CN111592836A - 一种uv解粘压敏胶组合物和压敏胶带 - Google Patents

一种uv解粘压敏胶组合物和压敏胶带 Download PDF

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CN111592836A
CN111592836A CN201910135583.1A CN201910135583A CN111592836A CN 111592836 A CN111592836 A CN 111592836A CN 201910135583 A CN201910135583 A CN 201910135583A CN 111592836 A CN111592836 A CN 111592836A
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sensitive adhesive
pressure
debonding
adhesive composition
ultraviolet
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CN111592836B (zh
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杨超
崔伟
殷冠南
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3M Innovative Properties Co
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3M Innovative Properties Co
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Priority to TW108111698A priority patent/TWI706015B/zh
Priority to US17/310,145 priority patent/US20220089915A1/en
Priority to PCT/IB2020/051260 priority patent/WO2020170099A1/en
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Abstract

本发明提供一种UV解粘压敏胶组合物和包含其的胶带。UV解粘压敏胶组合物包含聚丙烯酸酯压敏胶、可紫外光聚合的聚氨酯型寡聚物、阳离子型光引发剂和自由基型光引发剂，其中聚丙烯酸酯压敏胶的聚合单体包含具有环氧官能团的丙烯酸类单体。该UV解粘压敏胶组合物在紫外光照射后粘接力大幅下降，并且没有残胶。

Description

一种UV解粘压敏胶组合物和压敏胶带
技术领域
本发明涉及压敏胶领域，具体涉及UV解粘压敏胶组合物和包含其的压敏胶带。
背景技术
可紫外光解粘的压敏胶也称为UV解粘胶，是指一类可以通过UV光激发导致粘接力降低的压敏胶。UV解粘胶具有施工方便，初始粘结力高，UV解粘后易于移除的特点。UV解粘胶可以用于半导体加工，作为晶圆切割的临时固定与保护胶带。其也可以用于外观件在制造加工过程中的临时保护。其还可以应用在柔性电路板的制成输运胶带。其良好的粘接力，可以保证柔性电路板在化镍化金过程中不会脱落，同时经过解粘后易于移除，防止了柔性电路板在移除保护胶带时因为粘接力过大而导致的形变。其还可以应用在医疗领域，普通的医用胶带长期贴在皮肤上，粘接力会逐渐变大。对于部分皮肤比较脆弱的区域，移除普通医用胶带会导致皮肤撕裂。医用的UV解粘胶可以通过低剂量的UV光照射降低粘接力，降低病人在胶带移除时的痛苦。相比于传统保护膜，UV解粘胶在保护工程中粘接力更高，并且在解粘后更容易移除。
现有的UV解粘胶典型地由压敏胶，可紫外光聚合的寡聚物(也称为UV寡聚物，或解粘树脂)和自由基型光引发剂组成。压敏胶提供初始的粘接力。当受到紫外光照射时，UV寡聚物在自由基型光引发剂作用下发生交联反应，使得解粘胶整体的模量提高。这样，胶层变硬并且失去粘接力。
然而，现有的解粘胶组合物在进行解粘时，压敏胶与UV寡聚物的相互作用通常仅有分子链相互作用。压敏胶与UV寡聚物的相互作用不足常常导致压敏胶未受UV寡聚物的影响，进而导致在局部形成残胶，或者粘接力下降不足乃至异常变大。
发明内容
在一个方面，本发明提供一种UV解粘压敏胶组合物，所述UV解粘压敏胶组合物包含：
20至80重量份的聚丙烯酸酯压敏胶，所述聚丙烯酸酯压敏胶的聚合单体包含具有环氧官能团的丙烯酸类单体；
20至80重量份的可紫外光聚合的聚氨酯型寡聚物，所述可紫外光聚合的聚氨酯型寡聚物在紫外聚合后的玻璃化转变温度为60℃以上；
0.1至5重量份的阳离子型光引发剂；和
0.1至5重量份的自由基型光引发剂。
在一个实施方案中，所述可紫外光聚合的聚氨酯型寡聚物在紫外聚合后的玻璃化转变温度为90℃以上。
在一个实施方案中，所述具有环氧官能团的丙烯酸类单体占所述聚丙烯酸酯压敏胶的聚合单体的0.1重量％-10重量％。
在一个实施方案中，所述具有环氧官能团的丙烯酸类单体包含丙烯酸缩水甘油醚或甲基丙烯酸缩水甘油醚。
在一个实施方案中，所述聚丙烯酸酯压敏胶的聚合单体还包含不具有环氧官能团的选自丙烯酸酯和丙烯酸的单体。
在一个实施方案中，所述可紫外光聚合的聚氨酯型寡聚物在25℃下的粘度为1000mPa·s至100,000mPa·s。
在一个实施方案中，所述UV解粘压敏胶组合物还包含溶剂。
在另一个方面，本发明提供一种压敏胶带，所述胶带包含：
基底膜；和
在所述基底膜上的前述UV解粘压敏胶组合物的层。
在一个实施方案中，所述基底膜选自：聚烯烃膜、聚对苯二甲酸乙二醇酯膜、聚醚醚酮膜、聚酰胺膜、和聚氨酯膜。
具体实施方式
本发明提供一种UV解粘压敏胶组合物，所述UV解粘压敏胶组合物包含：
20至80重量份的聚丙烯酸酯压敏胶，所述聚丙烯酸酯压敏胶的聚合单体包含具有环氧官能团的丙烯酸类单体；
20至80重量份的可紫外光聚合的聚氨酯型寡聚物，所述可紫外光聚合的聚氨酯型寡聚物在紫外聚合后的玻璃化转变温度为60℃以上；
0.1至5重量份的阳离子型光引发剂；和
0.1至5重量份的自由基型光引发剂。
与常规的UV解粘胶相比，本发明的解粘胶组合物中的聚丙烯酸酯压敏胶的聚合单体包含具有环氧官能团的丙烯酸类单体，并且选用聚氨酯型寡聚物和阳离子型光引发剂，其中所述聚氨酯型寡聚物在紫外聚合后的玻璃化转变温度为60℃以上，优选在90℃以上。在聚丙烯酸酯压敏胶合成时引入具有环氧官能团的单体，可以使得所得的聚丙烯酸酯压敏胶在阳离子型光引发剂的作用下也发生快速UV交联固化。聚丙烯酸酯压敏胶固化和上述聚氨酯型寡聚物引起的固化同时发生，形成独特的紫外光双固化机理。此外，选择上述聚氨酯型寡聚物作为UV寡聚物，可以在发生交联反应的同时，与聚丙烯酸酯压敏胶上的环氧基团发生化学作用。这样，当使用UV进行解粘时，本发明的解粘胶组合物同时经历聚丙烯酸酯压敏胶交联反应、寡聚物交联反应、以及聚丙烯酸酯压敏胶与寡聚物相互作用。这三个过程协同发生，带来多种优点。首先，传统UV解粘胶在发生解粘反应时，压敏胶难以与解粘树脂形成有效的相互作用，导致残胶、局部粘接力变大等问题。本发明通过在聚丙烯酸酯压敏胶中设置环氧基团并选择特定的聚氨酯型寡聚物，可以有效避免这些问题。同时，相对于传统UV解粘胶，具有环氧基团的聚丙烯酸酯压敏胶树脂本身也可以通过阳离子型光引发剂的交联机制固化，从而提升压敏胶的模量，以进一步降低粘接力。
本发明的压敏胶组合物中的聚丙烯酸酯压敏胶是由丙烯酸类聚合单体聚合而成的。可以使用任何本领域常规的可以聚合制备聚丙烯酸酯压敏胶的丙烯酸类聚合单体，只要其与本发明的原则没有冲突即可。本发明的特征在于聚丙烯酸酯压敏胶的聚合单体必须包含具有环氧官能团的丙烯酸类单体。如上所述，具有环氧官能团的丙烯酸类单体提供双固化机理以及与聚氨酯型寡聚物的有益相互作用。
具有环氧官能团的丙烯酸类单体可以占所述聚丙烯酸酯压敏胶的聚合单体的0.1重量％-10重量％。当具有环氧官能团的丙烯酸类单体在此范围内时，提供良好的解粘效果，同时不影响解粘前压敏胶组合物的粘结性，并且从成本上是有利的。
具有环氧官能团的丙烯酸类单体的优选实例包括丙烯酸缩水甘油醚或甲基丙烯酸缩水甘油醚。
聚合单体还可以包含不具有环氧官能团的选自丙烯酸酯和丙烯酸的单体。在本文中，如无特别说明，丙烯酸酯和丙烯酸也包括甲基丙烯酸酯和甲基丙烯酸。丙烯酸酯可以是例如丙烯酸烷基酯，如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸-2-乙基乙酯、丙烯酸丁酯等，和取代的丙烯酸烷基酯，如丙烯酸羟乙酯等。
本发明的压敏胶组合物中的可紫外光聚合的聚氨酯型寡聚物是一种具有碳碳双键的寡聚物。其在紫外聚合后的玻璃化转变温度应为60℃以上。具有此性能的聚氨酯型寡聚物具有优秀的通过紫外光交联降低粘接力的能力。如果使用紫外聚合后的玻璃化转变温度过低的聚氨酯型寡聚物，得到的产品粘结力下降不够，不易解粘。
聚氨酯型寡聚物在25℃下的粘度为1000mPa·s至100,000mPa·s。具有此粘度的聚氨酯型寡聚物与聚丙烯酸酯压敏胶的主链上的环氧基团发生更好的相互作用，可以更好地避免残胶出现。
聚氨酯型寡聚物可以是可商购的产品，如沙多玛公司的CN8000NS、CN9006NS、CN983NS，长兴化学的6145-100等等。
本发明的压敏胶组合物中包含的阳离子型光引发剂和自由基型光引发剂可以是任何合适的光引发剂，只要其与本发明的原则没有冲突即可。
本发明的压敏胶组合物中的聚丙烯酸酯压敏胶、可紫外光聚合的聚氨酯型寡聚物、阳离子型光引发剂和自由基型光引发剂的重量比例为20-80∶20-80∶0.1-5∶0.1-5。在此范围内时，本发明的压敏胶组合物可以同时具有良好的粘结性和良好的解粘性能。
本发明的压敏胶组合物还可以包含适当的溶剂。溶剂用于为压敏胶组合物提供良好的混合。在将压敏胶组合物制成制品如胶带后，可以将溶剂蒸发掉。
本发明的压敏胶组合物初始粘接力高，并且解粘后无残胶。UV解粘后，粘结力可以下降90％以上。
本发明还提供一种压敏胶带，所述胶带包含：
基底膜；和
在所述基底膜上的前述UV解粘压敏胶组合物的层。
基底膜可以选择任何合适的基底膜，特别是用于保护的基底膜。合适的基底膜的实例可以包括聚烯烃膜、聚对苯二甲酸乙二醇酯膜、聚醚醚酮膜、聚酰胺膜、聚氨酯膜等。聚烯烃膜可以是例如聚丙烯膜或聚乙烯膜。
本发明的压敏胶带可以通过在基底膜上涂布本发明的UV解粘压敏胶组合物制备得到。该压敏胶带具有UV解粘功能。其初始粘接力高，并且解粘后无残胶。UV解粘后，粘结力可以下降90％以上。本发明的压敏胶带可以用于半导体加工、外观件在制造加工、柔性电路板加工、以及医疗等领域中。
以下通过实施例来说明本发明。应注意，实施例仅是示例性的，不意在限制本发明的范围。
实施例1
首先合成带有环氧官能团的丙烯酸压敏胶，将丙烯酸丁酯，丙烯酸甲酯，丙烯酸和甲基丙烯酸缩水甘油醚(重量比例为60∶30∶6∶4)加入反应釜中，以甲苯为溶剂，加入过氧化苯甲酰(BPO)作为引发剂，70℃反应24h出料。将所得的压敏胶中，加入聚氨酯型寡聚物(美国沙多玛公司CN8000NS)，再加入阳离子型光引发剂和自由基型光引发剂，具体配比如下表。在以下表中，重量百分数是基于除溶剂外组分的总量。
其中，阳离子型光引发剂是台湾双键化工生产的1176。自由基型光引发剂是BASF生产的184。CN8000NS在25℃的粘度为14000mPa·s，其紫外光交联后的玻璃化转变温度为65℃。
将胶水涂布在50um聚对苯二甲酸乙二醇酯(PET)膜上，烘干即可得UV解粘保护胶带。该胶带贴覆在阳极氧化铝表面上，初始粘接力在阳极氧化铝上为0.8N/mm，经过剂量为1000mJ/cm2的UV照射后，粘接力降低为0.005N/mm，胶带移除后，阳极氧化铝表面无残胶。
组成 重量百分数
压敏胶 60
CN8000NS 36
阳离子型光引发剂 2
自由基型光引发剂 2
实施例2
首先合成带有环氧官能团的丙烯酸压敏胶，将丙烯酸-2-乙基乙酯，丙烯酸甲酯，丙烯酸和丙烯酸缩水甘油醚(重量比例为55∶35∶7∶3)加入反应釜中，以甲苯为溶剂，加入BPO作为引发剂，70℃反应24h出料。将所得的压敏胶中，加入聚氨酯型寡聚物(美国沙多玛CN8000NS)，再加入阳离子型光引发剂和自由基型光引发剂，具体配比如下表。
其中，阳离子型光引发剂是台湾双键化工生产的1176。自由基型光引发剂是台湾双键化工生产的TPO-L。CN8000NS在25℃的粘度为14000mPa·s，其紫外光交联后的玻璃化转变温度为70℃。
将胶水涂布在PET膜上，烘干即可得UV解粘保护胶带。该胶带贴覆在阳极氧化铝板上，初始粘接力为0.86N/mm，经过剂量为750mJ/cm2的UV照射后，粘接力降低为0.003N/mm，胶带移除后，阳极氧化铝板表面无残胶。
组成 重量百分数
压敏胶 50
CN8000NS 45
阳离子型光引发剂 1
自由基型光引发剂 4
实施例3
首先合成带有环氧官能团的丙烯酸压敏胶，将丙烯酸-2-乙基乙酯，甲基丙烯酸甲酯，丙烯酸羟乙酯和甲基丙烯酸缩水甘油醚(重量比例为60∶26∶10∶4)加入反应釜中，以甲苯为溶剂，加入BPO作为引发剂，70℃反应24h出料。将所得的压敏胶中，加入聚氨酯型寡聚物(长兴化学的6145-100)，再加入阳离子型光引发剂和自由基型光引发剂，具体配比如下表。
其中，阳离子型光引发剂是Irgacure 250。自由基型光引发剂是TPO。6145-100在25℃的粘度为70000mPa.s，其紫外光交联后的玻璃化转变温度为104℃。
将胶水涂布在双向拉伸聚丙烯(BOPP)膜上，烘干即可得UV解粘保护胶带。该胶带贴覆在标准钢板表面上，初始粘接力为0.92N/mm，经过剂量为1000mJ/cm2的UV照射后，粘接力降低为0.002N/mm，胶带移除后，钢板表面无残胶。
组成 重量百分数
压敏胶 44.5
6145-100 50
阳离子型光引发剂 1.5
自由基型光引发剂 4
实施例4
首先合成带有环氧官能团的丙烯酸压敏胶，将丙烯酸-2-乙基乙酯，丙烯酸甲酯，丙烯酸和丙烯酸缩水甘油醚(重量比例为55∶35∶7∶3)加入反应釜中，以甲苯为溶剂，加入BPO作为引发剂，70℃反应24h出料。将所得的压敏胶中，加入聚氨酯型寡聚物(美国沙多玛CN9006NS)，再加入阳离子型光引发剂和自由基型光引发剂，具体配比如下表。
其中，阳离子型光引发剂是CPI-100P。自由基型光引发剂是TPO。CN9006NS的粘度为2000mPa·s，其紫外光交联后的玻璃化转变温度为145℃。
将胶水涂布在PET膜上，烘干即可得UV解粘保护胶带。该胶带贴覆在标准阳极氧化铝上，初始粘接力为0.82N/mm，经过剂量为500mJ/cm2的UV照射后，粘接力降低为0.005N/mm，胶带移除后，阳极氧化铝表面无残胶。
