CN111378136B - Active ester resin and preparation method thereof, thermosetting resin composition, prepreg, insulating film, laminated board and printed circuit board - Google Patents

Active ester resin and preparation method thereof, thermosetting resin composition, prepreg, insulating film, laminated board and printed circuit board Download PDF

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CN111378136B
CN111378136B CN202010370648.3A CN202010370648A CN111378136B CN 111378136 B CN111378136 B CN 111378136B CN 202010370648 A CN202010370648 A CN 202010370648A CN 111378136 B CN111378136 B CN 111378136B
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epoxy resin
resin
weight
parts
active ester
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CN111378136A (en
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黄荣辉
崔春梅
戴善凯
谌香秀
陈诚
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Suzhou Shengyi Technology Co Ltd
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B32B2307/73—Hydrophobic
    • 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
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    • B32B2457/08—PCBs, i.e. printed circuit boards
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    • 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
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    • 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
    • C08J2363/04—Epoxynovolacs
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    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
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    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/04—Epoxynovolacs
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention provides an active ester resin and a preparation method thereof. The preparation method comprises the step of reacting bisphenol-based end-capped silicone oil compound (a), phenolic hydroxyl-containing compound (b) and aromatic carboxylic acid or acyl halide compound (c) thereof as raw materials to prepare the active ester resin, wherein the active ester resin contains a bisphenol-based end-capped silicone oil structure. The invention also provides a thermosetting resin composition with the active ester resin, and a prepreg, an insulating film, a laminated board and a printed circuit board with the thermosetting resin composition. Compared with the prior art, the invention has the advantages of excellent dielectric property, unexpected improvement on toughness, combustibility and low water absorption, lower XY axis thermal expansion coefficient, application to IC packaging and high-speed and high-frequency fields and wide application prospect.

Description

Active ester resin and preparation method thereof, thermosetting resin composition, prepreg, insulating film, laminated board and printed circuit board
Technical Field
The invention belongs to the technical field of electronic materials, and particularly relates to an active ester resin, a preparation method thereof, a thermosetting resin composition with the active ester resin, a prepreg, an insulating film, a laminated board and a printed circuit board with the thermosetting resin composition, which can be applied to the fields of integrated circuit packaging, high speed and high frequency and the like.
Background
In the semiconductor packaging process, if the thermal expansion coefficient difference between the semiconductor element and the substrate is too large, stress is easily generated to cause substrate warpage, thereby causing serious problems such as poor connection between the semiconductor element and the substrate, and between the substrate and the PCB. Therefore, a lower thermal expansion coefficient is required for the substrate material in the X/Y axis direction. Meanwhile, with the development and scale of 5G, the high speed and high frequency of transmission signals require that the material has better dielectric properties, namely lower dielectric constant and dielectric loss.
The active ester resin is a common curing agent which is currently used in a resin formula with dielectric property requirements, secondary hydroxyl is not generated in the curing process of the active ester resin and epoxy resin, the polarity of the structure of the active ester resin is low, and a cured product has lower dielectric constant and dielectric loss. In addition, compared with other low dielectric curing agents, such as Styrene Maleic Anhydride (SMA), modified polyphenylene oxide (PPO) and the like, the active ester resin also has the characteristics of relatively low melt viscosity, relatively low active group equivalent, relatively high crosslinking density, easy structure design and the like, so that the active ester resin has better manufacturability and performance. However, active ester resins still have major disadvantages in terms of toughness, thermal expansion coefficient, flame retardancy and higher electrical property requirements.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide an improved active ester resin, a preparation method thereof, a thermosetting resin composition having the active ester resin, and a prepreg, an insulating film, a laminated board and a printed circuit board having the thermosetting resin composition.
In order to achieve the purpose, the invention adopts the following technical scheme.
An active ester resin is provided comprising the structure (1):
Figure BDA0002477972320000021
wherein R is an alkylene group or arylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 20.
The active ester resin is prepared by reacting bisphenol-terminated silicone oil compound (a), phenolic hydroxyl-containing compound (b) and aromatic carboxylic acid or acyl halide compound (c) thereof as raw materials.
Preferably, the bisphenol-based end-capped silicone oil compound (a) is 5 to 50 parts by weight based on 100 parts by weight of the total amount of the bisphenol-based end-capped silicone oil compound (a), the phenolic hydroxyl group-containing compound (b), and the aromatic carboxylic acid or its acid halide compound (c).
Preferably, the bisphenol-terminated silicone oil compound (a) has the structure:
Figure BDA0002477972320000022
wherein R is an alkylene group or arylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 20.
Preferably, the phenolic hydroxyl group-containing compound (b) is a monophenol compound selected from phenol, substituted phenol, naphthol, or substituted naphthol; or the phenolic hydroxyl group-containing compound (b) is a bisphenol compound selected from dihydroxybenzene, dihydroxybiphenyl or dihydroxynaphthalene; or the phenolic hydroxyl group-containing compound (b) is a polyphenol compound selected from polyhydroxy benzene, polyhydroxy biphenyl or polyhydroxy naphthalene; or the phenolic hydroxyl group-containing compound (b) is phenol-formaldehyde resin, bisphenol A-phenol-formaldehyde resin, o-cresol-phenol-formaldehyde resin, DCPD phenol-formaldehyde resin, biphenol-phenol-formaldehyde resin, naphthalene ring phenol-formaldehyde resin, XYLOK phenol-formaldehyde resin or trifunctional phenol-formaldehyde resin.
Preferably, the aromatic carboxylic acid or the acid halide compound (c) thereof is an aromatic compound which can form an ester bond by reacting with the phenolic hydroxyl group of the phenolic hydroxyl group-containing compound (b). Preferably, the aromatic compound is selected from benzoic acid, isophthalic acid, terephthalic acid, trimellitic acid, naphthoic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-2, 3-dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid or naphthalene-2, 7-dicarboxylic acid; or an acid halide selected from benzoic acid, isophthalic acid, terephthalic acid, trimellitic acid, naphthoic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-2, 3-dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid or naphthalene-2, 7-dicarboxylic acid.
Also provided is a thermosetting resin composition comprising 20-80 parts by weight of an epoxy resin and 20-80 parts by weight of an active ester resin, wherein the active ester resin comprises a structure (1):
Figure BDA0002477972320000031
wherein R is an alkylene group or arylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 20.
Preferably, the epoxy resin is selected from one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus epoxy resin, nitrogen epoxy resin, o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl novolac epoxy resin, alicyclic epoxy resin, epoxidized polybutadiene resin, glycidylamine epoxy resin, glycidylether epoxy resin, and glycidylether epoxy resin.
The epoxy resin may be further preferably a naphthalene ring type epoxy resin, a biphenyl type epoxy resin or a dicyclopentadiene type epoxy resin; wherein:
the general structural formula of the naphthalene ring type epoxy resin is a structure (3):
Figure BDA0002477972320000032
wherein p is an integer from 1 to 10;
the general structural formula of the biphenyl epoxy resin is structure (4):
Figure BDA0002477972320000041
wherein n is an integer of 1 to 10;
the general structural formula of the dicyclopentadiene epoxy resin is a structure (5):
Figure BDA0002477972320000042
wherein m is an integer of 1 to 10.
Preferably, the resin composition further comprises 1 to 50 parts by weight of cyanate ester resin or 1 to 50 parts by weight of polyphenylene ether resin or 1 to 50 parts by weight of benzoxazine resin or 1 to 50 parts by weight of hydrocarbon resin.
Preferably, the resin composition includes 30 to 70 parts by weight of the epoxy resin and 30 to 70 parts by weight of the active ester resin.
Preferably, the resin composition further comprises one or more of an amine compound, an amide compound, an acid anhydride compound, a phenol compound, and an active ester compound not containing the structure (1), and the total amount is 0 to 60 parts by weight.
Also provided is a prepreg including the resin composition.
Preferably, the prepreg further includes a reinforcing material, and the resin composition is attached to a surface of the reinforcing material.
Also provided is an insulating film comprising an insulating resin layer composed of the resin composition.
Preferably, the insulation film further includes a carrier film, and the insulation resin layer is attached to a surface of the carrier film through a coating process.
Preferably, the insulation film further comprises a protective film layer attached to a side of the insulation resin layer facing away from the carrier film and covering the insulation resin layer.
The laminated board is a metal foil-clad laminated board and comprises the prepreg and a metal foil attached to the surface of the prepreg.
Also provided is a printed circuit board including the insulating film or the prepreg; that is, it includes an insulating film or a prepreg including the resin composition.
Compared with the prior art, the invention has the following beneficial effects: the invention synthesizes the active ester resin by taking the bisphenol-based end-capped silicone oil compound as the raw material, the active ester resin comprises the structure (1), not only maintains the advantage that the active ester group does not generate secondary hydroxyl after being cured, thereby effectively reducing the dielectric constant and the dielectric loss, but also integrates the characteristics of low stress (low thermal expansion coefficient), high toughness, low water absorption rate and difficult combustion of the silicone oil compound, the thermosetting resin composition prepared by the active ester resin has excellent dielectric property, toughness, combustibility, low water absorption rate and thermal expansion coefficient, furthermore, prepregs, insulating films, laminated boards and the like obtained by the thermosetting resin composition have unexpected improvement on the aspects of toughness, combustibility and low water absorption rate and have lower XY axis thermal expansion coefficient, can be applied to the fields of IC packaging and high speed and high frequency, has wide application prospect.
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 invention provides an active ester resin with improved performance in the aspects of dielectric property, toughness, thermal expansion coefficient and the like, aiming at solving the defects of the existing active ester resin in the aspects of dielectric property, toughness, thermal expansion coefficient and the like, and the active ester resin is further applied to products such as thermosetting resin compositions, prepregs, insulating films, laminated plates, printed circuit boards and the like.
The active ester resin comprises the structure (1):
Figure BDA0002477972320000061
wherein R is an alkylene group or arylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 20.
The preparation method of the active ester resin comprises the following steps: the active ester resin is prepared by reacting bisphenol-terminated silicone oil compound (a), phenolic hydroxyl-containing compound (b) and aromatic carboxylic acid or acyl halide compound (c) thereof as raw materials.
Preferably, the bisphenol-based end-capped silicone oil compound (a) is 5 to 50 parts by weight based on 100 parts by weight of the total amount of the bisphenol-based end-capped silicone oil compound (a), the phenolic hydroxyl group-containing compound (b), and the aromatic carboxylic acid or its acid halide compound (c).
Preferably, the bisphenol-terminated silicone oil compound (a) has the structure:
Figure BDA0002477972320000062
wherein R is an alkylene group or arylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 20.
Preferably, the molecular structure of the phenolic hydroxyl group-containing compound (b) contains one or more phenolic hydroxyl groups.
Preferably, the phenolic hydroxyl group-containing compound (b) is a monophenol compound selected from phenol, substituted phenol, naphthol, or substituted naphthol; or the phenolic hydroxyl group-containing compound (b) is a bisphenol compound selected from dihydroxybenzene, dihydroxybiphenyl or dihydroxynaphthalene; or the phenolic hydroxyl group-containing compound (b) is a polyphenol compound selected from polyhydroxy benzene, polyhydroxy biphenyl or polyhydroxy naphthalene; or the phenolic hydroxyl group-containing compound (b) is phenol-formaldehyde resin, bisphenol A-phenol-formaldehyde resin, o-cresol-phenol-formaldehyde resin, DCPD phenol-formaldehyde resin, biphenol-phenol-formaldehyde resin, naphthalene ring phenol-formaldehyde resin, XYLOK phenol-formaldehyde resin or trifunctional phenol-formaldehyde resin.
Preferably, the aromatic carboxylic acid or the acid halide compound (c) thereof is an aromatic compound which can form an ester bond by reacting with the phenolic hydroxyl group of the phenolic hydroxyl group-containing compound (b). Preferably, the aromatic compound is selected from benzoic acid, isophthalic acid, terephthalic acid, trimellitic acid, naphthoic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-2, 3-dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid or naphthalene-2, 7-dicarboxylic acid; or an acid halide selected from benzoic acid, isophthalic acid, terephthalic acid, trimellitic acid, naphthoic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-2, 3-dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid or naphthalene-2, 7-dicarboxylic acid.
Further, the invention also provides a thermosetting resin composition, which comprises 20-80 parts by weight of epoxy resin and 20-80 parts by weight of active ester resin, wherein the active ester resin comprises a structure (1):
Figure BDA0002477972320000071
wherein R is an alkylene group or arylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 20. That is, the thermosetting resin composition includes the active ester resin described above.
Preferably, the epoxy resin is selected from one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus epoxy resin, nitrogen epoxy resin, o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl novolac epoxy resin, alicyclic epoxy resin, epoxidized polybutadiene resin, glycidylamine epoxy resin, glycidylether epoxy resin, and glycidylether epoxy resin.
The epoxy resin may be further preferably a naphthalene ring type epoxy resin, a biphenyl type epoxy resin or a dicyclopentadiene type epoxy resin; wherein:
the general structural formula of the naphthalene ring type epoxy resin is a structure (3):
Figure BDA0002477972320000072
wherein p is an integer from 1 to 10;
the general structural formula of the biphenyl epoxy resin is structure (4):
Figure BDA0002477972320000081
wherein n is an integer of 1 to 10;
the general structural formula of the dicyclopentadiene epoxy resin is a structure (5):
Figure BDA0002477972320000082
wherein m is an integer of 1 to 10.
Preferably, the resin composition further comprises 1 to 50 parts by weight of cyanate ester resin or 1 to 50 parts by weight of polyphenylene ether resin or 1 to 50 parts by weight of benzoxazine resin or 1 to 50 parts by weight of hydrocarbon resin.
Preferably, the resin composition includes 30 to 70 parts by weight of the epoxy resin and 30 to 70 parts by weight of the active ester resin.
