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WO1999057949A1 - Couche intermediaire pour ameliorer la resistance au pelage de feuilles de cuivre - Google Patents

Couche intermediaire pour ameliorer la resistance au pelage de feuilles de cuivre Download PDF

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Publication number
WO1999057949A1
WO1999057949A1 PCT/US1999/009551 US9909551W WO9957949A1 WO 1999057949 A1 WO1999057949 A1 WO 1999057949A1 US 9909551 W US9909551 W US 9909551W WO 9957949 A1 WO9957949 A1 WO 9957949A1
Authority
WO
WIPO (PCT)
Prior art keywords
laminate
peel strength
copper foil
organic resin
copper
Prior art date
Application number
PCT/US1999/009551
Other languages
English (en)
Inventor
Eric L. Holman
Original Assignee
Alliedsignal Inc.
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 Alliedsignal Inc. filed Critical Alliedsignal Inc.
Priority to EP99920252A priority Critical patent/EP1004227A1/fr
Priority to CA002298684A priority patent/CA2298684A1/fr
Publication of WO1999057949A1 publication Critical patent/WO1999057949A1/fr

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
    • B32B15/20—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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • 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
    • 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
    • H05K2201/0358—Resin coated copper [RCC]
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0756—Uses of liquids, e.g. rinsing, coating, dissolving
    • H05K2203/0759—Forming a polymer layer by liquid coating, e.g. a non-metallic protective coating or an organic bonding layer

