CN1105643C - 热稳定氢氧化铝,用其制备印刷电路板用层压板的方法以及层压板 - Google Patents

热稳定氢氧化铝,用其制备印刷电路板用层压板的方法以及层压板 Download PDF

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CN1105643C
CN1105643C CN98801686A CN98801686A CN1105643C CN 1105643 C CN1105643 C CN 1105643C CN 98801686 A CN98801686 A CN 98801686A CN 98801686 A CN98801686 A CN 98801686A CN 1105643 C CN1105643 C CN 1105643C
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thermally stable
aluminum hydroxide
laminate
resin
stable aluminum
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N·布朗
M·阿格莱顿
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Abstract

本发明涉及印刷电路板用的层压板，其特征是具有改善的热稳定性。其性能的改善是由于采用了新的氢氧化铝，该氢氧化铝用分子式Al2O3·nH2O来表示，其中n大于2.6小于2.9。

Description

热稳定氢氧化铝、用其制备印刷电路板用层压板的方法以及层压板
本发明涉及一种用于印刷电路板的热稳定的阻燃层压板，该层压板采用热稳定的氢氧化铝而不需要其它阻燃剂。
印刷电路层压板的类型由美国NEMA(国家电子生产商协会)标准确定，该术语是全世界所接受的。通常，层压板根据所用增强材料的类型(即纤维素纸或玻璃纤纸)来分类。通常，FR-2类只用纸，CEM-1类采用纸和机织玻璃纤维，而CEM-3类含有机织玻璃纤维和非织造玻璃纤维。FR-4类只含有机织玻璃纤维。
为了实现美国保险商实验室(American Underwriters Laboratory)标准UL-94所需的V0级别的阻燃性，需要在聚合物体系中加入阻燃性化学物质，或将卤素或磷掺入聚合物本身骨架中。在燃烧时，这些添加剂有助于熄火。然而，在这种方法中，它们产生了有毒的腐蚀性气体。在燃烧含有含磷化合物的FR-2层压板时，形成了磷酸。含有溴化环氧树脂的CEM-1、CEM-3和FR-4层压板则在燃烧时产生了有毒的腐蚀性溴化氢。
本领域中已熟知可用氢氧化铝来改善以例如环氧、聚酯和乙烯基酯为基的合成聚合物体系的阻燃性，因为聚合物分解的温度范围与氢氧化铝相同。然而，在部件焊接到印刷电路板层压板上所用温度下，三水铝矿形式的氢氧化铝(Al(OH)3或有时用Al2O3·3H2O表示)的热稳定性不够。这会使层压板起泡而不能使用。
已知当在空气中对三水铝矿形式的氢氧化铝进行热处理时，它会部分转变成单水合形式的勃姆石(AlOOH或Al2O3·H2O)，该勃姆石改善了热稳定性，但是损害了阻燃性。
日本专利出版物JP-A 60/203 438描述了一种含有经热处理过的三水铝矿型氢氧化铝的CEM-3层压板，该氢氧化铝的热稳定性比标准氢氧化铝有所改进，但是它不能提供所需级别的阻燃性，因此必须用溴化环氧树脂来达到UL 94 V0级别。在这种情况下，以及在没有优越阻燃性能情况下，另外还可采用无机材料如滑石或粘土。
本发明的目的是生产一种热稳定性好的CEM-3层压板，它不含卤素/磷，并满足UL 94 V0级别的要求。本发明的另一个目的是开发出一种热稳定的氢氧化铝，它能赋予层压板所需的性能。
