WO2017113522A1 - 一种环氧树脂组合物以及使用其的预浸料和层压板 - Google Patents

一种环氧树脂组合物以及使用其的预浸料和层压板 Download PDF

Info

Publication number
WO2017113522A1
WO2017113522A1 PCT/CN2016/077730 CN2016077730W WO2017113522A1 WO 2017113522 A1 WO2017113522 A1 WO 2017113522A1 CN 2016077730 W CN2016077730 W CN 2016077730W WO 2017113522 A1 WO2017113522 A1 WO 2017113522A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy resin
weight
component
parts
resin composition
Prior art date
Application number
PCT/CN2016/077730
Other languages
English (en)
French (fr)
Inventor
徐浩晟
曾宪平
何烈相
Original Assignee
广东生益科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to EP16785078.3A priority Critical patent/EP3211035B1/en
Priority to US15/305,759 priority patent/US10544255B2/en
Priority to AU2016247084A priority patent/AU2016247084B2/en
Publication of WO2017113522A1 publication Critical patent/WO2017113522A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/26—Di-epoxy compounds heterocyclic
    • 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
    • B32B15/092—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 epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • B32B2264/0257—Polyolefin particles, e.g. polyethylene or polypropylene homopolymers or ethylene-propylene copolymers
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/12—Mixture of at least two particles made of different materials
    • 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
    • B32B2307/206—Insulating
    • 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
    • B32B2307/308—Heat stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

