CN105339456B - 高温可脱粘粘合剂 - Google Patents

高温可脱粘粘合剂 Download PDF

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CN105339456B
CN105339456B CN201380077306.0A CN201380077306A CN105339456B CN 105339456 B CN105339456 B CN 105339456B CN 201380077306 A CN201380077306 A CN 201380077306A CN 105339456 B CN105339456 B CN 105339456B
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hydrogen
base material
group
unsticking
component
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CN105339456A (zh
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张文华
黄晓燕
孔胜前
X·A·俞
S·海因斯
J·欧阳
孙春宇
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Henkel AG and Co KGaA
Henkel IP and Holding GmbH
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Abstract

一种可脱粘粘合剂组合物，包含：(A)1，3，5，7‑四乙烯基‑1，3，5，7‑四甲基环四硅氧烷上的乙烯基基团和硅烷或具有末端Si‑H氢的硅氧烷上的末端Si‑H氢之间反应的硅氢化反应产物，(B)用于硅氢化反应产物的交联剂，以及(C)金属催化剂和/或自由基引发剂。在进一步的实施方式中，本发明涉及基材和用于基材的载体的组件，其中可脱粘的粘合剂组合物放置于基材之间，以及一种装配该组件的方法。可脱粘粘合剂组合物在300℃或更高的温度下保持其粘合性，并且在室温下以小于5N/25mm的力可机械脱粘。

Description

高温可脱粘粘合剂
技术领域
本发明涉及用于高温应用的可固化临时粘合剂，以及特别涉及用于临时粘结一个基材和另一个基材的粘合剂。
背景技术
在众多工业中，对于使用柔性和/或非常薄的基材的兴趣在不断增加，所述基材例如不锈钢、硅晶圆、玻璃、陶瓷、聚酰亚胺和聚酯膜。柔性和非常薄的基材太易碎而不能在下游生产条件中独立地进行处理，并且必须支撑在合适的载体上以进行处理。在完成制造过程后，基材必须从载体上无损地移除，优选在环境温度下。
在电子工业中，作为一个例子，图像显示器、传感器、光电池和RFID，不断增加对用于手机、电子记事簿、iPAD或TV显示器应用的薄和/或柔性基材的要求。一个示例性的基材为非常薄(100μm)的功能化包装的玻璃。在400℃下，对玻璃进行加工以放置薄膜晶体管(TFT)或在350℃下加工以沉积作为透明导体的氧化铟锡(ITO)。由于玻璃的易碎性和严格的加工条件，玻璃必须被强化或在制造过程中用更稳定的基材保护。
这样的用途需要可容易并干净地脱粘、允许在高温加工温度下临时粘接并且不会损坏基材的操作或性能的高温稳定的粘合剂。特别地，这是电子工业中的驱动力。这类粘合剂的开发将允许现有的制造方法，例如用于半导体、有源矩阵薄膜晶体管、接触膜或光电池的制造方法，使用现有生产工具和机器作为安装基础。绝大多数现有可获得的临时粘合剂在生产步骤的可高达400℃的最大加工温度下是非热稳定的。
适用于高温临时粘接应用的粘合剂，可随后在室温下被移除而不造成目标部件的破坏，将促进更薄或更柔性基材在多种工业中的应用。
发明内容
如说明书和权利要求中所用的，“基材”指的是用于制造过程中的目标部件，以及“载体”指的是针对“基材”的支撑结构。
本发明涉及粘合剂组合物，包含：(A)1，3，5，7-四乙烯基-1，3，5，7-四甲基环四硅氧烷上的乙烯基基团和硅烷或具有末端Si-H氢的硅氧烷上的末端Si-H氢之间反应的硅氢化反应产物，(B)用于硅氢化反应产物的交联剂，以及(C)金属催化剂和/或自由基引发剂。
1，3，5，7-四乙烯基-1，3，5，7-四甲基环四硅氧烷和硅烷或具有末端Si-H氢的硅氧烷之间反应的硅氢化反应产物(A)将在本说明书中称为乙烯基碳硅氧烷或VCS树脂或VCSR。
交联剂(B)是在乙烯基加成反应中与VCSR上的乙烯基基团反应的硅氧烷。催化剂将为金属催化剂和/或自由基引发剂，并且固化将为热固化或光固化。合适的金属催化剂包括可商业获得的铂或铑催化剂。合适的自由基引发剂有许多并且是本领域技术人员所熟知的；一种这样的自由基引发剂是过氧化二异丙苯。合适的自由基引发剂还包含光引发剂，例如那些以商品名DAROCURE 1173和IRGACURE 184或2100出售的。
粘合剂组合物在300℃或更高，不超过440℃的温度下保持其粘合性，并且可以在室温下以5N/25mm或更小的力，在一些实施方式中以3N/25mm或更小的力，并且在一些实施方式中以2N/25mm或更小的力，机械脱粘。
在另一个实施方式中，本发明涉及基材和载体的组件，其中粘合剂组合物设置于基材间。
在另一个实施方式中，本发明涉及从载体将基材脱粘的方法，包括：(a)提供基材和载体，(b)在基材和/或载体上设置可脱粘粘合剂，(c)将基材和载体接触以使可脱粘粘合剂置于之间，形成组件，(d)在温度或温度范围内加热组件以将基材粘合，或(e)将组件暴露于辐射中以将基材粘合，或(f)将组件暴露于辐射中并随后加热以将基材粘合，以及(g)使组件达到环境温度并且将基材机械分离。
当使用步骤(d)时，加热将在100℃至175℃的温度范围内的温度或温度范围进行1至30分钟。当使用步骤(e)时，使用400瓦特灯泡紫外辐射约1至4分钟；其他辐射源也可以在本领域技术人员的掌握内使用。当使用步骤(f)时，步骤(d)和(e)的参数将组合使用以获得需要的固化；合适的固化条件可在知道步骤(d)和(e)参数而无需过度实验，由本领域技术人员测定。
发明详述
本发明所开发的粘合剂能够在300℃至450℃的制造温度范围内在基材和载体之间提供足够的临时粘接，并且环境温度下在基材和载体的界面上粘合失效脱粘且不破坏基材。
组分(A)，VCSR，是1，3，5，7-四乙烯基-1，3，5，7-四甲基环四硅氧烷上的乙烯基和硅烷或具有末端Si-H氢的硅氧烷上的末端Si-H氢之间反应的硅氢化反应产物。1，3，5，7-四乙烯基-1，3，5，7-四甲基环四硅氧烷，具有如下结构：
用于与1，3，5，7-四乙烯基-1，3，5，7-四甲基环四硅氧烷反应的合适的硅烷或具有至少两个末端Si-H氢的硅氧烷包括具有如下结构的那些物质：
和
其中R选自由C1至C10烷基基团、芳基基团、氧、-(O-SiMe2)n-O-、-(O-SiAr2)n-O-、-(O-SiMeAr)n-O-以及这些基团任意组合组成的组，其中n至少为数字1，Me是甲基基团，并且Ar是芳基基团；以及其中R1、R2、R3、R4、R5和R6各自独立地为C1至C10烷基基团或芳基基团。
示例性的硅烷或硅氧烷包括聚烷基硅烷和聚烷基硅氧烷，其中硅原子上的烷基基团为C1至C10烷基基团。在多个实施方式中，硅烷和硅氧烷包括聚二甲基硅氧烷、聚甲基苯基硅氧烷以及四甲基二硅氧烷。这些化合物可从Gelest商业获得。
优选的VCSR反应产物(A)是那些具有下面理想化结构的，其中分子量为重均分子量。在多个实施方式中，VCSR反应产物的硅原子上的烷基基团包括C1至C10烷基基团。在下面理想化的结构中，描述了甲基基团，但是应该理解也可以使用其它C1至C10烷基基团。
VCSR-1，Mw＝1000-100,000
VCSR-2，Mw＝1000-150,000
