WO2017124668A1 - Resin composition, and prepreg and laminated board using same - Google Patents

Resin composition, and prepreg and laminated board using same Download PDF

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Publication number
WO2017124668A1
WO2017124668A1 PCT/CN2016/082107 CN2016082107W WO2017124668A1 WO 2017124668 A1 WO2017124668 A1 WO 2017124668A1 CN 2016082107 W CN2016082107 W CN 2016082107W WO 2017124668 A1 WO2017124668 A1 WO 2017124668A1
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Prior art keywords
epoxy resin
resin
parts
weight
polyphenylene ether
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PCT/CN2016/082107
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French (fr)
Chinese (zh)
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周应先
何岳山
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广东生益科技股份有限公司
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Publication of WO2017124668A1 publication Critical patent/WO2017124668A1/en

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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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/098—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions 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 C08L61/00 - C08L77/00
    • C08L79/04—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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • 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
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention belongs to the technical field of copper clad laminates, and in particular relates to a resin composition and a prepreg and a laminate using the same.
  • the polyphenylene ether resin has excellent water resistance, dimensional stability, flame retardancy, and dielectric properties, and is obtained by mixing with others to obtain a resin composition which is more excellent in overall performance.
  • it is widely used as a raw material in various fields, for example, plumbing fixtures, electrical boxes, automobile parts, and coated wires, copper foil laminates, and printed circuits.
  • the polyphenylene ether resin-based copper foil laminate can achieve excellent dielectric properties
  • the prior art application only the polyphenylene ether resin and other resin compositions are simply physically blended into a uniform glue varnish, immersed in A semi-cured film is obtained on the surface of the glass fiber cloth, and a series of processes such as curing and pressing are performed to obtain a copper foil laminate.
  • the polyphenylene ether resin has a low polarity and is inferior in compatibility with other resins in the resin composition, it affects the appearance of the prepreg; in addition, the impregnation property of the polyphenylene ether resin and the glass fiber cloth is not satisfactory. It is easy to aggregate the film on the surface of the glass cloth, which also affects the appearance of the prepreg, which in turn adversely affects the dielectric properties of the product.
  • Patent No. CN1556830 proposes a method for functionalizing polyphenylene ether, which is to react polyphenylene ether with bisphenol A epoxy resin under the action of an amine catalyst, and obtain two rings at both ends.
  • a polyphenylene ether/epoxy resin prepolymer of an oxygen group which improves the application of the above-mentioned polyphenylene ether to a certain extent, but the introduction of the bisphenol A type epoxy resin to the resin molecule
  • the dielectric properties have an adverse effect - making their Dk/Df increase.
  • One of the objects of the present invention is to provide a resin composition which is prepared by using an epoxy resin-modified polyphenylene ether resin prepolymer and a benzoxazine resin to have excellent appearance and high heat resistance. (The Tg measured by the DSC method reaches 180-210 ° C) and excellent dielectric properties and peel strength.
  • a resin composition comprising a prepolymer of an epoxy resin modified polyphenylene ether resin and a benzoxazine resin.
  • the invention converts a polyphenylene ether resin into a polyphenylene ether epoxy prepolymer having a group, and then reacts with a benzoxazine resin, and combines the low dielectric and benzoic acid of the polyphenylene ether resin.
  • the glass fiber cloth wettability of the resin composition of the prepolymer of the epoxy resin-modified polyphenylene ether resin gives the obtained resin composition excellent appearance performance, heat resistance, dielectric properties, peel strength, and high Tg.
  • the prepolymer of the epoxy resin modified polyphenylene ether resin has a structure as shown in formula (I):
  • R is a substituted or unsubstituted C1-C5 alkylene group, a single bond, -SO 2 -, -O-, -CO-, -SO- or -SC-;
  • Y is a functional group of the functionalized epoxy resin
  • Z 1 , Z 2 , Z 3 , and Z 4 are the same or different and are each independently a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms (for example, C1, C2, C3, C4, C5, C6 or C7) or Phenyl group;
  • n is a positive integer greater than one.
  • n represents the degree of polymerization of a polymer compound, and in each of the above formulae and each of the following formulae, n is the same or different value.
  • the molecular structure of the polyphenylene ether resin is as shown in formula (II):
  • R is a substituted or unsubstituted C1-C5 alkylene group, a single bond, -SO 2 -, -O-, -CO-, -SO- or -SC-;
  • Z 1 , Z 2 , Z 3 , and Z 4 are the same or different and are each independently a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms (for example, C1, C2, C3, C4, C5, C6 or C7) or Phenyl group;
  • n is a positive integer greater than one.
  • X in formula (II) is:
  • the molecular structure formula of the polyphenylene ether resin is as shown in formula (III) or formula (IV):
  • n is a positive integer greater than one.
  • the functionalized epoxy resin is an isocyanate modified bisphenol A epoxy resin, an isocyanate modified bisphenol F epoxy resin, an isocyanate modified bisphenol S epoxy resin, a phenol novolac epoxy resin, a bisphenol A Phenolic epoxy resin, o-cresol novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene epoxy resin, p-aminophenol epoxy resin, cyanuric acid epoxy resin , phosphorus-containing epoxy resin, nitrogen-containing epoxy resin, p-xylene epoxy resin, naphthalene epoxy resin, benzopyrene epoxy resin, biphenolic epoxy resin or phenolic phenylalkylphenol aldehyde epoxy Any one of the resins or a mixture of at least two.
  • Y in the formula (I) is any one of the following structures:
  • n and n are each independently a positive integer greater than one.
  • the prepolymer of the epoxy resin modified polyphenylene ether resin is obtained by reacting a solid polyphenylene ether resin with an epoxy resin according to the following method:
  • the reaction temperature and reaction time have an important influence on the quality of the product and the preparation efficiency.
  • the reaction temperature is lower than 125 ° C, the epoxy group and the hydroxyl group of the polyphenylene ether hardly react regardless of the reaction time, and the reaction temperature is higher than 160 ° C, which may cause a large side reaction such as epoxy self-polymerization or even crosslinking.
  • the use of a high boiling point solvent as a reaction solvent not only increases the reaction temperature of the prepolymerization, but also allows the reaction to proceed smoothly.
  • the low volatility of the solvent also provides a stable reaction environment.
  • the catalyst used in the present invention can selectively preferentially catalyze the reaction of the epoxy with the terminal hydroxyl group of the polyphenylene ether to obtain the target product of the epoxy-modified polyphenylene ether prepolymer, thereby avoiding the self-polymerization reaction of the epoxy resin itself.
  • the resulting reaction is excessive, resulting in an excessive molecular weight of the product, a small number of crosslinking points, and a decrease in the strength of the cured resin body.
  • a prepolymer of an epoxy resin modified polyphenylene ether resin having the same structure is prepared by preparing 100 parts of a solid polyphenylene ether resin, adding a polymerization solvent, and dissolving into a liquid polyphenylene ether resin solution, and then 24-35 parts of an epoxy resin and 0.001-5 parts of an imidazole catalyst are added to the solution, and the mixture is stirred and mixed at 100-120 for 1-3 hours to prepare a prepolymerized solution.
  • the organic solvent used in the method has a low boiling point, is easily volatilized under the problem of the base reaction, or causes the reaction temperature to be unstable. Further, this method neglects the self-polymerization reaction of the epoxy resin itself, resulting in overreaction, resulting in an excessive molecular weight of the product and a decrease in the strength of the cured resin body.
  • the catalyst is any one of a polyether, a cyclic crown ether, an amine, an inorganic strong base or an inorganic strong acid or a mixture of at least two.
  • the polyether is a chain polyethylene glycol (H-(OCH2CH2) n -OH) or/and a chain polyethylene glycol dialkyl ether (R(OCH2CH2) n -OR) or the like.
  • the cyclic crown ether is any one of 18 crown 6, 15 crown 5 or cyclodextrin, or a mixture of at least two.
  • the amine is any one of a quaternary ammonium salt, a tertiary amine or a pyridine compound or a mixture of at least two.
  • the quaternary ammonium salt is benzyltriethylammonium chloride (TEBA), tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate (TBAB), trioctylmethyl Any one or a mixture of at least two of ammonium chloride, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride;
  • TEBA benzyltriethylammonium chloride
  • TBAB tetrabutylammonium bromide
  • TBAB tetrabutylammonium hydrogen sulfate
  • trioctylmethyl Any one or a mixture of at least two of ammonium chloride, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride;
  • the tertiary amine is R 3 N, wherein R is a branched or linear alkyl group having 18 or less carbon atoms, a substituted or unsubstituted phenyl group, preferably triethylamine, tributylamine, dioctyl Any one or a mixture of at least two of an amine or diphenylmethylamine.
  • the pyridine compound is any one of pyridine, pyridine, phenylpyridine or bipyridine having a chain of 8 or less carbon atoms or a linear alkane substituent, or a mixture of at least two.
  • the inorganic strong base is sodium hydroxide or/and potassium hydroxide.
  • the inorganic strong acid is any one of concentrated sulfuric acid, hydrochloric acid or nitric acid, or a mixture of at least two.
  • the temperature of the stirring reaction is 135-150 ° C, and the stirring reaction time is 4-8 hours.
  • the organic solvent is any one of N,N-dimethylformamide, N,N-diethylformamide, cyclohexanone, toluene, xylene, trimethylbenzene or tetramethylbenzene or at least two Kind of mixed solvent.
  • the ratio of the raw materials used and the amount of the catalyst have an important influence on the quality of the product and the production efficiency.
  • the epoxy resin In terms of parts by weight, if the epoxy resin is less than 20 parts by weight relative to 50 parts by weight of the polyphenylene ether resin, the polyphenylene ether terminal functional group cannot be sufficiently bonded to the epoxy functional group, thereby affecting the epoxy of the polyphenylene ether resin.
  • Base improvement efficiency if the epoxy resin exceeds 80 parts by weight, excessive epoxy resin may affect the formulation design of the resin composition after the reaction is completed.
  • the epoxy resin is added in an amount of 30 to 70 parts by weight, preferably 40 to 60 parts by weight.
  • the catalyst is less than 0.005 parts by weight, the reaction rate is slow, resulting in a reaction time.
  • the length is long, which affects the reaction efficiency and cost; if the catalyst exceeds 10 parts by weight, the reaction rate is too fast, resulting in a side reaction resulting in self-polymerization of the epoxy group.
  • the catalyst is added in an amount of 0.005 to 5 parts by weight, preferably 0.005 to 1 part by weight.
  • the method comprises: adding 50 parts of the solid polyphenylene ether resin, adding a polymerization solvent, dissolving into a liquid polyphenylene ether resin solution, and then adding 30-70 parts of the epoxy resin and 0.005 to 1 part of the catalyst to the solution.
  • the reaction was stirred at 130 to 150 ° C for 4 to 8 hours to obtain a prepolymer solution.
  • the prepolymer of the epoxy resin-modified polyphenylene ether resin is added in an amount of 20 to 80 parts by weight in the resin composition.
  • the benzoxazine resin is bisphenol A benzoxazine, bisphenol F benzoxazine, bisphenol S benzoxazine, diamine benzoxazine, phenolphthalein benzoxazine or Any one or a mixture of at least two dicyclopentadiene type benzoxazines.
  • the curing agent is selected from any one of a novolac resin, a styrene maleic anhydride copolymer resin, DDS or DDM, or a mixture of two or more.
  • the resin composition further contains a curing accelerator in an amount of from 0.01 to 10 parts by weight.
  • the amount of the raw materials used has an important influence on the quality of the product and the production efficiency. Specifically, with respect to 50-90 parts by weight of the prepolymer of the epoxy resin-modified polyphenylene ether resin, if the curing agent is less than 5 parts by weight, the prepolymer end of the epoxy resin-modified polyphenylene ether resin The epoxy functional group is not sufficiently reacted and cured, so that the Tg (glass transition temperature) of the composition is too low; if the curing agent exceeds 50 parts by weight, an excess of unreacted crosslinking agent remains, so that the heat resistance of the composition, Tg Performance is not good.
  • the rate should be slow, and there is no obvious catalytic effect; if the curing accelerator exceeds 10 parts by weight, the reaction rate is too fast, which affects the preparation process of the product and the quality of the product.
  • the curing accelerator is selected from the group consisting of imidazole, boron trifluoride amine complex, ethyltriphenylphosphonium chloride, 2-methylimidazole (2-MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MZ), tri-phenylphosphine (TPP) Or a Lewis base of any one or a combination of at least two of 4-dimethylaminopyridine (DMAP), or any one selected from the group consisting of manganese, iron, cobalt, nickel, copper or zinc. Or a Lewis acid of at least two metal salt compounds, or an organic peroxide selected from, for example, dicumyl peroxide (DCP, Dicumyl Peroxide).
  • DCP dicumyl peroxide
  • the resin composition further comprises 5 to 60 parts by weight (for example, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight) Parts or 55 parts by weight of unprepolymerized epoxy resin.
  • the epoxy resin is an isocyanate modified bisphenol A epoxy resin, an isocyanate modified bisphenol F epoxy resin, an isocyanate modified bisphenol S epoxy resin, a phenol novolac epoxy resin, a bisphenol A phenolic ring Oxygen resin, o-cresol novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene epoxy resin, p-aminophenol epoxy resin, cyanuric acid epoxy resin, Phosphorus epoxy resin, nitrogen-containing epoxy resin, bromine-containing epoxy resin, p-xylene epoxy resin, naphthalene epoxy resin, benzopyrene epoxy resin, biphenolic epoxy resin or phenolic phenyl benzene Any one or a mixture of two or more kinds of phenolic epoxy resins.
  • the resin composition further comprises any one of an inorganic filler, a flame retardant, a surfactant, a dispersant, a silicone elastomer or a toughening agent, or a mixture of at least two.
  • the inorganic filler comprises silica (molten or non-molten and porous), alumina, magnesia, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum hydroxide, aluminum carbide Silicon, silicon carbide, sodium carbonate, titanium dioxide, zinc oxide, zirconia, quartz, diamond powder, diamond powder, graphite, magnesium carbonate, potassium titanate, ceramic fiber, mica, boehmite (ALOOH), high temperature resistance Aluminum hydroxide (ALH), zinc molybdate, ammonium molybdate, zinc borate, calcium phosphate, calcined talc, talc, silicon nitride, kaolin kaolin, clay, basic magnesium sulfate whisker, barium sulfate, magnesium hydroxide crystal Any one or a mixture of at least two of magnesium oxide whiskers, calcium oxide whiskers, carbon nanotubes, nano-sized inorganic powders or powder particles having an outer core of the nucleus
  • the inorganic filler is a particle powder having a particle diameter of 100 ⁇ m or less, preferably a particle powder having a particle diameter of 1 to 20 ⁇ m, preferably a particle diameter of 1 ⁇ m or less to a nano-sized granular powder.
  • the needle-like inorganic filler is a powder having a diameter of 50 ⁇ m or less and a length of 1-200 ⁇ m.
  • the flame retardant is selected from one or a combination of two or more of a phosphorus-containing flame retardant, a nitrogen-containing flame retardant, or a bromine-containing flame retardant.
  • a phosphorus-containing flame retardant such as OP-935, SPB-100 or PX-200
  • nitrogen-containing flame retardants such as MelamineCyanurate, bromine-containing flame retardants such as TBBPA or Tetra-Bromo-bisphenol A, all of which can be used in the present invention In the technical solution, and achieve a good flame retardant effect.
  • the surfactant (or siloxane coupling agent, siloxane) can be used, and is not particularly limited.
  • vinyltriethoxysilane or vinyltrimethoxysilane is preferably used.
  • the commonly used dispersing agents are BYK-103, BYK-901, BYK-161 and BYK-164, but not limited to this.
  • the silicone type is a rubber and resin type composite
  • the powder is preferably a spherical powder.
  • the addition of the silicone elastomer increases the heat resistance and impact absorbability of the resin composition.
  • commercially available silicone elastomers such as X-52-7030, KMP-605, KMP-602, KMP-601, KMP-600, KMP-590 and KMP-594 produced by Shin-Etsu are not limited to this. .
  • the silicone resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These various additives may be used singly or in combination of two or more kinds.
