CN112538184B - Interlayer bonding sheet for multilayer board and preparation method and application thereof - Google Patents

Interlayer bonding sheet for multilayer board and preparation method and application thereof Download PDF

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CN112538184B
CN112538184B CN201910833102.4A CN201910833102A CN112538184B CN 112538184 B CN112538184 B CN 112538184B CN 201910833102 A CN201910833102 A CN 201910833102A CN 112538184 B CN112538184 B CN 112538184B
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bonding sheet
interlayer bonding
ptfe substrate
ptfe
multilayer board
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CN112538184A (en
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苏民社
周如金
梁伟
郭浩勇
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2409/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2447/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides an interlayer bonding sheet for a multilayer board and a preparation method and application thereof, wherein the interlayer bonding sheet for the multilayer board comprises a PTFE substrate and a dielectric resin layer bonded on the surface of the PTFE substrate; the PTFE substrate is a PTFE substrate with the surface treated by plasma, and the surface treatment depth of the PTFE substrate is 5-15 nm. The surface of the PTFE substrate is subjected to plasma treatment to realize functional modification, the wettability is obviously improved, and the PTFE substrate can be stably bonded with a dielectric resin layer with high strength. The interlayer bonding sheet for the multilayer board has excellent dielectric property, fluidity and bonding strength through the cooperative matching of the PTFE substrate and the dielectric resin layer, the surface of which is subjected to plasma treatment, and the bonding sheet has high bonding stability and can fully meet the signal high-frequency requirement, stability and reliability requirement of the multilayer board.

Description

Interlayer bonding sheet for multilayer board and preparation method and application thereof
Technical Field
The invention belongs to the technical field of copper-clad plates, and particularly relates to an interlayer bonding sheet for a multilayer plate, and a preparation method and application thereof.
Background
The rapid development of information industry, advanced communication equipment and technology has brought new performance requirements for high-frequency electronic equipment widely used in the communication field, and signal processing and transmission power of electronic equipment is greatly increased, moving from MHz to GHz, and therefore, electronic circuit substrates for signal transmission are inevitably subject to a shift to high-frequency and high-speed characteristics. In the high-frequency and high-speed development process of electronic circuit base materials, the key point is that a material with excellent electrical performance is selected, the dielectric constant and the dielectric loss tangent of Polytetrafluoroethylene (PTFE) are small, and the Polytetrafluoroethylene (PTFE) is good in aging resistance and high and low temperature resistance and is an ideal high-frequency base material.
In recent years, the electronic industry based on microelectronics has driven the development of miniaturization, multi-functionalization and high performance of electronic products, and the miniaturization, the functionalization and the multilayering of printed circuit boards as essential components for circuit interconnection are also required. However, since PTFE resin has low surface energy and almost no fluidity and adhesiveness, and is difficult to be used as an adhesive material between layers of a multilayer board, the search for an interlayer adhesive material for a multilayer printed circuit board having excellent electrical properties is very important for the development of the entire circuit board industry.
CN101220160 discloses a prepreg applied to a printed circuit multilayer board, which comprises a reinforcing material and a resin composition, wherein the reinforcing material is glass fiber paper, and the resin composition comprises the following components in parts by weight: 20 to 84 parts of resin, 0 to 35 parts of filler, 0.01 to 0.3 part of curing accelerator and 10 to 45 parts of solvent; wherein the resin is one or more of cyanate resin, benzoxazine resin, bismaleimide resin, polyimide resin and polytetrafluoroethylene resin. The prepreg can be used as a material for processing a multilayer PCB, solves the problems of layering, board explosion, resin shrinkage and the like of the multilayer PCB after cold and hot impact, and has good reliability and low cost.
CN102051021A discloses a prepreg applied to a printed circuit board to fill a nano molecular sieve and a preparation method thereof, wherein the prepreg comprises a reinforcing material and a resin composition, the reinforcing material is glass fiber paper or glass fiber cloth, and the resin composition is a mixture of 30-72 parts of resin, 0-10 parts of filler, 0.01-0.5 part of curing accelerator and 5-50 parts of solvent; wherein the resin composition is one or more of epoxy resin, epoxy modified resin, cyanate ester, benzoxazine, bismaleimide, polyimide, polytetrafluoroethylene and phenolic resin, and the filler is a nano titanium silicalite molecular sieve or a mesoporous molecular sieve. The prepreg has low dielectric constant, high glass transition temperature and low thermal expansion coefficient, and can meet the requirements of advanced electronic equipment.
In the process of developing a PTFE multilayer board to higher performance and higher frequency, researchers find that a prepreg based on thermosetting resin such as epoxy and the like has good bonding performance, but has high dielectric constant and dielectric loss tangent, insufficient high-frequency characteristics and can not meet the requirement of signal high-frequency; the polyolefin resin has low dielectric loss tangent, but has poor tolerance, and is difficult to meet the process requirements and the use requirements for manufacturing the printed circuit board; although the prepreg prepared by using the fluorine-containing resin overcomes the defects of partial dielectric property and tolerance, the bonding property of the fluorine resin and a film material is poor, and the phenomena of layering, foaming and the like exist at high temperature, so that the obtained PTFE multilayer board has poor bonding heat-resistant reliability, and can not meet the subsequent application requirements.
