CN111961312B - Resin composition, prepreg, insulating film, metal foil-clad laminate, and printed wiring board each comprising the same - Google Patents

Resin composition, prepreg, insulating film, metal foil-clad laminate, and printed wiring board each comprising the same Download PDF

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CN111961312B
CN111961312B CN201910417976.1A CN201910417976A CN111961312B CN 111961312 B CN111961312 B CN 111961312B CN 201910417976 A CN201910417976 A CN 201910417976A CN 111961312 B CN111961312 B CN 111961312B
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epoxy resin
parts
weight
resin composition
resin
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CN111961312A (en
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崔春梅
杨宋
黄荣辉
陈诚
肖升高
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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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • 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
    • 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
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • 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
    • B32B2307/30—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
    • B32B2307/70—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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Epoxy Resins (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention provides a resin composition which has higher glass transition temperature, high peel strength, low coarsening degree, low dielectric loss, high heat resistance, low water absorption and good dielectric property compared with the existing resin composition; the invention also provides a prepreg, an insulating film, a metal foil-clad laminate and a printed wiring board prepared by using the resin composition.

Description

Resin composition, prepreg, insulating film, metal foil-clad laminate, and printed wiring board each comprising the same
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a resin composition with high cohesiveness, low coarsening degree, high heat resistance, low water absorption and good dielectric property, and a prepreg, an insulating film, a metal foil-clad laminated board and a printed circuit board with the resin composition.
Background
In recent years, the market for printed circuit boards has focused on shifting from computers to communications, particularly to smart phones and tablet mobile terminals. Therefore, the HDI board for mobile terminals is a major point of PCB growth. Mobile terminals, represented by smartphones, drive HDI boards to be higher density and lighter. It is reported in the literature that the line width/line spacing L/S (Line and Space) of a PCB is required to be 10/10 μm or less in the future, and therefore, the Ra value (roughness average) of the laminated insulating layer is required to be 300nm or less, and the adhesiveness is required to be 0.6kgf/cm or more. In addition, flip chips (Flip chips) are becoming the mainstream of future packaging in the packaging technology field, and thus lower coarsening degree and higher adhesion/peeling strength are required for the laminated insulating layer in the Flip chip packaging substrate, and an insulating material excellent in comprehensive performance is satisfied.
In the prior art JP2010090238 a resin composition is disclosed wherein the problems of low coarsening and high adhesion are solved with an active ester and a triazine structural phenolic resin in an epoxy resin system. The active ester curing agent does not generate polar hydroxyl when reacting with the epoxy resin, and the high symmetry of the triazine structure in the phenolic resin further reduces the coarsening degree, and the phenolic resin containing the polar hydroxyl is matched to improve the peeling strength.
Furthermore, JP2017019970 discloses a resin composition in which the problems of low coarsening and high adhesion are solved by using a triazine-hydroxyl-containing active ester compound in an epoxy resin system.
However, the hydroxyl groups contained in these compounds affect properties such as water absorption of the final cured product.
In view of the above, there is a need to provide a novel resin composition, and a prepreg, an insulating film, a metal foil-clad laminate, and a printed wiring board having the same to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to provide a resin composition with high cohesiveness, low coarsening degree, high heat resistance, low water absorption and good dielectric property, and a prepreg, an insulating film, a metal foil-clad laminate and a printed wiring board prepared by using the resin composition.
The terms "comprising", "containing" and "containing" in this specification mean that other components may be contained in addition to the components, and these other components are capable of imparting different properties to the resin composition.
In order to achieve the aim of the invention, the invention adopts the following technical scheme: a resin composition comprises 100 parts by weight of epoxy resin, 1-100 parts by weight of curing agent and 0.001-5 parts by weight of curing accelerator; the curing agent at least comprises an active ester compound shown as a structural formula (1):
wherein R is 1 Represents hydrogen or C1-C5 alkyl, A is a group containing at least two benzene ring groups, such as one of the following groups:
wherein R is 10 、R 11 、R 12 、R 13 Selected from hydrogen, C1-C5 alkyl, or C6-C10 aryl or aralkyl, respectively.
