WO2020215838A1 - 覆铜层压板和印制电路板 - Google Patents

覆铜层压板和印制电路板 Download PDF

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Publication number
WO2020215838A1
WO2020215838A1 PCT/CN2020/071878 CN2020071878W WO2020215838A1 WO 2020215838 A1 WO2020215838 A1 WO 2020215838A1 CN 2020071878 W CN2020071878 W CN 2020071878W WO 2020215838 A1 WO2020215838 A1 WO 2020215838A1
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WIPO (PCT)
Prior art keywords
resin
clad laminate
copper clad
polybutadiene
laminate according
Prior art date
Application number
PCT/CN2020/071878
Other languages
English (en)
French (fr)
Inventor
陈广兵
曾宪平
许永静
朱泳名
Original Assignee
广东生益科技股份有限公司
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Filing date
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Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to JP2021562832A priority Critical patent/JP7331134B2/ja
Priority to US17/605,820 priority patent/US20220210914A1/en
Priority to KR1020217035570A priority patent/KR102641705B1/ko
Publication of WO2020215838A1 publication Critical patent/WO2020215838A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • 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
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • 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
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—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
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/048—Natural or synthetic rubber
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • 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
    • H05K2201/0137—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
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive

Definitions

  • the present disclosure belongs to the technical field of electronic materials, and relates to a copper clad laminate and a printed circuit board.
  • PCB printed circuit board
  • PIM Passive Inter-Modulation
  • intermodulation distortion is caused by the nonlinear characteristics of various passive components in the radio frequency system.
  • the non-linearity of these passive devices will produce some frequency components relative to the operating frequency, and these frequency components and the operating frequency are mixed into the operating system. If these useless frequency components are large enough, It will affect the normal operation of the communication system.
  • the spurious intermodulation signal falls in the receiving frequency band of the base station, the sensitivity of the receiver will be reduced, which will lead to the reduction of the call quality or the system carrier-to-interference ratio, and the capacity of the communication system.
  • PIM has become an important parameter that limits the system capacity. .
  • the problem of passive intermodulation in the early stage mainly caused interference to high-power microwave devices such as circulators, waveguides, coaxial connectors, duplexers, attenuators, and antennas.
  • high-power microwave devices such as circulators, waveguides, coaxial connectors, duplexers, attenuators, and antennas.
  • the increase in signal power makes the PIM problem of the PCB substrate itself a barrier to the development of high-performance RF circuits.
  • electronic communication technology is developing toward faster transmission speed, larger transmission capacity, and higher integration.
  • high-power multi-channel transmitters, more sensitive receivers, shared antennas, complex modulation signals and dense The communication frequency band has put forward higher performance requirements for the power capacity and PIM indicators in PCB circuit design and manufacturing than traditional PCB substrates.
  • Low PIM and high-performance circuit substrates have become the foundation and key technology in this field.
  • CN205793612U and CN107197592A mainly select polytetrafluoroethylene (PTFE) as the dielectric insulating layer to make low-PIM high-performance ceramic substrates.
  • PTFE polytetrafluoroethylene
  • An object of the present disclosure is to provide a copper clad laminate having a passive intermodulation performance of less than -158dBc (700MHz/2600MHz) and a printed circuit board made of the copper clad laminate.
  • Another object of the present disclosure is to provide a copper clad laminate and a copper clad laminate with passive intermodulation performance less than -158dBc under the conditions of 700MHz-2600MHz and capable of meeting the high frequency and high speed requirements of the electronic information field Printed circuit board.
  • the inventors of the present invention have conducted in-depth and detailed research and found that the iron, nickel, cobalt and molybdenum elements in the copper foil layer of the copper-clad laminate will deteriorate the PIM of the printed circuit board.
  • a printed circuit board with a lower PIM can be obtained, for example, a PIM value can be obtained Printed circuit board less than -158dBc (700MHz/2600MHz).
  • the weight content of each element in the copper foil layer refers to the weight of the element divided by the total weight of the copper foil.
  • a copper clad laminate includes:
  • a copper foil layer, the copper foil layer is located on at least one surface of the dielectric substrate layer,
  • the weight content of iron element ⁇ 10ppm the weight content of nickel element ⁇ 10ppm, the weight content of cobalt element ⁇ 10ppm, and the weight content of molybdenum element ⁇ 10ppm.
  • the copper clad laminate has a passive intermodulation value of less than -158dBc at 700MHz-2600MHz.
  • the matte surface roughness of the copper foil is 0.5-3 ⁇ m.
  • the dielectric substrate layer includes:
  • the polymer matrix material is 30 to 70 weight percent; and the filler is 30 to 70 weight percent.
  • the polymer matrix material includes modified or unmodified polybutadiene resin, modified or unmodified polyisoprene resin, and modified or unmodified polyarylether One or more of resins.
  • the dielectric substrate layer has a dielectric constant of less than 3.5 and a loss factor of less than 0.006 at 10 GHz.
  • the polybutadiene resin is a polybutadiene homopolymer resin or a polybutadiene copolymer resin.
  • the polybutadiene copolymer resin is a polybutadiene-styrene copolymer resin.
  • the modified polybutadiene resin is selected from one of hydroxyl-terminated polybutadiene resin, methacrylate-terminated polybutadiene resin, and carboxylated polybutadiene resin. kind or more.
  • the polyisoprene resin is a polyisoprene homopolymer resin or a polyisoprene copolymer resin.
  • the polyisoprene copolymer resin is a polyisoprene-styrene copolymer resin.
  • the modified polyisoprene resin is a carboxylated polyisoprene resin.
  • the modified polyarylether resin is one or more of carboxyl functionalized polyarylether, methacrylate-terminated polyarylether, and vinyl-terminated polyarylether.
  • the polymer matrix material further includes co-curable polymers, free radical curing monomers, elastomer blocks other than polybutadiene resin, polyisoprene resin, and polyarylether resin.
  • co-curable polymers free radical curing monomers
  • elastomer blocks other than polybutadiene resin polyisoprene resin
  • polyarylether resin polyarylether resin.
  • the dielectric substrate layer contains reinforced materials or no reinforced materials.
  • the copper clad laminate further includes an adhesive layer and/or a resin film layer located between the copper foil and the dielectric substrate layer.
  • the present disclosure provides a printed circuit board including the copper clad laminate as described above.
  • the present disclosure provides a circuit including the printed circuit board described above.
  • the present disclosure provides a multilayer circuit including the printed circuit board described above.
  • a circuit or multilayer circuit including the printed circuit board described is used for an antenna.
  • the present disclosure by limiting the weight content of iron in the copper foil layer to ⁇ 10ppm, the weight content of nickel ⁇ 10ppm, the weight content of cobalt ⁇ 10ppm, and the weight content of molybdenum ⁇ 10ppm, it can provide passive intermodulation performance of less than -158dBc( 700MHz/2600MHz) copper clad laminates and printed circuit boards containing copper clad laminates.
  • it can also provide a copper clad laminate and a printed circuit board containing the copper clad laminate, which has a passive intermodulation performance of less than -158dBc (700MHz/2600MHz) and can meet the high-frequency and high-speed requirements of the electronic information field.
  • all numerical features refer to within the error range of the measurement, such as within ⁇ 10%, or within ⁇ 5%, or within ⁇ 1% of the defined value.
  • the amount, ratio, etc. are by weight.
  • the copper foil layer may also be simply referred to as copper foil.
  • the present disclosure provides a copper clad laminate, which includes:
  • a copper foil layer, the copper foil layer is located on at least one surface of the dielectric substrate layer,
  • the weight content of iron element ⁇ 10ppm the weight content of nickel element ⁇ 10ppm, the weight content of cobalt element ⁇ 10ppm, and the weight content of molybdenum element ⁇ 10ppm.
  • the iron element weight content is less than or equal to 7 ppm, more preferably less than or equal to 5 ppm.
  • the content of nickel by weight is less than or equal to 7 ppm, more preferably less than or equal to 5 ppm.
  • the weight content of cobalt element is less than or equal to 7 ppm, more preferably less than or equal to 5 ppm.
  • the weight content of the molybdenum element is less than or equal to 7 ppm, more preferably less than or equal to 5 ppm.
  • the total weight content of iron, nickel, cobalt, and molybdenum elements may be less than or equal to 35 ppm, preferably less than or equal to 30 ppm, more preferably less than or equal to 18 ppm, and further preferably less than or equal to 12 ppm, and Most preferably, it is less than or equal to 5 ppm.
  • the inventors of the present invention have conducted in-depth and detailed research and found that the iron, nickel, cobalt and molybdenum elements in the copper foil layer of the copper-clad laminate will deteriorate the PIM of the printed circuit board.
  • a printed circuit board with a lower PIM can be obtained, for example, a PIM value can be obtained
  • the passive intermodulation value at 700MHz-2600MHz refers to the passive intermodulation value (PIM) measured by the reflection method on the copper clad laminate between 700MHz and 2600MHz.
  • the passive intermodulation value less than -158dBc at 700MHz-2600MHz can also be expressed as -158dBc (700MHz/2600MHz).
