CN109988288A - 树脂组合物以及使用该组合物所制得的预浸渍片、金属箔积层板与印刷电路板 - Google Patents

树脂组合物以及使用该组合物所制得的预浸渍片、金属箔积层板与印刷电路板 Download PDF

Info

Publication number
CN109988288A
CN109988288A CN201810014021.7A CN201810014021A CN109988288A CN 109988288 A CN109988288 A CN 109988288A CN 201810014021 A CN201810014021 A CN 201810014021A CN 109988288 A CN109988288 A CN 109988288A
Authority
CN
China
Prior art keywords
resin
weight
resin combination
parts
metal foil
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.)
Granted
Application number
CN201810014021.7A
Other languages
English (en)
Other versions
CN109988288B (zh
Inventor
廖志伟
曾冠勋
林宗贤
黄竹鸣
游镇华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiwan Union Technology Corp
Original Assignee
Taiwan Union Technology Corp
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 Taiwan Union Technology Corp filed Critical Taiwan Union Technology Corp
Publication of CN109988288A publication Critical patent/CN109988288A/zh
Application granted granted Critical
Publication of CN109988288B publication Critical patent/CN109988288B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on 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
    • 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
    • B32B15/04—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
    • B32B15/12—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 paper or cardboard
    • 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B29/005—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to another layer of paper or cardboard layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—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
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof
    • 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
    • C08G59/62—Alcohols or phenols
    • 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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • 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
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0237—High frequency adaptations
    • H05K1/024—Dielectric details, e.g. changing the dielectric material around a transmission line
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/098—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/028—Paper 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
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06—Vegetal fibres
    • B32B2262/062—Cellulose fibres, e.g. cotton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—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
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • 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
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • 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
    • B32B2307/748—Releasability
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • 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
    • B32B2361/00—Phenoplast, aminoplast
    • 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
    • B32B2363/00—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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • 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
    • C08G59/4014—Nitrogen containing compounds
    • 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
    • C08G59/4064—Curing agents not provided for by the groups C08G59/42 - C08G59/66 sulfur containing compounds
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
    • 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
    • C08J2421/00—Characterised by the use of unspecified rubbers
    • 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
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • 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
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
    • 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
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with 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
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08J2461/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
    • C08J2461/10—Phenol-formaldehyde condensates
    • 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
    • C08J2465/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • C08J2465/02—Polyphenylenes
    • 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
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing 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
    • 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
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • 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
    • H05K1/036—Multilayers with layers of different types
    • 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
    • H05K2201/0212—Resin 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
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0227—Insulating particles having an insulating coating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31515—As intermediate layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31515—As intermediate layer
    • Y10T428/31518—Next to glass or quartz
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31515—As intermediate layer
    • Y10T428/31522—Next to metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31525—Next to glass or quartz
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31529—Next to metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31688—Next to aldehyde or ketone condensation product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31942—Of aldehyde or ketone condensation product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

本发明提供一种树脂组合物，其包含以下成分：(A)无卤环氧树脂；(B)硬化剂；以及(C)具有下式(I)结构的含磷酚醛树脂：其中，m、n、l、R1及R2为如本文中所定义。

