WO2015120650A1 - 一种无卤树脂组合物及其用途 - Google Patents

一种无卤树脂组合物及其用途 Download PDF

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Publication number
WO2015120650A1
WO2015120650A1 PCT/CN2014/073834 CN2014073834W WO2015120650A1 WO 2015120650 A1 WO2015120650 A1 WO 2015120650A1 CN 2014073834 W CN2014073834 W CN 2014073834W WO 2015120650 A1 WO2015120650 A1 WO 2015120650A1
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Prior art keywords
parts
weight
halogen
resin
resin composition
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PCT/CN2014/073834
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English (en)
French (fr)
Inventor
杨虎
何岳山
Original Assignee
广东生益科技股份有限公司
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Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to US15/022,154 priority Critical patent/US9840620B2/en
Priority to KR1020167006878A priority patent/KR101798798B1/ko
Priority to EP14882269.5A priority patent/EP3031863B1/en
Publication of WO2015120650A1 publication Critical patent/WO2015120650A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L79/02—Polyamines
    • 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
    • B32B15/20—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
    • B32B27/18—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • 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
    • C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
    • 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
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/02—Polyamines
    • 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
    • C08J2425/00—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 an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
    • C08J2425/10—Copolymers of styrene with conjugated dienes
    • 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
    • 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
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates

Definitions

  • Halogen-free resin composition and use thereof
  • the present invention relates to the field of copper-clad laminate production technology, and relates to a halogen-free resin composition and use thereof, and particularly to a halogen-free resin composition, a resin glue prepared by using the halogen-free resin composition, and a pre-treatment Dip, laminate and copper clad laminate.
  • a conventional copper-clad laminate for printed circuit is mainly made of brominated epoxy resin and realized by bromine.
  • epoxy resin circuit boards generally have a high dielectric constant and dielectric loss tangent (dielectric constant is greater than 4, medium).
  • the loss tangent is about 0.02), the high frequency characteristics are not sufficient, and it cannot meet the requirements of high frequency signal. Therefore, it is necessary to develop a resin excellent in dielectric properties, that is, a resin having a low dielectric constant and a dielectric loss tangent.
  • Thermophilic polybutadiene or copolymer resins of polybutadiene and styrene having good dielectric properties have been studied by those skilled in the art for a long time.
  • W097/38564 uses a non-polar styrene and a tetramer of butadiene and divinylbenzene to add a magnesium aluminosilicate filler, a circuit board made of glass fiber cloth as a reinforcing material, although excellent in dielectric properties,
  • the heat resistance of the substrate is very poor, the glass transition temperature is only about 100 ° C, and the thermal expansion coefficient is large, which is difficult to meet the high temperature (above 240 ° C) requirements of the lead-free process in the PCB manufacturing process.
  • US5571609 uses a low molecular weight 1,2-polybutadiene resin or polyisobutadiene having a molecular weight of less than 5,000 and a copolymer of high molecular weight butadiene and styrene, and adds a large amount of silicon micropowder as a filler to the glass.
  • the circuit board made of the fiber cloth as a reinforcing material has excellent dielectric properties, but the high molecular weight component is used in the patent to improve the tackiness of the prepreg, so that the process performance of the process for producing the prepreg is deteriorated; and because the entire resin
  • the ratio of the rigid structure benzene ring in the resin molecule of the system is small, and the segment after crosslinking is mostly composed of a methylene group having a very low rigidity, so that the produced sheet has poor rigidity and low bending strength.
  • US6569943 uses a liquid-modified polybutadiene resin with a vinyl group at the end of the molecule, a large amount of low molecular weight monomer (dibromostyrene) as a curing agent and diluent, and a circuit made of glass fiber cloth impregnated
  • the substrate has good dielectric properties, but since the resin system is liquid at normal temperature and cannot be made into a non-stick prepreg, it is difficult to use a common prepreg process when the sheet is pressed and formed, and the process operation is difficult.
  • CN101544841B uses a hydrocarbon resin having a molecular weight of 11,000 or less and a vinyl content of 60% or more.
  • allyl modified phenolic resin is used to improve the tackiness of the prepreg, and the peel strength is improved.
  • the heat resistance after curing of the system is low, and the copper clad laminate has delamination failure during PCB processing. The risk is higher.
  • the system based on hydrocarbon resin has low adhesion to metal and low heat resistance of the system, which brings a high probability of failure in the PCB processing process downstream of the copper clad laminate.
  • halogen-free resin composition which has a lower dielectric constant and dielectric properties using prepregs and laminates made of the halogen-free resin composition. Loss tangent, high peel strength, high glass transition temperature, excellent heat resistance and excellent flame retardant effect.
  • a halogen-free resin composition based on parts by weight of an organic solid, comprising:
  • the content of the component (A) allyl-modified benzoxazine resin is, for example, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 54 parts by weight, 56 Parts by weight, 58 parts by weight, 60 parts by weight, 62 parts by weight, 64 parts by weight, 66 parts by weight, 68 parts by weight, 70 parts by weight, 72 parts by weight, 74 parts by weight, 76 parts by weight or 78 parts by weight.
  • the content of the component (B) hydrocarbon resin is, for example, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight or 19 parts by weight.
  • the content of the component (C) allyl-modified polyphenylene ether resin is, for example, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight or 38 parts by weight.
  • the content of the component (D) initiator is, for example, 0.03 parts by weight, 0.05 parts by weight, 0.08 parts by weight, 0.1 parts by weight, 0.4 parts by weight, 0.7 parts by weight, 1 part by weight, 1.3 parts by weight, 1.5 parts by weight, 1.7. Parts by weight, 1.9 parts by weight, 2.1 parts by weight, 2.3 parts by weight, 2.5 parts by weight, 2.7 parts by weight or 2.9 parts by weight.
