WO2017020464A1 - 一种覆铜板用环氧树脂组合物及其应用 - Google Patents

一种覆铜板用环氧树脂组合物及其应用 Download PDF

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Publication number
WO2017020464A1
WO2017020464A1 PCT/CN2015/096519 CN2015096519W WO2017020464A1 WO 2017020464 A1 WO2017020464 A1 WO 2017020464A1 CN 2015096519 W CN2015096519 W CN 2015096519W WO 2017020464 A1 WO2017020464 A1 WO 2017020464A1
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Prior art keywords
epoxy resin
bromine
weight
resin composition
phosphorus
Prior art date
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PCT/CN2015/096519
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English (en)
French (fr)
Inventor
徐莹
方克洪
Original Assignee
广东生益科技股份有限公司
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Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to US15/744,005 priority Critical patent/US20180201776A1/en
Publication of WO2017020464A1 publication Critical patent/WO2017020464A1/zh

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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
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles

Definitions

  • the present invention relates to the field of laminate technology, and in particular to an epoxy resin composition, and more particularly to an epoxy resin composition for a copper clad laminate and a prepreg, a laminate and a printed circuit board produced therefrom.
  • Bromine flame retardant Most of the traditional FR4 uses bromine flame retardant. Bromine has high flame retardant efficiency, and flame retardant materials such as tetrabromobisphenol A are inexpensive and easy to promote. However, if only bromine is flame retarded, the total bromine content in ordinary FR4 generally reaches 15% (the bromine content accounts for the mass ratio of the organic solids in the sheet) to reach the UL94V-O level.
  • the higher bromine content is not only environmentally friendly, but also because the C-Br bond is easily broken, which also causes the heat resistance of the material itself to be seriously degraded; and the organic matter with high bromine content is not conducive to high temperature, high pressure, humidity and easily polluted environment.
  • phosphorus flame retardant can also achieve the purpose of flame retardant, because the phosphorus flame retardant system does not contain bromine, so the heat resistance is much better than the bromine flame retardant system.
  • the phosphorus element is easy to absorb moisture, and the moisture absorption rate of the flame retardant plate is high, which is not conducive to the stability of the electrical properties of the plate; and the current price of the phosphorus-based flame retardant is generally high, and the cost pressure is large, so although The call for halogen-free is high, but it is not possible to abandon bromine flame retardation for cost reasons.
  • Chinese patent CN102093670A discloses a method for achieving flame retardancy using a phosphorus-containing phenolic aldehyde containing a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) structure, although the water absorption rate of DOPO is It is lower than phosphate, but because of its large amount, the phosphorus content is also above 2%, so the moisture absorption rate is not improved.
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • CN101892027 and CN101808466 disclose the sharing of bromine and phosphorus, but due to the use of a large amount of nitrile rubber, the acrylonitrile structure has a higher water absorption rate than the epoxy resin, and the voltage resistance of the composite substrate is lowered, and in addition, the nitrile rubber is used.
  • the acrylonitrile structure accelerates the decomposition of bromine, which is detrimental to the CTI performance of the bromine-containing system.
  • not all of the phosphorus source and the bromine source used in the above two patents are connected to the polymer backbone, and the rubber has a negative influence on the Tg, so it is difficult to achieve a high glass transition temperature with the above two patents.
  • the object of the present invention is to provide an epoxy resin composition, in particular, an epoxy tree for copper clad laminates. Fat compositions and prepregs made therefrom, laminates and printed circuit boards.
  • the present invention adopts the following technical solutions:
  • the present invention provides an epoxy resin composition
  • an epoxy resin composition comprising, by weight of the organic solids, the following components:
  • (B) curing agent 1-50 parts by weight;
  • (C) curing accelerator 0.05-1.0 parts by weight
  • the bromine content is 5-12% of the sum of the weights of the organic solids in the composition; and the phosphorus content is 0.2-1.5 of the sum of the weights of the organic solids in the composition. %.
  • bromine-containing epoxy resin flame retardant materials Due to the use of bromine-containing epoxy resin flame retardant materials in the production of existing copper clad laminates, the bromine content usually exceeds 15% to achieve flame retardancy, but higher bromine content leads to poor heat resistance, CTI The value is also difficult to reach 600V; when the flame retardant is used alone for flame retardant, UL94V-0 grade is usually achieved at a higher phosphorus content. However, due to the high phosphorus content, there is a disadvantage of increasing moisture absorption rate. .
  • the invention combines the ratio of the bromine-containing epoxy resin and the phosphorus-containing epoxy resin in the epoxy resin composition by adding the bromine-containing epoxy resin and the phosphorus-containing epoxy resin at the same time, so that the bromine content is 5%-12 %, the phosphorus content is 0.2%-1.5%, which not only makes the flame retardancy reach UL94V-0 grade, but also has higher heat resistance than the copper clad laminate which is only flame-retardant with the bromine-containing epoxy resin flame retardant material, and It can achieve higher CTI value (CTI>600V), and has lower moisture absorption rate and longer dipping resistance time than copper clad laminate with flame retardant containing phosphorus.
  • CTI value CTI>600V
  • the mixture of the phosphorus-containing epoxy resin and the bromine-containing epoxy resin and other epoxy resins is 50-100 parts by weight, for example, 50 parts by weight, 52 parts by weight, 55 parts by weight, 58 parts by weight, 60 parts by weight, 62 parts by weight, 65 parts by weight, 68 parts by weight, 70 parts by weight, 72 parts by weight, 75 parts by weight Parts, 78 parts by weight, 80 parts by weight, 82 parts by weight, 85 parts by weight, 88 parts by weight, 90 parts by weight, 92 parts by weight, 95 parts by weight, 98 parts by weight, 100 parts by weight.
  • the curing agent is 1 to 50 parts by weight, and may be, for example, 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 22 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 45 parts by weight, 48 parts by weight, and 50 parts by weight.
  • the curing accelerator is 0.05-1.0 parts by weight, and may be, for example, 0.05 parts by weight, 0.08 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight. 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1.0 parts by weight.
  • the bromine content is 5-12% of the sum of the weights of the organic solids in the composition, and may be, for example, 5%, 5.5%, 6%, 6.5%, 7%, 7.5. %, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, preferably 5-10%, further preferably 5-8%.
  • the epoxy resin composition has a phosphorus content of 0.2 to 1.5% by weight of the total of the organic solids in the composition, and may be, for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%. 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, preferably 0.5-1.5%, and the difference is preferably 0.8-1.5%.
  • the bromine-containing epoxy resin is any one or at least two of a low bromine epoxy resin, a high bromine epoxy resin, a brominated isocyanate modified epoxy resin or a brominated bisphenol A phenolic epoxy resin.
  • a low bromine epoxy resin a high bromine epoxy resin
  • a brominated isocyanate modified epoxy resin a brominated bisphenol A phenolic epoxy resin.
  • the low bromine epoxy resin has a bromine content of 10% to 25%
  • the high bromine epoxy resin has a bromine content of 40% or more.
  • the phosphorus-containing epoxy resin is a phosphorus-containing phenanthrene-type compound.
  • the phosphorus-containing epoxy resin is 9,10-dihydro-9-oxo-10-phosphaphenanthrene or 9,10-dihydro-9-oxo-10-phosphaphenone Bismuth and bisphenol A epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol epoxy resin, dicyclopentadiene epoxy resin, MDI epoxy resin bisphenol F Any one or a mixture of at least two of a condensate of a type epoxy resin or a bisphenol S type epoxy resin.
  • the existing bromine-containing copper-clad laminates are mostly reactive flame retardants such as brominated epoxy
  • the bromine flame retardant system usually needs more than 15% bromine content to achieve stable flame retardancy, while high bromine content leads to It is a serious drop in heat resistance and tracking resistance.
  • the use of phosphorus-containing epoxy as a flame retardant also requires a phosphorus content of nearly 3% to achieve a stable UL94-V0 grade, and a high phosphorus content causes a sharp rise in the water absorption of the material, resulting in a decrease in the reliability of the material.
  • the invention adopts low bromine epoxy resin, high bromine epoxy resin, brominated isocyanate modified epoxy resin or brominated bisphenol A phenolic epoxy resin as a source of bromine element, and phosphorus-containing phenanthrene type which provides phosphorus source
  • the compound can be used in combination, and the two can exert a synergistic effect, and the flame retardancy of the substrate can be achieved to a UL94V-0 level by requiring only a low content of bromine and phosphorus, and the adhesion of the substrate can be further improved.
  • Processability and process operability and can achieve CTI 600V and lower water absorption, reducing the dependence of flame retardant on bromine elements, and thus more environmentally friendly.
  • both the phosphorus and bromine of the present invention are attached to the polymer backbone, the composite can achieve a higher glass transition temperature than the addition type of phosphorus bromine.
  • the other epoxy resin is an epoxy resin containing no phosphorus and bromine, specifically a bisphenol A epoxy resin, an o-cresol novolac epoxy resin, a bisphenol A novolac epoxy resin, and a phenol.
  • Type epoxy resin dicyclopentadiene type epoxy resin, MDI epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, tetrafunctional epoxy resin, naphthalene Any one or a mixture of at least two of a type epoxy resin or a biphenyl type epoxy resin.
  • the curing agent is a mixture of any one or at least two of a phenol resin, an aromatic diamine curing agent, dicyandiamide, an aliphatic amine, an acid anhydride, an active polyester or a cyanate.
  • the phenolic resin is a phenol type phenol resin, a bisphenol A type phenol resin, an o-cresol novolac resin, a trisphenol novolak resin, a naphthalene type phenol resin, a biphenyl type phenol resin or a dicyclopentadiene phenol resin. Any one or a mixture of at least two.
  • the aromatic diamine curing agent has the following chemical structural formula:
  • X is -CH 2 -, -O- or R 1 , R 3 and R 4 are H, -CH 3 or -C 2 H 5 , and R 2 is H, -CH 3 or -C 2 H 5 .
  • the curing accelerator is any one or a mixture of at least two of an imidazole curing accelerator, an organic phosphine curing accelerator, and a tertiary amine curing accelerator.
  • the imidazole curing accelerator is 2-methylimidazole, 2-methyl-4-ethylimidazole, 2-undecylimidazole, 2-phenylimidazole or 1-cyanoethyl-2- Any one or a mixture of at least two of ethyl-4-methylimidazole.
  • the organophosphine curing accelerator is tributylphosphine and/or triphenylphosphine.
  • the tertiary amine curing accelerator is benzyldimethylamine.
  • the amount of the curing accelerator added is not excessive, and the reaction is rapid when the amount is too large, and Conducive to process operations and material storage.
  • the epoxy resin composition further contains a filler, preferably an inorganic filler.
  • the filler is boehmite, aluminum hydroxide, barium sulfate, calcium fluoride, magnesium hydroxide, silica, glass powder, kaolin, talc, mica powder, alumina, zinc oxide, magnesium oxide, Any one or a mixture of at least two of boron nitride, aluminum nitride or calcium carbonate.
  • the filler has an average particle diameter of from 0.3 to 20 ⁇ m.
  • the content of the filler is 20-200 parts by weight, for example, 20 parts by weight, 30 parts by weight, based on 100 parts by weight of the total of the organic solids of the components in the epoxy resin composition. 50 parts by weight, 60 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 140 parts by weight, 150 parts by weight, 180 parts by weight, and 200 parts by weight.
  • the relative tracking index (CTI) of the substrate can be further increased, and the leakage tracking index (CTI) of the substrate can be made 600 V or more.
  • the epoxy resin composition may also be appropriately added with an auxiliary agent, and the auxiliary agent used is an aminosilane coupling agent.
  • an epoxy silane coupling agent such a coupling agent is free from heavy metals and has no adverse effect on human health, and is used in an amount of 0.5 to 2% by weight of the inorganic filler.
  • the epoxy resin composition further contains a solvent, and is preferably an organic solvent.
  • the solvent is any one or at least two of N,N'-dimethylformamide, ethylene glycol ethyl ether, propylene glycol methyl ether, acetone, methyl ethyl ketone, methanol, ethanol, benzene or toluene. mixing.
  • the viscosity can be adjusted using a solvent, and by using the above solvent, the solid component content in the epoxy resin composition can be adjusted to 40 to 80%.
  • the present invention provides a prepreg produced using the epoxy resin composition according to the first aspect of the present invention, comprising a base material; and an epoxy tree adhered thereto by dipping and drying Fat composition.
  • the matrix material is a nonwoven or woven fiberglass cloth.
  • the present invention also provides a laminate comprising the prepreg according to the second aspect of the invention.
  • the invention provides a printed circuit board comprising the laminate of the third aspect of the invention.
  • the present invention has the following beneficial effects:
  • the epoxy resin composition of the present invention can effectively control the cost while not only achieving the flame retardancy up to UL94V-0 level, but also improving the material leakage compared with the leakage of the material.
  • the index (CTI) can reach CTI>600V.
  • the epoxy resin composition of the present invention has better heat resistance than the pure bromine flame retardant system, and has a lower moisture absorption rate than the pure phosphorus flame retardant system, that is, the pure bromine is solved.
  • the flame retardant heat resistance is poor and the pure phosphorus flame retardant moisture absorption rate is high, and the comprehensive performance is excellent.
  • the present invention can further reduce the dependence of the flame retardant on the bromine element, thereby making it more environmentally friendly.
  • the epoxy resin, the curing agent, the filler and the curing accelerator are mixed with an organic solvent, uniformly mixed by a stirring and dispersing device, and the epoxy resin composition is pre-impregnated on the non-woven or spun fiberglass cloth. It is dried in a gluing machine (120-180 ° C) to prepare a prepreg for a printed circuit board in a semi-cured state.
  • the prepreg is laminated several times, and the copper foil is laminated on one side or both sides of the laminate, and then placed on a 120-200 ° C laminator, and hot-pressed to form a printed circuit board.
  • a copper clad laminate; the copper foil may also be replaced with an aluminum foil, a silver foil or a stainless steel foil.
  • the glass transition temperature, the tracking tracking index (CTI), the flame retardancy, the dipping time, the PCT water absorption rate, the 5% thermal weight loss and the drilling process were tested.
  • CTI tracking tracking index
  • the flame retardancy the flame retardancy
  • the dipping time the PCT water absorption rate
  • the 5% thermal weight loss the drilling process was tested.
  • the properties and the like are further explained and described as in the following Examples 1-5 and Comparative Examples 1-7.
  • the measurement was carried out according to the DSC method specified in IPC-TM-6502.4.25 by differential scanning calorimetry (DSC).
  • a double-sided copper foil sheet having a size of 100 ⁇ 100 mm was immersed in a solder bath heated to 288 ° C, and the time from the immersion to the occurrence of the delamination of the sheet was calculated.
  • the pre-dried sample was weighed and then cooked in an autoclave for 4 hours to see the rate of change in mass.
  • the temperature was raised to 500 ° C in a nitrogen atmosphere at a heating rate of 5 ° C / min, and the temperature at which the sample mass loss was 5% was recorded.
  • the two plates with a thickness of 1.6mm are stacked together, drilled with a 0.3mm drill bit, the drilling speed is 110krpm, the falling speed is 33mm/s, and 5000 holes are continuously drilled. Whenever the 1000 holes, the tip wear of the drill bit is observed. The size of the wear determines the processability of the drill.
  • Comparative Example 6 Synthetic rubber (commercial brand No. Nipol 1072CGX, produced by ZEON Corporation, USA) 23 parts by weight, brominated epoxy (manufactured by DER530A80, manufactured by DOW), 25 parts by weight, high 21 parts by weight of bromine epoxy (commercial brand No.
  • EPICLON 153-60M produced by Dainippon Ink
  • 25 parts by weight of biphenyl epoxy NC3000H, manufactured by Nippon Kayaku Co., Ltd.
  • 2E4MI manufactured by Shikoku Chemical Co., Ltd.
  • aromatic diamine 4,4-DDS produced by Taiwan Hygiene
  • SPB-100 phenoxyphosphazene
  • SPB-100 phosphorus content 13.4%
  • Yabao, USA 20 parts by weight
  • aluminum hydroxide manufactured by Yabao, USA
  • 8 parts by weight of barium sulfate Guizhou Red Star Co., Ltd.
  • the solvent MEK adjusted the solid content to 66%.
  • Comparative Example 7 33 parts by weight of a nitrile rubber-modified epoxy (SC-024, manufactured by SHIN-A), 67 parts by weight of a brominated epoxy resin (DEBR 530A80, manufactured by The Dow Chemical Co., Ltd.), 3 parts of dicyandiamide, 2 - 0.02 parts of methylimidazole, 6 parts by weight of tetrabromobisphenol A, 31 parts by weight of phosphorus phenolic aldehyde (LC950, produced by SHIN-A), 17 parts by weight of aluminum hydroxide (manufactured by Yabao, USA), boehmite Source quartz material Co., Ltd.) 34 parts by weight, barium sulfate (Guizhou Red Star Co., Ltd.) 9 parts by weight, solvent MEK adjusted solid content to 66%.
  • SC-024, manufactured by SHIN-A 67 parts by weight of a brominated epoxy resin
  • DEBR 530A80 brominated epoxy resin
  • LC950 phosphorus
  • Example 1-5 Compared with Comparative Example 3, the PCT water absorption rate of Example 1-5 is superior to that of Comparative Example 3, since only phosphorus-containing epoxy resin is used in Comparative Example 3, the phosphorus content thereof is as high as 2.21%, and the moisture absorption property thereof is high. Rising, and in Example 1-5, after using a phosphorus-containing epoxy resin and a bromine-containing epoxy resin, low moisture absorption can be achieved at a phosphorus content of only 0.2% to 1.5%, indicating that a phosphorus-containing epoxy resin is used. Substrate after bromine-containing epoxy resin compounding technology Low water absorption can be obtained.
  • Example 2-5 phosphorus-bromine synergistic flame-retarding requires only 11% or less of bromine to achieve flame retardant UL94V-0, while Comparative Example 2 only incorporates bromine flame retardant. Although the bromine content reaches 11%, it still does not reach the UL94V-0 level of flame retardant.
  • Example 1-5 utilizes a phosphorus-bromine synergistic flame-retardant route, and only needs 12% or less of bromine element in the case of achieving the flame retardant UL94V-0 level, so Examples 1-5 Compared with Comparative Example 1, it has higher chemical heat resistance, that is, the 5% weight loss temperature is 10 ° C or more higher than Comparative Example 1, and the dipping resistance time is also longer.
  • Comparative Example 6 and Comparative Example 7 The resin compositions invented by the patents CN 101808466A and CN 101892027A, respectively, have failed to reach CTI 600V under the same bromine content and phosphorus content as in the present invention and the same filler system. And the water absorption rate is significantly higher than the present invention, the dipping resistance time is less than 300 s, and the present invention exhibits better thermal shock resistance. Compared with Comparative Example 6, the present invention can achieve the glass transition temperature of the material without using the reactive phosphorus-bromine introduction method. In Comparative Example 7, although the phosphorus-containing phenolic aldehyde can be reacted, the reactivity itself is poor, and it is difficult to completely graft onto the polymer main chain, so that it affects the Tg of the sheet.
  • the epoxy resin composition of the present invention has a much higher heat resistance than the pure bromine flame retardant system and has a CTI of 600 V or more after adding a filler such as boehmite; compared to pure phosphorus resistance
  • the combustion system has lower water absorption rate, good drilling processability and good flame retardancy.
  • the prepreg and the copper clad laminate prepared by using the above epoxy resin composition have excellent CTI characteristics, so that the PCB can be significantly improved in a harsh environment. Adaptability; at the same time relatively high heat resistance, long time of dipping resistance, can be suitable for the needs of lead-free soldering. And the invention can further reduce the dependence of the flame retardant on the bromine element, thereby making it more environmentally friendly.
  • the present invention illustrates the process of the present invention by the above-described embodiments, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of the materials selected for the present invention, and the addition of the auxiliary ingredients, the selection of the specific means, etc., are all within the scope of the present invention.

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Abstract

本发明涉及一种覆铜板用环氧树脂组合物及其应用，该环氧树脂组合物可用于预浸料及覆铜箔层压板的制备。本发明通过采用低溴环氧树脂、高溴环氧树脂等溴化环氧树脂作为溴元素来源，以含磷有菲型化合物作为磷元素来源，并调节环氧树脂组合物中两者的比例，使溴含量控制在5-12％，磷含量控制在0.2-1.5％，其阻燃性可达UL94 V-0级；与纯溴阻燃的覆铜板相比具有更高的耐热性，且能达到较高CTI值；与纯磷阻燃的覆铜板相比吸湿率较低，并且能提供印制电路基材所需要的粘结性能，以及工艺操作性。与传统高CTI板材大量采用氢氧化铝相比，本发明可以用很少量或者不用氢氧化铝就能达到CTI＞600V。

Description

一种覆铜板用环氧树脂组合物及其应用 技术领域
本发明涉及层压板技术领域，具体涉及一种环氧树脂组合物，尤其涉及一种覆铜板用环氧树脂组合物及用其制作的预浸料，层压板与印刷电路板。
背景技术
随着欧盟指令WEEE(Waste Electrical and Electronic Equipment)和RoHS(Restriction ofHazardous Substances)的正式实施，全球电子业进入了无铅焊接时代。由于无铅焊接温度的提高，对印制电路覆铜板的耐热性和热稳定性提出了更高的要求。受欧盟颁发的“绿色”法规的影响，溴元素作为阻燃元素是否应该用在高分子领域又被推到了争议的风口浪尖上。虽然四溴双酚A作为阻燃剂还未发现其对环境有什么较大的负面影响，但是对于将其列为禁用物质的呼声越来越高。因此未来阻燃对于溴元素的依赖程度势必会逐渐降低。寻找一种耐热性好吸湿率低且对溴依存度较小的覆铜板技术就更加迫在眉睫。
传统FR4大都采用溴阻燃。溴元素阻燃效率高，并且如四溴双酚A这一类的阻燃物质成本低廉且容易推广。但如果仅靠溴阻燃，在普通FR4中总溴含量一般要到达15％(溴元素占板材中有机固形物的质量比)以上才能达到UL94V-O级。较高的溴含量不仅有悖于环境友好，同时由于C-Br键容易断裂，也导致材料本身的耐热性严重下降；而且高溴含量的有机物不利于在高温高压潮湿且容易受污染的环境下工作，因为溴元素会加速线路板两电路之间的材料漏电失效，因而降低溴含量可以使材料适应高压高湿等恶劣环境，如中国专利CN101654004A、CN102382420A公开的内容中，从环氧树脂及填料出发，采用降低树脂体系中溴含量到10-15％或者经特殊改性的环氧树脂，并添加大量 的氢氧化铝等无机填料使材料能适应恶劣环境。但是由于氢氧化铝用量过大，会产生耐热性下降的问题，这是因为氢氧化铝的热分解温度低，从200℃便开始脱水，而PCB焊接的温度在245-260℃，使得最终制成的板材在高温下容易出现分层起泡，从而影响产品的可靠性。
使用磷元素阻燃也能达到阻燃的目的，因为磷阻燃体系不含溴元素，因此耐热性方面要比溴阻燃体系好很多。但是磷元素容易吸潮，单纯靠磷元素阻燃的板材吸湿率较高，不利于板材的电性能的稳定性；且目前磷系阻燃剂价格普遍较高，成本压力较大，因此虽然对于无卤化的呼声很高，但由于成本原因要放弃溴阻燃目前也不太可能。中国专利CN102093670A公开了一种用含9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)结构的含磷酚醛实现阻燃的方法，虽然DOPO吸水率要比磷酸酯低，但由于其用量较大，磷含量也在2％以上，因此吸湿率也没有得到较好的改善。
CN101892027和CN101808466虽披露了溴与磷共用，但二者由于使用了大量丁腈橡胶，相对于环氧树脂，丙烯腈结构吸水率更高，复合基材的耐电压性下降，此外丁腈橡胶中的丙烯腈结构会加速溴的分解，对含溴体系的CTI性能不利。而以上两篇专利采用的磷源与溴源并不是所有的都连接在高分子主链上，且橡胶对于Tg具有负面影响，因此与以上两篇专利很难达到较高的玻璃化转变温度。
因此，寻找一种具有低吸潮性、高相对漏电起痕指数(CTI)值，并具有良好的耐热性、粘结性、反应性以及加工性的环氧树脂组合物是目前亟待解决的问题。
发明内容
本发明的目的在于提供一种环氧树脂组合物，特别是一种覆铜板用环氧树 脂组合物及用其制作的预浸料，层压板与印刷电路板。
为达到此发明目的，本发明采用以下技术方案：
第一方面，本发明提供了一种环氧树脂组合物，以有机固形物重量份计，包括如下组分：
(A)含磷环氧树脂与含溴环氧树脂和其他环氧树脂的混合物：50-100重量份；
(B)固化剂：1-50重量份；
(C)固化促进剂：0.05-1.0重量份；
其中，所述的环氧树脂组合物中，溴含量占所述组合物中有机固形物重量之和的5-12％；磷含量占所述组合物中有机固形物重量之和的0.2-1.5％。
由于现有的覆铜板制作中，单独采用含溴环氧树脂阻燃材料时，其溴含量通常要到15％以上才能达到阻燃，但是较高的溴含量会导致耐热性变差，CTI值也难以达到600V；而单独采用含磷阻燃剂进行阻燃时，通常也要在较高磷含量下才能实现UL94V-0级，然而由于磷含量太高又会有吸湿率增大的弊端。本发明通过同时加入含溴环氧树脂和含磷环氧树脂，并调整该环氧树脂组合物中含溴环氧树脂和含磷环氧树脂两者的比例，使溴含量在5％-12％，磷含量在0.2％-1.5％，不仅使阻燃性达到UL94V-0级，而且与单纯采用含溴环氧树脂阻燃材料阻燃的覆铜板相比具有更高的耐热性，且能达到较高CTI值(CTI＞600V)，与单独采用含磷阻燃剂阻燃的覆铜板相比吸湿率较低，耐浸焊时间较长。
本发明中，所述含磷环氧树脂与含溴环氧树脂和其他环氧树脂的混合物为50-100重量份，例如可以是50重量份、52重量份、55重量份、58重量份、60重量份、62重量份、65重量份、68重量份、70重量份、72重量份、75重量 份、78重量份、80重量份、82重量份、85重量份、88重量份、90重量份、92重量份、95重量份、98重量份、100重量份。
本发明中，所述固化剂为1-50重量份，例如可以是1重量份、5重量份、10重量份、15重量份、20重量份、22重量份、25重量份、28重量份、30重量份、32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。
本发明中，所述固化促进剂为0.05-1.0重量份，例如可以是0.05重量份、0.08重量份、0.1重量份、0.2重量份、0.3重量份、0.4重量份、0.5重量份、0.6重量份、0.7重量份、0.8重量份、0.9重量份、1.0重量份。
本发明所述环氧树脂组合物中，溴含量占所述组合物中有机固形物重量之和的5-12％，例如可以是5％、5.5％、6％、6.5％、7％、7.5％、8％、8.5％、9％、9.5％、10％、10.5％、11％、11.5％、12％，优选为5-10％，进一步优选为5-8％。
本发明中，所述环氧树脂组合物中，磷含量占所述组合物中有机固形物重量之和的0.2-1.5％，例如可以是0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％、1.0％、1.1％、1.2％、1.3％、1.4％、1.5％，优选为0.5-1.5％，差一步优选为0.8-1.5％。
本发明中，所述含溴环氧树脂为低溴环氧树脂、高溴环氧树脂、溴化异氰酸酯改性环氧树脂或溴化双酚A酚醛环氧树脂中的任意一种或至少两种的混合。
本发明中，所述低溴环氧树脂溴含量为10％-25％，所述高溴环氧树脂溴含量为40％以上。
本发明中，所述含磷环氧树脂为含磷有菲型化合物。
优选地，所述含磷环氧树脂为以9，10-二氢-9-氧-10-磷杂菲对苯二酚或9，10-二氢-9-氧-10-磷杂菲萘醌与双酚A型环氧树脂、邻甲酚型酚醛环氧树脂、双酚A型酚醛环氧树脂、苯酚型环氧树脂、双环戊二烯型环氧树脂、MDI环氧树脂双酚F型环氧树脂或双酚S型环氧树脂的缩合物中的任意一种或至少两种的混合。
由于现有的含溴体系覆铜板多是采用溴化环氧这类反应型阻燃剂，溴阻燃体系通常溴含量需要在15％以上才能实现稳定阻燃，而高溴含量带来的则是耐热性和耐漏电起痕性的严重下降。另外，使用含磷环氧作为阻燃剂也需要磷含量接近3％阻燃才能稳定达到UL94-V0级，且高磷含量使材料的吸水性急剧上升，从而导致材料的可靠性下降。
本发明通过采用低溴环氧树脂、高溴环氧树脂、溴化异氰酸酯改性环氧树脂或溴化双酚A酚醛环氧树脂作为溴元素来源，与提供磷元素来源的含磷有菲型化合物进行组合使用，两者可发挥协同作用，其只需较低含量的溴和磷元素即可实现基材的阻燃性达到UL94V-0级，而且，可进一步提高基材的粘结性、加工性和工艺操作性，并且能实现CTI 600V和较低的吸水率，减小了阻燃对溴元素的依赖，从而更加环保。且因为本发明的磷和溴都是连接在高分子主链上，因此相比于添加型的磷溴引入方式而言复合材料可以达到更高的玻璃化转变温度。
本发明中，所述其他环氧树脂为不含磷和溴的环氧树脂，具体为双酚A型环氧树脂、邻甲酚型酚醛环氧树脂、双酚A型酚醛环氧树脂、苯酚型环氧树脂、双环戊二烯型环氧树脂、MDI环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、双酚F型环氧树脂、四官能环氧树脂、萘型环氧树脂或联苯型环氧树脂中的任意一种或至少两种的混合。
本发明中，所述的固化剂为酚醛树脂、芳香二胺类固化剂、双氰胺、脂肪族胺、酸酐、活性聚酯或氰酸酯中的任意一种或至少两种的混合。
优选地，所述酚醛树脂为苯酚型酚醛树脂、双酚A型酚醛树脂、邻甲酚酚醛树脂、三酚酚醛树脂、萘型酚醛树脂、联苯型酚醛树脂或双环戊二烯酚醛树脂中的任意一种或至少两种的混合。
优选地，所述芳香二胺类固化剂具有如下化学结构式：
Figure PCTCN2015096519-appb-000001
其中，X为-CH2-、
Figure PCTCN2015096519-appb-000002
-O-或
Figure PCTCN2015096519-appb-000003
R1、R3与R4为H、-CH3或-C2H5，R2为H、-CH3或-C2H5。
优选地，所述固化剂的活性氢H摩尔数与所述环氧树脂的环氧基E摩尔数满足H/E＝0.8-1.2的关系式。
本发明中，所述固化促进剂为咪唑类固化促进剂、有机膦固化促进剂或三级胺固化促进剂中的任意一种或至少两种的混合。
优选地，所述咪唑类固化促进剂为2-甲基咪唑、2-甲基-4-乙基咪唑、2-十一烷基咪唑、2-苯基咪唑或1-氰乙基-2-乙基-4-甲基咪唑中的任意一种或至少两种的混合。
优选地，所述有机膦固化促进剂为三丁基膦和/或三苯基膦。
优选地，所述三级胺固化促进剂为苄基二甲基胺。
本发明中，固化促进剂的添加量不宜过量，添加量太大时反应会很快，不 利于工艺操作与材料的储存。
本发明中，所述环氧树脂组合物还含有填料，优选为无机填料。
优选地，所述填料为勃姆石、氢氧化铝、硫酸钡、氟化钙、氢氧化镁、二氧化硅、玻璃粉、高岭土、滑石粉、云母粉、氧化铝、氧化锌、氧化镁、氮化硼、氮化铝或碳酸钙中的任意一种或至少两种的混合。
优选地，所述填料的平均粒径为0.3-20μm。
优选地，按所述环氧树脂组合物中各组分的有机固形物之和为100重量份计，所述填料的含量为20-200重量份，例如可以是20重量份、30重量份、50重量份、60重量份、80重量份、100重量份、120重量份、140重量份、150重量份、180重量份、200重量份。
本发明通过添加氢氧化铝、硫酸钡或勃姆石等填料可进一步提高基板的相比漏电起痕指数(CTI)，使基板的相比漏电起痕指数(CTI)达到600V以上。
为使所述的无机填料在环氧树脂中分散均匀以及提升树脂与填料之间的结合力，所述的环氧树脂组合物还可以适当添加助剂，使用的助剂为氨基硅烷偶联剂或环氧基硅烷偶联剂，这类偶联剂无重金属存在，对人体健康无不良影响，使用量为无机填料的0.5-2％重量份。
本发明中，所述的环氧树脂组合物还含有溶剂，优选为有机溶剂。
优选地，所述的溶剂为N，N’-二甲基甲酰胺、乙二醇乙醚、丙二醇甲醚、丙酮、丁酮、甲醇、乙醇、苯或甲苯中的任意一种或至少两种的混合。
本发明的环氧树脂组合物，可以使用溶剂调节粘度，通过采用上述溶剂，能够调节所述环氧树脂组合物中固体组分含量达到40-80％。
第二方面，本发明还提供了一种使用如本发明第一方面所述的环氧树脂组合物制作的预浸料，其包括基体材料；和通过浸渍干燥后附着在其上的环氧树 脂组合物。
优选地，所述的基体材料为无纺或有纺玻璃纤维布。
第三方面，本发明还提供了一种层压板，其包含如本发明第二方面所述的预浸料。
第四方面，本发明提供了一种印刷电路板，其包含如本发明第三方面所述的层压板。
与现有技术相比，本发明具有以下有益效果：
(1)本发明所述的环氧树脂组合物通过采用特定的磷溴比例，在有效控制成本的同时，不仅使阻燃性可达UL94V-0级，还改善了材料的相比漏电起痕指数(CTI)，能达到CTI＞600V。
(2)本发明所述的环氧树脂组合物，与纯溴阻燃体系相比具有更好的耐热性，与纯磷阻燃体系相比具有更低的吸湿率，即解决了纯溴阻燃耐热性差和纯磷阻燃吸湿率高的问题，综合性能优异。
(3)使用本发明的环氧树脂组合物制作的预浸料和覆铜箔层压板，具有高玻璃化转变温度、高耐热性、高剥离强度、高相比漏电起痕指数(CTI)与良好的加工性，适合于无铅焊接。
(4)本发明可以进一步减小阻燃对溴元素的依赖性，从而更加环保。
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，但并不局限于此。
本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
实施例覆铜箔层压板的制备方法
将环氧树脂、固化剂、填料及固化促进剂，配合有机溶剂，利用搅拌分散设备，对其进行均匀混合，将所述的环氧树脂组合物预浸在无纺或有纺玻璃纤维布上，并在上胶机中(120-180℃)进行干燥，制成半固化状态的印制电路板用半固化片。
将上述半固化片数张叠合，叠层的单侧或双侧再叠合上铜箔，然后放置到120-200℃层压机上，热压固型，制成用于印制电路板加工的覆铜箔层压板；所述铜箔还可以采用铝箔、银箔或不锈钢箔进行替换。
针对上述实施例制成的覆铜箔层压板，测试其玻璃化转变温度、相比漏电起痕指数(CTI)、阻燃性、耐浸焊时间、PCT吸水率、5％热失重和钻孔加工性等性能，如下述实施例1-5与比较例1-7进一步给予说明与描述。
实施例1-5与比较例1-5的环氧树脂组合物中所用的各组分及其含量(按重量份计)如表1所示，表1中的环氧树脂组合物是按固体含量100％计算的；各组分代号及其对应的组分名称如下所示：
(A)环氧树脂：
(A1)溴化双酚A型环氧树脂：DER530A80，环氧当量为430g/eq，美国DOW化学公司生产；
(A2)溴化异氰酸酯改性环氧树脂：DER592A80，环氧当量为360g/eq，美国DOW化学公司生产；
(A3)高溴环氧树脂：EPICLON153-60M，溴含量48％环氧当量为380g/eq，大日本油墨公司生产；
(A4)含磷环氧树脂：GEBR521K70，环氧当量为540g/eq，宏昌树脂公司生产；
(A5)四官能环氧树脂：1031，环氧当量210g/eq，美国Momentive化学 公司生产；
(B)固化剂：
(B1)线性酚醛树脂：2812，美国Momentive化学公司生产；
(B2)芳香二胺：4，4-DDS，台湾寅生生产；
(C)填料：
(C1)勃姆石：蚌埠鑫源石英材料有限公司；
(C2)氢氧化铝：雅宝化学公司；
(C3)硫酸钡：贵州红星公司；
(D)固化促进剂：2-E-4MI，日本四国化成生产；
(E)有机溶剂：丁酮，陶氏化学有限公司。
采用以下方法对实施例1-5和比较例1-7制备的覆铜箔层压板进行测试，各性能参数的测试方法如下：
(A)玻璃化转变温度(Tg)
根据差示扫描量热法(DSC)，按照IPC-TM-6502.4.25所规定的DSC方法进行测定。
(B)相对漏电起痕指数(CTI)
按照GB/T 4207-84所规定的方法进行测试。
(C)耐浸焊时间
将尺寸100×100mm的双面带铜箔板材浸在加热到288℃的焊锡槽中，计算到其从浸入到出现板材分层爆板的时间。
(D)PCT吸水率
预先干燥样品称重后在放入高压锅中蒸煮4小时，看质量变化率。
(E)5％热失重
以5℃/min升温速率，在氮气氛下升温到500℃，记录样品质量损失5％时的温度。
(F)钻孔加工性
将厚度为1.6mm的板两块叠加在一起，用0.3mm钻头进行钻孔，钻速110krpm，落速33mm/s，连续钻5000孔，每1000孔时，观察钻头的刃尖磨损情况，由磨损的大小确定钻孔加工性好坏。
(G)阻燃性
按照UL 94所规定的方法进行测试。
对实施例1-5和比较例1-7制备的覆铜箔层压板进行测试的结果如表2和表3所示。
表1
Figure PCTCN2015096519-appb-000004
比较例6和比较例7的制备方法及材料厂商如下：
比较例6：合成橡胶(商品牌号Nipol 1072CGX，美国ZEON公司生产)23重量份，溴化环氧(商品牌号DER530A80，DOW公司生产)25重量份，高 溴环氧(商品牌号EPICLON 153-60M，大日本油墨生产)21重量份，联苯环氧(NC3000H，日本化药生产)25重量份，2E4MI(日本四国化成生产)0.2重量份，芳香二胺4，4-DDS(台湾寅生生产)10.1重量份，苯氧基磷腈(SPB-100，磷含量13.4％，美国雅宝生产)20重量份，氢氧化铝(美国雅宝生产)15重量份，勃姆石(蚌埠鑫源石英材料有限公司)31重量份，硫酸钡(贵州红星公司)8重量份，溶剂MEK调节固含量至66％。
计算：溴含量为12.0％，磷含量为0.2％，填料比例及配比与实施例1相同。
比较例7：丁腈橡胶改性环氧(SC-024，SHIN-A生产)33重量份，溴化环氧树脂(DEBR530A80，陶氏化学公司生产)67重量份，双氰胺3份，2-甲基咪唑0.02份，四溴双酚A 6重量份，含磷酚醛(LC950，SHIN-A生产)31重量份，氢氧化铝(美国雅宝生产)17重量份，勃姆石(蚌埠鑫源石英材料有限公司)34重量份，硫酸钡(贵州红星公司)9重量份，溶剂MEK调节固含量至66％。
计算：溴含量为12％，磷含量为0.2％，填料比例及配比与实施例1相同。
表2
测试项目 实施例1 实施例2 实施例3 实施例4 实施例5 比较例1 比较例2
Tg(DSC)(℃) 142 141 144 140 149 133 140
CTI(V) 600 600 600 175 600 500 600
耐浸焊 ＞600s ＞600s ＞600s ＞600s ＞600s ＜400s ＞600s
PCT吸水率％ 0.19 0.21 0.25 0.22 0.24 0.20 0.21
Td5％ 360 362 366 360 358 350 361
燃烧性 V-0 V-0 V-0 V-0 V-0 V-0 V-1
钻孔性 好 好 好 好 好 好 好
表3
测试项目 比较例3 比较例4 比较例5 比较例6 比较例7
Tg(DSC)(℃) 134 141 139 112 131
CTI(V) 600 300V 600V 525V 550V
耐浸焊 ＞600s ＜400s ＜300s ＜300s ＜300s
PCT吸水率％ 0.35 0.22 0.33 0.55 0.58
Td5％ 367 352 359 348 344
燃烧性 V-0 V-0 V-0 V-0 V-0
钻孔性 一般 一般 一般 好 好
从表1-表3可以看出以下几点：
(1)从实施例1-5可以看出，实施例1-5的环氧树脂组合物，其阻燃性均可达到UL 94V-0级，并且耐浸焊时间均大于600s，钻孔加工性良好。
(2)从实施例1-5可以看出，实施例1-3的环氧树脂组合物其相对漏电起痕指数(CTI)均可达到600V，而实施例4的环氧树脂组合物其相对漏电起痕指数(CTI)只有175V，说明采用在环氧树脂组合物中加入适量的填料，可使基板获得高CTI。
(3)与比较例3相比，实施例1-5的PCT吸水率优于比较例3，由于比较例3中只采用了含磷环氧树脂，其磷含量高达2.21％，其吸潮性上升，而实施例1-5采用含磷环氧树脂和含溴环氧树脂后，在磷含量只有0.2％-1.5％的情况下便可实现低吸潮性，说明采用含磷环氧树脂和含溴环氧树脂复配技术后，基板 可获得低吸水性。
(4)与比较例2相比，实施例2-5采用磷溴协同阻燃只需要11％以下的溴元素就能达到阻燃UL94V-0级，而比较例2只引入了溴元素阻燃，虽然溴含量到达11％，但仍然达不到阻燃UL94V-0级。
(5)与比较例1相比，实施例1-5由于采用磷溴协同阻燃路线，在同样达到阻燃UL94V-0级的情况下只需要12％以下溴元素，因此实施例1-5相比于比较例1具有更高的化学耐热性，即5％热失重温度要比比较例1高出10℃以上，耐浸焊时间也更长。
(6)比较例4和比较例5分别为溴含量和磷含量不在发明范围的情况，可以看出当溴含量为16.5％时，虽然也能阻燃，但是Td、耐浸焊时间都明显低于实施例1，CTI达不到600V；当磷含量为1.7％时，材料虽然CTI到600V，也能阻燃，但耐浸焊时间急剧下降到300s以下，且PCT吸水率到达0.3％以上。
(7)比较例6和比较例7分别为专利CN 101808466A和CN 101892027A所发明的树脂组合物在和本发明相同溴含量及磷含量以及同样的填料体系下，两篇专利都未能达到CTI 600V，且吸水率明显高于本发明，其耐浸焊时间未达到300s，而本发明则表现出更好的耐热冲击性能。本发明与比较例6相比，采用反应型磷溴引入方式可以做到不影响材料的玻璃化转变温度。比较例7虽然含磷酚醛可以反应，但是其本身反应性很差，较难完全接枝到高分子主链上，因此其会影响板材的Tg。
综上所述，本发明所述的环氧树脂组合物，相比于纯溴阻燃体系耐热性有很大提高且加入勃姆石等填料后CTI在600V以上；相比于纯磷阻燃体系吸水率更低，钻孔加工性好，阻燃性好。本发明使用上述环氧树脂组合物制作的半固化片与覆铜板，其优异的CTI特性，使得其能明显改善PCB在恶劣环境下的 适应能力；同时相对高的耐热性，耐浸焊时间长，能适合于无铅焊接的需要。并且该发明可以进一步减小阻燃对溴元素的依赖性，从而更加环保。
申请人声明，本发明通过上述实施例来说明本发明的工艺方法，但本发明并不局限于上述工艺步骤，即不意味着本发明必须依赖上述工艺步骤才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明所选用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 (10)

  1. 一种环氧树脂组合物，其特征在于，以有机固形物重量份计，包括如下组分：
    (A)含磷环氧树脂与含溴环氧树脂和其他环氧树脂的混合物：50-100重量份；
    (B)固化剂：1-50重量份；
    (C)固化促进剂：0.05-1.0重量份；
    其中，所述环氧树脂组合物中，溴含量占所述组合物中有机固形物重量之和的5-12％；磷含量占所述组合物中有机固形物重量之和的0.2-1.5％。
  2. 如权利要求1所述的环氧树脂组合物，其特征在于，所述环氧树脂组合物中，溴含量占所述组合物中有机固形物重量之和的5-10％，优选为5-8％；磷含量占所述组合物中有机固形物重量之和的0.5-1.5％，优选为0.8-1.5％。
  3. 如权利要求1或2所述的环氧树脂组合物，其特征在于，所述含溴环氧树脂为低溴环氧树脂、高溴环氧树脂、溴化异氰酸酯改性环氧树脂或溴化双酚A酚醛环氧树脂中的任意一种或至少两种的混合；
    优选地，所述低溴环氧树脂溴含量为10％-25％，所述高溴环氧树脂溴含量为40％以上；
    优选地，所述含磷环氧树脂为含磷有菲型化合物；
    优选地，所述含磷环氧树脂为以9，10-二氢-9-氧-10-磷杂菲对苯二酚或9，10-二氢-9-氧-10-磷杂菲萘醌与双酚A型环氧树脂、邻甲酚型酚醛环氧树脂、双酚A型酚醛环氧树脂、苯酚型环氧树脂、双环戊二烯型环氧树脂、MDI环氧树脂双酚F型环氧树脂或双酚S型环氧树脂的缩合物中的任意一种或至少两种的混合。
  4. 如权利要求1-3任一项所述的环氧树脂组合物，其特征在于，所述其他 环氧树脂为不含磷和溴的环氧树脂；具体为双酚A型环氧树脂、邻甲酚型酚醛环氧树脂、双酚A型酚醛环氧树脂、苯酚型环氧树脂、双环戊二烯型环氧树脂、MDI环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、四官能环氧树脂、萘型环氧树脂或联苯型环氧树脂中的任意一种或至少两种的混合。
  5. 如权利要求1-4任一项所述的环氧树脂组合物，其特征在于，所述固化剂为酚醛树脂、芳香二胺类固化剂、双氰胺、脂肪族胺、酸酐、活性聚酯或氰酸酯中的任意一种或至少两种的混合；
    优选地，所述酚醛树脂为苯酚型酚醛树脂、双酚A型酚醛树脂、邻甲酚酚醛树脂、三酚酚醛树脂、萘型酚醛树脂、联苯型酚醛树脂或双环戊二烯酚醛树脂中的任意一种或至少两种的混合；
    优选地，所述芳香二胺类固化剂具有如下化学结构式：
    Figure PCTCN2015096519-appb-100001
    其中，X为-CH2-、
    Figure PCTCN2015096519-appb-100002
    R1、R3与R4为H、-CH3或-C2H5，R2为H、-CH3或-C2H5；
    优选地，所述固化剂的活性氢H摩尔数与所述环氧树脂的环氧基E摩尔数满足H/E＝0.8-1.2的关系式。
  6. 如权利要求1-5任一项所述的环氧树脂组合物，其特征在于，所述固化 促进剂为咪唑类固化促进剂、有机膦固化促进剂或三级胺固化促进剂中的任意一种或至少两种的混合；
    优选地，所述咪唑类固化促进剂为2-甲基咪唑、2-甲基-4-乙基咪唑、2-十一烷基咪唑、2-苯基咪唑或1-氰乙基-2-乙基-4-甲基咪唑中的任意一种或至少两种的混合；
    优选地，所述有机膦固化促进剂为三丁基膦和/或三苯基膦；
    优选地，所述三级胺固化促进剂为苄基二甲基胺。
  7. 如权利要求1-6任一项所述的环氧树脂组合物，其特征在于，所述环氧树脂组合物还含有填料，优选为无机填料；
    优选地，所述填料为勃姆石、氢氧化铝、硫酸钡、氟化钙、氢氧化镁、二氧化硅、玻璃粉、高岭土、滑石粉、云母粉、氧化铝、氧化锌、氧化镁、氮化硼、氮化铝或碳酸钙中的任意一种或至少两种的混合；
    优选地，所述填料的平均粒径为0.3-20μm；
    优选地，按所述环氧树脂组合物中各组分的有机固形物之和为100重量份计，所述填料的含量为20-100重量份；
    优选地，所述环氧树脂组合物还含有溶剂，优选为有机溶剂；
    优选地，所述溶剂为N，N’-二甲基甲酰胺、乙二醇乙醚、丙二醇甲醚、丙酮、丁酮、甲醇、乙醇、苯或甲苯中的任意一种或至少两种的混合。
  8. 一种使用如权利要求1-7任一项所述的环氧树脂组合物制作的预浸料，其特征在于，其包括基体材料；和通过浸渍干燥后附着在其上的环氧树脂组合物；
    优选地，所述的基体材料为无纺或有纺玻璃纤维布。
  9. 一种层压板，其特征在于，其包含如权利要求8所述的预浸料。
  10. 一种印刷电路板，其特征在于，其包含如权利要求9所述的层压板。
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