CN110055005B - 电磁波屏蔽体形成用遮蔽带 - Google Patents

电磁波屏蔽体形成用遮蔽带 Download PDF

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CN110055005B
CN110055005B CN201910046967.6A CN201910046967A CN110055005B CN 110055005 B CN110055005 B CN 110055005B CN 201910046967 A CN201910046967 A CN 201910046967A CN 110055005 B CN110055005 B CN 110055005B
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adhesive layer
active energy
meth
masking tape
acrylate
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CN110055005A (zh
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大川雄士
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Nitto Denko Corp
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Nitto Denko Corp
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Abstract

提供电磁波屏蔽体形成用遮蔽带，其为电磁波屏蔽体形成时所用的遮蔽带，对凹凸的追随性优异、并且可从凹凸面无残胶地剥离。本发明的电磁波屏蔽体形成用遮蔽带具备弹性模量通过活性能量射线照射而成为活性能量射线照射前的20倍以上的粘合剂层，该粘合剂层的活性能量射线照射后的弹性模量为500MPa以下。

Description

电磁波屏蔽体形成用遮蔽带
技术领域
本发明涉及电磁波屏蔽体形成用遮蔽带。
背景技术
以往，在电子部件上设置有电磁波屏蔽体，实现了防止来自外部的电磁波导致的该电子部件的误动作、或防止由该电子部件产生的电磁波的泄漏。近年来，从电子部件的小型化的观点出发，通过溅射、镀覆、喷涂等方法在电子部件上直接形成电磁波屏蔽体(金属层)(例如，专利文献1)。此时，在电极形成面等不需要形成电磁波屏蔽体的面，为了遮蔽该面而粘附粘合带。
作为上述电子部件，有时使用具有凹凸面的电子部件(例如，具备凸块的电子部件)。对于遮蔽这种电子部件的凹凸面时使用的粘合带，要求良好地追随凹凸从而不在粘合带与粘附面之间产生不需要的空隙、在电磁波屏蔽体形成后可无残胶地剥离。
现有技术文献
专利文献
专利文献1：日本特开2014-183180号公报
发明内容
发明要解决的问题
本发明的课题在于，提供电磁波屏蔽体形成时所用的遮蔽带，该遮蔽带对凹凸的追随性优异、并且可从凹凸面无残胶地剥离。
用于解决问题的方案
本发明的电磁波屏蔽体形成用遮蔽带具备弹性模量通过活性能量射线照射而成为活性能量射线照射前的20倍以上的粘合剂层，该粘合剂层的活性能量射线照射后的弹性模量为500MPa以下。
1个实施方式中，上述电磁波屏蔽体形成用遮蔽带还具备基材，在该基材的至少一侧配置有前述粘合剂层。
1个实施方式中，上述电磁波屏蔽体形成用遮蔽带还具备配置于上述粘合剂层的一侧的中间层。
1个实施方式中，上述电磁波屏蔽体形成用遮蔽带还具备配置于上述粘合剂层与上述基材之间的中间层。
1个实施方式中，上述粘合剂层的弹性模量(活性能量射线照射前)为0.07MPa～0.70MPa。
1个实施方式中，上述中间层的弹性模量为0.07MPa～0.30MPa。
1个实施方式中，上述电磁波屏蔽体形成用遮蔽带供于进行60℃～300℃的加热的加热工序。
1个实施方式中，上述电磁波屏蔽体形成用遮蔽带用于具有高度50μm以上的凸块的面的遮蔽。
发明的效果
根据本发明，形成弹性模量可通过活性能量射线的照射而变化的粘合剂层，并将该弹性模量设为特定的范围，从而能够提供电磁波屏蔽体形成时所用的遮蔽带，该遮蔽带对凹凸的追随性优异、并且可从凹凸面无残胶地剥离。
附图说明
图1为本发明的1个实施方式的电磁波屏蔽体形成用遮蔽带的截面示意图。
图2为本发明的另一实施方式的电磁波屏蔽体形成用遮蔽带的截面示意图。
附图标记说明
10 基材
