CN112280245B - Resin composition, prepreg, metal foil-clad laminate, and circuit board - Google Patents

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

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Publication number
CN112280245B
CN112280245B CN202011177379.5A CN202011177379A CN112280245B CN 112280245 B CN112280245 B CN 112280245B CN 202011177379 A CN202011177379 A CN 202011177379A CN 112280245 B CN112280245 B CN 112280245B
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China
Prior art keywords
resin composition
resin
composition according
parts
benzoxazine
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CN202011177379.5A
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CN112280245A (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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • 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
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • 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
    • C08J2435/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2447/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2461/04, C08J2461/18, and C08J2461/20
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

Abstract

The invention provides a resin composition, which comprises a phosphorus-containing double bond-containing benzoxazine resin, and can lead a condensate to have more excellent low dielectric constant, low dielectric loss, halogen-free flame retardance and wet 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 foil-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 laminated plate and a circuit substrate.
Background
In the prior art, a halogen flame retardant is commonly adopted in a laminated board for a circuit substrate to achieve the aim of flame retardance, however, the halogen flame retardant generates highly corrosive halogenated gas in the combustion process, and the document reports that the halogen flame retardant can generate cancerogens such as dioxin, dibenzofuran and the like during high-temperature pyrolysis and combustion. Since the official practice of the instructions on scrapped electrical and electronic equipment and the instructions on restricting the use of harmful substances in electrical and electronic equipment issued by the European Union, the development of laminates for halogen-free flame retardant circuit substrates has become an important point in the industry.
At present, a phosphorus-containing compound is used for replacing the prior brominated flame retardant in a common method in the industry, but the product of the phosphorus-containing compound has the common problems of insufficient tin immersion heat resistance, easiness in 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, there has been a demand for a laminate for a circuit board to have higher dielectric properties. In short, the laminate material needs to have a low dielectric constant and dielectric loss to reduce delay, distortion and loss of signals at high speed transmission, and interference between signals. However, epoxy resins have high dielectric constants and dielectric losses, and it is difficult to satisfy the application in high frequency.
Benzoxazine is a benzoxazine intermediate obtained by carrying out cyclization reaction on primary amine, phenol and aldehyde on the basis of the traditional method for preparing phenolic resin, and the benzoxazine is subjected to ring opening under the condition of heating or a catalyst to generate a novel thermosetting resin with a net structure, wherein a cured product of the novel thermosetting resin has higher glass transition temperature, and the decomposition of the cured product is less than 1% when the thermal decomposition temperature is up to 350 ℃, and in addition, the benzoxazine has better flame retardance because of containing nitrogen element. Benzoxazines do not exhibit sufficient flame retardant effects and require the addition of additives such as bromine, phosphorus or chlorine compounds. These additives affect the workability of the copper clad laminate and have poor oxidation stability and physical properties at high temperatures.
In view of the above, there is a need to provide a novel resin composition, a prepreg prepared therefrom, a metal foil-clad laminate, and a circuit substrate to solve the above-described 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 no halogenation and high frequency, and the prepared prepreg, metal foil-clad laminated plate and circuit substrate have excellent low dielectric constant, low dielectric loss, halogen-free flame retardance and heat resistance.
In order to achieve the aim of the invention, the invention adopts the following technical scheme: a resin composition comprising, by weight:
epoxy resin: 10-80 parts;
crosslinking agent: 1-60 parts;
benzoxazine resin: 10-80 parts;
the benzoxazine resin comprises at least one of the following structural formulas:
wherein R1, R2, R3 and R4 are the same or different and are respectively selected from hydrogen, methyl, ethyl, propyl or tertiary butyl; r is methyl, ethyl, phenyl, vinyl, allyl, styryl, phenylallyl,At least one R group in each structural 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:
wherein R is methyl, ethyl, phenyl, vinyl or allylStyrene-based, phenylallyl,At least one R group in each structural 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 at least one of polybutadiene, modified polybutadiene, polypentadiene, modified polypentadiene, polyisoprene, modified polyisoprene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, hydrogenated diene-butadiene-styrene copolymer, maleated diene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer, maleated styrene-butadiene copolymer, cyclopentadiene, modified cyclopentadiene, dicyclopentadiene, modified dicyclopentadiene, styrene-pentadiene copolymer, styrene-polypentadiene copolymer, butadiene-cyclopentadiene copolymer, ethylene-cyclopentadiene copolymer, norbornene polymer, modified norbornene polymer, divinylbenzene, bis (vinylbenzyl) ether, triallyl isocyanurate, triallyl cyanurate, di (vinylphenyl) ethane, divinylbenzene, double bond-containing polyphenylene ether, maleimide, double bond-containing epoxy resin, double bond-containing cyanate ester, and double bond-containing phenolic resin.