  • the invention belongs to the technical field of copper clad laminates, and particularly relates to an epoxy resin composition and a prepreg, a laminate and a printed circuit board using the same.
  • circuit board is developed in the direction of high multi-layer and high wiring density, which requires that the substrate material not only has a low and stable dielectric constant and dielectric loss factor to meet the needs of high-frequency transmission of signals, but also requires good heat resistance. Sex to meet the needs of multilayer printed circuit board reliability.
  • CN101815734A proposes a method for synthesizing an isocyanate-modified epoxy by reacting a polyfunctional epoxy resin with a diisocyanate compound, the resin having a high softening point required for a powder coating;
  • CN102666633A proposes an epoxy oxazolidinone comprising two a reaction product of a vinyl arene dioxide, and an excess of a polyisocyanate, and a curable epoxy resin composition comprising a divinylarene dioxide and a polyisocyanate derived from divinylbenzene dioxide (DVBDO)
  • the epoxy oxazolidinone, at least one curing agent; and/or the catalyst, the composition has the characteristics of low viscosity and high heat resistance.
  • CN1333791A discloses a binder composition made of a polyepoxide and a polyisocyanate and a chain extender, which composition is advantageous for enhancing the adhesion between the copper foil and the laminate.
  • CN101695880A proposes a method for preparing a polyoxazolidinone laminate, which comprises reacting a diisocyanate with an epoxy under an imidazole catalyst to form a polyoxazolidinone, and then using the formed polyoxazolidinone to prepare a laminate, which is produced.
  • the laminate has better mechanical strength and heat resistance.
  • Japanese Patent Laid-Open No. 2003-252958 proposes to use a biphenyl type epoxy resin and an active ester curing agent.
  • the cured product of the reduced dielectric loss factor is obtained, but since the epoxy resin used is bifunctional, the crosslinking density with the active ester curing agent is low, and the glass transition temperature of the cured product is low.
  • an object of the present invention to provide an epoxy resin composition and a prepreg and laminate using the same.
  • the laminate produced using the resin composition has a low dielectric loss factor, low water absorption, and excellent moist heat resistance, meeting the performance requirements of printed laminates in the high frequency and high speed era.
  • the inventors of the present invention have found that the above object can be attained by an epoxy resin having an oxazolidinone structure, an active ester curing agent, a curing accelerator, and other components which are appropriately mixed with optional components.
  • An epoxy resin composition comprising the following components:
  • n and n are each independently selected from 0, 1, 2;
  • X is independently selected from:
  • R and R' are each independently selected from any organic group
  • the epoxy resin containing an oxazolidinone structure used in the present invention has a five-membered heterocyclic oxazolidinone structure of C, N, and O in the main chain, and has a large molecular chain rigidity, a low expansion coefficient, and a water absorption ratio. High, and the introduction of active ester reduces the formation of secondary hydroxyl groups during the curing process, reduces the water absorption rate, and ensures that the composition fully exhibits the low dielectric loss factor of the oxazolidinone structure.
  • the epoxy resin composition provided by the present invention utilizes the synergistic action of the epoxy resin containing the oxazolidinone structure and the active ester to ensure that the epoxy resin composition has a lower composition than the generally single isocyanate or active ester combination.
  • the dielectric loss factor also has a lower water absorption rate, thereby ensuring high reliability of the composition.
  • the present invention obtains the above epoxy resin composition by utilizing the mutual cooperation and synergistic promotion between the above three essential components.
  • the prepreg and laminate made of the epoxy resin composition have a low coefficient of thermal expansion, a low dielectric loss factor, a low water absorption rate, and excellent moist heat resistance.
  • the epoxy resin having the oxazolidinone structure of the component (A) has the structure of the formula (2):
  • R and R' have the same ranges as in claim 1;
  • R and R' are each independently selected from any one of the following structures:
  • said R and R' are the same.
  • the epoxy resin having the oxazolidinone structure of the component (A) is an oxazolidinone-containing structural epoxy resin having a bisphenol A and/or a tetrabromobisphenol A structure.
  • the ratio of the epoxy equivalent of the epoxy resin containing the oxazolidinone structure to the ester equivalent of the active ester curing agent is 1:0.9 to 1.1, for example, 1:0.92, 1:0.94, 1:0.96, 1 : 0.98, 1:1, 1:1.02, 1:1.04, 1:1.06 or 1:1.08.
  • the component (B) active ester curing agent is obtained by reacting a phenolic compound linked by an aliphatic cyclic hydrocarbon structure, a difunctional carboxylic aromatic compound or an acidic halogenated product, and a monohydroxy compound.
  • the amount of the difunctional carboxylic acid aromatic compound or acid halide is 1 mol
  • the amount of the phenolic compound linked by the aliphatic cyclic hydrocarbon structure is 0.05 to 0.75 mol
  • the amount of the monohydroxy compound is 0.25 to 0.95 mol.
  • component (B) active ester curing agent comprises an active ester of the structure of formula (3):
  • Y is a phenyl or naphthyl group, j is 0 or 1, k is 0 or 1, and n represents a repeating unit of 0.25 to 1.25.
  • a rigid structure such as phenyl, naphthyl or cyclopentadiene imparts high heat resistance to the active ester, and at the same time, due to its regularity of structure and reaction with epoxy resin No secondary hydroxyl groups are produced, giving it good electrical properties and low water absorption:
  • the component (C) curing accelerator of the present invention is selected from any one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl 4-methylimidazole or 2-phenylimidazole. Or a mixture of at least two.
  • An exemplary mixture of the component (C) curing accelerator may be a mixture of 4-dimethylaminopyridine and 2-methylimidazole, 2-methylimidazole and 2-ethyl 4-methylimidazole or 2-benzene.
  • the sum of the amounts of the epoxy resin containing the oxazolidinone structure of the component (A) and the active ester curing agent of the component (B) is 100 parts by weight, the component (C) curing accelerator
  • the amount added is 0.05 to 1 part by weight, for example, 0.08 parts by weight, 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight, 0.5 parts by weight. 0.55, 0.60 parts by weight, 0.65 parts by weight, 0.7 parts by weight, 0.75 parts by weight, 0.8 parts by weight, 0.85 parts by weight, 0.9 parts by weight or 0.95 parts by weight, preferably 0.5 to 0.8 parts by weight.
  • the epoxy resin composition of the present invention further comprises a cyanate resin.
  • the cyanate resin is a good catalyst for increasing the glass transition temperature of the composition and lowering the coefficient of thermal expansion of the composition.
  • the sum of the addition amount of the component (A) oxazolidone structure-containing epoxy resin, component (B) active ester curing agent, and component (C) curing accelerator is 100 parts by weight.
  • the cyanate resin is added in an amount of 50 parts by weight or less, for example, 12 parts by weight, 15 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 38 parts by weight, 43 parts by weight, 48 parts by weight or the like, preferably 40 parts by weight.
  • the remainder is preferably 20 to 30 parts by weight.
  • the sum of the addition amount of the component (A) oxazolidone structure-containing epoxy resin, component (B) active ester curing agent, and component (C) curing accelerator is 100 parts by weight.
  • the flame retardant is added in an amount of 5 to 50 parts by weight, for example, 5 parts by weight, 10 parts by weight, 15 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight or 45 parts by weight or the like.
  • the bromine-containing flame retardant is selected from any one of decabromodiphenylethane, brominated polystyrene, ethylene bistetrabromophthalimide or bromine-containing epoxy resin or at least A mixture of 2 kinds.
  • the halogen-free flame retardant is tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa- 10-phosphinophen-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa-10-phosphine Phenanthrene-10-oxide, phenoxyphosphazene compound, zinc borate, nitrogen-phosphorus expanded, organic polymer flame retardant, phosphorus-containing phenolic resin or phosphorus-containing bismaleimide, polyphosphonate, phosphine Any one or a mixture of at least two of a copolymer of an acid ester and a carbonate.
  • the epoxy resin composition further comprises a filler, which is an organic filler or/and an inorganic filler, which is mainly used to adjust some physical properties of the composition, such as lowering the coefficient of thermal expansion (CTE), Reduce water absorption and increase thermal conductivity.
  • a filler which is an organic filler or/and an inorganic filler, which is mainly used to adjust some physical properties of the composition, such as lowering the coefficient of thermal expansion (CTE), Reduce water absorption and increase thermal conductivity.
  • CTE coefficient of thermal expansion
  • the sum of the addition amount of the epoxy resin containing the oxazolidinone structure of the component (A), the active ester curing agent of the component (B), and the curing accelerator of the component (C) is 100 parts by weight.
  • the filler is added in an amount of 100 parts by weight or less, preferably 50 parts by weight or less, for example, 0.5 parts by weight, 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, or 30 parts by weight.
  • the weight part or the like is further preferably 20 to 40 parts by weight.
