WO2007090335A1 - Halogen-free phosphor-free fire-retardant epoxide resin composition - Google Patents

Halogen-free phosphor-free fire-retardant epoxide resin composition Download PDF

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Publication number
WO2007090335A1
WO2007090335A1 PCT/CN2007/000239 CN2007000239W WO2007090335A1 WO 2007090335 A1 WO2007090335 A1 WO 2007090335A1 CN 2007000239 W CN2007000239 W CN 2007000239W WO 2007090335 A1 WO2007090335 A1 WO 2007090335A1
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WIPO (PCT)
Prior art keywords
free
halogen
epoxy resin
phosphorus
resin composition
Prior art date
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PCT/CN2007/000239
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French (fr)
Chinese (zh)
Inventor
Rengchang Ning
Changlin Wei
Original Assignee
Nantong Xinghua Drako Industry Co., Ltd.
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Application filed by Nantong Xinghua Drako Industry Co., Ltd. filed Critical Nantong Xinghua Drako Industry Co., Ltd.
Publication of WO2007090335A1 publication Critical patent/WO2007090335A1/en

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Classifications

    • 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
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/302—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/55—Boron-containing compounds
    • 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

Definitions

  • Halogen-free and phosphorus-free flame retardant epoxy resin composition
  • This invention relates to an environmentally friendly flame retardant material, and more particularly to a material that can be used to make printed circuit board substrates. Background technique
  • PCB substrates use halogen-based flame retardants. These halogen-containing compounds produce dioxin substances that are extremely harmful to humans and the environment when incompletely burned. Many countries in the world have Formulation and enactment of substrate regulations that restrict or ban halogen-containing flame retardants, therefore, the halogen-free substrate has become a hot spot in the field of PCB development.
  • the halogen-free flame-retardant PCB substrate currently used is a phosphorus-containing compound, and although it is excellent in flame retardancy, it has problems of low heat resistance, low moisture resistance, and poor interlayer adhesion.
  • the page uses benzoxazine to prepare halogen-free and phosphorus-free flame-retardant PCB boards, although it has a high carbonization rate, a certain flame retardancy and Mechanical properties, but flame retardancy does not meet UL94V0 requirements.
  • a high thermal conductivity halogen-free and phosphorus-free flame retardant resin composition for a printed circuit board is disclosed in Chinese Patent Application No. 200310121169 (Publication No. 20050629).
  • the epoxy resin comprising (1) has a difunctional or polyfunctional group in an amount of from 10 to 50% by weight of the component. /.
  • the flame retardant has an amido, imido and hydroxide functional group structure, 10 to 30% by weight of the composition; (3) 10 to 50% by weight of the inorganic powder; (4) The high thermal conductive metal powder accounts for 10 to 30% by weight of the composition.
  • the high thermal conductivity halogen-free and phosphorus-free flame retardant resin does not have a phosphorus-containing flame retardant, and therefore, it does not cause environmental pollution problems due to hydrolysis.
  • the disadvantage is that the inorganic powder and the metal powder reduce the insulation and drilling performance of the PCB.
  • Chinese patent application 200410039268 publication number is 5050817) uses a halogen-free, phosphorus-free, high-nitrogen polycyclic structural compound as a flame retardant.
  • the flame retardant Since the flame retardant has an acylamino group and a hydroxyl functional group, it can be combined with an epoxy resin.
  • the chemical bond reaction is carried out to form a reactive flame-retardant semi-cured epoxy resin, and the flame-retardant semi-cured epoxy resin is added to the epoxy resin together with an inorganic additive to prepare an environmentally friendly halogen-free and phosphorus-free substrate or semiconductor package.
  • the flame retardant epoxy resin composition has the disadvantage that the inorganic additive brings about poor moisture resistance of the PCB. Summary of the invention
  • the technical problem to be solved by the present invention is to overcome the deficiencies in the prior art and provide a halogen-free and non-phosphorus flame-retardant epoxy resin composition, which has good insulation, flame retardancy, heat resistance and moisture resistance. Sex, good drilling, green and environmentally friendly.
  • the present invention solves the above technical problems by the following technical solutions.
  • the halogen-free and phosphorus-free flame retardant epoxy resin composition has a weight component ratio of:
  • the polyhydric phenol borate in the composition of the above halogen-free phosphorus-free epoxy resin may be trisorcinol borate, triseophenol borate or tribisphenol S triborate.
  • ⁇ -methacrylic acid passivated imidazole is formed by reacting an equivalent chemical equivalent of ⁇ -methacrylic acid with 2-ethyl and 4-methylimidazole.
  • the above components are dissolved in a solvent of acetone or absolute ethanol, and are uniformly condensed and then mixed to prepare a halogen-free and phosphorus-free flame-retardant epoxy resin composition.
  • the E-glass cloth/epoxy prepreg is prepared by impregnating the above-mentioned halogen-free and non-phosphorus flame-retardant epoxy resin composition with 0. 05-0. 2mm thick E-glass fiber plain cloth, removing acetone or absolute ethanol solvent.