Description

树脂组合物以及使用该组合物所制得的预浸渍片、金属箔积 层板与印刷电路板
技术领域
本发明涉及一种树脂组合物，特别涉及一种包含经9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)或其衍生物改质的含磷酚醛树脂的树脂组合物。本发明的树脂组合物可与玻璃纤维构成复合材料或预浸渍片，或进一步作为金属箔的接着剂，制成金属箔积层板或印刷电路板。
背景技术
随着电子通信技术中对于数据传输量的需求不断增加的趋势，电子产品的信号传输不断往更高频的区域去应用，使得电子材料必须具备更低的介电常数(Dk)与介电损耗因子(Df)。另外，为了落实无铅、无卤素的环保工艺，印刷电路板中的介电层材料必须使用无铅、无卤素的材料来制作，例如必须使用非卤素系统的阻燃剂、无卤素的环氧树脂等。然而，符合上述要求的树脂组合物配方所制得的电子材料在电性、耐热性、无卤阻燃等各方面特性并无法达到全面且均衡的状态。
已知可通过将酚醛树脂以DOPO改质后添加于环氧树脂组合物中，作为环氧树脂的硬化剂并提供提高难燃性的效果。例如US 20070221890 A1公开了一种DOPO改质酚化合物及DOPO改质酚醛化合物，其为一种非卤素系统的阻燃剂，也即业界熟知的含磷阻燃剂DOPO-BN(已存在许多商品化的产品，例如可购自Dow Chemical；型号：92741)。然而，使用此阻燃剂所制得的电子材料存在吸水性高、Df高等缺点，在高频材料方面的应用始终有所限制。
US 20120095170 A1也公开了一种经DOPO改质的含磷酚醛树脂，然而，其结构中具有非对称的-OH基，对电子材料的电学性质会产生不良影响，并且如该文献中所记载，使用此阻燃剂所制得的电子材料还存在耐热性不足的问题(玻璃转移温度(Tg)太低)，在应用上必须与一般线性酚醛树脂并用，来弥补此缺陷。
WO 2016101540A1也公开了一种DOPO改质含磷酚醛树脂，其化学结构中包含了二环戊二烯型酚(DCPD phenol)，然而，该含磷酚醛树脂中的二环戊二烯型酚结构所产生的立体障碍大，使得该含磷酚醛树脂溶解度不佳，产生了加工性方面的问题。
WO2016074288公开了一种包含聚苯醚树脂以及分子中具有DCPD结构及(1,1,3,3-四甲基)丁基结构基团的环氧树脂的树脂组合物，然而，除了前述DCPD的结构对溶解度所造成的不利影响外，该树脂组合物还存在所制得的电子材料难燃性不佳的问题，必须额外添加阻燃剂。
因此，虽然现有技术中已知以DOPO对酚醛树脂进行改质的作法，但在实际应用上仍有许多待改进的空间。尤其，目前仍亟需一种各项物化性质优异且同时具有低Dk值、低Df值、高Tg值等特性的无卤树脂组合物。
发明内容
有鉴于前述的现况，本发明提供一种树脂组合物配方，其中将无卤环氧树脂搭配硬化剂及具有特定结构的含磷酚醛树脂使用，该含磷酚醛树脂除因含有磷成分而能赋予本发明树脂组合物及其制品良好难燃特性外，还能够为树脂组合物带来良好电性、耐热性、尺寸安定性及耐湿性，从而能制得兼具良好电性及物化特性的电子材料。
因此，本发明的一目的在于提供一种树脂组合物，包含：
(A)无卤环氧树脂；
(B)硬化剂；以及
(C)具有下式(I)结构的含磷酚醛树脂：
式(I)，于式(I)中，m、n及l各自独立为0至10的整数，但m、n及l不同时为0，以及
R1及R2各自独立为9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、DOPO衍生物或胺基三氮杂苯酚醛(amino triazine novolac，ATN)树脂的残基或-O(CH2)3CH3，且条件为R1及R2中至少一者为DOPO或DOPO衍生物的残基。
于本发明的部分实施例中，式(I)中的R1及R2各自独立为DOPO的残基、的残基或-O(CH2)3CH3，且条件为R1及R2中至少一者为DOPO的残基。
于本发明的部分实施例中，该硬化剂选自以下群组：二胺基二苯砜(diaminodiphenyl sulfone，DDS)、胺基三氮杂苯酚醛(ATN)树脂、双马来酰亚胺(bismaleimide，BMI)树脂、多官能性马来酰亚胺树脂、苯乙烯马来酸酐(styrene maleicanhydride，SMA)树脂、苯并恶嗪树脂(benzoxazine)及其组合。
于本发明的部分实施例中，该硬化剂(B)对该含磷酚醛树脂(C)的重量比为约0.2：1至约3：1，较佳为约0.3：1至约1.5：1。
于本发明的部分实施例中，以100重量份的无卤环氧树脂(A)计，该硬化剂(B)的含量为约5重量份至约60重量份，且该含磷酚醛树脂(C)的含量为约10重量份至约50重量份。
于本发明的部分实施例中，树脂组合物还包含选自以下群组的共硬化剂：二氰二胺(Dicy)、氰酸酯(cyanate ester)树脂、酚醛树脂(phenol novolac，PN)、二胺基二苯甲烷(diaminodiphenylmethane)、苯乙烯-乙烯基酚共聚物及其组合。
于本发明的部分实施例中，树脂组合物还包含一核壳橡胶(core/shell rubber)。
于本发明的部分实施例中，树脂组合物还包含选自以下群组的成分：填料、阻燃剂、催化剂、分散剂、增韧剂及其组合。所述填料例如可选自以下群组：二氧化硅(如中空二氧化硅)、氧化铝、氧化镁、氢氧化镁、碳酸钙、滑石、黏土、氮化铝、氮化硼、氢氧化铝、碳化铝硅、碳化硅、碳酸钠、二氧化钛、氧化锌、氧化锆、石英、钻石、类钻石、石墨、煅烧高岭土、白岭土、云母、水滑石、聚四氟乙烯(PTFE)粉末、玻璃珠、陶瓷晶须、纳米碳管、纳米级无机粉体及其组合。
本发明的另一目的在于提供一种预浸渍片，其通过将一基材含浸或涂布如上所述的树脂组合物，并干燥该经含浸或涂布的基材而制得。
本发明的一目的在于提供一种金属箔积层板。其通过将如上所述的预浸渍片与金属箔加以层合而制得，或通过将如上所述的树脂组合物涂布于金属箔并干燥该经涂布的金属箔而制得。
本发明的一目的在于提供一种印刷电路板，其由如上所述的金属箔积层板所制得。
具体实施方式
为使本发明的上述目的、技术特征及优点能更明显易懂，下文以部分具体实施例进行详细说明。
以下将具体地描述根据本发明的部分具体实施例；但是，在不背离本发明的精神下，本发明还可以多种不同形式的实施例来实践，不应将本发明保护范围解释为限于说明书所陈述的。
除非文中有另外说明，于本说明书中(尤其是在权利要求书中)所使用之“一”、“该”及类似用语应理解为包含单数及复数形式。
除非文中有另外说明，于本说明书中描述溶液、混合物或组合物中所含的成分时，以固含量(dry weight)计算，即，未纳入溶剂的重量。
本文中，用词“约”是指所指定的量可增加或减少一本领域技术人员可认知为一般且合理的大小的量。
本发明对照现有技术的功效在于，本发明树脂组合物使用了特定结构的含磷酚醛树脂，其分子结构中具有非极性或低极性的烷基碳链段，可增益树脂组合物所制电子材料的电学性质，其分子结构末端的衍生自DOPO或DOPO衍生物的残基可赋予所制电子材料良好难燃性质，而其分子结构末端的低碳数烷基或衍生自胺基三氮杂苯酚醛(ATN)树脂的残基则可进一步增益所制电子材料的电学性质及提升树脂组合物的交联密度，使得所制电子材料的电性及耐热性(如Tg)更为优异。现就本发明树脂组合物的各成分及制备方式提供详细说明如下。
1.树脂组合物
本发明树脂组合物包含无卤环氧树脂(A)、硬化剂(B)、以及具有特定结构的含磷酚醛树脂(C)等必要成分，以及可视需要的选用成分。
1.1.无卤环氧树脂(A)