组成 重量百分数
压敏胶 62
CN9006NS 35
阳离子型光引发剂 1
自由基型光引发剂 2
实施例5
首先合成带有环氧官能团的丙烯酸压敏胶，将丙烯酸-2-乙基乙酯，甲基丙烯酸甲酯，丙烯酸和甲基丙烯酸缩水甘油醚(重量比例为60∶26∶10∶4)加入反应釜中，以甲苯为溶剂，加入BPO作为引发剂，70℃反应24h出料。将所得的压敏胶中，加入聚氨酯型寡聚物(美国沙多玛CN983NS)，再加入阳离子型光引发剂和自由基型光引发剂，具体配比如下表。
其中，阳离子型光引发剂是CPI-100P。自由基型光引发剂是Darocur 1173。CN983NS的粘度为5500mPa·s，其紫外光交联后的玻璃化转变温度为92℃。
将胶水涂布在BOPP膜上，烘干即可得UV解粘保护胶带。该胶带贴覆在标准钢板表面上，初始粘接力为0.95N/mm，经过剂量为800mJ/cm2的UV照射后，粘接力降低为0.002N/mm，胶带移除后，钢板表面无残胶。
组成 重量百分数
压敏胶 65
CN983NS 30
阳离子型光引发剂 2
自由基型光引发剂 3
从以上实施例可以看出，本发明的组合物在UV照射后粘接力大幅降低，并且没有残胶出现。
比较例1：
与实施例1相同，但将甲基丙烯酸缩水甘油醚替换为不含环氧基团的单体。结果显示，粘接力降低为0.13N/mm，UV照射后移除，在钢板表面有残胶。
比较例2：
与实施例1相同，但将聚氨酯型寡聚物替换为CN8009NS，粘度为517mPa·s，UV照射后Tg为10℃。经过1000mJ/cm2UV照射后，结果显示，粘接力为1.01N/mm，无法实现UV解粘。
比较例3：
与实施例2相同，但未加入阳离子型光引发剂。结果显示，粘接力降低为0.2N/mm，在钢板表面有残胶。

Claims (9)

1.一种UV解粘压敏胶组合物，所述UV解粘压敏胶组合物包含：
20至80重量份的聚丙烯酸酯压敏胶，所述聚丙烯酸酯压敏胶的聚合单体包含具有环氧官能团的丙烯酸类单体；
20至80重量份的可紫外光聚合的聚氨酯型寡聚物，所述可紫外光聚合的聚氨酯型寡聚物在紫外聚合后的玻璃化转变温度为60℃以上；
0.1至5重量份的阳离子型光引发剂；和
0.1至5重量份的自由基型光引发剂。
2.根据权利要求1所述的UV解粘压敏胶组合物，其中，
所述可紫外光聚合的聚氨酯型寡聚物在紫外聚合后的玻璃化转变温度为90℃以上。
3.根据权利要求1或2所述的UV解粘压敏胶组合物，其中，
所述具有环氧官能团的丙烯酸类单体占所述聚丙烯酸酯压敏胶的聚合单体的0.1重量％-10重量％。
4.根据权利要求1或2所述的UV解粘压敏胶组合物，其中，
所述具有环氧官能团的丙烯酸类单体包含丙烯酸缩水甘油醚或甲基丙烯酸缩水甘油醚。
5.根据权利要求1或2所述的UV解粘压敏胶组合物，其中，
所述聚丙烯酸酯压敏胶的聚合单体还包含不具有环氧官能团的选自丙烯酸酯和丙烯酸的单体。
6.根据权利要求1或2所述的UV解粘压敏胶组合物，其中，
所述可紫外光聚合的聚氨酯型寡聚物在25℃下的粘度为1000mPa·s至100,000mPa·s。
7.根据权利要求1或2所述的UV解粘压敏胶组合物，其中，
所述UV解粘压敏胶组合物还包含溶剂。
8.一种压敏胶带，所述胶带包含：
基底膜；和
在所述基底膜上的根据权利要求1至7中任一项所述的UV解粘压敏胶组合物的层。
9.根据权利要求8所述的压敏胶带，其中，
所述基底膜选自：聚烯烃膜、聚对苯二甲酸乙二醇酯膜、聚醚醚酮膜、聚酰胺膜、和聚氨酯膜。
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