CN1189847A - 硅改性环氧树脂作为电工或电子组件之浇铸材料的应用 - Google Patents
硅改性环氧树脂作为电工或电子组件之浇铸材料的应用 Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/296—Organo-silicon compounds
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- 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
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
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- C08K3/013—Fillers, pigments or reinforcing additives
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Abstract
本发明涉及用一种可硬化的环氧树脂混合物作为电工或电子组件之浇铸材料的应用。其特征是此混合物含有硅改性环氧树脂,该环氧树脂中含有环氧基团的有机部分与硅部分化学结合在一起,所述混合物还含有可调节热胀性能的矿物(必要时是硅烷化了的)填料,以可硬化树脂混合物为基准计算,此填料含量为40到75重量%。此可硬化环氧树脂混合物特别有利地应用于浇铸二极管。
Description
众所周知,为封装或涂覆电或电子组件使用了环氧树脂为基料的浇铸材料。作为这类组件的例子,可以例举高压点火线包,电子开关线路,或半导体元件如二极管、硅芯片或传感器。此种浇铸材料需满足一系列不同的要求,对不同的使用目的,这些要求以不同组合方式出现。此类浇铸材料特别应具有:
-好的流动性,在通常加工温度即室温和高达80℃的温度下具有好的流动性,以便在短时间内能完成一系列的加工;
-高的耐热性,以及具有一个尽可能高的玻璃转化温度;
-即使在频繁的温度变化下也可良好地粘附在基底上,为此应有较低的热胀系数和高的内柔性;
-好的介电特性,特别是小的介电损耗和至少在高压区使用时有高的电击穿强度,为此它们应尽可能不含离子性杂质,特别是碱含量要低;
-在环境温度以及高的运作温度下能耐住各种环境的影响,如空气氧的氧化分解、燃料、油和盐雾的影响;
-应有效保护金属基底免受腐蚀。
在US-A-3849187中叙述了用于晶体管和其他半导体元件的封装剂,该封装剂含有环氧树脂以及胺、酚醛树脂或羧酸酐作为硬化剂,另外加入0.1到5%具有二个或三个低级烃氧基团的烷基烃氧基硅烷(Alkylalkoxysilans),该硅烷在烷基上还带有一个氨基或环氧基团。此硅烷能改善封装剂的绝缘性和耐久性,使晶体管或半导体元件的预处理或钝化处理变成多余的。此种封装剂的缺点是由于其较高的脆性造成较差的抗温度变化的性能。
在DE-A1-3229558中叙述了用于电子组件的浸渍浇铸材料(ImprgnierverguBmassen),该材料由一种基于双酚A的环状脂族环氧化物的环氧树脂、作为硬化剂的改性二羧酸酐、作为促进剂的咪唑、以及作为填充剂的白垩组成。此浸渍浇铸材料不完全令人满意,这是因为它的玻璃转化温度较低,热胀系数较高,柔性却又较低。硬化后的浸渍材料易于收缩,形成裂纹,附着性不足。
在DE-C2-3913488中叙述了用于电和电子组件的浇铸材料,它含有低粘性环脂族环氧树脂,分子式为:或者是一种有一定聚合功能的环氧酚醛树脂;作为硬化剂的甲基桥甲撑基四氢苯二酸酐(也称甲基那狄克酸酐,Methylndicsaure-anhydrid);有基于咪唑的硬化促进剂;含有具有一定颗粒尺寸的用环氧硅烷预处理过的无定形二氧化硅;色素,以及作为填充剂的中空玻璃球。对于高要求组件,此浸渍物的长期热性能和温变性能还不足够好。