  • Another object of the present invention is to provide a prepreg comprising a reinforcing material and a resin composition as described above attached to the reinforcing material by impregnation and drying.
  • the reinforcing material is made of natural fibers, organic synthetic fibers, organic fabrics or inorganic fibers.
  • a third object of the present invention is to provide a laminate comprising at least one prepreg as described above which is obtained by heat-press molding at least one prepreg as described above.
  • a fourth object of the present invention is to provide a copper clad laminate comprising at least one laminated prepreg as described above and a side of the prepreg which is laminated on the laminated prepreg Or copper foil on both sides.
  • a fifth object of the present invention is to provide a laminate for printed wiring comprising at least one prepreg as described above.
  • the circuit board made of the above laminate can exhibit good heat resistance and dielectric properties, and is advantageous for signal transmission of a high frequency circuit board.
  • the present invention has the following beneficial effects:
  • the invention converts a polyphenylene ether resin into a polyphenylene ether epoxy prepolymer having a group, and then reacts with a benzoxazine resin, and combines the low dielectric and benzoic acid of the polyphenylene ether resin.
  • the glass fiber cloth wettability of the resin composition of the prepolymer of the epoxy resin-modified polyphenylene ether resin gives the obtained resin composition excellent appearance performance, heat resistance, dielectric properties, peel strength, and high Tg.
  • the method for synthesizing the epoxy resin modified polyphenylene ether resin prepolymer disclosed by the invention effectively suppresses the side reaction by using different catalysts, solvents, reaction time and reaction temperature, compared with the conventional synthesis technology.
  • the self-polymerization of epoxy resin can effectively bring the molecular weight of the prepolymer product to or near the theoretical value.
  • the epoxy resin modified polyphenylene ether resin prepolymer obtained by the method for preparing the epoxy resin modified polyphenylene ether resin prepolymer disclosed in the present invention is compounded with a benzoxazine resin.
  • the resulting laminate and copper clad laminate have good appearance, high heat resistance (Tg of 180-210 ° C as measured by the DSC method), and excellent dielectric properties and peel strength.
  • the method for prepolymerizing the epoxy resin modified polyphenylene ether resin disclosed in the invention is simple in operation, green in production process, low in cost, and feasible in mass production.
  • the laminate obtained by using the resin composition of the present invention can have a Tg of 180 to 210 ° C and a peel strength of 1.51 to 1.71 N/cm, which can be tested by PCT (3 hr), and the resistance to dip soldering (288 ° C) is more than 20 min. Dk can reach 3.75 ⁇ 3.87 at 1G, and Df is 0.005 ⁇ 0.008.
  • Figure 1 is a GPC chart of an epoxy resin.
  • FIG. 2 is a GPC chart of a polyphenylene ether resin.
  • Figure 3 is a GPC chart of a prepolymer of an epoxy resin modified polyphenylene ether resin.
  • FIG. 1 is a GPC chart of an epoxy resin, and the specific information is as follows:
  • a phosphorus-containing flame retardant PX-200, Nippon Daihatsu Chemical Co., Ltd.
  • the prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg.
  • the appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
  • epoxy resin modified polyphenylene ether resin 20 parts by weight of a phenol novolac resin, 40 parts by weight of a diamine type benzoxazine resin, 0.1 part by weight of 2-MI 100 parts by weight of molten silica, 20 parts by weight of a phosphorus-containing flame retardant (PX-200, Nippon Daihatsu Chemical Co., Ltd.), and 30 parts by weight of a methyl ethyl ketone solvent were mixed and uniformly dispersed.
  • PX-200 phosphorus-containing flame retardant
  • the prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg.
  • the appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
  • the prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg.
  • the appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
  • a phosphorus-containing flame retardant PX-200, Nippon Daihatsu Chemical Co., Ltd.
  • the prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg.
  • the appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
  • the prepolymer of the epoxy resin modified polyphenylene ether resin of the step (1) 60 parts by weight of the prepolymer of the epoxy resin modified polyphenylene ether resin of the step (1), 20 parts by weight of a phenol novolac resin, 40 parts by weight of a diamine type benzoxazine resin, and 0.1 part by weight of 2-MI 100 parts by weight of molten silica, 20 parts by weight of a phosphorus-containing flame retardant (PX-200, Nippon Daihatsu Chemical Co., Ltd.), and 30 parts by weight of a methyl ethyl ketone solvent were mixed and uniformly dispersed.
  • the weight average molecular weight was 6,400.
  • the prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg.
  • the appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
  • a phosphorus-containing flame retardant PX-200, Nippon Daihatsu Chemical Co., Ltd.
  • the prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg.
  • the appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
  • a phosphorus-containing flame retardant PX-200, Nippon Daihatsu Chemical Co., Ltd.
  • the prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg.
  • the appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
  • a phosphorus-containing flame retardant PX-200, Nippon Daihatsu Chemical Co., Ltd.
  • the prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg.
  • the appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
  • PPO solid polyphenylene ether resin 100 parts by weight of PPO solid polyphenylene ether resin is added to methyl ethyl ketone solvent to dissolve liquid polyphenylene ether resin solution, and then 24 parts by weight of bisphenol A type epoxy resin and 0.05 part by weight of 2-methylimidazole (2-methylimidazole, 2-MI), added to the butanone solution, and stirred at 120 ° C for 1-3 hours.
  • the obtained solution was measured by molecular weight of GPC, and the weight average molecular weight was 4,000.
  • a phosphorus-containing flame retardant PX-200, Nippon Daihatsu Chemical Co., Ltd.
  • the prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg.
  • the appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 3.
  • a phosphorus-containing flame retardant PX-200, Nippon Daihatsu Chemical Co., Ltd.
  • the prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg.
  • the appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 3.
  • the prepreg composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth and baked at 170 ° C for 3 minutes to prepare a prepreg prepreg as shown in Table 1;
  • the copper foil is laminated on both sides of the prepared four prepregs, and is pressed and synthesized by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 and a pressing time of 90 min to obtain a kind of copper foil.
  • a copper foil laminate in which the semi-cured film is cured to form an insulating layer between the two copper foils, and the performance test is shown in Table 3.
  • the epoxy resin and the benzoxazine resin composition were impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg.
  • the appearance of the prepreg is shown in Table 1; Superimposed on both sides of the prepared four prepregs, using a vacuum hot press, at a temperature of 190 ° C, a pressure of 35 kg / cm 2 , a pressing time of 90 min, press synthesis to obtain a copper foil product
  • the laminate, wherein the semi-cured film is cured to form an insulation layer between the two copper foils, and the performance test is shown in Table 3.
  • the epoxy resin, the benzoxazine resin and the unmodified polyphenylene ether resin composition are impregnated with the glass fiber cloth and baked at 170 ° C for 3 minutes to prepare a prepreg.
  • the appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed and synthesized by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 and a pressing time of 90 min.
  • a copper foil laminate in which a semi-cured film is cured to form an insulating layer between two copper foils, and the performance test is shown in Table 3.
  • the characteristic test data of the laminates obtained in Examples 1 to 9 are shown in Table 2, and the comparative examples are one to five.
  • the resulting laminates were subjected to characteristic test data as shown in Table 3.
  • the results of the examples show that the preparation method of the epoxy-modified polyphenylene ether resin of the present invention uses different epoxy resins (Examples 1, 2 and 9), the ratio of different epoxy resins to polyphenylene ether resins (Examples) Two to four), ideal epoxy-modified polyphenylene ether prepolymerization can be obtained at the reaction temperature of the present invention at 125-160 ° C (Examples 2, 5 and 6) and different catalyst types (Examples 1, 7 and 8). Things.
  • the ring disclosed in the present invention is contained in comparison with the obtained resin composition (Comparative Example 4) containing no epoxy-modified polyphenylene ether resin or the resin composition containing the unmodified polyphenylene ether resin (Comparative Example 5)
  • the resin composition obtained from the resin composition of the oxy resin modified polyphenylene ether resin has better dielectric properties (Dk/Df) and Tg (glass transition temperature), wherein lower Dk and Df values are preferred electrical properties, Tg temperature Higher is the preferred Tg.
  • Comparative Example 1 show that the reaction temperature is 100-120 ° C and the reaction time is 1-3 hours without modifying the polyphenylene ether resin, and the reaction time is prolonged to 6 hours in time (Comparative Example 2). The effect is not obvious.
  • the temperature is raised to 145 ° C, the dielectric properties and Tg of the laminate containing the resin prepolymer are significantly improved, but since the reaction time is too short, the epoxy group does not react with the hydroxyl group of the polyphenylene ether resin.
  • the resulting sheet properties were much lower than those obtained with the prepolymer at 145 ° C for 6 hours (Examples 1 through 9).
  • the properties of the sheets obtained in Comparative Examples 1 and 2 and Comparative Examples 4 and 5 were not much different. It also showed that the reaction at 100-120 ° C for 1-3 hours did not effectively modify the polyphenylene ether resin.
  • the method for preparing an epoxy-modified polyphenylene ether resin provided by the present invention and the resin composition comprising the epoxy-modified polyphenylene ether resin and the benzoxazine resin have a wide range of applications and have a large range. Production value.

Abstract

The present invention provides a resin composition, and a prepreg and a laminated board using the same. The resin composition comprises an epoxy resin-modified polyphenylene oxide resin prepolymer and a benzoxazine resin. The present invention applies the epoxy resin-modified polyphenylene oxide resin prepolymer in a resin composition for a printed circuit board, improving a dielectric performance of a copper clad laminate and increasing a glass fabric impregnation of the resin composition comprising the epoxy resin-modified polyphenylene oxide resin prepolymer. The resulting resin composition thereby provides excellent appearance, heat resistance, dielectric performance and peeling strength.

Description

一种树脂组合物以及使用它的预浸料和层压板Resin composition and prepreg and laminate using same 技术领域Technical field
本发明属于覆铜板技术领域，具体涉及一种树脂组合物以及使用它的预浸料和层压板。The invention belongs to the technical field of copper clad laminates, and in particular relates to a resin composition and a prepreg and a laminate using the same.
背景技术Background technique
聚苯醚树脂具有优良的耐水性、尺寸稳定性、阻燃性能和介电性能，而且通过与其他混合而获得综合性能更为优异的树脂组合物。从而作为原材料广泛的应用于各种领域，例如，管子附件(plumbing fixtures)，电器盒，汽车部件，和涂覆线材，铜箔层压板和印刷电路等。The polyphenylene ether resin has excellent water resistance, dimensional stability, flame retardancy, and dielectric properties, and is obtained by mixing with others to obtain a resin composition which is more excellent in overall performance. Thus, it is widely used as a raw material in various fields, for example, plumbing fixtures, electrical boxes, automobile parts, and coated wires, copper foil laminates, and printed circuits.
基于聚苯醚树脂的铜箔层压板虽可取得优秀的介电性能，但现有技术应用中，仅采用聚苯醚树脂与其它树脂组合物进行简单的物理共混成均一的胶水清漆，浸渍于玻璃纤维布表面而制得半固化胶片，进而进行固化压合等一系列工序而制得铜箔层合板。由于聚苯醚树脂极性较低，与树脂组合物中的其它树脂的相容性较差，进行影响预浸料的表观；此外，聚苯醚树脂与玻璃纤维布的含浸性也不理想，容易在玻璃布表面聚集成薄膜，这也会影响预浸料的表观，进而对产品的介电性能产生不利影响。Although the polyphenylene ether resin-based copper foil laminate can achieve excellent dielectric properties, in the prior art application, only the polyphenylene ether resin and other resin compositions are simply physically blended into a uniform glue varnish, immersed in A semi-cured film is obtained on the surface of the glass fiber cloth, and a series of processes such as curing and pressing are performed to obtain a copper foil laminate. Since the polyphenylene ether resin has a low polarity and is inferior in compatibility with other resins in the resin composition, it affects the appearance of the prepreg; in addition, the impregnation property of the polyphenylene ether resin and the glass fiber cloth is not satisfactory. It is easy to aggregate the film on the surface of the glass cloth, which also affects the appearance of the prepreg, which in turn adversely affects the dielectric properties of the product.
公开号为CN1556830的专利提出了一种官能化聚苯醚的方法，即将聚苯醚与双酚A型环氧树脂在胺类催化剂的作用下发生反应，获得了两端基分别具有两个环氧基团的聚苯醚/环氧树脂预聚体，该方法在一定程度上改善了上文所提到的聚苯醚的应用问题，但是引入的双酚A型环氧树脂却对树脂分子的介电性能产生了不利影响-使其Dk/Df增大。Patent No. CN1556830 proposes a method for functionalizing polyphenylene ether, which is to react polyphenylene ether with bisphenol A epoxy resin under the action of an amine catalyst, and obtain two rings at both ends. A polyphenylene ether/epoxy resin prepolymer of an oxygen group, which improves the application of the above-mentioned polyphenylene ether to a certain extent, but the introduction of the bisphenol A type epoxy resin to the resin molecule The dielectric properties have an adverse effect - making their Dk/Df increase.
发明内容 Summary of the invention
本发明的目的之一在于提供一种树脂组合物，其采用环氧树脂改性聚苯醚树脂预聚体与苯并噁嗪树脂配合，使其具有优异的外观表现、超高的耐热性(DSC方法测得的Tg达到180-210℃)以及优异的介电性能和剥离强度。One of the objects of the present invention is to provide a resin composition which is prepared by using an epoxy resin-modified polyphenylene ether resin prepolymer and a benzoxazine resin to have excellent appearance and high heat resistance. (The Tg measured by the DSC method reaches 180-210 ° C) and excellent dielectric properties and peel strength.
为了实现上述目的，本发明采用了如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种树脂组合物，该树脂组合物包含环氧树脂改性聚苯醚树脂的预聚体和苯并噁嗪树脂。A resin composition comprising a prepolymer of an epoxy resin modified polyphenylene ether resin and a benzoxazine resin.
本发明通过把聚苯醚树脂改性为带有基团的聚苯醚环氧预聚体，然后与苯并噁嗪树脂配合反应，同时结合了聚苯醚树脂的低介电和苯并噁嗪树脂的高耐热、高Tg和阻燃的优点。因此，将含有环氧改性的聚苯醚树脂预聚体和苯并噁嗪的树脂组合物用于印刷电路板的树脂组合物中，不仅能够改善覆铜板的介电性能，并提高含有该环氧树脂改性聚苯醚树脂的预聚体的树脂组合物的玻璃纤维布浸润性，使得到的树脂组合物具有优异的外观表现、耐热性、介电性能和剥离强度和高Tg。The invention converts a polyphenylene ether resin into a polyphenylene ether epoxy prepolymer having a group, and then reacts with a benzoxazine resin, and combines the low dielectric and benzoic acid of the polyphenylene ether resin. The advantages of high heat resistance, high Tg and flame retardancy of the azine resin. Therefore, the resin composition containing the epoxy-modified polyphenylene ether resin prepolymer and benzoxazine is used in the resin composition of the printed circuit board, not only can improve the dielectric properties of the copper clad laminate, but also improve the inclusion of the resin composition. The glass fiber cloth wettability of the resin composition of the prepolymer of the epoxy resin-modified polyphenylene ether resin gives the obtained resin composition excellent appearance performance, heat resistance, dielectric properties, peel strength, and high Tg.
优选地，所述环氧树脂改性聚苯醚树脂的预聚体具有如式(I)所示的结构：Preferably, the prepolymer of the epoxy resin modified polyphenylene ether resin has a structure as shown in formula (I):
Figure PCTCN2016082107-appb-000001
Figure PCTCN2016082107-appb-000001
其中，X为：
Figure PCTCN2016082107-appb-000002
Where X is:
Figure PCTCN2016082107-appb-000002
其中，R为取代或未取代的C1～C5的亚烷基、单键、-SO2-、-O-、-CO-、-SO-或-SC-；Wherein R is a substituted or unsubstituted C1-C5 alkylene group, a single bond, -SO 2 -, -O-, -CO-, -SO- or -SC-;
Y为官能化环氧树脂的官能基团； Y is a functional group of the functionalized epoxy resin;
Z1、Z2、Z3、Z4相同或不同，均独立地为氢原子、卤素原子、碳原子数8以下的烷基(例如C1、C2、C3、C4、C5、C6或C7)或苯基；Z 1 , Z 2 , Z 3 , and Z 4 are the same or different and are each independently a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms (for example, C1, C2, C3, C4, C5, C6 or C7) or Phenyl group;
n为大于1的正整数。需要说明的是，n表示高分子化合物的聚合度，上述各式及下面列举的各式中，n均分别取相同或不同的值。n is a positive integer greater than one. In addition, n represents the degree of polymerization of a polymer compound, and in each of the above formulae and each of the following formulae, n is the same or different value.