  • PIM can be measured as follows: each sample is tested 9 times, each time an intermodulation model and a frequency are selected, and the Summitek Instruments PIM analyzer is used to test, and the maximum value of the 9 test data is recorded, which is the PIM value of the sample.
  • the circuit design length of the intermodulation model is 12 inches (but not limited to 12 inches) arc and zigzag circuits (it can also be straight lines or other arbitrary shapes).
  • the thickness of the model is 10mil, 20mil and 30mil samples respectively, corresponding to the lines
  • the width is 24mil, 48mil and 74mil; the frequency is selected 700MHz, 1900MHz and 2600MHz respectively.
  • the 9 test data are: the model thickness is 10mil, the model line width is 24mil and the 3 data measured at 700MHz, 1900MHz and 2600MHz, the model thickness is 20mil, the model linewidth is 48mil and the model is measured at 700MHz, 1900MHz and 2600MHz. Three data measured at 700MHz, 1900MHz and 2600MHz with a thickness of 30mil and a model line width of 74mil.
  • the roughness (R Z ) of the copper foil may be 0.5-3 ⁇ m, so that better signal integrity can be obtained.
  • the content of iron element, nickel element, cobalt element and molybdenum element in the copper foil is achieved through a post-treatment process of electrolytic copper foil.
  • the typical post-treatment process of electrolytic copper foil is: degreasing ⁇ water washing ⁇ pickling and rust removal ⁇ water washing ⁇ alloy electroplating liquid plating ⁇ water washing ⁇ passivation ⁇ water washing ⁇ drying.
  • iron, nickel, cobalt and molybdenum corresponding salts can be dissolved, such as iron sulfate, molybdenum sulfate, nickel sulfate, cobalt sulfate, iron nitrate, molybdenum nitrate, cobalt nitrate, nickel nitrate, etc. .
  • concentration, current and temperature of the corresponding salts of iron, nickel, cobalt and molybdenum in the alloy electroplating solution the iron, nickel, cobalt and molybdenum elements in the copper foil in the electrolytic copper foil can be adjusted Content.
  • the thickness of the copper foil layer may be 0.1 to 10 OZ, preferably 0.2 to 5 OZ, and further preferably 0.5 to 2 OZ. 1OZ means 35 microns.
  • the dielectric substrate layer may be formed of a resin composition including a polymer matrix material and a filler.
  • the polymer matrix material is 30 to 70 weight percent; and the filler is 30 to 70 weight percent.
  • the dielectric substrate layer may or may not include reinforcing materials.
  • a composition containing the polymer matrix material and filler is attached to the reinforcing material to form a dielectric substrate layer.
  • the reinforcing material is a porous reinforcing material such as glass fiber.
  • the polymer matrix material includes one of a modified or unmodified polybutadiene resin, a modified or unmodified polyisoprene resin, and a modified or unmodified polyarylether resin. kind or more.
  • the dielectric substrate layer made of it has a dielectric constant less than about 3.5 and a loss factor less than about 0.006 at 10 GHz, which can meet the high-frequency and high-speed requirements of the electronic information field, and has a dielectric less than about 3.5 at 10 GHz.
  • a PCB substrate with a constant and a loss factor less than about 0.006 puts forward higher performance requirements for the PIM index than a PCB substrate with a dielectric constant greater than 3.5 and a loss factor greater than 0.006.
  • the relative amounts of various polymers such as polybutadiene or polyisoprene polymers, and other polymers may depend on the specific copper foil layer used, the desired circuit material, and the properties of the circuit laminate And similar considerations. It has been found that the use of polyarylether can provide enhanced bonding strength between the copper foil and the dielectric metal layer. The use of polybutadiene or polyisoprene polymer can improve the high temperature resistance of the laminate.
  • the polybutadiene resin may include a polybutadiene homopolymer or copolymer resin.
  • the polybutadiene copolymer resin may be a polybutadiene-styrene copolymer resin.
  • the modified polybutadiene resin may be selected from one or more of hydroxyl-terminated polybutadiene resin, methacrylate-terminated polybutadiene resin, and carboxylated polybutadiene resin.
  • the polyisoprene resin may include a polyisoprene homopolymer resin or a polyisoprene copolymer resin.
  • the polyisoprene copolymer resin may be a polyisoprene-styrene copolymer resin.
  • the modified polyisoprene homopolymer resin or polyisoprene copolymer resin may be a carboxylated polyisoprene resin.
  • the modified polyarylether resin may be one or more of carboxyl functionalized polyarylether, methacrylate-terminated polyarylether, and vinyl-terminated polyarylether.
  • polybutadiene resins and polyisoprene resins include homopolymers and copolymers containing units derived from butadiene, isoprene, or a mixture thereof. Units derived from other copolymerizable monomers may also be present in the resin, for example, optionally in grafted form.
  • Exemplary copolymerizable monomers include, but are not limited to, vinyl aromatic monomers, such as substituted and unsubstituted monovinyl aromatic monomers, such as styrene, 3-methylstyrene, 3,5-diethyl Styrene, 4-n-propylstyrene, ⁇ -methylstyrene, ⁇ -methylvinyltoluene, p-hydroxystyrene, p-methoxystyrene, ⁇ -chlorostyrene, ⁇ -bromostyrene, Dichlorostyrene, dibromostyrene, tetrachlorostyrene, etc.; and substituted and unsubstituted divinyl aromatic monomers such as divinylbenzene, divinyl toluene, etc.
  • vinyl aromatic monomers such as substituted and unsubstituted monovinyl aromatic monomers, such as styrene, 3-methylstyrene, 3,5-
  • thermosetting polybutadiene and/or polyisoprene resins include, but are not limited to, butadiene homopolymers, isoprene homopolymers, butadiene-vinyl aromatic copolymers such as butadiene- Styrene, isoprene-vinyl aromatic copolymers such as isoprene-styrene copolymers, etc., such as styrene-butadiene copolymer Ricon100 from Crayvally, or polybutadiene from Soda Ene B-1000.
  • the polybutadiene resin and/or the polyisoprene resin may be modified.
  • the resin may be hydroxyl-terminated, methacrylate-terminated, carboxylate-terminated, or the like.
  • the polybutadiene resin and polyisoprene resin may be epoxy-, maleic anhydride-, or urethane-modified butadiene or isoprene resin.
  • Polybutadiene resins and polyisoprene resins can also be cross-linked, for example by divinyl aromatic compounds such as divinylbenzene, such as polybutadiene-styrene cross-linked with divinylbenzene .
  • Exemplary resins are broadly classified as "polybutadiene” by their manufacturers such as Nippon Soda Co. (Tokyo, Japan) and Cray Valley Hydrocarbon Specialty Chemicals (Exton, Pennsylvania, U.S.). Mixtures of resins can also be used, such as a mixture of polybutadiene homopolymer and poly(butadiene-isoprene) copolymer. Combinations containing syndiotactic polybutadiene can also be used.
  • the polybutadiene or polyisoprene polymer may be carboxy functionalized.
  • Functionalization can be accomplished using multifunctional compounds that have (i) carbon-carbon double bonds or carbon-carbon triple bonds in the molecule; and (ii) one or more carboxyl groups, including carboxylic acids, anhydrides, amides, esters or Acid halide.
  • a specific carboxyl group is carboxylic acid or ester.
  • multifunctional compounds that can provide carboxylic acid functional groups include maleic acid, maleic anhydride, fumaric acid, and citric acid.
  • polybutadiene to which maleic anhydride is added can be used for thermosetting compositions.
  • Suitable maleic anhydride polybutadiene polymers are commercially available, for example from Cray Valley, under the trade names RICON 130MA8, RICON130MA13, RICON130MA20, RICON131MA5, RICON131MA10, RICON131MA17, RICON131MA20, and RICON156MA17.
  • Suitable maleic anhydride polybutadiene-styrene copolymers are commercially available, for example from Crayvally under the trade name RICON184MA6.
  • thermosetting polybutadiene and/or polyisoprene resin may be liquid or solid at room temperature.
  • Suitable liquid resins may have a number average molecular weight greater than about 5000, but generally have a number average molecular weight less than about 5000 (most preferably from about 1000 to about 3000).
  • Thermosetting polybutadiene and/or polyisoprene resins include resins with at least 90% by weight of 1,2 addition, which can be used for cross-linking due to a large amount of prominent vinyl groups that make them appear larger after curing. The crosslink density.
  • the polybutadiene and/or polyisoprene resin may account for the total polymer matrix composition in an amount up to 100% by weight, particularly up to about 75% by weight, more particularly about 10% relative to the total resin system. It is present in the polymer matrix composition in an amount of to 70% by weight, even more particularly from about 20 to about 60 or 70% by weight.
  • the modified polyphenylene ether resin is selected from polyphenylene ether resins with acryloyl groups at both ends, polyphenylene ether resins with styrene groups at both ends, and vinyl at both ends.
  • the modified polyphenylene ether resin is represented by the following formula (1):
  • a and b are each independently an integer from 1 to 30,
  • Z is a group represented by formula (2) or (3):
  • A is an arylene group having 6 to 30 carbon atoms, a carbonyl group, or an alkylene group having 1 to 10 carbon atoms
  • m is an integer of 0 to 10
  • R 1 to R 3 are each Is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 4 and R 6 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group; and R 5 and R 7 are each independently a hydrogen atom, a halogen atom , Alkyl or phenyl having 1 to 10 carbon atoms;
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or Phenyl; and B is an arylene group having 6 to 30 carbon atoms, an alkylene group having 1 to 10 carbon atoms, -O-, -CO-, -SO-, -CS- or -SO 2- .
  • the alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms. base.
  • Examples of the alkyl group having 1 to 8 carbon atoms may include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, as well as cyclopropyl, cyclobutyl, cyclopentyl and Cyclohexyl. Where there are isomeric forms, all isomeric forms are included.
  • butyl may include n-butyl, isobutyl, and tert-butyl.
  • Examples of the arylene group having 6 to 30 carbon atoms may include a phenylene group, a naphthylene group, and an anthrylene group.
  • the alkylene group having 1 to 10 carbon atoms is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 6 carbon atoms. 4 of alkylene.
  • alkylene groups having 1 to 10 carbon atoms may include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylidene and Decyl, as well as cyclopropylene, cyclobutylene, cyclopentylene, and cyclohexylene. Where there are isomeric forms, all isomeric forms are included.
  • halogen atom may include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the number average molecular weight of the polyphenylene ether resin may be 500 to 10000 g/mol, preferably 800 to 8000 g/mol, more preferably 1000 to 7000 g/mol.
  • Exemplary polyphenylene ethers may be methacrylate-based modified polyphenylene ether SA9000 from Sabic, or styryl-modified polyphenylene ether St-PPE-1 from Mitsubishi Chemical.
  • the filler may be selected from crystalline silica, fused silica, spherical silica, boron nitride, aluminum hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, magnesium oxide, barium sulfate One or more of borosilicate, aluminosilicate, and talc.
  • the filler can be in the form of solid, porous or hollow particles.
  • the filler can be treated with one or more coupling agents such as silane, zirconate or titanate.
  • the amount of filler usually accounts for 30 to 70 weight percent of the dielectric substrate layer.
  • An exemplary non-hollow inorganic filler may be DQ2028V from Jiangsu Lianrui.
  • An exemplary hollow inorganic filler may be iM16K from 3M.
  • the polymer matrix material can be added with other polymers that can be co-cured with thermosetting polybutadiene and/or polyisoprene resin and/or polyphenylene ether resin.
  • a lower molecular weight ethylene propylene elastomer can be used in the resin system.
  • the ethylene propylene elastomer used herein is a copolymer, terpolymer or other polymer mainly comprising ethylene and propylene.
  • Ethylene propylene elastomers can be further classified into EPM copolymers (ie, copolymers of ethylene and propylene monomers) or EPDM terpolymers (ie, terpolymers of ethylene, propylene and diene monomers).
  • EPM copolymers ie, copolymers of ethylene and propylene monomers
  • EPDM terpolymers ie, terpolymers of ethylene, propylene and diene monomers
  • ethylene propylene diene terpolymer rubber has a saturated main chain, and unsaturation in the main chain that can be easily crosslinked.
  • a liquid ethylene propylene diene terpolymer rubber in which the diene is dicyclopentadiene can be used.
  • the molecular weight of the ethylene propylene rubber may be less than a viscosity average molecular weight of 10,000.
  • Ethylene propylene rubber is present in an effective amount to maintain the properties of the matrix material, particularly the stability of the dielectric strength and mechanical properties over time. Generally, this amount is up to about 20% by weight relative to the total weight of the polymer matrix composition, more particularly from about 4 to about 20% by weight, even more particularly from about 6 to about 12% by weight.
  • An exemplary ethylene propylene rubber may be Trilene 67 from Lion Copolymer.
  • another type of co-curable polymer is an elastomer containing unsaturated polybutadiene or polyisoprene.
  • This component may be mainly 1,3-addition butadiene or isoprene and ethylenically unsaturated monomers such as vinyl aromatic compounds such as styrene or ⁇ -methylstyrene, acrylate or methyl Random copolymers or block copolymers of base acrylates such as methyl methacrylate or acrylonitrile.
  • Elastomers can be linear or graft-type blocks containing polybutadiene or polyisoprene blocks and thermoplastic blocks that can be derived from monovinyl aromatic monomers such as styrene or ⁇ -methylstyrene.
  • This type of block copolymers include styrene-butadiene-styrene triblock copolymers, styrene-butadiene diblock copolymers, and mixed triblock copolymers containing styrene and butadiene and Diblock copolymer.
  • An exemplary Kraton D1118 is a copolymer containing mixed diblock/triblock styrene and butadiene.
  • the elastomer component containing unsaturated polybutadiene-or polyisoprene-relative to the total polymer matrix composition in an amount of about 2wt.% to about 60wt.%, more particularly about 5wt. % To about 50 wt.%, or even more specifically from about 10 wt.% to about 40 or 50 wt.% is present in the resin system.
  • co-curable polymers other than polybutadiene resin, polyisoprene resin and polyarylether resin can be added, including but not limited to homopolymers or copolymers of ethylene , Such as polyethylene and ethylene oxide copolymers; natural rubber; norbornene polymers such as polydicyclopentadiene; hydrogenated styrene-isoprene-styrene copolymers and butadiene-acrylonitrile copolymers; no Saturated polyester etc.
  • the level of these copolymers is generally less than 50 wt.% of the total polymer in the matrix composition.
  • radical curable monomers can also be added, for example, to increase the crosslinking density of the resin system after curing.
  • exemplary monomers that can serve as suitable crosslinking agents include, for example, di-, tri-, or higher ethylenically unsaturated monomers such as divinylbenzene, triallyl cyanurate, diallyl terephthalate Esters, and multifunctional acrylate monomers (such as resins, available from SartomerUSA (Newtown Square, Pennsylvania), or combinations thereof, are commercially available.
  • the crosslinking agent accounts for the total polymer
  • the matrix composition is present in the resin system in an amount of up to about 20 wt.%, particularly 1 to 15 wt.%.
  • An initiator can be added to the resin system to accelerate the curing reaction of the polyene having olefin reaction sites.
  • Particularly useful initiators are organic peroxides such as dicumyl peroxide, dilauroyl peroxide, cumyl peroxide neodecanoate, tert-butyl peroxide neodecanoate, pivalate peroxide Amyl ester, tert-butyl peroxypivalate, tert-butyl peroxy isobutyrate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyacetate, peroxy Tert-butyl benzoate, 1,1-di-tert-butylperoxy-3,5,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, 2,2-bis( (Tert-butylperoxy)butane, bis(4-
  • Carbon-carbon initiators such as 2,3-dimethyl-2,3-diphenylbutane can also be used in resin systems.
  • the initiators can be used alone or in combination.
  • a typical initiator amount is about 1.5 to about 10 wt.% of the total polymer matrix composition.
  • Flame retardants can be added to the resin system to make electronic components have flame retardant properties.
  • the flame retardant may be selected from one or a mixture of at least two of halogen-based flame retardants and phosphorus-based flame retardants.
  • the brominated flame retardant can be selected from any one or at least one of decabromodiphenyl ether, hexabromobenzene, decabromodiphenylethane, ethylenebistetrabromophthalimide A mixture of the two.
  • the phosphorus-based flame retardant may be selected from tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9- Oxa-10-phosphinphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene or 10-phenyl-9,10-dihydro-9-oxa- One or a mixture of at least two of 10-phosphinphenanthrene-10-oxide.
  • An exemplary brominated flame retardant may be BT-93W from Albemarle, USA.
  • An exemplary brominated flame retardant can be XP-7866 from Albemarle, USA.
  • the solvent in the polymer matrix material in the present disclosure is not particularly limited. Specific examples include alcohols such as methanol, ethanol, butanol, ethyl cellosolve, butyl cellosolve, and glycol-methyl ether. , Carbitol, butyl carbitol and other ethers, acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones, toluene, xylene, mesitylene and other aromatics Hydrocarbons, ethoxyethyl acetate, ethyl acetate and other esters, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other nitrogen-containing Class solvent.
  • alcohols such as methanol, ethanol, butanol, ethyl cellosolve, butyl cellosolve,
  • the above-mentioned solvents can be used alone or in a mixture of two or more, preferably aromatic hydrocarbon solvents such as toluene, xylene, mesitylene and acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isopropyl Mixture of ketone solvents such as butyl ketone and cyclohexanone.
  • aromatic hydrocarbon solvents such as toluene, xylene, mesitylene and acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isopropyl Mixture of ketone solvents such as butyl ketone and cyclohexanone.
  • the viscosity of the resin composition can be adjusted by adding a viscosity modifier (selected based on its compatibility with the specific polymer matrix material mixture) to delay the separation of the filler from the dielectric composite material, that is, sedimentation or floating; and Provide media composite materials with a viscosity compatible with conventional laminating equipment.
  • a viscosity modifier selected based on its compatibility with the specific polymer matrix material mixture
  • Exemplary viscosity modifiers include, for example, polyacrylic acid compounds, nanofillers, ethylene propylene rubber, and the like.
  • additives may also be contained, and specific examples include antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, and the like. These various additives can be used alone, or two or more of them can be mixed and used.
  • the dielectric substrate layer may be a combination of optional polybutadiene resin, polyisoprene resin, polyarylether resin, other co-curable polymers, free radical curing monomers, elastomer block copolymers , Initiator, flame retardant, adhesion regulator, solvent, etc.
  • the polymer matrix material and filler mixed glue are coated on the release film to obtain a resin film layer, or the above polymer matrix material and filler can be mixed
  • the glue prepares a dielectric substrate layer containing the reinforcing material by dipping or coating the reinforcing material.
  • the reinforcing material optionally includes suitable fibers, in particular glass fibers (E and NE glass) or non-woven or woven thermally stable nets of high temperature polyester fibers.
  • suitable fibers in particular glass fibers (E and NE glass) or non-woven or woven thermally stable nets of high temperature polyester fibers.
  • thermally stable fiber reinforcements provide copper clad laminates with relatively high curing shrinkage and mechanical strength.
  • the copper foil and the dielectric substrate layer can be in direct contact, and an adhesive layer and/or a resin film layer may also be included between the copper foil and the dielectric substrate layer to improve the adhesion between the copper foil and the dielectric substrate layer. Improve its media performance.
  • the adhesive layer is obtained by applying a solution to the surface of the copper foil or dielectric substrate layer to provide a coating weight of 2 to 15 g/m 2.
  • the resin film layer may be obtained by applying a solution to the surface of the copper foil or dielectric substrate layer to provide a coating weight of 2 to 15 g/m2.
  • a resin film layer may also be included in the middle of the dielectric substrate layer.
  • the adhesive layer and/or the resin film layer may have the same composition as or different from the dielectric substrate layer, and may be uncured, partially cured or fully cured.
  • Exemplary preparation method the optional polybutadiene resin, polyisoprene resin, polyarylether resin, other co-curable polymers, free radical curing monomers, elastomer block copolymers, initiators , Flame retardant, bonding regulator, solvent, etc.
  • the polymer matrix material and filler mixed glue are impregnated or coated with reinforcing material (E glass cloth), through the clamping shaft to control the appropriate unit weight, and dried in an oven Sheet, remove the solvent, and prepare the dielectric substrate layer.
  • the present disclosure provides a circuit including the printed circuit board described above.
  • the present disclosure provides a multilayer circuit including the printed circuit board described above.
  • a circuit or multilayer circuit including the printed circuit board described is used for an antenna.
  • the present disclosure by limiting the weight content of iron in the copper foil layer to ⁇ 10ppm, the weight content of nickel ⁇ 10ppm, the weight content of cobalt ⁇ 10ppm, and the weight content of molybdenum ⁇ 10ppm, it can provide passive intermodulation performance of less than -158dBc( 700MHz/2600MHz) copper clad laminates and printed circuit boards containing copper clad laminates.
  • it can also provide a copper clad laminate and a printed circuit board containing the copper clad laminate, which has a passive intermodulation performance of less than -158dBc (700MHz/2600MHz) and can meet the high-frequency and high-speed requirements of the electronic information field.
  • the dielectric substrates and copper clad laminates of each of Examples 2-16 and Comparative Examples 1-16 were prepared in the same manner as in Example 1, except for the composition and amount of the dielectric substrate layer of the copper clad laminate and the copper foil
  • the thickness of the layer, the roughness of the matte surface, the content of iron, nickel, cobalt and molybdenum, the amount of filler and the physical properties of the copper clad laminate are shown in Table 2-5.