  • the invention mainly comprises an allyl modified benzoxazine resin, and provides excellent heat resistance and excellent electrical properties for the system, and is combined with an allyl modified polyphenylene ether resin and a hydrocarbon resin having excellent electrical properties. Improve the electrical properties of the curing system.
  • Each component in the resin composition contains a carbon-carbon double bond. Under the action of heat during the curing reaction, the initiator decomposes the active radical, and under the action of the active radical, the double bond of each component is free radical.
  • the mechanism of polymerization produces crosslinked macromolecular polymers. No polar groups such as hydroxyl groups are formed throughout the polymerization process, and the polymerization product retains the excellent dielectric properties and dielectric loss values of the raw materials to the utmost.
  • the adhesive sheet prepared by using the halogen-free high-frequency resin composition of the present invention has a low dielectric constant and dielectric loss tangent, a high peel strength, a high glass transition temperature, and excellent heat resistance. Good flame retardant effect; copper clad laminate made of the adhesive sheet has low dielectric constant and dielectric loss tangent, high peel strength, high glass transition temperature, and excellent Heat resistance, better flame retardant effect.
  • the component (A) allyl modified benzoxazine resin is selected from the group consisting of allyl modified bisphenol A type benzoxazine resin, olefin Modified bisphenol F type benzoxazine resin, allyl modified dicyclopentadiene phenol type benzoxazine resin, allyl modified bisphenol S type benzoxazine resin or diamine type benzo Any one or a mixture of at least two of the oxazine resins.
  • the mixture is, for example, a mixture of allyl modified bisphenol A type benzoxazine resin and allyl modified bisphenol F type benzoxazine resin, allyl modified dicyclopentadiene phenol type benzoxazole Pyridine resin and allyl modified bisphenol Mixture of S-type benzoxazine resin, mixture of diamine benzoxazine resin, allyl modified bisphenol A benzoxazine resin and allyl modified bisphenol F benzoxazine resin , a mixture of allyl modified dicyclopentadiene phenol type benzoxazine resin, allyl modified bisphenol S type benzoxazine resin and diamine type benzoxazine resin.
  • the hydrocarbon resin is a hydrocarbon resin having a number average molecular weight of 11,000 or less and a vinyl content of more than 60%, which is a liquid at room temperature.
  • the allyl-modified polyphenylene ether resin is an allyl-modified polyphenylene ether resin having a number average molecular weight of 5,000 or less, which ensures free radicals with other resins.
  • the polymerization reaction finally produces a uniform modified resin system, which reduces the probability of phase separation in the system and avoids a negative impact on the electrical properties of the system.
  • the initiator is a material capable of decomposing free radicals under the action of heat, and is selected from the group consisting of organic peroxides, preferably dicumyl peroxide, benzoyl peroxide. Any one or a mixture of at least two of tert-butyl formate or 2,5-di(2-ethylhexanoylperoxy)-2,5-dimethylhexanide.
  • the mixture is, for example, a mixture of dicumyl peroxide and t-butyl peroxybenzoate, 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexanide and peroxidized two a mixture of cumene, a mixture of tert-butyl peroxybenzoate and 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexanide, dicumyl peroxide, A mixture of t-butyl benzoate and 2,5-di(2-ethylhexanoylperoxy)-2,5-dimethylhexanide.
  • the resin-free composition further comprises (E) a filler.
  • the filler is contained in an amount of 1 to 100 parts by weight, for example, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 weights, based on the technical solution provided by the present invention.
  • the filler is selected from any one of silicon dioxide, titanium dioxide, barium titanate, barium titanate, boron nitride, aluminum nitride, silicon carbide or aluminum oxide.
  • a mixture of at least two, preferably crystalline silica, amorphous silica, spherical silica, titania, barium titanate, barium titanate, boron nitride, aluminum nitride, silicon carbide or alumina Any one or a mixture of at least two, such as a mixture of crystalline silica and amorphous silica, a mixture of spherical silica and titanium dioxide, a mixture of barium titanate and barium titanate, nitriding a mixture of boron and nitrogen, a mixture of silicon carbide and aluminum oxide, a mixture of crystalline silica, amorphous silica and spherical silica, a mixture of titanium dioxide, barium titanate and barium titanate, boron nitride, A mixture of aluminum nitride, silicon carbide and aluminum oxide.
  • the filler is silica.
  • the filler has a median diameter of 1 to 15 ⁇ m, such as 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m , 13 ⁇ or 14 ⁇ , preferably 1 to 10 ⁇ , further preferably 1 to 5 ⁇ .
  • the filler located in this particle size section has good dispersibility in the resin glue.
  • the resin-free composition further comprises (F) a phosphorus-containing flame retardant.
  • the content of the phosphorus-containing flame retardant is 0 to 80 parts by weight, excluding 0, for example, 0.05 parts by weight, 1 part by weight, 3 parts by weight, and 5 parts by weight. 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight Parts by weight, 72 Parts by weight, 74 parts by weight, 76 parts by weight or 78 parts by weight.
  • the phosphorus-containing flame retardant is tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9 , 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl-9,10- Any one or a mixture of at least two of dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or polyphenoxyphosphazene and a derivative thereof.
  • the halogen content of the halogen-free resin composition is 0.09% by weight or less, for example, 0.01% by weight, 0.02% by weight, 0.03% by weight, 0.04% by weight, and 0.05% by weight. 0.06 wt%, 0.07 wt% or 0.08 wt%.
  • An exemplary halogen-free resin composition based on parts by weight of the organic solids, comprising:
  • the halogen-free resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These various additives may be used singly or in combination of two or more kinds.
  • Another object of the present invention is to provide a resin glue obtained by dissolving or dispersing a halogen-free resin composition as described above in a solvent.
  • the solvent in the present invention is not particularly limited, and specific examples thereof include acetone, methyl ethyl ketone, cyclohexanone, ethylene glycol methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, benzene, toluene, and xylene. At least any one or a mixture of at least two may be used in an amount as needed, and is not particularly limited, so that the obtained resin glue can be brought to a viscosity suitable for use.