VCSR-3，Mw＝1000-100,000
粘合剂组合物的组分(B)是用于硅氢化反应产物(A)的交联剂，并在多个实施方式中将包含硅原子上的C1至C10烷基基团。在某些实施方式中，在与乙烯基碳硅氧烷反应产物(A)的交联硅氢化反应中所用的合适的交联化合物(B)包括聚(甲基氢)硅氧烷、甲基氢硅氧烷-二甲基硅氧烷共聚物、二甲基甲硅烷基苯基醚、聚甲基苯基硅氧烷以及聚(甲基氢)苯基硅氧烷。这些化合物可从Gelest商业获得。
在一些实施方式中，可以使用增链剂以延长Si-H交联剂化合物(B)并且增加粘合剂的分子量。合适的增链剂选自α，ω-乙烯基末端线性聚硅氧烷、二乙烯基硅烷和二乙烯基硅氧烷。在不同的实施方式中，硅原子上的烷基基团将为C1至C10烷基基团。在一个特定的实施方式中，增链剂为二乙烯基四甲基二硅氧烷。
当在反应混合物中使用增链剂以延长交联硅烷或硅氧烷，组分(A)和组分(B)之间的摩尔当量比例通过链增长后可获得的1，3，5，7-四乙烯基-1，3，5，7-四甲基环四硅氧烷和交联剂的摩尔数而计算。
粘合剂组合物的组分(C)是金属催化剂和/或自由基引发剂。当需要光学透明时，合适的催化剂是在最终的树脂混合物中以20ppm或更少的水平使用的液体铂催化剂。更高的水平可造成黄变，但是当无需避免黄变时可根据需要使用。在许多反应中，催化剂的水平仍然可以是有活性的并且仍然足够低从而使得没有必要将其从反应产物中分离。
可固化的临时粘合剂由乙烯基碳硅氧烷反应产物(A)和选择的交联化合物(B)以6-0.6∶1的摩尔当量比例，在金属催化剂和/或自由基引发剂的存在下而制备。
实施例
这些可脱粘的粘合剂的两个优选性能为：它们是稳定的并在300℃和更高，高达440℃的温度下保持其完整性，及其在环境温度下可以容易并干净地脱粘。在下面的实施例中，在高温下细微线性裂纹的可见证据表示了不稳定性，并且大于5N/25mm的剥离强度的证据表示了粘合剂不能被干净地移除。
实验介质是两个5cm×7.5cm的玻璃片的组件，来自VWR international，粘合剂组合物置于两个薄片之间。所有样品的粘合剂层厚度，除非另有提及，为0.125mm。组件放置于空气中，150℃下，在Cole Parmer Digital hotplate上30分钟以固化粘合剂。
为了测试高温稳定性，使用Thermo Scientific BF5800 Furnace加热组件至确定的温度。当对加热后显示细纹或裂缝的粘合剂目测检查时，粘合剂被测定为不稳定的。
使用实验介质中粘合剂的失重作为测定稳定性的另一个方法。失重越低，粘合剂越稳定。在使用来自Perkin Elmer的Pyris 1热失重分析仪(TGA)在400℃下加热一小时前后对样品称重，并进行失重计算。小于9.6％的失重被认为是可接受的并且粘合剂被认为是稳定的。在一个实施例中，优选失重为7.3％或更小。
在使用紫外作为固化方法的实施例中，使用Dymax EC系列450W紫外灯辐照实验介质一定时间。
使用Shimpo FGV-20XY数字测力仪进行脱粘测试：测试模型的上玻璃片从稳定的下玻璃片剥离并且对剥离力(被认为是脱粘力)计算并标准化为N/25mm。
实施例中所用的材料如下：
除了那些基于SYLGUARD 184和ECCOCOAT SC3613树脂样品(这些是比较例)，下面所有其他实施例包含约20ppm的来自SIP 6830.3铂复合物的铂催化剂。
实施例的配方和测试结果记录于下面的表中，并且表明：组分(A)与组分(B)的摩尔当量比例在高温稳定粘合剂的生成上是有效的。
制备实施例1至24中的粘合剂组合物，包含作为组分(A)的VCSR-2和作为组分(B)的多种交联剂。每个实验介质均在300℃下加热30分钟并且随后针对细纹或裂缝进行目测检查。任意细纹或裂缝的可见的证据被认为是粘合组合物的失效。结果见表1并且表明用于生成有效高温粘合剂的有效的VCSR与交联剂的比率在6-0.6∶1的范围内。
