WO2017152602A1 - 一种无卤热固性树脂组合物及使用它的预浸料和印制电路用层压板 - Google Patents

一种无卤热固性树脂组合物及使用它的预浸料和印制电路用层压板 Download PDF

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WO2017152602A1
WO2017152602A1 PCT/CN2016/098450 CN2016098450W WO2017152602A1 WO 2017152602 A1 WO2017152602 A1 WO 2017152602A1 CN 2016098450 W CN2016098450 W CN 2016098450W WO 2017152602 A1 WO2017152602 A1 WO 2017152602A1
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parts
halogen
weight
substituted
group
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PCT/CN2016/098450
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French (fr)
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罗成
唐国坊
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广东生益科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/098—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5398—Phosphorus bound to sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
    • 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
    • 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
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0271—Epoxy resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0285—Condensation resins of aldehydes, e.g. with phenols, ureas, melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
    • 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
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    • 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
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    • 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
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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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

Definitions

  • the present invention relates to a halogen-free thermosetting resin composition, and to a prepreg made of the halogen-free thermosetting resin composition and a laminate for a printed circuit.
  • the application frequency is constantly increasing.
  • the dielectric constant and dielectric loss values are required to be lower and lower, thus reducing Dk/Df. Has become a hot spot for the substrate industry.
  • the copper clad substrate material in order to meet the processing performance of the PCB and the performance requirements of the terminal electronic product, it is necessary to have good dielectric properties, heat resistance and mechanical properties, and also have good processing characteristics, high Peel strength, excellent heat and humidity resistance and UL94 V-0 halogen free flame retardant rating.
  • CN101796132A discloses a copper clad laminate obtained by blending cyanate ester, epoxy resin, polyphenylene ether resin and bromine-containing flame retardant to obtain heat resistance, good dielectric property and low CTE, but it is bromine-containing flame retardant;
  • patent CN103694642A discloses the use of epoxy resins, cyanate ester compounds or/and cyanate ester prepolymers, polyphosphonates or/and phosphonate-carbonate copolymers to prepare dielectric properties and good heat and humidity resistance.
  • Halogen UL94V-0 is flame retardant, but its peel strength, interlayer adhesion and bending strength are low.
  • the combination of cyanate ester, polyphenylene ether and phosphorus-containing bisphenol polymer as curing agent for epoxy resin can reflect their respective advantages and the synergistic effect of mutual catalysis.
  • Cyanate ester can bring high heat resistance and low dielectric loss value of the system; polyphenylene ether can make the system have excellent dielectric properties;
  • the phosphorus-containing bisphenol polymer reactive group includes both hydroxyl groups and phosphonate units.
  • the reaction of the phosphonate unit with the epoxy does not produce a secondary hydroxyl group, and the cured product has a high glass transition temperature and is excellent in dielectric properties and heat resistance.
  • the combination of these three epoxy curing agents also gives the system excellent peel strength.
  • the cyanate ester can be used as a catalyst for reacting polyphenylene ether and bisphenol polyphosphoric acid with an epoxy resin.
  • the phenolic hydroxyl group of polyphenylene ether and bisphenol polyphosphoric acid has low reactivity, and the epoxy resin can react at a very high temperature, and the -OCN group of the cyanate ester is easily combined with the above two at 90-120 ° C.
  • the low-activity hydroxyl group reacts and then decomposes above 130 ° C, and phenol oxygen anion is generated during the decomposition process.
  • the phenolic anion is easily reacted with the epoxy resin to lower the curing temperature of the system.
  • the phenolic hydroxyl groups in polyphenylene ether and bisphenol polyphosphoric acid can promote the solidification of cyanate ester, lower the curing temperature of cyanate ester, and cure cyanate ester to form triazine ring with high crosslink density and high symmetry.
  • the system has a high glass transition temperature and good dielectric properties.
  • the phosphorus-containing bisphenol polymer has more flexible chain ester chains, which can greatly improve the toughness of the system, and is embodied in the peeling strength.
  • one of the objects of the present invention is to provide a halogen-free thermosetting resin composition, and a prepreg and a laminate for printed circuit board using the same.
  • the printed circuit board laminate produced by using the resin composition has high glass transition temperature, excellent dielectric properties, high heat resistance, excellent peel strength and good processability, and can realize halogen-free flame retardant. , reached UL94 V-0.
  • the present inventors conducted intensive studies to achieve the above object, and as a result, found that a halogen-free epoxy resin, a cyanate resin, a polyphenylene ether resin, a phosphorus-containing bisphenol polymer, and optionally other substances are appropriately mixed.
  • the composition can achieve the above purpose.
  • thermosetting resin composition containing the following four substances as essential components, and the organic solid matter is 100 parts by weight, which comprises:
  • the halogen-free thermosetting resin composition of the present invention is a curing agent for an epoxy resin together with a cyanate ester, a polyphenylene ether or a phosphorus-containing bisphenol polymer.
  • the cyanate resin can make the co-curing system have high heat resistance and low dielectric loss value;
  • the polyphenylene ether resin can make the co-curing system have excellent dielectric properties and low water absorption;
  • the structure is highly symmetrical, and the phosphonate unit in the molecule can react with the secondary hydroxyl group of the epoxy resin, which can eliminate the disadvantage of poor dielectric properties caused by the polar secondary hydroxyl groups in the system, and the dielectric properties.
  • the cured product has a high Tg; in addition, the phosphorus-containing bisphenol polymer has a high phosphorus content and has a halogen-free flame retardant effect, and can achieve UL94 V-0 flame retardant with little or no additional flame retardant.
  • the invention utilizes synergy between cyanate ester, polyphenylene ether and phosphorus-containing bisphenol polymer The effect can significantly improve the glass transition temperature and heat resistance of the prepreg prepared by using the resin composition and the laminate for printed circuit, and has excellent dielectric properties, low water absorption, high peel strength, Good heat and humidity resistance and good processability, and achieve halogen-free flame retardant, reaching UL94 V-0.
  • the curing reaction rate of the cyanate ester, the phosphorus-containing bisphenol polymer and the epoxy resin is fast, and the curing reaction rate of the polyphenylene ether resin and the epoxy resin is slow, and the cyanate ester, the polyphenylene ether and the phosphorus-containing double are simultaneously used.
  • the phenolic polymer composite curing epoxy resin makes the curing reaction rate moderate and easy to control, greatly reducing the difficulty of production and processing.
  • the component (A) in the present invention that is, a cyanate resin, is used in an amount of 5 to 50 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. Parts, 35 parts by weight, 40 parts by weight, 45 parts by weight or 50 parts by weight.
  • the component (A) of the present invention, the cyanate resin has the following structure:
  • R 1 is -CH 2 -, Any one or a mixture of at least two;
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are each independently selected from a hydrogen atom, C1-C4 (for example, C1).
  • the component (A) is 2,2-bis(4-cyanooxyphenyl)propane, bis(4-cyanooxyphenyl)ethane, bis(3,5-dimethyl- 4-cyanooxyphenyl)methane, 2,2-bis(4-cyanooxyphenyl)-1,1,1,3,3,3- Hexafluoropropane, ⁇ , ⁇ '-bis(4-cyanooxyphenyl)-m-isopropylidenebenzene, cyclopentadiene-type cyanate, phenol novolac cyanate, cresol novolac cyanate , 2,2-bis(4-cyanooxyphenyl)propane prepolymer, bis(4-cyanooxyphenyl)ethane prepolymer, bis(3,5-dimethyl-4-cyanate) Phenyl)methane prepolymer, 2,2-bis(4-cyanooxyphenyl)-1,1,1,3,3,3-hexafluoropropane prepolymer, 2,
  • the component (B) in the present invention that is, a polyphenylene ether resin, is used in an amount of 5 to 40 parts by weight, for example, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight. Parts, 18 parts by weight, 20 parts by weight, 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 or 40 parts by weight.
  • the component (B), the polyphenylene ether resin has the following structure:
  • R 11 is any one of H, a substituted or unsubstituted linear alkyl group or a branched alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted phenyl group.
  • R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 are the same or different and are selected from H, F, substituted or unsubstituted straight chain having 1 to 4 carbon atoms. Any of an alkyl or branched alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted cyclohexyl group or an allyl group.
  • n 1 , n 2 , n 3 , and n 4 are each independently a positive integer of 0 to 40, and satisfy 8 ⁇ n 1 + n 2 + n 3 + n 4 ⁇ 40.
  • the component (C) of the present invention is a phosphorus-containing bisphenol polymer and is used in an amount of 5 to 30 parts by weight, for example, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 13 parts by weight, 14 Parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 28 parts by weight or 30 parts by weight .
  • the component (C), the phosphorus-containing bisphenol polymer has the following structure:
  • R 20 and R 21 are the same or different and are selected from the group consisting of Any one or a mixture of at least two.
  • R 11 is any one of H, a substituted or unsubstituted linear alkyl group or a branched alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted phenyl group.
  • R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 23 , R 24 are the same or different and are selected from H, F and have 1 to 4 carbon atoms (for example) a substituted or unsubstituted linear alkyl or branched alkyl group having 1 to 2, 3 or 4), a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted ring Any of the hexyl groups.
  • R 22 is a substituted or unsubstituted linear alkyl group of C1 to C20 (for example, C1, C2, C3, C4, C6, C8, C10, C12, C15, C18 or C20), and C1 to C20 (for example, C1).
  • n 2 is an arbitrary integer of 3 to 75, for example, 3, 4, 6, 8, 9, 10, 11, 13, 15, 17, 18, 19 , 20, 23, 26 , 28 , 30, 40, 45 , 50, 55, 67, 68, 70 or 75.
  • n 2 is any integer from 4 to 60; preferably n 2 is any integer from 5 to 50; preferably n 2 is any integer from 5 to 40; preferably n 2 is any integer from 8 to 30; preferably The ground n 2 is an arbitrary integer of 10 to 25.
  • n 3 and n 4 are the same or different and are integers of 0 to 4.
  • the component (D) of the present invention is a halogen-free epoxy resin, and is used in an amount of 30 to 60 parts by weight, for example, 30 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, and 45 parts by weight. Parts, 48 parts by weight, 50 parts by weight, 52 parts by weight, 54 parts by weight, 56 parts by weight, 58 parts by weight or 60 parts by weight.
  • the component (D) halogen-free epoxy resin means an epoxy resin having two or more epoxy groups in one molecule, and is selected from the group consisting of glycidyl ethers, glycidyl esters, and glycidylamines. Any one or a mixture of at least two of a alicyclic epoxy resin, an epoxidized olefin, a hyacinol epoxy resin or an imide epoxy resin.
  • the glycidyl ethers include bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, and trisphenol novolac epoxy resin.
  • Dicyclopentane Any one or a mixture of at least two of a diene novolac epoxy resin, a biphenyl type novolac epoxy resin, an alkylbenzene type novolac epoxy resin or a naphthol type novolac epoxy resin.
  • the above epoxy resins are all halogen-free epoxy resins.
  • the glycidyl ether is selected from the group consisting of epoxy resins having the following structure:
  • Z 1 , Z 2 and Z 3 are each independently selected from R 25 is a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group.
  • Y 1 and Y 2 are each independently selected from a single bond, -CH 2 -, And n 3 is an arbitrary integer of 1 to 10, for example, 2, 3, 4, 5, 6, 7, 8, or 9, and R 26 is selected from a hydrogen atom, a substituted or unsubstituted carbon number of 1 to Any of a linear alkyl group or a branched alkyl group of 5.
  • the glycidylamine is selected from the group consisting of triglycidyl-p-aminophenol, triglycidyl trimer isocyanate, tetraglycidyldiaminodimethylenebenzene, tetraglycidyl-4,4' -diaminodiphenylmethane, tetraglycidyl-3,4'-diaminodiphenyl ether, tetraglycidyl-4,4'-diaminodiphenyl ether or tetraglycidyl-1,3 Any one or a mixture of at least two of diaminomethylcyclohexane.
  • the halogen-free thermosetting resin composition of the present invention employs the halogen-free epoxy resin having the specific molecular structure described above, which has high functionality and good dielectric properties, and has a high Tg of cured product and low water absorption.
  • the halogen-free thermosetting resin composition of the present invention may further comprise component (E), that is, a phosphorus-containing flame retardant, with component (A), component (B), component (C), component (D)
  • component (E) phosphorus-containing flame retardant is added in an amount of from 0 to 5 parts by weight based on 100 parts by weight.
  • the phosphorus-containing flame retardant is tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa- 10-phosphinophen-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 a phenanthrene-10-oxide, a phenoxyphosphazene compound, a phosphate or a polyphosphate.
  • the halogen-free thermosetting resin composition of the present invention may further comprise component (F), that is, a curing accelerator.
  • the curing accelerator comprises an organic metal salt and any one or at least two selected from the group consisting of an imidazole compound, a derivative of an imidazole compound, a piperidine compound, a pyridine, a Lewis acid or a triphenylphosphine. mixture.
  • the organometallic salt in the curing accelerator comprises any one of a metal octoate, a metal isooctanoate, a metal acetylacetonate, a metal naphthenate, a metal salicylate or a metal stearate. Or a mixture of at least two, wherein the metal is selected from any one of zinc, copper, iron, tin, cobalt or aluminum or a mixture of at least two.
  • the imidazole compound is any one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole or a mixture of at least two .
  • the piperidine compound is 2,3-diaminopiperidine, 2,5-diaminopiperidine, 2,6-diaminopiperidine, 2-amino-3-methylpiperidine, 2- Any one of amino-4-methylpiperidine, 2-amino-3-nitropiperidine, 2-amino-5-nitropiperidine or 2-amino-4,4-dimethylpiperidine or a mixture of at least two.
  • the pyridine compound is any one or a mixture of at least two of 4-dimethylaminopyridine, 2-aminopyridine, 3-aminopyridine or 4-aminopyridine.
  • the total weight of the component (A), the component (B), the component (C) and the component (D) is 100.
  • the component (F) curing accelerator is added in an amount of 0.01 to 1 part by weight, preferably 0.025 to 0.85 part by weight, based on parts by weight.
  • the halogen-free thermosetting resin composition of the present invention may further comprise component (G), that is, a filler.
  • the filler is selected from the group consisting of organic or inorganic fillers, preferably inorganic fillers, further preferably surface treated inorganic fillers, most preferably surface treated silica.
  • the surface treated surface treatment agent is selected from any one or a mixture of at least two of a silane coupling agent, a silicone oligomer or a titanate coupling agent.
  • the surface treatment agent is used in an amount of 0.1 to 5.0 parts by weight, preferably 0.5 to 3.0 parts by weight, more preferably 0.75 to 2.0 parts by weight, based on 100 parts by weight of the inorganic filler.
  • the inorganic filler is selected from any one of a non-metal oxide, a metal nitride, a non-metal nitride, an inorganic hydrate, an inorganic salt, a metal hydrate or an inorganic phosphorus or a mixture of at least two, preferably molten Silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, titanium A mixture of one or at least two of acid strontium, calcium carbonate, calcium silicate or mica.
  • the organic filler is selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide or polyethersulfone powder.
  • the filler has a median particle diameter of from 0.01 to 50 ⁇ m, preferably from 0.01 to 20 ⁇ m, further preferably from 0.1 to 10 ⁇ m.
  • the addition amount of the component (G) filler is 100 parts by weight of the sum of the addition amounts of the component (A), the component (B), the component (C), and the component (D). 5 to 300 parts by weight, preferably 5 to 200 parts by weight, more preferably 5 to 150 parts by weight.
  • the halogen-free thermosetting resin composition may further contain various additives, and specific examples thereof include phosphorus-containing flame retardants, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, and colorants. Or a lubricant, etc. These various additives may be used singly or in combination of two or more kinds.
  • the halogen-free thermosetting resin composition of the present invention is conventionally prepared by first placing a solid substance, then adding a liquid solvent, stirring until the solid substance is completely dissolved, and then adding a liquid resin and a promoter, and continuing to stir uniformly.
  • the solvent in the present invention is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol, and butyl.
  • Ethers such as carbitol, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and ethoxyethyl acetate a nitrogen-containing solvent such as N,N-dimethylformamide or N,N-dimethylacetamide.
  • the above solvents may be used singly or in combination of two or more. Preference is given to ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone and cyclohexanone.
  • the amount of the solvent to be added is selected by those skilled in the art based on his own experience, so that the resin glue can reach a viscosity suitable for use.
  • the prepreg of the present invention comprises a reinforcing material and a halogen-free thermosetting resin composition as described above which is impregnated and adhered to the reinforcing material after drying, and the reinforcing material to be used is not particularly limited and may be an organic fiber, an inorganic fiber woven fabric or Non-woven fabric.
  • the organic fiber may be selected from aramid nonwoven fabric, and the inorganic fiber woven fabric may be E-glass fabric, D-glass fabric, S-glass fabric, T-glass fabric, NE-glass fabric. Or quartz cloth.
  • the thickness of the reinforcing material is not particularly limited, and the thickness of the woven fabric and the nonwoven fabric is preferably 0.01 to 0.2 mm, and preferably the fiber-opening treatment and the silane coupling agent are considered.
  • the surface treatment in order to provide good water resistance and heat resistance, the silane coupling agent is preferably any one or at least two of an epoxy silane coupling agent, an amino silane coupling agent or a vinyl silane coupling agent. kind of mixture.
  • the prepreg is obtained by impregnating the above-mentioned halogen-free thermosetting resin composition by baking at 100 to 250 ° C for 1 to 15 minutes.
  • the laminate for printed circuit of the present invention comprises a laminate prepared by bonding together one or two or more prepregs by heat and pressure, and a metal foil bonded to one or both sides of the laminate. .
  • the laminate is obtained by curing in a hot press at a curing temperature of 150 ° C to 250 ° C and a curing pressure of 10 to 60 kg / cm 2 .
  • the metal foil is copper foil, nickel foil, aluminum foil, SUS foil, etc., and the material thereof is not limited.
  • the present invention has at least the following beneficial effects:
  • the invention adopts cyanate ester, polyphenylene ether and phosphorus-containing bisphenol polymer together as a curing agent for epoxy resin, and can realize respective advantages in the system and has mutual synergistic effect; cyanate ester can bring system High heat resistance and low dielectric loss value; polyphenylene ether can make the system have excellent dielectric properties; phosphorus-containing bisphenol polymer reactive groups include hydroxyl groups and phosphonate units at both ends, and phosphonate units react with epoxy The secondary hydroxyl group is not produced, and the cured product has a high glass transition temperature and is excellent in dielectric properties and heat resistance. The combination of these three epoxy curing agents also gives the system excellent peel strength.
  • the cyanate ester can be used as a catalyst for reacting polyphenylene ether and bisphenol polyphosphoric acid with an epoxy resin.
  • the polyphenol ether and the phosphorus-containing bisphenol polymer have low reactivity with the phenolic hydroxyl group, and the epoxy resin can react at a very high temperature, and the -OCN group of the cyanate ester is easily at 90 to 120 ° C.
  • the low-active hydroxyl groups of the above two react, and then decompose at 130 ° C or higher, and phenol oxygen anions are generated during the decomposition.
  • the phenolic anion is easily reacted with the epoxy resin to lower the curing temperature of the system.
  • the phenolic hydroxyl groups in polyphenylene ether and bisphenol polyphosphoric acid can promote the solidification of cyanate ester, lower the curing temperature of cyanate ester, and cure cyanate ester to form triazine ring with high crosslink density and high symmetry.
  • the system has a high glass transition temperature and good dielectric properties.
  • the phosphorus-containing bisphenol polymer has more flexible chain ester chains, which can greatly improve the toughness of the system, and is embodied in the peeling strength.
  • the phosphorus-containing bisphenol polymer has a high phosphorus content, and has a halogen-free flame retardant effect as a curing agent, and can be added in a small amount or not Adding other flame retardants can achieve a UL94 V-0 halogen-free flame retardant effect.
  • the prepreg and the printed circuit board made of the halogen-free thermosetting resin composition provided by the invention have a glass transition temperature of up to 245 ° C; excellent dielectric properties, and the water absorption rate is controlled in the range of 0.07-0.11%. Internal; high heat resistance; peel strength of 0.9-1.2N/mm; excellent heat and humidity resistance and good processability, and can achieve halogen-free flame retardant, reaching UL94 V-0.
  • the cyanate resin, the polyphenylene ether resin, the phosphorus-containing bisphenol polymer, the halogen-free epoxy resin, the curing accelerator, the halogen-free flame retardant, and the filler are uniformly mixed in a solvent to control the solid content of the glue.
  • the above glue is impregnated with 2116 glass fiber cloth, the appropriate thickness is controlled, and then prepreg is prepared by baking in an oven at 115-175 ° C for 2-15 minutes, and then several prepregs are stacked together.
  • 18 ⁇ RTF copper foil is laminated on both sides, and the copper-clad laminate is prepared under the conditions of curing temperature of 170-250 ° C, curing pressure of 25-60 kg/cm 2 and curing time of 60-300 min.
  • Examples 1-8 and Comparative Examples 1-13 relate to materials and grade information as follows:
  • CE01PS Jiangsu Tianqi, bisphenol A type cyanate resin
  • CE01MO Jiangsu Tianqi, bisphenol A type cyanate resin
  • PPO-1 SA90, Saberky, small molecule difunctional polyphenylene ether, hydroxyl equivalent 850
  • OL-1001 Phosphorus-containing bisphenol polymer, FRX OL1001 (US FRX Polymers trade name, phosphorus content 8.5%)
  • FYROL PMP Suppesta halogen-free phosphorus-containing flame retardant with a phosphorus content of 17.5%
  • HP-7200HHH DIC, DCPD type epoxy resin, epoxy equivalent 288
  • HP-7200H-75M DIC, DCPD type epoxy resin, epoxy equivalent 280
  • HP-9900 DIC, naphthol type epoxy resin, epoxy equivalent 274
  • SPB-100 Otsuka Chemical, phosphazene flame retardant, phosphorus content 13.4%
  • Zinc isooctanoate BICAT Z, The Shepherd Chemical Company
  • Fused silica (average particle size 1 to 10 ⁇ m, purity 99% or more)
  • Tables 1-3 are the formulation compositions of Example 1-8 and Comparative Examples 1-13 and their physical property data.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 CY-40 25 25 PT30S 5 CE01PS 10 35 50 CE01MO 20 30 PPO-1 20 40 30 5 PPO-2 15 PPO-3 10 PPO-4 15 PPO-5 10 OL-1001 15 10 OL-3001 15 15 OL-5000 C1 5 C2 10 C3 30 15 FYROL PMP HP-7200H-M75 40 HP-7200HHH 45 HP-6000 45 40 HP-9900 60 NC-3000H 30 SKE-1 35 SKE-3 45 SPB-100 3 5 2E4MZ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Zinc isooctanoate 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Spherical silicon 25 25 25 25 25 25 25 25 25 150 Tg(DMA)/°C 185 193 198 211 215 220 230 242 Dk (10GHz) 3.8 3.75 3.7 3.7 3.7 3.7 3.9 Df (10GHz) 0.008 0.00
  • T g Glass transition temperature
  • PCT heat and humidity resistance
  • T300 Determined by TMA instrument according to the T300 test method specified in IPC-TM-650 2.4.24.1.
  • Comparative Example 1 in comparison with Example 1, the amount of the cyanate resin in the resin composition was small, the dielectric properties of the obtained copper clad laminate were poor, and the heat resistance was general; Comparative Example 2 Compared with Example 4, the amount of polyphenylene ether in the resin composition was small, resulting in less rigid structure in the system, so that the heat resistance was significantly reduced, specifically as shown in T300 of 5.6 min; Comparative Example 3 and Examples 8 contrast, too little epoxy resin is added, the curing agent is excessive in the system, the amount of epoxy is insufficient, the system can not be cured well, the glass transition temperature is lowered; and PPO and phosphorus-containing bisphenol are firstly cyanic acid in the system.
  • the copper clad laminate has poor heat and humidity resistance, heat resistance and peel strength; Comparative Example 11 has a too large amount of phosphorus-containing bisphenol polymer compared with Example 4, and the produced copper clad plate has a sharp drop in Tg, moist heat resistance and water absorption. Comparative Example 12 Compared with Example 1, the amount of epoxy resin was too large, and the curing agent was obviously insufficient, resulting in the electrical properties of the fabricated copper clad laminate. The comprehensive performance of energy, heat resistance and peel strength is obviously deteriorated; Comparative Example 13 Compared with Example 4, the halogen-free phosphorus-containing flame retardant used is a monophenolic phosphonate having only one curing active point.
  • Examples 1-8 with specific content of cyanate resin and poly A copper clad laminate made of a phenyl ether resin, a phosphorus-containing bisphenol polymer, and a halogen-free epoxy resin has a high glass transition temperature, excellent dielectric properties, low water absorption, high heat resistance, and high peel strength. Excellent heat and humidity resistance and good processability, and can achieve halogen-free flame retardant, reaching UL94 V-0.
  • the prepreg and the printed circuit board laminate made of the halogen-free thermosetting resin composition provided by the present invention have a high glass transition temperature and excellent dielectric properties as compared with a general laminate. Low water absorption, high heat resistance, high peel strength, excellent heat and humidity resistance, and good processability, and can achieve halogen-free flame retardant, reaching UL94 V-0.

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Abstract

提供了一种无卤热固性树脂组合物及使用它的预浸料和印制电路用层压板。所述无卤热固性树脂组合物，有机固化物按100重量份计，包含（A）氰酸酯树脂5-50份；（B）聚苯醚树脂5-40份；（C）含磷双酚聚合物5-30份；（D）无卤环氧树脂30-60份。所提供的无卤热固性树脂组合物制成的预浸料和印制电路用层压板，具有高玻璃化转变温度、优异的介电性能、低吸水率、高耐热性、高的抗剥离强度、优异的耐湿热性和良好的工艺加工性，并能实现无卤阻燃，达到UL94V-0。

Description

一种无卤热固性树脂组合物及使用它的预浸料和印制电路用层压板 技术领域
本发明涉及一种无卤热固性树脂组合物，还涉及该无卤热固性树脂组合物制成的预浸料及印制电路用层压板。
背景技术
传统的印制电路用层压板通常采用溴系阻燃剂来实现阻燃，特别是采用四溴双酚A型环氧树脂，这种溴化环氧树脂具有良好的阻燃性，但它在燃烧时会产生溴化氢气体。此外，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已检测出二噁英、二苯并呋喃等致癌物质，因此溴化环氧树脂的应用受到限制。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，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。
同时随着消费电子产品信息处理的高速化和多功能化，应用频率不断提高，除了环保的要求越来越高外，要求介电常数和介电损耗值越来越低，因此降低Dk/Df已成为基板业者的追逐热点。
另外，对于覆铜箔基板材料而言，为了满足PCB加工性能以及终端电子产品的性能要求，必须具备良好的介电性能、耐热性以及机械性能，同时还应具有良好的工艺加工特性，高的剥离强度，优异的耐湿热性以及UL94 V-0无卤阻燃级别。
CN101796132A中公开了采用氰酸酯、环氧树脂、聚苯醚树脂及含溴阻燃剂共混得到耐热性、介电性能好、低CTE的覆铜板，但其为含溴阻燃；专利 CN103694642A中公开了采用环氧树脂、氰酸酯化合物或/和氰酸酯预聚物、聚膦酸酯或/和膦酸酯-碳酸酯共聚物制备了介电性能、耐湿热性好的无卤UL94V-0阻燃，但其抗剥离强度、层间粘合力及弯曲强度较低。
众所周知，目前有多种材料具备低的介电常数、介质损耗正切值特性，如：聚烯烃、氟树脂、聚苯乙烯、聚苯醚、改性聚苯醚、双马来酰亚胺-三嗪树脂、聚乙烯基苯树脂。以上树脂虽然具有良好的介电性能，但是都存在工艺加工难、耐热性差，剥离强度差等缺陷，无法满足高频高速覆铜箔基板的要求。
发明内容
经发明人研究发现，以氰酸酯、聚苯醚、含磷双酚聚合物共同作为环氧树脂的固化剂，在体系中能体现各自的优点以及出现相互催化协同的效果。氰酸酯能带来体系的高耐热性及低介质损耗值；聚苯醚能使体系具有优异的介电性能；含磷双酚聚合物反应基团包括两端羟基和膦酸酯单元，膦酸酯单元与环氧反应不产生二次羟基，固化物玻璃化转变温度高，介电性能和耐热性优异。这三种环氧树脂固化剂共同作用还能使体系具有优异的抗剥离强度。
此外，氰酸酯能作为聚苯醚和双酚聚磷酸与环氧树脂反应的催化剂。聚苯醚和双酚聚磷酸的酚羟基反应活性很低，与环氧树脂要在很高温度下才能发生反应，而氰酸酯的-OCN基团在90～120℃就很容易与以上两者的低活性羟基发生反应，然后在130℃以上有发生分解，在分解过程中会产生酚氧负离子。酚氧负离子容易与环氧树脂反应，从而降低体系的固化温度。同时聚苯醚和双酚聚磷酸中的酚羟基能很好的促进氰酸酯固化，降低氰酸酯的固化温度，并且使氰酸酯固化形成交联密度大、对称性高的三嗪环，从而使体系具有高的玻璃化转变温度和好的介电性能。含磷双酚聚合物中具有较多的柔性链酯链，能使体系的韧性有较大提高，具体体现在抗剥离强度上。并且含磷双酚聚合物中磷含 量高，在用作固化剂的同时还有无卤阻燃的功效，可少量添加或无需在添加其它阻燃剂就可以使板材达到UL94 V-0无卤阻燃的效果。
基于此，本发明的目的之一在于提供一种无卤热固性树脂组合物，以及使用它的预浸料和印制电路用层压板。使用该树脂组合物制作的印制电路用层压板具有高玻璃化转变温度、优异的介电性能、高耐热性、优异的抗剥离强度及良好的工艺加工性，并能实现无卤阻燃，达到UL94 V-0。
本发明人为实现上述目的，进行了反复深入的研究，结果发现：将无卤环氧树脂、氰酸酯树脂、聚苯醚树脂、含磷双酚聚合物及任选地其他物质适当混合得到的组合物，可达到上述目的。
即，本发明采用如下技术方案：一种无卤热固性树脂组合物，含有以下四种物质作为必要组分，有机固形物按100重量份计，其包含：
(A)氰酸酯树脂：5～50重量份；
(B)聚苯醚树脂：5～40重量份；
(C)含磷双酚聚合物：5～30重量份；
(D)无卤环氧树脂：30～60重量份。
本发明的无卤热固性树脂组合物以氰酸酯、聚苯醚、含磷双酚聚合物一起共同作为环氧树脂的固化剂。其中氰酸酯树脂可以使共固化体系具有高的耐热性及低的介质损耗值；聚苯醚树脂可使共固化体系具有优异的介电性能和低的吸水率；含磷双酚聚合物结构对称性高，且分子中的膦酸酯单元可以与环氧树脂的二次羟基反应，可以消除体系中极性大的二次羟基带来的介电性能变差的缺点，使介电性能优异，且固化物Tg高；此外，该含磷双酚聚合物磷含量高，有无卤阻燃的功效，只需少量添加或无需额外添加阻燃剂就可以达到UL94 V-0阻燃。本发明利用氰酸酯、聚苯醚、含磷双酚聚合物三者之间的协同 效应，可以显著提高使用该树脂组合物制作的预浸料以及印制电路用层压板的玻璃化温度和耐热性，并使其具有优异的介电性能、低吸水率、高抗剥离强度、好的耐湿热性以及良好的工艺加工性，并实现无卤阻燃，达到UL94 V-0。此外，氰酸酯、含磷双酚聚合物与环氧树脂的固化反应速率快，而聚苯醚树脂与环氧树脂的固化反应速率缓慢，同时用氰酸酯、聚苯醚、含磷双酚聚合物复合固化环氧树脂使得固化反应速率适中容易控制，大大降低了生产和加工工艺的难度。
下面对各组分进行详细说明。
本发明中的组分(A)，即为氰酸酯树脂，使用量为5到50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重量份或50重量份。
本发明的组分(A)，氰酸酯树脂具有如下结构：
Figure PCTCN2016098450-appb-000001
其中，R1为-CH2-、
Figure PCTCN2016098450-appb-000002
中的任意一种或至少两种的混合物；R2、R3、R4、R5、R6、R7、R8、R9各自独立地选自氢原子、C1-C4(例如C1、C2、C3、C4)的取代或未取代的直链烷基或C1-C4(例如C1、C2、C3、C4)取代或未取代的支链烷基中的任意一种。
优选地，所述组分(A)为2，2-双(4-氰氧基苯基)丙烷、双(4-氰氧基苯基)乙烷、双(3，5-二甲基-4-氰氧基苯基)甲烷、2，2-双(4-氰氧基苯基)-1，1，1，3，3，3- 六氟丙烷、α，α′-双(4-氰氧基苯基)-间二异丙基苯、环戊二烯型氰酸酯、苯酚酚醛型氰酸酯、甲酚酚醛型氰酸酯、2，2-双(4-氰氧基苯基)丙烷预聚物、双(4-氰氧基苯基)乙烷预聚物、双(3，5-二甲基-4-氰氧基苯基)甲烷预聚物、2，2-双(4-氰氧基苯基)-1，1，1，3，3，3-六氟丙烷预聚物、α，α′-双(4-氰氧基苯基)-间二异丙基苯预聚物、环戊二烯型氰酸酯预聚物、苯酚酚醛型氰酸酯预聚物或甲酚酚醛型氰酸酯预聚物中的任意一种或至少两种的混合物，优选为2，2-双(4-氰氧基苯基)丙烷、α，α′-双(4-氰氧基苯基)-间二异丙基苯、双(3，5-二甲基-4-氰氧基苯基)甲烷、2，2-双(4-氰氧基苯基)丙烷预聚物、α，α′-双(4-氰氧基苯基)-间二异丙基苯预聚物或双(3，5-二甲基-4-氰氧基苯基)甲烷预聚物中的任意一种或至少两种的混合物。
本发明中的组分(B)，即为聚苯醚树脂，使用量为5到40重量份，例如为5重量份、8重量份、10重量份、12重量份、14重量份、16重量份、18重量份、20重量份、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重量份或40重量份。
所述组分(B)，聚苯醚树脂具有如下结构：
Figure PCTCN2016098450-appb-000003
其中，R10为
Figure PCTCN2016098450-appb-000004
Figure PCTCN2016098450-appb-000005
Figure PCTCN2016098450-appb-000006
中的任意一种或至少两种的混合物。
其中，R11为H、碳原子数为1～4的取代或未取代的直链烷基或支链烷基、取代或未取代的苯基中的任意一种。
其中，R12、R13、R14、R15、R16、R17、R18、R19相同或不同，选自H、F、碳原子数为1～4的取代或未取代的直链烷基或支链烷基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的环己基或烯丙基中的任意一种。
优选地，n1、n2、n3、n4独立为0～40的正整数，且满足8≤n1+n2+n3+n4≤40。
本发明的组分(C)，即为含磷双酚聚合物，使用量为5～30重量份，例如为5重量份、8重量份、10重量份、12重量份、13重量份、14重量份、15重量份、16重量份、17重量份、18重量份、19重量份、20重量份、22重量份、24重量份、25重量份、26重量份、28重量份或30重量份。
