WO2016101540A1 - 一种无卤环氧树脂组合物以及使用它的预浸料和层压板 - Google Patents

一种无卤环氧树脂组合物以及使用它的预浸料和层压板 Download PDF

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WO2016101540A1
WO2016101540A1 PCT/CN2015/080537 CN2015080537W WO2016101540A1 WO 2016101540 A1 WO2016101540 A1 WO 2016101540A1 CN 2015080537 W CN2015080537 W CN 2015080537W WO 2016101540 A1 WO2016101540 A1 WO 2016101540A1
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epoxy resin
halogen
weight
parts
resin composition
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PCT/CN2015/080537
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English (en)
French (fr)
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曾宪平
何烈相
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广东生益科技股份有限公司
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Priority to KR1020167022194A priority Critical patent/KR101798810B1/ko
Priority to US15/118,204 priority patent/US9873789B2/en
Priority to EP15871615.9A priority patent/EP3093315B1/en
Publication of WO2016101540A1 publication Critical patent/WO2016101540A1/zh

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    • 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
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
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    • H05K1/00—Printed circuits
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    • H05K1/0313—Organic insulating material
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Definitions

  • the invention belongs to the technical field of copper clad laminates, and particularly relates to a halogen-free epoxy resin composition and a prepreg, a laminate and a printed circuit board using the same.
  • halogen flame retardants For a long time, laminates for printed circuit boards usually use halogen flame retardants to achieve flame retardant purposes. However, when halogen flame retardants are burned, not only smoke is large, smell is unpleasant, and highly corrosive hydrogen halide gas is generated. . In other literatures, in recent years, halogen-containing flame retardants produce carcinogens such as dioxins and dibenzofurans during pyrolysis and combustion at high temperatures. Therefore, with the EU Directive on Waste Electrical and Electronic Equipment and The Directive on the Restriction of the Use of Hazardous Substances in Electrical and Electronic Equipment was officially implemented on July 1, 2006. The development of laminates for halogen-free flame-retardant printed circuit has become the focus of the industry.
  • DOPO is a commonly used additive in a resin composition, and its main purpose is to improve the flame retardancy of the resin composition so that the resin composition can maintain stability even when applied to a high temperature environment.
  • CNl03724997A uses polycyclic benzoxazine resin and polyfunctional epoxy resin and phosphorus-containing phenolic resin, which is a linear phosphorus-containing phenolic resin, although its heat resistance is high, but dielectric properties and water absorption rate are poor. .
  • CN 102585126 B The synthesis of a phosphorus-containing phenolic resin is carried out by reacting phenol with phosphorus oxychloride to synthesize a phosphorus-containing compound, followed by reaction with a phenolic resin.
  • CNl02206397B includes an epoxy resin, a hardening accelerator, a crosslinking agent, and a phosphorus-containing resin, which is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof.
  • a substituted bisphenol phenolic resin is used to synthesize a copper-clad laminate.
  • the bisphenol structure is present in the phosphorus-containing phenolic resin, it has poor moisture-heat resistance, high water absorption, and poor dielectric properties.
  • CN 103382242 A mentions the synthesis of a phenolic resin with a phenolic compound, a bisphenol compound and formaldehyde, followed by a polycondensation reaction by mixing a phenolic resin with an aromatic phosphate to obtain a phosphorus-containing flame retardant phenolic resin.
  • the bisphenol compound and the phenol compound By the structure of the bisphenol compound and the phenol compound, the problem of insufficient heat resistance of the existing phosphorus-containing bisphenol phenol resin alone is improved, but the bisphenol compound in the structure is bisphenol A/bisphenol F/double The heat resistance, dielectric properties and water absorption of phenol S and so on need to be further improved.
  • halogen-free epoxy resin composition and a prepreg and laminate using the same.
  • the laminate produced using the halogen-free epoxy resin composition has advantages of high heat resistance, low dielectric constant, low dielectric loss factor, and low water absorption, and can realize halogen-free flame retardancy.
  • the present inventors conducted intensive studies to achieve the above object, and as a result, found that the above object can be attained by a composition obtained by appropriately mixing an epoxy resin, a crosslinking agent, a phosphorus-containing phenol resin, and other optional components.
  • a halogen-free epoxy resin composition comprising the following components:
  • the phosphorus-containing phenolic resin has the following structure:
  • a and A 1 are each independently
  • p, q, m and n represent repeating units, each independently being an integer greater than or equal to 1;
  • X is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof, and X in different structures may be the same or different;
  • R is hydrogen, an aliphatic functional group or an aromatic functional group, and R may be the same or different in different structures.
  • a phosphorus-containing phenolic resin which is synthesized by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof, is synthesized with phenol and formaldehyde.
  • the phenolic resin can be used as a curing agent for epoxy resins and provides halogen-free flame retardant properties.
  • the invention adopts a phosphorus-containing phenolic resin, has better flame retardancy with respect to other kinds of phosphate compounds, and has better crosslinkability than DOPO compound or DOPO-HQ resin, thereby improving crosslinking density, Reactivity and glass transition temperature.
  • it because of its structure, it contains a dicyclopentadiene ring with high heat resistance, excellent dielectric properties and low water absorption, which has high heat resistance, low dielectric constant, low dielectric loss factor and low water absorption.
  • the addition of an epoxy resin can significantly improve the toughness and curing crosslink density of the cured product.
  • the crosslinking agent can effectively enhance the crosslinking and curing action of the epoxy resin.
  • the invention utilizes the mutual cooperation between the above three necessary components and the mutual synergistic promotion effect.
  • the halogen-free epoxy resin composition as above was obtained.
  • the prepreg and the laminate prepared by using the halogen-free epoxy resin composition have the advantages of high heat resistance, low dielectric constant, low dielectric loss factor and low water absorption, and can realize halogen-free flame retardancy.
  • the halogen-free epoxy resin is a biphenolic epoxy resin, a DCPD novolac epoxy resin, an alkylene novolac epoxy resin, a bisphenol A novolac epoxy resin, a bisphenol Z epoxy resin, and a double Phenolic AP type epoxy resin, bisphenol TMC type epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, Triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin , naphthol aralkyl type epoxy resin, naphthol-phenol copolycondensation novolak type epoxy resin, naphthol-cresol copolycondensation novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy Any one
  • the halogen-free epoxy resin is any one or a mixture of at least two of a biphenolic epoxy resin, a DCPD novolac epoxy resin or a bisphenol A type novolac epoxy resin, which has high heat resistance.
  • the epoxy resin is a biphenolic epoxy resin or/and a DCPD novolac epoxy resin, which has both good heat resistance and dielectric properties.
  • the crosslinking agent is any one of an active ester, an acid anhydride compound or a phenol resin or a mixture of at least two.
  • the active ester is an active ester crosslinking agent having a functional group ester group
  • the acid anhydride compound may be a compound such as styrene maleic anhydride.
  • the phenol resin may be a hydroxyl group-containing phenol resin such as a novolac resin, a biphenol novolac resin, an alkylphenol phenol resin, or a DCPD phenol resin.
  • the crosslinking agent is an active ester active/and anhydride compound, which is relative to a phenolic resin, Has better dielectric properties.
  • the crosslinking agent is an active ester having the following structure: a specific structure of the active ester, wherein a rigid structure such as a benzene ring, a naphthalene ring or a cyclopentadiene imparts high heat resistance to the active ester, Due to the regularity of its structure and the absence of secondary hydroxyl groups during the reaction with epoxy resin, it imparts good electrical properties and low water absorption.
  • X is a phenyl or naphthyl group, j is 0 or 1, k is 0 or 1, and n represents a repeating unit of 0.25 to 1.25.
  • the phosphorus-containing phenol resin is 30-70 parts by weight, for example, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, based on 100 parts by weight of the halogen-free epoxy resin.
  • 60 parts by weight or 65 parts by weight, preferably 35-65 parts by weight, of the crosslinking agent is 27-58 parts by weight, preferably 35-55 parts by weight.
  • the halogen-free epoxy resin composition may further comprise a cyanate ester or a benzoxazine, which can increase the glass transition temperature of the composition, and simultaneously achieve NP synergistic flame retardancy with the phosphorus-containing phenolic resin, and improve the resistance. Fuel efficiency.
  • the cyanate ester may be a cyanate ester compound containing at least two cyanooxy groups in a molecule such as a bisphenol A type cyanate ester or a prepolymer thereof, which is more than benzoxazine.
  • the glass transition temperature of the composition is well raised.
  • the cyanate ester or a prepolymer thereof is added in an amount of 20 to 40 parts by weight based on 100 parts by weight of the sum of the components (A), the component (B) and the component (C). For example, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight or 38 parts by weight.
  • the halogen-free epoxy resin composition further comprises a curing accelerator which cures the resin and adds Fast resin curing speed.
  • the curing agent accelerator is added in an amount of 0.05 to 1 part by weight, for example, 0.08, based on 100 parts by weight of the sum of the addition amounts of the component (A), the component (B), and the component (C).
  • 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, 0.60 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 parts by weight.
  • the curing accelerator is any one of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl 4-ethylimidazole or 2-phenylimidazole, zinc isooctanoate or at least two mixture.
  • the present invention may optionally additionally add at least one specific flame retardant compound.
  • the halogen-free epoxy resin composition may further include a flame retardant compound which is a flame retardant salt such as a phosphate compound or a nitrogen-containing phosphate compound, but is not limited thereto.
  • a flame retardant compound which is a flame retardant salt such as a phosphate compound or a nitrogen-containing phosphate compound, but is not limited thereto.
  • the flame retardant compound is added in an amount of from 0 to 50 parts by weight, based on 100 parts by weight of the sum of the addition amounts of the component (A), the component (B), and the component (C), and does not include 0, for example, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or 50 parts by weight.
  • the halogen-free epoxy resin composition further comprises a filler, which is an organic or/and inorganic filler, which is mainly used to adjust some physical effects of the composition, such as lowering coefficient of thermal expansion (CTE) and reducing water absorption. And improve thermal conductivity and so on.
  • a filler which is an organic or/and inorganic filler, which is mainly used to adjust some physical effects of the composition, such as lowering coefficient of thermal expansion (CTE) and reducing water absorption. And improve thermal conductivity and so on.
  • the filler is added in an amount of from 0 to 100 parts by weight and not including 0, based on 100 parts by weight of the sum of the components (A), the component (B) and the component (C). 0 to 50 parts by weight and excluding 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. Share, 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 Any one or a mixture of at least two of silicon, 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, and nitrided.
  • the organic filler is selected from any one of a polytetrafluoroethylene powder, a polyphenylene sulfide or a polyethersulfone powder or a mixture of at least two.
  • 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 the filler has a median particle diameter of 1 to 10 ⁇ m.
  • the halogen-free epoxy 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 or a lubricant. Wait. These various additives may be used singly or in combination of two or more kinds.
  • the conventional preparation method of the halogen-free epoxy resin composition of the invention taking a container, first putting the solid component, then adding the liquid solvent, stirring until completely dissolved, adding liquid resin, filler, flame retardant and curing promotion
  • the agent can be stirred evenly, and finally the solvent is used to adjust the liquid solid content to 60% to 80% to prepare a glue.
  • Another object of the present invention is to provide a prepreg comprising a reinforcing material and a halogen-free epoxy resin composition as described above adhered thereto by impregnation and drying.
  • Exemplary reinforcing materials are nonwoven fabrics and/or 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 to 170 ° C for 5 to 10 minutes by using a woven fabric or an organic fabric such as a glass cloth impregnated reinforcing material.
  • 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 printed circuit board comprising at least one prepreg as described above.
  • the present invention has the following beneficial effects:
  • the phosphorus-containing phenolic resin can be used as a curing agent for an epoxy resin, and can provide halogen-free flame retardant properties, and has a dicyclopentadiene ring in its main chain, so that it has not only a low dielectric constant but also a low dielectric constant. Dielectric loss value, low water absorption and a higher glass transition temperature.
  • Prepregs, laminates and metal foil-clad laminates made using the halogen-free epoxy resin composition have the advantages of high heat resistance, low dielectric constant, low dielectric loss factor, and low water absorption, and can Achieve halogen-free flame retardant.
  • the prepregs obtained by using a plurality of sheets are superposed on each other, and a copper foil is respectively pressed on both sides thereof and placed in a heat press to be cured to form the epoxy resin copper clad laminate.
  • the physical property data is shown in Table 1.
  • the production process is the same as that of the implementation column 1.
  • the formulation composition and physical property index are shown in Table 1.
  • the manufacturing process was the same as that of Example 1, and the formulation composition and physical property index are shown in Table 2.
  • the table is based on the weight of solid components.
  • NC-3000H Biphenol novolac epoxy resin (trade name of Nippon Chemical Co., Ltd.).
  • HPC-8000-65T Active ester curing agent (Japanese DIC trade name).
  • EF-40 styrene maleic anhydride (trade name of Sadoma).
  • CE01PS Yangzhou Tianqi's bisphenol A type cyanate (Yangzhou Tianqi Chemical Trade Name).
  • 2E4MI curing accelerator, 2-methyl-4-ethylimidazole (trade name of Shikoku Chemical Co., Japan).
  • DMAP curing accelerator, 4-dimethylaminopyridine (Golden Chemical Co., trade name).
  • Zinc isooctanoate curing accelerator (Alfa Aesar trade name)
  • Tg Glass transition temperature
  • PCT and PCT water absorption rate after etching the copper foil indicated by the copper clad board, the substrate is evaluated: the substrate is placed in a pressure cooker, and treated at 120 ° C, 150 KPa for two hours: after being immersed in a tin furnace at 288 ° C When the substrate is layered, the corresponding time is recorded: the evaluation can be ended when the substrate has not appeared bubbles or delamination in the tin furnace for more than 5 minutes.
  • the existing phosphorus-containing phenolic resin is used in the presence of a PCT layered blasting plate, which has poor dielectric properties and heat and humidity resistance and a low glass transition temperature.
  • Examples 1-9 were synthesized using a halogen-free epoxy resin, a crosslinking agent, and a 1,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide substituted with phenol and formaldehyde.
  • the phosphorus-containing phenolic resin a composition composed of three blends, has the advantages of high heat resistance, low dielectric constant, low dielectric loss factor and low water absorption, and can realize halogen-free flame retardant.
  • the halogen-free circuit substrate of the present invention has high heat resistance as compared with a general laminate. Low dielectric constant, low dielectric loss factor, low water absorption and halogen-free flame retardant.

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Abstract

本发明提供了一种无卤环氧树脂组合物以及使用它的预浸料和层压板。该无卤环氧树脂组合物包括：(A)无卤环氧树脂；(B)交联剂；(C)含磷酚醛树脂，该含磷酚醛树脂为9，10-二氢-9-氧杂-10-磷菲-10-氧化物或其衍生物所取代的双环戊二烯酚与苯酚及甲醛合成的酚醛树脂。使用这种无卤环氧树脂组合物制成的预浸料和层压板，具有高耐热性、低介电常数、低介电损耗因素和低吸水率的优点，且能实现无卤阻燃。

Description

一种无卤环氧树脂组合物以及使用它的预浸料和层压板 技术领域
本发明属于覆铜板技术领域，具体涉及一种无卤环氧树脂组合物以及使用它的预浸料、层压板和印制电路板。
背景技术
一直以来，印制电路用层压板通常采用卤素阻燃剂达到阻燃目的，但卤素阻燃剂在燃烧时，不但发烟量大，气味难闻，而且会产生腐蚀性很强的卤化氢气体。另有文献报道，近年来在含卤素的阻燃剂在高温裂解和燃烧时会产生二噁英、二苯并呋喃等致癌物质，因此，随着欧盟《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有害物质指令》于2006年7月1日正式实施，无卤阻燃型印制电路用层压板的开发成为了业界的重点。
另一方面，随着电子元器件朝着，小型轻量薄型化、高性能化、多功能化的方向发展，随之带来的是高频、高速的信号传输。除此之外，高多层PCB板因CCL的耐湿热性和吸水性差而导致的分层爆板问题，引起了极大的关注。
DOPO为树脂组合物中常用的添加剂，其主要目的在于提高树脂组合物的阻燃性，以使树脂组合物应用于高温环境时仍可保持稳定性。
宋晓云在该文章中公开了(宋晓云，含磷酚醛树脂的合成及应用，《第十二届中国覆铜板.市场研讨会论文集》，2009，第225页)采用DOPO与线性酚醛合成含磷酚醛树脂。
CNl03724997A采用多环苯并噁嗪树脂和多官能环氧树脂及含磷酚醛树脂，该含磷酚醛树脂为线性含磷酚醛树脂，虽然其耐热性较高，但介电性能和吸水率较差。
CN 102585126 B取苯酚与三氯氧磷反应合成含磷化物后，接着与酚醛树脂反应，合成一种含磷酚醛树脂。
CNl02206397B采用包括环氧树脂、硬化促进剂、交联剂以及含磷树脂，该含磷树脂为9，10-二氢-9-氧杂-10-磷菲-10-氧化物或其衍生物所取代的双酚酚醛树脂合成一种覆铜板，但由于该含磷酚醛树脂中，有双酚结构存在，使着其存在耐湿热性差、高吸水性、介电性能较差。
CN 103382242A提及用苯酚类化合物、双酚类化合物与甲醛合成酚醛树脂，然后将酚醛树脂与芳香性磷酸酯混合进行缩聚反应获得含磷阻燃酚醛树脂。通过双酚类化合物与苯酚类化合物的结构，改善单独采用现有含磷双酚酚醛树脂，耐热性不足的问题，但其结构中的双酚类化合物为双酚A/双酚F/双酚S等，其耐热性、介电性能及吸水率有待进一步提升。
为此，如何在保持组合物具有高的耐热性同时，兼具好的介电性能和低吸水率，又能实现无卤阻燃是本领域亟待解决的技术问题。
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无卤环氧树脂组合物以及使用它的预浸料和层压板。使用该无卤环氧树脂组合物制造的层压板具有高耐热性、低介电常数、低介电损耗因子和低吸水率的优点，且能实现无卤阻燃。
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：通过将环氧树脂、交联剂和含磷酚醛树脂，及其他可选地组分适当混合得到的组合物，可达到上述目的。
一种无卤环氧树脂组合物，其包括如下组分：
(A)无卤环氧树脂；
(B)交联剂；
(C)含磷酚醛树脂；
所述含磷酚醛树脂具有如下结构：
Figure PCTCN2015080537-appb-000001
A和A1均独立地为
Figure PCTCN2015080537-appb-000002
p、q、m和n表示重复单元，均独立地为大于等于1的整数；
X为9，10-二氢-9-氧杂-10-磷菲-10-氧化物或其衍生物，不同结构中的X可以相同也可以不同；
R为氢、脂肪族官能基或芳香族官能基，不同结构中R可以相同也可以不同。
在本发明中，含磷酚醛树脂，其为9，10-二氢-9-氧杂-10-磷菲-10-氧化物或其衍生物所取代的双环戊二烯酚与苯酚及甲醛合成的酚醛树脂，可作为环氧树脂的固化剂，又能提供无卤阻燃特性。本发明采用含磷酚醛树脂，相对于其它种类的磷酸盐化合物具有较佳的阻燃性，且其相较于DOPO化合物或DOPO-HQ树脂有较佳的交联性，可提高交联密度、反应性及玻璃转化温度。又因为其结构中含有含高耐热、介电性能优、低吸水率的双环戊二烯环，使其兼具有高耐热性、低介电常数、低介电损耗因素和低吸水率的优点。
在本发明中，环氧树脂加入可以明显改善固化物的韧性和固化交联密度。
在本发明中，交联剂可有效提升和环氧树脂的交联固化作用。
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，得 到了如上的无卤环氧树脂组合物。采用该无卤环氧树脂组合物制成的预浸料及层压板，兼具高耐热性、低介电常数、低介电损耗因素和低吸水率的优点，且能实现无卤阻燃。
优选地，所述无卤环氧树脂为联苯酚醛环氧树脂、DCPD酚醛环氧树脂、亚烷基酚醛环氧树脂、双酚A型酚醛环氧树脂、双酚Z型环氧树脂、双酚AP型环氧树脂、双酚TMC型环氧树脂、含联苯型环氧树脂、四甲基联苯型环氧树脂、苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、三苯基甲烷型环氧树脂、四苯基乙烷型环氧树脂、双环戊二烯-苯酚加成反应型环氧树脂、苯酚芳烷基型环氧树脂、萘酚酚醛清漆型环氧树脂、萘酚芳烷基型环氧树脂、萘酚-苯酚共缩聚酚醛清漆型环氧树脂、萘酚-甲酚共缩聚酚醛清漆型环氧树脂、芳香族烃甲醛树脂改性酚醛树脂型环氧树脂、联苯改性酚醛清漆型环氧树脂任意一种或者至少两种的混合物。
进一步优选地，所述无卤环氧树脂为联苯酚醛环氧树脂、DCPD酚醛环氧树脂或双酚A型酚醛环氧树脂任意一种或者至少两种的混合物，其具有高耐热性。
更优选，所述环氧树脂为联苯酚醛环氧树脂或/和DCPD酚醛环氧树脂，其兼具好的耐热性和介电性能。
优选地，所述交联剂为活性酯、酸酐化合物或酚醛树脂中的任意一种或者至少两种的混合物。
优选地，所述活性酯为具有官能团酯基的活性酯交联剂，酸酐化合物可以为苯乙烯马来酸酐等化合物。酚醛树脂可为线性酚醛树脂、联苯酚酚醛树脂、烷基酚酚醛树脂、DCPD酚醛树脂等含羟基的酚醛树脂。
进一步优选地，所述交联剂为活性酯活/和酸酐化合物，其相对酚醛树脂， 具有更好的介电性能。
更优选地，所述交联剂为具有如下结构的活性酯由于该活性酯的特殊结构，其中的苯环、萘环、环戊二烯等刚性结构赋予该活性酯高的耐热性，同时由于其结构的规整性及与环氧树脂反应过程中无二次羟基产生，赋予其良好的电性能和低的吸水性。
Figure PCTCN2015080537-appb-000003
X为苯基或者萘基，j为0或1，k为0或1，n表示重复单元为0.25～1.25。
优选地，以无卤环氧树脂的添加量为100重量份计，含磷酚醛树脂为30-70重量份，例如35重量份、40重量份、45重量份、50重量份、55重量份、60重量份或65重量份，优选35-65重量份，交联剂为27-58重量份，优选35-55重量份。
优选地，所述无卤环氧树脂组合物还可进一步包括氰酸酯或苯并噁嗪，其可提升组合物的玻璃化转变温度，同时与含磷酚醛树脂实现N-P协同阻燃，提高阻燃效率。
进一步优选地，其中所述氰酸酯可以为双酚A型氰酸酯等分子中含有至少2个氰氧基的氰酸酯化合物或及其预聚物，其相对于苯并噁嗪可更好地提升组合物的玻璃化转变温度。
以组分(A)、组分(B)和组分(C)的添加量之和为100重量份计，所述氰酸酯或及其预聚物的添加量为20-40重量份，例如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重量份或38重量份。
优选地，所述无卤环氧树脂组合物还包括固化促进剂，其使树脂固化并加 快树脂固化速度。
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、0.60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重量份。
优选地，所述固化促进剂为4-二甲氨基吡啶、2-甲基咪唑、2-甲基4-乙基咪唑或2-苯基咪唑、异辛酸锌中的任意一种或者至少两种的混合物。
为进一步提高无卤环氧树脂组合物的难燃特性，于较佳的情形中，本发明尚可选择性添加至少一种特定的阻燃性化合物。
优选地，所述无卤环氧树脂组合物还可包括阻燃性化合物，所述阻燃性化合物为阻燃性盐类，如磷酸盐化合物或含氮磷酸盐化合物，但并不仅限于此。
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，所述阻燃性化合物的添加量为0～50重量份且不包括0，例如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。
优选地，所述无卤环氧树脂组合物还包含填料，所述填料为有机或/和无机填料，其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)、降低吸水率和提高热导率等。
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，所述填料为二氧化硅，填料的粒径中度值为1～15μm，优选填料的粒径中度值为1～10μm。
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环氧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，所述无卤环氧树脂组合物还可以含有各种添加剂，作为具体例，可以举出抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂 等。这些各种添加剂可以单独使用，也可以两种或者两种以上混合使用。
本发明的无卤环氧树脂组合物的常规制作方法：取一容器，先将固体组分放入，然后加入液体溶剂，搅拌直至完全溶解后，加入液体树脂、填料、阻燃剂和固化促进剂，继续搅拌均匀即可，最后用溶剂调整液体固含量至60％～80％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环氧树脂组合物。
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155～170℃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印制电路板，其包括至少一张如上所述的预浸料。
与现有技术相比，本发明具有如下有益效果：
在本发明中，含磷酚醛树脂，可作为环氧树脂的固化剂，又能提供无卤阻燃特性，且其主链中含有双环戊二烯环，使其不仅具有低介电常数、低介质损耗值、低吸水率且具有更高的玻璃化转变温度。使用该无卤环氧树脂组合物制作的预浸料、层压板和覆金属箔层压板，具有高耐热性、低介电常数、低介电损耗因素、和低吸水率的优点，且能实现无卤阻燃。
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。
根据上述所制成的无卤环氧树脂组合物覆金属箔层压板，测试其玻璃化转变温度、介电常数、介电损耗因子、PCT和PCT吸水率、燃烧性，如下述实施例加于详细说明与描述，其中有机树脂的质量份按有机固形物质量份计。
制备例：9，10-二氢-9-氧杂-10-磷菲-10-氧化物取代双环戊二烯酚与苯酚及甲醛合成的酚醛树脂
在装有搅拌器、温度计、冷凝回流器的四口瓶中加入94g苯酚在水浴加热中溶化，称取三氟化硼·乙醚0.1g，加入四口烧瓶中，在滴液漏斗中加入66g双环戊二烯，控制好滴加速度，以便在2h内滴加完所有的双环戊二烯，升温至60℃，保温2h，冷却至室温，再加热至一定温度蒸馏出过量的双环戊二烯和苯酚，得到如下结构双环戊二烯苯酚。
在四口烧瓶中投入226g上一步反应双环戊二烯苯酚、94g苯酚，80g(37重量％甲醛水溶液)、0.2g二甲基咪唑和250g溶剂甲基异丁基酮，150℃下反应6～8h，反应结束后水洗、脱溶剂得到中间体。
Figure PCTCN2015080537-appb-000005
在一个配有回流冷凝管、搅拌、热电偶的反应器中，加入180g中间体、216gDOPO，1.5g醋酸钾，150g二甲苯，升温到170℃，搅拌，回流，反应8h。冷却后加入250g正丁醇，萃取3次，然后蒸馏出正丁醇、二甲苯，加入适量的丙二醇甲醚，配成固含量为60％含磷双环戊二烯酚醛树脂。
实施例1
取一容器，加入100重量份的NC-3000H和41重量份EF-40加入适量的 MEK，搅拌溶解后，加入54重量份制备例1中的含磷酚醛树脂，搅拌，加入适量的固化促进剂2E4MI，继续搅拌均匀，最后用溶剂调整液体固含量至60％～80％而制成胶液。用玻璃纤维布浸渍上述胶液，即成胶液。用玻璃纤维布浸渍上述胶液，并控制至适当厚度，然后烘干除去溶剂得到预浸料。使用数张所制得的预浸料相互叠合，在其两侧分别压覆一张铜箔，放进热压机中固化制成所述的环氧树脂覆铜板层压板。物性数据如表1所示。
实施列2～9：
制作工艺和实施列1相同，配方组成及其物性指标如表1所示。
比较例1～3：
制作工艺与实施例1相同，配方组成及其物性指标如表2所示。
表1.各实施例的配方组成及其物性数据
Figure PCTCN2015080537-appb-000006
表2 各比较例的配方组成及其物性数据
Figure PCTCN2015080537-appb-000007
注：表中皆以固体组分重量份计。
表1和表2列举的材料具体如下：
BI：9，10-二氢-9-氧杂-10-磷菲-10-氧化物取代双环戊二烯酚与苯酚及甲醛合成的酚醛树脂。
B2：芳香性磷酸酯取代的双酚A与苯酚及甲醛合成的酚醛树脂(江苏雅克DHP-60H)。
B3：DOW含磷双酚A酚醛树脂(陶氏化学XZ92741)。
NC-3000H：联苯酚醛环氧树脂(日本化药商品名)。
7200H-M75：DCPD型酚醛环氧树脂(日本DIC商品名)。
627：双酚A型酚醛环氧树脂(美国Hexion商品名)。HPC-8000-65T：活性酯固化剂(日本DIC商品名)。
EF-40：苯乙烯马来酸酐(沙多玛商品名)。
2812：线性酚醛树脂(韩国Momentive商品名)。
CE01PS：扬州天启的双酚A型氰酸酯(扬州天启化学商品名)。
2E4MI：固化促进剂，2-甲基-4-乙基咪唑(日本四国化成商品名)。
DMAP：固化促进剂，4-二甲氨基吡啶(广荣化学商品名)。
异辛酸锌：固化促进剂(阿法埃莎商品名)
以上特性的测试方法如下：
(1)玻璃化转变温度(Tg)：根据差示扫描量热法(DSC)，按照IPC-TM-6502.4.25所规定的DSC方法进行测定。
(2)介电常数和介电损耗因子：按照IPC-TM-6502.5.5.9所规定的方法进行测试，测试频率为10GHZ。
(3)PCT及PCT吸水率：将覆铜板表明的铜箔蚀刻后，评价基板：将基板放置压力锅中，在120℃、150KPa条件下，处理两个小时：后浸渍于288℃的锡炉中，当基材分层时，记录相应时间：当基板在锡炉中超过5min还没出现气泡或分层时即可结束评价。
(4)燃烧性：依照UL94法规定。
物性分析。
从表1和表2的物性数据可知，比较例中，采用现有的含磷酚醛树脂存在PCT分层爆板，介电性能和耐湿热性差且玻璃化转变温度低。实施例1～9采用无卤环氧树脂、交联剂及9，10-二氢-9-氧杂-10-磷菲-10-氧化物所取代的双环戊二烯酚与苯酚及甲醛合成的含磷酚醛树脂，三者共混组成的组合物，兼具高耐热性、低介电常数、低介电损耗因素和低吸水率的优点，且能实现无卤阻燃。
如上所述，与一般的层压板相比，本发明的无卤电路基板具有高耐热性、 低介电常数、低介电损耗因素、低吸水率且能实现无卤阻燃。
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方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (12)

  1. 一种无卤环氧树脂组合物，其特征在于，所述无卤环氧树脂组合物包括如下组分：
    (A)无卤环氧树脂；
    (B)交联剂；
    (C)含磷酚醛树脂；
    所述含磷酚醛树脂具有如下结构：
    Figure PCTCN2015080537-appb-100001
    A和A1均独立地为
    Figure PCTCN2015080537-appb-100002
    p、q、m和n表示重复单元，均独立地为大于等于1的整数；
    X为9，10-二氢-9-氧杂-10-磷菲-10-氧化物或其衍生物；
    R为氢、脂肪族官能基或芳香族官能基。
  2. 如权利要求1所述的无卤环氧树脂组合物，其特征在于，所述无卤环氧树脂为联苯酚醛环氧树脂、DCPD型酚醛环氧树脂、亚烷基酚醛环氧树脂、双酚A型酚醛环氧树脂、双酚F型环氧树脂、双酚Z型环氧树脂、双酚AP型环氧树脂、双酚TMC型环氧树脂、含联苯型环氧树脂、四甲基联苯型环氧树脂、苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、三苯基甲烷型环氧树脂、四苯基乙烷型环氧树脂、双环戊二烯-苯酚加成反应型环氧树脂、苯酚芳烷基型环氧树脂、萘酚酚醛清漆型环氧树脂、萘酚芳烷基型环氧树脂、萘酚-苯酚共缩聚酚醛清漆型环氧树脂、萘酚-甲酚共缩聚酚醛清漆型环氧树脂、芳香族烃甲醛 树脂改性酚醛树脂型环氧树脂、联苯改性酚醛清漆型环氧树脂或酰亚胺改性环氧树脂中的任意一种或者至少两种的混合物。
  3. 如权利要求1或2所述的无卤环氧树脂组合物，其特征在于，所述无卤环氧树脂为联苯酚醛环氧树脂、DCPD型酚醛环氧树脂或双酚A型酚醛环氧树脂中的任意一种或者至少两种的混合物。
  4. 如权利要求1-3之一所述的无卤环氧树脂组合物，其特征在于，所述无卤环氧树脂为联苯酚醛环氧树脂或/和DCPD型酚醛环氧树脂。
  5. 如权利要求1-4之一所述的无卤环氧树脂组合物，其特征在于，所述交联剂为活性酯、酸酐化合物或酚醛树脂中的任意一种或者至少两种的混合物；
    优选地，所述交联剂为活性酯或酸酐化合物；
    优选地，所述交联剂为活性酯；
    优选地，所述交联剂为具有如下结构的活性酯：
    Figure PCTCN2015080537-appb-100003
    X为苯基或者萘基，j为0或1，k为0或1，n表示重复单元为0.25～1.25；
    优选地，以无卤环氧树脂的添加量为100重量份计，含磷酚醛树脂为30-70重量份，交联剂为27-58重量份，优选为35～55重量份。
  6. 如权利要求1-5之一所述的无卤环氧树脂组合物，其特征在于，所述的无卤环氧树脂组合物进一步包括氰酸酯或及其预聚物；
    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，所述氰酸酯或及其预聚物的添加量为20-40重量份。
  7. 如权利要求1-6之一所述的无卤环氧树脂组合物，其特征在于，所述无 卤环氧树脂组合物还包括固化促进剂；
    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，所述固化剂促进剂的添加量为0.05～1重量份；
    优选地，所述固化促进剂为4-二甲氨基吡啶、2-甲基咪唑、2-甲基4-乙基咪唑或2-苯基咪唑、异辛酸锌中的任意一种或者至少两种的混合物。
  8. 如权利要求1-7之一所述的无卤环氧树脂组合物，其特征在于，所述无卤环氧树脂组合物还可包括阻燃性化合物，所述阻燃性化合物为阻燃性盐类，优选磷酸盐化合物或含氮磷酸盐化合物；
    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，所述阻燃性化合物的添加量为0～50重量份且不包括0。
  9. 如权利要求1-8之一所述的无卤环氧树脂组合物，其特征在于，所述无卤环氧树脂组合物还包含填料，所述填料为有机或/和无机填料；
    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；
    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；
    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；
    优选地，所述填料为二氧化硅，填料的粒径中度值为1～15μm，优选填料的粒径中度值为1～10μm。
  10. 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权利要求1-9之一所述的无卤环氧树脂组合物。
  11. 一种层压板，其包括至少一张如权利要求10所述的预浸料。
  12. 一种印制电路板，其包括至少一张如权利要求10所述的预浸料。
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