CN104371273B - 一种无卤树脂组合物及用其制作的预浸料与层压板 - Google Patents
一种无卤树脂组合物及用其制作的预浸料与层压板 Download PDFInfo
- Publication number
- CN104371273B CN104371273B CN201410633018.5A CN201410633018A CN104371273B CN 104371273 B CN104371273 B CN 104371273B CN 201410633018 A CN201410633018 A CN 201410633018A CN 104371273 B CN104371273 B CN 104371273B
- Authority
- CN
- China
- Prior art keywords
- halogen
- parts
- epoxy resin
- free
- resin composition
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—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
- B32B15/092—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
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- B32B27/28—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
- B32B27/285—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 comprising polyethers
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)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
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/024—Woven fabric
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
-
- 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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
-
- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with 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
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- 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
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/038—Textiles
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- 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
- 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
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
-
- 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
- B32B2307/732—Dimensional properties
-
- 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
- C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2435/06—Copolymers with vinyl aromatic monomers
-
- 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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2471/12—Polyphenylene oxides
-
- 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
- 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
- C08L2201/22—Halogen free composition
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/012—Flame-retardant; Preventing of inflammation
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0275—Fibers and reinforcement materials
- H05K2201/029—Woven fibrous reinforcement or textile
Abstract
本发明涉及一种无卤树脂组合物及用其制作的预浸料与层压板,所述的无卤树脂组合物按重量份包括如下组分:环氧树脂50‑100份;苯并噁嗪20‑70份;聚苯醚5‑40份;苯乙烯‑马来酸酐5‑30份;无卤阻燃剂5‑40份;固化促进剂0.2‑5份;填料20‑100份。用所述无卤树脂组合物制作的预浸料与层压板,具有低介电常数、低介质损耗、优异的耐热性、粘结性及耐湿性等综合性能,适合在无卤高多层电路板中使用。
Description
技术领域
本发明涉及层压板技术领域,具体涉及一种树脂组合物,尤其涉及一种无卤树脂组合物及用其制作的预浸料,层压板与印刷电路板。
背景技术
目前,含卤阻燃剂(特别是溴系阻燃剂)被广泛用于高分子阻燃材料,并起到了较好的阻燃作用。然而人们对火灾现场深入研究后得出结论:虽然含卤阻燃剂的阻燃效果好,且添加量少,但是采用含卤阻燃剂的高分子材料在燃烧过程中会产生大量的有毒且具有腐蚀性的气体和烟雾,容易使人窒息而死,其危害性比大火本身更为严重。因此,随着欧盟《关于报废电气电子设备指令》和《关于在电气电子设备中限制使用有害物质指令》于2006年7月1日的正式实施,无卤阻燃印刷线路板的开发成为了业内开发工作的重点,各覆铜箔层压板的厂家都纷纷推出自己的无卤阻燃覆铜箔层压板。
目前工业上普遍使用含磷树脂来实现阻燃效果,但过多磷的引入会使得基材的吸水性变高,耐化学性变差。近年来,以苯并噁嗪作为基体树脂用于无卤基材的开发越来越受到重视。苯并噁嗪是一类由氧原子和氮原子构成的苯并六元杂环体系,具有开环聚合的特点,聚合时无小分子释放,聚合后形成类似酚醛树脂的网状结构,制品的固化收缩小,孔隙率低,具有优良的力学、电学和阻燃性能等。
另一方面,随着电子工业的飞速发展,电子产品向轻、薄、短小、高密度化、安全化、高功能化发展,要求电子元件有更高的信号传播速度和传输效率,这样就对作为载体的印刷电路板提出了更高的性能要求,电子产品信息处理的高速化和多功能化,应用频率不断提高,3GHz以上将逐渐成为主流,除了保持对层压板材料的耐热性有更高的要求外,对其介电常数和介质损耗值的要求会越来越低。
现有的传统FR-4很难满足电子产品的高频及高速发展的使用需求,同时基板材料不再是扮演传统意义下的机械支撑角色,而是将与电子组件一起成为PCB和终端厂商设计者提升产品性能的一个重要途径。因为高介电常数(Dk)会使信号传递速率变慢,高介质损耗(Df)会使信号部分转化为热能损耗在基板材料中,因此具有低介电常数,低介质损耗的高频传输,尤其是无卤高频板材的开发已成为覆铜箔层压板行业的重点。
为了解决上述问题,CN101684191B提出了使用苯并噁嗪、苯乙烯-马来酸酐、含磷固化剂复合固化环氧树脂可以得到一种具有较低介电常数及介质损耗的固化物,但是仅仅以苯乙烯-马来酸酐来降低材料的介电性能不可避免的会出现很多其他方面的问题,对粘结性影响尤为显著,因为苯乙烯-马来酸酐(SMA)分子结构中非极性的苯乙烯结构单元降低了改性基体树脂的极性,削弱了树脂与铜箔之间的相互作用力;同时,因为SMA中大量的苯环结构增大了树脂交联网络的脆性,也对动态条件下的粘结性能产生不利影响,从而降低了基材之间及基材与铜箔的粘结强度。
CN100523081C提出了使用苯并噁嗪、苯乙烯-马来酸酐和其他固化剂复合固化含磷及无卤无磷环氧组合物可以得到一种具有较低介电常数及介质损耗的固化物,但以含磷环氧树脂作为主体树脂,虽然可以达到优异的阻燃性,但磷的过多引入,必然对基材的吸水性产生极大影响,这势必会对板材的其它很多性能有负面影响。
CN103131131A提出了使用苯并噁嗪、苯乙烯-马来酸酐和胺类固化剂复合固化环氧树脂,可以得到一种具有较低介电常数及介质损耗的固化物,但使用普通的苯并噁嗪虽然可以达到固化环氧树脂及阻燃的目的,但由于普通苯并噁嗪的介电常数较高,往往难以满足高频高速传输,且胺类固化剂的引入虽然可以提升粘结性,但其存在吸湿性较大及用其固化环氧树脂耐热性不足的缺陷,必然会对其在高多层电路板中的使用产生负面影响。
因此,如何生产一种具有低介电常数、低介质损耗,同时保证其耐化学性优良的预浸料及层压板是目前亟待解决的问题。
发明内容
本发明的目的在于提供一种树脂组合物,特别是一种无卤树脂组合物及用其制作的预浸料,层压板与印刷电路板。
为达到此发明目的,本发明采用以下技术方案:
第一方面,本发明提供了一种无卤树脂组合物,该组合物按重量份包括如下组分:环氧树脂50-100份;苯并噁嗪20-70份;聚苯醚5-40份;苯乙烯-马来酸酐5-30份;无卤阻燃剂5-40份;固化促进剂0.2-5份;填料20-100份。
本发明的环氧树脂至少含有一种如下化学结构式所示的具有双环戊二烯烷基苯酚结构的环氧树脂:
本发明的环氧树脂还可以选自双酚A型环氧树脂、双酚F型环氧树脂、联苯环氧树脂、烷基酚醛环氧树脂、双环戊二烯环氧树脂、双酚A型酚醛环氧树脂、邻甲酚型酚醛环氧树脂、苯酚型酚醛环氧树脂、三官能环氧树脂、四官能环氧树脂、异氰酸酯改性环氧树脂、萘型环氧树脂或含磷环氧树脂中的任意一种或至少两种的混合物。
本发明的环氧树脂含量为50-100份,例如可以是50份、55份、60份、65份、70份、75份、80份、85份、90份、95份、100份,优选为50-90份,进一步优选为50份。
本发明的环氧树脂组合物中包含了一种双环戊二烯烷基苯酚结构的环氧树脂,该环氧树脂有利于降低基材的介电性能,同时烷基结构不仅能进一步优化介电性能,并且使基材的吸水率大大降低。