本文中，无卤环氧树脂是指在一分子中具有至少两个环氧官能基且不含卤素的热硬化型树脂，例如多官能基环氧树脂、线性酚醛环氧树脂或其组合。所述多官能基环氧树脂包括双官能基环氧树脂、四官能基环氧树脂、八官能基环氧树脂等。无卤环氧树脂的实施例包括但不限于：酚醛型环氧树脂、双酚型环氧树脂、二环戊二烯(DCPD)型环氧树脂、二苯乙烯型环氧树脂、含三嗪(triazine)骨架的环氧树脂、含茀骨架的环氧树脂、三酚基甲烷型环氧树脂、联苯型环氧树脂、伸茬基型环氧树脂、联苯芳烷基型环氧树脂、萘型环氧树脂、脂环式环氧树脂及其组合。酚醛型环氧树脂的实施例包括但不限于苯酚酚醛型环氧树脂、甲酚酚醛型环氧树脂、双酚A酚醛型环氧树脂及双酚F酚醛型环氧树脂。双酚型环氧树脂的实施例包括但不限于双酚A型环氧树脂、双酚F型环氧树脂及双酚S型环氧树脂。环氧树脂的实施例还可包括多官能酚类及蒽等多环芳香族类的二缩水甘油醚化合物。此外，可导入磷至环氧树脂中而形成含磷环氧树脂，例如经DOPO改质的环氧树脂。
1.2.硬化剂(B)
硬化剂含有反应性官能基的成分，其可参与固化反应，并形成网状结构，从而增益所制电子材料的特性，例如改良其玻璃转移温度(Tg)、吸水性、Df等特性。
一般而言，于本发明的树脂组合物中，以100重量份的无卤环氧树脂(A)计，硬化剂(B)的含量为约5重量份至约60重量份，例如6重量份、7重量份、8重量份、9重量份、10重量份、11重量份、12重量份、13重量份、14重量份、15重量份、17重量份、19重量份、20重量份、22重量份、24重量份、25重量份、27重量份、30重量份、32重量份、35重量份、37重量份、40重量份、42重量份、45重量份、48重量份、50重量份、52重量份、55重量份或58重量份，但本发明不以此为限，本发明所属技术领域的技术人员仍可依据实际需要调整硬化剂(B)的用量。
于本发明的部分实施例中，硬化剂(B)选自以下群组：二胺基二苯砜(DDS)、胺基三氮杂苯酚醛(ATN)树脂、双马来酰亚胺(BMI)树脂、多官能性马来酰亚胺树脂、苯乙烯马来酸酐(SMA)树脂、苯并恶嗪树脂及其组合。于使用上述硬化剂的情况下，所制电子材料可具有更好的耐热性(玻璃转移温度(Tg)更高)。以下现就上述硬化剂提供进一步说明。
1.2.1.二胺基二苯砜(DDS)树脂
二胺基二苯砜(DDS)树脂是一种芳香族胺类硬化剂，其实施例包括但不限于3,3,-二胺基二苯砜及4,4,-二胺基二苯砜
1.2.2.胺基三氮杂苯酚醛(ATN)树脂
胺基三氮杂苯酚醛(ATN)树脂可改善所制电子材料的耐热性，同时又可提高金属箔积层板的介电层与金属箔的附着力。一般而言，胺基三氮杂苯酚醛树脂可通过将苯酚化合物、醛类化合物及胍胺化合物，在酸性触媒(如草酸、对甲苯磺酸等)存在下，进行反应而制得。苯酚化合物的实例包括苯酚、甲酚或二甲苯酚；醛类化合物的实例包括甲醛以及胍胺化合物可为如下结构式所代表的一或多种化合物：
其中R可为胺基(蜜胺)、苯基(苄胍胺)或如甲基(甲基胍胺)等烷基。
胺基三氮杂苯酚醛树脂的实施例包括但不限于以下结构式所表示的化合物：
1.2.3.双马来酰亚胺(BMI)树脂
双马来酰亚胺树脂是一种具有两个马来酰亚胺官能基的化合物。马来酰亚胺官能基具有反应性碳-碳双键，可与树脂组合物中的其他不饱和官能基进行反应而发生交联固化作用，并且可改善树脂组合物固化后所得的材料的耐热性。具体而言，双马来酰亚胺树脂可由以下结构式表示：
其中，R3为一有机基团，且较佳选自以下群组的基团：伸甲基(-CH2-)、4,4'-二苯甲烷基间伸苯基双酚A二苯醚基3,3'-二甲基-5,5'-二乙基-4,4'-二苯甲烷基4-甲基-1,3-伸苯基及(2,2,4-三甲基)伸己基
双马来酰亚胺树脂的具体实施例包括但不限于：1,2-双马来酰亚胺基乙烷、1,6-双马来酰亚胺基己烷、1,3-双马来酰亚胺基苯、1,4-双马来酰亚胺基苯、2,4-双马来酰亚胺基甲苯、4,4'-双马来酰亚胺基二苯基甲烷、4,4'-双马来酰亚胺基二苯基醚、3,3'-双马来酰亚胺基二苯基砜、4,4'-双马来酰亚胺基二苯基砜、4,4'-双马来酰亚胺基二环己基甲烷、3,5-双(4-马来酰亚胺基苯基)吡啶、2,6-双马来酰亚胺基吡啶、1,3-双(马来酰亚胺基甲基)环己烷、1,3-双(马来酰亚胺基甲基)苯、1,1-双(4-马来酰亚胺基苯基)环己烷、1,3-双(二氯马来酰亚胺基)苯、4,4'-双柠康酰亚胺基二苯基甲烷(4,4'-biscitraconimidodiphenylmethane)、2,2-双(4-马来酰亚胺基苯基)丙烷、1-苯基-1,1-双(4-马来酰亚胺基苯基)乙烷、α,α-双(4-马来酰亚胺基苯基)甲苯、3,5-双马来酰亚胺基-1,2,4-三唑、N,N'-伸乙基双马来酰亚胺、N,N'-六亚甲基双马来酰亚胺、N,N'-间-伸苯基双马来酰亚胺、N,N'-对-伸苯基双马来酰亚胺、N,N'-4,4'-二苯基甲烷双马来酰亚胺、N,N'-4,4'-二苯基醚双马来酰亚胺、N,N'-4,4'-二苯基砜双马来酰亚胺、N,N'-4,4'-二环己基甲烷双马来酰亚胺、N,N'-α,α'-4,4'-二亚甲基环己烷双马来酰亚胺、N,N'-间二甲苯双马来酰亚胺、N,N'-4,4'-二苯基环己烷双马来酰亚胺及N,N'-亚甲基双(3-氯-对-伸苯基)双马来酰亚胺。商业上可购得的双马来酰亚胺树脂包括KI Chemical公司的型号为BMI-70及BMI-80的产品，以及大和化成工业的型号为BMI-1000、BMI-4000、BMI-5000、BMI-5100及BMI-7000的产品。前述双马来酰亚胺可单独使用或混合使用，本领域技术人员可依据实际需要而自行调配。于后附实施例中，使用BMI-70(R3为3,3'-二甲基-5,5'-二乙基-4,4'-二苯甲烷基)。
1.2.4.多官能性马来酰亚胺树脂
于本文中，多官能性马来酰亚胺树脂是指具有多个马来酰亚胺官能基的寡聚物，通常为苯胺(aniline)或甲醛(formaldehyde)与马来酸酐(maleic anhydride)的缩合反应产物。具体而言，多官能性马来酰亚胺树脂可由以下结构式表示：
其中，p为1至10的整数。
有关多官能性马来酰亚胺树脂的说明可参考US 4,435,560，该专利文献全文在此引入作为参考。商业上可购得的多官能性马来酰亚胺树脂包括大和化成工业的型号为BMI-2000及BMI-2300(CAS号：67784-74-1)的产品。
1.2.5.苯乙烯马来酸酐(SMA)树脂
苯乙烯-马来酸酐(SMA)树脂为苯乙烯单体与马来酸酐单体的共聚物，具有降低Dk及Df的效果，此外，其分子中的衍生自马来酸酐的基团为优良的官能基，能与环氧树脂充分进行反应，因此另有提升Tg的效果。具体而言，苯乙烯-马来酸酐树脂具有以下重复单元的聚合物：
其中，q1一般为1至10的整数，q2一般为10至40的整数。
于苯乙烯-马来酸酐树脂中，苯乙烯的摩尔比占比越高(即q1值越大者)，所制得的电子材料的Df值越低，故电学性质较佳，但玻璃转移温度(Tg)较差(q1＝1时，Tg为约155℃，q1＝8时，Tg则仅为约104℃)；此外，若苯乙烯的摩尔比占比过高(如q1≧8)，将使得所制得的预浸渍片的表面沾黏性提高，而容易产生自身黏合，如此将不利加工操作。反之，苯乙烯的摩尔比占比越低(例如q1≦3)，所制得的电子材料的Tg越高，故耐热性越好，但所制材料的质地较脆，加工时易产生粉屑污染。因此，在上述重复单元中q1值较佳为3至8，满足此条件的苯乙烯-马来酸酐树脂包括可购自Cray Valley公司的型号为SMA EF-40(q1＝4)与EF-30(q1＝3)的产品。
1.2.6.苯并恶嗪树脂
苯并恶嗪树脂是指由酚类羟基化合物、一级胺及甲醛依下列反应所制得的化学物质：
