TW201829662A - 伸縮性樹脂層形成用硬化性組成物 - Google Patents
伸縮性樹脂層形成用硬化性組成物 Download PDFInfo
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- TW201829662A TW201829662A TW106136864A TW106136864A TW201829662A TW 201829662 A TW201829662 A TW 201829662A TW 106136864 A TW106136864 A TW 106136864A TW 106136864 A TW106136864 A TW 106136864A TW 201829662 A TW201829662 A TW 201829662A
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- Prior art keywords
- meth
- acrylate
- resin layer
- curable composition
- stretchable resin
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Classifications
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Abstract
本發明揭示有一種伸縮性樹脂層形成用硬化性組成物,其含有:(A)具有聚苯乙烯鏈的彈性體、(B)單官能的直鏈烷基(甲基)丙烯酸酯、(C)具有脂環基的單官能的(甲基)丙烯酸酯、(D)具有2個以上的乙烯性不飽和基的2官能以上的化合物、及(E)聚合起始劑。
Description
本發明是有關於一種形成伸縮性樹脂層的硬化性組成物、及具有伸縮性樹脂層的半導體裝置。
近年來,可穿戴(wearable)機器的要求提高。可穿戴機器除了要求小型化以外,亦要求具有對身體曲面的穿裝的容易性、及用於抑制伴隨脫下的連接不良的柔性及伸縮性。要求柔性及伸縮性的構件通常可由液狀矽酮或液狀聚胺基甲酸酯形成。
專利文獻1中揭示有含有苯乙烯系彈性體的可撓性樹脂層形成用樹脂組成物。
專利文獻2中揭示有包括包含聚苯乙烯鏈的嵌段的共聚物橡膠的耐熱性防濕絕緣塗料。專利文獻3中揭示有含有具有乙烯性不飽和雙鍵的胺基甲酸酯化合物、及具有環狀脂肪側基的光聚合性單量體的光硬化性樹脂組成物。 [現有技術文獻] [專利文獻]
[專利文獻1]國際公開第2016/080346號 [專利文獻2]日本專利特開2005-162986號公報 [專利文獻3]日本專利特開2007-308681號公報
[發明所欲解決之課題] 例如,理想的是對可穿戴機器上所搭載的半導體元件進行密封的密封樹脂層具有高的伸縮性。另外,亦要求與構成可穿戴機器等的柔性基材之類的伸縮性基材具有充分的密接性的伸縮性樹脂層。
因此,本發明的一方面的目的在於提供一種可形成具有充分的伸縮性及密接性的伸縮性樹脂層的硬化性組成物。 [解決課題之手段]
本發明的一方面為提供一種伸縮性樹脂層形成用硬化性組成物,其含有:(A)具有聚苯乙烯鏈的彈性體、(B)單官能的直鏈烷基(甲基)丙烯酸酯、(C)具有脂環基的單官能的(甲基)丙烯酸酯、(D)具有2個以上的乙烯性不飽和基的2官能以上的化合物、及(E)聚合起始劑。換言之,本發明的一方面是有關於所述硬化性組成物的用於製造伸縮性樹脂層的應用或使用。
本發明者等人進行了努力研究,結果發現包含所述特定成分的組合的硬化性組成物可形成具有充分的伸縮性及密接性的伸縮性樹脂層。 [發明的效果]
本發明的一方面的硬化性組成物可形成具有充分的伸縮性及密接性的伸縮性樹脂層。
以下,對本發明的若干實施形態進行詳細說明。但,本發明並不限定於以下的實施形態。
[硬化性組成物] 一實施形態的硬化性組成物含有:(A)具有聚苯乙烯鏈的彈性體、(B)單官能的直鏈烷基(甲基)丙烯酸酯、(C)具有脂環基的單官能的(甲基)丙烯酸酯、(D)具有2個以上的乙烯性不飽和基的2官能以上的化合物、及(E)聚合起始劑。該硬化性組成物可藉由光化射線的照射或加熱而硬化,從而形成具有伸縮性的硬化物或硬化膜。