Further, the resin composition includes, by weight:
epoxy resin: 20-60 parts;
benzoxazine resin: 10-60 parts;
polyphenylene ether containing double bonds: 5-50 parts.
Further, the resin composition further includes a curing agent.
Further, the curing agent comprises 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;
crosslinking agent: 5-30 parts;
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 the structural formulae (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 benzoxazine resin shown in the structural formula (1) to structural formula (5) is contained in an amount of 10 to 100 parts by weight based on 100 parts by weight of the benzoxazine resin.
Further, the content of the benzoxazine resin other than the structural formulae (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 the group consisting of a phosphorus-containing phenolic resin, a phosphazene or modified phosphazene, a phosphate, melamine cyanurate, a polyorganosiloxane, DOPO-HQ, DOPO-NQ,(m is an integer of 1 to 5),Or DPO.
Further, the resin composition further includes an initiator.
Further, the initiator is a free radical initiator; the initiator is selected from at least one of dicumyl peroxide, or 2, 5-dimethyl-2, 5-bis (tertiary butyl peroxy) hexane, or tertiary butyl isopropyl peroxide, or di-tertiary butyl peroxide, or alpha, alpha' -bis (tertiary butyl peroxy) diisopropylbenzene and 2, 5-dimethyl-2, 5-bis (tertiary butyl peroxy) hexyne-3.
Further, the resin composition further comprises a catalyst.
Further, the catalyst comprises 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 comprises 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 at least one selected from nonmetal oxide, metal nitride, nonmetal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus; preferably, the inorganic filler is at least one selected from fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, 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 filler has a median particle size of 1 μm to 15 μm.
Further, the resin composition further 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 also provides a prepreg comprising a reinforcing material, and the above resin composition attached to the surface of the reinforcing material.
In order to achieve the above object, the present invention also provides a metal foil-clad laminate comprising 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 substrate comprising at least one prepreg as described above, or at least one metal foil-clad laminate as described above.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
in the resin composition, by adopting the benzoxazine resin containing phosphorus and olefin groups, on one hand, the epoxy resin is matched with the crosslinking agent, namely, the epoxy groups in the epoxy resin react with the benzoxazine groups in the benzoxazine resin, and meanwhile, the double bonds in the benzoxazine resin react with the crosslinking agent, so that the resin composition meeting the requirements of no halogenation and high frequency can be obtained, and a cured product with higher crosslinking density can be obtained, wherein the cured product has excellent low dielectric constant, low dielectric loss, no halogen flame retardance and heat resistance; on the other hand, the phosphorus-containing olefin-based benzoxazine resin contains nitrogen, phosphorus and phosphorus-nitrogen, and is synergistic in flame retardance, so that the flame retardance 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 olefin groups has a large number of hydrogen bonds, so that the problems of poor cohesiveness, poor toughness and the like caused by fewer polar groups can be avoided, and the cohesiveness and toughness of a cured product are obviously improved.
Detailed Description
The following description is given of specific embodiments of the present invention, and it should be noted that, for those skilled in the art, it is possible to make several improvements and modifications without departing from the principle of the embodiments of the present invention, and these improvements and modifications are also considered as the protection scope of the embodiments of the present invention.
The terms "comprising", "including" and "containing" in this specification mean that other components which are capable of imparting different properties to the resin composition may be contained in addition to the components.
In the present specification, "based on 100 parts by weight of the resin composition" means that the total amount of components excluding the curing agent, flame retardant, initiator, catalyst, filler, and auxiliary agent is 100 parts by weight.
The present invention provides a resin composition comprising, by weight:
epoxy resin: 10-80 parts;
crosslinking agent: 1-60 parts;
benzoxazine resin: 10-80 parts;
the benzoxazine resin comprises at least one of the following structural formulas:
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, R4 are the same, and the R1, R2, R3, R4 are selected from hydrogen or methyl.
Further, R is methyl, ethyl, phenyl, vinyl, allyl, styryl, phenylallyl,
Further, at least one R group in each formula is an unsaturated double bond containing group.
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 one embodiment, the benzoxazine resin other than 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; of course, this is not a limitation.
Specifically, the benzoxazine resin represented by the structural formula (1) to structural formula (5) is contained in an amount of 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 the structural formula (1) is included in the benzoxazine resin, "the content of the benzoxazine resin represented by the structural formula (1) to the structural formula (5) is 10 to 100 parts by weight", that is, the content of the benzoxazine resin represented by the structural formula (1) is 10 to 100 parts by weight; in the embodiment in which the benzoxazine resin includes only the benzoxazine resin represented by the structural formula (1) and the structural formula (2), the "the content of the benzoxazine resin represented by the structural formula (1) to the structural formula (5) is 10 to 100 parts by weight", that is, the content of the benzoxazine resin represented by the structural formula (1) and the structural formula (2) is 10 to 100 parts by weight, and so on, the description thereof will not be repeated.
Specifically, the content of the benzoxazine resin other than the structural formulae (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 an unsaturated double bond to enhance the reactivity of the crosslinking agent with the double bond in the benzoxazine resin.
Specifically, the cross-linking agent is at least one of polybutadiene, modified polybutadiene, polypentadiene, modified polypentadiene, polyisoprene, modified polyisoprene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, hydrogenated diene-butadiene-styrene copolymer, maleated diene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer, maleated styrene-butadiene copolymer, cyclopentadiene, modified cyclopentadiene, dicyclopentadiene, modified dicyclopentadiene, styrene-pentadiene copolymer, styrene-polypentadiene copolymer, butadiene-cyclopentadiene copolymer, ethylene-cyclopentadiene copolymer, norbornene polymer, modified norbornene polymer, divinylbenzene, bis (vinylbenzyl) ether, triallyl isocyanurate, triallyl cyanurate, di (vinylphenyl) ethane, divinylbenzene, double bond-containing polyphenylene ether, maleimide, double bond-containing epoxy resin, double bond-containing cyanate ester, and double bond-containing phenolic resin.
In one embodiment, the cross-linking agent is polybutadiene, wherein the content of 1, 2-vinyl is more than 45%, and the reactivity of the cross-linking agent and the double bond in the benzoxazine resin is further improved.
In another embodiment, the resin composition comprises 20 to 60 parts by weight of the epoxy resin, 10 to 60 parts by weight of the benzoxazine resin, and 5 to 50 parts by weight of the double bond-containing polyphenylene ether, i.e., in this embodiment, the crosslinking agent is a double bond-containing polyphenylene ether. Of course, this is not a limitation.
Specifically, the double bond-containing polyphenyl ether is selected from at least one of the following structural formulas:
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
in the structural formula, a and b are the same or different, a and b are integers of 1-10, and n is an integer of 0-5 (including 0);
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
in the structural formula, a and b are the same or different, a and b are integers of 1-10, and n is an integer of 1-5.
Further, the resin composition further comprises 5 to 30 parts of a curing agent based on 100 parts of the resin composition, so that the curing crosslinking density of the resin composition can be increased, and the crosslinking structure of the whole cured product is more compact, thereby improving the heat resistance and toughness of the cured product and obtaining the cured product with excellent comprehensive performance.
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 comprises 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, diaminodiphenyl sulfone, diethylenetriamine, dicarboxyl phthalimide 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 type naphthol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin or trimethylol methane resin. The active ester compound is a compound shown in the following structural formula (6), which is not limited to the following.
