WO2015188310A1 - 一种无卤树脂组合物以及使用它的预浸料和印制电路用层压板 - Google Patents

一种无卤树脂组合物以及使用它的预浸料和印制电路用层压板 Download PDF

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WO2015188310A1
WO2015188310A1 PCT/CN2014/079567 CN2014079567W WO2015188310A1 WO 2015188310 A1 WO2015188310 A1 WO 2015188310A1 CN 2014079567 W CN2014079567 W CN 2014079567W WO 2015188310 A1 WO2015188310 A1 WO 2015188310A1
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Prior art keywords
weight
parts
halogen
resin composition
free resin
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PCT/CN2014/079567
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English (en)
French (fr)
Inventor
游江
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广东生益科技股份有限公司
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Priority to PCT/CN2014/079567 priority Critical patent/WO2015188310A1/zh
Priority to KR1020167021439A priority patent/KR101769264B1/ko
Priority to US15/027,374 priority patent/US9963590B2/en
Priority to EP14894564.5A priority patent/EP3156451B1/en
Publication of WO2015188310A1 publication Critical patent/WO2015188310A1/zh

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    • 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
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J2479/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/012—Flame-retardant; Preventing of inflammation
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/015—Fluoropolymer, e.g. polytetrafluoroethylene [PTFE]

Definitions

  • the present invention relates to a halogen-free resin composition and a prepreg and laminate using the same, which have a low dielectric constant Low dielectric loss factor, low water absorption, high dimensional stability, high heat resistance, and good flame retardancy, processability and chemical resistance. Background technique
  • Halogen-free flame-retardant copper clad laminates Development has become a hot spot in the industry, and various copper foil laminate manufacturers have launched their own halogen-free flame-retardant copper clad laminates. With the high-speed and multi-functionalization of electronic product information processing, the application frequency is constantly increasing. In addition to the higher requirements on the heat resistance of laminate materials, the dielectric constant and dielectric loss values are required to be lower and lower. ⁇ Decreasing Dk/Df has become a hot spot for substrate manufacturers.
  • Conventional FR-4 materials use dicyandiamide as a curing agent. This curing agent has a tertiary reaction amine and has good process operability.
  • phenolic resin was used as a curing agent for epoxy in the industry.
  • the phenolic resin has a high-density benzene ring structure, so the heat resistance of the system after curing with epoxy Excellent, but at the same time the dielectric properties of the cured product tend to deteriorate.
  • CN 101914265 A discloses a halogen-free phosphorus-containing flame retardant high frequency epoxy resin composition.
  • the resin composition of the invention employs a multifunctional epoxy resin instead of the conventional brominated difunctional epoxy resin.
  • a linear phenolic resin is used in place of the conventional dicyandiamide as a curing agent.
  • the epoxy resin composition is composed of a benzoxazine type epoxy resin, a tetraphenol acetonitrile epoxy resin, a DOPO modified phenol resin, an alkyl modified phenol resin, an imidazole accelerator, an inorganic filler, and an inorganic auxiliary. Flame retardant filler and other components.
  • the adhesive sheet and the copper clad laminate for a printed circuit board prepared by using the epoxy resin composition not only have green flame retardancy but also excellent dielectric properties, but the water absorption ratio of the bonding sheet and the copper clad laminate is as high as 0.3. % ⁇ 0.4%, it is easy to absorb moisture and blast in the subsequent PCB process, and the dielectric properties are general. It is difficult to meet the high-frequency development of electronic signal transmission and the high-speed development of information processing in the printed circuit CCL industry.
  • the laminate for printed circuit board produced using the resin composition has low dielectric constant, low dielectric loss factor, low water absorption, high dimensional stability, high heat resistance, and good flame retardancy, processability, and chemical resistance. Sex and other advantages.
  • the inventors conducted intensive studies to achieve the above, and found that: by alkylphenol epoxy resin with benzoxazine resin, alkylphenol phenolic curing agent, phosphorus-containing flame retardant and other optional groups
  • the above object can be attained by a suitably mixed composition.
  • a halogen-free resin composition comprising the following components:
  • the alkylphenol epoxy resin used in the present invention has more fluorenyl branches in its molecular structure, making it It has high glass transition temperature, low water absorption, good heat resistance and excellent dielectric properties. Mixing benzoxazine resin can further reduce the dielectric constant, dielectric loss and water absorption of the cured product.
  • the phenol phenolic aldehyde is a curing agent, which fully exerts the advantage that the structure has more alkyl groups and has excellent dielectric properties and low water absorption.
  • the present invention utilizes the mutual cooperation and mutual synergistic action between the above three essential components, and adds a phosphorus-containing flame retardant to obtain the above halogen-free low dielectric resin composition.
  • a prepreg and printed circuit laminate made of the halogen-free low dielectric resin composition, having a low dielectric constant, a low dielectric loss factor, low water absorption, high dimensional stability, high heat resistance, and Good flame retardancy, processability and chemical resistance.
  • the component (A) in the present invention i.e., a nonylphenol epoxy resin
  • the nonylphenol epoxy resin is added in an amount of 10 to 50 parts by weight, for example, 13 parts by weight, 16 parts by weight, 19 parts by weight, 22 parts by weight, 25 parts by weight, based on 100 parts by weight of the organic solid matter. Parts by weight, 31 parts by weight, 34 parts by weight, 37 parts by weight, 40 parts by weight, 43 parts by weight, 46 parts by weight or 49 parts by weight, preferably 20-50 parts by weight.
  • the alkylphenol epoxy resin can be used to significantly improve the dielectric properties of the cured product and maintain a synergistic force of 3 ⁇ 4. : ⁇
  • the nonylphenol epoxy resin has the following structure:
  • n is an integer between 2 and 20, For example, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19.
  • the n-butyl or n-octyl structure is regular, dielectric properties and heat resistance are good.
  • the benzoxazine resin is added in an amount of 10 to 70 parts by weight, for example, 13 parts by weight, 16 parts by weight, 19 parts by weight, 22 parts by weight, 25 parts by weight, based on 100 parts by weight of the organic solid. 28 parts by weight, 31 parts by weight, 34 parts by weight, 37 parts by weight, 40 parts by weight, 43 parts by weight, 46 parts by weight, 49 parts by weight, 52 parts by weight, 55 parts by weight, 58 parts by weight, 61 parts by weight, 64 parts by weight Parts by weight, 67 parts by weight or 69 parts by weight.
  • the benzoxazine resin is selected in an amount to increase the heat resistance and rigidity of the cured product and to lower the water absorption rate.
  • the benzoxazine resin is a bisphenol A type benzoxazine resin, a bisphenol F type benzoxazine resin, and an MDA (4,4-diaminobenzidine) type benzoxazine. Any one or a mixture of at least two of a resin, a phenolphthalein type benzoxazine resin or a dicyclopentadiene type benzoxazine resin.
  • the mixture is, for example, a mixture of a bisphenol A type benzoxazine resin and a bisphenol F type benzoxazine resin, a mixture of an MDA type benzoxazine resin and a phenolphthalein type benzoxazine resin, a dicyclopentadiene type benzene a mixture of an oxazine resin and a bisphenol A type benzoxazine resin, a bisphenol F type benzoxazine resin, a MDA type benzoxazine resin, a phenolphthalein type benzoxazine resin, and a dicyclopentadiene type benzophenone a mixture of oxazine resins.
  • the alkyl phenol phenolic curing agent is added in an amount of 5 to 25 parts by weight, for example, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight based on 100 parts by weight of the organic solid. Parts, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight or 24 parts by weight.
  • the alkyl phenol phenolic curing agent is selected in such an amount to improve both the dielectric properties of the cured product and the high adhesion.
  • the nonylphenol phenolic curing agent has the following structure:
  • R 3 , R 4 and R 5 are each independently a substituted or unsubstituted linear alkyl group or a branched alkyl group having 4 to 8 carbon atoms, preferably n-butyl or n-octyl group, ! ⁇ is ⁇ .
  • the phosphorus-containing flame retardant makes the resin composition have flame retardant properties, meets the requirements of UL 94V-0, and at the same time, the benzoxazine resin and the phosphorus-containing flame retardant have a synergistic flame retardant effect, and the flame retardancy of the cured product is reduced.
  • the phosphorus content required for UL 94V-0 further reduces the water absorption.
  • the phosphorus-containing flame retardant is added in an amount of 5 to 50 parts by weight based on 100 parts by weight of the sum of the components (A), the component (B) and the component (C).
  • 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 or 10-phenyl-9, 10-dihydro-9-oxa-10-phosphine Phenanthrene-10-oxide, phenoxyphosphazene compound, phosphate or Any one or a mixture of at least two of polyphosphates.
  • the halogen-free resin composition further includes a curing accelerator to cure the resin and accelerate the curing speed of the resin.
  • the curing agent accelerator is added in an amount of 0.05 to 1 part by weight based on 100 parts by weight of the sum of the components (A), the component (B), the component (C), and the component (D).
  • 0.08 parts by weight 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight, 0.5 parts by weight, 0.55 parts by weight, 0.6 parts by weight, 0.65 parts by weight, 0.7 parts by weight, 0.75 parts by weight, 0.8 parts by weight, 0.85 parts by weight, 0.9 parts by weight or 0.95 weight
  • the curing accelerator is selected from any one of imidazoles or/and pyridine curing accelerators or a mixture of at least two, preferably 2-methylimidazole, 2-ethyl-4-methylimidazole, Any one or a mixture of at least two of 2-phenylimidazole, 2-undecylimidazole, triethylamine, benzyldimethylamine or dimethylaminopyridine.
  • the halogen-free resin composition further comprises a filler, which is an organic or/and inorganic filler, and is mainly used to adjust some physical effects of the composition, such as lowering coefficient of thermal expansion (CTE), reducing water absorption, and increasing heat. Conductivity, etc.
  • a filler which is an organic or/and inorganic filler, and is mainly used to adjust some physical effects of the composition, such as lowering coefficient of thermal expansion (CTE), reducing water absorption, and increasing heat. Conductivity, etc.
  • the filler is added in an amount of from 0 to 100 parts by weight based on 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). Does not include 0, preferably 0 to 50 parts by weight and does not include 0.
  • the filler is added in an amount of, for example, 0.5 parts by weight, 1 part by weight, 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, and 45 parts by weight. Parts, 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.
  • the inorganic filler is selected from the group consisting of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, carbonization silicon, Any one or a mixture of at least two of barium sulfate, barium titanate, barium titanate, calcium carbonate, calcium silicate, mica or fiberglass powder.
  • the mixture is, for example, a mixture of fused silica and crystalline silica, a mixture of spherical silica and hollow silica, a mixture of aluminum hydroxide and aluminum oxide, a mixture of talc and aluminum nitride, nitrided.
  • the organic filler is selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide or polyethersulfone powder.
  • the mixture is, for example, a mixture of polytetrafluoroethylene powder and polyphenylene sulfide, a mixture of polyethersulfone powder and polytetrafluoroethylene powder, a mixture of polyphenylene sulfide and polyethersulfone powder, polytetrafluoroethylene powder, polyphenylene a mixture of thioether and polyethersulfone powder.
  • the filler is silica, and the filler has a median particle diameter of 1 to 15 ⁇ m, and preferably has a median particle diameter of 1 to 10 ⁇ m, and the filler located in the particle size segment has good dispersibility.
  • 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.
  • the conventional preparation method of the resin composition of the invention is as follows: firstly, the solid matter is put into, then the liquid solvent is added, and after stirring until the solid matter is completely dissolved, the liquid resin and the curing accelerator are added, and the stirring is continued uniformly, and finally the solvent is adjusted.
  • the solid content of the solution is from 65% to 75% to form a glue.
  • Another object of the present invention is to provide a prepreg comprising a reinforcing material and a halogen-free resin composition as described above adhered thereto by impregnation and drying.
  • Exemplary reinforcing materials are nonwoven fabrics or/and other fabrics such as natural fibers, organic synthetic fibers, and inorganic fibers.
  • the prepreg is obtained by heating and drying the impregnated reinforcing material in an oven at 155 ° C for 5 to 10 minutes using the immersion reinforcing material such as glass cloth or the organic fabric.
  • a third object of the present invention is to provide a laminate comprising at least one prepreg as described above.
  • a fourth object of the present invention is to provide a metal foil-clad laminate comprising at least one prepreg as described above and a metal foil pressed on one or both sides of the laminated prepreg by heating Made by press forming.
  • the metal foil-clad laminate was laminated by using the above-mentioned prepreg 10 sheets and two sheets of 1 ounce (35 ⁇ m thick) metal foil, and laminated by a hot press to be pressed into a metal foil-clad laminate.
  • the lamination shall meet the following requirements: 1
  • the heating rate of the lamination shall be controlled at 1.5-2.5 °C/min at a material temperature of 80-120 Torr ; 2 the pressure setting of the lamination, and the temperature of the outer layer is 120-150 ⁇ . Full pressure is applied, the full pressure is about 350 psi; 3
  • the temperature is controlled at 190 ° C and held for 90 min.
  • the metal foil is a foil, a ruthenium foil, an aluminum foil, a SUS foil, etc., and the material thereof is not limited.
  • the present invention has the following beneficial effects:
  • the halogen-free low dielectric resin composition of the invention adopts an alkylphenol epoxy resin as one of the components, and the epoxy resin has the advantages of high glass transition temperature, low water absorption rate and good heat resistance. It has excellent dielectric properties; 2 mixed with benzoxazine resin can further reduce the dielectric constant, dielectric loss value and water absorption rate of the cured product; in addition, the benzoxazine resin and the phosphorus-containing flame retardant have synergistic flame retardant effect.
  • the halogen-free low dielectric resin composition of the present invention has an alkylphenol phenol aldehyde as a curing agent, and fully exerts the advantages of having more alkyl groups in the structure to have excellent dielectric properties and low water absorption; 4 using the resin composition Prepreg, printed circuit laminates have low dielectric constant, low dielectric loss factor, low water absorption, high heat resistance, high dimensional stability, and good flame retardancy, processability and chemical resistance. advantage.
  • the laminate for a printed circuit (10 sheets of prepreg) prepared as described above was tested for its glass transition temperature, dielectric constant, dielectric loss factor, bending strength, water absorption, heat resistance, flame retardancy, and the like. The following examples are further described and described in detail.
  • Spherical silicon micropowder (average particle size 1 to ⁇ , purity 99% or more)
  • Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
  • Tg Glass transition temperature
  • DSC differential scanning calorimetry
  • the dielectric loss and dielectric loss at 1 GHz were measured in accordance with IPC-TM-6502.5.5.5.
  • the measurement was carried out in accordance with the method of BPC-TM-650 2.4.4, and the load was applied to a sample having a predetermined size and shape at room temperature.
  • the stratified foaming time was observed in accordance with IPC-TM-650 2.4.13.1.
  • Examples 1-5 are obtained by co-curing an alkylphenol epoxy resin with a benzoxazine resin and a nonylphenol phenolic curing agent, and the resulting laminate has excellent dielectric properties, low water absorption, high bending strength, and High heat resistance.
  • the laminate for printed circuit of the present invention has superior dielectric properties, moisture resistance and dimensional stability as compared with a general halogen-free laminate, and is suitable for use in a high-density interconnection field. Further, the present invention fully utilizes the synergistic properties of the benzoxazine resin and the phosphorus-containing flame retardant, and the halogen content can reach the V-0 standard of the flame retardancy test UL94 within the requirements of the JPCA halogen-free standard, and has an environmentally friendly effect.

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Abstract

提供了一种无卤树脂组合物以及使用它的预浸料和印制电路用层压板。所述无卤树脂组合物包括：烷基苯酚环氧树脂，苯并噁嗪树脂，烷基苯酚酚醛固化剂，含磷阻燃剂。由上述无卤树脂组合物制成的预浸料及印制电路用层压板，具有低介电常数、低介电损耗因素、低吸水率、高尺寸稳定性、高耐热性以及良好的阻燃性、加工性能和耐化学性。

Description

一种无卤树脂组合物以及使用它的预浸料和印制电路用层压板 技术领域 本发明涉及一种无卤树脂组合物以及使用它的预浸料和层压板， 其具有低 介电常数、 低介电损耗因素、 低吸水率、 高尺寸稳定性、 高耐热性以及良好的 阻燃性、 加工性能和耐化学性等优说点。 背景技术
书
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。 随着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， 除了对 层压板材料的耐热性有更高的要求外， 要求介电常数和介电损耗值越来越低， 国茈降低 Dk/Df已成为基板业者的追逐热点。 传统的 FR-4材料多采用双氰胺作 为固化剂， 这种固化剂具有三级反应胺， 具有良好的工艺操作性， 但由于其 C-N键较弱， 在高温下容易裂解， 导致固化物的热分解温度较低， 无法满足无 铅制程的耐热要求。 在此背景下， 随着 2006年无铅工艺的大范围实施， 行内 开始采用酚醛树脂作为环氧的固化剂， 酚醛树脂具有高密度的苯环结构， 所以 和环氧固化后体系的耐热性优异， 但同时固化物的介电性能有被恶化的趋势。 CN 101914265A公开了一种无卤含磷阻燃高频环氧树脂类组合物。 该发明 的树脂类组合物采用多官能环氧树脂， 取代传统的溴化二官能环氧树脂。 采用 线性酚醛树脂取代传统的双氰胺作固化剂。 所述环氧树脂类组合物是由苯并恶 嗪型环氧树脂、 四酚基乙垸环氧树脂、 DOPO改性酚醛树脂、 烷基改性酚醛树 脂、 咪唑促进剂、 无机填料及无机辅助阻燃填料等组成。 用该环氧树脂类组合 物所制备的印刷电路板用粘结片和覆铜板， 不仅具有绿色环保的阻燃性， 还具 有优良的介电性能， 但粘结片和覆铜板吸水率高达 0.3%~0.4%， 在后续 PCB制 程中易吸潮爆板， 且介电性能一般， 难以满足印制电路覆铜板行业电子信号传 输的高频化和信息处理的高速化发展要求。
发明内容
针对已有技术的问题， 本发明的目的在于提供一种新型的无卤低介电树脂 组合物， 以及使用它的预浸料和层压板。 使用该树脂组合物制造的印制电路用 层压板具有低介电常数、 低介电损耗因素、 低吸水率、 高尺寸稳定性、 高耐热 性以及良好的阻燃性、 加工性能、 耐化学性等优点。
本发明人为实现上述自的进行了反复深入的研究， 结果发现： 通过将烷基 苯酚环氧树脂与苯并噁嗪树脂、 烷基苯酚酚醛固化剂、 含磷阻燃剂及其他可选 地组分适当混合的组合物， 可达到上述目的。
一种无卤树脂组合物， 其包括如下组分：
(A)垸基苯酚环氧树脂；
(B)苯并噁嗪树脂；
(C)垸基苯酚酚醛固化剂；
(D)含磷阻燃剂。
本发明所采用的烷基苯酚环氧树脂分子结构中有较多垸基支链， 使其在拥 有较高玻璃化转变温度、 低吸水率、 良好耐热性的同时有优异的介电性能； 混 入苯并噁嗪树脂可以进一步降低固化物介电常数、 介电损耗值和吸水率； 以垸 基苯酚酚醛为固化剂， 充分发挥了其结构中有较多烷基从而介电性能优异吸水 率低的优势。
本发明利用上述三种必要组分之间的相互配合以及相互协同促进作用， 并 添加含磷阻燃剂， 得到了如上的无卤低介电树脂组合物。 采用这种无卤低介电 树脂组合物制成的预浸料及印制电路用层压板， 具有低介电常数、 低介电损耗 因素、 低吸水率、 高尺寸稳定性、 高耐热性以及良好的阻燃性、 加工性能和耐 化学性。
本发明中的组分 （A) ， 即垸基苯酚环氧树脂， 可以提高固化后树脂及其 制成的层压板所需的电性能、 耐湿性、 耐热性以及力学性能。 以有机固形物按 100重量份计， 所述垸基苯酚环氧树脂的添加量为 10〜50重量份， 例如 13重量 份、 16重量份、 19重量份、 22重量份、 25重量份、 28重量份、 31重量份、 34 重量份、 37重量份、 40重量份、 43 重量份、 46重量份或 49 重量份， 优选 20-50重量份。
在本发明中， 烷基苯酚环氧树脂采用上述添加量既可明显改善固化物介电 性能也可保持较 ¾的¾合力。 ： ―
优选地， 所述垸基苯酚环氧树脂具有如下结构：
Figure imgf000005_0001
式中， 和 均独立地为取代或未取代的碳原子数为 4〜8的直链烷基或支 链烷基， 优选正丁基或正辛基， n为 2〜20之间的整数， 例如 3、 4、 5、 6、 7、 8、 9、 10、 11、 12、 13、 14、 15、 16、 17、 18或 19。
在本发明中， 正丁基或正辛基结构规整、 介电性能和耐热性较好。
优选地， 以有机固形物按 100 重量份计， 所述苯并噁嗪树脂的添加量为 10-70重量份， 例如 13重量份、 16重量份、 19重量份、 22重量份、 25重量 份、 28重量份、 31重量份、 34重量份、 37重量份、 40重量份、 43重量份、 46 重量份、 49重量份、 52重量份、 55重量份、 58重量份、 61重量份、 64重量 份、 67重量份或 69重量份。
在本发明中， 苯并噁嗪树脂选择上述添加量能提高固化物耐热性和刚性并 降低吸水率。
优选地， 所述苯并噁嗪树脂为双酚 A型苯并噁嗪树脂、 双酚 F型苯并噁嗪 树脂、 MDA (4,4-二胺基二苯甲垸） 型苯并噁嗪树脂、 酚酞型苯并噁嗪树脂或 双环戊二烯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 例如双酚 A型苯并噁嗪树脂和双酚 F型苯并噁嗪树脂的混合物， MDA型苯并 噁嗪树脂和酚酞型苯并噁嗪树脂的混合物， 双环戊二烯型苯并噁嗪树脂和双酚 A型苯并噁嗪树脂的混合物， 双酚 F型苯并噁嗪树脂、 MDA型苯并噁嗪树脂、 酚酞型苯并噁嗪树脂和双环戊二烯型苯并噁嗪树脂的混合物。 优选地， 以有机固形物按 100重量份计， 所述烷基苯酚酚醛固化剂的添加 量为 5~25重量份， 例如 6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重量份或 24重量份。
在本发明中， 烷基苯酚酚醛固化剂选择上述添加量既能改善固化物介电性 能也可保持较高的粘合力。
优选地， 所述垸基苯酚酚醛固化剂具有如下结构：
Figure imgf000006_0001
式中， R3、 R4和 R5均独立地为取代或未取代的碳原子数为 4〜8的直链烷基 或支链垸基， 优选为正丁基或正辛基， ！^为 〜。之间的整数， 例如 3、 4、 5、 6、 7、 8、 9、 10、 11、 12、 13、 14、 15、 16、 17、 18或 19。
含磷阻燃剂的添加使树脂组合物具有阻燃特性， 符合 UL 94V-0要求， 同 时， 苯并噁嗪树脂与含磷阻燃剂有协同阻燃效果， 减少了固化物阻燃性达到 UL 94V-0所需磷含量， 进一步地降低了吸水率。 优选地， 以组分 （A) 、 组分 (B)和组分（C) 的添加量之和为 100重量份计， 所述含磷阻燃剂的添加量为 5~50重畺份， 例如 7重量份、 9重量份、 11重量份、 13重量份、 16重量份、 19重量份、 22重量份、 25重量份、 28重量份、 31重量份、 34重量份、 37重 量份、 40重量份、 43重量份、 46重量份或 49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)膦基苯或 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。
优选地， 所述无卤树脂组合物还包括固化促进剂， 使树脂固化并加快树脂 固化速度。 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， 所述固化剂促进剂的添加量为 0.05~1重量份， 例如 0.08重量 份、 0.1重量份、 0.15重量份、 0.2重量份、 0.25重量份、 0.3重量份、 0.35重量 份、 0.4重量份、 0.45重量份、 0.5重量份、 0.55重量份、 0.6重量份、 0.65重量 份、 0.7重量份、 0.75重量份、 0.8重量份、 0.85重量份、 0.9重量份或 0.95重
优选地， 所述固化促进剂选自咪唑类或 /和吡啶类固化促进剂中的任意一 种或者至少两种的混合物， 优选 2-甲基咪唑、 2-乙基 -4-甲基咪唑、 2-苯基咪 唑、 2-十一烷基咪唑、 三乙胺、 苄基二甲胺或二甲氨基吡啶中的任意一种或者 至少两种的混合物。
优选地， 所述无卤树脂组合物还包含填料， 所述填料为有机或 /和无机填 料， 主要用来调整组合物的一些物性效果， 如降低热膨胀系数 （CTE) 、 降低 吸水率、 提高热导率等。
优选地， 以组分 （A) 、 组分 （B ) 、 组分 （C) 和组分 （D) 的添加量之 和 100重量份计， 所述填料的添加量为 0〜100重量份且不包括 0， 优选 0~50 重量份且不包括 0。 所述填料的添加量例如为 0.5 重量份、 1 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、 75重量份、 80重量份、 85重量份、 90重量份或 95重量份。
优选地， 所述无机填料选自熔融二氧化硅、 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、 云母或玻璃纤维粉中的任意一种 或者至少两种的混合物。 所述混合物例如熔融二氧化硅和结晶型二氧化硅的混 合物， 球型二氧化硅和空心二氧化硅的混合物， 氢氧化铝和氧化铝的混合物， 滑石粉和氮化铝的混合物， 氮化硼和碳化硅的混合物， 硫酸钡和钛酸钡的混合 物， 钛酸锶和碳酸钙的混合物， 硅酸钙、 云母和玻璃纤维粉的混合物， 熔融二 氧化硅、 结晶型二氧化硅和球型二氧化硅的混合物， 空心二氧化硅、 氢氧化铝 和氧化铝的混合物， 滑石粉、 氮化铝和氮化硼的混合物， 碳化硅、 硫酸钡和钛 酸钡的混合物， 钛酸锶、 碳酸钙、 硅酸钙、 云母和玻璃纤维粉的混合物。
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 任意一种或者至少两种的混合物。 所述混合物例如聚四氟乙烯粉末和聚苯硫醚 的混合物， 聚醚砜粉末和聚四氟乙烯粉末的混合物， 聚苯硫醚和聚醚砜粉末的 混合物， 聚四氟乙烯粉末、 聚苯硫醚和聚醚砜粉末的混合物。
优选地， 所¾填料为二氧化硅， 填料的粒径中度值为 1~15μιη， 优选填料 的粒径中度值为 1~10μιη， 位于此粒径段的填料具有良好的分散性。
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 ， 还可以替换为封趙式的 "为"或 "由……组成" 。 ―
例如， 所述无卤树脂组合物还可以含有各种添加剂， 作为具体例， 可以举 出抗氧剂、 热稳定剂、 抗静电剂、 紫外线吸收剂、 颜料、 着色剂或润滑剂等。 这些各种添加剂可以单独使用， 也可以两种或者两种以上混合使用。
本发明树脂组合物的常规制备方法为： 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， 再加入液态树脂和固化促进剂， 继续搅拌均匀 即可， 最后用溶剂调整溶液固体含量至 65%~75%而制成胶液。 本发明的目的之二在于提供一种预浸料， 其包括增强材料及通过含浸干燥 后附着其上的如上所述的无卤树脂组合物。
示例性的增强材料如无纺织物或 /和其他织物， 例如天然纤维、 有机合成 纤维以及无机纤维。
使用该胶液含浸增强材料如玻璃布等织物或有机织物， 将含浸好的增强材 料在 155°C的烘箱中加热干燥 5-10分钟即可得到预浸料。
本发明的目的之三在于提供一种层压板， 其包括至少一张如上所述的预浸 料。
本发明的目的之四在于提供一种覆金属箔层压板， 其包括至少一张如上所 述的预浸料及压覆在叠合的预浸料一侧或两侧的金属箔， 其通过加热加压成形 而制得。
所述的覆金属箔层压板是使用上述的预浸料 10片和 2片 1盎司 （35μιη厚 度） 的金属箔叠合在一起， 通过热压机层压， 从而压制成覆金属箔层压板。 所 述的层压须满足以下要求： ①层压的升温速率通常在料温 80-120Ό时应控制在 1.5-2.5 °C/min; ②层压的压力设置， 外层料温在 120-150Ό施加满压， 满压压力 为 350psi左右； ③固化时， 控制料温在 190°C， 并保温 90min。 所述的金属箔 为靈箔、 镡箔、 铝箔及 SUS箔等， 其材质不限。
与已有技术相比， 本发明具有如下有益效果：
①本发明涉及的无卤低介电树脂组合物采用烷基苯酚环氧树脂作为组分之 一， 该环氧树脂除了拥有玻璃化转变温度高、 吸水率低、 耐热性好等优点外还 有着优异的介电性能； ②混入苯并噁嗪树脂可以进一步降低固化物介电常数、 介电损耗值、 吸水率； 此外， 苯并噁嗪树脂与含磷阻燃剂有协同阻燃效果， 能 减少固化物阻燃性达到 UL 94V-0所需磷含量， 更进一步降低吸水率； ③本发 明的无卤低介电树脂组合物以烷基苯酚酚醛为固化剂， 充分发挥了其结构中有 较多烷基从而介电性能优异且吸水率低的优势； ④使用该树脂组合物制成的预 浸料、 印制电路用层压板具有低介电常数、 低介电损耗因素、 低吸水率、 高耐 热性、 高尺寸稳定性以及良好的阻燃性、 加工性能和耐化学性的优点。
具体实«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。
针对上述制成的印制电路用层压板（10片预浸料)测试其玻璃化转变温度、 介电常数、 介电损耗因素、 弯曲强度、 吸水性、 耐热性、 阻燃性等性能， 如下 实施例进一步详细说明与描述。
兹将本发明实施例详细说明如下， 但本发明并非局限在实施例范围。 下文 中无特别说明， 其份代表重量份， 其％代表 "重量％" 。
(A)环氧树脂
(A-1 )垸基苯酚环氧树脂
KES-7595 (韩国 KOLON商品名）
(A-2)双酚 A酚醛环氧树脂
EPR627MEK80 (美国 Hexion商品名）
― (B )苯并噁嗪树脂 _
LZ 8290H62 (HUNTSMAN商品名）
(C) 固化剂
(C-1 )烷基苯酚酚醛固化剂
KPT-F1350E (韩国 KOLON商品名）
(C-2) 线性酚醛固化剂
2812 (韩国 MOMENTIVE商品名） (D)含磷阻燃剂
DOW XZ92741 (美国 DOW商品名）
(E) 2-苯基咪唑 （日本四国化成）
(F)填料
球型硅微粉 （平均粒径为 1至 ΙΟμηι, 纯度 99%以上)
表 1、 各实施例比较例的配方组成及其物性数据
实施例 1 实施例 2 实施例 3 实施例 4 实施例 5
A-1 50 40 30 20 10
Α-2 ― ― ― -— ―
Β 10 25 40 55 70
C-1 25 20 15 10 5
C-2 ― ― ― ― ―
D 15 15 15 35 5
Ε 适量 适量 适量 适量 适量
F 40 40 40 40 40 玻璃化转变温度 172 164 166 158 175 (DSC) °C
介电常数 ( 1GHz) 3.55 3.57 3.61 3.60 3.67 介电损耗（1GHz) 0.0088 0.0085 0.0092 0.0090 0.0098 弯曲强度（N/mm2) 504 532 551 575 578 吸水性 （％) 0.08 0.07 0.06 0.06 0.06 耐浸焊 288°C， s >120 >120 >120 >120 >120 难燃烧性 V-0 V-0 V-0 V-0 V-0 表 2、 各比较例的配方组成及其物性数据
Figure imgf000012_0001
以上特性的测试方法如下：
(a)玻璃化转变温度 (Tg): 根据差示扫描量热法 (DSC)， 按照 IPC-TM-650 所规定的 DSC方法进行测定。 (b )介电常数、 介电损耗因素
根据使用条状线的共振法， 按照 IPC-TM-6502.5.5.5测定 1GHz下的介电损 耗、 介电损耗因素。
( c ) 弯曲强度
按照 BPC-TM-650 2.4.4方法进行， 在室温下把负载施加于规定尺寸和形状 的试样上进行测定。
( d) 吸水性
按照 IPC-TM-650 2.6.2.1方法进行测定。
( e ) 耐浸焊性
按照 IPC-TM-650 2.4.13.1观察分层起泡时间。
( f) 难燃烧性
依据 UL 94垂直燃烧法测定。
从表 1和表 2的物性数据可知， 比较例 1中使用垸基苯酚环氧树脂与烷基 苯酚酚醛固化剂固化时介电性能较好， 但吸水率高同时弯曲强度低耐热性差； 比较例 2中用双酚 A酚醛环氧树脂与苯并噁嗪树脂、 烷基苯酚酚醛固化剂共固 化， 比较例 3中用烷基苯酚环氧树脂与苯并噁嗪树脂、 线性酚醛树脂共固化， 当； 基苯酚环氧树脂与垸基苯酚酚驚固化剂只存其一时固化物介电性能较差， 介电常数和介电损耗均偏高。 实施例 1-5是用了烷基苯酚环氧树脂与苯并噁嗪 树脂和垸基苯酚酚醛固化剂共固化后， 得到的层压板拥有优异的介电性能、 低 吸水率、 高弯曲强度和高耐热性。
由此可以得知， 只有当垸基苯酚环氧树脂、 苯并噁嗪树脂和烷基苯酚酚醛 固化剂三者同时存在时， 由于三种组分之间的相互协同促进作用， 才可以得到 综合性能优异的层压板。 而比较例 1~3中分别未采用苯并噁嗪树脂、 烷基苯酚 环氧树脂以及烷基苯酚酚醛固化剂， 因此， 比较例 1~3中的层压板的综合性能 明显劣于实施例 1〜5中的层压板。
因此， 与一般的无卤层压板相比， 本发明的印制电路用层压板在具有更优 异的介电性能、 耐湿性和尺寸稳定性， 适用于高密度互联领域。 另外本发明充 分利用了苯并噁嗪树脂与含磷阻燃剂的协同特性， 卤素含量在 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， 有环保的功效。
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。
申请人声明， 本发明通过上述实施例来说明本发明的详细组成， 但本发明 并不局限于上述详细组成， 即不意味着本发明必须依赖上述详细组成才能实 施。 所属技术领域的技术人员应该明了， 对本发明的任何改进， 对本发明产品 各原料的等效替换及辅助成分的添加、 具体方式的选择等， 均落在本发明的保 护范围和公开范围之内。

Claims

权 利 要 求 书
1、 一种无卤树脂组合物， 其特征在于， 其包括如下组分：
(A) 垸基苯酚环氧树脂；
(B ) 苯并噁嗪树脂；
(C ) 垸基苯酚酚醛固化剂；
(D) 含磷阻燃剂。
2、 如权利要求 1 所述的无卤树脂组合物， 其特征在于， 以有机固形物按 100重量份计， 所述垸基苯酚环氧树脂的添加量为 10〜50重量份， 优选 20〜50 重量份。
3、如权利要求 1所述的无卤树脂组合物， 其特征在于， 所述垸基苯酚环氧 树脂具有如下结构：
Figure imgf000015_0001
Ri R2
式中， R^P R2均独立地为取代或未取代的碳原子数为 4〜8的直链垸基或支 链垸基， 优选正丁基或正辛基， n为 2〜20之间的整数。
4、 如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 以有机固形物 按 100重量份计， 所述苯并噁嗪树脂的添加量为 10〜70重量份。
5、如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 所述苯并噁嗪 树脂为双酚 A型苯并噁嗪树脂、 双酚 F型苯并噁嗪树脂、 MDA型苯并噁嗪树 脂、 酚酞型苯并噁嗪树脂或双环戊二烯型苯并噁嗪树脂中的任意一种或者至少 两种的混合物。
6、 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 按 100重量份计， 所述垸基苯酚酚醛固化剂的添加量为 5〜25重量份。
7、如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 所述垸基苯酚 酚醛固化剂具有如下结构：
Figure imgf000016_0001
R3 R4 R5
式中， R3、 R4和 R5均独立地为取代或未取代的碳原子数为 4〜8的直链垸基 或支链垸基， 优选为正丁基或正辛基， ^为？^。之间的整数。
8、 如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 以组分 (A)、 组分 （B )和组分 （C ) 的添加量之和为 100重量份计， 所述含磷阻燃剂的添加 量为 5〜50重量份。
9、如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 所述含磷阻燃 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)膦基苯或 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。
10、 如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 所述无卤树 脂组合物还包括固化促进剂， 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， 所述固化促进剂的添加量为 0.05〜1重量份。
11、如权利要求 10所述的无卤树脂组合物， 其特征在于， 所述固化促进剂 选自咪唑类或 /和吡啶类固化促进剂中的任意一种或者至少两种的混合物， 优 选 2-甲基咪唑、 2-乙基 -4-甲基咪唑、 2-苯基咪唑、 2H ^—垸基咪唑、 三乙胺、 苄基二甲胺或二甲氨基吡啶中的任意一种或者至少两种的混合物。
12、 如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 所述无卤树 脂组合物还包含填料， 所述填料为有机或 /和无机填料。
13、 如权利要求 12所述的无卤树脂组合物， 其特征在于， 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， 所述填料 的添加量为 0〜100重量份且不包括 0， 优选 0〜50重量份且不包括 0。
14、如权利要求 12所述的无卤树脂组合物， 其特征在于， 所述无机填料选 自熔融二氧化硅、 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、 云母或玻璃纤维粉中的任意一种或者至少两种的混合物。
15、如权利要求 12所述的无卤树脂组合物， 其特征在于， 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者至少两种的混合 物。
16、 如权利要求 12 所述的无卤树脂组合物， 其特征在于， 所述填料为二 氧化硅， 填料的粒径中度值为 1〜15μιη， 优选填料的粒径中度值为 1〜10μιη。
17、 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其 上的如权利要求 1-16之一所述的无卤树脂组合物。
18、 一种层压板， 其特征在于， 其包括至少一张如权利要求 17 所述的预 浸料。
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