WO2015120651A1 - Halogen-free resin composition and use for same - Google Patents

Halogen-free resin composition and use for same Download PDF

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Publication number
WO2015120651A1
WO2015120651A1 PCT/CN2014/073839 CN2014073839W WO2015120651A1 WO 2015120651 A1 WO2015120651 A1 WO 2015120651A1 CN 2014073839 W CN2014073839 W CN 2014073839W WO 2015120651 A1 WO2015120651 A1 WO 2015120651A1
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Prior art keywords
weight
parts
resin
halogen
allyl
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PCT/CN2014/073839
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French (fr)
Chinese (zh)
Inventor
杨虎
何岳山
Original Assignee
广东生益科技股份有限公司
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Publication of WO2015120651A1 publication Critical patent/WO2015120651A1/en

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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
    • 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
    • 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
    • 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
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • C08J2325/00—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
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • C08J2325/10—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
    • 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
    • C08J2379/04—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
    • 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
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—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
    • 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

Definitions

  • Halogen-free resin composition and use thereof
  • the invention belongs to the technical field of copper-clad laminate preparation, relates to a halogen-free resin composition and a use thereof, and particularly relates to a halogen-free resin composition, a resin glue prepared by using the halogen-free resin composition, and a prepreg. , laminates and copper clad laminates.
  • the traditional copper-clad laminate for printed circuit is mainly made of brominated epoxy resin, which realizes the flame-retardant function of the board through bromine.
  • carcinogens such as dioxins and dibenzofurans have been detected in the combustion products of electrical and electronic equipment wastes containing halogens such as bromine and chlorine, and halogen-containing products may release highly toxic substances during combustion. Hydrogen halide.
  • the EU's two environmental directives, the Waste Electrical and Electronic Equipment Directive and the Directive on the Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment were officially implemented.
  • 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 a diluent, and a circuit board made of glass fiber cloth. Although the dielectric properties are very good, since the resin system is liquid at normal temperature and cannot be made into a non-stick prepreg, it is difficult to use a general prepreg process in the press forming of the sheet, 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 loss than prepregs and laminates prepared using the halogen-free resin composition. Tangent value, high peel strength, excellent heat resistance and excellent flame retardant effect.
  • a halogen-free resin composition based on parts by weight of an organic solid, comprising:
  • the allyl-modified benzoxazine resin mainly contributes excellent heat resistance and adhesion to the system, but its dielectric properties are relatively poor; and the hydrocarbon resin is mainly composed of excellent contribution to the system. Electrical properties; however, its heat resistance and adhesion are relatively poor.
  • the present invention utilizes an allyl-modified benzoxazine resin to provide excellent heat resistance and excellent adhesion to a system, and is compatible with a hydrocarbon resin excellent in electrical properties to further improve the electrical properties of the cured system.
  • the allyl-modified benzoxazine resin and the carbon-carbon double bond in the hydrocarbon resin are rapidly radically grown into a crosslinked resin network having a large molecular weight by a radical addition reaction under the action of an initiator, and the obtained cured product is excellent. Heat resistance, adhesion and dielectric properties.
  • 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, 22 parts by weight, 24 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, 38 parts by weight, 40 parts by weight, 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 or 58 parts by weight.
  • the content of the component (C) 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.
  • a halogen-free resin composition based on the weight of the organic solid, comprises:
  • the content of the allyl-modified benzoxazine resin is greater than the content of the hydrocarbon resin.
  • the allyl-modified benzoxazine resin mainly contributes excellent heat resistance and adhesion to the system, but its dielectric properties are relatively poor; and the hydrocarbon resin is mainly composed of excellent contribution to the system. Electrical properties; however, its heat resistance and adhesion are relatively poor.
  • the invention adopts an allyl modified benzoxazine resin as a main resin, which provides excellent heat resistance and excellent adhesion to the system, and is combined with a hydrocarbon resin excellent in electrical properties to further improve the electrical properties of the curing system. .
  • the allyl-modified benzoxazine resin and the carbon-carbon double bond in the hydrocarbon resin undergo a radical addition reaction under the action of an initiator, and rapidly grow into a network of a crosslinked resin having a large molecular weight due to the allyl group.
  • Modified benzoxazine resin as the main resin so the system The heat resistance and adhesion are significantly improved compared with the hydrocarbon resin, and the electrical properties of the cured product are well maintained.
  • a halogen-free resin composition based on the weight of the organic solid, comprises:
  • the content of the hydrocarbon resin is greater than the content of the allyl-modified benzoxazine resin.
  • the present invention can be realized by adjusting the hydrocarbon resin content to be larger than the allyl modified benzoxazine resin.
  • a halogen-free resin composition based on the weight of the organic solid, comprises:
  • 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 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 (D) a filler.
  • the content of the filler is 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 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, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight or 95 parts by weight, preferably 10 to 100 parts by weight.
  • the filler is selected from the group consisting of silica and Any one or a mixture of at least two of titanium oxide, barium titanate, barium titanate, boron nitride, aluminum nitride, silicon carbide or aluminum oxide, preferably crystalline silica, amorphous silica, spherical Any one or a mixture of at least two of silicon dioxide, titanium dioxide, barium titanate, barium titanate, boron nitride, aluminum nitride, silicon carbide or aluminum oxide, such as crystalline silica and a mixture of shaped silica, a mixture of spherical silica and titania, a mixture of barium titanate and barium titanate, a mixture of boron nitride and nitride, a mixture of silicon carbide and alumina, crystalline silica, a mixture of shaped silica and spherical silica, a,
  • the filler is silica.
  • the median diameter of the filler is
  • the filler located in this particle size section has good dispersibility in the resin glue.
  • the resin-free composition further comprises a (phosphorus) 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- Dihydro-9-oxa-10-phosphinophen-10-oxide or poly Any one or a mixture of at least two of phenoxyphosphazene and its derivatives.
  • 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:
  • 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 added. Liquid resin and initiator, continue to stir evenly. When used, the solvent can be adjusted by adjusting the solid content of the solution by 65 ⁇ 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 a dielectric loss tangent, a higher peel strength, 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.
  • 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, an excellent heat resistance, and a better flame retardant effect.
  • An exemplary copper clad laminate is prepared by laminating four sheets of the prepreg described above and two sheets of one ounce (35 ⁇ m thick) copper foil, laminated by a hot press, and pressed into two sides. Copper-clad laminate; the copper-clad laminate lamination needs to meet the following requirements: 1.
  • the heating rate of lamination is usually controlled at 1.0 ⁇ 3.0 °C/min when the material temperature is 80 ⁇ 220 °C;
  • the pressure of the lamination is set. When the temperature of the outer layer is 80 to 100 degrees Celsius, the full pressure is applied, and the full pressure is about 300 psi. 3.
  • the temperature of the material is controlled at 220 ° C and kept for 120 minutes;
  • the metal foil covered In addition to the copper foil, it may be a nickel foil, an aluminum foil, a SUS foil, or the like, and the material thereof is not limited.
  • the present invention has the following beneficial effects:
  • the invention mainly comprises an allyl-modified benzoxazine resin, provides excellent heat resistance and excellent electrical properties for the system, and cooperates with a hydrocarbon resin excellent in electrical properties to further improve the electrical properties of the curing system.
  • the allyl-modified benzoxazine resin and the carbon-carbon double bond in the hydrocarbon resin undergo a radical addition reaction under the action of an initiator, and rapidly grow into a crosslinked resin network having a large molecular weight, due to the olefin.
  • the propyl-modified benzoxazine resin is the main resin, so the heat resistance and adhesion of the system are significantly improved compared with the hydrocarbon resin, and the electrical properties of the cured product are well maintained.
  • the prepreg prepared by using the halogen-free resin composition of the invention has a lower dielectric constant and a dielectric loss tangent, a higher peel strength, an excellent heat resistance, and a better flame retardant effect; Copper clad laminate made of prepreg which has a lower Dielectric constant and dielectric loss tangent, high peel strength, excellent heat resistance, and good 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 Table 2.
  • halogen-free resin composition The specific components of the halogen-free resin composition are as follows:
  • Phosphorus-containing flame retardant Polyphenoxyphosphazene compound, SPB-100 (trade name of Otsuka Chemical Co., Ltd., Japan).
  • Comparative Example 2 Also included is another bulk styrene-based resin having a medium-low molecular weight and containing an unsaturated double bond.
  • Comparative Example 3* also includes an allyl modified phenolic resin, which is also flame retarded using a bromine-based flame retardant.
  • Halogen contains C1 0.04 0.05 0.04 0.05 0.005 0.004 0.05 0.05
  • Tg Glass transition temperature
  • DSC differential scanning calorimetry
  • Peel strength The peel strength of the metal cap layer was tested in accordance with the "after thermal stress" experimental conditions in the IPC-TM-650 2.4.8 method. Flammability: Measured according to UL 94 vertical burning method. Thermal stratification time T-288: Measured according to the IPC-TM-650 2.4.24.1 method. Coefficient of thermal expansion 2 axes 01 £ (TMA) : Measured according to IPC-TM-650 2.4.24. Thermal decomposition temperature Td: Measured according to the IPC-TM-650 2.4.26 method. Water absorption: The measurement was carried out in accordance with the method of IPC-TM-650 2.6.2.1. Dielectric loss tangent, dielectric constant: According to the resonance method using strip lines,
  • IPC-TM-650 2.5.5.9 Determines the dielectric loss tangent at 10 GHz.
  • Comparative Example 4 Compared with Comparative Example 4, the proportion of the hydrocarbon resin in Comparative Example 4 was large, and the system had a lower dielectric loss and dielectric constant after the curing reaction, but the Tg, adhesion, heat resistance of the system, and There was a significant drop in flammability.
  • the flame retardancy test can be achieved within the requirements of the JPCA halogen-free standard.
  • the V-0 standard in UL94 has a low coefficient of thermal expansion, high thermal decomposition, low water absorption, and a halogen content of less than 0.09%, which meets environmental requirements.
  • the halogen-free resin composition of the present invention uses a special benzoxazine resin, a polyphenylene ether resin, a hydrocarbon resin, a curing agent, and other components to have good synergistic properties in the use of phosphorus.
  • the element is flame retardant and has a halogen content of less than 0.09% to meet environmental standards.
  • the bonding sheet produced using the halogen-free resin composition has excellent electrical properties, a high glass transition temperature, excellent heat resistance, a good flame retarding effect, and low water absorption.

Abstract

Disclosed in the present invention is a halogen-free composition and prepreg material and laminate made thereof; based on organic solid matter parts by weight, said halogen-free resin composition comprises: (A) 40-80 parts by weight of allyl modified benzoxazine resin; (B) 20-60 parts by weight of hydrocarbon resin; (C) 0.01-3 parts by weight of initiator agent; (D) 10-100 parts by weight of filler; and (E) 0-80 parts by weight of phosphorus-containing flame retardants. Prepreg material and laminate made using the present halogen-free resin composition have a low dielectric constant and dielectric loss tangent value, high peel strength, good thermal resistance, and good flame retardancy.

Description

一种无卤树脂组合物及其用途 技术领域  Halogen-free resin composition and use thereof
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。  The invention belongs to the technical field of copper-clad laminate preparation, relates to a halogen-free resin composition and a use thereof, and particularly relates to a halogen-free resin composition, a resin glue prepared by using the halogen-free resin composition, and a prepreg. , laminates and copper clad laminates.
背景技术 Background technique
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 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。  The traditional copper-clad laminate for printed circuit is mainly made of brominated epoxy resin, which realizes the flame-retardant function of the board through bromine. However, in recent years, carcinogens such as dioxins and dibenzofurans have been detected in the combustion products of electrical and electronic equipment wastes containing halogens such as bromine and chlorine, and halogen-containing products may release highly toxic substances during combustion. Hydrogen halide. In addition, on July 1, 2006, the EU's two environmental directives, the Waste Electrical and Electronic Equipment Directive and the Directive on the Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment, were officially implemented. Due to the environmental non-environment of the combustion products of halogen-containing products and the implementation of two environmental protection directives in the European Union, the development of halogen-free flame-retardant copper-clad laminates has become a hot spot in the industry, and various copper-clad laminate manufacturers have launched their own Halogen flame retardant copper clad laminate.
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。 In recent years, with the development of high performance, high functionality, and networking of computers and information communication equipment, in order to transmit and process large-capacity information at high speed, operational signals tend to be high-frequency, and thus materials for circuit boards have been demanded. Among the materials used for printed circuit boards, epoxy resins having excellent adhesion properties are widely used. However, the epoxy resin circuit board generally has a high dielectric constant and dielectric loss tangent (dielectric constant greater than 4, dielectric loss tangent 0.02 or so), and high frequency characteristics are insufficient, and 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。  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 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。  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 a diluent, and a circuit board made of glass fiber cloth. Although the dielectric properties are very good, since the resin system is liquid at normal temperature and cannot be made into a non-stick prepreg, it is difficult to use a general prepreg process in the press forming of the sheet, and the process operation is difficult.
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。 另外该发明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可以改善剥离强度。  CN1280337C The use of polyphenylene ether resins with unsaturated double bonds at the molecular end, using low molecular weight low molecular weight vinyl monomers (such as dibromostyrene) as curing agents, but because of the low boiling point of these low molecular weight monomers, The impregnated glass fiber cloth will evaporate during the drying process of the prepreg, and it is difficult to ensure a sufficient amount of curing agent. Further, although the invention mentions that the viscosity of the system can be modified by using a polybutadiene-based resin, it is not explicitly proposed to use a polybutadiene-based resin having a polar group and a polybutadiene having a polar group. The diene resin can improve the peel strength.
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。 CN101544841B uses a hydrocarbon resin having a molecular weight of 11,000 or less and a vinyl content of 60% or more. As the main body, allyl modified phenolic resin is used to improve the tackiness of the prepreg, and the peel strength is improved. However, 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.
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。  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.
发明内容 Summary of the invention
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备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， 优良的耐热性以及优异的阻燃效果。  In view of the problems in the prior art, it is an object of the present invention to provide a halogen-free resin composition, which has a lower dielectric constant and dielectric loss than prepregs and laminates prepared using the halogen-free resin composition. Tangent value, high peel strength, excellent heat resistance and excellent flame retardant effect.
为了达到上述目的， 本发明采用了如下技术方案：  In order to achieve the above object, the present invention adopts the following technical solutions:
一种无卤树脂组合物， 以有机固形物重量份计， 其包含：  A halogen-free resin composition, based on parts by weight of an organic solid, comprising:
(A) 烯丙基改性苯并噁嗪树脂， 40~80重量份；  (A) allyl modified benzoxazine resin, 40 to 80 parts by weight;
(B ) 碳氢树脂， 20~60重量份；  (B) hydrocarbon resin, 20 to 60 parts by weight;
(C) 引发剂， 0.01~3重量份。  (C) Initiator, 0.01 to 3 parts by weight.
该树脂体系中， 烯丙基改性苯并噁嗪树脂主要为体系贡献优良的耐热性和 粘合性， 但是其介电性能相对较差； 而碳氢树脂则主要为体系贡献优异的介电 性能； 但是其耐热性和粘合性相对较差。 本发明利用烯丙基改性苯并噁嗪树脂 为体系提供优异的耐热性以及优良的粘合性， 配合电性能优异的碳氢树脂， 进 一歩改善固化体系的电性能。 烯丙基改性苯并噁嗪树脂与碳氢树脂中的碳碳双 键在引发剂的作用下经自由基加成反应， 迅速成长成分子量巨大的交联树脂网 络， 得到的固化产物具有优异的耐热性、 粘合性以及介电性能。  In the resin system, the allyl-modified benzoxazine resin mainly contributes excellent heat resistance and adhesion to the system, but its dielectric properties are relatively poor; and the hydrocarbon resin is mainly composed of excellent contribution to the system. Electrical properties; however, its heat resistance and adhesion are relatively poor. The present invention utilizes an allyl-modified benzoxazine resin to provide excellent heat resistance and excellent adhesion to a system, and is compatible with a hydrocarbon resin excellent in electrical properties to further improve the electrical properties of the cured system. The allyl-modified benzoxazine resin and the carbon-carbon double bond in the hydrocarbon resin are rapidly radically grown into a crosslinked resin network having a large molecular weight by a radical addition reaction under the action of an initiator, and the obtained cured product is excellent. Heat resistance, adhesion and dielectric properties.
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。 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.
所述组分（B )碳氢树脂的含量例如为 22重量份、 24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、 38重量份、 40重 量份、 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重量份或 58重量份。  The content of the component (B) hydrocarbon resin is, for example, 22 parts by weight, 24 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, 38 parts by weight, 40 parts by weight, 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 or 58 parts by weight.
所述组分 （C) 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。  The content of the component (C) 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.
优选地， 在本发明提供的技术方案的基础上， 一种无卤树脂组合物， 以有 机固形物重量份计， 其包含：  Preferably, based on the technical solution provided by the present invention, a halogen-free resin composition, based on the weight of the organic solid, comprises:
(A) 烯丙基改性苯并噁嗪树脂， 40~80重量份；  (A) allyl modified benzoxazine resin, 40 to 80 parts by weight;
(B ) 碳氢树脂， 20~60重量份；  (B) hydrocarbon resin, 20 to 60 parts by weight;
(C) 引发剂， 0.01~3重量份；  (C) initiator, 0.01~3 parts by weight;
其中， 烯丙基改性苯并噁嗪树脂的含量大于碳氢树脂的含量。  Wherein, the content of the allyl-modified benzoxazine resin is greater than the content of the hydrocarbon resin.
该树脂体系中， 烯丙基改性苯并噁嗪树脂主要为体系贡献优良的耐热性和 粘合性， 但是其介电性能相对较差； 而碳氢树脂则主要为体系贡献优异的介电 性能； 但是其耐热性和粘合性相对较差。 本发明以烯丙基改性苯并噁嗪树脂为 主体树脂， 其为体系提供优异的耐热性以及优良的粘合性， 配合电性能优异的 碳氢树脂， 进一歩改善固化体系的电性能。 而且， 烯丙基改性苯并噁嗪树脂与 碳氢树脂中的碳碳双键在引发剂的作用下经自由基加成反应， 迅速成长成分子 量巨大的交联树脂网络， 由于烯丙基改性苯并噁嗪树脂为主体树脂， 故体系的 耐热性和粘合性较碳氢树脂有显著提高， 同时固化产物的电性能得到了较好的 保持。 In the resin system, the allyl-modified benzoxazine resin mainly contributes excellent heat resistance and adhesion to the system, but its dielectric properties are relatively poor; and the hydrocarbon resin is mainly composed of excellent contribution to the system. Electrical properties; however, its heat resistance and adhesion are relatively poor. The invention adopts an allyl modified benzoxazine resin as a main resin, which provides excellent heat resistance and excellent adhesion to the system, and is combined with a hydrocarbon resin excellent in electrical properties to further improve the electrical properties of the curing system. . Moreover, the allyl-modified benzoxazine resin and the carbon-carbon double bond in the hydrocarbon resin undergo a radical addition reaction under the action of an initiator, and rapidly grow into a network of a crosslinked resin having a large molecular weight due to the allyl group. Modified benzoxazine resin as the main resin, so the system The heat resistance and adhesion are significantly improved compared with the hydrocarbon resin, and the electrical properties of the cured product are well maintained.
优选地， 在本发明提供的技术方案的基础上， 一种无卤树脂组合物， 以有 机固形物重量份计， 其包含：  Preferably, based on the technical solution provided by the present invention, a halogen-free resin composition, based on the weight of the organic solid, comprises:
(A) 烯丙基改性苯并噁嗪树脂， 40~80重量份；  (A) allyl modified benzoxazine resin, 40 to 80 parts by weight;
(B) 碳氢树脂， 20~60重量份；  (B) Hydrocarbon resin, 20 to 60 parts by weight;
(C) 引发剂， 0.01~3重量份；  (C) initiator, 0.01~3 parts by weight;
其中， 碳氢树脂的含量大于烯丙基改性苯并噁嗪树脂的含量。  Wherein, the content of the hydrocarbon resin is greater than the content of the allyl-modified benzoxazine resin.
在覆铜板领域对于不同用途的覆铜板对体系的耐热性、 粘合性以及介电性 能有不同的侧重需求， 所以对于对体系的介电性能有更高要求的特定用途的覆 铜板而言， 可以在一定范围内适当降低对覆铜板耐热性和粘结性要求时， 本发 明可通过调整碳氢树脂含量大于烯丙基改性苯并噁嗪树脂实现。  In the field of CCL, there are different requirements for the heat resistance, adhesion and dielectric properties of the CCL for different applications, so for the specific purpose CCL with higher dielectric properties for the system. When the heat resistance and adhesion requirements of the copper clad laminate can be appropriately reduced within a certain range, the present invention can be realized by adjusting the hydrocarbon resin content to be larger than the allyl modified benzoxazine resin.
优选地， 在本发明提供的技术方案的基础上， 一种无卤树脂组合物， 以有 机固形物重量份计， 其包含：  Preferably, based on the technical solution provided by the present invention, a halogen-free resin composition, based on the weight of the organic solid, comprises:
(A) 烯丙基改性苯并噁嗪树脂， 60~80重量份；  (A) allyl modified benzoxazine resin, 60 to 80 parts by weight;
(B) 碳氢树脂， 40~50重量份；  (B) Hydrocarbon resin, 40 to 50 parts by weight;
(C) 引发剂， 0.01~3重量份。  (C) Initiator, 0.01 to 3 parts by weight.
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。 Preferably, based on the technical solution provided by the present invention, 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.
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。  Preferably, based on the technical solution provided by the present invention, 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. A hydrocarbon resin having a number average molecular weight of less than 7,000 and a 1,2 addition of a vinyl content of more than 70%, which is a liquid at room temperature, is preferred.
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。  Preferably, based on the technical solution provided by the present invention, 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.
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 (D) 填料。  Preferably, based on the technical solution provided by the present invention, the resin-free composition further comprises (D) a filler.
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。  Preferably, based on the technical solution provided by the present invention, the content of the filler is 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 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, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight or 95 parts by weight, preferably 10 to 100 parts by weight.
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。 Preferably, based on the technical solution provided by the present invention, the filler is selected from the group consisting of silica and Any one or a mixture of at least two of titanium oxide, barium titanate, barium titanate, boron nitride, aluminum nitride, silicon carbide or aluminum oxide, preferably crystalline silica, amorphous silica, spherical Any one or a mixture of at least two of silicon dioxide, titanium dioxide, barium titanate, barium titanate, boron nitride, aluminum nitride, silicon carbide or aluminum oxide, such as crystalline silica and a mixture of shaped silica, a mixture of spherical silica and titania, a mixture of barium titanate and barium titanate, a mixture of boron nitride and nitride, a mixture of silicon carbide and alumina, crystalline silica, a mixture of shaped silica and spherical silica, a mixture of titanium dioxide, barium titanate and barium titanate, a mixture of boron nitride, aluminum nitride, silicon carbide and aluminum oxide.
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。  Preferably, based on the technical solution provided by the present invention, the filler is silica.
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 Preferably, based on the technical solution provided by the present invention, the median diameter of the filler is
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。 1~15μπι, for example 2μπι, 3μπι, 4μπι, 5μπι, 6μπι, 7μπι, 8μπι, 9μπι, 10μπι, 11μπι, 12μπι, 13μπι or 14μπι, preferably 1~10μπι, further preferably 1~5μπι. The filler located in this particle size section has good dispersibility in the resin glue.
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 (Ε) 含磷阻燃剂。  Preferably, based on the technical solution provided by the present invention, the resin-free composition further comprises a (phosphorus) phosphorus-containing flame retardant.
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。  Preferably, based on the technical solution provided by the present invention, 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.
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。 Preferably, based on the technical solution provided by the present invention, 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- Dihydro-9-oxa-10-phosphinophen-10-oxide or poly Any one or a mixture of at least two of phenoxyphosphazene and its derivatives.
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％。  Preferably, based on the technical solution provided by the present invention, 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%.
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：  An exemplary halogen-free resin composition, based on parts by weight of the organic solids, comprising:
(A) 烯丙基改性苯并噁嗪树脂， 40~80重量份；  (A) allyl modified benzoxazine resin, 40 to 80 parts by weight;
(B) ：树脂， 20~60重量份;  (B): resin, 20 to 60 parts by weight;
(C) 引发剂， 0.01-3重量份；  (C) initiator, 0.01-3 parts by weight;
(D) 填料， 1~100重量份；  (D) filler, 1 to 100 parts by weight;
(E) 含磷阻燃剂， 0~80重量份， 不包括 0。  (E) Phosphorus-containing flame retardant, 0 to 80 parts by weight, excluding 0.
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:  An exemplary halogen-free resin composition, based on parts by weight of the organic solids, comprising:
(A) 烯丙基改性苯并噁嗪树脂， 40~80重量份；  (A) allyl modified benzoxazine resin, 40 to 80 parts by weight;
(B) ：树脂， 20~60重量份;  (B): resin, 20 to 60 parts by weight;
(C) 引发剂， 0.01~3重量份；  (C) initiator, 0.01~3 parts by weight;
(D) 填料， 1~100重量份；  (D) filler, 1 to 100 parts by weight;
(E) 含磷阻燃剂， 0~80重量份， 不包括 0;  (E) phosphorus-containing flame retardant, 0 to 80 parts by weight, excluding 0;
其中， 烯丙基改性苯并噁嗪树脂的含量大于碳氢树脂的含:  Wherein the content of the allyl-modified benzoxazine resin is greater than the content of the hydrocarbon resin:
小例性的一种无卤树脂组合物， 以有机固形  a small halogen-free resin composition with an organic solid
(A) 烯丙基改性苯并噁嗪树脂， 60~80重量份;  (A) allyl modified benzoxazine resin, 60 to 80 parts by weight;
(B) ：树脂， 40~50重量份;  (B): resin, 40 to 50 parts by weight;
(C) 引发剂， 0.01-3重量份；  (C) initiator, 0.01-3 parts by weight;
(D) 填料， 1~100重量份；  (D) filler, 1 to 100 parts by weight;
(E) 含磷阻燃剂， 0~80重量份， 不包括 0( 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"。 (E) Phosphorus-containing flame retardant, 0~80 parts by weight, excluding 0 ( The term "comprising" as used in the present invention means that it may include other components in addition to the components, and these other components impart different characteristics to the halogen-free resin composition. In addition, the "include" of the present invention may be replaced by a closed "for" or "consisting of".
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。  For example, 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.
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。  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.
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。  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.
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， 再加入适当的填 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。  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 added. Liquid resin and initiator, continue to stir evenly. When used, the solvent can be adjusted by adjusting the solid content of the solution by 65~75%.
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， 优良的耐热性、 较好的阻燃效 果。  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 a dielectric loss tangent, a higher peel strength, an excellent heat resistance, and a better flame retardant effect.
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。  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.
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。 Immersing the above resin glue with a fabric such as a reinforced fiberglass cloth or an organic fabric, and impregnating it The reinforcing material was baked in an oven at 170 ° C for 5 to 8 minutes to prepare a prepreg for printed circuit.
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。  A fourth object of the present invention is to provide a laminate comprising at least one prepreg as described above.
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， 优良的耐热性、 较好的阻燃效果。  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, an excellent heat resistance, and a better flame retardant effect.
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。  An exemplary copper clad laminate is prepared by laminating four sheets of the prepreg described above and two sheets of one ounce (35 μm thick) copper foil, laminated by a hot press, and pressed into two sides. Copper-clad laminate; the copper-clad laminate lamination needs to meet the following requirements: 1. The heating rate of lamination is usually controlled at 1.0~3.0 °C/min when the material temperature is 80~220 °C; The pressure of the lamination is set. When the temperature of the outer layer is 80 to 100 degrees Celsius, the full pressure is applied, and the full pressure is about 300 psi. 3. When curing, the temperature of the material is controlled at 220 ° C and kept for 120 minutes; the metal foil covered In addition to the copper foil, it may be a nickel foil, an aluminum foil, a SUS foil, or the like, and the material thereof is not limited.
与已有技术相比， 本发明具有如下有益效果：  Compared with the prior art, the present invention has the following beneficial effects:
本发明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， 配合电性能优异的碳氢树脂， 进一歩改善固化体系的电性能。 本发明中， 烯丙基改性苯并噁嗪树脂与碳氢树脂中的碳碳双键在引发剂的作用 下经自由基加成反应， 迅速成长成分子量巨大的交联树脂网络， 由于烯丙基改 性苯并噁嗪树脂为主体树脂， 故体系的耐热性和粘合性较碳氢树脂有显著提 高， 同时固化产物的电性能得到了较好的保持。 使用本发明的无卤树脂组合物 制成的预浸料具有较低的介电常数和介电损耗正切值， 较高的剥离强度， 优良 的耐热性、 较好的阻燃效果； 使用该预浸料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， 优良的耐热性、 较好的阻燃效 果。 The invention mainly comprises an allyl-modified benzoxazine resin, provides excellent heat resistance and excellent electrical properties for the system, and cooperates with a hydrocarbon resin excellent in electrical properties to further improve the electrical properties of the curing system. In the present invention, the allyl-modified benzoxazine resin and the carbon-carbon double bond in the hydrocarbon resin undergo a radical addition reaction under the action of an initiator, and rapidly grow into a crosslinked resin network having a large molecular weight, due to the olefin. The propyl-modified benzoxazine resin is the main resin, so the heat resistance and adhesion of the system are significantly improved compared with the hydrocarbon resin, and the electrical properties of the cured product are well maintained. The prepreg prepared by using the halogen-free resin composition of the invention has a lower dielectric constant and a dielectric loss tangent, a higher peel strength, an excellent heat resistance, and a better flame retardant effect; Copper clad laminate made of prepreg which has a lower Dielectric constant and dielectric loss tangent, high peel strength, excellent heat resistance, and good flame retardant effect.
具体实施方式 detailed description
下面通过具体实施方式来进一歩说明本发明的技术方案。  The technical solution of the present invention will be further described below by way of specific embodiments.
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。  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 Table 2.
所述无卤树脂组合物的具体组分如下：  The specific components of the halogen-free resin composition are as follows:
(A) 烯丙基改性苯并噁嗪树脂  (A) Allyl modified benzoxazine resin
A-1烯丙基改性双酚 A型苯并噁嗪树脂  A-1 allyl modified bisphenol A type benzoxazine resin
A-2烯丙基改性双环戊二烯酚型苯并噁嗪树脂  A-2 allyl modified dicyclopentadiene phenol type benzoxazine resin
A-3烯丙基改性双酚 F型苯并噁嗪树脂  A-3 allyl modified bisphenol F type benzoxazine resin
(B) 碳氢树脂  (B) Hydrocarbon resin
B-1丁苯树脂 （商品型号 Ricon l04H， Sartomer)  B-1 styrene resin (product model Ricon l04H, Sartomer)
B-2丁苯树脂 （商品型号 Ricon 153H, Sartomer)  B-2 styrene resin (product model Ricon 153H, Sartomer)
B-3丁苯树脂 （商品型号 Ricon 100， Sartomer)  B-3 styrene resin (product model Ricon 100, Sartomer)
(C) 引发剂： 过氧化二异丙苯 （上海高桥）  (C) Initiator: Dicumyl peroxide (Shanghai Gaoqiao)
(D) 填料： 球形硅微粉 （商品名 SFP-30M, 电气化学工业株式会社） (D) Filler: Spherical silicon micropowder (trade name SFP-30M, Denki Kogyo Co., Ltd.)
(E) 含磷阻燃剂： 聚苯氧基磷腈化合物， SPB-100 (日本大塚化学株式会 社商品名） 。 (E) Phosphorus-containing flame retardant: Polyphenoxyphosphazene compound, SPB-100 (trade name of Otsuka Chemical Co., Ltd., Japan).
表 1.各实施例和比较例的配方组成
Figure imgf000012_0001
A-3 75 Table 1. Formulation composition of each of the examples and comparative examples
Figure imgf000012_0001
A-3 75
B-l 35 10 62 90  B-l 35 10 62 90
B-2 20 15 20  B-2 20 15 20
B-3 60 50 38 B-3 60 50 38
C 2.5 0.03 3 1.5 3 3 5.6 2 C 2.5 0.03 3 1.5 3 3 5.6 2
D 10 60 30 40 100 60 40 60  D 10 60 30 40 100 60 40 60
E 25 5 15 10 80 5 25 50 酚醛树  E 25 5 15 10 80 5 25 50 Phenolic tree
20  20
脂  fat
含有不饱  Containing insufficient
和双键的  And double-key
38  38
固体苯乙  Solid phenyl b
烯基树脂  Alkenyl resin
烯丙基改  Allyl modification
性酚醛树 52  Phenolic tree 52
m  m
2、 对比例 Γ用酚醛树脂与烯丙基改性双环戊二烯酚型苯并噁嗪树月 开环固化。 2. Comparative Example The phenolic resin and allyl modified dicyclopentadiene phenol type benzoxazine tree were opened and cured.
3、 对比例 2"还包括另一种组分为中低分子量且含有不饱和双键的 体苯乙烯基树脂。  3. Comparative Example 2" Also included is another bulk styrene-based resin having a medium-low molecular weight and containing an unsaturated double bond.
4、 对比例 3*"还包括烯丙基改性酚醛树脂， 同时其使用溴系阻燃剂阻 燃。  4. Comparative Example 3*" also includes an allyl modified phenolic resin, which is also flame retarded using a bromine-based flame retardant.
表 2.各实施例和比较例的物性数据  Table 2. Physical properties of each of the examples and comparative examples
Figure imgf000013_0001
热分层时间
Figure imgf000013_0001
Thermal stratification time
>15 >60 >45 >60 >30 >60 2 >15 >5 >15 >60 >45 >60 >30 >60 2 >15 >5
T-288 (分钟） T-288 (minutes)
热膨胀系数  Thermal expansion coefficient
Ζ轴 CTE  Ζ axis CTE
( ΤΜΑ) 3.3 2.5 3.2 2.7 3.2 2.2 4.2 2.8 3.0 ( 30- 260 °C ) %  ( ΤΜΑ) 3.3 2.5 3.2 2.7 3.2 2.2 4.2 2.8 3.0 ( 30- 260 ° C ) %
热分解温度  Thermal decomposition temperature
360 400 380 390 360 410 350 355 380 Td C TGA, °C )  360 400 380 390 360 410 350 355 380 Td C TGA, °C )
吸水性 （％) 0.08 0.10 0.08 0.09 0.08 0.12 0.08 0.08 0.07 介质损耗角正  Water absorption (%) 0.08 0.10 0.08 0.09 0.08 0.12 0.08 0.08 0.07 Dielectric loss angle positive
切 Df 0.0052 0.0072 0.0056 0.0068 0.0065 0.012 0.0035 0.0065 0.0032 ( (10GHZ))  Cut Df 0.0052 0.0072 0.0056 0.0068 0.0065 0.012 0.0035 0.0065 0.0032 ( (10GHZ))
介电常数 Dk  Dielectric constant Dk
3.62 3.82 3.77 3.8 3.8 4.2 3.45 3.56 3.48 (10GHZ)  3.62 3.82 3.77 3.8 3.8 4.2 3.45 3.56 3.48 (10GHZ)
卤素含 C1 0.04 0.05 0.04 0.05 0.005 0.004 0.05 0.05 0.05 量测试  Halogen contains C1 0.04 0.05 0.04 0.05 0.005 0.004 0.05 0.05
Br 0 0 0 0 0 0 0 >1 0 (%)  Br 0 0 0 0 0 0 0 >1 0 (%)
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  The test methods for the above characteristics are as follows: Glass transition temperature (Tg): According to differential scanning calorimetry (DSC), according to 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The determination is carried out by the DSC method specified in 2.4.25. Peel strength (PS): The peel strength of the metal cap layer was tested in accordance with the "after thermal stress" experimental conditions in the IPC-TM-650 2.4.8 method. Flammability: Measured according to UL 94 vertical burning method. Thermal stratification time T-288: Measured according to the IPC-TM-650 2.4.24.1 method. Coefficient of thermal expansion 2 axes 01 £ (TMA) : Measured according to IPC-TM-650 2.4.24. Thermal decomposition temperature Td: Measured according to the IPC-TM-650 2.4.26 method. Water absorption: The measurement was carried out in accordance with the method of IPC-TM-650 2.6.2.1. Dielectric loss tangent, dielectric constant: According to the resonance method using strip lines,
IPC-TM-650 2.5.5.9测定 10GHz下的介质损耗角正切。 IPC-TM-650 2.5.5.9 Determines the dielectric loss tangent at 10 GHz.
( 10) 卤素含量测试： 按照 IPC-TM-650 2.3.41方法进行测定。  (10) Halogen content test: Measured according to IPC-TM-650 2.3.41 method.
物性分析  Physical analysis
从表 2的物性数据可知实施例 1-4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。  From the physical property data of Table 2, it was found that the copper clad laminate produced in Examples 1-4 had excellent dielectric properties and a high glass transition temperature.
实施例与比较例 1相比， 随着碳氢树脂的加入， 体系的介电性能有显著的 提升， 而体系的耐热性与剥离强度得到了较好的保持。 实施例与比较例 2 相 比， 随着烯丙基改性苯并噁嗪树脂的加入， 体系的剥离强度和耐热性有显著的 提升， 同时体系的介电性能得到最大限度的保持。 实施例与比较例 3相比， 烯 丙基改性苯并噁嗪树脂的加入显著提高了体系的 Tg， 同时实现了无卤阻燃实 现绿色环保。  Compared with Comparative Example 1, the dielectric properties of the system were significantly improved with the addition of the hydrocarbon resin, and the heat resistance and peel strength of the system were well maintained. Compared with Comparative Example 2, with the addition of the allyl-modified benzoxazine resin, the peel strength and heat resistance of the system were significantly improved, and the dielectric properties of the system were maintained to the utmost. In the examples, compared with Comparative Example 3, the addition of the allyl-modified benzoxazine resin significantly increased the Tg of the system, and at the same time, achieved halogen-free flame retardant and achieved environmental protection.
实施例与比较例 4相比， 比较例 4中碳氢树脂的比例很大， 固化反应后体 系拥有更低的介电损耗和介电常数， 但是体系的 Tg、 粘合性、 耐热性以及燃 烧性均出现明显的下降。  Compared with Comparative Example 4, the proportion of the hydrocarbon resin in Comparative Example 4 was large, and the system had a lower dielectric loss and dielectric constant after the curing reaction, but the Tg, adhesion, heat resistance of the system, and There was a significant drop in flammability.
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。  The flame retardancy test can be achieved within the requirements of the JPCA halogen-free standard. The V-0 standard in UL94 has a low coefficient of thermal expansion, high thermal decomposition, low water absorption, and a halogen content of less than 0.09%, which meets environmental requirements.
综上所述， 本发明所述的无卤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。 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。 In summary, the halogen-free resin composition of the present invention uses a special benzoxazine resin, a polyphenylene ether resin, a hydrocarbon resin, a curing agent, and other components to have good synergistic properties in the use of phosphorus. The element is flame retardant and has a halogen content of less than 0.09% to meet environmental standards. Further, the bonding sheet produced using the halogen-free resin composition has excellent electrical properties, a high glass transition temperature, excellent heat resistance, a good flame retarding effect, and low water absorption. The Applicant claims that the present invention is described by the above-described embodiments, but the present invention is not limited to the above detailed methods, that is, it does not mean that the present invention must be implemented by the above detailed methods. It will be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, and addition of auxiliary components, selection of specific means, etc., are all within the scope of the present invention.

Claims

权 利 要 求 书 claims
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： 1. A halogen-free resin composition, characterized in that, in parts by weight of organic solids, it contains:
(A) 烯丙基改性苯并噁嗪树脂， 40~80重量份； (A) Allyl modified benzoxazine resin, 40 to 80 parts by weight;
(B) 碳氢树脂， 20~60重量份； (B) Hydrocarbon resin, 20~60 parts by weight;
(C) 引发剂， 0.01~3重量份。 (C) Initiator, 0.01~3 parts by weight.
2、 如权利要求 1 所述的无卤树脂组合物， 其特征在于， 以有机固形物重 量份计， 其包含： 2. The halogen-free resin composition according to claim 1, characterized in that, based on the weight of organic solids, it contains:
(A) 烯丙基改性苯并噁嗪树脂， 40~80重量份； (A) Allyl modified benzoxazine resin, 40 to 80 parts by weight;
(B) 碳氢树脂， 20~60重量份； (B) Hydrocarbon resin, 20~60 parts by weight;
(C) 引发剂， 0.01~3重量份； (C) Initiator, 0.01~3 parts by weight;
其中， 烯丙基改性苯并噁嗪树脂的含量大于碳氢树脂的含量。 Among them, the content of allyl-modified benzoxazine resin is greater than that of hydrocarbon resin.
3、 如权利要求 1 所述的无卤树脂组合物， 其特征在于， 以有机固形物重 量份计， 其包含： 3. The halogen-free resin composition according to claim 1, characterized in that, based on the weight of organic solids, it contains:
(A) 烯丙基改性苯并噁嗪树脂， 40~80重量份； (A) Allyl modified benzoxazine resin, 40 to 80 parts by weight;
(B) 碳氢树脂， 20~60重量份； (B) Hydrocarbon resin, 20~60 parts by weight;
(C) 引发剂， 0.01~3重量份； (C) Initiator, 0.01~3 parts by weight;
其中， 碳氢树脂的含量大于烯丙基改性苯并噁嗪树脂的含量。 Among them, the content of hydrocarbon resin is greater than that of allyl-modified benzoxazine resin.
4、 如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 以有机固形物 重量份计， 其包含： 4. The halogen-free resin composition according to claim 1 or 2, characterized in that, in parts by weight of organic solids, it contains:
(A) 烯丙基改性苯并噁嗪树脂， 60~80重量份； (A) Allyl modified benzoxazine resin, 60~80 parts by weight;
(B) 碳氢树脂， 40~50重量份； (B) Hydrocarbon resin, 40~50 parts by weight;
(C) 引发剂， 0.01~3重量份。 (C) Initiator, 0.01~3 parts by weight.
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 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； 5. The halogen-free resin composition according to any one of claims 1 to 4, characterized in that, the allyl The modified benzoxazine resin is selected from the group consisting of allyl-modified bisphenol A-type benzoxazine resin, allyl-modified bisphenol F-type benzoxazine resin, and allyl-modified dicyclopentadienol-type benzoxazine resin. Any one or a mixture of at least two of benzoxazine resins, allyl-modified bisphenol S-type benzoxazine resins or diamine-type benzoxazine resins. Preferably, the hydrocarbon resin is number-average. A hydrocarbon resin with a molecular weight of less than 11,000 and consisting of two elements, hydrocarbon and hydrogen, with a vinyl content greater than 60% and which is liquid at room temperature. Preferably, the number average molecular weight is less than 7,000 and the vinyl content added at positions 1 and 2 is greater than 70%. Hydrocarbon resins that are liquid at room temperature;
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 )-2,5-二甲基己垸中的任意一种或者至少两 种的混合物。 Preferably, the initiator is selected from organic peroxides, preferably dicumyl peroxide, tert-butyl peroxybenzoate or 2,5-di(2-ethylhexanoylperoxy)-2,5- Any one of dimethylhexane or a mixture of at least two.
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 脂组合物还包括 （D) 填料； 6. The halogen-free resin composition according to claim 1, wherein the halogen-free resin composition further includes (D) filler;
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； Preferably, the content of the filler is 1 to 100 parts by weight, preferably 10 to 100 parts by weight; Preferably, the filler is selected from silica, titanium dioxide, strontium titanate, barium titanate, boron nitride, nitride Any one or a mixture of at least two of aluminum, silicon carbide or alumina, preferably crystalline silica, amorphous silica, spherical silica, titanium dioxide, strontium titanate, barium titanate, boron nitride , any one or a mixture of at least two of aluminum nitride, silicon carbide or aluminum oxide;
优选地， 所述填料为二氧化硅； Preferably, the filler is silica;
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 1~5μπΐ; Preferably, the medium particle size value of the filler is 1 to 15 μm, preferably 1 to 10 μm, and further preferably 1 to 5 μm;
优选地， 所述无卤树脂组合物还包括 （Ε) 含磷阻燃剂； Preferably, the halogen-free resin composition further includes (E) a phosphorus-containing flame retardant;
优选地， 所述含磷阻燃剂的含量为 0~80重量份， 不包括 0; Preferably, the content of the phosphorus-containing flame retardant is 0 to 80 parts by weight, excluding 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； Preferably, the phosphorus-containing flame retardant is tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxybenzene base) -9,10-dihydro-9-oxa-10-phosphine-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl- Any one or a mixture of at least two of 9,10-dihydro-9-oxa-10-phosphinophene-10-oxide or polyphenoxyphosphazene and its derivatives;
优选地， 所述无卤树脂组合物的卤素含量在 0.09重量％以下。 Preferably, the halogen content of the halogen-free resin composition is less than 0.09% by weight.
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。 7. A resin glue solution, characterized in that it is obtained by dissolving or dispersing the halogen-free resin composition according to any one of claims 1 to 6 in a solvent.
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。 8. A prepreg, characterized in that it includes a reinforcing material and the halogen-free resin composition according to any one of claims 1 to 6 attached to the reinforcing material after being impregnated and dried.
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。 9. A laminate, characterized in that the laminate contains at least one piece of the prepreg according to claim 8.
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。 10. A copper-clad laminate, characterized in that, the copper-clad laminate includes at least one stacked prepreg as claimed in claim 8 and a layer pressed on the stacked prepreg. Copper foil on one or both sides.
PCT/CN2014/073839 2014-02-14 2014-03-21 Halogen-free resin composition and use for same WO2015120651A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101544841A (en) * 2009-04-10 2009-09-30 广东生益科技股份有限公司 Composite material and high frequency circuit substrate made of the same
CN102977551A (en) * 2011-09-02 2013-03-20 广东生益科技股份有限公司 Halogen-free resin composition and method for preparing copper-clad plate from the halogen-free resin composition

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101684191B (en) * 2009-08-27 2012-03-07 广东生益科技股份有限公司 Halogen-less high frequency resin composition, and prepreg and laminate manufacturing by using same
CN102161823B (en) * 2010-07-14 2012-09-26 广东生益科技股份有限公司 Composite material, high-frequency circuit substrate therefrom and manufacture method thereof
CN102093666B (en) * 2010-12-23 2012-09-26 广东生益科技股份有限公司 Halogen-free resin composite and preparation method of halogen-free copper clad laminate using same
CN102850726A (en) * 2012-09-07 2013-01-02 广东生益科技股份有限公司 Composite material, high frequency circuit substrate produced by using composite material, and production method of high frequency circuit substrate
CN103265791B (en) * 2013-05-29 2015-04-08 苏州生益科技有限公司 Thermosetting resin composition for integrated circuit as well as prepreg and laminated board both fabricated by using composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101544841A (en) * 2009-04-10 2009-09-30 广东生益科技股份有限公司 Composite material and high frequency circuit substrate made of the same
CN102977551A (en) * 2011-09-02 2013-03-20 广东生益科技股份有限公司 Halogen-free resin composition and method for preparing copper-clad plate from the halogen-free resin composition

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