The active ester compound shown in the structural formula (1) in the curing agent is an active ester compound containing two reactive groups, wherein the active ester group does not generate hydroxyl with stronger polarity when reacting with the epoxy resin, so that the curing agent has excellent dielectric property and low coarsening degree after reaction, and meanwhile, the aromatic amino at the tail end reacts with the epoxy resin to obtain an insulating layer with high cohesiveness, so that the two opposite properties of low coarsening degree and high peel strength are solved; in addition, the active ester group and the aromatic amino group in the active ester compound shown in the structural formula (1) are subjected to curing reaction with the epoxy resin, so that the crosslinking density of a cured product can be effectively improved, and more excellent heat resistance, low water absorption and high rigidity can be obtained.
Preferably, said R 1 May be hydrogen, methyl, ethyl, propyl or tert-butyl, more preferably, R 1 May be hydrogen or methyl.
Preferably, R10, R11, R12, R13 are each independently selected from hydrogen, methyl, ethyl, propyl or tert-butyl, or phenyl, biphenyl or naphthyl, more preferably hydrogen, methyl or phenyl.
Preferably, a in the active ester compound represented by the structural formula (1) contains dicyclopentadienyl, naphthyl or tricyclopentadienyl.
For example, at said R 1 When hydrogen and A are dicyclopentadienyl, the active ester compound shown in the structural formula (1) is dicyclopentadiene active ester, and the structural formula is shown as follows:
the preparation method of the active ester compound shown in the structural formula (1) comprises the following steps: the active ester compound is obtained by subjecting an aromatic phenol resin and p-aminobenzoic acid (PABA) or a halogen compound thereof (p-aminobenzoyl halide compound) to an esterification reaction. The following takes the preparation of dicyclopentadiene active ester as an example, and the reaction mechanism is as follows:
alternatively, it is prepared by the following method: firstly, reacting aromatic phenol resin with p-nitrobenzoic acid or halide thereof, and then carrying out reduction reaction on terminal nitro to obtain the active ester compound. The first step:
and a second step of:
of course, it is not limited thereto, and other methods may be used to prepare the active ester compound represented by the structural formula (1), i.e., all methods capable of preparing the active ester compound represented by the structural formula (1) are within the scope of the present invention.
As a further improvement of the present invention, the content of the active ester compound represented by the structural formula (1) in the curing agent is 1 to 100 parts by weight per 100 parts by weight of the epoxy resin. More preferably 5 to 50 parts by weight; for example, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, 40 parts by weight, 41 parts by weight, 42 parts by weight, 43 parts by weight, 44 parts by weight, 45 parts by weight, 46 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 or 100 parts, and specific point values between the above values, the present invention is not intended to be exhaustive of the specific values within the range, given the space and for brevity.
As a further improvement of the present invention, the curing agent further contains at least one of an amine compound, an amide compound, an acid anhydride compound, a phenol compound, and an active ester compound different from the structural formula (1). The content thereof is 0 to 99 parts by weight, preferably 5 to 60 parts by weight, for example, 0 part by weight, 5 parts by weight, 10 parts by weight, 25 parts by weight, 35 parts by weight, 60 parts by weight, 70 parts by weight, 85 parts by weight, 99 parts by weight, and specific point values between the above-mentioned values, based on 100 parts by weight of the total amount of the curing agent, are limited in terms of space and for brevity, and the present invention is not exhaustive to list the specific point values included in the range.
Specifically, the amine-based compound may be diaminodiphenylmethane, diaminodiphenyl sulfone, diethylenetriamine, dicarboxyphthalimide, imidazole, or the like, preferably diaminodiphenylmethane and diaminodiphenyl sulfone; the amide compound may be dicyandiamide, low molecular polyamide, or the like, and is preferably dicyandiamide; the acid anhydride compound may be phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, nadic anhydride, or the like, and is preferably styrene-maleic anhydride; the phenolic compound may be 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, trimethylol methane resin, etc.; the active ester compound different from the structural formula (1) can be selected from compounds shown in the structural formula (2):
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.