优选地，式(I)中，X为Preferably, in the formula (I), X is
Figure PCTCN2016082107-appb-000003
Figure PCTCN2016082107-appb-000003
优选地，所述聚苯醚树脂分子结构如式(II)所示：Preferably, the molecular structure of the polyphenylene ether resin is as shown in formula (II):
Figure PCTCN2016082107-appb-000004
Figure PCTCN2016082107-appb-000004
其中，X为：
Figure PCTCN2016082107-appb-000005
Where X is:
Figure PCTCN2016082107-appb-000005
其中，R为取代或未取代的C1～C5的亚烷基、单键、-SO2-、-O-、-CO-、-SO-或-SC-；Wherein R is a substituted or unsubstituted C1-C5 alkylene group, a single bond, -SO 2 -, -O-, -CO-, -SO- or -SC-;
Z1、Z2、Z3、Z4相同或不同，均独立地为氢原子、卤素原子、碳原子数8以下的烷基(例如C1、C2、C3、C4、C5、C6或C7)或苯基；Z 1 , Z 2 , Z 3 , and Z 4 are the same or different and are each independently a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms (for example, C1, C2, C3, C4, C5, C6 or C7) or Phenyl group;
n为大于1的正整数。n is a positive integer greater than one.
优选地，式(II)中的X为： Preferably, X in formula (II) is:
Figure PCTCN2016082107-appb-000006
Figure PCTCN2016082107-appb-000006
优选地，所述聚苯醚树脂的分子结构式如式(III)或式(IV)所示：Preferably, the molecular structure formula of the polyphenylene ether resin is as shown in formula (III) or formula (IV):
Figure PCTCN2016082107-appb-000007
Figure PCTCN2016082107-appb-000007
n为大于1的正整数。n is a positive integer greater than one.
优选地，所述官能化环氧树脂为异氰酸酯改性双酚A环氧树脂、异氰酸酯改性双酚F环氧树脂、异氰酸酯改性双酚S环氧树脂、苯酚酚醛环氧树脂、双酚A酚醛环氧树脂、邻甲酚酚醛环氧树脂、三官能基环氧树脂、四官能基环氧树脂、二环戊二烯环氧树脂、对氨基苯酚环氧树脂、三聚氰酸环氧树脂、含磷环氧树脂、含氮环氧树脂、对二甲苯环氧树脂、萘型环氧树脂、苯并呱喃型环氧树脂、联苯酚醛环氧树脂或酚基苯烷基酚醛环氧树脂中的任意一种或者至少两种的混合物。Preferably, the functionalized epoxy resin is an isocyanate modified bisphenol A epoxy resin, an isocyanate modified bisphenol F epoxy resin, an isocyanate modified bisphenol S epoxy resin, a phenol novolac epoxy resin, a bisphenol A Phenolic epoxy resin, o-cresol novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene epoxy resin, p-aminophenol epoxy resin, cyanuric acid epoxy resin , phosphorus-containing epoxy resin, nitrogen-containing epoxy resin, p-xylene epoxy resin, naphthalene epoxy resin, benzopyrene epoxy resin, biphenolic epoxy resin or phenolic phenylalkylphenol aldehyde epoxy Any one of the resins or a mixture of at least two.
优选地，式(I)中Y为如下结构中的任意一种：Preferably, Y in the formula (I) is any one of the following structures:
Figure PCTCN2016082107-appb-000008
Figure PCTCN2016082107-appb-000008
Figure PCTCN2016082107-appb-000009
Figure PCTCN2016082107-appb-000009
Figure PCTCN2016082107-appb-000010
Figure PCTCN2016082107-appb-000010
其中，m和n均独立地为大于1的正整数。Wherein m and n are each independently a positive integer greater than one.
优选地，所述环氧树脂改性聚苯醚树脂的预聚体是由固态的聚苯醚树脂与环氧树脂按照如下方法反应而制得：Preferably, the prepolymer of the epoxy resin modified polyphenylene ether resin is obtained by reacting a solid polyphenylene ether resin with an epoxy resin according to the following method:
将环氧树脂20-80重量份及催化剂0.005～10重量份，在升温及搅拌下溶解；再将固态的聚苯醚树脂50重量份，溶解于有机溶剂制成固含量为30～70％的聚苯醚树脂溶液，然后将其缓慢滴加入上述环氧树脂熔融体中，滴加完毕后于125～160℃(例如125℃、130℃、135℃、140℃、145℃、150℃或155℃)下搅拌反应3.5-12小时(例如4小时、5小时、6小时、7小时、8小时、9小时、10小时或11小时)，制得环氧树脂改性聚苯醚树脂的预聚体溶液。20-80 parts by weight of the epoxy resin and 0.005-10 parts by weight of the catalyst are dissolved under heating and stirring; and 50 parts by weight of the solid polyphenylene ether resin is dissolved in an organic solvent to obtain a solid content of 30 to 70%. a polyphenylene ether resin solution, which is then slowly added dropwise to the above epoxy resin melt, and after the addition is completed, at 125 to 160 ° C (for example, 125 ° C, 130 ° C, 135 ° C, 140 ° C, 145 ° C, 150 ° C or 155) The reaction is stirred for 3.5-12 hours (for example, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours or 11 hours) to prepare a prepolymerized epoxy resin modified polyphenylene ether resin. Body solution.
在环氧树脂改性聚苯醚树脂的预聚体制备过程中，反应温度和反应时间对于产物的质量和制备效率存在重要的影响。当反应温度低于125℃，无论反应时间多长，环氧基团和聚苯醚的羟基几乎不发生反应，而反应温度高于160℃则会导致环氧自聚甚至交联等副反应大大增加，均无法得到环氧改性聚苯醚预 聚体；当反应温度高于125℃时，反应时间若少于3.5小时则聚苯醚末端官能基不能充分接上环氧官能基，从而影响环氧改性聚苯醚树脂在树脂组合物中的改善效果，若反应时间长于12小时则会导致副反应产生而引起环氧基团自聚。In the preparation of the prepolymer of the epoxy resin modified polyphenylene ether resin, the reaction temperature and reaction time have an important influence on the quality of the product and the preparation efficiency. When the reaction temperature is lower than 125 ° C, the epoxy group and the hydroxyl group of the polyphenylene ether hardly react regardless of the reaction time, and the reaction temperature is higher than 160 ° C, which may cause a large side reaction such as epoxy self-polymerization or even crosslinking. No increase in epoxy-modified polyphenylene ether When the reaction temperature is higher than 125 ° C, if the reaction time is less than 3.5 hours, the polyphenylene ether terminal functional group cannot be sufficiently bonded to the epoxy functional group, thereby affecting the epoxy modified polyphenylene ether resin in the resin composition. The improvement effect, if the reaction time is longer than 12 hours, causes a side reaction to occur and causes the epoxy group to self-polymerize.
采用本发明的环氧树脂改性聚苯醚树脂的预聚体的制备方法的优点在于：Advantages of the method for preparing a prepolymer using the epoxy resin modified polyphenylene ether resin of the present invention are:
利用高沸点溶剂作为反应溶剂，不仅可以提高预聚的反应温度使反应顺利进行，溶剂的低挥发性还可以提供稳定的反应环境。此外，本发明中所用的催化剂能够选择性地优先催化环氧与聚苯醚端羟基的反应，得到环氧改性的聚苯醚预聚体目标产品，避免了环氧树脂本身的自聚反应而导致的反应过度，造成产物的分子量过大、交联点少，降低树脂固化体的强度。如制备同样结构的环氧树脂改性聚苯醚树脂的预聚体，采用的制备方法是：将固态的聚苯醚树脂100份、添加聚合反应溶剂后溶成液态聚苯醚树脂溶液，再将环氧树脂24-35份及咪唑类催化剂0.001-5份，加入溶液中，于100-120下搅拌混合1-3小时而制得预聚合溶液。该方法采用的有机溶剂沸点低，容易在基反应问题下挥发，或是造成其反应温度不稳定。此外，该方法忽略了环氧树脂本身的自聚反应，从而导致反应过度，造成产物的分子量过大，降低了树脂固化体的强度。The use of a high boiling point solvent as a reaction solvent not only increases the reaction temperature of the prepolymerization, but also allows the reaction to proceed smoothly. The low volatility of the solvent also provides a stable reaction environment. In addition, the catalyst used in the present invention can selectively preferentially catalyze the reaction of the epoxy with the terminal hydroxyl group of the polyphenylene ether to obtain the target product of the epoxy-modified polyphenylene ether prepolymer, thereby avoiding the self-polymerization reaction of the epoxy resin itself. The resulting reaction is excessive, resulting in an excessive molecular weight of the product, a small number of crosslinking points, and a decrease in the strength of the cured resin body. For example, a prepolymer of an epoxy resin modified polyphenylene ether resin having the same structure is prepared by preparing 100 parts of a solid polyphenylene ether resin, adding a polymerization solvent, and dissolving into a liquid polyphenylene ether resin solution, and then 24-35 parts of an epoxy resin and 0.001-5 parts of an imidazole catalyst are added to the solution, and the mixture is stirred and mixed at 100-120 for 1-3 hours to prepare a prepolymerized solution. The organic solvent used in the method has a low boiling point, is easily volatilized under the problem of the base reaction, or causes the reaction temperature to be unstable. Further, this method neglects the self-polymerization reaction of the epoxy resin itself, resulting in overreaction, resulting in an excessive molecular weight of the product and a decrease in the strength of the cured resin body.
优选地，所述催化剂为聚醚类、环状冠醚类、胺类、无机强碱或无机强酸中的任意一种或者至少两种的混合物。Preferably, the catalyst is any one of a polyether, a cyclic crown ether, an amine, an inorganic strong base or an inorganic strong acid or a mixture of at least two.
优选地，所述聚醚类为链状聚乙二醇(H-(OCH2CH2)n-OH)或/和链状聚乙二醇二烷基醚(R(OCH2CH2)n-OR)等。Preferably, the polyether is a chain polyethylene glycol (H-(OCH2CH2) n -OH) or/and a chain polyethylene glycol dialkyl ether (R(OCH2CH2) n -OR) or the like.
优选地，所述环状冠醚类为18冠6、15冠5或环糊精等中的任意一种或者至少两种的混合物。Preferably, the cyclic crown ether is any one of 18 crown 6, 15 crown 5 or cyclodextrin, or a mixture of at least two.
优选地，所述胺类为季铵盐、叔胺或吡啶化合物中的任意一种或者至少两种的混合物。 Preferably, the amine is any one of a quaternary ammonium salt, a tertiary amine or a pyridine compound or a mixture of at least two.
优选地，所述季铵盐为苄基三乙基氯化铵(TEBA)、四丁基溴化铵、四丁基氯化铵、四丁基硫酸氢铵(TBAB)、三辛基甲基氯化铵、十二烷基三甲基氯化铵或十四烷基三甲基氯化铵等中的任意一种或者至少两种的混合物；Preferably, the quaternary ammonium salt is benzyltriethylammonium chloride (TEBA), tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate (TBAB), trioctylmethyl Any one or a mixture of at least two of ammonium chloride, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride;
优选地，所述叔胺为R3N，其中R为碳原子数18以下的支链或直链烷基、取代或不取代的苯基，优选三乙胺、三丁胺、二辛基甲胺或二苯基甲胺等中的任意一种或者至少两种的混合物。Preferably, the tertiary amine is R 3 N, wherein R is a branched or linear alkyl group having 18 or less carbon atoms, a substituted or unsubstituted phenyl group, preferably triethylamine, tributylamine, dioctyl Any one or a mixture of at least two of an amine or diphenylmethylamine.
优选地，所述吡啶化合物为吡啶、带有8个以下碳原子支链或直链烷烃取代基的吡啶、苯基吡啶或联吡啶等中的任意一种或者至少两种的混合物。Preferably, the pyridine compound is any one of pyridine, pyridine, phenylpyridine or bipyridine having a chain of 8 or less carbon atoms or a linear alkane substituent, or a mixture of at least two.
优选地，所述联吡啶为2，2’-联吡啶、4，4’-联吡啶、2，4’-联吡啶或2，3’-联吡啶中的任意一种或者至少两种的混合物。Preferably, the bipyridine is any one of 2,2'-bipyridine, 4,4'-bipyridine, 2,4'-bipyridine or 2,3'-bipyridine or a mixture of at least two .
优选地，所述无机强碱为氢氧化钠或/和氢氧化钾。Preferably, the inorganic strong base is sodium hydroxide or/and potassium hydroxide.
优选地，所述无机强酸为浓硫酸、盐酸或硝酸等中的任意一种或者至少两种的混合物。Preferably, the inorganic strong acid is any one of concentrated sulfuric acid, hydrochloric acid or nitric acid, or a mixture of at least two.
优选地，所述搅拌反应的温度为135-150℃，搅拌反应的时间为4-8小时。Preferably, the temperature of the stirring reaction is 135-150 ° C, and the stirring reaction time is 4-8 hours.
优选地，所述有机溶剂为N，N-二甲基甲酰胺、N，N-二乙基甲酰胺、环己酮、甲苯、二甲苯、三甲苯或四甲苯中的任意一种或者至少两种的混合溶剂。Preferably, the organic solvent is any one of N,N-dimethylformamide, N,N-diethylformamide, cyclohexanone, toluene, xylene, trimethylbenzene or tetramethylbenzene or at least two Kind of mixed solvent.
在环氧树脂改性聚苯醚树脂的预聚体制备过程中，所用原料的配比以及催化剂的用量对于产物的质量和制备效率存在重要的影响。In the preparation of the prepolymer of the epoxy resin modified polyphenylene ether resin, the ratio of the raw materials used and the amount of the catalyst have an important influence on the quality of the product and the production efficiency.
以重量份计，相对于50重量份的聚苯醚树脂，若环氧树脂不足20重量份，则聚苯醚末端官能基不能充分接上环氧官能基，从而影响聚苯醚树脂的环氧基改善效率；若环氧树脂超过80重量份，则反应完成后，过多的环氧树脂会影响树脂组合物的配方设计。优选地，环氧树脂的添加量为30～70重量份，优选为40～60重量份。另外，若催化剂不足0.005重量份则反应速率较慢，导致反应时 间变长，影响反应效率及成本；若催化剂超过10重量份则会使反应速率太快，导致副反应产生而引起环氧基团自聚。优选地，催化剂的添加量为0.005～5重量份，优选0.005～1重量份。In terms of parts by weight, if the epoxy resin is less than 20 parts by weight relative to 50 parts by weight of the polyphenylene ether resin, the polyphenylene ether terminal functional group cannot be sufficiently bonded to the epoxy functional group, thereby affecting the epoxy of the polyphenylene ether resin. Base improvement efficiency; if the epoxy resin exceeds 80 parts by weight, excessive epoxy resin may affect the formulation design of the resin composition after the reaction is completed. Preferably, the epoxy resin is added in an amount of 30 to 70 parts by weight, preferably 40 to 60 parts by weight. In addition, if the catalyst is less than 0.005 parts by weight, the reaction rate is slow, resulting in a reaction time. The length is long, which affects the reaction efficiency and cost; if the catalyst exceeds 10 parts by weight, the reaction rate is too fast, resulting in a side reaction resulting in self-polymerization of the epoxy group. Preferably, the catalyst is added in an amount of 0.005 to 5 parts by weight, preferably 0.005 to 1 part by weight.
优选地，所述方法为：将固态的聚苯醚树脂50份，添加聚合反应溶剂后溶成液态聚苯醚树脂溶液，再将环氧树脂30-70份及催化剂0.005～1份，加入溶液中，于130～150℃下搅拌反应4～8小时而得预聚体溶液。Preferably, the method comprises: adding 50 parts of the solid polyphenylene ether resin, adding a polymerization solvent, dissolving into a liquid polyphenylene ether resin solution, and then adding 30-70 parts of the epoxy resin and 0.005 to 1 part of the catalyst to the solution. The reaction was stirred at 130 to 150 ° C for 4 to 8 hours to obtain a prepolymer solution.