于上述反应式中，该酚类羟基化合物的实施例包括但不限于多官能基酚(如邻苯二酚、间苯二酚或对苯二酚)、联酚化合物、双酚化合物(如双酚A、双酚F或双酚S)、三酚化合物及酚醛树脂(如酚醛清漆树脂或蜜胺酚醛树脂)。一级胺(R4-NH2)的R4可为烷基、环烷基、苯基或经烷基或烷氧基取代的苯基，其实施例包括但不限于甲胺及经或未经取代的苯胺。甲醛(HCHO)可以福尔马林或多聚甲醛的方式提供。
苯并恶嗪树脂可于添加至本发明的树脂组合物前，预先经过开环聚合反应，而以预聚物的形式添加至树脂组合物中。关于此类预聚物的制备与使用，可见US 2012097437A(申请人：Taiwan Union Technology公司)，该专利申请案的全文并于此作为参照。
1.3.具有式(I)结构的含磷酚醛树脂(C)
本发明树脂组合物中包含具有以下式(I)结构的含磷酚醛树脂(C)，其通过DOPO或DOPO衍生物于分子末端改质，且在酚醛主链的苯酚结构中引入了三级丁基及/或(1,1,3,3)四甲基丁基。式(I)。
于式(I)中，m、n及l各自独立为0至10的整数，但m、n及l不同时为0，以及R1及R2各自独立为DOPO、DOPO衍生物或胺基三氮杂苯酚醛(ATN)树脂的残基或-O(CH2)3CH3，且条件为R1及R2中至少一者为DOPO或DOPO衍生物的残基，以赋予所制电子材料难燃性质。
于式(I)中，m、n、l的值越大，主链上的-OH基越多，越能提升树脂组合物固化后的交联密度。当R1及R2分别为DOPO或DOPO衍生物的残基时，该含磷酚醛树脂具有较佳的难燃性质。当R1及R2仅其中的一者为DOPO或DOPO衍生物的残基，另一者为-O(CH2)3CH3时，该含磷酚醛树脂具有较佳的电学性质。当R1及R2仅其中的一者为DOPO或DOPO衍生物的残基，另一者为ATN的残基时，该含磷酚醛树脂具有较佳的反应性。
上述具式(I)结构的含磷酚醛树脂(C)的制备方法并无特殊限制且并非本发明的技术重点所在，本领域技术人员观得本申请说明书内容后当可依所具备的通常知识视需要选择合宜的方式自行制备或以商购方式取得。例如，可依一般方法制得具有式(I)主链结构的酚醛树脂后，再以DOPO、DOPO衍生物、ATN等进行酚醛树脂的末端改质，以制得具有式(I)结构的含磷酚醛树脂(C)。相关改质方法可参照例如US 20070221890、US 8124716、US20140249253等，上述文献及其引用文献，在此引入全文作为参考。于后附实施例中，使用购自Kolon Industries公司的型号为KEG3320B65的产品，其中R1及R2各自独立为DOPO的残基、的残基或-O(CH2)3CH3。具有式(I)结构的含磷酚醛树脂(C)还可购自Dow Chemical公司。
于本发明的树脂组合物中，以100重量份的无卤环氧树脂(A)计，该含磷酚醛树脂(C)的含量为约10重量份至约50重量份，例如11重量份、12重量份、13重量份、14重量份、15重量份、17重量份、19重量份、20重量份、22重量份、24重量份、25重量份、27重量份、30重量份、32重量份、35重量份、37重量份、40重量份或45重量份。
于本发明的树脂组合物中，硬化剂(B)对该含磷酚醛树脂(C)的重量比为约0.2：1至约3：1，较佳为约0.3：1至约1.5：1，例如0.36：1、0.37：1、0.4：1、0.5：1、0.55：1、0.6：1、0.65：1、0.7：1、0.75：1、0.8：1、0.85：1、0.9：1、1：1、1.05：1、1.1：1、1.15：1、1.2：1、1.25：1、1.3：1、1.35：1、1.4：1或1.45：1。
1.4.视需要的其他成分
于本发明树脂组合物中，可视需要包含其他成分，例如下文所述的共硬化剂、核壳橡胶及本领域所现有的添加剂，以改良树脂组合物所制电子材料的物化性质或树脂组合物在制造过程中的可加工性。
1.4.1.共硬化剂
于本发明的树脂组合物中，除硬化剂(B)外，可进一步包含其他现有的可适用于环氧树脂的硬化剂，例如含-OH基的化合物、含胺基的化合物、酸酐化合物及活性酯化合物；且共硬化剂的用量并无特殊限制，可由本发明所属技术领域的技术人员依据实际需要进行调整。共硬化剂的实施例包括但不限于二氰二胺(Dicy)、氰酸酯(cyanate ester)树脂、酚醛树脂(phenol novolac，PN)、二胺基二苯甲烷(diaminodiphenylmethane)及苯乙烯-乙烯基酚共聚物，且前述共硬化剂可单独使用或任意组合使用。于后附实施例中使用二氰二胺(Dicy)。
1.4.2.核壳橡胶
本发明的树脂组合物中可进一步包含核壳橡胶作为增韧剂，以改善所制电子材料的脆性，使电子材料变得强韧。本文中，核壳橡胶是指一种具有双层结构的橡胶。该双层结构包括核层(内层)及一包覆该核层的壳层(外层)。核层通常由二烯类弹性体(dieneelastomer)或硅氧烷(siloxane)所构成，主要功能为吸收应力。壳层通常由与树脂组合物中其他成分兼容性高的高分子材料所构成，例如由丙烯酸类单体、甲基丙烯酸类单体、苯乙烯单体及丙烯腈单体的一或多者所形成的聚合物或共聚物，其主要功能为包覆在核层的外部，以利于核壳橡胶与树脂组合物的兼容，而于树脂组合物中具有良好的分散性。
核壳橡胶可通过本领域现有的任意制备方法来制备，例如可通过US 2009/0298970中所公开的方法来制备，该专利文献全文在此引入作为参考。商业上可购得的核壳橡胶的实施例包括KANEKA公司的型号为MX-120、MX-125、MX-130、MX-156、MX-551及KANEACE系列的产品，以及Mitsubishi Rayon公司的型号为METABLEN SX-006的产品。
一般而言，为了在不影响树脂组合物本身特性的前提下提供所欲的增韧功效，核壳橡胶的含量以树脂组合物固含量计，通常为约1重量％至约20重量％，例如2重量％、4重量％、4.5重量％、6重量％、7重量％、8重量％、8.5重量％、9重量％、10重量％、12重量％、13重量％、14重量％、16重量％、17重量％、18重量％或19重量％，较佳约1重量％至约15重量％，更佳约1重量％至约5重量％，但本发明不以此为限。
1.4.3.其他添加剂
可应用于本发明的树脂组合物中的添加剂的实施例包括但不限于填料、阻燃剂、催化剂、分散剂及增韧剂，且各添加剂可单独使用或组合使用。
于本发明的部分实施例中，树脂组合物中进一步添加填料，以增益所制得的电子材料的物化性质。所述填料的实施例包括但不限于二氧化硅(如中空二氧化硅)、氧化铝、氧化镁、氢氧化镁、碳酸钙、滑石、黏土、氮化铝、氮化硼、氢氧化铝、碳化铝硅、碳化硅、碳酸钠、二氧化钛、氧化锌、氧化锆、石英、钻石、类钻石、石墨、煅烧高岭土、白岭土、云母、水滑石、聚四氟乙烯(polytetrafluoroethylene，PTFE)粉末、玻璃珠、陶瓷晶须、纳米碳管及纳米级无机粉体，且各填料可单独使用或任意组合使用。一般而言，以树脂组合物固含量计，填料的含量通常为0重量％至约40重量％，例如1重量％、3重量％、5重量％、7重量％、10重量％、15重量％、20重量％、22重量％、25重量％、30重量％或35重量％，但不以此为限，本发明所属技术领域的技术人员仍可依据实际需要进行调整。
于本发明的部分实施例中，树脂组合物中进一步添加催化剂，以促进环氧官能基开环进行交联反应，并降低树脂组合物的固化反应温度。催化剂的种类并无特殊限制，只要其能促进环氧官能基开环并降低固化反应温度即可。举例言之，催化剂可为三级胺、四级胺、咪唑化合物或吡啶化合物，且各催化剂可单独使用或混合使用。催化剂的实施例包括但不限于2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、二甲苄胺、2-(二甲胺甲基)苯酚、2,4,6-三(二甲胺甲基)苯酚、2,3-二胺基吡啶、2,5-二胺基吡啶、2,6-二胺基吡啶、4-二甲基胺基吡啶、2-胺基-3-甲基吡啶、2-胺基-4-甲基吡啶及2-胺基-3-硝基吡啶。一般而言，以树脂组合物固含量计，催化剂的含量通常为约0.5重量％至约5重量％，例如1重量％、1.5重量％、2重量％、2.5重量％、3重量％、3.5重量％、4重量％或4.5重量％，但不以此为限，本发明所属技术领域的技术人员仍可依据实际需要进行调整。
1.5树脂组合物的制备
关于本发明树脂组合物的制备，可通过将树脂组合物各成分，包括无卤环氧树脂、硬化剂、具有式(I)的含磷酚醛树脂及视需要的其他成分，以搅拌器均匀混合并溶解或分散于溶剂中而制成清漆状的形式，供后续加工利用。所述溶剂可为任何可溶解或分散树脂组合物各成分、但不与这些成分反应的惰性溶剂。举例言之，可用以溶解或分散树脂组合物各成分的溶剂包含但不限于甲苯、γ-丁内酯、甲乙酮、环己酮、丁酮、丙酮、二甲苯、甲基异丁基酮、N,N-二甲基甲酰胺(N,N-dimethyl formamide，DMF)、N,N-二甲基乙酰胺(N,N-dimethyl acetamide，DMAc)及N-甲基吡咯烷酮(N-methyl-pyrolidone，NMP)，且各溶剂可单独使用或混合使用。溶剂的用量并无特殊限制，原则上只要能使树脂组合物各组分均匀溶解或分散于其中即可。于本发明的部分实施例中，使用甲苯、甲乙酮及γ-丁内酯的混合物作为溶剂。
2.预浸渍片
本发明也提供一种由上述树脂组合物所制得的预浸渍片，其中通过将一基材含浸如上述的树脂组合物或将上述的树脂组合物涂布于一基材，并进行干燥而制得。常用的基材包括玻璃纤维补强材料(如玻璃纤维织物或不织物、玻璃纸或玻璃毡)、牛皮纸、短绒棉纸、天然纤维布、有机纤维布(如液晶高分子)等。于本发明的部分实施例中，使用2116强化玻璃纤维布作为补强材，并在175℃下加热干燥2至15分钟(B-阶段)，从而制得半固化状态的预浸渍片。
3.金属箔积层板及印刷电路板
本发明也提供一种由上述预浸渍片制得的金属箔积层板，其包括一介电层及一金属层，其中该介电层由如上述的预浸渍片所提供。其中，可层叠多层上述预浸渍片，且于层叠该预浸渍片所构成的介电层的至少一外侧表面层叠一金属箔(如铜箔)以提供一层叠物，并对该层叠物进行一热压操作而得到金属箔积层板。或者，可将上述的树脂组合物直接涂布于一金属箔并进行干燥，而制得金属箔积层板。此外，可通过进一步图案化金属箔积层板的外侧金属箔，而制得印刷电路板。
4.实施例
4.1.测量方式说明
现以下列具体实施例进一步例示说明本发明，其中，所采用的测量仪器及方法分别如下：
[吸水性测试]
进行压力锅蒸煮试验(pressure cooker test，PCT)试验，将金属箔积层板置于压力容器中，在121℃、饱和相对湿度(100％R.H.)及1.2大气压的环境下2小时，测试金属箔积层板的耐湿能力。
[耐浸焊性测试]
将干燥过的金属箔积层板在288℃的锡焊浴中浸泡一定时间后，观察是否出现爆板情形，例如观察金属箔积层板是否产生分层或胀泡现象。
[抗撕强度测试]
抗撕强度是指金属箔对经热压层合的预浸渍片的附着力而言，于本文中是以1/8英寸宽度的铜箔自板面上垂直撕起，以其所需力量的大小来表达附着力的强弱。
[玻璃转移温度(Tg)测试]
利用动态机械分析仪(Differential Scanning Calorimeter，DSC)测量玻璃转移温度(Tg)。玻璃转移温度的测试规范为电子电路互联与封装学会(The Institute forInterconnecting and Packaging Electronic Circuits，IPC)的IPC-TM-650.2.4.25C及24C号检测方法。
[热膨胀率测试]
以TA仪器(TA instrument)公司的热膨胀分析仪(机型TA2940)测量，测量条件为在50℃至260℃的温度区间以每分钟10℃的升温速率升温，测量样品(3平方毫米大小的金属箔积层板)在厚度方向(Z轴方向)的热膨胀率。
[难燃性测试]
利用UL94V：垂直燃烧测试方法，将金属箔积层板以垂直位置固定，以本生灯燃烧，比较其自燃熄灭与助燃特性。难燃等级的排序为：V0>V1>V2。
[介电常数(Dk)与介电损耗因子(Df)测量]
根据ASTM D150规范，在工作频率10GHz下，计算介电常数(Dk)与介电损耗因子(Df)。用于测试的预浸渍片的树脂含量(Resin Content，RC)为约53％。
[耐碱性测试]
将不含铜箔的积层板(即，仅使用本发明预浸渍片层合并经热压而成的积层板)浸泡于浓度20重量％的NaOH溶液中，于90℃下持续10分钟，之后观察积层板外观是否有被咬蚀现象，若无咬蚀现象则记录为“通过”，若有咬蚀现象则记录为“失败”。
[钻针磨耗测试]
以直径0.3毫米的钻针对金属箔积层板钻孔，并于钻孔次数达2000次之后观察钻针头部的磨耗。由于钻针的切削边缘(cutting edge，CE)在钻孔过程中会不断与积层板接触磨耗，在切削边缘CE的切削转角(cutting corner，CC)处会产生磨耗，因此本测试中是针对切削转角CC处进行测量以得到磨耗率。
4.2.原物料信息列表：
4.3.树脂组合物的制备
以表1所示的比例配制实施例1至7及比较例1至3的树脂组合物，其中将各成分于室温下使用搅拌器混合，并加入甲苯、甲乙酮及γ-丁内酯(均购自Fluka公司)，接着将所得混合物于室温下搅拌60至120分钟后，制得各树脂组合物。
表1：
4.4.金属箔积层板的制备及性质测量
分别使用所制得的树脂组合物制备实施例1至7及比较例1至3的金属箔积层板。首先，通过辊式涂布机，将玻璃纤维布(型号：2116，厚度：0.08毫米)分别浸渍于实施例1至7及比较例1至3的树脂组合物中，并控制玻璃纤维布的厚度至一合适程度。接着，将浸渍后的玻璃纤维布置于175℃的干燥机中加热干燥2至15分钟，借此制得半固化状态(B-stage)的预浸渍片(预浸渍片的树脂含量为约53％)。之后，将四片预浸渍片层合，并在其两侧的最外层各层合一张0.5盎司的铜箔，随后置于热压机中进行高温热压固化。热压条件为：以3.0℃/分钟的升温速度升温至200℃至220℃，并在该温度下，以全压15公斤/平方公分(初压8公斤/平方公分)的压力热压180分钟。
依照前文所记载测量方法测量实施例1至7及比较例1至3的预浸渍片与金属箔积层板的各项性质，包括吸水性、耐浸焊性、抗撕强度、玻璃转移温度(Tg)、热膨胀率、难燃等级、介电常数(Dk)、散逸因子(Df)、耐碱性及钻针磨耗％，并将结果纪录于表2中。
表2：
如表2所示，使用本发明树脂组合物所制得的电子材料在各项物化性质表现均可达到令人满意的程度，尤其具有优异的吸水性、耐热性及电学性质，且具有优异的加工性(钻针磨耗率)。具体言之，实施例1与比较例1、实施例2与比较例2及实施例7与比较例3的比较均显示，相较于其他DOPO改质的含磷酚醛树脂，本发明使用具有式(I)结构的含磷酚醛树脂可提供更低的吸水率、热膨胀率、Df及钻针磨耗率以及更好的耐热性(Tg高)。
上述实施例仅为例示性说明本发明的原理及其功效，并阐述本发明的技术特征，而并非用于限制本发明的保护范围。本领域技术人员在不违背本发明的技术原理及精神下，可轻易完成的改变或安排，均属于本发明所主张的保护范围。因此，本发明的保护范围应以权利要求书所界定为准。

Claims (13)

1.一种树脂组合物，其特征在于，包含：
(A)无卤环氧树脂；
(B)硬化剂；以及
(C)具有下式(I)结构的含磷酚醛树脂：
于式(I)中，m、n及l各自独立为0至10的整数，但m、n及l不同时为0，以及
R1及R2各自独立为9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、DOPO衍生物或胺基三氮杂苯酚醛(amino triazine novolac，ATN)树脂的残基或-O(CH2)3CH3，且条件为R1及R2中至少一者为DOPO或DOPO衍生物的残基。
2.如权利要求1所述的树脂组合物，其特征在于，于式(I)中，R1及R2各自独立为DOPO的残基、的残基或-O(CH2)3CH3，且条件为R1及R2中至少一者为DOPO的残基。
3.如权利要求1所述的树脂组合物，其特征在于，该硬化剂选自以下群组：二胺基二苯砜(diaminodiphenyl sulfone，DDS)、胺基三氮杂苯酚醛(ATN)树脂、双马来酰亚胺(bismaleimide，BMI)树脂、多官能性马来酰亚胺树脂、苯乙烯马来酸酐(styrene maleicanhydride，SMA)树脂、苯并恶嗪(benzoxazine)树脂及其组合。
4.如权利要求1至3中任一项所述的树脂组合物，其特征在于，该硬化剂(B)对该含磷酚醛树脂(C)的重量比为约0.2：1至约3：1。
5.如权利要求4所述的树脂组合物，其特征在于，该硬化剂(B)对该含磷酚醛树脂(C)的重量比为约0.3：1至约1.5：1。
6.如权利要求1至3中任一项所述的树脂组合物，其特征在于，以100重量份的无卤环氧树脂(A)计，该硬化剂(B)的含量为约5重量份至约60重量份，且该含磷酚醛树脂(C)的含量为约10重量份至约50重量份。
7.如权利要求1至3中任一项所述的树脂组合物，其特征在于，所述树脂组合物还包含选自以下群组的共硬化剂：二氰二胺(Dicy)、氰酸酯(cyanate ester)树脂、酚醛树脂(phenol novolac，PN)、二胺基二苯甲烷(diaminodiphenylmethane)、苯乙烯-乙烯基酚共聚物及其组合。
8.如权利要求1至3中任一项所述的树脂组合物，其特征在于，所述树脂组合物还包含一核壳橡胶(core/shell rubber)。
9.如权利要求1至3中任一项所述的树脂组合物，其特征在于，所述树脂组合物还包含选自以下群组的成分：填料、阻燃剂、催化剂、分散剂、增韧剂及其组合。
10.如权利要求9所述的树脂组合物，其特征在于，该填料选自以下群组：二氧化硅、氧化铝、氧化镁、氢氧化镁、碳酸钙、滑石、黏土、氮化铝、氮化硼、氢氧化铝、碳化铝硅、碳化硅、碳酸钠、二氧化钛、氧化锌、氧化锆、石英、钻石、类钻石、石墨、煅烧高岭土、白岭土、云母、水滑石、聚四氟乙烯(polytetrafluoroethylene，PTFE)粉末、玻璃珠、陶瓷晶须、纳米碳管、纳米级无机粉体及其组合。
11.一种预浸渍片，其特征在于，其通过将一基材含浸或涂布如权利要求1至10中任一项所述的树脂组合物，并干燥该经含浸或涂布的基材而制得。
12.一种金属箔积层板，其特征在于，其通过将如权利要求11所述的预浸渍片与金属箔加以层合而制得，或通过将权利要求1至10中任一项所述的树脂组合物涂布于金属箔并干燥该经涂布的金属箔而制得。
13.一种印刷电路板，其特征在于，其由如权利要求12所述的金属箔积层板所制得。
CN201810014021.7A 2018-01-03 2018-01-08 树脂组合物以及使用该组合物所制得的预浸渍片、金属箔积层板与印刷电路板 Active CN109988288B (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TW107100199A TWI671355B (zh) 2018-01-03 2018-01-03 樹脂組合物，以及使用該組合物所製得之預浸漬片、金屬箔積層板、與印刷電路板
TW107100199 2018-01-03