Of course, it is not limited thereto, and it is understood that other active ester compounds may be selected as well, other than the active ester compound of the structural formula (1).
As a further improvement of the present invention, the epoxy resin further comprises 0 to 200 parts by weight of a filler per 100 parts by weight, and it is understood that the filler may be contained or not contained in the resin composition.
When the filler is contained in the resin composition, the filler content is preferably 10 to 100 parts by weight, more preferably 30 to 70 parts by weight, for example 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, 150 parts by weight, 160 parts by weight, 170 parts by weight, 180 parts by weight, 190 parts by weight, or 200 parts by weight, based on 100 parts by weight of the epoxy resin; and the particular values of points between the values recited above, are limited in space and are for brevity and the invention is not intended to provide an exhaustive list of the particular values of points within the range.
Specifically, 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 oxides, metal nitrides, non-metal nitrides, inorganic hydrates, inorganic salts, metal hydrates or inorganic phosphorus; the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
More preferably, when the filler is an inorganic filler, at least one selected from the group consisting of 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 is used.
Preferably, the filler is silica, more preferably, surface treated silica.
Preferably, the filler has a median particle size of 1 to 15 μm, for example 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, and specific point values between the above values, limited in space and for brevity, the invention is not intended to be exhaustive of the specific point values comprised in the range.
More preferably, the filler has a median particle size of 1 to 10 μm.
Specifically, the surface treatment agent is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent.
As a further improvement of the present invention, the epoxy resin is selected from one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, phosphorus containing epoxy resin, nitrogen containing epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol a phenol formaldehyde epoxy resin, cresol formaldehyde epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, aralkyl novolac epoxy resin, alicyclic type epoxy resin, glycidylamine type epoxy resin, glycidylether type epoxy resin, glycidylester type epoxy resin.
More preferably, the epoxy resin may be naphthalene ring type epoxy resin having a structural formula shown in structural formula (3), biphenyl type epoxy resin having a structural formula shown in structural formula (4), or dicyclopentadiene type epoxy resin having a structural formula shown in structural formula (5):
in the present invention, the curing accelerator is at least one selected from the group consisting of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, and zinc isooctanoate, for example: a mixture of 4-dimethylaminopyridine and 2-methylimidazole, a mixture of 2-methylimidazole and 2-methyl 4-ethylimidazole, a mixture of 2-phenylimidazole and zinc isooctanoate, and a mixture of 2-methylimidazole, 2-methyl 4-ethylimidazole and 2-phenylimidazole, although not limited thereto.
The curing accelerator is contained in an amount of 0.001 to 5 parts by weight, for example, 0.001 part by weight, 0.01 part by weight, 1 part by weight, 2.5 parts by weight, 5 parts by weight, and specific point values between the above values, based on 100 parts by weight of the epoxy resin, are limited in space and for brevity, and the present invention is not exhaustive of the specific point values included in the range.
More preferably, the curing accelerator is contained in an amount of 0.01 to 1 part by weight.
Further, a phenol resin or a cyanate resin or a combination thereof is also added to the resin composition.
Preferably, in order to control the surface roughening degree of the insulating layer, the phenoxy resin is selected from a phenoxy resin represented by structural formula (6), an alicyclic modified phenoxy resin, or other modified phenoxy resin, and the alicyclic is a cyclopentadienyl group, a tricyclopentadienyl group, or a terpene group. Such as a phosphorus-containing phenoxy resin or a fluorenyl phenoxy resin, etc.
Wherein R is 20 、R 21 Respectively one of-H, -OH or epoxy groups, and the molecular weight is 1.5-10 ten thousand.
Further, the content of the phenol-oxygen resin is 1 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the epoxy resin, for the sake of brevity and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
Further, the cyanate resin is selected from one or more of bisphenol A type cyanate, bisphenol F type cyanate, dicyclopentadiene type cyanate, phenolic type cyanate, tetramethyl bisphenol F type cyanate, bisphenol M type cyanate, bisphenol E type cyanate, phosphorus-containing cyanate and prepolymer of the cyanate, so as to improve the dielectric property of the cured product.
Further, the cyanate ester resin is contained in an amount of 1 to 50 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the epoxy resin, for the sake of brevity and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
In a preferred resin composition of the present invention, it specifically comprises the following components: 100 parts of epoxy resin, 20-60 parts of active ester compound shown in structural formula (1), 1-30 parts of other components except the active ester compound shown in structural formula (1) in the curing agent, 1-30 parts of phenol-oxygen resin, 0-200 parts of filler and 0.001-5 parts of curing accelerator.
In another preferred resin composition of the present invention, it specifically comprises the following components: 100 parts of epoxy resin, 20-60 parts of active ester compound shown in structural formula (1), 1-30 parts of other components except the active ester compound shown in structural formula (1) in a curing agent, and cyanate: 5-20 parts of filler, 0-200 parts of curing accelerator and 0.001-5 parts of curing accelerator.
Of course, and without limitation, it is understood that the components and amounts thereof in the resin composition may be modified according to specific requirements.
It is understood that the components other than the active ester compound represented by the structural formula (1) in the curing agent specifically means: the amine compound, amide compound, acid anhydride compound, phenol compound and other active ester compound shown in the non-structure (1) contained in the curing agent.
According to the present invention, the resin composition further includes a flame retardant to improve the flame retardancy of the finally formed cured product, which can be understood as a prepreg, an insulating film, a metal foil-clad laminate, a printed wiring board, and the like.
Further, the content of the flame retardant is 1 to 80 parts by weight, for example, 1 part by weight, 5 parts by weight, 10 parts by weight, 20 parts by weight, 50 parts by weight, 70 parts by weight, 80 parts by weight, and specific point values between the above values, based on 100 parts by weight of the epoxy resin, is limited in space and for brevity, and the present invention is not exhaustive of the specific point values included in the range.
Preferably, the content of the flame retardant is 5 to 50 parts by weight.
Specifically, the flame retardant may be a brominated flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an organometallic salt flame retardant, an inorganic flame retardant, or the like. Wherein the brominated flame retardant can be decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalic acid amide. The phosphorus flame retardant may be an organic phosphorus-containing compound such as inorganic phosphorus, a phosphate compound, a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2, 6-dimethylphenyl) phosphine, phosphazene, or the like. The nitrogen-based flame retardant may be a triazine compound, cyanuric acid compound, isocyanic acid compound, phenothiazine, or the like. The silicone flame retardant may be silicone oil, silicone rubber, silicone resin, or the like. The organometallic flame retardant may be ferrocene, acetylacetonate metal complex, organometallic carbonyl compound, or the like. The inorganic flame retardant may be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, or the like.
Of course, the type of the flame retardant is not limited thereto, and it is understood that the added flame retardant may be selected according to the specific application field of the laminate, for example, an application field requiring halogen, and preferably a non-halogen flame retardant such as a phosphorus-containing or nitrogen-containing flame retardant.
Preferably, when the phosphorus-containing flame retardant is selected, the phosphorus-containing flame retardant can form nitrogen-phosphorus synergistic flame retardance with nitrogen elements of the active ester compound in the curing agent, so that the flame retardance efficiency is improved.
The preparation method of the resin composition provided by the invention is a conventional technical means in the field, and specifically comprises the following steps: taking a container, firstly placing solid components into the container, then adding liquid organic solvent, stirring until the solid components are completely dissolved, then adding liquid resin, filler and curing accelerator, continuously stirring uniformly, and finally regulating the solid content of the liquid to 50-80% by using the solvent to prepare the glue solution, wherein the solid content is calculated by weight.
The organic solvent and the solvent in the present invention are not particularly limited. For example, the organic solvent may be one or a combination of several selected from acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene and cyclohexane.
The amount of the solvent to be added is selected by a person skilled in the art according to his own experience, as long as the resulting dope can be brought to a viscosity suitable for use.
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.
Wherein the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric, and the inorganic fabric is preferably glass fiber cloth, and the glass fiber cloth is preferably open cloth or flat 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 coupling agent treatment. The coupling agent used is preferably epoxy silane or amino silane or the like to provide good water resistance and heat resistance.
The preparation method of the prepreg comprises the following steps: and (3) dipping the reinforcing material in the resin composition glue solution, then baking the dipped reinforcing material for 1-10min at 50-170 ℃ and drying to obtain the prepreg.
In order to achieve the above object, the present invention also provides an insulating film comprising a carrier film, the above resin composition coated on the surface of the carrier film.
The preparation method of the insulating film comprises the following steps: and adding the resin composition into a solvent, dissolving to prepare a glue solution, coating the glue solution on a carrier film, heating and drying the carrier film coated with the glue solution, and forming an insulating resin layer by the glue solution to obtain the insulating film.
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.
The carrier film may be a polyethylene terephthalate (PET) film, a release film, a copper foil, an aluminum foil, or the like, and the carrier film is preferably a PET film.
The above-mentioned heating and drying conditions are, but not limited to, baking at 50-170 ℃ for 1-10 minutes.
Further, a side of the insulating resin layer facing away from the carrier film is covered with a protective film to protect the insulating resin layer.
Specifically, the material of the protective film is the same as that of the carrier film, which is not limited to this.
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.
The metal foil-clad laminated board is formed by bonding one or two prepregs together by heating and pressurizing, and then bonding metal foil on one or two sides of the laminated board by heating and pressurizing.
The preparation steps of the metal foil-clad laminated board are as follows: 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 metal foil and the laminated board are pressed for 2 to 4 hours under the pressure of 0.2 to 2MPa and the temperature of 180 to 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.
In order to achieve the above object, the present invention also provides a printed wiring board comprising at least one of the above prepregs or at least one of the above insulating films.
The beneficial effects of the invention are as follows: the invention adopts the active ester compound shown in the structural formula (1) containing two reaction groups, wherein the active ester group does not generate hydroxyl with stronger polarity when reacting with epoxy resin, so that the insulating layer with excellent dielectric property and low coarsening degree is obtained, and the terminal aromatic amino group reacts with the epoxy resin to obtain the insulating layer with high cohesiveness, so that the two opposite performances of low coarsening degree and high peel strength are solved, and the insulating layer is better applied to a high multi-layer laminated circuit board.
Meanwhile, the active ester group and the aromatic amino group in the active ester compound shown in the structural formula (1) are subjected to curing reaction with the epoxy resin, so that the crosslinking density of a cured product is effectively improved, and more excellent heat resistance, low water absorption and high rigidity are obtained, and the prepreg and the insulating film can better meet the heat resistance and rigidity requirements of an organic packaging substrate and a coreless substrate.
In addition, experiments show that the resin composition has excellent low coarsening degree, high peeling strength, dielectric property, heat resistance and low water absorption rate after being cured.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments.
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.
Embodiments of the present invention will be further described below with reference to a number of examples. It is to be understood that the embodiments of the present invention are not limited to the following specific embodiments. The modification can be appropriately performed within the scope of the claims.
Synthesis example 1: synthesis of biscyclopentadienyl active ester compounds
Taking 1mol of dicyclopentadiene phenol resin and 2mol of para aminobenzoic acid (PABA), stirring and dissolving uniformly in a toluene solvent, introducing nitrogen at the temperature of 60 ℃, adding a tetrabutylammonium bromide catalyst, slowly dripping a 20% sodium hydroxide aqueous solution, reacting for 4 hours, and drying for 5 hours under the vacuum condition of 105 ℃ after the reaction is finished and washing for several times, thereby obtaining the dicyclopentadienyl active ester compound which is denoted as active ester A.