  • the inorganic filler is selected from the group consisting of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, carbonization Silicon, Any one or a mixture of at least two of barium sulfate, barium titanate, barium titanate, calcium carbonate, calcium silicate, mica or fiberglass powder.
  • the mixture is, for example, a mixture of fused silica and crystalline silica, a mixture of spherical silica and hollow silica, a mixture of aluminum hydroxide and aluminum oxide, a mixture of talc and aluminum nitride, and nitrided.
  • the organic filler is selected from any one of a polytetrafluoroethylene powder, a polyphenylene sulfide or a polyethersulfone powder or a mixture of at least two.
  • the mixture is, for example, a mixture of polytetrafluoroethylene powder and polyphenylene sulfide, a mixture of polyethersulfone powder and polytetrafluoroethylene powder, a mixture of polyphenylene sulfide and polyethersulfone powder, polytetrafluoroethylene powder, polyphenylene a mixture of thioether and polyethersulfone powder.
  • the filler is silica, and the filler has a median particle diameter of 1 to 15 ⁇ m, and preferably the filler has a median particle diameter of 1 to 10 ⁇ m.
  • Comprising as used herein means that in addition to the components, it may include other components which impart different characteristics to the epoxy resin composition.
  • the "include” of the present invention may also be replaced by a closed “for” or “consisting of”.
  • the epoxy 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.
  • the conventional preparation method of the resin composition of the present invention taking a container, first putting the solid component, then adding the liquid solvent, stirring until completely dissolved, adding the liquid resin, the filler, the flame retardant, the curing accelerator, and continuing to stir. Evenly, finally adjust the liquid solid content to 60% ⁇ 80% with solvent to make glue liquid.
  • Another object of the present invention is to provide a prepreg comprising a reinforcing material and an epoxy resin composition as described above adhered thereto by impregnation and drying.
  • Exemplary reinforcing materials are nonwoven fabrics and/or other fabrics such as natural fibers, organic synthetic fibers, and inorganic fibers.
  • the prepreg is obtained by heating and drying the impregnated reinforcing material in an oven at 155 ° C for 5 to 10 minutes using the woven fabric or the organic fabric of the impregnated reinforcing material such as glass cloth.
  • a third object of the present invention is to provide a laminate comprising at least one prepreg as described above.
  • a fourth object of the present invention is to provide a laminate capable of lowering the Df value and water absorption, the laminate comprising at least one prepreg according to the second aspect;
  • the present invention adopts the following technical solutions:
  • the present invention has the following beneficial effects:
  • the epoxy resin composition of the present invention employs an epoxy resin having a molecular structure containing an oxazolidinone structure, which introduces a rigid five-membered ring structure in the main chain, and has a large molecular chain rigidity, so that the cured product has low expansion. coefficient.
  • the epoxy resin composition of the present invention uses an active ester as a curing agent, and fully exhibits that the active ester does not react with the epoxy resin to form a polar group such as a secondary hydroxyl group, so that the cured product has low water absorbability.
  • the epoxy composition of the present invention overcomes the wet heat resistance of a composition system of an oxazolidinone-containing epoxy resin, a phenolic curing agent, an amine curing agent, and the like, by utilizing synergistic effects between the components.
  • Disadvantages of high dielectric loss factor, prepreg, laminate and printed circuit board made of the epoxy resin composition have low thermal expansion coefficient, low dielectric loss factor Df value ⁇ 0.0084, low water absorption rate water absorption rate ⁇ 0.46% and excellent moisture and heat resistance.
  • the glass transition temperature, thermal decomposition temperature, thermal expansion coefficient, dielectric constant, dielectric loss factor factor, and PCT and PCT water absorption rates were tested as follows. The examples are given in the detailed description and description in which the parts by mass of the organic resin are based on parts by mass of the organic solid.
  • An epoxy resin having a different structure as claimed in claim 1 is synthesized by the method of preparing an epoxy resin containing an oxazolidinone structure by reacting a conventional epoxy resin with a polyisocyanate as disclosed in U.S. Patent No. 5,112,932.
  • the structure of the epoxy resin containing bisphenol A structure and diphenylmethane structure is as follows:
  • R and R' are both
  • Synthesis Example 2 Synthesis of tetrabromobisphenol A structure and diphenylmethane structure epoxy epoxy resin
  • the structure of the tetrabromobisphenol A structure and the diphenylmethane structure epoxy epoxy resin is as follows:
  • the structure of the epoxy resin containing bisphenol A structure and 2,4-toluene structure is as follows:
  • R and R' are both
  • Synthesis Example 4 Synthesis of tetrabromobisphenol A structure and 2,4-toluene structure epoxy epoxy resin
  • the epoxy resin containing tetrabromobisphenol A structure and 2,4-toluene structure is as follows:
  • the production process is the same as that of the first embodiment, and the formulation composition and physical property index are shown in Table 1.
  • the production process is the same as that of the embodiment 9, and the formulation composition and physical property index are as shown in Table 1.
  • a plurality of prepared prepregs are superposed on each other, and an RTF copper foil is respectively pressed on both sides thereof and placed in a heat press to be cured to form the epoxy resin copper clad laminate.
  • the composition of the formula and its physical property data are shown in Table 1.
  • the production process is the same as that in the first embodiment, and the formulation composition and physical property index are as shown in Table 1.
  • the manufacturing process was the same as that of Example 1, and the formulation composition and physical property index are shown in Table 2.
  • Example 1 The formulation composition and partial performance test results of Examples 1 to 8 are shown in Table 1; the formulation compositions and partial performance test results of Examples 9 to 14 are shown in Table 2; the formulation composition and partial properties of Example 1 and Comparative Examples The test results are shown in Table 3;
  • Epoxy resin 1 biphenyl type novolac epoxy resin NC-3000H (Japanese chemical product trade name).
  • Epoxy Resin 2 Dicyclopentadiene type phenolic epoxy resin HP-7200HHH (Japanese DIC trade name).
  • Phenolic resin 1 linear phenolic curing agent KPH-2002 (KOLON trade name)
  • Active ester active ester crosslinker HPC-8000-65T (Japan DIC trade name)
  • Cyanate ester bisphenol A type cyanate resin CE01PS (Yangzhou Tianqi trade name).
  • DMAP curing accelerator, 4-dimethylaminopyridine (Golden Chemical Co., trade name).
  • Zinc isooctanoate curing accelerator, (Alfa Aesar trade name).
  • CTE Thermal expansion coefficient
  • the thermal expansion coefficient and the dielectric loss factor of the second embodiment and the third embodiment are lower than those of the first embodiment, but the water absorption rate is higher than that of the first embodiment. It is indicated that the introduction of cyanate ester can lower the thermal expansion coefficient and dielectric loss factor of the composition but also increase the water absorption of the composition.
  • Example 3 Comparing Example 2 with Example 3, the coefficient of thermal expansion and the dielectric loss factor of Example 3 are lower than those of Example 2, but the water absorption rate is high, indicating that the composition is increased as the cyanate content is introduced. It has a lower dielectric loss factor and higher water absorption.
  • Example 6, Example 7, and Example 8 have similar dielectric loss factors and water absorption rates as compared with Example 1.
  • the component containing Br has a relatively large water absorption rate and dielectric loss factor.
  • the epoxy resin having a diphenylmethane structure has better symmetry with respect to the epoxy resin having a methyl structure, and thus has a lower dielectric loss factor.
  • Examples 9 to 14 show that the thermal expansion coefficient and the dielectric loss factor of the composition after the addition of the filler are decreased, but the water absorption rate is increased, but the moisture heat resistance is still good; and the spherical silicon fine powder can be brought about with the molten silicon fine powder. Lower dielectric loss factor and water absorption.
  • the ketone epoxy resin and the active ester composition are compared with the biphenyl epoxy and active ester composition of Comparative Example 1 and the dicyclopentadiene epoxy and active ester composition of Comparative Example 4, and Examples 1 and 6 PCT burst phenomenon did not occur in ⁇ 8, and the oxazolidinone-containing epoxy resin and the active ester composition had lower dielectric loss factor and more than the other two types of compositions of Comparative Example 1 and Comparative Example 4.
  • Low water absorption It can be seen that both the epoxy resin containing the oxazolidinone structure and the active ester can exert a synergistic effect, ensuring that the composition has a lower dielectric loss factor and a lower expansion coefficient than the composition using the single component. And the water absorption rate, while ensuring the moisture and heat resistance of the composition.
  • the present invention has characteristics of a low coefficient of thermal expansion, a low dielectric loss factor, a low water absorption rate, and excellent heat and humidity resistance as compared with a general laminate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Fluid Mechanics (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明涉及一种环氧树脂组合物，其包括如下组分：(A)含有噁唑烷酮结构的环氧树脂，其具有式(1)的结构；(B)活性酯固化剂；(C)固化促进剂。本发明提供的环氧组合物，以及使用该环氧树脂组合物制作的预浸料、层压板和印制电路板，具有低热膨胀系数、低介质损耗因子Df值≤0.0084、低吸水率且耐湿热性能优异的特点。

Description

一种环氧树脂组合物以及使用其的预浸料和层压板 技术领域
本发明属于覆铜板技术领域，具体涉及一种环氧树脂组合物以及使用它的预浸料、层压板和印制电路板。
背景技术
近年来，随着信息通讯设备高性能化、高功能化以及网络化的发展，为了高速传输及处理大容量信息，操作信号趋向于高频化，同时，为了满足各类电子产品的发展趋势要求，电路板向着高多层、高布线密度的方向发展，这就要求基板材料不仅具有较低且稳定介电常数和介质损耗因子来满足信号高频传输的需要，而且要求其具有良好的耐热性来满足多层印制电路板可靠性的需求。
CN101815734A提出一种通过多官能环氧树脂与二异氰酸酯化合物反应合成异氰酸酯改性环氧的方法，该树脂具有粉末涂料所需的高软化点；CN102666633A提出一种环氧噁唑烷酮，其包括二乙烯基芳烃二氧化物，和过量的多异氰酸酯的反应产物和可固化的环氧树脂组合物，其包含衍生自二乙烯基苯二氧化物(DVBDO)的二乙烯基芳烃二氧化物和多异氰酸酯的环氧噁唑烷酮，至少一种固化剂；和/或催化剂，组合物具有低粘度高耐热性的特点。
CN1333791A公开一种由多环氧化物与多异氰酸酯及扩链剂制成的粘结剂组合物，该组合物有利于增强铜箔与层压板之间的粘合性。
CN101695880A提出一种聚噁唑烷酮层压板的制作方法，其采用二异氰酸酯与环氧在咪唑催化剂下反应生成聚噁唑烷酮，然后利用生成的聚噁唑烷酮制作层压板，其制作出的层压板具有更好的机械强度及耐热性。
日本专利特开2003-252958提出采用联苯型环氧树脂和活性酯固化剂，可 以得到降和介质损耗因子的固化产物，但是由于采用的环氧树脂为双官能度，其与活性酯固化剂的交联密度低，固化物的玻璃化转变温度低。
以上现有专利技术中，虽然都提出了异氰酸酯改性环氧或聚噁唑烷酮自身及其组合物具有良好的粘结性、耐热性及韧性，但均存在耐湿热性能欠佳、可靠性较低，介电损耗因子相对较高等缺点，限制其在高速材料中的应用。
发明内容
针对已有技术的问题，本发明的目的在于提供一种环氧树脂组合物以及使用它的预浸料和层压板。使用该树脂组合物制造的层压板具有低介质损耗因子、低吸水性且具有优异的耐湿热性能，满足高频高速时代对印制层压板的性能要求。
本发明发明人研究发现：含有噁唑烷酮结构的环氧树脂、活性酯固化剂和固化促进剂，及其他可选地组分适当混合得到的组合物，可实现上述目的。
一种环氧树脂组合物，其包括如下组分：
Figure PCTCN2016077730-appb-000001
式(1)中，m和n各自独立地选自0、1、2；
X的结构独立地选自：
Figure PCTCN2016077730-appb-000002
Figure PCTCN2016077730-appb-000003
R和R’各自独立地选自任意的有机基团；
(B)活性酯固化剂；
(C)固化促进剂。
本发明所采用的含有噁唑烷酮结构的环氧树脂，主链中含有C、N、O的五元杂环噁唑烷酮结构，其分子链刚性大，膨胀系数低但其吸水率较高，而活性酯的引入在固化过程中降低二次羟基的形成，降低吸水率的同时，保证组合物充分发挥噁唑烷酮自身结构具有低介电损耗因子的特点。本发明提供的环氧树脂组合物利用含有噁唑烷酮结构的环氧树脂与活性酯的协同作用，保证了所述环氧树脂组合物比一般单一使用异氰酸酯或活性酯的组合物具有更低的介电损耗因子同时具有更低的吸水率，从而保证组合物具有高可靠性。
本发明利用上述三种必要组分之间的相互配合以及相互协同促进作用，得到了如上的环氧树脂组合物。采用该环氧树脂组合物制成的预浸料及层压板，具有低热膨胀系数、低介质损耗因子、低吸水率及优异的耐湿热性能。
优选地，式(1)的结构中，m＝0且n＝0，所述组分(A)含有噁唑烷酮结构的环氧树脂具有式(2)的结构：
Figure PCTCN2016077730-appb-000004
Figure PCTCN2016077730-appb-000005
式(2)中，R和R’具有与权利要求1相同的范围；
优选地，式(1)和式(2)中，R和R’各自独立地选自如下结构中的任意1种：
Figure PCTCN2016077730-appb-000006
优选地，所述R和R’相同。
优选地，所述组分(A)含有噁唑烷酮结构的环氧树脂为具有双酚A和/或四溴双酚A结构的含噁唑烷酮结构环氧树脂。
优选地，所述含有噁唑烷酮结构的环氧树脂环氧当量与活性酯固化剂的酯基当量的比值为1∶0.9～1.1，例如1∶0.92、1∶0.94、1∶0.96、1∶0.98、1∶1、1∶1.02、1∶1.04、1∶1.06或1∶1.08。
优选地，所述组分(B)活性酯固化剂是由一种通过脂肪环烃结构连接的酚类化合物、二官能度羧酸芳香族化合物或酸性卤代物及一种单羟基化合物反应而得。所述二官能羧酸芳香族化合物或酸性卤化物用量为1mol，通过脂肪环烃结构连接的酚类化合物用量为0.05～0.75mol，单羟基化合物用量为0.25～0.95mol。
更优选地，所述组分(B)活性酯固化剂包括如式(3)结构的活性酯：
Figure PCTCN2016077730-appb-000007
Y为苯基或者萘基，j为0或1，k为0或1，n表示重复单元为0.25～1.25。
由于所述活性酯固化剂的特殊结构，其中的苯基、萘基、环戊二烯等刚性结构赋予该活性酯高的耐热性，同时由于其结构的规整性及与环氧树脂反应过程中无二次羟基产生，赋予其良好的电性能和低吸水性：
作为优选，本发明所述组分(C)固化促进剂选自4-二甲氨基吡啶、2-甲基咪唑、2-乙基4-甲基咪唑或2-苯基咪唑中的任意1种或者至少2种的混合物。
所述组分(C)固化促进剂的示例性混合物可以是4-二甲氨基吡啶和2-甲基咪唑的混合物，2-甲基咪唑和2-乙基4-甲基咪唑或2-苯基咪唑的混合物，4-二甲氨基吡啶、2-甲基咪唑和2-苯基咪唑的混合物等。
优选地，以组分(A)含噁唑烷酮结构的环氧树脂和组分(B)活性酯固化剂添加量之和为100重量份计，所述组分(C)固化促进剂的添加量为0.05～1重量份，，例如0.08重量份、0.1重量份、0.15重量份、0.2重量份、0.25重量份、0.3重量份、0.35重量份、0.4重量份、0.45重量份、0.5重量份、0.55重量、0.60重量份、0.65重量份、0.7重量份、0.75重量份、0.8重量份、0.85重量份、0.9重量份或0.95重量份，优选0.5～0.8重量份。
作为优选，本发明所述环氧树脂组合物还包括氰酸酯树脂。
氰酸酯树脂能很好地提高组合物的玻璃化转变温度和降低组合物的热膨胀系数。
优选地，以组分(A)含噁唑烷酮结构的环氧树脂、组分(B)活性酯固化剂和组分(C)固化促进剂添加量之和为100重量份计，所述氰酸酯树脂的添加量为50重量份以下，例如12重量份、15重量份、25重量份、30重量份、35重量份、38重量份、43重量份、48重量份等，优选40重量份以下，进一步优选20～30重量份。
优选地，以组分(A)含噁唑烷酮结构的环氧树脂、组分(B)活性酯固化剂和组分(C)固化促进剂添加量之和为100重量份计，所述阻燃剂的添加量为5～50重量份，例如5重量份、10重量份、15重量份、25重量份、30重量份、35重量份、40重量份或45重量份等。
优选地，所述含溴阻燃剂选自十溴二苯乙烷、溴化聚苯乙烯、乙撑双四溴邻苯二甲酰亚胺或含溴环氧树脂中的任意1种或者至少2种的混合物。
优选地，所述无卤阻燃剂为三(2，6-二甲基苯基)膦、10-(2，5-二羟基苯基)-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、2，6-二(2，6-二甲基苯基)膦基苯、10-苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基膦腈化合物、硼酸锌、氮磷系膨胀型、有机聚合物阻燃剂、含磷酚醛树脂或含磷双马来酰亚胺、聚膦酸酯、膦酸酯与碳酸酯的共聚物中的任意1种或者至少2种的混合物。
优选地，如有需要，所述环氧树脂组合物还包含填料，所述填料为有机填料或/和无机填料，其主要用来调整组合物的一些物性效果，如降低热膨胀系数(CTE)、降低吸水率和提高热导率等。
优选地，以组分(A)含噁唑烷酮结构的环氧树脂、组分(B)活性酯固化剂和组分(C)固化促进剂的添加量之和为100重量份计，所述填料的添加量为100重量份以下，优选50重量份以下，例如为0.5重量份、1重量份、5重量份、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、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份、85重量份、90重量份或95重量份等，进一步优选20～40重量份。
优选地，所述无机填料选自熔融二氧化硅、结晶型二氧化硅、球型二氧化硅、空心二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、 硫酸钡、钛酸钡、钛酸锶、碳酸钙、硅酸钙、云母或玻璃纤维粉中的任意一种或者至少两种的混合物。所述混合物例如熔融二氧化硅和结晶型二氧化硅的混合物，球型二氧化硅和空心二氧化硅的混合物，氢氧化铝和氧化铝的混合物，滑石粉和氮化铝的混合物，氮化硼和碳化硅的混合物，硫酸钡和钛酸钡的混合物，钛酸锶和碳酸钙的混合物，硅酸钙、云母和玻璃纤维粉的混合物，熔融二氧化硅、结晶型二氧化硅和球型二氧化硅的混合物，空心二氧化硅、氢氧化铝和氧化铝的混合物，滑石粉、氮化铝和氮化硼的混合物，碳化硅、硫酸钡和钛酸钡的混合物，钛酸锶、碳酸钙、硅酸钙、云母和玻璃纤维粉的混合物。
优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少两种的混合物。所述混合物例如聚四氟乙烯粉末和聚苯硫醚的混合物，聚醚砜粉末和聚四氟乙烯粉末的混合物，聚苯硫醚和聚醚砜粉末的混合物，聚四氟乙烯粉末、聚苯硫醚和聚醚砜粉末的混合物。
优选地，所述填料为二氧化硅，填料的粒径中度值为1～15μm，优选填料的粒径中度值为1～10μm。
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环氧树脂组合物不同的特性。除此之外，本发明所述的“包括”，还可以替换为封闭式的“为”或“由......组成”。
例如，所述环氧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。
本发明的树脂组合物的常规制作方法：取一容器，先将固体组分放入，然后加入液体溶剂，搅拌直至完全溶解后，加入液体树脂、填料、阻燃剂、固化促进剂，继续搅拌均匀即可，最后用溶剂调整液体固含量至60％～80％而制成胶 液。
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其上的如上所述的环氧树脂组合物。
示例性的增强材料如无纺织物或/和其他织物，例如天然纤维、有机合成纤维以及无机纤维。
使用该胶液含浸增强材料如玻璃布等织物或有机织物，将含浸好的增强材料在155℃的烘箱中加热干燥5～10分钟即可得到预浸料。
本发明的目的之三在于提供一种层压板，其包括至少一张如上所述的预浸料。
本发明的目的之四在于提供了一种能够降低Df值和吸水率的层压板，所述层压板含有至少一张如第二方面所述的预浸料；
为达到此发明目的，本发明采用以下技术方案：
与现有技术相比，本发明具有如下有益效果：
(1)本发明的环氧树脂组合物采用分子结构含有噁唑烷酮结构的环氧树脂，其在主链中引入刚性大的五元环结构，分子链刚性大，使固化物具有低膨胀系数。
(2)本发明的环氧树脂组合物以活性酯作为固化剂，充分发挥了活性酯在和环氧树脂反应不生成二次羟基等极性基团，使着固化物具有低吸水性。
(3)本发明的环氧组合物利用组分之间相互协同促进作用克服了含噁唑烷酮的环氧树脂与酚醛固化剂、胺类固化剂等固化剂的组合物体系耐湿热性能差，介电损耗因子高的缺点，使用该环氧树脂组合物制作的预浸料、层压板和印制电路板，具有低热膨胀系数、低介质损耗因子Df值≤0.0084、低吸水率吸水率≤0.46％且耐湿热性能优异的特点。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