利用本发明所述的用于印刷电路板的层压板、制备层压板的方法、本发明所述的热稳定的氢氧化铝，就可实现本发明的目的。
CEM-3类层压板一般由外侧两层机织玻璃纤维和芯部三层非织造玻璃纤维薄纱构成。根据本发明，用于印刷电路板的层压板的表面层包含浸渍了可固化树脂的机织玻璃织物，中间层包含浸渍了可固化树脂的非织造玻璃纤维织物，其特征在于中间层含有200-275％(重量)(以树脂重量计)的热稳定氢氧化铝，氢氧化铝的分子式为Al2O3·nH2O，其中n大于2.6小于2.9。
可固化树脂可以是不饱和的聚酯树脂、环氧树脂、乙烯基酯或任何合适的热固性化合物，其燃烧时的分解温度范围与热稳定的氢氧化铝相同。
层压板以环氧树脂为基时，可以用批量法制造。层压板也可用不饱和的聚酯或乙烯基酯(即通过自由基机理聚合的树脂)用连续法制造。但是，本发明的特征并不局限在层压板的制造方法上。
当层压板的制造以环氧树脂为基时，通常是将两层预先浸渍了环氧树脂的机织玻璃纤维层与三层预先浸渍了环氧树脂并含有热稳定氢氧化铝的非织造玻璃纤维结合。然后，通常在这五层的外侧结合一或两层铜箔，再对装配件加热和加压使树脂聚合并使层压板固化。
用于电气和电子用途的大多数环氧树脂从双酚A或环脂族物质衍生获得。最常用的固化剂是双氰胺。
根据本发明的方法，含有浸渍了可固化树脂的非织造玻璃纤维中间层含有200-275重量％(较佳的为225-250重量％(以可固化树脂重量计))的热稳定氢氧化铝。
在分子式中，Al2O3·nH2O中的n值宜在2.7至2.8之间。
本发明的不含卤素和磷的环氧树脂层压板的特征是采用热稳定的氢氧化铝作为唯一的阻燃剂。
现有技术描述了通过除去氢氧化铝中的部分水含量来改善其热稳定性。如果除去的水不够，则含有这种氢氧化铝的层压板不能经受焊接操作。然而，现有技术的局限性还在于，如果除去过多的水，则所得氢氧化铝的含水量又太少，不能有效地起阻燃剂作用。
进一步的困难是形成了热稳定性更大的氢氧化铝相(勃姆石)，它不仅含有原来三水合铝(aluminium trihydroxide)(三水铝矿)三分之一的水，而且它还将这份水保留到520℃才释放。这进一步降低了阻燃效果。
本领域中已经知道，氢氧化铝原料越细，它在加热时形成不希望的勃姆石相的可能性就越小。然而，在避免勃姆石形成所需的粒径(小于1μm)条件下，却难以将该氢氧化铝原料在合成树脂中进行混合处理。另一方面，可混合处理的热稳定氢氧化铝会含有过量勃姆石，从而妨碍了符合UL 94 V0标准的无卤素环氧层压板的生产。
本发明的热稳定氢氧化铝的新特征在本质上是，相对于平均粒径的勃姆石含量令人惊奇地低。这就使得能获得更低的n值，从而在不损害阻燃性质效果的情况下改善水稳定性。因此，若n小于2.6，则获得所需阻燃性能的水不够(并且勃姆石太多)，而当n大于2.9时，则水又太多，无法获得所需的耐焊料性能。
在预先的热处理步骤之前，通过适当地机械处理较粗的氢氧化铝聚集物(平均粒径约为60μm)，就可使勃姆石的形成与粒径之间没有关系。适当的机械处理例如是：向氢氧化铝施加压力使其变为许多小晶体。虽然并无任何理论解释，但是看来用这种方式来破坏结构为水分更容易扩散进入晶体外部创造了条件，从而最大程度地减少晶体内积聚水热压力的程度，因而减少了勃姆石形成的趋势。
实际的做法是使从典型Bayer方法—铝酸钠溶液中结晶出来的中位粒径(average particle size)D50％为40-80μm(更佳的为50-70μm)的氢氧化铝聚集物的粒径减小，就可制得本发明的产品。
可采用任何减小粒径的方法(如球磨法)，它可将存在于较粗聚集物中的一些小晶体分离出来，而总体上很少或不破坏单个的小晶体。由于磨损产生的粒径分布变宽和总体上没有破坏晶体，此热稳定的氢氧化铝在各树脂体系中的可加工性得到改善。
随后的热稳定化可通过简单地加热经粒径减小处理所得的材料来实现，加热温度和时间应足以使其灼烧的失水量从34.5重量％(n＝3)减少到对应于本发明n值的水平。
本发明的热稳定的氢氧化铝宜具有2至10m2/g的比表面积(经BET法测得)。非常重要的一点是粒径分布，它应给出较细的中位粒径并有一定的粒径宽度。这就改善了热稳定氢氧化铝在树脂中的分散性，并且同时最大程度地减少了粗颗粒在混合过程中的沉降趋势，并避免了非织造玻璃纤维对它的过滤作用。最优粒径分布能使得树脂/填料混合料的粘度最小，又能以足够高的填料量获得所需的层压板阻燃性能而不需加入其它阻燃剂。
本发明的热稳定氢氧化铝的中位粒径D50％在5-10μm范围内。粒径分布的宽度则用D10％范围(即10重量％的颗粒粒径小于0.5-1.5μm)和D90％的范围(即90重量％的颗粒粒径小于20-35μm)表示。
根据标准方法DIN 53199测得，热稳定氢氧化铝的吸油量在25-35ml/100g范围内。
热稳定氢氧化铝掺入可固化树脂可用本领域技术人员已知的方法来实现，即，通常是利用合适的装置(如剪切头混合器)将填料加入预先溶解的树脂和固化剂的混合物中。如果需要，在混合物中可加入其它无机热稳定填料，如细的硅土、粘土或滑石，但是这些物质均不会显著增大阻燃性能。
进一步将树脂/填料混合物制成“预浸渍层”，然后制成固化的层压板，这些是本领域中所公知的，在文献如“环氧树脂手册(Handbook of Epoxide Resins)”(McGraw-Hill Book Company出版)中有所描述。
根据本发明制得的固化层压板表现出良好的热稳定性，当其浸在260℃的熔融焊料中时，它在超过90秒仍没有显示出有起泡现象。此层压板还具有优秀的阻燃性能，满足UL 94 V-0的需求。
附图：
图1显示了通过X-射线衍射测得加热不同粒径的氢氧化铝(根据“灼烧损失LOI”的测定结果作为衡量)对形成的勃姆石(AlOOH)百分数的影响。
曲线1至3是粒径为60μm(ON，曲线1)、10μm(ON-310，曲线2)和1.5μm(OL-104，曲线3)的标准氢氧化铝(MartinalON型，Martinswerk GmbH，Bergheim，Germany)，与之比较的是本发明的热稳定的氢氧化铝(曲线4)。
图2显示了本发明的热稳定氢氧化铝(曲线1)与标准氢氧化铝(MartinalON-310，Martinswerk GmbH，Bergheim，Germany)的差示扫描量热法结果比较。
实施例：
在50kg/dm3铝酸钠溶液投入下列浓度的种子溶液：Na2O-140kg/dm3，Al2O3-150kg/dm3，总Na2O-150kg/dm3，使氢氧化铝细晶体(平均粒径1-2μm)聚集至平均粒径约为60μm的聚集物。结晶器工作容量为1m3。在75℃的结晶温度下保持24小时。
氧化铝料液产量约为40kg/dm3。用去离子水洗涤结晶产物并在105℃下干燥4小时。
氢氧化铝颗粒的粒径减小用振动磨(KHD公司的Palla 200型)来实现。研磨条件如下：马达-1000rpm；研磨用的氧化铝棒装料量-约65％体积；氧化铝棒尺寸-12mm×12mm；研磨产量约50kg/h。在这些条件下，氢氧化铝原料的粒径降低到表1给出的粒径。
将上述经研磨的材料在220℃烘箱内加热约2小时，使其灼烧损失从34.5％(重量)降低至约31％(重量)，从而实现最后的热稳定化步骤。热稳定材料的性能也列在表1中。表中示出了本发明氢氧化铝的物理性质与标准氢氧化铝(Martinswerk GmbH，Bergheim，Germany)以及现有技术中经热处理的氢氧化铝(如JP-A 60 203 438中所述)的比较。
表1
本发明的热稳定氢氧化铝与标准氢氧化铝(MartinalON-310，MartinswerkGmbH，Bergheim，Germany)及现有技术热稳定氢氧化铝(JP-A 60/203 438)的性能比较
物理参数 本发明氢氧化铝 标准的氢氧化铝 现有技术氢氧化铝
Al2O3·nH2O n值     2.7     3.0     2.4
粒径D10％(μm)     1.0     2.0     0.6
粒径D50％(μm)     7.5     10.0     1.0
粒径D90％(μm)     28.0     20.0     1.8
比表面积(m2/g)     6.0     2.5     50.0
吸油量(ml/100g)     28.0     27     33.0
差示扫描量热法显示，与MartinalON-310代表的标准氢氧化铝相比，基本上没有由于勃姆石引起的吸热现象(见图2)。
分批法
将溶解在30份丙酮中的100份环氧当量为400-500的环氧树脂(DOW DER652)与预先溶解在36份2-甲氧基乙醇中的4份双氰胺混合。在该混合物中加入0.1份2-甲基咪唑，以加速树脂固化(混合物A)。
用混合物A浸渍机织玻璃纤维织物(Interglass生产的7628型)至树脂含量为42％，使树脂在160℃B阶段处理2分钟，制得干的预浸渍层。
另外在混合物A中加入250phr(即每百份树脂所含份数)表2所示不同类型的氢氧化铝。将每种混合物浸渍在非织造玻璃纤维(Owens Coming生产的E 105型)中，此时增重占总重量的90％。该氢氧化铝预先分散在适量丙酮中，以便获得最后混合物的合适粘度。然后使树脂体系在160℃下进行B阶段处理3分钟，以制得干的可操作的预浸渍层。
将三层非织造玻璃纤维预浸渍层夹在两层机织玻璃纤维预浸渍层之间。在其两侧上再各一层放置铜箔，在180℃、50巴压力下层压90分钟，制得1.6mm厚的包铜层压板。
连续法
在上述实施例中，可用通过自由基聚合反应固化的树脂体系代替环氧树脂，使得产生的挥发性排放物数量很少。这些树脂的例子是不饱和的聚酯、环氧丙烯酸酯或乙烯基酯树脂。
在连续法时，将机织玻璃纤纸布(7628型，Interglass)连续浸渍通过(例如)含有100重量份树脂和1.5份过氧苯甲酰的液态乙烯基酯树脂(DOW Derakane)。另外，将非织造玻璃纤维织物连续浸渍通过含有250phr本发明氢氧化铝的乙烯基酯/过氧苯甲酰混合物。
在隧道式烘箱内于120℃下初步固化10分钟后，在五层的外面覆上两层铜箔，使这七层在传送带式移动平台中150℃加热加压15分钟。这样制得的连续层压板的厚度为1.6mm。
测试结果
用上述几种方法制得的层压板的热稳定性和阻燃性取决于所含氢氧化铝的性能和含量，而不是取决于聚合物和层压板的生产方法。
表2中给出了采用非卤化环氧树脂时获得的结果。这些结果应被视为对描述的所有类型聚合物有代表性。
比较本发明的氢氧化铝与标准氢氧化铝(MartinalON-310，MartinswerkGmbH，Bergheim，Germany)和现有技术中热稳定氢氧化铝(JP-A 60/203 438)间的热稳定性。
用以下方式测定耐焊料性：将层压板整个浸在260℃下的熔融焊料中。当氢氧化铝开始分解时，可以听到层压板鼓泡的声音，且逸出的水分在焊料表面产生“波纹”。测定可检测到鼓泡/波纹所经过的时间。
阻燃性由美国保险商实验室UL 94标准定义，它将阻燃性能分为V-0(最佳)、V-1和HB(最差)三个级别。对于印刷电路板用途，层压板必须满足V-0级别。
                            表2
               耐焊料件和可燃性测试结果
    测试 含本发明氢氧化铝的层压板 含标准氢氧化铝的层压板 含现有技术氢氧化铝的层压板
n值 2.7 3.0 2.9 2.4
氢氧化铝含量 250phr 250phr 250phr 250phr
耐焊料性 ＞90s 20s 20s ＞90s
阻燃性UL 94 V0 V0 V0 HB

Claims (11)

1.一种热稳定氢氧化铝，其分子式为Al2O3·nH2O，其中n大于2.6小于2.9，其比表面积经BET方法测得为2至10m2/g，中位粒径D50％范围为5至10μm。
2.根据权利要求1所述的热稳定氢氧化铝，其粒径D10％范围为0.5-1.5μm，D90％范围为20-35μm。
3.根据权利要求1或2所述的热稳定氢氧化铝，其吸油量为25-35ml/100g。
4.一种用权利要求1所述的热稳定氢氧化铝来制备印刷电路板用层压板的方法，该方法是将包含浸渍了可固化树脂的机织玻璃纤维织物的表面层与包含浸渍了可固化树脂的非织造玻璃纤维织物的中间层复合在一起，其特征在于浸渍了可固化树脂的非织造玻璃纤维织物含有，以中间层中的树脂计，200-275重量％的热稳定氢氧化铝，该氢氧化铝的分子式为Al2O3·nH2O，其中n大于2.6小于2.9，氢氧化铝的比表面积经BET方法测得为2至10m2/g，中位粒径D50％范围为5至10μm。
5.根据权利要求4所述的方法，其中热稳定氢氧化铝粒径D10％范围为0.5-1.5μm，D90％范围为20-35μm。
6.根据权利要求4或5所述的方法，其中热稳定氢氧化铝的吸油量为25-35ml/100g。
7.根据权利要求4或5所述的方法，其中用不饱和聚酯树脂、环氧树脂或乙烯基酯作为可固化树脂。
8.一种印刷电路板用的层压板，其表面层包含浸渍了可固化树脂的机织玻璃纤维织物，中间层包含浸渍了可固化树脂的非织造玻璃纤维织物，其特征在于中间层含有，以中间层中的树脂计，200-275重量％的热稳定氢氧化铝，该氢氧化铝的分子式为Al2O3·nH2O，其中n大于2.6小于2.9，氢氧化铝的比表面积经BET方法测得为2至10m2/g，中位粒径D50％范围为5至10μm。
9.根据权利要求8所述的层压板，其中热稳定氢氧化铝粒径D10％范围为0.5-1.5μm，D90％范围为20-35μm。
10.根据权利要求8或9所述的层压板，其中热稳定氢氧化铝的吸油量为25-35ml/100g。
11.根据权利要求8或9所述的层压板，其中用不饱和聚酯树脂、环氧树脂或乙烯基酯作为可固化树脂。
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US7063883B2 (en) 2006-06-20
ATE218100T1 (de) 2002-06-15
EP0952917A1 (en) 1999-11-03
CA2274952A1 (en) 1998-07-23
US6514477B2 (en) 2003-02-04
EP0952917B1 (en) 2002-05-29
GB9700708D0 (en) 1997-03-05
US20030054152A1 (en) 2003-03-20
KR20000070145A (ko) 2000-11-25
ES2178161T3 (es) 2002-12-16
WO1998031538A1 (en) 1998-07-23
US7029746B2 (en) 2006-04-18
CN1248197A (zh) 2000-03-22
DE69805599T2 (de) 2003-01-23
DE69805599D1 (de) 2002-07-04
US7029551B2 (en) 2006-04-18
JP2001508002A (ja) 2001-06-19
KR100361196B1 (ko) 2002-11-30
AU6094298A (en) 1998-08-07
US20030059367A1 (en) 2003-03-27
US20020102206A1 (en) 2002-08-01
US20030077482A1 (en) 2003-04-24
HK1020701A1 (en) 2000-05-19

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