Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
  • 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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material 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
  • 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
• • 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
  • C08G73/1067—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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
  • H05K1/0393—Flexible materials
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/03—3 layers
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/04—4 layers
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/05—5 or more layers
• • 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
  • B32B2307/412—Transparent
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
  • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0104—Properties and characteristics in general
  • H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0137—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
  • H05K2201/01—Dielectrics
  • H05K2201/0183—Dielectric layers
  • H05K2201/0195—Dielectric or adhesive layers comprising a plurality of layers, e.g. in a multilayer structure
• • 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
  • H05K2201/06—Thermal details
  • H05K2201/068—Thermal details wherein the coefficient of thermal expansion is important
• • 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
  • H05K3/0011—Working of insulating substrates or insulating layers
  • H05K3/0014—Shaping of the substrate, e.g. by moulding
• • 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

Definitions

• the field of this disclosure is multilayer films used in electronic circuitry applications.
• Polyimide films are used in the manufacture of flexible printed circuit boards due to their good electrical insulating properties, mechanical strength, high temperature stability, and chemical resistance properties. Polyimide films are adhered to metal foils to form metal-clad laminates, and find broad usage for die pad bonding of flexible print connection boards, semiconductor devices or packaging materials for chip scale package, chip on flex, chip on lead, lead on chip, multi-chip module, ball grid array (or micro-ball grid array), and/or tape automated bonding, among other applications.
• U.S. Patent No. 7,285,321 describes a multilayer laminate having a low glass transition temperature (T g ) polyimide layer, a high T g polyimide layer, and a conductive layer.
• the high T g polyimide layer is a thermoset polyimide and the low T g polyimide layer is a thermoplastic polyimide.
• U.S. Patent No. 6,379,784 describes an aromatic polyimide laminate composed of an aromatic polyimide composite film, a metal film and a release film.
• the aromatic polyimide composite film is composed of an aromatic polyimide substrate film and two thermoplastic aromatic polyimide layers. The metal film and the release film are adhered to opposite sides of the aromatic polyimide laminate without the use of additional adhesive layers.
• Some electronics manufacturing processes require good optical clarity, for instance, when optical registration is used to align various layers in a printed circuit board.
• high transmission and low haze can be critical for circuit designs with extremely fine features.
• Metal-clad laminates may undergo hot-bar processing or spot welding at temperatures in excess of 300°C. Under these conditions, a low T g thermoplastic polyimide layer is susceptible to adhesion loss and delamination, distortion and blistering which can be accompanied by a decrease in optical transmission and an increase in haze.
• a multilayer film in a first aspect, includes a first outer layer including a first thermoplastic polyimide, a core layer including a polyimide, and a second outer layer including a second thermoplastic polyimide.
• the polyimide of the core layer includes a first aromatic dianhydride including 3,3',4,4'-biphenyl tetracarboxylic dianhydride and a first aromatic diamine including p- phenylenediamine.
• the multilayer film has a total thickness in a range of from 5 to 150 m.
• a thickness of the core layer is in a range of from 35 to 73% of the total thickness of the multilayer film.
• a minimum peel strength for at least one of the first and second outer layers, when adhered to copper foil and tested following ASTM method IPC-TM-650, method No. 2.4.9B, is greater than 0.9 kgf/cm (0.88 N/mm).
• a metal-clad laminate in a second aspect, includes the multilayer film of the first aspect and a first metal layer adhered to an outer surface of the first outer layer of the multilayer film.
• a multilayer film in a first aspect, includes a first outer layer including a first thermoplastic polyimide, a core layer including a polyimide, and a second outer layer including a second thermoplastic polyimide.
• the polyimide of the core layer includes a first aromatic dianhydride including 3,3',4,4'-biphenyl tetracarboxylic dianhydride and a first aromatic diamine including p- phenylenediamine.
• the multilayer film has a total thickness in a range of from 5 to 150 m.
• a thickness of the core layer is in a range of from 35 to at least one of the first and second outer layers, when adhered to copper foil and tested following ASTM method IPC-TM-650, method No. 2.4.9B, is greater than 0.9 kgf/cm (0.88 N/mm).
• the first thermoplastic polyimide includes an aromatic dianhydride selected from the group consisting of 4,4'- oxydiphthalic dianhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic
• aromatic diamine selected from the group consisting of 1 ,3-bis(4-aminophenxoxy) benzene, 2,2-bis-(4-[4- aminophenoxy]phenyl) propane and mixtures thereof.
• the aromatic dianhydride includes pyromellitic dianhydride and 4,4'-oxydiphthalic dianhydride; and the aromatic diamine includes 1 ,3-bis(4- aminophenoxy) benzene.
• the second thermoplastic polyimide includes an aromatic dianhydride selected from the group consisting of 4, 4'-oxydiphthalic dianhydride, pyromellitic dianhydride, 3,3', 4,4'- biphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride and mixtures thereof; and an aromatic diamine selected from the group consisting of 1 ,3-bis(4-aminophenxoxy) benzene, hexamethylene diamine and mixtures thereof.
• aromatic dianhydride selected from the group consisting of 4, 4'-oxydiphthalic dianhydride, pyromellitic dianhydride, 3,3', 4,4'- biphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride and mixtures thereof.
• the aromatic dianhydride includes pyromellitic dianhydride and 4,4'-oxydiphthalic dianhydride; and the aromatic diamine includes 1 ,3-bis(4-aminophenoxy) benzene.
• thermoplastic polyimide and second thermoplastic polyimide are the same.
• the core layer further includes a second aromatic dianhydride.
• the second aromatic dianhydride is selected from the group consisting of 4,4'- oxydiphthalic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, bisphenol A dianhydride, 1 ,2,5,6-naphthalene tetracarboxylic dianhydride, 1 ,4,5,8-naphthalene tetracarboxylic dianhydride, and 2,3,6,7-naphthalene tetracarboxylic dianhydride.
• the core layer further includes a second aromatic diamine.
• the second aromatic diamine is selected from the group consisting of 4,4'- diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-bis(trifluoromethyl) benzidine, m-phenylenediamine and 4,4'-diaminodiphenylmethane.
• the core layer further includes both a second aromatic dianhydride and a second aromatic diamine.
• the polyimide of the core layer includes at least 80 mole percent 3,3',4,4'-biphenyl tetracarboxylic dianhydride based on a total dianhydride content of the polyimide and at least 80 mole percent p-phenylenediamine based on a total diamine content of the polyimide.
• the multilayer film has a coefficient of thermal expansion of less than 25 m/(meter-°C) over a temperature in the range of from 50 to 400°C.
• thermoplastic polyimide and the second thermoplastic polyimide each have a T g in the range of from 150 to 320°C.
• the multilayer film has a transmission of at least 50% and a haze of less than 30%.
• the multilayer film has a total thickness in a range of from 5 to 75 pm.
• the minimum peel strength of each of the first and second outer layers is greater than 0.9 kgf/cm (0.88 N/mm).
• a metal-clad laminate includes the multilayer film of the first aspect and a first metal layer adhered to an outer surface of the first outer layer of the multilayer film.
• the metal-clad laminate further includes a second metal layer adhered to an outer surface of the second outer layer of the multilayer film.
• a core layer for a multilayer film includes a polyimide synthesized by a poly-condensation reaction, involving the reaction of a first aromatic dianhydride comprising 3,3',4,4'-biphenyl tetracarboxylic dianhydride with a first aromatic diamine comprising p-phenylenediamine.
• the polyimide can include one or more additional aromatic dianhydrides, one or more additional aromatic diamines, or both additional aromatic dianhydrides and additional aromatic diamines.
• a second aromatic dianhydride can be selected from the group consisting of 4,4'-oxydiphthalic dianhydride, pyromellitic dianhydride, 3, 3', 4,4'- benzophenone tetracarboxylic dianhydride, bisphenol A dianhydride, 1 ,2,5,6- naphthalene tetracarboxylic dianhydride, 1 ,4,5,8-naphthalene tetracarboxylic dianhydride, and 2,3,6,7-naphthalene tetracarboxylic dianhydride.
• a second aromatic diamine can be selected from the group consisting of 4,4'-diaminodiphenyl ether (ODA), 3,4'-diaminodiphenyl ether, 2,2'-bis(trifluoromethyl) benzidine (TFMB), m-phenylenediamine (MPD) and 4,4'-diaminodiphenylmethane (MDA).
• ODA 4,4'-diaminodiphenyl ether
• TFMB 2,2'-bis(trifluoromethyl) benzidine
• MPD m-phenylenediamine
• MDA 4,4'-diaminodiphenylmethane
• the polyimide can include an aliphatic diamine.
• the core layer can be a thermoset polyimide.
• the core layer can include a polyimide with some thermoplastic properties.
• a first outer layer for a multilayer film includes a first thermoplastic polyimide.
• the first thermoplastic polyimide can be synthesized by a poly-condensation reaction, involving the reaction of an aromatic dianhydride and an aromatic diamine.
• the first thermoplastic polyimide can include one or more additional aromatic dianhydrides, one or more additional aromatic diamines, or both additional aromatic dianhydrides and additional aromatic diamines.
• a second outer layer for a multilayer film includes a second thermoplastic polyimide.
• the second thermoplastic polyimide can be synthesized by a poly-condensation reaction, involving the reaction of an aromatic dianhydride and an aromatic diamine.
• the second thermoplastic polyimide can include one or more additional aromatic dianhydrides, one or more additional aromatic diamines, or both additional aromatic dianhydrides and additional aromatic diamines.
• the first outer layer, the second outer layer, or both the first and the second outer layers can include one or more aliphatic diamines, which may be useful to lower the T g of the outer layers, if desired.
• the first thermoplastic polyimide and the second thermoplastic polyimide can be the same or different.
• an "aromatic diamine” is intended to mean a diamine having at least one aromatic ring, either alone (i.e., a substituted or unsubstituted, functionalized or unfunctionalized benzene or similar-type aromatic ring) or connected to another (aromatic or aliphatic) ring, and such an amine is to be deemed aromatic, regardless of any non-aromatic moieties that might also be a component of the diamine.
• an aromatic diamine backbone chain segment is intended to mean at least one aromatic moiety between two adjacent imide linkages.
• an "aliphatic diamine” is intended to mean any organic diamine that does not meet the definition of an aromatic diamine.
• diamine as used herein is intended to mean: (i) the unreacted form (i.e., a diamine monomer); (ii) a partially reacted form (i.e., the portion or portions of an oligomer or other polyimide precursor derived from or otherwise attributable to diamine monomer) or (iii) a fully reacted form (the portion or portions of the polyimide derived from or otherwise attributable to diamine monomer).
• the diamine can be
• diamine is not intended to be limiting (or interpreted literally) as to the number of amine moieties in the diamine component.
• (ii) and (iii) above include polymeric materials that may have two, one, or zero amine moieties.
• the diamine may be functionalized with additional amine moieties (in addition to the amine moieties at the ends of the monomer that react with dianhydride to propagate a polymeric chain). Such additional amine moieties could be used to crosslink the polymer or to provide other functionality to the polymer.
• dianhydride as used herein is intended to mean the component that reacts with (is complimentary to) the diamine and in combination is capable of reacting to form an intermediate polyamic acid (which can then be cured into a polyimide).
• dianhydride as used herein is intended to mean the component that reacts with (is complimentary to) the diamine and in combination is capable of reacting to form an intermediate polyamic acid (which can then be cured into a polyimide).
• anhydride as used herein can mean not only an anhydride moiety per se, but also a precursor to an anhydride moiety, such as: (i) a pair of carboxylic acid groups (which can be converted to anhydride by a de-watering or similar- type reaction); or (ii) an acid halide (e.g., chloride) ester functionality (or any other functionality presently known or developed in the future which is) capable of conversion to anhydride functionality.
• an acid halide e.g., chloride
• dianhydride can mean: (i) the unreacted form (i.e. a dianhydride monomer, whether the anhydride functionality is in a true anhydride form or a precursor anhydride form, as discussed in the prior above paragraph); (ii) a partially reacted form (i.e., the portion or portions of an oligomer or other partially reacted or precursor polyimide composition reacted from or otherwise attributable to dianhydride monomer) or (iii) a fully reacted form (the portion or portions of the polyimide derived from or otherwise attributable to dianhydride monomer).
• the dianhydride can be functionalized with one or more moieties, depending upon the particular embodiment selected in the practice of the present invention.
• the term "dianhydride” is not intended to be limiting (or interpreted literally) as to the number of anhydride moieties in the dianhydride component.
• (i), (ii) and (iii) include organic substances that may have two, one, or zero anhydride moieties, depending upon whether the anhydride is in a precursor state or a reacted state.
• the dianhydride component may be
• additional anhydride type moieties in addition to the anhydride moieties that react with diamine to provide a polyimide.
• additional anhydride moieties could be used to crosslink the polymer or to provide other functionality to the polymer.
• any one of a number of polyimide manufacturing processes may be used to prepare multilayer films. It would be impossible to discuss or describe all possible polyimide manufacturing processes useful in the practice of the present invention. It should be appreciated that the monomer systems of the present invention are capable of providing the above-described advantageous properties in a variety of manufacturing processes.
• the compositions of the present invention can be manufactured as described herein and can be readily manufactured in any one of many (perhaps countless) ways by those of ordinarily skilled in the art, using any
• 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 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).
• Useful organic solvents for the synthesis of the polyimides of the present invention are preferably capable of dissolving the polyimide precursor materials.
• Such a solvent should also have a relatively low boiling point, such as below 225°C, so the polymer can be dried at moderate (i.e., more convenient and less costly) temperatures.
• a boiling point of less than 210, 205, 200, 195, 190, or 180°C is preferred.
• Solvents of the present invention may be used alone or in combination with other solvents (i.e., co-solvents).
• Useful organic solvents include: N- methylpyrrolidone (NMP), dimethylacetamide (DMAc), N,N'-dimethyl- formamide (DMF), dimethyl sulfoxide (DMSO), tetramethyl urea (TMU), diethyleneglycol diethyl ether, 1 ,2-dimethoxyethane (monoglyme), diethylene glycol dimethyl ether (diglyme), 1 ,2-bis-(2-methoxyethoxy) ethane (triglyme), bis [2-(2-methoxyethoxy) ethyl)] ether (tetraglyme), gamma-butyrolactone, and bis-(2-methoxyethyl) ether, tetrahydrofuran.
• preferred solvents include N-methylpyrrolidone (NMP) and dimethylace
• Co-solvents can generally be used at about 5 to 50 weight percent of the total solvent, and useful such co-solvents include xylene, toluene, benzene, "Cellosolve” (glycol ethyl ether), and "Cellosolve acetate"
• any number of suitable aromatic diamines can also be included in the core layer polyimide, including m- phenylenediamine (MPD), 2,5-dimethyl-1 ,4-diaminobenzene, trifluoromethyl- 2,4-diaminobenzene, trifluoromethyl-3,5-diaminobenzene, 2,5-dimethyl-1 ,4- phenylenediamine (DPX), 2,2-bis-(4-aminophenyl) propane, 4,4'- diaminobiphenyl, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane (MDA), 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'- diaminodiphenyl
• MDA 4,4'-diaminodiphenyl sulfide
• aromatic diamines include 2,2'-bis(trifluoromethyl) benzidine (TFMB), 1 ,2-bis-(4-aminophenoxy)benzene, 1 ,3-bis-(4- aminophenoxy) benzene, 1 ,2-bis-(3-aminophenoxy)benzene, 1 ,3-bis-(3- aminophenoxy) benzene, 1 -(4-aminophenoxy)-3-(3-aminophenoxy) benzene, 1 ,4-bis-(4-aminophenoxy) benzene, 1 ,4-bis-(3-aminophenoxy) benzene, 1 -(4- aminophenoxy)-4-(3-aminophenoxy) benzene, 2,2-bis-(4-[4- aminophenoxy]phenyl) propane (BAPP), 2,2'-bis-(4-aminophenyl)-hexafluoro propane (6F diamine), 2,2'-bis-
• useful aromatic diamines include the isomers of bis-aminophenoxybenzenes (APB), aminophenoxyphenylpropane (BAPP), dimethylphenylenediamine (DPX), bisaniline P, and combinations thereof, and the use of these particular aromatic diamines can lower the lamination temperature of the polyimide, and can increase the peel strength of the polyimide when adhered to other materials, especially metals.
• APIB bis-aminophenoxybenzenes
• BAPP aminophenoxyphenylpropane
• DPX dimethylphenylenediamine
• bisaniline P bisaniline P
• thermoplastic polyimide of the outer layers can include one or more of any of the aromatic diamines listed above for the core layer, including p-phenylenediamine.
• the core layer includes 3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA) as a first aromatic dianhydride
• BPDA 3,3',4,4'-biphenyl tetracarboxylic dianhydride
• any aromatic dianhydride or combination of aromatic dianhydrides can be used as additional dianhydride monomers in forming the core layer polyimide.
• the dianhydrides can be used in their tetra-acid form (or as mono, di, tri, or tetra esters of the tetra acid), or as their diester acid halides (chlorides).
• the dianhydride form can be preferred, because it is generally more reactive than the acid or the ester.
• aromatic dianhydrides include, 1 ,2,5,6- naphthalene tetracarboxylic dianhydride, 1 ,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 2-(3',4'- dicarboxyphenyl) 5,6-dicarboxybenzimidazole dianhydride, 2-(3',4'- dicarboxyphenyl) 5,6-dicarboxybenzoxazole dianhydride, 2-(3',4'- dicarboxyphenyl) 5,6-dicarboxybenzothiazole dianhydride, 2, 2', 3,3'- benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dian
• thermoplastic polyimide of the outer layers can include one or more of any of the aromatic dianhydrides listed above for the core layer, including 3,3',4,4'-biphenyl tetracarboxylic dianhydride.
• Polyimide film layers according to the present invention can be produced by combining the diamine and dianhydride (monomer or other polyimide precursor form) together with a solvent to form a polyamic acid (also called a polyamide acid) solution.
• the dianhydride and diamine can be combined in a molar ratio of about 0.90 to 1 .10.
• the molecular weight of the polyamic acid formed therefrom can be adjusted by adjusting the molar ratio of the dianhydride and diamine.
• a polyamic acid casting solution is derived from the polyamic acid solution.
• the polyamic acid casting solution preferably comprises the polyamic acid solution can optionally be combined with conversion chemicals like: i.) one or more dehydrating agents, such as, aliphatic acid anhydrides (acetic anhydride, etc.) and/or aromatic acid anhydrides; and ii.) one or more catalysts, such as, aliphatic tertiary amines (triethyl amine, etc.), aromatic tertiary amines (dimethyl aniline, etc.) and heterocyclic tertiary amines (pyridine, picoline, isoquinoline, etc.).
• dehydrating agents such as, aliphatic acid anhydrides (acetic anhydride, etc.) and/or aromatic acid anhydrides
• catalysts such as, aliphatic tertiary amines (triethyl amine, etc.), aromatic tertiary amines (dimethyl
• the anhydride dehydrating material it is often used in molar excess compared to the amount of amide acid groups in the polyamic acid.
• the amount of acetic anhydride used is typically about 2.0 - 4.0 moles per equivalent (repeat unit) of polyamic acid.
• a comparable amount of tertiary amine catalyst is used.
• the polyamic acid solution, and/or the polyamic acid casting solution is dissolved in an organic solvent at a concentration from about 5.0 or 10 % to about 15, 20, 25, 30, 35 and 40 % by weight.
• the polyamic acid (and casting solution) can further comprise any one of a number of additives, such as processing aids (e.g., oligomers),
• inorganic fillers include thermally conductive fillers, like metal oxides, inorganic nitrides and metal carbides, and electrically conductive fillers like metals, graphitic carbon and carbon fibers, and electrically conductive polymers.
• thermally conductive fillers like metal oxides, inorganic nitrides and metal carbides, and electrically conductive fillers like metals, graphitic carbon and carbon fibers, and electrically conductive polymers.
• Common inorganic fillers are alumina, silica, silicon carbide, diamond, clay, boron nitride, aluminum nitride, titanium dioxide, dicalcium phosphate, and fumed metal oxides.
• Common organic fillers include polyaniline, polythiophene, polypyrrole, polyphenylenevinylene, polydialkylfluorenes, carbon black, graphite, multiwalled and single walled carbon nanotubes and carbon nanofibers.
• the solvated mixture (the polyamic acid casting solution) can then be cast or applied onto a support, such as an endless belt or rotating drum, to give a film.
• the solvent containing-film can be converted into a self- supporting film by heating at an appropriate temperature (thermal curing) together with conversion chemical reactants (chemical curing).
• the film can then be separated from the support, oriented such as by tentering, with continued thermal and chemical curing to provide a polyimide film.
• Useful methods for producing polyimide film in accordance with the present invention can be found in U.S. Patent Nos. 5, 166,308 and 5,298,331 , which are incorporate by reference into this specification for all teachings therein. Numerous variations are also possible, such as,
• each polyimide layer may be adjusted, depending on the intended purpose of the film or final application specifications.
• the multilayer film has a total thickness of from about 5 to about 150 pm. In one embodiment, the multilayer film has a total thickness of from about 5 to about 75 pm. In one embodiment, the thickness of the core layer is in a range of from about 35 to about 73% of the total thickness of the multilayer film.
• a multilayer film might have an overall thickness of 30 pm, with a 22 pm core layer and 4 pm first and second outer layers on either side of the core layer.
• a multilayer film might have an overall thickness of 50 pm, with a 34 pm core layer and 7 pm first and second outer layers on either side of the core layer.
• a multilayer film might have an overall thickness of 5 pm, with a 2 pm core layer and 1 .5 pm first and second outer layers on either side of the core layer.
• the thickness of the core layer is in a range of from about 55 to about 73% of the total thickness of the multilayer film.
• a minimum thickness of the outer layers with thermoplastic polyimide is needed to provide sufficient adhesion to metal layers to form a useful metal- clad laminate for electronic circuitry applications.
• a minimum thickness of the core layer is needed to maintain the mechanical integrity of the multilayer film.
• the first thermoplastic polyimide and the second thermoplastic polyimide of the multilayer film both have a T g in the range of from about 150 to about 320°C. In a specific embodiment, the first thermoplastic polyimide and the second thermoplastic polyimide of the multilayer film both have a T g in the range of from about 230 to about 320°C. In a more specific embodiment, the first thermoplastic polyimide and the second thermoplastic polyimide of the multilayer film both have a T g in the range of from about 270 to about 320°C. Having thermoplastic polyimides in the outer layers with a higher T g improves the thermal durability of the multilayer film.
• Metal-clad laminates may undergo post-lamination processes such as hot-bar processing or spot welding at temperatures in excess of 300°C. Under these conditions, a low T g thermoplastic polyimide layer is susceptible to adhesion loss and delamination, distortion and blistering which can be accompanied by a decrease in optical transmission and an increase in haze. Maintaining good optical clarity can be extremely important for some electronics manufacturing processes, for instance, when optical registration is used to align various layers in a printed circuit board. In these applications, high transmission and low haze can be critical for circuit designs with extremely fine features. It is important to maintain optical clarity even during higher temperature curing, which may be used to stabilize materials that will be subjected to these higher temperature post-lamination processes. In one embodiment, the multilayer film has a transmission of at least 50% and a haze of less than 30%.
• the core layer and the outer layers can be simultaneously solution cast by co-extrusion.
• the polyimides can be in the form of a polyamic acid solution.
• the cast solutions form an uncured polyamic acid film that is later cured to a polyimide.
• the adhesion strength of such laminates can be improved by employing various techniques for elevating adhesion strength.
• a finished polyamic acid solution is filtered and pumped to a slot die, where the flow is divided in such a manner as to form the first outer layer and the second outer layer of a three-layer coextruded film.
• a second stream of polyimide is filtered, then pumped to a casting die, in such a manner as to form the middle polyimide core layer of a three-layer coextruded film. The flow rates of the solutions can be adjusted to achieve the desired layer thickness.
• the multilayer film is prepared by
• the layers are extruded through a single or multi-cavity extrusion die.
• the multilayer film is produced using a single-cavity die. If a single-cavity die is used, the laminar flow of the streams should be of high enough viscosity to prevent comingling of the streams and to provide even layering.
• the multilayer film is prepared by casting from the slot die onto a moving stainless-steel belt. In one embodiment, the belt is then passed through a convective oven, to evaporate solvent and partially imidize the polymer, to produce a "green" film. The green film can be stripped off the casting belt and wound up. The green film can then be passed through a tenter oven to produce a fully cured polyimide film. In some embodiments, during tentering, shrinkage can be minimized by constraining the film along the edges (i.e., using clips or pins).
• the outer layers of the present invention can also be applied to the core layer during an intermediate manufacturing stage of making polyimide film such as to gel film or to green film.
• gel film refers to a polyamic acid sheet, which is laden with volatiles, primarily solvent, to such an extent that the polyamic acid is in a gel- swollen, or rubbery condition, and may be formed in a chemical conversion process.
• volatile content is usually in the range of 70 to 90 % by weight and the polymer content usually in the range of 10 to 30 % by weight of the gel film.
• the final film becomes "self-supporting" in the gel film stage. It can be stripped from the support on which it was cast and heated to a final curing temperature.
• the gel film generally has an amic acid to imide ratio between 10:90 and 50:50, most often 30:70.
• the gel film structure can be prepared by the method described in U.S.
• Patent No. 3,410,826 discloses mixing a chemical converting agent and a catalyst, such as a lower fatty acid anhydride and a tertiary amine, into the polyamic-acid solution at a low temperature. This is followed by casting the polyamic-acid solution in film-form, onto a casting drum. The film is mildly heated after casting, at for example 100°C, to activate the conversion agent and catalyst in order to transform the cast film to a polyamic acid / polyimide gel film.
• a catalyst such as a lower fatty acid anhydride and a tertiary amine
• Green film is a "green film" which is partially polyamic acid and partially polyimide, and may be formed in a thermal conversion process.
• Green film contains generally about 50 to 75% by weight polymer and 25 to 50 % by weight solvent. Generally, it should be sufficiently strong to be substantially self-supporting.
• Green film can be prepared by casting the polyamic acid solution into film form onto a suitable support such as a casting drum or belt and removing the solvent by mild heating at up to 150°C. A low proportion of amic acid units in the polymer, e.g., up to 25 %, may be converted to imide units.
• polyimide films of the present invention can be accomplished in any number of ways. Such methods include using a slot die, dip coating, or kiss-roll coating a film followed by metering with doctor knife, doctor rolls, squeeze rolls, or an air knife.
• the coating may also be applied by brushing or spraying.
• it is possible to prepare both one and two-sided coated laminates. In preparation of the two-side coated structures, one can apply the coatings to the two sides of a polyimide either simultaneously or consecutively before going to the curing and drying stage of the polyimide.
• the multilayer film has a coefficient of thermal expansion (CTE) of less than 25 pm/(meter-°C) over a temperature in the range of from about 50 to about 400°C. Keeping a low CTE over a broad temperature enables the multilayer film to maintain good adhesion even during higher temperature curing, which may be used to stabilize materials that will be subjected to higher temperature post-lamination processing.
• CTE coefficient of thermal expansion
• Metal-clad laminates may undergo hot-bar processing or spot welding at temperatures in excess of 300°C. Under these conditions, a multilayer film with a CTE of greater than 25 pm/(meter-°C) over a temperature in the range of from about 50 to about 400°C is susceptible to adhesion loss and delamination, distortion and blistering.
• a conductive layer of the present invention can be created by:
• a lamination process may be used to form a metal-clad laminate with a multilayer film.
• a first outer layer including a first thermoplastic polyimide is placed between a first conductive layer and a core layer, and a second outer layer including a second thermoplastic polyimide is placed on the opposite side of the core layer.
• a second conductive layer is placed in contact with the second outer layer on a side opposite the core layer.
• the polyimide film prior to the step of applying the multilayer film of the present invention onto a metal foil, can be subjected to a pre-treatment step.
• Pre-treatment steps can include, heat treatment, corona treatment, plasma treatment under atmospheric pressure, plasma treatment under reduced pressure, treatment with coupling agents like silanes and titanates, sandblasting, alkali-treatment, acid-treatments, and coating polyamic acids.
• coupling agents like silanes and titanates
• sandblasting alkali-treatment
• acid-treatments and coating polyamic acids.
• the conductive metal surface may be treated with various organic and inorganic treatments. These treatments include using silanes, imidazoles, triazoles, oxide and reduced oxide treatments, tin oxide treatment, and surface cleaning/roughening (called micro-etching) via acid or alkaline reagents.
• the polyamic acid precursor (to a polyimide film of the present invention) may be coated on a fully cured polyimide base film or directly on a metal substrate and subsequently imidized by heat treatment.
• the polyimide base film may be prepared by either a chemical or thermal conversion process and may be surface treated, e.g. by chemical etching, corona treatment, laser etching etc., to improve adhesion.
• conductive layers and “conductive foils” mean metal layers or metal foils (thin compositions having at least 50% of the electrical conductivity of a high-grade copper).
• Conductive foils are typically metal foils. Metal foils do not have to be used as elements in pure form; they may also be used as metal foil alloys, such as copper alloys containing nickel, chromium, iron, and other metals.
• the conductive layers may also be alloys of metals and are typically applied to the polyimides of the present invention via a sputtering step followed by an electro-plating step. In these types of processes, a metal seed coat layer is first sputtered onto a polyimide film. Finally, a thicker coating of metal is applied to the seed coat via electroplating or electro-deposition. Such sputtered metal layers may also be hot pressed above the glass transition temperature of the polymer for enhanced peel strength.
• Particularly suitable metallic substrates are foils of rolled, annealed copper or rolled, annealed copper alloy.
• This pre- treatment may include, but is not limited to, electro-deposition or immersion- deposition on the metal of a thin layer of copper, zinc, chrome, tin, nickel, cobalt, other metals, and alloys of these metals.
• the pre-treatment may consist of a chemical treatment or a mechanical roughening treatment. It has been found that this pre-treatment enables the adhesion of the polyimide layer and, hence, the peel strength to be further increased.
• a multilayer film when adhered to a copper foil and tested following ASTM method IPC-TM-650, method No. 2.4.9B, has a minimum peel strength of greater than 0.9 kgf/cm (0.88 N/mm) for at least one of the first and second outer layers. In a specific embodiment, the multilayer film has a minimum peel strength of greater than 0.9 kgf/cm (0.88 N/mm) for each of the first and second outer layers.
• a metal-clad laminate can include the multilayer film and a first metal layer adhered to an outer surface of the first outer layer of the multilayer film.
• a metal-clad laminate can include a second metal layer adhered to an outer surface of the second outer layer of the multilayer film.
• the first metal layer, the second metal layer or both metal layers can be copper.
• a metal-clad laminate of the present invention comprising a double side copper-clad can be prepared by laminating copper foil to both sides of the multilayer film.
• the polyimide films of the present invention generally also have a low loss-tangent value. Loss-tangent is typically measured at 10 GHz and is used to measure a dielectric material's degradation of a nearby digital signal that is passing through a metal circuit trace. Different loss-tangent values exist for different dielectric materials. The lower the loss-tangent value for a given dielectric material, the (increasingly) superior a material is for digital circuitry applications.
• the polyimides of the present invention exhibit excellent, low loss-tangent values. In one embodiment, the loss-tangent value for the polyimide layers was less than 0.010, about 0.004, at 10 GHz.
• the polyimides of present invention may also be used in applications ranging from 1 to 100 GHz, with 1 to 20 GHz being most common.
• the multilayer films of the present invention are used as a material to construct a planar transformer component.
• planar transformer components are commonly used in power supply devices.
• the polyimide films of the present invention may be used with thick metal foils to form flexible heaters. These heaters are typically used in automotive and aerospace applications.
• the multilayer films of the present invention exhibit excellent attenuation.
• the polyimides of the present invention can often exhibit an attenuation value, measured in decibels per inch, of about 0.3 at 10 GHz using a 50-ohm micro strip.
• a polyimide precursor for a core layer and polyimide precursors for first and second outer layers are cast simultaneously (using a multi-port die) to form a multilayer polyimide film (after curing of the polyamic acid layers).
• This multilayer film is then bonded to metal layer(s) using the thermoplastic polyimide of the outer layer(s) as the bonding layer to the metal layer(s).
• a multilayer film metal-clad laminate formed comprises the multilayer film and at least one conductive layer. Bonding of the multilayer polyimide/metal-clad laminates, when a metal foil is used as the conductive layer, can take place in a double belt press in roll to roll processing, or in an autoclave in sheet to sheet processing.
• the polyimides of the present invention are particularly useful for die pad bonding of flexible print connection boards or semiconductor devices or packaging materials for CSP (chip scale package), chip on flex (COF), COL
• BGA micro-ball grid array
• TAB tape automated bonding
• the multilayer films of the present invention are used for wafer level integrated circuit packaging, where a composite is made using a multilayer film according to the present invention interposed between a conductive layer (typically a metal) having a thickness of less than 100 m, and a wafer comprising a plurality of integrated circuit dies.
• a conductive layer typically a metal
• the conductive passageway is connected to the dies by a conductive passageway, such as a wire bond, a conductive metal, a solder bump or the like.
• Transparency was measured using a Haze-Guard Plus (BYK-Gardner GmbH, Germany). The total transmittance (normal and diffuse transmitted light) was recorded over a wavelength range of 400-700 nm and is reported as percent transmission.
• Haze was also measured using the Haze-Guard Plus, with the haze measured in transmission by collecting forward scattered light using the method described by ASTM1003. Percent haze was determined by measuring the amount of light which deviates from the incident beam by more than 2.5 degrees on average.
• Polyamic acid solutions for producing the core layer and outer layers were separately prepared by a chemical reaction between the appropriate molar equivalents of the monomers in dimethylacetamide (DMAc) solvent.
• DMAc dimethylacetamide
• the diamine dissolved in DMAc was stirred under nitrogen, and the dianhydride was added as a solid over a period of several minutes. Stirring was continued to obtain maximum viscosity of the polyamic acid. The viscosity was adjusted by controlling the amount of dianhydride in the polyamic acid composition.
• Multilayer films were cast by co-extrusion. Three separate polyamic polymer streams were simultaneously extruded through a multi-cavity extrusion die onto a heated moving belt to form a co-extruded three-layer polyimide film. The thicknesses of the polyimide core layer and the top and bottom thermoplastic polyimide outer layers were adjusted by varying the amounts of polyamic acids fed to the extruder.
• the extruded multilayer film was dried at an oven temperature in the range of from about 95 to about 150°C.
• the self-supporting film was peeled from the belt and heated with radiant heaters in a tenter oven at a
• Example 1 the radiant heating set point temperature used to cure the film was 805°C.
• the core layer polymer composition contained a polyimide derived from an approximately 1 : 1 molar ratio of dianhydride to diamine.
• the dianhydride composition contained the monomers
• the thermoplastic outer layers also contained a polyimide derived from an approximately 1 : 1 molar ratio of dianhydride to diamine.
• the dianhydride composition contained the monomers PMDA and ODPA in a 20:80 molar ratio and the diamine composition was 100 mole % RODA monomer.
• the flow rates of the polyamic acid solutions were adjusted to yield a three-layer film in which the thermoplastic outer layers were approximately 8.1 and 7.1 pm thick, respectively.
• a cross sectional scanning electron microscope (SEM) image of the three-layer film was obtained to determine the thicknesses of the multilayer film and the individual core and outer layers.
• SEM scanning electron microscope
• a portion of the multilayer film was used to prepare a copper-clad laminate for measuring peel strength.
• Cu foil was laminated to both sides of the multilayer film.
• Roll dads were made by continuous lamination of the adhesive coated dielectric film to copper foil using a high temperature nip roll laminator with one surface heated to 350°C.
• Adhesion, or peel strength, of the polyimide copper-clad laminates was measured following ASTM method IPC-TM-650, Method No. 2.4.9B, with resulting peel strengths of 1 .0 kgf/cm (0.98 N/mm) and 1.13 kgf/cm (1.1 N/mm).
• Comparative Example 1 For Comparative Example 1 (CE1 ), a film was co-extruded to form a three-layer film using a process similar to that of E .
• the compositions of the core layer and the outer layers were the same as in E1.
• the flow rates of the polyamic acid solutions were adjusted to yield a three-layer architecture in which the two outer layers were approximately 6.6 and 6.1 pm thick, respectively.
• the total thickness of the multilayer film was 48.7 ⁇ , and the core layer thickness as a percentage of the total multilayer film thickness was 73.9%.
• the transmission of CE1 , 46.1 %, was significantly lower than that of E1 , while the haze, 35.2%, was noticeably higher.
• Example 2 For Example 2 (E2), a film was co-extruded to form a three-layer film using a process similar to that of E1 .
• the compositions of the core layer and the outer layers were the same as in E1 .
• the flow rates of the polyamic acid solutions were adjusted to yield a three-layer architecture in which the two outer layers were each approximately 1 .8 pm thick.
• the total thickness of the multilayer film was 12.4 ⁇ .
• the core layer thickness as a percentage of the total multilayer film thickness was 71 .1 %.
• Example 2 For Comparative Example 2 (CE2), a film was co-extruded to form a three-layer film using a process similar to that of E1 .
• the compositions of the core layer and the outer layers were the same as in E1.
• the flow rates of the polyamic acid solutions were adjusted to yield a three-layer architecture in which the two outer layers were approximately 3.0 and 4.6 ⁇ thick, respectively.
• the total thickness of the multilayer film was 31.4 ⁇ .
• the core layer thickness as a percentage of the total multilayer film thickness was 76.0%.
• Example 3 For Comparative Example 3 (CE3), a film was co-extruded to form a three-layer film using a process similar to that of E1 .
• the core layer polymer composition contained a polyimide derived from a 1 : 1 molar ratio of dianhydride (BPDA) and diamine (PPD).
• BPDA dianhydride
• PPD diamine
• the compositions of the outer layers were the same as in E1 .
• the flow rates of the polyamic acid solutions were adjusted to yield a three-layer architecture in which the two outer layers were approximately 4.6 and 5.8 ⁇ thick, respectively.
• the total thickness of the multilayer film was 54.9 ⁇ .
• the core layer thickness as a percentage of the total multilayer film thickness was 81 .1 %.
• the transmission, 66.9%, and haze, 5.2%, of CE3 were both good, but the peel strengths of CE3, 0.82 kgf/cm (0.80 N/mm) and 0.85 kgf/cm (0.83 N/mm) were noticeably lower than for E1 .

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• 2018
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