Therefore, it is a research focus in the field to develop an interlayer adhesive material for a multi-layer board with good adhesive property, heat resistance and reliability to satisfy various properties and application requirements of a high frequency multi-layer printed circuit board.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an interlayer bonding sheet for a multilayer board, a preparation method and application thereof, wherein the interlayer bonding sheet for the multilayer board comprises a PTFE substrate and a dielectric resin layer bonded on the surface of the PTFE substrate; the PTFE substrate generates free radicals and active sites after plasma surface treatment, so that the functional modification of the surface of the PTFE substrate is realized, and the bonding property is obviously improved. The interlayer bonding sheet for the multilayer board has excellent dielectric property, fluidity and bonding strength through the cooperative matching of the PTFE substrate and the dielectric resin layer, the surfaces of which are subjected to plasma treatment, and can meet the signal high-frequency requirement, stability and reliability requirement of the multilayer board.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an interlayer bonding sheet for a multilayer sheet, comprising a PTFE substrate, and a dielectric resin layer bonded to a surface of the PTFE substrate.
The PTFE substrate is a PTFE substrate having a plasma-treated surface, the PTFE substrate has a surface treatment depth of 5 to 15nm, such as 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, or 14nm, and specific values therebetween, for reasons of brevity and clarity, the present invention is not exhaustive and does not list the specific values included in the range.
The interlayer bonding sheet for the multilayer board comprises a PTFE substrate with the surface subjected to plasma treatment and a dielectric resin layer bonded on the PTFE substrate, wherein the PTFE substrate and the dielectric resin layer have excellent dielectric properties, low dielectric constant and dielectric loss tangent and sufficient high-frequency characteristics, and can meet the electrical property requirements of the multilayer board.
The plasma surface treatment refers to a physical or chemical action process of plasma of non-polymerizable gas on the surface of a high molecular material. The PTFE material on the PTFE substrate has the characteristics of high crystallinity, low surface energy and difficult wetting, and meanwhile, the difference between the solubility parameter and the solubility parameter of a common adhesive is large, and the interfaces are difficult to diffuse mutually at will, so the PTFE material is a difficult-to-bond material. The PTFE substrate of the present invention is processed by passing various gases (e.g., he, ne, O) during plasma treatment 2 、H 2 、N 2 、Ar、CO 2 、SO 2 、NH 3 、CH 4 Or any one of water vapor or a combination of at least two of water vapor) to activate and functionalize the PTFE surface; the dissipation process of the energy is the process of obtaining modification on the surface of the PTFE substrate; the PTFE substrate generates free radicals on the surface through plasma treatment, and the formed active sites can continuously react with gas components in plasma to cause a series of surface modification. The PTFE substrate surface of the invention is treated by plasma, the reaction activity is enhanced, the PTFE substrate can be stably bonded with the dielectric resin layer with high strength, the heat resistance and the high-temperature reliability are high, and the requirement of a multilayer printed circuit can be metThe manufacturing process requirements and the subsequent application requirements of the board.
In addition, the dielectric resin layer in the interlayer bonding sheet for the multilayer board has excellent dielectric property and heat resistance, and also has good chemical resistance and mechanical property, toughness capable of meeting the process requirement of the multilayer board, good fluidity and bonding property, and capability of ensuring strong interlayer bonding force and high bonding stability between circuit boards.
In conclusion, the interlayer bonding sheet for the multilayer board provided by the invention has excellent dielectric property, fluidity and bonding strength through the synergistic cooperation of the PTFE substrate and the dielectric resin layer, the surface of which is subjected to plasma treatment, and can fully meet the signal high-frequency requirement, stability and reliability requirement of the multilayer board.
When the surface treatment depth of the PTFE substrate is within the range of 5 to 15nm, the PTFE substrate and the dielectric resin layer have the best bonding strength and high bonding stability. When the plasma treatment depth is less than 5nm, the plasma etching depth is shallow, the surface area is low, and ideal bonding cannot be formed; when the plasma treatment depth is more than 15nm, the treatment is excessive, the surface activation is weakened, the improvement of wettability is affected, and a desired bond cannot be formed.
Preferably, the PTFE substrate has a contact angle of 84 to 98 °, such as 85 °, 86 °, 87 °, 88 °, 89 °, 90 °, 91 °, 92 °, 93 °, 94 °, 95 °, 96 °, or 97 °, and specific values therebetween, for brevity and clarity, are not exhaustive of the specific values included in the ranges.
The contact angle of the PTFE substrate is 84-98 degrees, and if the contact angle is larger than 98 degrees, the wettability of the PTFE substrate is poor, and the PTFE substrate is difficult to be tightly adhered to the dielectric resin layer; if the contact angle is less than 84 °, the surface is excessively treated with plasma, which reduces the surface activation, lowers the wettability of the substrate surface, and prevents high-strength adhesion with the dielectric resin layer.
Preferably, the interlayer bonding sheet for a multilayer board includes a PTFE substrate, and dielectric resin layers bonded to upper and lower surfaces of the PTFE substrate.
Preferably, the PTFE substrate has a thickness of 0.3 to 1.5mm, such as 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, 1.1mm, 1.2mm, 1.3mm or 1.4mm, and specific values therebetween, not to be limited in space and for the sake of brevity, the present invention is not exhaustive of the specific values included in the ranges.
Preferably, the PTFE substrate is glass cloth with a PTFE layer on the surface.
Preferably, the glass cloth is electronic-grade glass cloth or once-desized glass cloth; for example, the electronic grade glass cloth may be 1037, 106, 1080, 1078, and the like.
Preferably, the PTFE substrate is obtained by soaking glass cloth in PTFE emulsion, drying and sintering.
The PTFE emulsion of the present invention means an aqueous dispersion containing a PTFE resin.
Preferably, the PTFE emulsion is a PTFE emulsion containing a powder filler.
Preferably, the powder filler is selected from any one of or a combination of at least two of silica, titanium dioxide, strontium titanate, barium titanate, boron nitride, aluminum nitride, silicon carbide, alumina, glass fiber, polytetrafluoroethylene, polyphenylene sulfide or polyether sulfone, and further preferably is silica.
Illustratively, the silica may be any one of crystalline silica, fused silica, or spherical silica, or a combination of at least two thereof.
Preferably, the powder filler has a median particle diameter of 1 to 15 μm, for example 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm or 14 μm, and specific values therebetween, not to be limited in space and for the sake of brevity, the invention is not exhaustive of the specific values included in the range, and more preferably 1 to 10 μm.
Preferably, the thickness of the dielectric resin layer is 5 to 60 μm, such as 6 μm, 8 μm, 10 μm, 12 μm, 15 μm, 17 μm, 20 μm, 22 μm, 25 μm, 28 μm, 30 μm, 33 μm, 35 μm, 37 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 53 μm, 55 μm, 57 μm or 59 μm, and the specific dot values therebetween are not exhaustive and are not limited to the specific dot values included in the range, and are more preferably 20 to 50 μm, in view of space and conciseness.
Preferably, the raw materials for preparing the dielectric resin layer comprise the following components in parts by weight: 20 to 70 parts of polymer matrix material, 0 to 70 parts of powder filler and 1 to 3 parts of initiator.
Preferably, the polymer matrix material is selected from any one of polybutadiene, polyisoprene, butadiene-styrene copolymer, polyphenylene oxide or ethylene propylene rubber or a combination of at least two of the same.
The resin compositions disclosed in the prior art to meet the above requirements can be used to prepare the dielectric resin layer of the present invention. Such prior art includes, by way of example and not limitation: CN106867173A discloses a composite material, comprising: (1) 20-70 parts of a thermosetting mixture comprising: (A) A thermosetting resin based on polybutadiene having a molecular weight of 11000 or less and containing 60% or more of vinyl groups or a copolymer resin of polybutadiene and styrene, which is composed of hydrocarbon elements; and (B) an ethylene-propylene rubber which is solid at room temperature and has a weight average molecular weight of more than 10 ten thousand and less than 15 ten thousand and a number average molecular weight of more than 6 ten thousand and less than 10 ten thousand; (2) 10-60 parts of glass fiber cloth; (3) 0-70 parts of powder filler; and (4) 1-3 parts of curing initiator. CN102161823A discloses a composite material, which comprises more than one vinyl liquid resin with molecular weight less than 10000 and polar functional groups, a polyphenylene ether resin with molecular weight less than 5000 and unsaturated double bonds at the molecular terminals, glass fiber cloth, powder filler, flame retardant and curing initiator. CN101643565B discloses a composite material, which comprises resin which is composed of hydrocarbon elements and has molecular weight of less than 11000 and contains more than 60 percent of vinyl, solid styrene-based resin with middle-low molecular weight and unsaturated double bonds, glass fiber cloth, powder filler, flame retardant and curing initiator. CN102807658A discloses a polyphenylene ether resin composition component comprising a functionalized polyphenylene ether resin, a crosslinking curing agent and an initiator; the functionalized polyphenylene ether resin is polyphenylene ether resin with a number average molecular weight of 500-5000 and unsaturated double bonds at the molecular tail end, and the crosslinking curing agent is olefin resin with a number average molecular weight of 500-10000 and containing 10-50 wt% of styrene structure, and the molecule of the resin contains 1,2 bit addition butadiene structure. CN102993683A discloses a modified polyphenylene ether resin and an organosilicon compound containing unsaturated double bonds.
In the raw materials for preparing the polymer matrix material of the present invention, the content of the polymer matrix material may be 22 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 45 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 55 parts by weight, 58 parts by weight, 60 parts by weight, 62 parts by weight, 65 parts by weight, 68 parts by weight, 69 parts by weight, or the like.
The content of the powder filler may be 2 parts by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 68 parts by weight, or the like.
The initiator may be present in an amount of 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.4 parts by weight, 2.6 parts by weight, 2.8 parts by weight, 2.9 parts by weight, or the like.
As a preferred embodiment of the present invention, the polymer matrix material comprises: (A) A thermosetting resin based on polybutadiene or butadiene-styrene copolymer having a molecular weight of 11000g/mol or less (e.g., 10500g/mol, 10000g/mol, 9800g/mol, 9500g/mol, 9300g/mol, 9000g/mol, 8800g/mol, 8500g/mol, 8300g/mol, 8000g/mol, etc.), consisting of hydrocarbon elements and containing 60% or more (e.g., 61%, 63%, 65%, 67%, 69%, 71%, 73%, 75%, 77%, etc.) vinyl groups, and comprising (B) a solid rubber having a weight average molecular weight of 100000 to 150000g/mol (e.g., 105000g/mol, 110000g/mol, 115000g/mol, 120000g/mol, 125000g/mol, 130000g/mol, 135000g/mol, 140000g/mol or 145000g/mol, etc.), a number average molecular weight of 60000 to 100000g/mol (e.g/mol, 6500 g/mol, 65000g/mol, 75000g/mol, 80000g/mol, 800000 g/mol, 80000g/mol, 9500g/mol, 800000 g/mol, etc.), a solid ethylene-propylene rubber having a molecular weight of 11000g/mol or more, and the like, and room temperature.
The molecular weight, weight average molecular weight and number average molecular weight data are obtained by testing according to the method specified in GB/T21863-2008 standard, and are measured by gel permeation chromatography based on polystyrene calibration.
Preferably, the initiator is an organic peroxide initiator.
Illustratively, the organic peroxide initiator includes benzoyl peroxide, dicumyl peroxide, or t-butyl peroxybenzoate, and the like.
Preferably, the powder filler is selected from any one of or a combination of at least two of silica, titanium dioxide, strontium titanate, barium titanate, boron nitride, aluminum nitride, silicon carbide, alumina, glass fiber, polytetrafluoroethylene, polyphenylene sulfide or polyether sulfone, and further preferably is silica.
Illustratively, the silica may be crystalline silica, fused silica, or spherical silica, among others.
Preferably, the powder filler has a median particle diameter of 1 to 15 μm, such as 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm or 14 μm, and specific values therebetween, not to be limited by space and for the sake of brevity, the present invention is not exhaustive enumeration of the specific values included in the range, and more preferably 1 to 10 μm.
In another aspect, the present invention provides a method for preparing an interlayer bonding sheet for a multilayer sheet according to the first aspect, comprising the steps of:
(1) Treating the PTFE substrate by using plasma to obtain a PTFE substrate after surface plasma treatment;
(2) And (2) coating a dielectric resin layer on the PTFE substrate subjected to the surface plasma treatment obtained in the step (1), and curing to obtain the interlayer bonding sheet for the multilayer board.
Preferably, the atmosphere of the plasma treatment in the step (1) is selected from He, ne and O 2 、H 2 、N 2 、Ar、CO 2 、SO 2 、NH 3 、CH 4 Or water vapor, or a combination of at least two of them.
Preferably, the plasma treatment of step (1) is performed by a low-temperature plasma generation device.
Preferably, the voltage of the plasma treatment in step (1) is 500 to 10000V, such as 550V, 600V, 700V, 800V, 900V, 1000V, 1500V, 2000V, 3000V, 4000V, 5000V, 6000V, 7000V, 8000V, 9000V or 9500V, and specific point values therebetween, and the invention is not exhaustive for reasons of space and simplicity.
Preferably, the plasma treatment time of step (1) is 5 to 600s, such as 6s, 8s, 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 120s, 150s, 180s, 200s, 220s, 250s, 280s, 300s, 320s, 350s, 380s, 400s, 420s, 450s, 480s, 500s, 520s, 550s, 570s, or 590s, and specific point values between the above point values are limited in terms of breadth and for brevity, the present invention is not exhaustive with the specific point values included in the range.
Preferably, the system vacuum degree of the plasma treatment in step (1) is 133-1333 Pa, such as 135Pa, 140Pa, 150Pa, 170Pa, 190Pa, 200Pa, 230Pa, 250Pa, 280Pa, 300Pa, 350Pa, 400Pa, 500Pa, 600Pa, 700Pa, 800Pa, 900Pa, 1000Pa, 1100Pa, 1200Pa or 1300Pa, and specific point values therebetween are limited in space and for the sake of brevity, and the invention does not exhaust the specific point values included in the range.
Preferably, the rf power of the plasma treatment in step (1) is 1-5 kW, such as 1.2kW, 1.4kW, 1.6kW, 1.8kW, 2kW, 2.2kW, 2.5kW, 2.8kW, 3kW, 3.2kW, 3.5kW, 3.8kW, 4kW, 4.2kW, 4.5kW, 4.7kW, or 4.9kW, and the specific points therebetween are limited to space and for simplicity, and the invention is not exhaustive with the specific points included in the range.
Preferably, the coating method in the step (2) is roll coating.
Preferably, the curing temperature in step (2) is 160 to 250 ℃, for example 165 ℃, 170 ℃, 175 ℃,180 ℃, 185 ℃, 190 ℃, 195 ℃,200 ℃, 205 ℃,210 ℃, 215 ℃,220 ℃, 225 ℃,230 ℃, 235 ℃, 240 ℃ or 245 ℃, and more preferably 180 to 230 ℃.
Preferably, the curing time in step (2) is 1 to 4 hours, such as 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, 2.3 hours, 2.5 hours, 2.8 hours, 3 hours, 3.5 hours or 3.8 hours, and the like, and more preferably 1.5 to 3 hours.
Preferably, the preparation method specifically comprises the following steps:
(1) Placing the cleaned PTFE substrate in a low-temperature plasma generator to perform surface plasma treatment in a treatment atmosphere selected from He, ne and O 2 、H 2 、N 2 、Ar、CO 2 、SO 2 、NH 3 、CH 4 Or any one of water vapor or the combination of at least two of the water vapor, the processing voltage is 500-10000V, the vacuum degree of a processing system is 133-1333 Pa, the radio frequency power of the processing is 1-5 kW, and the processing time is 5-600 s, so that the PTFE substrate after surface plasma processing is obtained.
(2) And (2) coating a dielectric resin layer on the PTFE substrate subjected to the surface plasma treatment obtained in the step (1), and curing at 160-250 ℃ for 1-4 h to obtain the interlayer bonding sheet for the multilayer board.
In another aspect, the present invention provides a multilayer board comprising at least two PTFE double-sided circuit boards, and an interlayer bonding sheet for a multilayer board according to the first aspect interposed between the two PTFE double-sided circuit boards.
In another aspect, the present invention provides an electronic device including the multilayer board as described above.
Compared with the prior art, the invention has the following beneficial effects:
the interlayer bonding sheet for the multilayer board comprises a PTFE substrate with the surface subjected to plasma treatment and a dielectric resin layer bonded on the PTFE substrate, wherein the PTFE substrate and the dielectric resin layer have excellent dielectric properties, low dielectric constant and dielectric loss tangent and sufficient high-frequency characteristics, and can meet the electrical property requirements of the multilayer board; after the surface of the PTFE substrate is subjected to plasma treatment, the wettability is obviously improved, the PTFE substrate can be stably bonded with a dielectric resin layer with high strength, the heat resistance and the high-temperature reliability are high, and the manufacturing process requirements and the subsequent application requirements of a multilayer printed circuit board can be met; the dielectric resin layer has good fluidity and bonding property, and can ensure strong interlayer bonding force and high bonding stability between circuit boards. Therefore, the interlayer bonding sheet for the multilayer board provided by the invention has excellent dielectric property, fluidity and bonding strength through the synergistic matching of the PTFE substrate with the surface treated by the plasma body and the dielectric resin layer, the multilayer board containing the interlayer bonding sheet for the multilayer board has no delamination and foaming phenomenon at 288 ℃ in a high-temperature environment, the bonding stability is high, and the signal high-frequency requirement, the stability and the reliability requirement of the multilayer board can be fully met.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
The experimental materials used in the examples and comparative examples of the present invention were as follows:
(1) A PTFE substrate: soaking 1078 type electronic grade glass cloth in PTFE emulsion (average particle size of PTFE is 0.1-0.5 μm) at normal temperature, drying at 150 deg.C, and sintering at 360 deg.C for 30min to obtain; such materials are available from dupont, usa.
(2) Dielectric resin treatment liquid I: 30 parts by weight of ethylene propylene rubber (number average molecular weight 80000g/mol, lion chemical company, usa), 40 parts by weight of polybutadiene (molecular weight 3200g/mol, japan caokada corporation), 30 parts by weight of silica (median particle diameter 5 μm, new materials, inc. Of jun) and 2 parts by weight of benzoyl peroxide (shanghai kang bio-technology, inc.) were dissolved in 50 parts by weight of xylene, and mixed uniformly to obtain a dielectric resin treatment liquid I;
dielectric resin treatment liquid II:25 parts by weight of ethylene-propylene rubber (number average molecular weight 80000g/mol, lion chemical, USA), 35 parts by weight of butadiene-styrene copolymer (number average molecular weight 4500g/mol, saedoma, USA), 10 parts by weight of polyphenylene ether (weight average molecular weight 1700g/mol, SABIC), 30 parts by weight of silica (median particle diameter 10 μm, ningsu Birrio New materials Co., ltd.) and 2 parts by weight of benzoyl peroxide (Shanghai Kanglang Biotech Co., ltd.) were dissolved in 50 parts by weight of xylene and mixed uniformly to obtain dielectric resin treatment liquid II.
Dielectric resin treatment liquid III:25 parts by weight of a butadiene-styrene copolymer (number average molecular weight 8900g/mol, saedoma, USA), 15 parts by weight of polybutadiene (number average molecular weight 3200g/mol, nippon Caoda corporation), 30 parts by weight of polyphenylene ether (weight average molecular weight 1700g/mol, SABIC), 30 parts by weight of silica (median particle diameter 10 μm, jiangsu Binrei New Material Co., ltd.) and 2 parts by weight of benzoyl peroxide (Shanghai Kanglang Biotech Co., ltd.) were dissolved in 50 parts by weight of xylene and mixed uniformly to obtain a dielectric resin treatment liquid III.
(3) Low-temperature plasma generating device: model CD1200 plasma processor from europlas corporation, belgium.
(4) Self-made PTFE double-sided circuit board.
Example 1
This example provides an interlayer bonding sheet for a multilayer board, which is prepared by the following steps:
(1) Cleaning a PTFE substrate with the thickness of 0.5mm by using acetone, removing oil stains, and drying; then placing the plasma in a low-temperature plasma generating device, setting the voltage to be 3000V, the system vacuum degree to be 155Pa, the radio frequency power to be 1kW and the power to be N 2 、H 2 In a mixed atmosphere of (N) 2 、H 2 The volume ratio of (1) to (2) is 8), taking out after treatment for 600s, and obtaining the PTFE substrate after surface plasma treatment;
(2) Respectively rolling dielectric resin treatment liquid I on the upper surface and the lower surface of the PTFE substrate subjected to the surface plasma treatment obtained in the step (1) to obtain dielectric resin layers with the thickness of 25 mu m on the upper surface and the lower surface, and curing at 180 ℃ for 2.5h to obtain the interlayer bonding sheet for the multilayer board.
Example 2
This example provides an interlayer bonding sheet for a multilayer board, which is prepared by the following steps:
(1) Cleaning a PTFE substrate with the thickness of 0.9mm by using ethanol, removing oil stains, and drying; then placing the film in a low-temperature plasma generating device, setting the voltage to be 3000V, the system vacuum degree to be 560Pa, the radio frequency power to be 3kW, and the film is placed in Ar and H 2 In mixed atmosphere of (Ar, H) 2 The volume ratio of (1) is 9), treating for 240s, and taking out to obtain the PTFE substrate after surface plasma treatment;
(2) Respectively rolling dielectric resin treatment liquid I on the upper surface and the lower surface of the PTFE substrate subjected to the surface plasma treatment obtained in the step (1) to obtain dielectric resin layers with the thickness of 40 mu m on the upper surface and the lower surface, and curing at 210 ℃ for 2h to obtain the interlayer bonding sheet for the multilayer board.
Example 3
This example provides an interlayer bonding sheet for multilayer boards, which is prepared as follows:
(1) Cleaning a PTFE substrate with the thickness of 1.3mm by using ethanol, removing oil stains, and drying; then placing the substrate in a low-temperature plasma generating device, setting the voltage to be 6000V, the system vacuum degree to be 1224Pa and the radio frequency power to be 5kW, treating the substrate in Ar atmosphere for 60s, and taking out the substrate to obtain the PTFE substrate subjected to surface plasma treatment;
(2) Respectively rolling dielectric resin treatment liquid I on the upper surface and the lower surface of the PTFE substrate subjected to the surface plasma treatment obtained in the step (1) to obtain dielectric resin layers with the thicknesses of both the upper surface and the lower surface being 50 mu m, and curing at 200 ℃ for 3h to obtain the interlayer bonding sheet for the multilayer board.
Example 4
This example provides an interlayer bonding sheet for a multilayer board, which is prepared by the following steps:
(1) Cleaning a PTFE substrate with the thickness of 1.2mm by using acetone, removing oil stains, and drying; then placing the film in a low-temperature plasma generating device, setting the voltage to be 8000V, the system vacuum degree to be 1333Pa, the radio frequency power to be 1kW, the power to be in Ar and O 2 In mixed atmosphere of (Ar, O) 2 The volume ratio of (1) is 7;
(2) Respectively rolling dielectric resin treatment liquid I on the upper surface and the lower surface of the PTFE substrate subjected to the surface plasma treatment obtained in the step (1) to obtain dielectric resin layers with the thicknesses of both the upper surface and the lower surface being 30 mu m, and curing at 230 ℃ for 1.5h to obtain the interlayer bonding sheet for the multilayer board.
Example 5
This example provides an interlayer bonding sheet for a multilayer board, which is prepared by the following steps:
(1) Cleaning a PTFE substrate with the thickness of 0.8mm by using ethanol, removing oil stains, and drying; then placing the plasma in a low-temperature plasma generating device, setting the voltage to be 1000V, the vacuum degree of a system to be 280Pa, the radio frequency power to be 4kW and the power to be in CO 2 Treating for 500s in the atmosphere, and taking out to obtain the PTFE substrate after surface plasma treatment;
(2) Respectively rolling dielectric resin treatment liquid I on the upper surface and the lower surface of the PTFE substrate subjected to the surface plasma treatment obtained in the step (1) to obtain dielectric resin layers with the thicknesses of both the upper surface and the lower surface being 50 mu m, and curing at 200 ℃ for 3h to obtain the interlayer bonding sheet for the multilayer board.
Example 6
This example provides an interlayer bonding sheet for a multilayer board, which is prepared by the following steps:
(1) Cleaning a PTFE substrate with the thickness of 1.0mm by using acetone, removing oil stains, and drying; then placing the plasma in a low-temperature plasma generating device, setting the voltage to be 600V, the system vacuum degree to be 950Pa, the radio frequency power to be 2.5kW and the power to be in CH 4 Treating for 180s in the atmosphere, and taking out to obtain the PTFE substrate after surface plasma treatment;
(2) Respectively rolling dielectric resin treatment liquid II on the upper surface and the lower surface of the PTFE substrate subjected to the surface plasma treatment obtained in the step (1) to obtain dielectric resin layers with the thickness of 40 mu m on the upper surface and the lower surface, and curing at 210 ℃ for 3h to obtain the interlayer bonding sheet for the multilayer board.
Example 7
This example provides an interlayer bonding sheet for a multilayer board, which is prepared by the following steps:
(1) Cleaning a PTFE substrate with the thickness of 1.0mm by using acetone, removing oil stains, and drying; then placing it in a low-temperature plasma generatorSetting voltage at 800V, vacuum degree at 550Pa, RF power at 2kW, and power at NH 3 Treating for 300s in the atmosphere, and taking out to obtain the PTFE substrate after surface plasma treatment;
(2) Respectively rolling dielectric resin treatment liquid III on the upper surface and the lower surface of the PTFE substrate subjected to the surface plasma treatment obtained in the step (1) to obtain dielectric resin layers with the thicknesses of both the upper surface and the lower surface being 30 mu m, and curing at 220 ℃ for 2.5h to obtain the interlayer bonding sheet for the multilayer board.
Comparative example 1
The comparative example provides an interlayer bonding sheet for a multilayer board, the preparation method comprising:
(1) Cleaning a PTFE substrate with the thickness of 0.8mm by using ethanol, removing oil stains, and drying; then placing the PTFE substrate in a low-temperature plasma generating device, setting the voltage to be 800V, the system vacuum degree to be 155Pa, the radio frequency power to be 1kW, and taking out the PTFE substrate after treatment in Ar atmosphere for 20s to obtain the PTFE substrate after surface plasma treatment;
(2) Respectively rolling dielectric resin treatment liquid I on the upper surface and the lower surface of the PTFE substrate subjected to the surface plasma treatment obtained in the step (1) to obtain dielectric resin layers with the thicknesses of both the upper surface and the lower surface being 50 mu m, and curing at 220 ℃ for 3h to obtain the interlayer bonding sheet for the multilayer board.
Comparative example 2
The comparative example provides an interlayer bonding sheet for a multilayer board, the preparation method comprising:
(1) Cleaning a PTFE substrate with the thickness of 0.8mm by using ethanol, removing oil stains, and drying; then placing the substrate in a low-temperature plasma generating device, setting the voltage to be 10000V, the system vacuum degree to be 1224Pa and the radio frequency power to be 5kW, processing the substrate for 900s in Ar atmosphere, and taking out the substrate to obtain the PTFE substrate processed by surface plasma;
(2) Respectively rolling dielectric resin treatment liquid I on the upper surface and the lower surface of the PTFE substrate subjected to the surface plasma treatment obtained in the step (1) to obtain dielectric resin layers with the thicknesses of both the upper surface and the lower surface being 50 mu m, and curing at 220 ℃ for 3h to obtain the interlayer bonding sheet for the multilayer board.
Comparative example 3
The comparative example provides an interlayer bonding sheet for a multilayer board, the preparation method comprising:
(1) Cleaning a PTFE substrate with the thickness of 0.8mm by using ethanol, removing oil stains, and drying;
(2) Respectively rolling a dielectric resin treatment solution I on the upper surface and the lower surface of the PTFE substrate obtained in the step (1) to obtain dielectric resin layers with the thicknesses of the upper surface and the lower surface being 30 mu m, and curing at 210 ℃ for 2h to obtain the interlayer bonding sheet for the multilayer board.
Application example
A multilayer board is prepared by the following steps:
the interlayer adhesive sheets for the multilayer boards provided in examples 1 to 7 and comparative examples 1 to 3 were placed between two pieces of PTFE double-sided circuit boards with circuit patterns, respectively, pressed at 190 ℃ for 90 minutes in a press, and then cooled and taken out to obtain the multilayer boards.
And (4) performance testing:
(1) Surface treatment depth of PTFE substrate: and manufacturing a section by using a Hitachi S-3400N type scanning electron microscope to observe the surface treatment depth of the substrate subjected to plasma treatment.
(2) Contact angle: the static contact angle of deionized water on the surface of the plasma treated PTFE substrate was measured using a DSA20 contact angle tester, KRUSS, germany.
(3) Adhesive property: the multilayer board provided in the application example is placed in a soldering tin furnace at 288 ℃ to be soaked for 5 minutes, and is taken out to be sliced and observed, if obvious layering and foaming phenomena occur, the adhesion and the adhesion stability are poor; if no delamination and foaming occurred, the adhesion and adhesion stability were good.
The interlayer adhesive sheets for multilayer sheets provided in examples 1 to 7 and comparative examples 1 to 3 were tested for their adhesive properties, and for the surface treatment depth and contact angle of the PTFE substrate according to the methods described above, and the specific data are shown in table 1:
TABLE 1
Surface treatment depth/nm Contact Angle/° Adhesive property
Example 1 13 94 Without delamination of the foam
Example 2 11 84 Without delamination of the foam
Example 3 7 92 Without delamination of the foam
Example 4 5 96 Without delamination of the foam
Example 5 15 85 Without delamination of the foam
Example 6 10 89 Without delamination of the foam
Example 7 12 87 Without delamination of the foam
Comparative example 1 3 97 Distinct layered blistering
Comparative example 2 21 101 Distinct layered blistering
Comparative example 3 0 122 Apparent delamination of bubbles
As can be seen from the data in table 1, in the interlayer adhesive sheets for multilayer boards provided in examples 1 to 7 of the present invention, the PTFE substrate was subjected to plasma treatment, and the surface treatment depth was in the range of 5 to 15nm defined in the present invention, and the contact angle was in the range of 84 to 98 ° defined in the present invention, and the interlayer adhesive sheets were excellent in adhesive properties, high in adhesive stability, and free from delamination and foaming during high-temperature treatment at 288 ℃. If the surface depth of the PTFE substrate subjected to plasma treatment is too low (comparative example 1), too high (comparative example 2), or not subjected to plasma treatment (comparative example 3), the adhesion properties of the interlayer adhesive sheet for a multilayer board are affected, the adhesion stability under high temperature treatment is low, and delamination and foaming phenomena are evident in the adhesive structure.
The applicant states that the present invention is illustrated by the above examples of the interlayer bonding sheet for multilayer boards of the present invention and the preparation method and application thereof, but the present invention is not limited to the above process steps, that is, it is not meant that the present invention must be implemented depending on the above process steps. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (34)

1. An interlayer bonding sheet for a multilayer board, comprising a PTFE substrate, and a dielectric resin layer bonded to the surface of the PTFE substrate;
the PTFE substrate is a PTFE substrate with the surface treated by plasma, and the surface treatment depth of the PTFE substrate is 5-15 nm; the contact angle of the PTFE substrate is 84-98 degrees;
the preparation raw materials of the dielectric resin layer comprise the following components in parts by weight: 20-70 parts of polymer matrix material, 10-70 parts of powder filler and 1-3 parts of initiator; the polymer matrix material is selected from any one or combination of at least two of polybutadiene, polyisoprene, butadiene-styrene copolymer, polyphenyl ether or ethylene propylene rubber.
2. The interlayer bonding sheet for a multilayer sheet according to claim 1, comprising a PTFE substrate, and dielectric resin layers bonded to the upper and lower surfaces of the PTFE substrate.
3. The interlayer bonding sheet for a multilayer sheet according to claim 1, wherein the thickness of the PTFE substrate is 0.3 to 1.5mm.
4. The interlayer bonding sheet for a multilayer board according to claim 1, wherein the PTFE substrate is a glass cloth having a PTFE layer on the surface.
5. The interlayer bonding sheet for a multilayer board according to claim 4, wherein the glass cloth is an electronic grade glass cloth or a once-desized glass cloth.
6. The interlayer bonding sheet for a multilayer board according to claim 4, wherein the PTFE substrate is obtained by dipping a glass cloth in a PTFE emulsion, drying, and sintering.
7. The interlayer bonding sheet for a multilayer sheet according to claim 6, wherein the PTFE emulsion is a PTFE emulsion containing a powder filler.
8. The interlayer bonding sheet for a multilayer sheet according to claim 7, wherein the powder filler is selected from any one or a combination of at least two of silica, titanium dioxide, strontium titanate, barium titanate, boron nitride, aluminum nitride, silicon carbide, alumina, glass fiber, polytetrafluoroethylene, polyphenylene sulfide, or polyether sulfone.
9. The interlayer bonding sheet for a multilayer board according to claim 7, wherein the powder filler is silica.
10. The interlayer bonding sheet for multilayer boards according to claim 7, wherein the powder filler has a median particle diameter of 1 to 15 μm.
11. The interlayer bonding sheet for multilayer boards according to claim 7, wherein the powder filler has a median particle diameter of 1 to 10 μm.
12. The interlayer bonding sheet for a multilayer board according to claim 1, wherein the thickness of the dielectric resin layer is 5 to 60 μm.
13. The interlayer bonding sheet for a multilayer board according to claim 1, wherein the thickness of the dielectric resin layer is 20 to 50 μm.
14. The interlayer bonding sheet for multilayer sheets according to claim 1, wherein the initiator is an organic peroxide initiator.
15. The interlayer bonding sheet for a multilayer sheet according to claim 1, wherein the powder filler is selected from any one or a combination of at least two of silica, titanium dioxide, strontium titanate, barium titanate, boron nitride, aluminum nitride, silicon carbide, alumina, glass fiber, polytetrafluoroethylene, polyphenylene sulfide, or polyether sulfone.
16. The interlayer bonding sheet for a multilayer board according to claim 1, wherein the powder filler is silica.
17. The interlayer bonding sheet for multilayer boards according to claim 1, wherein the powder filler has a median particle diameter of 1 to 15 μm.
18. The interlayer bonding sheet for multilayer boards according to claim 1, wherein the powder filler has a median particle diameter of 1 to 10 μm.
19. A method for preparing an interlayer bonding sheet for a multilayer board according to any one of claims 1 to 18, comprising the steps of:
(1) Treating the PTFE substrate by using plasma to obtain the PTFE substrate after surface plasma treatment;
(2) And (2) coating a dielectric resin layer on the PTFE substrate subjected to the surface plasma treatment obtained in the step (1), and curing to obtain the interlayer bonding sheet for the multilayer board.
20. The method according to claim 19, wherein an atmosphere of the plasma treatment in the step (1) is selected from He, ne, O 2 、H 2 、N 2 、Ar、CO 2 、SO 2 、NH 3 、CH 4 Or in water vapourEither one or a combination of at least two.
21. The production method according to claim 19, wherein the plasma treatment of step (1) is performed by a low-temperature plasma generation apparatus.
22. The method according to claim 19, wherein the voltage of the plasma treatment in the step (1) is 500 to 10000V.
23. The method according to claim 19, wherein the plasma treatment in the step (1) is performed for a time of 5 to 600 seconds.
24. The method according to claim 19, wherein the plasma treatment time in the step (1) is 50 to 600 seconds.
25. The production method according to claim 19, wherein the system vacuum degree of the plasma treatment in the step (1) is 133 to 1333Pa.
26. The method according to claim 19, wherein the rf power of the plasma treatment in step (1) is 1 to 5kW.
27. The method of claim 19, wherein the step (2) of coating is roll coating.
28. The method according to claim 19, wherein the curing temperature in the step (2) is 160 to 250 ℃.
29. The method according to claim 19, wherein the curing temperature in the step (2) is 180 to 230 ℃.
30. The method according to claim 19, wherein the curing time in step (2) is 1 to 4 hours.
31. The method according to claim 19, wherein the curing time in step (2) is 1.5 to 3 hours.
32. The method according to claim 19, comprising the steps of:
(1) Placing the cleaned PTFE substrate in a low-temperature plasma generator to perform surface plasma treatment in a treatment atmosphere selected from He, ne and O 2 、H 2 、N 2 、Ar、CO 2 、SO 2 、NH 3 、CH 4 Or any one or the combination of at least two of water vapor, the processing voltage is 500-10000V, the vacuum degree of a processing system is 133-1333 Pa, the radio frequency power of the processing is 1-5 kW, and the processing time is 5-600 s, so that the PTFE substrate after surface plasma processing is obtained;
(2) And (2) coating a dielectric resin layer on the PTFE substrate subjected to the surface plasma treatment obtained in the step (1), and curing at 160-250 ℃ for 1-4 h to obtain the interlayer bonding sheet for the multilayer board.
33. A multilayer board comprising at least two PTFE double-sided circuit boards, and the interlayer bonding sheet for multilayer boards according to any one of claims 1 to 18 interposed between the two PTFE double-sided circuit boards.
34. An electronic device, characterized in that it comprises the multilayer board according to claim 33.
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