所述组分(C)，含磷双酚聚合物具有如下结构：
Figure PCTCN2016098450-appb-000007
其中R20、R21为相同或不同，选自
Figure PCTCN2016098450-appb-000008
Figure PCTCN2016098450-appb-000009
Figure PCTCN2016098450-appb-000010
Figure PCTCN2016098450-appb-000011
中的任意一种或至少两种的混合物。
其中，R11为H、碳原子数为1～4的取代或未取代的直链烷基或支链烷基、取代或未取代的苯基中的任意一种。
其中，R12、R13、R14、R15、R16、R17、R18、R19、R23、R24相同或不同，选自H、F、碳原子数为1～4(例如碳原子数为1、2、3或4)的取代或未取代的直链烷基或支链烷基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的环己基中的任意一种。
其中，R22为C1～C20(例如C1、C2、C3、C4、C6、C8、C10、C12、C15、C18或C20)的取代或未取代的直链烷基、C1～C20(例如C1、C2、C3、C4、C6、C8、C10、C12、C15、C18或C20)的取代或未取代的支链烷基、C2～C20(例如C2、C3、C4、C6、C8、C10、C12、C15、C18或C20)的取代或未取 代的直链烯烃基、C2～C20(例如C2、C3、C4、C6、C8、C10、C12、C15、C18或C20)的取代或未取代的支链烯烃基、C2～C20(例如C2、C3、C4、C6、C8、C10、C12、C15、C18或C20)的取代或未取代的直链亚烷基、C2～C20(例如C2、C3、C4、C6、C8、C10、C12、C15、C18或C20)的取代或未取代的支链亚烷基、C5～C20(例如C5、C6、C8、C10、C12、C15、C18或C20)的取代或未取代的环烷基或C6～C20(例如C6、C8、C10、C12、C15、C18或C20)的取代或未取代的芳基中的任意一种。
其中，n2为3～75的任意整数，例如3、4、6、8、9、10、11、13、15、17、18、19、20、23、26、28、30、40、45、50、55、67、68、70或75。优选地，n2为4～60的任意整数；优选地n2为5～50的任意整数；优选地n2为5～40的任意整数；优选地n2为8～30的任意整数；优选地n2为10～25的任意整数。
其中，n3、n4相同或不同，为0～4的整数。
其中，k、j为0或1，但不能同时为0。
本发明的组分(D)，即为无卤环氧树脂，使用量为30～60重量份，例如为30重量份、35重量份、38重量份、40重量份、42重量份、45重量份、48重量份、50重量份、52重量份、54重量份、56重量份、58重量份或60重量份。
所述组分(D)无卤环氧树脂是指在1个分子中具有两个或两个以上环氧基团的环氧树脂，选自缩水甘油醚类、缩水甘油酯类、缩水甘油胺类、脂环族环氧树脂、环氧化烯烃类、海因环氧树脂或酰亚胺环氧树脂中的任意一种或者至少两种的混合物。
优选地，所述缩水甘油醚类包括双酚A型环氧树脂、双酚F型环氧树脂、邻甲酚酚醛环氧树脂、双酚A型酚醛环氧树脂、三酚型酚醛环氧树脂、双环戊 二烯酚醛环氧树脂、联苯型酚醛环氧树脂、烷基苯型酚醛环氧树脂或萘酚型酚醛环氧树脂中的任意一种或至少两种的混合物。上述环氧树脂均为无卤的环氧树脂。
优选地，所述缩水甘油醚类选自具有如下结构的环氧树脂：
Figure PCTCN2016098450-appb-000012
其中，Z1、Z2和Z3各自独立地选自
Figure PCTCN2016098450-appb-000013
R25为氢原子、取代或未取代的含碳数1～5的直链烷基或支链烷基中的任意一种。
Y1和Y2各自独立地选自单键、-CH2-、
Figure PCTCN2016098450-appb-000014
Figure PCTCN2016098450-appb-000015
和的任意一种，n3为1～10的任意整数，例如2、3、4、5、6、7、8或9，R26选自氢原子、取代或未取代的含碳数1～5的直链烷基或支链烷基中的任意一种。
优选地，所述缩水甘油胺类选自三缩水甘油基-p-氨基苯酚、三缩水甘油基三聚异氰酸酯、四缩水甘油基二氨基二亚甲基苯、四缩水甘油基-4，4`-二胺基二苯甲烷、四缩水甘油基-3，4`-二胺基二苯醚、四缩水甘油基-4，4`-二胺基二苯醚或四缩水甘油基-1，3-二氨基甲基环己烷中的任意一种或至少两种的混合物。
本发明的无卤热固性树脂组合物采用上述特定分子结构的无卤环氧树脂，其具有较高的官能度和良好的介电性能，其固化物Tg较高，吸水率低。
本发明的无卤热固性树脂组合物还可以包括组分(E)，即为含磷阻燃剂，以组分(A)、组分(B)、组分(C)、组分(D)添加量之和为100重量份计，组分(E)含磷阻燃剂的添加量为0～5重量份。
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、苯氧基磷腈化合物、磷酸酯或聚磷酸酯中的任意一种或者至少两种的混合物。
本发明的无卤热固性树脂组合物还可以包括组分(F)，即为固化促进剂。
优选地，所述固化促进剂包括有机金属盐和选自咪唑类化合物、咪唑类化合物的衍生物、哌啶类化合物、吡啶类、路易斯酸或三苯基膦中的任意一种或至少两种的混合物。
优选地，所述固化促进剂中的有机金属盐包括辛酸金属盐、异辛酸金属盐、乙酰丙酮金属盐、环烷酸金属盐、水杨酸金属盐或硬脂酸金属盐中的任意一种或者至少两种的混合物，其中，所述金属选自锌、铜、铁、锡、钴或铝中的任意一种或者至少两种的混合物。
优选地，所述咪唑类化合物为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或2-十一烷基咪唑中的任意一种或至少两种的混合物。
优选地，所述哌啶类化合物为2，3-二氨基哌啶、2，5-二氨基哌啶、2，6-二氨基哌啶、2-氨基-3-甲基哌啶、2-氨基-4-甲基哌啶、2-氨基-3-硝基哌啶、2-氨基-5-硝基哌啶或2-氨基-4，4-二甲基哌啶中的任意一种或至少两种的混合物。
优选地，所述吡啶类化合物为4-二甲氨基吡啶、2-氨基吡啶、3-氨基吡啶或4-氨基吡啶中的任意一种或至少两种混合物。
优选地，以组份(A)、组份(B)、组份(C)及组份(D)的总重为100 重量份计，所述组份(F)固化促进剂的添加量为0.01～1重量份，优选0.025～0.85重量份。
本发明的无卤热固性树脂组合物还可以包括组分(G)，即为填料。
优选地，所述填料选自有机填料或无机填料，优选无机填料，进一步优选经过表面处理的无机填料，最优选经过表面处理的二氧化硅。
优选地，所述表面处理的表面处理剂选自硅烷偶联剂、有机硅低聚物或钛酸酯偶联剂中的任意一种或至少两种的混合物。
优选地，以无机填料为100重量份计，所述表面处理剂的用量为0.1～5.0重量份，优选0.5～3.0重量份，更优选0.75～2.0重量份。
优选地，所述无机填料选自非金属氧化物、金属氮化物、非金属氮化物、无机水合物、无机盐、金属水合物或无机磷中的任意一种或者至少两种的混合物，优选熔融二氧化硅、结晶型二氧化硅、球型二氧化硅、空心二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、碳酸钙、硅酸钙或云母中的一种或至少两种的混合物。
优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或至少两种的混合物。
优选地，所述填料的中位粒径为0.01～50μm，优选0.01～20μm，进一步优选0.1～10μm。
优选地，以组分(A)、组分(B)、组分(C)和组分(D)的添加量之和为100重量份计，所述组分(G)填料的添加量为5～300重量份，优选5～200重量份，进一步优选5～150重量份。
本发明所述的“包括”，意指其除所述组份外，还可以包括其他组份，这些其他组份赋予所述无卤热固性树脂组合物不同的特性。除此之外，本发明所述 的“包括”，还可以替换为封闭式的“为”或“由……组成”。
例如，所述无卤热固性树脂组合物还可以含有各种添加剂，作为具体例，可以举出含磷阻燃剂、抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂等。这些各种添加剂可以单独使用，也可以两种或者两种以上混合使用。
本发明的无卤热固性树脂组合物常规制备方法为：先将固形物放入，然后加入液态溶剂，搅拌至固形物完全溶解后，再加入液态树脂和促进剂，继续搅拌均匀即可。
作为本发明中的溶剂，没有特别的限定，作为具体例，可以列举出甲醇、乙醇、丁醇等醇类，乙基溶纤剂、丁基溶纤剂、乙二醇甲醚、卡必醇、丁基卡必醇等醚类，丙酮、丁酮、甲基乙基甲酮、环己酮等酮类；甲苯、二甲苯等芳香烃类；醋酸乙酯、乙氧基乙基乙酸酯等酯类；N，N-二甲基甲酰胺、N，N-二甲基乙酰胺等含氮类溶剂。以上溶剂可单独使用，也可两种或两种以上混合使用。优选丙酮、丁酮、甲基乙基甲酮、环己酮等酮类。所述溶剂的添加量由本领域技术人员根据自己经验来选择，使得树脂胶液达到适合使用的粘度即可。
本发明的预浸料包括增强材料及含浸干燥后附着在增强材料上的如上所述的无卤热固性树脂组合物，所使用的增强材料无特别的限定，可以为有机纤维、无机纤维编织布或无纺布。所述的有机纤维可以选择芳纶无纺布，所述的无机纤维编织布可以为E-玻纤布、D-玻纤布、S-玻纤布、T玻纤布、NE-玻纤布或石英布。所述增强材料的厚度无特别限定，处于层压板有良好的尺寸稳定性的考虑，所述编织布及无纺布厚度优选0.01～0.2mm，且最好是经过开纤处理及硅烷偶联剂表面处理的，为了提供良好的耐水性和耐热性，所述硅烷偶联剂优选为环氧硅烷偶联剂、氨基硅烷偶联剂或乙烯基硅烷偶联剂中的任意一种或至少两 种的混合物。将增强材料通过含浸上述的无卤热固性树脂组合物，在100～250℃条件下，烘烤1～15分钟得到所述预浸料。
本发明的印制电路用层压板包括通过加热和加压、使一片或两片以上的预浸料粘合在一起而制成的层压板，以及粘合在层压板一面或两面以上的金属箔。所述的层压板是在热压机中固化制得，固化温度为150℃～250℃，固化压力为10～60Kg/cm2。所述的金属箔为铜箔、镍箔、铝箔及SUS箔等，其材质不限。
与现有技术相比，本发明至少具有以下有益效果：
本发明以氰酸酯、聚苯醚、含磷双酚聚合物共同作为环氧树脂的固化剂，在体系中能体现各自的优点并具有相互催化协同的效果；氰酸酯能带来体系的高耐热性及低介质损耗值；聚苯醚能使体系具有优异的介电性能；含磷双酚聚合物反应基团包括两端羟基和膦酸酯单元，膦酸酯单元与环氧反应不产生二次羟基，固化物玻璃化转变温度高，介电性能和耐热性优异。这三种环氧树脂固化剂共同作用还能使体系具有优异的抗剥离强度。
此外，氰酸酯能作为聚苯醚和双酚聚磷酸与环氧树脂反应的催化剂。聚苯醚和含磷双酚聚合物的酚羟基反应活性很低，与环氧树脂要在很高温度下才能发生反应，而氰酸酯的-OCN基团在90～120℃就很容易与以上两者的低活性羟基发生反应，然后在130℃以上有发生分解，在分解过程中会产生酚氧负离子。酚氧负离子容易与环氧树脂反应，从而降低体系的固化温度。同时聚苯醚和双酚聚磷酸中的酚羟基能很好的促进氰酸酯固化，降低氰酸酯的固化温度，并且使氰酸酯固化形成交联密度大、对称性高的三嗪环，从而使体系具有高的玻璃化转变温度和好的介电性能。含磷双酚聚合物中具有较多的柔性链酯链，能使体系的韧性有较大提高，具体体现在抗剥离强度上。并且含磷双酚聚合物中磷含量高，在用作固化剂的同时还有无卤阻燃的功效，可少量添加或无需在 添加其它阻燃剂就可以使板材达到UL94 V-0无卤阻燃的效果。
本发明所提供的无卤热固性树脂组合物制成的预浸料和印制电路用层压板，具有高达245℃的玻璃化转变温度；优异的介电性能，吸水率控制在0.07-0.11％范围内；高耐热性；抗剥离强度为0.9-1.2N/mm；优异的耐湿热性和良好的工艺加工性，并能实现无卤阻燃，达到UL94 V-0。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
以下所述是本发明实施例的具体实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明实施例的保护范围。
下面分多个实施例对本发明实施例进行进一步的说明。本发明实施例不限定于以下的具体实施例。在不改变权利要求的范围内，可以适当的进行变更实施。
1、聚苯醚再分配
将4000g甲苯于装有搅拌器、冷凝回流管、温度计的三颈瓶中搅拌加热到100℃，然后加入2000g数均分子量为20000的PPO树脂，当变为均一相后加入250g 3，5，3′，5′-四甲基-4，4′-二羟基联苯，搅拌30min，然后加入溶于甲苯中的150g过氧化苯甲酰(BPO)，并保持温度为92℃，反应240min。然后将产物冷却到室温然后加入4000ml甲醇，并剧烈搅拌，过滤、干燥，得到小分子化的双官能基PPO树脂(PPO-2)2100g，通过GPC测试其Mn＝2118。
将4000g甲苯于装有搅拌器、冷凝回流管、温度计的三颈瓶中搅拌加热到100℃，然后加入2000g数均分子量为20000的PPO树脂，当变为均一相后加入120g双酚A(BPA)，搅拌30min，然后加入溶于甲苯中的60g过氧化苯甲酰 (BPO)，并保持温度为92℃，反应360min。然后将产物冷却到室温然后加入4000ml甲醇，并剧烈搅拌，过滤、干燥，得到小分子化的双官能基PPO树脂(PPO-3)2000g，通过GPC测试其Mn＝4088。
将4000g甲苯于装有搅拌器、冷凝回流管、温度计的三颈瓶中搅拌加热到100℃，然后加入2000g数均分子量为20000的PPO树脂，当变为均一相后加入120g TrisP-PA(本州化学)
Figure PCTCN2016098450-appb-000016
搅拌30min，然后加入溶于甲苯中的60g过氧化苯甲酰(BPO)，并保持温度为92℃，反应360min。然后将产物冷却到室温然后加入4000ml甲醇，并剧烈搅拌，过滤、干燥，得到小分子化的双官能基PPO树脂(PPO-4)2000g，通过GPC测试其Mn＝3120。
将4000g甲苯于装有搅拌器、冷凝回流管、温度计的三颈瓶中搅拌加热到100℃，然后加入2000g数均分子量为20000的PPO树脂，当变为均一相后加入120g TekP-4HBPA(本州化学)
Figure PCTCN2016098450-appb-000017
搅拌30min，然后加入溶于甲苯中的60g过氧化苯甲酰(BPO)，并保持温度为 92℃，反应360min。然后将产物冷却到室温然后加入4000ml甲醇，并剧烈搅拌，过滤、干燥，得到小分子化的双官能基PPO树脂(PPO-5)2000g，通过GPC测试其Mn＝2480。
2、含磷双酚聚合物的制备
在N2条件下，加入77g对苯二酚(0.70mol)和130.5g二苯基甲基膦酸酯(DPP，0.526mol)以及催化剂四苯基鏻酚盐(TPPP(30％苯酚)，0.051g，0.083mol)，将真空度降低到10mmHg，同时将混合物加热到240℃，反应10小时。蒸去副产物苯酚，补加0.255g催化剂，并保持210℃/10mmHg条件4小时。后处理提纯，得到链的两个末端为反应性的酚羟基的含磷双酚聚合物C-1。通过GPC测试其Mn＝8510。
在N2条件下，加入147g4，4`-联苯二酚(Biphenol，0.79mol)和130.5g二苯基甲基膦酸酯(DPP，0.526mol)以及催化剂四苯基鏻酚盐(TPPP(30％苯酚)，0.051g，0.083mol)，将真空度降低到10mmHg，同时将混合物加热到265℃，反应5小时。蒸去副产物苯酚，补加0.255g催化剂，并保持265℃/10mmHg条件2小时。后处理提纯，得到链的两个末端为反应性的酚羟基的含磷双酚聚合物C-2。通过GPC测试其Mn＝2600。
在N2条件下，加入232.8g BisP-TMC(本州化学)(0.75mol)和130.5g二苯基甲基膦酸酯(DPP，0.526mol)以及催化剂四苯基鏻酚盐(TPPP(30％苯酚)，0.051g，0.083mol)，将真空度降低到10mmHg，同时将混合物加热到265℃，反应5小时。蒸去副产物苯酚，补加0.255g催化剂，并保持265℃/10mmHg条件2小时。后处理提纯，得到链的两个末端为反应性的酚羟基的含磷双酚聚合物C-3。通过GPC测试其Mn＝4960。
将氰酸酯树脂、聚苯醚树脂、含磷双酚聚合物、无卤环氧树脂以及固化促 进剂、无卤阻燃剂、填料按一定比例于溶剂中混合均匀，控制胶液固含量为65％，用2116玻纤布浸渍上述胶液，控制合适厚度，然后在115～175℃的烘箱中烘烤2～15min制成预浸料，然后将数张预浸料叠在一起，在其两侧叠上18μRTF铜箔，在固化温度为170～250℃，固化压力为25～60kg/cm2，固化时间为60～300min条件下制成覆铜板。
实施例1-8和对比例1-13涉及材料及牌号信息如下：
(A)氰酸酯
CY-40：吴桥树酯厂，DCPD型氰酸酯树脂
PT30S：LONCZ，酚醛型氰酸酯树脂
CE01PS：江苏天启，双酚A型氰酸酯树脂
CE01MO：江苏天启，双酚A型氰酸酯树脂
(B)PPO
PPO-1：SA90，沙伯基，小分子化双官能基聚苯醚，羟基当量850
PPO-2：自制小分子PPO树脂，Mn＝2118
Figure PCTCN2016098450-appb-000018
PPO-3：自制小分子PPO树脂，Mn＝4088
Figure PCTCN2016098450-appb-000019
PPO-4：自制小分子PPO树脂，Mn＝3120
Figure PCTCN2016098450-appb-000020
PPO-5：自制小分子PPO树脂，Mn＝2480
Figure PCTCN2016098450-appb-000021
(C)含磷双酚聚合物
C1，自制，含磷双酚聚合物，磷含量18％，Mn＝8510
Figure PCTCN2016098450-appb-000022
C2，自制，含磷双酚聚合物，磷含量11.7％，Mn＝2600
Figure PCTCN2016098450-appb-000023
C3，自制，含磷双酚聚合物，磷含量7.8％，Mn＝4960
Figure PCTCN2016098450-appb-000024
OL-1001：含磷双酚聚合物，FRX OL1001(美国FRX Polymers商品名，磷含量8.5％)
Figure PCTCN2016098450-appb-000025
OL-3001：含磷双酚聚合物，(美国FRX Polymers商品名，磷含量10％)
Figure PCTCN2016098450-appb-000026
FYROL PMP：Supresta无卤含磷阻燃剂，磷含量17.5％
Figure PCTCN2016098450-appb-000027
(D)环氧树脂
HP-7200HHH：DIC，DCPD型环氧树脂，环氧当量288
HP-7200H-75M：DIC，DCPD型环氧树脂，环氧当量280
HP-6000：DIC，环氧树脂，环氧当量250
HP-9900：DIC，萘酚型环氧树脂，环氧当量274
NC-3000H：日本化药，联苯环氧树脂，环氧当量294
SKE-1：尚科特，特种环氧树脂，环氧当量120
SKE-3：尚科特，特种环氧树脂，环氧当量120
(E)含磷阻燃剂
SPB-100：大琢化学，膦腈类阻燃剂，磷含量13.4％
(F)促进剂
2E4MZ：2-乙基-4-甲基咪唑，四国化成
异辛酸锌：BICAT Z，The Shepherd Chemical Company
(G)填料
熔融二氧化硅(平均粒径为1至10μm，纯度99％以上)
表1-3是实施例1-8和对比例1-13的配方组成及其物性数据。
表1
  实施例1 实施例2 实施例3 实施例4 实施例5 实施例6 实施例7 实施例8
CY-40       25 25      
PT30S 5              
CE01PS   10         35 50
CE01MO     20     30    
PPO-1 20 40 30 5        
PPO-2             15  
PPO-3               10
PPO-4         15      
PPO-5           10    
OL-1001 15             10
OL-3001         15 15    
OL-5000                
C1   5            
C2     10          
C3       30     15  
FYROL PMP                
HP-7200H-M75       40        
HP-7200HHH         45      
HP-6000   45 40          
HP-9900 60              
NC-3000H               30
SKE-1             35  
SKE-3           45    
SPB-100 3             5
2E4MZ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
异辛酸锌 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05
球硅 25 25 25 25 25 25 25 150
Tg(DMA)/℃ 185 193 198 211 215 220 230 242
Dk(10GHz) 3.8 3.75 3.7 3.7 3.7 3.7 3.7 3.9
Df(10GHz) 0.008 0.006 0.006 0.006 0.006 0.005 0.005 0.005
剥离强度(N/mm) 1.2 0.9 1 1.1 1.1 1.1 1.2 0.9
吸水性/％ 0.07 0.08 0.08 0.08 0.1 0.08 0.1 0.004
PCT/6h OOO OOO OOO OOO OOO OOO OOO OOO
高温高湿/192h OOO OOO OOO OOO OOO OOO OOO OOO
T300/min ＞60 ＞60 ＞60 ＞60 ＞60 ＞60 ＞60 ＞60
难燃烧性 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
表2
Figure PCTCN2016098450-appb-000028
Figure PCTCN2016098450-appb-000029
表3
Figure PCTCN2016098450-appb-000030
Figure PCTCN2016098450-appb-000031
以上特性的测试方法如下：
(1)玻璃化转变温度(Tg)：使用DMA测试，按照IPC-TM-650 2.4.24所规定的DMA测试方法进行测定。
(2)介电常数和介电损耗因子：按照SPDR方法测试。
(3)耐湿热性(PCT)评价：将覆铜板表面的铜箔蚀刻后，评价基板；将基板放置压力锅中，在120℃、105KPa条件下处理6小时后，浸渍在288℃的锡炉中，当基板分层爆板时记录相应时间；当基板在锡炉中超过5min还没出现起泡或分层时即可结束评价，PCT/6h性能图标的补充说明：×为分层爆板，O为不分层爆板，每块板材选取三个样本做三次实验。
(4)耐湿热性(高温高湿)评价：将覆铜板表面的铜箔蚀刻后，评价基板；将基板温度为85℃、湿度为85％的恒温恒湿箱中192小时后，浸渍在288℃的锡炉中，当基板分层爆板时记录相应时间；当基板在锡炉中超过5min还没出现起泡或分层时即可结束评价，高温高湿/192h性能图标的补充说明：×为分层爆板，O为不分层爆板，每块板材选取三个样本做三次实验。
(5)吸水性：按照IPC-TM-650 2.6.2.1所规定的吸水性测试方法进行测定。
(6)抗剥离强度：按照IPC-TM-650 2.4.8所规定的抗剥离强度测试方法进行测定。
(7)T300：用TMA仪，按照IPC-TM-650 2.4.24.1所规定的T300测试方法进行测定。
(8)阻燃性：按照UL 94标准方法进行。
从表1-3的物性数据可以看出，对比例1与实施例1对比，树脂组合物中氰酸酯树脂用量少，制成的覆铜板介电性能较差，且耐热性一般；对比例2与实施例4对比，树脂组合物中聚苯醚用量少，导致体系中刚性结构少，从而使其耐热性明显下降，具体体现在T300只有5.6min；对比例3与实施例8对比，添加了过少的环氧树脂，体系中固化剂过量，环氧量不足，体系不能很好的固化，玻璃化转变温度下降；并且PPO和含磷双酚在体系中先与氰酸酯反应后还会分解，导致PPO和含磷双酚在体系中充当增塑剂的作用，也使体系玻璃化转变温度下降；并且氰酸酯用量过多，也会导致耐湿热性(PCT、高温高湿)性能变差；对比例4与实施例2相比，含磷双酚聚合物用量过少，制成的覆铜板介电性能较差；对比例5中未添加氰酸酯树脂所制成的覆铜板耐热性较差；对比例6中未添加聚苯醚树脂和对比例7中未添加含磷双酚聚合物以及对比例8中未添加无卤环氧树脂所制成的覆铜板介电性能和剥离强度均较差；对比例9与实施例7相比，氰酸酯树脂用量过多，环氧树脂用量较少，所制成的覆铜板介电性能较差；对比例10与实施例2相比，聚苯醚用量过多，制成的覆铜板耐湿热性、耐热性和剥离强度较差；对比例11与实施例4相比，含磷双酚聚合物用量过多，制成的覆铜板Tg急剧下降，耐湿热性和吸水率变差；对比例12与实施例1相比，环氧树脂用量过多，固化剂明显不足，导致制成的覆铜板电性 能、耐热性、剥离强度等综合性能明显变差；对比例13与实施例4相比，使用的无卤含磷阻燃剂，为单酚类膦酸酯，其只有一个固化活性点，导致其一端能参与固化，另一端受热时能够扰动的自由端，导致其Tg、T300、介电性能、耐湿热性等都变差；实施例1-8以特定含量的氰酸酯树脂与聚苯醚树脂、含磷双酚聚合物和无卤环氧树脂所制成的覆铜板具有高玻璃化转变温度、优异的介电性能、低吸水率、高耐热性、高的抗剥离强度、优异的耐湿热性和良好的工艺加工性，并能实现无卤阻燃，达到UL94 V-0。
如上所述，与一般的层压板相比，本发明所提供的无卤热固性树脂组合物制成的预浸料和印制电路用层压板，具有高玻璃化转变温度、优异的介电性能、低吸水率、高耐热性、高的抗剥离强度、优异的耐湿热性和良好的工艺加工性，并能实现无卤阻燃，达到UL94 V-0。
以上所述，仅为本发明的较佳实施例，对于本领域的普通技术人员来说，可以根据本发明的技术方案和技术构思做出其他各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的范围。

Claims (12)

  1. 一种无卤热固性树脂组合物，有机固形物按100重量份计，其包含：
    (A)氰酸酯树脂5～50重量份；
    (B)聚苯醚树脂5～40重量份；
    (C)含磷双酚聚合物5～30重量份；
    (D)无卤环氧树脂30～60重量份。
  2. 如权利要求1所述的无卤热固性树脂组合物，其特征在于，所述氰酸酯树脂具有如下结构：
    Figure PCTCN2016098450-appb-100001
    其中，R1为-CH2-、
    Figure PCTCN2016098450-appb-100002
    中的任意一种或至少两种的混合物；R2、R3、R4、R5、R6、R7、R8、R9各自独立地选自氢原子、C1-C4的取代或未取代的直链烷基或C1-C4取代或未取代的支链烷基中的任意一种。
  3. 如权利要求1所述的无卤热固性树脂组合物，其特征在于，所述氰酸酯树脂为2，2-双(4-氰氧基苯基)丙烷、双(4-氰氧基苯基)乙烷、双(3，5-二甲基-4-氰氧基苯基)甲烷、2，2-双(4-氰氧基苯基)-1，1，1，3，3，3-六氟丙烷、α，α′-双(4-氰氧基苯基)-间二异丙基苯、环戊二烯型氰酸酯、苯酚酚醛型氰酸酯、甲酚酚醛型氰酸酯、2，2-双(4-氰氧基苯基)丙烷预聚物、双(4-氰氧基苯基)乙烷预聚物、双(3，5-二甲基-4-氰氧基苯基)甲烷预聚物、2，2-双(4-氰氧基苯基)-1，1，1，3，3，3-六氟丙烷预聚物、α，α′-双(4-氰氧基苯基)-间二异丙基苯预聚物、双环戊二烯型氰酸酯预聚物、苯酚酚醛型氰酸酯预聚物或甲酚酚醛型氰酸酯预 聚物中的任意一种或至少两种的混合物。
  4. 如权利要求1所述的无卤热固性树脂组合物，其特征在于，所述氰酸酯树脂为2，2-双(4-氰氧基苯基)丙烷、α，α′-双(4-氰氧基苯基)-间二异丙基苯、双(3，5-二甲基-4-氰氧基苯基)甲烷、2，2-双(4-氰氧基苯基)丙烷预聚物、α，α′-双(4-氰氧基苯基)-间二异丙基苯预聚物或双(3，5-二甲基-4-氰氧基苯基)甲烷预聚物中的任意一种或至少两种的混合物。
  5. 如权利要求1-4之一所述的无卤热固性树脂组合物，其特征在于，所述聚苯醚树脂具有如下结构：
    Figure PCTCN2016098450-appb-100003
    其中，R10为
    Figure PCTCN2016098450-appb-100004
    Figure PCTCN2016098450-appb-100005
    Figure PCTCN2016098450-appb-100006
    Figure PCTCN2016098450-appb-100007
    中的任意一种或至少两种的混合物；
    其中，R11为H、碳原子数为1～4的取代或未取代的直链烷基或支链烷基、取代或未取代的苯基中的任意一种；
    其中，R12、R13、R14、R15、R16、R17、R18、R19相同或不同，选自H、F、碳原子数为1～4的取代或未取代的直链烷基或支链烷基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的环己基或烯丙基中的任意一种；
    优选地，n1、n2、n3、n4独立为0～40的正整数，且满足8≤n1+n2+n3+n4≤40
  6. 如权利要求1-5之一所述的无卤热固性树脂组合物，其特征在于，所述含磷双酚聚合物具有如下结构：
    Figure PCTCN2016098450-appb-100008
    其中，R20、R21为相同或不同，选自
    Figure PCTCN2016098450-appb-100009
    Figure PCTCN2016098450-appb-100010
    Figure PCTCN2016098450-appb-100011
    Figure PCTCN2016098450-appb-100012
    中的任意一种或至少两种的混合物；
    其中，R11为H、碳原子数为1～4的取代或未取代的直链烷基或支链烷基、取代或未取代的苯基中的任意一种；
    其中，R12、R13、R14、R15、R16、R17、R18、R19、R23、R24相同或不同，选自H、F、碳原子数为1～4的取代或未取代的直链烷基或支链烷基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的环己基或烯丙基中的任意一种；
    其中，R22为C1～C20的取代或未取代的直链烷基、C1～C20的取代或未取代的支链烷基、C2～C20的取代或未取代的直链烯烃基、C2～C20的取代或未取代的支链烯烃基、C2～C20的取代或未取代的直链亚烷基、C2～C20的取代或未取代的支链亚烷基、C5～C20的取代或未取代的环烷基或C6～C20的取代或未取代的芳基中的任意一种；
    其中，n2为3～75的任意整数；优选n2为4～60的任意整数；进一步优选n2为5～50的任意整数；再进一步优选n2为5～40的任意整数；更进一步优选n2为8～30的任意整数；再进一步优选n2为10～25的任意整数；
    其中，n3、n4相同或不同，选自0～4的整数；
    其中，k、j为0或1，但不能同时为0。
  7. 如权利要求1-6之一所述的无卤热固性树脂组合物，其特征在于，所述无卤环氧树脂为缩水甘油醚类、缩水甘油酯类、缩水甘油胺类、脂环族环氧树脂、环氧化烯烃类、海因环氧树脂或酰亚胺环氧树脂中的任意一种或至少两种 的混合物；
    优选地，所述缩水甘油醚类为双酚A型环氧树脂、双酚F型环氧树脂、邻甲酚酚醛环氧树脂、双酚A型酚醛环氧树脂、三酚型酚醛环氧树脂、双环戊二烯酚醛环氧树脂、联苯型酚醛环氧树脂、烷基苯型酚醛环氧树脂或萘酚型酚醛环氧树脂中的任意一种或至少两种的混合物；
    优选地，所述缩水甘油醚类为具有如下结构的环氧树脂：
    Figure PCTCN2016098450-appb-100013
    其中，Z1、Z2和Z3各自独立地选自
    Figure PCTCN2016098450-appb-100014
    R27选自氢原子、取代或未取代的含碳数1～5的直链烷基或支链烷基中的任意一种；
    Y1和Y2各自独立地选自单键、-CH2-、
    Figure PCTCN2016098450-appb-100015
    Figure PCTCN2016098450-appb-100016
    中的任意一种，R28选自氢原子、取代或未取代的含碳数1～5的直链烷基或支链烷基中的任意一种；
    n8为1～10的任意整数；
    优选地，所述缩水甘油胺类选自三缩水甘油基-p-氨基苯酚、三缩水甘油基三聚异氰酸酯、四缩水甘油基二氨基二亚甲基苯、四缩水甘油基-4，4`-二胺基二苯甲烷、四缩水甘油基-3，4`-二胺基二苯醚、四缩水甘油基-4，4`-二胺基二苯醚或四缩水甘油基-1，3-二氨基甲基环己烷中的任意一种或至少两种的混合物。
  8. 如权利要求1-7之一所述的无卤热固性树脂组合物，其特征在于，所述无卤热固性树脂组合物还包括组分(E)含磷阻燃剂；
    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、苯氧基磷腈化合物、磷酸酯或聚磷酸酯中的任意一种或至少两种的混合物；
    优选地，以组分(A)、组分(B)、组分(C)、组分(D)添加量之和为100重量份计，组分(E)含磷阻燃剂的添加量为0～5重量份；
    优选地，所述无卤热固性树脂组合物还包括组分(F)固化促进剂；
    优选地，所述固化促进剂为有机金属盐、咪唑类化合物、咪唑类化合物的衍生物、哌啶类化合物、吡啶类、路易斯酸或三苯基膦中的任意一种或至少两种的混合物；
    优选地，所述有机金属盐为辛酸金属盐、异辛酸金属盐、乙酰丙酮金属盐、环烷酸金属盐、水杨酸金属盐或硬脂酸金属盐中的任意一种或至少两种的混合物，其中，所述金属为锌、铜、铁、锡、钴或铝中的任意一种或至少两种的混合物；
    优选地，所述咪唑类化合物为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或2-十一烷基咪唑中的任意一种或至少两种的混合物；
    优选地，所述哌啶类化合物为2，3-二氨基哌啶、2，5-二氨基哌啶、2，6-二氨基哌啶、2-氨基-3-甲基哌啶、2-氨基-4-甲基哌啶、2-氨基-3-硝基哌啶、2-氨基-5-硝基哌啶或2-氨基-4，4-二甲基哌啶中的任意一种或至少两种的混合物；
    优选地，所述吡啶类化合物为4-二甲氨基吡啶、2-氨基吡啶、3-氨基吡啶或4-氨基吡啶中的任意一种或至少两种的混合物；
    优选地，以组份(A)、组份(B)、组份(C)和组份(D)的添加量之和为100重量份计，所述组份(F)固化促进剂的添加量为0.01～1重量份，优选为0.025～0.85重量份。
  9. 如权利要求1-8之一所述的无卤热固性树脂组合物，其特征在于，所述无卤热固性树脂组合物还包括组分(G)填料；
    优选地，所述填料选自有机填料或无机填料，优选为无机填料，进一步优选为经过表面处理的无机填料，更优选为经过表面处理的二氧化硅；
    优选地，所述表面处理的表面处理剂选自硅烷偶联剂、有机硅低聚物或钛酸酯偶联剂中的任意一种或至少两种的混合物；
    优选地，以无机填料为100重量份计，所述表面处理剂的用量为0.1～5.0重量份，优选为0.5～3.0重量份，进一步优选为0.75～2.0重量份；
    优选地，所述无机填料选自非金属氧化物、金属氮化物、非金属氮化物、无机水合物、无机盐、金属水合物或无机磷中的任意一种或至少两种的混合物，优选为熔融二氧化硅、结晶型二氧化硅、球型二氧化硅、空心二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、碳酸钙、硅酸钙或云母中的一种或至少两种的混合物；
    优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或至少两种的混合物；
    优选地，所述填料的中位粒径为0.01～50μm，优选为0.01～20μm，进一步优选为0.1～10μm；
    优选地，以组分(A)、组分(B)、组分(C)和组分(D)的添加量之和为100重量份计，所述组分(G)填料的添加量为5～300重量份，优选为5～200重量份，进一步优选为5～150重量份。
  10. 一种预浸料，其包括增强材料及通过浸渍干燥后附着在其上的如权利要求1-9之一所述的无卤热固性树脂组合物。
  11. 一种层压板，所述层压板含有至少一张如权利要求10所述的预浸料。
  12. 一种无卤高频电路基板，所述基板含有至少一张如权利要求10所述的预浸料以及覆于叠合后的预浸料一侧或两侧的金属箔。
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