本发明的苯并噁嗪可以为氟化苯并噁嗪树脂、脂肪族苯并噁嗪树脂或双环戊二烯型苯并噁嗪树脂中的任意一种或至少两种的混合物。
本发明的氟化苯并噁嗪树脂为下述化学结构式中的任意一种或至少两种的混合物:
本发明的脂肪族苯并噁嗪树脂的化学结构式为:
其中,n为2或3。
本发明的双环戊二烯型苯并噁嗪树脂的化学结构式为:
本发明的苯并噁嗪含量为20-70份,例如可以是20份、25份、30份、35份、40份、45份、50份、55份、60份、65份、70份,优选为40-50份,进一步优选为45份。
本发明的聚苯醚为低分子量聚苯醚,数均分子量在1000-4000。
本发明的聚苯醚含量为5-40份,例如可以是5份、10份、15份、20份、25份、30份、35份、40份,优选为25份。
本发明的苯乙烯-马来酸酐的化学结构式为:
其中,x为1-4,6,8;n为1-12;x,n均为整数。
本发明的苯乙烯-马来酸酐含量为5-30份,例如可以是5份、10份、15份、17份、20份、22份、25份、30份,优选为10-20份,进一步优选为20份。
本发明采用苯乙烯-马来酸酐与苯并噁嗪复合固化环氧组合物,可使基材获得低的介电常数及介质损耗,较好的耐热性及耐湿性。
本发明的无卤阻燃剂可以为磷腈、聚磷酸铵、三(2-羧乙基)膦、三(异丙基氯)磷酸盐、三甲基磷酸盐、二甲基-甲基磷酸盐、间苯二酚双二甲苯基磷酸盐、磷氮基化合物、聚磷酸三聚氰胺、三聚氰胺氰尿酸酯、三-羟乙基异氰尿酸酯、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物或含DOPO酚醛树脂中的任意一种或至少两种的混合物。
本发明的无卤阻燃剂含量为5-40份,例如可以是5份、10份、15份、20份、22份、25份、30份、40份,优选为20-22份,进一步优选为22份。
本发明以具有阻燃作用的苯并噁嗪为主要固化剂,同时添加少量含磷阻燃剂,不仅实现了磷氮协同阻燃效应,而且在大大减少组分中磷含量的同时还提高了基材的阻燃性,并且使基材具有较好的耐湿性。
本发明的固化促进剂可以为咪唑类促进剂,所述的咪唑类促进剂为2-甲基咪唑、十一烷基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或1-氰乙基取代咪唑中的任意一种或至少两种的混合物。
本发明的固化促进剂含量为0.2-5份,例如可以是0.2份、0.5份、1份、2份、3份、4份、5份。
本发明的填料可以为无机或有机填料;当所述填料为无机填料时,可以为氢氧化铝、氧化铝、氢氧化镁、氧化镁、三氧化二铝、二氧化硅、碳酸钙、氮化铝、氮化硼、碳化硅、二氧化钛、氧化锌、氧化锆、云母、勃姆石、煅烧滑石、滑石粉、氮化硅或煅烧高岭土中的任意一种或至少两种的混合物;当所述填料为有机填料时,可以为聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或至少两种的混合物。
本发明的二氧化硅可以选择结晶型、熔融型或球形二氧化硅。
本发明填料的粒径为0.01-50μm,例如可以是0.01μm、0.05μm、1μm、5μm、10μm、15μm、20μm、25μm、30μm、40μm、50μm,优选为1-15μm。
本发明的填料含量为20-100份,例如可以是20份、30份、40份、50份、60份、70份、80份、90份、100份,优选为50份。
为使所述的填料在本发明的树脂组合物中分散均匀,还可以添加入分散剂,使用的分散剂为氨基硅烷偶联剂或环氧基硅烷偶联剂,用来改善无机以及织造玻璃布间的结合性能,从而达到分散均匀的目的,且这类偶联剂无重金属存在,不会对人体产生不良影响,使用量为填料的0.5-2%重量份,若使用量太高,则加快反应,影响储存时间,用量太小,则无显著改善结合稳定性的效果。
第二方面,本发明还提供了一种使用如本发明第一方面所述的无卤树脂组合物制作的预浸料,该预浸料包括基体材料;和通过浸渍干燥后附着在其上的无卤树脂组合物。
本发明的基体材料为无纺或有纺玻璃纤维布。
第三方面,本发明还提供了一种层压板,该层压板包括如本发明第二方面所述的预浸料。
第四方面,本发明还提供了一种印刷电路板,其包含如本发明第三方面所述的层压板。
与现有技术相比,本发明具有以下有益效果:
采用本发明的无卤树脂组合物制备得到的层压板,其介电常数可控制在3.7及以下,介质损耗最高值仅为0.0057,可达到阻燃性试验UL-94中的V-0标准,PCT吸水率为0.27-0.30;因而,该层压板在保证无卤阻燃的同时,还具有低介电常数、低介质损耗、优异的耐热性、粘结性及耐湿性等综合性能,适合在无卤高多层电路板中使用。
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。
制备例、双环戊二烯烷基苯酚环氧树脂的合成
在装有聚四氟乙烯搅拌器、温度计、冷凝回流器的四口瓶(500mL)中加入270.0g对(1,1,3,3-四甲基)丁基苯酚在水浴加热中溶化,称取三氟化硼·乙醚1.83g,加入500mL四口烧瓶中,在滴液漏斗中加入50.1g双环戊二烯,控制好滴加速度以便在2h内滴加完所有的双环戊二烯,升温至100℃,保温4h,冷却至室温,再加热至一定温度蒸馏出过量的双环戊二烯和对(1,1,3,3-四甲基)丁基苯酚,产物即为双环戊二烯烷基苯酚树脂;
将上一步所得到的双环戊二烯烷基苯酚树脂放入四口烧瓶中,再称取100.0g环氧氯丙烷缓慢加入,待其溶解后,开始升温,并在滴液漏斗中加入1mol的质量分数为33%的KOH溶液,控制速度,使其在1h内滴加完,控制反应温度在100℃,滴加完后保温4h,冷却后水洗,再升温至120℃蒸馏,蒸出过量环氧氯丙烷,得如下化学结构式所示的具有双环戊二烯烷基苯酚结构的环氧树脂:
实施例、覆铜箔层压板的制备方法
将环氧树脂、苯并噁嗪、聚苯醚、聚乙烯-马来酸酐、无卤阻燃剂、固化促进剂、填料及溶剂等,放入容器中,搅拌使其混合均匀,制成胶水,用溶剂调整溶液固体含量至60%-70%而制成胶液,即得到本发明的无卤树脂组合物胶液,用2116电子级玻璃纤维布浸渍胶液,经烘箱烘烤成半固化片,取6张2116半固化片,双面再覆上35μm厚的电解铜箔,在热压机作真空层压,固化190℃/120min,制成覆铜箔层压板。
实施例1-9以及对比例1-5中所用的各组分及其含量(按重量份计)如表1所示,各组分代号及其对应的组分名称如下所示:
(A)环氧树脂
(A-1)制备例中合成的双环戊二烯烷基苯酚环氧树脂
(A-2)联苯型环氧树脂:NC-3000-H(日本化药商品名)
(A-3)双环戊二烯型环氧树脂:HP-7200H(大日本油墨商品名)
(B)苯并噁嗪
(B-1)脂肪族苯并噁嗪树脂:KAH-F5404(韩国Kolon商品名)
(B-2)氟化苯并噁嗪:KAH-F5301(韩国Kolon商品名)
(B-3)双酚F型苯并噁嗪:LZ8280(亨斯曼先进材料)
(B-4)双环戊二烯苯并噁嗪:LZ8260(亨斯曼先进材料)
(C-1)低分子量聚苯醚:MX90(SABIC Innovative Plastics商品名),数均分子量1000-4000
(C-2)高分子量聚苯醚:Sabic640-111(SABIC Innovative Plastics商品名)数均分子量15000-20000
(D)苯乙烯-马来酸酐低聚物:SMA-EF40(美国Sartomer商品名)
(E)含磷酚醛树脂:XZ92741(DOW化学商品名)
(F)固化促进剂:2E4MZ(四国化成商品名)
(G)填料:熔融二氧化硅。
实施例1-9和对比例1-5采用的覆铜箔层压板的制备方法与实施例相同。
采用以下测试方法对实施例1-4和对比例1-4制备的覆铜箔层压板的玻璃化转变温度(Tg)、剥离强度(PS)、介电常数(Dk)与介质损耗角正切值(Df)、阻燃性和PCT 2小时后耐浸焊性及吸水率进行测试,测试结果如表2所示。
各性能参数的测试方法如下:
A玻璃化转变温度(Tg)
根据差示扫描量热法(DSC),按照IPC-TM-650 2.4.25所规定的DSC方法进行测定;
B剥离强度(PS)
按照IPC-TM-650 2.4.8方法中的“热应力后”实验条件,测试金属盖层的剥离强度;
C介电常数(Dk)与介质损耗角正切值(Df)
使用条状线的共振法,按照IPC-TM-650 2.5.5.5测定1GHz下的介电常数(Dk)与介质损耗角正切值(Df);
D阻燃性
按照UL-94标准进行测试;
E PCT 2小时后耐浸焊性及吸水率
将覆铜箔层压板浸渍在铜蚀刻液中,除去表面铜箔评价基板;将基板放置在压力锅中,在121℃,2atm下处理2h,测试吸水率后,浸渍在温度为288℃的锡炉中,当基材出现起泡或分裂时记录相应的时间。当基材在锡炉中超过5min还没有出现起泡或分层时结束评价。
表1
表2
通过表1和表2可以看出以下几点:
(1)将实施例1与对比例1相比可知,实施例1比对比例1的介电常数、介质损耗和吸水率比对比例1要低,说明实施例1采用其合成的双环戊二烯烷基苯酚环氧树脂比对比例1使用联苯型环氧树脂可以获得更低的介电常数、介质损耗以及PCT吸水率;
(2)将实施例2和对比例2相比可知,实施例2比对比例2的玻璃化转化温度稍低,但介电常数、介质损耗和PCT吸水率比对比例2都要低,说明实施例2采用实施例1中合成的双环戊二烯烷基苯酚环氧树脂比对比例2使用双环戊二烯型环氧树脂可以获得更低的介电常数、介质损耗以及PCT吸水率。
(3)将实施例3和实施例5和对比例3相比可知,实施例实施例3和实施例5比对比例3的玻璃化转化温度要高,而其介电常数、介质损耗以及PCT吸水率比对比例3的都要低,阻燃性可达到V-0级,说明实施例3和实施例5分别采用脂肪族苯并噁嗪及氟化苯并噁嗪比对比例3使用双酚F苯并噁嗪可以获得更高的玻璃化转化温度,更低的介电常数、介质损耗以及PCT吸水率,且阻燃性更高;实施例4和7可知,使用双环戊二烯苯并噁嗪与脂肪族苯并噁嗪均可实现较高的玻璃化转变温度、较低的介电常数,其中使用脂肪族苯并噁嗪具有更高的玻璃化转变温度及更低的介电常数。
(4)将实施例4和对比例4相比,实施例4比对比例4具有更低的介电常数、介质损耗和PCT吸水率,说明实施例4采用加入低分子量聚苯醚后比对比例4未加入该组分时可获得更低的介电常数、介质损耗和PCT吸水率;将实施例1与对比例5相比可知,虽然两者的综合性能相当,但使用高分子量的聚苯醚导致加工性变差。
(5)将实施例1-4相比,实施例1介质损耗、PCT吸水率也最高,实施例4的介质损耗以及PCT吸水率最低,说明随着制备例中合成的双环戊二烯烷基苯酚环氧树脂加入量的增加,介电常数、介质损耗、PCT吸水率均降低。
通过实施例1-9可以得出,在无卤树脂组合物中采用双环戊二烯烷基苯酚环氧树脂相比本领域常用的环氧树脂,可以使基材的介电性能更加突出,采用苯乙烯-马来酸酐与苯并噁嗪复合固化环氧组合物,同时添加少量含磷阻燃剂和低分子量聚苯醚,可以提高基材的阻燃性、粘结性和耐湿性,从而使其获得更优异的综合性能,适合在无卤高多层电路板中使用,具有重要的应用价值。
当然,以上所述之实施例,只是本发明的较佳实例而已,并非用来限制本发明的实施范围,故凡依本发明申请专利范围所述的原理所做的等效变化或修饰,均包括于本发明申请专利范围内。
