TW201932556A - 電磁波屏蔽形成用遮蔽帶 - Google Patents

電磁波屏蔽形成用遮蔽帶 Download PDF

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Publication number
TW201932556A
TW201932556A TW108101043A TW108101043A TW201932556A TW 201932556 A TW201932556 A TW 201932556A TW 108101043 A TW108101043 A TW 108101043A TW 108101043 A TW108101043 A TW 108101043A TW 201932556 A TW201932556 A TW 201932556A
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Taiwan
Prior art keywords
adhesive layer
masking tape
active energy
electromagnetic wave
mpa
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TW108101043A
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English (en)
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TWI795508B (zh
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大川雄士
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日商日東電工股份有限公司
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
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    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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    • C09J7/00—Adhesives in the form of films or foils
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Abstract

本發明之課題在於提供一種於形成電磁波屏蔽時使用之遮蔽帶，其對凹凸之追隨性優異、並且可自凹凸面無糊劑殘留地剝離。
本發明之電磁波屏蔽形成用遮蔽帶具備彈性模數藉由活性能量線照射而成為活性能量線照射前之20倍以上之黏著劑層，且該黏著劑層之活性能量線照射後之彈性模數為500 MPa以下。

Description

電磁波屏蔽形成用遮蔽帶
本發明係關於一種電磁波屏蔽形成用遮蔽帶。
先前，對電子零件設置電磁波屏蔽，實現防止來自外部之電磁波導致之該電子零件之誤動作、或防止由該電子零件產生之電磁波之洩漏。近年來，就電子零件之小型化之觀點而言，藉由濺鍍、鍍覆、噴塗等方法於電子零件上直接形成電磁波屏蔽(金屬層)(例如，專利文獻1)。此時，於電極形成面等無需形成電磁波屏蔽之面，為了遮蔽該面而貼合膠帶。
作為上述電子零件，有時使用具有凹凸面之電子零件(例如，具備凸塊之電子零件)。對於遮蔽此種電子零件之凹凸面時使用之膠帶，要求良好地追隨凹凸而不會於膠帶與貼合面之間產生不需要之空隙、且於形成電磁波屏蔽後可無糊劑殘留地剝離。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本專利特開2014-183180號公報
[發明所欲解決之問題]
本發明之課題在於提供一種形成電磁波屏蔽時所使用之遮蔽帶，其對凹凸之追隨性優異，並且可自凹凸面無糊劑殘留地剝離。
[解決問題之技術手段]
本發明之電磁波屏蔽形成用遮蔽帶具備彈性模數藉由活性能量線照射而成為活性能量線照射前之20倍以上之黏著劑層，且該黏著劑層之活性能量線照射後之彈性模數為500 MPa以下。
於一個實施形態中，上述電磁波屏蔽形成用遮蔽帶進而具備基材，於該基材之至少一側配置有上述黏著劑層。
於一個實施形態中，上述電磁波屏蔽形成用遮蔽帶進而具備配置於上述黏著劑層之一側之中間層。
於一個實施形態中，上述電磁波屏蔽形成用遮蔽帶進而具備配置於上述黏著劑層與上述基材之間之中間層。
於一個實施形態中，上述黏著劑層之彈性模數(活性能量線照射前)為0.07 MPa～0.70 MPa。
於一個實施形態中，上述中間層之彈性模數為0.07 MPa～0.30 MPa。