Specifically, for example, the resin composition comprises 30 to 70 parts by weight of the epoxy resin, 30 to 70 parts by weight of the active ester resin, and 1 to 50 parts by weight of a cyanate ester resin; preferably, the cyanate ester resin is one or a mixture of more of bisphenol a cyanate ester, biphenyl cyanate ester, naphthalene ring cyanate ester, bisphenol F cyanate ester, dicyclopentadiene cyanate ester, phenol-formaldehyde cyanate ester, tetramethyl bisphenol F cyanate ester, bisphenol M cyanate ester, bisphenol E cyanate ester or prepolymers thereof;
or the resin composition comprises 30-70 parts by weight of the epoxy resin, 30-70 parts by weight of the active ester resin and 1-50 parts by weight of polyphenylene oxide resin; preferably, the polyphenylene ether resin is a thermosetting polyphenylene ether resin selected from one or a mixture of more of styrene-modified polyphenylene ether, acrylate-modified polyphenylene ether, polybutadiene-modified polyphenylene ether, allyl-modified polyphenylene ether, maleimide-modified polyphenylene ether, amino-modified polyphenylene ether or phenol-modified polyphenylene ether;
or the resin composition comprises 30-70 parts by weight of the epoxy resin, 30-70 parts by weight of the active ester resin and 1-50 parts by weight of benzoxazine resin; preferably, the benzoxazine resin is one or a mixture of more of bisphenol a benzoxazine resin, bisphenol F benzoxazine resin, 4' diaminodiphenylmethane benzoxazine resin, diaminodiphenyl ether benzoxazine resin, diaminodiphenyl sulfone benzoxazine resin, dicyclopentadiene benzoxazine resin, phenolphthalein benzoxazine resin, allyl benzoxazine resin, cyanate ester benzoxazine resin, epoxy modified benzoxazine resin and maleimide modified benzoxazine resin;
or the resin composition comprises 30-70 parts by weight of the epoxy resin, 30-70 parts by weight of the active ester resin and 1-50 parts by weight of hydrocarbon resin; preferably, the hydrocarbon resin is one or a mixture of several 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, norbornene polymer and modified norbornene polymer.
Preferably, the resin composition further comprises one or more of an amine compound, an amide compound, an acid anhydride compound, a phenol compound, and an active ester compound not containing the structure (1), and the total amount is 0 to 60 parts by weight.
Preferably, the amine compound is selected from one or more of diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, dicarboxyphthalimide, and imidazole, and more preferably diaminodiphenylmethane and diaminodiphenylsulfone.
Preferably, the amide compound is one or more selected from dicyandiamide and low molecular polyamide, and more preferably dicyandiamide.
Preferably, the acid anhydride compound is selected from one or more of phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, and nadic anhydride, and more preferably, a styrene-maleic anhydride copolymer.
Preferably, the phenolic compound is selected from one or more of bisphenol a phenolic resin, phenol phenolic resin, naphthol phenolic resin, biphenyl phenol type phenolic resin, dicyclopentadiene phenol addition type resin, naphthol aralkyl resin and trimethylolmethane resin.
Preferably, the active ester compound not containing structure (1) has structure (6):
Figure BDA0002477972320000101
wherein, X is phenyl or naphthyl; j is 0 or 1; k is 0 or 1; n is 0.25 to 1.25. Of course, the present invention is not limited thereto, and it is understood that the active ester compound not containing the structure (1) may be selected from other active ester compounds not containing the structure (1).
Preferably, the resin composition further comprises any one or any more or all of 0-200 parts by weight of a filler, 0.001-5 parts by weight of an accelerator, and 0-50 parts by weight of a flame retardant, based on 100 parts by weight of the resin contained in the resin composition.
Preferably, the filler is an organic filler or an inorganic filler.
Wherein 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; more preferably, it 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.
The organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
More preferably, the filler is silica, preferably surface treated spherical silica. Wherein the surface treating agent is a silane coupling agent, such as an epoxy silane coupling agent or an amino silane coupling agent.
Preferably, the filler has a median particle size 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 not intended to be exhaustive, and for brevity, the invention is not intended to be limited to the specific values included in the ranges.
More preferably, the median value of the particle size of the filler is 1-10 μm.
Preferably, the accelerator may be a tertiary amine accelerator such as triethylamine, tripropylamine, etc.; imidazole accelerators such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, etc.; peroxide accelerators such as benzoyl peroxide and dicumyl peroxide; transition metal carboxylate accelerators such as zinc naphthenate, zinc octoate, aluminum acetylacetonate, and the like; organic phosphorus accelerators such as triphenyl phosphorus, triphenyl phosphite, and the like; pyridine accelerators, such as dimethylaminopyridine. The accelerator is selected from one or a mixture of more than one of the accelerators.
Preferably, the flame retardant is a brominated flame retardant, such as tribromophenyl maleimide, tetrabromobisphenol a allyl ether, decabromodiphenylethane, brominated polystyrene, brominated polycarbonate, tetrabromobisphenol a, brominated epoxy resin, and the like; phosphorus-containing flame retardants such as phosphorus-containing epoxy resins, phosphorus-containing phenolic resins, phosphorus-containing active esters, bis-DOPO ethane, phosphazene compounds, phosphate ester compounds, phosphorus-containing cyanate esters, phosphorus-containing bismaleimides, and the like; nitrogen-containing compounds such as melamine cyanurate, etc.; silicon-containing compounds such as silsesquioxane (POSS), silicone resin powders, and the like. The flame retardant is selected from one or more than one of the flame retardants.
Preferably, the resin composition may further comprise other auxiliary agents besides the accelerator and/or the flame retardant, such as any one or more of coupling agent, dispersant, defoamer, leveling agent, anti-aging agent, antioxidant and dye, according to different requirements of the final product.
The coupling agent is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent; the dispersant is various dispersants such as amino silane compounds having amino groups and hydrolytic groups or hydroxyl groups, such as gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and the like, epoxy silane compounds having epoxy groups and hydrolytic groups or hydroxyl groups, such as 3-acryloxypropyltrimethoxysilane and the like, vinyl silane compounds having vinyl groups and hydrolytic groups or hydroxyl groups, such as gamma-methacryloxypropyltrimethoxysilane and the like, and cationic silane coupling agents, and BYK products are given names of Disperbyk-110, 111, 118, 180, 161, 2009, BYK-W996, W9010 and W903; the dye is fluorescent dye and black dye, wherein the fluorescent dye is pyrazoline and the like, and the black dye is carbon black (liquid or powder), pyridine complex, azo complex, aniline black, black talcum powder, cobalt chromium metal oxide, azine, phthalocyanine and the like.
Further, the present invention also provides a prepreg comprising the resin composition.
Preferably, the prepreg further includes a reinforcing material, and the resin composition is attached to a surface of the reinforcing material.
Preferably, the reinforcing material is selected from natural fibers, organic synthetic fibers, organic fabrics or inorganic fabrics, more preferably, the reinforcing material is glass fiber cloth, and the glass fiber cloth is preferably open fiber cloth or flat cloth; and the glass fiber cloth is preferably chemically treated with a coupling agent such as epoxy silane or amino silane to provide good water resistance and heat resistance, improving the bonding between the interface of the resin composition and the glass fiber cloth.
The preparation method of the prepreg comprises the following steps: and (2) dipping the reinforcing material in the glue solution of the resin composition, then baking the dipped reinforcing material for 1-10min at the temperature of 100-200 ℃, and drying to obtain the prepreg.
Further, the present invention also provides an insulating film comprising an insulating resin layer composed of the resin composition.
Preferably, the insulation film further includes a carrier film, and the insulation resin layer is attached to a surface of the carrier film through a coating process.
Preferably, the carrier film is selected from polyethylene terephthalate film, release film, copper foil or aluminum foil, preferably polyethylene terephthalate film.
Preferably, the insulation film further comprises a protective film layer attached to a side of the insulation resin layer facing away from the carrier film and covering the insulation resin layer. Preferably, the materials of the protective film layer and the carrier film are the same, although not limited thereto.
The preparation method of the insulating film comprises the following steps: adding the resin composition into a solvent to be dissolved to prepare a glue solution of the resin composition; coating the glue solution of the resin composition on the carrier film; and then heating and drying the carrier film, and then forming the insulating resin layer by the glue solution of the resin composition to obtain the insulating film.
Preferably, the solvent is one or more selected from acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether and propylene glycol methyl ether.
Preferably, in the step of "drying the carrier film by heating", the drying condition is baking at 100-.
Furthermore, the invention also provides a laminated board, in particular a metal foil-clad laminated board, which comprises the prepreg and a metal foil attached to the surface of the prepreg.
Preferably, the number of the prepregs in the laminate can be selected according to the thickness requirement of the laminate, for example, one or more prepregs can be selected; preferably, the metal foil may be a copper foil, an aluminum foil or other metal material, and the thickness thereof may preferably be, for example, 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.
The preparation method of the laminated board comprises the following steps: and coating a metal foil on one surface or two surfaces of one prepreg, or coating a metal foil on one surface or two surfaces of a prepreg laminated body formed by laminating at least two prepregs, and forming the laminated plate by hot pressing.
Wherein the hot pressing conditions are as follows: pressing for 2-4 hours under the pressure of 0.2-5 MPa and the temperature of 180-250 ℃.
Furthermore, the invention also provides a printed circuit board, which comprises the insulating film or the prepreg; that is, the printed circuit board includes an insulating film or a prepreg, and the insulating film or the prepreg includes the resin composition.
Compared with the prior art, the invention has the following beneficial effects: the active ester resin is synthesized by taking the bisphenol-based end-capped silicone oil compound as a raw material, and comprises the structure (1), so that secondary hydroxyl is not generated in the curing process of the active ester group, the dielectric constant and the dielectric loss of a cured product can be effectively reduced, and the main chain of the molecule of the silicone oil compound contains extremely flexible silicon-oxygen bonds, so that the cured product can have the advantages of low stress, high toughness, low water absorption, difficult combustion and the like, and the active ester resin has excellent dielectric property and is unexpectedly and remarkably improved in the aspects of toughness, thermal expansion coefficient, flame retardance and the like compared with the existing active ester resin; the thermosetting resin composition further prepared based on the active ester resin has excellent dielectric property, toughness, combustibility and low water absorption rate, and simultaneously, the prepreg, the insulating film and the laminated board obtained from the thermosetting resin composition have lower XY axis thermal expansion coefficients, can be applied to the fields of IC packaging and high speed and high frequency, and have wide application prospects.
The present invention will be described in detail with reference to specific examples; and the present invention is not limited to these examples.
Synthesis example 1
In a flask in nitrogen atmosphere, 39.5 parts by weight of naphthalene ring phenolic resin, 12.5 parts by weight of bisphenol-terminated silicone oil compound (specifically, X-22-1821 product of shin-Etsu chemical Co., Ltd.), 15 parts by weight of 1-naphthol and 150 parts by weight of toluene are added, and the mixture is uniformly stirred and dissolved to form a mixed solution;
then, 32.5 parts by weight of isophthaloyl dichloride was added to the mixed solution in the flask, and further stirred to dissolve it;
controlling the temperature of the system below 60 ℃, and dropwise adding 45g of 20% sodium hydroxide aqueous solution within 3 hours;
after the dropwise addition of the sodium hydroxide aqueous solution is finished, the state is maintained, and the stirring is continued for 1 hour to ensure that the reaction is full;
thereafter, the mixture obtained by the reaction was allowed to stand, separated and the water layer was removed, and this operation was repeated (that is, the operation was repeated: the mixture obtained by the reaction was allowed to stand, separated and the water layer was removed) until the pH of the water layer became 7, followed by distillation under heating and reduced pressure to remove toluene and the like, to obtain an active ester resin comprising the structure (1) described in the present invention, the ester equivalent being 240 g/mol.
Synthesis example 2
In a flask, 31.5 parts by weight of a naphthalene ring phenol resin, 30 parts by weight of a bisphenol-terminated silicone oil compound (specifically, a product X-22-1821 from shin-Etsu chemical Co., Ltd.), 12 parts by weight of 1-naphthol, and 150 parts by weight of toluene were charged, and the mixture was dissolved while replacing the system with nitrogen under reduced pressure;
then, 26.5 parts by weight of isophthaloyl dichloride was added to the mixed solution in the flask and dissolved while replacing the inside of the system with nitrogen under reduced pressure;
while purging with nitrogen gas, the temperature in the system was controlled to 60 ℃ or lower, and 40g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours;
after the dropwise addition of the sodium hydroxide aqueous solution is finished, the state is maintained, and the stirring is continued for 1 hour to ensure that the reaction is full;
thereafter, the mixture obtained by the reaction was allowed to stand, separated and the water layer was removed, and this operation was repeated (that is, the operation was repeated: the mixture obtained by the reaction was allowed to stand, separated and the water layer was removed) until the pH of the water layer became 7, followed by distillation under heating and reduced pressure to remove toluene and the like, to obtain an active ester resin comprising the structure (1) described in the present invention, having an equivalent weight of 290 g/mol.
Synthesis example 3
In the same manner as in Synthesis example 2 except that the naphthalene ring phenol resin in Synthesis example 2 was replaced with a diphenol aldehyde compound, an active ester resin comprising the structure (1) described in the present invention and having an ester equivalent of 300g/mol was prepared.
Synthesis example 4
A flask was charged with 45 parts by weight of a naphthalene ring phenol resin, 17 parts by weight of 1-naphthol, and 150 parts by weight of toluene, and the mixture was dissolved while replacing the system with nitrogen under reduced pressure to obtain a mixed solution;
then, 38 parts by weight of isophthaloyl dichloride was added to the mixed solution in the flask and the inside of the system was dissolved while being replaced with nitrogen under reduced pressure;
while purging with nitrogen gas, 50g of a 20% aqueous solution of sodium hydroxide was added dropwise over 3 hours while controlling the temperature in the system to 60 ℃ or lower;
after the dropwise addition of the sodium hydroxide aqueous solution is finished, the state is maintained, and the stirring is continued for 1 hour to ensure that the reaction is full;
thereafter, the mixture obtained by the reaction was allowed to stand, separated and the water layer was removed, and this operation was repeated (that is, the operation was repeated: the mixture obtained by the reaction was allowed to stand, separated and the water layer was removed) until the pH of the water layer became 7, followed by distillation under heating and reduced pressure to remove toluene and the like, to obtain an active ester resin comprising the structure (1) described in the present invention, having an ester equivalent of 210 g/mol.
Example 1
Dissolving 50 parts by weight of the active ester resin obtained in synthesis example 1, 50 parts by weight of naphthalene ring epoxy resin, 0.5 part by weight of dimethylaminopyridine and 10 parts by weight of bis-DOPO ethane in a proper amount of butanone, and uniformly stirring and mixing to obtain a glue solution with a solid content of about 65%;
dipping the obtained glue solution by 2116E glass fiber cloth, and drying in a drying oven at 160 ℃ for 5min to obtain a prepreg;
and (3) orderly stacking 4 prepregs to form a laminated body, stacking 12-micron low-profile electrolytic copper foils on the upper side and the lower side of the laminated body respectively, and then placing the laminated body in a vacuum hot press to press for 1.5 hours at the pressure of 2.5Mpa and the temperature of 220 ℃ to obtain the copper-clad laminated plate.
Example 2
Dissolving 40 parts by weight of the active ester resin obtained in synthesis example 1, 40 parts by weight of the diphenol aldehyde epoxy resin, 20 parts by weight of bismaleimide, 0.2 part by weight of 2E4MZ 0.2, 150 parts by weight of spherical silica powder and 10 parts by weight of allylated cyclophosphazene resin in a proper amount of butanone, and uniformly stirring and mixing to obtain a glue solution with a solid content of about 70%;
the prepreg and the copper clad laminate were prepared in the same manner as in example 1.
Example 3
Dissolving 50 parts by weight of the active ester resin obtained in the synthetic example 2, 50 parts by weight of naphthalene ring epoxy resin, 0.5 part by weight of dimethylaminopyridine and 10 parts by weight of bis-DOPO ethane in a proper amount of butanone, and uniformly stirring and mixing to obtain a glue solution with a solid content of about 65%;
the prepreg and the copper clad laminate were prepared in the same manner as in example 1.
Example 4
Dissolving 35 parts by weight of the active ester resin obtained in synthetic example 2, 35 parts by weight of the diphenol epoxy resin, 30 parts by weight of bisphenol A cyanate ester, 0.5 part by weight of 2E4MZ 0.5, 0.02 part by weight of zinc naphthenate (8% zn), 150 parts by weight of spherical silica micropowder and 10 parts by weight of bis-DOPO ethane with a proper amount of butanone, and uniformly stirring and mixing to obtain a glue solution with a solid content of about 70%;
the prepreg and the copper clad laminate were prepared in the same manner as in example 1.
Example 5
Dissolving 35 parts by weight of the active ester resin obtained in the synthetic example 2, 35 parts by weight of naphthalene ring epoxy resin, 30 parts by weight of diaminodiphenyl ether type benzoxazine resin, 0.2 part by weight of 2E4MZ 0.2, 150 parts by weight of spherical silica micropowder and 10 parts by weight of bis-DOPO ethane by using a proper amount of butanone, and uniformly stirring and mixing to obtain a glue solution with the solid content of about 70%;
the prepreg and the copper clad laminate were prepared in the same manner as in example 1.
Example 6
Dissolving 50 parts by weight of the active ester resin obtained in synthesis example 1, 30 parts by weight of naphthalene ring epoxy resin, 20 parts by weight of epoxidized polybutadiene resin, 0.5 part by weight of dimethylaminopyridine and 10 parts by weight of bis-DOPO ethane in a proper amount of butanone, and uniformly stirring and mixing to obtain a glue solution with a solid content of about 65%;
the prepreg and the copper clad laminate were prepared in the same manner as in example 1.
Example 7
Dissolving 35 parts by weight of the active ester resin obtained in synthesis example 3, 35 parts by weight of a diphenol aldehyde epoxy resin, 30 parts by weight of bisphenol a cyanate ester, 0.5 part by weight of 2E4MZ 0.5, 0.02 part by weight of zinc naphthenate (8% zn), 150 parts by weight of spherical silica powder and 10 parts by weight of bis-DOPO ethane in a proper amount of butanone, and uniformly stirring and mixing to obtain a glue solution with a solid content of about 70%;
the prepreg and the copper clad laminate were prepared in the same manner as in example 1.
Comparative example 1
Dissolving 50 parts by weight of the active ester resin obtained in the synthesis example 4, 50 parts by weight of naphthalene ring epoxy resin, 0.5 part by weight of dimethylaminopyridine and 10 parts by weight of bis-DOPO ethane in a proper amount of butanone, and uniformly stirring and mixing to obtain a glue solution with a solid content of about 65%;
the prepreg and the copper clad laminate were prepared in the same manner as in example 1.
Comparative example 2
Dissolving 50 parts by weight of the active ester resin obtained in synthetic example 4, 50 parts by weight of naphthalene ring epoxy resin, 0.5 part by weight of dimethylaminopyridine, 10 parts by weight of bis-DOPO ethane and 250 parts by weight of spherical silica micropowder with a proper amount of butanone, and uniformly stirring and mixing to obtain a glue solution with a solid content of about 65%;
the prepreg and the copper clad laminate were prepared in the same manner as in example 1.
The properties of the copper-clad laminates obtained in each of examples 1 to 7, comparative example 1 and comparative example 2 above are shown in table 1.
[ TABLE 1 ]
Figure BDA0002477972320000181
Table 1 notes:
1) the glass transition temperature adopts DMA, the heating rate is 10 ℃/min, and the frequency is 10 Hz;
2) PCT 5hrs water absorption: taking 3 samples of 10cm × 10cm, 0.40mm in thickness and with metal foils removed on both sides, drying at 100 ℃ for 2 hours, weighing, wherein the weight is recorded as W1, then processing in a Pressure Cooker cooking test (Pressure Cooker test) machine at 121 ℃ and 2 atmospheric pressures for 5 hours, weighing, wherein the weight is recorded as W2, and the water absorption rate is (W2-W1)/W1 is 100%;
3) x-axis CTE: adopting TMA (three-dimensional model), raising the temperature rate, and testing the temperature range to be 30-100 ℃;
4) and (3) impact toughness testing: using 5512 impact instrument, the height of falling weight of the impact instrument is 45cm, and the weight of falling weight is 1 kg;
evaluation of toughness: the cross is clear and fine, which shows that the product has good toughness; in contrast, a fuzzy or no cross indicates a poor toughness of the product; is indicated by: |.
5) Dielectric constant: the dielectric constant and dielectric loss were measured at 10GHz using a Keysight network analyzer.
As can be seen from table 1: comparative example 1 shows insufficient thermal expansion coefficient, water absorption, flame retardancy and toughness as compared with examples 1 and 3, and even though comparative example 2 uses a large amount of filler for reducing the thermal expansion coefficient, the degree of reduction of the thermal expansion coefficient is limited, and rather toughness and dielectric constant are greatly deteriorated; in contrast, examples 1 and 3 significantly improved these deficiencies, while maintaining excellent dielectric properties, and had excellent thermal expansion coefficient, water absorption, flame retardancy, and toughness.
In conclusion, the active ester resin and the thermosetting resin composition with the active ester resin have excellent dielectric property, thermal expansion coefficient, toughness, combustibility and low water absorption rate, so that the prepreg, the insulating film, the laminated board and the printed circuit board containing the thermosetting resin composition have excellent dielectric property, toughness, combustibility and low water absorption rate, and simultaneously have excellent characteristics of lower XY axis thermal expansion coefficient and the like.
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 list of details is only for the concrete description of the feasible embodiments of the present application, they are not intended to limit the scope of the present application, and all equivalent embodiments or modifications that do not depart from the technical spirit of the present application are intended to be included within the scope of the present application.

Claims (9)

1. A thermosetting resin composition, comprising 20 to 80 parts by weight of an epoxy resin and 20 to 80 parts by weight of an active ester resin, wherein the active ester resin comprises a structure (1):
Figure FDA0003320880680000011
wherein R is an alkylene group or arylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 20.
2. The thermosetting resin composition according to claim 1, wherein the epoxy resin is selected from one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus epoxy resin, nitrogen epoxy resin, o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl novolac epoxy resin, alicyclic epoxy resin, epoxidized polybutadiene resin, glycidyl amine epoxy resin, glycidyl ether epoxy resin, and glycidyl ester epoxy resin;
the general structural formula of the naphthalene ring type epoxy resin is a structure (3):
Figure FDA0003320880680000012
wherein p is an integer from 1 to 10;
the general structural formula of the biphenyl epoxy resin is structure (4):
Figure FDA0003320880680000021
wherein n is an integer of 1 to 10;
the general structural formula of the dicyclopentadiene epoxy resin is a structure (5):
Figure FDA0003320880680000022
wherein m is an integer of 1 to 10.
3. The thermosetting resin composition as claimed in claim 1, further comprising 1 to 50 parts by weight of a cyanate ester resin or 1 to 50 parts by weight of a polyphenylene ether resin or 1 to 50 parts by weight of a benzoxazine resin or 1 to 50 parts by weight of a hydrocarbon resin;
the epoxy resin composition comprises 30-70 parts by weight of the epoxy resin and 30-70 parts by weight of the active ester resin;
further comprising one or more of an amine compound, an amide compound, an acid anhydride compound, a phenol compound, and an active ester compound not containing the structure (1), in a total amount of 0 to 60 parts by weight;
the active ester compound without structure (1) has structure (6):
Figure FDA0003320880680000023
wherein, X is phenyl or naphthyl; j is 0 or 1; k is 0 or 1; n is 0.25 to 1.25.
4. A prepreg comprising the thermosetting resin composition according to any one of claims 1 to 3.
5. The prepreg according to claim 4, further comprising a reinforcing material, wherein the resin composition is adhered to a surface of the reinforcing material;
the reinforcing material is selected from natural fibers, organic synthetic fibers, organic fabrics or inorganic fabrics.
6. An insulation film comprising an insulation resin layer composed of the thermosetting resin composition according to any one of claims 1 to 3.
7. The insulation film according to claim 6, further comprising a carrier film, the insulation resin layer being adhered to a surface of the carrier film;
the carrier film is selected from polyethylene terephthalate film, release film, copper foil or aluminum foil;
the carrier film is characterized by further comprising a protective film layer, wherein the protective film layer is attached to one side, away from the carrier film, of the insulating resin layer and covers the insulating resin layer.
8. A laminate comprising the prepreg according to claim 4 and a metal foil attached to a surface of the prepreg.
9. A printed circuit board comprising an insulating film or a prepreg comprising the thermosetting resin composition according to any one of claims 1 to 3.
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