Claims (21)
1.一种无卤树脂组合物,其特征在于,按重量份包括如下组分:环氧树脂50-100份,且至少含有一种如下化学结构式所示的具有双环戊二烯烷基结构的环氧树脂:
苯并噁嗪20-70份;聚苯醚5-40份;苯乙烯-马来酸酐5-30份;无卤阻燃剂5-40份;固化促进剂0.2-5份;填料20-100份;
所述的聚苯醚数均分子量在1000-4000。
2.如权利要求1所述的无卤树脂组合物,其特征在于,所述的环氧树脂还含有选自双酚A型环氧树脂、双酚F型环氧树脂、联苯环氧树脂、烷基酚醛环氧树脂、双环戊二烯环氧树脂、双酚A型酚醛环氧树脂、邻甲酚型酚醛环氧树脂、苯酚型酚醛环氧树脂、三官能环氧树脂、四官能环氧树脂、异氰酸酯改性环氧树脂、萘型环氧树脂或含磷环氧树脂中的任意一种或至少两种的混合物。
3.如权利要求1所述的无卤树脂组合物,其特征在于,所述的苯并噁嗪为氟化苯并噁嗪树脂、脂肪族苯并噁嗪树脂或双环戊二烯型苯并噁嗪树脂中的任意一种或至少两种的混合物。
4.如权利要求3所述的无卤树脂组合物,其特征在于,所述的苯并噁嗪为氟化苯并噁嗪树脂或脂肪族苯并噁嗪树脂中的任意一种或至少两种的混合物。
5.如权利要求3所述的无卤树脂组合物,其特征在于,所述的氟化苯并噁嗪树脂为下述化学结构式中的任意一种或至少两种的混合物:
6.如权利要求3所述的无卤树脂组合物,其特征在于,所述脂肪族苯并噁嗪树脂的化学结构式为:
其中,n为2或3。
7.如权利要求3所述的无卤树脂组合物,其特征在于,所述双环戊二烯型苯并噁嗪树脂的化学结构式为:
8.如权利要求1所述的无卤树脂组合物,其特征在于,所述的苯乙烯-马来酸酐的化学结构式为:
其中,x选自1-4,6,8;n选自1-12;x,n均为整数。
9.如权利要求1所述的无卤树脂组合物,其特征在于,所述的无卤阻燃剂为聚磷酸铵、三(2-羧乙基)膦、三甲基磷酸盐、间苯二酚双二甲苯基磷酸盐、磷腈、聚磷酸三聚氰胺、三聚氰胺氰尿酸酯、三-羟乙基异氰尿酸酯、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物或含DOPO酚醛树脂中的任意一种或至少两种的混合物。
10.如权利要求1所述的无卤树脂组合物,其特征在于,所述的固化促进剂为咪唑类促进剂。
11.如权利要求10所述的无卤树脂组合物,其特征在于,所述的固化促进剂为2-甲基咪唑、十一烷基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或1-氰乙基取代咪唑中的任意一种或至少两种的混合物。
12.如权利要求1所述的无卤树脂组合物,其特征在于,所述的填料为无机或有机填料。
13.如权利要求12所述的无卤树脂组合物,其特征在于,所述的填料为无机填料,所述的无机填料为氢氧化铝、氧化铝、氢氧化镁、氧化镁、二氧化硅、碳酸钙、氮化铝、氮化硼、碳化硅、二氧化钛、氧化锌、氧化锆、云母、勃姆石、煅烧滑石、滑石粉、氮化硅或煅烧高岭土中的任意一种或至少两种的混合物。
14.如权利要求12所述的无卤树脂组合物,其特征在于,所述的填料为有机填料,所述的有机填料为聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或至少两种的混合物。
15.如权利要求12所述的无卤树脂组合物,其特征在于,所述填料的粒径为0.01-50μm。
16.如权利要求15所述的无卤树脂组合物,其特征在于,所述填料的粒径为1-15μm。
17.如权利要求16所述的无卤树脂组合物,其特征在于,所述填料的粒径为1-5μm。
18.一种使用如权利要求1-17之一所述的无卤树脂组合物制作的预浸料,其特征在于,所述预浸料包括基体材料;和通过浸渍干燥后附着在其上的无卤树脂组合物。
19.如权利要求18所述的预浸料,其特征在于,所述基体材料为无纺或有纺玻璃纤维布。
20.一种层压板,其特征在于,包含如权利要求19所述的预浸料。
21.一种印刷电路板,其特征在于,其包含如权利要求20所述的层压板。
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410633018.5A CN104371273B (zh) | 2014-11-11 | 2014-11-11 | 一种无卤树脂组合物及用其制作的预浸料与层压板 |
AU2014411040A AU2014411040B2 (en) | 2014-11-11 | 2014-12-02 | Halogen-free resin composition and prepreg and laminate prepared therefrom |
JP2017525534A JP6381802B2 (ja) | 2014-11-11 | 2014-12-02 | ノンハロゲン樹脂組成物、及びそれを用いて製造されたプリプレグと積層板 |
PCT/CN2014/092842 WO2016074291A1 (zh) | 2014-11-11 | 2014-12-02 | 一种无卤树脂组合物及用其制作的预浸料与层压板 |
EP14905928.9A EP3219757B1 (en) | 2014-11-11 | 2014-12-02 | Halogen-free resin composition and prepreg and laminate prepared therefrom |
KR1020177015916A KR101897426B1 (ko) | 2014-11-11 | 2014-12-02 | 무할로겐 수지 조성물 및 이로 제조된 프리프레그와 적층판 |