Definitions

  • the circuitry board has a low dielectric constant (Dk) and a high glass transition temperature (Tg) .
  • Dk dielectric constant
  • Tg glass transition temperature
  • Peel strength refers to the strength of adhesion of coated copper layers to a circuit board substrate and high peel strength is generally desirable. Peel strength may be even more severely reduced when low or very low profile copper foils are employed.
  • low or very low profile copper foils are critical to the success of circuit board laminates for use in very dense circuit ⁇ esigns.
  • One form of adhesive that is sometimes used to and in bonding of resin to foil is to first coat the foil with a layer of uncured liquid resin itself which is intended to assist an integrating the foil to the laminate. Often such upper foils are coated with silane, which is believed to aid adhesion.
  • U.S. Patents 5,525,433 and 5,629,433 describe some multifunctional epoxy compounds which can be used to attach foils to a laminate pre-preg.
  • the present invention is a method of manufacturing a copper-clad laminate having enhanced peel strength comprising the step of applying an organic resin coating selected from the group consisting of high molecular weight epoxy or phenoxy resins or combinations thereof to a surface of a copper foil and laminating the copper foil to a low Dk laminate.
  • the present invention is also a copper-clad laminate made by applying an organic resin coating to a surface of a copper foil and laminating the copper foil to a laminate, the organic resin selected from the group consisting of epoxy or phenoxy resins or combinations thereof. It is an object of the present invention to provide a copper-clad laminate having a low dielectric constant, a high glass transition temperature, and a peel strength that meets industry standards . Other objects, advantages, and features of the present invention will become apparent after review of the specification and drawings.
  • Fig. 1 is a plot of peel values (pli) of copper-clad laminate after thermal stress conditioning as a function of the number average molecular weight (Mn) of the organic resin coating applied to the copper foil prior to lamination.
  • the present invention is a method of manufacturing a low Dk, high Tg copper-clad laminate having enhanced peel strength comprising the step of applying a high molecular weight organic resin coating to a surface of the copper foil prior to lamination.
  • the present invention is also directed to the laminate materials and circuit boards made using this method.
  • the organic resin coating for use within the present invention is preferably an uncured epoxy or phenoxy resin, or combinations thereof, having an average molecular weight greater than 4500. It has been found that high molecular weight epoxy and phenoxy compounds provided greater peel strength for low Dk and high Tg boards than other adhesives of lower molecular weight .
  • enhanced peel strength it is meant that the peel strength after thermal stress conditioning exceeds the peel strength of a control laminate in which lamination occurs without applying an organic resin coating to a surface of the copper foil prior to lamination.
  • the peel strength is enhanced at least about 100% greater than the peel strength of a comparable laminate lacking the organic resin coating on the copper film. Determining the peel strength of a laminate by standard methods is well within the ability of one of ordinary skill in the art.
  • peel strength is affected by numerous factors, including the dielectric constant (Dk) and glass transition temperature (Tg) of the laminate, the profile of the copper foil, the number average molecular weight (Mn) of the organic resin coating on the copper foil, and the thickness of the organic resin coating applied.
  • Dk dielectric constant
  • Tg glass transition temperature
  • Mn number average molecular weight
  • Fig 1 the number average molecular weight of the organic resin coating on the copper foil
  • peel strength For a particular laminate and foil, there exists a direct linear relationship between peel strength and Mn of the organic resin employed (Fig 1) .
  • a laminate product having a low Dk and a high Tg e.g., AlliedSignal Laminate Systems product FR408
  • a very low profile copper foil e.g. AlliedSignal Oak-Mitsui 1 oz .
  • a laminate having a low Dk and a high Tg it is meant a laminate having a Dk of less than about 4.5 and a Tg of greater than about 170°C.
  • the Dk value of the fiberglass and the impregnating resin are different and thus the Dk depends on the resin content of the laminate.
  • Low Dk laminates generally have Dk values between 2.5 and 4.5 and preferably between 3.0 and 4.0. These values may be measured using a Hewlett Packard Materials/Impedance Analyzer, Model 4291A, operating at 100 MH Z .
  • the peel strength increases with the treatment thickness of the organic resin applied to the copper foil prior to lamination.
  • the minimum treatment thickness required to achieve a particular peel strength may vary depending on the laminate, the copper foil, and the organic resin.
  • the preferred range of thickness of this organic resin is between .05 mils and .50 mils, with the most preferred being .08 to .16 mils. However, it is well within the ability of one of ordinary skill in the art to determine the minimum treatment thickness required for a particular selection of starting materials.
  • the copper-clad laminates described in the examples were prepared by applying the organic resin to the copper foil prior to lamination, it is anticipated that the organic resin could be applied to the laminate prior to lamination of the copper foil. It is also specifically envisioned that copper foils can be pre-treated with the organic resin and stored until needed for lamination. What is important is simply the use of the organic resin to bind the copper foil to the laminate material.
  • the examples below describe a method for manufacturing a copper clad laminate having a high peel strength using commercial epoxy or phenoxy products obtained from Phenoxy Specialties or Ciba-Geigy as the organic resin. It is expected that any epoxy or phenoxy resin could be employed in the practice of the present invention, provided that the resin has a sufficiently high number average molecular number. It is reasonably anticipated that any polymer that has a sufficiently high molecular weight and which is reactive toward epoxy resins or epoxy curatives could be used in the practice of the present invention.
  • a copper-clad laminate was made by laminating, 2 plies of 7628- (41% resin content) (.014 inches) and AlliedSignal Oak-Mitsui 1 oz . MLS (reverse-treated, coated, very low profile) copper foil
  • a plot of Mn versus peel strength for these resins shows a positive linear relationship between the Mn of the organic resin and peel strength (Fig. 1) .
  • the plot indicates that when employing the FR408 laminate product or an equivalent and a standard HTE-1 oz . foil, the resin must have a Mn of at least about 4500 to meet the MIL-S-13949 specification of 8.0 pli.
  • PKHS-40 phenoxy resin solution was diluted to various levels of solids content and brush applied to produce different dry film thickness levels on the copper foil substrate (CircuitFoils standard profile NTTW-HTE-l/2 oz . ) to evaluate the effect of treatment thickness on peel strength of copper- clad FR408 laminates.
  • the treatment thickness was determined using a Veeco MP-900 B-Backscatter thickness measuring unit. The results indicate a minimum thickness requirement at or about 0.1 mils in order to obtain significant improvement in peel strength (Table 3) .
  • the preferred range is 0.5 -.5 mils, thus minimizing any increase in thickness caused by the adhesive while supplying adequate strength, with the most preferred thickness being .08 to .16 mils.
  • the best practice to date for manufacturing the treated foil product on a large scale consists of reverse roll coating foils as supplied from the foil manufacturer.
  • any process method of coating may be employed as long as the resultant coating thickness is in the desired range.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

L'invention porte sur un procédé permettant d'obtenir, au moyen d'un composé intermédiaire de résine organique, une meilleure adhérence ou résistance au pelage entre des feuilles de cuivre et un laminé de carte de circuit présentant un diélectrique faible et une température de transition du verre élevée. On préfère des résines époxy et phénoxy dont le poids moléculaire moyen dépasse 4500 pour pouvoir accroître la résistance au pelage des matériaux laminés à faible diélectrique des cartes de circuit.
PCT/US1999/009551 1998-05-01 1999-04-29 Couche intermediaire pour ameliorer la resistance au pelage de feuilles de cuivre WO1999057949A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP99920252A EP1004227A1 (fr) 1998-05-01 1999-04-29 Couche intermediaire pour ameliorer la resistance au pelage de feuilles de cuivre
CA002298684A CA2298684A1 (fr) 1998-05-01 1999-04-29 Couche intermediaire pour ameliorer la resistance au pelage de feuilles de cuivre