  • the prepreg is laminated, placed in a steel mold and pressed on a flat plate hot press to obtain an E-glass cloth/halogen-free phosphorus-free flame-retardant epoxy resin laminate; using the same process as above, using copper
  • the foil is pressed together with an E-glass cloth/epoxy laminate to form a copper clad laminate. Test laminates or copper clad laminates, all of which exceed the performance specifications specified in the FR-4 Flame Retardant Basic Materials Standard. ,
  • the phenolic hydroxyl group in the polyphenol phenol borate of the present invention can completely react with the epoxy group under the catalytic action of ⁇ -methacrylic acid passivated imidazole, and the cured product has a high glass transition temperature;
  • the ⁇ - 0 bond in phenol borate has high chemical bond energy and thermo-oxidative stability, and is resistant to flame combustion.
  • Polyphenolate borate has a very high residual weight under high temperature and hot oxygen conditions, 70 (TC) The residual amount is more than 65%; the B-0 bond has good toughness, which is beneficial to the anti-peeling ability of the PCB; the outermost layer of boron in the polyphenol phenol borate has 6 electrons, which is very strong.
  • the trapping of free radical electrons can delay the combustion of the flame and reduce the smokyness in the combustion;
  • the diphenyl sulfone group in the bisphenol S epoxy resin of the invention has high thermo-oxidative stability and high residual weight. With high glass transition temperature, the sulfone group has strong bonding ability with glass fiber and copper foil, which is beneficial to the anti-peeling performance of the copper-clad laminate.
  • the ⁇ -methacrylic acid passivated imidazole of the present invention is mixed with polyphenol phenol borate and bisphenol S epoxy, and has good stability at room temperature. When it is higher than 100 ⁇ , it can catalyze rapid reaction of phenol light base with epoxy. It is beneficial to the processing of PCB; in the invention, hydrazine-glycidyl ether propyl trimethoxysilane can improve the wettability of the mixed resin solution and the glass cloth and the copper foil, and is favorable for improving the interface bonding strength, and the material is a kind A 3: [ ⁇ 0 ⁇ key flame retardant material. 3.
  • the halogen-free and phosphorus-free epoxy resin in the present invention is an organic-inorganic hybrid resin system, which has excellent comprehensive properties such as flame retardancy, electrical properties, heat resistance, moisture resistance and mechanical properties. detailed description
  • halogen-free and phosphorus-free flame retardant epoxy resin composition of the present invention will be further described below in conjunction with the examples.
  • the halogen-free and phosphorus-free flame-retardant epoxy resin composition of the present invention has the following weight-to-component ratio:
  • the above components are dissolved in a solvent of acetone or absolute ethanol, and are uniformly transparent and mixed to prepare a halogen-free and phosphorus-free flame-retardant epoxy resin composition.
  • ⁇ -methacrylic acid passivated imidazole is formed by the reaction of an equivalent chemical equivalent of ct-methacrylic acid with 2-ethyl, 4-methylimidazole.
  • the E-glass cloth/epoxy prepreg is prepared by impregnating the above-mentioned halogen-free and non-phosphorus flame-retardant epoxy resin composition with 0. 05-0. 2mm thick E-glass fiber plain cloth, removing acetone or absolute ethanol solvent. After the prepreg was laminated, it was placed in a steel mold and pressed on a flat plate hot press to obtain an E-glass cloth/halogen-free phosphorus-free flame-retardant epoxy resin laminate.
  • the halogen-free and phosphorus-free flame-retardant epoxy resin composition of the present invention has the following weight-to-component ratio - polyphenol borate 15
  • Each of the above components is dissolved in acetone or absolute ethanol solvent, and is uniformly transparent and mixed to form a halogen-free and phosphorus-free flame retardant epoxy resin composition.
  • the above ⁇ -methacrylic acid passivated imidazole is formed by reacting an equivalent chemical equivalent of ⁇ -methacrylic acid with 2-ethyl, 4-methylimidazole.
  • the E-glass cloth/epoxy prepreg is prepared by impregnating the above-mentioned halogen-free and non-phosphorus flame-retardant epoxy resin composition with 0. 05-0. 2mm thick E-glass fiber plain cloth, removing acetone or absolute ethanol solvent. After the prepreg was laminated, it was placed in a steel mold and pressed on a flat plate hot press to obtain an E-glass cloth/halogen-free phosphorus-free flame-retardant epoxy resin laminate. The copper clad laminate was pressed together with the E-glass cloth/epoxy laminate using the same process as above.
  • the laminate has a glass transition temperature (DSC method) of 154 ⁇ , an oxygen index of 61.6%, a flame retardant performance of UL94V0, a peel strength of 289 ⁇ , a 10 s condition of 1. 9 N/mm, and a water absorption rate of 0. 25%, bending strength is 510MPa, and each performance exceeds the performance index specified by FR-4 flame retardant basic material standard.
  • DSC method glass transition temperature
  • the halogen-free and phosphorus-free flame-retardant epoxy resin composition of the present invention has the following weight-to-component ratio:
  • the above components are dissolved in a solvent of acetone or absolute ethanol, and are uniformly transparent and mixed to prepare a halogen-free and phosphorus-free flame-retardant epoxy resin composition.
  • a-methacrylic acid passivated imidazole is formed by the reaction of an equivalent chemical equivalent of a-methacrylic acid with 2-ethyl, 4-methylimidazole.
  • the E-glass cloth/epoxy prepreg is prepared by impregnating the above-mentioned halogen-free and non-phosphorus flame-retardant epoxy resin composition with 0. 05-0. 2mm thick E-glass fiber plain cloth, removing acetone or absolute ethanol solvent. After the prepreg was laminated, it was placed in a steel mold and pressed on a flat plate hot press to obtain an E-glass cloth/halogen-free phosphorus-free flame-retardant epoxy resin laminate. The copper clad laminate was pressed together with the E-glass cloth/epoxy laminate using the same process as above.
  • the test has a glass transition temperature (DSC method) 153 C, an oxygen index of 61.6%, a flame retardant performance of UL94V0, a peel strength of 288 ⁇ , a 10 s condition of 1. 9 N/mm, a water absorption rate of 0. 25%, bending strength is 510MPa, and each performance exceeds the performance index specified by FR-4 flame retardant basic material standard.
  • DSC method glass transition temperature
  • the halogen-free and phosphorus-free flame-retardant epoxy resin composition of the present invention has the following weight-to-component ratio:
  • the above components are dissolved in a solvent of acetone or absolute ethanol, and are uniformly transparent and mixed to prepare a halogen-free and phosphorus-free flame-retardant epoxy resin composition.
  • ⁇ -methacrylic acid passivated imidazole is produced by reacting an equivalent chemical equivalent of ⁇ -methacrylic acid with 2-ethyl, 4-methylimidazole.
  • the E-glass cloth/epoxy prepreg is prepared by impregnating the above-mentioned halogen-free and non-phosphorus flame-retardant epoxy resin composition with 0. 05-0. 2mm thick E-glass fiber plain cloth, removing acetone or absolute ethanol solvent. After the prepreg was laminated, it was placed in a steel mold and pressed on a flat plate hot press to obtain an E-glass cloth/halogen-free phosphorus-free flame-retardant epoxy resin laminate. The copper clad laminate was pressed together with the E-glass cloth/epoxy laminate using the same process as above.
  • the test has a glass transition temperature (DSC method) of 155 ° C, an oxygen index of 61.8%, a flame retardant performance of UL94V0, a peeling strength of 288 ° C, a 10 s condition of 1. 9 N / mm, water absorption The rate is 0. 25 ° /.
  • the flexural strength is 510 MPa, and all performances exceed the performance specifications of the FR-4 flame retardant basic material standard.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A halogen-free, phosphor-free and fire-retardant epoxide resin composition, which comprises polyhydric benzene phenol boric acid ester, dihydroxydiphenyl sulfone epoxy resin, alpha-methacrylic acid deactivated imidazole and gamma-glycidol ether propyl trimethoxysilicane with the weight ratio of 10-50 : 20-50 : 0.5-15: 0.5-10.

Description

无卤无磷阻燃环氧树脂组成物 技术领域  Halogen-free and phosphorus-free flame retardant epoxy resin composition
本发明涉及一种环保阻燃材料，更具体地说涉及一种可用于制造印制电路板基材的材料。 背景技术  This invention relates to an environmentally friendly flame retardant material, and more particularly to a material that can be used to make printed circuit board substrates. Background technique
传统的阻燃印制电路板 (PCB)基材采用卤系阻燃剂，这类含卤素类化合物进行不完全燃 烧时会产生对人体、 环境极为有害的二噁英物质， 世界上许多国家已制定， 颁布了限制或禁 用含卤素阻燃剂的基材法规， 因此， 基材无卤化成为 PCB领域发展的热点。 目前所采用的无 卤阻燃 PCB基材， 是添加含磷化合物， 虽然能很好地阻燃， 但存在着耐热性、 耐湿性低以及 层间粘接性差的问题。 日本专利特开昭 61-148219 中公开了用脂肪族化合物上结合磷原子制 备含磷化合阻燃剂， 用于无卤阻燃 PCB的制造。 虽然改善了阻燃性， 但耐热性、 耐湿性不够。 日本专利特开昭 11-60689提出了将环氧树脂与苯基磷酸化合物进行反应的技术路线， 但耐湿 性改善不明显。 2005年出版的 《覆铜板资¾》杂志第 4期 PP14- 15 .页中用苯并噁嗪制备无卤 无磷阻燃 PCB板，虽然有较高的成碳率，一定的阻燃性和机械性能，但阻燃性不能达到 UL94V0 级的要求。 中国专利申请 200310121169 (公开日 20050629)公开了一种印刷电路板用高导热 无卤无磷阻燃型树脂组成物。 包括（1 )环氧树脂具有双官能基或多官能基占组分的 10至 50 重量。 /。； (2)阻燃剂具有酰氨基、 亚酰氨基及氢氧化物基官能基结构、 占组合物 10至 30重量 %; (3)无机粉体占组合物的 10至 50重量％; (4) 高导热金属粉体占组合物 10至 30重量％。 此种高导热无卤无磷阻燃树脂不具有含磷阻燃剂， 因此， 不会因水解导致环境污染问题， 缺 点是无机粉体和金属粉体降低了 PCB板的绝缘性和钻孔性能。中国专利申请 200410039268(公 开日为 20050817) 中使用无卤无磷高含氮量的多环结构化合物当作阻燃剂， 由于此阻燃剂中 具有酰氨基及羟基官能团， 故可与环氧树脂进行化学键反应， 形成反应型阻燃半固化环氧树 脂， 再将此阻燃半固化环氧树脂搭配无机添加剂添加于环氧树脂， 即可配制成可用于 PCB或 半导体封装的环保无卤无磷的阻燃环氧树脂组成物， 缺点也是无机添加剂带来了 PCB耐湿性 差。 发明内容  Conventional flame-retardant printed circuit board (PCB) substrates use halogen-based flame retardants. These halogen-containing compounds produce dioxin substances that are extremely harmful to humans and the environment when incompletely burned. Many countries in the world have Formulation and enactment of substrate regulations that restrict or ban halogen-containing flame retardants, therefore, the halogen-free substrate has become a hot spot in the field of PCB development. The halogen-free flame-retardant PCB substrate currently used is a phosphorus-containing compound, and although it is excellent in flame retardancy, it has problems of low heat resistance, low moisture resistance, and poor interlayer adhesion. The production of a phosphorus-containing flame retardant by using an aliphatic compound in combination with a phosphorus atom is disclosed in Japanese Patent Laid-Open Publication No. SHO 61-148219, which is incorporated herein by reference. Although the flame retardancy is improved, heat resistance and moisture resistance are insufficient. Japanese Patent Laid-Open No. 11-60689 proposes a technical route for reacting an epoxy resin with a phenyl phosphate compound, but the improvement in moisture resistance is not remarkable. 2005, "Copper-Copper Sheets", No. 4, PP14-15. The page uses benzoxazine to prepare halogen-free and phosphorus-free flame-retardant PCB boards, although it has a high carbonization rate, a certain flame retardancy and Mechanical properties, but flame retardancy does not meet UL94V0 requirements. A high thermal conductivity halogen-free and phosphorus-free flame retardant resin composition for a printed circuit board is disclosed in Chinese Patent Application No. 200310121169 (Publication No. 20050629). The epoxy resin comprising (1) has a difunctional or polyfunctional group in an amount of from 10 to 50% by weight of the component. /. (2) The flame retardant has an amido, imido and hydroxide functional group structure, 10 to 30% by weight of the composition; (3) 10 to 50% by weight of the inorganic powder; (4) The high thermal conductive metal powder accounts for 10 to 30% by weight of the composition. The high thermal conductivity halogen-free and phosphorus-free flame retardant resin does not have a phosphorus-containing flame retardant, and therefore, it does not cause environmental pollution problems due to hydrolysis. The disadvantage is that the inorganic powder and the metal powder reduce the insulation and drilling performance of the PCB. . Chinese patent application 200410039268 (publication number is 5050817) uses a halogen-free, phosphorus-free, high-nitrogen polycyclic structural compound as a flame retardant. Since the flame retardant has an acylamino group and a hydroxyl functional group, it can be combined with an epoxy resin. The chemical bond reaction is carried out to form a reactive flame-retardant semi-cured epoxy resin, and the flame-retardant semi-cured epoxy resin is added to the epoxy resin together with an inorganic additive to prepare an environmentally friendly halogen-free and phosphorus-free substrate or semiconductor package. The flame retardant epoxy resin composition has the disadvantage that the inorganic additive brings about poor moisture resistance of the PCB. Summary of the invention
本发明所要解决的技术问题是克服现有技术中的不足， 提供一种无卤无磷阻燃环氧树脂 组成物， 该组成物具有很好的绝缘性、 阻燃性、 耐热性、 耐湿性， 钻孔性好， 绿色环保。 本发明为解决上述技术问题是通过下列技术方案来实现的， 上述无卤无磷阻燃环氧树脂 组成物， 重量组份比为： The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art and provide a halogen-free and non-phosphorus flame-retardant epoxy resin composition, which has good insulation, flame retardancy, heat resistance and moisture resistance. Sex, good drilling, green and environmentally friendly. The present invention solves the above technical problems by the following technical solutions. The halogen-free and phosphorus-free flame retardant epoxy resin composition has a weight component ratio of:
多元苯酚硼酸酯 10 - 50  Polyphenolate borate 10 - 50
双酚 S环氧树脂 20-50  Bisphenol S epoxy resin 20-50
α -甲基丙烯酸钝化咪唑 0. 5-15  Α-methacrylic acid passivated imidazole 0. 5-15
Υ -缩水甘油醚丙基三甲氧基硅烷 0. 5-10  Υ - glycidyl ether propyl trimethoxy silane 0. 5-10
上述无卤无磷环氧树脂组成中的多元苯酚硼酸酯可以是三对苯二酚硼酸酯， 也可以是三 伺苯二酚硼酸酯或者是三双酚 S三硼酸酯。  The polyhydric phenol borate in the composition of the above halogen-free phosphorus-free epoxy resin may be trisorcinol borate, triseophenol borate or tribisphenol S triborate.
上述 α -甲基丙烯酸钝化咪唑的是由等化学当量的 α -甲基丙烯酸与 2 -乙基， 4-甲基咪唑 反应生成。  The above α-methacrylic acid passivated imidazole is formed by reacting an equivalent chemical equivalent of α-methacrylic acid with 2-ethyl and 4-methylimidazole.
将上述各组份溶于丙酮或无水乙醇溶剂中， 待均勾透明后混合制成无卤无磷阻燃环氧树 脂组成物。  The above components are dissolved in a solvent of acetone or absolute ethanol, and are uniformly condensed and then mixed to prepare a halogen-free and phosphorus-free flame-retardant epoxy resin composition.
将上述无卤无磷阻燃环氧树脂组成物浸渍 0. 05-0. 2mm厚的 E-玻璃纤维平纹布， 除去丙 酮或无水乙醇溶剂， 制成 E-玻璃布 /环氧树脂预浸料， 将预浸料多层叠放后， 置于钢模具中在 平板热压机上压制， 得到 E-玻璃布 /无卤无磷阻燃环氧树脂层压板； 用与上述相同的工艺， 用 铜箔与 E-玻璃布 /环氧树脂层压板一起压制成覆铜板。测试层压板或覆铜板，其各项性能均超 过 FR-4阻燃基本材料标准规定的性能指标。 ，  The E-glass cloth/epoxy prepreg is prepared by impregnating the above-mentioned halogen-free and non-phosphorus flame-retardant epoxy resin composition with 0. 05-0. 2mm thick E-glass fiber plain cloth, removing acetone or absolute ethanol solvent. The prepreg is laminated, placed in a steel mold and pressed on a flat plate hot press to obtain an E-glass cloth/halogen-free phosphorus-free flame-retardant epoxy resin laminate; using the same process as above, using copper The foil is pressed together with an E-glass cloth/epoxy laminate to form a copper clad laminate. Test laminates or copper clad laminates, all of which exceed the performance specifications specified in the FR-4 Flame Retardant Basic Materials Standard. ,
本发明与现有技术相比具有的有益效果是：  The beneficial effects of the present invention over the prior art are:
1、本发明中多元苯酚硼酸酯中的酚羟基在 α -甲基丙烯酸钝化咪唑的催化作用下，可与环 氧基完全反应， 固化后的产物有较高的玻璃化转变温度； 多元苯酚硼酸酯中的 Β— 0键， 有很 高的化学键能和热氧稳定性， 耐火焰燃烧性好； 多元苯酚硼酸酯在高温热氧条件下有很髙的 残余重量， 70(TC残余量大于 65%; B— 0键有很好的韧性， 有利于提髙 PCB板抗剥离能力； 多 元苯酚硼酸酯中的硼的原子结构中最外层为 6个电子， 具有很强的捕灭自由基电子作用， 可 以推迟火焰燃烧， 减少燃烧中的发烟性； 本发明中的双酚 S环氧树脂中二苯基砜基团， 具有 很高的热氧稳定性、 高残余重量和高玻璃化转变温度， 砜基与玻璃纤维和铜箔有很强的粘接 能力， 有利于提髙覆铜板抗剥离性能。  1. The phenolic hydroxyl group in the polyphenol phenol borate of the present invention can completely react with the epoxy group under the catalytic action of α-methacrylic acid passivated imidazole, and the cured product has a high glass transition temperature; The Β- 0 bond in phenol borate has high chemical bond energy and thermo-oxidative stability, and is resistant to flame combustion. Polyphenolate borate has a very high residual weight under high temperature and hot oxygen conditions, 70 (TC) The residual amount is more than 65%; the B-0 bond has good toughness, which is beneficial to the anti-peeling ability of the PCB; the outermost layer of boron in the polyphenol phenol borate has 6 electrons, which is very strong. The trapping of free radical electrons can delay the combustion of the flame and reduce the smokyness in the combustion; the diphenyl sulfone group in the bisphenol S epoxy resin of the invention has high thermo-oxidative stability and high residual weight. With high glass transition temperature, the sulfone group has strong bonding ability with glass fiber and copper foil, which is beneficial to the anti-peeling performance of the copper-clad laminate.
2、本发明中的 α -甲基丙烯酸钝化咪唑与多元苯酚硼酸酯和双酚 S环氧混合后，室温下稳 定性好， 高于 100Ό时可催化酚轻基与环氧快速反应， 有利于 PCB的加工； 本发明中 Υ -缩水 甘油醚丙基三甲氧基硅垸能改善混合树脂溶液与玻璃布和铜箔的浸润性， 有利于提高界面粘 接强度， 这种材料是一种一 3：[~0~键的阻燃材料。 3、本发明中的无卤无磷环氧树脂是一种有机无机杂化的树脂体系，具有优异的阻燃性能、 电性能、 耐热性、 耐湿性和机械性能等综合性能。 具体实施方式 2. The α-methacrylic acid passivated imidazole of the present invention is mixed with polyphenol phenol borate and bisphenol S epoxy, and has good stability at room temperature. When it is higher than 100 Ό, it can catalyze rapid reaction of phenol light base with epoxy. It is beneficial to the processing of PCB; in the invention, hydrazine-glycidyl ether propyl trimethoxysilane can improve the wettability of the mixed resin solution and the glass cloth and the copper foil, and is favorable for improving the interface bonding strength, and the material is a kind A 3: [~0~ key flame retardant material. 3. The halogen-free and phosphorus-free epoxy resin in the present invention is an organic-inorganic hybrid resin system, which has excellent comprehensive properties such as flame retardancy, electrical properties, heat resistance, moisture resistance and mechanical properties. detailed description
下面结合实施例对本发明的无卤无磷阻燃环氧树脂组成物作进一步说明。  The halogen-free and phosphorus-free flame retardant epoxy resin composition of the present invention will be further described below in conjunction with the examples.
实施例 1  Example 1
本发明的无卤无磷阻燃环氧树脂组成物， 按以下重量组份比：  The halogen-free and phosphorus-free flame-retardant epoxy resin composition of the present invention has the following weight-to-component ratio:
多元苯酚硼酸酯 25  Polyphenolate borate 25
双酚 S环氧树脂 30  Bisphenol S epoxy resin 30
-甲基丙烯酸钝化咪唑 10  -methacrylic acid passivated imidazole 10
Υ -缩水甘油醚丙基三甲氧基硅烷 3  Υ - glycidyl ether propyl trimethoxy silane 3
将上述各组份溶于丙酮或无水乙醇溶剂中，待均匀透明后混合制成无卤无磷阻燃环氧树脂 组成物。  The above components are dissolved in a solvent of acetone or absolute ethanol, and are uniformly transparent and mixed to prepare a halogen-free and phosphorus-free flame-retardant epoxy resin composition.
上述 α -甲基丙烯酸钝化咪唑的是由等化学当量的 ct -甲基丙烯酸与 2-乙基， 4-甲基咪唑反 应生成。  The above α-methacrylic acid passivated imidazole is formed by the reaction of an equivalent chemical equivalent of ct-methacrylic acid with 2-ethyl, 4-methylimidazole.
将上述无卤无磷阻燃环氧树脂组成物浸渍 0. 05-0. 2mm厚的 E-玻璃纤维平紋布， 除去丙酮 或无水乙醇溶剂， 制成 E-玻璃布 /环氧树脂预浸料， 将预浸料多层叠放后， 置于钢模具中在平 板热压机上压制， 得到 E-玻璃布 /无卤无磷阻燃环氧树脂层压板。用与上述相同的工艺， 用铜 箔与 E-玻璃布 /环氧树脂层压板一起压制成覆铜板；测试层压板或覆铜板，其玻璃化转变温度 (DSC法） 152Ό，氧指数 61. 2%，阻燃性能达到 UL94V0级，剥离强度 288°C， 10s条件为 1. 9N/mm, 吸水率为 0. 25%， 弯曲强度为 510MPa， 各项性能均超过 FR- 4阻燃基本材料标准规定的性能指 标。  The E-glass cloth/epoxy prepreg is prepared by impregnating the above-mentioned halogen-free and non-phosphorus flame-retardant epoxy resin composition with 0. 05-0. 2mm thick E-glass fiber plain cloth, removing acetone or absolute ethanol solvent. After the prepreg was laminated, it was placed in a steel mold and pressed on a flat plate hot press to obtain an E-glass cloth/halogen-free phosphorus-free flame-retardant epoxy resin laminate. Using the same process as above, using copper foil and E-glass cloth / epoxy resin laminate together pressed to form a copper clad laminate; test laminate or copper clad laminate, its glass transition temperature (DSC method) 152 Ό, oxygen index 61.2 %, the flame retardant performance is UL94V0 grade, the peeling strength is 288 °C, the 10s condition is 1. 9N/mm, the water absorption rate is 0.25%, the bending strength is 510MPa, and the performance exceeds the FR-4 flame retardant basic material standard. Specified performance indicators.
实施例 2  Example 2
本发明的无卤无磷阻燃环氧树脂组成物， 按以下重量组份比 - 多元苯酚硼酸酯 15  The halogen-free and phosphorus-free flame-retardant epoxy resin composition of the present invention has the following weight-to-component ratio - polyphenol borate 15
双酚 S环氧树脂 20  Bisphenol S epoxy resin 20
α -甲基丙烯酸钝化咪唑 5  Α-methacrylic acid passivated imidazole 5
Υ -缩水甘油醚丙基三甲氧基硅垸 8  Υ - glycidyl ether propyl trimethoxysilane 垸 8
4每上述各组份溶于丙酮或无水乙醇溶剂中，待均匀透明后混合制成无卤无磷阻燃环氧树脂 组成物。 上述 α -甲基丙烯酸钝化咪唑的是由等化学当量的 α -甲基丙烯酸与 2-乙基, 4 -甲基咪唑反 应生成。 4 Each of the above components is dissolved in acetone or absolute ethanol solvent, and is uniformly transparent and mixed to form a halogen-free and phosphorus-free flame retardant epoxy resin composition. The above α-methacrylic acid passivated imidazole is formed by reacting an equivalent chemical equivalent of α-methacrylic acid with 2-ethyl, 4-methylimidazole.
将上述无卤无磷阻燃环氧树脂组成物浸渍 0. 05-0. 2mm厚的 E-玻璃纤维平紋布， 除去丙 酮或无水乙醇溶剂， 制成 E-玻璃布 /环氧树脂预浸料， 将预浸料多层叠放后， 置于钢模具中在 平板热压机上压制， 得到 E-玻璃布 /无卤无磷阻燃环氧树脂层压板。用与上述相同的工艺， 用 铜箔与 E-玻璃布 /环氧树脂层压板一起压制成覆铜板。测试层压板或覆铜板，其玻璃化转变温 度 （DSC法） 154Ό， 氧指数 61. 6%， 阻燃性能达到 UL94V0级， 剥离强度 289 Ό， 10s条件为 1. 9N/mm, 吸水率为 0. 25%， 弯曲强度为 510MPa， 各项性能均超过 FR- 4阻燃基本材料标准规 定的性能指标。  The E-glass cloth/epoxy prepreg is prepared by impregnating the above-mentioned halogen-free and non-phosphorus flame-retardant epoxy resin composition with 0. 05-0. 2mm thick E-glass fiber plain cloth, removing acetone or absolute ethanol solvent. After the prepreg was laminated, it was placed in a steel mold and pressed on a flat plate hot press to obtain an E-glass cloth/halogen-free phosphorus-free flame-retardant epoxy resin laminate. The copper clad laminate was pressed together with the E-glass cloth/epoxy laminate using the same process as above. The laminate has a glass transition temperature (DSC method) of 154 Å, an oxygen index of 61.6%, a flame retardant performance of UL94V0, a peel strength of 289 Ό, a 10 s condition of 1. 9 N/mm, and a water absorption rate of 0. 25%, bending strength is 510MPa, and each performance exceeds the performance index specified by FR-4 flame retardant basic material standard.
实施例 3  Example 3
本发明的无卤无磷阻燃环氧树月旨组成物， 按以下重量组份比：  The halogen-free and phosphorus-free flame-retardant epoxy resin composition of the present invention has the following weight-to-component ratio:
多元苯酚硼酸酯 10  Polyphenolate borate 10
双酚 S环氧树脂 50  Bisphenol S epoxy resin 50
a -甲基丙烯酸钝化咪唑 1  A-methacrylic acid passivated imidazole 1
Y -缩水甘油醚丙基三甲氧基硅烷 10  Y-glycidyl ether propyl trimethoxysilane 10
将上述各组份溶于丙酮或无水乙醇溶剂中，待均匀透明后混合制成无卤无磷阻燃环氧树脂 组成物。  The above components are dissolved in a solvent of acetone or absolute ethanol, and are uniformly transparent and mixed to prepare a halogen-free and phosphorus-free flame-retardant epoxy resin composition.
上述 a -甲基丙烯酸钝化咪唑的是由等化学当量的 a -甲基丙烯酸与 2-乙基， 4-甲基咪唑反 应生成。  The above a-methacrylic acid passivated imidazole is formed by the reaction of an equivalent chemical equivalent of a-methacrylic acid with 2-ethyl, 4-methylimidazole.
将上述无卤无磷阻燃环氧树脂组成物浸渍 0. 05-0. 2mm厚的 E-玻璃纤维平紋布， 除去丙 酮或无水乙醇溶剂， 制成 E-玻璃布 /环氧树脂预浸料， 将预浸料多层叠放后， 置于钢模具中在 平板热压机上压制， 得到 E-玻璃布 /无卤无磷阻燃环氧树脂层压板。用与上述相同的工艺，用 铜箔与 E-玻璃布 /环氧树脂层压板一起压制成覆铜板。测试层压板或覆铜板，其玻璃化转变温 度 (DSC法） 153 C， 氧指数 61. 6%, 阻燃性能达到 UL94V0级， 剥离强度 288Ό , 10s条件为 1. 9N/mm, 吸水率为 0. 25%， 弯曲强度为 510MPa， 各项性能均超过 FR-4阻燃基本材料标准规 定的性能指标。  The E-glass cloth/epoxy prepreg is prepared by impregnating the above-mentioned halogen-free and non-phosphorus flame-retardant epoxy resin composition with 0. 05-0. 2mm thick E-glass fiber plain cloth, removing acetone or absolute ethanol solvent. After the prepreg was laminated, it was placed in a steel mold and pressed on a flat plate hot press to obtain an E-glass cloth/halogen-free phosphorus-free flame-retardant epoxy resin laminate. The copper clad laminate was pressed together with the E-glass cloth/epoxy laminate using the same process as above. The test has a glass transition temperature (DSC method) 153 C, an oxygen index of 61.6%, a flame retardant performance of UL94V0, a peel strength of 288 Ό, a 10 s condition of 1. 9 N/mm, a water absorption rate of 0. 25%, bending strength is 510MPa, and each performance exceeds the performance index specified by FR-4 flame retardant basic material standard.
实施例 4  Example 4
本发明的无卤无磷阻燃环氧树脂组成物， 按以下重量组份比：  The halogen-free and phosphorus-free flame-retardant epoxy resin composition of the present invention has the following weight-to-component ratio:
多元苯酚硼酸酯 50  Polyphenolate borate 50
双酚 S环氧树脂 20 α -甲基丙烯酸钝化咪唑 15 Bisphenol S epoxy resin 20 Α-methacrylic acid passivated imidazole 15
Υ -縮水甘油醚丙基三甲氧基娃烷 1  Υ - glycidyl ether propyl trimethoxy siloxane 1
将上述各组份溶于丙酮或无水乙醇溶剂中，待均匀透明后混合制成无卤无磷阻燃环氧树脂 组成物。  The above components are dissolved in a solvent of acetone or absolute ethanol, and are uniformly transparent and mixed to prepare a halogen-free and phosphorus-free flame-retardant epoxy resin composition.
上述 α -甲基丙烯酸钝化咪唑的是由等化学当量的 α -甲基丙烯酸与 2-乙基， 4-甲基咪唑反 应生成。  The above α-methacrylic acid passivated imidazole is produced by reacting an equivalent chemical equivalent of α-methacrylic acid with 2-ethyl, 4-methylimidazole.
将上述无卤无磷阻燃环氧树脂组成物浸渍 0. 05-0. 2mm厚的 E-玻璃纤维平纹布， 除去丙 酮或无水乙醇溶剂， 制成 E-玻璃布 /环氧树脂预浸料， 将预浸料多层叠放后， 置于钢模具中在 平板热压机上压制， 得到 E-玻璃布 /无卤无磷阻燃环氧树脂层压板。用与上述相同的工艺， 用 铜箔与 E-玻璃布 /环氧树脂层压板一起压制成覆铜板。测试层压板或覆铜板，其玻璃化转变温 度（DSC法） 155°C， 氧指数 61. 8%， 阻燃性能达到 UL94V0级， 剥离强度 288°C， 10s条件为 1. 9N/mm, 吸水率为 0. 25°/。， 弯曲强度为 510MPa， 各项性能均超过 FR- 4阻燃基本材料标准规 定的性能指标。  The E-glass cloth/epoxy prepreg is prepared by impregnating the above-mentioned halogen-free and non-phosphorus flame-retardant epoxy resin composition with 0. 05-0. 2mm thick E-glass fiber plain cloth, removing acetone or absolute ethanol solvent. After the prepreg was laminated, it was placed in a steel mold and pressed on a flat plate hot press to obtain an E-glass cloth/halogen-free phosphorus-free flame-retardant epoxy resin laminate. The copper clad laminate was pressed together with the E-glass cloth/epoxy laminate using the same process as above. The test has a glass transition temperature (DSC method) of 155 ° C, an oxygen index of 61.8%, a flame retardant performance of UL94V0, a peeling strength of 288 ° C, a 10 s condition of 1. 9 N / mm, water absorption The rate is 0. 25 ° /. The flexural strength is 510 MPa, and all performances exceed the performance specifications of the FR-4 flame retardant basic material standard.

Claims

一—种无卤无磷阻燃环氧树脂组成物， 其特征在于含下列重量比组份： A halogen-free, phosphorus-free flame-retardant epoxy resin composition characterized by comprising the following weight ratio components:
多元苯酚硼酸酯 10-50  Polyphenolate borate 10-50
双酚 S环氧树脂 20-50  Bisphenol S epoxy resin 20-50
α -甲基丙烯酸钝化咪唑 0. 5-15  Α-methacrylic acid passivated imidazole 0. 5-15
y -缩水甘油醚丙基三甲氧基硅烷 0. 5-10。  y - glycidyl ether propyl trimethoxy silane 0. 5-10.
2、根据权利要求 1所述的无卤无磷阻燃环氧树脂组成物， 其特征在于： 上述多元苯酚硼酸酯 是三对苯二酚硼酸酯或是三间苯二酚硼酸酯或是三双酚 S三硼酸酯。 The halogen-free, phosphorus-free flame-retardant epoxy resin composition according to claim 1, wherein: said polyhydric phenol borate is trisorcinol borate or trisphenol phenolate Or tris-bisphenol S triborate.
3、 根据权利要求 1所述的无卤无磷阻燃环氧树脂组成物， 其特征在于： 上述 a -甲基丙烯酸 钝化咪唑由等化学当量的 α -甲基丙烯酸与 2-乙基, 4-甲基咪唑反应生成。  3. The halogen-free, phosphorus-free flame-retardant epoxy resin composition according to claim 1, wherein: the a-methacrylic acid passivated imidazole is composed of an equivalent chemical equivalent of α-methacrylic acid and 2-ethyl group. 4-methylimidazole is produced by reaction.
PCT/CN2007/000239 2006-02-06 2007-01-23 Halogen-free phosphor-free fire-retardant epoxide resin composition WO2007090335A1 (en)

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Publication number Priority date Publication date Assignee Title
CN1184131A (en) * 1996-12-06 1998-06-10 索玛株式会社 Flame-retardant epoxy resin composition for case potting of film capacitors
CN1631972A (en) * 2003-12-22 2005-06-29 合正科技股份有限公司 High heat conduction, halogen free, phosphorus free and flame retardant resin composition for printed circuit board

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1184131A (en) * 1996-12-06 1998-06-10 索玛株式会社 Flame-retardant epoxy resin composition for case potting of film capacitors
CN1631972A (en) * 2003-12-22 2005-06-29 合正科技股份有限公司 High heat conduction, halogen free, phosphorus free and flame retardant resin composition for printed circuit board

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