US15/525,884 US10336875B2 (en) | 2014-11-11 | 2014-12-02 | Halogen-free resin composition and prepreg and laminate prepared therefrom |
TW104101384A TWI555791B (zh) | 2014-11-11 | 2015-01-15 | A halogen-free resin composition and a prepreg and laminate produced therefrom |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410633018.5A CN104371273B (zh) | 2014-11-11 | 2014-11-11 | 一种无卤树脂组合物及用其制作的预浸料与层压板 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104371273A CN104371273A (zh) | 2015-02-25 |
CN104371273B true CN104371273B (zh) | 2017-05-24 |
Family
ID=52550482
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410633018.5A Active CN104371273B (zh) | 2014-11-11 | 2014-11-11 | 一种无卤树脂组合物及用其制作的预浸料与层压板 |
Country Status (8)
Country | Link |
---|---|
US (1) | US10336875B2 (zh) |
EP (1) | EP3219757B1 (zh) |
JP (1) | JP6381802B2 (zh) |
KR (1) | KR101897426B1 (zh) |
CN (1) | CN104371273B (zh) |
AU (1) | AU2014411040B2 (zh) |
TW (1) | TWI555791B (zh) |
WO (1) | WO2016074291A1 (zh) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3219760B1 (en) * | 2014-11-11 | 2019-10-09 | Shengyi Technology Co., Ltd. | Thermoset resin composition, and prepreg and laminated board made of same |
CN106832764A (zh) * | 2015-12-04 | 2017-06-13 | 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含有它的预浸料、层压板和印制电路板 |
CN106117972A (zh) * | 2016-06-23 | 2016-11-16 | 安徽酷米智能科技有限公司 | 一种电路布线板用环氧树脂组合物 |
JP6849698B2 (ja) * | 2016-12-09 | 2021-03-24 | Eneos株式会社 | 硬化樹脂用組成物、該硬化樹脂用組成物の硬化物及び硬化方法、並びに半導体装置 |
JP6809200B2 (ja) * | 2016-12-19 | 2021-01-06 | Dic株式会社 | エポキシ樹脂、硬化性樹脂組成物及びその硬化物 |
CN106675023B (zh) * | 2016-12-30 | 2019-03-19 | 广东生益科技股份有限公司 | 一种无卤阻燃型树脂组合物及其制成的预浸料和覆铜箔层压板 |
CN107509312A (zh) * | 2017-06-29 | 2017-12-22 | 安徽升鸿电子有限公司 | 一种Dk>10的覆铜板的制作方法 |
US11578166B2 (en) | 2017-10-27 | 2023-02-14 | Eneos Corporation | Composition for curable resin, cured product of said composition, production method for said composition and said cured product, and semiconductor device |
CN107987471B (zh) * | 2017-11-08 | 2021-04-13 | 淮北绿洲新材料有限责任公司 | 一种高频低介电性主链苯并噁嗪复合树脂、制备方法及其应用 |
CN108003564B (zh) * | 2017-11-08 | 2021-04-13 | 淮北绿洲新材料有限责任公司 | 高频低介电性功能化石墨烯/主链苯并噁嗪复合树脂及其原位插层溶液制备方法 |
JP6896591B2 (ja) * | 2017-11-14 | 2021-06-30 | Eneos株式会社 | プリプレグ、繊維強化複合材料及び成形体 |
CN108410128B (zh) * | 2018-02-12 | 2020-06-30 | 浙江华正新材料股份有限公司 | 一种高速高频印制电路板用树脂组合物、半固化片及层压板 |
JP2019173009A (ja) * | 2018-03-28 | 2019-10-10 | 積水化学工業株式会社 | 硬化体、樹脂材料及び多層プリント配線板 |
CN109705532B (zh) * | 2018-12-29 | 2021-05-11 | 广东生益科技股份有限公司 | 一种无卤无磷无氮的阻燃树脂组合物、包含其的半固化片和覆金属箔层压板 |
JP7124770B2 (ja) * | 2019-03-07 | 2022-08-24 | 味の素株式会社 | 樹脂組成物 |
CN110845706B (zh) * | 2019-11-29 | 2022-06-24 | 陕西生益科技有限公司 | 一种热固性树脂组合物、使用其的预浸料、层压板及印制电路板 |
CN111072980B (zh) * | 2019-12-30 | 2021-11-23 | 四川东材科技集团股份有限公司 | 一种改性碳氢树脂预聚物、改性碳氢-dcpd环氧复合材料覆铜板及制备方法 |
WO2021212326A1 (zh) * | 2020-04-21 | 2021-10-28 | 穗晔实业股份有限公司 | 热固型树脂组成物 |
CN111732817A (zh) * | 2020-06-19 | 2020-10-02 | 林州致远电子科技有限公司 | 一种无卤低损耗覆铜板及其胶液和制备方法 |
EP4335256A1 (en) | 2021-05-07 | 2024-03-13 | AT & S Austria Technologie & Systemtechnik Aktiengesellschaft | Component carrier with photosensitive adhesion promoter and method of manufacturing the same |
CN116333491B (zh) * | 2023-05-26 | 2023-08-04 | 汕头超声覆铜板科技有限公司 | 一种适用于高速通信的无卤树脂组合物及其应用 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200413467A (en) * | 2003-01-16 | 2004-08-01 | Chang Chun Plastics Co Ltd | Resin composition without containing halogen |
CN102119184A (zh) | 2008-08-12 | 2011-07-06 | 亨斯迈先进材料(瑞士)有限公司 | 热固性组合物 |
CN103295992A (zh) * | 2008-10-10 | 2013-09-11 | 住友电木株式会社 | 半导体装置 |
TWI424021B (zh) * | 2009-06-30 | 2014-01-21 | Elite Material Co Ltd | 熱固性樹脂組成以及銅箔層合板 |
CN101684191B (zh) * | 2009-08-27 | 2012-03-07 | 广东生益科技股份有限公司 | 无卤高频树脂组合物及用其制成的预浸料与层压板 |
JP2011074123A (ja) * | 2009-09-29 | 2011-04-14 | Panasonic Electric Works Co Ltd | 樹脂組成物、樹脂ワニス、プリプレグ、金属張積層板、及びプリント配線板 |
AU2011379445B2 (en) | 2011-10-18 | 2014-07-17 | Shengyi Technology Co., Ltd. | Halogen-free low-dielectric resin composition, and prepreg and copper foil laminate made by using same |
CN103131131B (zh) | 2011-11-23 | 2015-07-15 | 台光电子材料股份有限公司 | 无卤素树脂组合物及其应用的铜箔基板及印刷电路板 |
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 |
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 |
WO2014036711A1 (zh) | 2012-09-07 | 2014-03-13 | 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 |
CN102964775B (zh) | 2012-10-16 | 2015-09-16 | 广东生益科技股份有限公司 | 一种热固性树脂组合物及其用途 |
CN103265810B (zh) | 2013-05-29 | 2015-09-23 | 苏州生益科技有限公司 | 一种用于高频高速基板的树脂组合物及使用其制作的半固化片及层压板 |
CN103980708B (zh) * | 2014-05-28 | 2017-01-11 | 苏州生益科技有限公司 | 用于集成电路的无卤阻燃热固性树脂组合物、半固化片及层压板 |
WO2016074288A1 (zh) * | 2014-11-11 | 2016-05-19 | 广东生益科技股份有限公司 | 一种热固性树脂组合物及用其制作的预浸料与层压板 |
-
2014