Synthesis example 2: synthesis of tricyclopentadienyl active ester Compounds
Taking 1mol of tricyclopentadienyl phenol resin and 2mol of p-aminobenzoic acid (PABA), stirring and dissolving uniformly in toluene solvent, simultaneously introducing nitrogen at the temperature of 60 ℃, adding tetrabutylammonium bromide catalyst, then slowly dripping sodium hydroxide aqueous solution with the concentration of 20%, reacting for 4 hours, washing for several times after the reaction is finished, and drying for 5 hours under the vacuum condition of 105 ℃ to obtain the tricyclopentadienyl active ester compound which is marked as active ester B.
Synthesis example 3: synthesis of naphthyl active ester compounds
Taking 1mol of naphthol resin and 2mol of p-aminobenzoic acid (PABA), stirring and dissolving uniformly in a toluene solvent, introducing nitrogen at the temperature of 60 ℃, adding a tetrabutylammonium bromide catalyst, slowly dripping a sodium hydroxide aqueous solution with the concentration of 20%, reacting for 4 hours, washing for several times after the reaction is finished, and drying for 5 hours under the vacuum condition of 105 ℃ to obtain the naphthyl active ester compound which is marked as active ester C.
Synthesis example 4: synthesis of dicyclopentadiene naphthyl active ester compounds
Taking 1mol of dicyclopentadiene naphthol resin and 2mol of para aminobenzoic acid (PABA), stirring and dissolving uniformly in a toluene solvent, introducing nitrogen at the temperature of 60 ℃, adding a tetrabutylammonium bromide catalyst, slowly dripping a 20% sodium hydroxide aqueous solution, reacting for 4 hours, washing for several times after the reaction is finished, and drying for 5 hours under the vacuum condition of 105 ℃ to obtain the dicyclopentadiene naphthyl active ester compound which is marked as active ester D.
Synthesis example 5: synthesis of monophenyl active ester compounds
Taking 1mol of p-hydroxyphenol and 2mol of p-aminobenzoic acid (PABA), stirring and dissolving uniformly in a toluene solvent, introducing nitrogen at the temperature of 60 ℃, adding a tetrabutylammonium bromide catalyst, slowly dripping a sodium hydroxide aqueous solution with the concentration of 20%, reacting for 4 hours, washing for several times after the reaction is finished, and drying for 5 hours under the vacuum condition of 105 ℃ to obtain the monophenyl active ester compound which is marked as active ester F.
Examples 1 to 9 and comparative examples 1 to 3, 4:
the components and contents of the resin compositions of examples 1 to 9 and comparative examples 1 to 3, 4 are shown in Table 1 below:
TABLE 1
The component information concerning examples 1 to 9 and comparative examples 1 to 4 is shown in the following Table 2: />
TABLE 2
The resin compositions of examples 1 to 9 and comparative examples 1, 3 and 4 were prepared by a conventional method, specifically: the epoxy resin, the active ester compounds A to D shown in the structural formula (1) obtained in Synthesis examples 1 to 4, the active ester compound E (active ester compound in the prior art) and the active ester compound F obtained in Synthesis example 5 were mixed with a curing agent (phenol resin, DDS), a phenol resin, a cyanate ester resin, a curing accelerator (imidazole), a filler (silica), a flame retardant and a proper amount of butanone solvent, respectively, according to the component contents in Table 1, and stirred and mixed uniformly to obtain a glue solution having a solid content of 65%, wherein the solid content is 65% by weight.
Prepregs were prepared using the prepared resin compositions of examples 1 to 9 and comparative examples 1, 3, and 4, and the preparation method thereof was as follows: e glass fiber cloth (7628) is soaked in the glue solution, and the soaked E glass fiber cloth is baked in a baking oven at 160 ℃ for 5min to prepare the prepreg.
The insulating films were prepared using the prepared resin compositions of examples 1 to 9 and comparative examples 1, 3, and 4, and the preparation method thereof was as follows: coating the glue solution on a PET carrier, and baking in a 160 ℃ oven for 5min to obtain the insulating film.
Sample laminates a, b were prepared for performance evaluation:
(1) Preparation of Metal foil clad laminate a
And (3) placing 18 mu m metal copper foil on the prepreg, and placing the prepreg in a vacuum hot press for hot pressing to obtain a metal foil-clad laminated board a.
