WO2020155291A1 - 一种热固性树脂组合物、包含其的预浸料以及覆金属箔层压板和印制电路板 - Google Patents

一种热固性树脂组合物、包含其的预浸料以及覆金属箔层压板和印制电路板 Download PDF

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Publication number
WO2020155291A1
WO2020155291A1 PCT/CN2019/077162 CN2019077162W WO2020155291A1 WO 2020155291 A1 WO2020155291 A1 WO 2020155291A1 CN 2019077162 W CN2019077162 W CN 2019077162W WO 2020155291 A1 WO2020155291 A1 WO 2020155291A1
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Prior art keywords
resin
resin composition
weight
parts
combination
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PCT/CN2019/077162
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English (en)
French (fr)
Inventor
陈振文
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广东生益科技股份有限公司
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Priority to JP2021537036A priority Critical patent/JP7232915B2/ja
Priority to EP19914093.0A priority patent/EP3919566A4/en
Priority to US17/417,901 priority patent/US11975507B2/en
Priority to KR1020217024539A priority patent/KR102561771B1/ko
Publication of WO2020155291A1 publication Critical patent/WO2020155291A1/zh

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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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/40—Pretreated particles
    • B32B2264/402—Pretreated particles with organic substances
    • B32B2264/4021—Pretreated particles with organic substances with silicon-containing compounds
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    • 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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    • 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
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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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • 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
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/718—Weight, e.g. weight per square meter
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • 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
    • C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2361/04, C08J2361/18, and C08J2361/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/06—Thermal details
    • H05K2201/068—Thermal details wherein the coefficient of thermal expansion is important
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates

Definitions

  • the invention belongs to the technical field of copper-clad laminates, and relates to a thermosetting resin composition, a prepreg containing the same, a metal-clad laminate and a printed circuit board.
  • CN104725781A discloses a resin composition and prepregs and laminates using it.
  • the resin composition includes 15-55% of amine modified bismaleimide (BMI), 10-45% of benzoxazine resin and 0-75% of epoxy resin according to the weight percentage of each component. %, although the dielectric properties and temperature resistance of the copper clad laminate are improved, there is still much room for improvement in the T g , dielectric constant, and dielectric loss of the composition.
  • CN104845363 discloses a halogen-free resin composition and its use.
  • the halogen-free resin composition comprises (A) 40-80 parts by weight of an allyl-modified benzoxazine resin based on the weight of organic solids; (B) ) 10-20 parts by weight of hydrocarbon resin; (C) 10-40 parts by weight of allyl-modified polyphenylene ether resin; (D) 10-20 parts by weight of allyl-modified bismaleimide resin; (E) 0.01-3 parts by weight of initiator; (F) 10-100 parts by weight of filler and (G) 0-80 parts by weight of phosphorus-containing flame retardant.
  • the laminate finally obtained by this invention has lower Dk and Df, And good flame retardant effect, but because some components need to be self-made, the cost is high and the preparation method is complicated; and the glass transition temperature T g and CTE of the finally obtained laminate still has room for further improvement.
  • CN107459650A discloses a modified bismaleimide resin prepolymer and its preparation method. It adopts a melting process and uses allyl compounds, aminophenylacetylene, and benzoxazine to copolymerize bismaleimide. Chain toughening modification, the obtained modified bismaleimide resin prepolymer has high heat resistance, but the dielectric properties and dielectric loss properties of the material are not considered in the modification process.
  • the object of the present invention is to provide a thermosetting resin composition, a prepreg containing the same, a metal-clad laminate and a printed circuit board.
  • the metal-clad laminate prepared by using the resin composition provided by the present invention has high glass transition temperature, low thermal expansion coefficient, high high temperature modulus, high peel strength, low dielectric constant, low dielectric loss factor, and Good heat resistance and good processability.
  • the present invention adopts the following technical solutions:
  • the present invention provides a thermosetting resin composition, the resin composition comprising the following components: a combination of bismaleimide resin and benzoxazine resin or a combination of bismaleimide resin and benzene And oxazine resin prepolymer, epoxy resin and active ester.
  • the combination of bismaleimide resin and benzoxazine resin or the prepolymer of bismaleimide resin and benzoxazine resin and active ester are added to the cured resin together, and the bismaleimide resin
  • the addition of lysimide significantly increases the glass transition temperature of the resin composition system, while the addition of benzoxazine resin can improve the heat resistance and electrical properties of the resin composition.
  • the addition of active resin composition Ester can neutralize the shortcomings of increased dielectric properties of the system due to the addition of bismaleimide and benzoxazine resins.
  • the addition of active esters can reduce the dielectric properties of the resin composition, especially the dielectric loss factor. Therefore, the three work together to make the finally obtained resin composition have high glass transition temperature, high heat resistance, low dielectric constant and low dielectric loss factor.
  • adding a certain amount of epoxy resin in the present invention can balance the deficiencies of other performance parts caused by bismaleimide resin, benzoxazine resin and active ester, and increase the resin to a certain extent.
  • the adhesiveness of the composition can balance the deficiencies of other performance parts caused by bismaleimide resin, benzoxazine resin and active ester, and increase the resin to a certain extent.
  • the monomer of the bismaleimide resin has a structure represented by formula I:
  • R 1 is a substituted or unsubstituted C1-C4 alkyl group
  • R 2 is a C3 or higher alkyl group.
  • R 1 is a substituted or unsubstituted C3-C4 alkyl group.
  • the C1-C4 alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and the like.
  • the C3 or higher alkyl group may be propyl, isopropyl, n-butyl, isobutyl and the like.
  • the bismaleimide resin with the above structure is selected, the ratio of C and H is increased, and the spatial compactness is decreased, which can further reduce the dielectric constant and dielectric loss factor of the finally obtained resin composition.
  • the resin composition further includes a phosphorus-containing flame retardant.
  • the resin composition includes the following components in parts by weight:
  • the resin composition includes the following components: a prepolymer of a bismaleimide resin and a benzoxazine resin, an epoxy resin, an active ester, and a phosphorus-containing flame retardant.
  • the thermal expansion coefficient of the finally obtained resin composition is lower and the sizing processability is better.
  • the bismaleimide resin is 15-50 parts by weight, such as 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, etc.
  • the prepolymer of the bismaleimide resin and the benzoxazine resin is 30-80 parts by weight, such as 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight , 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, etc.
  • the benzoxazine resin is 15-30 parts by weight, such as 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, etc.
  • the benzoxazine resin includes an allyl-containing benzoxazine resin, a bisphenol A type benzoxazine resin, a bisphenol F type benzoxazine resin, and a diamine type benzoxazine resin , Phenolphthalein type benzoxazine resin, dicyclopentadiene type benzoxazine resin or bisphenol fluorene type benzoxazine resin any one or a combination of at least two, preferably allyl-containing benzoxazine Oxazine resin.
  • the benzoxazine resin with allyl groups is selected as an additive component, which can further improve the toughness and dielectric properties of the finally obtained copper clad laminate or laminate, and is more conducive to controlling the process during the processing.
  • the epoxy resin is 15-30 parts by weight, such as 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, etc.
  • the epoxy resin is a halogen-free and phosphorus-free epoxy resin selected from the group consisting of biphenyl epoxy resin, naphthol type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, and aralkyl group. Any one or a mixture of at least two types of epoxy resins or polyfunctional epoxy resins, preferably any one of biphenyl epoxy resin, dicyclopentadiene epoxy resin or naphthol epoxy resin A combination of at least two, and more preferably biphenyl epoxy resin.
  • the active ester is 2-20 parts by weight, such as 4 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 16 parts by weight, 18 parts by weight, etc.
  • the active ester includes an active ester having a structure as shown in formula II and/or an active ester having a structure as shown in formula III;
  • X is a phenyl group or a naphthyl group
  • R 3 and R 4 are each independently selected from a hydrogen atom or a methyl group
  • k is 0 or 1
  • the average value of n is 0.2-2, such as 0.3, 0.5, 0.7, 0.8, 0.9, 1.0, 1.2, 1.5, 1.8, etc.
  • La is phenyl or naphthyl
  • Y in (Y) q is selected from a methyl group, a hydrogen atom or an ester group
  • q is 1, 2 or 3
  • j is an integer of 1-10, such as 2, 3, 4 , 5, 6, 7, 8, 9, etc.
  • m is an integer of 1-10, such as 2, 3, 4, 5, 6, 7, 8, 9 and so on.
  • the phosphorus-containing flame retardant is 0-10 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, etc.
  • the phosphorus-containing flame retardant is tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa- 10-phosphinophenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa-10-phosphine Any one or a combination of at least two of phenanthrene-10-oxide or phosphazene.
  • the resin composition further includes 0.01 to 1 parts by weight of a curing accelerator, such as 0.02 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 0.8 parts by weight, and the like.
  • a curing accelerator such as 0.02 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 0.8 parts by weight, and the like.
  • the curing accelerator is any one or a combination of at least two of imidazoles, 4-dimethylaminopyridine, triphenylphosphine, boron trifluoride monoethylamine or zinc octoate.
  • the resin composition further comprises 5 to 300 parts by weight of filler, such as 10 parts by weight, 15 parts by weight, 20 parts by weight, 50 parts by weight, 80 parts by weight, 100 parts by weight, 150 parts by weight, 180 parts by weight, 250 parts by weight, 280 parts by weight, etc.
  • filler such as 10 parts by weight, 15 parts by weight, 20 parts by weight, 50 parts by weight, 80 parts by weight, 100 parts by weight, 150 parts by weight, 180 parts by weight, 250 parts by weight, 280 parts by weight, etc.
  • the median particle size of the filler is 0.01-50 ⁇ m, such as 0.02 ⁇ m, 0.05 ⁇ m, 0.15 ⁇ m, 0.2 ⁇ m, 0.5 ⁇ m, 0.8 ⁇ m, 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 15 ⁇ m, 25 ⁇ m, 30 ⁇ m, 40 ⁇ m, 45 ⁇ m, etc., more preferably 0.01-20 ⁇ m, still more preferably 0.1-10 ⁇ m.
  • the filler is selected from organic fillers or inorganic fillers, more preferably inorganic fillers, still more preferably surface-treated inorganic fillers, most preferably surface-treated silica.
  • the surface treatment agent for the surface treatment is selected from any one or a combination of at least two of silane coupling agents, silicone oligomers or titanate coupling agents.
  • the amount of the surface treatment agent is 0.1-5.0 parts by weight, such as 0.2 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1.0 parts by weight, 1.2 parts by weight, 1.5 parts by weight , 2.0 parts by weight, 2.5 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, etc., more preferably 0.5-3.0 parts by weight, still more preferably 0.75-2.0 parts by weight.
  • the inorganic filler is selected from any one or a combination of at least two of non-metal oxides, metal nitrides, non-metal nitrides, inorganic hydrates or inorganic salts, and more preferably fused silica, crystalline Silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, boehmite Any one or a combination of at least two of, calcium carbonate, calcium silicate or mica.
  • the organic filler is selected from any one or a combination of at least two of polytetrafluoroethylene, polyphenylene sulfide or polyethersulfone.
  • the “comprising” in the present invention means that in addition to the aforementioned components, it can also include other components, which impart different characteristics to the resin composition.