根据上述所制成的一种环氧树脂组合物覆金属箔层压板，测试其玻璃化转变温度、热分解温度、热膨胀系数、介电常数、介质损耗因子因子和PCT及PCT吸水率，如下述实施例加于详细说明与描述，其中有机树脂的质量份按有机固形物质量份计。
参照美国专利US5112932中公开的采用传统环氧树脂与多异氰酸酯反应制备含噁唑烷酮结构的环氧树脂的方法合成制备如权利要求1所述中不同结构的环氧树脂。
合成例1：含双酚A结构及二苯基甲烷结构环氧树脂的合成
含双酚A结构及二苯基甲烷结构环氧树脂的结构如下：
Figure PCTCN2016077730-appb-000008
其中，
Figure PCTCN2016077730-appb-000009
R和R’均为
Figure PCTCN2016077730-appb-000010
在装有搅拌器、温度计、冷凝回流器的三口瓶(1000mL)中加入400g双酚A型环氧树脂，在氮气保护下升温至145～150℃，加入2-苯基咪唑(0.175g)后升温至160℃，在160℃下30min内向上述混合溶液中逐滴加入100g二苯基甲烷二异氰酸酯(MDI)，待MDI加入完毕后，在氮气保护下于160℃恒温反应15min后停止反应。将反应后的溶液缓慢注入搅拌的蒸馏水中，使聚合物析出，过滤后水洗干燥，然后再用甲醇浸泡24h后过滤，真空干燥得到产物。
合成例2：含四溴双酚A结构及二苯基甲烷结构环氧环氧树脂的合成
含四溴双酚A结构及二苯基甲烷结构环氧环氧树脂的结构如下：
Figure PCTCN2016077730-appb-000011
其中，
Figure PCTCN2016077730-appb-000012
在装有搅拌器、温度计、冷凝回流器的三口瓶(1000mL)中加入245g双酚A型环氧树脂及185g四溴双酚A环氧树脂，在氮气保护下升温至145-150℃，加入0.2g 2-苯基咪唑后升温至160℃，在160℃下30min内向上述混合溶液中逐滴加入90g二苯基甲烷二异氰酸酯(MDI)，待MDI加入完毕后，在氮气保护下于160℃恒温反应15min后停止反应。将反应后的溶液缓慢注入搅拌的蒸馏水中，使聚合物析出，过滤后水洗干燥，然后再用甲醇浸泡24h后过滤，真空干燥得到产物。
合成例3：含双酚A结构及2，4-甲苯结构环氧树脂的合成
含双酚A结构及2，4-甲苯结构环氧树脂的结构如下：
Figure PCTCN2016077730-appb-000013
其中，
Figure PCTCN2016077730-appb-000014
R和R’均为
Figure PCTCN2016077730-appb-000015
在装有搅拌器、温度计、冷凝回流器的三口瓶(1000mL)中加入400g双酚A型环氧树脂；在氮气保护下，升温至135-140℃；加入2-苯基咪唑(0.175g)后升温至160℃，在160℃下30min内向上述混合溶液中逐滴加入100g甲苯-2，4-二异氰酸酯(TDI)，待TDI加入完毕后，在氮气保护下于160℃恒温反应15min后停止反应。将反应后的溶液缓慢注入搅拌的蒸馏水中，使聚合物析出，过滤后水洗干燥，然后再用甲醇浸泡24h后过滤，真空干燥得到产物。
合成例4：含四溴双酚A结构及2，4-甲苯结构环氧环氧树脂的合成
含四溴双酚A结构及2，4-甲苯结构环氧环氧树脂如下：
Figure PCTCN2016077730-appb-000016
其中，
Figure PCTCN2016077730-appb-000017
在装有搅拌器、温度计、冷凝回流器的三口瓶(1000mL)中加入245g双酚A型环氧树脂及185g四溴双酚A环氧树脂，在氮气保护下升温至135-140℃，加入2-苯基咪唑(0.2g)后升温至160℃，在160℃下30min内向上述混合溶液中逐滴加入90g甲苯-2，4-二异氰酸酯(TDI)，待TDI加入完毕后，在氮气保护下于160℃恒温反应15min后停止反应。将反应后的溶液缓慢注入搅拌的蒸馏水中，使聚合物析出，过滤后水洗干燥，然后再用甲醇浸泡24h后过滤，真空干燥得到产物。
实施例1
取一容器，加入60重量份的合成例1，加入适量的MEK搅拌至完全溶解，随后加入活性酯、提前溶解好的固化促进剂DMAP，继续搅拌均匀，最后用溶剂调整液体固含量至60％～80％，从而制成胶液。用玻璃纤维布浸渍上述胶液，并控制至适当厚度，然后烘干除去溶剂得到预浸料。使用数张所制得的预浸料相互叠合，在其两侧分别压覆一张RTF铜箔，放进热压机中固化制成所述的环氧树脂覆铜箔层压板。配方组成及其物性数据如表1所示。
实施例2
取一容器，加入65重量份的合成例1，加入适量的MEK搅拌至完全溶解，随后加入活性酯、提前溶解好的固化促进剂DMAP，继续搅拌均匀，再加入氰酸酯及提前预溶好的异辛酸锌，最后用溶剂调整液体固含量至60％～80％，从而制成胶液。用玻璃纤维布浸渍上述胶液，并控制至适当厚度，然后烘干除去溶剂得到预浸料。使用数张所制得的预浸料相互叠合，在其两侧分别压覆一张RTF铜箔，放进热压机中固化制成所述的环氧树脂覆铜箔层压板。配方组成及其物性数据如表1所示。
实施例3
制作工艺与实施例2相同，配方组成及其物性指标如表1所示
实施例4～8
制作工艺与实施例1相同，配方组成及其物性指标如表1所示
实施例9
取一容器，加入60重量份的合成例1，加入适量的MEK搅拌至完全溶解，随后加入活性酯、提前溶解好的固化促进剂DMAP，再加如相应比例的填料继续搅拌均匀，最后用溶剂调整液体固含量至60％～80％，从而制成胶液。用玻璃纤维布浸渍上述胶液，并控制至适当厚度，然后烘干除去溶剂得到预浸料。使用数张所制得的预浸料相互叠合，在其两侧分别压覆一张RTF铜箔，放进热压机中固化制成所述的环氧树脂覆铜箔层压板。配方组成及其物性数据如表1所示。
实施例10
制作工艺与实施例9相同，配方组成及其物性指标如续表1所示
实施例11
取一容器，加入65重量份的合成例1，加入适量的MEK搅拌至完全溶解，随后加入活性酯、提前溶解好的固化促进剂DMAP，继续搅拌均匀，再加入氰酸酯及提前预溶好的异辛酸锌，再加入相应比例的填料，最后用溶剂调整液体固含量至60％～80％，从而制成胶液。用玻璃纤维布浸渍上述胶液，并控制至适当厚度，然后烘干除去溶剂得到预浸料。使用数张所制得的预浸料相互叠合，在其两侧分别压覆一张RTF铜箔，放进热压机中固化制成所述的环氧树脂覆铜箔层压板。配方组成及其物性数据如表1所示。
实施例12～14
制作工艺与实施例11相同，配方组成及其物性指标如续表1所示
比较例1～4
制作工艺与实施例1相同，配方组成及其物性指标如表2所示。
比较例5～6
制作工艺与实施例2相同，配方组成及其物性指标如表2所示。
实施例1～8的配方组成和部分性能测试结果如表1所示；实施例9～14的配方组成和部分性能测试结果如表2所示；实施例1和对比例的配方组成和部分性能测试结果如表3所示；
表1实施例1～8的配方组成和部分性能测试结果
Figure PCTCN2016077730-appb-000018
表2实施例9～14的配方组成和部分性能测试结果
Figure PCTCN2016077730-appb-000019
Figure PCTCN2016077730-appb-000020
表3实施例1和对比例的配方组成和部分性能测试结果
Figure PCTCN2016077730-appb-000021
在表1、表2和表3中，当配方中主体树脂组分为双组分时，固化剂比例以环氧树脂的当量比关系表示；当配方中主体树脂为多组分(超过两组分)时，固化剂比例以环氧组分的固体重量比关系表示。
表1和表2列举的材料具体如下：
环氧树脂1：联苯型酚醛环氧树脂NC-3000H(日本化药商品名)。
环氧树脂2：双环戊二烯型酚醛环氧树脂HP-7200HHH(日本DIC商品名)。
酚醛树脂1：线性酚醛固化剂KPH-2002(KOLON商品名)
活性酯：活性酯交联剂HPC-8000-65T(日本DIC商品名)
氰酸酯：双酚A型氰酸酯树脂CE01PS(扬州天启商品名)。
DMAP：固化促进剂，4-二甲氨基吡啶(广荣化学商品名)。
异辛酸锌：固化促进剂，(阿法埃莎商品名)。
以上特性的测试方法如下：
(1)热膨胀系数(CTE)：根据热机械分析仪(TMA)，按照IPC-TM-6502.4.24.6所规定的TMA方法进行测定。
(2)介电常数和介质损耗因子：按照IPC-TM-6502.5.5.13的方法进行测试，测试频率为10GHz。
(3)PCT后耐浸焊性评价：将覆铜板表面的铜箔蚀刻后，评价基板；将基板放置压力锅中，在120℃、105KPa条件下处理2h；后浸渍在288℃的锡炉中，当基板分层爆板时记录相应时间；当基板在锡炉中超过5min还没出现气泡或分层时即可结束评价。3块中如有0，1，2，3块出现气泡或分层现象记为0/3，1/3，2/3，3/3。
(4)PCT吸水率：将覆铜板表面的铜箔蚀刻后，称重并记录为m1，将基板放置压力锅中，在120℃、105KPa条件下处理2h后取出，用干布擦干试样后立即称重，记录为m2。则PCT吸水率％＝(m2-m1)/m1×100％。
物性分析
(1)实施例2、实施例3和实施例1相比可知，实施例2和实施例3的热膨胀系数、介质损耗因子比实施例1的更低，但吸水率比实施例1更高，说明氰酸酯的引入可以降低组合物的热膨胀系数、介质损耗因子但也带来组合物吸水率地升高。
(2)实施例2和实施例3相比可知，实施例3的热膨胀系数、介质损耗因子比实施例2的更低，但吸水率高，说明随着引入氰酸酯含量地提高，组合物 具有更低的介电损耗因子及更高的吸水率。
(3)实施例6、实施例7、实施例8与实施例1相比，均具有相近的介电损耗因子及吸水率。但是含有Br元素的组分，其吸水率及介电损耗因子相对较大。此外，含有二苯基甲烷结构的环氧树脂相对于甲基结构的环氧树脂具有更好的对称性，因而具有更低的介电损耗因子。
(4)实施例9～14说明加入填料后组合物的热膨胀系数及介电损耗因子降低，但吸水率增加，但仍具有良好的耐湿热性能；相对于熔融硅微粉，球形硅微粉能带来更低的介电损耗因子及吸水率。
(4)由比较例2和比较例3可知，比较例3中含噁唑烷酮环氧树脂与酚醛树脂组合物出现PCT爆板现象，说明其耐湿热性差，而比较例2中联苯环氧与酚醛树脂组合物未出现PCT爆板现象，且相对于比较例3该组合物体系具有更低的介电损耗因子及吸水率；而实施例1及实施例6～8中含噁唑烷酮环氧树脂与活性酯组合物相对于比较例1中的联苯环氧与活性酯组合物及比较例4中的双环戊二烯环氧与活性酯组合物，实施例1及实施例6～8中未出现PCT爆板现象，并且相对于比较例1及比较例4的其他两类组合物，含噁唑烷酮环氧树脂与活性酯组合物具有更低的介电损耗因子及更低的吸水率。由此可知，含噁唑烷酮结构的环氧树脂与活性酯两者能够发挥协同作用，保证组合物相对于使用单一组分的组合物具有更低的介电损耗因子，更低的膨胀系数及吸水率的同时，保证组合物的耐湿热性能。
(5)将实施例2、实施例3与比较例5、比较例6对比可知，其热膨胀系数、介质损耗因子和吸水率相对于比较例4、比较例5的要低，说明氰酸酯地引入仍能发挥三者的协同作用，使组合物具有更低的损耗因子，膨胀系数及吸水率。
(6)从实施例1～14可以看出，采用本发明的组合物在PCT后耐浸焊性评价中，所有实验样本均不存在分层气泡及爆板现象，说明其具有优异的耐湿热性能。
如上所述，与一般的层压板相比，本发明具有低热膨胀系数、低介质损耗因子、低吸水率且耐湿热性能优异的特点。
以上所述，仅为本发明的较佳实施例，对于本领域的普通技术人员来说，可以根据本发明的技术方案和技术构思做出其他各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的范围。
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。

