CN104292753A - 覆铜板用高cti无卤环氧树脂组合物及其应用 - Google Patents

覆铜板用高cti无卤环氧树脂组合物及其应用 Download PDF

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Publication number
CN104292753A
CN104292753A CN201410515073.4A CN201410515073A CN104292753A CN 104292753 A CN104292753 A CN 104292753A CN 201410515073 A CN201410515073 A CN 201410515073A CN 104292753 A CN104292753 A CN 104292753A
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Prior art keywords
epoxy resin
halogen
copper
resin composition
free
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CN201410515073.4A
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CN104292753B (zh
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吴永光
林仁宗
宋黄明
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Zhuhai Epoxy Base Electronic Material Corp Ltd
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Zhuhai Epoxy Base Electronic Material Corp Ltd
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Priority to CN201410515073.4A priority Critical patent/CN104292753B/zh
Priority to US15/511,324 priority patent/US10189988B2/en
Priority to PCT/CN2014/093414 priority patent/WO2016049981A1/zh
Priority to JP2017516155A priority patent/JP6470400B2/ja
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
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    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
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Abstract

本发明公开了一种覆铜板用高CTI无卤环氧树脂组合物及其应用，按重量份数计算，其配方由以下组分组成：无卤含磷环氧树脂100～140份、双环戊二烯类酚醛环氧树脂10～35份、苯并恶嗪32～60份、酚醛树脂1～5份、促进剂0.05～0.5份、填料25～70份。依本发明所制得的铜箔基板，可达到高CTI(CTI≧500V)、高耐热(Tg≧150℃，PCT,2h>6min)、阻燃达UL-94V0级的要求，广泛应用于电机电器、白色家电等的电子材料。

Description

覆铜板用高CTI无卤环氧树脂组合物及其应用
技术领域
本发明属于高分子材料领域，具体地为一种具有高CTI、高耐热等特性，适用于电机电器、白色家电等电路板使用的树脂组合物。
背景技术
随着科学技术飞速发展，大规模工业集成化的形成，对人类自身居住环境造成无法弥补的损害，从而环境保护变得很迫切。近年来，电子技术飞速发展，电子产品对环境产生的影响日益严重，特别是电子垃圾产品，目前绝大部分电子产品系卤系阻燃，卤系燃烧后，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。另据文献报道，含卤素的阻燃剂在高温裂解和燃烧时会产生二恶英，二苯并呋喃等致癌物质，欧洲出台了《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》，要求2006年7月1日后电子产品不得含有铅、隔、汞、六价铬等六种物质，日本也相应提出无卤阻燃之相关法令，特别SONY提出全部采用无卤材料，因此开发无卤素阻燃之基板材料势在必行，已经成为业界的工业重点。
另一方面，人类生活的安全性越来越广受社会的关注。为提高电子产品的安全可靠性，特别对于潮湿环境条件下使用的绝缘材料(如电机、电器等)安全可靠性，开发高绝缘性产品保证电子产品安全可靠性就是近年来的一个重要的发展方向。高分子材料覆铜板所测试的CTI值(Comparative Tracking Index)，指材料表面能经受住50滴电解液(0.1％氯化铵水溶液)而没有形成漏电痕迹的最高电压值，其在一定程度上衡量此材料的绝缘安全性能，此值越高，代表材料的绝缘性越好，因此高CTI产品已成为电子行业研究发展趋势。
近年的一些高CTI材料主要是CEM-3材料，但自从电子电气相关行业实行无铅化以来，产品应用的高温环境要求也相应地在不断提高，对材料的耐热性提出新的要求，因此，CEM-3材料达到以上的要求就有些力不从心，并且现有的一些高CTI的FR4板材也存在耐热性不好的问题，此种板材一般都是用双氢胺固化，通过添加氢氧化铝来提高CTI，因此，耐热性不好。
因此业界迫于研究出一种同时具备耐热性好、较高的CTI的电路板使用的树脂组合物。
发明内容
本发明的目的在于提供一种覆铜板用无卤环氧树脂组合物，其CTI值高且耐热性佳。
本发明的另一个目的是提供上述无卤环氧树脂组合物的应用。
本发明的目的是这样实现的：一种覆铜板用高CTI的无卤环氧树脂组合物，按重量份数计算，其配方由以下组分组成：无卤含磷环氧树脂100～140份；双环戊二烯类酚醛环氧树脂10～35份；酚醛树脂1～5份；苯并恶嗪32～60份；促进剂0.05～0.5份；填料25～70份。
进一步地，所述无卤含磷环氧树脂的合成方法为：
1).按照配方秤取各原料，所述配方包含如下质量百分比的原料：环氧树脂55～75％；反应型含磷化合物25～45％；其中，所述环氧树脂为直链型环氧树脂；
2).制备无卤含磷环氧树脂：于反应槽中加入所述直链型环氧树脂和反应型含磷化合物，升温溶解，于110～130℃加入触媒，然后升温至170～190℃，反应2～4小时，降温加溶剂溶解，得到固含量为65～75％，磷含量为2.5～4.5％，环氧当量为500～1000g/eq的无卤含磷环氧树脂。
所述触媒与反应型含磷化合物的质量比为0.05～0.15∶100，优选为0.1～100；所述触媒选自三苯基磷、磷酸三苯酯、季铵盐或季膦盐。
更优选地，所述直链型环氧树脂选自BPA型、BPF型、双酚S型线性环氧树脂中的一种或两种以上混合；所述反应型含磷化合物选自DOPO-HQ、DOPO-NQ中的一种或两种混合；所述步骤2)中溶剂选自丁酮、丙二醇甲醚、环己酮中的一种或两种以上混合。
其中，所述双环戊二烯类酚醛环氧树脂的结构式如下，其为日本DIC公司产品：
更进一步地，所述苯并恶嗪选自BPA型苯并恶嗪、BPF型苯并恶嗪、DDM型苯并恶嗪中的一种或两种以上混合。
进一步地，所述酚醛树脂选自线性酚醛树脂、邻甲酚醛树脂、BPA型酚醛树脂中的一种或两种以上混合。
优选地，所述促进剂选自咪唑类化合物中的2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑中的一种或两种以上混合。
优选地，所述填料选自氢氧化铝、氢氧化镁中的一种或两种混合。
上述的覆铜板用高CTI无卤环氧树脂组合物在制作印刷电路积层板的应用。
所述的应用中，以有机溶剂调整上述环氧树脂组合物，形成固形份为50-70％的组成物，将玻璃纤维布浸渍于所述环氧树脂组合物中，再经过加热烘烤，使浸渍的玻璃纤维布干燥成为预浸渍体，在该预浸渍体的任一面或两面放置铜箔，使其一个或多个预浸渍体迭成层，并加热加压该迭片制得铜箔基板，迭片固化温度范围为50～250℃。
所述有机溶剂选自丁酮、丙二醇甲醚、环己酮、丙二醇甲醚醋酸酯中的一种或两种以上混合。
本发明的覆铜板用高CTI无卤环氧树脂组合物，制作的板材具有高CTI、高耐热性等特点，各项性能如CTI、耐热性等皆达较优。依本发明所制得的铜箔基板，可达到高CTI(CTI≧500V)、高耐热(Tg≧150℃，PCT,2h>6min)、阻燃达UL-94V0级的要求，广泛应用于电机电器及白色家电等电子材料。
具体实施方式
本发明提供一种覆铜板用高CTI的无卤环氧树脂组合物，按重量份数计算，其配方由以下组分组成：无卤含磷环氧树脂100～140份；双环戊二烯类酚醛环氧树脂10～35份、苯并恶嗪32～60份；酚醛树脂1～5份；促进剂0.05～0.5份；填料25～70份。
所述无卤含磷环氧树脂是由直链型环氧树脂和反应型含磷化合物反应而成，得到磷含量为2.5～4.5％，环氧当量为500～1000g/eq的无卤含磷环氧树脂。
此树脂以直链型含磷环氧树脂为主体，具有高CTI值、阻燃性、较好的韧性及黏结性。所述直链型环氧树脂选自BPA型、BPF型或双酚S型线性环氧树脂；所述反应型含磷化合物选自DOPO-HQ、DOPO-NQ中的一种或两种混合。该环氧树脂的合成方法为：1).按照配方秤取各原料，所述配方包含如下质量百分比的原料：环氧树脂55～75％；反应型含磷化合物25～45％；其中，所述环氧树脂为直链型环氧树脂；2).制备无卤含磷环氧树脂：于反应槽中加入所述直链型环氧树脂和反应型含磷化合物，升温溶解，于110～130℃加入触媒，然后升温至170～190℃，反应2～4小时，再降温加溶剂溶解，得到固含量为65～75％。其中，所述触媒与反应型含磷化合物的质量比为0.05～0.15：100，质量比优选为0.1～100。所述触媒选自三苯基磷、磷酸三苯酯、季铵盐或季膦盐一种或两种以上混合。所述步骤2)中溶剂选自丁酮、丙二醇甲醚、环己酮中的一种或两种以上混合。
所述双环戊二烯类酚醛环氧树脂的结构如下：
此类树脂具有高耐热性和化学稳定性、阻燃性好，可提高组合物的CTI值。
所述苯并恶嗪是由酚、醛及胺合成的一种含氮酚醛化合物，具有优异的耐热性和阻燃性，其含氮结构与含磷环氧形成磷氮协同效应，提高产品的阻燃特性，选自BPA型苯并恶嗪、BPF型苯并恶嗪、DDM型苯并恶嗪中的一种或两种以上混合。
所述酚醛树脂具有高耐热性，选自线性酚醛树脂、邻甲酚醛树脂、BPA型酚醛树脂中的一种或两种以上混合。
所述促进剂选自咪唑类化合物中的2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑中的一种或两种以上混合。
所述填料选自氢氧化铝、氢氧化镁中的一种或两种以上混合。
上述覆铜板用高CTI无卤环氧树脂组合物在制作印刷电路积层板的应用。
所述应用中，以有机溶剂调整上述环氧树脂组合物，形成固形份为50-70％的组成物，将玻璃纤维布浸渍于所述环氧树脂组合物中，再经过加热烘烤，使浸渍的玻璃纤维布干燥成为预浸渍体(Prepreg)，在该预浸渍体的任一面或两面放置铜箔，使其一个或多个预浸渍体迭成层，并加热加压该迭片制得铜箔基板，迭片固化温度范围为50～250℃。所述有机溶剂选自丁酮、丙二醇甲醚、环己酮、丙二醇甲醚醋酸酯中的一种或两种以上混合。
下面结合较佳的实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。实施例及比较例中的各代号及成份如下：
树脂1：本发明的无卤含磷环氧树脂(A1)的合成为：于反应槽中加入BPA型液态环氧树脂(60～70％)和反应型含磷化合物(30～40％)升温溶解，于120℃加入触媒三苯基磷TPP，升温至170～190℃，反应2～4小时，降温加环己酮溶解成固含量为70％。磷含量为3.0～4.0％，其环氧当量介于700～900g/eq。
树脂2：本发明的无卤含磷环氧树脂(A2)的合成为：于反应槽中加入BPF型液态环氧树脂(60～70％)和反应型含磷化合物(35～45％)升温溶解，于120℃加入触媒三苯基磷TPP，升温至170～190℃，反应2～4小时，降温加环己酮溶解成固含量为70％。磷含量为3.0～4.0％，其环氧当量介于700～900g/eq。
树脂3：双环戊二烯类酚醛环氧树脂7200HHH，为日本DIC公司产品。
树脂4:邻甲酚醛环氧树脂704，为南亚公司。
树脂5：宏昌电子材料股份有限公司生产的无卤树脂，商品名为GEBR589K75。
固化剂1：DDM型苯并恶嗪。
固化剂2：酚醛树脂GERH833K65，为宏昌电子材料股份有限公司产品。
固化剂3：双氰胺，10wt％溶于DMF。
填料：氢氧化铝。
固化促进剂2PI：2-苯基咪唑，1wt％溶于PM。
玻璃纤维布为7628布。
实施例1
使用本发明的成份(A1+7200HHH)为主体树脂，搭配固化剂DDM型苯并恶嗪和酚醛树脂GERH833K65，填料使用氢氧化铝，其配方组成详于表1，以丁酮(MEK)、丙二醇甲醚(PM)或丙二醇甲醚醋酸酯调整固形份为55％的清漆组成物，将7628玻璃纤维布浸渍于上述清漆树脂液，然后于含浸机温度170～180℃，干燥数分钟，由调整控制干燥时间，使干燥后的预浸渍体熔融黏度为800～1800Pa.s之间，最后将8片胶片层层相迭于两片35μm厚的铜箔间，在25Kg/cm2压力，温度控制如下：
经过热压后，可得到1.6mm后的铜箔基板。此组成物的CTI达500V以上，Tg达150℃以上，耐热性好，阻燃达V0级。功能详于表1。
实施例2
重复实施例1，改变成份A1和7200HHH的配比，所得组成物的CTI达500V以上，Tg达150℃以上，耐热性好，阻燃达V0级。功能详于表1。
实施例3
使用本发明的成份(A2+7200HHH)为主体树脂，搭配固化剂DDM型苯并恶嗪和酚醛树脂GERH833K65，填料使用氢氧化铝，其配方组成详于表1，重复实施例1的制作基板过程。所得组成物的CTI达500V以上，Tg达150℃以上，耐热性好，阻燃达V0级。功能详于表1。
实施例4
重复实施例3，改变成份A2和7200HHH的配比，所得组成物的CTI达500V以上，Tg达150℃以上，耐热性好，阻燃达V0级。功能详于表1。
比较例1
重复实施例4，将成份704代替7200HHH，所得组成物的耐热性好，但CTI值不到400V，阻燃只达V1级。功能详于表1。
比较例2
使用GEBR589K75为主体树脂，搭配固化剂双氰胺，重复实施例1制造铜箔基板步骤，所得组成物的耐热性较差(PCT爆板不达6min，T288不达60min)。功能详于表1。
比较例3
重复实施比较例2，固化剂改为DDM型苯并恶嗪和酚醛树脂GERH833K65，所得组成物的CTI及阻燃性差，具体地，其CTI值不到400V，阻燃只达V1级。功能详于表1。
量测说明
1)清漆胶化时间(sec)：
取0.3ml树脂清漆于170℃胶化测试仪上，量测其胶化时间。
2)玻璃化转变温度(Tg,℃)：
根据IPC-TM-650之2.4.25测定。
3)剥离强度(lb/in)：
根据IPC-TM-650之2.4.8测定。
4)PCT爆板(min)：
于2个大气压下，120℃的压力锅中，蒸煮2小时，再将样品于288℃的锡炉浸泡，观察分层时间。
5)CTI值(V,50D)：
根据GB/T4207-2003测定。
6)T288测试(min)
用TMA法测试样品分层时间。
7)耐燃性：
根据UL94垂直燃烧法测试。
发明功效
从表1的实施例1-4及比较例1-3的性能检测结果可以得出：使用本发明的高CTI无卤含磷环氧树脂，搭配固化剂苯并恶嗪和酚醛树脂，制作的板材具有高CTI、高耐热性等特点。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含本发明的保护范围之内。

Claims (10)

1.一种覆铜板用高CTI的无卤环氧树脂组合物，其特征在于：按重量份数计算，其配方由以下组分组成：
2.根据权利要求1所述的覆铜板用高CTI无卤环氧树脂组合物，其特征在于：所述无卤含磷环氧树脂的合成方法为：
1).按照配方秤取各原料，所述配方包含如下质量百分比的原料：
环氧树脂          55～75％；
反应型含磷化合物  25～45％；其中，
所述环氧树脂为直链型环氧树脂；
2).制备无卤含磷环氧树脂：于反应槽中加入所述直链型环氧树脂和反应型含磷化合物，升温溶解，于110～130℃加入触媒，然后升温至170～190℃，反应2～4小时，降温加溶剂溶解，得到固含量为65～75％，磷含量为2.5～4.5％，环氧当量为500～1000g/eq的无卤含磷环氧树脂。
3.根据权利要求2所述的覆铜板用高CTI无卤环氧树脂组合物，其特征在于：所述触媒与反应型含磷化合物的质量比为0.05～0.15∶100，所述触媒选自三苯基磷、磷酸三苯酯、季铵盐或季膦盐。
4.根据权利要求1-3任一权利要求所述的覆铜板用高CTI无卤环氧树脂组合物，其特征在于：所述直链型环氧树脂选自BPA型、BPF型、双酚S型线性环氧树脂中的一种或两种以上混合；所述反应型含磷化合物选自DOPO-HQ、DOPO-NQ中的一种或两种混合。
5.根据权利要求1-3任一权利要求所述的覆铜板用高CTI无卤环氧树脂组合物，其特征在于：所述苯并恶嗪选自BPA型苯并恶嗪、BPF型苯并恶嗪、DDM型苯并恶嗪中的一种或两种以上混合。
6.根据权利要求1-3任一权利要求所述的覆铜板用高CTI无卤环氧树脂组合物，其特征在于：所述酚醛树脂选自线性酚醛树脂、邻甲酚醛树脂、BPA型酚醛树脂中的一种或两种以上混合。
7.根据权利要求1-3任一权利要求所述的覆铜板用高CTI无卤环氧树脂组合物，其特征在于：所述促进剂选自咪唑类化合物中的2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑中的一种或两种以上混合。
8.权利要求1-7中任一权利要求所述的覆铜板用高CTI无卤环氧树脂组合物在制作印刷电路积层板的应用。
9.根据权利要求8所述的应用，其特征在于：以有机溶剂调整上述环氧树脂组合物，形成固形份为50-70％的组成物，将玻璃纤维布浸渍于所述环氧树脂组合物中，再经过加热烘烤，使浸渍的玻璃纤维布干燥成为预浸渍体，在该预浸渍体的任一面或两面放置铜箔，使其一个或多个预浸渍体迭成层，并加热加压该迭片制得铜箔基板，迭片固化温度范围为50～250℃。
10.根据权利要求9所述的应用，其特征在于：所述有机溶剂选自丁酮、丙二醇甲醚、环己酮、丙二醇甲醚醋酸酯中的一种或两种以上混合。
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