CN112280245A - Resin composition, prepreg, metal-clad laminate, and circuit board - Google Patents

Resin composition, prepreg, metal-clad laminate, and circuit board Download PDF

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Publication number
CN112280245A
CN112280245A CN202011177379.5A CN202011177379A CN112280245A CN 112280245 A CN112280245 A CN 112280245A CN 202011177379 A CN202011177379 A CN 202011177379A CN 112280245 A CN112280245 A CN 112280245A
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Prior art keywords
resin
parts
resin composition
benzoxazine
copolymer
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CN202011177379.5A
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CN112280245B (en
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杨宋
马建
熊峰
崔春梅
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Suzhou Shengyi Technology Co Ltd
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Suzhou Shengyi Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2361/04, C08J2361/18, and C08J2361/20
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    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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    • C08J2435/00—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 carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
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    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
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Abstract

The invention provides a resin composition, which comprises a phosphorus-containing double-bond-containing benzoxazine resin, so that a cured product has excellent low dielectric constant, low dielectric loss, halogen-free flame retardance and moist heat resistance; the invention also provides a prepreg, a metal foil-clad laminate and a circuit substrate prepared by using the resin composition.

Description

Resin composition, prepreg, metal-clad laminate, and circuit board
Technical Field
The invention relates to the technical field of electronic materials, in particular to a resin composition, a prepreg prepared from the resin composition, a metal foil-clad laminate and a circuit substrate.
Background
In the prior art, a halogen flame retardant is generally adopted in a laminated board for a circuit substrate to achieve the purpose of flame retardance, however, the halogen flame retardant generates strongly corrosive halogenated gas in the combustion process, and the halogen flame retardant generates carcinogens such as dioxin, dibenzofuran and the like in pyrolysis and combustion according to literature reports. Since the official implementation of the directive on scrapping of electrical and electronic devices and the directive on limiting the use of hazardous substances in electrical and electronic devices issued in the european union, the development of laminates for halogen-free flame-retardant circuit boards has become a major research and development point in the industry.
At present, phosphorus-containing compounds are used to replace the conventional bromine flame retardants in the commonly adopted method in the industry, but the products of the phosphorus-containing compounds generally have the problems of insufficient tin immersion heat resistance, easy moisture absorption, insufficient tin immersion heat resistance after moisture treatment and the like.
With the recent increase in the speed and frequency of information processing and information transmission, a laminate for a circuit board has been required to have higher dielectric properties. In short, the laminate material needs to have low dielectric constant and dielectric loss to reduce the delay, distortion and loss of signals in high-speed transmission and the interference between signals. However, epoxy resins have high dielectric constants and dielectric losses, and are difficult to meet high frequency applications.
On the basis of the traditional phenolic resin preparation method, benzoxazine is subjected to cyclization reaction through primary amine, phenol and aldehyde to obtain a benzoxazine intermediate, under the condition of heating or a catalyst, benzoxazine is subjected to ring opening to generate a novel thermosetting resin with a net structure, a cured product of the benzoxazine has high glass transition temperature, the decomposition temperature is less than 1% when reaching 350 ℃, and in addition, the benzoxazine contains nitrogen elements, so that the benzoxazine has good flame retardance. However, benzoxazines do not exhibit sufficient flame retardant effect and require the addition of additives such as bromine, phosphorus or chlorine compounds. These additives affect the processability of copper clad laminates and have poor oxidation stability and physical properties at high temperatures.
In view of the above, it is desirable to provide a novel resin composition, a prepreg, a metal-clad laminate, and a circuit substrate prepared therefrom to solve the above problems.
Disclosure of Invention
The invention aims to provide a resin composition, a prepreg prepared from the resin composition, a metal foil-clad laminate and a circuit substrate. The resin composition can simultaneously meet the requirements of non-halogenation and high frequency, and the prepared prepreg, the metal foil-clad laminated board and the circuit substrate have excellent low dielectric constant, low dielectric loss, halogen-free flame retardance and heat resistance.
In order to achieve the purpose, the invention adopts the following technical scheme: a resin composition comprising, by weight:
epoxy resin: 10-80 parts;
a crosslinking agent: 1-60 parts;
benzoxazine resin: 10-80 parts;
the benzoxazine resin comprises at least one of the following structural formulas:
Figure BDA0002749096010000021
Figure BDA0002749096010000031
wherein R1, R2, R3 and R4 are the same or different and are respectively selected from hydrogen, methyl, ethyl, propyl or tert-butylA group; r is methyl, ethyl, phenyl, vinyl, allyl, styryl, allyl,
Figure BDA0002749096010000032
at least one R group in each formula is a group containing an unsaturated double bond; x is phenyl, methyl or ethyl;
and/or, the benzoxazine resin is selected from at least one of the following structural formulas:
Figure BDA0002749096010000033
wherein, R is methyl, ethyl, phenyl, vinyl, allyl, styryl, allyl, allyl,
Figure BDA0002749096010000034
At least one R group in each formula is a group containing an unsaturated double bond; x is phenyl, methyl or ethyl.
Further, the crosslinking agent has an unsaturated double bond.
Further, the crosslinking agent is polybutadiene, modified polybutadiene, polypentadiene, modified polypentadiene, polyisoprene, modified polyisoprene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, hydrogenated diene-butadiene-styrene copolymer, maleic anhydride-diene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer, maleic anhydride-styrene-butadiene copolymer, cyclopentadiene, modified cyclopentadiene, dicyclopentadiene, modified dicyclopentadiene, styrene-pentadiene copolymer, styrene-polypentadiene copolymer, butadiene-cyclopentadiene copolymer, ethylene-cyclopentadiene copolymer, polyisoprene, isoprene, At least one of norbornene polymer, modified norbornene polymer, divinylbenzene, bis (vinylbenzyl) ether, triallyl isocyanurate, triallyl cyanurate, bis (vinylphenyl) ethane, divinylbiphenyl, polyphenylene ether having double bonds, maleimide, epoxy resin having double bonds, cyanate ester having double bonds, and phenol resin having double bonds.
Further, the resin composition includes, by weight:
epoxy resin: 20-60 parts;
benzoxazine resin: 10-60 parts;
double bond-containing polyphenylene ether: 5-50 parts.
Further, the resin composition further comprises a curing agent.
The curing agent further includes at least one of an amine compound, an amide compound, an acid anhydride compound, a phenol compound, and an active ester compound.
Further, the resin composition includes, by weight:
epoxy resin: 20-60 parts;
benzoxazine resin: 20-60 parts;
a crosslinking agent: 5-30 parts of a stabilizer;
styrene-maleic anhydride copolymer: 5-40 parts.
Further, the benzoxazine resin also includes benzoxazine resins other than structural formulas (1) to (5).
Further, the benzoxazine resin other than structural formulas (1) to (5) is at least one of bisphenol a type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin, or bisphenol E type benzoxazine resin.
Further, the content of the benzoxazine resin represented by the structural formulas (1) to (5) is 10 to 100 parts by weight based on 100 parts by weight of the benzoxazine resin.
Further, the content of the benzoxazine resin except for structural formulas (1) to (5) is 1 to 40 parts by weight based on 100 parts by weight of the benzoxazine resin.
Further, the resin composition further includes a flame retardant.
Further, the flame retardant is selected from phosphorus-containing phenolic resin, phosphazene or modified phosphazene, phosphate ester and trimerizationCyanamide cyanurate, polyorganosiloxane, DOPO-HQ, DOPO-NQ,
Figure BDA0002749096010000051
(m is an integer of 1 to 5),
Figure BDA0002749096010000052
Or DPO.
Further, the resin composition further comprises an initiator.
Further, the initiator is a free radical initiator; the initiator is at least one selected from dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, alpha' -bis (tert-butylperoxy) diisopropylbenzene and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexyne-3.
Further, the resin composition further includes a catalyst.
Further, the catalyst includes at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole, and 1-cyanoethyl-2-methylimidazole.
Further, the resin composition further includes a filler.
Further, the filler is an organic filler; the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
Further, the filler is an inorganic filler; the inorganic filler is selected from at least one of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus; preferably, the inorganic filler is at least one selected from the group consisting of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.
Further, the filler is spherical silica surface-treated with a silane coupling agent.
Further, the median particle size of the filler is 1-15 μm.
Further, the resin composition also comprises an auxiliary agent, wherein the auxiliary agent comprises at least one of a coupling agent, a dispersing agent and a dye.
In order to achieve the above object, the present invention further provides a prepreg, which includes a reinforcing material, and the above resin composition attached to a surface of the reinforcing material.
In order to achieve the above object, the present invention further provides a metal foil-clad laminate including at least one prepreg as described above, and a metal foil formed on at least one side of the prepreg.
In order to achieve the above object, the present invention further provides a circuit board, which includes at least one prepreg as described above, or at least one metal-clad laminate as described above.
Has the advantages that: compared with the prior art, the invention has the following advantages:
according to the resin composition, the phosphorus-containing and alkene-containing benzoxazine resin is adopted, on one hand, the epoxy resin and the cross-linking agent are matched, namely, epoxy groups in the epoxy resin react with benzoxazine groups in the benzoxazine resin, and double bonds in the benzoxazine resin react with the cross-linking agent, so that the resin composition meeting the requirements of non-halogenation and high frequency simultaneously is obtained, and a cured product with high cross-linking density can be obtained, and the cured product has excellent low dielectric constant, low dielectric loss, halogen-free flame retardance and heat resistance; on the other hand, the phosphorus-containing and alkene-containing benzoxazine resin contains nitrogen and phosphorus, and phosphorus and nitrogen are synergistically flame-retardant, so that the flame retardant efficiency of a system is greatly improved, phosphorus groups can be well introduced into a cured product, and the dielectric property and the water absorption rate of the cured product are further improved on the basis of improving the heat resistance and the flame retardance of the cured product; meanwhile, the benzoxazine resin containing phosphorus and alkene has a large number of hydrogen bonds, so that the problems of poor adhesion, poor toughness and the like caused by few polar groups can be solved, and the adhesion and the toughness of a cured product are remarkably improved.
Detailed Description
While the following is a detailed description of the embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
The "comprising" and "containing" in the present specification mean that other components capable of imparting different characteristics to the resin composition may be contained in addition to the components.
The expression "based on 100 parts by weight of the resin composition" in the present specification means that the total amount of components other than the curing agent, flame retardant, initiator, catalyst, filler, and auxiliary agent is 100 parts by weight.
The invention provides a resin composition, which comprises the following components in percentage by weight:
epoxy resin: 10-80 parts;
a crosslinking agent: 1-60 parts;
benzoxazine resin: 10-80 parts;
the benzoxazine resin comprises at least one of the following structural formulas:
Figure BDA0002749096010000071
wherein R1, R2, R3 and R4 in the structural formulas (1) to (3) are the same or different, and specifically, R1, R2, R3 and R4 are respectively selected from hydrogen, methyl, ethyl, propyl or tert-butyl.
Further, the R1, R2, R3 and R4 are the same, and the R1, R2, R3 and R4 are selected from hydrogen or methyl.
Further, the R group is methyl, ethyl, phenyl, vinyl, allyl, styryl, styrylpropyl, or,
Figure BDA0002749096010000081
Further, at least one R group in each structural formula is a group containing an unsaturated double bond.
Further, X is phenyl, methyl or ethyl.
Further, X is phenyl or methyl.
Further, the benzoxazine resin also includes benzoxazine resins other than structural formulas (1) to (5).
In a specific embodiment, the benzoxazine resin other than structural formulas (1) to (5) is at least one of bisphenol a type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin, or bisphenol E type benzoxazine resin; of course, this is not a limitation.
Specifically, the content of the benzoxazine resins represented by the structural formulas (1) to (5) is 10 to 100 parts by weight based on 100 parts by weight of the benzoxazine resin.
The above-mentioned "the content of the benzoxazine resin represented by the structural formulae (1) to (5) is 10 to 100 parts by weight" means the content of the benzoxazine resin represented by the structural formulae (1) to (5) contained in the benzoxazine resin. That is, in the embodiment in which only the benzoxazine resin represented by structural formula (1) is included in the benzoxazine resin, "the content of the benzoxazine resin represented by structural formulae (1) to (5) is 10 to 100 parts by weight", which means that the content of the benzoxazine resin represented by structural formula (1) is 10 to 100 parts by weight; in the embodiment that the benzoxazine resin only includes benzoxazine resins represented by structural formulas (1) and (2), "the content of the benzoxazine resin represented by structural formulas (1) to (5) is 10 to 100 parts by weight", that is, the content of the benzoxazine resin represented by structural formulas (1) and (2) is 10 to 100 parts by weight, and so on, and thus, the description thereof is omitted.