本說明書中,「伸縮性」是指於藉由拉伸負荷而產生應變後,可藉由自負荷的釋放而恢復到原來的形狀或與其相近的形狀的性質。例如,於藉由拉伸負荷而產生50%的應變後,可恢復到原來的形狀或與其相近的形狀的材料可謂是具有伸縮性。更具體而言,後述的伸縮恢復率為80%以上的樹脂層可謂是伸縮性樹脂層。
(A)彈性體 具有聚苯乙烯鏈的彈性體(以下,有時稱為「苯乙烯系彈性體」)例如可為具有作為硬段的聚苯乙烯鏈、與作為軟段的聚二烯鏈(例如,聚丁二烯鏈、聚異戊二烯鏈)的共聚物。作為此種苯乙烯系彈性體的市售品,例如可列舉:JSR(股)的「戴納龍(Dynaron)SEBS系列」、日本科騰聚合物(Kraton polymers Japan)(股)的「科騰(Kraton)D聚合物系列」、阿隆化成(Aronkasei)(股)的「AR系列」。
苯乙烯系彈性體的聚二烯鏈的雙鍵可藉由氫化而飽和。具有經氫化的聚丁二烯鏈的苯乙烯系彈性體可為苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物(氫化型苯乙烯丁二烯共聚聚合物)。具有經氫化的聚異戊二烯鏈的苯乙烯系彈性體可為苯乙烯-乙烯/丙烯-苯乙烯嵌段共聚物(氫化苯乙烯異戊二烯共聚聚合物)。認為具有經氫化的聚二烯鏈的苯乙烯系彈性體有助於耐候性提高。作為具有經氫化的聚二烯鏈的苯乙烯系彈性體的市售品,例如可列舉:JSR(股)的「戴納龍(Dynaron)HSBR系列」、日本科騰聚合物(Kraton polymers Japan)(股)的「科騰(Kraton)G聚合物系列」、旭化成(Asahi Kasei)(股)的「圖特克(Tuftec)系列」、可樂麗(Kuraray)(股)「賽普頓(septon)系列」的。
就硬化性組成物的塗敷性的觀點而言,苯乙烯系彈性體的重量平均分子量可為30000~200000、或50000~150000。此處,重量平均分子量(Mw)是指藉由凝膠滲透層析法(Gel Permeation Chromatography,GPC)求出的標準聚苯乙烯換算值。
相對於(A)成分、(B)成分、(C)成分及(D)成分的總量,(A)成分的苯乙烯系彈性體的含量可為10質量%~50質量%、或20質量%~40質量%。若苯乙烯系彈性體的含量為10質量%以上,則存在伸縮性容易提高的傾向。若苯乙烯系彈性體的含量為50質量%以下,則硬化性組成物的黏度變低而存在塗敷性提高的傾向。
(B)單官能的直鏈烷基(甲基)丙烯酸酯 單官能的直鏈烷基(甲基)丙烯酸酯為具有1個(甲基)丙烯醯基及直鏈烷基的酯化合物。通常,單官能的直鏈烷基(甲基)丙烯酸酯為由(甲基)丙烯酸與直鏈烷基醇形成的酯化合物。直鏈烷基(甲基)丙烯酸酯所具有的直鏈烷基的碳數可為12以下、或10以下。若該碳數為12以下,則尤其於使用具有經氫化的聚二烯鏈的彈性體時,存在由硬化性組成物形成的硬化物難以白濁的傾向。直鏈烷基的碳數可為6以上或8以上。
作為單官能的直鏈烷基(甲基)丙烯酸酯的例子,可列舉:(甲基)丙烯酸異辛酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、丙烯酸異硬脂酯、丙烯酸硬脂酯及丙烯酸十三基酯。該些中,可選擇選自具有碳數12以下的直鏈烷基的、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異癸酯、及(甲基)丙烯酸月桂酯中的一種以上的化合物。該些化合物可單獨使用或者將兩種以上組合使用,亦可將該些化合物與其他單官能的直鏈烷基(甲基)丙烯酸酯組合。
相對於(A)成分、(B)成分、(C)成分及(D)成分的總量,(B)成分的單官能的直鏈烷基(甲基)丙烯酸酯的含量可為10質量%~50質量%、或20質量%~40質量%。若(B)成分的含量為10質量%以上,則存在伸縮性提高的效果相對變大的傾向。若(B)成分的含量為50質量%以下,則存在密接性提高的效果相對提高的傾向。
(C)具有脂環基的單官能的(甲基)丙烯酸酯 具有脂環基的單官能的(甲基)丙烯酸酯通常為由(甲基)丙烯酸與具有脂環基的醇化合物形成的酯化合物。具有脂環基的單官能的(甲基)丙烯酸酯例如可為選自丙烯酸環己酯、3,3,5-三甲基環己醇(甲基)丙烯酸酯、4-第三丁基環己醇(甲基)丙烯酸酯、丙烯酸異冰片酯、丙烯酸二環戊酯(丙烯酸三環癸酯)、及丙烯酸四氫糠酯中的一種以上的化合物。該些化合物可單獨使用或者將兩種以上組合使用,亦可將該些化合物與其他具有脂環基的單官能的(甲基)丙烯酸酯組合。
相對於(A)成分、(B)成分、(C)成分及(D)成分的總量,(C)成分的具有脂環基的單官能的(甲基)丙烯酸酯的含量可為10質量%~50質量%、或20質量%~40質量%。若(C)成分的含量為10質量%以上,則存在密接性提高的效果相對提高的傾向。若(C)成分的含量為50質量%以下,則存在伸縮性提高的效果相對提高的傾向。
(D)具有2個以上的乙烯性不飽和基的2官能以上的化合物 具有2個以上的乙烯性不飽和基的2官能以上的化合物所具有的乙烯性不飽和基例如可為(甲基)丙烯醯基、乙烯基、或該些的組合。作為具有2個以上的乙烯性不飽和基的2官能以上的化合物,例如可列舉:(甲基)丙烯酸酯、偏二鹵乙烯、乙烯醚、乙烯酯、乙烯基吡啶、乙烯基醯胺、芳基化乙烯。該些中,就伸縮性樹脂層的透明性的觀點而言,可選擇(甲基)丙烯酸酯或芳基化乙烯中的至少一種。
作為具有2個(甲基)丙烯醯基的2官能(甲基)丙烯酸酯,例如可列舉:乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、四丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、乙氧基化聚丙二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、3-甲基-1,5-戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、2-丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、及乙氧基化-2-甲基-1,3-丙二醇二(甲基)丙烯酸酯等脂肪族(甲基)丙烯酸酯;環己烷二甲醇二(甲基)丙烯酸酯、乙氧基化環己烷二甲醇二(甲基)丙烯酸酯、丙氧基化環己烷二甲醇二(甲基)丙烯酸酯、乙氧基化丙氧基化環己烷二甲醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、乙氧基化三環癸烷二甲醇二(甲基)丙烯酸酯、丙氧基化三環癸烷二甲醇二(甲基)丙烯酸酯、乙氧基化丙氧基化三環癸烷二甲醇二(甲基)丙烯酸酯、乙氧基化氫化雙酚A二(甲基)丙烯酸酯、丙氧基化氫化雙酚A二(甲基)丙烯酸酯、乙氧基化丙氧基化氫化雙酚A二(甲基)丙烯酸酯、乙氧基化氫化雙酚F二(甲基)丙烯酸酯、丙氧基化氫化雙酚F二(甲基)丙烯酸酯、及乙氧基化丙氧基化氫化雙酚F二(甲基)丙烯酸酯等脂環式(甲基)丙烯酸酯;乙氧基化雙酚A二(甲基)丙烯酸酯、丙氧基化雙酚A二(甲基)丙烯酸酯、乙氧基化丙氧基化雙酚A二(甲基)丙烯酸酯、乙氧基化雙酚F二(甲基)丙烯酸酯、丙氧基化雙酚F二(甲基)丙烯酸酯、乙氧基化丙氧基化雙酚F二(甲基)丙烯酸酯、乙氧基化雙酚AF二(甲基)丙烯酸酯、丙氧基化雙酚AF二(甲基)丙烯酸酯、乙氧基化丙氧基化雙酚AF二(甲基)丙烯酸酯、乙氧基化茀型二(甲基)丙烯酸酯、丙氧基化茀型二(甲基)丙烯酸酯、及乙氧基化丙氧基化茀型二(甲基)丙烯酸酯等芳香族(甲基)丙烯酸酯;乙氧基化異氰脲酸二(甲基)丙烯酸酯、丙氧基化異氰脲酸二(甲基)丙烯酸酯、及乙氧基化丙氧基化異氰脲酸二(甲基)丙烯酸酯等雜環式(甲基)丙烯酸酯;該些化合物的己內酯改質體;新戊二醇型環氧基(甲基)丙烯酸酯等脂肪族環氧基(甲基)丙烯酸酯;環己烷二甲醇型環氧基(甲基)丙烯酸酯、氫化雙酚A型環氧基(甲基)丙烯酸酯、及氫化雙酚F型環氧基(甲基)丙烯酸酯等脂環式環氧基(甲基)丙烯酸酯;以及間苯二酚型環氧基(甲基)丙烯酸酯、雙酚A型環氧基(甲基)丙烯酸酯、雙酚F型環氧基(甲基)丙烯酸酯、雙酚AF型環氧基(甲基)丙烯酸酯、及茀型環氧基(甲基)丙烯酸酯等芳香族環氧基(甲基)丙烯酸酯。
作為具有3個以上的(甲基)丙烯醯基的3官能以上的多官能(甲基)丙烯酸酯,例如可列舉:三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、丙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化丙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、乙氧基化季戊四醇三(甲基)丙烯酸酯、丙氧基化季戊四醇三(甲基)丙烯酸酯、乙氧基化丙氧基化季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、乙氧基化季戊四醇四(甲基)丙烯酸酯、丙氧基化季戊四醇四(甲基)丙烯酸酯、乙氧基化丙氧基化季戊四醇四(甲基)丙烯酸酯、二-三羥甲基丙烷四丙烯酸酯、及二季戊四醇六(甲基)丙烯酸酯等脂肪族(甲基)丙烯酸酯;乙氧基化異氰脲酸三(甲基)丙烯酸酯、丙氧基化異氰脲酸三(甲基)丙烯酸酯、及乙氧基化丙氧基化異氰脲酸三(甲基)丙烯酸酯等雜環式(甲基)丙烯酸酯;該些化合物的己內酯改質體;以及苯酚酚醛清漆型環氧基(甲基)丙烯酸酯、及甲酚酚醛清漆型環氧基(甲基)丙烯酸酯等芳香族環氧基(甲基)丙烯酸酯。
就與苯乙烯系彈性體的相容性、透明性、耐熱性、對聚醯亞胺及銅箔的密接性的觀點而言,(D)成分可為具有脂環基的化合物,作為其例,可列舉:環己烷二甲醇二(甲基)丙烯酸酯、及三環癸烷二甲醇二(甲基)丙烯酸酯。
以上例示的化合物可單獨使用或者將兩種以上組合使用,亦可將所選擇的化合物與其他2官能以上的化合物組合。
相對於(A)成分、(B)成分、(C)成分及(D)成分的總量,(D)成分的2官能以上的化合物的含量可為0.3質量%~20質量%、0.5質量%~10質量%、或1質量%~5質量%。若(D)成分的含量為0.3質量%以上,則存在硬化後的黏性降低的傾向、及伸縮性提高的效果相對提高的傾向。若(D)成分的含量為20質量%以下,則存在伸縮性提高的效果相對提高的傾向。
(E)聚合起始劑 聚合起始劑為藉由加熱或紫外線等的照射而使聚合開始的化合物,例如可為熱自由基聚合起始劑、或光自由基聚合起始劑。由於硬化速度快且可進行常溫硬化,因此可選擇光自由基聚合起始劑。
作為熱自由基聚合起始劑,例如可列舉:甲基乙基酮過氧化物、環己酮過氧化物、及甲基環己酮過氧化物等酮過氧化物;1,1-雙(第三丁基過氧基)環己烷、1,1-雙(第三丁基過氧基)-2-甲基環己烷、1,1-雙(第三丁基過氧基)-3,3,5-三甲基環己烷、1,1-雙(第三己基過氧基)環己烷、及1,1-雙(第三己基過氧基)-3,3,5-三甲基環己烷等過氧化縮酮;對薄荷烷氫過氧化物等氫過氧化物;α,α'-雙(第三丁基過氧基)二異丙基苯、二枯基過氧化物、第三丁基枯基過氧化物、及二-第三丁基過氧化物等二烷基過氧化物;辛醯基過氧化物、月桂醯基過氧化物、硬脂基過氧化物、及苯甲醯基過氧化物等二醯基過氧化物;過氧化二碳酸雙(4-第三丁基環己基)酯、過氧化二碳酸二-2-乙氧基乙酯、過氧化二碳酸二-2-乙基己酯、及過氧化碳酸二-3-甲氧基丁酯等過氧化碳酸酯;過氧化三甲基乙酸第三丁酯、過氧化三甲基乙酸第三己酯、過氧化-2-乙基己酸-1,1,3,3-四甲基丁酯、2,5-二甲基-2,5-雙(2-乙基己醯基過氧基)己烷、過氧化-2-乙基己酸第三己酯、過氧化-2-乙基己酸第三丁酯、過氧化異丁酸第三丁酯、過氧化異丙基單碳酸第三己酯、過氧化-3,5,5-三甲基己酸第三丁酯、過氧化月桂酸第三丁酯、過氧化異丙基單碳酸第三丁酯、過氧化-2-乙基己基單碳酸第三丁酯、過氧化苯甲酸第三丁酯、過氧化苯甲酸第三己酯、2,5-二甲基-2,5-雙(苯甲醯基過氧基)己烷、過氧化乙酸第三丁酯等過氧化酯;以及2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2,4-二甲基戊腈)、及2,2'-偶氮雙(4-甲氧基-2'-二甲基戊腈)等偶氮化合物。就硬化性、透明性、及耐熱性的觀點而言,熱自由基聚合起始劑可為所述二醯基過氧化物、所述過氧化酯、所述偶氮化合物、或該些的組合。
作為光自由基聚合起始劑,例如可列舉:2,2-二甲氧基-1,2-二苯基乙烷-1-酮等安息香縮酮;1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、及1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙烷-1-酮等α-羥基酮;2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁烷-1-酮、及1,2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮等α-胺基酮;1-[(4-苯硫基)苯基]-1,2-辛二酮-2-(苯甲醯基)肟等肟酯;雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基氧化膦、及2,4,6-三甲基苯甲醯基二苯基氧化膦等氧化膦;2-(鄰氯苯基)-4,5-二苯基咪唑二聚體、2-(鄰氯苯基)-4,5-二(甲氧基苯基)咪唑二聚體、2-(鄰氟苯基)-4,5-二苯基咪唑二聚體、2-(鄰甲氧基苯基)-4,5-二苯基咪唑二聚體、及2-(對甲氧基苯基)-4,5-二苯基咪唑二聚體等2,4,5-三芳基咪唑二聚體;二苯甲酮、N,N,N',N'-四甲基-4,4'-二胺基二苯甲酮、N,N,N',N'-四乙基-4,4'-二胺基二苯甲酮、及4-甲氧基-4'-二甲基胺基二苯甲酮等二苯甲酮化合物;2-乙基蒽醌、菲醌、2-第三丁基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-苯并蒽醌、2-苯基蒽醌、2,3-二苯基蒽醌、1-氯蒽醌、2-甲基蒽醌、1,4-萘醌、9,10-菲醌、2-甲基-1,4-萘醌、及2,3-二甲基蒽醌等醌化合物;安息香甲醚、安息香乙醚、及安息香苯醚等安息香醚;安息香、甲基安息香、及乙基安息香等安息香化合物;苄基二甲基縮酮等苄基化合物;9-苯基吖啶、1,7-雙(9,9'-吖啶基庚烷)等吖啶化合物;N-苯基甘胺酸;以及香豆素等。
2,4,5-三芳基咪唑二聚體中,兩個三芳基咪唑部位的芳基的取代基可相同而提供對稱的化合物,亦可不同而提供不對稱的化合物。亦可如二乙基硫雜蒽酮與二甲基胺基苯甲酸的組合般,將硫雜蒽酮化合物與三級胺加以組合。
就硬化性、透明性、及耐熱性的觀點而言,光自由基聚合起始劑可為所述α-羥基酮、所述氧化膦或該些的組合。該些熱自由基聚合起始劑及光自由基聚合起始劑可單獨使用或者將兩種以上組合使用。該些亦可與適當的增感劑組合。
相對於(A)成分、(B)成分、(C)成分及(D)成分的總量100質量份,(E)成分的聚合起始劑的含量可為0.1質量份~10質量份、0.3質量份~7質量份、或0.5質量份~5質量份。若(E)成分的含量為0.1質量份以上,則硬化容易充分地進行。若(E)成分的含量為10質量份以下,則存在光透過性提高的傾向。
可直接使用液狀或固體的硬化性組成物,亦可利用有機溶劑對硬化性組成物進行稀釋而製成樹脂清漆。室溫(25℃)下的液狀的無溶劑的硬化性組成物於並無有機溶劑的排出的方面、可容易塗佈於局部部分的方面等有利。
有機溶劑可自可溶解硬化性組成物的各成分者中選擇。有機溶劑例如可列舉:甲苯、二甲苯、均三甲苯、枯烯、及對異丙基甲苯(p-cymene)等芳香族烴;四氫呋喃、及1,4-二噁烷等環狀醚;丙酮、甲基乙基酮、甲基異丁基酮、環己酮、及4-羥基-4-甲基-2-戊酮等酮;乙酸甲酯、乙酸乙酯、乙酸丁酯、乳酸甲酯、乳酸乙酯、及γ-丁內酯等酯;碳酸伸乙酯、及碳酸伸丙酯等碳酸酯;N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、及N-甲基-2-吡咯啶酮等醯胺。就溶解性及沸點的觀點而言,有機溶劑可為甲苯、N,N-二甲基乙醯胺或該些的組合。該些有機溶劑可單獨使用或者將兩種以上組合使用。
除了所述說明的成分以外,硬化性組成物視需要亦可進而含有其他成分。作為其他成分,例如可列舉抗氧化劑、抗黃變劑、紫外線吸收劑、可見光吸收劑、著色劑、塑化劑、穩定劑、填充劑之類的添加劑。相對於硬化性組成物中的有機溶劑以外的成分的總量,(A)成分、(B)成分、(C)成分及(D)成分的合計的含量例如可為85質量%以上、90質量%以上、或95質量%以上。
[硬化物(伸縮性樹脂層)] 由硬化性組成物形成的硬化物(伸縮性樹脂層)的彈性係數可為0.1 MPa以上且100 MPa以下、0.2 MPa以上且50 MPa以下、或0.3 MPa以上且30 MPa以下。若硬化物的彈性係數為0.1 MPa以上,則存在難以產生因黏連而硬化物彼此貼附的問題。若硬化物的彈性係數為100 MPa以下,則柔軟性及伸縮性提高的效果可相對提高。
由硬化性組成物形成的硬化物(伸縮性樹脂層)的拉伸試驗的斷裂伸長率可為100%以上。若硬化物的斷裂伸長率為100%以上,則可獲得進一步更優異的伸縮性。就相同的觀點而言,硬化物的斷裂伸長率可為150%以上、或者200%以上。
由硬化性組成物形成的硬化物(伸縮性樹脂層)可具有高的伸縮性。伸縮性可將以包含兩次拉伸試驗的以下順序測定的伸縮恢復性作為指標來進行評價。 1)準備長度70 mm、寬度5 mm的長條狀的硬化物作為試驗片。 2)以夾頭間距離為50 mm的夾頭保持試驗片,並於該狀態下以第1次的拉伸試驗拉伸試驗片直至位移量(應變)X。 3)使夾頭回到初始位置。 4)進行第2次拉伸試驗,記錄開始施加負荷的位置(負荷上升的位置)的位移量(應變)與X的差Y。 5)由式:伸縮恢復率R=(Y/X)×100算出伸縮恢復率。 拉伸試驗是於25℃的環境下進行。X可設定為位移量25 mm(應變50%)。作為試驗機,例如可使用微力試驗機(microforce tester)(伊利諾斯工具公司(Illinois Tool Works Inc)、「英斯特朗(Instron)5948」)。圖1為由用於求出伸縮恢復性的拉伸試驗所獲得的應力-應變曲線的例子。用於評價伸縮恢復性的試驗片的厚度可為100±10 μm。
就對重複使用的耐性的觀點而言,所述伸縮恢復率可為80%以上、85%以上、或90%以上。伸縮率的上限並無特別限制,可為100%。所述實施形態的硬化性組成物通常可容易地形成示出80%的伸縮恢復率的硬化物。
就透明性的觀點而言,由硬化性組成物形成的硬化物(伸縮性樹脂層)可具有80%以上的全光線透過率、5.0以下的黃化指數(Yellowness Index,YI)、以及5.0%以下的霧度。全光線透過率、YI及霧度可使用分光霧度計(日本電色工業(股)製造、分光霧度計「SH7000」)來測定。全光線透過率可為85%以上,YI可為4.0以下,霧度可為4.0%以下。全光線透過率可為90%以上,YI可為3.0以下,霧度可為3.0%以下。
由硬化性組成物形成的硬化物(伸縮性樹脂層)例如可作為構成可穿戴機器的伸縮性的密封樹脂層而應用或使用。
[半導體裝置] 圖2是示意性表示一實施形態的半導體裝置的剖面圖。本實施形態的半導體裝置100包括如下的電路基板,所述電路基板包括:具有伸縮性的可撓性基板1、電路零件2、以及伸縮性樹脂層3。可撓性基板1可為伸縮性樹脂層。電路零件2安裝於可撓性基板1上。伸縮性樹脂層3可為由所述實施形態的硬化性組成物形成的硬化物(硬化膜)。伸縮性樹脂層3藉由使成膜的硬化性組成物硬化而形成。伸縮性樹脂層3將可撓性基板1以及電路零件2密封,來保護電路基板的表面。
可撓性基板1的構成材料可根據目的而選擇。可撓性基板1的構成材料可為選自由聚醯亞胺樹脂、丙烯酸樹脂、矽酮樹脂、胺基甲酸酯樹脂、雙順丁烯二醯亞胺樹脂、環氧樹脂及聚乙二醇樹脂所組成的組群中的至少一種。其中,就伸縮性更優異的觀點而言,可撓性基板1的構成材料可為選自由具有矽氧烷結構、脂肪族醚結構或二烯結構的聚醯亞胺樹脂、丙烯酸樹脂、矽酮樹脂、胺基甲酸酯樹脂、具有長鏈烷基鏈(例如碳數1~20的烷基鏈)的雙順丁烯二醯亞胺樹脂、環氧樹脂、以及具有輪烷結構的聚乙二醇樹脂所組成的組群中的至少一種。進而,就伸縮性更優異的觀點而言,可撓性基板1的構成材料可為選自由具有矽氧烷結構或脂肪族醚結構或二烯結構的聚醯亞胺樹脂、矽酮樹脂、胺基甲酸酯樹脂、以及具有長鏈烷基鏈的雙順丁烯二醯亞胺樹脂所組成的組群中的至少一種。作為可撓性基板1的構成材料,可單獨使用選自該些樹脂中的一種,或者將兩種以上組合使用。
電路零件2例如為:記憶體晶片、發光二極體(light emitting diode,LED)、無線射頻(radio frequency,RF)標籤(無線射頻辨識系統(radio frequency identification,RFID))、溫度感測器、加速度感測器等安裝零件。於1個可撓性基板1上,可安裝一種電路零件,亦可混合安裝兩種以上的電路零件。於1個可撓性基板1上,可安裝1個或多個電路零件2。
以下,對本實施形態的半導體裝置的製造方法進行說明。
(步驟1:安裝步驟) 首先,如圖3所示,於可撓性基板1上安裝電路零件2。
(步驟2:密封步驟) 繼而,將可撓性基板1及電路零件2以作為密封構件的硬化性組成物加以密封。可撓性基板1及電路零件2例如可藉由將密封構件積層於可撓性基板1上,將密封構件印刷於可撓性基板1上,或者於密封構件中浸漬可撓性基板1並進行乾燥而密封。可利用印刷法、分配、浸漬法等來進行密封。其中,輥對輥(Roll to Roll)的製程中可使用的方法可縮短製造步驟。
(步驟3:硬化步驟) 於密封步驟中將可撓性基板1及電路零件2以密封構件加以密封後,藉由使密封構件(硬化性組成物)硬化而形成伸縮性樹脂層3,獲得具有伸縮性樹脂層3的電路基板。藉此,獲得圖1所示的半導體裝置100。硬化可為利用加熱的熱硬化、或者利用曝光的光硬化。
(步驟4:切斷步驟) 半導體裝置的製造方法可視需要而包括如下步驟:例如如圖4所示,藉由將電路基板切斷分離而獲得具有電路零件的多個半導體裝置。藉此,可一次性大面積地製造多個半導體裝置,從而容易減少製造步驟。 [實施例]
以下,列舉實施例,對本發明進一步進行具體說明。但,本發明並不限定於該些實施例。
1.樹脂清漆(硬化性組成物)的製備 實施例1 將作為(A)成分的30質量份的氫化苯乙烯異戊二烯共聚聚合物(可樂麗(Kuraray)(股)製造的「賽普頓(septon)2002」)、作為(B)成分的30質量份的丙烯酸異癸酯(阿科瑪(Arkema)(股)製造的「沙托瑪(Sartomer)SR395」)、作為(C)成分的37質量份的4-第三丁基環己醇丙烯酸酯(阿科瑪(Arkema)(股)製造的「沙托瑪(Sartomer)SR217」)、作為(D)成分的2質量份的三環癸烷二甲醇二丙烯酸酯(新中村化學工業(股)製造的「NK酯(NK ester)A-DCP」)以及作為(E)成分的1質量份的雙(2,4,6-三甲基苯甲醯基)苯基氧化膦(巴斯夫(BASF)公司製造的「豔佳固(Irgacure)819」)於500 ml燒瓶內以60℃邊攪拌邊進行混合,獲得樹脂清漆。
實施例2~實施例10及比較例1~比較例3 按照表1所示的調配比(質量份)並與實施例1同樣地進行而獲得樹脂清漆。
2.評價 [彈性係數、伸長率] 於表面脫模處理PET膜(帝人杜邦膜(Teijin dupont film)(股)製造的「皮來庫斯(Purex)A31」、厚度25 μm)的脫模處理面上,使用刮刀塗佈機(康井精機(股)製造的「SNC-350」)來塗佈各實施例、比較例的樹脂清漆。藉由紫外線曝光機(米卡薩(Mikasa)(股)製造的「ML-320FSAT」)以2000 mJ/cm2
的曝光量對樹脂清漆的塗膜照射紫外線(波長365 nm),形成物性評價用的硬化膜(伸縮性樹脂層、厚度100 μm)。
自硬化膜切出長度40 mm、寬度10 mm的長條狀的試驗片。於25℃的環境下,使用奧托古拉夫(autograph)(島津製作所(股)製造的「EZ-S」)進行該試驗片的拉伸試驗。根據所獲得的應力-應變曲線求出硬化膜的彈性係數及伸長率。拉伸試驗是以夾頭間距離20 mm、拉伸速度50 mm/分鐘的條件進行。彈性係數是根據負荷0.5 N~1.0 N的範圍內的應力-應變曲線的傾斜度而求出。伸長率是根據硬化膜斷裂的時點的應變(斷裂伸長率)而求出。
[伸縮恢復率] 自所述評價用的硬化膜,切出長度70 mm、寬度5 mm的長條狀的試驗片。於25℃的環境下,藉由使用微力試驗機(microforce tester)(伊利諾斯工具公司(Illinois Tool Works Inc)、「英斯特朗(Instron)5948」)的2次拉伸試驗測定該試驗片的恢復率。藉由第1次拉伸試驗拉伸試驗片直至位移量(應變)X,其後使夾頭回到初始位置,之後進行第2次拉伸試驗。於第2次拉伸試驗中,將開始施加負荷的位置(負荷上升的位置)的位移量(應變)與X的差設為Y時,伸縮恢復率R是藉由式:R=(Y/X)×100進行計算而得的值。本測定中將初始長度(夾頭間的距離)設為50 mm,將X設為25 mm(應變50%)。