  • An exemplary method for preparing a halogen-free resin composition is as follows: First, the solid matter in the above components is placed in a suitable container, then the solvent is added, stirred until completely dissolved, then the appropriate filler is added, and finally the liquid is added. Resin and initiator, continue to stir evenly. When used, the solvent can be appropriately adjusted by adjusting the solid content of the solution by 65 to 75%.
  • a third object of the present invention is to provide a prepreg comprising a reinforcing material and a halogen-free resin composition as described above adhered to the reinforcing material by impregnation and drying.
  • the prepreg has a lower dielectric constant and dielectric loss tangent, a higher peel strength, a higher glass transition temperature, an excellent heat resistance, and a better flame retardant effect.
  • the reinforcing material is a reinforcing material disclosed in the prior art, such as a non-woven fabric or a woven fabric, exemplified by, for example, natural fibers, organic synthetic fibers, and inorganic fibers, preferably electronic grade glass fiber cloth.
  • the prepreg for printed circuit is prepared by impregnating the above-mentioned resin glue with a fabric such as a reinforced fiberglass cloth or an organic fabric, and baking the impregnated reinforcing material in an oven at 170 ° C for 5 to 8 minutes.
  • a fourth object of the present invention is to provide a laminate comprising at least one prepreg as described above.
  • a fifth object of the present invention is to provide a copper clad laminate comprising at least one laminated prepreg as described above and a side of a prepreg which is laminated on the laminated prepreg Or copper foil on both sides.
  • the copper clad laminate has a lower dielectric constant and a dielectric loss tangent, a higher peel strength, a higher glass transition temperature, an excellent heat resistance, and a better flame retardant effect.
  • An exemplary copper clad laminate is prepared by: using the above prepreg 4 pieces and two pieces of one ounce
  • the copper foil of the company (35 ⁇ thick) is laminated and laminated by a hot press to be pressed into a double-sided copper-clad laminate; the copper-clad laminate is required to meet the following requirements: 1.
  • Laminating temperature rise The rate is usually controlled at 1.0 ⁇ 3.0°C/min when the material temperature is 80 ⁇ 220 °C. 2.
  • the pressure setting of the lamination, the full temperature of the outer layer is 80 ⁇ 100 degrees Celsius, and the full pressure is 300psi. 3, when curing, the temperature of the control material is 220 ° C, and is kept for 120 minutes;
  • the metal foil covered may be nickel foil, aluminum foil and SUS foil, etc., and the material thereof is not limited.
  • the present invention has the following beneficial effects:
  • the invention mainly comprises an allyl modified benzoxazine resin, and provides excellent heat resistance and excellent electrical properties for the system, and is combined with an allyl modified polyphenylene ether resin and a hydrocarbon resin having excellent electrical properties. Improve the electrical properties of the curing system.
  • Each component in the resin composition contains a carbon-carbon double bond. Under the action of heat during the curing reaction, the initiator decomposes the active radical, and under the action of the active radical, the double bond of each component is free radical.
  • the mechanism of polymerization produces crosslinked macromolecular polymers. No polar groups such as hydroxyl groups are formed throughout the polymerization process, and the polymerization product retains the excellent dielectric properties and dielectric loss values of the raw materials to the utmost.
  • the adhesive sheet prepared by using the halogen-free high-frequency resin composition of the present invention has a low dielectric constant and dielectric loss tangent, a high peel strength, a high glass transition temperature, and excellent heat resistance. Good flame retardant effect; copper clad laminate made of the adhesive sheet has low dielectric constant and dielectric loss tangent, high peel strength, high glass transition temperature, and excellent Heat resistance, better flame retardant effect.
  • the formulation of the composition of the examples is shown in Table 1.
  • the copper-clad laminates for printed circuit boards produced by the above method have physical properties such as dielectric constant, dielectric loss factor and flame retardancy as shown in Tables 2 and 3.
  • ** is a polyphenylene ether resin which is generally free of allyl groups.
  • Comparative Examples 3 and 4 used a common dicyclopentadiene type benzoxazine without a double bond and a polyphenylene ether resin containing no allyl double bond, respectively, and the three subject resins could not be radically polymerized during the curing reaction.
  • Motivate The reaction is carried out, and the resulting polymer system will have a phase separation structure which adversely affects the electrical properties of the system.
  • each resin component in the system can form a uniform curing component by radical polymerization under the action of a promoter. There is a significant decrease in dielectric loss and dielectric constant.
  • the halogen-free high-frequency resin composition of the present invention has a good synergistic property with a special benzoxazine resin, a polyphenylene ether resin, a hydrocarbon resin, a curing agent, and other components.
  • the halogen content is below 0.09%, thus achieving environmental standards.
  • the bonding sheet made of the halogen-free high-frequency resin composition has excellent electrical properties, high glass transition temperature, excellent heat resistance, good flame retardancy, and low water absorption.
  • Glass transition temperature Measured according to differential scanning calorimetry (DSC) according to the DSC method specified in IPC-TM-650 2.4.25.
  • Peel Strength (PS) The peel strength of the metal cap was tested according to the "after thermal stress” experimental conditions in the IPC-TM-650 2.4.8 method.
  • Flammability Measured according to UL 94 vertical combustion method.
  • Thermal stratification time T-288 Measured according to IPC-TM-650 2.4.24.1.
  • TMA Coefficient of thermal expansion 2 axis 01 £
  • Dielectric loss tangent, dielectric constant According to the resonance method using a strip line, the dielectric loss tangent at 10 GHz was measured in accordance with IPC-TM-650 2.5.5.9. (10) Halogen content test: Measured according to IPC-TM-650 2.3.41 method.