20 粘合剂层
30 中间层
100 遮蔽带
具体实施方式
A.电磁波屏蔽体形成用遮蔽带的概要
图1为本发明的1个实施方式的电磁波屏蔽体形成用遮蔽带的截面示意图。该实施方式的电磁波屏蔽体形成用遮蔽带100具备基材10和配置于基材10的至少一侧的粘合剂层20。虽然未图示，但本发明的遮蔽带可以在直至供于使用之前的期间内出于保护粘合面的目的而在粘合剂层的外侧设置有剥离衬垫。需要说明的是，以下，本说明书中，有时也将电磁波屏蔽体形成用遮蔽带简称为遮蔽带。
本发明的遮蔽带具备的粘合剂层的弹性模量可通过活性能量射线的照射而变化。更具体而言，上述粘合剂层的弹性模量通过活性能量射线的照射而变高，弹性模量成为活性能量射线照射前的20倍以上。作为活性能量射线，例如，可列举出γ射线、紫外线、可见光、红外线(热射线)、无线电波、α射线、β射线、电子束、等离子体流、电离射线、粒子束等。1个实施方式中，活性能量射线的照射为累积光量500mJ/cm2～4000mJ/cm2(优选800mJ/cm2～1500mJ/cm2、更优选1000mJ/cm2～1500mJ/cm2)的紫外线(使用以波长365nm为中心的高压汞灯)照射。粘合剂层的温度会因长时间照射而成为100℃以上的情况下，优选分多次进行照射。具备如上所述的粘合剂层的上述遮蔽带在粘附时具有适度的柔软性，能够追随性良好地粘附于具有凹凸的面(例如，封装体的凸块形成面)，能防止在粘附面与遮蔽带之间产生不需要的空隙。若利用这样的遮蔽带来遮蔽封装体的凸块形成面，则可防止在该封装体上设置电磁波屏蔽体时在凸块形成面上形成不需要的金属层。另一方面，在粘附后，通过活性能量射线照射，能够提高遮蔽带(实质上为粘合剂层)的弹性模量。例如，即使在带有遮蔽带的封装体供于加热工序(例如，60℃～270℃、优选60℃～200℃)的情况下，若使用本发明的遮蔽带，则粘合剂层的弹性模量高，因此也可防止该粘合剂层不必要地进入起因于凹凸而形成的空隙(例如，凸块下部与凸块形成面的间隙)。其结果，可防止在将该遮蔽带剥离掉时粘合剂层成分在粘附面上的残留(所谓残胶)。这样，本发明的成果之一是：可提供具备可表现出适于各工序的弹性模量的粘合剂层的遮蔽带作为电磁波屏蔽体形成时所用的遮蔽带。
图2为本发明的另一实施方式的电磁波屏蔽体形成用遮蔽带的截面示意图。该实施方式的电磁波屏蔽体形成用遮蔽带200还具备中间层30。中间层30配置于粘合剂层20的一侧。如图2所示，电磁波屏蔽体形成用遮蔽带200具备基材10的情况下，中间层30配置于粘合剂层20与基材10之间。1个实施方式中，中间层具有比活性能量射线照射后的粘合剂层的弹性模量低的弹性模量。通过形成中间层，从而防止粘合剂层不必要地进入起因于凹凸而形成的空隙(例如，凸块下部与凸块形成面的间隙)，并且作为遮蔽带整体会维持适度的柔软性，能够得到可良好地遮蔽凹凸面的遮蔽带。
将本发明的遮蔽带粘附于不锈钢板时的在23℃下的初始粘合力优选为0.4N/20mm以上、更优选为0.5N/20mm以上。为这样的范围时，能够得到适合作为电子部件用途的遮蔽带。将遮蔽带粘附于不锈钢板时的在23℃下的初始粘合力的上限例如为35N/20mm。需要说明的是，粘合力基于JIS Z 0237：2000来测定。具体而言，通过使2kg的辊往返1次，将遮蔽带粘附于不锈钢板(算术平均表面粗糙度Ra：50±25nm)，在23℃下放置30分钟后，在剥离角度180°、剥离速度(拉伸速度)300mm/分钟的条件下剥离遮蔽带，来进行测定。本说明书中，“初始粘合力”是指活性能量射线的照射前的粘合力。
对于本发明的遮蔽带，粘合力可以通过活性能量射线照射而降低，优选具有规定的粘合力。将遮蔽带粘附于不锈钢板，照射紫外线(累积光量500mJ/cm2～4000mJ/cm2(优选800mJ/cm2～1500mJ/cm2、更优选1000mJ/cm2～1200mJ/cm2)后的在23℃下的粘合力优选为0.07N/20mm～0.5N/20mm、更优选为0.08N/20mm～0.3N/20mm。为这样的范围时，能够得到在电子部件上形成电磁波屏蔽体的工序(例如，溅射工序、镀覆工序或喷涂工序)中可良好地遮蔽该电子部件的遮蔽带。
遮蔽带的厚度优选为70μm～600μm、更优选为80μm～500μm、进一步优选为100μm～500μm。
B.粘合剂层
如上所述，粘合剂层的弹性模量通过活性能量射线照射而成为活性能量射线照射前的20倍以上。优选的是，粘合剂层的弹性模量通过活性能量射线照射而成为活性能量射线照射前的20倍～6000倍、更优选成为50倍～5500倍、进一步优选成为100倍～4000倍。为这样的范围时，本申请发明的上述效果变得更显著。需要说明的是，本说明书中，只要没有特别说明，则“粘合剂层”是指活性能量射线照射前的粘合剂层。