於一個實施形態中，上述電磁波屏蔽形成用遮蔽帶供於進行60℃～300℃之加熱之加熱步驟。
於一個實施形態中，上述電磁波屏蔽形成用遮蔽帶用於具有高度50 μm以上之凸塊之面之遮蔽。
[發明之效果]
根據本發明，形成彈性模數可藉由活性能量線之照射而變化之黏著劑層，並將該彈性模數設為特定之範圍，藉此能夠提供形成電磁波屏蔽時所使用之對凹凸之追隨性優異、並且可自凹凸面無糊劑殘留地剝離的遮蔽帶。
A. 電磁波屏蔽形成用遮蔽帶之概要
圖1為本發明之一個實施形態之電磁波屏蔽形成用遮蔽帶之概略剖視圖。該實施方式之電磁波屏蔽形成用遮蔽帶100具備基材10及配置於基材10之至少一側之黏著劑層20。雖然未圖示，但本發明之遮蔽帶可於供於使用前之期間內出於保護黏著面之目的而於黏著劑層之外側設置有剝離襯墊。再者，以下，本說明書中，有時亦將電磁波屏蔽形成用遮蔽帶簡稱為遮蔽帶。
本發明之遮蔽帶具備之黏著劑層之彈性模數可藉由活性能量線之照射而變化。更具體而言，上述黏著劑層之彈性模數藉由活性能量線之照射而變高，彈性模數成為活性能量線照射前之20倍以上。作為活性能量線，例如，可列舉γ射線、紫外線、可見光、紅外線(熱線)、射頻波、α射線、β射線、電子束、電漿流、游離輻射、粒子束等。於一個實施形態中，活性能量線之照射為累積光量500 mJ/cm2 ～4000 mJ/cm2 (較佳為800 mJ/cm2 ～1500 mJ/cm2 、更佳為1000 mJ/cm2 ～1500 mJ/cm2 )之紫外線(使用以波長365 nm為中心之高壓水銀燈)照射。於黏著劑層之溫度會因長時間照射而成為100℃以上之情形時，較佳為分複數次進行照射。具備如上所述之黏著劑層之上述遮蔽帶於貼合時具有適度之柔軟性，能夠追隨性良好地貼合於具有凹凸之面(例如，封裝之凸塊形成面)，能防止於貼合面與遮蔽帶之間產生不需要之空隙。若利用此種遮蔽帶來遮蔽封裝之凸塊形成面，則可防止於該封裝上設置電磁波屏蔽時於凸塊形成面上形成不需要之金屬層。另一方面，於貼合後，藉由活性能量線照射，能夠提高遮蔽帶(實質上為黏著劑層)之彈性模數。例如，即使於附遮蔽帶之封裝供於加熱步驟(例如，60℃～270℃、較佳為60℃～200℃)之情形時，若使用本發明之遮蔽帶，則由於黏著劑層之彈性模數高，故而亦能夠防止該黏著劑層不必要地進入至起因於凹凸而形成之空隙(例如，凸塊下部與凸塊形成面之間隙)。其結果，可防止於將該遮蔽帶剝離時黏著劑層成分於貼合面上之殘留(所謂糊劑殘留)。如此，本發明之成果之一為可提供具備可表現出適於各步驟之彈性模數之黏著劑層的遮蔽帶作為形成電磁波屏蔽時所使用之遮蔽帶。
圖2為本發明之另一實施形態之電磁波屏蔽形成用遮蔽帶之概略剖視圖。該實施方式之電磁波屏蔽形成用遮蔽帶200進而具備中間層30。中間層30配置於黏著劑層20之一側。如圖2所示，於電磁波屏蔽形成用遮蔽帶200具備基材10之情形時，中間層30配置於黏著劑層20與基材10之間。於一個實施形態中，中間層具有較活性能量線照射後之黏著劑層之彈性模數低之彈性模數。藉由形成中間層，從而防止黏著劑層不必要地進入至起因於凹凸而形成之空隙(例如，凸塊下部與凸塊形成面之間隙)，並且遮蔽帶整體維持適度之柔軟性，能夠獲得可良好地遮蔽凹凸面之遮蔽帶。
將本發明之遮蔽帶貼合於不鏽鋼板時於23℃下之初始黏著力較佳為0.4 N/20 mm以上、更佳為0.5 N/20 mm以上。若為此種範圍，則能夠獲得適合作為電子零件用之遮蔽帶。將遮蔽帶貼合於不鏽鋼板時於23℃下之初始黏著力之上限例如為35 N/20 mm。再者，黏著力係基於JIS Z 0237：2000來測定。具體而言，藉由使2 kg之輥往返1次，而將遮蔽帶貼合於不鏽鋼板(算術平均表面粗糙度Ra：50±25 nm)，於23℃下放置30分鐘後，於剝離角度180°、剝離速度(拉伸速度)300 mm/分鐘之條件下剝離遮蔽帶進行測定。本說明書中，「初始黏著力」係指活性能量線照射前之黏著力。
本發明之遮蔽帶雖然可藉由活性能量線照射而降低黏著力，但較佳為具有特定之黏著力。將遮蔽帶貼合於不鏽鋼板，照射紫外線(累積光量500 mJ/cm2 ～4000 mJ/cm2 (較佳為800 mJ/cm2 ～1500 mJ/cm2 、更佳為1000 mJ/cm2 ～1200 mJ/cm2 )後於23℃下之黏著力較佳為0.07 N/20 mm～0.5 N/20 mm、更佳為0.08 N/20 mm～0.3 N/20 mm。若為此種範圍，則能夠獲得於電子零件上形成電磁波屏蔽之步驟(例如，濺鍍步驟、鍍覆步驟或噴塗步驟)中可良好地遮蔽該電子零件之遮蔽帶。
遮蔽帶之厚度較佳為70 μm～600 μm、更佳為80 μm～500 μm、進而較佳為100 μm～500 μm。
B. 黏著劑層