Abstract

本发明公开了一种无卤树脂组合物及用其制成的预浸料与层压板，以有机固形物重量份计，其包含：（A）烯丙基改性苯并噁嗪树脂，40~80重量份；（B）碳氢树脂，10~20重量份；（C）烯丙基改性聚苯醚树脂，10~40重量份；（D）引发剂，0.01~3重量份；（E）填料，10~100重量份；及（F）含磷阻燃剂，0~80重量份。用所述无卤树脂组合物制成的预浸料和层压板，其具有较低的介电常数和介电损耗正切值，较高的剥离强度，较高的玻璃化转变温度、优良的耐热性、较好的阻燃效果。

Description

一种无卤树脂组合物及其用途
技术领域 本发明属于覆铜箔层压板制备技术领域， 涉及一种无卤树脂组合物及其用 途， 具体涉及一种无卤树脂组合物、 使用该无卤树脂组合物制备的树脂胶液、 预浸料、 层压板以及覆铜箔层压板。 背景技术 说 传统的印制电路用覆铜箔层压板， 主要采用溴化环氧树脂， 通过溴来实现 书
板材的阻燃功能。 但近年来， 在含溴、 氯等卤素的电子电气设备废弃物的燃烧 产物中检验出二噁英、 二苯并呋喃等致癌物质， 并且含卤产品在燃烧过程中有 可能释放出剧毒物质卤化氢。 此外， 2006年 7月 1日， 欧盟的两份环保指令《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某些有害物质 指令》 正式实施。 由于含卤素产品燃烧产物的不环保性和欧盟的两份环保指令 的实施， 使得无卤阻燃覆铜箔层压板的开发成为业界的热点， 各覆铜箔层压板 厂家都纷纷推出自己的无卤阻燃覆铜箔层压板。 近年来， 随着计算机和信息通讯设备高性能化、 高功能化以及网络化的发 展， 为了高速传输及处理大容量信息， 操作信号趋向于高频化， 因而对电路基 板的材料提出了要求。 现有的用于印制电路基板的材料中， 广泛使用粘接特性 优异的环氧树脂， 然而， 环氧树脂电路基板一般介电常数和介质损耗角正切较 高 （介电常数大于 4， 介质损耗角正切 0.02左右） ， 高频特性不充分， 不能适 应信号高频化的要求。 因此必须研制介电特性优异的 树脂， 即介电常数和介 质损耗角正切低的树脂。 长期以来本领域的技术人员对介电性能很好的热固性 的聚丁二烯或聚丁二烯与苯乙烯的共聚物树脂进行了研究。 W097/38564 采用非极性的苯乙烯与丁二烯和二乙烯基苯的四聚物添加硅 铝酸镁填料， 以玻璃纤维布作为增强材料制成的电路基板， 虽然介电性能优 异， 但是基板的耐热性很差， 玻璃化转变温度只有 100°C左右， 热膨胀系数很 大， 很难满足 PCB制作过程无铅化制程的高温 （240°C以上） 要求。
US5571609采用分子量小于 5000的低分子量的 1,2-聚丁二烯树脂或聚异丁 二烯和高分子量的丁二烯与苯乙烯的共聚物配合， 并加入大量的硅微粉作为填 料， 以玻璃纤维布作为增强材料制作的电路基板， 虽然介电性能优异， 但是因 为在该专利中采用了高分子量的成分来改善半固化片粘手状况， 使得制作半固 化片的过程的工艺性能变差； 而且因为整个树脂体系的树脂分子中的刚性结构 苯环的比例很少， 而且交联以后的链段大都由刚性很低的亚甲基组成， 因此制 作成的板材刚性不好， 弯曲强度很低。
US6569943 使用分子末端带有乙烯基的胺基改性的液体聚丁二烯树脂， 添 加大量的低分子量的单体 （二溴苯乙烯） 作为固化剂和稀释剂， 浸渍玻璃纤维 布制作成的电路基板， 虽然介电性能很好， 但是因为树脂体系在常温下是液 体， 不能制作成不粘手的半固化片， 因此在板材的压制成型时， 很难采用通用 的半固化片叠卜工艺， 工艺操作比较困难。
CN1280337C 使用分子末端带有不饱和双键的聚苯醚树脂， 采用低分子量 的低分子量的乙烯基单体 （如二溴苯乙烯） 作为固化剂， 但由于这些低分子量 的单体沸点低， 在浸渍玻璃纤维布制作半固化片的烘干过程中会挥发掉， 难于 保证充分的固化剂用量。 另外该专利虽然提及可以采用聚丁二烯类树脂去改性 体系的粘度， 但是未明确提出采用带有极性基团的聚丁二烯类树脂以及采用带 有极性基团的聚丁二烯类树脂去改善剥离强度。
CN101544841B使用分子量 11000以下乙烯基含量 60%以上的碳氢树脂作 为主体， 采用烯丙基改性的酚醛树脂改进半固化片发粘的特性， 剥离强度有一 定提升， 但是体系固化后的耐热性低， 覆铜箔层压板在 PCB加工过程中出现分 层失效的风险较高。
以碳氢树脂为主体的体系， 其与金属的粘合力以及体系的耐热性较低， 对 于覆铜板下游的 PCB加工过程中带来较大几率的失效风险。
发明内容
针对已有技术中的问题， 本发明的目的之一在于提供一种无卤树脂组合 物， 使用该无卤树脂组合物制成的预浸料和层压板具有较低的介电常数和介电 损耗正切值， 较高的剥离强度， 较高的玻璃化转变温度、 优良的耐热性以及优 异的阻燃效果。
为了达到上述目的， 本发明采用了如下技术方案：
一种无卤树脂组合物， 以有机固形物重量份计， 其包含：
(A) 烯丙基改性苯并噁嗪树脂， 40~80重量份；
(B ) 碳氢树脂， 10~20重量份;
(C) 烯丙基改性聚苯醚树脂， 10~40重量份；
(D) 引发剂， 0.01~3重量份。
所述组分（A)烯丙基改性苯并噁嗪树脂的含量例如为 42重量份、 44重量 份、 46重量份、 48重量份、 50重量份、 52重量份、 54重量份、 56重量份、 58 重量份、 60重量份、 62重量份、 64重量份、 66重量份、 68重量份、 70重量 份、 72重量份、 74重量份、 76重量份或 78重量份。
所述组分（B)碳氢树脂的含量例如为 11重量份、 12重量份、 13重量份、 14重量份、 15重量份、 16重量份、 17重量份、 18重量份或 19重量份。
所述组分 (C)烯丙基改性聚苯醚树脂的含量例如为 12重量份、 14重量份、 16重量份、 18重量份、 20重量份、 22重量份、 26重量份、 28重量份、 30重 量份、 32重量份、 34重量份、 36重量份或 38重量份。
所述组分 （D) 引发剂的含量例如为 0.03重量份、 0.05重量份、 0.08重量 份、 0.1重量份、 0.4重量份、 0.7重量份、 1重量份、 1.3重量份、 1.5重量份、 1.7重量份、 1.9重量份、 2.1重量份、 2.3重量份、 2.5重量份、 2.7重量份或 2.9 重量份。
本发明以烯丙基改性苯并噁嗪树脂为主体， 为体系提供优异的耐热性以及 优良的电性能， 配合电性能优异的烯丙基改性聚苯醚树脂和碳氢树脂， 进一歩 改善固化体系的电性能。 该树脂组合物中各组分均包含碳碳双键， 固化反应过 程中在热的作用下， 引发剂分解出活性自由基， 在活性自由基的作用下各组分 树脂的双键按照自由基聚合的机理生成交联的大分子聚合物。 在整个聚合过程 中无羟基等极性基团生成， 聚合产物最大限度的保留了原材料优异的介电性能 和介电损耗值。 使用本发明无卤高频树脂组合物制成的粘结片具有较低的介电 常数和介电损耗正切值， 较高的剥离强度， 较高的玻璃化转变温度、 优良的耐 热性、 较好的阻燃效果； 使用该粘结片制成的覆铜箔层压板其具有较低的介电 常数和介电损耗正切值， 较高的剥离强度， 较高的玻璃化转变温度、 优良的耐 热性、 较好的阻燃效果。
优选地， 在本发明提供的技术方案的基础上， 所述组分 （A) 烯丙基改性 苯并噁嗪树脂选自烯丙基改性双酚 A型苯并噁嗪树脂、 烯丙基改性双酚 F型苯 并噁嗪树脂、 烯丙基改性双环戊二烯酚型苯并噁嗪树脂、 烯丙基改性双酚 S型 苯并噁嗪树脂或二胺型苯并噁嗪树脂中的任意一种或者至少两种的混合物。 所 述混合物例如烯丙基改性双酚 A型苯并噁嗪树脂和烯丙基改性双酚 F型苯并噁 嗪树脂的混合物， 烯丙基改性双环戊二烯酚型苯并噁嗪树脂和烯丙基改性双酚 S型苯并噁嗪树脂的混合物， 二胺型苯并噁嗪树脂、 烯丙基改性双酚 A型苯并 噁嗪树脂和烯丙基改性双酚 F型苯并噁嗪树脂的混合物， 烯丙基改性双环戊二 烯酚型苯并噁嗪树脂、 烯丙基改性双酚 S型苯并噁嗪树脂和二胺型苯并噁嗪树 脂的混合物。
优选地， 在本发明提供的技术方案的基础上， 所述碳氢树脂为数均分子量 在 11000以下由碳氢两种元素组成的乙烯基含量大于 60%， 在室温下为液体的 碳氢树脂， 优选数均分子量小于 7000且 1,2位加成的乙烯基含量大于 70%， 在 室温下为液体的碳氢树脂。
优选地， 在本发明提供的技术方案的基础上， 所述烯丙基改性聚苯醚树脂 为数均分子量在 5000 以下的烯丙基改性聚苯醚树脂， 保证其与其他树脂发生 自由基聚合反应， 最终生成均一的的改性树脂体系， 降低体系出现相分离的几 率， 避免对体系的电性能产生负面影响。
优选地， 在本发明提供的技术方案的基础上， 所述引发剂为在热的作用下 能分解出自由基的材料， 选自有机过氧化物， 优选过氧化二异丙苯、 过氧化苯 甲酸叔丁酯或 2,5-二 (2-乙基己酰过氧 )-2,5-二甲基己垸中任意一种或者至少两种 的混合物。 所述混合物例如过氧化二异丙苯和过氧化苯甲酸叔丁酯的混合物， 2,5-二 (2-乙基己酰过氧 )-2,5-二甲基己垸和过氧化二异丙苯的混合物， 过氧化苯 甲酸叔丁酯和 2,5-二 (2-乙基己酰过氧 )-2,5-二甲基己垸的混合物， 过氧化二异丙 苯、 过氧化苯甲酸叔丁酯和 2,5-二 (2-乙基己酰过氧 )-2,5-二甲基己垸的混合物。
优选地， 在本发明提供的技术方案的基础上， 所述无 ¾树脂组合物还包括 (E) 填料。
优选地， 在本发明提供的技术方案的基础上， 所述填料的含量为 1~100重 量份， 例如为 5重量份、 10重量份、 15重量份、 20重量份、 25重量份、 30重 量份、 35重量份、 40重量份、 45重量份、 50重量份、 55重量份、 60重量份、 65重量份、 70重量份、 75重量份、 80重量份、 85重量份、 90重量份或 95重 量份， 优选 10~100重量份。
优选地， 在本发明提供的技术方案的基础上， 所述填料选自二氧化硅、 二 氧化钛、 钛酸锶、 钛酸钡、 氮化硼、 氮化铝、 碳化硅或氧化铝中的任意一种或 者至少两种的混合物， 优选结晶型二氧化硅、 无定形二氧化硅、 球形二氧化 硅、 二氧化钛、 钛酸锶、 钛酸钡、 氮化硼、 氮化铝、 碳化硅或氧化铝中的任意 一种或者至少两种的混合物， 所述混合物例如结晶型二氧化硅和无定形二氧化 硅的混合物， 球形二氧化硅和二氧化钛的混合物， 钛酸锶和钛酸钡的混合物， 氮化硼和氮化的混合物， 碳化硅和氧化铝的混合物， 结晶型二氧化硅、 无定形 二氧化硅和球形二氧化硅的混合物， 二氧化钛、 钛酸锶和钛酸钡的混合物， 氮 化硼、 氮化铝、 碳化硅和氧化铝的混合物。
优选地， 在本发明提供的技术方案的基础上， 所述填料为二氧化硅。
优选地， 在本发明提供的技术方案的基础上， 所述填料的粒径中度值为 1~15μπι , 例如 2μπι、 3μπι、 4μπι、 5μπι、 6μπι、 7μπι、 8μπι、 9μπι、 10μπι、 11μπι、 12μπι、 13μπι或 14μπι， 优选 1~10μπι， 进一歩优选 1~5μπι。 位于该粒径 段的填料在树脂胶液中具有良好的分散性。
优选地， 在本发明提供的技术方案的基础上， 所述无 ¾树脂组合物还包括 (F) 含磷阻燃剂。
优选地， 在本发明提供的技术方案的基础上， 所述含磷阻燃剂的含量为 0~80重量份， 不包括 0， 例如 0.05重量份、 1重量份、 3重量份、 5重量份、 10 重量份、 15重量份、 20重量份、 25重量份、 30重量份、 35重量份、 40重量 份、 45重量份、 50重量份、 55重量份、 60重量份、 65重量份、 70重量份、 72 重量份、 74重量份、 76重量份或 78重量份。
优选地， 在本发明提供的技术方案的基础上， 所述含磷阻燃剂为三 (2,6-二 甲基苯基)膦、 10-(2,5-二羟基苯基) -9,10-二氢 -9-氧杂 -10-膦菲 -10-氧化物、 2,6- 二 (2,6-二甲基苯基)膦基苯、 10-苯基 -9,10-二氢 -9-氧杂 -10-膦菲 -10-氧化物或聚 苯氧基磷腈及其衍生物中的任意一种或者至少两种的混合物。
优选地， 在本发明提供的技术方案的基础上， 所述无卤树脂组合物的卤素 含量在 0.09重量％以下， 例如 0.01重量％、 0.02重量％、 0.03重量％、 0.04重 量％、 0.05重量％、 0.06重量％、 0.07重量％或 0.08重量％。
示例性的一种无卤树脂组合物， 以有机固形物重量份计， 其包含：
(A) 烯丙基改性苯并噁嗪树脂， 40~80重量份；
(B ) 碳氢树脂， 10~20重量份;
(C) 烯丙基改性聚苯醚树脂， 10~40重量份；
(D) 引发剂， 0.01~3重量份；
(E) 填料， 1~100重量份；
(F) 含磷阻燃剂， 0~80重量份。
本发明所述的 "包括"， 意指其除所述组份外， 还可以包括其他组份， 这些 其他组份赋予所述无卤树脂组合物不同的特性。 除此之外， 本发明所述的 "包 括"， 还可以替换为封闭式的 "为"或 "由……组成"。
例如， 所述无卤树脂组合物还可以含有各种添加剂， 作为具体例， 可以举 出抗氧剂、 热稳定剂、 抗静电剂、 紫外线吸收剂、 颜料、 着色剂或润滑剂等。 这些各种添加剂可以单独使用， 也可以两种或者两种以上混合使用。
本发明的目的之二在于提供一种树脂胶液， 其是将如上所述的无卤树脂组 合物溶解或分散在溶剂中得到。 作为本发明中的溶剂， 没有特别限定， 作为具体例， 可以举出丙酮、 丁酮、 环己酮、 乙二醇甲醚、 丙二醇甲醚、 丙二醇甲醚醋酸酯、 苯、 甲苯以及二甲苯 中的至少任意一种或者至少两种的混合物， 其用量可根据需要而定， 不作具体 限定， 使得到的树脂胶液达到适于使用的粘度即可。
示例性的无卤树脂组合物胶液常规的制备方法为： 首先将上述组分中的固 形物放入适当的容器中， 然后加溶剂， 搅拌直至完全溶解后， 再加入适当填料， 最后加入液体树脂和引发剂， 继续搅拌均匀即可。 使用时可用溶剂适当调整溶 液的固体含量 65~75%而制成胶液。
本发明的目的之三在于提供一种预浸料， 其包括增强材料及通过含浸干燥 后附着在增强材料上的如上所述的无卤树脂组合物。 所述预浸料其具有较低的 介电常数和介电损耗正切值， 较高的剥离强度， 较高的玻璃化转变温度、 优良 的耐热性、 较好的阻燃效果。
所述增强材料为已有技术中公开的增强材料， 如无纺织物或编织织物， 示 例性的例如天然纤维、有机合成纤维以及无机纤维， 优选为电子级玻璃纤维布。
使用增强材料玻璃纤维布等织物或有机织物含浸上述树脂胶液， 将含浸好 的增强材料在 170°C的烘箱中烘 5~8分钟制成印制电路用预浸料。
本发明的目的之四在于提供一种层压板， 所述层压板含有至少一张如上所 述的预浸料。
本发明的目的之五在于提供一种覆铜箔层压板， 所述覆铜箔层压板包括至 少一张叠合的如上所述的预浸料及压覆在叠合后的预浸料的一侧或两侧的铜 箔。 所述覆铜箔层压板， 其具有较低的介电常数和介电损耗正切值， 较高的剥 离强度， 较高的玻璃化转变温度、 优良的耐热性、 较好的阻燃效果。
