CN110591598B - 一种光伏材料粘结促进剂及其制备方法 - Google Patents
一种光伏材料粘结促进剂及其制备方法 Download PDFInfo
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- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/341—Dicarboxylic acids, esters of polycarboxylic acids containing two carboxylic acid groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract
本发明公开一种光伏材料粘结促进剂及其制备方法。本发明包括低沸点溶剂、乙酰丙酮铝或二茂铁及其衍生物、磷酸酯化合物或巯基化合物、环氧丙烯酸酯或聚氨酯甲基丙烯酸酯聚合物。本发明在作为半导体硅片制造用硅块和酚醛树脂板厌氧胶粘结促进剂，二茂铁及其衍生物、乙酰丙酮铝、能促进厌氧胶固化，磷酸或巯基基团能够与硅块和玻璃板中的重金属离子络合，增强厌氧胶的粘结力，而环氧丙烯酸酯或聚氨酯甲基丙烯酸酯聚合物能够渗透到硅块和玻璃板表面的缝隙或凹凸之处，固化后在界面区形成许多小钩和榫头，在胶粘剂与硅块和玻璃板之间产生啮合力，类似钉子与木材的接合，由此使厌氧胶的粘结强度显著提高。
Description
技术领域
本发明属于半导体材料工业制造技术领域，涉及厌氧胶粘结材料的表面处理，具体是一种半导体硅片制造用硅块和玻璃板厌氧胶粘结促进剂及其制备方法。
背景技术
厌氧胶是利用氧对自由基阻聚原理制成的单组份密封粘合剂，厌氧胶分解产生自由基，大量的氧起到阻聚的作用；当隔绝氧气后，溶解于厌氧胶中的微量氧被产生的自由基消耗尽，进而引发聚合，交联固化。厌氧胶既可用于粘接又可用于密封，当涂胶面与空气隔绝并在催化的情况下便能在室温快速聚合而固化。由于厌氧胶的具有独特的厌氧特性，使之在机械制造及装配领域有着许多其它胶粘剂不可比拟的优势，目前已经广泛的用于汽车、机械、电子、航空及石化等行业。厌氧胶粘剂的固化除了隔绝氧气的自由基聚合，还有金属离子存在的阴离子聚合反应，因此固化受被粘物表面性质和物理状态的影响。一些惰性表面材料(如纯铝、不锈钢、锌、镉、金、玻璃、陶瓷、塑料等)的厌氧胶粘结固化速度慢，粘接强度低，必须经过表面处理，涂上表面促进剂后，才能进行有效粘接。
韩胜利、艾少华和朱华娟等发明了一种低毒快干型厌氧胶气雾底涂剂及其制备方法(申请号：201010589746.2)。它的主要成分包含：(A)0.01～10Wt％有机羧酸铜盐；(B)10～99.98Wt％碳链小于9的醇类、醚类、酮类、烷烃类、酯类或其衍生物有机溶剂；(C)0.01～1％Wt％香精，灌入气雾罐中并充气、装喷头，制成厌氧胶气雾底涂剂。近年来光伏能源得到了飞速发展，因此太阳能电池用的光伏硅片同样快速发展。在硅片切割生产过程中通常使用厌氧胶粘结固定硅块与玻璃板，使用上面厌氧胶的底涂剂虽然能引发厌氧胶的快速固化，但粘结强度不够高，并不能适应硅片制造的工艺要求。东风汽车公司杨丹、陈谦等发明了一种厌氧胶促进底剂及其制备方法(授权公告号：CN1231550C)。它是以铜氨络离子、邻苯甲酰磺酰亚胺为主要成分，配合少量非离子型表面活性剂和亚硝酸盐的水溶液。其制备方法为：将五水合硫酸铜溶于去离子水后边搅拌边向其中滴加氨水至溶液由浅蓝色混浊变为深蓝色透明液体，继而加入适量邻苯甲酰磺酰亚胺及亚硝酸钠并使之溶解，最后滴入表面活性剂OP-10搅匀得到成品。这种厌氧胶促进底剂可使厌氧胶的定位速度提高几十倍，其催化效率高于常用有机促进剂，且以水为溶剂，便于包装、存放且环保，但由于水溶剂挥发速度很慢，需要等待挥发的时间较长且粘结强度不够高，并不能适应粘结要求高的应用。
发明内容
本发明针对现有技术的不足，提供一种半导体硅片制造用硅块和玻璃板厌氧胶粘结促进剂。
本发明促进剂的原料和配比(重量份数)如下：
所述的低沸点溶剂为乙醇和丙酮中的一种或二种混合；
所述的二茂铁衍生物为1,1’-二甲基二茂铁或乙酰基二茂铁；