如上所述，黏著劑層之彈性模數藉由活性能量線照射而成為活性能量線照射前之20倍以上。較佳為黏著劑層之彈性模數藉由活性能量線照射而成為活性能量線照射前之20倍～6000倍、更佳為成為50倍～5500倍、進而較佳為成為100倍～4000倍。若為此種範圍，則本案發明之上述效果變得更顯著。再者，本說明書中，只要無特別說明，則「黏著劑層」係指活性能量線照射前之黏著劑層。
上述黏著劑層之彈性模數(活性能量線照射前)較佳為0.07 MPa～0.7 MPa、更佳為0.075 MPa～0.6 MPa、進而較佳為0.08 MPa～0.5 MPa、尤佳為0.1 MPa以上且未達0.5 MPa。若為此種範圍，則能夠獲得可適度地追隨貼合面之凹凸之遮蔽帶。又，能夠防止於捲繞遮蔽帶時遮蔽帶彼此黏住。亦可對捲筒形狀之端面部分照射活性能量線來防止黏著劑之溢出。
上述黏著劑層之活性能量線照射後之彈性模數為500 MPa以下。若為此種範圍，則可獲得於活性能量線照射後亦不易破裂之黏著劑層，可防止貼合面上之糊劑殘留。於貼合面為凹凸面之情形時，有進入至凹凸之黏著劑層破裂，從而容易產生糊劑殘留之傾向，但本發明之遮蔽帶於能夠防止如此產生之糊劑殘留之方面有用。上述黏著劑層之活性能量線照射後之彈性模數較佳為10 MPa～500 MPa、更佳為100 MPa～470 MPa、進而較佳為120 MPa～400 MPa。若為此種範圍，則本案發明之上述效果變得更顯著。於一個實施形態中，活性能量線之照射如上所述為累積光量500 mJ/cm2 ～4000 mJ/cm2 (較佳為800 mJ/cm2 ～1500 mJ/cm2 、更佳為1000 mJ/cm2 ～1200 mJ/cm2 )之紫外線(使用以波長365 nm為中心之高壓水銀燈)照射。
於本說明書中，彈性模數係指室溫下(23℃)之基於奈米壓痕法之彈性模數。基於奈米壓痕法之彈性模數可於下述條件下測定。
(測定裝置及測定條件)
裝置：Hysitron Inc.製造之Tribo Indenter
使用壓頭：Berkovich(三角錐型)
測定方法：單一壓入測定
壓入深度設定：2500 nm
壓入速度：2000 nm/秒
測定氣氛：空氣中
試樣尺寸：1 cm×1 cm
上述黏著劑層之厚度較佳為3 μm～500 μm、更佳為5 μm～450 μm、進而較佳為10 μm～400 μm。若為此種範圍，則能夠獲得可適度地追隨貼合面之凹凸之遮蔽帶。於一個實施形態中，於遮蔽帶不具有中間層之情形時，黏著劑層之厚度較佳為70 μm～500 μm、更佳為80 μm～450 μm、進而較佳為100 μm～400 μm。於另一實施形態中，於遮蔽帶具有中間層之情形時，黏著劑層之厚度較佳為3 μm～100 μm、更佳為5 μm～80 μm、進而較佳為10 μm～50 μm。於遮蔽帶具有中間層之情形時，可利用該中間層確保遮蔽帶之柔軟性，因此能夠減薄黏著劑層之厚度。
於一個實施形態中，黏著劑層包含活性能量線硬化型黏著劑。
於一個實施形態中，作為活性能量線硬化型黏著劑，使用包含成為母劑之基礎聚合物及可與該基礎聚合物鍵結之活性能量線反應性化合物(單體或低聚物)的活性能量線硬化型黏著劑(A1)。於另一實施形態中，使用包含活性能量線反應性聚合物作為基礎聚合物之活性能量線硬化型黏著劑(A2)。較佳為上述基礎聚合物具有可與光聚合起始劑反應之官能基。作為該官能基，例如，可列舉羥基、羧基等。於本發明中，黏著劑層之彈性模數可藉由例如基礎聚合物之種類、分子量；活性能量線反應性化合物之種類、量；活性能量線反應性聚合物之種類、分子量；活性能量線硬化型黏著劑中包含之添加劑(例如，交聯劑)之種類、量等來適當地調整。
作為上述黏著劑(A1)中使用之基礎聚合物，例如，可列舉天然橡膠、聚異丁烯橡膠、苯乙烯-丁二烯橡膠、苯乙烯-異戊二烯-苯乙烯嵌段共聚物橡膠、再生橡膠、丁基橡膠、聚異丁烯橡膠、丁腈橡膠(NBR)等橡膠系聚合物；聚矽氧系聚合物；丙烯酸系聚合物等。該等聚合物可單獨使用或組合2種以上使用。其中較佳為丙烯酸系聚合物。若使用丙烯酸系聚合物，則能夠形成具有適於半導體製程之特性(例如，黏著力、彈性模數等)之黏著劑層。
上述丙烯酸系聚合物代表性地為以1種或2種以上(甲基)丙烯酸烷基酯為單體成分而形成之丙烯酸系聚合物(均聚物或共聚物)。作為上述(甲基)丙烯酸烷基酯之具體例，可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(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)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(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。
對於上述丙烯酸系聚合物，出於凝集力、耐熱性、交聯性等之改質之目的，可根據需要包含對應於可與上述(甲基)丙烯酸烷基酯共聚之其他單體成分之結構單元。作為此種單體成分，例如，可列舉丙烯酸、甲基丙烯酸等含羧基單體；馬來酸酐、伊康酸酐等酸酐單體；(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯等含羥基單體；苯乙烯磺酸、烯丙基磺酸等含磺酸基單體；(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺等(N-取代)醯胺系單體；(甲基)丙烯酸胺基乙酯等(甲基)丙烯酸胺基烷基酯系單體；(甲基)丙烯酸甲氧基乙酯等(甲基)丙烯酸烷氧基烷基酯系單體；N-環己基馬來醯亞胺、N-異丙基馬來醯亞胺等馬來醯亞胺系單體；N-甲基伊康醯亞胺、N-乙基伊康醯亞胺等伊康醯亞胺系單體；琥珀醯亞胺系單體；乙酸乙烯酯、丙酸乙烯酯、N-乙烯基吡咯啶酮、甲基乙烯基吡咯啶酮等乙烯基系單體；丙烯腈、甲基丙烯腈等氰基丙烯酸酯單體；(甲基)丙烯酸縮水甘油酯等含環氧基丙烯酸系單體；(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單體；(甲基)丙烯酸四氫糠基酯、氟(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯等具有雜環、鹵素原子、矽原子等之丙烯酸酯系單體；異戊二烯、丁二烯、異丁烯等烯烴系單體；乙烯基醚等乙烯基醚系單體等。該等單體成分可單獨使用或組合2種以上使用。上述之中，更佳為含羧基單體(尤佳為丙烯酸或甲基丙烯酸)或含羥基單體(尤佳為(甲基)丙烯酸羥基乙酯)。若導入源自此種單體之結構單元，則可使光聚合起始劑與丙烯酸系聚合物(基礎聚合物)鍵結，本發明之效果變得更顯著。源自含羧基單體之結構單元之含有比例相對於丙烯酸系聚合物100重量份較佳為0.5重量份～20重量份、更佳為1重量份～10重量份。源自含羥基單體之結構單元之含有比例相對於丙烯酸系聚合物100重量份較佳為0.5重量份～20重量份、更佳為1重量份～15重量份。
作為上述黏著劑(A1)中可使用之上述活性能量線反應性化合物，例如，可列舉具有丙烯醯基、甲基丙烯醯基、乙烯基、烯丙基、乙炔基等具有聚合性碳-碳多重鍵之官能基的光反應性之單體或低聚物。作為該光反應性之單體之具體例，可列舉三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(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、二季戊四醇單羥基五(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)丙烯酸與多元醇之酯化物；多官能(甲基)丙烯酸胺基甲酸酯；環氧(甲基)丙烯酸酯；(甲基)丙烯酸低聚酯等。又，可使用甲基丙烯醯異氰酸酯、異氰酸2-甲基丙烯醯氧基乙酯(甲基丙烯酸2-異氰酸基乙酯)、間異丙烯基-α,α-二甲基苄基異氰酸酯等單體。作為光反應性之低聚物之具體例，可列舉上述單體之2～5聚物等。
又，作為上述活性能量線反應性化合物，可使用環氧化丁二烯、甲基丙烯酸縮水甘油酯、丙烯醯胺、乙烯基矽氧烷等單體；或由該單體構成之低聚物。
進而，作為上述活性能量線反應性化合物，可使用鎓鹽等有機鹽類與分子內具有複數個雜環之化合物之混合物。該混合物藉由活性能量線(例如，紫外線、電子束)之照射，有機鹽斷裂而生成離子，其成為起始種而引起雜環之開環反應，可形成3維網絡結構。作為上述有機鹽類，例如，可列舉錪鹽、鏻鹽、銻鹽、鋶鹽、硼酸鹽等。作為上述分子內具有多個雜環之化合物中之雜環，可列舉環氧乙烷、氧雜環丁烷、氧雜環戊烷、環硫乙烷、氮丙啶等。
上述黏著劑(A1)中，活性能量線反應性化合物之含有比例相對於基礎聚合物100重量份較佳為0.1重量份～500重量份、更佳為1重量份～300重量份、進而較佳為2重量份～200重量份。
作為上述黏著劑(A2)中包含之活性能量線反應性聚合物(基礎聚合物)，例如，可列舉具有丙烯醯基、甲基丙烯醯基、乙烯基、烯丙基、乙炔基等具有碳-碳多重鍵之官能基之聚合物。作為具有活性能量線反應性官能基之聚合物之具體例，可列舉由多官能(甲基)丙烯酸酯構成之聚合物；光陽離子聚合型聚合物；聚肉桂酸乙烯酯等含有肉桂醯基之聚合物；經重氮化之胺基酚醛清漆樹脂；聚丙烯醯胺；等。
上述黏著劑(A2)可進而包含上述活性能量線反應性化合物(單體或低聚物)。
構成上述黏著劑之基礎聚合物之重量平均分子量較佳為30萬～200萬、更佳為50萬～150萬。重量平均分子量可藉由GPC(gel permeation chromatography，凝膠滲透層析法)(溶劑：THF(tetrahydrofuran，四氫呋喃))測定。
構成上述黏著劑之基礎聚合物之玻璃轉移溫度較佳為-50℃～30℃、更佳為-40℃～20℃。若為此種範圍，則能夠獲得耐熱性優異、可良好地用於加熱步驟之黏著片。
