CN1236002C - 具有改进贮存性能的热硬化单组分低粘度粘合剂系统 - Google Patents
具有改进贮存性能的热硬化单组分低粘度粘合剂系统 Download PDFInfo
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Abstract
本发明涉及一种改善贮存性能并能保持其低粘度的浇注树脂系统，它适宜于尺寸公差在μm和小于μm范围内的精密粘合。改进的贮存性能与加少量锌配合物到粘合剂配方中有关。
Description
本发明涉及一种具有改进贮存性能的浇注树脂系统。它适宜于尺寸公差在μm和小于μm范围内的粘合。
从内容涉及本发明的主题的94E 1887(DE19629082)中已知一种热硬化单组分粘合剂系统，它在长期贮存中，也就是说例如贮存6个月或更长些时间其粘度会升高。粘度升高导致粘合剂系统的滴流性和流动性改变，使计量难于准确。特别是应用在微粘合技术使用较小量粘合剂时经常造成困难，对于大批量生产例如在微光学领域就会造成可重复性粘合剂涂抹的困难。为了抑制混合物中所含的引发剂，此种粘合剂系统经常加有碱性添加剂。这种经常易挥发的碱性添加剂在加工时会产生有损健康的气味，并在粘合时影响硬化反应，尤其是对薄层物。
因此需要一种粘合剂系统，可不加碱性添加剂，同时由于保持低粘度，从而改善了贮存稳定性能，即经贮存时间后它的粘度接近于不变。
因此本发明的任务是提供一种粘合剂系统，它可不加碱性添加剂，并由于其低粘度可改善贮存稳定性。
本发明的原理是添加少量的金属配合物，优选锌配合物到已知的粘合剂系统中，该粘合剂系统贮存在冰箱中(约5℃-8℃)可保持相当长时间的低粘度。
本发明的目的是提供一种热硬化单组分粘合剂系统，它包含下面的组分：
60-98％(重量)的浇注树脂，
2-30％(重量)的醇类或糖类，
0.2-2.0％(重量)的热引发剂，
0.2-2.0％(重量)的粘附剂和/或
0-3.0％(重量)的助流剂和/或
0-4％(重量)的摇溶剂和/或一种流动改性剂和
0.2-5.0％(重量)的金属配合物。
优选的是，所述粘合剂系统包含：
85-93％(重量)的环氧浇注树脂，
4.5-12％(重量)的多价醇类，
0.7-1.0％(重量)的热引发剂，
0.3-0.6％(重量)的粘附剂和/或
0-1.5％(重量)的助流剂和/或
0-2.0％(重量)的摇溶剂和/或一种流动改性剂和
0.5-2.0％(重量)的金属配合物。
由此，本发明的目的是应用该粘合剂系统于尺寸公差为μm和μm以下范围内的粘合中。
本发明中，各组分的百分比之和必为100％。
本发明的“浇注树脂”的意思可理解为热可硬化树脂系统和反应树脂，它的粘度是这样低，可通过浇注可注满相应的铸模，然后热固化，即在有适宜的添加剂(引发剂、加速剂、其它组分)存在下通过升温硬化。按本发明环氧浇注树脂是一种优选的浇注树脂。按本发明配方含该浇注型树脂为60-98％(重量)，优选为75-95％(重量)，较优选为80-95％(重量)和特别优选为85-93％(重量)。
作为“环氧浇注树脂”可加入环化-脂肪族环氧树脂如Ciba Geigy公司的CY 177树脂(双3，4环氧基-环-己基甲基)-己二酸酯或者Ciba Geigy公司的CY 179树脂(3，4-环氧-环-己基甲基-3′，4′-环氧-环-己基羧酸酯)。此外线性脂肪族的环氧树脂，如环氧化聚丁二烯或环氧化大豆油也是适宜的。其它的阳离子硬化树脂如乙烯基醚或乙烯基芳族化合物同样也是适宜的。此处缩水甘油醚型的环氧树脂是适宜的。作为缩水甘油基醚的基体可以是：双酚类如双酚A；二或聚羟基芳族化合物如间苯二酚、带酚OH基的多芳基烃化合物、酚醛清漆、聚烯烃乙二醇或多醇类如丁二醇，己二醇，丙三醇或季戊四醇。其它适宜的化合物有缩水甘油醚-酯类型化合物如对羟基苯甲酸-缩水甘油醚酯；含脂肪族的或芳香族核的多羧酸的纯缩水甘油酯如六氢化邻苯二甲酸或邻苯二甲酸。
按本发明可使用含1-15个羟基的醇类或糖类作为“醇或糖”。优选应用含1-5个羟基的醇。醇类或糖类的主要基体是可随意变化的，它能是脂肪的、环化的或双环的，它也可由单键或多键组成，它也可以是芳族系统。优选使用如Hoechst公司的TCD-醇DM，即3(4)，8(9)-双(羟甲基)-三环[5.2.1.02，6]癸烷。这种优选为多价的醇在粘合剂配方中的含量为2-30％(重量)。它的含量优选为2.5～20％(重量)，特别优选为4.5～12％(重量)。
作为热引发剂可使用所有按阳离子机理的硬化可行的引发剂，如鎓类盐。这里优选用由Aldrich公司的S-苄基硫醇六氟锑酸盐。
作为粘附剂可用Huls公司的A 187，即3-缩水甘油基氧丙基三甲氧基硅烷。
作为助流剂可用Monsanto公司的Modaflow，作为流动改性剂或摇溶剂可用Degussa公司提供的商业用的一种高度分散的硅胶。