Claims (10)

  1. 一种环氧树脂组合物，其特征在于，其包括如下组分：
    (A)含有噁唑烷酮结构的环氧树脂，其具有式(1)的结构；
    Figure PCTCN2016077730-appb-100001
    式(1)中，m和n各自独立地选自0、1、2；
    X的结构独立地选自：
    Figure PCTCN2016077730-appb-100002
    R和R’各自独立地选自任意的有机基团；
    (B)活性酯固化剂；
    (C)固化促进剂。
  2. 如权利要求1所述的环氧树脂组合物，其特征在于，式(1)的结构中，m＝0且n＝0，所述组分(A)含有噁唑烷酮结构的环氧树脂具有式(2)的结构：
    Figure PCTCN2016077730-appb-100003
    式(2)中，R和R’具有与权利要求1相同的范围。
  3. 如权利要求1或2所述的环氧树脂组合物，其特征在于，式(1)和式(2)中，R和R’各自独立地选自如下结构中的任意1种：
    Figure PCTCN2016077730-appb-100004
  4. 如权利要求1～3之一所述的环氧树脂组合物，其特征在于，所述R和R’相同；
    优选地，所述组分(A)含有噁唑烷酮结构的环氧树脂为具有双酚A和/或四溴双酚A结构的含噁唑烷酮结构的环氧树脂；
    优选地，所述组分(A)含有噁唑烷酮结构的环氧树脂的环氧当量与组分(B)活性酯固化剂的酯基当量的比值为1∶0.9～1.1。
  5. 如权利要求1～4之一所述的环氧树脂组合物，其特征在于，所述组分(B)活性酯固化剂是由一种通过脂肪环烃结构连接的酚类化合物、二官能度羧酸芳香族化合物或酸性卤代物及一种单羟基化合物反应而得；
    优选地，所述组分(B)活性酯固化剂为包括式(3)结构的活性酯：
    Figure PCTCN2016077730-appb-100005
    Y为苯基或者萘基，j为0或1，k为0或1，n表示重复单元为0.25～1.25；
    优选地，所述组分(C)固化促进剂为4-二甲氨基吡啶、2-甲基咪唑、2-乙基4-甲基咪唑或2-苯基咪唑中的任意1种或者至少2种的混合物；
    优选地，以组分(A)含有噁唑烷酮结构的环氧树脂和组分(B)活性酯固化剂添加量之和为100重量份计，所述组分(C)固化促进剂的添加量为0.05～1重量份，优选0.5～0.8重量份。
  6. 如权利要求1～5之一所述的环氧树脂组合物，其特征在于，所述环氧树脂组合物还包括氰酸酯树脂；
    优选地，以组分(A)含有噁唑烷酮结构的环氧树脂、组分(B)活性酯固化剂和组分(C)固化促进剂添加量之和为100重量份计，所述氰酸酯树脂的添加量为50重量份以下，优选40重量份，进一步优选20～30重量份；
    优选地，所述环氧树脂组合物还包括阻燃剂；
    优选地，所述阻燃剂为含溴阻燃剂或/和无卤阻燃剂；
    优选地，以组分(A)、组分(B)及组分(C)添加量之和为100重量份计，所述阻燃剂的添加量为5～50重量份；
    优选地，所述含溴阻燃剂选自十溴二苯乙烷、溴化聚苯乙烯、乙撑双四溴邻苯二甲酰亚胺或含溴环氧树脂中的任意一种或者至少两种的混合物；
    优选地，所述无卤阻燃剂为三(2，6-二甲基苯基)膦、10-(2，5-二羟基苯基)-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、2，6-二(2，6-二甲基苯基)膦基苯、10-苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基膦腈化合物、硼酸锌、氮磷系膨胀型、有机聚合物阻燃剂、含磷酚醛树脂或含磷双马来酰亚胺、聚膦酸酯、膦酸酯与碳酸酯的共聚物中的任意1种或者至少2种的混合物。
  7. 如权利要求1～6之一所述的环氧树脂组合物，其特征在于，所述环氧树脂组合物还包含填料，所述填料为有机填料或/和无机填料；
    优选地，以组分(A)含有噁唑烷酮结构的环氧树脂、组分(B)活性酯固化剂和组分(C)固化促进剂的添加量之和为100重量份计，所述填料的添加量 为100重量份以下，优选50重量份以下，进一步优选20～40重量份；
    优选地，所述无机填料选自熔融二氧化硅、结晶型二氧化硅、球型二氧化硅、空心二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、碳酸钙、硅酸钙、云母或玻璃纤维粉中的任意一种或者至少两种的混合物；
    优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少两种的混合物；
    优选地，所述填料为二氧化硅，填料的粒径中度值为1～15μm，优选填料的粒径中度值为1～10μm。
  8. 一种预浸料，其包括增强材料及通过含浸干燥后附着其上的如权利要求1～7之一所述的环氧树脂组合物。
  9. 一种层压板，其包括至少一张如权利要求8所述的预浸料。
  10. 一种印制电路板，其包括至少一张如权利要求9所述的层压板。
PCT/CN2016/077730 2015-12-28 2016-03-29 一种环氧树脂组合物以及使用其的预浸料和层压板 WO2017113522A1 (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP16785078.3A EP3211035B1 (en) 2015-12-28 2016-03-29 Epoxy resin composition as well as prepreg and laminated board using the same
US15/305,759 US10544255B2 (en) 2015-12-28 2016-03-29 Epoxy resin composition, prepreg and laminate prepared therefrom
AU2016247084A AU2016247084B2 (en) 2015-12-28 2016-03-29 An epoxy resin composition, prepreg and laminate prepared therefrom

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201511019388.0A CN106916282B (zh) 2015-12-28 2015-12-28 一种环氧树脂组合物以及使用其的预浸料和层压板
CN201511019388.0 2015-12-28

Publications (1)

Publication Number Publication Date
WO2017113522A1 true WO2017113522A1 (zh) 2017-07-06

Family

ID=59224343

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/077730 WO2017113522A1 (zh) 2015-12-28 2016-03-29 一种环氧树脂组合物以及使用其的预浸料和层压板

Country Status (6)

Country Link
US (1) US10544255B2 (zh)
EP (1) EP3211035B1 (zh)
CN (1) CN106916282B (zh)
AU (1) AU2016247084B2 (zh)
TW (1) TWI588204B (zh)
WO (1) WO2017113522A1 (zh)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103834168B (zh) 2014-02-25 2016-09-07 广东生益科技股份有限公司 一种无卤阻燃型树脂组合物
CN105778414B (zh) 2014-12-26 2018-05-29 广东生益科技股份有限公司 一种环氧树脂组合物以及使用它的预浸料和层压板
JP6795349B2 (ja) * 2015-11-10 2020-12-02 Nok株式会社 キャリアフィルム付きガスケットの取り扱い方法
US10899871B2 (en) * 2019-04-23 2021-01-26 Chang Chun Plastics Co., Ltd. Phosphorous containing epoxy resins and process for synthesis
CN112538155A (zh) * 2020-11-02 2021-03-23 建滔（江苏）化工有限公司 一种含磷无卤环氧树脂及其制备方法和应用

