CN1392883A - 含磷环氧树脂,含该树脂的阻燃性高耐热环氧树脂组合物及层压板 - Google Patents

含磷环氧树脂,含该树脂的阻燃性高耐热环氧树脂组合物及层压板 Download PDF

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CN1392883A
CN1392883A CN01802749A CN01802749A CN1392883A CN 1392883 A CN1392883 A CN 1392883A CN 01802749 A CN01802749 A CN 01802749A CN 01802749 A CN01802749 A CN 01802749A CN 1392883 A CN1392883 A CN 1392883A
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epoxy resin
phosphorous
flame
epoxy
highly heat
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安田清美
铃木照文
田原修二
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Mitsui Chemicals Inc
Mitsui Chemical Industry Co Ltd
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Abstract

一种含磷环氧树脂，通过有机磷化合物、三官能环氧树脂、双官能环氧树脂和任选的双官能酚化合物反应制得；一种包含上述含磷环氧树脂的阻燃性高耐热环氧树脂组合物。用所述含磷环氧树脂组合物可制得具有优良阻燃性和耐热性的产品。所述树脂可用于生产预浸渍件(prepreg)或层压板。

Description

含磷环氧树脂，含该树脂的阻燃性高耐热环氧树脂组合物及层压板
技术领域
本发明涉及一种含磷的环氧树脂，它具有优良的阻燃性和高耐热性，且无需使用任何卤化物阻燃剂。本发明还涉及一种含上述含磷环氧树脂的阻燃性高耐热环氧树脂组合物。本发明还涉及用所述阻燃性高耐热环氧树脂组合物制得的预浸渍件和层压板。
发明背景
环氧树脂组合物因其性能优良而广泛用于例如电子和电子设备领域，但为了防火安全，通常需要另外赋予其阻燃性。为了赋予此类树脂阻燃性，一般采用卤化物，例如环氧溴化物。虽然卤化物具有优良的阻燃性，但是它们已经被指会因热分解而形成卤化氢、多溴化二苯并二噁烯和呋喃等有害的卤化物，造成环境污染问题等。因此，为了取代溴化物阻燃剂，目前正对以磷化合物作为阻燃剂进行研究。
有关磷化合物的阻燃机制概述可参见例如“最新阻燃剂和阻燃技术”第113页，Technical Information Institure Co.，Ltd.，Japan，1999。正在对多种化合物进行检测，以寻找阻燃性磷化合物。具体地说，正在研究如何通过与环氧树脂的化学反应将磷化合物加入环氧树脂骨架，从而不影响其优良特性例如环氧树脂固化产物的耐热性。
例如，已公开了一种采用含有能与表氧基反应的活泼氢的磷化合物将磷化合物加入环氧树脂的方法。作为此类磷化合物，可用例如含有一个活泼氢的磷化合物，如9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物，参见日本专利申请43(1968)-34168，或含有两个活泼氢的磷化合物，如10-(2，5-二羟基苯基)-10H-9-氧杂-10-磷杂菲-10-氧化物，参见日本专利申请58(1983)-231508。
然而，当采用含有一个能与表氧基反应的活泼氢的磷化合物时，它在与环氧树脂的反应中是作为封端剂，所以所得固化产物的网络结构不完整，使其耐热性不佳。为此对采用含两个能与表氧基反应的活泼氢的磷化合物进行了研究。然而，即使采用此类磷化合物，通过现有方法(例如日本专利申请11(1999)-16485)，仍然无法获得具有(例如)半导体基材所要求的优良耐热性的固化产物。
所以，本发明目的是提供一种不采用卤化物阻燃剂仍可获得具有优良阻燃性和耐热性的固化产物的含磷环氧树脂，提供一种含有所述含磷环氧树脂的阻燃性高耐热环氧树脂组合物，并提供一种用所述阻燃性高耐热环氧树脂组合物制成的预浸渍件和绝缘层压板。
本发明描述
本发明的发明人为了解决前述问题进行了广泛而深入的研究，结果发现，使用本发明所述量的本发明所述组分，例如三官能环氧树脂，无需使用卤化物阻燃剂，仍可获得具有优良阻燃性和高耐热性的含磷环氧树脂，获得含有所述含磷环氧树脂的阻燃性高耐热环氧树脂组合物，获得用所述组合物制成的预浸渍件或层压板。在这方面，本发明发现，作为所述含磷环氧树脂，最好的是具有两个或两个以上能与表氧基反应的活泼氢的有机磷化合物与含芳环的三官能环氧树脂反应所得的那些。本发明就是基于以上技术方案完成的。
所以，本发明的主要内容如下所述。
本发明的含磷环氧树脂是由以下组分反应生成的：5-50重量份有机磷化合物，30-70重量份三官能环氧树脂，5-50重量份双官能环氧树脂和0-20重量份双官能酚化合物。以上重量份均是相对于每100重量份含磷环氧树脂的量。
较好的是，所述有机磷化合物能与表氧基反应。
还要好的是，所述有机磷化合物含有两个或两个以上活泼氢，所述三官能环氧树脂含有芳环。
较好的是，所述有机磷化合物是含一个与磷原子相连的活泼氢的化合物与醌反应生成的有机磷化合物。
较好的是，本发明含磷环氧树脂的环氧当量为250-1000g/eq。
本发明的阻燃性高耐热环氧树脂组合物含有上述含磷环氧树脂和固化剂。
本发明的预浸渍件用上述阻燃性高耐热环氧树脂组合物制得。
本发明的层压板用上述阻燃性高耐热环氧树脂组合物制得。
本发明的优选实施方式
                           含磷环氧树脂
本发明的含磷环氧树脂是所述量的所述有机磷化合物，三官能环氧树脂和双官能环氧树脂，或许还有双官能酚化合物反应生成的。有关这方面的详细描述见后文。三官能环氧树脂
本发明要求，按照含磷环氧树脂重量计算，其中三官能环氧树脂衍生组分的含量为30-70wt％，以35-65wt％为佳。
较好的是，用于生产含磷环氧树脂的三官能环氧树脂用量为，以每百份有机磷化合物加三官能环氧树脂加双官能环氧树脂加双官能酚化合物总量计，30-70重量份，以35-65重量份为佳。
当三官能环氧树脂或由其衍生所得组分的含量低于30wt％时，不仅难以赋予固化产物阻燃性，而且会造成玻璃转化温度(Tg)的不良下降。另一方面，如果所述量或含量过高，会造成分子量过高以至于降低产物的溶解度和浸渍容量(capability)。
较好的是，本发明所用的三官能环氧树脂含有芳环。它可由例如三酚化合物与表氯醇化合物按已知方法缩合反应制得。所述三酚化合物虽没有特别限制，但就阻燃性而言，优选含芳环的三酚化合物，例如：
1-[α-甲基-α-(4-羟基苯基)乙基]-4-[α，α-二-(4-羟基苯基)乙基]苯，
1，3，5-三[α-甲基-α-(4-羟基苯基)乙基]苯，
1，1，1-三(羟基苯基)甲烷，
1-[α-甲基-α-(4-羟基苯基)乙基]-3-[α，α-二-(4-羟基苯基)乙基]苯，和
1，1，1-三(4-羟基苯基)乙烷。
在本发明所用三官能环氧树脂中，三官能缩水甘油基化组分含量以60％或以上为宜，80％或以上更好。
当官能度为5或更高的缩水甘油基化组分比例升高时，在与有机磷化合物反应时会促使分子量不良升高以至于降低在溶剂中的溶解度，浸渍容量和Tg温度。而且，基于同样的理由，环氧树脂不是不用而是尽可能少用，由其是对酚醛清漆环氧树脂而言。有机磷化合物
较好的是，本发明的有机磷化合物能与表氧基反应，最好含有两个或两个以上活泼氢。较好的是，这些活泼氢能与表氧基反应。
较好的是，上述有机磷化合物是至少含一个与磷原子相连的活泼氢的化合物与醌化合物反应所得。
例如，较好的是，所述有机磷化合物由至少含一个与磷原子相连的活泼氢的化合物，例如9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物或氧化二苯基膦，与醌化合物，例如1，4-苯醌，1，4-萘醌或甲苯醌，反应制得。
本发明中，有机磷化合物衍生组分的含量为5-50wt％，以10-35wt％为佳。
用于生成含磷环氧树脂的有机磷化合物为，以每百份有机磷化合物加三官能环氧树脂加双官能环氧树脂加双官能酚化合物总量计，5-50重量份，以10-35重量份为佳。
当有机磷化合物含量或用量过低时，阻燃性可能不够理想。另一方面，过高时，含磷环氧树脂的分子量会过高，以至于溶解度和浸渍容量下降。双官能环氧树脂和双官能酚化合物
本发明中，为了将环氧当量控制在要求的范围内并获得性能高于目标水平的固化产物，采用了本发明所述量的双官能环氧树脂与所述有机磷化合物和三官能环氧树脂联用。
而且，还可以将一种双官能酚化合物与所述有机磷化合物，三官能环氧树脂和双官能环氧树脂联用。与双官能酚化合物联用有助于将含磷环氧树脂的环氧当量控制在350g/eq或以上。
虽然双官能环氧树脂和双官能酚化合物衍生组分各自的含量会因有机磷化合物和三官能环氧树脂种类和用量的不同而不同，但双官能环氧树脂衍生组分量的优选范围为每百份含磷环氧树脂5-50重量份，双官能酚化合物衍生组分为0-20重量份。
还要好的是，双官能环氧树脂衍生组分的量为10-40重量份，双官能酚化合物衍生组分为0-10重量份。由其好的是，双官能酚化合物衍生组分的含量为0-7重量份。
含磷环氧树脂生产中双官能环氧树脂的用量以，按每百份有机磷化合物加三官能环氧树脂加双官能环氧树脂加双官能酚化合物总量计，5-50重量份为宜，10-40重量份更好。
含磷环氧树脂生产中双官能酚化合物用量以，按每百份有机磷化合物加三官能环氧树脂加双官能环氧树脂加双官能酚化合物总量计，0-20重量份为宜，0-10重量份为佳，0-7重量份更好。
当双官能环氧树脂用量过少时，含磷环氧树脂的分子量会不良升高以至于溶解度和浸渍容量变差。另一方面，用量过多则会令固化产物的Tg不良降低。
此外，当双官能酚化合物用量过多时，含磷环氧树脂的分子量会不良地升高过度。
可以采用市售的双官能环氧树脂和双官能酚化合物。具体地说，就阻燃性和Tg考虑，优选双酚A，双酚E和及其双酚化合物和缩水甘油基化衍生物。其他组分
本发明中，还可以在所述含磷环氧树脂中加入其他环氧树脂。虽然对可加入环氧树脂的种类和加量没有特别限制，但较好的是，其使用以不损害本发明含磷环氧树脂的性能为度。优选的是多官能高芳环含量环氧树脂，例如芳烷基酚醛树脂的环氧化物和邻-苯基酚醛清漆树脂的环氧化物。含磷环氧树脂
对生产本发明含磷环氧树脂的方法没有特别限制。将所述量的有机磷化合物，三官能环氧树脂和双官能环氧树脂，以及可选的双官能酚化合物和其他组分混合，并将该混合物加热至100-200℃，约3-10小时，使之反应，即可大致定量地获得所述含磷环氧树脂。
如上所得含磷环氧树脂的环氧当量为250-1000g/eq，通常，350-600g/eq更好。当环氧当量落在上述范围内时，本发明含磷环氧树脂固化产物受潮引起的耐热性降低和吸水性升高可得到抑制。尤其，当环氧当量为350g/eq或以上时，可获得令人满意的上述效果。
当环氧当量低于所述范围时，阻燃性和耐热性会因需使用更多固化剂而变差。另一方面，当环氧当量高于所述范围时，固化产物的浸渍容量和溶解度变差，Tg不良降低。
如果需要降低下述阻燃性高耐热环氧树脂组合物中的固化剂含量，含磷环氧树脂的环氧当量以低于300g/eq为宜，尤其是250-300g/eq。阻燃性高耐热环氧树脂组合物及其预浸渍件或层压板
本发明的阻燃性高耐热环氧树脂组合物包含上述含磷环氧树脂和固化剂。虽然可采用环氧树脂的常用固化剂，但优选的是双氰胺，芳烷基酚醛树脂，邻-线型酚醛清漆树脂，对-线型酚醛清漆树脂，间二苯酚酚醛清漆树脂，氢醌清漆树脂等。本发明特别优选双氰胺。
固化剂的用量以每环氧当量含磷环氧树脂0.30-1.2eq.为宜，0.35-0.6eq.更好。
采用双氰胺时，其用量以每环氧当量含磷环氧树脂0.35-0.7eq.为宜，0.35-0.6eq.更好。
具体地说，本发明使用所述量的三官能环氧树脂，这样，即使固化剂例如双氰胺的用量为0.35-0.45eq.，仍可获得表现出优良阻燃性和耐热性的环氧树脂。
而且，还可以联合使用本发明所用含两个活泼氢的有机磷化合物作为固化剂。
可在本发明阻燃性高耐热环氧树脂组合物中加入固化促进剂，适合的是例如2-乙基-4-甲基咪唑，2-苯基咪唑和1-丁基-2-甲基咪唑等咪唑类。还可以使用膦。
当向阻燃性高耐热环氧树脂组合物中加入溶剂时，对溶剂种类没有特别限定，只要它不与所述阻燃性高耐热环氧树脂组合物反应即可。例如，可采用乙二醇单乙醚，乙二醇单乙醚，丙二醇单甲醚，二甲基甲酰胺，N-甲基吡咯烷酮，甲基·乙基酮，环己酮，甲苯和二甲苯。可使用它们的混合物。
所述阻燃性高耐热环氧树脂组合物可用玻璃布或玻璃纤维强化后使用。所述阻燃性高耐热环氧树脂可用三聚氰胺或含磷组分之类阻燃剂和二氧化硅、滑石、水合氧化铝或氢氧化铝之类填料来充填。当使用上述填料时可减少有机磷化合物的量。本发明阻燃性高耐热环氧树脂组合物不仅可用于预浸渍件和层压板，还可用于表面涂层，含树脂的铜箔，胶粘剂等。
将所述阻燃性高耐热环氧树脂组合物用在层压板中时，首先，需将其溶于溶剂形成清漆。然后，用该清漆浸渍玻璃布织造或非织造物或非玻璃织造或非织造物，80-170℃干燥后制得预浸渍件。将所需数量的预浸渍件彼此层叠，并与一层铜箔结合。加压加热，于是制成层压板。而且，本发明阻燃性高耐热环氧树脂组合物还可以用在涂料中，涂在金属箔例如铜箔上，还可以与填料混合成浆状物后成形为片材、膜材等以供使用。
如上所得预浸渍件和层压板可用在电路和电子元件等中。工业实用性
本发明提供了一种含磷环氧树脂，用它，无需使用卤化物阻燃剂而可由其形成阻燃性优良且高耐热的固化产物。而且，本发明还提供了含有含磷环氧树脂与固化剂混合物的阻燃性高耐热含磷环氧树脂组合物。本发明还提供了预浸渍件或层压板，可满足日益增长的对无卤材料的需要。
实施例
以下将结合实施例对本发明进行进一步描述，但它们并非对本发明范围的限定。评价和测量按以下方法进行。
三官能环氧化物含量以GPC法测得的柱状图面积比表示。所用层析柱为两根Shodex KF801柱和两根Shodex KF802柱联用。采用UV检测器，THF为洗脱液，以1ml/min的速度从柱中流过。
环氧当量用盐酸/二噁烷法测定。Tg用Seiko Instruments Inc.制作的TMA/SS100测定。测定以压缩模式进行，负载为5g，升温速度为10℃/min。
燃烧试验，用按照UL-94进行的垂直燃烧试验进行评价。铜箔剥离强度和焊料耐热性按照日本工业标准(JIS)C6481测定。在焊料耐热性试验中，每份样品都在121℃，100％湿度的蒸汽相中吸收5小时水分，并在260℃焊料浴中浸渍20秒。检查是否出现气泡或剥落等外观异常。如果没有外观异常，则将焊料耐热性评定为A，有异常，则评定为C。
在以下实施例和比较实施例中，所用有机磷化合物为10-(2，5-二羟基苯基)-10H-9-氧杂-10-磷杂菲-10-氧化物(Sanko Chemical Industry Co.，Ltd.生产的HCA-HQ)，二苯基膦基氢醌(Hokko Chemical Industry Co.，Ltd.生产的PPQ)，和9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(Sanko Chemical Industry Co.，Ltd.生产的HCA)。
合成实施例1
在一个5L可分式烧瓶中加入70.5g有机磷化合物10-(2，5-二羟基苯基)-10H-9-氧杂-10-磷杂菲-10-氧化物(Sanko Chemical Industry Co.，Ltd.生产的HCA-HQ)，165g1-[α-甲基-α-(4-羟基苯基)乙基]-4-[α，α-二-(4-羟基苯基)乙基]苯的环氧树脂(Mitsui Chemical，Inc.生产的TECHMORE VG3101，环氧当量：210g/eq，三官能缩水甘油基化组分：87％)，64.5g双酚A环氧树脂(Mitsui Chemical，Inc.生产的EPOMIK R139S)和0.1g三苯基膦，150℃加热5小时。于是得到环氧当量为472g/eq，含磷量为2.25wt％的含磷环氧树脂。
合成实施例2-7
用表1所列的加入物，按照合成实施例1所述的方法生产含磷环氧树脂。合成实施例2-7的结果见表1。
合成实施例8
在一个5L可分式烧瓶中加入62.7g有机磷化合物10-(2，5-二羟基苯基)-10H-9-氧杂-10-磷杂菲-10-氧化物(Sanko Chemical Industry Co.，Ltd.生产的HCA-HQ)，237.3g酚醛清漆树脂的环氧树脂(环氧当量：190g/eq)和0.1g三苯基膦，150℃加热并搅拌。反应过程中，反应产物发生胶凝，反应因此中断。
合成实施例9-11
用表1所列的加入物，按照合成实施例1所述的方法生产含磷环氧树脂。合成实施例9-11的结果见表1。
                               表1
                                                  合成实施例
  1   2   3   4   5   6   7   8   9   10   11
环氧树脂(*)
三官能  E-1E-2E-3E-4   165 135 165   165 135 165 135   222.3   165   237
双官能  E-5E-6E-7E-8E-9 64.5 87.6 57 64.5 95.7 67.5 81.3   237.3 19.9 51.6
酚化合物双酚A双酚E双酚F双酚 6.9 6.6 3.9 9.9 12.9 21
有机磷化合物HCA-HQPPQHCA 70.5 70.5 78 70.5 62.7 63.5 73.8 62.7 62.7 70.5 42
催化剂TPP(G)   0.1   0.1   0.1   0.1   0.1   0.1   0.1   0.1   0.1   0.1   0.1
环氧当量：g/eq含磷量：(％) 4722.25 4182.25 3962.5 4512.25 4532.0 4452.25 4632.35 反应中胶凝 不溶于MEK，THF 4482.25 4202.0
*环氧树脂E-1至9的说明见表1-1
                                 表1-1
环氧树脂  环氧当量(g/eq) 三官能缩水甘油基化组分含量
E-1：1-[α-甲基-α-(4-羟基苯基)乙基]-4-[α，α-二-(4-羟基苯基)乙基]苯环氧树脂E-2：1，1，1-三(羟基苯基)甲烷环氧树脂E-3：1，3，5-三[α-甲基-α-(4-羟基苯基)乙基]苯环氧树脂E-4：1，1，1-三(4-羟基苯基)乙烷环氧树脂E-5：线型酚醛清漆树脂环氧树脂E-6：双酚E环氧树脂E-7：双酚A环氧树脂E-8：双酚F环氧树脂E-9：双酚环氧树脂     210166243168190174186170161     87％86％86％87％
实施例1
将100g合成实施例1的含磷环氧树脂溶于50g甲基·乙基酮。在所得溶液中加入22g以甲基溶纤剂与二甲基甲酰胺3∶2混合物配制的10wt％双氰胺溶液和2g以甲基溶纤剂配制的10wt％2-乙基-4-甲基咪唑溶液，搅拌混合，于是得到清漆组合物。然后，用该清漆组合物浸渍100μm的玻璃布(Nitto Boseki Co.，Ltd.制造的WE116E)，在150℃烘箱内干燥5分钟，于是制得预浸渍件。将4片预浸渍件重叠，用真空热压机170℃固化60分钟，由此得到用于燃烧试验的试验件。类似的，用12片预浸渍件制成测定Tg的测试样品；将4片预浸渍件重叠，在4层重叠件的上下表面各加一片18μm厚的铜箔(Mitsui & Semlting Co.，Ltd.制造的3CE-III)，制成测定铜箔结合强度和受潮后耐热性的试验样品。测定结果为：Tg：174℃；阻燃性按照UL-94标准为V-0；铜箔剥离强度为14.1N/cm；在C-6/121/100吸湿(121℃，100％湿度的蒸汽相中吸收6小时水分)后的焊料耐热性试验中，既无气泡也无剥落。
实施例2-7和9-11
对合成实施例1-7制得的含磷环氧树脂重复实施例1所述过程。结果见表2。
实施例8
将90g合成实施例3制得的环氧树脂与10g芳烷基酚醛环氧树脂(MistsuiChemicals，Inc.生产的E-XLC-LL，环氧当量：244g/eq)混合制成树脂，对该树脂重复实施例1所述过程。结果见表2。
比较实施例1-4
对合成实施例8-11制得的含磷环氧树脂重复实施例1所述过程。评定结果见表3。
                                          表2
                                                    实施例
1 2 3 4 5 6 7 8 9 10 11
合成实施例1合成实施例2合成实施例3合成实施例4合成实施例5合成实施例6合成实施例7合成实施例8合成实施例9合成实施例10合成实施例11E-XLC-LL   100 100 100 100 100 100 100 9010   100   100   100
双氰胺活泼氢/表氧基   2.20.49   2.50.50   2.70.51   2.30.49   2.30.50   2.40.51   2.30.51   2.80.50   1.80.40   2.70.60   1.60.35
2E4MZ   0.2   0.2   0.2   0.2   0.2   0.2   0.2   0.2   0.2   0.2   0.2
阻燃性，UL-94Tg ℃/TMA铜箔剥离强度(N/cm)焊料耐热性   V-014714.1A   V-017014.0A   V-016914.5A   V-016214.8A   V-016514.7A   V-016014.0A   V-016613.9A   V-016615.9A   V-017913.9A   V-017014.2A   V-017014.0A
E-XLC-LL：芳烷基酚醛环氧树脂，环氧当量244g/eq。
                                        表3
  比较实施例1   比较实施例2   比较实施例3   比较实施例4
合成实施例1合成实施例2合成实施例3合成实施例4合成实施例5合成实施例6合成实施例7合成实施例8合成实施例9合成实施例10合成实施例11E-XLC-LL 100 100 100 100
双氰胺活泼氢/表氧基       -      -      2.30.49      2.50.50
2E4MZ      0.2      0.3
阻燃性，UL-94Tg ℃/TMA铜箔剥离强度(N/cm)焊料耐热性     无法评定     无法评定      V-014514.5A      V-016011.8C

Claims (8)

1.一种含磷环氧树脂，按每百份有机磷化合物加三官能环氧树脂加双官能环氧树脂加双官能酚化合物总量计，由5-50重量份有机磷化合物，30-70之类三官能环氧树脂，5-50重量份双官能环氧树脂和0-20重量份双官能酚化合物反应制得。
2.根据权利要求1所述的含磷环氧树脂，所述有机磷化合物是能与表氧基反应的有机磷化合物。
3.根据权利要求2所述的含磷环氧树脂，所述有机磷化合物含有两个或两个以上活泼氢，所述三官能环氧树脂含有芳环。
4.根据权利要求2或3所述的含磷环氧树脂，所述有机磷化合物是含一个与磷原子相连的活泼氢的化合物与醌化合物反应所得的有机磷化合物。
5.根据权利要求1至4中任一项所述的含磷环氧树脂，其环氧当量为250-1000g/eq。
6.一种阻燃性高耐热环氧树脂组合物，包含权利要求1至5中任一项所述的含磷环氧树脂和固化剂。
7.一种预浸渍件，是用权利要求6所述阻燃性高耐热环氧树脂组合物制成。
8.一种层压板，是用权利要求6所述阻燃性高耐热环氧树脂组合物制成。
CN01802749A 2000-09-12 2001-09-05 含磷环氧树脂,含该树脂的阻燃性高耐热环氧树脂组合物及层压板 Pending CN1392883A (zh)

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