上述活性能量線硬化型黏著劑可包含光聚合起始劑。作為光聚合起始劑，可使用任意適當之光聚合起始劑。例如，可列舉BASF公司製造之商品名「Irgacure 369」、「Irgacure 379ex」、「Irgacure 819」、「Irgacure OXE2」、「Irgacure 127」；Lamberti公司製造之商品名「Esacure one」、「Esacure 1001m」；旭電化工業公司製造之商品名「Adeka Optomer N-1414」、「Adeka Optomer N-1606」、「Adeka Optomer N-1717」等。光聚合起始劑之含有比例相對於黏著劑中之基礎聚合物100重量份較佳為1重量份～20重量份、更佳為2重量份～10重量份。
較佳為上述黏著劑層包含交聯劑。作為交聯劑，例如，可列舉異氰酸酯系交聯劑、環氧系交聯劑、㗁唑啉系交聯劑、氮丙啶系交聯劑、三聚氰胺系交聯劑、過氧化物系交聯劑、脲系交聯劑、金屬烷氧化物系交聯劑、金屬螯合物系交聯劑、金屬鹽系交聯劑、碳二醯亞胺系交聯劑、胺系交聯劑等。
上述交聯劑之含有比例相對於黏著劑之基礎聚合物100重量份較佳為0.5重量份～10重量份、更佳為1重量份～8重量份。若為此種範圍，則能夠形成適當地調整了彈性模數之黏著劑層。進而，使用包含具有碳-碳雙鍵之基礎聚合物之黏著劑之情形時，藉由使交聯劑(較佳為異氰酸酯系交聯劑)之含有比例為上述範圍，從而能夠提高加熱後之碳-碳雙鍵之上述殘存率。其結果，能夠獲得即使加熱亦可良好地硬化之黏著劑層。
於一個實施形態中，較佳為使用異氰酸酯系交聯劑。異氰酸酯系交聯劑於可與多種官能基反應之方面而言較佳。作為上述異氰酸酯系交聯劑之具體例，可列舉二異氰酸丁二酯、六亞甲基二異氰酸酯等低級脂肪族多異氰酸酯類；二異氰酸環戊二酯、二異氰酸環己二酯、異佛爾酮二異氰酸酯等脂環族異氰酸酯類；2,4-甲伸苯基二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、苯二甲基二異氰酸酯等芳香族異氰酸酯類；三羥甲基丙烷/甲伸苯基二異氰酸酯三聚物加成物(Nippon Polyurethane Industry 公司製造、商品名「CORONATE L」)、三羥甲基丙烷/六亞甲基二異氰酸酯三聚物加成物(Nippon Polyurethane Industry公司製造、商品名「CORONATE HL」)、六亞甲基二異氰酸酯之異氰脲酸酯體(Nippon Polyurethane Industry公司製造、商品名「CORONATE HX」)等異氰酸酯加成物；等。較佳為使用具有3個以上異氰酸酯基之交聯劑。
活性能量線硬化型黏著劑根據需要可進而含有任意適當之添加劑。作為添加劑，例如，可列舉活性能量線聚合促進劑、自由基捕捉劑、黏著賦予劑、塑化劑(例如，偏苯三甲酸酯系塑化劑、均苯四甲酸酯系塑化劑等)、顏料、染料、填充劑、防老化劑、導電材、抗靜電劑、紫外線吸收劑、光穩定劑、剝離調整劑、軟化劑、界面活性劑、阻燃劑、抗氧化劑等。
C. 基材
上述基材可由任意適當之樹脂構成。作為該樹脂，例如，可列舉低密度聚乙烯、直鏈狀聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、無規共聚聚丙烯、嵌段共聚聚丙烯、均聚聚丙烯、聚丁烯、聚甲基戊烯等聚烯烴、乙烯-乙酸乙烯酯共聚物、離子聚合物樹脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯(無規、交替)共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物、聚胺基甲酸酯、聚萘二甲酸乙二酯等聚酯、聚醯亞胺、聚醚酮、聚苯乙烯、聚氯乙烯、聚偏二氯乙烯、氟樹脂、矽樹脂、纖維素系樹脂、及該等之交聯物等。
構成上述基材之樹脂之玻璃轉移溫度較佳為60℃～500℃、更佳為100℃～500℃。若為此種範圍，則能夠獲得耐熱性優異、可良好地用於加熱步驟之黏著片。再者，「玻璃轉移溫度」係指於DMA(Dynamic Mechanical Analysis，動態熱機械分析)法(拉伸法)中於升溫速度5℃/分鐘、樣品寬度5 mm、夾頭間距離20 mm、頻率10 Hz之條件下確認到之顯示損耗正切(tanδ)之峰之溫度。
上述基材之厚度較佳為12 μm～250 μm、更佳為25 μm～200 μm、進而較佳為50 μm～150 μm。
上述基材之彈性模數較佳為300 MPa～6000 MPa、更佳為400 MPa～5000 MPa。若為此種範圍，則能夠獲得可適度地追隨貼合面之凹凸之遮蔽帶。
對於上述基材之表面，為了提高與鄰接之層之密接性及保持性等，可實施任意表面處理。作為上述表面處理，例如，可列舉鉻酸處理、臭氧暴露、火焰暴露、高壓電擊暴露、游離輻射處理等化學處理或物理處理、塗佈處理。
D. 中間層
中間層之彈性模數較佳為較活性能量線照射後之黏著劑層之彈性模數低。又，中間層亦可為其彈性模數藉由活性能量線照射而變化之構成，較佳為活性能量線照射後之中間層之彈性模數較活性能量線照射後之黏著劑層之彈性模數低。