已知的以环氧树脂为基础的浇铸材料是不含硅化合物的。在US-A-4560716中公布了环氧树脂混合物,它含有:(a)环氧树脂、(b)硬化剂、(c)防锈添加剂,该防锈添加剂含有二硫代磷酸、一定的二硫代磷酸衍生物和/或二硫代氨基甲酸的金属盐或氧化石蜡。此外该环氧树脂混合物还含有(d)第二种添加剂,它含有烷芳基倍半硅氧烷(Alkylarylsilsesquioxan)和/或有机硅氧烷聚合物。此烷芳基倍半硅氧烷的通式为:式中R1到R6是相同的或不同的烷基、芳基、脂烯基或芳烷基。所述有机硅氧烷聚合物的通式为:式中R7到R16为烷基、芳基、脂烯基、烷芳基、氢或羟基,n和m是0或1或更大的整数。上述文献中还叙述了一种环氧树脂混合物,它含有环状或开链状的硅树脂,但不含弹性的聚有机硅氧烷化合物。此环氧树脂混合物被推荐用作电组件的封装材料。它的防锈作用基于一下事实:其添加剂不和环氧树脂反应,在封装后它们游离在封装过的组件表面上并在那儿形成一层防锈的保护膜。作为任选添加剂的硅有机材料,它另外也减少了电绝缘性能的损失。
由DE-C2-3634084可知一种可作硬塑性(Duroplasten)加工的、经改性的反应树脂混合物,它可含有环氧树脂作为反应树脂,还含有三维交联的直径从0.01到50微米的颗粒状聚合有机硅氧烷橡胶,它在表面上有反应基团。在作为反应中介体的辅助剂存在下,此反应基团和反应树脂起化学反应。据文献说,此反应树脂混合物特别适宜制造有断裂韧性和冲击韧性以及可成形的硬塑性塑料、纤维增强塑料、电工业中的绝缘物和层压材料。不推荐它们作为电或电子组件的浇铸材料。
本发明的优点:
按本发明应用可硬化的含有硅改性环氧树脂的环氧树脂混合物的作为电工和电子组件的浇铸材料将具有优点,此优点一方面与加工技术状况,另一方面又与硬化的浇铸材料以及被浇铸组件的性质有关。作为浇铸材料,它们特别适用于浇铸以半导体如芯片和二极管为基础的电子组件,这些组件对高的内柔性有更多要求,而对断裂或冲击韧性要求较少。
按本发明的改性环氧树脂混合物不必用溶剂稀释就有快速加工所需的足够低的粘度,在普通的直到大约80℃的加工温度下,其粘度值一般低于50000mPa.s。因而它们也适宜于大批量制造,这是因为硬化时间短促,在不同温度下只为10到120分钟。此浇铸材料在硬化后能出色地保护封装组件抵抗环境影响,包括湿气的腐蚀。后者值得注意,因为按本发明的浇铸材料不必含有成膜材料,在按US-A-4560716的封装剂中此种膜应阻碍生成锈,而本硅改性环氧树脂的硅部分在化学上和其它有机的环氧基部分结合在一起,所以是不可移动的。此种硅部分不能像包含在US A 4560716之封装材料中的有机硅化合物一样地按这样的方式起作用,即与环氧树脂不作化学结合,而在封装组件表面上游离,并在那二展开其阻碍腐蚀的效果(第九栏,第44到60行)。
本发明用的含有硅改性环氧树脂的环氧树脂混合物在硬化状态时具有高的玻璃转化温度,如直到220℃,并在接近此玻璃转化温度时还显示出所要求的介电性质。特别在有目的地选择矿物填充剂的类型和数量后,它们显示出低的热胀系数,因而在温度改变时没有或只有少量的收缩和形成裂纹,并在频繁的温度变更下很好地附着在基底上。此种硬化了的浇铸材料能在较高的运行温度下长时间地抵抗住环境的影响,显示出很好的抵抗空气氧的能力和同样好的抵抗燃料、油和盐雾的能力。此种由弹性硅聚合物改性的环氧树脂混合物特别有利地用于作为发电机二极管的浇铸材料。
本发明的描述
按权利要求1到12采用可硬化的含有经硅改性的环氧树脂以及矿物填充剂的环氧树脂混合物作为浇铸材料,能得到所叙述的优点。
本发明的重要特征是作为浇铸材料用的环氧树脂混合物含有一种硅改性的环氧树脂,其中含有的有机环氧基团部分在化学上和硅部分结合在一起。所述硅部分可以是弹性的颗粒尺寸为1到25微米、最好为1到20微米的颗粒状硅聚合物。这种硅改性环氧树脂也可以是在其表面上化学结合着环氧基团的颗粒状弹性聚合有机硅氧烷。此时此化学链通过环氧树脂的反应基团直接与硅颗粒表面上存在的反应基团进行反应而起作用。或者它们也可以通过桥分子(Brückenmoleküle)来完成。桥分子的反应基团既与硅颗粒表面的反应基团反应,也与在环氧树脂分子内的反应基团反应。所述类型的硅改性环氧树脂及其制备已在上面提到的德国专利3634084中描述,并为专利权利持有人Hanse化学有限公司所持有。
硅改性环氧树脂的另一种变化方案是在一个分子内部含有的有机环氧基团部分与硅部分在化学上结合,在此涉及硅-嵌段共聚物,所述共聚物含有一个或多个聚合有机硅氧烷和一个或多个有机嵌段,并载有环氧基团,还以适当的方式比如通过醚桥或羧酸酯基团与硅嵌段在化学上结合起来。作为这里的例子,硅改性环氧树脂的分子式为:式中BPA是双酚A分子的基团,R是2价有机基团,比如乙烯基或丙烯基,R1是低级烷基比如甲基,X和Y分别为整数。所述类型的硅-嵌段共聚物是已知的,也同样为Hanse化学有限公司所拥有。
除了硅改性环氧树脂外还可以采用别的一般性环氧树脂。已知的基于多价芳族或环脂族羟基化合物的环氧树脂特别适合作为这种环氧树脂。芳族羟基化合物衍生物例如可是双酚A或双酚F的缩水甘油醚以及酚醛树脂或甲酚酚醛树脂的缩水甘油醚。可用的环脂族环氧树脂比如是双环氧化的1,2,3,6-四氢化苯甲酸-β-1′,2′,3′,6′-四氢化苯基乙基酯,六氢化邻苯二甲酸-双缩水甘油酯等。像1,4-丁二醇二缩水甘油醚那种脂族环氧树脂,也适于用作添加用的环氧树脂。
按本发明用的环氧树脂混合物的硅含量,如果是颗粒状的则是指化学上和含有环氧基的有机基团相结合的弹性硅聚合物,如果是硅氧烷嵌段形态则是指硅-嵌段共聚物,以硅改性环氧树脂和一起使用的其他环氧树脂为基准计算,硅含量总量为5到40重量%,特别为10到20重量%。当硅含量小于上述值时,所希望的产品性质将受影响,特别是使所希望有的硬化后的环氧树脂混合物的内柔性减少。
按本发明所用的环氧树脂混合物的其他重要特点是它们含有矿物填料。通过选择矿物填料可改善环氧树脂混合物的功能特性。当用于浇铸以半导体、特别是二极管为基础的电子组件时,特别可靠的是无定形二氧化硅。此时涉及相应的经粉碎的电熔硅酸。其他适宜的矿物填料是比如石英粉、氧化铝和白云石(见如Kunststoffe,72(1982)S.228ff.)。(为改善矿物填料对环氧树脂的可使用性,可用已知方式对矿物填料进行硅烷化,它们一般有3到30微米的平均颗粒直径,有窄的或宽的粒径分布。以环氧树脂和硬化剂总量为基准,加入的填料量为40到75重量%,特别是50到65重量%。
此环氧树脂混合物可以不加硬化剂而按一种离子机理自己硬化。这样除了环氧树脂外它含有一种引发剂,比如一种硫盐(见EP-A2-0379464)。一般它们还含有已知的硬化剂,此硬化剂与环氧树脂发生成链或交联反应,硬化剂比如是多价羧酸、多价羧酸酐或多价胺。特别适宜的硬化剂是烯族不饱和二羧酸酐的二烯加成产物(Dien-Additionsprodukte),如马来酸酐与二烯属特别是环二烯如:环戊二烯和甲基环戊二烯的二烯加成产物。用此种羧酸酐硬化的环氧树脂混合物显示出特别高的玻璃转化温度。
环氧树脂和硬化剂按一定的当量使用。比如这个或那个组份的摩尔数稍为过量10%,此环氧树脂混合物的功能特性就可以被优化。
按本发明作为浇铸材料使用的环氧树脂混合物可以含有其他普通的添加剂,例如称为硬化加速剂的叔胺或咪唑,还有色素,碳黑,色浆,流动改进剂,沉降阻止剂,消泡剂和/或粘合剂,它们可以以常用的量加入。
按本发明所用的环氧树脂混合物可以以普通的方法制备和加工。当此混合物用硬化剂硬化后不是立刻被加工时,建议用双组份***去制备和储存。为此,在第一组份中有硅改性环氧树脂,必要时有未改性的环氧树脂和填料(或一部分填料),另一方面在第二组份中有硬化剂,必要时有硬化加速剂,其他填料和/或一种或多种已知添加剂。然后在加工时将二者混合至均匀,形成适于浇铸的混合物。对于组成或组份能起到足够的剪切作用的普通混合器如静态混合管、连续式搅拌机或振动混合器均适用于全部混合过程。此混合操作可以在室温或在稍稍提高温度下比如到约80℃下进行。此可浇铸混合物可以以一般的方式比如以封装二极管的浇铸方式来使用。按设备的设计不同这里可以提供一种或多种浇铸嘴。
实施例
在一个静态混合管中将下列组份混合直至均匀状态以制备一种浇铸材料。
25重量份的六氢苯二甲酸双甘油脂,其用40重量%的平均颗粒直径10微米的硅粒改性,硅粒是按DE-A2-3634084制造的;
105重量份的甲基那狄克酸酐用作硬化剂;
1重量份的咪唑用作加速剂;
330重量份的无定形石英粉,其平均粒径为20微米。
用此混合物作为浇铸材料去浇铸发电机用的二极管。此二极管被加热到100℃,一小时,然后到200℃再保持几个小时,以使浇铸材料硬化。此硬化了的浇铸材料有如下性质。
线性收缩 :0.02%/K
玻璃转化温度(Tg) :210-215℃
热胀系数
-下限(Tg)(10-6/K) :25-30
-上限(Tg)(10-6/K) :90-100
氯化物 :<10ppm
碱金属 :<2ppm
Claims (12)
1、一种可硬化的环氧树脂混合物作为电工或电子组件之浇铸材料的应用,其特征在于,此混合物含有硅改性环氧树脂,该环氧树脂中含有环氧基团的有机部分与硅部分化学地结合在一起,此混合物中还含有也可经过硅烷化的能调节热胀性能的矿物填料,以可硬化的环氧树脂混合物为基准,该填料含量为40到75重量%。
2、按权利要求1的应用,其特征在于,所述硅部分为粒状弹性硅聚合物,其平均粒径为1到25微米。
3、按权利要求2的应用,其特征在于,所述粒状弹性硅聚合物通过桥分子与硅改性环氧树脂中含有环氧树脂的部分相连结。
4、按权利要求1的应用,其特征在于,所述硅部分是硅氧烷链,它与含有环氧基团的部分形成硅氧烷-嵌段共聚物。
5、按权利要求1到4之一的应用,其特征在于,所述可硬化环氧树脂混合物除了含有硅改性的环氧树脂外,还含有普通的环氧树脂。
6、按权利要求1到5之一的应用,其特征在于,所述环氧树脂混合物含有多价有机羧酸、此种酸的酸酐或多价胺作为环氧树脂硬化剂。
7、按权利要求6的应用,其特征在于,所述硬化剂是烯族不饱和二羧酸酐和环二烯的二烯加成产物。
8、按权利要求1到5之一的应用,其特征在于,所述环氧树脂混合物含有使环氧树脂作阳离子交联的引发剂。
9、按权利要求1到8之一的应用,其特征在于,所述矿物填料为无定形二氧化硅。
10、按权利要求1到9之一的应用,其特征在于,所述浇铸材料还含有硬化加速剂、色素、炭黑、色浆、沉降阻止剂、消泡剂和/或粘合剂作为附加的添加剂。
11、按权利要求1到10之一的应用,其特征在于,所述浇铸材料被用于浇铸基于半导体的电子组件。
12、按权利要求11的应用,其特征在于,所述电子组件是二极管。
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DE1745545A1 (de) * | 1967-12-01 | 1969-10-02 | Vni I P Ki Elektrovozostrojeni | Verfahren zur Herstellung von Elektroisolierkoerpern und -ueberzuegen |
US3849187A (en) * | 1970-03-08 | 1974-11-19 | Dexter Corp | Encapsulant compositions for semiconductors |
DE3229558C2 (de) * | 1982-08-07 | 1984-11-08 | Robert Bosch Gmbh, 7000 Stuttgart | Imprägniervergußmasse für elektrische Bauteile |
US4560716A (en) * | 1983-08-30 | 1985-12-24 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Rust preventing epoxy resin compositions |
JPS61271319A (ja) * | 1985-05-24 | 1986-12-01 | Shin Etsu Chem Co Ltd | 半導体封止用エポキシ樹脂組成物 |
DE3634084A1 (de) * | 1986-10-07 | 1988-04-21 | Hanse Chemie Gmbh | Modifiziertes reaktionsharz, verfahren zu seiner herstellung und seine verwendung |
JPH0617458B2 (ja) * | 1987-03-16 | 1994-03-09 | 信越化学工業株式会社 | エポキシ樹脂組成物 |
US5120803A (en) * | 1988-09-07 | 1992-06-09 | Mitsui Toatsu Chemicals, Inc. | Resin compositions for sealing semiconductor |
DE59000858D1 (de) * | 1989-01-16 | 1993-03-25 | Ciba Geigy Ag | Araliphatische sulfoniumsalze und deren verwendung. |
JPH0362844A (ja) * | 1989-02-27 | 1991-03-18 | Shin Etsu Chem Co Ltd | 半導体封止用エポキシ樹脂組成物及び半導体装置 |
DE3913488C2 (de) * | 1989-04-25 | 1994-02-03 | Bosch Gmbh Robert | Vergußmasse für elektrische und elektronische Bauteile |
JP3367964B2 (ja) * | 1992-04-21 | 2003-01-20 | 東レ・ダウコーニング・シリコーン株式会社 | 硬化性樹脂組成物 |
JP3359410B2 (ja) * | 1994-03-04 | 2002-12-24 | 三菱電機株式会社 | 成形用エポキシ樹脂組成物ならびにそれを用いた高電圧機器用モールド製品およびその製法 |
-
1995
- 1995-06-30 DE DE19523897A patent/DE19523897C2/de not_active Expired - Lifetime
-
1996
- 1996-06-05 ES ES96915973T patent/ES2152527T3/es not_active Expired - Lifetime
- 1996-06-05 JP JP50468697A patent/JP4138001B2/ja not_active Expired - Fee Related
- 1996-06-05 CN CN96195169A patent/CN1093866C/zh not_active Expired - Lifetime
- 1996-06-05 WO PCT/DE1996/000993 patent/WO1997002321A1/de not_active Application Discontinuation
- 1996-06-05 DE DE59606048T patent/DE59606048D1/de not_active Expired - Lifetime
- 1996-06-05 EP EP96915973A patent/EP0835287B1/de not_active Expired - Lifetime
- 1996-06-05 US US09/000,405 patent/US5965637A/en not_active Expired - Lifetime
- 1996-06-05 KR KR1019970709817A patent/KR19990028499A/ko not_active Application Discontinuation
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101821817B (zh) * | 2007-10-08 | 2012-09-05 | Abb研究有限公司 | 聚合物混凝土电绝缘体系 |
CN102317344A (zh) * | 2009-02-10 | 2012-01-11 | 西门子公司 | 开关装置中绝缘材料用的铸模树脂体系 |
US8349937B2 (en) | 2009-02-10 | 2013-01-08 | Siemens Aktiengesellschaft | Casting resin system for insulating materials in switch gears |
CN101928443A (zh) * | 2009-06-17 | 2010-12-29 | 株式会社日立产机*** | 电气设备用绝缘铸型树脂及使用其的高电压电气设备 |
Also Published As
Publication number | Publication date |
---|---|
DE19523897A1 (de) | 1997-01-02 |
EP0835287A1 (de) | 1998-04-15 |
WO1997002321A1 (de) | 1997-01-23 |
JPH11508928A (ja) | 1999-08-03 |
DE19523897C2 (de) | 2002-10-24 |
ES2152527T3 (es) | 2001-02-01 |
US5965637A (en) | 1999-10-12 |
JP4138001B2 (ja) | 2008-08-20 |
DE59606048D1 (de) | 2000-11-30 |
KR19990028499A (ko) | 1999-04-15 |
CN1093866C (zh) | 2002-11-06 |
EP0835287B1 (de) | 2000-10-25 |
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