- 2014-11-11 CN CN201410633018.5A patent/CN104371273B/zh active Active
- 2014-12-02 KR KR1020177015916A patent/KR101897426B1/ko active IP Right Grant
- 2014-12-02 JP JP2017525534A patent/JP6381802B2/ja not_active Expired - Fee Related
- 2014-12-02 EP EP14905928.9A patent/EP3219757B1/en active Active
- 2014-12-02 WO PCT/CN2014/092842 patent/WO2016074291A1/zh active Application Filing
- 2014-12-02 AU AU2014411040A patent/AU2014411040B2/en not_active Ceased
- 2014-12-02 US US15/525,884 patent/US10336875B2/en not_active Expired - Fee Related
-
2015
- 2015-01-15 TW TW104101384A patent/TWI555791B/zh active
Also Published As
Publication number | Publication date |
---|---|
KR101897426B1 (ko) | 2018-09-10 |
AU2014411040B2 (en) | 2018-10-25 |
JP6381802B2 (ja) | 2018-08-29 |
WO2016074291A1 (zh) | 2016-05-19 |
US10336875B2 (en) | 2019-07-02 |
AU2014411040A1 (en) | 2017-06-08 |
CN104371273A (zh) | 2015-02-25 |
KR20170085076A (ko) | 2017-07-21 |
TW201617398A (zh) | 2016-05-16 |
EP3219757A4 (en) | 2018-06-27 |
EP3219757B1 (en) | 2019-07-10 |
JP2018502937A (ja) | 2018-02-01 |
EP3219757A1 (en) | 2017-09-20 |
TWI555791B (zh) | 2016-11-01 |
US20180327558A1 (en) | 2018-11-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104371273B (zh) | 一种无卤树脂组合物及用其制作的预浸料与层压板 | |
CN104448702B (zh) | 一种无卤树脂组合物及用其制作的预浸料与层压板 | |
CN106832226B (zh) | 一种无卤环氧树脂组合物以及含有它的预浸料、层压板和印制电路板 | |
CN105778413B (zh) | 一种无卤环氧树脂组合物以及使用它的预浸料和层压板 | |
EP2290009B1 (en) | Halogen-free flame retardant resin composition, and, prepreg, laminate, and laminate for printed circuit made therefrom | |
TWI555793B (zh) | 一種熱固性樹脂組合物及用其製作之預浸料與層壓板 | |
CN106832764A (zh) | 一种无卤环氧树脂组合物以及含有它的预浸料、层压板和印制电路板 | |
EP3112422A1 (en) | Halogen-free flame retardant type resin composition | |
WO2017080134A1 (zh) | 一种环氧树脂组合物及其应用 | |
TWI555785B (zh) | A thermosetting resin composition and a prepreg and laminate produced therewith | |
CN108047718A (zh) | 马来酰亚胺树脂组合物、预浸料、层压板和印刷电路板 | |
CN106543686B (zh) | 一种树脂组合物及使用其制作的半固化片、层压板和层间绝缘膜 | |
CN106749952A (zh) | 树脂组合物及使用其制作的半固化片、层压板和层间绝缘膜 | |
CN106751821B (zh) | 一种无卤阻燃型树脂组合物以及使用它的粘结片及覆铜箔层压板 | |
CN108047647A (zh) | 一种无卤热固性树脂组合物及使用它的预浸料、层压板、覆金属箔层压板和印刷电路板 | |
CN108192281A (zh) | 一种无卤热固性树脂组合物及使用它的预浸料、层压板、覆金属箔层压板和印刷电路板 | |
CN104371321B (zh) | 一种热固性树脂组合物及用其制作的预浸料与层压板 | |
CN104371320B (zh) | 一种热固性树脂组合物及用其制作的预浸料与层压板 | |
CN108976706A (zh) | 一种环氧树脂组合物以及使用它的预浸料和层压板 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |