WO2015120652A1 - 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
WO2015120652A1
WO2015120652A1 PCT/CN2014/073842 CN2014073842W WO2015120652A1 WO 2015120652 A1 WO2015120652 A1 WO 2015120652A1 CN 2014073842 W CN2014073842 W CN 2014073842W WO 2015120652 A1 WO2015120652 A1 WO 2015120652A1
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Prior art keywords
weight
parts
resin
halogen
allyl
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PCT/CN2014/073842
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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 WO2015120652A1 publication Critical patent/WO2015120652A1/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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
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    • 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
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • 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
    • C08J2379/04—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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—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
    • C08L2205/03—Polymer mixtures characterised by other features containing three 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.
  • CN 100547033C discloses the use of a low molecular polyphenylene ether resin as a main resin, and a triallyl isocyanurate as a crosslinking curing agent to obtain a cured product excellent in electrical properties, but it requires 8 to 20% of bromine as a flame retardant. Moreover, the water absorption rate of the cured product is high, which greatly limits its application in the printed circuit industry.
  • CN 102093666A discloses the use of a polyphenylene ether resin benzoxazine resin, an epoxy resin composition and a copper clad laminate using the same. It uses an epoxy group of a hydroxyl group-terminated polyphenylene ether and an epoxy resin, and a ring-opening reaction of an oxazine ring of a benzoxazine resin, and the reaction product will retain a hydroxyl group or form a new hydroxyl group, which will affect A decrease in the dielectric constant of the cured product.
  • polyphenylene ether resin is added to the resin system, and its adhesion to metal is low, which brings a high probability of failure to 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: (A) an allyl-modified benzoxazine resin, 40 to 80 parts by weight;
  • 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) allyl-modified polyphenylene ether 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. Parts, 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 that of the allyl-modified polyphenylene ether resin, and the allyl-modified benzoxazine resin of the present invention is mainly used to provide excellent heat resistance to the system. as well as Excellent electrical properties, combined with allyl modified polyphenylene ether resin with excellent electrical properties, during the curing process of the system, allyl modified benzoxazine resin and allyl modified polyphenylene ether resin are produced by thermal cracking. The free radical undergoes radical polymerization, and no polar groups are generated during the reaction, and the cured product maintains the excellent electrical properties of the raw material to the utmost extent.
  • 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 Mixture of a azine resin and an allyl modified bisphenol S type benzoxazine resin, a diamine type benzoxazine resin, an allyl modified bisphenol A type benzoxazine resin and an allyl modified double Mixture of phenolic F type benzoxazine resin, allyl modified dicyclopentadiene phenol type benzoxazine resin, allyl modified bisphenol S type benzoxazine resin and diamine type benzoxazine a mixture of resins.
  • 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.
  • 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 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 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- 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 wt% or less, for example 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt 0/0, 0.05 Weight 0 / 0 , 0.06 weight 0 / 0 , 0.07 weight 0 / 0 or 0.08 weight 0 / 0 .
  • An exemplary halogen-free resin composition based on parts by weight of the organic solids, comprising:
  • (C) initiator 0.01 to 3 parts by weight;
  • (D) filler 1 to 100 parts by weight;
  • An exemplary halogen-free resin composition based on parts by weight of the organic solids, comprising:
  • the content of the allyl-modified benzoxazine resin is greater than that of the allyl-modified polyphenylene ether resin containing an exemplary halogen-free resin composition, based on the weight of the organic solid, 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.
  • a second object of the present invention is to provide a resin glue which is a halogen-free resin group as described above.
  • the compound is dissolved or dispersed 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 halogen-free resin composition glue is conventionally prepared by first placing the solid matter in the above components in a suitable container, then adding a solvent, stirring until completely dissolved, then adding a suitable filler, and finally adding a liquid resin. With the initiator, continue to stir evenly.
  • 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 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 is required to meet the following requirements: 1.
  • the heating rate of lamination is usually controlled at 1.0 ⁇ 3.0 °C/min when the 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 control material is 220 ° C, and the temperature is kept for 120 minutes; the covered metal foil 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 is matched with a modified polyphenylene ether resin excellent in electrical properties, and is a benzoic acid in the curing process of the system.
  • the pyrimidine resin and the polyphenylene ether resin undergo radical polymerization by radicals generated by thermal cracking, and no polar groups are generated during the reaction, and the cured product maintains the excellent electrical properties of the raw materials to the utmost.
  • the bonding sheet prepared by using the halogen-free resin composition of the invention has a lower dielectric constant and dielectric loss tangent, a higher peel strength, a higher glass transition temperature, and an excellent heat resistance, preferably. Flame-retardant effect; copper-clad laminate made of the bonding sheet has low dielectric constant and dielectric loss tangent, high peel strength, high glass transition temperature, and excellent resistance Heat, excellent flame retardant effect. Concrete J ⁇ r
  • the formulation of the composition of the examples is shown in Table i.
  • 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.
  • halogen-free resin composition The specific components of the halogen-free resin composition are as follows:
  • the table is based on the weight of solid components.
  • Halogen contains C1 0.04 0.05 0.04 0.05 0.005
  • TMA Z-axis CTE 2.0 3.5 3.0 2.8 3.5
  • the comparative example used a vinyl modified polyphenylene ether resin, which greatly increased the vinyl modified polyphenylene due to the strong conjugation effect of the double bond of the vinyl group and the benzene ring.
  • the difficulty of radical polymerization of vinyl double bonds in ether resin leads to the fact that some polyphenylene ether resins cannot participate in free radical polymerization during the curing process of the system. They exist as additive resins in the curing system, and phase separation exists in the cured product. In the end, the adhesion of the curing system will be seriously affected, and at the same time, the dielectric loss and dielectric constant of the cured product will be negatively affected.
  • the double bond in the allyl group has a methylene group in the middle of the benzene ring, it greatly reduces the conjugation effect, and greatly reduces the double bond for free radicals. Difficulty in polymerization, the curing system is more likely to form a uniform single-phase system, which has a positive effect on the adhesion of the cured product, the dielectric loss, and the decrease in the dielectric constant.
  • Example 2 compared with Comparative Example 3, the comparative example used a vinyl modified benzoxazine resin, B
  • the double bond in the alkenyl group has a strong conjugation effect with the double bond of the benzene ring in the benzoxazine resin, which improves the stability of the double bond.
  • some vinyl modified benzoxazine is present.
  • the vinyl group in the resin cannot participate in the radical polymerization. Under the action of heat, ring-opening polymerization of the oxazine ring will occur, and the solidified product will undergo phase separation, which can improve the adhesion of the cured product, but will significantly increase the solidification product. Electrical loss and dielectric constant.
  • 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 stability, 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 has excellent synergistic properties with an allyl-modified benzoxazine resin, an allyl-modified polyphenylene ether resin, an initiator, and other components.
  • the halogen content is below 0.09%, thereby achieving environmental standards.
  • the bonding sheet made of the halogen-free 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 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.
  • 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.

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 allyl modified polyphenylene ether 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, a high glass transition temperature, good thermal resistance, and excellent 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。 CN 100547033C公开了使用低分子聚苯醚树脂为主体树脂， 异氰尿酸三烯 酯为交联固化剂， 得到电性能优异的固化产物， 但是其需使用 8〜20%的溴作为 阻燃剂， 且其固化产物的吸水率较高， 大大的限制了其在印制电路行业的运 用。 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 bonding properties are widely used. However, 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. CN 100547033C discloses the use of a low molecular polyphenylene ether resin as a main resin, and a triallyl isocyanurate as a crosslinking curing agent to obtain a cured product excellent in electrical properties, but it requires 8 to 20% of bromine as a flame retardant. Moreover, the water absorption rate of the cured product is high, which greatly limits its application in the printed circuit industry.
CN 102093666A公开了使用聚苯醚树脂苯并噁嗪树脂、 环氧树脂组合物及 使用该组合物的覆铜板。 其使用的是末端带羟基的聚苯醚与环氧树脂的环氧基 团以及使苯并噁嗪树脂的噁嗪环开环反应， 反应产物将会残留羟基或生成新的 羟基， 将会影响固化产物介电常数的降低。  CN 102093666A discloses the use of a polyphenylene ether resin benzoxazine resin, an epoxy resin composition and a copper clad laminate using the same. It uses an epoxy group of a hydroxyl group-terminated polyphenylene ether and an epoxy resin, and a ring-opening reaction of an oxazine ring of a benzoxazine resin, and the reaction product will retain a hydroxyl group or form a new hydroxyl group, which will affect A decrease in the dielectric constant of the cured product.
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。  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. In addition, although the patent 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 improves the peel strength.
一般情况下树脂体系中添加了聚苯醚树脂， 其与金属的粘合力较低， 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。  In general, polyphenylene ether resin is added to the resin system, and its adhesion to metal is low, which brings a high probability of failure to 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。  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 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.
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) 烯丙基改性苯并噁嗪树脂， 40〜80重量份； A halogen-free resin composition, based on parts by weight of an organic solid, comprising: (A) an allyl-modified benzoxazine resin, 40 to 80 parts by weight;
(B ) 烯丙基改性聚苯醚树脂， 20〜60重量份；  (B) allyl modified polyphenylene ether 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.
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)烯丙基改性聚苯醚树脂的含量例如为 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) allyl-modified polyphenylene ether 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. Parts, 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) an allyl-modified benzoxazine resin, 40 to 80 parts by weight;
(B ) 烯丙基改性聚苯醚树脂， 20〜60重量份；  (B) allyl modified polyphenylene ether 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;
其中， 烯丙基改性苯并噁嗪树脂的含量大于烯丙基改性聚苯醚树脂的含 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， 在体系固化过程中 烯丙基改性苯并噁嗪树脂与烯丙基改性聚苯醚树脂通过热裂解产生的自由基进 行自由基聚合反应， 反应过程中无极性基团产生， 固化产物最大限度的保持了 原材料优异的电性能。 Wherein, the content of the allyl-modified benzoxazine resin is greater than that of the allyl-modified polyphenylene ether resin, and the allyl-modified benzoxazine resin of the present invention is mainly used to provide excellent heat resistance to the system. as well as Excellent electrical properties, combined with allyl modified polyphenylene ether resin with excellent electrical properties, during the curing process of the system, allyl modified benzoxazine resin and allyl modified polyphenylene ether resin are produced by thermal cracking. The free radical undergoes radical polymerization, and no polar groups are generated during the reaction, and the cured product maintains the excellent electrical properties of the raw material to the utmost extent.
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) 烯丙基改性聚苯醚树脂， 40〜50重量份；  (B) allyl modified polyphenylene ether 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 Mixture of a azine resin and an allyl modified bisphenol S type benzoxazine resin, a diamine type benzoxazine resin, an allyl modified bisphenol A type benzoxazine resin and an allyl modified double Mixture of phenolic F type benzoxazine resin, allyl modified dicyclopentadiene phenol type benzoxazine resin, allyl modified bisphenol S type benzoxazine resin and diamine type benzoxazine a mixture of resins.
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。 Preferably, based on the technical solution provided by the present invention, 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. 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。 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 selected from any one of silicon dioxide, titanium dioxide, barium titanate, barium titanate, boron nitride, aluminum nitride, silicon carbide or aluminum oxide. Or 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. 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
1〜15μηι， 例如 2μηι、 3μηι、 4μηι、 5μηι、 6μηι、 7μηι、 8μηι、 9μηι、 10μηι、 11μιη、 12μιη、 13μιη或 14μιη， 优选 1〜10μιη， 进一步优选 1〜5μιη。 位于该粒径 段的填料在树脂胶液中具有良好的分散性。 1~15μηι, such as 2μηι, 3μηι, 4μηι, 5μηι, 6μηι, 7μηι, 8μηι, 9μηι, 10μηι, 11μηη, 12μηη, 13μηη or 14μηη, preferably 1~10μηη, further preferably 1~5μιη. 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- Any one or a mixture of at least two of dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or polyphenoxyphosphazene and a derivative thereof.
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 /0、 0.05重量0 /0、 0.06重量0 /0、 0.07重量0 /0或 0.08重量0 /0。 Preferably, on the basis of the technical solution provided by the present invention, the halogen content of the halogen-free resin composition is 0.09 wt% or less, for example 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt 0/0, 0.05 Weight 0 / 0 , 0.06 weight 0 / 0 , 0.07 weight 0 / 0 or 0.08 weight 0 / 0 .
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:
(Α) 烯丙基改性苯并噁嗪树脂， 40〜80重量份；  (Α) allyl modified benzoxazine resin, 40 to 80 parts by weight;
(Β ) 烯丙基改性聚苯醚树脂， 20〜60重量份；  (Β) allyl modified polyphenylene ether resin, 20 to 60 parts by weight;
(C) 引发剂， 0.01〜3重量份； (D) 填料， 1〜100重量份; (C) initiator, 0.01 to 3 parts by weight; (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.
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) an allyl-modified benzoxazine resin, 40 to 80 parts by weight;
(B) 烯丙基改性聚苯醚树脂， 20〜60重量份；  (B) allyl modified polyphenylene ether 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;
(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烯丙基改性聚苯醚树脂的含 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：  Wherein the content of the allyl-modified benzoxazine resin is greater than that of the allyl-modified polyphenylene ether resin containing an exemplary halogen-free resin composition, based on the weight of the organic solid, comprising:
(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) 烯丙基改性聚苯醚树脂， 40〜50重量份；  (B) allyl modified polyphenylene ether 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;
(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.
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"。  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 to this, 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。 A second object of the present invention is to provide a resin glue which is a halogen-free resin group as described above. The compound is dissolved or dispersed 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。  An exemplary halogen-free resin composition glue is conventionally prepared by first placing the solid matter in the above components in a suitable container, then adding a solvent, stirring until completely dissolved, then adding a suitable filler, and finally adding a liquid resin. With the 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%.
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。  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.
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。  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.
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， 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 （35μιη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。 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 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 is required to meet the following requirements: 1. The heating rate of lamination is usually controlled at 1.0~3.0 °C/min when the 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 control material is 220 ° C, and the temperature is kept for 120 minutes; the covered metal foil 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， 配合电性能优异的改性聚苯醚树脂， 在体系固化过程中苯并噁 嗪树脂与聚苯醚树脂通过热裂解产生的自由基进行自由基聚合反应， 反应过程 中无极性基团产生， 固化产物最大限度的保持了原材料优异的电性能。 使用本 发明无卤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、 优异的阻燃效果。 具体实 J ^r式  The invention mainly comprises an allyl-modified benzoxazine resin, provides excellent heat resistance and excellent electrical properties for the system, and is matched with a modified polyphenylene ether resin excellent in electrical properties, and is a benzoic acid in the curing process of the system. The pyrimidine resin and the polyphenylene ether resin undergo radical polymerization by radicals generated by thermal cracking, and no polar groups are generated during the reaction, and the cured product maintains the excellent electrical properties of the raw materials to the utmost. The bonding sheet prepared by using the halogen-free resin composition of the invention has a lower dielectric constant and dielectric loss tangent, a higher peel strength, a higher glass transition temperature, and an excellent heat resistance, preferably. Flame-retardant effect; copper-clad laminate made of the bonding sheet has low dielectric constant and dielectric loss tangent, high peel strength, high glass transition temperature, and excellent resistance Heat, excellent flame retardant effect. Concrete J ^r
下面通过具体实施方式来进一步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 i。 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。  The formulation of the composition of the examples is shown in Table i. 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.
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 A-2烯丙基改性双环戊二烯酚型苯并噁嗪树脂 A-1 allyl modified bisphenol A benzoxazine 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) 烯丙基改性聚苯醚树脂 （商品型号 PP501 , 台湾晋一）  (B) Allyl modified polyphenylene ether resin (product model PP501, Jinyi, Taiwan)
(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) 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 ) (E) Flame Retardant: Polyphenoxyphosphazene compound, SPB-100 (Japan Otsuka Chemical Co., Ltd.)
表 1.各实施例和比较例的配方组成  Table 1. Formulation composition of each of the examples and comparative examples
Figure imgf000011_0001
Figure imgf000011_0001
注： 1、 表中皆以固体组分重量份计。 Note: 1. The table is based on the weight of solid components.
表 2.各实施例的物性数据 实施例  Table 2. Physical property data of each embodiment
1 2 3 4 5 玻璃化转变温度  1 2 3 4 5 Glass transition temperature
160 175 165 175 145  160 175 165 175 145
Tg (DSC, V ) 剥离强度  Tg (DSC, V ) peel strength
1.0 1.4 1.2 1.3 1.1  1.0 1.4 1.2 1.3 1.1
PS (N/mm)  PS (N/mm)
燃烧性 （UL94) V-0 V-0 V-0 V-0 V-0 热分层时间 T-288 Flammability (UL94) V-0 V-0 V-0 V-0 V-0 Thermal stratification time T-288
〉45 >60 >45 >60 >30 〉45 >60 >45 >60 >30
(分钟） 热膨胀系数 (minutes) thermal expansion coefficient
Ζ轴 CTE (ΤΜΑ) 2.6 2.1 2.5 2.2 3.0 ( 30-260 °C ) % 热分解温度 Td  Ζ Axis CTE (ΤΜΑ) 2.6 2.1 2.5 2.2 3.0 ( 30-260 °C ) % Thermal decomposition temperature Td
375 400 385 395 370 (TGA， °C )  375 400 385 395 370 (TGA, °C)
吸水性 （％) 0.10 0.08 0.10 0.08 0.10 介质损耗角正切  Water absorption (%) 0.10 0.08 0.10 0.08 0.10 Dielectric loss tangent
0.0026 0.0043 0.0036 0.0040 0.0040 Df ( (1GHZ)) 介电常数 Dk  0.0026 0.0043 0.0036 0.0040 0.0040 Df ( (1GHZ)) Dielectric constant Dk
3.68 3.96 3.71 3.86 3.75 (1GHZ)  3.68 3.96 3.71 3.86 3.75 (1GHZ)
卤素含 C1 0.04 0.05 0.04 0.05 0.005 量测试  Halogen contains C1 0.04 0.05 0.04 0.05 0.005
Br 0 0 0 0 0 (%)  Br 0 0 0 0 0 (%)
表 3各对比例的物性数据 比较例  Table 3 Physical properties of each comparative example Comparative example
1 2 3 4 5 玻璃化转变温度  1 2 3 4 5 Glass transition temperature
175 160 170 165 165 175 160 170 165 165
Tg (DSC, °C ) 剥离强度 Tg (DSC, °C) peel strength
1.4 0.6 0.9 1.0 0.7 PS (N/mm)  1.4 0.6 0.9 1.0 0.7 PS (N/mm)
燃烧性 （UL94) V-0 V-0 V-0 V-0 V-0 热分层时间 T-288 Flammability (UL94) V-0 V-0 V-0 V-0 V-0 Thermal stratification time T-288
>60 >20 >15 >30 >45 >60 >20 >15 >30 >45
(分钟） 热膨胀系数 (minute) Thermal expansion coefficient
Z轴 CTE (TMA) 2.0 3.5 3.0 2.8 3.5  Z-axis CTE (TMA) 2.0 3.5 3.0 2.8 3.5
(30-260°C ) % 热分解温度 Td  (30-260 ° C) % thermal decomposition temperature Td
410 385 395 385 370  410 385 395 385 370
(TGA， °C )  (TGA, °C)
吸水性 （％) 0.06 0.12 0.08 0.10 0.08 介质损耗角正切 Df  Water absorption (%) 0.06 0.12 0.08 0.10 0.08 Dielectric loss tangent Df
0.0100 0.0025 0.0068 0.0061 0.0020  0.0100 0.0025 0.0068 0.0061 0.0020
( (1GHZ)) 介电常数 Dk  ( (1GHZ)) Dielectric constant Dk
4.6 3.56 4.12 4.02 3.69  4.6 3.56 4.12 4.02 3.69
(1GHZ)  (1GHZ)
卤素含量 C1 0.004 0.05 0.05 0.05 0.05  Halogen content C1 0.004 0.05 0.05 0.05
测试 (％) Br 0 0 0 0 0  Test (%) Br 0 0 0 0 0
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， 与比较例相比在保证体系电性能较低的情况下显 著提升体系的剥离强度。  From the physical property data of Table 2, it is understood that the copper-clad laminate produced in Examples 1-4 has excellent dielectric properties and a high glass transition temperature, and the system has lower electrical properties than the comparative example. Significantly improve the peel strength of the system.
实施例 1与比较例 4相比， 比较例使用的是乙烯基改性聚苯醚树脂， 由于 乙烯基的双键与苯环产生较强的共轭效应， 大大增加了乙烯基改性聚苯醚树脂 中乙烯基双键进行自由基聚合的难度， 导致体系固化过程中， 将出现部分聚苯 醚树脂不能参加自由基聚合， 其在固化体系中以添加型树脂存在， 固化产物中 存在相分离情况， 最终将严重影响固化体系的粘合性， 同时对固化产物的介电 损耗和介电常数产生负面影响。 烯丙基改性聚苯醚树脂中， 由于烯丙基中的双 键与苯环中间多了一个亚甲基， 其在很大程度上降低其共轭效应， 大大降低了 双键进行自由基聚合的难度， 固化体系更容易形成均一的单相体系， 对固化产 物的粘合性的提高、 介电损耗以及介电常数的降低有正面效果。  Compared with Comparative Example 4, the comparative example used a vinyl modified polyphenylene ether resin, which greatly increased the vinyl modified polyphenylene due to the strong conjugation effect of the double bond of the vinyl group and the benzene ring. The difficulty of radical polymerization of vinyl double bonds in ether resin leads to the fact that some polyphenylene ether resins cannot participate in free radical polymerization during the curing process of the system. They exist as additive resins in the curing system, and phase separation exists in the cured product. In the end, the adhesion of the curing system will be seriously affected, and at the same time, the dielectric loss and dielectric constant of the cured product will be negatively affected. In the allyl-modified polyphenylene ether resin, since the double bond in the allyl group has a methylene group in the middle of the benzene ring, it greatly reduces the conjugation effect, and greatly reduces the double bond for free radicals. Difficulty in polymerization, the curing system is more likely to form a uniform single-phase system, which has a positive effect on the adhesion of the cured product, the dielectric loss, and the decrease in the dielectric constant.
实施例 2与比较例 3相比， 比较例使用的是乙烯基改性苯并噁嗪树脂， 乙 烯基中的双键与苯并噁嗪树脂中苯环的双键存在较强的共轭效应， 提高了双键 的稳定性， 在热固化反应中， 有部分乙烯基改性苯并噁嗪树脂中的乙烯基不能 参与自由基聚合， 在热的作用下将发生噁嗪环开环聚合， 固化产物将发生相分 离， 虽可以提升固化产物的粘合性， 但是会显著增加固化产物的介电损耗和介 电常数。 Example 2 compared with Comparative Example 3, the comparative example used a vinyl modified benzoxazine resin, B The double bond in the alkenyl group has a strong conjugation effect with the double bond of the benzene ring in the benzoxazine resin, which improves the stability of the double bond. In the heat curing reaction, some vinyl modified benzoxazine is present. The vinyl group in the resin cannot participate in the radical polymerization. Under the action of heat, ring-opening polymerization of the oxazine ring will occur, and the solidified product will undergo phase separation, which can improve the adhesion of the cured product, but will significantly increase the solidification product. Electrical loss and dielectric constant.
比较例 5中， 由于烯丙基改性聚苯醚的添加量较高， 固化产物的粘合力有 较显著降低， 同时其介电损耗和介电常数也有一定降低， 在 PCB的常规运用领 域中， 较低的粘合力将导致 PCB失效的风险显著提高。  In Comparative Example 5, since the addition amount of the allyl-modified polyphenylene ether is high, the adhesive strength of the cured product is remarkably lowered, and the dielectric loss and dielectric constant are also lowered, which is in the conventional application field of the PCB. Medium, lower adhesion will result in a significant increase in the risk of PCB failure.
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 stability, 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烯丙基改性苯并噁嗪树脂、 烯 丙基改性聚苯醚树脂、 引发剂以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。  In summary, the halogen-free resin composition of the present invention has excellent synergistic properties with an allyl-modified benzoxazine resin, an allyl-modified polyphenylene ether resin, an initiator, and other components. In addition to the flame retardant using phosphorus, the halogen content is below 0.09%, thereby achieving environmental standards. Further, the bonding sheet made of the halogen-free resin composition has excellent electrical properties, high glass transition temperature, excellent heat resistance, good flame retardancy and low water absorption.
以上特性的测试方法如下：  The test methods for the above characteristics are as follows:
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。  Glass transition temperature (Tg): Measured according to differential scanning calorimetry (DSC) according to the DSC method specified in IPC-TM-650 2.4.25.
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。  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.
燃烧性： 依据 UL 94垂直燃烧法测定。  Flammability: Measured according to UL 94 vertical combustion method.
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。 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.
吸水性： 按照 IPC-TM-650 2.6.2.1方法进行测定。  Water absorption: The measurement was carried out in accordance with the method of IPC-TM-650 2.6.2.1.
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。  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) 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.
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。  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 rely on the detailed methods described above. 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, addition of auxiliary components, selection of specific means, and the like, are all within the scope of protection and disclosure 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 ) 烯丙基改性聚苯醚树脂， 20~60重量份； (B) Allyl modified polyphenylene ether 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 ) 烯丙基改性聚苯醚树脂， 20〜60重量份； (B) Allyl modified polyphenylene ether 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烯丙基改性聚苯醚树脂的含 Among them, the content of allyl-modified benzoxazine resin is greater than that of allyl-modified polyphenylene ether resin.
3、 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： 3. 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 ) 烯丙基改性聚苯醚树脂， 40 50重量份； (B) Allyl modified polyphenylene ether resin, 40-50 parts by weight;
(C ) 引发剂， 0.01〜3重量份。 (C) Initiator, 0.01~3 parts by weight.
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； 4. The halogen-free resin composition according to claim 1, wherein the allyl-modified benzoxazine resin is selected from the group consisting of allyl-modified bisphenol A-type benzoxazines. Resin, allyl-modified bisphenol F-type benzoxazine resin, allyl-modified dicyclopentadienol-type benzoxazine resin, allyl-modified bisphenol S-type benzoxazine resin or dicyclopentadienyl-type benzoxazine resin Any one or a mixture of at least two amine benzoxazine resins;
优选地， 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； Preferably, the allyl modified polyphenylene ether resin is an allyl resin with a number average molecular weight below 5000. Modified polyphenylene ether resin;
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。 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.
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 （D) 填料； 5. 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； Preferably, the content of the filler is 1 to 100 parts by weight, preferably 10 to 100 parts by weight;
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 filler is selected from any one or a mixture of at least two of silica, titanium dioxide, strontium titanate, barium titanate, boron nitride, aluminum nitride, silicon carbide or aluminum oxide, preferably in crystalline form Any one or a mixture of at least two of silica, amorphous silica, spherical silica, titanium dioxide, strontium titanate, barium titanate, boron nitride, 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 1〜15μιη， 优选 1〜10μιη， 进一步优选 1〜5μηι。 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.
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 （Ε) 含磷阻燃剂； 6. The halogen-free resin composition according to claim 1, wherein 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-dihydroxyphenyl)-9,10-dihydro-9-oxa- 10-Phosphophenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl- 9 , 10 -dihydro-9-oxa- 10 -phosphine Any one or a mixture of at least two of phenanthrene- 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 liquid, characterized in that it is a halogen-free tree as described in one of claims 1-6. The lipid composition is dissolved or dispersed 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/CN2014/073842 2014-02-14 2014-03-21 Halogen-free resin composition and use for same WO2015120652A1 (en)

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