  • the "including” mentioned in the present invention can also be replaced with a closed “being” or “consisting of”.
  • the resin composition may further contain various additives.
  • additives include coupling agents, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, and the like. These various additives can be used alone, or two or more of them can be used in combination.
  • the present invention provides a resin glue solution, which is obtained by dissolving or dispersing the thermosetting resin composition as described in the first aspect in a solvent.
  • the present invention provides a prepreg, the prepreg comprising a reinforcing material, and the thermosetting resin composition as described in the first aspect attached to the reinforcing material after being impregnated and dried.
  • the present invention provides a laminate, which includes one or at least two laminated prepregs as described in the third aspect.
  • the present invention provides a metal-clad laminate, the metal-clad laminate includes one or at least two stacked prepregs as described in the third aspect and a laminate covered on the prepreg. Metal foil on one or both sides of the outside of the material.
  • the present invention provides a printed circuit board, the printed circuit board comprising at least one prepreg as described in the third aspect.
  • the present invention has the following beneficial effects:
  • the combination of bismaleimide resin and benzoxazine resin or prepolymer of bismaleimide resin and benzoxazine resin and active ester are added to the cured resin .
  • the addition of bismaleimide significantly increases the glass transition temperature of the resin composition system, while the addition of benzoxazine resin can improve the heat resistance and electrical properties of the resin composition.
  • the addition of active ester can neutralize the shortcomings of increased dielectric performance of the system due to the addition of bismaleimide and benzoxazine resin.
  • the addition of active ester can reduce the dielectric performance of the resin composition, especially Dielectric loss factor. Therefore, the three work together to make the finally obtained resin composition have high glass transition temperature, high heat resistance, low dielectric constant and low dielectric loss factor.
  • the copper clad laminate prepared from the resin composition provided by the present invention has high glass transition temperature, low thermal expansion coefficient, high high temperature modulus, high peel strength, low dielectric constant, low dielectric loss factor, and resistance to Good thermal properties and good processability.
  • the glass transition temperature can reach above 230°C
  • the thermal expansion coefficient can reach 1.8%
  • the dielectric constant (1GHz) can reach 3.81
  • the dielectric loss (1GHz) can reach 0.0045. .
  • A-1 3,3'-Dimethyl-4,4'-diamino-5,5'-diisopropyldiphenylmethane bismaleimide, D937, the specific structure is as follows:
  • A-2 4,4'-Diamino-3,3',5,5'-tetraisopropyldiphenylmethane bismaleimide, East Material Technology, the specific structure is as follows:
  • A-4 Diphenylmethane type bismaleimide, BMI-01 from Hubei Honghu Shuangma Resin Factory, the specific structure is as follows:
  • C-1 DCPD type epoxy resin, HP-7200H, Japan DIC;
  • C-2 Biphenyl type epoxy resin, NC-3000L, Nippon Kayaku;
  • D-1 DCPD type active ester, 8000, Japan DIC;
  • D-2 DCPD modified active ester, 8000L, Japan DIC;
  • E-1 Containing allyl phosphazene, SPV-100, Otsuka Chemical;
  • E-2 Additive phosphorus-containing flame retardant, OP930, Clariant, Germany;
  • E-3 Phosphorus-containing phenolic, XZ-92741, Olin, USA;
  • G-1 Spherical silica, SC2050, Japanese admateches
  • G-2 Angle silica, 525, Sibelco.
  • thermosetting resin composition was prepared according to the components shown in Table 1 (the amount of raw materials is in parts by weight), and the metal-clad laminate sample was made according to the following laminate production method:
  • thermosetting resin composition was prepared according to the components shown in Table 1 (the amount of raw materials is in parts by weight), and the copper clad laminate sample was prepared according to the following laminate production method:
  • thermosetting resin composition was prepared according to the components shown in Table 2 and Table 3 (the amount of raw materials is in parts by weight), and the copper clad laminate samples were prepared according to the laminate manufacturing method described in Examples 5-10.
  • test methods are as follows:
  • Modulus Use DMA test to measure according to the DMA test method specified in IPC-TM-650 2.4.24;
  • CTE Coefficient of Thermal Expansion
  • Dielectric constant (Dk) and dielectric loss factor (Df) Determine the dielectric constant and dielectric loss factor at 1 GHz according to IPC-TM-650 2.5.5.9 using the plate capacitor method;
  • Anti-peel strength Measure according to the anti-peel strength test method specified in IPC-TM-650 2.4.8;
  • T-288 Use a TMA instrument to measure it according to the T-288 test method specified in IPC-TM-650 2.4.24.1;
  • PCT According to IPC standard method, the test condition is 105KPa/60min, 288°C limit;
  • the unit weight is within the standard ⁇ 4g/m 2 , the appearance is relatively flat, and there are no visible defects;
  • the copper clad laminate prepared by the resin composition provided by the present invention has a high glass transition temperature, a low thermal expansion coefficient, a high high temperature modulus, a relatively high peel strength, and a relatively low dielectric. Constant and dielectric loss factor, as well as good heat resistance, and good processability.
  • the glass transition temperature can reach 230°C or more
  • the thermal expansion coefficient can reach 1.8%
  • the dielectric constant (1GHz) can reach 3.81.
  • the electrical loss (1GHz) can be as low as 0.0045.
  • Example 2 the resin composition used the bismaleimide resin and the benzoxazine resin to form a prepolymer, and then mixed with other components to prepare a prepreg.
  • Example 5 the direct The bismaleimide resin and the benzoxazine resin are mixed with other components. From the comparison of Example 2 and Example 5, it can be seen that in the present invention, the bismaleimide resin and the benzoxazine resin are used.
  • the prepolymer of oxazine resin can make the finally obtained copper clad laminate have a lower thermal expansion coefficient and better sizing process.
  • Example 2 From the comparison of Example 2 and Examples 8-10, it can be seen that the bismaleimide having the structure of formula I and the allyl-containing benzoxazine resin are preferably used in conjunction with the bismaleimide resin in the present invention. At this time, the finally obtained copper clad laminate Has better overall performance.
  • Example 5 From the comparison of Example 5 and Comparative Examples 1-6, it can be seen that in the present invention, the bismaleimide resin, benzoxazine resin, and active ester work together to synergize, so that the final copper clad laminate It has high glass transition temperature, low dielectric constant and low dielectric loss factor, and other properties are also excellent. All three are indispensable.
  • thermosetting resin composition of the present invention including its prepreg, metal-clad laminate and printed circuit board
  • present invention is not limited to the above detailed method, namely It does not mean that the present invention must rely on the above detailed methods to be implemented.
  • Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc. fall within the scope of protection and disclosure of the present invention.

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Abstract

本发明提供了一种热固性树脂组合物，包含其的预浸料以及覆金属箔层压板和印制电路板，所述树脂组合物包括如下组分：双马来酰亚胺树脂和苯并噁嗪树脂的组合或双马来酰亚胺树脂与苯并噁嗪树脂的预聚物、环氧树脂以及活性酯。利用本发明提供的树脂组合物制备得到的覆金属箔层压板具有高玻璃化转变温度、低热膨胀系数、较高的高温模量、高剥离强度、低介电常数、低介电损耗因子，以及耐热性良好，工艺加工性良好。

Description

一种热固性树脂组合物、包含其的预浸料以及覆金属箔层压板和印制电路板 技术领域
本发明属于覆铜板技术领域，涉及一种热固性树脂组合物，包含其的预浸料以及覆金属箔层压板和印制电路板。
背景技术
随着电子产品信息处理的高速化和多功能化，应用频率不断提高，要求介电常数(Dk)和介电损耗值(Df)越来越低，因此降低Dk/Df已成为基板业者的追逐热点。为了实现低Dk和低Df，各种低极性树脂如苯乙烯-马来酸酐低聚物(SMA)被广泛使用，SMA能赋予基板优异的介电性能和耐热性等，但存在着吸水率高和热膨胀系数(CTE)较大的问题。
目前，虽然一般的覆铜箔层压板可以实现低Dk和低Df，或者可实现较高T g和较低CTE，但是目前行业中可以同时满足高T g和低CTE，低Dk和低Df，并满足HDI甚至封装应用的覆铜板等并不多见。虽然现在类载板类覆铜板的出现和应用在快速发展，但这类类载板的T g、CTE、模量等，甚至Dk/Df还有待进一步提升，才能满足电子工业的发展对覆铜板材料性能提升的需求。
CN104725781A公开了一种树脂组合物以及使用它的预浸料和层压板。所述树脂组合物，其按各组分占的重量百分比包括：胺改性双马来酰亚胺(BMI)15-55％、苯并噁嗪树脂10-45％以及环氧树脂0-75％，虽然改善了覆铜板的介电性能以及耐温性，但是组合物的T g、介电常数以及介电损耗等性能仍有很大提升空间。CN104845363公开了一种无卤树脂组合物及其用途，以有机固形物重量份计，该无卤树脂组合物包含(A)烯丙基改性苯并噁嗪树脂40-80重量份；(B)碳氢树脂10-20重量份；(C)烯丙基改性聚苯醚树脂10-40重量份； (D)烯丙基改性的双马来酰亚胺树脂10-20重量份；(E)引发剂0.01-3重量份；(F)填料10-100重量份及(G)含磷阻燃剂0-80重量份，该发明最后得到的层压板具有较低的Dk和Df，以及较好的阻燃效果，但是由于一些组分需要自制，成本较高且制备方法复杂；并且，最后得到的层压板的玻璃化转变温度T g以及CTE等仍有进一步提高的空间。CN107459650A公开了一种改性双马来酰亚胺树脂预聚物及其制备方法，采用熔融工艺，利用烯丙基化合物、氨基苯乙炔、苯并噁嗪对双马来酰亚胺进行共聚扩链增韧改性，所得改性双马来酰亚胺树脂预聚物具有高耐热性，但是在改性过程中并没有考虑到材料的介电性能以及介电损耗性能。
因此，如何开发一种新的组合物，可以在保证最后制备的覆铜板具有较高的玻璃化转变温度的同时，具有较低介电常数、介电损耗因子且具有较低的热膨胀系数是本领域亟待解决的问题。
发明内容
本发明的目的在于提供一种热固性树脂组合物，包含其的预浸料以及覆金属箔层压板和印制电路板。利用本发明提供的树脂组合物制备得到的覆金属箔层压板具有高玻璃化转变温度、低热膨胀系数、较高的高温模量、高剥离强度、低介电常数、低介电损耗因子，以及耐热性良好，工艺加工性良好。
为达此目的，本发明采用以下技术方案：
第一方面，本发明提供了一种热固性树脂组合物，所述树脂组合物包括如下组分：双马来酰亚胺树脂和苯并噁嗪树脂的组合或双马来酰亚胺树脂与苯并噁嗪树脂的预聚物、环氧树脂以及活性酯。
在本发明中，双马来酰亚胺树脂和苯并噁嗪树脂的组合或双马来酰亚胺树脂与苯并噁嗪树脂的预聚物以及活性酯共同加入树脂固化物中，双马来酰亚胺 的加入显著地提高了树脂组合物体系的玻璃化转变温度，而苯并噁嗪树脂的加入可以提高树脂组合物的耐热性以及电性能，同时，在树脂组合物中加入活性酯可以中和由于双马来酰亚胺以及苯并噁嗪树脂的加入而导致的体系介电性能增大的缺点，活性酯的加入可以降低树脂组合物的介电性能，尤其是介电损耗因子。因此，三者共同作用，使最后得到的树脂组合物具有高玻璃化转变温度、高耐热性，且具有低介电常数以及低介电损耗因子。
同时，在本发明中加入了一定量的环氧树脂，可以平衡双马来酰亚胺树脂、苯并噁嗪树脂以及活性酯带来的其他性能部分的不足，且可以在一定程度上增加树脂组合物的粘结性。
优选地，所述双马来酰亚胺树脂的单体具有式I所示结构：
Figure PCTCN2019077162-appb-000001
其中，R 1为取代或未取代的C1-C4的烷基，R 2为C3以上的烷基。
优选地，R 1为取代或未取代的C3-C4的烷基。
C1-C4的烷基可以为甲基、乙基、丙基、异丙基、正丁基、异丁基等。
C3以上的烷基可以为丙基、异丙基、正丁基、异丁基等。
本发明选用上述结构的双马来酰亚胺树脂，C、H比例增大，空间致密性减小，可以进一步降低最后得到的树脂组合物的介电常数和介电损耗因子。
优选地，所述树脂组合物还包括含磷阻燃剂。
优选地，所述树脂组合物按重量份计包括如下组分：
Figure PCTCN2019077162-appb-000002
或：
Figure PCTCN2019077162-appb-000003
优选地，所述树脂组合物包括如下组分：双马来酰亚胺树脂与苯并噁嗪树脂的预聚物、环氧树脂、活性酯以及含磷阻燃剂。
当本发明选择双马来酰亚胺树脂与苯并噁嗪树脂的预聚物作为添加组分时，最后得到的树脂组合物的热膨胀系数更低且上胶工艺性更好。
在本发明中，所述双马来酰亚胺树脂15-50重量份，例如20重量份、25重量份、30重量份、35重量份、40重量份、45重量份等。
在本发明中，所述双马来酰亚胺树脂与苯并噁嗪树脂的预聚物30-80重量份，例如35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份、70重量份、75重量份等。
在本发明中，所述苯并噁嗪树脂15-30重量份，例如18重量份、20重量份、22重量份、24重量份、26重量份、28重量份等。
优选地，所述苯并噁嗪树脂包括含烯丙基的苯并噁嗪树脂、双酚A型苯并噁嗪树脂、双酚F型苯并噁嗪树脂、二胺型苯并噁嗪树脂、酚酞型苯并噁嗪树 脂、双环戊二烯型苯并噁嗪树脂或双酚芴型苯并噁嗪树脂中的任意一种或者至少两种的组合，优选含烯丙基的苯并噁嗪树脂。
本发明选择带有烯丙基的苯并噁嗪树脂作为添加组分，可以进一步提高最后得到的覆铜板或层压板的韧性、介电性能以及更有利于在加工过程中控制工艺。
在本发明中，所述环氧树脂15-30重量份，例如18重量份、20重量份、22重量份、24重量份、26重量份、28重量份等。
优选地，所述环氧树脂为无卤无磷环氧树脂，选自联苯环氧树脂、萘酚型环氧树脂、酚醛型环氧树脂、双环戊二烯型环氧树脂、芳烷基型环氧树脂或多官能团环氧树脂中的任意一种或者至少两种的混合物，优选联苯环氧树脂、双环戊二烯型环氧树脂或萘酚型环氧树脂中的任意一种或至少两种的组合，进一步优选联苯环氧树脂。
在本发明中，所述活性酯2-20重量份，例如4重量份、8重量份、10重量份、12重量份、15重量份、16重量份、18重量份等。
优选地，所述活性酯包括具有如式II所示结构的活性酯和/或如式III所示结构的活性酯；
Figure PCTCN2019077162-appb-000004
其中，X为苯基或萘基，R 3、R 4各自独立地选自氢原子或甲基，k为0或1，n的平均值为0.2-2，例如0.3、0.5、0.7、0.8、0.9、1.0、1.2、1.5、1.8等。
Figure PCTCN2019077162-appb-000005
其中，La为苯基或萘基，(Y) q中的Y选自甲基、氢原子或酯基，q为1、2或3，j为1-10的整数，例如2、3、4、5、6、7、8、9等，m为1-10的整数，例如2、3、4、5、6、7、8、9等。
在本发明中，所述含磷阻燃剂0-10重量份，例如1重量份、2重量份、3重量份、4重量份、5重量份、6重量份、7重量份、8重量份、9重量份等。
优选地，所述含磷阻燃剂为三(2，6-二甲基苯基)膦、10-(2，5-二羟基苯基)-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、2，6-二(2，6-二甲基苯基)膦基苯、10-苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物或磷腈中的任意一种或至少两种的组合。
优选地，所述树脂组合物还包括固化促进剂0.01-1重量份，例如0.02重量份、0.05重量份、0.1重量份、0.5重量份、0.8重量份等。
优选地，所述固化促进剂为咪唑类、4-二甲氨基吡啶、三苯基膦、三氟化硼单乙胺或辛酸锌中的任意一种或者至少两种的组合。
优选地，所述树脂组合物还包括填料5-300重量份，例如10重量份、15重量份、20重量份、50重量份、80重量份、100重量份、150重量份、180重量份、250重量份、280重量份等。
优选地，所述填料的中位粒径为0.01-50μm，例如0.02μm、0.05μm、0.15μm、0.2μm、0.5μm、0.8μm、1μm、1.5μm、2μm、5μm、8μm、10μm、15μm、25μm、30μm、40μm、45μm等，进一步优选0.01-20μm，更进一步优选 0.1-10μm。
优选地，所述填料选自有机填料或无机填料，进一步优选无机填料，更进一步优选经过表面处理的无机填料，最优选经过表面处理的二氧化硅。
优选地，所述表面处理的表面处理剂选自硅烷偶联剂、有机硅低聚物或钛酸酯偶联剂中的任意一种或至少两种的组合。
优选地，以无机填料为100重量份计，所述表面处理剂的用量为0.1-5.0重量份，例如0.2重量份、0.5重量份、0.8重量份、1.0重量份、1.2重量份、1.5重量份、2.0重量份、2.5重量份、3.5重量份、4重量份、4.5重量份等，进一步优选0.5-3.0重量份，更进一步优选0.75-2.0重量份。
优选地，所述无机填料选自非金属氧化物、金属氮化物、非金属氮化物、无机水合物或无机盐中的任意一种或者至少两种的组合，进一步优选熔融二氧化硅、结晶型二氧化硅、球型二氧化硅、空心二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、勃姆石、碳酸钙、硅酸钙或云母中的任意一种或至少两种的组合。
优选地，所述有机填料选自聚四氟乙烯、聚苯硫醚或聚醚砜中的任意一种或至少两种的组合。
本发明所述的“包括”，意指其除所述组份外，还可以包括其他组份，这些其他组份赋予所述树脂组合物不同的特性。除此之外，本发明所述的“包括”，还可以替换为封闭式的“为”或“由......组成”。
例如，所述树脂组合物还可以含有各种添加剂，作为具体例，可以举出偶联剂、抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂等。这些各种添加剂可以单独使用，也可以两种或者两种以上混合使用。
第二方面，本发明提供了一种树脂胶液，所述树脂胶液是将如第一方面所 述的热固性树脂组合物溶解或分散在溶剂中得到。
第三方面，本发明提供了一种预浸料，所述预浸料包括增强材料，和通过含浸干燥后附着在所述增强材料上的如第一方面所述的热固性树脂组合物。
第四方面，本发明提供了一种层压板，所述层压板包括一张或至少两张叠合的如第三方面所述的预浸料。
第五方面，本发明提供了一种覆金属箔层压板，所述覆金属箔层压板包括一张或至少两张叠合的如第三方面所述的预浸料和覆于所述预浸料外侧的一侧或两侧的金属箔。
第六方面，本发明提供了一种印制电路板，所述印制电路板包括至少一张如第三方面所述的预浸料。
相对于现有技术，本发明具有以下有益效果：
(1)在本发明中，双马来酰亚胺树脂和苯并噁嗪树脂的组合或双马来酰亚胺树脂与苯并噁嗪树脂的预聚物以及活性酯共同加入树脂固化物中，双马来酰亚胺的加入显著地提高了树脂组合物体系的玻璃化转变温度，而苯并噁嗪树脂的加入可以提高树脂组合物的耐热性以及电性能，同时，在树脂组合物中加入活性酯可以中和由于双马来酰亚胺以及苯并噁嗪树脂的加入而导致的体系介电性能增大的缺点，活性酯的加入可以降低树脂组合物的介电性能，尤其是介电损耗因子。因此，三者共同作用，使最后得到的树脂组合物具有高玻璃化转变温度、高耐热性，且具有低介电常数以及低介电损耗因子。
(2)当本发明选择双马来酰亚胺树脂与苯并噁嗪树脂的预聚物作为添加组分时，最后得到的树脂组合物的热膨胀系数更低且上胶工艺性更好。
(3)由本发明提供的树脂组合物制备得到的覆铜板具有高玻璃化转变温度、低热膨胀系数、较高的高温模量、高剥离强度、低介电常数、低介电损耗 因子，以及耐热性良好，工艺加工性良好，其中，玻璃化温度最高可达到230℃以上，热膨胀系数最低可达到1.8％，介电常数(1GHz)最低可达到3.81，介电损耗(1GHz)最低可达到0.0045。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
下述实施例和对比例所涉及的材料及牌号信息如下：
(A)双马来酰亚胺树脂
A-1：3，3′-二甲基-4，4′-二氨基-5，5′-二异丙基二苯甲烷双马来酰亚胺，东材科技D937，具体结构如下：
Figure PCTCN2019077162-appb-000006
A-2：4，4′-二氨基-3，3′，5，5′-四异丙基二苯甲烷双马来酰亚胺，东材科技，具体结构如下：
Figure PCTCN2019077162-appb-000007
A-3：2，2′-双[4-(4-马来酰亚胺基苯氧基)苯基]丙烷，日本KI chemical BMI-80，具体结构如下：
Figure PCTCN2019077162-appb-000008
A-4：二苯甲烷型双马来酰亚胺，湖北洪湖双马树脂厂BMI-01，具体结构如下：
Figure PCTCN2019077162-appb-000009
(B)苯并噁嗪树脂
B-1：含烯丙基的苯并噁嗪树脂，东材的D148；
B-2：含烯丙基的苯并噁嗪树脂，科龙的5031；
B-3：非烯丙基苯并噁嗪，Huntaman的DCPD型苯并噁嗪树脂8260；
(C)环氧树脂
C-1：DCPD型环氧树脂，HP-7200H，日本DIC；
C-2：联苯型环氧树脂，NC-3000L，日本化药；
C-3：含萘环型环氧树脂，NC-7300L，日本化药；
(D)活性酯
D-1：DCPD型活性酯，8000，日本DIC；
D-2：DCPD改进型活性酯，8000L，日本DIC；
D-3：含萘环型活性酯，8150，日本DIC；
(E)含磷阻燃剂
E-1：含烯丙基磷腈，SPV-100，日本大塚化学；
E-2：添加型含磷阻燃剂，OP930，德国科莱恩；
E-3：含磷酚醛，XZ-92741，美国Olin；
(F)固化促进剂：二甲基咪唑，2-MI，日本四国化成；
(G)填料
G-1：球型二氧化硅，SC2050，日本admateches；
G-2：角型二氧化硅，525，矽比科。
实施例1-4
按表1所示组分配制热固性树脂组合物(原料用量单位均为重量份数)，并按照如下层压板的制作方法制作覆金属箔层压板样品：
(1)将双马来酰亚胺树脂与苯并噁嗪树脂在DMF溶液中在130-160℃下反应0.5-8h，得到双马来酰亚胺树脂与苯并噁嗪树脂的预聚物，然后加入其他组份，混合均匀，得到树脂胶液；
(2)将树脂胶液浸润2116电子级玻纤布，烘除溶剂并烘至半固化的状态，得到适合树脂含量的半固化片预浸料，然后将一定数量的预浸料叠起来，上下各放一张覆铜板专用的电解铜箔，再用高温压机在220℃/90min进行固化层压，得到覆铜板。
实施例5-10
按表1所示组分配制热固性树脂组合物(原料用量单位均为重量份数)，并按照如下层压板的制作方法制作覆铜箔层压板样品：
(1)将配方量的双马来酰亚胺树脂、苯并噁嗪树脂、环氧树脂以及活性酯等组分在DMF溶液中混合均匀，得到树脂胶液；
(2)将树脂胶液浸润2116电子级玻纤布，烘除溶剂并烘至半固化的状态，得到适合树脂含量的半固化片预浸料，然后将一定数量的预浸料叠起来，上下 各放一张覆铜板专用的电解铜箔，再用高温压机在220℃/90min进行固化层压，得到覆铜板。
对比例1-14
按表2和表3所示组分配制热固性树脂组合物(原料用量单位均为重量份数)，按照实施例5-10中所述层压板的制作方法制作覆铜箔层压板样品。
表1
Figure PCTCN2019077162-appb-000010
Figure PCTCN2019077162-appb-000011
表2
Figure PCTCN2019077162-appb-000012
Figure PCTCN2019077162-appb-000013
表3
Figure PCTCN2019077162-appb-000014
Figure PCTCN2019077162-appb-000015
性能测试
对实施例1-10和对比例1-14提供的覆铜箔层压板进行性能测试，测试方法如下：
(1)玻璃化转变温度(T g)：使用DMA测试，按照IPC-TM-650 2.4.24所规定的DMA测试方法进行测定；
(2)模量：使用DMA测试，按照IPC-TM-650 2.4.24所规定的DMA测试方法进行测定；
(3)热膨胀系数(CTE)：按照IPC-TM-650 2.4.24C所规定的CTE测试方法进行测定；
(4)介电常数(Dk)和介电损耗因子(Df)：根据使用平板电容法，按照IPC-TM-650 2.5.5.9的方法测定1GHz下的介电常数、介电损耗因子；
(5)抗剥离强度：按照IPC-TM-650 2.4.8所规定的抗剥离强度测试方法进行测定；
(6)耐热裂时间(T-288)：用TMA仪，按照IPC-TM-650 2.4.24.1所规定的T-288测试方法进行测定；
(7)PCT：按IPC标准方法，测试条件为105KPa/60min，288℃极限；
(8)2116上胶工艺：观察半固化片表观并取样称重，得到单位面积重量的高低，以此对比评价半固化片表观和单重是否容易调控，其中：
优：单重在标准±4g/m 2内，表观平整光滑，无肉眼可见的缺陷；
一般：单重在标准±4g/m 2内，表观较平整，无肉眼可见的缺陷；
差：单重不在标准±4g/m 2内，表观有流挂或气泡等肉眼可见的缺陷。
对实施例1-8和对比例1-14提供的层压板的测试结果表4-7：
表4
Figure PCTCN2019077162-appb-000016
表5
Figure PCTCN2019077162-appb-000017
表6
Figure PCTCN2019077162-appb-000018
Figure PCTCN2019077162-appb-000019
表7
Figure PCTCN2019077162-appb-000020
由实施例和性能测试可知，本发明提供的树脂组合物制备得到的覆铜板具有高玻璃化转变温度、低热膨胀系数、较高的高温模量、相对较高的剥离强度、相对低的介电常数和介电损耗因子，以及耐热性良好，工艺加工性良好，其中， 玻璃化温度最高可达到230℃以上，热膨胀系数最低可达到1.8％，介电常数(1GHz)最低可达到3.81，介电损耗(1GHz)最低可达到0.0045。
由实施例1和实施例4的对比可知，当式I结构的R 1为取代或未取代的C3-C4的烷基时，最后得到的覆铜板的玻璃化转变温度更高且可以获得相对低的介电常数和介电损耗因子。
在实施例2中，树脂组合物采用了先使双马来酰亚胺树脂和苯并噁嗪树脂生成预聚物，再与其他组分混合制备预浸料，而在实施例5中，直接采用双马来酰亚胺树脂和苯并噁嗪树脂与其他组分相混合，由实施例2和实施例5的对比可知，在本发明中，采用双马来酰亚胺树脂与苯并噁嗪树脂的预聚物，可以使最后得到的覆铜板具有更低的热膨胀系数并且上胶工艺性更好。
由实施例2和实施例8-10的对比可知，本发明优选具有式I结构的双马来酰亚胺与含烯丙基的苯并噁嗪树脂配合使用，此时，最后得到的覆铜板具有更好的综合性能。