Specifically, the content of the benzoxazine resin other than the structural formulas (1) to (5) is 1 to 40 parts by weight based on 100 parts by weight of the benzoxazine resin.
Further, the crosslinking agent has unsaturated double bonds to improve the reactivity of the crosslinking agent with the double bonds in the benzoxazine resin.
Specifically, the crosslinking agent is polybutadiene, modified polybutadiene, polypentadiene, modified polypentadiene, polyisoprene, modified polyisoprene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, hydrogenated diene-butadiene-styrene copolymer, maleic anhydride-diene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer, maleic anhydride-styrene-butadiene copolymer, cyclopentadiene, modified cyclopentadiene, dicyclopentadiene, modified dicyclopentadiene, styrene-pentadiene copolymer, styrene-polypentadiene copolymer, butadiene-cyclopentadiene copolymer, ethylene-cyclopentadiene copolymer, polyisoprene, isoprene, at least one of norbornene polymer, modified norbornene polymer, divinylbenzene, bis (vinylbenzyl) ether, triallyl isocyanurate, triallyl cyanurate, bis (vinylphenyl) ethane, divinylbiphenyl, polyphenylene ether having double bonds, maleimide, epoxy resin having double bonds, cyanate ester having double bonds, and phenol resin having double bonds.
In a specific embodiment, the cross-linking agent is polybutadiene, wherein the content of 1, 2-vinyl is 45% or more, so that the reactivity of the cross-linking agent with double bonds in the benzoxazine resin is further improved.
In another specific embodiment, the resin composition comprises 20 parts to 60 parts of epoxy resin, 10 parts to 60 parts of benzoxazine resin and 5 parts to 50 parts of polyphenylene oxide containing double bonds by weight, that is, in this embodiment, the crosslinking agent is polyphenylene oxide containing double bonds. Of course, this is not a limitation.
Specifically, the polyphenylene ether containing double bonds is selected from at least one of the following structural formulas:
Figure BDA0002749096010000091
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096010000092
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096010000101
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096010000102
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096010000103
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096010000104
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096010000105
in the structural formula, a and b are the same or different, a and b are both integers of 1-10, and n is an integer (including 0) of 0-5;
Figure BDA0002749096010000106
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096010000107
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096010000111
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096010000112
in the structural formula, a and b are the same or different, a and b are integers from 1 to 10, and n is an integer from 1 to 5.
Furthermore, the resin composition also comprises 5-30 parts of curing agent based on 100 parts of the resin composition, so that the curing crosslinking density of the resin composition can be improved, the crosslinking structure of the whole cured product is more compact, the heat resistance and toughness of the cured product are improved, and the cured product with excellent comprehensive performance is obtained.
The cured product in the present invention may be understood as a prepreg, an insulating film, a metal foil-clad laminate, a circuit board, or the like.
Specifically, the curing agent includes at least one of an amine compound, an amide compound, an acid anhydride compound, a phenol compound, and an active ester compound.
Wherein the amine compound is selected from diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, dicarboxyphthalimide or imidazole. The amide compound is selected from dicyandiamide or low molecular polyamide. The acid anhydride compound is selected from phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, nadic anhydride or styrene-maleic anhydride. The phenolic compound is selected from bisphenol A phenolic resin, phenol phenolic resin, naphthol phenolic resin, biphenyl phenol naphthol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin or trimethylolmethane resin. The active ester compound is selected from the compounds shown in the following structural formula (6), and certainly, the active ester compound is not limited to the following compounds:
Figure BDA0002749096010000121
wherein, X is phenyl or naphthyl; j is 0 or 1; k is 0 or 1; n represents a repeating unit and is 0.25 to 1.25.
In one embodiment, the curing agent is selected from styrene-maleic anhydride copolymer or active ester compounds.
In one embodiment where the curing agent is selected from styrene-maleic anhydride copolymers, the resin composition of the present invention comprises, by weight: 20-60 parts of epoxy resin, 20-60 parts of benzoxazine resin, 5-30 parts of cross-linking agent and 5-40 parts of styrene-maleic anhydride copolymer. Of course, this is not a limitation.
Further, the resin composition further comprises 5 to 40 parts of a flame retardant based on 100 parts of the resin composition to improve the flame retardancy of a finally formed cured product, which can be understood as a prepreg, an insulating film, a metal foil clad laminate, a circuit board and the like.
Specifically, the flame retardant is selected from phosphorus-containing phenolic resin, phosphazene or modified phosphazene, phosphate ester, melamine cyanurate, polyorganosiloxane, DOPO-HQ, DOPO-NQ, phosphorus oxychloride,
Figure BDA0002749096010000122
(m is an integer of 1 to 5),
Figure BDA0002749096010000123
Or DPO.
Wherein the structural formula of DOPO is as follows:
Figure BDA0002749096010000124
the structural formula of the DOPO-HQ is as follows:
Figure BDA0002749096010000131
the structural formula of DOPO-NQ is as follows:
Figure BDA0002749096010000132
the above-mentioned
Figure BDA0002749096010000133
The structural formula of (A) is:
Figure BDA0002749096010000134
the above-mentioned
Figure BDA0002749096010000135
Structural formula is
Figure BDA0002749096010000136
Further, the flame retardant is preferably a phosphorus-containing compound, the phosphorus-containing compound is preferably an additive phosphorus-containing compound, and specifically, the additive phosphorus-containing compound can be phosphazene, such as the trademark SPB-100; or selecting modified phosphazene, such as trade marks of BP-PZ, PP-PZ, SPCN-100, SPV-100 and SPB-100L; or is selected from
Figure BDA0002749096010000137
Or is selected from
Figure BDA0002749096010000138
Further, the resin composition comprises 0.1-4 parts of initiator based on 100 parts of the resin composition, and the initiator is used for opening double bonds in benzoxazine and a crosslinking agent so as to increase the reactivity of the benzoxazine and the double bonds in the crosslinking agent, obtain a tighter crosslinking network structure and improve the heat resistance of a cured product.
Specifically, the initiator is a free radical initiator selected from at least one of dicumyl peroxide, or 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, or t-butylcumyl peroxide, or di-t-butyl peroxide, or α, α' -bis (t-butylperoxy) diisopropylbenzene and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexyne-3.
Further, the resin composition also comprises 0.01 to 2 parts of catalyst based on 100 parts of the resin composition. The catalyst is selected from at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole and 1-cyanoethyl-2-methylimidazole.
Further, the resin composition may further include 20 parts to 100 parts of a filler based on 100 parts of the resin composition, but it is understood that the resin composition may or may not include the filler.
Specifically, the filler is at least one of an organic filler or an inorganic filler.
The inorganic filler is selected from one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus.
Preferably, the inorganic filler is at least one selected from the group consisting of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.
Further, the filler is silicon dioxide, particularly spherical silicon dioxide subjected to surface treatment, so that the filler is easier to disperse and can prevent agglomeration, and meanwhile, the spherical silicon dioxide subjected to surface treatment has a low thermal expansion coefficient and can prevent the final product from warping.
Specifically, the surface treatment agent for treating the spherical silica is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent.
The organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
In addition, the filler has a particle size median value of 1 to 15 μm, such as 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, and specific values therebetween are limited by space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the ranges.
More preferably, the particle size median of the filler is 1-10 μm, so that the filler is easier to disperse and better in anti-agglomeration effect.
Further, the resin composition may further comprise an auxiliary agent according to different requirements of the final product of the present invention, and it is understood that the resin composition may or may not contain the auxiliary agent according to different requirements of the final product, or a suitable auxiliary agent may be selected according to requirements.
In the embodiment that the resin composition contains the auxiliary, the content of the auxiliary is 0-5 parts by 100 parts by weight of the resin composition.
Specifically, the other auxiliary agents comprise coupling agents, dispersing agents and dyes. The coupling agent is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent; the dispersant is an amino silane compound having an amino group and a hydrolyzable group or a hydroxyl group such as γ -aminopropyltriethoxysilane, N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, an epoxy silane compound having an epoxy group and a hydrolyzable group or a hydroxyl group such as 3-acryloxypropyltrimethoxysilane, a vinyl silane compound having a vinyl group and a hydrolyzable group or a hydroxyl group such as γ -methacryloxypropyltrimethoxysilane, or a cationic silane coupling agent, and the dispersant can be Disperbyk-110, 111, 118, 180, 161, 2009, BYK-W996, W9010, or W903 manufactured by BYK, and the above symbols are product names; the dye is a fluorescent dye and a black dye, wherein the fluorescent dye is pyrazoline and the like, and the black dye is liquid or powdery carbon black, a pyridine complex, an azo complex, aniline black, black talcum powder, cobalt chromium metal oxide, azine or phthalocyanine and the like.
It is understood that the resin composition also comprises a proper amount of organic solvent, and the components of the resin composition and the organic solvent are mixed to form a resin composition glue solution for standby.
Specifically, the organic solvent may be selected from one or a combination of any of acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.
The amount of the organic solvent to be used in the present invention is not particularly limited. The amount of the solvent to be added is selected by a person skilled in the art from his or her own experience, as long as the viscosity of the resulting resin composition dope can be adjusted to a suitable viscosity for use.
The invention further provides a prepreg, which comprises a reinforcing material and any one of the resin compositions attached to the surface of the reinforcing material.
Specifically, the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric; preferably, the reinforcing material is glass fiber cloth, and open fiber cloth or flat cloth is preferably used in the glass fiber cloth.
In addition, when the reinforcing material is a glass cloth, the glass cloth generally needs to be chemically treated to improve the interface between the resin composition and the glass cloth. The main method of the chemical treatment is a coupling agent treatment, and the coupling agent is preferably epoxy silane or amino silane or the like to provide good water resistance and heat resistance.
The preparation method of the prepreg comprises the following steps: and (2) soaking a reinforcing material in the resin composition glue solution, and then heating and drying the soaked reinforcing material to obtain the prepreg.
In a specific embodiment, the impregnated reinforcing material is baked at 50-170 ℃ for 1-10 min, and the prepreg is obtained after drying.
The invention further provides a metal foil-clad laminate which comprises at least one prepreg and metal foil formed on at least one surface of the prepreg.
In an embodiment where the metal-clad laminate includes at least two prepregs described above, the laminate is formed by stacking the at least two prepregs, bonding the stacked prepregs by heating and pressing, and then bonding a metal foil on one or both surfaces of the bonded prepregs by heating and pressing.
Specifically, the metal-clad laminate is prepared by the following steps: and covering a metal foil on one or two sides of one prepreg, or covering a metal foil on one or two sides of at least 2 prepregs after laminating, and performing hot press forming to obtain the metal foil laminated board.
The pressing conditions of the metal-clad laminate are as follows: pressing for 2-4 hours under the pressure of 0.2-2 MPa and the temperature of 180-250 ℃.
Specifically, the number of prepregs may be determined according to the thickness of a desired laminate, and one or more prepregs may be used.
The metal foil can be copper foil or aluminum foil, and the material is not limited; the thickness of the metal foil is also not particularly limited, and may be, for example, 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.
Furthermore, the invention also provides a circuit substrate, wherein the circuit substrate comprises at least one prepreg or at least one metal foil-clad laminate.
The preparation method of the circuit substrate can adopt the existing process, and the details are not repeated.
The present invention will be described in detail with reference to specific examples; of course, it is to be understood that the embodiments of the present invention are not limited to these embodiments.
Examples 1 to 5 and comparative examples 1 to 3:
the components and contents of the resin compositions of examples 1 to 5 and comparative examples 1 to 3 are shown in the following table 1:
TABLE 1
Figure BDA0002749096010000171
Figure BDA0002749096010000181
Wherein, the structural formula of benzoxazine a in table 1 above is:
Figure BDA0002749096010000182
the reaction mechanism for preparing the benzoxazine A is shown as follows:
Figure BDA0002749096010000183
the structural formula of benzoxazine B in table 1 above is:
Figure BDA0002749096010000184
the reaction mechanism for preparing the benzoxazine B is shown as follows:
Figure BDA0002749096010000191
the structural formula of the benzoxazine C in table 1 above is:
Figure BDA0002749096010000192
the reaction mechanism for preparing the benzoxazine C is as follows:
Figure BDA0002749096010000193
the structural formula of the benzoxazine D in table 1 above is:
Figure BDA0002749096010000194
it can be seen that benzoxazine a, benzoxazine B, and benzoxazine C belong to the benzoxazine resin represented by the structural formula (2). The benzoxazine D does not belong to the benzoxazine resins represented by the structural formulae (1) to (5).
In addition, the information on the other components other than benzoxazine a, benzoxazine B, benzoxazine C, benzoxazine D referred to in table 1 above is shown in table 2 below:
TABLE 2
Figure BDA0002749096010000195
Figure BDA0002749096010000201
The resin compositions of examples 1 to 5 and comparative examples 1 to 3 were prepared by a conventional method, specifically: according to the components and the corresponding content in the table 1, benzoxazine A, benzoxazine B, benzoxazine C, benzoxazine D, bisphenol A type benzoxazine, bisphenol A type epoxy resin, biphenyl type epoxy resin, polybutadiene, polyphenyl ether, dicyandiamide, phosphate ester, SMA, filler, initiator and catalyst are mixed by using a proper amount of organic solvent, emulsified by using a high-speed emulsifier, and uniformly dispersed and mixed to obtain a resin composition glue solution with the solid content of 65%, wherein the solid content of 65% is calculated by weight.
The obtained resin composition glues of examples 1 to 5 and comparative examples 1 to 3 were respectively impregnatedAnd coated on E glass cloth (2116, single weight 104 g/m)2) And then baked in an oven at 145 ℃ for 6min to obtain prepregs with 50% of resin content in examples 1-5 and comparative examples 1-2, respectively.
Sample laminates prepared for performance evaluation were evaluated:
(1) preparation of Metal foil-clad laminate
The prepregs with the resin content of 50% prepared in the above examples 1 to 5 and comparative examples 1 to 2 were placed one metal foil on each of the upper and lower sides, and pressed in a vacuum hot press to obtain metal foil laminates, respectively. The specific pressing process is pressing for 2 hours under the pressure of 1.5MPa and the temperature of 220 ℃.
The performance evaluation method comprises the following steps:
(1) dielectric constant (Dk)/dielectric loss (Df): network analyzer (SPDR) method;
(2) glass transition temperature (Tg): the Dynamic Mechanical Analysis (DMA) instrument is used for testing whether the system has phase separation, and generally two or more Tg's show that the system has poor compatibility and phase separation.
(3) Flame retardancy: the UL94V method is adopted.
(4) Moist heat resistance (PCT): 3 pieces of a metal-clad laminate sheet having a thickness of 0.80mm and a thickness of 10cm × 10cm and having metal foils removed on both sides were dried at 100 ℃ for 2 hours, then treated at 121 ℃ under 2 atmospheres using a Pressure Cooker test (Pressure Cooker test) machine for 3 hours, and then dipped in tin at 288 ℃ for 20 seconds, and visually observed whether or not there was any delamination. If there are 0, 1, 2, 3 blocks in the 3 blocks, the layering phenomena are respectively recorded as 0/3, 1/3, 2/3, 3/3.
The properties of the metal foil-clad laminates obtained using the prepregs of examples 1 to 5 and comparative examples 1 to 3 are shown in table 3 below.
TABLE 3
Figure BDA0002749096010000211
As can be seen from table 3, the metal-clad laminate obtained by using the resin composition of the present invention has excellent low dielectric constant, low dielectric loss, halogen-free flame retardancy, and wet heat resistance, and has a high glass transition temperature.
In particular, it is understood from the parallel comparison between example 1 and comparative examples 1 and 3 that example 1 has a lower dielectric constant, a lower dielectric loss, halogen-free flame retardancy, and moist heat resistance than comparative examples 1 and 3, and that example 2 has a lower dielectric constant, a lower dielectric loss, halogen-free flame retardancy, and moist heat resistance than comparative example 2.
It should be understood that although the present description refers to embodiments, not every embodiment contains only a single technical solution, and such description is for clarity only, and those skilled in the art should make the description as a whole, and the technical solutions in the embodiments can also be combined appropriately to form other embodiments understood by those skilled in the art.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.

Claims (10)

1. A resin composition characterized by comprising, by weight:
epoxy resin: 10-80 parts;
a crosslinking agent: 1-60 parts;
benzoxazine resin: 10-80 parts;
the benzoxazine resin comprises at least one of the following structural formulas:
Figure FDA0002749094000000011
wherein R1, R2, R3 and R4 are the same or different and are respectively selected from hydrogen, methyl, ethyl, propyl or tert-butyl; r is methyl, ethyl or phenylVinyl, allyl, styryl, styrylpropyl, allyl, styrylpropyl,
Figure FDA0002749094000000012
at least one R group in each formula is a group containing an unsaturated double bond; x is phenyl, methyl or ethyl;
and/or, the benzoxazine resin is selected from at least one of the following structural formulas:
Figure FDA0002749094000000021
wherein, R is methyl, ethyl, phenyl, vinyl, allyl, styryl, allyl, allyl,
Figure FDA0002749094000000022
At least one R group in each formula is a group containing an unsaturated double bond; x is phenyl, methyl or ethyl.
2. The resin composition according to claim 1, characterized in that: the crosslinking agent has an unsaturated double bond; the crosslinking agent is polybutadiene, modified polybutadiene, polypentadiene, modified polypentadiene, polyisoprene, modified polyisoprene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, hydrogenated diene-butadiene-styrene copolymer, maleic anhydride diene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer, maleic anhydride styrene-butadiene copolymer, cyclopentadiene, modified cyclopentadiene, dicyclopentadiene, modified dicyclopentadiene, styrene-pentadiene copolymer, styrene-polypentadiene copolymer, butadiene-cyclopentadiene copolymer, ethylene-cyclopentadiene copolymer, polyisoprene, isoprene-butadiene copolymer, styrene-isoprene copolymer, isoprene-, At least one of norbornene polymer, modified norbornene polymer, divinylbenzene, bis (vinylbenzyl) ether, triallyl isocyanurate, triallyl cyanurate, bis (vinylphenyl) ethane, divinylbiphenyl, polyphenylene ether having double bonds, maleimide, epoxy resin having double bonds, cyanate ester having double bonds, and phenol resin having double bonds.
3. The resin composition according to claim 2, characterized in that: comprises the following components in parts by weight:
epoxy resin: 20-60 parts;
benzoxazine resin: 10-60 parts;
double bond-containing polyphenylene ether: 5-50 parts.
4. The resin composition according to claim 1, characterized in that: the resin composition further comprises a curing agent; the curing agent comprises at least one of an amine compound, an amide compound, an anhydride compound, a phenol compound and an active ester compound.
5. The resin composition according to claim 4, comprising by weight:
epoxy resin: 20-60 parts;
benzoxazine resin: 20-60 parts;
a crosslinking agent: 5-30 parts of a stabilizer;
styrene-maleic anhydride copolymer: 5-40 parts.
6. The resin composition according to claim 1, characterized in that: the benzoxazine resin also comprises benzoxazine resins except structural formulas (1) to (5); the benzoxazine resin except the structural formulas (1) to (5) is at least one of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin or bisphenol E type benzoxazine resin; the content of the benzoxazine resin shown in structural formulas (1) to (5) is 10 to 100 parts by weight based on 100 parts by weight of the benzoxazine resin, and the content of the benzoxazine resin except for the structural formulas (1) to (5) is 1 to 40 parts by weight.
7. The resin composition according to claim 1, characterized in that: the resin composition further comprises a flame retardant, and/or an initiator, and/or a catalyst, and/or a filler, and/or an auxiliary agent.
8. A prepreg characterized in that: a resin composition according to any one of claims 1 to 7 comprising a reinforcing material attached to a surface of the reinforcing material.
9. A metal-clad laminate characterized by: comprising at least one prepreg according to claim 8, a metal foil being formed on at least one side of the prepreg.
10. A circuit substrate, characterized in that: comprising at least one prepreg according to claim 8 or comprising at least one metal-foil-clad laminate according to claim 9.
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CN114836147A (en) * 2022-04-21 2022-08-02 深圳市纽菲斯新材料科技有限公司 Novel FC-BGA packaging substrate is with increasing layer glued membrane and use rubber coating copper foil of its preparation

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