上述粘合剂层的弹性模量(活性能量射线照射前)优选为0.07MPa～0.7MPa、更优选为0.075MPa～0.6MPa、进一步优选为0.08MPa～0.5MPa、特别优选为0.1MPa以上且不足0.5MPa。为这样的范围时，能够得到可适度地追随粘附面的凹凸的遮蔽带。另外，能够防止在将遮蔽带卷绕起来时遮蔽带彼此黏住。也可以对卷形状的端面部分照射活性能量射线来防止粘合剂的渗出。
上述粘合剂层的活性能量射线照射后的弹性模量为500MPa以下。为这样的范围时，在活性能量射线照射后，也可得到不易破裂的粘合剂层、可防止粘附面上的残胶。粘附面为凹凸面的情况下，有进入至凹凸中的粘合剂层破裂，从而容易产生残胶的倾向，但本发明的遮蔽带在能够防止如此产生的残胶的方面是有用的。上述粘合剂层的活性能量射线照射后的弹性模量优选为10MPa～500MPa、更优选为100MPa～470MPa、进一步优选为120MPa～400MPa。为这样的范围时，本申请发明的上述效果变得更显著。1个实施方式中，活性能量射线的照射如上所述为累积光量500mJ/cm2～4000mJ/cm2(优选800mJ/cm2～1500mJ/cm2、更优选1000mJ/cm2～1200mJ/cm2)的紫外线(使用以波长365nm为中心的高压汞灯)照射。
本说明书中，弹性模量是指室温下(23℃)的基于纳米压痕法的弹性模量。基于纳米压痕法的弹性模量可在下述条件下测定。
(测定装置及测定条件)
装置：Hysitron Inc.制Tribo Indenter
使用压头：Berkovich(三角锥型)
测定方法：单一压入测定
压入深度设定：2500nm
压入速度：2000nm/秒
测定气氛：空气中
试样尺寸：1cm×1cm
上述粘合剂层的厚度优选为3μm～500μm、更优选为5μm～450μm、进一步优选为10μm～400μm。为这样的范围时，能够得到可适度地追随粘附面的凹凸的遮蔽带。1个实施方式中，遮蔽带不具有中间层的情况下，粘合剂层的厚度优选为70μm～500μm、更优选为80μm～450μm、进一步优选为100μm～400μm。另一实施方式中，遮蔽带具有中间层的情况下，粘合剂层的厚度优选为3μm～100μm、更优选为5μm～80μm、进一步优选为10μm～50μm。遮蔽带具有中间层的情况下，可利用该中间层确保遮蔽带的柔软性，因此能够减薄粘合剂层的厚度。
1个实施方式中，粘合剂层由活性能量射线固化型粘合剂构成。
1个实施方式中，作为活性能量射线固化型粘合剂，使用包含作为母剂的基础聚合物和可与该基础聚合物键合的活性能量射线反应性化合物(单体或低聚物)的活性能量射线固化型粘合剂(A1)。另一实施方式中，使用包含活性能量射线反应性聚合物作为基础聚合物的活性能量射线固化型粘合剂(A2)。优选上述基础聚合物具有可与光聚合引发剂反应的官能团。作为该官能团，例如，可列举出羟基、羧基等。本发明中，粘合剂层的弹性模量可以通过例如基础聚合物的种类、分子量；活性能量射线反应性化合物的种类、量；活性能量射线反应性聚合物的种类、分子量；活性能量射线固化型粘合剂中包含的添加剂(例如，交联剂)的种类、量等来适当地调整。
作为上述粘合剂(A1)中使用的基础聚合物，例如，可列举出天然橡胶、聚异丁烯橡胶、苯乙烯-丁二烯橡胶、苯乙烯-异戊二烯-苯乙烯嵌段共聚物橡胶、再生橡胶、丁基橡胶、聚异丁烯橡胶、丁腈橡胶(NBR)等橡胶系聚合物；有机硅系聚合物；丙烯酸类聚合物等。这些聚合物可以单独使用或组合使用2种以上。其中优选为丙烯酸类聚合物。使用丙烯酸类聚合物时，能够形成具有适于半导体工艺的特性(例如，粘合力、弹性模量等)的粘合剂层。
上述丙烯酸类聚合物代表性地为以1种或2种以上(甲基)丙烯酸烷基酯为单体成分而形成的丙烯酸类聚合物(均聚物或共聚合)。作为上述(甲基)丙烯酸烷基酯的具体例，可列举出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸异戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸异壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等(甲基)丙烯酸C1-20烷基酯。
对于上述丙烯酸类聚合物，出于内聚力、耐热性、交联性等的改性的目的，根据需要可以包含对应于可与上述(甲基)丙烯酸烷基酯共聚的其它单体成分的结构单元。作为这样的单体成分，例如，可列举出丙烯酸、甲基丙烯酸等含羧基单体；马来酸酐、衣康酸酐等酸酐单体；(甲基)丙烯酸羟基乙酯、(甲基)丙烯酸羟基丙酯等含羟基单体；苯乙烯磺酸、烯丙基磺酸等含磺酸基单体；(甲基)丙烯酰胺、N,N-二甲基(甲基)丙烯酰胺等(N-取代)酰胺系单体；(甲基)丙烯酸氨基乙酯等(甲基)丙烯酸氨基烷基酯系单体；(甲基)丙烯酸甲氧基乙酯等(甲基)丙烯酸烷氧基烷基酯系单体；N-环己基马来酰亚胺、N-异丙基马来酰亚胺等马来酰亚胺系单体；N-甲基衣康酰亚胺、N-乙基衣康酰亚胺等衣康酰亚胺系单体；琥珀酰亚胺系单体；乙酸乙烯酯、丙酸乙烯酯、N-乙烯基吡咯烷酮、甲基乙烯基吡咯烷酮等乙烯基系单体；丙烯腈、甲基丙烯腈等氰基丙烯酸酯单体；(甲基)丙烯酸缩水甘油酯等含环氧基丙烯酸类单体；(甲基)丙烯酸聚乙二醇酯、(甲基)丙烯酸聚丙二醇酯等二醇系丙烯酸酯单体；(甲基)丙烯酸四氢糠基酯、氟(甲基)丙烯酸酯、有机硅(甲基)丙烯酸酯等具有杂环、卤素原子、硅原子等的丙烯酸酯系单体；异戊二烯、丁二烯、异丁烯等烯烃系单体；乙烯基醚等乙烯基醚系单体等。这些单体成分可以单独使用或组合使用2种以上。上述之中，更优选为含羧基单体(特别优选丙烯酸或甲基丙烯酸)或含羟基单体(特别优选(甲基)丙烯酸羟基乙酯)。导入源自这样的单体的结构单元时，可使光聚合引发剂与丙烯酸类聚合物(基础聚合物)键合，本发明的效果变得更显著。源自含羧基单体的结构单元的含有比例相对于丙烯酸类聚合物100重量份优选为0.5重量份～20重量份、更优选为1重量份～10重量份。源自含羟基单体的结构单元的含有比例相对于丙烯酸类聚合物100重量份优选为0.5重量份～20重量份、更优选为1重量份～15重量份。
作为上述粘合剂(A1)中可使用的上述活性能量射线反应性化合物，例如，可列举出具有丙烯酰基、甲基丙烯酰基、乙烯基、烯丙基、乙炔基等具有聚合性碳-碳多重键的官能团的光反应性的单体或低聚物。作为该光反应性的单体的具体例，可列举出三羟甲基丙烷三(甲基)丙烯酸酯、四羟甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇单羟基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯等(甲基)丙烯酸与多元醇的酯化物；多官能氨基甲酸酯(甲基)丙烯酸酯；环氧(甲基)丙烯酸酯；低聚酯(甲基)丙烯酸酯等。另外，可以使用甲基丙烯酰异氰酸酯、2-甲基丙烯酰氧基乙基异氰酸酯(甲基丙烯酸2-异氰酸根合乙酯)、间异丙烯基-α,α-二甲基苄基异氰酸酯等单体。作为光反应性的低聚物的具体例，可列举出上述单体的2～5聚体等。
另外，作为上述活性能量射线反应性化合物，可以使用环氧化丁二烯、甲基丙烯酸缩水甘油酯、丙烯酰胺、乙烯基硅氧烷等单体；或由该单体构成的低聚物。
进而，作为上述活性能量射线反应性化合物，可以使用鎓盐等有机盐类与分子内具有多个杂环的化合物的混合物。对于该混合物，通过活性能量射线(例如，紫外线、电子束)的照射，有机盐断裂而生成离子，其成为引发种而引起杂环的开环反应，可形成3维网络结构。作为上述有机盐类，例如，可列举出碘鎓盐、鏻盐、锑盐、锍盐、硼酸盐等。作为上述分子内具有多个杂环的化合物中的杂环，可列举出环氧乙烷、氧杂环丁烷、氧杂环戊烷、环硫乙烷、氮丙啶等。
上述粘合剂(A1)中，活性能量射线反应性化合物的含有比例相对于基础聚合物100重量份优选为0.1重量份～500重量份、更优选为1重量份～300重量份、进一步优选为2重量份～200重量份。
作为上述粘合剂(A2)中包含的活性能量射线反应性聚合物(基础聚合物)，例如，可列举出具有丙烯酰基、甲基丙烯酰基、乙烯基、烯丙基、乙炔基等具有碳-碳多重键的官能团的聚合物。作为具有活性能量射线反应性官能团的聚合物的具体例，可列举出由多官能(甲基)丙烯酸酯构成的聚合物；光阳离子聚合型聚合物；聚肉桂酸乙烯酯等含有肉桂酰基的聚合物；经重氮化的氨基酚醛清漆树脂；聚丙烯酰胺；等。
上述粘合剂(A2)还可以包含上述活性能量射线反应性化合物(单体或低聚物)。
构成上述粘合剂的基础聚合物的重均分子量优选为30万～200万、更优选为50万～150万。重均分子量可以通过GPC(溶剂：THF)来测定。
构成上述粘合剂的基础聚合物的玻璃化转变温度优选为-50℃～30℃、更优选为-40℃～20℃。为这样的范围时，能够得到耐热性优异、可适合在加热工序中使用的粘合片。
上述活性能量射线固化型粘合剂可包含光聚合引发剂。作为光聚合引发剂，可使用任意适当的光聚合引发剂。例如，可列举出BASF公司制的商品名“Irgacure 369”、“Irgacure 379ex”、“Irgacure 819”、“Irgacure OXE2”、“Irgacure 127”；Lamberti公司制的商品名“Esacure one”、“Esacure 1001m”；旭电化工业株式会社制的商品名“AdekaOptomer N-1414”、“Adeka Optomer N-1606”、“Adeka Optomer N-1717”等。光聚合引发剂的含有比例相对于粘合剂中的基础聚合物100重量份优选为1重量份～20重量份、更优选为2重量份～10重量份。
优选上述粘合剂层包含交联剂。作为交联剂，例如，可列举出异氰酸酯系交联剂、环氧系交联剂、噁唑啉系交联剂、氮丙啶系交联剂、三聚氰胺系交联剂、过氧化物系交联剂、尿素系交联剂、金属醇盐系交联剂、金属螯合物系交联剂、金属盐系交联剂、碳二亚胺系交联剂、胺系交联剂等。
上述交联剂的含有比例相对于粘合剂的基础聚合物100重量份优选为0.5重量份～10重量份、更优选为1重量份～8重量份。为这样的范围时，能够形成适当地调整了弹性模量的粘合剂层。进而，使用包含具有碳-碳双键的基础聚合物的粘合剂的情况下，通过使交联剂(优选异氰酸酯系交联剂)的含有比例为上述范围，从而能够提高加热后的碳-碳双键的上述残留率。其结果，能够得到即使加热也可良好地固化的粘合剂层。
1个实施方式中，优选使用异氰酸酯系交联剂。异氰酸酯系交联剂在可与多种官能团反应的方面是优选的。作为上述异氰酸酯系交联剂的具体例，可列举出亚丁基二异氰酸酯、六亚甲基二异氰酸酯等低级脂肪族多异氰酸酯类；亚环戊基二异氰酸酯、亚环己基二异氰酸酯、异佛尔酮二异氰酸酯等脂环族异氰酸酯类；2,4-甲苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、苯二甲基二异氰酸酯等芳香族异氰酸酯类；三羟甲基丙烷/甲苯二异氰酸酯三聚体加成物(Nippon Polyurethane Industry Co.,Ltd.制、商品名“CORONATE L”)、三羟甲基丙烷/六亚甲基二异氰酸酯三聚体加成物(Nippon Polyurethane Industry Co.,Ltd.制、商品名“CORONATE HL”)、六亚甲基二异氰酸酯的异氰脲酸酯体(Nippon PolyurethaneIndustry Co.,Ltd.制、商品名“CORONATE HX”)等异氰酸酯加成物；等。优选使用具有3个以上异氰酸酯基的交联剂。
活性能量射线固化型粘合剂根据需要可以还含有任意适当的添加剂。作为添加剂，例如，可列举出活性能量射线聚合促进剂、自由基捕捉剂、增粘剂、增塑剂(例如，偏苯三酸酯系增塑剂、均苯四甲酸酯系增塑剂等)、颜料、染料、填充剂、防老剂、导电材料、抗静电剂、紫外线吸收剂、光稳定剂、剥离调节剂、软化剂、表面活性剂、阻燃剂、抗氧化剂等。
C.基材
上述基材可以由任意适当的树脂构成。作为该树脂，例如，可列举出低密度聚乙烯、直链状聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、无规共聚聚丙烯、嵌段共聚聚丙烯、均聚聚丙烯、聚丁烯、聚甲基戊烯等聚烯烃、乙烯-乙酸乙烯酯共聚物、离聚物树脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯(无规、交替)共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物、聚氨酯、聚萘二甲酸乙二醇酯等聚酯、聚酰亚胺、聚醚酮、聚苯乙烯、聚氯乙烯、聚偏氯乙烯、氟树脂、硅树脂、纤维素系树脂、及它们的交联体等。
构成上述基材的树脂的玻璃化转变温度优选为60℃～500℃、更优选为100℃～500℃。为这样的范围时，能够得到耐热性优异、可适合在加热工序中使用的粘合片。需要说明的是，“玻璃化转变温度”是指在DMA法(拉伸法)中在升温速度5℃/分钟、样品宽度5mm、卡盘间距离20mm、频率10Hz的条件下确认到的显示损耗角正切(tanδ)的峰的温度。
上述基材的厚度优选为12μm～250μm、更优选为25μm～200μm、进一步优选为50μm～150μm。
上述基材的弹性模量优选为300MPa～6000MPa、更优选为400MPa～5000MPa。为这样的范围时，能够得到可适度地追随粘附面的凹凸的遮蔽带。
对于上述基材的表面，为了提高与邻接的层的密合性及保持性等，可以实施任意表面处理。作为上述表面处理，例如，可列举出铬酸处理、臭氧暴露、火焰暴露、高压电击暴露、电离辐射线处理等化学处理或物理处理、涂布处理。
D.中间层
中间层的弹性模量优选比活性能量射线照射后的粘合剂层的弹性模量低。另外，中间层可以为其弹性模量通过活性能量射线照射而变化的构成，优选活性能量射线照射后的中间层的弹性模量比活性能量射线照射后的粘合剂层的弹性模量低。
中间层的弹性模量(弹性模量通过活性能量射线照射而变化的情况下为紫外线照射前的弹性模量)优选为0.07MPa～0.7MPa、更优选为0.075MPa～0.6MPa、进一步优选为0.08MPa～0.5MPa。为这样的范围时，能够得到可适度地追随粘附面的凹凸的遮蔽带。
中间层的弹性模量通过活性能量射线照射而变化的情况下，活性能量射线照射后的中间层的弹性模量优选为0.05MPa～25MPa、更优选为0.08MPa～20MPa、进一步优选为0.1MPa～15MPa。为这样的范围时，能够得到可适度地追随粘附面的凹凸的遮蔽带。
中间层的厚度优选为100μm～500μm、更优选为200μm～400μm。为这样的范围时，能够得到可适度地追随粘附面的凹凸的遮蔽带。
上述遮蔽带具备中间层的情况下，中间层的厚度与粘合剂层的厚度的合计厚度优选为103μm～510μm、更优选为120μm～450μm、进一步优选为160μm～400μm。为这样的范围时，能够得到可适度地追随粘附面的凹凸的遮蔽带。
作为构成上述中间层的材料，可使用任意适当的材料。1个实施方式中，作为中间层的构成材料，使用包含上述B项中说明的基础聚合物(优选丙烯酸类聚合物)的中间层形成用组合物(B1)、包含上述B项中说明的基础聚合物(优选丙烯酸类聚合物)和上述B项中说明的活性能量射线反应性化合物(单体或低聚物)的中间层形成用组合物(B2)、或包含上述B项中说明的活性能量射线反应性聚合物的中间层形成用组合物(B3)。1个实施方式中，使用可通过活性能量射线照射而固化的组合物作为中间层形成用组合物的情况下，本发明的遮蔽带以具备固化后的中间层的遮蔽带的形式来提供。换言之，该实施方式中，上述遮蔽带具备固化后的中间层和固化前的粘合剂层。
中间层形成用组合物(B2)中，活性能量射线反应性化合物的含有比例相对于基础聚合物100重量份优选为0.01重量份～50重量份、更优选为0.03重量份～40重量份、进一步优选为0.04重量份～30重量份。
上述中间层形成用组合物可包含光聚合引发剂。作为光聚合引发剂，可以使用任意适当的光聚合引发剂。例如，可列举出BASF公司制的商品名“Irgacure 369”、“Irgacure379ex”、“Irgacure 819”、“Irgacure OXE2”、“Irgacure 127”；Lamberti公司制的商品名“Esacure one”、“Esacure 1001m”；旭电化工业株式会社制的商品名“Adeka Optomer N-1414”、“Adeka Optomer N-1606”、“Adeka Optomer N-1717”等。光聚合引发剂的含有比例相对于中间层形成用组合物中的基础聚合物100重量份优选为0.5重量份～20重量份、更优选为2重量份～10重量份。
优选上述中间层形成用组合物包含交联剂。作为交联剂，例如，可列举出异氰酸酯系交联剂、环氧系交联剂、噁唑啉系交联剂、氮丙啶系交联剂、三聚氰胺系交联剂、过氧化物系交联剂、尿素系交联剂、金属醇盐系交联剂、金属螯合物系交联剂、金属盐系交联剂、碳二亚胺系交联剂、胺系交联剂等。
上述交联剂的含有比例相对于中间层形成用组合物的基础聚合物100重量份优选为0.1重量份～10重量份、更优选为0.5重量份～8重量份。
1个实施方式中，优选使用异氰酸酯系交联剂。作为上述异氰酸酯系交联剂的具体例，可列举出上述B项中说明的化合物。
中间层形成用组合物根据需要还可以含有任意适当的添加剂。作为添加剂，例如，可列举出活性能量射线聚合促进剂、自由基捕捉剂、增粘剂、增塑剂(例如，偏苯三酸酯系增塑剂、均苯四甲酸酯系增塑剂等)、颜料、染料、填充剂、防老剂、导电材料、抗静电剂、紫外线吸收剂、光稳定剂、剥离调节剂、软化剂、表面活性剂、阻燃剂、抗氧化剂等。
E.遮蔽带的制造方法
上述遮蔽带可以通过任意适当的方法来制造。例如可以在基材上涂覆上述粘合剂来得到遮蔽带。作为涂覆方法，可以采用棒涂机涂覆、气刀涂覆、凹版涂覆、凹版反向涂覆、反向辊涂覆、唇涂覆、模涂覆、浸渍涂覆、胶版印刷、柔性印刷、丝网印刷等各种方法。另外，也可以采用另行在剥离衬垫上形成粘合剂层后，使其贴合于基材的方法等。另外，遮蔽带具备中间层的情况下，可以在基材上涂覆中间层形成用组合物(根据需要，使其固化)而形成中间层后，将上述粘合剂涂覆到中间层上来获得该遮蔽带。
F.遮蔽带的用途