所述的巯基化合物为乙二醇二(3-巯基丙酸酯)，三羟甲基丙烷三(3-巯基丙酸酯)或季戊四醇四(3-巯基丙酸酯)；
所述的磷酸酯化合物为乙二醇甲基丙烯酸磷酸酯；
所述的环氧丙烯酸酯的合成：
在装有搅拌器、温度计、滴液漏斗、冷凝管的四口烧瓶中加入140～180克双酚F环氧树脂和8～20克辛二酸或丁二酸，加热升温至90～100℃。然后滴加含有2～4克催化剂二月桂酸二丁基锡或三乙胺、0.1～0.3克阻聚剂和60～80克甲基丙烯酸的混合液，反应时间控制在3～5h，反应结束后降温至40℃出料。
所述的阻聚剂为对苯二酚、对甲氧基苯酚或2，6-二叔丁基对甲苯酚中的一种；
所述的聚氨酯甲基丙烯酸酯聚合物的合成：
在装有回流冷凝管、温度计、搅拌器、滴液漏斗的四口烧瓶中加入聚醚二元醇(Mn＝2000)190～230克，100～110℃下真空脱水1～2h。将反应温度控制在50～60℃，充氮气保护，再滴加70～80克异佛尔酮二异氰酸酯(IPDI)和0.6～1.2克二月桂酸二丁基锡的混合液，反应时间控制在2～3h。升高反应温度至70～80℃，然后滴加6～8克甲基丙烯酸羟乙酯，反应时间控制在2～3h。结束反应后，再加入对0.2～0.5克对苯二酚，搅拌降温出料。
本发明还提供上述半导体硅片制造用硅块和酚醛树脂板厌氧胶粘结促进剂的其制备方法，该方法具体步骤如下:
常温下，在低沸点溶剂中加入乙酰丙酮铝或二茂铁及其衍生物，溶解后依次加入磷酸酯化合物或巯基化合物，环氧丙烯酸酯或聚氨酯甲基丙烯酸酯聚合物，搅拌均匀后过滤除去杂质即可得到硅块和玻璃板厌氧胶粘结促进剂。
本发明在作为半导体硅片制造用硅块和酚醛树脂板厌氧胶粘结促进剂，二茂铁及其衍生物、乙酰丙酮铝、能促进厌氧胶固化，磷酸或巯基基团能够与硅块和玻璃板中的重金属离子络合，增强厌氧胶的粘结力，而环氧丙烯酸酯或聚氨酯甲基丙烯酸酯聚合物能够渗透到硅块和玻璃板表面的缝隙或凹凸之处，固化后在界面区形成许多小钩和榫头，在胶粘剂与硅块和玻璃板之间产生啮合力，类似钉子与木材的接合，由此使厌氧胶的粘结强度显著提高。
具体实施方式
下面结合具体实施例对本发明做进一步的分析。
实施例1：
1)在装有搅拌器、温度计、滴液漏斗、冷凝管的四口烧瓶中加入180克双酚F环氧树脂和10克辛二酸，加热升温至90℃。然后滴加含有4克三乙胺、0.1克阻聚剂对苯二酚和60克甲基丙烯酸的混合液，反应时间控制在3h，反应结束后降温至40℃出料。
2)常温下，在91.5g乙醇中加入2g二茂铁，溶解后依次加入0.5g乙二醇甲基丙烯酸磷酸酯和6g上述环氧丙烯酸酯聚合物，搅拌均匀后过滤除去杂质即可得到硅片或玻璃板厌氧胶粘结促进剂。
实施例2：
1)在装有搅拌器、温度计、滴液漏斗、冷凝管的四口烧瓶中加入140克双酚F环氧树脂和8克辛二酸，加热升温至90℃。然后滴加含有4克二月桂酸二丁基锡、0.1克阻聚剂2，6-二叔丁基对甲苯酚和80克甲基丙烯酸的混合液，反应时间控制在3h，反应结束后降温至40℃出料。
2)常温下，在91g乙醇中加入2g乙酰丙酮铝，溶解后依次加入1g乙二醇二(3-巯基丙酸酯)和6g上述环氧丙烯酸酯聚合物，搅拌均匀后过滤除去杂质即可得到硅片或玻璃板厌氧胶粘结促进剂。
实施例3：
1)在装有回流冷凝管、温度计、搅拌器、滴液漏斗的四口烧瓶中加入聚醚二元醇(Mn＝2000)230克，100℃下真空脱水2h。将反应温度控制在50℃，充氮气保护，再滴加70克异佛尔酮二异氰酸酯(IPDI)和0.6克二月桂酸二丁基锡的混合液，反应时间控制在2h。升高反应温度至80℃，然后滴加8克甲基丙烯酸羟乙酯，反应时间控制在2h。结束反应后，再加入0.5克对苯二酚，搅拌降温出料得到聚氨酯甲基丙烯酸酯聚合物。
2)常温下，在90g丙酮中加入4g二茂铁，溶解后依次加入1g乙二醇甲基丙烯酸磷酸酯和5g聚氨酯甲基丙烯酸酯聚合物，搅拌均匀后过滤除去杂质即可得到厌氧胶粘结促进剂。
实施例4：
1)在装有回流冷凝管、温度计、搅拌器、滴液漏斗的四口烧瓶中加入聚醚二元醇(Mn＝2000)190克，110℃下真空脱水1h。将反应温度控制在60℃，充氮气保护，再滴加80克异佛尔酮二异氰酸酯(IPDI)和1.2克二月桂酸二丁基锡的混合液，反应时间控制在3h。升高反应温度至70℃，然后滴加6克甲基丙烯酸羟乙酯，反应时间控制在3h。结束反应后，再加入0.2克对苯二酚，搅拌降温出料得到聚氨酯甲基丙烯酸酯聚合物。
2)常温下，在88g丙酮中加入5g1,1’-二甲基二茂铁，溶解后依次加入1g三羟甲基丙烷三(3-巯基丙酸酯)和6g聚氨酯甲基丙烯酸酯聚合物，搅拌均匀后过滤除去杂质即可得到厌氧胶粘结促进剂。
实施例5：
1)在装有回流冷凝管、温度计、搅拌器、滴液漏斗的四口烧瓶中加入聚醚二元醇(Mn＝2000)230克，105℃下真空脱水1h。将反应温度控制在55℃，充氮气保护，再滴加70克异佛尔酮二异氰酸酯(IPDI)和1克二月桂酸二丁基锡的混合液，反应时间控制在3h。升高反应温度至70℃，然后滴加7克甲基丙烯酸羟乙酯，反应时间控制在3h。结束反应后，再加入0.3克对苯二酚，搅拌降温出料得到聚氨酯甲基丙烯酸酯聚合物。
2)常温下，在95g乙醇中加入2g二茂铁，溶解后依次加入1g乙二醇甲基丙烯酸磷酸酯和2g上述聚氨酯甲基丙烯酸酯聚合物，搅拌均匀后过滤除去杂质即可得到厌氧胶粘结促进剂。
实验项目及方法：
按照国家标准GB/T7124—2008将实验材料板制成25mm×100mm的规格，胶接面制作成12.5mm×25mm的规格。用无水乙醇或者丙酮溶液将硅板和玻璃板表面清洗干净，然后用脱脂棉蘸取表面处理剂，用微力轻轻涂覆在实验材料表面，待表干后均匀地涂覆厌氧胶(胶接面积12.5mm×25mm)，厚度控制在0.2mm左右，制备的胶接件在(25±2)℃的条件下固化，待试件充分固化后(2小时)，测其压剪强度。对比例配比：乙醇99.5克，乙酸铜0.5克。
上述实施例并非是对于本发明的限制，本发明并非仅限于上述实施例，只要符合本发明要求，均属于本发明的保护范围。
Claims (5)
1.一种光伏材料粘结促进剂，其特征在于包括以下各重量份数的组分：
低沸点溶剂 88～95.5份
乙酰丙酮铝或二茂铁或二茂铁衍生物 2.0～5.0份
磷酸酯化合物或巯基化合物 0.5～1.0份
环氧丙烯酸酯或聚氨酯甲基丙烯酸酯聚合物 2.0～6.0份
所述的环氧丙烯酸酯的合成：
在装有搅拌器、温度计、滴液漏斗、冷凝管的四口烧瓶中加入140～180克双酚F环氧树脂和8～20克辛二酸或丁二酸，加热升温至90～100℃；然后滴加含有2～4克催化剂二月桂酸二丁基锡或三乙胺、0.1～0.3克阻聚剂和60～80克甲基丙烯酸的混合液，反应时间控制在3～5h，反应结束后降温至40℃出料；
所述的聚氨酯甲基丙烯酸酯聚合物的合成：
在装有回流冷凝管、温度计、搅拌器、滴液漏斗的四口烧瓶中加入聚醚二元醇（Mn=2000）190～230克，100～110℃下真空脱水1～2h；将反应温度控制在50～60℃，充氮气保护，再滴加70～80克异佛尔酮二异氰酸酯和0.6～1.2克二月桂酸二丁基锡的混合液，反应时间控制在2～3h；升高反应温度至70～80℃，然后滴加6～8克甲基丙烯酸羟乙酯，反应时间控制在2～3 h；结束反应后，再加入对0.2～0.5克对苯二酚，搅拌降温出料；
所述的巯基化合物为乙二醇二（3-巯基丙酸酯），三羟甲基丙烷三（3-巯基丙酸酯）或季戊四醇四（3-巯基丙酸酯）；
所述的磷酸酯化合物为乙二醇甲基丙烯酸磷酸酯。
2.如权利要求1所述的一种光伏材料粘结促进剂，其特征在于所述的低沸点溶剂为乙醇和丙酮中的一种或二种混合。
3.如权利要求1或2所述的一种光伏材料粘结促进剂，其特征在于所述的二茂铁衍生物为1,1’-二甲基二茂铁或乙酰基二茂铁。
4.如权利要求1或2任一所述的一种光伏材料粘结促进剂，其特征在于所述的阻聚剂为对苯二酚、对甲氧基苯酚或2，6-二叔丁基对甲苯酚中的一种。
5.如权利要求1-4任一所述的一种光伏材料粘结促进剂的制备方法，其特征在于常温下，在低沸点溶剂中加入乙酰丙酮铝或二茂铁或二茂铁衍生物，溶解后依次加入磷酸酯化合物或巯基化合物，环氧丙烯酸酯或聚氨酯甲基丙烯酸酯聚合物，搅拌均匀后过滤除去杂质即可得到。
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