优选地，在树脂组合物中，环氧树脂改性聚苯醚树脂的预聚体的添加量为20-80重量份。Preferably, the prepolymer of the epoxy resin-modified polyphenylene ether resin is added in an amount of 20 to 80 parts by weight in the resin composition.
优选地，在树脂组合物中，所述苯并噁嗪树脂的含量为10-60重量份，例如15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份、50重量份或55重量份。Preferably, in the resin composition, the content of the benzoxazine resin is 10 to 60 parts by weight, for example, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight or 55 parts by weight.
优选地，所述苯并噁嗪树脂为双酚A苯并噁嗪、双酚F苯并噁嗪、双酚S苯并噁嗪、二胺型苯并噁嗪、酚酞型苯并噁嗪或二环戊二烯型苯并噁嗪中的任意一种或者至少两种的混合物。Preferably, the benzoxazine resin is bisphenol A benzoxazine, bisphenol F benzoxazine, bisphenol S benzoxazine, diamine benzoxazine, phenolphthalein benzoxazine or Any one or a mixture of at least two dicyclopentadiene type benzoxazines.
优选地，所述树脂组合物中还包含固化剂，其含量为5～50重量份。Preferably, the resin composition further contains a curing agent in an amount of 5 to 50 parts by weight.
优选地，所述固化剂选自线性酚醛树脂、苯乙烯马来酸酐共聚物树脂、DDS或DDM等中的任意一种或者两种以上的混合物。Preferably, the curing agent is selected from any one of a novolac resin, a styrene maleic anhydride copolymer resin, DDS or DDM, or a mixture of two or more.
优选地，所述树脂组合物中还包含固化促进剂，其含量为0.01～10重量份。Preferably, the resin composition further contains a curing accelerator in an amount of from 0.01 to 10 parts by weight.
本发明所揭露的树脂组合物，所用原料的用量对于产物的质量、制备效率存在重要的影响。具体而言，相对于50-90重量份的环氧树脂改性聚苯醚树脂的预聚体，若固化剂不足5重量份，则环氧树脂改性聚苯醚树脂的预聚体末端的环氧官能基不能充分反应固化，使得组合物的Tg(玻璃转化温度)过低；若固化剂超过50重量份则会残留过量未反应的交联剂，使得组合物的耐热性、Tg 等性能不佳。In the resin composition disclosed by the present invention, the amount of the raw materials used has an important influence on the quality of the product and the production efficiency. Specifically, with respect to 50-90 parts by weight of the prepolymer of the epoxy resin-modified polyphenylene ether resin, if the curing agent is less than 5 parts by weight, the prepolymer end of the epoxy resin-modified polyphenylene ether resin The epoxy functional group is not sufficiently reacted and cured, so that the Tg (glass transition temperature) of the composition is too low; if the curing agent exceeds 50 parts by weight, an excess of unreacted crosslinking agent remains, so that the heat resistance of the composition, Tg Performance is not good.
若固化促进剂不足0.01重量份则应速率较慢，无明显催化效果；若固化促进剂超过10重量份则使反应速率太快，影响产物的制备过程和产物的质量。If the curing accelerator is less than 0.01 parts by weight, the rate should be slow, and there is no obvious catalytic effect; if the curing accelerator exceeds 10 parts by weight, the reaction rate is too fast, which affects the preparation process of the product and the quality of the product.
优选地，所述固化促进剂选自咪唑(imidazole)、三氟化硼胺复合物、氯化乙基三苯基鏻(ethyltriphenylphosphoniumchloride)、2-甲基咪唑(2-methylimidazole，2-MI)、2-苯基咪唑(2-phenyl-1H-imidazole，2PZ)、2-乙基-4-甲基咪唑(2-ethyl-4-methylimidazole，2E4MZ)、三苯基膦(tri-phenylphosphine，TPP)或4-二甲基胺基吡啶(4-dimethylaminopyridine，DMAP)中的任意一种或者至少两种的组合的刘易斯碱，或选自锰、铁、钴、镍、铜或锌中的任意一种或者至少两种的金属盐化合物的刘易斯酸，或选自有机过氧化物，如过氧化二异丙苯(DCP，DicumylPeroxide)。Preferably, the curing accelerator is selected from the group consisting of imidazole, boron trifluoride amine complex, ethyltriphenylphosphonium chloride, 2-methylimidazole (2-MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MZ), tri-phenylphosphine (TPP) Or a Lewis base of any one or a combination of at least two of 4-dimethylaminopyridine (DMAP), or any one selected from the group consisting of manganese, iron, cobalt, nickel, copper or zinc. Or a Lewis acid of at least two metal salt compounds, or an organic peroxide selected from, for example, dicumyl peroxide (DCP, Dicumyl Peroxide).
优选地，所述树脂组成进一步包括5～60重量份(例如10重量份、15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份、50重量份或55重量份)的未经预聚合的环氧树脂。Preferably, the resin composition further comprises 5 to 60 parts by weight (for example, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight) Parts or 55 parts by weight of unprepolymerized epoxy resin.
优选地，所述环氧树脂为异氰酸酯改性双酚A环氧树脂、异氰酸酯改性双酚F环氧树脂、异氰酸酯改性双酚S环氧树脂、苯酚酚醛环氧树脂、双酚A酚醛环氧树脂、邻甲酚酚醛环氧树脂、三官能基环氧树脂、四官能基环氧树脂、二环戊二烯环氧树脂、对氨基苯酚环氧树脂、三聚氰酸环氧树脂、含磷环氧树脂、含氮环氧树脂、含溴环氧树脂、对二甲苯环氧树脂、萘型环氧树脂、苯并呱喃型环氧树脂、联苯酚醛环氧树脂或酚基苯烷基酚醛环氧树脂中的任意一种或者两种以上的混合物。Preferably, the epoxy resin is an isocyanate modified bisphenol A epoxy resin, an isocyanate modified bisphenol F epoxy resin, an isocyanate modified bisphenol S epoxy resin, a phenol novolac epoxy resin, a bisphenol A phenolic ring Oxygen resin, o-cresol novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene epoxy resin, p-aminophenol epoxy resin, cyanuric acid epoxy resin, Phosphorus epoxy resin, nitrogen-containing epoxy resin, bromine-containing epoxy resin, p-xylene epoxy resin, naphthalene epoxy resin, benzopyrene epoxy resin, biphenolic epoxy resin or phenolic phenyl benzene Any one or a mixture of two or more kinds of phenolic epoxy resins.
优选地，所述树脂组合物中进一步包含无机填料、阻燃剂、界面活性剂、分散剂、有机硅弹性体或增韧剂中的任意一种或者至少两种的混合物。 Preferably, the resin composition further comprises any one of an inorganic filler, a flame retardant, a surfactant, a dispersant, a silicone elastomer or a toughening agent, or a mixture of at least two.
优选地，所述无机填料包含二氧化硅(熔融态或非熔融态与多孔质)、氧化铝、氧化镁、氢氧化镁、碳酸钙、氮化铝、氮化硼、氢氧化铝、碳化铝硅、碳化硅、碳酸钠、二氧化钛、氧化锌、氧化锆、石英、钻石粉、类钻石粉、石墨、碳酸镁、钛酸钾、陶瓷纤维、云母、勃姆石(boehmite，ALOOH)、耐高温氢氧化铝(ALH)、钼酸锌、钼酸铵、硼酸锌、磷酸钙、煅烧滑石、滑石、氮化硅、段烧高岭土、黏土、碱式硫酸镁晶须、硫酸钡、氢氧化镁晶须、氧化镁晶须、氧化钙晶须、奈米碳管、奈米级无机粉体或具有机核外层壳为绝缘体修饰之粉体粒子中的任意一种或者至少两种的混合物，且无机填料为球型或针须状，或者选择性经由接***性剂预处理。Preferably, the inorganic filler comprises silica (molten or non-molten and porous), alumina, magnesia, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum hydroxide, aluminum carbide Silicon, silicon carbide, sodium carbonate, titanium dioxide, zinc oxide, zirconia, quartz, diamond powder, diamond powder, graphite, magnesium carbonate, potassium titanate, ceramic fiber, mica, boehmite (ALOOH), high temperature resistance Aluminum hydroxide (ALH), zinc molybdate, ammonium molybdate, zinc borate, calcium phosphate, calcined talc, talc, silicon nitride, kaolin kaolin, clay, basic magnesium sulfate whisker, barium sulfate, magnesium hydroxide crystal Any one or a mixture of at least two of magnesium oxide whiskers, calcium oxide whiskers, carbon nanotubes, nano-sized inorganic powders or powder particles having an outer core of the nucleus and an insulator modified, and The inorganic filler is spherical or needle-shaped or optionally pretreated via an interface active agent.
另外，为了保证成品良好的介电性能，无机填充物为粒径100μm以下之颗粒粉末，优选为粒径1-20μm之颗粒粉末，最优为粒径1μm以下至纳米尺寸颗粒状粉末。针须状无机填充物为直径50μm以下且长度为1-200μm的粉末。Further, in order to ensure good dielectric properties of the finished product, the inorganic filler is a particle powder having a particle diameter of 100 μm or less, preferably a particle powder having a particle diameter of 1 to 20 μm, preferably a particle diameter of 1 μm or less to a nano-sized granular powder. The needle-like inorganic filler is a powder having a diameter of 50 μm or less and a length of 1-200 μm.
优选地，所述阻燃剂选自含磷阻燃剂、含氮阻燃剂或含溴阻燃剂的一种或者两种以上的组合。其中，常见的含磷阻燃剂如OP-935、SPB-100或PX-200；含氮阻燃剂如MelamineCyanurate，含溴阻燃剂如TBBPA或Tetra-Bromo-bisphenolA，其均可用于本发明的技术方案中，并达到良好的阻燃效果。Preferably, the flame retardant is selected from one or a combination of two or more of a phosphorus-containing flame retardant, a nitrogen-containing flame retardant, or a bromine-containing flame retardant. Among them, common phosphorus-containing flame retardants such as OP-935, SPB-100 or PX-200; nitrogen-containing flame retardants such as MelamineCyanurate, bromine-containing flame retardants such as TBBPA or Tetra-Bromo-bisphenol A, all of which can be used in the present invention In the technical solution, and achieve a good flame retardant effect.
优选地，所述界面活性剂(或称硅氧烷偶合剂，siloxane)可使用公知者，并无特别限定，具体而言，优选使用乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基参(β-甲氧基-乙氧基硅烷)、γ-环氧丙氧基丙基三甲氧基硅烷或γ-胺丙基三乙氧基硅烷。其中分散剂常用的有德国毕克BYK-103、BYK-901、BYK-161和BYK-164等产品，但不以此为限。Preferably, the surfactant (or siloxane coupling agent, siloxane) can be used, and is not particularly limited. Specifically, vinyltriethoxysilane or vinyltrimethoxysilane is preferably used. Vinyl ginseng (β-methoxy-ethoxysilane), γ-glycidoxypropyltrimethoxysilane or γ-aminopropyltriethoxysilane. Among them, the commonly used dispersing agents are BYK-103, BYK-901, BYK-161 and BYK-164, but not limited to this.
优选地，所述有机硅弹性体(hybridtypesiliconepowder)为橡胶及树脂型复合 粉体，较佳为球状粉体。添加有机硅弹性体可增加该树脂组合物的耐热性和冲击吸收性。一般市售之有机硅弹性体如信越生产的X-52-7030、KMP-605、KMP-602、KMP-601、KMP-600、KMP-590和KMP-594等产品，但不以此为限。Preferably, the silicone type (hybrid type siliconepowder) is a rubber and resin type composite The powder is preferably a spherical powder. The addition of the silicone elastomer increases the heat resistance and impact absorbability of the resin composition. Generally, commercially available silicone elastomers such as X-52-7030, KMP-605, KMP-602, KMP-601, KMP-600, KMP-590 and KMP-594 produced by Shin-Etsu are not limited to this. .
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”。The term "comprising" as used in the present invention means that it may include other components in addition to the components, and these other components impart different characteristics to the resin composition. In addition, the "include" of the present invention may also be replaced by a closed "for" or "consisting of".
例如，所述硅树脂组合物还可以含有各种添加剂，作为具体例，可以举出抗氧剂、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。For example, the silicone resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These various additives may be used singly or in combination of two or more kinds.
本发明的目的之二在于提供一种预浸料，其包括增强材料及通过含浸干燥后附着在增强材料上的如上所述的树脂组合物。Another object of the present invention is to provide a prepreg comprising a reinforcing material and a resin composition as described above attached to the reinforcing material by impregnation and drying.
所述的增强材料采用天然的纤维、有机合成纤维、有机织物或无机纤维制成。The reinforcing material is made of natural fibers, organic synthetic fibers, organic fabrics or inorganic fibers.
本发明的目的之三在于提供一种层压板，所述层压板含有至少一张如上所述的预浸料，其通过将至少一张如上所述的预浸料加热加压成型得到。A third object of the present invention is to provide a laminate comprising at least one prepreg as described above which is obtained by heat-press molding at least one prepreg as described above.
本发明的目的之四在于提供一种覆铜箔层压板，所述覆铜箔层压板包括至少一张叠合的如上所述的预浸料及压覆在叠合后的预浸料的一侧或两侧的铜箔。A fourth object of the present invention is to provide a copper clad laminate comprising at least one laminated prepreg as described above and a side of the prepreg which is laminated on the laminated prepreg Or copper foil on both sides.
本发明的目的之五在于提供一种印制线路用层压板，其含有至少一张如上所述的预浸料。采用上述层压板制成的电路板，能够表现出良好的耐热性和介电性能，有利于高频线路板的信号传输。A fifth object of the present invention is to provide a laminate for printed wiring comprising at least one prepreg as described above. The circuit board made of the above laminate can exhibit good heat resistance and dielectric properties, and is advantageous for signal transmission of a high frequency circuit board.
与已有技术相比，本发明具有如下有益效果： Compared with the prior art, the present invention has the following beneficial effects:
本发明通过把聚苯醚树脂改性为带有基团的聚苯醚环氧预聚体，然后与苯并噁嗪树脂配合反应，同时结合了聚苯醚树脂的低介电和苯并噁嗪树脂的高耐热、高Tg和阻燃的优点。因此，将含有环氧改性的聚苯醚树脂预聚体和苯并噁嗪的树脂组合物用于印刷电路板的树脂组合物中，不仅能够改善覆铜板的介电性能，并提高含有该环氧树脂改性聚苯醚树脂的预聚体的树脂组合物的玻璃纤维布浸润性，使得到的树脂组合物具有优异的外观表现、耐热性、介电性能和剥离强度和高Tg。The invention converts a polyphenylene ether resin into a polyphenylene ether epoxy prepolymer having a group, and then reacts with a benzoxazine resin, and combines the low dielectric and benzoic acid of the polyphenylene ether resin. The advantages of high heat resistance, high Tg and flame retardancy of the azine resin. Therefore, the resin composition containing the epoxy-modified polyphenylene ether resin prepolymer and benzoxazine is used in the resin composition of the printed circuit board, not only can improve the dielectric properties of the copper clad laminate, but also improve the inclusion of the resin composition. The glass fiber cloth wettability of the resin composition of the prepolymer of the epoxy resin-modified polyphenylene ether resin gives the obtained resin composition excellent appearance performance, heat resistance, dielectric properties, peel strength, and high Tg.
此外，本发明所揭示的合成环氧树脂改性聚苯醚树脂预聚体的方法，较之以往的合成技术，因选用不同催化剂、溶剂、反应时间以及反应温度等，有效的抑制了副反应——环氧树脂自聚的反应，能够有效的使预聚体产物的分子量达到或接近理论值。In addition, the method for synthesizing the epoxy resin modified polyphenylene ether resin prepolymer disclosed by the invention effectively suppresses the side reaction by using different catalysts, solvents, reaction time and reaction temperature, compared with the conventional synthesis technology. - The self-polymerization of epoxy resin can effectively bring the molecular weight of the prepolymer product to or near the theoretical value.