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7124498A 1998-05-01 1998-05-01
US09/071,244 1998-05-01

Publications (1)

Publication Number Publication Date
WO1999057949A1 true WO1999057949A1 (fr) 1999-11-11

Family

ID=22100156

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/009551 WO1999057949A1 (fr) 1998-05-01 1999-04-29 Couche intermediaire pour ameliorer la resistance au pelage de feuilles de cuivre

Country Status (4)

Country Link
EP (1) EP1004227A1 (fr)
CA (1) CA2298684A1 (fr)
TW (1) TW486430B (fr)
WO (1) WO1999057949A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6395378B2 (en) 2000-01-14 2002-05-28 Telefonaktiebolaget Lm Ericsson PCB and method for making PCB with thin copper layer
US6811917B2 (en) 2000-08-14 2004-11-02 World Properties, Inc. Thermosetting composition for electrochemical cell components and methods of making thereof
US7138203B2 (en) 2001-01-19 2006-11-21 World Properties, Inc. Apparatus and method of manufacture of electrochemical cell components
US8257820B2 (en) 2006-08-08 2012-09-04 World Properties, Inc. Circuit materials with improved bond, method of manufacture thereof, and articles formed therefrom
US8431222B2 (en) 2006-08-08 2013-04-30 World Properties, Inc. Circuit materials with improved bond, method of manufacture thereof, and articles formed therefrom
US8632874B2 (en) 2006-08-08 2014-01-21 Rogers Corporation Dielectric materials, methods of forming subassemblies therefrom, and the subassemblies formed therewith

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873637A (en) * 1973-02-23 1975-03-25 Sony Corp Adhesive composition containing phenoxy and epoxy resins and a cross-linking agent therefor
EP0227002A1 (fr) * 1985-12-20 1987-07-01 Advanced Interconnection Technology, Inc. Adhésifs activables par la chaleur pour circuits imprimés
US5486655A (en) * 1992-08-17 1996-01-23 Hitachi Chemical Co., Ltd. Multiple wire adhesive on a multiple wire wiring board

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873637A (en) * 1973-02-23 1975-03-25 Sony Corp Adhesive composition containing phenoxy and epoxy resins and a cross-linking agent therefor
EP0227002A1 (fr) * 1985-12-20 1987-07-01 Advanced Interconnection Technology, Inc. Adhésifs activables par la chaleur pour circuits imprimés
US5486655A (en) * 1992-08-17 1996-01-23 Hitachi Chemical Co., Ltd. Multiple wire adhesive on a multiple wire wiring board

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6395378B2 (en) 2000-01-14 2002-05-28 Telefonaktiebolaget Lm Ericsson PCB and method for making PCB with thin copper layer
US6811917B2 (en) 2000-08-14 2004-11-02 World Properties, Inc. Thermosetting composition for electrochemical cell components and methods of making thereof
US7138203B2 (en) 2001-01-19 2006-11-21 World Properties, Inc. Apparatus and method of manufacture of electrochemical cell components
US8257820B2 (en) 2006-08-08 2012-09-04 World Properties, Inc. Circuit materials with improved bond, method of manufacture thereof, and articles formed therefrom
US8431222B2 (en) 2006-08-08 2013-04-30 World Properties, Inc. Circuit materials with improved bond, method of manufacture thereof, and articles formed therefrom
US8632874B2 (en) 2006-08-08 2014-01-21 Rogers Corporation Dielectric materials, methods of forming subassemblies therefrom, and the subassemblies formed therewith
DE112007001861B4 (de) 2006-08-08 2022-08-11 World Properties, Inc. Schaltungsmaterial mit verbesserter Bindung, Verfahren zu dessen Herstellung und mehrschichtige Schaltung
US8519273B2 (en) 2008-04-10 2013-08-27 Sankar Paul Circuit materials with improved bond, method of manufacture thereof, and articles formed therefrom

Also Published As

Publication number Publication date
CA2298684A1 (fr) 1999-11-11
TW486430B (en) 2002-05-11
EP1004227A1 (fr) 2000-05-31

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