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5112932A (en) 1989-06-06 1992-05-12 The Dow Chemical Company Epoxy-terminated polyoxazolidones and process for the preparation thereof
CN1333791A (zh) 1998-12-11 2002-01-30 陶氏化学公司 由多环氧化物和多异氰酸酯制得的聚噁唑烷酮粘合剂树脂组合物
JP2003252958A (ja) 2002-02-28 2003-09-10 Dainippon Ink & Chem Inc エポキシ樹脂組成物およびその硬化物
CN1989203A (zh) * 2004-06-29 2007-06-27 旭化成化学株式会社 阻燃环氧树脂组合物
CN101244645A (zh) * 2007-12-07 2008-08-20 中电电气集团有限公司 噁唑烷酮环氧玻璃布层压板的制造方法
CN101695880A (zh) 2009-10-30 2010-04-21 衡阳恒缘电工材料有限公司 聚噁唑烷酮层压板的生产方法
CN101815734A (zh) 2007-10-05 2010-08-25 陶氏环球技术公司 异氰酸酯改性环氧树脂及其环氧粉末涂料组合物
CN102051022A (zh) * 2010-12-09 2011-05-11 广东生益科技股份有限公司 环氧树脂组合物及使用其制作的半固化片与层压板
CN102399415A (zh) * 2010-09-14 2012-04-04 联茂电子股份有限公司 预浸体组合物及应用该预浸体组合物所制成的胶片和基板
CN102666633A (zh) 2009-11-12 2012-09-12 陶氏环球技术有限责任公司 聚噁唑烷酮树脂

Family Cites Families (61)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH634558A5 (de) 1978-04-06 1983-02-15 Ciba Geigy Ag Verfahren zur herstellung von aliphatischen n-substituierten maleinimiden.
ZA839459B (en) 1982-12-30 1985-08-28 Mobil Oil Corp Polyoxazolidone powder coating compositions
JPH068298B2 (ja) 1985-01-21 1994-02-02 住友化学工業株式会社 芳香族系イミドエポキシエ−テル
US4927736A (en) 1987-07-21 1990-05-22 Hoechst Celanese Corporation Hydroxy polyimides and high temperature positive photoresists therefrom
JPH01319528A (ja) 1988-06-20 1989-12-25 Mitsubishi Electric Corp 半導体封止用エポキシ樹脂組成物
JPH1152567A (ja) 1997-08-08 1999-02-26 Fuji Photo Film Co Ltd ポジ型フォトレジスト組成物
US6096853A (en) 1998-12-21 2000-08-01 General Electric Company Synthesis of phenolic monomers containing imide or diimide moieties and high heat carbonate polymers prepared therefrom
JP2000186133A (ja) 1998-12-22 2000-07-04 Mitsui Chemicals Inc エポキシ樹脂組成物およびその用途
JP3721950B2 (ja) 2000-06-06 2005-11-30 松下電工株式会社 エポキシ樹脂組成物、プリプレグ、多層プリント配線板
JP2003231753A (ja) 2001-10-30 2003-08-19 Mitsui Chemicals Inc 新規ポリイミド、該ポリイミドからなる耐熱性接着剤、ポリイミドフィルム、接着性絶縁テープおよび金属積層体
US20040247882A1 (en) * 2001-11-07 2004-12-09 Shinji Kouchi Epoxy resin compositions for fiber-reinforced composite materials, process for production of the materials and fiber-reinforced composite materials
EP1724306A4 (en) * 2004-03-02 2009-04-01 Toray Industries EPOXY RESIN COMPOSITION FOR FIBER REINFORCED COMPOSITE MATERIAL, PREIMPREGNE AND FIBER REINFORCED COMPOSITE MATERIAL
CN100351254C (zh) 2005-01-13 2007-11-28 吉林大学 含有酰亚胺结构双酚单体的合成方法
US8344262B2 (en) * 2006-09-14 2013-01-01 Panasonic Corporation Epoxy resin composition for printed wiring board, resin composition varnish, prepreg, metal clad laminate, printed wiring board and multilayer printed wiring board
EP2113524A4 (en) * 2007-02-23 2011-03-30 Panasonic Elec Works Co Ltd EPOXY RESIN COMPOSITION, PREPREG, LAMINATES AND PCB
JP5628678B2 (ja) * 2007-10-31 2014-11-19 ダウ グローバル テクノロジーズ エルエルシー 融着エポキシ樹脂用の非焼結イソシアネート改質エポキシ樹脂
JP5181769B2 (ja) * 2008-03-26 2013-04-10 Ｄｉｃ株式会社 エポキシ樹脂組成物、及びその硬化物
JP5304105B2 (ja) 2008-08-28 2013-10-02 三菱化学株式会社 ビスイミドフェノール化合物及びその製造方法
JP5304106B2 (ja) 2008-08-28 2013-10-02 三菱化学株式会社 ビスイミドフェノール化合物及びその製造方法
JP5655284B2 (ja) 2008-09-11 2015-01-21 三菱化学株式会社 可溶性イミド骨格樹脂、可溶性イミド骨格樹脂溶液組成物、硬化性樹脂組成物、およびその硬化物
JP2010100802A (ja) 2008-09-24 2010-05-06 Sekisui Chem Co Ltd エポキシ系樹脂組成物、シート状成形体、プリプレグ、硬化体、積層板及び多層積層板
JP2011173827A (ja) 2010-02-24 2011-09-08 Mitsubishi Chemicals Corp ビスイミドフェノール誘導体及びその製造方法並びに高分子化合物
CN102206397B (zh) 2010-03-29 2012-11-28 台光电子材料股份有限公司 树脂组合物及包含其的半固化胶片、层合板和电路板
KR101642518B1 (ko) 2010-03-29 2016-07-26 삼성전기주식회사 열경화성 조성물 및 그를 이용하는 인쇄회로기판
WO2011132408A1 (ja) 2010-04-23 2011-10-27 パナソニック電工株式会社 エポキシ樹脂組成物、プリプレグ、金属張積層板およびプリント配線板
CN101831051B (zh) 2010-05-07 2012-01-04 黄山市善孚化工有限公司 含萘环、双环戊二烯环和酰亚胺结构的耐高温环氧树脂及其制备方法
US20120129414A1 (en) * 2010-11-24 2012-05-24 Chung-Hao Chang Thermosetting resin composition and prepreg or laminate using the same
US8663803B2 (en) 2010-11-29 2014-03-04 Iteq Corporation Varnish composition, and pre-impregnated manufacture thereof
CN102134375B (zh) 2010-12-23 2013-03-06 广东生益科技股份有限公司 无卤高Tg树脂组合物及用其制成的预浸料与层压板
KR101236642B1 (ko) 2011-01-06 2013-02-22 주식회사 두산 수지 조성물, 이를 이용한 프리프레그 및 프린트 배선판
JP5811172B2 (ja) 2011-03-16 2015-11-11 東レ株式会社 エポキシ樹脂組成物およびその製造方法ならびにそれを用いた半導体装置
WO2012147401A1 (ja) * 2011-04-27 2012-11-01 東レ株式会社 プリプレグ、繊維強化複合材料およびプリプレグの製造方法
CN102977551B (zh) 2011-09-02 2014-12-10 广东生益科技股份有限公司 无卤树脂组合物以及使用其制作覆铜板的方法
CN102443138A (zh) * 2011-10-18 2012-05-09 广东生益科技股份有限公司 环氧树脂组合物以及使用其制作的半固化片与覆铜箔层压板
WO2013056411A1 (zh) * 2011-10-18 2013-04-25 广东生益科技股份有限公司 环氧树脂组合物以及使用其制作的半固化片与覆铜箔层压板
CN102516541B (zh) 2011-11-22 2013-08-07 中国航空工业集团公司北京航空材料研究院 一种含酚羟基的聚酰亚胺
US9005761B2 (en) 2011-12-22 2015-04-14 Elite Material Co., Ltd. Halogen-free resin composition and its application for copper clad laminate and printed circuit board
CN102558858B (zh) 2011-12-22 2014-03-26 云南云天化股份有限公司 覆铜层压板用树脂组合物及半固化片
CN103421273B (zh) 2012-05-22 2016-02-10 中山台光电子材料有限公司 无卤素树脂组成物
CN102732029B (zh) 2012-06-21 2014-01-08 广东生益科技股份有限公司 无卤树脂组合物及粘结片与覆铜箔层压板
CN102850722B (zh) * 2012-09-07 2015-08-19 广东生益科技股份有限公司 环氧树脂组合物以及使用其制作的半固化片与覆铜箔层压板
WO2014040261A1 (zh) * 2012-09-14 2014-03-20 广东生益科技股份有限公司 环氧树脂组合物以及使用其制作的半固化片与覆铜箔层压板
CN102850545A (zh) 2012-10-10 2013-01-02 四川大学 一种高韧性高耐热性聚苯并噁嗪/双马来酰亚胺共混树脂及其制备方法
TWI572665B (zh) * 2012-10-17 2017-03-01 Dainippon Ink & Chemicals 活性酯樹脂、環氧樹脂組成物、其硬化物、預浸體、 電路基板以及積層膜
SG11201503362QA (en) * 2012-11-14 2015-05-28 Bayer Materialscience Ag Method for the production of oxazolidinone compounds
JP6314456B2 (ja) 2012-12-06 2018-04-25 三菱ケミカル株式会社 エポキシ樹脂、エポキシ樹脂組成物、硬化物及び電気・電子回路用積層板
US20140228483A1 (en) * 2013-02-13 2014-08-14 Momentive Specialty Chemicals Inc. Compositions useful for preparing composites and composites produced therewith
JP6187581B2 (ja) * 2013-03-22 2017-08-30 日本ゼオン株式会社 硬化性エポキシ組成物、フィルム、積層フィルム、プリプレグ、積層体、硬化物、及び複合体
EP2980135B1 (en) * 2013-03-29 2018-01-31 JXTG Nippon Oil & Energy Corporation Prepreg, fiber-reinforced composite material, and resin composition containing particles
CN103265791B (zh) 2013-05-29 2015-04-08 苏州生益科技有限公司 一种用于集成电路的热固性树脂组合物及使用其制作的半固化片及层压板
CN103382242B (zh) 2013-06-25 2015-06-24 江苏雅克科技股份有限公司 含磷阻燃酚醛树脂及以其为原料制备的阻燃环氧树脂固化物
CN103540220A (zh) * 2013-09-26 2014-01-29 上海海隆石油化工研究所 一种管道用耐磨型环氧粉末涂料
CN103834168B (zh) 2014-02-25 2016-09-07 广东生益科技股份有限公司 一种无卤阻燃型树脂组合物
WO2015179232A1 (en) * 2014-05-21 2015-11-26 Icl-Ip America Inc. Halogen-free active ester curing agent compound for epoxy resins, flame retardant composition comprising same, articles made therefrom and method of making said compound
CN103992621B (zh) 2014-06-04 2016-06-01 苏州生益科技有限公司 一种热固性树脂组合物及使用其制作的半固化片和层压板
CN104592467A (zh) 2014-08-15 2015-05-06 江苏雅克科技股份有限公司 含磷酚醛树脂化合物及以其为原料制备的含磷阻燃环氧树脂固化物
CN105778414B (zh) 2014-12-26 2018-05-29 广东生益科技股份有限公司 一种环氧树脂组合物以及使用它的预浸料和层压板
CN105778413B (zh) 2014-12-26 2018-11-27 广东生益科技股份有限公司 一种无卤环氧树脂组合物以及使用它的预浸料和层压板
CN105295041B (zh) 2015-12-03 2017-07-25 苏州太湖电工新材料股份有限公司 一种聚噁唑烷酮树脂、其制备方法及在浸渍漆中的应用
CN105482076A (zh) 2015-12-15 2016-04-13 广东广山新材料有限公司 一种异氰酸酯改性环氧树脂及用途
CN105440263A (zh) 2015-12-15 2016-03-30 广东广山新材料有限公司 一种环氧树脂固化剂及其制备方法和用途