中間層之彈性模數(彈性模數藉由活性能量線照射而變化之情形時為紫外線照射前之彈性模數)較佳為0.07 MPa～0.7 MPa、更佳為0.075 MPa～0.6 MPa、進而較佳為0.08 MPa～0.5 MPa。若為此種範圍，則能夠獲得可適度地追隨貼合面之凹凸之遮蔽帶。
中間層之彈性模數藉由活性能量線照射而變化之情形時，活性能量線照射後之中間層之彈性模數較佳為0.05 MPa～25 MPa、更佳為0.08 MPa～20 MPa、進而較佳為0.1 MPa～15 MPa。若為此種範圍，則能夠獲得可適度地追隨貼合面之凹凸之遮蔽帶。
中間層之厚度較佳為100 μm～500 μm、更佳為200 μm～400 μm。若為此種範圍，則能夠獲得可適度地追隨貼合面之凹凸之遮蔽帶。
於上述遮蔽帶具備中間層之情形時，中間層之厚度與黏著劑層之厚度之合計厚度較佳為103 μm～510 μm、更佳為120 μm～450 μm、進而較佳為160 μm～400 μm。若為此種範圍，則能夠獲得可適度地追隨貼合面之凹凸之遮蔽帶。
作為構成上述中間層之材料，可使用任意適當之材料。於一個實施形態中，作為中間層之構成材料，使用包含上述B項中說明之基礎聚合物(較佳為丙烯酸系聚合物)之中間層形成用組合物(B1)、包含上述B項中說明之基礎聚合物(較佳為丙烯酸系聚合物)與上述B項中說明之活性能量線反應性化合物(單體或低聚物)之中間層形成用組合物(B2)、或包含上述B項中說明之活性能量線反應性聚合物之中間層形成用組合物(B3)。於一個實施形態中，於使用可藉由活性能量線照射而硬化之組合物作為中間層形成用組合物之情形時，本發明之遮蔽帶以具備硬化後之中間層之遮蔽帶之形式提供。換言之，該實施方式中，上述遮蔽帶具備硬化後之中間層與硬化前之黏著劑層。
中間層形成用組合物(B2)中，活性能量線反應性化合物之含有比例相對於基礎聚合物100重量份較佳為0.01重量份～50重量份、更佳為0.03重量份～40重量份、進而較佳為0.04重量份～30重量份。
上述中間層形成用組合物可包含光聚合起始劑。作為光聚合起始劑，可使用任意適當之光聚合起始劑。例如，可列舉BASF公司製造之商品名「Irgacure 369」、「Irgacure 379ex」、「Irgacure 819」、「Irgacure OXE2」、「Irgacure 127」；Lamberti公司製造之商品名「Esacure one」、「Esacure 1001m」；旭電化工業公司製造之商品名「Adeka Optomer N-1414」、「Adeka Optomer N-1606」、「Adeka Optomer N-1717」等。光聚合起始劑之含有比例相對於中間層形成用組合物中之基礎聚合物100重量份較佳為0.5重量份～20重量份、更佳為2重量份～10重量份。
較佳為上述中間層形成用組合物包含交聯劑。作為交聯劑，例如，可列舉異氰酸酯系交聯劑、環氧系交聯劑、㗁唑啉系交聯劑、氮丙啶系交聯劑、三聚氰胺系交聯劑、過氧化物系交聯劑、脲系交聯劑、金屬烷氧化物系交聯劑、金屬螯合物系交聯劑、金屬鹽系交聯劑、碳二醯亞胺系交聯劑、胺系交聯劑等。
上述交聯劑之含有比例相對於中間層形成用組合物之基礎聚合物100重量份較佳為0.1重量份～10重量份、更佳為0.5重量份～8重量份。
於一個實施形態中，較佳為使用異氰酸酯系交聯劑。作為上述異氰酸酯系交聯劑之具體例，可列舉上述B項中說明之化合物。
中間層形成用組合物根據需要可進而含有任意適當之添加劑。作為添加劑，例如，可列舉活性能量線聚合促進劑、自由基捕捉劑、黏著賦予劑、塑化劑(例如，偏苯三甲酸酯系塑化劑、均苯四甲酸酯系塑化劑等)、顏料、染料、填充劑、防老化劑、導電材、抗靜電劑、紫外線吸收劑、光穩定劑、剝離調整劑、軟化劑、界面活性劑、阻燃劑、抗氧化劑等。
E. 遮蔽帶之製造方法
上述遮蔽帶可藉由任意適當之方法製造。例如可於基材上塗覆上述黏著劑而獲得遮蔽帶。作為塗覆方法，可採用棒塗機塗覆、氣刀塗覆、凹版塗覆、凹版反向塗覆、反向輥塗覆、模唇塗覆、模嘴塗覆、浸漬塗覆、膠版印刷、軟版印刷、絲網印刷等各種方法。又，亦可採用另行於剝離襯墊上形成黏著劑層後，使其貼合於基材之方法等。又，於遮蔽帶具備中間層之情形時，可於基材上塗覆中間層形成用組合物(根據需要，使其硬化)而形成中間層後，將上述黏著劑塗覆至中間層上而獲得。
F. 遮蔽帶之用途
於在具有凹凸面之電子零件(例如，具備凸塊之電子零件)上設置電磁波屏蔽時，可於遮蔽無需形成電磁波屏蔽之凹凸面(凸塊形成面)時良好地使用本發明之遮蔽帶。又，可良好地用作將經遮蔽之電子零件供於加熱步驟之情形時之遮蔽帶。
於一個實施形態中，本發明之遮蔽帶用於具有高度為50 μm以上(例如，50 μm～400 μm)之凸塊之面之遮蔽。通常，於該面設置有複數個凸塊。該凸塊之配置間隔例如為100 μm～500 μm。又，於一個實施形態中，凸塊之俯視形狀為圓形，其直徑為100 μm～300 μm。若使用本發明之遮蔽帶，則能夠良好地遮蔽具有如上所述之凸塊之面，又，本發明之遮蔽帶能夠自該面無糊劑殘留地剝離。