示例性的覆铜箔层压板的制备方法为： 使用上述的预浸料 4片和两片一盎 司 （35μπι厚） 的铜箔叠合在一起， 通过热压机中层压， 从而压制成双面覆铜箔 层压板； 所述的覆铜箔层压需满足以下要求： 1、 层压的升温速率， 通常在料温 80~220 °C时， 控制在 1.0~3.0°C/分钟; 2、 层压的压力设置， 外层料温在 80~100 摄氏度时施加满压， 满压压力为 300psi左右； 3、 固化时， 控制料温在 220°C， 并保温 120分钟；所覆盖的金属箔除铜箔外，还可以是镍箔、铝箔及 SUS箔等， 其材质不限。
与已有技术相比， 本发明具有如下有益效果：
本发明以烯丙基改性苯并噁嗪树脂为主体， 为体系提供优异的耐热性以及 优良的电性能， 配合电性能优异的烯丙基改性聚苯醚树脂和碳氢树脂， 进一歩 改善固化体系的电性能。 该树脂组合物中各组分均包含碳碳双键， 固化反应过 程中在热的作用下， 引发剂分解出活性自由基， 在活性自由基的作用下各组分 树脂的双键按照自由基聚合的机理生成交联的大分子聚合物。 在整个聚合过程 中无羟基等极性基团生成， 聚合产物最大限度的保留了原材料优异的介电性能 和介电损耗值。 使用本发明无卤高频树脂组合物制成的粘结片具有较低的介电 常数和介电损耗正切值， 较高的剥离强度， 较高的玻璃化转变温度、 优良的耐 热性、 较好的阻燃效果； 使用该粘结片制成的覆铜箔层压板其具有较低的介电 常数和介电损耗正切值， 较高的剥离强度， 较高的玻璃化转变温度、 优良的耐 热性、 较好的阻燃效果。
具体实施方式
下面通过具体实施方式来进一歩说明本发明的技术方案。
所述实施例组合物配方见表 1。 采用上述方法制成的印刷电路板用的覆铜 箔层压板， 其介电常数、 介电损耗因数和阻燃性等物性数据见表 2和表 3。
所述无卤高频树脂组合物的具体组分如下： (A) 烯丙基改性苯并噁嗪树脂
A-1烯丙基改性双酚 A型苯并噁嗪树脂
A-2烯丙基改性双环戊二烯酚型苯并噁嗪树脂
A-3烯丙基改性双酚 F型苯并噁嗪树脂
(B) 碳氢树脂
B-1丁苯树脂 （商品型号 Ricon l04H， Sartomer)
B-2丁苯树脂 （商品型号 Ricon l53H， Sartomer)
(C) 烯丙基改性聚苯醚树脂 （商品型号 PP501 , 台湾晋一）
(D) 引发剂： 过氧化二异丙苯 （上海高桥）
(E) 填料： 球形硅微粉 （商品名 SFP-30M, 电气化学工业株式会社）
(F)阻燃剂： 聚苯氧基磷腈化合物， SPB-100 (日本大塚化学株式会 ί ） 。
表 1.各实施例和比较例的配方组成
Figure imgf000011_0001
注： 1、 表中皆以固体组分重量份计。 2、 *为普通不含烯丙基的双环戊二烯苯并噁嗪树脂。
3、 **为普通不含烯丙基的聚苯醚树脂。
表 2.各实施例的物性数据
Figure imgf000012_0001
表 3 130 170 140 110 玻璃化转变温度
175
Tg (DSC, V )
0.5 1.2 0.9 0.6 剥离强度
1.3
PS (N/mm)
燃烧性 （UL94) V-0 V-1 V-0 V-0 V-1 热分层时间 T-288 (分钟） >60 >5 >60 >45 >5 热膨胀系数 2.6 2.0 2.2 3.0
Ζ轴 CTE ( ΤΜΑ) 2.2
( 30-260 °C ) %
热分解温度 Td ( TGA， °C ) 395 370 410 380 380 吸水性 （％) 0.08 0.07 0.10 0.10 0.07 介质损耗角正切 Df(lGHZ) 0.0042 0.0021 0.0065 0.0052 0.0025 介电常数 Dk 3.47 3.90 3.7 3.4
3.90
(1GHZ)
C1 0.05 0.004 0.005 0.005 0.005 卤素含量测试 (％)
Br 0 0 0 0 0
从表 2的物性数据可知实施例 1-5制成的覆铜箔层压板具有优异的介电性 能、 较高的玻璃化转变温度。 体系在保持典性能的基础上剥离强度和 T288 有 明显的提升。 在 JPCA无卤标准要求范围内能达到难燃性试验 UL94 中的 V-0 标准， 热膨胀系数低， 热分解稳定高， 吸水性低， 且卤素含量在 0.09%以下， 达到环保的要求。
与对实施例 4对比， 比较例 1体系中少碳氢树脂组分， 其介电损耗和介电 常数较高； 比较例 2 中由于少了烯丙基改性苯并噁嗪组分， 体系的粘合性、 Tg、 耐热性以及阻燃性均明显上升。
比较例 3和 4分别使用了不含双键的普通双环戊二烯型苯并噁嗪和不含烯 丙基双键的聚苯醚树脂， 在固化反应时三种主题树脂无法按照自由基聚合激励 进行反应， 最终得到的聚合物体系将出现相分离结构对体系的电性能造成负面 影响。 与实施例 2 比较， 由于烯丙基改性双环戊二烯型苯并噁嗪树脂的加入， 体系中各树脂组分在促进剂的作用下能通过自由基聚合形成均一的固化组分， 其介电损耗和介电常数有明显的降低。
比较例 5中由于碳氢树脂的量较大， 给固化反应后体系的 Tg、 耐热性、 粘 合性以及阻燃性带来了非常大的负面影响。
综上所述， 本发明所述的无卤高频树脂组合物用特种苯并噁嗪树脂、 聚苯 醚树脂、 碳氢树脂、 固化剂、 及其他组分使之具有良好的协同特性， 在使用磷 元素阻燃外， 卤素含量在 0.09%以下， 从而达到环保标准。 且使用该无卤高频 树脂组合物制成的粘结片具有优异的电性能、 较高的玻璃化转变温度、 优良的 耐热性、 较好的阻燃效果及较低的吸水性。