Wherein X is phenyl or naphthyl; j is 0 or 1; k is 0 or 1; n represents a repeating unit of 0.25 to 1.25.
In one embodiment, the curing agent is selected from the group consisting of styrene-maleic anhydride copolymers and reactive esters.
In one embodiment wherein 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 includes 5 parts to 40 parts of a flame retardant based on 100 parts of the resin composition to improve flame retardancy of a finally formed cured product, which may be understood as a prepreg, an insulating film, a metal foil-clad laminate, a circuit substrate, and the like.
Specifically, the flame retardant is selected from the group consisting of phosphorus-containing phenolic resins, phosphazenes or modified phosphazenes, phosphates, melamine cyanurate, polyorganosiloxanes, DOPO-HQ, DOPO-NQ,(m is an integer of 1 to 5),Or DPO.
Wherein, structural formula of DOPO is:
the structural formula of DOPO-HQ is as follows:
the structural formula of DOPO-NQ is as follows:
the saidThe structural formula is as follows: />
The saidThe structure is that
Further, the flame retardant is preferably a phosphorus-containing compound, the phosphorus-containing compound is preferably an additive-type phosphorus-containing compound, and specifically, the additive-type phosphorus-containing compound can be phosphazene, such as the trademark SPB-100; or modified phosphazenes such as BP-PZ, PP-PZ, SPCN-100, SPV-100 and SPB-100L; or choose to useOr choose to use
Further, the resin composition further comprises 0.1 to 4 parts of an initiator for opening double bonds in the benzoxazine and the crosslinking agent based on 100 parts of the resin composition, so that the reactivity of the double bonds in the benzoxazine and the crosslinking agent is increased, a tighter crosslinked network structure is obtained, and the heat resistance of a cured product is improved.
Specifically, the initiator is a free radical initiator and is selected from at least one of dicumyl peroxide, or 2, 5-dimethyl-2, 5-bis (tertiary butyl peroxy) hexane, or tertiary butyl isopropyl peroxide, or di-tertiary butyl peroxide, or alpha, alpha' -bis (tertiary butyl peroxy) dicumyl and 2, 5-dimethyl-2, 5-bis (tertiary butyl peroxy) hexyne-3.
Further, the resin composition further comprises 0.01 to 2 parts of a catalyst based on 100 parts of the resin composition. The catalyst is at least one selected from 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 comprises 20 parts to 100 parts of a filler per 100 parts of the resin composition, and it is understood that the filler may be contained or not contained in the resin composition.
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 fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, 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 silica, especially spherical silica subjected to surface treatment, is easier to disperse, can prevent agglomeration, and meanwhile, the spherical silica subjected to surface treatment is low in thermal expansion coefficient, so that warping of a final product can be prevented.
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 median particle size of the filler is 1 to 15. Mu.m, for example 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, and the specific values between the above values, are limited in space and in the interest of brevity, the invention is not intended to be exhaustive of the specific values included in the ranges.
More preferably, the particle size of the filler has a median value of 1-10 mu m, is easier to disperse and has better anti-agglomeration effect.
Further, the resin composition may further comprise an auxiliary agent according to the different requirements of the final product of the present invention, and it is understood that the resin composition may or may not comprise an auxiliary agent according to the different requirements of the final product, or a suitable auxiliary agent may be selected according to the requirements.
In the embodiment in which the resin composition contains an auxiliary agent, the content of the auxiliary agent is 0 to 5 parts by weight per 100 parts by weight of the resin composition.
Specifically, the other auxiliary agents comprise a coupling agent, a dispersing agent and a dye. The coupling agent is a silane coupling agent, such as an epoxy silane coupling agent or an amino silane coupling agent; the dispersant may be an amino silane compound having an amino group and having a hydrolyzable group or a hydroxyl group, such as γ -aminopropyl triethoxysilane, N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane, an epoxy silane compound having an epoxy group and having a hydrolyzable group or a hydroxyl group, such as 3-acryloxypropyl trimethoxysilane, a vinyl silane compound having a vinyl group and having a hydrolyzable group or a hydroxyl group, such as γ -methacryloxypropyl trimethoxysilane, or a cationic silane coupling agent, and for example, the dispersant may be Disperbyk-110, 111, 118, 180, 161, 2009, BYK-W996, W9010, W903 manufactured by BYK, the aforementioned code numbers being all the 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 powder carbon black, pyridine complex, azo complex, nigrosine, black talcum powder, cobalt chromium metal oxide, azine or phthalocyanine and the like.
It will be appreciated that the resin composition further comprises an appropriate amount of an organic solvent, and the above components of the resin composition and the organic solvent are mixed to form a resin composition glue solution for use.
Specifically, the organic solvent may be selected from one or a combination of any several 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 one skilled in the art according to his own experience, as long as the resulting resin composition dope can be brought to a viscosity suitable for use.
Further, the invention also 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 a glass fiber cloth, and a split cloth or a flat cloth is preferably used in the glass fiber cloth.
In addition, when the reinforcing material is a glass fiber cloth, the glass fiber cloth generally needs to be chemically treated to improve the bonding between the resin composition and the interface of the glass fiber cloth. The main method of the chemical treatment is treatment of a coupling agent, and the coupling agent is preferably epoxy silane or amino silane, etc. to provide good water resistance and heat resistance.
The preparation method of the prepreg comprises the following steps: and (3) dipping the reinforcing material in the resin composition glue solution, and then heating and drying the dipped reinforcing material to obtain the prepreg.
In one embodiment, the impregnated reinforcing material is baked for 1min to 10min at the temperature of 50 ℃ to 170 ℃ and dried to obtain the prepreg.
The invention further provides a metal foil-clad laminated board which comprises at least one prepreg and a metal foil formed on at least one surface of the prepreg.
In the embodiment in which the metal foil-clad laminate includes at least two prepregs as described above, the at least two prepregs are stacked and bonded together by heating and pressurizing, and then a metal foil is bonded on one or both sides of the bonded prepregs by heating and pressurizing to form the laminate.
Specifically, the metal foil-clad laminate is prepared by the steps of: and (3) coating metal foil on one side or both sides of one piece of the prepreg, or coating metal foil on one side or both sides of at least 2 pieces of the prepreg after overlapping, and performing hot press forming to obtain the metal foil laminated plate.
The pressing conditions of the metal foil-clad laminated plate are as follows: pressing for 2-4 hours under the pressure of 0.2-2 MPa and the temperature of 180-250 ℃.
In particular, the number of prepregs may be determined according to the thickness of the laminate as desired, and one or more prepregs may be used.
The metal foil can be copper foil or aluminum foil, and the material of the metal foil 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.
Further, the invention also provides a circuit substrate, which comprises at least one prepreg or at least one metal foil-clad laminated plate.
The preparation method of the circuit substrate can adopt the existing technology, and is not repeated here.
The following describes the present invention in detail with reference to specific examples; of course, it is to be understood that the embodiments of the invention are not limited to these embodiments.
Examples 1-5 and comparative examples 1-3:
the components and contents of the resin compositions of examples 1 to 5 and comparative examples 1 to 3 are shown in Table 1 below:
TABLE 1
/>
Wherein, the structural formula of the benzoxazine A in the table 1 is:
the reaction mechanism for preparing the benzoxazine A is as follows:
the structural formula of benzoxazine B in table 1 above is:
the reaction mechanism for preparing the benzoxazine B is as follows:
the structural formula of the benzoxazine C in table 1 above is:
the reaction mechanism for preparing the benzoxazine C is as follows:
the structural formula of the benzoxazine D in table 1 above is:
it can be seen that the benzoxazines a, B, C belong to the benzoxazine resins shown in the above structural formula (2). The benzoxazine D does not belong to the benzoxazine resins represented by the structural formulae (1) to (5).
In addition, the other component information than benzoxazine a, benzoxazine B, benzoxazine C, benzoxazine D referred to in table 1 above is shown in table 2 below:
TABLE 2
The preparation methods of the resin compositions of examples 1 to 5 and comparative examples 1 to 3 employ conventional preparation methods, specifically: according to the components and the corresponding contents in 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, SMA, filler, initiator and catalyst are mixed with a proper amount of organic solvent, and are emulsified by adopting a high-speed emulsifier, and the mixture is dispersed and uniformly mixed to obtain a resin composition glue solution with 65% of solid content, wherein the solid content is calculated by weight.
The obtained resin composition solutions of examples 1 to 5 and comparative examples 1 to 3 were respectively impregnated and coated on E glass cloth (2116, weight 104g/m 2 ) Prepregs with 50% resin content in examples 1-5 and comparative examples 1-2 were prepared, respectively, by drying in an oven at 145 ℃ for 6 min.
Preparation for performance evaluation sample laminates were evaluated:
(1) Preparation of Metal foil clad laminate
Prepregs with 50% resin content prepared in examples 1-5 and comparative examples 1-2 were each put one metal foil up and down, and placed in a vacuum hot press to be pressed to obtain metal foil laminates, respectively. The specific pressing process is to press for 2 hours at the temperature of 220 ℃ under the pressure of 1.5 MPa.
The performance evaluation method comprises the following steps:
(1) Dielectric constant (Dk)/dielectric loss (Df): a network analyzer (SPDR) method;
(2) Glass transition temperature (Tg): the Dynamic Mechanical Analysis (DMA) instrument is adopted for testing, and can be used for analyzing 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 was used.
(4) Wet heat resistance (PCT): 3 metal foil-clad laminates of 10cm X10 cm and 0.80mm thickness with metal foil removed on both sides were dried at 100℃for 2 hours, then treated with a autoclave retort test (Pressure Cooker test) machine at 121℃for 3 hours under 2 atmospheres, and then tin-immersed in a tin oven at 288℃for 20 seconds, and visually inspected for delamination. The layering phenomenon of the blocks 0,1,2 and 3 in the 3 blocks is respectively marked as 0/3,1/3,2/3 and 3/3.
The properties of the metal foil-clad laminates obtained using the prepregs in examples 1 to 5 and comparative examples 1 to 3, respectively, are shown in table 3 below.
TABLE 3 Table 3
As can be seen from table 3, the metal foil-clad laminate obtained by using the resin composition of the present invention has more excellent low dielectric constant, low dielectric loss, halogen-free flame retardance, wet heat resistance, and has a higher glass transition temperature.
In particular, as is clear from the parallel comparison of example 1 and comparative examples 1 and 3, example 1 has more excellent low dielectric constant, low dielectric loss, halogen-free flame retardancy, and wet heat resistance than comparative examples 1 and 3, and as is clear from the parallel comparison of example 2 and comparative example 2, example 2 has more excellent low dielectric constant, low dielectric loss, halogen-free flame retardancy, and wet heat resistance than comparative example 2.
It should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is for clarity only, and that the skilled artisan should recognize that the embodiments may be combined as appropriate to form other embodiments that will be understood by those skilled in the art.
The above list of detailed descriptions is only specific to practical embodiments of the present invention, and they are not intended to limit the scope of the present invention, and all equivalent embodiments or modifications that do not depart from the spirit of the present invention should be included in the scope of the present invention.

Claims (26)

1. A resin composition comprising, by weight:
epoxy resin: 10-80 parts;
crosslinking agent: 1-60 parts of cross-linking agent with unsaturated double bond;
benzoxazine resin: 10-80 parts;
the benzoxazine resin comprises at least one of the following structural formulas:
structural formula (1);
structural formula (2);
structural formula (3);
wherein R is 1 、R 2 、R 3 、R 4 Are identical or different and are each selected from hydrogen, methyl, ethyl, propyl or tert-butyl; r is methyl, ethyl, phenyl, vinyl, allyl, styryl, phenylallyl,、/>Or->At least one R group in each structural 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:structural formula (4);
structural formula (5);
wherein R is methyl, ethyl, phenyl, vinyl, allyl, styryl, phenylallyl,、Or->At least one R group in each structural formula is a group containing an unsaturated double bond; x is phenyl, methyl or ethyl.