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5112932A (en) 1989-06-06 1992-05-12 The Dow Chemical Company Epoxy-terminated polyoxazolidones and process for the preparation thereof
CN1333791A (zh) 1998-12-11 2002-01-30 陶氏化学公司 由多环氧化物和多异氰酸酯制得的聚噁唑烷酮粘合剂树脂组合物
JP2003252958A (ja) 2002-02-28 2003-09-10 Dainippon Ink & Chem Inc エポキシ樹脂組成物およびその硬化物
CN1989203A (zh) * 2004-06-29 2007-06-27 旭化成化学株式会社 阻燃环氧树脂组合物
CN101815734A (zh) 2007-10-05 2010-08-25 陶氏环球技术公司 异氰酸酯改性环氧树脂及其环氧粉末涂料组合物
CN101244645A (zh) * 2007-12-07 2008-08-20 中电电气集团有限公司 噁唑烷酮环氧玻璃布层压板的制造方法
CN101695880A (zh) 2009-10-30 2010-04-21 衡阳恒缘电工材料有限公司 聚噁唑烷酮层压板的生产方法
CN102666633A (zh) 2009-11-12 2012-09-12 陶氏环球技术有限责任公司 聚噁唑烷酮树脂
CN102399415A (zh) * 2010-09-14 2012-04-04 联茂电子股份有限公司 预浸体组合物及应用该预浸体组合物所制成的胶片和基板
CN102051022A (zh) * 2010-12-09 2011-05-11 广东生益科技股份有限公司 环氧树脂组合物及使用其制作的半固化片与层压板

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3211035A4

Also Published As

Publication number Publication date
US10544255B2 (en) 2020-01-28
TWI588204B (zh) 2017-06-21
EP3211035A1 (en) 2017-08-30
AU2016247084A1 (en) 2017-07-13
CN106916282B (zh) 2019-07-26
TW201723069A (zh) 2017-07-01
CN106916282A (zh) 2017-07-04
EP3211035A4 (en) 2018-01-10
AU2016247084B2 (en) 2018-03-15
EP3211035B1 (en) 2020-01-15
US20180016387A1 (en) 2018-01-18

Similar Documents

Publication Publication Date Title
KR102561771B1 (ko) 열경화성 수지 조성물 및 이를 포함한 프리프레그, 금속박적층판 및 인쇄회로기판
TWI588204B (zh) An epoxy resin composition and a prepreg and a laminate using the same
CN112250865B (zh) 改性马来酰亚胺树脂预聚物及其制备方法、树脂组合物、半固化片、层压板和印刷电路板
KR101738291B1 (ko) 시아네이트 수지 조성물 및 그 용도
WO2016101539A1 (zh) 一种环氧树脂组合物以及使用它的预浸料和层压板
CN102558759B (zh) 氰酸酯树脂组合物及使用其制作的预浸料与层压材料
CN104725781A (zh) 一种树脂组合物以及使用它的预浸料和层压板
CN109988298A (zh) 一种改性聚苯醚树脂、热固性树脂组合物及其用途
EP3392286B1 (en) Epoxy resin composition and prepreg, laminated board and printed-circuit board comprising same
WO2015154314A1 (zh) 一种热固性树脂组合物
JP2019531262A (ja) リン含有活性エステル、そのノンハロゲン組成物及び銅張積層板
WO2016101538A1 (zh) 一种环氧树脂组合物以及使用它的预浸料和层压板
WO2015154315A1 (zh) 一种无卤无磷阻燃树脂组合物
TW201420675A (zh) 氰酸酯樹脂組合物及使用其製作的預浸料、層壓材料與覆金屬箔層壓材料(一)
CN115850710B (zh) 改性双马来酰亚胺预聚物、树脂组合物及树脂组合物的应用
WO2019127391A1 (zh) 马来酰亚胺树脂组合物、预浸料、层压板和印刷电路板
ES2740952T3 (es) Composición de resina epoxi y sustrato de circuito electrónico de alta frecuencia fabricado usando la misma
TW201420676A (zh) 氰酸酯樹脂組合物及使用其製作的預浸料、層壓材料與覆金屬箔層壓材料(二)
KR20160097278A (ko) 열경화성 에폭시 수지 조성물 및 그 용도
KR101738292B1 (ko) 시아네이트 수지 조성물 및 그 용도
CN109661422B (zh) 用于半导体封装的树脂组合物、使用其的预浸料和金属包层层合体
WO2018098908A1 (zh) 一种热固性树脂组合物
TWI710596B (zh) 一種樹脂組合物、包含其的預浸料以及層壓板和印刷電路板
CN109971130B (zh) 氰酸酯树脂组合物及其用途
WO2014059653A1 (zh) 氰酸酯树脂组合物及使用其制作的预浸料、层压材料与覆金属箔层压材料

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 15305759

Country of ref document: US

REEP Request for entry into the european phase

Ref document number: 2016785078

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2016785078

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2016247084

Country of ref document: AU

Date of ref document: 20160329

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16785078

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE