US20150336354A1 - Polyimide metal clad laminate - Google Patents

Polyimide metal clad laminate Download PDF

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Publication number
US20150336354A1
US20150336354A1 US14/410,115 US201314410115A US2015336354A1 US 20150336354 A1 US20150336354 A1 US 20150336354A1 US 201314410115 A US201314410115 A US 201314410115A US 2015336354 A1 US2015336354 A1 US 2015336354A1
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US
United States
Prior art keywords
polyimide
mole
electrically insulating
insulating layer
layer
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.)
Abandoned
Application number
US14/410,115
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English (en)
Inventor
Sidney G. Cox
Christopher Dennis Simone
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US14/410,115 priority Critical patent/US20150336354A1/en
Priority claimed from PCT/US2013/046936 external-priority patent/WO2013192469A1/en
Publication of US20150336354A1 publication Critical patent/US20150336354A1/en
Assigned to E. I. DU PONT DE NEMOURS AND COMPANY reassignment E. I. DU PONT DE NEMOURS AND COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SIMONE, CHRISTOPHER DENNIS, COX, G. SYDNEY
Abandoned legal-status Critical Current

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Classifications

    • 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
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
    • H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
    • H01B3/306—Polyimides or polyesterimides
    • 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
    • H05K1/0271—Arrangements for reducing stress or warp in rigid printed circuit boards, e.g. caused by loads, vibrations or differences in thermal expansion
    • 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
    • H05K1/0296—Conductive pattern lay-out details not covered by sub groups H05K1/02 - H05K1/0295
    • H05K1/0298—Multilayer circuits
    • 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
    • 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
    • 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
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/302—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • H05K2201/0154—Polyimide
    • 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
    • H05K2201/032—Materials
    • H05K2201/0323—Carbon
    • 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
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24851—Intermediate layer is discontinuous or differential
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/266—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension of base or substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]

Definitions

  • This disclosure relates generally to a polyimide metal clad laminate.
  • Metal clad laminates for circuit board construction are constructed by laminating a polyimide film to a metal foil with an adhesive layer in between.
  • the adhesive layer may consist of conventional adhesives (acrylates, epoxides, polyamides, phenolic resins, etc.) where the adhesive is cured during the metal foil lamination.
  • these conventional adhesives do not usually possess the high temperature heat stability of the base polyimide dielectric, and the strength of the adhesive bonds in the multiplayer laminate structure deteriorates rapidly when subjected to elevated temperatures. These adhesives also show high electric loss in high speed circuit layers due to the high loss tangent of these adhesives.
  • One means to an adhesiveless laminate is to coat a high modulus polyimide film core layer with a thin layer of polyamic acid precursor solution on both sides, dry this layer, and finally imidize the applied coating to create a thermoplastic polyimide. Copper foil is then laminated with heat and pressure to create a double sided copper clad laminate.
  • a polyimide precursor can also be coated directly onto copper foil and then cured to create a polyimide film with copper foil on one side.
  • This is a common method of making adhesiveless copper clad films but can create polyimide clads with copper on just one side.
  • Another method of making adhesiveless polyimide copper clad laminates is to start with a standard rigid polyimide base film. A thin metal layer is deposited, typically by sputtering or vapor deposition to improve adhesion between the metal and the polyimide. Then the copper is electroplated up to the required thickness to create a double sided copper clad laminate.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a method, process, article, or apparatus that comprises a list of elements is not necessarily limited only to those elements but may include other elements not expressly listed or inherent to such method, process, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • dianhydride as used herein is intended to include precursors, derivatives or analogs thereof, which may not technically be a dianhydride but would nevertheless react with a diamine to form a polyamic acid which could in turn be converted into a polyimide.
  • diamine as used herein is intended to include precursors, derivatives or analogs thereof, which may not technically be a diamine but would nevertheless react with a dianhydride to form a polyamic acid which could in turn be converted into a polyimide.
  • polyamic acid as used herein is intended to include any polyimide precursor material derived from a combination of dianhydride and diamine and capable of conversion to a polyimide.
  • film as used herein is intended to mean a free-standing film or a (self-supporting or non-self-supporting) coating.
  • film is used interchangeably with the term “layer”.
  • chemical conversion denotes the use of a catalyst (accelerator) or dehydrating agent (or both) to convert the polyamic acid to polyimide and is intended to include a partially chemically converted polyimide which is then dried at elevated temperatures to a solids level greater than 98%.
  • metal as used herein is intended to include elemental metals and metal alloys.
  • direct contact as used herein is intended to mean that layers are in contact with one another at their interface and an intervening layer, such as an adhesive layer, is not present.
  • Numerical values are to be understood to have the precision of the number of significant figures provided.
  • the number 1 shall be understood to encompass a range from 0.5 to 1.4
  • the number 1.0 shall be understood to encompass a range from 0.95 to 1.04, including the end points of the stated ranges. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.
  • thermoset polyimide film that can be directly adhered to metal and have good peel strength without the need for an additional adhesive layer.
  • Good peel strength, for a metal clad laminate for the purpose of this disclosure is at least 1 N/mm.
  • Good peel strength for a coverlay or a bondply is 0.7 to 2 N/mm.
  • a polyimide film (polyimide layer or polyimide coverlay or polyimide bondply or electrically insulating layer) comprises a polyimide derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 20 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 80 mole % 4,4′-oxydianiline and is capable of directly adhering to metal and other polymers at lamination temperatures from 300 to 380° C.
  • a polyimide film (polyimide layer or polyimide coverlay or polyimide bondply or electrically insulating layer) comprises a polyimide derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 20 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 80 mole % 4,4′-oxydianiline and is capable of directly adhering to metal and other polymers at lamination temperatures from 330 to 380° C.
  • a polyimide film (polyimide layer or polyimide coverlay or polyimide bondply or electrically insulating layer) comprises a polyimide derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 40 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 60 mole % 4,4′-oxydianiline and is capable of directly adhering to metal and other polymers at lamination temperatures from 320 to 380° C.
  • a polyimide film (polyimide layer or polyimide coverlay or polyimide bondply or electrically insulating layer) comprises a polyimide derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 20 to 30 mole % 2,2′-bis(trifluoromethyl)benzidine, and 70 to 80 mole % 4,4′-oxydianiline and is capable of directly adhering to metal and other polymers at lamination temperatures from 330 to 380° C.
  • a polyimide film (polyimide layer or polyimide coverlay or polyimide bondply or electrically insulating layer) comprises a polyimide derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 20 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 80 mole % 4,4′-oxydianiline and is capable of directly adhering to metal and other polymers at lamination temperatures of at least 300, 320, 330 or 350° C.
  • a polyimide film (polyimide layer or polyimide coverlay or polyimide bondply or electrically insulating layer) comprises a polyimide derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 40 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 80 mole % 4,4′-oxydianiline is capable of directly adhering to metal and other polymers at lamination temperatures of at least 300, 320, 330 or 350° C.
  • a polyimide derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 100 mole % 2,2′-bis(trifluoromethyl)benzidine, is capable of directly adhering to metal and other polymers at lamination temperatures from 380 to 404° C.
  • polyimides of the present disclosure are useful for any application where direct adherence of a polyimide to metal is beneficial and thin, flexible electronic components with low CTE, low moisture absorption are desired such as, but not limited to, metal clad laminates, coverlays and bondplys.
  • the polyimide metal clad laminate of the present disclosure comprises a metal foil and a polyimide layer.
  • the polyimide layer having a first side and a second side, the first side in direct contact with the metal foil, the polyimide layer comprising: a polyimide derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 20 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 80 mole % 4,4′-oxydianiline; wherein the polyimide metal clad laminate does not have an adhesive layer between the metal foil and the polyimide layer.
  • the polyimide metal clad laminate has a peel strength of from 1 to 3.3 N/mm, as measured in accordance with IPC-TM-650-2.4.9d, when the metal foil and the polyimide layer are laminated together at a lamination temperature from 320 to 380° C. and a pressure from 150 psi (10.55 Kg/cm) to 400 psi (28.13 Kg/cm).
  • the polyimide metal clad laminate of the present disclosure comprises a metal foil and a polyimide layer.
  • the polyimide layer having a first side and a second side, the first side in direct contact with the metal foil, the polyimide layer comprising: a polyimide derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 40 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 60 mole % 4,4′-oxydianiline; wherein the polyimide metal clad laminate does not have an adhesive layer between the metal foil and the polyimide layer.
  • the polyimide metal clad laminate has a peel strength of from 1 to 3 N/mm, as measured in accordance with IPC-TM-650-2.4.9d, when the metal foil and the polyimide layer are laminated together at a lamination temperature from 320 to 380° C. and a pressure from 150 psi (10.55 Kg/cm) to 400 psi (28.13 Kg/cm).
  • the polyimide metal clad laminate of the present disclosure comprises a metal foil and a polyimide layer.
  • the polyimide layer having a first side and a second side, the first side in direct contact with the metal foil, the polyimide layer comprising: a polyimide derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 20 to 30 mole % 2,2′-bis(trifluoromethyl)benzidine, and 70 to 80 mole % 4,4′-oxydianiline; wherein the polyimide metal clad laminate does not have an adhesive layer between the metal foil and the polyimide layer.
  • the polyimide metal clad laminate has a peel strength of from 1 to 3.2 N/mm, as measured in accordance with IPC-TM-650-2.4.9d, when the metal foil and the polyimide layer are laminated together at a lamination temperature from 330 to 350° C. and a pressure from 150 psi (10.55 Kg/cm) to 400 psi (28.13 Kg/cm).
  • polyimide metal clad laminate comprises a metal foil and a polyimide layer having a first side and a second side, the first side in direct contact with the metal foil, the polyimide layer comprising: a polyimide derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, and 100 mole % 2,2′-bis(trifluoromethyl)benzidine; wherein the polyimide metal clad laminate does not have an adhesive layer between the metal foil and the polyimide layer, and wherein the polyimide metal clad laminate has a peel strength of from 1 to 3 N/mm, as measured in accordance with IPC-TM-650-2.4.9d, when the metal foil and the polyimide layer are laminated together at a lamination temperature from 380 to 400° C. and a pressure from 150 psi (10.55 Kg/cm) to 400 psi (28.13 Kg/cm).
  • the polyimide metal clad laminate of the present disclosure comprises a metal foil and a polyimide layer.
  • the polyimide layer having a first side and a second side, the first side in direct contact with the metal foil, the polyimide layer comprising: a polyimide derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 20 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 80 mole % 4,4′-oxydianiline; wherein the polyimide metal clad laminate does not have an adhesive layer between the metal foil and the polyimide layer.
  • the polyimide metal clad laminate has a peel strength of at least 1 N/mm, as measured in accordance with IPC-TM-650-2.4.9d, when the metal foil and the polyimide layer are laminated together at a lamination temperature of at least 320° C. and a pressure from 150 psi (10.55 Kg/cm) to 400 psi (28.13 Kg/cm).
  • the polyimide is derived from 100 mole % 3.3′,4,4′-biphenyl tetracarboxylic dianhydride, between and including any two of the following: 20, 30, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 and 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and between and including any two of the following: 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 70 and 80 mole % 4,4′-oxydianiline.
  • the polyimide metal clad further comprises a second metal foil in direct contact with the second side of the polyimide layer and wherein the polyimide metal clad laminate does not have an adhesive layer between the second metal foil and the polyimide layer.
  • the polyimide metal clad laminate comprises:
  • the polyimide metal clad laminate comprises:
  • polyimides of the present disclosure have good peel strength with metals, and imaged metal having exposed polymer areas where the metal was removed, without the need for an adhesive when laminated at temperatures from 320 to 380° C., and in some embodiments, laminated at temperatures from 380 to 400° C., and maintain a good balance of mechanical and electrical properties as well as low CTE. Not all low Tg polyimides have good peel strength, balance of properties and low CTE.
  • Desirable electrical properties and mechanical properties will depend on the desired end use that the material will be used for. Ordinary skill and experimentation may be necessary in fine tuning properties for desired end use. Generally, good MD tensile modulus is greater than 2.75 GPa, MD tensile strength is greater than 125 MPa, MD elongation is greater than 25%, water uptake less than 1.5%, dielectric constant at 100 Hz less than 3.5 and loss tangent below 0.006.
  • Another advantage of a single layer polyimide film having the ability to directly adhere to metal foil is film thickness uniformity can be more easily controlled for thicknesses less than 25 microns via a single slot casting die than a multilayer casted film which relies on a sophisticated layer combining system.
  • All polyimide copper clad laminates can be made with 3 layers; a rigid thermoset polyimide core and thin thermoplastic polyimide coatings on both sides of the polyimide core.
  • Another advantage of a single layer of polyimide film of the present disclosure is that it produces the properties expected of copper clad laminate with a rigid polyimide core and also produces adhesion to copper similar to a thermoplastic polyimide. Good adhesion to copper foil could be achieved with an all thermoplastic polyimide film. However, the all thermoplastic films would have large CTE values (>50) that are unacceptable for metal clad laminates. Also the dimensional stability is poor.
  • Another advantage is that thinner polyimide films can be made allowing for higher thermal conductivity while maintaining electrical properties.
  • the polyimide layer (of the polyimide metal clad laminate) is from, between and including any two of the following: 2, 5, 10, 15, 20, 26, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 and 105 microns thick. In some embodiments, the polyimide layer is from 2 to 26 micron thick. In some embodiments, the polyimide layer is from 27 to 105 micron thick.
  • the metal foil is elemental metal. In some embodiments, the metal foil is a metal alloy. In some embodiments, the metal foil is copper. In some embodiments, the metal alloy comprises 50 to 72 weight % nickel. In another embodiment, the metal alloy comprises 50 to 72% weight % nickel an 14 to 24 weight % Chromium. In some embodiments, the metal foil is aluminum.
  • the polyimide metal clad laminate further comprises a second metal foil in direct contact with the second side of the polyimide layer and wherein the polyimide metal clad laminate does not have an adhesive layer between the second metal foil and the polyimide layer.
  • the second metal foil is elemental metal. In some embodiments, the second metal foil is a metal alloy. In some embodiments, the second metal foil is copper. In some embodiments, the metal alloy comprises 50 to 72 weight % nickel. In another embodiment, the metal alloy comprises 50 to 72% weight % nickel an 14 to 24 weight % Chromium. In some embodiments, the metal foil is aluminum.
  • the metal foil is from 5 to 72 microns thick. In some embodiments, the metal foil is between and including any two of the following: 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 and 72 microns thick. In some embodiments, the metal foil is surface treated to improve adhesion to electrically insulating layers.
  • the second metal foil is from 5 to 72 microns thick. In some embodiments, the second metal foil is between and including any two of the following: 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 and 72 microns thick. In some embodiments, the second metal foil is surface treated to improve adhesion to electrically insulating layers.
  • the polyimide layer comprises from 1 to 55 weight percent of a thermally conductive filler, dielectric fillers or mixtures thereof. In some embodiments, the polyimide layer comprises between and including any two of the following: 1, 5, 10, 20, 25, 30, 35, 40, 45, 50 and 55 weight percent of a thermally conductive filler, dielectric fillers or mixtures thereof. In some embodiments the thermally conductive filler, dielectric fillers or mixtures thereof are milled to obtain desired filler size and/or break up any agglomerates that may have formed.
  • the polyimide of the present disclosure can be made by any known thermal conversion or chemical conversion method for making polyimide films or filled polyimide films.
  • it is desirable to use chemical conversion due to the advantages chemical conversion over thermal conversion such as but not limited to, lower CTE and films are matte on both sides even when cast on to a smooth surface.
  • the polyimide layer can be a free standing film that is then directly adhered to metal foil, on one or both sides, using nip roll lamination or vacuum press to form a metal clad laminate.
  • the nip roll or vacuum press must be capable of reaching the required temperature and pressure.
  • a polyamic acid can be cast on to metal foil and cured. This process can produce very thin electrically insulating layers (dielectric layers). And optionally another metal foil can be adhered to the other side of the polyimide layer using a nip roll process or vacuum press, capable of reaching the required temperature and pressure.
  • the polyimide film can be a free standing film that is then directly adhered to metal foil, on one or both sides, using nip roll lamination or vacuum press to form a metal clad laminate.
  • a polyimide derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 40 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 60 mole % 4,4′-oxydianiline is used as a coverlay.
  • the polyimide is directly adhered to copper and typically another polyimide layer which is exposed after the copper has been imaged to form circuitry.
  • the circuit board comprises:
  • the first polyimide coverlay has a peel strength from 1 to 2 N/mm, as measured in accordance with IPC-TM-650-2.4.9d, when the first polyimide coverlay is laminated to the first imaged metal layer and exposed areas of the first side of the first electrically insulating layer at a lamination temperature from 320 to 380° C. and a pressure from 150 psi (10.55 Kg/cm) to 400 psi (28.13 Kg/cm).
  • the first electrically insulating layer is any electrically insulating material that can withstand the lamination temperature from 320 to 380° C.
  • the circuit board comprises:
  • the circuit board comprises:
  • the first polyimide coverlay is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, between and including any two of the following: 20, 30, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 and 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and between and including any two of the following: 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 70, and 80 mole % 4,4′-oxydianiline.
  • the circuit board further comprises a second imaged metal layer on the second side of the first electrically insulating layer.
  • the circuit board further comprises a second polyimide coverlay derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride 20 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 80 mole % 4,4′-oxydianiline and in direct contact with the second imaged metal layer and exposed areas of the second side of the first electrically insulating layer.
  • An adhesive layer is not present between the second imaged metal layer and the second polyimide coverlay.
  • the second polyimide coverlay has a peel strength from 0.7 to 2 N/mm, as measured in accordance with IPC-TM-650-2.4.9d, when the second polyimide coverlay is laminated to the second imaged metal layer and the exposed areas of the second side of the first electrically insulating layer at a lamination temperature from 300 to 380° C. and a pressure from 150 psi (10.55 Kg/cm) to 400 psi (28.13 Kg/cm).
  • the circuit board further comprises a second polyimide coverlay derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 40 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 60 mole % 4,4′-oxydianiline and in direct contact with the second imaged metal layer and exposed areas of the second side of the first electrically insulating layer.
  • An adhesive layer is not present between the second imaged metal layer and the second polyimide coverlay.
  • the second polyimide coverlay has a peel strength from 1 to 2 N/mm, as measured in accordance with IPC-TM-650-2.4.9d, when the second polyimide coverlay is laminated to the second imaged metal layer and the exposed areas of the second side of the first electrically insulating layer at a lamination temperature from 320 to 380° C. and a pressure from 150 psi (10.55 Kg/cm) to 400 psi (28.13 Kg/cm).
  • the second polyimide coverlay is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, between and including any two of the following: 20, 30, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 and 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and between and including any two of the following: 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 70 and 80 mole % 4,4′-oxydianiline.
  • the optical density (opacity) desirable is greater than or equal to 2.
  • An optical density of 2 is intended to mean 1 ⁇ 10 ⁇ 2 or 1% of light is transmitted through the film.
  • the optical density is measured with a Macbeth TD904 optical densitometer.
  • the optical density can be increased by making a thicker coverlay. This is undesirable since the trend is for coverlays to be increasingly thin.
  • the optical density can be increased by adding filler.
  • a pigment is added is increase the optical density.
  • a matting agent is added to increase the optical density.
  • a combination of pigment and matting agents can be added.
  • the pigment is a low conductivity carbon black. In some embodiments, the pigment is a non-carbon black pigment.
  • a low conductivity carbon black is used.
  • Low conductivity carbon black is intended to mean, channel type black or furnace black.
  • the low conductivity carbon black is a surface oxidized carbon black.
  • One method for assessing the extent of surface oxidation (of the carbon black) is to measure the carbon black's volatile content. The volatile content can be measured by calculating weight loss when calcined at 950° C. for 7 minutes.
  • a highly surface oxidized carbon black (high volatile content) can be readily dispersed into a polyamic acid solution (polyimide precursor), which in turn can be imidized into a (well dispersed) filled polyimide polymer of the present disclosure.
  • the low conductivity carbon black has a volatile content greater than or equal to 1%. In some embodiments, the low conductivity carbon black has a volatile content greater than or equal to 5, 9, or 13%. In some embodiments, furnace black may be surface treated to increase the volatile content. In some embodiments a bone black is used.
  • the low conductivity carbon black is present in amount between and optionally including any two of the following: 2, 3, 4, 5, 6, 7, 8 and 9 weight percent of the polyimide coverlay.
  • the first polyimide coverlay comprises a low conductivity carbon black present in an amount from 2 to 9 weight percent.
  • the second polyimide coverlay comprises a low conductivity carbon black present in an amount from 2 to 9 weight percent.
  • the first polyimide coverlay and the second polyimide coverlay both comprises a low conductivity carbon black present in an amount from 2 to 9 weight percent.
  • the first polyimide coverlay comprises a pigment and a matting agent. In some embodiments, the first polyimide coverlay, the second polyimide coverlay or both comprise a pigment and a matting agent.
  • useful non-carbon black pigments include but are not limited to the following: Barium Lemon Yellow, Cadmium Yellow Lemon, Cadmium Yellow Lemon, Cadmium Yellow Light, Cadmium Yellow Middle, Cadmium Yellow Orange, Scarlet Lake, Cadmium Red, Cadmium Vermilion, Alizarin Crimson, Permanent Magenta, Van Dyke brown, Raw Umber Greenish, or Burnt Umber.
  • useful black pigments include: cobalt oxide, Fe—Mn—Bi black, Fe—Mn oxide spinel black, (Fe,Mn)2O3 black, copper chromite black spinel, lampblack, bone black, bone ash, bone char, hematite, black iron oxide, micaceous iron oxide, black complex inorganic color pigments (CICP), CuCr2O4 black, (Ni,Mn,CoXCr,Fe)2O4 black, Aniline black, Perylene black, Anthraquinone black, Chromium Green-Black Hematite, Chrome Iron Oxide, Pigment Green 17, Pigment Black 26, Pigment Black 27, Pigment Black 28, Pigment Brown 29, Pigment Black 30, Pigment Black 32, Pigment Black 33 or mixtures thereof.
  • the first polyimide coverlay comprises a non-carbon black pigment present in an amount from 10 to 60 weight percent. In some embodiments, the second polyimide coverlay comprises a non-carbon black pigment present in an amount from 10 to 60 weight percent. In some embodiments, the first polyimide coverlay, the second polyimide coverlay or both comprise a non-carbon black pigment present in an amount from 10 to 60 weight percent. In some embodiments, the first polyimide coverlay comprises a non-carbon black pigment present in an amount between and including any two of the following: 10, 20, 30, 40, 50 and 60 weight percent. In some embodiments, the second polyimide coverlay comprises a non-carbon black pigment present in an amount between and including any two of the following: 10, 20, 30, 40, 50 and 60 weight percent.
  • the first polyimide coverlay comprises a low conductivity carbon black present in an amount from 2 to 9 weight percent and the second polyimide coverlay comprises a non-carbon black pigment present in an amount from 10 to 60 weight percent.
  • a uniform dispersion of isolated, individual particles (aggregates) not only decreases the electrical conductivity, but additionally tends to produce uniform color intensity.
  • the low conductivity carbon black is milled.
  • the mean particle size of the low conductivity carbon black is between (and optionally including) any two of the following sizes: 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and 1.0 microns.
  • dyes may be used.
  • useful dye are, but not limited to nigrosin black, monoazo chromium complex black, or mixtures thereof.
  • a mixture of dye and pigment may be used.
  • a coverlay with a matte appearance In some embodiments it is desirable to have a coverlay with a matte appearance.
  • Polymeric materials typically have inherent surface gloss.
  • the additive approaches are all based upon the same fundamental physics—to create a modified surface which is (on a micro-scale) coarse and irregular shaped and therefore allows less light to be reflected back to the distant (e.g., greater than 50 centimeters) observer.
  • the same source of light hits a matte (ie. irregular) surface, the light is scattered in many different directions and also a much higher fraction is absorbed.
  • a matte ie. irregular
  • Gloss meters used to characterize a specific surface for gloss level are based on this same principle.
  • a light source hits a surface at a fixed angle and after reflection the amount of reflected light is read by a photo cell. Reflection can be read at multiple angles. Maximum gloss performance for a perfectly glossy surface tends to demonstrate 100% reflection, whereas a fully dull surface tends to demonstrate 0% reflection.
  • Silicas are inorganic particles that can be ground and filtered to specific particle size ranges. The very irregular shape and porosity of silica particles and low cost make it a popular matting agent.
  • Other potential matting agents can include: i. other ceramics, such as, borides, nitrides, carbides and other oxides (e.g., alumina, titania, etc); and ii. organic particles, provided the organic particle can withstand the high temperature processing of a chemically converted polyimide (processing temperatures of from about 250° C. to about 550° C., depending upon the particular polyimide process chosen).
  • One organic matting agent that can withstand the thermal conditions of polyimide synthesis are polyimide particles.
  • the matting agent is polyimide particles.
  • the first polyimide coverlay comprises polyimide particles.
  • the second polyimide coverlay comprises polyimide particles.
  • both the first polyimide coverlay and the second polyimide coverlay comprise polyimide particles.
  • the amount of matting agent, median particle size and density must be sufficient to produce the desired 60 degree gloss value.
  • the 60 degree gloss value is between and optionally including any two of the following: 2, 5, 10, 15, 20, 25, 30 and 35. In some embodiments, the 60 degree gloss value is from 10 to 35. In some embodiments, the 60 degree gloss value is from 2 to 25. The 60 degree gloss value is measured using Micro-TRI-Gloss gloss meter.
  • the matting agent is present in an amount between and optionally including any two of the following: 1.6, 2, 3, 4, 5, 6, 7, 8, 9 and 10 weight percent of the first polyimide coverlay or the second polyimide coverlay.
  • the matting agent has a median particle size between and optionally including any two of the following: 1.3, 2, 3, 4, 5, 6, 7, 8, 9 and 10 microns.
  • the matting agent particles should have an average particle size of less than (or equal to) about 10 microns and greater than (or equal to) about 1.3 microns. Larger matting agent particles may negatively impact mechanical properties.
  • the matting agent has a density between and optionally including any two of the following: 2, 3, 4 and 4.5 g/cc.
  • the matting agent is selected from the group consisting of silica, alumina, barium sulfate and mixtures thereof.
  • the first polyimide coverlay comprises a pigment and a matting agent.
  • the pigment and the matting agent are both a low conductivity carbon black and in such embodiments, the low conductivity carbon black is present in the first polyimide coverlay in an amount from 2 to 20 weight percent.
  • the pigment and the matting agent are both a low conductivity carbon black and in such embodiments, the low conductivity carbon black is present in the first polyimide coverlay in an amount between and including any two of the following: 2, 5, 10, 15 and 20 weight percent.
  • the pigment and the matting agent are both a low conductivity carbon black and in such embodiments, the low conductivity carbon black is present in the second polyimide coverlay in an amount between and including any two of the following: 2, 5, 10, 15 and 20 weight percent.
  • the second polyimide coverlay comprises a pigment and a matting agent.
  • the pigment and the matting agent in both the first polyimide coverlay and the second polyimide coverlay are a low conductivity carbon black and the low conductivity carbon black is present in the first polyimide coverlay in an amount from 2 to 20 weight percent and the low conductivity carbon black is present in the second polyimide coverlay in an amount from 2 to 20 weight percent.
  • the pigment and the matting agent are both a low conductivity carbon black and the low conductivity carbon black is present in the first polyimide coverlay in an amount from 2 to 20 weight percent.
  • the pigment and the matting agent are both a low conductivity carbon black and the low conductivity carbon black is present in the first polyimide coverlay, the second polyimide coverlay or both in an amount from 2 to 20 weight percent.
  • the first polyimide coverlay comprises a low conductivity carbon black present in an amount from 2 to 9 weight percent and the second polyimide coverlay comprises a non-carbon black pigment present in an amount from 10 to 60 weight percent.
  • the first polyimide coverlay comprises a low conductivity carbon black present in an amount from 2 to 9 weight percent and the second polyimide coverlay comprises a pigment and a matting agent.
  • the pigment and the matting agent in the second polyimide coverlay are both a low conductivity carbon black, the carbon black present in an amount from 2 to 20 weight percent.
  • the first polyimide coverlay comprises a low conductivity carbon black present in an amount from 2 to 9 weight percent and the second polyimide coverlay comprises a pigment and a matting agent, and wherein the matting agent is polyimide particles.
  • the first polyimide coverlay is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, and 100 mole % 2,2′-bis(trifluoromethyl)benzidine;
  • the circuit board comprises
  • circuit board further comprises a second polyimide coverlay derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, and 100 mole % 2,2′-bis(trifluoromethyl)benzidine.
  • the circuit board comprises
  • the first electrically insulating layer is any electrically insulating material that can withstand the lamination temperature from 300 to 400° C.; in some embodiments 300 to 380° C. or in other embodiments 320 to 380° C.
  • the first electrically insulating layer is derived from a polyimide. In some embodiments, the first electrically insulating layer is derived from an aromatic polyimide.
  • the first electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 20 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine and 10 to 80 mole % 4,4′-oxydianiline.
  • the first electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 40 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine
  • the first electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 100 mole % 2,2′-bis(trifluoromethyl)benzidine.
  • the first electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 20 to 30 mole % 2,2′-bis(trifluoromethyl)benzidine.
  • the first electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, between and including any two of the following: 20, 30, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 and 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and between and including any two of the following: 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 60, 70 and 80 mole % 4,4′-oxydianiline.
  • the first electrically insulating layer comprises from 1 to 55 weight percent of a thermally conductive filler, a dielectric filler or mixtures thereof.
  • the first imaged metal layer is copper. In some embodiments, the first imaged metal layer, the second imaged layer or both are copper. In some embodiments, the first imaged metal layer is elemental metal. In some embodiments, the first imaged metal layer is a metal alloy. In some embodiments, the first imaged metal layer is aluminum.
  • the second imaged metal layer is elemental metal. In some embodiments, the second imaged metal layer is a metal alloy. In some embodiments, the second imaged metal layer is copper. In some embodiments, the second imaged metal layer is aluminum.
  • both the first imaged metal layer and the second imaged metal layer are elemental metal. In some embodiments, both the first imaged metal layer and the second imaged metal layer are a metal alloy. In some embodiments, the first imaged metal layer and the second imaged metal layer are copper.
  • the metal alloy comprises 50 to 72 weight % nickel. In another embodiment, the metal alloy comprises 50 to 72% weight % nickel and 14 to 24 weight % Chromium. In some embodiments, the metal foil is aluminum.
  • the first imaged metal layer is from 5 to 72 microns thick. In some embodiments, the first imaged metal layer is between and including any two of the following: 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 and 72 microns thick. In some embodiments, the first imaged metal layer is surface treated to improve adhesion to electrically insulating layers.
  • the second imaged metal layer is from 5 to 72 microns thick. In some embodiments, the second imaged metal layer is between and including any two of the following: 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 and 72 microns thick. In some embodiments, the second imaged metal layer is surface treated to improve adhesion to electrically insulating layers.
  • the first imaged metal layer and the second imaged metal layer are made by imaging a metal foil/metal layer with a photoresist and copper etching to created imaged metal layers having lines of different widths using standard procedures in the flexible printed circuit board industry.
  • the first electrically insulating layer comprises from 1 to 55 weight percent of a thermally conductive filler, a dielectric filler or mixtures thereof, the first imaged metal layer is copper and wherein the first polyimide coverlay comprises: a low conductivity carbon black present in an amount from 2 to 9 weight percent or a non-carbon black pigment present in an amount from 10 to 60 weight percent.
  • the first electrically insulating layer comprises from 1 to 55 weight percent of a thermally conductive filler, a dielectric filler or mixtures thereof; the first imaged metal layer is copper and wherein the first polyimide coverlay comprises a pigment and a matting agent, wherein the pigment and the matting agent are both a low conductivity carbon black, the low conductivity carbon black is present in the first polyimide coverlay in an amount from 2 to 20 weight percent.
  • the first electrically insulating layer comprises from 1 to 55 weight percent of a thermally conductive filler, a dielectric filler or mixtures thereof; the first imaged metal layer is copper and wherein the first polyimide coverlay comprises a pigment and a matting agent, wherein the matting agent is polyimide particles.
  • the first electrically insulating layer comprises from 1 to 55 weight percent of a thermally conductive filler, a dielectric filler or mixtures thereof and the first imaged metal layer, the second imaged metal layer or both are copper.
  • the first electrically insulating layer comprises from 1 to 55 weight percent of a thermally conductive filler, a dielectric filler or mixtures thereof. In some embodiments, the first electrically insulating layer comprises from 1 to 55 weight percent of a thermally conductive filler, a dielectric filler or mixtures thereof and the first imaged metal layer is copper. In some embodiments, first the electrically insulating layer comprises between and including any two of the following: 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 and 55 weight percent of a thermally conductive filler, a dielectric filler or mixtures thereof.
  • the first electrically insulating layer comprises between and including any two of the following: 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 and 55 weight percent of a thermally conductive filler, a dielectric filler or mixtures thereof and the first imaged metal layer is copper.
  • the circuit board comprises:
  • the circuit board comprises:
  • the circuit board comprises:
  • the circuit board comprises:
  • the first polyimide coverlay and the second polyimide coverlay each independently have a thickness from 5 to 152 microns. In some embodiments, the first polyimide coverlay has a thickness between and including any two of the following: 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 105, 110, 120, 130, 140 and 152 microns. In some embodiments, the second polyimide coverlay has a thickness between and including any two of the following: 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 105, 110, 120, 130, 140 and 152 microns. In some embodiments, the first polyimide coverlay and the second polyimide coverlay each independently have a thickness from 5 to 105 micron. In yet another embodiment, the first polyimide coverlay and the second polyimide coverlay each independently have a thickness from 10 to 40 microns.
  • the polyimide coverlay(s) of the present disclosure can be made by any known thermal conversion or chemical conversion method for making filled polyimides.
  • it is desirable to use chemical conversion due to the advantages chemical conversion over thermal conversion such as but not limited to, lower CTE and films are matte on both sides even when cast on to a smooth surface.
  • the circuit board is made by taking a single-sided clad (electrically insulating layer and an imaged metal layer) and laminating with a first polyimide coverlay at a lamination temperature of 320 to 380° C. and a pressure from 150 psi (10.55 Kg/cm) to 400 psi (28.13 Kg/cm) such that the first polyimide coverlay is in direct contact with the first imaged metal layer and exposed areas of the first side of the first electrically insulating layer.
  • the circuit board is made by taking a double-sided clad (first imaged metal layer, first electrically insulating layer and a second imaged metal layer) and laminating with a first polyimide coverlay and a second polyimide coverlay at a lamination temperature of 320 to 380° C. and a pressure from 150 psi (10.55 Kg/cm) to 400 psi (28.13 Kg/cm) such that the first polyimide coverlay is in direct contact with the first imaged metal layer and exposed areas of the first side of the first electrically insulating layer and the second polyimide coverlay is laminated to the second imaged metal layer and the exposed areas of the second side of the first electrically insulating layer.
  • a double-sided clad first imaged metal layer, first electrically insulating layer and a second imaged metal layer
  • a vacuum platen press is used.
  • One embodiment of the present disclosure is a polyimide bondply for a circuit board.
  • the circuit board comprises, in the following order:
  • the circuit board comprises, in the following order:
  • the polyimide bondply is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, between and including any two of the following: 20, 30, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 and 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and between and including any two of the following: 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 70 and 80 mole % 4,4′-oxydianiline.
  • the polyimide bondply comprises from 1 to 55 weight percent of a thermally conductive filler, dielectric filler or mixtures thereof. In some embodiments, the polyimide bondply comprises between and including any two of the following: 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 and 55 weight percent of a thermally conductive filler, a dielectric filler or mixtures thereof.
  • the polyimide bondply is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, and 100 mole % 2,2′-bis(trifluoromethyl)benzidine and can be laminated at a lamination temperature from 380 to 400° C. and a pressure from 150 psi (10.55 Kg/cm) to 400 psi (28.13 Kg/cm).
  • the first electrically insulating layer is any electrically insulating material that can withstand the lamination temperature from 300 to 380° C. In some embodiments, the first electrically insulating layer is derived from a polyimide. In some embodiments, the first electrically insulating layer is derived from an aromatic polyimide.
  • the second electrically insulating layer is any electrically insulating material that can withstand the lamination temperature from 300 to 380° C.
  • the second electrically insulating layer is derived from a polyimide. In some embodiments, the second electrically insulating layer is derived from an aromatic polyimide.
  • the first electrically insulating layer and the second electrically insulating layer are any electrically insulating material that can withstand the lamination temperature from 320 to 380° C.
  • the first electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 20 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine and 10 to 80 mole % 4,4′-oxydianiline.
  • the first electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 40 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine
  • the first electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 100 mole % 2,2′-bis(trifluoromethyl)benzidine.
  • the first electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 20 to 30 mole % 2,2′-bis(trifluoromethyl)benzidine.
  • the first electrically insulating layer, the second electrically insulating layer or both are derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, between and including any two of the following: 20, 30, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 and 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and between and including any two of the following: 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 60, 70 and 80 mole % 4,4′-oxydianiline.
  • the first electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 40 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 60 mole % 4,4′-oxydianiline and is direct contact with first imaged metal layer, the second imaged metal layer and exposed areas of the polyimide bondply.
  • the second electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 40 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 60 mole % 4,4′-oxydianiline and is direct contact with fourth imaged metal layer, the third imaged metal layer and exposed areas of the polyimide bondply.
  • the first electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 20 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 80 mole % 4,4′-oxydianiline and is direct contact with first imaged metal layer
  • the second imaged metal layer and exposed areas of the polyimide bondply and the second electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 20 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 80 mole % 4,4′-oxydianiline and is direct contact with fourth imaged metal layer, the third imaged metal layer and exposed areas of the polyimide bondply.
  • the first electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 40 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 60 mole % 4,4′-oxydianiline and is direct contact with first imaged metal layer, the second imaged metal layer and exposed areas of the polyimide bondply and the second electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 40 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 60 mole % 4,4′-oxydianiline and is direct contact with fourth imaged metal layer, the third imaged metal layer and exposed areas of the polyimide bondply.
  • the first electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, and 100 mole % 2,2′-bis(trifluoromethyl)benzidine and can be laminated at a lamination temperature from 380 to 400° C. and a pressure from 150 psi (10.55 Kg/cm) to 400 psi (28.13 Kg/cm).
  • the second electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, and 100 mole % 2,2′-bis(trifluoromethyl)benzidine and can be laminated at a lamination temperature from 380 to 400° C. and a pressure from 150 psi (10.55 Kg/cm) to 400 psi (28.13 Kg/cm).
  • the first electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, and 100 mole % 2,2′-bis(trifluoromethyl)benzidine and is direct contact with first imaged metal layer, the second imaged metal layer and exposed areas of the polyimide bondply and the second electrically insulating layer is derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, and 100 mole % 2,2′-bis(trifluoromethyl)benzidine and is direct contact with fourth imaged metal layer, the third imaged metal layer and exposed areas of the polyimide bondply.
  • the first electrically insulating layer comprises from 1 to 55 weight percent of a thermally conductive filler, dielectric fillers or mixtures thereof. In some embodiments, the second electrically insulating layer comprises from 1 to 55 weight percent of a thermally conductive filler, dielectric fillers or mixtures thereof. In some embodiments, the first electrically insulating layer, the second electrically insulating layer or both comprise from 1 to 55 weight percent of a thermally conductive filler, dielectric filler or mixtures thereof.
  • the first electrically insulating layer, the second electrically insulating layer or both comprise from 1 to 55 weight percent of a thermally conductive filler, a dielectric filler or mixtures thereof.
  • the first imaged metal layer is elemental metal. In some embodiments, the first imaged metal layer is a metal alloy. In some embodiments, the first imaged metal layer is copper. In some embodiments, the first imaged metal layer is aluminum.
  • the second imaged metal layer is elemental metal. In some embodiments, the second imaged metal layer is a metal alloy. In some embodiments, the second imaged metal layer is copper. In some embodiments, the second imaged metal layer is aluminum.
  • the third imaged metal layer is elemental metal. In some embodiments, the third imaged metal layer is a metal alloy. In some embodiments, the third imaged metal layer is copper. In some embodiments, the third imaged metal layer is aluminum.
  • the fourth imaged metal layer is elemental metal. In some embodiments, the fourth imaged metal layer is a metal alloy. In some embodiments, the fourth imaged metal layer is copper. In some embodiments, the fourth imaged metal layer is aluminum.
  • the first imaged metal layer, the second imaged metal layer, the third imaged metal layer and the fourth imaged metal layer are elemental metal. In some embodiments, the first imaged metal layer, the second imaged metal layer, the third imaged metal layer and the fourth imaged metal layer are a metal alloy. In some embodiments, the first imaged metal layer, the second imaged metal layer, the third imaged metal layer and the fourth imaged metal layer are copper. In some embodiments, the first imaged metal layer, the second imaged metal layer, the third imaged metal layer and the fourth imaged metal layer are aluminum.
  • the metal alloy comprises 50 to 72 weight % nickel. In another embodiment, the metal alloy comprises 50 to 72% weight % nickel and 14 to 24 weight % Chromium.
  • the first imaged metal layer, the second imaged metal layer, the third imaged metal layer and the fourth imaged metal layer are independently from 5 to 72 microns thick. In some embodiments, the first imaged metal layer, the second imaged metal layer, the third imaged metal layer and the fourth imaged metal layer are independently between and including any two of the following: 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 and 72 microns thick. In some embodiments, the first imaged metal layer, the second imaged metal layer, the third imaged metal layer and the fourth imaged metal layer are independently surface treated to improve adhesion to electrically insulating layers.
  • the first imaged metal layer, the second imaged metal layer, the third imaged metal layer and the fourth imaged metal layer are made by imaging a metal foil/metal layer with a photoresist and copper etching to created imaged metal layers having lines of different widths using standard procedures in the flexible printed circuit board industry.
  • the polyimide bondply comprises from 1 to 55 weight percent of a thermally conductive filler, dielectric fillers or mixtures thereof and the first electrically insulating layer, the second electrically insulating layer or both comprise from 1 to 55 weight percent of a thermally conductive filler, dielectric fillers or mixtures thereof and the first imaged metal layer, the second imaged metal layer, the third imaged metal layer and the fourth imaged metal layer are copper.
  • the circuit board comprises, in the following order
  • the circuit board comprises, in the following order:
  • the circuit board further comprises an adhesive and a first coverlay wherein the adhesive is between and in direct contact with the first imaged metal layer and the exposed areas of the first side of the first electrically insulating layer and the first coverlay. In some embodiments, the circuit board further comprises a second adhesive and a second coverlay wherein the second adhesive is between and in direct contact with the fourth imaged metal layer and the exposed areas of the second side of the second electrically insulating layer and the second coverlay.
  • the circuit board further comprises an adhesive and a first coverlay wherein the adhesive is between and in direct contact with the first imaged metal layer and the exposed areas of the first side of the first electrically insulating layer and the first coverlay and a second adhesive and a second coverlay wherein the second adhesive is between and in direct contact with the fourth imaged layer and the exposed areas of the second side of the second electrically insulating layer and the second coverlay.
  • the adhesive and the second adhesive can be any traditional adhesive used to bond a coverlay to an imaged metal layer when the coverlay is added after the circuit board is formed.
  • the circuit board can have any number of imaged metal layers and electrically insulating layers.
  • two imaged metal layers separated by an electrically insulating layer can be called a clad or metal clad. And number of these clads can be adhered to each other via the polyimide bondply of the present disclosure.
  • circuit board comprises in the following order
  • the circuit board comprises in the following order:
  • the first polyimide coverlay is in direct contact with the first imaged metal layer and exposed areas of the first side of the first electrically insulating layer and wherein the second polyimide coverlay is in direct contact with the fourth imaged metal layer and exposed areas of the second side of the second electrically insulating layer and the first electrically insulating layer and the second electrically insulating layer are any electrically insulating material that can withstand the lamination temperature from 320 to 380° C.
  • circuit board comprising in the following order:
  • circuit board comprising in the following order:
  • circuit board comprising in the following order:
  • circuit board comprising in the following order:
  • a coverlay with a matte appearance In some embodiments it is desirable to have a coverlay with a matte appearance.
  • Polymeric materials typically have inherent surface gloss. To control gloss (and thereby produce matte surface characteristics) various additive approaches are possible to achieve dull and low gloss surface characteristics.
  • Silicas are inorganic particles that can be ground and filtered to specific particle size ranges. The very irregular shape and porosity of silica particles and low cost make it a popular matting agent.
  • Other potential matting agents can include: i. other ceramics, such as, borides, nitrides, carbides and other oxides (e.g., alumina, titania, etc); and ii. organic particles.
  • the organic particles must withstand the high temperature processing of a chemically converted polyimide (processing temperatures of from about 250° C. to about 550° C., depending upon the particular polyimide process chosen) when the coverlay is a polyimide coverlay.
  • polyimide particles One organic matting agent that can withstand the thermal conditions of polyimide synthesis are polyimide particles.
  • the matting agent is polyimide particles.
  • the first polyimide coverlay comprises polyimide particles.
  • the second polyimide coverlay comprises polyimide particles.
  • both the first polyimide coverlay and the second polyimide coverlay comprise polyimide particles.
  • the amount of matting agent, median particle size and density must be sufficient to produce the desired 60 degree gloss value.
  • the 60 degree gloss value is between and optionally including any two of the following: 2, 5, 10, 15, 20, 25, 30 and 35. In some embodiments, the 60 degree gloss value is from 10 to 35. In some embodiments, the 60 degree gloss value is from 2 to 25. The 60 degree gloss value is measured using Micro-TRI Gloss gloss meter.
  • the first polyimide coverlay and the second polyimide coverlay independently comprise, a matting agent present in an amount between and optionally including any two of the following: 1.6, 2, 3, 4, 5, 6, 7, 8, 9 and 10 weight percent of polyimide coverlay.
  • the matting agent has a median particle size between and optionally including any two of the following: 1.3, 2, 3, 4, 5, 6, 7, 8, 9 and 10 microns.
  • the matting agent particles should have an average particle size of less than (or equal to) about 10 microns and greater than (or equal to) about 1.3 microns. Larger matting agent particles may negatively impact mechanical properties.
  • the matting agent has a density between and optionally including any two of the following: 2, 3, 4 and 4.5 g/cc.
  • the matting agent is selected from the group consisting of silica, alumina, barium sulfate and mixtures thereof.
  • the first polyimide coverlay comprises a pigment and a matting agent. In some embodiments, the second polyimide coverlay comprises a pigment and a matting agent. In some embodiments the first polyimide coverlay, the second polyimide coverlay or both comprise a pigment and a matting agent.
  • the pigment and the matting agent are both a low conductivity carbon black and in such embodiments, the low conductivity carbon black is present in the first polyimide coverlay in an amount from 2 to 20 weight percent.
  • the pigment and the matting agent are both a low conductivity carbon black and in such embodiments, the low conductivity carbon black is present in the first polyimide coverlay in an amount between and including any two of the following: 2, 5, 10, 15 and 20 weight percent.
  • the pigment and the matting agent are both a low conductivity carbon black and in such embodiments, the low conductivity carbon black is present in the second polyimide coverlay in an amount between and including any two of the following: 2, 5, 10, 15 and 20 weight percent.
  • the pigment and the matting agent in both the first polyimide coverlay and the second polyimide coverlay are a low conductivity carbon black and the low conductivity carbon black is present in the first polyimide coverlay in an amount from 2 to 20 weight percent and the low conductivity carbon black is present in the second polyimide coverlay in an amount from 2 to 20 weight percent.
  • the pigment and the matting agent are both a low conductivity carbon black and the low conductivity carbon black is present in the first polyimide coverlay, the second polyimide coverlay or both in an amount from 2 to 20 weight percent.
  • the matting agent is polyimide particles.
  • the first polyimide coverlay, the second polyimide coverlay or both comprise a low conductivity carbon black and a matting agent.
  • the pigment and the matting agent are both a low conductivity carbon black and in such embodiments, the low conductivity carbon black is present in the first polyimide coverlay in an amount between and including any two of the following: 2, 5, 10, 15 and 20 weight percent.
  • the first polyimide coverlay comprises a low conductivity carbon black present in an amount from 2 to 9 weight percent and the second polyimide coverlay comprises a non-carbon black pigment present in an amount from 10 to 60 weight percent.
  • the first polyimide coverlay comprises a low conductivity carbon black present in an amount from 2 to 9 weight percent and the second polyimide coverlay comprises a pigment and a matting agent.
  • the pigment and the matting agent in the second polyimide coverlay are both a low conductivity carbon black, the carbon black present in an amount from 2 to 20 weight percent.
  • the first polyimide coverlay comprises a low conductivity carbon black present in an amount from 2 to 9 weight percent and the second polyimide coverlay comprises a pigment and a matting agent, and wherein the matting agent is polyimide particles.
  • the circuit board comprises in the following order:
  • the circuit board comprises in the following order:
  • the circuit board comprises in the following order:
  • the circuit board comprises in the following order:
  • circuit board comprising in the following order:
  • circuit board comprising in the following order:
  • circuit board comprising in the following order:
  • circuit board comprising in the following order:
  • circuit board comprising in the following order
  • circuit board comprising in the following order
  • circuit board comprising in the following order:
  • circuit board comprising in the following order
  • circuit board comprising in the following order
  • a circuit board in accordance with any of the above embodiments wherein the first polyimide coverlay, the first electrically insulating layer, the polyimide bondply, the second electrically insulating layer and the second polyimide coverlay are derived from 100 mole % 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 20 to 90 mole % 2,2′-bis(trifluoromethyl)benzidine, and 10 to 80 mole % 4,4′-oxydianiline.
  • circuit board comprising in the following order
  • the circuit board is made by taking a first polyimide coverlay (if present), a double-sided clad (first imaged metal layer, first electrically insulating layer and a second imaged metal layer), bondply, a second double-sided clad (third imaged metal layer, second electrically insulating layer and a fourth imaged metal layer) and a second polyimide coverlay (if present) and laminating at lamination temperature of 320 to 380° C. and a pressure from 150 psi (10.55 Kg/cm) to 400 psi (28.13 Kg/cm) using a vacuum platen press.
  • the glass transition temperatures of the polyimide films of the present invention were determined using a TA Instruments 2980 dynamic mechanical analyzer.
  • the Tg measurement method used a sampling frequency of about 1.0 Hz (an amplitude of about 10.0 ⁇ m) and a pre-load force of about 0.01 N.
  • a temperature ramp rate of about 5° C. min-1 was used.
  • the Tg was measured at the peak of the tan ⁇
  • Dielectric Constant was measured as described in ASTM D150, “Standard Test Methods for AC Loss Characteristics and Permittivity (Dielectric Constant) of Solid Electrical Insulation”. The composite film dielectric constant was calculated based on the measured capacitance of the 2.5 cm diameter capacitors.
  • In-plane CTE of a polyimide films of the present invention were measured using a TA Instruments TMA 2940 thermal mechanical analyzer. The expansion of a film was measured between about 50° C. and about 250° C. on a second pass. The expansion was then divided by the temperature difference (and sample length) to obtain the CTE in ppm ° C.-1. The first pass was used to remove shrinkage from the sample over the same temperature range as well as to dry out the sample. As such, the second pass then provided a CTE value characteristic of the film's inherent properties (e.g. minus water absorption and the effect water would have on a film's CTE). This method employed a 0.05 N load force and operated within the above mentioned temperature range ramping temperature at a rate of about 10° C. per minute
  • Moisture absorption was determined by IPC-TM-650, Method 2.6.2.
  • Peel strength data reported in this application are the average of 8 to 12 measurements, consistent with requirement for statistically valid data per IPC-TM650 2.4.8d test method.
  • the copper foil for the peel strength testing was 35 um thick roll annealed (RA) copper foil with pink treatment available from Somers Corporation.
  • Example 1 shows that a polyimide derived from 100 mole % BPDA and 100 mole % TFMB has a peel strength of at least 1 N/mm when laminated at a temperature of 380° C. or greater.
  • TFMB 2,2′-bis(trifluoromethyl)benzidine
  • DMAc N,N-dimethylacetamide
  • BPDA 3,3′,4,4′-biphenyltetracarboxylic dianhydride
  • a polyimide film derived from the above polyamic acid was chemically imidized through the use of a catalytic solution.
  • the chemically imidized film was prepared by casting the polyamic acid solution onto a support sheet of DuPont MYLAR® film.
  • the cast polyamic acid solution (and support sheet) was immersed into a catalytic solution comprising a 1:1 ratio of acetic anhydride and fl-picoline.
  • a gel film was formed. The gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).
  • the gel film was then heated using a forced air oven to further imidize the polymer and remove solvent.
  • the gel film was exposed to the following oven temperatures for about 1 ⁇ 2 hour at each temperature, 150° C., 250° C., 300° C. and 325° C.
  • the polyimide film was removed from the pin frame and analyzed. The data is shown in Table 1.
  • Examples 2-12 show that a polyimide derived from 100 mole % BPDA, 20 to 90 mole % TFMB and 10 to 80 mole % 4,4′-ODA has a peel strength of at least 1 N/mm when laminated at a temperature of 330° C. or greater
  • TFMB 2,2′-bis(trifluoromethyl)benzidine
  • DMAc N,N-dimethylacetamide
  • BPDA 3,3′,4,4′-biphenyltetracarboxylic dianhydride
  • a polyimide film derived from the above polyamic acid was chemically imidized through the use of a catalytic solution.
  • the chemically imidized film was prepared by casting the polyamic acid solution onto a support sheet of DuPont MYLAR® film.
  • the cast polyamic acid solution (and support sheet) was immersed into a catalytic solution comprising a 1:1 ratio of acetic anhydride and ⁇ -picoline.
  • a gel film was formed. The gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).
  • the gel film was then heated using a forced air oven to further imidize the polymer and remove solvent.
  • the gel film was exposed to the following oven temperatures for about 1 ⁇ 2 hour at each temperature, 150° C., 250° C., 300° C. and 325° C.
  • the polyimide film was removed from the pin frame and analyzed. The data is shown in Table 1.
  • BPDA 3,3′,4,4′-biphenyltetracarboxylic dianhydride
  • a polyimide film derived from the above polyamic acid was chemically imidized through the use of a catalytic solution.
  • the chemically imidized film was prepared by casting the polyamic acid solution onto a support sheet of DuPont MYLAR® film.
  • the cast polyamic acid solution (and support sheet) was immersed into a catalytic solution comprising a 1:1 ratio of acetic anhydride and ⁇ -picoline.
  • a gel film was formed. The gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).
  • the gel film was then heated using a forced air oven to further imidize the polymer and remove solvent.
  • the gel film was exposed to the following oven temperatures for about 1 ⁇ 2 hour at each temperature, 150° C., 250° C., 300° C. and 325° C.
  • the film was removed from the pin frame and analyzed. The data is shown in Table 1.
  • TFMB 2,2′-bis(trifluoromethyl)benzidine
  • DMAc N,N-dimethylacetamide
  • BPDA 3,3′,4,4′-biphenyltetracarboxylic dianhydride
  • a polyimide film derived from the above polyamic acid was chemically imidized through the use of a catalytic solution.
  • the chemically imidized film was prepared by casting the polyamic acid solution onto a support sheet of DuPont MYLAR® film.
  • the cast polyamic acid solution (and support sheet) was immersed into a catalytic solution comprising a 1:1 ratio of acetic anhydride and ⁇ -picoline.
  • a gel film was formed. The gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).
  • the gel film was then heated using a forced air oven to further imidize the polymer and remove solvent.
  • the gel film was exposed to the following oven temperatures for about 1 ⁇ 2 hour at each temperature, 150° C., 250° C., 300° C. and 325° C.
  • the polyimide film was removed from the pin frame and analyzed. The data is shown in Table 1.
  • BPDA 3,3′,4,4′-biphenyltetracarboxylic dianhydride
  • a polyimide film derived from the above polyamic acid was chemically imidized through the use of a catalytic solution.
  • the chemically imidized film was prepared by casting the polyamic acid solution onto a support sheet of DuPont MYLAR® film.
  • the cast polyamic acid solution (and support sheet) was immersed into a catalytic solution comprising a 1:1 ratio of acetic anhydride and f-picoline.
  • a gel film was formed. The gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).
  • the gel film was then heated using a forced air oven to further imidize the polymer and remove solvent.
  • the gel film was exposed to the following oven temperatures for about 1 ⁇ 2 hour at each temperature, 150° C., 250° C., 300° C. and 325° C.
  • the resulting polyimide film was removed from the pin frame and analyzed. The data is shown in Table 1.
  • TFMB 2,2′-bis(trifluoromethyl)benzidine
  • DMAc N,N-dimethylacetamide
  • BPDA 3,3′,4,4′-biphenyltetracarboxylic dianhydride
  • a polyimide film derived from the above polyamic acid was chemically imidized through the use of a catalytic solution.
  • the chemically imidized film was prepared by casting the polyamic acid solution onto a support sheet of DuPont MYLAR® film.
  • the cast polyamic acid solution (and support sheet) was immersed into a catalytic solution comprising a 1:1 ratio of acetic anhydride and ⁇ -picoline.
  • a gel film was formed. The gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).
  • the gel film was then heated using a forced air oven to further imidize the polymer and remove solvent.
  • the gel film was exposed to the following oven temperatures for about 1 ⁇ 2 hour at each temperature, 150° C., 250° C., 300° C. and 325° C.
  • the film was removed from the pin frame and analyzed. The data is shown in Table 1.
  • the mixture was heated and stirred at 35° C. for several minutes until the diamines had completely dissolved resulting in a straw colored solution.
  • the speeds of the anchor, disperser, and emulsifier are adjusted as needed to ensure efficient mixing and dissolution, without excessively heating the mixture.
  • 21.4 kg (72.84 moles) of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) was added to the diamine solution within the reaction vessel. Stirring was continued until all of the solids dissolved and the reaction formed a polyamic acid solution.
  • the viscosity of the resulting polyamic acid solution was adjusted by chain extension through an addition of a stoichiometric amount of 6 wt % PMDA solution in DMAc or alternatively an equivalent stoichiometric amount of BPDA solids so that the resulting solution had a viscosity of about 2000 poise.
  • the finished solution is filtered through a 20 micron bag filter and vacuum degassed to remove entrained air.
  • the polyamic acid solution was cooled to approximately ⁇ 6° C., acetic anhydride dehydrating agent (0.14 cm 3 /cm 3 polymer solution), the imidization catalyst 3-picoline (0.15 cm 3 /cm 3 polymer solution) were metered in and mixed, and a film was cast using a slot die, onto a 90° C. hot, rotating drum. The resulting gel film was stripped off the drum and fed into a tenter oven, where it was dried and cured to a solids level greater than 98%, using convective and radiant heating.
  • thermocouple Into a dried 50 gallon tank, equipped with nitrogen inlet, three independently controlled agitator shafts; a low speed anchor mixer, a high speed disk disperser, and a high shear rotor-stator emulsifier, and thermocouple was placed 11.56 kg (36.12 moles) of 2,2′-bis(trifluoromethyl)benzidine (TFMB), 7.23 kg (36.12 moles) 4,4′-oxydianiline (ODA), and 159.6 kg of N,N-dimethylacetamide (DMAc).
  • TFMB 2,2′-bis(trifluoromethyl)benzidine
  • ODA 4,4′-oxydianiline
  • DMAc N,N-dimethylacetamide
  • the mixture was heated and stirred at 35° C. for several minutes until the diamines had completely dissolved resulting in a straw colored solution.
  • the speeds of the anchor, disperser, and emulsifier are adjusted as needed to ensure efficient mixing and dissolution, without excessively heating the mixture.
  • 21.1 kg (71.73 moles) of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) was added to the diamine solution within the reaction vessel. Stirring was continued until all of the solids dissolved and the reaction formed a polyamic acid solution.
  • the viscosity of the resulting polyamic acid solution was adjusted by chain extension through an addition of a stoichiometric amount of 6 wt % PMDA solution in DMAc or alternatively an equivalent stoichiometric amount of BPDA solids so that the resulting solution had a viscosity of about 1500 poise.
  • a small amount of belt release agent was added to the polyamic acid solution (which enables the cast green film to be readily stripped from the casting belt)
  • a thin polymer film was produced by extruding the film through a slot die onto a moving stainless steel belt. The belt passes into a convective oven, to evaporate solvent and partially imidizing the polymer, to produce a “green” film.
  • Green film solids (as measured by weight loss upon heating to 300° C.) was ⁇ 70%. The green film was then stripped off the casting belt and wound up. The green film was then fed into a tenter oven where it was dried and cured to a solids level greater than 98%, using convective and radiant heating to produce a fully cured polyimide film. During tentering, shrinkage was controlled by constraining the film along the edges.
  • a thin film was prepared by casting a portion of the solution onto a copper foil (12 um Mitsui 3EC-M35-HTE ED copper) using a doctor blade.
  • the coated copper foil was then restrained within a clip frame film and heated using a forced air oven to remove the solvent and imidize the polymer.
  • the film was exposed to the following oven temperatures for about 1 ⁇ 2 hour, 150° C., 250° C., and 330° C.
  • the resulting single sided copper coated polyimide was then removed from the clip frame and then laminated to another sheet of copper foil of the same specification as described above in a vacuum platen press at 350 psi pressure and a temperature of 350° C.
  • the peel strength data was measured per IPC-TM650 2.4.9d test method. The data is shown in Table 1.
  • thermocouple Into a dried 50 gallon tank, equipped with nitrogen inlet, three independently controlled agitator shafts; a low speed anchor mixer, a high speed disk disperser, and a high shear rotor-stator emulsifier, and thermocouple is placed 11.56 kg (36.12 moles) of 2,2′-bis(trifluoromethyl)benzidine (TFMB), 7.23 kg (36.12 moles) 4,4′-oxydianiline (ODA), and 159.6 kg of N,N-dimethylacetamide (DMAc).
  • TFMB 2,2′-bis(trifluoromethyl)benzidine
  • ODA 4,4′-oxydianiline
  • DMAc N,N-dimethylacetamide
  • the mixture is heated and stirred at 35° C. for several minutes until the diamines are completely dissolved resulting in a straw colored solution.
  • the speeds of the anchor, disperser, and emulsifier can be adjusted as needed to ensure efficient mixing and dissolution, without excessively heating the mixture.
  • 21.1 kg (71.73 moles) of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) is added to the diamine solution within the reaction vessel. Stirring is continued until all of the solids dissolved and the reaction forms a polyamic acid solution.
  • BPDA 3,3′,4,4′-biphenyltetracarboxylic dianhydride
  • the viscosity of the resulting polyamic acid solution is adjusted by chain extension through an addition of a stoichiometric amount of 6 wt % PMDA solution in DMAc or alternatively an equivalent stoichiometric amount of BPDA solids so that the resulting solution has a viscosity of about 2000 poise.
  • the finished solution can be filtered through a 20 micron bag filter and vacuum degassed to remove entrained air.
  • the polyamic acid solution is cooled to approximately ⁇ 6° C.
  • acetic anhydride dehydrating agent (0.14 cm 3 /cm 3 polymer solution)
  • the imidization catalyst 3-picoline (0.15 cm 3 /cm 3 polymer solution) is metered in and mixed, and a film is cast using a slot die, onto a 90° C. hot, rotating drum.
  • the resulting gel film is stripped off the drum and fed into a tenter oven, where it is dried and cured to a solids level greater than 98%, using convective and radiant heating.
  • Two sheets of the film are laminated between two sheets of 35 um thick treated copper foil in a vacuum platen press at 350 psi. It is expected that the laminate would have good peel strength measured per IPC-TM650 2.4.9d test method.
  • TFMB 2,2′-bis(trifluoromethyl)benzidine
  • DMAc N,N-dimethylacetamide
  • BPDA 3,3′,4,4′-biphenyltetracarboxylic dianhydride
  • a polyimide film derived from the above polyamic acid was chemically imidized through the use of a catalytic solution.
  • the chemically imidized film was prepared by casting the polyamic acid solution onto a support sheet of DuPont MYLAR® film.
  • the cast polyamic acid solution (and support sheet) was immersed into a catalytic solution comprising a 1:1 ratio of acetic anhydride and ⁇ -picoline.
  • a gel film was formed. The gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).
  • the gel film was then heated using a forced air oven to further imidize the polymer and remove solvent.
  • the gel film was exposed to the following oven temperatures for about 1 ⁇ 2 hour at each temperature, 150° C., 250° C., 300° C. and 325° C.
  • the polyimide film was removed from the pin frame and analyzed. The data is shown in Table 1.
  • TFMB 2,2′-bis(trifluoromethyl)benzidine
  • DMAc N,N-dimethylacetamide
  • BPDA 3,3′,4,4′-biphenyltetracarboxylic dianhydride
  • a polyimide film derived from the above polyamic acid was chemically imidized through the use of a catalytic solution.
  • the chemically imidized film was prepared by casting the polyamic acid solution onto a support sheet of DuPont MYLAR® film.
  • the cast polyamic acid solution (and support sheet) was immersed into a catalytic solution comprising a 1:1 ratio of acetic anhydride and ⁇ -picoline.
  • a gel film was formed. The gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).
  • the gel film was then heated using a forced air oven to further imidize the polymer and remove solvent.
  • the gel film was exposed to the following oven temperatures for about 1 ⁇ 2 hour at each temperature, 150° C., 250° C., 300° C. and 325° C.
  • the polyimide film was removed from the pin frame and analyzed. The data is shown in Table 1.
  • Example 13 shows polyimides of the present disclosure have good conformation over circuitry and are useful as a coverlay.
  • a sheet of Pyralux® AP flexible copper clad laminate with 18 micron thick copper foil (available from DuPont) was imaged with photoresist and copper etching to created imaged copper foil lines of different widths using standard procedures in the flexible printed circuit board industry.
  • the polymer created in example 7 (film thickness 32 microns) was laminated over the imaged circuit lines to form a coverlay over the imaged flexible circuit.
  • the polyimide coverlay was laminated in a vacuum platen press at 350 psi and 320 C peak lamination temperature. The polyimide coverlay showed very good conformation over the circuitry with no air voids observed. The polyimide coverlay was able to cover the top of the circuitry with very little thinning.
  • Example 14 shows polyimides of the present disclosure are have good peel strength when laminated at a temperature of 320° C.
  • Example 15 shows polyimides of the present disclosure have good conformation over circuitry and are useful as a bondply.
  • Example 16 shows that good peel strength is achieved with metal alloys.
  • Comparative example 1 shows eliminating TFMB compromises properties, including peel strength.
  • a polyimide film derived from the above polyamic acid was chemically imidized through the use of a catalytic solution.
  • the chemically imidized film was prepared by casting the polyamic acid solution onto a support sheet of DuPont MYLAR® film.
  • the cast polyamic acid solution (and support sheet) was immersed into a catalytic solution comprising a 1:1 ratio of acetic anhydride and fl-picoline.
  • a gel film was formed. The gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).
  • the gel film was then heated using a forced air oven to further imidize the polymer and remove solvent.
  • the gel film was exposed to the following oven temperatures for about 1 ⁇ 2 hour at each temperature, 150° C., 250° C., 300° C. and 325° C.
  • the resulting polyimide film was removed from the pin frame and analyzed. The data is shown in Table 1.
  • Comparative example 2 shows that even though the film can be thermoformed, it has poor adhesion to copper.
  • a polyimide film derived from the above polyamic acid was chemically imidized through the use of a catalytic solution.
  • the chemically imidized film was prepared by casting the polyamic acid solution onto a support sheet of DuPont MYLAR® film.
  • the cast polyamic acid solution (and support sheet) was immersed into a catalytic solution comprising a 1:1 ratio of acetic anhydride and f-picoline.
  • a gel film was formed. The gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).
  • the gel film was then heated using a forced air oven to further imidize the polymer and remove solvent.
  • the gel film was exposed to the following oven temperatures for about 1 ⁇ 2 hour at each temperature, 150° C., 250° C. 300° C. and 325° C.
  • the resulting polyimide film was removed from the pin frame and analyzed. The data is shown in Table 1.
  • Comparative example 3 shows when BPDA is replaced with PMDA the polyimide is brittle and has poor peel strength.
  • a polyimide film derived from the above polyamic acid was chemically imidized through the use of a catalytic solution.
  • the chemically imidized film was prepared by casting the polyamic acid solution onto a support sheet of DuPont MYLAR® film.
  • the cast polyamic acid solution (and support sheet) was immersed into a catalytic solution comprising a 1:1 ratio of acetic anhydride and f-picoline.
  • a gel film was formed. The gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).
  • the gel film was then heated using a forced air oven to further imidize the polymer and remove solvent.
  • the gel film was exposed to the following oven temperatures for about 1 ⁇ 2 hour, 150° C., 250° C., 300° C. and 325° C.
  • the resulting polyimide film was removed from the pin frame and analyzed. The data is shown in Table 1.
  • Comparative example 4 shows that replacing TFMB with a chemically similar diamine but with 2,2′-methyl benzidine functionality does not yield equivalent peel strength.
  • BPDA 3,3′,4,4′-biphenyltetracarboxylic dianhydride
  • a polyimide film derived from the above polyamic acid was chemically imidized through the use of a catalytic solution.
  • the chemically imidized film was prepared by casting the polyamic acid solution onto a support sheet of DuPont MYLAR® film.
  • the cast polyamic acid solution (and support sheet) was immersed into a catalytic solution comprising a 1:1 ratio of acetic anhydride and f-picoline.
  • a gel film was formed. The gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).
  • the gel film was then heated using a forced air oven to further imidize the polymer and remove solvent.
  • the gel film was exposed to the following oven temperatures for about 1 ⁇ 2 hour at each temperature, 150° C., 250° C., 300° C. and 325° C.
  • the resulting polyimide film was removed from the pin frame and analyzed. The data is shown in Table 1.
  • Comparative example 5 has poor mechanical properties.
  • thermocouple Into a dried 50 gallon tank, equipped with nitrogen inlet, three independently controlled agitator shafts: a low speed anchor mixer, a high speed disk disperser, and a high shear rotor-stator emulsifier, and thermocouple was placed 20.02 kg (68.49 moles) of 1,3-bis(4-aminophenoxy)benzene (RODA) and 159.6 kg of N,N-dimethylacetamide (DMAc).
  • RODA 1,3-bis(4-aminophenoxy)benzene
  • DMAc N,N-dimethylacetamide
  • the mixture was heated and stirred at 35° C. for several minutes until the diamines had completely dissolved resulting in a straw colored solution.
  • the speeds of the anchor, disperser, and emulsifier are adjusted as needed to ensure efficient mixing and dissolution, without excessively heating the mixture.
  • 16.99 kg (54.79 moles) of 4,4′-oxydiphthalic anhydride (ODPA) and 2.88 kg (13.21 moles) pyromellitic dianhydride (PMDA) was added to the diamine solution within the reaction vessel. Stirring was continued until all of the solids dissolved and the reaction formed a polyamic acid solution.
  • the viscosity of the resulting polyamic acid solution was adjusted by chain extension through an addition of a stoichiometric amount of 6 wt % PMDA solution in DMAc or alternatively an equivalent stoichiometric amount of BPDA solids so that the resulting solution had a viscosity of about 2000 poise.
  • the finished solution is filtered through a 20 micron bag filter and vacuum degassed to remove entrained air.
  • the polyamic acid solution was cooled to approximately ⁇ 6° C., acetic anhydride dehydrating agent (0.14 cm 3 /cm 3 polymer solution), the imidization catalyst 3-picoline (0.15 cm 3 /cm 3 polymer solution) were metered in and mixed, and a film was cast using a slot die, onto a 90° C. hot, rotating drum. The resulting gel film was stripped off the drum and fed into a tenter oven, where it was dried and cured to a solids level greater than 98%, using convective and radiant heating.
  • Comparative example 6 has poor peel strength.
  • Comparative example 7 has poor peel strength.
  • Examples 17 and 18 show that a polyimide derived from 80-90 mole % BPDA, 10 to 20 mole % ODPA and 100 mole % TFMB has a peel of at least 1.3 N/mm when laminated at a temperature of 350° C. or greater.
  • TFMB 2,2′-bis(trifluoromethyl)benzidine
  • DMAc N,N-dimethylacetamide
  • a polyimide film derived from the above polyamic acid was chemically imidized through the use of a catalytic solution.
  • the chemically imidized film was prepared by casting the polyamic acid solution onto a sheet of DuPont MYLAR® film.
  • the polymer (and support sheet) was immersed into a catalytic solution comprising a 1:1 ratio of acetic anhydride and ⁇ -picoline.
  • a gel film was formed.
  • the gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).
  • the film was then heated using a forced air oven to further imidize the polymer and remove solvent.
  • the film was exposed to the following oven temperatures for about 1 ⁇ 2 hour, 150° C., 250° C., and 330° C.
  • the film was removed from the pin frame and analyzed.
  • TFMB 2,2′-bis(trifluoromethyl)benzidine
  • DMAc N,N-dimethylacetamide
  • BPDA 3,3′,4,4′-biphenyltetracarboxylic dianhydride
  • ODPA 4,4′-oxydiphthalic anhydride
  • a polyimide film derived from the above polyamic acid was chemically imidized through the use of a catalytic solution.
  • the chemically imidized film was prepared by casting the polyamic acid solution onto a sheet of DuPont MYLAR® film.
  • the polymer (and support sheet) was immersed into a catalytic solution comprising a 1:1 ratio of acetic anhydride and 6-picoline.
  • a gel film was formed.
  • the gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).
  • the film was then heated using a forced air oven to further imidize the polymer and remove solvent.
  • the film was exposed to the following oven temperatures for about 1 ⁇ 2 hour, 150° C., 250° C., and 330° C.
  • the film was removed from the pin frame and analyzed.
  • Comparative example 8 shows a film could not me made for testing when 40 mole percent of ODPA is used.
  • TFMB 2,2′-bis(trifluoromethyl)benzidine
  • DMAc N,N-dimethylacetamide
  • a polyimide film derived from the above polyamic acid was chemically imidized through the use of a catalytic solution.
  • the chemically imidized film was prepared by casting the polyamic acid solution onto a support sheet of DuPont MYLAR® film.
  • the cast polyamic acid solution (and support sheet) was immersed into a catalytic solution comprising a 1:1 ratio of acetic anhydride and f-picoline.
  • a gel film was formed. The gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).
  • the gel film was then heated using a forced air oven to further imidize the polymer and remove solvent.
  • the gel film was exposed to the following oven temperatures for about 1 ⁇ 2 hour at each temperature, 150° C., 250° C., 300° C. and 325° C.
  • a viable polyimide film to conduct testing on could not be obtained using this procedure due extreme wrinkling, curl, and tear-out from the restraining frame after cure.
  • Comparative example 9 shows when 10 mole percent of TFMB is used the peel strength is low when laminated at 350 degrees C.
  • TFMB 2,2′-bis(trifluoromethyl)benzidine
  • DMAc N,N-dimethylacetamide
  • BPDA 3,3′,4,4′-biphenyltetracarboxylic dianhydride
  • a polyimide film derived from the above polyamic acid was chemically imidized through the use of a catalytic solution.
  • the chemically imidized film was prepared by casting the polyamic acid solution onto a support sheet of DuPont MYLAR® film.
  • the cast polyamic acid solution (and support sheet) was immersed into a catalytic solution comprising a 1:1 ratio of acetic anhydride and ⁇ -picoline.
  • a gel film was formed. The gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).
  • the gel film was then heated using a forced air oven to further imidize the polymer and remove solvent.
  • the gel film was exposed to the following oven temperatures for about 1 ⁇ 2 hour at each temperature, 150° C., 250° C., 300° C. and 325° C.
  • the polyimide film was removed from the pin frame and analyzed. The data is shown in Table 1.

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