Specifically, the hot pressing process is to press for 2 hours at a pressure of 1.5Mpa and a temperature of 220 ℃.
(2) Preparation of laminate b
And (3) taking a core plate, placing the insulating films prepared above on the upper surface and the lower surface of the core plate respectively, placing the core plate in a vacuum hot press for pressing, and stripping the PET carrier after pressing. The specific pressing process is to press for 2 hours at 220 ℃ under the pressure of 1.5 Mpa.
Then coarsening the surface insulating film layer by a potassium permanganate method, wherein the method comprises the following steps:
(1) Immersing the plate in the swelling liquid for 10min, and taking out; wherein the swelling liquid is diethylene glycol monobutyl ether solution;
(2) Immersing the taken-out plate in an oxidant solution for 20min, and taking out; wherein the oxidant is potassium permanganate solution;
(3) Immersing the taken-out plate in the neutralization solution for 10min, and taking out; wherein the neutralization solution is hydroxylamine sulfate aqueous solution;
(4) Drying at 80℃for 30min gave laminate b, which was tested for coarseness.
The properties of the metal foil-clad laminates a and b obtained by using the resin compositions of examples 1 to 9 and comparative examples 1 to 4, respectively, are shown in Table 3.
TABLE 3 Table 3
The test method of the performance is as follows:
(1) Glass transition temperature Tg (c): the measurement was performed according to the DSC method defined in IPC-TM-6502.4.25 by differential scanning calorimetry.
(2) Peel Strength (PS): the peel strength of the metallic capping layer was tested using laminate a according to the "post thermal stress" experimental conditions in the IPC-TM-650 method.
(3) Coarsening degree: the average roughness (Ra) value was calculated by testing 10 point values with laminate b using a non-contact surface roughness meter.
(4) Dielectric constant: the dielectric constant at 1GHz was measured using the plate method according to IPC-TM-650 2.5.5.9 using laminate a.
(5) Dielectric loss tangent: the dielectric loss factor at 1GHz was measured using the plate method according to IPC-TM-650 2.5.5.9 with laminate a.
(6) Tin immersion heat resistance: the laminate a was immersed in a solder of 288℃using a 50X 50mm copper-clad double-sided sample, and the time required for delamination and foaming of the sample was recorded, wherein Δ represents 30 minutes or more and doctor blade represents 30 minutes or less.
(7) Tin immersion heat resistance after moisture treatment: 3 substrate samples of 100X 100mm were kept in a pressure-cooker treatment apparatus at 121℃and 105KPa for 3 hours using a laminate a, and then immersed in a solder bath at 288℃for 2 minutes to observe whether or not the samples had delaminated and bubbling, wherein 3 samples were marked as 3/3 when delamination and bubbling did not occur in any of the 3 samples, 2 samples were marked as 2/3 when delamination and bubbling did not occur in any of the 1 samples, and 0 samples were marked as 0/3 when delamination and bubbling did not occur in any of the 1 samples.
(8) Water absorption rate: the laminate a was used and measured according to the standard method specified in IPC-TM-650, D23 ℃ C./24 h.
In combination with table 1 and table 3, it can be seen that the comparison:
comparing examples 1 to 4 with comparative example 1, it is clear that the resin composition containing the active ester compound represented by the structural formula (1) of the present invention has higher glass transition temperature, high peel strength and high heat resistance than the resin composition containing other active ester compounds of the prior art; comparing example 5 with comparative example 1, it is clear that the resin composition of the present invention has higher glass transition temperature, high peel strength, low dielectric constant, high heat resistance; further, as is clear from comparison of examples 1 to 9 with comparative example 1 using a general active ester compound and comparative example 3 using an aromatic amine curing agent, the resin composition of the present invention has higher heat resistance; in comparative example 4, in which monophenyl active ester was used again, the heat resistance was very poor, and in particular, the tin immersion heat resistance after the wet treatment was unsatisfactory.