以上特性的测试方法如下：
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。
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。
燃烧性： 依据 UL 94垂直燃烧法测定。
热分层时间 T-288: 按照 IPC-TM-650 2.4.24.1方法进行测定。
热膨胀系数 2轴01£ (TMA) ： 按照 IPC-TM-650 2.4.24.方法进行测定。 热分解温度 Td: 按照 IPC-TM-650 2.4.26方法进行测定。
吸水性： 按照 IPC-TM-650 2.6.2.1方法进行测定。
介质损耗角正切、 介电常数： 根据使用条状线的共振法， 按照 IPC-TM-650 2.5.5.9测定 10GHz下的介质损耗角正切。 ( 10) 卤素含量测试： 按照 IPC-TM-650 2.3.41方法进行测定。 申请人声明， 本发明通过上述实施例来说明本发明的详细方法， 但本发明 并不局限于上述详细方法， 即不意味着本发明必须依赖上述详细方法才能实 施。 所属技术领域的技术人员应该明了， 对本发明的任何改进， 对本发明产品 各原料的等效替换及辅助成分的添加、 具体方式的选择等， 均落在本发明的保 护范围和公开范围之内。

Claims

权 利 要 求 书
1、 一种无卤树脂组合物， 其特征在于， 以有机固形物重量份计， 其包 含：
(A) 烯丙基改性苯并噁嗪树脂， 40~80重量份；
(B) 碳氢树脂， 10~20重量份;
(C) 烯丙基改性聚苯醚树脂， 10~40重量份；
(D) 引发剂， 0.01~3重量份。
2、 如权利要求 1 所述的无卤树脂组合物， 其特征在于， 所述烯丙基改性 苯并噁嗪树脂选自烯丙基改性双酚 A型苯并噁嗪树脂、 烯丙基改性双酚 F型苯 并噁嗪树脂、 烯丙基改性双环戊二烯酚型苯并噁嗪树脂、 烯丙基改性双酚 S型 苯并噁嗪树脂或二胺型苯并噁嗪树脂中的任意一种或者至少两种的混合物； 优选地， 所述碳氢树脂为数均分子量在 11000 以下由碳氢两种元素组成的 乙烯基含量大于 60%， 在室温下为液体的碳氢树脂， 优选数均分子量小于 7000 且 1,2位加成的乙烯基含量大于 70%， 在室温下为液体的碳氢树脂。
3、 如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 所述烯丙基改 性聚苯醚树脂为数均分子量在 5000以下的烯丙基改性聚苯醚树脂；
优选地， 所述引发剂选自有机过氧化物， 优选过氧化二异丙苯、 过氧化苯 甲酸叔丁酯或 2,5-二 (2-乙基己酰过氧 )-2,5-二甲基己垸中任意一种或者至少两种 的混合物。
4、 如权利要求 1-3之一所述的无卤树脂组合物， 其特征在于， 所述无卤树 脂组合物还包括 （E) 填料；
优选地， 所述填料的含量为 1~100重量份， 优选 10~100重量份； 优选地， 所述填料选自二氧化硅、 二氧化钛、 钛酸锶、 钛酸钡、 氮化硼、 氮化铝、 碳化硅或氧化铝中的任意一种或者至少两种的混合物， 优选结晶型二 氧化硅、 无定形二氧化硅、 球形二氧化硅、 二氧化钛、 钛酸锶、 钛酸钡、 氮化 硼、 氮化铝、 碳化硅或氧化铝中的任意一种或者至少两种的混合物；
优选地， 所述填料为二氧化硅；
优选地， 所述填料的粒径中度值为 1~15μπι， 优选 1~10μπι， 进一歩优选 1~5μπι。
5、 如权利要求 1-4之一所述的无卤树脂组合物， 其特征在于， 所述无卤树 脂组合物还包括 （F) 含磷阻燃剂；
优选地， 所述含磷阻燃剂的含量为 0~80重量份， 不包括 0;
优选地， 所述含磷阻燃剂为三 (2,6-二甲基苯基）膦、 10-(2,5-二羟基苯 基) -9,10-二氢 -9-氧杂 -10-膦菲 -10-氧化物、 2,6-二 (2,6-二甲基苯基)膦基苯、 10- 苯基 -9,10-二氢 -9-氧杂 -10-膦菲 -10-氧化物或聚苯氧基磷腈及其衍生物中的任意 一种或者至少两种的混合物。
6、 如权利要求 1-5之一所述的无卤树脂组合物， 其特征在于， 所述无卤树 脂组合物的卤素含量在 0.09重量％以下。
7、 一种树脂胶液， 其特征在于， 其是将如权利要求 1-6之一所述的无卤树 脂组合物溶解或分散在溶剂中得到。
8、 一种预浸料， 其特征在于， 其包括增强材料及通过含浸干燥后附着在 增强材料上的如权利要求 1-6之一所述的无卤树脂组合物。
9、 一种层压板， 其特征在于， 所述层压板含有至少一张如权利要求 8 所 述的预浸料。
10、 一种覆铜箔层压板， 其特征在于， 所述覆铜箔层压板包括至少一张叠 合的如权利要求 8 所述的预浸料及压覆在叠合后的预浸料的一侧或两侧的铜 箔。
PCT/CN2014/073834 2014-02-14 2014-03-21 一种无卤树脂组合物及其用途 WO2015120650A1 (zh)

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