2. The resin composition according to claim 1, wherein: the cross-linking agent is at least one of 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, norbornene polymer, modified norbornene polymer, divinylbenzene, bis (vinylbenzyl) ether, triallyl isocyanurate, triallyl cyanurate, bis (vinylphenyl) ethane, divinylbenzene, double bond-containing polyphenylene oxide, maleimide, double bond-containing epoxy resin, double bond-containing cyanate ester, double bond-containing phenolic resin.
3. The resin composition according to claim 1, wherein: comprises the following components in parts by weight:
epoxy resin: 20-60 parts;
benzoxazine resin: 10-60 parts;
polyphenylene ether containing double bonds: 5-50 parts.
4. The resin composition according to claim 1, wherein: the resin composition further includes a curing agent.
5. The resin composition according to claim 4, wherein: 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.
6. The resin composition according to claim 4, comprising, by weight:
epoxy resin: 20-60 parts;
benzoxazine resin: 20-60 parts;
crosslinking agent: 5-30 parts;
styrene-maleic anhydride copolymer: 5-40 parts.
7. The resin composition according to claim 1, wherein: the benzoxazine resin further comprises benzoxazine resins except structural formulas (1) - (5).
8. The resin composition according to claim 7, wherein: the benzoxazine resin other than 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.
9. The resin composition according to claim 7, wherein: and the content of the benzoxazine resin shown in the structural formula (1) to the structural formula (5) is 10-100 parts by weight based on 100 parts by weight of the benzoxazine resin.
10. The resin composition according to claim 7, wherein: the content of the benzoxazine resin except the structural formula (1) to the structural formula (5) is 1-40 parts by weight based on 100 parts by weight of the benzoxazine resin.
11. The resin composition according to claim 1, wherein: the resin composition further includes a flame retardant.
12. The resin composition according to claim 11, wherein: the flame retardant is selected from phosphorus-containing phenolic resin, phosphazene or modified phosphazene, phosphate, melamine cyanurate, polyorganosiloxane, DOPO-HQ, DOPO-NQ,、/>Or DPO; wherein m is an integer of 1 to 5.
13. The resin composition according to claim 1, wherein: the resin composition further includes an initiator.
14. The resin composition according to claim 13, wherein: the initiator is a free radical initiator; the initiator is at least one selected from dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (tertiary butyl peroxy) hexane, tertiary butyl isopropyl phenyl peroxide, di-tertiary butyl peroxide, alpha' -bis (tertiary butyl peroxy) dicumyl peroxide and 2, 5-dimethyl-2, 5-bis (tertiary butyl peroxy) hexyne-3.
15. The resin composition according to claim 1, wherein: the resin composition further includes a catalyst.
16. The resin composition according to claim 15, wherein: the catalyst comprises 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.
17. The resin composition according to claim 1, wherein: the resin composition further includes a filler.
18. The resin composition according to claim 17, wherein: the filler is an organic filler; the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
19. The resin composition according to claim 17, wherein: the filler is an inorganic filler; the inorganic filler is at least one selected from nonmetal oxides, metal nitrides, nonmetal nitrides, inorganic hydrates, inorganic salts, metal hydrates or inorganic phosphorus.
20. The resin composition according to claim 19, wherein: the inorganic filler is at least one selected from fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talcum powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica and glass fiber powder.
21. The resin composition according to claim 20, wherein: the filler is spherical silica surface-treated with a silane coupling agent.
22. The resin composition according to claim 17, wherein: the particle size median of the filler is 1-15 μm.
23. The resin composition according to claim 1, wherein: the resin composition further comprises an auxiliary agent, wherein the auxiliary agent comprises at least one of a coupling agent, a dispersing agent and a dye.
24. A prepreg, characterized in that: a resin composition according to any one of claims 1 to 23 comprising a reinforcing material, attached to the surface of said reinforcing material.
25. A metal foil-clad laminate characterized by: comprising at least one prepreg according to claim 24, a metal foil formed on at least one side of the prepreg.
26. A circuit substrate, characterized in that: comprising at least one prepreg according to claim 24 or comprising at least one metal foil-clad laminate according to claim 25.
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