一些实施例表明在此比例范围外的良好性能。但是发现，在6-0.6∶1摩尔当量比例范围的端值的比例处反应条件的微小变化导致影响粘合剂稳定性的性质的差别。因此，优选摩尔当量比例在可接受性能的较宽的范围的中间。因此，可以理解的是，那些落在6-0.6∶1的范围外的单独的例子仍可以给出好的稳定性。
(样品并不总是按数字顺序记录。)
实施例25和26中的粘合剂组合物包含作为组分(A)的VCSR-2，以及作为组分(B)的SIB1090.0交联剂。组合物还包含AEROSIL R972气相法二氧化硅作为填料。粘合剂层厚度为0.125mm。每个测试介质在300℃下加热30分钟并且随后针对细纹或裂缝进行目测检查。可以看到的任意的细纹或裂缝被认为是粘合剂组合物的失败。结果记录于表2中并且表明填料可以用于配方中而不损失高温性能。
实施例27和28中的粘合剂组合物包含作为组分(A)的VCSR-2，以及作为组分(B)的表3中注明的两种交联剂的组合。实施例27包含SIB1090.0和HMS-301R交联剂，而实施例28包含SIP6826.0和PDV-0535交联剂。粘合剂层厚度为0.150mm。每个测试介质在300℃下加热30分钟并且随后针对细纹或裂缝进行目测检查。可以看到的任意的细纹或裂缝被认为是粘合剂组合物的失败。针对总的(B)组分给出摩尔当量比率。实施例30在Pt(IV)催化剂在8W/cm2的紫外总能量的400W紫外灯下通过紫外辐射加热四分钟。结果记录于表3中。
实施例27、28、29和33在高温和低粘合剂层厚度下测试性能。加热条件的温度为℃，时间为分钟，粘合剂层厚度为mm，以及性能结果如表4所记录并且表明了摩尔比率的重要性。
进一步使用TGA测定表5中实施例的失重以及上面所述的脱粘力。测试条件和结果如表5所记录并且表明了可接受的重量稳定性和导致易移除性的低粘接力。
实施例31和32是使用可商业获得硅酮产品的比较例。从这些材料制备的组合物可在300℃下保持30分钟，但是在更高的温度下表现出裂缝而不能使用5N/mm或更少的力而脱粘。它们由于通过TGA测定的不可接受的热失重，在350℃或更高的温度下不具有热稳定性。加热条件中的温度为℃，时间为分钟，粘合剂层厚度为mm，性能结果如表6所示。
实施例35至38由与实施例27相同的组分而制备，进一步添加了DAROCURE1173光引发剂。使用UVAloc 1000在约120mW/cm2进行120秒而完成固化。在辐照固化后，样品在150℃下热固化15分钟，并且随后在350℃下老化30分钟。以剥离强度测试脱粘力并且测试TGA。结果如表7所示并且表明粘合剂是稳定的而且可干净地移除。
实施例39至41由89wt％与实施例27相同的组分、1wt％DAROCURE1173光引发剂，以及添加10wt％的丙烯酸酯化或甲基丙烯酸酯化的硅氧烷树脂而制备。实施例42至44由89wt％与实施例28相同的组分、1wt％DAROCURE 1173光引发剂，以及添加10wt％的的丙烯酸酯化或甲基丙烯酸酯化的硅氧烷树脂而制备。使用UVAloc 1000在约120mW/cm2下完成固化，并且测量了实验介质的玻璃薄片手工固定所需要的固化时间。六个样品的时间均为30秒。脱粘力，以剥离强度测定，对其进行计算并标准化为N/25mm。脱粘力和以10wt％添加的具体丙烯酸酯化或甲基丙烯酸酯化的硅氧烷树脂如表8所记录。
这些结果表明光引发剂以及额外的丙烯酸酯化和/或甲基丙烯酸酯化的硅氧烷树脂的添加有利于更快地设置或固定粘合剂，从而提供更快的总体生产过程。

Claims (15)

1.可脱粘粘合剂组合物，包含：
(A)1,3,5,7-四乙烯基-1,3,5,7-四甲基环四硅氧烷上的乙烯基基团和硅烷或具有末端Si-H氢的硅氧烷上的末端Si-H氢之间反应的硅氢化反应产物，
(B)用于硅氢化反应产物的交联剂，以及
(C)金属催化剂和/或自由基引发剂。
2.根据权利要求1的可脱粘粘合剂，其中(A)的硅烷或具有末端Si-H氢的硅氧烷的结构如下：
其中R选自由C1至C10烷基基团、芳基基团、氧、-(O-SiMe2)n-O-、-(O-SiAr2)n-O-、-(O-SiMeAr)n-O-，以及这些基团任意组合组成的组，其中n至少为数字1，Me是甲基基团，并且Ar是芳基基团；并且其中R1、R2、R3、R4、R5和R6各自独立地为C1至C10烷基基团或芳基基团。
3.根据权利要求2的可脱粘粘合剂，其中硅烷或具有末端Si-H氢的硅氧烷选自由聚二甲基硅氧烷、聚甲基苯基硅氧烷和四甲基二硅氧烷组成的组。
4.根据权利要求1的可脱粘粘合剂，其中用于硅氢化产物(A)的交联剂(B)选自由聚(甲基氢)硅氧烷、甲基氢硅氧烷-二甲基硅氧烷共聚物、二甲基甲硅烷基苯基醚、聚甲基苯基硅氧烷以及聚(甲基氢)苯基硅氧烷组成的组。
5.权利要求1的可脱粘粘合剂，其中自由基引发剂是光引发剂。
6.权利要求1的可脱粘粘合剂，其中硅氢化反应产物(A)与交联剂(B)的摩尔当量比例的范围为6-0.6:1。
7.权利要求1的可脱粘粘合剂，进一步包含丙烯酸酯化和/或甲基丙烯酸酯化的聚硅氧烷。
8.基材和载体以及放置于之间的可脱粘粘合剂的组件，其中可脱粘粘合剂包含：
(A)1,3,5,7-四乙烯基-1,3,5,7-四甲基环四硅氧烷上的乙烯基基团和硅烷或具有末端Si-H氢的硅氧烷上的末端Si-H氢之间反应的硅氢化反应产物，
(B)用于硅氢化反应产物的交联剂，以及
(C)金属催化剂或自由基引发剂。
9.权利要求8的组件，其中(A)的硅烷或具有末端Si-H氢的硅氧烷的结构如下：
其中R选自由C1至C10烷基基团、芳基基团、氧、-(O-SiMe2)n-O-、-(O-SiAr2)n-O-、-(O-SiMeAr)n-O-，以及这些基团任意组合组成的组，其中n至少为数字1，Me是甲基基团，并且Ar是芳基基团；以及其中R1、R2、R3、R4、R5和R6各自独立地为C1至C10烷基基团或芳基基团。
10.权利要求9的组件，其中硅烷或具有末端Si-H氢的硅氧烷选自由聚二甲基硅氧烷、聚甲基苯基硅氧烷和四甲基二硅氧烷组成的组。
11.权利要求8的组件，其中用于硅氢化产物(A)的交联剂(B)选自由聚(甲基氢)硅氧烷、甲基氢硅氧烷-二甲基硅氧烷共聚物、二甲基甲硅烷基苯基醚、聚甲基苯基硅氧烷以及聚(甲基氢)苯基硅氧烷组成的组。
12.权利要求8的组件，其中可脱粘粘合剂中的自由基引发剂是光引发剂。
13.权利要求8的组件，其中硅氢化反应产物(A)与交联剂(B)的摩尔当量比例的范围为6-0.6:1。
14.权利要求8的组件，其中可脱粘粘合剂进一步包含丙烯酸酯化和/或甲基丙烯酸酯化的聚硅氧烷。
15.一种从载体上将基材脱粘的方法，包括：
(A)提供基材和载体，
(B)在基材和/或载体上设置根据权利要求1所述的可脱粘粘合剂组合物，
(C)将基材和载体接触以使所述可脱粘粘合剂组合物置于其之间，形成组件，
(D)在温度或温度范围内加热组件以将基材粘合，或
(E)将组件暴露于辐射中以将基材粘合，或
(F)将组件暴露于辐射中并随后加热以将基材粘合，以及
(G)使组件达到环境温度并且将基材以机械方式分离。
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KR20160026862A (ko) 2016-03-09
EP3017012A4 (en) 2017-04-05
EP3017012A1 (en) 2016-05-11
JP2016529342A (ja) 2016-09-23
JP6241801B2 (ja) 2017-12-06
KR101930128B1 (ko) 2018-12-17
WO2015000150A1 (en) 2015-01-08
US20160068720A1 (en) 2016-03-10
EP3017012B1 (en) 2018-03-21
TW201510152A (zh) 2015-03-16

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