 DS+Q, 7 Infiltration was carried out for 300 seconds at a temperature below 0.00. Next, the pressure in the t1 mold was increased to 2100 psig and held for 30 seconds.

The press is then opened and the laminated assembly is removed and allowed to cool to room temperature. I made him reject it. The obtained laminate was shielded and etched according to the above PC test. After peeling, a peel strength of less than 1 pound per 1 inch channel was obtained.

Comparative example Pure TEFLON - PI and thermoset polymer/copper laminate FE (E, 1. du Pont de Ne1ours andcoi+ Dany's Skybutt sheet was purchased from a commercial supplier. Approximately 31 A sheet of this material with a thickness of It was placed between two sheets of wrought steel foil. Place the resulting assembly in a forming press. It was then infiltrated for 300 seconds at a pressure of 30 psio and a temperature of below 700 psio. Next The pressure in the mold was then increased to 2100 psig and held for 30 seconds.

The press is then opened and the laminated assembly is removed and allowed to cool to room temperature. I let it happen. The resulting laminate was screened, etched and etched according to the above IPC test. and I11 separation, and a peel strength of 1 pointl per 11 nch was obtained.

Comparative example B Epoxy Tree II T-Al EPO from Shell O’il Company N828 (diglycidyl ether bisphenol lactone) was added to 11 parts of Epoxy Mixed with TETA (triethylenetetramine) in a ratio of xylene: 1 part TETA.

Apply this mixture to a 0.005” thick applicator using a doctor blade applicator. It was applied to a sheet of clear, untreated ri-wrought copper foil of 1-ounce J.

Place a second sheet of copper foil on top of the epoxy mixture and heat the entire assembly to 5 psi. It was cured in a press at 160° C. for 3 hours under a pressure of 1.3 g. Then open the press The laminated assembly was removed and allowed to cool to room temperature. obtained The laminate was screened, etched and peeled according to the IPC test described above. A peel strength of less than 0.8 pOund per inch was obtained.

Comparative example C ERIHIDElo 50 Bismaleimi from Rhone-Pou 1enc Cu resin in a ratio of 2 parts Kerilide: 1 part curethane. mixed with retianct (methylene dianiline). The mixture was diluted with N-methylpi A 50% w/w solution was prepared by dissolving in Lolidone. Apply this solution with a doctor blade. 1-ounce J smooth, untreated, wrought-copper using a door applicator applied to foil to a thickness of 0.005” and heated in a vacuum oven at 60°C for 12 hours. The solvent was expelled. Place a second sheet of copper foil on top of the t’lW8 mixture and The assembly was heated in a press at 60°C for 4 hours under a pressure of 5 psio. Ta. The press is then opened and the laminated assembly is removed and allowed to come to room temperature. Allowed to cool. The resulting laminate was screened and etched according to the above IPC test. and peeling to obtain a peel strength of less than Q, 5 pounds per 1 nch. It was.

Procedural amendment (voluntary) March 22, 1990

Claims (26)