Publications (2)

Publication Number Publication Date
CN109988288A true CN109988288A (zh) 2019-07-09
CN109988288B CN109988288B (zh) 2022-05-31

Family

ID=67059345

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810014021.7A Active CN109988288B (zh) 2018-01-03 2018-01-08 树脂组合物以及使用该组合物所制得的预浸渍片、金属箔积层板与印刷电路板

Country Status (3)

Country Link
US (1) US11339258B2 (zh)
CN (1) CN109988288B (zh)
TW (1) TWI671355B (zh)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6904441B1 (ja) * 2020-01-30 2021-07-14 横浜ゴム株式会社 プリプレグ用エポキシ樹脂組成物およびプリプレグ
CN113025248B (zh) * 2021-03-17 2021-11-23 东莞市德聚胶接技术有限公司 一种热固环氧胶及其制备方法
WO2023074646A1 (ja) * 2021-10-27 2023-05-04 株式会社レゾナック 樹脂付き金属箔、プリント配線板及びその製造方法、並びに半導体パッケージ
CN113956750B (zh) * 2021-11-12 2022-10-11 中国林业科学研究院林产化学工业研究所 一种苯并噁嗪/环氧树脂复合阻燃防腐涂层及其制备方法
TWI795183B (zh) * 2022-01-21 2023-03-01 聯茂電子股份有限公司 無鹵環氧樹脂組成物

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130161080A1 (en) * 2011-12-22 2013-06-27 Yu-Te Lin Halogen-free resin composition and its application for copper clad laminate and printed circuit board
KR20170080401A (ko) * 2015-12-31 2017-07-10 코오롱인더스트리 주식회사 비할로겐 난연성 중합체, 이의 제조방법 및 이를 함유하는 난연성 중합체 조성물

Family Cites Families (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW490474B (en) * 2000-01-04 2002-06-11 Nat Science Council Phosphorus group containing flame retardant hardener, advanced epoxy resins and cured epoxy resins thereof
WO2005118604A1 (en) 2004-05-28 2005-12-15 Dow Global Technologies Inc. Phosphorus-containing compounds useful for making halogen-free, ignition-resistant polymers
TWI382055B (zh) * 2006-10-03 2013-01-11 Tech Advance Ind Co Ltd 熱固性樹脂組合物
WO2008085286A1 (en) 2006-12-19 2008-07-17 Henkel Corporation (meth)acrylate compositions containing dispersions of core shell rubbers in (meth)acrylates
WO2009045817A1 (en) * 2007-09-28 2009-04-09 Dow Global Technologies Inc. Epoxy resin formulations
US20100261837A1 (en) * 2007-11-29 2010-10-14 Dow Global Technologies Inc. Dimethylformamide-free formulations using dicyanadiamide as curing agent for thermosetting epoxy resins
KR101141305B1 (ko) 2009-03-31 2012-05-04 코오롱인더스트리 주식회사 인-변성 페놀 노볼락 수지, 이를 포함하는 경화제 및 에폭시 수지 조성물
TWI503339B (zh) * 2009-05-19 2015-10-11 Albemarle Corp Ｄｏｐｏ衍生的阻燃劑及環氧樹脂組合物
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
TWI445727B (zh) 2010-10-21 2014-07-21 Taiwan Union Technology Corp 樹脂組合物及由其製成之預浸材與印刷電路板
SG194859A1 (en) 2011-05-25 2013-12-30 Dow Global Technologies Llc Phosphorus-containing compounds useful for making halogen-free, ignition-resistant polymers
TWI475040B (zh) * 2011-11-15 2015-03-01 Taiwan Union Technology Corp 樹脂組合物及其應用
KR101597746B1 (ko) * 2012-03-29 2016-02-25 디아이씨 가부시끼가이샤 경화성 수지 조성물, 그 경화물, 프린트 배선 기판용 수지 조성물, 및 프린트 배선 기판
US20150183976A1 (en) * 2012-09-07 2015-07-02 Dow Global Technologies Llc Toughening masterblends
CN104119639B (zh) * 2013-04-24 2016-08-03 台光电子材料(昆山)有限公司 无卤素树脂组合物及应用其的铜箔基板及印刷电路板
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
US8703986B1 (en) * 2013-07-01 2014-04-22 Ufc Corporation Process for preparing 10-chloro-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound
CN103450265A (zh) * 2013-07-27 2013-12-18 梁劲捷 磷改性酚醛树脂的制备方法
CN103450426A (zh) * 2013-07-27 2013-12-18 广西藤县通轩立信化学有限公司 磷改性酚醛树脂及其制备方法
CN103450421A (zh) * 2013-07-27 2013-12-18 梁劲捷 磷改性酚醛树脂的制备方法
CN103450263A (zh) * 2013-07-27 2013-12-18 梁劲捷 磷改性酚醛树脂的制备方法
CN103450264A (zh) * 2013-07-27 2013-12-18 梁劲捷 磷改性酚醛树脂的制备方法
CN103450422A (zh) * 2013-07-27 2013-12-18 梁劲捷 磷改性酚醛树脂的制备方法
CN103450429A (zh) * 2013-07-27 2013-12-18 广西藤县通轩立信化学有限公司 磷改性酚醛树脂及其制备方法
CN103450427A (zh) * 2013-07-27 2013-12-18 广西藤县通轩立信化学有限公司 磷改性酚醛树脂及其制备方法
US9963590B2 (en) * 2014-06-10 2018-05-08 Shengyi Technology Co., Ltd. Halogen-free resin composition, and a prepreg and a laminate used for printed circuit using the same
CN105331053B (zh) * 2014-07-22 2017-12-05 广东生益科技股份有限公司 一种无卤树脂组合物以及使用它的预浸料和印制电路用层压板
WO2016029453A1 (en) * 2014-08-29 2016-03-03 Blue Cube Ip Llc Halogen-free and flame retardant compositions with low thermal expansion for high density printed wiring boards
KR101915918B1 (ko) 2014-11-11 2018-11-06 셍기 테크놀로지 코. 엘티디. 열경화성 수지 조성물 및 이로 제조한 프리프레그와 적층판
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
CN105801814B (zh) * 2014-12-29 2018-05-04 广东生益科技股份有限公司 一种无卤热固性树脂组合物及使用它的预浸料和印制电路用层压板
TWI731986B (zh) * 2016-06-29 2021-07-01 日商迪愛生股份有限公司 苯酚酚醛清漆樹脂、硬化性樹脂組成物及其硬化物
TWI654243B (zh) * 2018-01-04 2019-03-21 Taiwan Union Technology Corporation 樹脂組合物，以及使用該組合物所製得之預浸漬片、金屬箔積層板、與印刷電路板
TWI647265B (zh) * 2018-02-05 2019-01-11 Taiwan Union Technology Corporation 樹脂組合物，以及使用該組合物所製得之預浸漬片、金屬箔積層板、與印刷電路板
CN110551257B (zh) * 2018-06-04 2021-10-08 台燿科技股份有限公司 树脂组合物及其预浸渍片、金属箔积层板和印刷电路板
TWI700320B (zh) * 2018-06-13 2020-08-01 台燿科技股份有限公司 樹脂組合物，以及使用該組合物所製得之預浸漬片、金屬箔積層板與印刷電路板
TWI686436B (zh) * 2018-08-28 2020-03-01 台燿科技股份有限公司 無鹵素低介電樹脂組合物，以及使用該組合物所製得之預浸漬片、金屬箔積層板與印刷電路板
TWI700332B (zh) * 2018-12-06 2020-08-01 台燿科技股份有限公司 無鹵素低介電樹脂組合物，使用彼所製得之預浸漬片、金屬箔積層板及印刷電路板

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130161080A1 (en) * 2011-12-22 2013-06-27 Yu-Te Lin Halogen-free resin composition and its application for copper clad laminate and printed circuit board
KR20170080401A (ko) * 2015-12-31 2017-07-10 코오롱인더스트리 주식회사 비할로겐 난연성 중합체, 이의 제조방법 및 이를 함유하는 난연성 중합체 조성물

Also Published As

Publication number Publication date
US20190203003A1 (en) 2019-07-04
CN109988288B (zh) 2022-05-31
US11339258B2 (en) 2022-05-24
TW201930448A (zh) 2019-08-01
TWI671355B (zh) 2019-09-11

Similar Documents

Publication Publication Date Title
US10689512B2 (en) Resin composition, and prepreg, metal-clad laminate, and printed circuit board using the same
CN109988288A (zh) 树脂组合物以及使用该组合物所制得的预浸渍片、金属箔积层板与印刷电路板
US10322565B2 (en) Resin composition and uses of the same
TWI745627B (zh) 熱固性樹脂組合物，使用彼所製得之預浸漬片、金屬箔積層板及印刷電路板
US10994516B2 (en) Resin composition, and pre-preg, metal-clad laminate and printed circuit board prepared using the same
TWI620763B (zh) 樹脂組成物、及使用該樹脂組成物所製得之預浸漬片、金屬箔積層板及印刷電路板
TWI654243B (zh) 樹脂組合物，以及使用該組合物所製得之預浸漬片、金屬箔積層板、與印刷電路板
JP2012001486A (ja) ポリアゾメチンを有するビスマレイミド誘導体とその製造方法、並びに熱硬化性樹脂組成物、プリプレグ及び積層板
TWI700320B (zh) 樹脂組合物，以及使用該組合物所製得之預浸漬片、金屬箔積層板與印刷電路板
CN108047718A (zh) 马来酰亚胺树脂组合物、预浸料、层压板和印刷电路板
TWI647265B (zh) 樹脂組合物，以及使用該組合物所製得之預浸漬片、金屬箔積層板、與印刷電路板
US9006377B2 (en) Resin composition and uses of the same
TWI740204B (zh) 樹脂組成物、及使用該樹脂組成物所製得之預浸漬片、金屬箔積層板及印刷電路板
TW201136981A (en) Epoxy resin composition, preprey and printed circuit board manufactured thereof
US11306239B2 (en) High thermal conductivity prepreg and uses of the same
TWI401269B (zh) 環氧樹脂組成物及其製成的預浸材和印刷電路板
US8846790B2 (en) Resin composition, and prepreg and printed circuit board prepared using the same
TWI620785B (zh) 樹脂組成物、及使用該樹脂組成物所製得之預浸漬片、金屬箔積層板及印刷電路板
US9656443B2 (en) Stable solution of ring-opened polymer and the use thereof
CN102295742B (zh) 环氧树脂组合物及其制成的预浸材料和印刷电路板
CN102838729B (zh) 树脂组合物及由其制成的半固化片与积层板
TWI359826B (zh)

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant