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WO2008008170A1 - Ensembles utiles pour préparer des composants électroniques et leurs procédés de fabrication - Google Patents

Ensembles utiles pour préparer des composants électroniques et leurs procédés de fabrication Download PDF

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Publication number
WO2008008170A1
WO2008008170A1 PCT/US2007/014716 US2007014716W WO2008008170A1 WO 2008008170 A1 WO2008008170 A1 WO 2008008170A1 US 2007014716 W US2007014716 W US 2007014716W WO 2008008170 A1 WO2008008170 A1 WO 2008008170A1
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WO
WIPO (PCT)
Prior art keywords
reinforced thermoplastic
layer
assembly according
thermoplastic
conductive 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.)
Ceased
Application number
PCT/US2007/014716
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English (en)
Inventor
Matthew Raymond Himes
John Charles Frankosky
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.)
Arlon LLC
Original Assignee
Arlon LLC
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 Arlon LLC filed Critical Arlon LLC
Priority to EP20070809866 priority Critical patent/EP2039231A1/fr
Publication of WO2008008170A1 publication Critical patent/WO2008008170A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D1/00—Woven fabrics designed to make specified articles
    • D03D1/0082—Fabrics for 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
    • 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
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • 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
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0237—High frequency adaptations
    • H05K1/024—Dielectric details, e.g. changing the dielectric material around a transmission line
    • 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
    • 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
    • H05K2201/0158—Polyalkene or polyolefin, e.g. polyethylene [PE], polypropylene [PP]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0275—Fibers and reinforcement materials
    • H05K2201/0278—Polymeric fibers
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]

Definitions

  • the present invention relates to assemblies and laminate structures, methods for making same, and uses thereof.
  • Invention assemblies and laminate structures are useful, for example, in the preparation of components used in RF applications, applications where low electrical loss products are required, e.g., in cellular telecommunications, RF antennas, satellite communications, radar, power amplifiers, high speed digital applications, laminate-based chip carriers, and the like.
  • Laminate structures employed in cellular telecommunications, laminate- based chip carriers, and the like must meet a number of physical and electrical performance criteria, e.g., low loss, low dielectric constant, good heat resistance, good dimensional stability, low density, and the like.
  • thermoplastic resins are commonly used for the preparation of substrates for laminate and prepreg systems.
  • thermoplastics frequently have limitations which may preclude their use as a substrate material in foil-clad laminate structures. These limitations may include insufficient the ⁇ no-mechanical stability and an inability to form a sufficient bond with the foil cladding,
  • Thermoplastic materials used in the preparation of laminate and prepreg systems preferably have glass and melt transition temperatures which are higher than the maximum temperatures achieved during processing of the substrate (e.g., the temperature achieved for processing of a printed circuit board).
  • the maximum temperatures achieved during processing of the substrate e.g., the temperature achieved for processing of a printed circuit board.
  • thermoplastic materials are frequently expensive.
  • a thermally-resistant reinforcement is added to a thermoplastic polymer to form a composite substrate.
  • One method for adding reinforcement to the substrate includes uniformly blending microfibers into the polymer for the preparation of the substrate, However, the amount of microfiber that may be incorporated into a substrate by this method is limited.
  • An alternate method for preparing a reinforced substrate is to coat a fabric- like reinforcement with a thermoplastic polymer.
  • this method has limitations as this route of preparation maybe limited to co-extrusion, which can be difficult to perform with light-weight reinforcements, as are typically required for use with PCB substrates.
  • inventions there are provided novel assemblies and laminate structures, methods for the preparation thereof, and various uses therefor.
  • invention materials are useful, for example, in the preparation of components used in RF applications, applications where low electrical loss products are required, e.g., in cellular telecommunications, RF antennas, satellite communications, radar, power amplifiers, high speed digital applications, laminate-based chip carriers, and the like.
  • assemblies comprising: (a) a first reinforced thermoplastic-containing layer and (b) a first non-reinforced thermoplastic layer, wherein the reinforced thermoplastic-containing layer and the non-reinforced thermoplastic layer are capable of interacting sufficiently so as to form a bond therebetween, wherein said first reinforced thermoplastic-containing layer comprises a porous substrate impregnated with a composition comprising:
  • thermoset (b) a second component which is capable of crosslinking to produce a thermoset in the presence of the first component
  • assembly refers to a structure comprising at least one reinforced thermoplastic layer and at least one non-reinforced thermoplastic layer for use in the preparation of a multilayer structure.
  • thermoplastic-containing layer As employed herein, the term "reinforced thermoplastic-containing layer"
  • thermoset resin refers to a porous substrate which is impregnated with a composition which includes a thermoplastic and thermoset resin.
  • the thermoset resin is partially cured, and may also include fillers and/or additives.
  • Exemplary reinforced thermoplastic containing layers are described, for example, in U.S. Ser. No. 11/006,211, filed December 6, 2004, which is incorporated by reference herein in its entirety.
  • porous substrate refers to a woven or non- woven substrate which can include, but is not limited to, woven glass, non- woven glass, woven aramid fibers, non-woven aramid fibers, woven liquid crystal polymer fibers, non- woven liquid crystal polymer fibers, woven synthetic polymer fibers, non-woven synthetic polymer fibers, randomly dispersed fiber reinforcements, expanded polytetrafluoroethylene (PTFE) structures and combinations of any two or more thereof.
  • PTFE polytetrafluoroethylene
  • materials contemplated for use as the "porous substrate” can include, but are not limited to, fiberglass, quartz, polyester fiber, polyamide fiber, polyphenylene sulfide fiber, polyetherimide fiber, cyclic olefin copolymer fiber, polyalkylene fiber, liquid crystalline polymer, poly(p-phenylene-2,6-benzobisoxazole), copolymers of polytetrafluoroethylene and perfluoromethylvinyl ether (MFA) and combinations of any two or more thereof.
  • MFA perfluoromethylvinyl ether
  • non-reinforced thermoplastic-containing layer refers to a substrate which includes a thermoplastic resin and does not include a porous substrate.
  • thermoplastic polymers refers to polymers which will repeatedly soften when heated and harden when cooled.
  • thermoplastic polymers may melt and possibly flow at elevated temperatures.
  • Exemplary thermoplastic polymers suitable for use in the present invention can include, but are not limited to, cyclic olefin copolymers, terpolymers, block copolymers, or combinations of any two or more thereof.
  • the thermoplastic polymer or resin employed for the reinforced and non- reinforced layers may be the same or may be different.
  • the thermoplastic polymers for the reinforced and non-reinforced layers have similar glass transition temperatures and coefficients of thermal expansion.
  • the thermoplastic resin is selected from cyclic olefin copolymers, polyetherimides, polyether ether ketones (PEEKs), liquid crystal polymers (LCPs), polytetrafluoroethlyene, polyphenylenesulfide, polyphenyleneoxide, polyphenylene ether, polymethylpentene (TPX), polypropylene, and. polyethylene.
  • cyclic olefin copolymers polyetherimides, polyether ether ketones (PEEKs), liquid crystal polymers (LCPs), polytetrafluoroethlyene, polyphenylenesulfide, polyphenyleneoxide, polyphenylene ether, polymethylpentene (TPX), polypropylene, and. polyethylene.
  • the thickness of the non-reinforced thermoplastic layer can vary widely, typically falling in the range of about 10 up to about 3000 microns or higher. In preferred embodiments, the non-reinforced thermoplastic layer has a thickness of at least 25 microns, up to about 1300 microns. In especially preferred embodiments, the reinforced thermoplastic layer has a thickness of at least 25 microns up to about 400 microns.
  • the reinforced thermoplastic-containing layer and the non-reinforced thermoplastic layer can interact to form a bond therebetween in a variety of ways.
  • the layers may interact as a result of having compatible melt solubility properties.
  • the reinforced thermoplastic-containing layer and the non-reinforced thermoplastic layer are capable of interacting to form an adhesive bond therebetween.
  • the reinforced thermoplastic-containing layer and the non-reinforced thermoplastic layer are capable of interacting to form a mechanical bond therebetween.
  • the reinforced thermoplastic-containing layer and the non-reinforced thermoplastic layer interact sufficiently, regardless of the mechanism of interaction, to produce an interlayer peel strength of at least about four pounds per linear inch.
  • cohesive bond refers to the intramolecular attractive forces which hold two or more bodies of like composition together.
  • adheresive bond refers to the forces, such as dipole bonds, which attract adhesives and base materials to each other.
  • low loss refers to materials which cause minimal energy dissipation when associated with electromagnetic signal transmission.
  • dielectric constant refers to the permittivity of a volume of material relative to that same volume of free space.
  • inventive materials have a dielectric constant of less than about 4.5, more preferably less than 3.0, and even more preferably close to about 2.5.
  • thermoset refers to a polymer or resin material which cures (sets) by a chemical reaction.
  • the thermoset may also require heat and/or pressure.
  • hydrocarbyl thermoplastic resins refers to polymeric materials which are prepared from non-heteroatom containing, unsaturated hydrocarbons, e.g., polyolefins, co-polymers including olefin monomers, cyclic olefin monomers, and the like, terpolymers, block copolymers, and the like.
  • Low loss, low dielectric constant, hydrocarbyl thermoplastic resins contemplated for use in the practice of the present invention can be characterized, for example, as materials which, when laminated, have a dielectric constant ⁇ 4.5 nominal, and an electrical loss tangent ⁇ 0.02.
  • the dielectric constant of the assembly is between 2.0 and 4.5.
  • such materials contemplated for use in the practice of the present invention may further be characterized as having a glass transition temperature > 80 0 C.
  • low loss, low dielectric constant, hydrocarbyl thermoplastic materials contemplated for use in the practice of the present invention may be further characterized as being capable of undergoing further crosslinking.
  • such materials can be rendered capable of undergoing further crosslinking by the presence of residual unsaturation thereon.
  • the low loss, low dielectric constant, hydrocarbyl thermoplastic resin can be rendered crosslinkable by the presence of one or more crosslinkable substituents thereon.
  • Exemplary low loss, low dielectric constant, hydrocarbyl thermoplastic resins contemplated for use in the practice of the present invention include cyclic olefin- containing copolymers, terpolymers, block copolymers, or combinations of any two or more thereof.
  • Examples of cyclic olefin-containing copolymers include copolymers of an aliphatic olefin and a cyclic olefin, copolymers of an olefin and norbornene, and the like.
  • copolymers can be synthesized in a variety of ways, e.g., by addition polymerization, by ring opening polymerization of norbornene with an olefin, and the like.
  • the molar ratio of olefin to norbornene can vary widely, typically falling in the range of about 1 :6 up to about 1 : 1.5.
  • the molecular weight of cyclic olefin-containing copolymers contemplated for use in the practice of the present invention can vary widely, typically falling in the range of about 500 up to about 100,000, with a preferred molecular weight typically falling in the range of about 20,000 up to about 90,000, with a molecular weight in the range of about 70,000 up to about 90,000 being the presently most preferred.
  • Components contemplated for use in the practice of the present invention which are capable of cros slinking to produce a thermoset in the presence of the first component can be monomelic, oligomeric or polymeric. Typically, such compounds are free-radically crosslinkable. In one aspect of the invention, such compounds are substantially non-polar.
  • thermoset exemplary components contemplated for use in the practice of the present invention which are capable of crosslinking to produce a thermoset have the structure (II) as follows:
  • q is an integer between 1 and 6, provided, however, that not all q's are 1 ,
  • each R is independently selected from hydrogen or lower alkyl
  • each Q when present, is independently selected from -CH 2 -, — O-, — O— C(O)-, -C(O)- or -C(O)-O-, and
  • each Y is independently a monovalent or polyvalent moiety, provided, however, that not all Y's are monovalent.
  • Monovalent or polyvalent Y can be selected from among many possibilities, such as, for example, hydrocarbyl, substituted hydrocarbyl, heteroatom- containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, and technically feasible combinations of any of the above with a linker selected from the group consisting of a covalent bond, -O-, -S-, - NR-, -O-C(O)-, -0-C(O)-O-, -0-C(O)-NR-, -NR-C(O)-, -NR-C(O)-O-, -NR-C(O)-NR-, -S-C(O)-, -S-C(O)-O-, -S-C(O)-NR-, -0-S(O) 2 -, -0-S(O) 2 -O
  • hydrocarbyl embraces alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic heterocylic, substituted monocyclic heterocyclic, monocyclic aromatic, monosubstituted monocyclic aromatic, or the like.
  • alkyl refers to hydrocarbyl radicals having 1 up to
  • substituted alkyl comprises alkyl groups further bearing one or more substituents selected from hydroxy, alkoxy (of a lower alkyl group), mercapto (of a lower alkyl group), cycloalkyl, substituted cycloalkyl, heterocyclic, substituted heterocyclic, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, substituted aryloxy, halogen, trifluoromethyl, cyano, nitro, nitrone, amino, amido, C(O)H, acyl, oxyacyl, carboxyl, carbamate, sulfonyl, sulfonamide, sulfuryl, and the like.
  • alkoxy refers to the moiety -O-alkyl-, wherein alkyl is as defined above, and "substituted alkoxy” refers to alkoxy groups further bearing one or more substituents as set forth above.
  • cycloalkyl refers to cyclic ring-containing groups containing in the range of about 3 up to S carbon atoms
  • substituted cycloalkyl refers to cycloalkyl groups further bearing one or more substituents as set forth above.
  • heterocyclic refers to cyclic (i.e., ring- containing) groups containing one or more heteroatoms (e.g., N, O, S, or the like) as part of the ring structure, and having in the range of 3 up to 14 carbon atoms and "substituted heterocyclic” refers to heterocyclic groups further bearing one or more substituents as set forth above.
  • heteroatoms e.g., N, O, S, or the like
  • alkenyl refers to straight or branched chain hydrocarbyl groups having at least one carbon-carbon double bond, and having in the range of about 2 up to 12 carbon atoms
  • substituted alkenyl refers to alkenyl groups further bearing one or more substituents as set forth above.
  • alkynyl refers to straight or branched chain hydrocarbyl groups having at least one carbon-carbon triple bond, and having in the range of about 2 up to 12 carbon atoms
  • substituted alkynyl refers to alkynylene groups further bearing one or more substituents as set forth above.
  • monocyclic aromatic refers to aromatic groups having in the range of 5 up to 7 carbon atoms and “monosubstituted monocyclic aromatic” refers to aromatic groups further bearing one of the substituents set forth above.
  • alkylene refers to divalent hydrocarbyl radicals having 1 up to 20 carbon atoms, preferably 2-10 carbon atoms; and "substituted alkylene” comprises alkylene groups further bearing one or more substituents as set forth above.
  • cycloalkylene refers to divalent cyclic ring- containing groups containing in the range of about 3 up to 8 carbon atoms
  • substituted cycloalkylene refers to cycloalkylene groups further bearing one or more substituents as set forth above.
  • cycloalkenylene refers to divalent, ene- functionalized (e.g., vinyl or allyl groups) cycloaliphatic groups containing in the range of about 3 up to 8 carbon atoms
  • substituted cycloalkenylene refers to cycloalkenylene groups further bearing one or more substituents as set forth above.
  • oxyalkylene refers to the divalent moiety -O- alkylene-, wherein alkylene is as defined above, and "substituted oxyalkylene” refers to oxyalkylene groups further bearing one or more substituents as set forth above.
  • oxyalkenylene refers to the divalent, ene- functionalized moiety -O-alkenylene-, wherein alkenylene is as defined herein, and "substituted oxyalkenylene” refers to oxyalkenylene groups further bearing one or more substituents as set forth above.
  • alkenylene refers to divalent, straight or branched chain hydrocarbyl groups having at least one carbon-carbon double bond, and having in the range of about 2 up to 12 carbon atoms
  • substituted alkenylene refers to alkenylene groups further bearing one or more substituents as set forth above.
  • alkynylene refers to divalent linear or branched chain hydrocarbyl groups having at least one carbon-carbon triple bond, and having in the range of about 2 up to 12 carbon atoms
  • substituted alkynylene refers to alkynylene groups further bearing one or more substituents as set forth above.
  • arylene refers to divalent aromatic groups having in the range of 6 up to 14 carbon atoms and "substituted arylene” refers to arylene groups further bearing one or more substituents as set forth above.
  • alkylarylene refers to alkyl-substituted arylene groups and "substituted alkylarylene” refers to alkylarylene groups further bearing one or more substituents as set forth above.
  • arylalkylene refers to aryl-substituted alkylene groups and "substituted arylalkylene” refers to arylalkylene groups further bearing one or more substituents as set forth above.
  • aryl alkenylene refers to aryl-substituted alkenylene groups and "substituted arylalkenylene” refers to arylalkenylene groups further bearing one or more substituents as set forth above.
  • arylalkynylene refers to aryl-substituted alkynylene groups and "substituted arylalkynylene” refers to arylalkynylene groups further bearing one or more substituents as set forth above.
  • thermoset presently preferred components contemplated for use in the practice of the present invention which are capable of crosslinking to produce a thermoset include thermally stable dielectric materials such as di-allylic compound(s), tri-allylic compound(s), di-vinylic compound(s), tri-vinylic compound(s), conjugated diene(s), non- conjugated diene(s), di(meth)acrylate compound(s), tri(meth)acrylate compound(s), and the like, as well as mixtures of any two or more thereof.
  • di-allylic compound(s), tri-allylic compound(s), di-vinylic compound(s), tri-vinylic compound(s), conjugated diene(s), non- conjugated diene(s), di(meth)acrylate compound(s), tri(meth)acrylate compound(s), and the like as well as mixtures of any two or more thereof.
  • the weight ratio between component (a) and component (b) of invention compositions can vary widely. Typically, such ratio falls in the range of about 1 :1 up to about 100:1. In preferred embodiments, the weight ratio between component (a) and component (b) of invention compositions falls in the range of about 1.5:1 up to about 99:1.
  • Free radical sources contemplated for use in the practice of the present invention can be either thermally or photochemically activated.
  • Free radical sources that are capable of being activated thermally include peroxides, azo compounds, redox initiators, azides, and the like, as well as mixtures of any two or more thereof.
  • Presently preferred peroxides are those having a decomposition temperature of at least about 50 0 C.
  • Exemplary peroxides contemplated for use in the practice of the present invention include ketone peroxides (e.g., methyl ethyl ketone peroxide, cyclohexanone peroxide, and the like), peroxyketals (e.g., l ,l-bis(t-butyl peroxy)-3,3,5-trimethylcyclohexane, 2,2-bis(t-butyl peroxy)butane, and the like), hydroperoxides (e.g., t-butyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and the like), dialkyl peroxides (e.g., dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxy)hexyne-3, o ⁇ fi'-bis
  • Exemplary redox initiators contemplated for use in the practice of the present invention include combinations of peroxides (e.g., H2O 2 ) and a ferrous salt, and the like.
  • An exemplary azide contemplated for use in the practice of the present invention is acetyl azide.
  • Exemplary compounds contemplated for use in this aspect of the present invention include benzophenone, 9-phenyl acridine, ethyl Michler's ketone (EMK), zinc acetylacetonate, triphenyl phosphine oxide, and the like, as well as mixtures of any two or more thereof.
  • the amount of free radical source incorporated into invention compositions can vary widely. Typically, the amount of component (c) employed in invention compositions will fall in the range of about 0.01- 10 weight percent, based on the total weight of the composition.
  • Optional additives contemplated for use in the practice of the present invention include fire retardants, fillers, fluorescent dyes, pigments, flow modifiers, plasticizers, cure retardants, cure accelerators, strength enhancers, UV protectors (especially UV blocking dyes appropriate to enable Automatic-Optical Inspection (AOI) of Circuitry) , and the like, as well as mixtures of any two or more thereof.
  • fire retardants include fire retardants, fillers, fluorescent dyes, pigments, flow modifiers, plasticizers, cure retardants, cure accelerators, strength enhancers, UV protectors (especially UV blocking dyes appropriate to enable Automatic-Optical Inspection (AOI) of Circuitry) , and the like, as well as mixtures of any two or more thereof.
  • Fire retardants contemplated for use in the practice of the present invention include substantially halogen-free fire retardants, halogenated fire retardants, phosphorus- containing fire retardants, additive and/or reactive flame retardants which may serve as intumescents or char formers, silanes, siloxanes, low melting glasses, zinc-, boron-, aluminum-, or magnesium-based fire retardants, and the like.
  • fire retardants include phosphites, phosphates (e.g., butylated triphenyl phosphate, ammonium polyphosphate (APP), and the like), phosphonates, nitrogenes (e.g., melamine derivatives), bromine- containing fire retardants (e.g., brominated styrenes), zinc- and/or boron-based fire retardants (e.g., zinc borate, zinc stannate, borax, and the like), aluminum-based fire retardants (e.g., aluminum trihydrate (ATH)), magnesium-based fire retardants (e.g., magnesium hydroxide), and the like, as well as combinations of any two or more thereof.
  • phosphates e.g., butylated triphenyl phosphate, ammonium polyphosphate (APP), and the like
  • phosphonates e.g., nitrogene.g., melamine derivatives
  • bromine- containing fire retardants e.g., brominated
  • Fillers contemplated for use in the practice of the present invention can be either organic or inorganic.
  • Exemplary fillers include ceramic fillers (which provide dimensional stability), fused silica, glass bubbles, glass spheres, chopped glass, polymeric spheres, polymeric bubbles, and the like, as well as combinations of any two or more thereof.
  • Fillers contemplated for optional use in the practice of the present invention may optionally be conductive (electrically and/or thermally).
  • Electrically conductive fillers contemplated for use in the practice of the present invention include, for example, silver, nickel, gold, cobalt, copper, aluminum, graphite, silver-coated graphite, nickel- coated graphite, alloys of such metals, and the like, as well as mixtures thereof.
  • Both powder and flake forms of filler may be used in the compositions of the present invention.
  • the flake has a thickness of less than about 2 microns, with planar dimensions of about 20 to about 25 microns.
  • Flake employed herein preferably has a surface area of about 0.15 to 5.0 m 2 /g and a tap density of about 0.4 up to about 5.5 g/cc. It is presently preferred that powder employed in the practice of the invention has a diameter of about 0.5 to 15 microns. If present, the filler typically comprises in the range of about 30 % up to about 70 % by weight of the adhesive formulation.
  • Thermally conductive fillers contemplated for optional use in the practice of the present invention include, for example, aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, magnesia, silica, alumina, and the like.
  • the particle size of these fillers will be about 20 microns. If aluminum nitride is used as a filler, it is preferred that it be passivated via an adherent, conformal coating (e.g., silica, or the like).
  • Fillers that are not electrical conductors may be used in the practice of the present invention. Such fillers may be desirable to impart some other property to the composition according to the invention, such as, for example, reduced thermal expansion of the cured material, increased or reduced dielectric constant, improved toughness, increased hydrophobicity, and the like.
  • fillers include perfluorinated hydrocarbon polymers (i.e., TEFLONTM), thermoplastic polymers, thermoplastic elastomers, mica, fused silica, glass powder, titanium dioxide, strontium oxide, and the like.
  • Dyes contemplated for use in certain embodiments of the present invention include nigrosine, Orasol blue GN, phthalocyanines, Fluoral green gold dye, and the like. When used, organic dyes in relatively low amounts (i.e., amounts less than about 0.2 % by weight) provide contrast.
  • Pigments contemplated for use in certain embodiments of the present invention include any particulate material added solely for the purpose of imparting color to the formulation, e.g., carbon black, metal oxides (e.g., Fe 2 Os, titanium oxide), and the like. When present, pigments are typically present in the range of about 0.5 wt. % up to about 5 wt. %, relative to the base formulation.
  • Flow modifiers may optionally be employed in the practice of the present invention to alter the resin flow in order to facilitate achieving desired fill and/or lamination properties.
  • Use of such optional additives may thereby (1) enhance intra- laminar adhesion and/or (2) produce a multi-layered board by bonding resinous prepregs to layers comprising etched circuitry.
  • such additives are likely to be used at minimum loading levels (e.g., in the range of about 1 up to about 10 weight percent, based on the total weight of the formulation) to gain the benefit such additives can impart (e.g., enhanced heat and pressure induced flow) without compromising other physical and electrical properties.
  • Flow modifiers contemplated for use herein may be non-reactive or reactive (i.e., capable of participating in oxidative cross-linking). Such materials will desirably exhibit electrical and physical properties which are compatible with all of the components of the above-described compositions.
  • Exemplary flow modifiers contemplated for use in the practice of the present invention include monomelic, oligomeric, or polymeric (i.e., thermoplastic) saturated (aliphatic) hydrocarbons, unsaturated hydrocarbons, and the like.
  • Plasticizers also called flexibilizers
  • Plasticizers contemplated for use in certain embodiments of the present invention include compounds that reduce the brittleness of the formulation, such as, for example, branched polyalkanes or polysiloxanes that lower the glass transition temperature (Tg) of the formulation.
  • plasticizers include, for example, polyethers, polyesters, polythiols, polysulfides, and the like.
  • Plasticizers, when employed, are typically present in the range of about 0.5 wt. % up to about 30 wt. % of the formulation.
  • Cure retardants also known as cell size regulators or quenching agents
  • Cure retardants include compounds which form radicals of low reactivity, such as, for example, silicone surfactants (generally), and the like.
  • Cure accelerators contemplated for use in certain embodiments of the present invention include compounds which enhance the rate of cure of the base polymer system, such as, for example, catalytically active materials, water, and the like.
  • Strength enhancers contemplated for use in certain embodiments of the present invention include compounds which increase the performance properties of the polymeric material to which they are added, such as, for example, crosslinking agents, and the like.
  • UV protectors contemplated for use in certain embodiments of the present ' invention include compounds which absorb incident ultraviolet (UV) radiation, thereby reducing the negative effects of such exposure on the resin or polymer system to which the protector has been added.
  • UV protectors include bis(l ,2,2,6,6-pentamethyl-4- piperidinyl) sebacate, silicon, powdered metallic compounds, hindered amines (known in the art as "HALS"), and the like.
  • Optional diluents contemplated for use in the practice of the present invention include aromatic, aliphatic, cycloaliphatic, and the like, as well as combinations of any two or more thereof.
  • Presently preferred diluents contemplated for optional use in the practice of the present invention are relatively non-polar.
  • Exemplary diluents contemplated for use herein include toluene, hexane, cyclohexane, and the like, as well as mixtures of any two or more thereof.
  • Assemblies of the invention can optionally include a first conductive layer.
  • Such a conductive layer can be applied on either face of the above-described assembly, i.e., on either the reinforced thermoplastic layer of the assembly, or on the non-reinforced layer of the assembly.
  • the first conductive layer is electrically conductive.
  • Suitable materials contemplated for use as the electrically conductive layer, when present, include copper or an alloy thereof, nickel or an alloy thereof, nickel plated copper, nickel alloy plated copper, rolled copper-invar-copper, aluminum, or a combination of any two or more thereof.
  • the electrically conductive layer is copper or an alloy thereof.
  • the electrically conductive layer can be converted into frequency circuitry. This can be accomplished employing standard methodology, i.e., the invention assembly provides the advantage that it can be subjected to conventional processing conditions for the preparation of circuitry thereon.
  • inventive assemblies can further comprise a second conductive layer, wherein the second conductive layer can optionally be electrically conductive.
  • the second electrically conductive layer may be formed into a second frequency dependent circuit element, or it may be left intact to define a ground plane. This can be prepared employing standard techniques known in the art.
  • Suitable materials contemplated for use as the second conductive layer include copper or an alloy thereof, nickel or an alloy thereof, nickel plated copper, nickel alloy plated copper, rolled copper-invar-copper, aluminum, or a combination of any two or more thereof.
  • the second conductive layer is copper or an alloy thereof.
  • the second conductive layer can define a ground plane.
  • inventive assemblies can be applied to a variety of substrates.
  • substrates suitable for use in the practice of the present invention can include, but are not limited to, polyesters, polyamides, polyolefins, polyphenylene oxides, conductive metals, and the like, as well as combinations of any two or more thereof.
  • conductive metal substrates such materials as silver, nickel, gold, cobalt, copper, aluminum, graphite, silver-coated graphite, nickel-coated graphite, alloys of such metals, and the like, are contemplated for use herein.
  • laminated sheets produced by layering and molding one or more layer(s) of reinforced thermoplastic-containing layer and/or one or more non-reinforced thermoplastic layer(s).
  • Laminated sheets according to the invention have many particularly beneficial properties, such as, for example, low dielectric constant, low electrical loss tangent, a glass transition temperature which is approximately the same as the glass transition temperature of the hydrocarbyl thermoplastic resin employed to prepare the assembly from which the laminate is prepared, high thermal decomposition temperature, and the like.
  • laminated sheets according to the present invention have a dielectric constant ⁇ 4.5 nominal, electrical loss tangent ⁇ 0.02, and a glass transition temperature of at least 80 0 C.
  • printed wiring boards produced by forming conductive patterns on the surface of the above-described laminated sheet(s).
  • methods of making printed wiring boards comprising forming conductive patterns on the surface of a laminated sheet according to the invention.
  • multilayer printed wiring boards produced by layering and molding a prescribed number of reinforced thermoplastic-containing layer(s) and non-reinforced thermoplastic layer(s), to obtain a printed wiring board for an inner layer, and layering a prescribed number of reinforced thermoplastic-containing layer(s) and non-reinforced thermoplastic layer(s) on the resulting printed wiring board for an inner layer, to obtain conductive patterns on the surface.
  • methods of making multilayer printed wiring board comprising layering and molding a prescribed number of reinforced thermoplastic-containing layer(s) and non-reinforced thermoplastic layer(s) according to the invention, to obtain a printed wiring board for an inner layer, and layering a prescribed number of reinforced thermoplastic-containing layer(s) and non-reinforced thermoplastic layer(s) on the printed wiring board for an inner layer which forms conductive patterns on the surface.
  • thermoset component of the reinforced thermoplastic-containing layer e.g., a cohesive or adhesive bond
  • thermoplastic components of the reinforced and non-reinforced layers e.g., a cohesive or adhesive bond
  • the lengths of the reinforced and non-reinforced thermoplastic-containing layers in the assembly are the same.
  • Component layers can be subjected to sufficient pressure to produce assemblies with substantially no air entrapped between the layers thereof, and without substantially altering the thickness of the component layers.
  • the assembly can include a first conductive layer, and optionally can include a second conductive layer.
  • the reinforced thermoplastic-containing layer of the laminate can include a porous substrate impregnated with a composition comprising: a first component comprising a low loss, low dielectric constant, hydrocarbyl thermoplastic resin; a second component which is capable of crosslinking to produce a thermoset in the presence of the first component; and a free radical source.
  • the first reinforced thermoplastic- containing layer can include one or more additives and/or a diluent.
  • the resulting impregnated substrate is subjected to conditions suitable to remove substantially all of any diluent therein.
  • the laminate can include one or more conductive layers.
  • the conditions to which the assembly are subjected include heating the assembly to a temperature sufficient to cause the thermoplastic polymer of the reinforced layer to flow.
  • the assembly is heated to a temperature greater than the melt transition temperature of the thermoplastic polymer of the reinforced layer, but not greater than the melt transition temperature of the thermoplastic polymer included in the non-reinforced layer, preferably to a temperature sufficient to cause the thermoplastic polymer of the reinforced layer to melt and sufficient to soften, but not melt, the thermoplastic polymer of the non-reinforced layer, thus permitting molecular miscibility of the non-reinforced layer.
  • thermoplastic polymer of the reinforced layer can flow, while the thermoplastic polymer of the non-reinforced layer retains its shape while allowing permeation by the thermoplastic polymer of the reinforced layer.
  • the assembly may be heated to a temperature sufficient to cure the thermoset resin.
  • thermoplastic layers may optionally include additives and/or fillers, and may be produced by any suitable means, (e.g., slot extrusion, blown-film extrusion, sheet casting or the like).
  • Resulting laminate structures may include a first conductive layer, which can be further processed to create circuitry on the first conductive layer.
  • the circuitry can be frequency dependent.
  • the frequency dependent circuitry can define a high frequency or digital device (e.g., a microwave antenna). Alternatively, a plurality of circuits can be created on the first conductive layer.
  • Resulting laminate structures may also include a second conductive layer, which can be further processed to create a second frequency dependent circuit element, or it may be left intact to define a ground plane.
  • resulting laminate structures which also include a second conductive layer, can be further processed to create circuitry on the first conductive layer of the assembly and a ground plane on the second conductive layer of the assembly.
  • the resulting laminate structure can be cut to the desired size and/or shape.
  • the resulting laminate can be applied to a suitable substrate.
  • Assemblies of the present invention are preferably resistant to attack by acidic aqueous media, basic aqueous media and/or organic media, making it possible to subject such assemblies to a variety of processing conditions commonly used in PCB manufacturing, such as, for example, chemical etching to introduce circuitry thereto.
  • invention assemblies can be applied to any of a variety of substrates for use.
  • circuits produced employing invention assemblies can be mounted on support structures, such as aluminum or composite materials intended as stiffeners, or the like, or can be combined with covers that act as protection from weather, for instance.
  • multilayer assemblies comprising a plurality of the above-described assemblies of the invention.
  • a "plurality" of assemblies embraces stacking 2 up to greater than about 20 assemblies to produce complex interconnected circuitry.
  • such stacked assemblies may be internally interconnected by one or more through-holes.
  • the assembly may be a thermoset laminate coated with a thermoplastic varnish compound.
  • the thermoplastic varnish compound includes a thermosetting resin (preferably a low loss thermosetting resin) and a thermoplastic resin.
  • the varnish optionally includes additives and fillers.
  • the major component in the thermoplastic varnish is a thermoplastic resin.
  • the thermoplastic resin included in the thermoplastic varnish preferably has a melt solubility compatible with that of the thermoplastic material included in the reinforced and non- reinforced thermoplastic layers. Additionally, it is preferred that the thermoplastic component of the varnish has lower melt and glass transition temperature than that of the reinforced and non-reinforced thermoplastic layers.
  • Topas 6017 grade cycHc-olefin copolymer (Topas Advanced Polymers) was extruded into approximately 0.020" sheets. Dielectric Constant and Loss Tangent of this sample were evaluated in the X-Band frequency range. Results are summarized in Table 2.
  • Constructions were pressed in a production scale press and were composed of two plies of the prepreg described in EXAMPLE 1 (at ⁇ 0.0036" each) sandwiched around a -0.024" sheet of the extruded Topas 6017 sheet described in EXAMPLE 2 for a laminated thickness of 0.031". Constructions were clad with 1 A oz. copper foil. Product was held at 28O 0 F (138°C) for 15 minutes and then cured at 38O 0 F (193°C) for 60 minutes at 360 PSI. Properties of the construction were evaluated and are summarized in Table 4.
  • Constructions were pressed in a production scale press and were composed often plies of the prepreg described in EXAMPLE .1 (at -0.0036" each) interleaved with nine plies of 0.003" film of the extruded Topas 6017 resin described in EXAMPLE 2, for a laminated thickness of 0.063".
  • Product was held at 32O 0 F (160 0 C) for 20 minutes and then cured at 365 0 F (185°C) for 60 minutes at 150 PSI. Properties of the construction were evaluated and are summarized in Table 5.
  • invention assemblies comprising foil cladding on a combination of a reinforced thermoplastic-containing layer and a non-reinforced thermoplastic layer. Specifically, invention assemblies display optimal low loss, peel performance and dielectric constant.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

La présente invention concerne des ensembles utiles pour diverses applications, notamment des applications HF où l'on souhaite obtenir es produits à faible perte électrique, par exemple dans les communications cellulaires, les antennes HF, les communications satellite, les radars, les amplificateurs de puissance, les applications numériques haut débit, les vecteurs de puce à base de stratifié et autres. Les ensembles comprennent une combinaison d'une première couche thermoplastique renforcée et d'une première couche thermoplastique non renforcée ; ces deux couches peuvent former une liaison (par exemple une couche cohésive ou adhésive) entre deux, fournissant ainsi des propriétés de performances (par ex., des performances électriques et une liaison de placage résistante) supérieures à celles de chaque matériau pris seul. La couche thermoplastique renforcée peut comprendre un substrat poreux imprégné d'une composition comprenant : un premier composant (à savoir un thermoplastique d'hydrocarbyle, à faible constante diélectrique et faible perte), un second composant (à savoir un composant capable de se réticuler pour produire une matière thermodurcie en présence du premier composant) et une source de radicaux libres. L'invention concerne également des procédés pour préparer les ensembles susmentionnés.
PCT/US2007/014716 2006-07-07 2007-06-25 Ensembles utiles pour préparer des composants électroniques et leurs procédés de fabrication Ceased WO2008008170A1 (fr)

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