由实施例5和对比例1-6的对比可知，在本发明中，双马来酰亚胺树脂、苯并噁嗪树脂以及活性酯三者共同作用，协同增效，使得最后得到的覆铜板具有高玻璃化转变温度、低介电常数和低介电损耗因子，同时其他性能也优异，三者缺一不可。
由实施例5-7和对比例7-14的对比可知，在本发明中，双马来酰亚胺树脂、苯并噁嗪树脂、环氧树脂以及活性酯的添加量需均在本发明范围内，高于或低于本发明的范围均无法得到本发明的有益效果。
申请人声明，本发明通过上述实施例来说明本发明的热固性树脂组合物，包含其的预浸料以及覆金属箔层压板和印制电路板，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域 的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (11)

  1. 一种热固性树脂组合物，其特征在于，所述树脂组合物包括如下组分：双马来酰亚胺树脂和苯并噁嗪树脂的组合或双马来酰亚胺树脂与苯并噁嗪树脂的预聚物、环氧树脂以及活性酯。
  2. 根据权利要求1所述的热固性树脂组合物，其特征在于，所述双马来酰亚胺树脂的单体具有式I所示结构：
    Figure PCTCN2019077162-appb-100001
    其中，R 1为取代或未取代的C1-C4的烷基，R 2为C3以上的烷基。
  3. 根据权利要求1或2所述的热固性树脂组合物，其特征在于，R 1为取代或未取代的C3-C4的烷基。
  4. 根据权利要求1-3中的任一项所述的热固性树脂组合物，其特征在于，所述树脂组合物还包括含磷阻燃剂；
    优选地，所述树脂组合物按重量份计包括如下组分：
    Figure PCTCN2019077162-appb-100002
    Figure PCTCN2019077162-appb-100003
    优选地，所述树脂组合物包括如下组分：双马来酰亚胺树脂与苯并噁嗪树脂的预聚物、环氧树脂、活性酯以及含磷阻燃剂。
  5. 根据权利要求1-4中的任一项所述的树脂组合物，其特征在于，所述苯并噁嗪树脂为含烯丙基的苯并噁嗪树脂；
    优选地，所述环氧树脂为无卤无磷环氧树脂，选自联苯环氧树脂、萘酚型环氧树脂、酚醛型环氧树脂、双环戊二烯型环氧树脂、芳烷基型环氧树脂或多官能团环氧树脂中的任意一种或者至少两种的混合物，优选联苯环氧树脂、双环戊二烯型环氧树脂或萘酚型环氧树脂中的任意一种或至少两种的组合，进一步优选联苯环氧树脂；
    优选地，所述活性酯包括具有如式II所示结构的活性酯和/或如式III所示结构的活性酯；
    Figure PCTCN2019077162-appb-100004
    其中，X为苯基或萘基，R 3、R 4各自独立地选自氢原子或甲基，k为0或1，n的平均值为0.2-2；
    Figure PCTCN2019077162-appb-100005
    其中，La为苯基或萘基，(Y) q中的Y选自甲基、氢原子或酯基，q为1、2或3，j为1-10的整数，m为1-10的整数；
    优选地，所述含磷阻燃剂为三(2，6-二甲基苯基)膦、10-(2，5-二羟基苯基)-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、2，6-二(2，6-二甲基苯基)膦基苯、10-苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物或磷腈中的任意一种或至少两种的组合。
  6. 根据权利要求1-5中的任一项所述的树脂组合物，其特征在于，所述树脂组合物还包括固化促进剂0.01-1重量份；
    优选地，所述固化促进剂为咪唑类、4-二甲氨基吡啶、三苯基膦、三氟化硼单乙胺或辛酸锌中的任意一种或者至少两种的组合；
    优选地，所述树脂组合物还包括填料5-300重量份；
    优选地，所述填料的中位粒径为0.01-50μm，进一步优选0.01-20μm，更进一步优选0.1-10μm；
    优选地，所述填料选自有机填料或无机填料，进一步优选无机填料，更进一步优选经过表面处理的无机填料，最优选经过表面处理的二氧化硅；
    优选地，所述表面处理的表面处理剂选自硅烷偶联剂、有机硅低聚物或钛酸酯偶联剂中的任意一种或至少两种的组合；
    优选地，以无机填料为100重量份计，所述表面处理剂的用量为0.1-5.0重量份，进一步优选0.5-3.0重量份，更进一步优选0.75-2.0重量份；
    优选地，所述无机填料选自非金属氧化物、金属氮化物、非金属氮化物、无机水合物或无机盐中的任意一种或者至少两种的组合，进一步优选熔融二氧化硅、结晶型二氧化硅、球型二氧化硅、空心二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、勃姆石、碳酸 钙、硅酸钙或云母中的任意一种或至少两种的组合；
    优选地，所述有机填料选自聚四氟乙烯、聚苯硫醚或聚醚砜中的任意一种或至少两种的组合。
  7. 一种树脂胶液，其特征在于，所述树脂胶液是将如权利要求1—6任一项所述的热固性树脂组合物溶解或分散在溶剂中得到。
  8. 一种预浸料，其特征在于，所述预浸料包括增强材料，和通过含浸干燥后附着在所述增强材料上的如权利要求1-6任一项所述的热固性树脂组合物。
  9. 一种层压板，其特征在于，所述层压板包括一张或至少两张叠合的如权利要求8所述的预浸料。
  10. 一种覆金属箔层压板，其特征在于，所述覆金属箔层压板包括一张或至少两张叠合的如权利要求8所述的预浸料和覆于所述预浸料外侧的一侧或两侧的金属箔。
  11. 一种印制电路板，其特征在于，所述印制电路板包括至少一张如权利要求8所述的预浸料。
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