From the above results, it is seen that in the present invention, by adding an active ester compound represented by the structural formula (1) to a curing agent for a resin composition, the resulting resin composition can be improved in peel strength of an insulating layer while satisfying a low roughening degree, and a cured product having high heat resistance and low water absorption can be obtained.
In summary, compared with a cured product formed by preparing a general resin composition, for example, a laminate formed by preparing a resin composition of the present invention has higher glass transition temperature, high peel strength, low coarsening, low dielectric loss, high heat resistance, low water absorption, and good dielectric properties.
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 (16)

1. A resin composition characterized in that: the resin composition comprises 100 parts by weight of epoxy resin, 1-100 parts by weight of curing agent and 0.001-5 parts by weight of curing accelerator; wherein the curing agent at least comprises an active ester compound shown in a structural formula (1):
structure (1)
Wherein R is 1 Represents hydrogen or C1-C5 alkyl, A is selected from one of the following groups:
、/>、/>、、/>、/>、、/>；
wherein R is 11 、R 12 Respectively selected from hydrogen, C 1 -C 5 Or C is an alkyl group of 6 -C 10 Aryl or aralkyl of (a).
2. The resin composition of claim 1, wherein: the content of the active ester compound shown as the structural formula (1) is 1-100 parts by weight based on 100 parts by weight of the epoxy resin.
3. The resin composition of claim 1, wherein: the curing agent further contains at least one of an amine compound, an amide compound, an acid anhydride compound, a phenol compound, and an active ester compound different from the structural formula (1).
4. The resin composition of claim 1, wherein: the epoxy resin composition further comprises 0 to 200 parts by weight of a filler per 100 parts by weight of the epoxy resin.
5. The resin composition of claim 4, wherein: the filler is an organic filler; the organic filler is at least one of polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
6. The resin composition of claim 4, wherein: the filler is an inorganic filler, and 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.
7. The resin composition of claim 4, wherein: the particle size median of the filler is 1-15 mu m.
8. The resin composition of claim 1, wherein: the epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, phosphorus-containing epoxy resin, nitrogen-containing epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol A phenolic epoxy resin, phenol phenolic epoxy resin, cresol phenolic epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, aralkyl type phenolic epoxy resin, alicyclic type epoxy resin, glycidylamine type epoxy resin, glycidylether type epoxy resin and glycidylester type epoxy resin.
9. The resin composition of claim 1, wherein: the curing accelerator is at least one selected from 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole and zinc isooctanoate.
10. The resin composition of claim 1, wherein: a phenol-oxygen resin or a cyanate resin is also added to the resin composition.
11. The resin composition of claim 10, wherein: the resin composition is also added with a phenol-oxygen resin, wherein the phenol-oxygen resin is selected from the phenol-oxygen resins shown in the following structural formula and alicyclic modified phenol-oxygen resins;
wherein R is 20 、R 21 Respectively one of-H, -OH or epoxy groups, and the molecular weight is 1.5-10 ten thousand.
12. The resin composition of claim 1, wherein: the resin composition further comprises a flame retardant, wherein the content of the flame retardant is 1-80 parts by weight based on 100 parts by weight of the epoxy resin.
13. A prepreg, characterized in that: the prepreg comprising a reinforcing material, the resin composition of any one of claims 1-12 attached to the surface of the reinforcing material.
14. An insulating film, characterized in that: the insulating film comprising a carrier film, the resin composition according to any one of claims 1 to 12 coated on the surface of the carrier film.
15. A metal foil-clad laminate characterized by: the metal foil-clad laminated board comprises at least one prepreg and a metal foil formed on at least one surface of the prepreg; the prepreg according to claim 13.
16. A printed wiring board, characterized in that: the printed wiring board comprises at least one prepreg according to claim 13 or at least one insulating film according to claim 14.
CN201910417976.1A 2019-05-20 2019-05-20 Resin composition, prepreg, insulating film, metal foil-clad laminate, and printed wiring board each comprising the same Active CN111961312B (en)

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