  • the unit of the components of the dielectric substrate layer including fillers in Table 2-5 is grams.
  • Copper foil roughness non-contact laser method.
  • the circuit design of the intermodulation model is a 12-inch arc and zigzag circuit.
  • the thickness of the model is 10mil, 20mil and 30mil samples, corresponding to the line width of 24mil, 48mil and 74mil respectively; the frequency is selected as 700MHz, 1900MHz and 2600MHz respectively.
  • Dk/Df test method adopt IPC-TM-650 2.5.5.5 standard method, frequency 10GHz.
  • Examples 1-16 that the weight content of iron element ⁇ 10ppm, the weight content of nickel element ⁇ 10ppm, the weight content of cobalt element ⁇ 10ppm, and the weight content of molybdenum element ⁇ 10ppm are adopted, and the prepared dielectric substrate and copper clad laminate have less than -158dBc (700MHz/2600MHz) passive intermodulation PIM performance, excellent performance.
  • the copper clad laminates prepared in Examples 1-16 can meet the high-frequency and high-speed requirements in the electronic information field.
  • Comparing Comparative Example 1-16 with Example 1-16 it can be seen that the prepared dielectric substrate and copper-clad laminate have a copper foil layer with iron element weight content> 10 ppm, nickel element weight content> 10 ppm, and cobalt element weight content> 10 ppm. And/or the weight content of molybdenum element>10ppm, the performance of PIM is poor, and it cannot meet the requirements of customers for PIM performance.

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Abstract

本公开提供一种覆铜层压板及印制电路板。所述覆铜层压板包含介质基板层和铜箔层，所述铜箔层位于所述介质基板层的至少一个表面上，其中在所述铜箔层中，铁元素重量含量<10ppm，镍元素重量含量<10ppm，钴元素重量含量<10ppm，并且钼元素重量含量<10ppm。所述覆铜层压板具有小于-158dBc(700MHz/2600MHz)的无源互调PIM。

Description

覆铜层压板和印制电路板 技术领域
本公开属于电子材料技术领域，涉及一种覆铜层压板和印制电路板。
背景技术
随着电子信息技术的发展，数字电路逐渐步入信息处理高速化、信号传输高频化阶段，为了处理不断增加的数据，电子设备的频率变得越来越高，这时电路基板的电性能将严重影响数字电路的特性，因此对印制电路板(PCB)基板的性能提出了更新的要求。
无源互调(Passive Inter-Modulation)，简称PIM，又叫互调失真，是由射频***中各种无源器件的非线性特性引起的。在大功率、多信道***中，这些无源器件的非线性会产生相对于工作频率的一些频率分量，而这些频率分量和工作频率混合在一起进入工作***，如果这些无用的频率分量足够大，就会影响通信***的正常工作。当杂散互调信号落在基站的接收频带内，接收机的灵敏度就会降低，从而导致通话质量或***载波干扰比的降低，和通信***的容量减少，PIM成为了限制***容量的重要参数。
无源互调问题早期主要对环行器、波导、同轴连接器、双工器、衰减器和天线等大功率微波器件产生干扰。随着印刷电路板被越来越广泛地应用于微波电路领域研发平板型集成射频前端，信号功率增大使得PCB基板自身的PIM问题成为阻碍高性能射频电路发展的一个拦路虎。目前，电子通信技术向更快传输速度、更大传输容量、更高的集成度发展，现代微波通信电路中大功率多通道发射机、更灵敏的接收机、共用天线、复杂调制信号和密集的通讯频带都对PCB电路设计和制造中的功率容量及PIM指标提出了比传统PCB基板更高的性能要求，低PIM高性能电路基板成为这个领域的基础和关键技术。
CN205793612U和CN107197592A主要选用聚四氟乙烯(PTFE)作为介质绝缘层制作低PIM高性能陶瓷基板。
但是，仍然需要提供一种无源互调值较低的覆铜层压板和包含覆铜层压板的印制电路板。
发明内容
本公开的一个目的在于提供一种具有无源互调性能小于-158dBc(700MHz/2600MHz)的覆铜层压板和包含覆铜层压板制备的印制电路板。
本公开的另一个目的在于提供一种具有在700MHz-2600MHz条件下无源互调性能均小于-158dBc并且能够满足电子信息领域的高频高速的要求的覆铜层压板和包含覆铜层压板的印制电路板。
本发明的发明人经深入细致的研究，发现覆铜层压板的铜箔层中的铁元素、镍元素、钴元素和钼元素会对印制电路板的PIM造成恶化。当铜箔层中铁元素重量含量<10ppm，镍元素重量含量<10ppm，钴元素重量含量<10ppm，并且钼元素重量含量<10ppm时，可以获得PIM较低的印制电路板，例如可以获得PIM值小于-158dBc(700MHz/2600MHz)的印制电路板。
铜箔层中各元素的重量含量是指，该元素的重量除以铜箔总重量。
在一个方面，本公开提供一种覆铜层压板一种覆铜层压板，包括：
介质基板层，和
铜箔层，所述铜箔层位于所述介质基板层的至少一个表面上，
其中在所述铜箔层中，铁元素重量含量<10ppm，镍元素重量含量<10ppm，钴元素重量含量<10ppm，并且钼元素重量含量<10ppm。
在一个实施方案中，所述覆铜层压板具有在700MHz-2600MHz下小于-158dBc的无源互调值。
在一个实施方案中，所述铜箔的毛面粗糙度为0.5-3μm。
在一个实施方案中，所述介质基板层包括：
聚合物基质材料；和
填料；
其中按所述介质基板层的重量计，所述聚合物基质材料为30至70重量百分比；并且所述填料为30至70重量百分比。
在一个实施方案中，所述聚合物基质材料包括改性或未改性的聚丁二 烯树脂、改性或未改性的聚异戊二烯树脂和改性或未改性的聚芳醚树脂中的一种或多种。
在一个实施方案中，所述介质基板层在10GHz处具有小于3.5的介质常数和小于0.006的损耗因子。
在一个实施方案中，所述聚丁二烯树脂是聚丁二烯均聚物树脂或聚丁二烯共聚物树脂。
在一个实施方案中，所述聚丁二烯共聚物树脂是聚丁二烯-苯乙烯共聚物树脂。
在一个实施方案中，所述改性的聚丁二烯树脂选自羟基封端的聚丁二烯树脂、甲基丙烯酸酯封端的聚丁二烯树脂和羧基化的聚丁二烯树脂中的一种或多种。
在一个实施方案中，所述聚异戊二烯树脂是聚异戊二烯均聚物树脂或聚异戊二烯共聚物树脂。
在一个实施方案中，所述聚异戊二烯共聚物树脂是聚异戊二烯-苯乙烯共聚物树脂。
在一个实施方案中，所述改性的聚异戊二烯树脂是羧基化的聚异戊二烯树脂。
在一个实施方案中，所述改性的聚芳醚树脂为羧基官能化的聚芳醚、甲基丙烯酸酯封端的聚芳醚、含乙烯基封端的聚芳醚中的一种或多种。
在一个实施方案中，所述聚合物基质材料还包括除聚丁二烯树脂、聚异戊二烯树脂和聚芳醚树脂以外的可共固化聚合物、自由基固化单体、弹性体嵌段共聚物、引发剂、阻燃剂、粘结调节剂和溶剂中的一种或多种。
在一个实施方案中，所述介质基板层包含增强材料或者无增强材料。
在一个实施方案中，所述覆铜层压板还包括位于所述铜箔与所述介质基板层之间的粘结剂层和/或树脂薄膜层。
在另一个方面，本公开提供一种包括上面任一项所述的覆铜层压板的印制电路板。
在又一个方面，本公开提供一种包括上面所述的印制电路板的电路。
在再一个方面，本公开提供一种包括上面所述的印制电路板的多层电路。
在一个实施方案中，包括所述的印制电路板的电路或多层电路被用于天线。
根据本公开，通过限制铜箔层中铁元素重量含量<10ppm，镍元素重量含量<10ppm，钴元素重量含量<10ppm，并且钼元素重量含量<10ppm，可以提供具有无源互调性能小于-158dBc(700MHz/2600MHz)的覆铜层压板和包含覆铜层压板的印制电路板。
此外，还可以提供一种具有无源互调性能小于-158dBc(700MHz/2600MHz)并且能够满足电子信息领域的高频高速要求的覆铜层压板和包含覆铜层压板的印制电路板。
具体实施方式
下面将结合本发明的具体实施方案，对本发明的实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施方案和/或实施例仅仅是本发明的实施方案和/或实施例的一部分，而不是全部的实施方案和/或实施例。基于本发明的实施方案和/或实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方案和/或所有其他实施例都落入本公开保护的范围内。
在本公开中，所有数值特征都指在测量的误差范围之内，例如在所限定的数值的±10％之内，或±5％之内，或±1％之内。
本公开所述的“包含”、“包括”或“含有”，意指其除所述组份外，还可以具有其他组份，这些其他组份赋予预浸料不同的特性。除此之外，本公开所述的“包含”、“包括”或“含有”，还可以包括“基本上由……组成”，并且可以替换为“为”或“由……组成”。
在本公开中，如果没有具体指明，量、比例等是按重量计的。
在本公开中，铜箔层有时也可以简称为铜箔。
本公开提供一种覆铜层压板，其包括：
介质基板层，和
铜箔层，所述铜箔层位于所述介质基板层的至少一个表面上，
其中在所述铜箔层中，铁元素重量含量<10ppm，镍元素重量含量<10ppm，钴元素重量含量<10ppm，并且钼元素重量含量<10ppm。
优选铁元素重量含量小于或等于7ppm，更优选小于或等于5ppm。
优选镍元素重量含量小于或等于7ppm，更优选小于或等于5ppm。
优选钴元素重量含量小于或等于7ppm，更优选小于或等于5ppm。
优选钼元素重量含量小于或等于7ppm，更优选小于或等于5ppm。
进一步地，在所述铜箔层中，铁、镍、钴和钼元素重量含量之和可以小于或等于35ppm，优选小于或等于30ppm，更优选小于或等于18ppm，进一步优选小于或等于12ppm，并且最优选小于或等于5ppm。
本发明的发明人经深入细致的研究，发现覆铜层压板的铜箔层中的铁元素、镍元素、钴元素和钼元素会对印制电路板的PIM造成恶化。当铜箔层中铁元素重量含量<10ppm，镍元素重量含量<10ppm，钴元素重量含量<10ppm，并且钼元素重量含量<10ppm时，可以获得PIM较低的印制电路板，例如可以获得PIM值小于-158dBc(700MHz/2600MHz)，优选小于或等于-160dBc(700MHz/2600MHz)，更优选小于或等于-163dBc(700MHz/2600MHz)的印制电路板。
在700MHz-2600MHz下的无源互调值是指覆铜层压板在700MHz和2600MHz两个频率之间下通过反射法测量得到的无源互调值(PIM)。
在700MHz-2600MHz下小于-158dBc的无源互调值也可以表示为-158dBc(700MHz/2600MHz)。
PIM可以通过如下测量：每个样品分别测试9次，每次分别选取一个互调模型和一个频率，使用Summitek Instruments PIM分析仪进行测试，记录9次测试数据的最大值，为样品的PIM值。互调模型的线路设计长度为12英寸(但不仅限于12英寸)的弧形和锯齿形线路(也可以是直线或其它任意形状线路)，模型厚度分别为10mil、20mil和30mil样品，分别对应线宽为24mil、48mil和74mil；频率分别选取700MHz、1900MHz和2600MHz。即9次测试数据是：模型厚度为10mil，模型线宽为24mil在700MHz、1900MHz和2600MHz下测量的3个数据、模型厚度为20mil，模型线宽为48mil在700MHz、1900MHz和2600MHz下测量的3个数据和模型厚度为30mil，模型线宽为74mil在700MHz、1900MHz和2600MHz下测量的3个数据。
在一实施方案中，铜箔的毛面粗糙度(R Z)可以为0.5-3μm，由此可 以获得更好的信号完整性。
在一实施方案中，铜箔中铁元素、镍元素、钴元素和钼元素含量的多少，是通过电解铜箔后处理工艺得以实现。典型的电解铜箔的后处理工艺流程为：除油→水洗→酸洗除锈→水洗→合金电镀液电镀→水洗→钝化→水洗→烘干。在合金电镀液电镀中，可以溶解有铁元素、镍元素、钴元素和钼元素对应的盐，如硫酸铁、硫酸钼、硫酸镍、硫酸钴、硝酸铁、硝酸钼、硝酸钴、硝酸镍等。通过控制合金电镀液中的铁元素、镍元素、钴元素和钼元素对应的盐的浓度、电流及温度等工艺参数，可以调节电解铜箔中铜箔中铁元素、镍元素、钴元素和钼元素的含量。
铜箔层的厚度可以为0.1至10OZ，优选0.2至5OZ，并且进一步优选0.5至2OZ。1OZ表示35微米。
介质基板层可以由包括聚合物基质材料和填料的树脂组合物形成。
其中按所述介质基板层的重量计，所述聚合物基质材料为30至70重量百分比；并且所述填料为30至70重量百分比。
可选地，介质基板层可以包括增强材料或不包括增强材料。在包括增强材料的情况下，包含所述聚合物基质材料和填料的组合物附着在所述增强材料上构成介质基板层。优选地，增强材料为多孔增强材料如玻璃纤维。
可选地，聚合物基质材料包括改性或未改性的聚丁二烯树脂、改性或未改性的聚异戊二烯树脂和改性或未改性的聚芳醚树脂中的一种或多种。
可选地，用其制作的介质基板层在10GHz处具有小于约3.5的介质常数和小于约0.006的损耗因子，能满足电子信息领域的高频高速要求，且在10GHz处具有小于约3.5的介质常数和小于约0.006的损耗因子的PCB基板，对PIM指标提出了比在大于3.5以上的介质常数和大于0.006的损耗因子的PCB基板更高的性能要求。
可选地，各种聚合物例如聚丁二烯或聚异戊二烯聚合物、和其他聚合物的相对量可以取决于所用的具体的铜箔层、期望的电路材料和电路层合体的性能以及类似的考虑因素。已发现聚芳醚的使用可以提供铜箔与介质金属层增强的结合强度。聚丁二烯或聚异戊二烯聚合物的使用可以提高层合体的耐高温性。
可选地，聚丁二烯树脂可以包括聚丁二烯均聚物或共聚物树脂。聚丁 二烯共聚物树脂可以是聚丁二烯-苯乙烯共聚物树脂。改性的聚丁二烯树脂可以选自羟基封端的聚丁二烯树脂、甲基丙烯酸酯封端的聚丁二烯树脂和羧基化的聚丁二烯树脂中的一种或多种。
可选地，聚异戊二烯树脂可以包括聚异戊二烯均聚物树脂或聚异戊二烯共聚物树脂。聚异戊二烯共聚物树脂可以是聚异戊二烯-苯乙烯共聚物树脂。所述改性的聚异戊二烯均聚物树脂或聚异戊二烯共聚物树脂可以是羧基化的聚异戊二烯树脂。
可选地，改性的聚芳醚树脂可以为羧基官能化的聚芳醚、甲基丙烯酸酯封端的聚芳醚、含乙烯基封端的聚芳醚中的一种或多种。
具体地，聚丁二烯树脂、聚异戊二烯树脂包括含有源自丁二烯、异戊二烯或其混合物的单元的均聚物和共聚物。源自其他可共聚单体的单元也可以存在于树脂中，例如可选地以接枝的形式存在。示例性的可共聚单体包括但不限于乙烯基芳香族单体，例如取代和未取代的单乙烯基芳香族单体，如苯乙烯、3-甲基苯乙烯、3,5-二乙基苯乙烯、4-正丙基苯乙烯、α-甲基苯乙烯、α-甲基乙烯基甲苯、对羟基苯乙烯、对甲氧基苯乙烯、α-氯苯乙烯、α-溴苯乙烯、二氯苯乙烯、二溴苯乙烯、四氯苯乙烯等；以及取代的和未取代的二乙烯基芳香族单体如二乙烯基苯、二乙烯基甲苯等。也可以使用包含至少一种前述可共聚单体的组合物。示例性热固性聚丁二烯和/或聚异戊二烯树脂包括但不限于丁二烯均聚物、异戊二烯均聚物、丁二烯-乙烯基芳香族共聚物如丁二烯-苯乙烯、异戊二烯-乙烯基芳香族共聚物如异戊二烯-苯乙烯共聚物等，例如来自Crayvally的苯乙烯-丁二烯共聚物Ricon100，或是来自日本曹达的聚丁二烯B-1000。
可选地，聚丁二烯树脂和/或聚异戊二烯树脂可以被改性，例如树脂可以是羟基封端、甲基丙烯酸酯封端、羧酸酯封端等的树脂。聚丁二烯树脂、聚异戊二烯树脂可以是环氧-、顺丁烯酸酐-、或尿烷-改性的丁二烯或异戊二烯树脂。聚丁二烯树脂、聚异戊二烯树脂也可以被交联，例如经二乙烯基芳香族化合物如二乙烯基苯交联，如用二乙烯基苯交联的聚丁二烯-苯乙烯。示例性树脂在广义上被其制造商如Nippon Soda Co.(日本东京)和Cray Valley Hydrocarbon Specialty Chemicals(美国宾夕法尼亚州埃克斯(Exton))分类为“聚丁二烯”。也可以使用树脂的混合物，例如聚丁二 烯均聚物和聚(丁二烯-异戊二烯)共聚物的混合物。还可以使用包含间规聚丁二烯的组合。
可选地，聚丁二烯或聚异戊二烯聚合物可以是羧基官能化的。官能化可以利用如下多官能化合物完成：其在分子内具有(i)碳-碳双键或碳-碳三键；和(ii)一个或多个羧基，包括羧酸、酸酐、酰胺、酯或酸性卤化物。一种特定的羧基是羧酸或酯。可提供羧酸官能团的多官能化合物的实例包括顺丁烯二酸、顺丁烯二酸酐、反丁烯二酸、和柠檬酸。特别地，加合顺丁烯二酸酐的聚丁二烯可用于热固性组合物。合适的马来酸酐化聚丁二烯聚合物可市购获得，例如来自CrayValley，商品名为RICON 130MA8、RICON130MA13、RICON130MA20、RICON131MA5、RICON131MA10、RICON131MA17、RICON131MA20、和RICON 156MA17。合适的马来酸酐化聚丁二烯-苯乙烯共聚物可市购获得，例如来自Crayvally，商品名为RICON184MA6。
可选地，热固性聚丁二烯和/或聚异戊二烯树脂在室温下可以是液态或固态。合适的液态树脂可具有大于约5000的数均分子量，但是通常具有小于约5000(最优选约1000至约3000)的数均分子量。热固性聚丁二烯和/或聚异戊二烯树脂包括具有至少90wt％的1,2加成的树脂，其因大量突出的乙烯基能用于交联而使它们在固化后呈现出较大的交联密度。
可选地，聚丁二烯和/或聚异戊二烯树脂可以占总的聚合物基质组合物以相对于总树脂体系高达100wt％、特别地高达约75wt％的量，更特别地约10至70wt％、甚至更特别地约20至约60或70wt％的量存在于聚合物基质组合物中。
可选地，改性的聚苯醚树脂选自两末端改性基为丙烯酰基的聚苯醚树脂、两末端改性基为苯乙烯基的聚苯醚树脂、两末端改性基为乙烯基的聚苯醚树脂中的一种或为其中至少两种的混合物。
优选地，改性的聚苯醚树脂由下式(1)所示：
Figure PCTCN2020071878-appb-000001
式(1)中，a和b各自独立地为1至30的整数，
Z为由式(2)或(3)所示的基团：
Figure PCTCN2020071878-appb-000002
式(3)中，A为碳原子数为6至30的亚芳基、羰基、或碳原子数为1至10的亚烷基，m为0至10的整数，并且R 1至R 3各自独立地为氢原子或者碳原子数为1至10的烷基；
式(1)中的-(-O-Y-)-为由式(4)所示的基团：
Figure PCTCN2020071878-appb-000003
式(4)中，R 4和R 6各自独立地为氢原子、卤原子、碳原子数为1至10的烷基或苯基；并且R 5和R 7各自独立地为氢原子，卤原子、碳原子数为1至10的烷基或苯基；
式(1)中的-(-O-X-O-)-为由式(5)所示的基团：
Figure PCTCN2020071878-appb-000004
式(5)中，R 8、R 9、R 10、R 11、R 12、R 13、R 14和R 15各自独立地为氢原子，卤原子、碳原子数为1至10的烷基或苯基；并且B为碳原子数为6至30的亚芳基、碳原子数为1至10的亚烷基、-O-、-CO-、-SO-、-CS-或-SO 2-。
碳原子数为1至10的烷基优选为碳原子数为1至8的烷基，再优选为碳原子数为1至6的烷基，再更优选为碳原子数为1至4的烷基。碳原子数为1至8的烷基的实例可以包括甲基、乙基、丙基、丁基、戊基、己基、庚基和辛基，以及环丙基、环丁基、环戊基和环己基。在存在异构形式的 情况下，包含所有的异构形式。例如，丁基可以包括正丁基、异丁基和叔丁基。
碳原子数为6至30的亚芳基的实例可以包括亚苯基、亚萘基和亚蒽基。
碳原子数为1至10的亚烷基优选为碳原子数为1至8的亚烷基，更优选为碳原子数为1至6的亚烷基，再更优选为碳原子数为1至4的亚烷基。碳原子数为1至10的亚烷基的实例可以包括亚甲基、亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基和亚癸基，以及亚环丙基、亚环丁基、亚环戊基和亚环己基。在存在异构形式的情况下，包含所有的异构形式。
卤原子的实例可以包括氟原子、氯原子、溴原子和碘原子。
优选地，所述聚苯醚树脂的数均分子量可以为500至10000g/mol，优选800至8000g/mol，进一步优选1000至7000g/mol。示例性的聚苯醚可以是来自Sabic的甲基丙烯酸酯基改性的聚苯醚SA9000、或是来自三菱化学的苯乙烯基改性的聚苯醚St-PPE-1。
可选地，填料可以选自结晶型二氧化硅、熔融二氧化硅、球形二氧化硅、氮化硼、氢氧化铝、二氧化钛、钛酸锶、钛酸钡、氧化铝、氧化镁、硫酸钡、硼硅酸盐、铝硅酸盐、及滑石粉中的一种或多种。填料可为实心、多孔或中空颗粒的形式。为了提高填料和聚合物之间的粘合，可用一种或更多种偶联剂例如硅烷、锆酸盐或钛酸盐处理填料。在使用时，填料的量通常占介质基板层的30至70重量百分比。一种示例性的非中空的无机填料可以是来自江苏联瑞的DQ2028V。一种示例性的中空的无机填料可以是来自3M的iM16K。
为了特定的性能或工艺改变，聚合物基质材料可以添加能与热固性聚丁二烯和/或聚异戊二烯树脂和/或聚苯醚树脂共固化的其他聚合物。例如，为了提高电基板材料的介电强度和机械性能随时间的稳定性，可以在树脂体系中使用较低分子量的乙烯丙烯弹性体。本文使用的乙烯丙烯弹性体是主要包含乙烯和丙烯的共聚物、三元共聚物或其他聚合物。乙烯丙烯弹性体可以进一步分为EPM共聚物(即乙烯和丙烯单体的共聚物)或EPDM三元共聚物(即乙烯、丙烯和二烯单体的三元共聚物)。特别地，乙烯丙烯二烯三元共聚物橡胶具有饱和主链，以及主链中可易于交联的不饱和度。 可以使用其中二烯为二环戊二烯的液态乙烯丙烯二烯三元共聚物橡胶。
可选地，乙烯丙烯橡胶的分子量可以小于10,000的粘均分子量。乙烯丙烯橡胶以保持基质材料的性能、特别是介电强度和机械性能随时间推移的稳定性的有效量存在。通常，此量相对于聚合物基质组合物的总重量高达约20wt％，更特别为约4至约20wt％，甚至更特别为约6至约12wt％。一种示例性的乙烯丙烯橡胶可以是来自lion Copolymer的Trilene 67。
可选地，另一种类型的可共固化聚合物是含有不饱和的聚丁二烯或聚异戊二烯的弹性体。该组分可以是主要为1,3-加成丁二烯或异戊二烯与烯键式不饱和单体例如乙烯基芳香族化合物如苯乙烯或α-甲基苯乙烯、丙烯酸酯或甲基丙烯酸酯如甲基丙烯酸甲酯、或丙烯腈的无规共聚物或嵌段共聚物。弹性体可以为包含具有聚丁二烯或聚异戊二烯嵌段和可以源自单乙烯基芳香族单体如苯乙烯或α-甲基苯乙烯的热塑性嵌段的线性或接枝型嵌段共聚物的固态、热塑性弹性体。这种类型的嵌段共聚物包括苯乙烯-丁二烯-苯乙烯三嵌段共聚物，苯乙烯-丁二烯二嵌段共聚物，以及含有苯乙烯和丁二烯的混合三嵌段和二嵌段共聚物。示例性的Kraton D1118是含有混合的二嵌段/三嵌段苯乙烯和丁二烯的共聚物。
通常，含有不饱和聚丁二烯-或聚异戊二烯-的弹性体组分以相对于总聚合物基质组合物约2wt.％至约60wt.％的量，更特别地为约5wt.％至约50wt.％、或甚至更特别地约10wt.％至约40或50wt.％的量存在于树脂体系中。
为了特定的性能或工艺改变，可以添加除聚丁二烯树脂、聚异戊二烯树脂和聚芳醚树脂以外的其他可共固化聚合物，其包括但不限于乙烯的均聚物或共聚物，例如聚乙烯和环氧乙烷共聚物；天然橡胶；降冰片聚合物如聚双环戊二烯；氢化苯乙烯-异戊二烯-苯乙烯共聚物和丁二烯-丙烯腈共聚物；不饱和聚酯等。这些共聚物的水平通常低于基质组合物中的总聚合物的50wt.％。
为了特定的性能或工艺改变，还可以添加可自由基固化单体，例如以提高固化后树脂体系的交联密度。能作为合适交联剂的示例性单体包括例如二-、三-、或更高的烯键式不饱和单体如二乙烯基苯、氰尿酸三烯丙酯、对苯二甲酸二烯丙酯、和多官能丙烯酸酯单体(如树脂，可购自 SartomerUSA(宾夕法尼亚州新城广场(NewtownSquare))、或其组合物，它们均可市购获得。使用时，交联剂以占总聚合物基质组合物高达约20wt.％、特别地1至15wt.％的量存在于树脂体系中。
可以将引发剂加入树脂体系中以加速具有烯烃反应位点的多烯的固化反应。特别有用的引发剂是有机过氧化物，例如过氧化二异丙苯、过氧化二月桂酰、过氧化新葵酸异丙苯酯、过氧化新葵酸叔丁酯、过氧化特戊酸特戊酯、过氧化特戊酸叔丁酯、叔丁基过氧化异丁酸酯、叔丁基过氧化-3,5,5-三甲基己酸酯、过氧化乙酸叔丁酯、过氧化苯甲酸叔丁酯、1,1-二叔丁基过氧化-3,5,5-三甲基环己烷、1,1-二叔丁基过氧化环己烷、2,2-二(叔丁基过氧化)丁烷、双(4-叔丁基环己基)过氧化二碳酸酯、过氧化二碳酸酯十六酯、过氧化二碳酸酯十四酯、二特戊己过氧化物、二异丙苯过氧化物、双(叔丁基过氧化异丙基)苯、2,5-二甲基-2,5-二叔丁基过氧化己烷、2,5-二甲基-2,5-二叔丁基过氧化己炔、二异丙苯过氧化氢、特戊基过氧化氢、叔丁基过氧化氢、过氧化碳酸酯-2-乙基己酸叔丁酯、叔丁基过氧化碳酸-2-乙基己酯、4,4-二(叔丁基过氧化)戊酸正丁酯、过氧化甲乙酮和过氧化环己烷中的任意一种或者至少两种的混合物，它们均可市购获得。在树脂体系中也可以使用碳-碳引发剂，例如2,3-二甲基-2,3二苯基丁烷。引发剂可以单独使用或结合使用。典型的引发剂量为总聚合物基质组合物的约1.5至约10wt.％。
可以将阻燃剂加入树脂体系中以使电子组件具备阻燃性能。阻燃剂可以选自卤系阻燃剂、磷系阻燃剂中的一种或者至少两种的混合物。
可选地，所述溴系阻燃剂可以选自十溴二苯醚、六溴苯、十溴二苯乙烷、乙撑双四溴邻苯二甲酰亚胺中的任意一种或者至少两种的混合物。
可选地，所述磷系阻燃剂可以选自三(2,6-二甲基苯基)膦、10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、2,6-二(2,6-二甲基苯基)膦基苯或10-苯基-9,10-二氢-9-氧杂-10-膦菲-10-氧化物中的一种或者至少两种的混合物。
一种示例性的含溴阻燃剂可以是来自美国雅宝的BT-93W。
一种示例性的含溴阻燃剂可以是来自美国雅宝的XP-7866。
作为本公开中的聚合物基质材料中的溶剂，没有特别限定，作为具体 例，可以举出甲醇、乙醇、丁醇等醇类，乙基溶纤剂、丁基溶纤剂、乙二醇-甲醚、卡必醇、丁基卡必醇等醚类，丙酮、丁酮、甲基乙基甲酮、甲基异丁基甲酮、环己酮等酮类，甲苯、二甲苯、均三甲苯等芳香族烃类，乙氧基乙基乙酸酯、醋酸乙酯等酯类，N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮等含氮类溶剂。上述溶剂可以单独使用一种，也可以两种或者两种以上混合使用，优选甲苯、二甲苯、均三甲苯等芳香族烃类溶剂与丙酮、丁酮、甲基乙基甲酮、甲基异丁基甲酮、环己酮等酮类熔剂混合使用。本领域技术人员可以根据自己的经验来选择溶剂的使用量，使得到的树脂胶液达到适于使用的粘度即可。
可以通过添加粘度调节剂(基于其与具体的聚合物基质材料的混合物的相容性而选择)来调节树脂组合物的粘度，以延迟填料从介电复合材料中分离，即沉降或漂浮；并且提供具有与常规层合设备相容的粘度的介质复合材料。示例性粘度调节剂包括例如聚丙烯酸化合物、纳米填料、乙丙橡胶等。
还可以含有各种添加剂，作为具体例，可以举出抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂等。这些各种添加剂可以单独使用，也可以两种或者两种以上混合使用。
可选地，介质基板层可以是将可选的聚丁二烯树脂、聚异戊二烯树脂、聚芳醚树脂、其它可共固化聚合物、自由基固化单体、弹性体嵌段共聚物、引发剂、阻燃剂、粘结调节剂、溶剂等组成的聚合物基质材料以及填料混合的胶水涂覆在离型膜上获得树脂薄膜层，也可以将上述聚合物基质材料以及填料混合的胶水通过浸渍或涂覆增强材料制备包含增强材料的介质基板层。
