CN116353167A - Metal foil-clad laminated board and application thereof - Google Patents

Metal foil-clad laminated board and application thereof Download PDF

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Publication number
CN116353167A
CN116353167A CN202111621419.5A CN202111621419A CN116353167A CN 116353167 A CN116353167 A CN 116353167A CN 202111621419 A CN202111621419 A CN 202111621419A CN 116353167 A CN116353167 A CN 116353167A
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metal foil
parts
resin
coupling agent
silane coupling
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Chinese (zh)
Inventor
陈宇航
曾宪平
陈广兵
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Priority to CN202111621419.5A priority Critical patent/CN116353167A/en
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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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • 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
    • C08J2415/00—Characterised by the use of rubber derivatives
    • 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
    • C08J2425/00—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 an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
    • C08J2425/10—Copolymers of styrene with conjugated dienes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (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 a metal foil-clad laminate and application thereof, wherein the metal foil-clad laminate comprises at least one prepreg and a metal foil arranged on at least one side of the prepreg; the prepreg includes a reinforcing material and a resin composition attached to the reinforcing material; the resin composition includes a matrix resin and maleic anhydride-modified polybutadiene; and a silane coupling agent layer is arranged on one side of the metal foil, which is contacted with the prepreg, and the silane coupling agent comprises an amino-containing silane coupling agent and/or an epoxy-containing silane coupling agent. The invention solves the problem of poor binding force between the polyphenyl ether resin system and the metal foil, and remarkably improves the binding strength between the resin composition and the metal foil, and the metal foil-clad laminated plate has excellent heat resistance, dielectric property and reliability, has good fluidity and processability, and fully meets the requirements of high-frequency high-speed electronic circuit base materials on the comprehensive properties such as low dielectric loss, high copper foil heat resistance, high peeling strength and the like.

Description

Metal foil-clad laminated board and application thereof
Technical Field
The invention belongs to the technical field of copper-clad plates, and particularly relates to a metal foil-clad laminated plate and application thereof.
Background
In recent years, with the development of high performance, high functionality, and networking of computers and information communication apparatuses, operation signals tend to be high-frequency in order to transmit and process large-capacity information at high speed, and thus, there is a demand for materials for circuit boards, particularly in electronic apparatuses (such as mobile communication devices) using broadband.
Among the existing materials for printed circuit boards, epoxy resins are most widely used, and have good adhesion performance, processability and cost advantages. However, epoxy resin circuit boards have poor dielectric properties, generally have high dielectric constants and dielectric loss tangents (dielectric constants of more than 4 and dielectric loss tangents of about 0.02), and have insufficient high-frequency characteristics, and cannot meet the requirements for increasing the frequency of signals. Therefore, development of a resin excellent in dielectric characteristics, that is, a resin having a low dielectric constant and low dielectric loss tangent is a hot spot problem in recent years.
The research shows that the polyphenyl ether resin has lower dielectric constant and low dielectric loss, and is a high-frequency material with good dielectric property. For example, CN103467967a discloses a thermosetting resin composition comprising a polyphenylene ether resin containing an unsaturated double bond, an epoxy resin, a curing agent and an initiator, and may further comprise a compound containing both an epoxy group and an ethylenic bond, a flame retardant, an accelerator, and the like. The thermosetting resin composition has low dielectric constant and dielectric loss, but the polyphenyl ether resin has poor fluidity and processing performance, and the molecular structure of the polyphenyl ether resin has symmetry, low polarity and poor binding force with copper foil. In addition, since the polyphenyl ether is applied to the high-speed field and needs to be a multi-layer board, the polyphenyl ether has high requirements on heat resistance, and if the binding force with the copper foil is poor and the heat resistance is insufficient, the problem of layered board explosion easily occurs, so that the performance reliability has a great hidden trouble.
Polyolefin resin (hydrocarbon resin) has good dielectric property and good fluidity, and attracts intensive researches of vast technicians. For example, CN108659504a discloses a hydrocarbon polymer composition, and a prepreg and a thermosetting copper-clad plate prepared from the same, where the composition is composed of six components including a matrix resin, a compatilizer, a modified resin, a filler, a flame retardant and an initiator, and the matrix resin is a composite mixture of one or more of vinyl modified polyphenylene oxides and one or more of polydienes; the composite material has good dielectric property, but has poor heat resistance, and is easy to generate layering explosion plate at high temperature. CN111393724a discloses a resin composition comprising an unsaturated polyphenylene ether resin, a polyolefin resin, a rosin resin, and an initiator, and a prepreg and a circuit material using the same. The resin composition has good adhesion and dielectric properties, but the resin composition has low glass transition temperature, unsatisfactory heat resistance and low bonding strength with copper foil.
Therefore, development of a metal-clad sheet having excellent dielectric properties, heat resistance and strong bonding force with a metal foil is a problem to be solved in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a metal foil-clad laminated board and application thereof, which obviously improves the binding force between the resin composition and a metal foil through the component design of the resin composition and the compounding action of the resin composition and the metal foil containing a silane coupling agent layer, and ensures that the metal foil-clad laminated board has excellent dielectric property and heat resistance, thereby effectively solving the reliability problem of the high-frequency high-speed multilayer metal foil-clad laminated board.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a metal foil-clad laminate comprising at least one prepreg and a metal foil disposed on at least one side of the prepreg; the prepreg includes a reinforcing material and a resin composition attached to the reinforcing material.
The resin composition includes a matrix resin and maleic anhydride-modified polybutadiene, the matrix resin including a polyphenylene ether resin; the mass of the maleic anhydride modified polybutadiene is 0.5-3 parts based on 100 parts of the mass of the matrix resin; and a silane coupling agent layer is arranged on one side of the metal foil, which is contacted with the prepreg, and the silane coupling agent comprises an amino-containing silane coupling agent and/or an epoxy-containing silane coupling agent.
The metal foil-clad laminated board provided by the invention comprises a combination of matrix resin and maleic anhydride modified polybutadiene, wherein the side of the metal foil, which is contacted with prepreg (resin composition), is provided with a silane coupling agent layer containing amino groups and/or epoxy groups, and the silane coupling agent layer and the resin composition are mutually cooperated, so that the problem of poor binding force between a polyphenyl ether resin system and the metal foil is solved pertinently, the binding strength between the resin composition and the metal foil is obviously improved, and the metal foil-clad laminated board has high glass transition temperature (T) g ) The high-frequency high-speed electronic circuit substrate has the advantages of excellent heat resistance, dielectric property, low thermal expansion rate, improved reliability, good fluidity and processability, and fully meets the requirements of the high-frequency high-speed electronic circuit substrate on the comprehensive performances such as low dielectric loss, high copper foil heat resistance, high peel strength and the like.
In the resin composition, the mass of the maleic anhydride-modified polybutadiene is 0.5 to 3 parts, for example, 0.6 part, 0.8 part, 1 part, 1.2 part, 1.5 part, 1.8 part, 2 parts, 2.2 parts, 2.5 parts or 2.8 parts, and specific point values between the above point values are not limited to a spread and are not exhaustive for the sake of brevity, based on 100 parts by mass of the matrix resin (the matrix resin of the present invention means that the resin component added in an amount exceeding 5 parts by mass of the total matrix resin is calculated as the matrix resin, and the mass of the maleic anhydride-modified polybutadiene is only 0.5 to 3 parts by mass, not calculated as the matrix resin). The addition of the maleic anhydride modified polybutadiene with a specific dosage can improve the binding force between the resin composition and the metal foil, reduce the thermal expansion rate of the plate and improve the reliability; if the amount of the maleic anhydride-modified polybutadiene is too low, the bonding force between the resin composition and the metal foil cannot be effectively improved, and the thermal expansion rate of the sheet is large; if the amount of the maleic anhydride-modified polybutadiene added is too large, the dielectric properties and rheological properties of the resin composition are affected.
And a silane coupling agent layer is arranged on one side of the metal foil, which is contacted with the prepreg, and the silane coupling agent comprises an amino-containing silane coupling agent and/or an epoxy-containing silane coupling agent. The silane coupling agent may be contained in an amount of 0.01 to 2wt% of the metal foil, for example, 0.03wt%, 0.05wt%, 0.08wt%, 0.1wt%, 0.3wt%, 0.5wt%, 0.8wt%, 1wt%, 1.2wt%, 1.5wt% or 1.8wt%, and specific point values between the above point values are limited in length and for the sake of brevity, the present invention is not exhaustive list of specific point values included in the range. According to the invention, the amino silane coupling agent and/or the epoxy silane coupling agent is adopted to treat the metal foil, and the amino silane coupling agent and/or the epoxy silane coupling agent are added into the matrix resin, so that the binding force between the resin composition and the metal foil can be synergistically improved, and the binding force between the resin composition and the metal foil, which is superior to the binding force between other coupling agents such as the methacryloxy silane coupling agent and the like and the resin composition used in combination with the maleic anhydride modified polybutadiene, is achieved. When the content of the silane coupling agent on the surface of the metal foil is too low, the peeling strength PS is low; when the content of the silane coupling agent on the surface of the metal foil is too high, the dispersing effect of the coupling agent is poor, and PS is also caused to be low.
The metal foil-clad laminate provided by the invention comprises at least one prepreg; illustratively, the number of sheets of the prepreg is 1 to 20, and may be, for example, 1,2, 3,5,7, 9, 10, 11, 13, 15, 17, 19, or the like.
When the metal foil-clad laminated board comprises a piece of prepreg, the metal foil is arranged on one side or two sides of the prepreg; when the metal foil-clad laminated plate comprises at least two prepregs, all the prepregs are overlapped to form a laminated plate, and the metal foil is arranged on one side or two sides of the laminated plate.
Preferably, the polyphenylene ether resin is an unsaturated group-containing polyphenylene ether resin, and further preferably an unsaturated group-containing polyphenylene ether resin at the end.
Preferably, the polyphenylene ether resin has a number average molecular weight of 500 to 10000g/mol, and may be, for example, 600g/mol, 800g/mol, 1000g/mol, 2000g/mol, 3000g/mol, 4000g/mol, 5000g/mol, 6000g/mol, 7000g/mol, 8000g/mol or 9000g/mol, and specific point values between the above point values, and the present invention is not exhaustive of the specific point values included in the range for reasons of brevity and conciseness. The molecular weight (number average molecular weight, weight average molecular weight) of the present invention was measured by gel permeation chromatography based on polystyrene calibration as GB/T21863-2008.
Preferably, the polyphenylene ether resin has a structure as shown in formula I:
Figure BDA0003438164540000051
in the formula I, Z is
Figure BDA0003438164540000052
A is selected from any one of carbonyl, C6-C30 (such as C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28) arylene, C1-C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight chain or branched alkylene;
R 5 、R 6 、R 7 each independently selected from any of hydrogen, C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) straight or branched alkyl;
n, m are each independently selected from integers from 0 to 10, for example may be 0,1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; when n is 0, representing that the benzene ring is connected with the main chain of the formula I through a single bond; when m is 0, it represents alkenyl linked to the backbone of formula I by a single bond.
In the formula I, X is
Figure BDA0003438164540000053
R 1 、R 2 、R 3 、R 4 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 Each independently ofThe site is selected from any one of hydrogen, halogen, phenyl, C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) straight or branched alkyl.
Y is selected from a single bond, a C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight or branched alkylene group,
Figure BDA0003438164540000061
Any one of the following.
In formula I, a and b represent the number of repeating units and are each independently selected from integers ranging from 1 to 30, and may be, for example, 2,5, 8, 10, 12, 15, 18, 20, 22, 25 or 28, and specific point values between the above point values, although the invention is not limited in scope and for brevity, exhaustive list of specific point values included in the range is not intended.
The dotted line represents the attachment site of the group.
Preferably, said Z is selected from
Figure BDA0003438164540000062
Any one of them; the dotted line represents the attachment site of the group.
Preferably, said R 5 Is hydrogen or methyl.
As a preferable embodiment of the present invention, Z is any one selected from vinylbenzyl, vinylphenyl, acrylate or methacrylate groups.
As a preferable technical scheme of the invention, the polyphenyl ether resin is polyphenyl ether resin with unsaturated groups at the tail end; the unsaturated group is selected from any one of vinylbenzyl, vinylphenyl, acrylate or methacrylate.
Preferably, the matrix resin further comprises a polyolefin resin.
Preferably, the polyolefin resin includes any one or a combination of at least two of a styrene-butadiene copolymer, a styrene-isoprene copolymer, a hydrogenated styrene-butadiene copolymer, a hydrogenated styrene-isoprene copolymer, a styrene-butadiene-styrene block copolymer, a hydrogenated styrene-butadiene-styrene block copolymer, or polybutadiene.
The polyolefin resin may be unmodified or modified with a group such as an acryl group or maleic anhydride, for example, a maleic anhydride-modified hydrogenated styrene-butadiene-styrene block copolymer, a maleic anhydride-modified polybutadiene, or the like.
Preferably, the matrix resin includes 40 to 80 parts of polyphenylene ether resin and 20 to 60 parts of polyolefin resin based on 100 parts by mass of the matrix resin.
Preferably, the polyphenylene ether resin in the matrix resin is 40-80 parts, for example, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts or 78 parts, and specific point values among the above point values are limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the polyolefin resin in the matrix resin is 20-60 parts, for example, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts or 58 parts, and specific point values between the above point values are limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range.
As a preferred technical scheme of the invention, the matrix resin comprises a combination of polyphenyl ether resin and polyolefin resin, and the polyphenyl ether resin and the polyolefin resin are compounded, so that the system compatibility, dielectric property, rheological property and processability of the resin composition are improved, and the bonding strength of the resin composition and the metal foil is further improved. If the amount of polyolefin resin used is small, fluidity and processability of the resin composition are affected; if the amount of the polyolefin resin is too high, the bonding force of the resin composition to the metal foil is reduced, and the formation of a prepreg having a uniform thickness is also disadvantageous.
Preferably, the number average molecular weight of the maleic anhydride-modified polybutadiene is 2000-10000g/mol, for example 3000g/mol, 4000g/mol, 5000g/mol, 6000g/mol, 7000g/mol, 8000g/mol or 9000g/mol, and specific point values between the above point values, are limited in length and for the sake of brevity the invention is not exhaustive list of the specific point values comprised in the range.
Preferably, the maleic anhydride-modified polybutadiene has a mass percent of maleic anhydride structural units of 3-15%, for example, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13% or 14%, and specific point values between the above point values, although the invention is not limited in this regard and for brevity, the invention is not intended to be exhaustive of the specific point values included in the ranges.
In the present invention, the maleic anhydride-modified polybutadiene is commercially available, and may be, for example, ricon 131MA10 and/or Ricon 131MA20 of Cray Valley company.
Preferably, the resin composition further comprises a free radical initiator.
Preferably, the mass of the radical initiator is 0.01 to 5 parts, for example, 0.05 parts, 0.1 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts, based on 100 parts of the mass of the matrix resin, and specific point values between the above point values are limited in terms of length and brevity, and the present invention is not exhaustive to list the specific point values included in the range.
Preferably, the half-life temperature of the free radical initiator is not less than 130 ℃, for example, 132 ℃, 135 ℃, 138 ℃, 140 ℃, 142 ℃, 145 ℃ or the like.
Preferably, the radical initiator includes any one or a combination of at least two of an organic peroxide, an azo compound or a carbon-based radical initiator, and further preferably an organic peroxide.
Preferably, the organic peroxide comprises any one or a combination of at least two of dicumyl peroxide, tert-butyl peroxybenzoate, 2, 5-bis (2-ethylhexanoylperoxy) -2, 5-dimethylhexane, di (tert-butylperoxyisopropyl) benzene, 2, 4-dichlorobenzoyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, tert-butyl peroxy-2-ethylhexyl carbonate, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) -3-hexyne, butyl 4, 4-bis (tert-butylperoxy) valerate, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane, 3,5, 7-pentamethyl-1, 2, 4-trioxepane, di-tert-butyl peroxide or tert-butylcumyl peroxide.
Preferably, the resin composition further comprises a filler.
Preferably, the filler is 20 to 100 parts by mass based on 100 parts by mass of the matrix resin, and for example, the filler may be 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts or 95 parts, and specific point values between the above point values are limited in length and for brevity, the present invention does not exhaustively list specific point values included in the range.
Preferably, the filler comprises an inorganic filler and/or an organic filler.
Preferably, the inorganic filler comprises any one or a combination of at least two of crystalline silica, fused silica, spherical silica, angular silica, chemical silica, hollow silica, silica fume, glass frit, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, barium sulfate, talc, calcium silicate, calcium carbonate, or mica.
Preferably, the organic filler includes any one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide powder, polyetherimide powder, polyphenylene oxide powder, or polyethersulfone powder.
Preferably, the resin composition further comprises a flame retardant.
Preferably, the mass of the flame retardant is 0.1 to 25 parts, for example, 0.5 parts, 1 part, 3 parts, 5 parts, 7 parts, 9 parts, 10 parts, 11 parts, 13 parts, 15 parts, 17 parts, 19 parts, 20 parts, 22 parts or 24 parts, and specific point values between the above point values, based on 100 parts by mass of the matrix resin, are not exhaustive for the sake of brevity and conciseness.
Preferably, the flame retardant includes any one or a combination of at least two of a halogen flame retardant, a phosphorus flame retardant, or a nitrogen flame retardant.
As a preferred embodiment of the present invention, the resin composition comprises the following components in parts by weight: 100 parts of matrix resin, 0.5-3 parts of maleic anhydride modified polybutadiene and 0.01-5 parts of free radical initiator; the matrix resin comprises 40-80 parts of polyphenyl ether resin and 20-60 parts of polyolefin resin.
As another preferred embodiment of the present invention, the resin composition comprises the following components in parts by weight: 100 parts of matrix resin, 0.5-3 parts of maleic anhydride modified polybutadiene, 0.01-5 parts of free radical initiator, 20-200 parts of filler and 0.1-20 parts of flame retardant; the matrix resin comprises 40-80 parts of polyphenyl ether resin and 20-60 parts of polyolefin resin.
In view of the preparation and processing requirements, the resin composition further includes a solvent, and the amount of the solvent is not limited as long as the viscosity of the dope of the resin composition satisfies the processing requirements.
The type of the solvent is not particularly limited, and includes any one or a combination of at least two of an alcohol solvent, an ether solvent, an aromatic hydrocarbon solvent, an ester solvent, a ketone solvent, or a nitrogen-containing solvent; exemplary include, but are not limited to: methanol, ethanol, butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol, butyl carbitol, acetone, butanone, methyl ethyl ketone, cyclohexanone, toluene, xylene, ethyl acetate, ethoxyethyl acetate, N-dimethylformamide or N, N-dimethylacetamide; the above solvents may be used alone or in combination of two or more.
Preferably, the solvent comprises any one or a combination of at least two of acetone, butanone, methyl ethyl ketone, cyclohexanone, toluene or xylene.
Preferably, the reinforcing material includes any one of an organic fiber cloth, an inorganic fiber woven cloth or a non-woven cloth.
Preferably, the reinforcing material comprises any one of glass fiber cloth, quartz glass blended cloth, glass fiber paper, non-woven cloth or organic fiber cloth; exemplary include, but are not limited to: e-glass fiber cloth, D-glass fiber cloth, S-glass fiber cloth, T-glass fiber cloth, NE-glass fiber cloth or quartz cloth.
Preferably, the organic fiber cloth comprises an aramid cloth.
Preferably, the thickness of the reinforcing material is between 0.01 and 0.2mm, which may be, for example, 0.03mm, 0.05mm, 0.08mm, 0.1mm, 0.11mm, 0.13mm, 0.15mm, 0.17mm or 0.19mm, and the specific point values between the above point values, are limited in length and for brevity, the invention is not intended to be exhaustive of the specific point values comprised in the range.
Preferably, the reinforcing material is subjected to a fiber opening treatment and/or a silane coupling agent treatment.
Preferably, the silane coupling agent includes any one or a combination of at least two of an epoxy silane coupling agent, an amino silane coupling agent, or a vinyl silane coupling agent.
Preferably, the preparation method of the silane coupling agent layer on the metal foil comprises the following steps: and uniformly coating the aqueous solution of the silane coupling agent on the metal foil, and drying to obtain the silane coupling agent layer.
Preferably, the metal foil includes any one of copper foil, nickel foil, aluminum foil, or SUS foil, and further preferably copper foil.
In the invention, the side of the metal foil, which is contacted with the prepreg, is provided with the silane coupling agent layer, and the side of the metal foil, which is far away from the prepreg, is not particularly limited, and may or may not be provided with the silane coupling agent layer.
In the invention, the copper foil comprises any one of common copper foil, roughness copper foil or low-profile copper foil, and HVLP copper foil is preferred in the high-speed field; the thickness of the copper foil is not particularly limited.
The method for preparing the metal foil-clad laminated board provided by the invention comprises the following steps of: pressing metal foil on one side or two sides of a piece of prepreg, and curing to obtain the metal foil-clad laminated board; or, laminating at least two prepregs on a laminated board, laminating metal foils on one side or two sides of the laminated board, and curing to obtain the metal foil-clad laminated board; the side of the metal foil, which is contacted with the prepreg, is provided with a silane coupling agent layer.
Preferably, the temperature of the curing is 200-250 ℃, for example 205 ℃, 210 ℃, 212 ℃, 215 ℃, 218 ℃, 220 ℃, 223 ℃, 225 ℃, 228 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, etc., more preferably 210-230 ℃.
Preferably, the curing pressure is 10-60kg/cm 2 For example 15kg/cm 2 、20kg/cm 2 、25kg/cm 2 、30kg/cm 2 、35kg/cm 2 、40kg/cm 2 、45kg/cm 2 、50kg/cm 2 Or 55kg/cm 2 Etc.
Preferably, the curing time is 30-180min, such as 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min or 175min, etc.
Preferably, the prepreg is prepared by a process comprising: and impregnating the reinforcing material with the resin glue solution of the resin composition, and then drying to obtain the prepreg.
Preferably, the drying temperature is 100-180deg.C, such as 105deg.C, 110deg.C, 115 deg.C, 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C, 145 deg.C, 150 deg.C, 155 deg.C, 160 deg.C, 165 deg.C, 170 deg.C, 175 deg.C, etc.
Preferably, the drying time is 1-10min, such as 2min, 3min, 4min, 5min, 6min, 7min, 8min or 9min, etc.
In a second aspect, the present invention provides a printed wiring board comprising at least one metal foil-clad laminate according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
the metal-clad laminate provided by the invention solves the problem of poor binding force between a polyphenyl ether resin system and a metal foil by designing the components of the resin composition and compounding the resin composition with the metal foil containing a silane coupling agent layer, obviously improves the binding strength between the resin composition and the metal foil, has the A-state peeling strength of more than 0.70N/mm and the peeling strength of more than 0.65N/mm after heat stress treatment in the metal-clad laminate of HOZ copper foil, and has the advantages that the adhesive strength of the metal-clad laminate is improved, and the adhesive strength of the metal-clad laminate is improvedThe foil laminate has a high glass transition temperature, T g The high-frequency high-speed electronic circuit substrate has excellent heat resistance, dielectric property and reliability at the temperature of more than 190 ℃, has good fluidity and processability, and fully meets the requirements of the high-frequency high-speed electronic circuit substrate on the comprehensive properties such as low dielectric loss, high copper foil heat resistance, high peeling strength and the like.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The following examples and comparative examples of the present invention were designed to include:
(1) Polyphenylene ether resin
SA9000, thermosetting polyphenylene ether having a methacrylate group at the end, sabic company;
OPE-2ST, thermosetting polyphenylene ether with vinyl benzyl at the end, mitsubishi chemical;
(2) Polyolefin resin
Ricon 100, styrene-butadiene copolymer, cray Valley company;
d1118, styrene-butadiene-styrene copolymer, kraton;
(3) Maleic anhydride modified polybutadiene
Ricon 131MA10,Cray Valley company;
ricon 131MA20,Cray Valley company;
b3000, polybutadiene (unmodified, as a comparison), japan soida;
(4) Free radical initiator
DCP, dicumyl peroxide, shanghai Gao Qiao;
(5) Silane coupling agent
KBM-403, epoxy silane coupling agent, believed to be more chemical;
KBM-602, aminosilane coupling agent, believed to be more chemical;
KBM-503, methacryloxy silane coupling agent, believed to be more chemical;
(6) Packing material
SC6500-SVC, molten silicon micropowder with average particle diameter of 2.5 μm, ademeatacs company;
(7) Flame retardant
DE-295, phosphorus flame retardants, jiangsu Jack;
(8) Reinforcing material
Glass fiber cloth 2116, taiwan glass;
(9) Metal foil
BFNN, HOZ copper foil, luxembourg (RZ. Ltoreq.1.5 μm);
BFNN,1OZ copper foil, luxembourg (RZ. Ltoreq.1.5 μm).
Example 1
A metal foil-clad laminate comprising 6 prepregs and copper foils disposed on both sides of the laminate; the prepreg includes a reinforcing material (glass fiber cloth, 2116) and a resin composition attached to the reinforcing material.
The resin composition comprises the following components in parts by weight: 60 parts of polyphenyl ether resin SA9000, 40 parts of polyolefin resin Ricon 100,1.0 parts of maleic anhydride modified polybutadiene Ricon 131MA10,2.0 parts of free radical initiator DCP,50 parts of filler SC6500-SVC and 3.0 parts of flame retardant DE-295.
The surface of the copper foil is provided with a silane coupling agent layer containing epoxy groups, and the arrangement method is as follows: dispersing a silane coupling agent KBM-403 in an aqueous solution, coating the aqueous solution on a HOZ copper foil, and drying to obtain a silane coupling agent layer; the content of the epoxy-containing silane coupling agent is 0.5wt% of the metal foil.
The preparation method of the metal foil-clad laminated plate comprises the following steps:
(1) Mixing the resin composition with Methyl Ethyl Ketone (MEK) according to the formula amount to prepare a resin glue solution with the solid content of 65%; soaking the glass fiber cloth with the resin glue solution, and drying at 150 ℃ for 3min to obtain a prepreg;
(2) Laminating 6 prepregs, covering copper foil with silane coupling agent layers on upper and lower sides, placing in a press at 200deg.C under pressure of 25kg/cm 2 And curing for 2 hours to obtain the metal foil-clad laminated board.
Examples 2 to 4 and comparative examples 1 to 6 were prepared in the same manner as in example 1, and the amounts of the components added are shown in tables 1 and 2.
The metal foil-clad laminates provided in examples 1-4, comparative examples 1-6 were subjected to the following performance tests:
(1) Dielectric constant Dk and dielectric dissipation factor Df: the test frequency was 10GHz according to the separation medium column cavity SPDR (Split Post Dielectric Resonator) method.
(2) Peel strength (a state): the test was performed according to the method in IPC-TM-650.2.4.8, and the test instrument was a copper foil stripping resistance instrument.
(3) Peel strength (thermal stress): after the metal foil-clad laminate to be tested was tin-dipped at 288 ℃ for 20min, the tensile force required to peel each millimeter of copper foil from the metal foil-clad laminate was tested with reference to IPC-TM-650.4.8 method.
(4) Glass transition temperature T g : the test was performed by dynamic mechanical thermal analyzer (DMA) using the IPC-TM-6502.4.24.4 standard method.
(5) Fluidity PP (RF): the test was carried out in a press using the method described in IPC-TM-650.2.3.17.
The addition amounts of the components and the test results are shown in tables 1 and 2:
TABLE 1
Figure BDA0003438164540000151
Figure BDA0003438164540000161
TABLE 2
Figure BDA0003438164540000162
Figure BDA0003438164540000171
Remarks: the dimensionless addition amounts in tables 1 and 2 refer to "parts by mass", and the addition amount of the silane coupling agent refers to the weight percentage of the metal foil. The copper foil of HOZ was used in examples 1 to 4 and comparative examples 1 to 6, and the peel strength of the system was far lower than that of thick copper because of the low roughness of copper foil (RZ. Ltoreq.1.5 μm) and the thin copper. Example 5 using a 1OZ copper foil, the peel strength of the resulting board was as high as 1.4N/mm.
As can be seen from the performance data of Table 1, in the metal foil-clad laminate provided by the invention, by introducing maleic anhydride modified polybutadiene into the resin composition and compounding with a metal foil containing a specific type of silane coupling agent layer, the bonding strength between the resin composition and the metal foil is remarkably improved, the peel strength in the A state reaches 0.73-0.79N/mm (HOZ copper foil, RZ is less than or equal to 1.5 μm), the peel strength after heat stress treatment at 288 ℃ for 20min is as high as 0.66-0.74N/mm (HOZ copper foil, RZ is less than or equal to 1.5 μm), and the metal foil-clad laminate has a high T g The processability is good.
As is clear from comparative example 1 and comparative example 1, if the copper foil is treated with a silane coupling agent other than the amino-containing silane coupling agent and the epoxy-containing silane coupling agent, the peel strength of the resin composition and the copper foil is low. As can be seen from comparative examples 2 to 3, the copper foil treated with the silane coupling agent alone was low in peel strength without adding maleic anhydride-modified polybutadiene. From a comparison of example 1 and comparative example 4, it is understood that the substitution of polybutadiene for maleic anhydride-modified polybutadiene and the lack of synergistic compounding of maleic anhydride by the coupling agent on the copper foil surface resulted in deterioration of peel strength. As is clear from a comparison of example 1 and comparative example 5, the addition of maleic anhydride-modified polybutadiene to the resin composition, while the copper foil which has not been treated with the coupling agent, the bonding strength of the resin composition to the copper foil is very low. Comparative example 6 was obtained by adding a large amount of maleic anhydride-modified polybutadiene as compared with example 1, and the sheet material had significantly reduced flowability and poor processability although the peel strength was improved.
The applicant states that the present invention is described by way of the above embodiments as a metal foil clad laminate and its use, but the present invention is not limited to, i.e. it is not meant that the present invention must be practiced in dependence upon, the above embodiments. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (10)

1. A metal foil-clad laminate, characterized in that the metal foil-clad laminate comprises at least one prepreg and a metal foil arranged on at least one side of the prepreg;
the prepreg includes a reinforcing material and a resin composition attached to the reinforcing material;
the resin composition includes a matrix resin and maleic anhydride-modified polybutadiene, the matrix resin including a polyphenylene ether resin; the mass of the maleic anhydride modified polybutadiene is 0.5-3 parts based on 100 parts of the mass of the matrix resin;
and a silane coupling agent layer is arranged on one side of the metal foil, which is contacted with the prepreg, and the silane coupling agent comprises an amino-containing silane coupling agent and/or an epoxy-containing silane coupling agent.
2. The metal foil-clad laminate of claim 1 wherein the polyphenylene ether resin is an unsaturated group-containing polyphenylene ether resin;
preferably, the polyphenylene ether resin has a number average molecular weight of 500 to 10000g/mol;
preferably, the silane coupling agent is present in an amount of 0.01 to 2wt% of the metal foil.
3. The metal foil-clad laminate of claim 1 or 2 wherein the polyphenylene ether resin has a structure as shown in formula I:
Figure FDA0003438164530000011
wherein Z is
Figure FDA0003438164530000012
A is selected from any one of carbonyl, C6-C30 arylene and C1-C10 straight-chain or branched alkylene;
R 5 、R 6 、R 7 each independently selected from any one of hydrogen, C1-C10 straight or branched alkyl;
n and m are each independently selected from integers of 0 to 10;
x is
Figure FDA0003438164530000021
R 1 、R 2 、R 3 、R 4 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 Each independently selected from any one of hydrogen, halogen, phenyl, C1-C10 straight or branched alkyl;
y is selected from single bond, C1-C10 straight chain or branched chain alkylene,
Figure FDA0003438164530000022
Figure FDA0003438164530000023
Any one of them;
a. b are each independently selected from integers from 1 to 30;
the dotted line represents the attachment site of the group.
4. The metal foil-clad laminate of any one of claims 1-3 wherein the matrix resin further comprises a polyolefin resin;
preferably, the polyolefin resin comprises any one or a combination of at least two of a styrene-butadiene copolymer, a styrene-isoprene copolymer, a hydrogenated styrene-butadiene copolymer, a hydrogenated styrene-isoprene copolymer, a styrene-butadiene-styrene block copolymer, a hydrogenated styrene-butadiene-styrene block copolymer, or polybutadiene;
preferably, the matrix resin includes 40 to 80 parts of polyphenylene ether resin and 20 to 60 parts of polyolefin resin based on 100 parts by mass of the matrix resin.
5. The metal clad laminate of any one of claims 1-4 wherein the maleic anhydride modified polybutadiene has a number average molecular weight of 2000-10000g/mol;
preferably, the maleic anhydride structural unit content in the maleic anhydride-modified polybutadiene is 3-15% by mass.
6. The metal foil clad laminate of any one of claims 1-5 wherein the resin composition further comprises a free radical initiator;
preferably, the mass of the radical initiator is 0.01 to 5 parts based on 100 parts by mass of the matrix resin;
preferably, the radical initiator includes any one or a combination of at least two of an organic peroxide, an azo compound or a carbon-based radical initiator, and further preferably an organic peroxide.
7. The metal foil-clad laminate of any one of claims 1-6 wherein the resin composition further comprises a filler;
preferably, the filler is 20 to 100 parts by mass based on 100 parts by mass of the matrix resin;
preferably, the filler comprises an inorganic filler and/or an organic filler;
preferably, the resin composition further comprises a flame retardant;
preferably, the mass of the flame retardant is 0.1 to 25 parts based on 100 parts by mass of the matrix resin.
8. The metal foil-clad laminate of any one of claims 1-7 wherein the reinforcement material comprises any one of fiberglass cloth, quartz glass blend cloth, fiberglass paper, non-woven cloth, or organic fiber cloth;
preferably, the thickness of the reinforcement material is 0.01-0.2mm.
9. The metal foil-clad laminate of any one of claims 1-8 wherein the method of preparing the silane coupling agent layer on the metal foil comprises: coating an aqueous solution of a silane coupling agent on a metal foil, and drying to obtain the silane coupling agent layer;
preferably, the metal foil includes any one of copper foil, nickel foil, aluminum foil, or SUS foil, and further preferably copper foil.
10. A printed wiring board comprising at least one metal foil-clad laminate according to any one of claims 1-9.
CN202111621419.5A 2021-12-28 2021-12-28 Metal foil-clad laminated board and application thereof Pending CN116353167A (en)

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