CN1073132C - 一种不含卤素的阻燃环氧树脂组合物 - Google Patents

一种不含卤素的阻燃环氧树脂组合物 Download PDF

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CN1073132C
CN1073132C CN96190181A CN96190181A CN1073132C CN 1073132 C CN1073132 C CN 1073132C CN 96190181 A CN96190181 A CN 96190181A CN 96190181 A CN96190181 A CN 96190181A CN 1073132 C CN1073132 C CN 1073132C
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preg
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CN1148402A (zh
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本田信行
杉山强
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Kyocera Chemical Corp
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Abstract

一种不含卤素的阻燃环氧树脂组合物，包括(A)双酚A型环氧树脂，(B)固化剂，(C)在每个颗粒上有覆盖层的红磷颗粒，该覆盖层至少在最外层是由树脂形成的，和(D)无机填料。

Description

一种不含卤素的阻燃环氧树脂组合物
                        技术领域
本发明涉及一种不含卤素的阻燃环氧树脂组合物，一种含有环氧树脂组合物的预浸处理物(prepreg)，和一种层压板，一种覆铜的层压板，以及使用该预浸处理物形成的印刷线路板。
                        背景技术
最近一种对有关世界范围的环境问题以及人体的安全性已引起了关注，除了要求阻燃外，还要求电学/电子产品危害更少而更安全，更确切地说，要求电学/电子产品难于燃烧，并且产生极少的有害气体及烟雾。固定有电学/电子产品的常规印刷线路板，通常具有玻璃-环氧树脂基材。一般是溴化环氧树脂，特别是四溴双酚A型环氧树脂，在基材中通常用作含溴的阻燃环氧树脂。
这种溴化环氧树脂具有良好的阻燃性。但是它在燃烧时也会产生一种有害的卤化氢(溴化氢)气体。因为这个原因，溴化环氧树脂的用途就受到抑制。在这种情况下，已开发了这样的组合物，把一种不含卤素的阻燃剂如氮化合物、磷化合物、或一种无机化合物加到常规的环氧树脂中(例如，见英国专利No.1,112,139和日本专利申请公开本No.2-269730)。但是用这些添加剂所得到的阻燃性有一些问题：它们会对环氧树脂固化产生不利的影响，降低固化组合物的耐湿蒸汽性，并且削弱组合物浸渍到玻璃布里。
从增进安全性考虑，另一个与阻燃性同样重要的特征是，抗漏流径形成性(tracking resistance)。对高压电路基材来说，抗漏流径形成性是特别要求的，例如是在空调和电视的印刷线路板上。
为赋予抗漏流径形成性，向印刷线路上的树脂组合物中添加一种链状烃、环状化合物或无机材料作为基材，它是一种难于碳化的物质。但是这些物质也有一些缺点，链状烃和环状烃化会降低印刷线路板的耐热性，并且无机材料的用量必须很大。
因此，本发明的目的是提供一种能具有很好阻燃性的环氧树脂组合物，不含有但却也有良好的抗潜心流径形成性。
本发明的另一目的是提供浸渍有这样一种环氧树脂的预浸处理物，以及一种层压板，覆铜的层压板和由这种预浸处理物形成的印刷线路板。
                        发明的公开
为达到上述目的，本发明提供一种不含卤素的阻燃环氧树脂组合物，包括(A)双酚A型环氧树脂，(B)固化剂，(C)覆有覆盖层的红磷颗粒，且至少是覆盖层的最外层是由树脂形成的，和(D)无机填料。
本发明进一步提供一种浸渍有本发明的不含卤素的阻燃环氧树脂组合物的预浸处理物，并且提供一种层压板，一种覆铜的层压板和用这种预浸处理物形成的印刷线路板。本发明的预浸处理物包括用本发明的环氧树脂组合物浸渍的玻璃基材。本发明的层压板包括多片相互层压的本发明的预浸处理物，其中的环氧树脂组合物被固化。本发明的覆铜层压板包括至少一个表面上覆有一层铜箔的本发明的层压板。本发明的印刷线路板包括在本发明的覆铜层压板，在其上有一线路层。
                  实施本发明的最佳方式
本发明将在下面进行详细说明。
本发明的环氧树脂组合物包括作为组分(A)的双酚A型环氧树脂。如本领域所知，这种双酚A型环氧树脂是双酚A和表氯醇(epichlorohy-drin)或诸如此类的反应产物。用在本发明中的双酚A型环氧树脂，通常有170或更高的环氧当量。环氧当量优选不超过1000，因为玻璃布不能充分浸渍这样的组合物。这种双酚A型环氧树脂可以在市场上买到，例如那些从日本Yuka Shell买到的商品名为EPIKOTE的系列产品，和从CIBA-GAIGY买到的ARALDITE系列产品。双酚A型环氧树脂可单独使用或二种或多种混合使用。
本发明的环氧树脂组合物的组分(B)是一种固化剂。固化剂(B)可以是任何一种常规上可用于环氧树脂的固化剂。这种固化剂包括胺固化剂和含酚(phenolic)固化剂。胺固化剂的例子包括双氰胺，芳香胺(苄胺)。含酚固化剂的例子包括苯酚型酚醛清漆树脂、甲酚型酚醛清漆醛树脂、双酚A型酚醛清漆树脂等等。
本发明的环氧树脂组合物的特征组分，组分(C)，包括覆盖有至少一层树脂的红磷颗粒。本发明人已发现涂敷的红磷颗粒不仅可作为赋予环氧树脂阻燃性的一种试剂，而且可赋予用本发明的环氧树脂形成的印刷线路板抗漏流径形成性。红磷颗粒优选为平均直径为200μm或更少的且是成球形的颗粒。包在红磷颗粒外的覆盖层至少在最外层是由一种树脂形成的，特别是一种热固性树脂。这种树脂的包层可提高红磷颗粒的耐湿蒸汽性。优选每个红磷颗粒有两个覆盖层。第一层是由无机材料颗粒粘附到红磷颗粒的表面构成的。第二层覆盖在第一层上，它是由一种树脂，特别是由热固性树脂构成的。构成第一层的无机颗粒优选由氢氧化铝和/或氢氧化锌颗粒形成。构成第二层的热固性树脂是由如下的一种热固性树脂构成的，如酚类/甲醛树脂、尿素/甲醛树脂、三聚氰胺/甲醛树脂、糠醇/甲醛树脂(furfuryl alcohol/formaline resin)、苯胺/甲醛树脂。涂敷的红磷颗粒本身及其制备公开在日本专利申请KOKOKU公开No.s4-37862和6-27217中。简单地说，白磷经过热处理可变成球形颗粒的红磷。然后，将球形的红磷颗粒悬浮在水中。往这种悬浮液中加入一种水溶性的铝或锌盐的水溶液(例如，硫酸铝，氯化铝，硫酸锌，氯化锌)。通过与氢氧化钠的中和反应或碳酸氢铵的二次分解，氢氧化铝或氢氧化锌就吸附在每个红磷颗粒上。氢氧化物的量优选为每100份红磷有1-30份(重量)。往这种涂敷氢氧化物的红磷颗粒的悬浮液中加入前面提到的热固性树脂的原料或其最初的缩聚产品，然后进行热处理。结果，可得到由固化树脂形成的第二层。包层树脂的量优选为每100重量份的红磷颗粒为1-30重量份。
本发明环氧树脂组合物中所含的组分(D)是一种无机填料，它还赋予环氧树脂组合物阻燃性、耐热性性、和耐湿蒸汽性。这种填料的例子包括滑石、氧化硅、氧化铝、氢氧化铝、氢氧化镁粉末等。这些填料可单独使用，也可两种或多种混合使用。
在本发明的环氧树脂组合物中，优选一种树脂组合，即(组分(A)+组分(B)的量为占组分(A)、(B)、(C)和(D)总重量的50-90％。因此优选组分(C)和(D)的和为组分(A)、(B)、(C)和(D)总重量的50-10％。组分(C)，即，涂敷的红磷的量优选为(A)、(B)、(C)和(D)总重量的0.5-20％。
当作为环氧树脂的固化剂的组分(B)是含酚(phenolic)固化剂的情况下，环氧树脂组分(组分(A))和含酚树脂固化剂的加人优选使得含酚(phenolic)固化剂的每一个氢氧当量有0.8-1.2的环氧当量，更优选0.95-1.05环氧当量。当作为环氧树脂的固化剂组分(B)是胺固化剂的情况下，胺固化剂占环氧树脂组分(组分(A))的量优选在1-10％重量份的范围内。特别是如果胺固化剂是双氰胺时，优选使用量为环氧树脂组分(A)的重量的2-3％(重量)范围内的固化剂。
应当注意，本发明的环氧树脂组合物可含有固化促进剂以缩短组合物的固化时间。作为这种固化促进剂，就可使用任何一种试剂，只要它通常可用于促进一种环氧树脂的固化即可。这种固化促进剂的例子包括咪唑化合物，如2-乙基-4-甲基咪唑和1-苯基-2-甲基咪唑。这种固化促进剂可以单独使用，也可两种或多种混合使用。这些固化促进剂可用很小的量，就足够促进环氧树脂的固化。
在用上面说明的本发明的环氧树脂组合物时，可采用如下的常规方法来制备预浸处理物，其步骤包括用适当的有机溶剂，如丙二醇单甲基醚，稀释环氧树脂组合物以制成清漆，以及用这种清漆，涂覆并浸渍一种多孔的玻璃基材如非编织的玻璃织物或玻璃布，接着再加热。进而，就可通过将多个预浸处理物层压在一起形成层压状结构，并把铜箔放在层压结构的一或两个表面上，在常规条件下对这种结构进行加热和加压，就可制成玻璃环氧型覆铜的层压板。如果在不用铜的情况下，可得到一种层压板。通过用常规方法可得到多层板，其步骤包括在覆铜的层压板(内层板)上形成一个电路、刻蚀铜箔、将预浸处理物和铜箔层压到内层板的两个表面的至少一个表面上、并对所得到这种结构进行加热和加压，例如，在170℃和40kg/cm2的条件下进行90分钟，就可制成多层板。进而，再通过用常规的方法可得到印刷线路板，其步骤包括在覆铜的层压板或多层板上进行穿孔、熨平穿孔和形成一个预定电路。
本发明将参考下面实例进行说明。
                       实施例1
通过往260重量份的双酚(A)型环氧树脂，即EPIKOTE1001(由Yu-ka Shell生产，环氧当量为456，树脂固含量为70％重量)、65重量份甲酚型酚醛清漆环氧树脂，即YDCN-704P(由Totokasei生产，环氧当量为210，固含量为70％重量)、25重量份的涂敷的红磷颗粒(用氢氧化铝和苯酚树脂包裹，红磷含量为85％重量)、104重量份的双酚A型酚醛清漆树脂(氢氧值为118，固含量为70％重量份)、100重量份的氢氧化铝、和0.1重量份的2-乙基-4-甲基咪唑的混合物中，加入一种作为溶剂的丙二醇单甲基醚(PGM)，制备一种含有树脂固含量为65％(重量)的环氧树脂清漆混合物。
                      实施例2
通过往260重量份的双酚A型环氧树脂EPIKOTE1001(如上所述)、65重量份甲酚型酚醛清漆环氧树脂YDCN-704P(如上所述)、50重量份涂敷的红磷颗粒(用氢氧化铝和苯酚树脂包裹，红磷含量为85％重量份)、104重量份的双酚A型酚醛清漆树脂(氢氧值为118，固含量为70％重量份)、175重量份的氢氧化铝、和0.1重量份的2-乙基-4-甲基咪唑的混合物中，加入PGM，制备一种含有树脂固含量为65％(重量)的环氧树脂清漆混合物。
                      实施例3
通过往260重量份的双酚A型环氧树脂EPIKOTE1001(如上所述)、65重量份甲酚型酚醛清漆环氧树脂YCDN-704P(如上所述)、35重量份涂敷的红磷颗粒(用氢氧化铝和苯酚树脂包裹，红磷含量为85％重量份)、115重量份的氢氧化铝、和6重量份的双氰胺的混合物中，加入PGM，制备一种含有树脂固含量为65％(重量)的环氧树脂清漆混合物。
                       对比例1
通过往由283重量份的溴化环氧树脂(由Dainippon Ink和Chemi-cals,Inc生产，环氧当量为490，固含量为75％重量份)、34重量份甲酚型酚醛清漆环氧树脂YCDN-704P(如上所述)、92重量份的双酚A型酚醛清漆树脂(由Dainippon Ink和Chemicals,Inc生产，氢氧值118，固含量70％重量份)、200重量份的氢氧化铝、和0.1重量份的2-乙基-4-甲基咪唑的混合物中，加入PGM，制备一种含有树脂固含量为65％(重量)的环氧树脂清漆混合物。
                       对比例2
通过往由360重量份的用在对比例1中的溴化环氧树脂、43重量份甲酚型酚醛清漆环氧树脂YCDN-704P(如上所述)、7.5重量份的双氰胺、200重量份的氢氧化铝、和0.1重量份的2-乙基-4-甲基咪唑的混合物中，加入二甲基甲酰胺，制备一种含有树脂固含量为65％(重量)的环氧树脂清漆混合物。
用从实施例1到3和对比例1和2所得的每一种环氧树脂清漆混合物，来连续涂敷和浸渍非编织玻璃织物或玻璃布。所得到的织物在160℃下进行干燥，就形成了预浸处理片材(prepreg sheet)。8片预浸处理片材相互叠合，并把18μm厚的铜箔放在所得到的这种结构的两个表面上。这种层压结构在170℃的温度和40kg/cm2的压力下，经受90分钟的加热和加压处理。最后，得到一片厚度为1.6mm的玻璃-环氧型覆铜的层压板。
覆铜的层压板经受阻燃性、抗漏流径形成性、绝缘电阻、铜箔在开始时及老化后的剥离强度、耐热性和耐湿蒸汽性几项检测，结果见表1。
                                         表1
                组合物特性                实施例           对比例
     1       2     3      1      2
阻燃性*1     V-0      V-0    V-1     V-0     V-0
抗漏流径形成性*2     600V      600V    600V     200V     200V
绝缘电阻(Ω)*3 8.0×1012 4.0×1012 1.0×1012 2.0×1012 2.0×1012
剥离强度*4  开始     1.50      1.50    1.55     1.50     1.60
 老化后     1.45      1.40    1.45     0.90     0.95
耐热性*5  5分钟      ○       ○     ○      ○      ○
 10分钟      ○       ○     ○      ○      ○
 15分钟      ○       ○     ○      ○      ○
 20分钟      ○       ○     ○      ○      △
耐湿蒸汽性*6  条件A      ○       ○     ○      ○      ○
 条件B      ○       ○     ○      ○      ○
注：
*1：按UL 94阻燃实验测定。
*2：按IEC-PB112测定。
*3：按JIS-C-6481测定。
*4：按JIS-C-6481测定(单位：KN/m)。
*5：样品浮在260℃的焊料浴中持续如表中所示的时间。根据下面的标准对气泡(blister)进行观察和评价：
  …没观察到气泡；
○…观察到一部分有气泡；
△…观察到大部分有气泡；
x…观察到全部有气泡。
*6：样品在条件A(沸腾6小时)或条件B(在120℃,2atm的水蒸汽下保持静置7小时)下进行处理，并在260℃的焊料浴中浸泡30秒。然后根据下面的标准对气泡(blister)进行观察和评价：
  …没观察到气泡；
○…观察到一部分有气泡；
△…观察到大部分有气泡；
x…观察到全部有气泡。
                       实施例4
用从实施例2得到的环氧树脂清漆混合物连续涂覆和浸渍非编织玻璃织物或玻璃布。所得到的织物在160℃下进行干燥，就制成了预浸处理物。8个预浸处理片材相互叠合，并在170℃的温度和40kg/cm2的压力下，经受90分钟的加热/加压处理。最后，就可得到一片玻璃环氧型的层压板。
                       实施例5
按实施例4的相同方法可得到一种预浸处理物。这些预浸处理片材相互叠合，并把35μm厚的铜箔放在所得到的这种预浸处理片材结构的两个表面上。所得到的这种结构经受与实施例4中相同加热/加压处理。最后，就可得到一片厚度为0.8mm的内层板。在所得到的内层板的两个表面的每一个表面上，放置从上面得到的预浸处理物。而且，在每个预浸处理物上放置18μm厚的铜箔。用与所述相同的方法，对所得到的这种结构进行加热/加压处理，因此就制成了1.6mm厚的多层板。
如上所述，根据本发明，提供了展示其优异阻燃性的一种环氧树脂组合物，该组合物不含有卤素，并且提供了一种具有优异耐热性、耐湿蒸汽性和抗漏流径形成性的玻璃环氧型覆铜层压板。而且，用这样的一种玻璃环氧型覆铜层压板，就可得到具有各种性能优异的印刷线路板。

Claims (7)

1．一种不含卤素的阻燃环氧树脂组合物，包括(A)双酚A型环氧树脂；(B)一种固化剂，包括为双氰胺或酚类物质；(C)每个颗粒上有两个覆盖层的红磷颗粒，其包括由氢氧化铝和/或氢氧化锌构成的第一层，及在所述的第一层上由下列树脂制成的第二层；酚类/甲醛树脂、尿素/甲醛树脂、三聚氰胺/甲醛树脂、糠醇/甲醛树脂、苯胺/甲醛树脂；和(D)无机填料；其中所述的组分(A)和(B)的量占组分(A)、(B)、(C)和(D)总重量的50-90％(重量)；所述的组分(C)占组分(A)、(B)、(C)和(D)总重量的0.5-2％(重量)，且当所述固化剂包括所述酚类物质时，则其用量是使得酚固化剂的每一个氢氧当量有0.8-1.2的环氧当量或当所述固化剂包括双氰胺时，其用量基于占环氧树脂组分(A)为1-10重量％。
2．根据权利要求1的组合物，其中所述的双酚A型环氧树脂有170-1000的环氧当量。
3．根据权利要求1的组合物，其中所述的固化剂包括苯酚型酚醛清漆树脂、甲酚型酚醛清漆醛树脂或双酚A型酚醛清漆树脂。
4．一种包含用根据权利要求1到3中的任一项的环氧树脂组合物浸渍的玻璃基材的预浸处理物。
5．一种含有层压的多个根据权利要求4的预浸处理物的层压板，其中所述的环氧树脂是被固化了的。
6．一种覆铜的层压板，包含由权利要求4的至少一个预浸处理物形成的基材，其所述的环氧树脂组合物被固化了，且一片铜箔被粘附到所述基材的至少一个表面上。
7．一种印刷线路板，包含由权利要求4的至少一个预浸处理物形成的基材，其所述的环氧树脂组合物被固化了，且一线路层形成在所述基材的至少一个表面上。
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