而且，将采用本发明所揭示的环氧树脂改性聚苯醚树脂预的聚体的制备方法而得到的环氧树脂改性聚苯醚树脂预的聚体，与苯并噁嗪树脂配合，得到的层压材料及覆铜层压板，其具有良好的外观表现、超高的耐热性(DSC方法测得的Tg达到180-210℃)以及优异的介电性能和剥离强度。Moreover, the epoxy resin modified polyphenylene ether resin prepolymer obtained by the method for preparing the epoxy resin modified polyphenylene ether resin prepolymer disclosed in the present invention is compounded with a benzoxazine resin. The resulting laminate and copper clad laminate have good appearance, high heat resistance (Tg of 180-210 ° C as measured by the DSC method), and excellent dielectric properties and peel strength.
另外，本发明所揭示的环氧树脂改性聚苯醚树脂的预聚体的方法操作简便，生产过程绿色环保，成本低廉，具有大规模生产的可行性。In addition, the method for prepolymerizing the epoxy resin modified polyphenylene ether resin disclosed in the invention is simple in operation, green in production process, low in cost, and feasible in mass production.
综上，采用本发明的树脂组合物得到的层压板的Tg可达到180～210℃，剥离强度可达到1.51～1.71N/cm，可通过PCT(3hr)测试，耐浸焊(288℃)大于20min，1G下Dk可达到3.75～3.87，Df为0.005～0.008。In summary, the laminate obtained by using the resin composition of the present invention can have a Tg of 180 to 210 ° C and a peel strength of 1.51 to 1.71 N/cm, which can be tested by PCT (3 hr), and the resistance to dip soldering (288 ° C) is more than 20 min. Dk can reach 3.75~3.87 at 1G, and Df is 0.005~0.008.
附图说明DRAWINGS
图1是环氧树脂的GPC图。Figure 1 is a GPC chart of an epoxy resin.
图2是聚苯醚树脂的GPC图。 2 is a GPC chart of a polyphenylene ether resin.
图3是环氧树脂改性聚苯醚树脂的预聚体的GPC图。Figure 3 is a GPC chart of a prepolymer of an epoxy resin modified polyphenylene ether resin.
具体实施方式detailed description
下面通过具体实施方式来进一步说明本发明的技术方案。The technical solution of the present invention will be further described below by way of specific embodiments.
在本发明中，图1是环氧树脂的GPC图，具体信息如下：In the present invention, FIG. 1 is a GPC chart of an epoxy resin, and the specific information is as follows:
Figure PCTCN2016082107-appb-000011
Figure PCTCN2016082107-appb-000011
在本发明中，图2是聚苯醚的GPC图，具体信息如下：In the present invention, Fig. 2 is a GPC chart of polyphenylene ether, and the specific information is as follows:
Figure PCTCN2016082107-appb-000012
Figure PCTCN2016082107-appb-000012
在本发明中，图3是环氧树脂改性聚苯醚树脂的预聚体的GPC图，具体信息如下：In the present invention, FIG. 3 is a GPC chart of a prepolymer of an epoxy resin-modified polyphenylene ether resin, and the specific information is as follows:
Figure PCTCN2016082107-appb-000013
Figure PCTCN2016082107-appb-000013
Figure PCTCN2016082107-appb-000014
Figure PCTCN2016082107-appb-000014
实施例一 Embodiment 1
(1)环氧树脂改性聚苯醚树脂的预聚体溶液制备：(1) Preparation of prepolymer solution of epoxy resin modified polyphenylene ether resin:
将双酚A型环氧树脂50份及吡啶0.005份，在升温及搅拌下溶解；再将固态的聚苯醚树脂50份，溶解于二甲苯溶剂制成固含量为30～70％的聚苯醚树脂溶液，缓慢滴加入上述环氧树脂熔融体中，滴加完毕后于145℃下搅拌反应6小时而得环氧树脂改性聚苯醚树脂的预聚体溶液。环氧树脂，聚苯醚以及环氧树脂改性聚苯醚树脂的预聚体产物的GPC图分别如图1、图2和图3所示。50 parts of bisphenol A type epoxy resin and 0.005 parts of pyridine were dissolved under heating and stirring; 50 parts of solid polyphenylene ether resin was dissolved in xylene solvent to prepare polyphenylene having a solid content of 30-70%. The ether resin solution was slowly dropped into the above-mentioned epoxy resin melt, and after completion of the dropwise addition, the reaction was stirred at 145 ° C for 6 hours to obtain a prepolymer solution of the epoxy resin-modified polyphenylene ether resin. The GPC patterns of the prepolymer products of epoxy resin, polyphenylene ether and epoxy resin modified polyphenylene ether resin are shown in Fig. 1, Fig. 2 and Fig. 3, respectively.
(2)环氧树脂改性聚苯醚树脂的预聚体组合物的制备(2) Preparation of prepolymer composition of epoxy resin modified polyphenylene ether resin
将60重量份的步骤(1)环氧树脂改性聚苯醚树脂的预聚体、20重量份的苯酚酚醛树脂、40重量份双酚A型苯并噁嗪树脂、0.1重量份的2-MI、100重量份的熔融态二氧化硅、20重量份的含磷阻燃剂(PX-200，日本大八化学)和30重量份的丁酮溶剂混合、分散均匀。60 parts by weight of the prepolymer of the epoxy resin modified polyphenylene ether resin of the step (1), 20 parts by weight of a phenol novolac resin, 40 parts by weight of a bisphenol A type benzoxazine resin, and 0.1 part by weight of 2- MI, 100 parts by weight of molten silica, 20 parts by weight of a phosphorus-containing flame retardant (PX-200, Nippon Daihatsu Chemical Co., Ltd.), and 30 parts by weight of a methyl ethyl ketone solvent were mixed and uniformly dispersed.
(3)树脂组合物的半固化及基板的制备(3) Semi-curing of resin composition and preparation of substrate
将上述的环氧树脂改性聚苯醚树脂的预聚体组合物经与玻纤维布含浸后，在170℃烘烤3分钟制作预浸料，预浸料外观入表一所示；再将两片铜箔迭合于所制得的4片预浸料两侧，采用真空热压机，在温度190℃、压力35kg/cm2、压合时间90min条件下，压合成型，以获得一种铜箔积层板，性能测试如表二所示。The prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg. The appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
实施例二Embodiment 2
(1)环氧树脂改性聚苯醚树脂的预聚体溶液制备：(1) Preparation of prepolymer solution of epoxy resin modified polyphenylene ether resin:
将DCPD环氧树脂50份及吡啶0.005份，在升温及搅拌下溶解；再将固态的聚苯醚树脂50份，溶解于二甲苯溶剂制成固含量为30～70％的聚苯醚树脂溶 液，缓慢滴加入上述环氧树脂熔融体中，滴加完毕后于145℃下搅拌反应6小时而得环氧树脂改性聚苯醚树脂的预聚体溶液。在所得的环氧树脂改性聚苯醚树脂的预聚体利用GPC的分子量测定中，重均分子量为6200。50 parts of DCPD epoxy resin and 0.005 parts of pyridine were dissolved under heating and stirring; 50 parts of solid polyphenylene ether resin was dissolved in xylene solvent to prepare polyphenylene ether resin with solid content of 30-70%. The liquid was slowly added dropwise to the above-mentioned epoxy resin melt, and after completion of the dropwise addition, the reaction was stirred at 145 ° C for 6 hours to obtain a prepolymer solution of the epoxy resin-modified polyphenylene ether resin. In the molecular weight measurement of the prepolymer of the obtained epoxy resin-modified polyphenylene ether resin by GPC, the weight average molecular weight was 6,200.
(2)环氧树脂改性聚苯醚树脂的预聚体组合物的制备(2) Preparation of prepolymer composition of epoxy resin modified polyphenylene ether resin
将60重量份之步骤(1)环氧树脂改性聚苯醚树脂的预聚体、20重量份的苯酚酚醛树脂、40重量份二胺型苯并噁嗪树脂、0.1重量份的2-MI、100重量份的熔融态二氧化硅、20重量份的含磷阻燃剂(PX-200，日本大八化学)和30重量份的丁酮溶剂混合、分散均匀。60 parts by weight of the prepolymer of the step (1) epoxy resin modified polyphenylene ether resin, 20 parts by weight of a phenol novolac resin, 40 parts by weight of a diamine type benzoxazine resin, 0.1 part by weight of 2-MI 100 parts by weight of molten silica, 20 parts by weight of a phosphorus-containing flame retardant (PX-200, Nippon Daihatsu Chemical Co., Ltd.), and 30 parts by weight of a methyl ethyl ketone solvent were mixed and uniformly dispersed.
(3)树脂组合物的半固化及基板的制备(3) Semi-curing of resin composition and preparation of substrate
将上述的环氧树脂改性聚苯醚树脂的预聚体组合物经与玻纤维布含浸后，在170℃烘烤3分钟制作预浸料，预浸料外观入表一所示；再将两片铜箔迭合于所制得的4片预浸料两侧，采用真空热压机，在温度190℃、压力35kg/cm2、压合时间90min条件下，压合成型，以获得一种铜箔积层板，性能测试如表二所示。The prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg. The appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
实施例三Embodiment 3
(1)环氧树脂改性聚苯醚树脂的预聚体溶液制备：(1) Preparation of prepolymer solution of epoxy resin modified polyphenylene ether resin:
将DCPD环氧树脂20份及吡啶0.005份，在升温及搅拌下溶解；再将固态的聚苯醚树脂50份，溶解于甲苯溶剂制成固含量为30～70％的聚苯醚树脂溶液，缓慢滴加入上述环氧树脂熔融体中，滴加完毕后于145℃下搅拌反应6小时而得环氧树脂改性聚苯醚树脂的预聚体溶液。在所得的环氧树脂改性聚苯醚树脂的预聚体利用GPC的分子量测定中，重均分子量为6200。20 parts of DCPD epoxy resin and 0.005 parts of pyridine were dissolved under heating and stirring; 50 parts of solid polyphenylene ether resin was dissolved in toluene solvent to prepare a polyphenylene ether resin solution having a solid content of 30 to 70%. The epoxy resin melt was slowly added dropwise, and after completion of the dropwise addition, the reaction was stirred at 145 ° C for 6 hours to obtain a prepolymer solution of the epoxy resin-modified polyphenylene ether resin. In the molecular weight measurement of the prepolymer of the obtained epoxy resin-modified polyphenylene ether resin by GPC, the weight average molecular weight was 6,200.
(2)环氧树脂改性聚苯醚树脂的预聚体组合物的制备(2) Preparation of prepolymer composition of epoxy resin modified polyphenylene ether resin
将60重量份的步骤(1)环氧树脂改性聚苯醚树脂的预聚体、20重量份的苯 酚酚醛树脂、40重量份二胺型苯并噁嗪树脂、0.1重量份的2-MI、100重量份的熔融态二氧化硅、20重量份的含磷阻燃剂(PX-200，日本大八化学)和30重量份的丁酮溶剂混合、分散均匀。60 parts by weight of the prepolymer of the epoxy resin modified polyphenylene ether resin of the step (1), 20 parts by weight of benzene Phenolic phenolic resin, 40 parts by weight of diamine-type benzoxazine resin, 0.1 parts by weight of 2-MI, 100 parts by weight of molten silica, 20 parts by weight of phosphorus-containing flame retardant (PX-200, Japan Eight chemistry) and 30 parts by weight of methyl ethyl ketone solvent were mixed and dispersed uniformly.
(3)树脂组合物的半固化及基板的制备(3) Semi-curing of resin composition and preparation of substrate
将上述的环氧树脂改性聚苯醚树脂的预聚体组合物经与玻纤维布含浸后，在170℃烘烤3分钟制作预浸料，预浸料外观入表一所示；再将两片铜箔迭合于所制得的4片预浸料两侧，采用真空热压机，在温度190℃、压力35kg/cm2、压合时间90min条件下，压合成型，以获得一种铜箔积层板，性能测试如表二所示。The prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg. The appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
实施例四Embodiment 4
(1)环氧树脂改性聚苯醚树脂的预聚体溶液制备：(1) Preparation of prepolymer solution of epoxy resin modified polyphenylene ether resin:
将DCPD环氧树脂80份及吡啶0.005份，在升温及搅拌下溶解；再将固态的聚苯醚树脂50份，溶解于二甲苯溶剂制成固含量为30～70％的聚苯醚树脂溶液，缓慢滴加入上述环氧树脂熔融体中，滴加完毕后于145℃下搅拌反应6小时而得环氧树脂改性聚苯醚树脂的预聚体溶液。在所得的环氧树脂改性聚苯醚树脂的预聚体利用GPC的分子量测定中，重均分子量为6600。80 parts of DCPD epoxy resin and 0.005 parts of pyridine were dissolved under heating and stirring; then 50 parts of solid polyphenylene ether resin was dissolved in xylene solvent to prepare a polyphenylene ether resin solution having a solid content of 30-70%. The epoxy resin melt was slowly added dropwise thereto, and after the dropwise addition was completed, the reaction was stirred at 145 ° C for 6 hours to obtain a prepolymer solution of the epoxy resin-modified polyphenylene ether resin. In the molecular weight measurement of the prepolymer of the obtained epoxy resin-modified polyphenylene ether resin by GPC, the weight average molecular weight was 6,600.
(2)环氧树脂改性聚苯醚树脂的预聚体组合物的制备(2) Preparation of prepolymer composition of epoxy resin modified polyphenylene ether resin
将60重量份的步骤(1)环氧树脂改性聚苯醚树脂的预聚体、20重量份的苯酚酚醛树脂、40重量份二胺型苯并噁嗪树脂、0.1重量份的2-MI、100重量份的熔融态二氧化硅、20重量份的含磷阻燃剂(PX-200，日本大八化学)和30重量份的丁酮溶剂混合、分散均匀。60 parts by weight of the prepolymer of the epoxy resin modified polyphenylene ether resin of the step (1), 20 parts by weight of a phenol novolac resin, 40 parts by weight of a diamine type benzoxazine resin, and 0.1 part by weight of 2-MI 100 parts by weight of molten silica, 20 parts by weight of a phosphorus-containing flame retardant (PX-200, Nippon Daihatsu Chemical Co., Ltd.), and 30 parts by weight of a methyl ethyl ketone solvent were mixed and uniformly dispersed.
(3)树脂组合物的半固化及基板的制备(3) Semi-curing of resin composition and preparation of substrate
将上述的环氧树脂改性聚苯醚树脂的预聚体组合物经与玻纤维布含浸后， 在170℃烘烤3分钟制作预浸料，预浸料外观入表一所示；再将两片铜箔迭合于所制得的4片预浸料两侧，采用真空热压机，在温度190℃、压力35kg/cm2、压合时间90min条件下，压合成型，以获得一种铜箔积层板，性能测试如表二所示。The prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg. The appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
实施例五Embodiment 5
(1)环氧树脂改性聚苯醚树脂的预聚体溶液制备：(1) Preparation of prepolymer solution of epoxy resin modified polyphenylene ether resin:
将DCPD环氧树脂50份及吡啶0.005份，在升温及搅拌下溶解；再将固态的聚苯醚树脂50份，溶解于二甲苯溶剂制成固含量为30～70％的聚苯醚树脂溶液，缓慢滴加入上述环氧树脂熔融体中，滴加完毕后于160℃下搅拌反应6小时而得环氧树脂改性聚苯醚树脂的预聚体溶液。50 parts of DCPD epoxy resin and 0.005 parts of pyridine were dissolved under heating and stirring; 50 parts of solid polyphenylene ether resin was dissolved in xylene solvent to prepare a polyphenylene ether resin solution having a solid content of 30-70%. The epoxy resin melt was slowly added dropwise, and after the dropwise addition was completed, the reaction was stirred at 160 ° C for 6 hours to obtain a prepolymer solution of the epoxy resin-modified polyphenylene ether resin.
(2)环氧树脂改性聚苯醚树脂的预聚体组合物的制备(2) Preparation of prepolymer composition of epoxy resin modified polyphenylene ether resin
将60重量份的步骤(1)环氧树脂改性聚苯醚树脂的预聚体、20重量份的苯酚酚醛树脂、40重量份二胺型苯并噁嗪树脂、0.1重量份的2-MI、100重量份的熔融态二氧化硅、20重量份的含磷阻燃剂(PX-200，日本大八化学)和30重量份的丁酮溶剂混合、分散均匀。在所得的环氧树脂改性聚苯醚树脂的预聚体利用GPC的分子量测定中，重均分子量为6400。60 parts by weight of the prepolymer of the epoxy resin modified polyphenylene ether resin of the step (1), 20 parts by weight of a phenol novolac resin, 40 parts by weight of a diamine type benzoxazine resin, and 0.1 part by weight of 2-MI 100 parts by weight of molten silica, 20 parts by weight of a phosphorus-containing flame retardant (PX-200, Nippon Daihatsu Chemical Co., Ltd.), and 30 parts by weight of a methyl ethyl ketone solvent were mixed and uniformly dispersed. In the molecular weight measurement of the prepolymer of the obtained epoxy resin-modified polyphenylene ether resin by GPC, the weight average molecular weight was 6,400.
(3)树脂组合物的半固化及基板的制备(3) Semi-curing of resin composition and preparation of substrate
将上述的环氧树脂改性聚苯醚树脂的预聚体组合物经与玻纤维布含浸后，在170℃烘烤3分钟制作预浸料，预浸料外观入表一所示；再将两片铜箔迭合于所制得的4片预浸料两侧，采用真空热压机，在温度190℃、压力35kg/cm2、压合时间90min条件下，压合成型，以获得一种铜箔积层板，性能测试如表二所示。The prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg. The appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
实施例六 Embodiment 6
(1)环氧树脂改性聚苯醚树脂的预聚体溶液制备：(1) Preparation of prepolymer solution of epoxy resin modified polyphenylene ether resin:
将DCPD环氧树脂50份及吡啶0.005份，在升温及搅拌下溶解；再将固态的聚苯醚树脂50份，溶解于二甲苯溶剂制成固含量为30～70％的聚苯醚树脂溶液，缓慢滴加入上述环氧树脂熔融体中，滴加完毕后于125℃下搅拌反应6小时而得环氧树脂改性聚苯醚树脂的预聚体溶液。在所得的环氧树脂改性聚苯醚树脂的预聚体利用GPC的分子量测定中，重均分子量为6150。50 parts of DCPD epoxy resin and 0.005 parts of pyridine were dissolved under heating and stirring; 50 parts of solid polyphenylene ether resin was dissolved in xylene solvent to prepare a polyphenylene ether resin solution having a solid content of 30-70%. The epoxy resin melt was slowly added dropwise, and after the dropwise addition was completed, the reaction was stirred at 125 ° C for 6 hours to obtain a prepolymer solution of the epoxy resin-modified polyphenylene ether resin. In the measurement of the molecular weight of the prepolymer of the obtained epoxy resin-modified polyphenylene ether resin by GPC, the weight average molecular weight was 6,150.
(2)环氧树脂改性聚苯醚树脂的预聚体组合物的制备(2) Preparation of prepolymer composition of epoxy resin modified polyphenylene ether resin
将60重量份的步骤(1)环氧树脂改性聚苯醚树脂的预聚体、20重量份的苯酚酚醛树脂、40重量份二胺型苯并噁嗪树脂、0.1重量份的2-MI、100重量份的熔融态二氧化硅、20重量份的含磷阻燃剂(PX-200，日本大八化学)和30重量份的丁酮溶剂混合、分散均匀。60 parts by weight of the prepolymer of the epoxy resin modified polyphenylene ether resin of the step (1), 20 parts by weight of a phenol novolac resin, 40 parts by weight of a diamine type benzoxazine resin, and 0.1 part by weight of 2-MI 100 parts by weight of molten silica, 20 parts by weight of a phosphorus-containing flame retardant (PX-200, Nippon Daihatsu Chemical Co., Ltd.), and 30 parts by weight of a methyl ethyl ketone solvent were mixed and uniformly dispersed.
(3)树脂组合物的半固化及基板的制备(3) Semi-curing of resin composition and preparation of substrate
将上述的环氧树脂改性聚苯醚树脂的预聚体组合物经与玻纤维布含浸后，在170℃烘烤3分钟制作预浸料，预浸料外观入表一所示；再将两片铜箔迭合于所制得的4片预浸料两侧，采用真空热压机，在温度190℃、压力35kg/cm2、压合时间90min条件下，压合成型，以获得一种铜箔积层板，性能测试如表二所示。The prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg. The appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
实施例七Example 7
(1)环氧树脂改性聚苯醚树脂的预聚体溶液制备：(1) Preparation of prepolymer solution of epoxy resin modified polyphenylene ether resin:
将双酚A型环氧树脂50份及浓硫酸0.005份，在升温及搅拌下溶解；再将固态的聚苯醚树脂50份，溶解于二甲苯溶剂制成固含量为30～70％的聚苯醚树脂溶液，缓慢滴加入上述环氧树脂熔融体中，滴加完毕后于145℃下搅拌反应6小时而得环氧树脂改性聚苯醚树脂预聚体溶液。在所得的环氧树脂改性聚苯醚 树脂的预聚体利用GPC的分子量测定中，重均分子量为5700。50 parts of bisphenol A type epoxy resin and 0.005 parts of concentrated sulfuric acid were dissolved under heating and stirring; 50 parts of solid polyphenylene ether resin was dissolved in xylene solvent to prepare a solid content of 30-70%. The phenyl ether resin solution was slowly dropped into the above-mentioned epoxy resin melt, and after completion of the dropwise addition, the reaction was stirred at 145 ° C for 6 hours to obtain an epoxy resin-modified polyphenylene ether resin prepolymer solution. The resulting epoxy resin modified polyphenylene ether The prepolymer of the resin had a weight average molecular weight of 5,700 in terms of molecular weight measurement by GPC.
(2)环氧树脂改性聚苯醚树脂的预聚体组合物的制备(2) Preparation of prepolymer composition of epoxy resin modified polyphenylene ether resin
将60重量份的步骤(1)环氧树脂改性聚苯醚树脂的预聚体、20重量份的苯酚酚醛树脂、40重量份双酚A型苯并噁嗪树脂、0.1重量份的2-MI、100重量份的熔融态二氧化硅、20重量份的含磷阻燃剂(PX-200，日本大八化学)和30重量份的丁酮溶剂混合、分散均匀。60 parts by weight of the prepolymer of the epoxy resin modified polyphenylene ether resin of the step (1), 20 parts by weight of a phenol novolac resin, 40 parts by weight of a bisphenol A type benzoxazine resin, and 0.1 part by weight of 2- MI, 100 parts by weight of molten silica, 20 parts by weight of a phosphorus-containing flame retardant (PX-200, Nippon Daihatsu Chemical Co., Ltd.), and 30 parts by weight of a methyl ethyl ketone solvent were mixed and uniformly dispersed.
(3)树脂组合物的半固化及基板的制备(3) Semi-curing of resin composition and preparation of substrate
将上述的环氧树脂改性聚苯醚树脂的预聚体组合物经与玻纤维布含浸后，在170℃烘烤3分钟制作预浸料，预浸料外观入表一所示；再将两片铜箔迭合于所制得的4片预浸料两侧，采用真空热压机，在温度190℃、压力35kg/cm2、压合时间90min条件下，压合成型，以获得一种铜箔积层板，性能测试如表二所示。The prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg. The appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
实施例八Example eight
(1)环氧树脂改性聚苯醚树脂的预聚体溶液制备：(1) Preparation of prepolymer solution of epoxy resin modified polyphenylene ether resin:
将双酚A型环氧树脂50份及0.005份聚乙二醇400，在升温及搅拌下溶解；再将固态的聚苯醚树脂50份，溶解于甲苯溶剂制成固含量为30～70％的聚苯醚树脂溶液，缓慢滴加入上述环氧树脂熔融体中，滴加完毕后于145℃下搅拌反应6小时而得环氧树脂改性聚苯醚树脂预聚体溶液。在所得的环氧树脂改性聚苯醚树脂的预聚体利用GPC的分子量测定中，重均分子量为5600。50 parts of bisphenol A type epoxy resin and 0.005 parts of polyethylene glycol 400 are dissolved under heating and stirring; 50 parts of solid polyphenylene ether resin is dissolved in toluene solvent to obtain a solid content of 30 to 70%. The polyphenylene ether resin solution was slowly dropped into the above-mentioned epoxy resin melt, and after completion of the dropwise addition, the reaction was stirred at 145 ° C for 6 hours to obtain an epoxy resin-modified polyphenylene ether resin prepolymer solution. In the measurement of the molecular weight of the prepolymer of the obtained epoxy resin-modified polyphenylene ether resin by GPC, the weight average molecular weight was 5,600.
(2)环氧树脂改性聚苯醚树脂的预聚体组合物的制备(2) Preparation of prepolymer composition of epoxy resin modified polyphenylene ether resin
将60重量份的步骤(1)环氧树脂改性聚苯醚树脂的预聚体、20重量份饿苯酚酚醛树脂、40重量份双酚A型苯并噁嗪树脂、0.1重量份的2-MI、100重量份的熔融态二氧化硅、20重量份的含磷阻燃剂(PX-200，日本大八化学)和30 重量份的丁酮溶剂混合、分散均匀。60 parts by weight of the prepolymer of the epoxy resin modified polyphenylene ether resin of the step (1), 20 parts by weight of the phenol phenolic phenol resin, 40 parts by weight of the bisphenol A type benzoxazine resin, 0.1 parts by weight of 2- MI, 100 parts by weight of molten silica, 20 parts by weight of a phosphorus-containing flame retardant (PX-200, Japan Daiba Chemical) and 30 The parts by weight of the methyl ethyl ketone solvent are mixed and uniformly dispersed.
(3)树脂组合物的半固化及基板的制备(3) Semi-curing of resin composition and preparation of substrate
将上述的环氧树脂改性聚苯醚树脂的预聚体组合物经与玻纤维布含浸后，在170℃烘烤3分钟制作预浸料，预浸料外观入表一所示；再将两片铜箔迭合于所制得的4片预浸料两侧，采用真空热压机，在温度190℃、压力35kg/cm2、压合时间90min条件下，压合成型，以获得一种铜箔积层板，性能测试如表二所示。The prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg. The appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
实施例九Example nine
(1)环氧树脂改性聚苯醚树脂的预聚体溶液制备：(1) Preparation of prepolymer solution of epoxy resin modified polyphenylene ether resin:
将联苯基芳烷基型酚醛清漆环氧树脂50份及吡啶0.005份，在升温及搅拌下溶解；再将固态的聚苯醚树脂50份，溶解于甲苯溶剂制成固含量为30～70％的聚苯醚树脂溶液，缓慢滴加入上述环氧树脂熔融体中，滴加完毕后于145℃下搅拌反应6小时而得环氧树脂改性聚苯醚树脂预聚体溶液。50 parts of biphenyl aralkyl novolac epoxy resin and 0.005 parts of pyridine were dissolved under heating and stirring; 50 parts of solid polyphenylene ether resin was dissolved in toluene solvent to prepare a solid content of 30-70. The polyphenylene ether resin solution was slowly added dropwise to the above epoxy resin melt, and after completion of the dropwise addition, the reaction was stirred at 145 ° C for 6 hours to obtain an epoxy resin-modified polyphenylene ether resin prepolymer solution.
(2)环氧树脂改性聚苯醚树脂的预聚体组合物的制备(2) Preparation of prepolymer composition of epoxy resin modified polyphenylene ether resin
将60重量份的步骤(1)环氧树脂改性聚苯醚树脂的预聚体、20重量份的苯酚酚醛树脂、40重量份二胺型苯并噁嗪树脂、0.1重量份的2-MI、100重量份的熔融态二氧化硅、20重量份的含磷阻燃剂(PX-200，日本大八化学)和30重量份的丁酮溶剂混合、分散均匀。60 parts by weight of the prepolymer of the epoxy resin modified polyphenylene ether resin of the step (1), 20 parts by weight of a phenol novolac resin, 40 parts by weight of a diamine type benzoxazine resin, and 0.1 part by weight of 2-MI 100 parts by weight of molten silica, 20 parts by weight of a phosphorus-containing flame retardant (PX-200, Nippon Daihatsu Chemical Co., Ltd.), and 30 parts by weight of a methyl ethyl ketone solvent were mixed and uniformly dispersed.
(3)树脂组合物的半固化及基板的制备(3) Semi-curing of resin composition and preparation of substrate
将上述的环氧树脂改性聚苯醚树脂的预聚体组合物经与玻纤维布含浸后，在170℃烘烤3分钟制作预浸料，预浸料外观入表一所示；再将两片铜箔迭合于所制得的4片预浸料两侧，采用真空热压机，在温度190℃、压力35kg/cm2、压合时间90min条件下，压合成型，以获得一种铜箔积层板，性能测试如表二 所示。The prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg. The appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 2.
比较例一Comparative example one
(1)环氧树脂改性聚苯醚树脂的预聚体溶液制备：(1) Preparation of prepolymer solution of epoxy resin modified polyphenylene ether resin:
将100重量份的PPO固态聚苯醚树脂添加入丁酮溶剂中，溶成液态聚苯醚树脂溶液，再将24重量份的双酚A型环氧树脂及0.05重量份的2-甲基咪唑(2-methylimidazole，2-MI)，加入丁酮溶液中，于120℃下搅拌混合1-3小时而到的溶液。所得的溶液体利用GPC的分子量测定中，重均分子量为4000。100 parts by weight of PPO solid polyphenylene ether resin is added to methyl ethyl ketone solvent to dissolve liquid polyphenylene ether resin solution, and then 24 parts by weight of bisphenol A type epoxy resin and 0.05 part by weight of 2-methylimidazole (2-methylimidazole, 2-MI), added to the butanone solution, and stirred at 120 ° C for 1-3 hours. The obtained solution was measured by molecular weight of GPC, and the weight average molecular weight was 4,000.
(2)环氧树脂改性聚苯醚树脂的预聚体组合物的制备(2) Preparation of prepolymer composition of epoxy resin modified polyphenylene ether resin
将60重量份的步骤(1)环氧树脂改性聚苯醚树脂的预聚体、20重量份的苯酚酚醛树脂、40重量份双酚A型苯并噁嗪树脂、0.1重量份的2-MI、100重量份的熔融态二氧化硅、20重量份的含磷阻燃剂(PX-200，日本大八化学)和30重量份的丁酮溶剂混合、分散均匀。60 parts by weight of the prepolymer of the epoxy resin modified polyphenylene ether resin of the step (1), 20 parts by weight of a phenol novolac resin, 40 parts by weight of a bisphenol A type benzoxazine resin, and 0.1 part by weight of 2- MI, 100 parts by weight of molten silica, 20 parts by weight of a phosphorus-containing flame retardant (PX-200, Nippon Daihatsu Chemical Co., Ltd.), and 30 parts by weight of a methyl ethyl ketone solvent were mixed and uniformly dispersed.
(3)树脂组合物的半固化及基板的制备(3) Semi-curing of resin composition and preparation of substrate
将上述的环氧树脂改性聚苯醚树脂的预聚体组合物经与玻纤维布含浸后，在170℃烘烤3分钟制作预浸料，预浸料外观入表一所示；再将两片铜箔迭合于所制得的4片预浸料两侧，采用真空热压机，在温度190℃、压力35kg/cm2、压合时间90min条件下，压合成型，以获得一种铜箔积层板，性能测试如表三所示。The prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg. The appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 3.
比较例二Comparative example two
(1)环氧树脂改性聚苯醚树脂的预聚体溶液制备：(1) Preparation of prepolymer solution of epoxy resin modified polyphenylene ether resin:
将DCPD环氧树脂50份及吡啶0.005份，在升温及搅拌下溶解；再将固态的聚苯醚树脂50份，溶解于二甲苯溶剂制成固含量为30～70％的聚苯醚树脂溶液，缓慢滴加入上述环氧树脂熔融体中，滴加完毕后于100-120℃下搅拌反应6 小时而得环氧树脂改性聚苯醚树脂预聚体溶液。在所得的环氧树脂改性聚苯醚树脂的预聚体利用GPC的分子量测定中，重均分子量为4000。50 parts of DCPD epoxy resin and 0.005 parts of pyridine were dissolved under heating and stirring; 50 parts of solid polyphenylene ether resin was dissolved in xylene solvent to prepare a polyphenylene ether resin solution having a solid content of 30-70%. , slowly add dropwise to the above epoxy resin melt, and stir the reaction at 100-120 ° C after the addition is completed. An epoxy resin modified polyphenylene ether resin prepolymer solution is obtained in an hour. In the molecular weight measurement of the prepolymer of the obtained epoxy resin-modified polyphenylene ether resin by GPC, the weight average molecular weight was 4,000.
(2)环氧树脂改性聚苯醚树脂的预聚体组合物的制备(2) Preparation of prepolymer composition of epoxy resin modified polyphenylene ether resin
将60重量份的步骤(1)环氧树脂改性聚苯醚树脂的预聚体、20重量份之苯酚酚醛树脂、40重量份双酚A型苯并噁嗪树脂、0.1重量份的2-MI、100重量份的熔融态二氧化硅、20重量份的含磷阻燃剂(PX-200，日本大八化学)和30重量份的丁酮溶剂混合、分散均匀。60 parts by weight of the prepolymer of the epoxy resin modified polyphenylene ether resin of the step (1), 20 parts by weight of a phenol novolac resin, 40 parts by weight of a bisphenol A type benzoxazine resin, and 0.1 part by weight of 2- MI, 100 parts by weight of molten silica, 20 parts by weight of a phosphorus-containing flame retardant (PX-200, Nippon Daihatsu Chemical Co., Ltd.), and 30 parts by weight of a methyl ethyl ketone solvent were mixed and uniformly dispersed.
(3)树脂组合物的半固化及基板的制备(3) Semi-curing of resin composition and preparation of substrate
将上述的环氧树脂改性聚苯醚树脂的预聚体组合物经与玻纤维布含浸后，在170℃烘烤3分钟制作预浸料，预浸料外观入表一所示；再将两片铜箔迭合于所制得之4片预浸料两侧，采用真空热压机，在温度190℃、压力35kg/cm2、压合时间90min条件下，压合成型，以获得一种铜箔积层板，性能测试如表三所示。The prepolymer composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg. The appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed into a type by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 , and a pressing time of 90 min to obtain a A copper foil laminate, performance test is shown in Table 3.
比较例三Comparative example three
(1)环氧树脂改性聚苯醚树脂的预聚体溶液制备：(1) Preparation of prepolymer solution of epoxy resin modified polyphenylene ether resin:
将DCPD环氧树脂50份及吡啶0.005份，在升温及搅拌下溶解；再将固态的聚苯醚树脂50份，溶解于二甲苯溶剂制成固含量为30～70％的聚苯醚树脂溶液，缓慢滴加入上述环氧树脂熔融体中，滴加完毕后于145℃下搅拌反应1-3小时而得环氧树脂改性聚苯醚树脂预聚体溶液。在所得的环氧树脂改性聚苯醚树脂的预聚体利用GPC的分子量测定中，重均分子量为4500。50 parts of DCPD epoxy resin and 0.005 parts of pyridine were dissolved under heating and stirring; 50 parts of solid polyphenylene ether resin was dissolved in xylene solvent to prepare a polyphenylene ether resin solution having a solid content of 30-70%. The mixture was slowly added dropwise to the above epoxy resin melt, and after completion of the dropwise addition, the reaction was stirred at 145 ° C for 1-3 hours to obtain an epoxy resin-modified polyphenylene ether resin prepolymer solution. In the measurement of the molecular weight of the prepolymer of the obtained epoxy resin-modified polyphenylene ether resin by GPC, the weight average molecular weight was 4500.
(2)环氧树脂改性聚苯醚树脂的预聚体组合物的制备(2) Preparation of prepolymer composition of epoxy resin modified polyphenylene ether resin
将60重量份的步骤(1)环氧树脂改性聚苯醚树脂的预聚体、20重量份的苯酚酚醛树脂、100重量份二胺型苯并噁嗪树脂、0.1重量份的2-MI、100重量份 的熔融态二氧化硅、20重量份的含磷阻燃剂(PX-200，日本大八化学)和30重量份的丁酮溶剂混合、分散均匀。60 parts by weight of the prepolymer of the epoxy resin modified polyphenylene ether resin of the step (1), 20 parts by weight of a phenol novolac resin, 100 parts by weight of a diamine type benzoxazine resin, 0.1 part by weight of 2-MI , 100 parts by weight The molten silica, 20 parts by weight of a phosphorus-containing flame retardant (PX-200, Nippon Daihatsu Chemical Co., Ltd.) and 30 parts by weight of a methyl ethyl ketone solvent were mixed and uniformly dispersed.
(3)树脂组合物的半固化及基板的制备(3) Semi-curing of resin composition and preparation of substrate
将上述的环氧树脂改性聚苯醚树脂的预聚体组合物经与玻纤维布含浸后，在170℃烘烤3分钟制作预浸料预浸料外观入表一所示；再将两片铜箔迭合于所制得之4片预浸料两侧，采用真空热压机，在温度190℃、压力35kg/cm2、压合时间90min条件下，压合成型，以获得一种铜箔积层板，其中半固化胶片固化形成两铜箔间之绝缘层，性能测试如表三所示。The prepreg composition of the above epoxy resin-modified polyphenylene ether resin is impregnated with a glass fiber cloth and baked at 170 ° C for 3 minutes to prepare a prepreg prepreg as shown in Table 1; The copper foil is laminated on both sides of the prepared four prepregs, and is pressed and synthesized by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 and a pressing time of 90 min to obtain a kind of copper foil. A copper foil laminate in which the semi-cured film is cured to form an insulating layer between the two copper foils, and the performance test is shown in Table 3.
比较例四Comparative example four
(1)环氧树脂与苯并噁嗪树脂组合物的制备(1) Preparation of epoxy resin and benzoxazine resin composition
将20重量份的苯酚酚醛树脂、100重量份二胺型苯并噁嗪树脂、0.1重量份的2-MI、100重量份的熔融态二氧化硅、20重量份的含磷阻燃剂(PX-200，日本大八化学)和30重量份的丁酮溶剂混合、分散均匀。20 parts by weight of a phenol novolac resin, 100 parts by weight of a diamine type benzoxazine resin, 0.1 part by weight of 2-MI, 100 parts by weight of molten silica, and 20 parts by weight of a phosphorus-containing flame retardant (PX) -200, Japan Da Ba Chemical) and 30 parts by weight of methyl ethyl ketone solvent were mixed and dispersed uniformly.
(2)树脂组合物的半固化及基板的制备(2) Semi-curing of resin composition and preparation of substrate
将上述的环氧树脂与苯并噁嗪树脂组合物经与玻纤维布含浸后，在170℃烘烤3分钟制作预浸料，预浸料外观入表一所示；再将两片铜箔迭合于所制得之4片预浸料两侧，采用真空热压机，在温度190℃、压力35kg/cm2、压合时间90min条件下，压合成型，以获得一种铜箔积层板，其中半固化胶片固化形成两铜箔间之绝缘层，性能测试如表三所示。The epoxy resin and the benzoxazine resin composition were impregnated with a glass fiber cloth, and baked at 170 ° C for 3 minutes to prepare a prepreg. The appearance of the prepreg is shown in Table 1; Superimposed on both sides of the prepared four prepregs, using a vacuum hot press, at a temperature of 190 ° C, a pressure of 35 kg / cm 2 , a pressing time of 90 min, press synthesis to obtain a copper foil product The laminate, wherein the semi-cured film is cured to form an insulation layer between the two copper foils, and the performance test is shown in Table 3.
比较例五Comparative example five
(1)环氧树脂、苯并噁嗪树脂及未改性聚苯醚树脂组合物的制备(1) Preparation of epoxy resin, benzoxazine resin and unmodified polyphenylene ether resin composition
将60重量份的未改性聚苯醚树脂、20重量份的苯酚酚醛树脂、100重量份二胺型苯并噁嗪树脂、0.1重量份的2-MI、100重量份的熔融态二氧化硅、20 重量份的含磷阻燃剂(PX-200，日本大八化学)和30重量份的丁酮溶剂混合、分散均匀。60 parts by weight of unmodified polyphenylene ether resin, 20 parts by weight of phenol novolac resin, 100 parts by weight of diamine type benzoxazine resin, 0.1 parts by weight of 2-MI, 100 parts by weight of molten silica 20 The parts by weight of the phosphorus-containing flame retardant (PX-200, Nippon Daihatsu Chemical Co., Ltd.) and 30 parts by weight of the methyl ethyl ketone solvent were mixed and uniformly dispersed.
(2)树脂组合物的半固化及基板的制备(2) Semi-curing of resin composition and preparation of substrate
环氧树脂、苯并噁嗪树脂及未改性聚苯醚树脂组合物经与玻纤维布含浸后，在170℃烘烤3分钟制作预浸料，预浸料外观入表一所示；再将两片铜箔迭合于所制得之4片预浸料两侧，采用真空热压机，在温度190℃、压力35kg/cm2、压合时间90min条件下，压合成型，以获得一种铜箔积层板，其中半固化胶片固化形成两铜箔间之绝缘层，性能测试如表三所示。The epoxy resin, the benzoxazine resin and the unmodified polyphenylene ether resin composition are impregnated with the glass fiber cloth and baked at 170 ° C for 3 minutes to prepare a prepreg. The appearance of the prepreg is shown in Table 1; Two pieces of copper foil were laminated on both sides of the prepared four prepregs, and pressed and synthesized by a vacuum hot press at a temperature of 190 ° C, a pressure of 35 kg/cm 2 and a pressing time of 90 min. A copper foil laminate in which a semi-cured film is cured to form an insulating layer between two copper foils, and the performance test is shown in Table 3.
将实施例一到九及比较例一到五所得的预浸料观察其外观并记录如表一所示，结果显示实施例一到九的预浸料外观较平整，且内部气泡量较少。比较例一到五的预浸料外观则非常粗糙，且玻纤布于含浸时表面会成膜，造成含浸性不良，显示本发明揭示的环氧官能基改性的聚苯醚树脂能有效改善预浸料的浸润性。The appearances of the prepregs obtained in Examples 1 to 9 and Comparative Examples 1 to 5 were observed and recorded as shown in Table 1. The results showed that the prepregs of Examples 1 to 9 had a flat appearance and a small amount of internal bubbles. The appearance of the prepreg of Comparative Examples 1 to 5 is very rough, and the surface of the glass fiber cloth is formed into a film upon impregnation, resulting in poor impregnation, indicating that the epoxy functional modified polyphenylene ether resin disclosed in the present invention can be effectively improved. The wettability of the prepreg.
表一 预浸料外观Table 1 Prepreg appearance
Figure PCTCN2016082107-appb-000015
Figure PCTCN2016082107-appb-000015
实施例一到九所得的层合板进行特性测试数据如表二所示，对比例一到五 所得的层合板进行特性测试数据如表三所示。实施例结果表明本发明的环氧改性聚苯醚树脂的制备方法在使用不同的环氧树脂(实施例一、二和九)、不同的环氧树脂与聚苯醚树脂的比例(实施例二到四)，在本发明反应温度125-160℃下(实施例二、五和六)以及不同催化剂种类(实施例一、七和八)都能获得理想环氧改性聚苯醚预聚物。与不含有环氧改性聚苯醚树脂的树脂组合物(对比例四)或含有未改性聚苯醚树脂的树脂组合物(对比例五)所得板材相比，含有本发明所揭露的环氧树脂改性聚苯醚树脂的树脂组合物所得板材具有更佳的介电性能(Dk/Df)及Tg(玻璃转化温度)，其中Dk及Df值较低为较佳的电性能，Tg温度较高为较佳的Tg。The characteristic test data of the laminates obtained in Examples 1 to 9 are shown in Table 2, and the comparative examples are one to five. The resulting laminates were subjected to characteristic test data as shown in Table 3. The results of the examples show that the preparation method of the epoxy-modified polyphenylene ether resin of the present invention uses different epoxy resins (Examples 1, 2 and 9), the ratio of different epoxy resins to polyphenylene ether resins (Examples) Two to four), ideal epoxy-modified polyphenylene ether prepolymerization can be obtained at the reaction temperature of the present invention at 125-160 ° C (Examples 2, 5 and 6) and different catalyst types (Examples 1, 7 and 8). Things. The ring disclosed in the present invention is contained in comparison with the obtained resin composition (Comparative Example 4) containing no epoxy-modified polyphenylene ether resin or the resin composition containing the unmodified polyphenylene ether resin (Comparative Example 5) The resin composition obtained from the resin composition of the oxy resin modified polyphenylene ether resin has better dielectric properties (Dk/Df) and Tg (glass transition temperature), wherein lower Dk and Df values are preferred electrical properties, Tg temperature Higher is the preferred Tg.
对比例一的结果表明利用咪唑作为催化剂，反应温度100-120℃，反应时间为1-3小时并未对聚苯醚树脂起到改性效果，及时延长反应时间至6小时(对比例二)，效果也并不明显。当温度升高到145℃时，含有该树脂预聚物的层压板的介电性能和Tg得到较明显的改善，但是由于反应时间太短，环氧基团与聚苯醚树脂的羟基反应不充分，因而所得板材性能远远低于在145℃下反应6小时条件下的预聚体所得的板材(实施例一到九)。此外，对比例一、二和对比例四、五所得板材性能相差不大，也说明了在100-120℃下反应1-3小时对聚苯醚树脂没有起到有效的改性作用。The results of Comparative Example 1 show that the reaction temperature is 100-120 ° C and the reaction time is 1-3 hours without modifying the polyphenylene ether resin, and the reaction time is prolonged to 6 hours in time (Comparative Example 2). The effect is not obvious. When the temperature is raised to 145 ° C, the dielectric properties and Tg of the laminate containing the resin prepolymer are significantly improved, but since the reaction time is too short, the epoxy group does not react with the hydroxyl group of the polyphenylene ether resin. Sufficient, the resulting sheet properties were much lower than those obtained with the prepolymer at 145 ° C for 6 hours (Examples 1 through 9). In addition, the properties of the sheets obtained in Comparative Examples 1 and 2 and Comparative Examples 4 and 5 were not much different. It also showed that the reaction at 100-120 ° C for 1-3 hours did not effectively modify the polyphenylene ether resin.
因此，本发明提供的制备环氧改性聚苯醚树脂的方法，以及含有该环氧改性聚苯醚树脂与苯并噁嗪树脂的树脂组合物所得的板材应用范围广泛，具有较大的生产价值。Therefore, the method for preparing an epoxy-modified polyphenylene ether resin provided by the present invention, and the resin composition comprising the epoxy-modified polyphenylene ether resin and the benzoxazine resin have a wide range of applications and have a large range. Production value.
表二 实施例组合物层压板特性 Table 2 Example Composition Laminate Characteristics
Figure PCTCN2016082107-appb-000016
Figure PCTCN2016082107-appb-000016
表三 比较例组合物层压板特性Table III Comparative Example Composition Laminate Characteristics
性能performance 对比例一Comparative example one 对比例二Comparative example two 对比例三Comparative example three 对比例四Comparative example four 对比例五Comparative example five
Tg(DSC)/℃Tg(DSC)/°C 144144 145145 159159 154154 146146
剥离强度(N/mm)Peel strength (N/mm) 1.311.31 1.301.30 1.401.40 1.431.43 1.341.34
PCT(3hr)PCT (3hr) PassPass PassPass PassPass PassPass PassPass
耐浸焊(288℃)/minDip resistance (288 ° C) / min 1010 1010 1212 2020 1515
DK@1GDK@1G 4.384.38 4.354.35 4.264.26 4.404.40 4.324.32
Df@1GDf@1G 0.0130.013 0.0130.013 0.0100.010 0.0120.012 0.0120.012
申请人声明，本发明通过上述实施例来说明本发明的详细方法，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。 The Applicant declares that the present invention is described by the above-described embodiments, but the present invention is not limited to the above detailed methods, that is, it does not mean that the present invention must be implemented by the above detailed methods. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Claims (12)

  1. 一种树脂组合物，该树脂组合物包含环氧树脂改性聚苯醚树脂的预聚体和苯并噁嗪树脂。A resin composition comprising a prepolymer of an epoxy resin modified polyphenylene ether resin and a benzoxazine resin.
  2. 如权利要求1所述的树脂组合物，其特征在于，所述环氧树脂改性聚苯醚树脂的预聚体具有如式(I)所示的结构：The resin composition according to claim 1, wherein the prepolymer of the epoxy resin-modified polyphenylene ether resin has a structure represented by the formula (I):
    Figure PCTCN2016082107-appb-100001
    Figure PCTCN2016082107-appb-100001
    其中，X为：
    Figure PCTCN2016082107-appb-100002
    Where X is:
    Figure PCTCN2016082107-appb-100002
    其中，R为取代或未取代的C1～C5的亚烷基、单键、-SO2-、-O-、-CO-、-SO-或-SC-；Wherein R is a substituted or unsubstituted C1-C5 alkylene group, a single bond, -SO 2 -, -O-, -CO-, -SO- or -SC-;
    Y为官能化环氧树脂的官能基团；Y is a functional group of the functionalized epoxy resin;
    Z1、Z2、Z3、Z4相同或不同，均独立地为氢原子、卤素原子、碳原子数8以下的烷基或苯基；Z 1 , Z 2 , Z 3 , and Z 4 are the same or different and each independently represents a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group;
    n为大于1的正整数。n is a positive integer greater than one.
  3. 如权利要求2所述的树脂组合物，其特征在于，式(I)中，X为
    Figure PCTCN2016082107-appb-100003
    The resin composition according to claim 2, wherein in the formula (I), X is
    Figure PCTCN2016082107-appb-100003
  4. 如权利要求1-3之一所述的树脂组合物，其特征在于，所述聚苯醚树脂分子结构如式(II)所示： The resin composition according to any one of claims 1 to 3, wherein the polyphenylene ether resin has a molecular structure as shown in the formula (II):
    Figure PCTCN2016082107-appb-100004
    Figure PCTCN2016082107-appb-100004
    其中，X为：
    Figure PCTCN2016082107-appb-100005
    Where X is:
    Figure PCTCN2016082107-appb-100005
    其中，R为取代或未取代的C1～C5的亚烷基、单键、-SO2-、-O-、-CO-、-SO-或-SC-；Wherein R is a substituted or unsubstituted C1-C5 alkylene group, a single bond, -SO 2 -, -O-, -CO-, -SO- or -SC-;
    Z1、Z2、Z3、Z4相同或不同，均独立地为氢原子、卤素原子、碳原子数8以下的烷基或苯基；Z 1 , Z 2 , Z 3 , and Z 4 are the same or different and each independently represents a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group;
    n为大于1的正整数；n is a positive integer greater than one;
    优选地，式(II)中的X为：Preferably, X in formula (II) is:
    Figure PCTCN2016082107-appb-100006
    Figure PCTCN2016082107-appb-100006
    优选地，所述聚苯醚树脂的分子结构式如式(III)或式(IV)所示：Preferably, the molecular structure formula of the polyphenylene ether resin is as shown in formula (III) or formula (IV):
    Figure PCTCN2016082107-appb-100007
    Figure PCTCN2016082107-appb-100007
    n为大于1的正整数；n is a positive integer greater than one;
    优选地，所述官能化环氧树脂为异氰酸酯改性双酚A环氧树脂、异氰酸酯改性双酚F环氧树脂、异氰酸酯改性双酚S环氧树脂、苯酚酚醛环氧树脂、双酚A酚醛环氧树脂、邻甲酚酚醛环氧树脂、三官能基环氧树脂、四官能基环氧树脂、二环戊二烯环氧树脂、对氨基苯酚环氧树脂、三聚氰酸环氧树脂、含磷环氧树脂、含氮环氧树脂、对二甲苯环氧树脂、萘型环氧树脂、苯并呱喃型环氧树脂、联苯酚醛环氧树脂或酚基苯烷基酚醛环氧树脂中的任意一种或者至少两种的混合物；Preferably, the functionalized epoxy resin is an isocyanate modified bisphenol A epoxy resin, an isocyanate modified bisphenol F epoxy resin, an isocyanate modified bisphenol S epoxy resin, a phenol novolac epoxy resin, a bisphenol A Phenolic epoxy resin, o-cresol novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene epoxy resin, p-aminophenol epoxy resin, cyanuric acid epoxy resin , phosphorus-containing epoxy resin, nitrogen-containing epoxy resin, p-xylene epoxy resin, naphthalene epoxy resin, benzopyrene epoxy resin, biphenolic epoxy resin or phenolic phenylalkylphenol aldehyde epoxy Any one or a mixture of at least two of the resins;
    优选地，式(I)中Y为如下结构中的任意一种：Preferably, Y in the formula (I) is any one of the following structures:
    Figure PCTCN2016082107-appb-100008
    Figure PCTCN2016082107-appb-100008
    Figure PCTCN2016082107-appb-100009
    Figure PCTCN2016082107-appb-100009
    其中，m和n均独立地为大于1的正整数。Wherein m and n are each independently a positive integer greater than one.
  5. 如权利要求1-4之一所述的树脂组合物，其特征在于，所述环氧树脂改 性聚苯醚树脂的预聚体是由固态的聚苯醚树脂与环氧树脂按照如下方法反应而制得：The resin composition according to any one of claims 1 to 4, wherein the epoxy resin is modified The prepolymer of the polyphenylene ether resin is obtained by reacting a solid polyphenylene ether resin with an epoxy resin according to the following method:
    将环氧树脂20-80重量份及催化剂0.005～10重量份，在升温及搅拌下溶解；再将固态的聚苯醚树脂50重量份，溶解于有机溶剂制成固含量为30～70％的聚苯醚树脂溶液，然后将其缓慢滴加入上述环氧树脂熔融体中，滴加完毕后于125～160℃下搅拌反应3.5-12小时，制得环氧树脂改性聚苯醚树脂的预聚体溶液。20-80 parts by weight of the epoxy resin and 0.005-10 parts by weight of the catalyst are dissolved under heating and stirring; and 50 parts by weight of the solid polyphenylene ether resin is dissolved in an organic solvent to obtain a solid content of 30 to 70%. The polyphenylene ether resin solution is then slowly added dropwise to the above epoxy resin melt, and after the dropwise addition is completed, the reaction is stirred at 125 to 160 ° C for 3.5 to 12 hours to obtain a pretreatment of the epoxy resin modified polyphenylene ether resin. Polymer solution.
  6. 如权利要求5所述的树脂组合物，其特征在于，环氧树脂的添加量为30～70重量份，优选为40～60重量份；The resin composition according to claim 5, wherein the epoxy resin is added in an amount of 30 to 70 parts by weight, preferably 40 to 60 parts by weight;
    优选地，催化剂的添加量为0.005～5重量份，优选0.005～1重量份；Preferably, the catalyst is added in an amount of 0.005 to 5 parts by weight, preferably 0.005 to 1 part by weight;
    优选地，所述催化剂为聚醚类、环状冠醚类、胺类、无机强碱或无机强酸中的任意一种或者至少两种的混合物；Preferably, the catalyst is any one of a polyether, a cyclic crown ether, an amine, an inorganic strong base or an inorganic strong acid or a mixture of at least two;
    优选地，所述聚醚类为链状聚乙二醇或/和链状聚乙二醇二烷基醚；Preferably, the polyether is a chain polyethylene glycol or/and a chain polyethylene glycol dialkyl ether;
    优选地，所述环状冠醚类为18冠6、15冠5或环糊精等中的任意一种或者至少两种的混合物；Preferably, the cyclic crown ether is any one of 18 crown 6, 15 crown 5 or cyclodextrin, or a mixture of at least two;
    优选地，所述胺类为季铵盐、叔胺或吡啶化合物中的任意一种或者至少两种的混合物；Preferably, the amine is any one of a quaternary ammonium salt, a tertiary amine or a pyridine compound or a mixture of at least two;
    优选地，所述季铵盐为苄基三乙基氯化铵、四丁基溴化铵、四丁基氯化铵、四丁基硫酸氢铵、三辛基甲基氯化铵、十二烷基三甲基氯化铵或十四烷基三甲基氯化铵等中的任意一种或者至少两种的混合物；Preferably, the quaternary ammonium salt is benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, twelve Any one or a mixture of at least two of alkyltrimethylammonium chloride or tetradecyltrimethylammonium chloride;
    优选地，所述叔胺为R3N，其中R为碳原子数18以下的支链或直链烷基、取代或不取代的苯基，优选三乙胺、三丁胺、二辛基甲胺或二苯基甲胺等中的任意一种或者至少两种的混合物； Preferably, the tertiary amine is R 3 N, wherein R is a branched or linear alkyl group having 18 or less carbon atoms, a substituted or unsubstituted phenyl group, preferably triethylamine, tributylamine, dioctyl Any one or a mixture of at least two of an amine or diphenylmethylamine;
    优选地，所述吡啶化合物为吡啶、带有8个以下碳原子支链或直链烷烃取代基的吡啶、苯基吡啶或联吡啶等中的任意一种或者至少两种的混合物；Preferably, the pyridine compound is any one of pyridine, pyridine, phenylpyridine or bipyridine having a chain of 8 or less carbon atoms or a linear alkane substituent, or a mixture of at least two;
    优选地，所述联吡啶为2，2’-联吡啶、4，4’-联吡啶、2，4’-联吡啶或2，3’-联吡啶中的任意一种或者至少两种的混合物；Preferably, the bipyridine is any one of 2,2'-bipyridine, 4,4'-bipyridine, 2,4'-bipyridine or 2,3'-bipyridine or a mixture of at least two ;
    优选地，所述无机强碱为氢氧化钠或/和氢氧化钾；Preferably, the inorganic strong base is sodium hydroxide or/and potassium hydroxide;
    优选地，所述无机强酸为浓硫酸、盐酸或硝酸等中的任意一种或者至少两种的混合物；Preferably, the inorganic strong acid is any one of concentrated sulfuric acid, hydrochloric acid or nitric acid, or a mixture of at least two;
    优选地，所述搅拌反应的温度为130-150℃，搅拌反应的时间为4-8小时；Preferably, the temperature of the stirring reaction is 130-150 ° C, and the stirring reaction time is 4-8 hours;
    优选地，所述有机溶剂为N，N-二甲基甲酰胺、N，N-二乙基甲酰胺、环己酮、甲苯、二甲苯、三甲苯或四甲苯中的任意一种或者至少两种的混合溶剂。Preferably, the organic solvent is any one of N,N-dimethylformamide, N,N-diethylformamide, cyclohexanone, toluene, xylene, trimethylbenzene or tetramethylbenzene or at least two Kind of mixed solvent.
  7. 如权利要求1-6之一所述的树脂组合物，其特征在于，在树脂组合物中，环氧树脂改性聚苯醚树脂的预聚体的添加量为20-80重量份；The resin composition according to any one of claims 1 to 6, wherein in the resin composition, the prepolymer of the epoxy resin-modified polyphenylene ether resin is added in an amount of 20 to 80 parts by weight;
    优选地，在树脂组合物中，所述苯并噁嗪树脂的含量为10-60重量份；Preferably, in the resin composition, the content of the benzoxazine resin is 10 to 60 parts by weight;
    优选地，所述苯并噁嗪树脂为双酚A苯并噁嗪、双酚F苯并噁嗪、双酚S苯并噁嗪、二胺型苯并噁嗪、酚酞型苯并噁嗪或二环戊二烯型苯并噁嗪中的任意一种或者至少两种的混合物。Preferably, the benzoxazine resin is bisphenol A benzoxazine, bisphenol F benzoxazine, bisphenol S benzoxazine, diamine benzoxazine, phenolphthalein benzoxazine or Any one or a mixture of at least two dicyclopentadiene type benzoxazines.
  8. 如权利要求1-7之一所述的树脂组合物，其特征在于，所述树脂组合物中还包含固化剂，其含量为5～50重量份；The resin composition according to any one of claims 1 to 7, wherein the resin composition further comprises a curing agent in an amount of 5 to 50 parts by weight;
    优选地，所述固化剂选自线性酚醛树脂、苯乙烯马来酸酐共聚物树脂、DDS或DDM中的任意一种或者两种以上的混合物；Preferably, the curing agent is selected from the group consisting of a linear phenolic resin, a styrene maleic anhydride copolymer resin, DDS or DDM, or a mixture of two or more;
    优选地，所述树脂组合物中还包含固化促进剂，其含量为0.01～10重量份；Preferably, the resin composition further comprises a curing accelerator in an amount of 0.01 to 10 parts by weight;
    优选地，所述固化促进剂选自咪唑、三氟化硼胺复合物、氯化乙基三苯基鏻、2-甲基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑、三苯基膦或4-二甲基胺基 吡啶中的任意一种或者至少两种的组合的刘易斯碱，或选自锰、铁、钴、镍、铜或锌中的任意一种或者至少两种的金属盐化合物的刘易斯酸，或选自有机过氧化物；Preferably, the curing accelerator is selected from the group consisting of imidazole, boron trifluoride amine complex, ethyl triphenylphosphonium chloride, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methyl Imidazole, triphenylphosphine or 4-dimethylamino a Lewis base of any one or a combination of at least two of pyridine, or a Lewis acid of a metal salt compound selected from any one of manganese, iron, cobalt, nickel, copper or zinc or at least two, or selected from the group consisting of Organic peroxide
    优选地，所述树脂组成进一步包括5～60重量份的未经预聚合的环氧树脂；Preferably, the resin composition further comprises 5 to 60 parts by weight of an unprepolymerized epoxy resin;
    优选地，所述环氧树脂为异氰酸酯改性双酚A环氧树脂、异氰酸酯改性双酚F环氧树脂、异氰酸酯改性双酚S环氧树脂、苯酚酚醛环氧树脂、双酚A酚醛环氧树脂、邻甲酚酚醛环氧树脂、三官能基环氧树脂、四官能基环氧树脂、二环戊二烯环氧树脂、对氨基苯酚环氧树脂、三聚氰酸环氧树脂、含磷环氧树脂、含氮环氧树脂、含溴环氧树脂、对二甲苯环氧树脂、萘型环氧树脂、苯并呱喃型环氧树脂、联苯酚醛环氧树脂或酚基苯烷基酚醛环氧树脂中的任意一种或者两种以上的混合物；Preferably, the epoxy resin is an isocyanate modified bisphenol A epoxy resin, an isocyanate modified bisphenol F epoxy resin, an isocyanate modified bisphenol S epoxy resin, a phenol novolac epoxy resin, a bisphenol A phenolic ring Oxygen resin, o-cresol novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene epoxy resin, p-aminophenol epoxy resin, cyanuric acid epoxy resin, Phosphorus epoxy resin, nitrogen-containing epoxy resin, bromine-containing epoxy resin, p-xylene epoxy resin, naphthalene epoxy resin, benzopyrene epoxy resin, biphenolic epoxy resin or phenolic phenyl benzene Any one or a mixture of two or more kinds of phenolic epoxy resins;
    优选地，所述树脂组合物中进一步包含无机填料、阻燃剂、界面活性剂、分散剂、有机硅弹性体或增韧剂中的任意一种或者至少两种的混合物。Preferably, the resin composition further comprises any one of an inorganic filler, a flame retardant, a surfactant, a dispersant, a silicone elastomer or a toughening agent, or a mixture of at least two.
  9. 一种预浸料，其包括增强材料及通过含浸干燥后附着在增强材料上的如权利要求1-8之一所述的树脂组合物。A prepreg comprising a reinforcing material and a resin composition according to any one of claims 1 to 8 adhered to the reinforcing material by impregnation and drying.
  10. 一种层压板，所述层压板含有至少一张如权利要求9所述的预浸料。A laminate comprising at least one prepreg according to claim 9.
  11. 一种覆铜箔层压板，所述覆铜箔层压板包括至少一张叠合的如权利要求9所述的预浸料及压覆在叠合后的预浸料的一侧或两侧的铜箔。A copper clad laminate comprising at least one laminated prepreg according to claim 9 and copper laminated on one or both sides of the laminated prepreg Foil.
  12. 一种印制线路用层压板，其含有至少一张如权利要求9所述的预浸料。 A laminate for printed wiring comprising at least one prepreg according to claim 9.
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