增强材料可选地包括合适的纤维，特别地玻璃纤维(E和NE玻璃)或者高温聚酯纤维的非织造或织造的热稳定网。这样的热稳定性纤维强化物为覆铜层压板提供相对高的固化收缩率和机械强度。
本公开的覆铜层压板中，铜箔与介质基板层可以直接接触，之间还可以包括粘结剂层和/或树脂薄膜层，以提高铜箔与介质基板层之间的粘结性或改善其介质性能。粘结剂层是以溶液形式施用到铜箔或介质基板层的表面上以提供2至15克/平方米的涂层重量而获得所述粘合剂层。树脂薄膜 层可以是以溶液形式施用到铜箔或介质基板层的表面上以提供2至15克/平方米的涂层重量而获得所述树脂薄膜层。
本公开的覆铜层压板中，介质基板层中间也可以包括树脂薄膜层。
粘结剂层和/或树脂薄膜层可以与介质基板层的组成相同，也可以不同，可以不固化、部分固化或完全固化。
示例性的制备方法：将可选的聚丁二烯树脂、聚异戊二烯树脂、聚芳醚树脂、其它可共固化聚合物、自由基固化单体、弹性体嵌段共聚物、引发剂、阻燃剂、粘结调节剂、溶剂等组成的聚合物基质材料以及填料混合的胶水通过浸渍或涂覆增强材料(E玻璃布)，过夹轴控制适合的单重，并在烘箱中烘片，除去溶剂，制备介质基板层。将一张或多张介质基板层重叠，上下两面配以铜箔，在压机中真空层压固化60-120min，固化压力25-50Kg/cm 2，固化温度180-220℃，制得覆铜层压板。
在又一个方面，本公开提供一种包括上面所述的印制电路板的电路。
在再一个方面，本公开提供一种包括上面所述的印制电路板的多层电路。
在一个实施方案中，包括所述的印制电路板的电路或多层电路被用于天线。
根据本公开，通过限制铜箔层中铁元素重量含量<10ppm，镍元素重量含量<10ppm，钴元素重量含量<10ppm，并且钼元素重量含量<10ppm，可以提供具有无源互调性能小于-158dBc(700MHz/2600MHz)的覆铜层压板和包含覆铜层压板的印制电路板。
此外，还可以提供一种具有无源互调性能小于-158dBc(700MHz/2600MHz)并且能够满足电子信息领域的高频高速要求的覆铜层压板和包含覆铜层压板的印制电路板。
下面通过具体实施方式来进一步说明本公开的技术方案。在下列实施例和对比例中，如果没有具体指明，百分比、比例等是按重量计的。
实施例
本发明实施例制备的高速电子电路基材所选取的原料如下表所示：
表1
制造厂商 产品名称或牌号 材料描述
Sabic SA90 端羟基聚苯醚树脂
Sabic SA9000 甲基丙烯酸酯改性聚苯醚树脂
三菱化学 St-PPE-1 苯乙烯基改性聚苯醚树脂
Crayvally Ricon100 苯乙烯-丁二烯共聚物
Crayvally Ricon130MA8 马来酸酐化聚丁二烯树脂
Kraton D1118 苯乙烯-丁二烯-苯乙烯嵌段共聚物
Lion Copolymer Trilene 67 乙烯丙烯弹性体
日本曹达 B1000 聚丁二烯树脂
上海高桥 DCP 过氧化二异丙苯
阿克苏诺贝尔 Perkadox 30 2,3-二甲基-2,3-二苯基丁烷
江苏联瑞 DQ1028L 熔融硅微粉
美国雅宝 BT-93W 含溴阻燃剂
美国雅宝 XP-7866 含磷阻燃剂
3M iM16K 中空硼硅酸盐微球
上海宏和 1078 玻璃纤维布
实施例1
将20g的聚丁二烯树脂B1000、5g的苯乙烯-丁二烯-苯乙烯嵌段共聚物D1118、4g的乙烯丙烯弹性体Trilene 67、1g的马来酸酐化聚丁二烯树脂Ricon130MA8、1g的2,3-二甲基-2,3-二苯基丁烷Perkadox 30、12g含溴阻燃剂BT-93W、70g无机填料DQ2028L，溶解于甲苯溶剂中，并调节至粘度为50秒(采用4号粘度杯测试)。用1078玻纤布浸润胶水，过夹轴 控制单重为190g，并在烘箱中烘片，除去甲苯溶剂，制得1078预浸料。将6张1078预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力25Kg/cm 2，固化温度180℃，制得覆铜层压板。覆铜层压板的介质基板层的组分和用量以及铜箔层的厚度、毛面粗糙度及铁、镍、钴和钼的含量、填料的用量和覆铜层压板的物理性能如表2所示。
实施例2-16和比较例1-16
以与实施例1相同的方式制备实施例2-16和比较例1-16各自的介质基板和覆铜层压板，不同之处在于覆铜层压板的介质基板层的组分和用量以及铜箔层的厚度、毛面粗糙度及铁、镍、钴和钼的含量、填料的用量和覆铜层压板的物理性能分别如表2-5所示。表2-5中介质基板层包括填料在内的组分的单位是克。
表2
Figure PCTCN2020071878-appb-000005
表3
Figure PCTCN2020071878-appb-000006
Figure PCTCN2020071878-appb-000007
表4
Figure PCTCN2020071878-appb-000008
表5
Figure PCTCN2020071878-appb-000009
本公开中提及的以下性能的测试方法：
铜箔毛面粗糙度：非接触式激光法。
铜箔层中元素含量测试：电感耦合等离子体质谱法。
PIM：每个样品分别测试9次，每次分别选取一个互调模型和一个频率，使用Summitek Instruments PIM分析仪进行测试，记录9次测试数据的最大值，为样品的PIM值。互调模型的线路设计长度为12英寸的弧形和锯齿形线路，模型厚度分别为10mil、20mil和30mil样品，分别对应线宽为24mil、48mil和74mil；频率分别选取700MHz、1900MHz和2600MHz。
Dk/Df测试方法：采用IPC-TM-650 2.5.5.5标准方法，频率10GHz。
分子量测试方法：国家标准GB T21863-2008-凝胶渗透色谱法(GPC)，用四氢呋喃做淋洗液。
物性分析：
从实施例1-16可知，采用了铁元素重量含量<10ppm，镍元素重量含量<10ppm，钴元素重量含量<10ppm，钼元素重量含量<10ppm，所制备的介质基板和覆铜层压板具有小于-158dBc(700MHz/2600MHz)的无源互调PIM性能，表现优异。实施例1-16制备的覆铜层压板能够满足电子信息领域高频高速的要求。
比较例1-16与实施例1-16对比可知，所制备的介质基板和覆铜层压板，其铜箔层铁元素重量含量>10ppm，镍元素重量含量>10ppm，钴元素重量含量>10ppm，和/或钼元素重量含量>10ppm，PIM性能表现差，不能满足客户对PIM性能的要求。
显然，本领域的技术人员可以对本发明实施例进行各种改动和变型而不脱离本公开的精神和范围。这样，倘若本公开的这些修改和变型属于本公开根据权利要求及其等同技术的范围之内，则本公开也意图包含这些改动和变型在内。

Claims (17)

  1. 一种覆铜层压板，包括：
    介质基板层，和
    铜箔层，所述铜箔层位于所述介质基板层的至少一个表面上，
    其中在所述铜箔层中，铁元素重量含量<10ppm，镍元素重量含量<10ppm，钴元素重量含量<10ppm，并且钼元素重量含量<10ppm。
  2. 根据权利要求1所述的覆铜层压板，其中所述覆铜层压板具有在700MHz-2600MHz下小于-158dBc的无源互调值。
  3. 根据权利要求1所述的覆铜层压板，其中所述铜箔的毛面粗糙度为0.5-3μm。
  4. 根据权利要求1所述的覆铜层压板，其中所述介质基板层包括
    聚合物基质材料；和
    填料；
    其中按所述介质基板层的重量计，所述聚合物基质材料为30至70重量百分比；并且所述填料为30至70重量百分比。
  5. 根据权利要求4所述的覆铜层压板，其中所述聚合物基质材料包括改性或未改性的聚丁二烯树脂、改性或未改性的聚异戊二烯树脂和改性或未改性的聚芳醚树脂中的一种或多种。
  6. 根据权利要求1所述的覆铜层压板，其中所述介质基板层在10GHz处具有小于3.5的介质常数和小于0.006的损耗因子。
  7. 根据权利要求5所述的覆铜层压板，其中所述聚丁二烯树脂是聚丁二烯均聚物树脂或聚丁二烯共聚物树脂。
  8. 根据权利要求7所述的覆铜层压板，其中所述聚丁二烯共聚物树脂是聚丁二烯-苯乙烯共聚物树脂。
  9. 根据权利要求5所述的覆铜层压板，其中所述改性的聚丁二烯树脂选自羟基封端的聚丁二烯树脂、甲基丙烯酸酯封端的聚丁二烯树脂和羧基化的聚丁二烯树脂中的一种或多种。
  10. 根据权利要求5所述的覆铜层压板，其中所述聚异戊二烯树脂是聚异戊二烯均聚物树脂或聚异戊二烯共聚物树脂。
  11. 根据权利要求10所述的覆铜层压板，其中所述聚异戊二烯共聚物树脂是聚异戊二烯-苯乙烯共聚物树脂。
  12. 根据权利要求5所述的覆铜层压板，其中所述改性的聚异戊二烯树脂是羧基化的聚异戊二烯树脂。
  13. 根据权利要求5所述的覆铜层压板，其中所述改性的聚芳醚树脂为羧基官能化的聚芳醚、甲基丙烯酸酯封端的聚芳醚、含乙烯基封端的聚芳醚中的一种或多种。
  14. 根据权利要求5所述的覆铜层压板，其中所述聚合物基质材料还包括除聚丁二烯树脂、聚异戊二烯树脂和聚芳醚树脂以外的可共固化聚合物、自由基固化单体、弹性体嵌段共聚物、引发剂、阻燃剂、粘结调节剂和溶剂中的一种或多种。
  15. 根据权利要求1所述的覆铜层压板，其中所述介质基板层包含增强材料或者不包含增强材料。
  16. 根据权利要求1所述的覆铜层压板，还包括位于所述铜箔与所述介质基板层之间的粘结剂层和/或树脂薄膜层。
  17. 一种包括权利要求1至16中任一项所述的覆铜层压板的印制电路板。
PCT/CN2020/071878 2019-04-24 2020-01-14 覆铜层压板和印制电路板 WO2020215838A1 (zh)

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