作为金属配合物优选可用Zn2+-化合物或其它过渡金属如锆、铁、钴、钛、镍、钼和锰或者锡、镁或铝以及烯土元素如铈与通用的有机配位体如氨基酸、醋酸盐、一般的羧酸、胺类和乙酰丙酮化合物的金属配合物。锌配合物的加入量为0.2-5％(重量)，优选小于3％(重量)，特别优选的加入量为小于1％(重量)。
除了上述组分外，本发明的粘合剂系统中还能含有其它的已知附加物和添加剂。由此可使粘合剂系统获得附加性能，如特殊的颜色或透明性以及耐燃性或耐温性。因此在此意义上的添加剂有如颜料、染料、流动改性剂、通用的稳定剂、防火剂或矿物填料或其它填料。因此可通过加入添加剂达到所需的性能，例如通过加入颜料达到选择性吸收或透明。
粘合剂系统的生产如通常的方法。将配方组分如环氧树脂多价醇、热引发剂、粘附剂和金属配合物进行均匀混合，需要时适当加热以及加入可除去的溶剂。粘合剂制备也可采用现有技术中的可靠方法。
下面再用一个实施例对本发明进行详细说明。
表I是有代表性的粘合剂系统的配方组分。从给出的四种粘合剂系统中，2种(用星号*表示)含本发明所述的锌配合物(HK 170*和HK191*)，其它二种对比系统，不含锌配合物，相当于现有技术(HK 170和HK 191)。
表1 配方的组分和化学名称
| 组分(货源)，化学名称 | HK170[MT] | HK170*[MT] | HK191[MT] | HK191*[MT] |
| 树脂：CY 177(Ciba Geigy公司)双(3，4-环氧基环己基甲基)-己二酸酯CY 179(Ciba Geigy公司)3，4-环氧-环-己基甲基-3′，4′-环氧-环-己基羧酸酯 | 100 | 100 | 90 | 90 |
| 多价醇：TCD-醇DM(Hoechst公司)3(4)，8(9)-双(羟基甲基)-三环[5.2.1.02，6]癸烷 | 5 | 5 | 10 | 10 |
| 热引发剂：S-苄基硫醇六氟锑酸盐(Aldrich公司) | 0.5 | 0.5 | 0.8 | 0.8 |
| 粘附剂：A 187(Hüls公司)3-缩水甘油基丙氧基三甲氧基硅烷 | 0.5 | 0.5 | 0.5 | 0.5 |
| 锌配合物：L 230(Brlocher公司)二-(2-乙基己酸)锌 | 0.4 | 0.5 |
然后对表1中所列的化合物做贮存时间试验。由此比较在8℃贮存温度下含锌配合物的粘合剂系统和不含锌配合物的粘合剂系统的贮存稳定性。起始粘度为120mPas(在60℃下测试粘度)的HK 170在8℃下贮存6个月后粘度上升至200mPas，而含0.4％(重量)L 230-锌配合物的HK 170*在一年内，即贮存期增加一倍，其它条件相同下其粘度仅上升到140mPas。因此由HK 170和HK 170*化合物实例可知，不含锌配合物的化合物在6个月贮存期后的粘度在比含锌配合物的粘合剂系统贮存12个月后的粘度有更明显的上升。这表明，加入如0.4％(重量)的少量锌配合物可使配方的贮存稳定性明显提高。在基片如玻璃、PA(聚酰胺)、PPA(聚邻苯二酰胺)，PMMA(聚甲基丙烯酸酯)和PP(聚丙烯)上的配方的硬化性能并未由于加入锌配合物而受影响。
DSC研究(差示扫描量热法)表明，改进的浇注型树脂系统的具有稍微较高的起始反应温度。但在通常120℃硬化温度下的硬化性能没有明显的差别(见表3)：
表3：挑选的DSC参数
| HK 191 | HK 191* | |
| T-开始反应温度[℃]T-高峰温度[℃]ΔHR[-J/g] | 129146564 | 142161546 |
| 120℃下30分钟后的基反应[％] | 15.0 | 18.6 |
由此可见本发明的粘合剂系统可适用于μm和/或μm以下范围内的电子部件和光电部件的自动的和可靠的微计量。本发明的含锌配合物的单组分环氧树脂不会马上硬化，这样就可使各个构件的接缝都进料直至固定。
环氧树脂组分以及整个粘合剂系统的粘度是足够的低，可应用于微粘合。由于加入锌配合物，在粘合剂系统加工时就没有因碱性的添加物的蒸发而出现气味的问题。该粘合剂配方在8℃的冰箱温度下可稳定的贮存12个月，其粘度不会有明显的提高。与其它现有技术的粘合剂比较，本发明的粘合剂系统能保持低粘度就使其在贮存较长时间后不会出现问题，特别是可适用于微计量技术。
Claims (6)
1.一种热可硬化单组分的粘合剂系统，包含下列组分：
60-98重量％的环氧浇注树脂，
2-30重量％的醇类或糖类，
0.2-2.0重量％的热引发剂，
0.2-2.0重量％的粘附剂和/或
0-3.0重量％的助流剂和/或
0-4重量％的一种摇溶剂和/或一种流动改性剂和
0.2-5.0重量％的一种金属配合物，其选自：
过渡金属锆、铁、钴、钛、镍、钼和锰，或
锡、镁或铝，以及
稀土
与通常的有机配位体形成的金属配合物，以及
二(2-乙基己酸)锌；
所述各组分的百分比之和为100重量％。
2.权利要求1所述的粘合剂系统，其中所述稀土为铈，所述通常的有机配位体选自氨基酸、酯酸盐、一般的羧酸、胺类及乙酰丙酮化合物。
3.按权利要求1或2的粘合剂系统，包含：
85-93重量％的环氧浇注树脂，
4.5-12重量％的多价醇类，
0.7-1.0重量％的热引发剂，
0.3-0.6重量％的粘附剂和/或
0-1.5重量％的助流剂和/或
0-2.0重量％的摇溶剂和/或一种流动改性剂和
0.5-2.0重量％的金属配合物。
4.按权利要求1或2的粘合剂系统，包含：
88.4重量％的环氧浇注树脂，
9.82重量％的多价醇类，
0.79重量％的热引发剂，
0.49重量％的粘附剂和
0.49重量％的一种金属配合物，
其中粘合剂系统中所有成分的总重量百分比为100％重量。
5.按权利要求1或2的粘合剂系统，在其中，所述树脂是：
双(3，4-环氧基-环-己基甲基)-己二酸酯，或
3，4-环氧-环化的-己基甲基-3′，4′-环氧-环-己基羧酸酯；
所述多价醇为：3(4)，8(9)-双(羟甲基)-三环(5.2.1.02，6)癸烷，和
所述金属的配合物为：二(2-乙基己酸)锌。
6.权利要求1的粘合剂系统在公差为μm和μm以下的精密粘合中的应用。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19629750A DE19629750A1 (de) | 1996-07-23 | 1996-07-23 | Thermisch härtbares einkomponentiges Low Viskosity Adhesive-Klebstoffsystem mit verbesserten Lagerungseigenschaften |
| DE19629750.8 | 1996-07-23 |
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| Publication Number | Publication Date |
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| CN1226281A CN1226281A (zh) | 1999-08-18 |
| CN1236002C true CN1236002C (zh) | 2006-01-11 |
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| CNB971966672A Expired - Fee Related CN1236002C (zh) | 1996-07-23 | 1997-07-16 | 具有改进贮存性能的热硬化单组分低粘度粘合剂系统 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6297344B1 (zh) |
| EP (1) | EP0914398B1 (zh) |
| CN (1) | CN1236002C (zh) |
| DE (2) | DE19629750A1 (zh) |
| NO (1) | NO990310L (zh) |
| TW (1) | TW496890B (zh) |
| WO (1) | WO1998003605A1 (zh) |
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| US20030087052A1 (en) * | 2001-11-05 | 2003-05-08 | Wideman Thomas W. | Spoolable composite tubing with a catalytically cured matrix |
| DE102005040126A1 (de) * | 2005-08-25 | 2007-03-01 | Altana Electrical Insulation Gmbh | Überzugsmasse |
| US20110305911A1 (en) * | 2008-04-30 | 2011-12-15 | Bluestar Silicones France | Article having antifouling properties and intended to be used in aquatic applications, particularly marine applications |
| US9388275B2 (en) * | 2009-06-01 | 2016-07-12 | International Business Machines Corporation | Method of ring-opening polymerization, and related compositions and articles |
| AU2018351611B2 (en) * | 2017-10-20 | 2023-12-07 | Construction Research & Technology Gmbh | Set control composition for cementitious systems |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE211120C (zh) * | ||||
| US4216288A (en) * | 1978-09-08 | 1980-08-05 | General Electric Company | Heat curable cationically polymerizable compositions and method of curing same with onium salts and reducing agents |
| JPS55118429A (en) | 1979-03-05 | 1980-09-11 | Mitsubishi Petrochem Co Ltd | Preparation of tricyclodecanedimethylol |
| US4480059A (en) | 1982-08-26 | 1984-10-30 | General Electric Company | Epoxy adhesives for poly(butylene terephthalate) |
| US4482679A (en) * | 1982-09-18 | 1984-11-13 | Ciba-Geigy Corporation | Heat-curable epoxy compositions containing diaryliodosyl salts |
| AU595593B2 (en) * | 1986-05-07 | 1990-04-05 | Minnesota Mining And Manufacturing Company | Epoxy resin composition |
| CA2108260A1 (en) * | 1991-05-16 | 1992-11-17 | Kam Chu Wu | Epoxide-based adhesive |
| ES2106851T3 (es) * | 1991-06-19 | 1997-11-16 | Ciba Geigy Ag | Nuevo sistema de resinas con baja temperatura de moldeo. |
-
1996
- 1996-07-23 DE DE19629750A patent/DE19629750A1/de not_active Ceased
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1997
- 1997-06-16 US US09/230,310 patent/US6297344B1/en not_active Expired - Fee Related
- 1997-07-16 WO PCT/DE1997/001504 patent/WO1998003605A1/de active IP Right Grant
- 1997-07-16 CN CNB971966672A patent/CN1236002C/zh not_active Expired - Fee Related
- 1997-07-16 DE DE59710898T patent/DE59710898D1/de not_active Expired - Fee Related
- 1997-07-16 EP EP97936557A patent/EP0914398B1/de not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| US6297344B1 (en) | 2001-10-02 |
| DE59710898D1 (de) | 2003-11-27 |
| WO1998003605A1 (de) | 1998-01-29 |
| EP0914398A1 (de) | 1999-05-12 |
| TW496890B (en) | 2002-08-01 |
| NO990310D0 (no) | 1999-01-22 |
| DE19629750A1 (de) | 1998-01-29 |
| CN1226281A (zh) | 1999-08-18 |
| NO990310L (no) | 1999-01-22 |
| EP0914398B1 (de) | 2003-10-22 |
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