於一個實施形態中，本發明之遮蔽帶供於進行60℃～270℃(較佳為60℃～200℃)之加熱之加熱步驟。更詳細而言，本發明之遮蔽帶於藉由活性能量線之照射使黏著劑層高彈性模數化後供於上述加熱步驟。本發明之遮蔽帶即使於供於此種步驟之情形時，亦能防止黏著劑層不必要地進入起因於凹凸而形成之空隙(例如，凸塊下部與凸塊形成面之間隙)。其結果，若使用本發明之遮蔽帶，則於需要剝離該遮蔽帶之步驟中可防止糊劑殘留。
[實施例]
以下，藉由實施例具體地對本發明進行說明，但本發明不受該等實施例之限定。實施例中之試驗及評價方法如下。又，只要無特別說明，則「份」及「%」為重量基準。
(1)彈性模數
將遮蔽帶之黏著劑層切出為1 cm見方，將其作為測定用試樣。將測定用試樣固定於特定之支持體，用奈米壓痕儀測定彈性模數。
奈米壓痕儀裝置以及測定條件如下述。
(測定裝置及測定條件)
裝置：Hysitron Inc.製造之Tribo Indenter
使用壓頭：Berkovich(三角錐型)
測定方法：單一壓入測定
壓入深度設定：2500 nm
壓入速度：2000 nm/秒
測定氣氛：空氣中、23℃
試樣尺寸：1 cm×1 cm
又，使用日東精機公司製造之UM-810，對黏著劑層照射累積光量1000 mJ/cm2 之紫外線，然後，藉由上述方法測定黏著劑層之彈性模數。
(2)遮蔽帶之浮起評價
將遮蔽帶貼合於BGA(Ball Grid Array，球柵陣列)半導體封裝之凸塊形成面，使用日東精機公司製造之UM-810，對黏著劑層照射累積光量1000 mJ/cm2 之紫外線。然後，用SHIBAURA MECHATRONICS公司製造之CCS-1300，藉由濺鍍於封裝上製作由SUS 0.2 μm/Cu 5 μm/SUS 0.5 μm構成之層。繼而，將遮蔽帶剝離，用顯微鏡觀察凸塊面，根據封裝周邊部之金屬侵入量，按照下述基準對遮蔽帶之浮起進行評價。再者，BGA半導體封裝使用尺寸10 mm×10 mm×0.9 mmt、BGA(凸塊)之高度為200 μm、直徑為200 μm者。又，遮蔽帶之貼合係於40℃之環境下、藉由使2 kg之橡膠輥往返1次而進行。
〇：封裝之周邊之金屬侵入為50 μm以下
×：封裝之周邊之金屬侵入為100 μm以上
(3)遮蔽帶之糊劑殘留評價
如上述(2)般，將遮蔽帶貼合於BGA半導體封裝後，使用日東精機公司製造之UM-810，對黏著劑層照射累積光量1000 mJ/cm2 之紫外線。然後，將遮蔽帶剝離，用SEM(Scanning Electron Microscope，掃描式電子顯微鏡)(50倍)確認殘留於凸塊形成面之黏著劑層成分之有無。
〇：無糊劑殘留
△：以數十 μm水平少量存在認為對電連接不造成問題之糊劑殘留
×：觀察到多個100 μm以上之糊劑殘留
[製造例1]黏著劑A之製備
於具備冷卻管、氮氣導入管、溫度計及攪拌裝置之反應容器中放入丙烯酸2-乙基己酯(以下，稱為「2EHA」)88.8份、丙烯酸-2-羥基乙酯(以下，稱為「HEA」)11.2份、過氧化苯甲醯0.2份及甲苯65份，於氮氣氣流中、於61℃下進行6小時聚合處理，獲得重量平均分子量85萬之丙烯酸系聚合物A。2EHA與HEA之莫耳比設為100 mol：20 mol。
於該丙烯酸系聚合物A中添加異氰酸2-甲基丙烯醯氧基乙酯(以下，稱為「MOI」)12份(相對於HEA為80 mol%)，於空氣氣流中、於50℃下進行48小時加成反應處理，獲得丙烯酸系聚合物A'。
其次，相對於丙烯酸系聚合物A' 100份，添加多異氰酸酯化合物(商品名「CORONATE L」、Nippon Polyurethane Industry公司製造)2.5份、及光聚合起始劑(商品名「Irgacure 127」、BASF公司製造)5份、二季戊四醇五丙烯酸酯及二季戊四醇六丙烯酸酯之混合物(商品名「KAYARAD DPHA」、日本化藥公司製造)30份、及丙烯酸聚胺基甲酸酯(商品名「紫光UV-3000B」、日本合成化學工業公司製造)6份，製作黏著劑A。
[製造例2]黏著劑B之製備
將「KAYARAD DPHA」之調配量設為60份、將「紫光UV-3000B」之調配量設為12份，除此以外，以與製造例1相同之方式製備黏著劑B。
[製造例3]黏著劑C之製備
將「KAYARAD DPHA」之調配量設為100份、不調配「紫光UV-3000B」，除此以外，以與製造例1相同之方式製備黏著劑C。
[製造例4]黏著劑D之製備
「KAYARAD DPHA」、「紫光UV-3000B」均不調配，除此以外，以與製造例1相同之方式製備黏著劑D。
[製造例5]黏著劑E之製備
將「KAYARAD DPHA」之調配量設為130份、不調配「紫光UV-3000B」，除此以外，以與製造例1相同之方式製備黏著劑E。
[製造例6]中間層之製作
將丙烯酸2-乙基己酯(2EHA)90份、丙烯酸(AA)10份、光聚合起始劑(商品名「Irgacure 184」、BASF公司製造)0.05份、及光聚合起始劑(商品名「Irgacure 651」、BASF公司製造)0.05份投入至4口燒瓶中。然後，將混合物於氮氣氣氛下暴露於紫外線而部分地進行光聚合，藉此獲得聚合率約8質量%之部分聚合物(丙烯酸系聚合物漿液)。
於上述丙烯酸系聚合物漿液100份中添加光聚合起始劑(商品名「Irgacure 651」、BASF公司製造)0.04份及二季戊四醇六丙烯酸酯0.04份後，將該等均勻混合，製備中間層形成用組合物。
將上述之丙烯酸系黏著劑組合物以最終厚度成為300 μm之方式塗佈於用聚矽氧對單面進行了剝離處理之厚度38 μm之聚酯膜(商品名：MRF、三菱化學聚酯公司製造)之剝離處理面，形成塗佈層。其次，將用聚矽氧對單面進行了剝離處理之厚度38 μm之聚酯膜(商品名：MRE、三菱化學聚酯公司製造)以該膜之剝離處理面成為塗佈層側之方式積層於所塗佈之丙烯酸系黏著劑組合物之表面。藉此，將光學用丙烯酸系黏著劑組合物之塗佈層(黏著劑層)與氧遮斷。對如此獲得之積層體，使用高壓水銀燈(TOSHIBA LIGHTING & TECHNOLOGY CORPORATION製造)，照射照度200 mW/cm2 (利用在約350 nm具有最大感度之TOPCON UVR-T1進行測定)之紫外線，進行紫外線照射直至光量達到3000 mW/cm2 ，獲得經聚酯膜夾持之中間層。
[實施例1-1]
將黏著劑A塗佈於PET基材(厚度：100 μm)之實施了聚矽氧處理之面上，於120℃下進行2分鐘加熱交聯，形成厚度10 μm之黏著劑層。
其次，將製造例6中獲得之中間層轉印至上述黏著劑層後，於50℃之環境下保存48小時，獲得遮蔽帶(基材(100 μm)/中間層(300 μm)/黏著劑層(10 μm))。
將所得遮蔽帶供於上述評價(2)及(3)。將結果示於表1。
[實施例2-1、實施例3-1、比較例1-1、比較例2-1]
使用表1所示之黏著劑來代替黏著劑A，除此以外，以與實施例1-1相同之方式獲得遮蔽帶。將所得遮蔽帶供於上述評價(2)及(3)。將結果示於表1。
[實施例1-2]
將黏著劑A塗佈於PET基材(厚度：100 μm)之實施了聚矽氧處理之面上，於80℃下進行5分鐘加熱交聯，形成厚度135 μm之黏著劑層a。
另行於PET剝離襯墊上塗佈黏著劑A，於80℃下進行5分鐘加熱交聯，形成厚度135 μm之黏著劑層b。
將黏著劑層b轉印至黏著劑層a，然後，將所得積層體於50℃下保存48小時，獲得具有厚度270 μm之黏著劑層之遮蔽帶。
將所得遮蔽帶供於上述評價(2)及(3)。將結果示於表1。
[實施例2-2、實施例3-2、比較例1-2、比較例2-2]
使用表1所示之黏著劑來代替黏著劑A，除此以外，以與實施例1-2相同之方式獲得遮蔽帶。將所得遮蔽帶供於上述評價(2)及(3)。將結果示於表1。
[表1]
[產業上之可利用性]
本發明之遮蔽帶可良好地用作真空製程(例如，半導體製造中之真空製程)用之遮蔽帶。
10‧‧‧基材
20‧‧‧黏著劑層
30‧‧‧中間層
100‧‧‧遮蔽帶
200‧‧‧遮蔽帶
圖1為本發明之一個實施形態之電磁波屏蔽形成用遮蔽帶之概略剖視圖。
圖2為本發明之另一實施形態之電磁波屏蔽形成用遮蔽帶之概略剖視圖。

Claims (10)

  1. 一種電磁波屏蔽形成用遮蔽帶，其具備彈性模數藉由活性能量線照射而成為活性能量線照射前之20倍以上之黏著劑層，且 該黏著劑層之活性能量線照射後之彈性模數為500 MPa以下。
  2. 如請求項1之電磁波屏蔽形成用遮蔽帶，其進而具備基材，且 於該基材之至少一側配置有上述黏著劑層。
  3. 如請求項1之電磁波屏蔽形成用遮蔽帶，其進而具備配置於上述黏著劑層之一側之中間層。
  4. 如請求項2之電磁波屏蔽形成用遮蔽帶，其進而具備配置於上述黏著劑層與上述基材之間之中間層。
  5. 如請求項1之電磁波屏蔽形成用遮蔽帶，其中上述黏著劑層之彈性模數(活性能量線照射前)為0.07 MPa～0.70 MPa。
  6. 如請求項2之電磁波屏蔽形成用遮蔽帶，其中上述黏著劑層之彈性模數(活性能量線照射前)為0.07 MPa～0.70 MPa。
  7. 如請求項3之電磁波屏蔽形成用遮蔽帶，其中上述中間層之彈性模數為0.07 MPa～0.70 MPa。
  8. 如請求項4之電磁波屏蔽形成用遮蔽帶，其中上述中間層之彈性模數為0.07 MPa～0.70 MPa。
  9. 如請求項1之電磁波屏蔽形成用遮蔽帶，其供於進行60℃～270℃之加熱之加熱步驟。
  10. 如請求項1之電磁波屏蔽形成用遮蔽帶，其用於具有高度50 μm以上之凸塊之面之遮蔽。
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TWI795508B (zh) 2023-03-11
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