对于本发明的遮蔽带，在具有凹凸面的电子部件(例如，具备凸块的电子部件)上设置电磁波屏蔽体时，可适合在遮蔽不需要形成电磁波屏蔽体的凹凸面(凸块形成面)时使用。另外，可适合用作将经遮蔽的电子部件供于加热工序时的遮蔽带。
1个实施方式中，本发明的遮蔽带用于具有高度为50μm以上(例如，50μm～400μm)的凸块的面的遮蔽。通常，在该面设置有多个凸块。该凸块的配置间隔例如为100μm～500μm。另外，1个实施方式中，凸块的俯视形状为圆形，其直径为100μm～300μm。若使用本发明的遮蔽带，则能够良好地遮蔽具有如上所述的凸块的面，另外，本发明的遮蔽带能够从该面无残胶地剥离。
1个实施方式中，本发明的遮蔽带供于进行60℃～270℃(优选60℃～200℃)的加热的加热工序。更详细而言，本发明的遮蔽带在通过活性能量射线的照射使粘合剂层高弹性模量化后供于上述加热工序。本发明的遮蔽带即使在供于这样的工序的情况下，也能防止粘合剂层不必要地进入起因于凹凸而形成的空隙(例如，凸块下部与凸块形成面的间隙)。其结果，若使用本发明的遮蔽带，则在需要剥离该遮蔽带的工序中可防止残胶。
实施例
以下，通过实施例具体地对本发明进行说明，但本发明不受这些实施例的限定。实施例中的试验及评价方法如下。另外，只要没有特别说明，则“份”及“％”为重量基准。
(1)弹性模量
将遮蔽带的粘合剂层切出为1cm见方，将其作为测定用试样。将测定用试样固定于规定的支撑体，用纳米压痕仪测定弹性模量。
纳米压痕仪装置以及测定条件如下述。
(测定装置及测定条件)
装置：Hysitron Inc.制Tribo Indenter
使用压头：Berkovich(三角锥型)
测定方法：单一压入测定
压入深度设定：2500nm
压入速度：2000nm/秒
测定气氛：空气中、23℃
试样尺寸：1cm×1cm
另外，使用日东精机株式会社制的UM-810，对粘合剂层照射累积光量1000mJ/cm2的紫外线，然后，通过上述方法测定粘合剂层的弹性模量。
(2)遮蔽带的浮起评价
将遮蔽带粘附于BGA半导体封装体的凸块形成面，使用日东精机株式会社制的UM-810，对粘合剂层照射累积光量1000mJ/cm2的紫外线。然后，用SHIBAURA MECHATRONICSCORPORATION制的CCS-1300，通过溅射在封装体上制作由SUS0.2μm/Cu5μm/SUS0.5μm构成的层。接着，将遮蔽带剥离，用显微镜观察凸块面，根据封装体周边部的金属侵入量，按照下述基准对遮蔽带的浮起进行评价。需要说明的是，BGA半导体封装体使用尺寸10mm×10mm×0.9mmt、BGA(凸块)的高度为200μm、直径为200μm的封装体。另外，遮蔽带的粘附在40℃的环境下、通过使2kg的橡胶辊往返1次来进行。
〇：封装体的周边的金属侵入为50μm以下
×：封装体的周边的金属侵入为100μm以上
(3)遮蔽带的残胶评价
如上述(2)那样，将遮蔽带粘附于BGA半导体封装体后，使用日东精机株式会社制的UM-810，对粘合剂层照射累积光量1000mJ/cm2的紫外线。然后，将遮蔽带剥离，用SEM(50倍)确认残留于凸块形成面的粘合剂层成分的有无。
〇：没有残胶
Δ：以几十μm水平少量存在可认为电连接没问题的残胶
×：多处观察到100μm以上的残胶
[制造例1]粘合剂A的制备
在具备冷却管、氮气导入管、温度计及搅拌装置的反应容器中放入丙烯酸2-乙基己酯(以下，称为“2EHA”。)88.8份、丙烯酸-2-羟基乙酯(以下，称为“HEA”。)11.2份、过氧化苯甲酰0.2份及甲苯65份，在氮气气流中、在61℃下进行6小时聚合处理，得到重均分子量85万的丙烯酸类聚合物A。2EHA与HEA的摩尔比为100mol：20mol。
在该丙烯酸类聚合物A中加入2-甲基丙烯酰氧基乙基异氰酸酯(以下，称为“MOI”。)12份(相对于HEA为80mol％)，在空气气流中、在50℃下进行48小时加成反应处理，得到丙烯酸类聚合物A’。
接着，相对于丙烯酸类聚合物A’100份，加入多异氰酸酯化合物(商品名“CORONATEL”、Nippon Polyurethane Industry Co.,Ltd.制)2.5份、及光聚合引发剂(商品名“Irgacure 127”、BASF公司制)5份、二季戊四醇五丙烯酸酯及二季戊四醇六丙烯酸酯的混合物(商品名“KAYARAD DPHA”、日本化药株式会社制)30份、和聚氨酯丙烯酸酯(商品名“紫光UV-3000B”、日本合成化学工业株式会社制)6份，制作粘合剂A。
[制造例2]粘合剂B的制备
将“KAYARAD DPHA”的配混量设为60份、将“紫光UV-3000B”的配混量设为12份，除此以外，与制造例1同样地操作，制备粘合剂B。
[制造例3]粘合剂C的制备
将“KAYARAD DPHA”的配混量设为100份、不配混“紫光UV-3000B”，除此以外，与制造例1同样地操作，制备粘合剂C。
[制造例4]粘合剂D的制备
“KAYARAD DPHA”、“紫光UV-3000B”均不配混，除此以外，与制造例1同样地操作，制备粘合剂D。
[制造例5]粘合剂E的制备
将“KAYARAD DPHA”的配混量设为130份、不配混“紫光UV-3000B”，除此以外，与制造例1同样地操作，制备粘合剂E。
[制造例6]中间层的制作
将丙烯酸2-乙基己酯(2EHA)90份、丙烯酸(AA)10份、光聚合引发剂(商品名“Irgacure 184”、BASF公司制)0.05份、及光聚合引发剂(商品名“Irgacure 651”、BASF公司制)0.05份投入到4口烧瓶中。然后，将混合物在氮气气氛下暴露于紫外线而部分地进行光聚合，由此得到聚合率约8质量％的部分聚合物(丙烯酸类聚合物浆液)。
在上述丙烯酸类聚合物浆液100份中添加光聚合引发剂(商品名“Irgacure 651”、BASF公司制)0.04份及二季戊四醇六丙烯酸酯0.04份后，将它们均匀混合，制备中间层形成用组合物。
将上述的丙烯酸类粘合剂组合物以最终厚度成为300μm的方式涂布于用有机硅对单面进行了剥离处理的厚度38μm的聚酯薄膜(商品名：MRF、三菱化学聚酯株式会社制)的剥离处理面，形成涂布层。接着，将用有机硅对单面进行了剥离处理的厚度38μm的聚酯薄膜(商品名：MRE、三菱化学聚酯株式会社制)以该薄膜的剥离处理面成为涂布层侧的方式层叠于所涂布的丙烯酸类粘合剂组合物的表面。由此，将光学用丙烯酸类粘合剂组合物的涂布层(粘合剂层)与氧遮断。对如此得到的层叠体，使用高压汞灯(TOSHIBA LIGHTING&TECHNOLOGY CORPORATION制)，照射照度200mW/cm2(用在约350nm具有最大灵敏度的TOPCONUVR-T1进行测定)的紫外线至紫外线达到光量3000mW/cm2为止，得到被聚酯薄膜夹持的中间层。
[实施例1-1]
将粘合剂A涂布于PET基材(厚度：100μm)的实施了有机硅处理的面上，在120℃下进行2分钟加热交联，形成厚度10μm的粘合剂层。
接着，将制造例6中得到的中间层转印至上述粘合剂层后，在50℃的环境下保存48小时，得到遮蔽带(基材(100μm)/中间层(300μm)/粘合剂层(10μm))。
将所得遮蔽带供于上述评价(2)及(3)。将结果示于表1。
[实施例2-1、实施例3-1、比较例1-1、比较例2-1]
使用表1所示的粘合剂来代替粘合剂A，除此以外，与实施例1-1同样地操作，得到遮蔽带。将所得遮蔽带供于上述评价(2)及(3)。将结果示于表1。
[实施例1-2]
将粘合剂A涂布于PET基材(厚度：100μm)的实施了有机硅处理的面上，在80℃下进行5分钟加热交联，形成了厚度135μm的粘合剂层a。
另行在PET剥离衬垫上涂布粘合剂A，在80℃下进行5分钟加热交联，形成厚度135μm的粘合剂层b。
将粘合剂层b转印至粘合剂层a，然后，将所得层叠体在50℃下保存48小时，得到具有厚度270μm的粘合剂层的遮蔽带。
将所得遮蔽带供于上述评价(2)及(3)。将结果示于表1。
[实施例2-2、实施例3-2、比较例1-2、比较例2-2]
使用表1所示的粘合剂来代替粘合剂A，除此以外，与实施例1-2同样地操作，得到遮蔽带。将所得遮蔽带供于上述评价(2)及(3)。将结果示于表1。
[表1]
Figure BDA0001949530910000211
产业上的可利用性
本发明的遮蔽带可以适合用作真空工艺(例如，半导体制造中的真空工艺)用的遮蔽带。

Claims (3)

1.一种电磁波屏蔽体形成用遮蔽带，其具备弹性模量通过活性能量射线照射而成为活性能量射线照射前的20倍以上的粘合剂层，
该粘合剂层的活性能量射线照射后的弹性模量为500MPa以下，
所述电磁波屏蔽体形成用遮蔽带还具备基材、和配置于所述粘合剂层与所述基材之间的中间层，所述中间层的弹性模量为0.07MPa～0.70MPa，所述粘合剂层的活性能量射线照射前的弹性模量为0.07MPa～0.70MPa，中间层的弹性模量比活性能量射线照射后的粘合剂层的弹性模量低。
2.根据权利要求1所述的电磁波屏蔽体形成用遮蔽带，其供于进行60℃～270℃的加热的加热工序。
3.根据权利要求1所述的电磁波屏蔽体形成用遮蔽带，其用于具有高度50μm以上的凸块的面的遮蔽。
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