[Claims] 1. At least one layer of smooth, untreated, wrought metal and perfluoroalkoko Cyvinyl ether copolymer, perfluorinated poly(ethylene-copropylene) ), poly(ethylene-coated tetrafluoroethylene), liquid crystal polyarylester syndiotactic 1,2-polybutadiene, polyenamine, polycyano Aryl ethers, polyarylsulfones, polynorbornenes and polyaryls characterized by comprising at least one layer of a polymer selected from the group consisting of Polymer/metal laminate. 2. the polymer has a weight ratio of monomers between 90:10 and 10:90 The laminate of claim 1 which is a copolymer comprising: 3. The smooth, untreated, wrought metal has a thickness of between about 25 and about 50 microns. A laminate according to claim 1. 4. 5. The layer of polymer has a thickness of between about 50 and about 150 microns. Lamination of item 1. 5. The layer of polymer is free of filler on the surface, but the layer of water remer is free of filler. 2. A laminate according to claim 1, further comprising a filler in the inner part of the layer. 6. The filler may be fumed SiO2, glass fiber, ceramic particles, foil, etc. Claim 5 selected from the group consisting of fibers on scars and polyaramid fibers. Laminate of sections. 7. Smooth, untreated, wrought metal surface and barfluoroalkoxy vinyl ether copolymers, perfluorinated poly(ethylene-copropylene), poly(ethylene-copropylene), (Ren-cotetrafluoroethylene), liquid crystal polyarylester, syndiota Cutic 1,2-polybutadiene, polyenamine, polycyanoarylethe polyaryl sulfone, polynorbornene and polyaryl ketone. under lamination conditions sufficient to form a laminate. A method for producing a polymer/metal laminate, characterized in that the polymer/metal laminate is contacted at 8. The above polymer is PFA, liquid crystal polyester, in the range of 10:90 to 40:60. A copolymer of ethylene and tetrafluoroethylene with a molar ratio of PE:TFE of claim 1 selected from the group consisting of remer, FEP and 1,2-polybutadiene. Method of Section 7. 9. 3. The smooth, wrought metal having a thickness of between about 25 and about 50 microns. The method in Box 7. 10. Said polymer layer is free of filler at said surface but in front of said polymer. 8. The method of claim 7, further comprising a filler in the interior portion of said layer. 11. The above-mentioned filler can be used as fumed SiO2, glass fiber, ceramic particles, or The person according to claim 10 selected from the group consisting of fibers on chairs and polyamide fibers. Law. 12. Claims wherein said contacting is performed at a temperature between about 350°F and about 800°F. Method of Section 7. 13. Claims wherein said contacting is performed at a pressure between about 1 and about 10,000 psig. The method in Box 7. 14. Under bonding conditions, a smooth, untreated, wrought copper surface and a polymer layer surface are bonded together. A polymer/copper laminate produced by a method consisting of contacting wherein said polymer is thermoplastic and does not contain an adhesion promoter; Any electrical discharge pre-treatment to said surface of said layer of polymer before or during lamination. The polymer/copper laminate described above is characterized in that it does not contain any minerals. 15. The polymer is a perfluoroalkoxy vinyl ether copolymer, Perfluorinated poly(ethylene-copropyrene), poly(ethylene-coated) (fluoroethylene), liquid crystal polyarylester, syndiotactic 1,2 -Polybutadiene, polyenamine, polycyanoaryl ether, polyaryl selected from the group consisting of rusulfone, polynorbornene and polyaryl ketone. A laminate according to claim 14. 16. 12. The smooth wrought copper has a thickness of between about 25 and about 50 microns. Section 14 Lamination. 17. 10. The polymeric layer of claim 1, wherein said layer of polymer has a thickness of between about 50 and about 150 microns. Laminate of item 14. 18. a layer of said polymer is free of filler on said surface, but A laminate according to claim 14 additionally containing a filler in the inner part of the layer of mer. to. 19. The filler may be fumed SiO2, glass fiber, ceramic particles, or fiber. fibers, particles, fumed SiO2 whiskers and beads, glass, ceramics 19. The laminate of claim 18 selected from the group consisting of . 20. Smooth, untreated, wrought copper surfaces and ports without any surface discharge pretreatment. The rimer layer is brought into contact with the laminate under lamination conditions sufficient to form a laminate. A method for manufacturing a polymer/copper laminate. 21. The above polymer can be converted into a barfluoroalkoxyether copolymer, a barf Fluorinated poly(ethylene-copropylene), poly(ethylene-coated trifluoride) (oroethylene), liquid crystal polyarylester, syndiotactic 1,2-poly Butadiene, polyenamine, polycyanoaryl ether, polyaryl sulfur Claims selected from the group consisting of polynorbornene, polynorbornene and polyaryl ketone. The method of Box 20. 22. 2. The smooth, wrought copper having a thickness of between about 25 and about 50 microns. The method of Box 20. 23. Although said polymer layer is free of filler at said surface, said polymer 21. The method of claim 20, wherein the inner portion of the layer additionally contains a filler. 24. The above-mentioned fillers can be added to fumed SiO2, glass fibers, ceramic particles, fibers, etc. fibers, particles, fumed SiO2 whiskers and beads, glass, ceramics 24. The method of claim 23, wherein the material is selected from the group consisting of carbon fibers and polyaramids. 25. Claims wherein said contacting is performed at a temperature between about 350°F and about 800°F. The method of Section 20. 26. Claims wherein said contacting is performed at a pressure between about 1 and about 10,000 psig. The method of Box 20.