[全光線透過率、YI、霧度] 自所述評價用的硬化膜,切出長度30 mm、寬度30 mm的試驗片。於25℃的環境下,使用分光霧度計(日本電色工業(股)的「SH7000」)來測定該試驗片的全光線透過率、YI及霧度。
[密接性的評價] 於厚度50 μm的聚醯亞胺膜(東麗杜邦(Toray Dupont)(股)製造的「開普頓(Kapton)100H」)上使用刮刀塗佈機(康井精機(股)製造的「SNC-350」)來塗佈樹脂清漆。藉由紫外線曝光機(米卡薩(Mikasa)(股)的「ML-320FSAT」)以2000 mJ/cm2
的曝光量對樹脂清漆的塗膜照射紫外線(波長365 nm),從而於聚醯亞胺膜上形成硬化膜(伸縮性樹脂層、厚度100 μm)。自聚醯亞胺膜與硬化膜的積層體切出長度50 mm、寬度10 mm的長條狀的試驗片。使用接著劑(塞美達因(cemedine)(股)製造的「塞美達因斯帕X高德(cemedine super X gold)」)將該試驗片的硬化膜側固定於銅板上。於25℃的環境下,使用奧托古拉夫(autograph)(島津製作所(股)製造的「EZ-S」)於與硬化膜成90度的角度的方向上以50 mm/分鐘的速度自固定於銅板上的硬化膜剝離聚醯亞胺膜。基於此時的每單位寬度的拉伸應力(N/cm)的最大值對密接性進行評價。
[表1]
(A)彈性體 1)賽普頓(septon)2002(氫化苯乙烯異戊二烯共聚聚合物、可樂麗(Kuraray)(股)、重量平均分子量:55,000) 2)科騰(Kraton)MD6951(氫化型苯乙烯丁二烯共聚聚合物、日本科騰聚合物(Kraton polymers Japan)(股)、重量平均分子量:60,000) 3)卡夫庫斯(Kayaflex)BPAM-155(橡膠改質聚醯胺、日本化藥(股)、重量平均分子量:31,000) (B)單官能的直鏈烷基(甲基)丙烯酸酯 4)SR395(丙烯酸異癸酯、阿科瑪(Arkema)(股)、「沙托瑪(Sartomer)SR395」) 5)SR440(丙烯酸異辛酯、阿科瑪(Arkema)(股)、「沙托瑪(Sartomer)SR440」) 6)LA(丙烯酸月桂酯、大阪有機化學工業(股)) (C)具有脂環式基的單官能的(甲基)丙烯酸酯 7)SR217(4-第三丁基環己醇丙烯酸酯、阿科瑪(Arkema)(股)、「沙托瑪(Sartomer)SR217」) 8)SR420(3,3,5-三甲基環己醇丙烯酸酯、阿科瑪(Arkema)(股)、「沙托瑪(Sartomer)SR420」) 9)FA-513AS(丙烯酸二環戊酯、日立化成(股)、「範克力(Fancryl)FA-513AS」) 10)布蘭莫(Blemmer)CHA(丙烯酸環己酯、日油(股)) (D)2官能以上的化合物 11)A-DCP(三環癸烷二甲醇二丙烯酸酯、新中村化學工業(股)、「NK酯(NK ester)A-DCP」) 12)CD406(環己烷二甲醇二丙烯酸酯、阿科瑪(Arkema)(股)、「沙托瑪(Sartomer)CD406」) 13)FA-129AS(壬二醇二丙烯酸酯、日立化成(股)、「範克力(Fancryl)FA-129AS」) (E)聚合起始劑 14)豔佳固(Irgacure)819(雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、日本巴斯夫(BASF Japan)(股))
表1中示出評價結果。由各實施例的樹脂清漆(硬化性組成物)形成的硬化膜(伸縮性樹脂層)示出充分優異的伸縮性及密接性。另一方面,由並不包含(C)成分的比較例1的樹脂清漆形成的硬化膜示出低的密接性。由並不包含(B)成分的比較例2的樹脂清漆形成的硬化膜的伸縮性低,且伸長率亦低。由包含橡膠改質聚醯胺作為彈性體的比較例3的樹脂清漆形成的硬化膜的伸縮率低,另外,於光學特性的方面而言亦不充分。 [產業上的可利用性]
由本發明的硬化性組成物形成的硬化物(伸縮性樹脂層)示出優異的伸縮性及密接性,因此例如可作為用於保護可穿戴機器的電路基板的密封層而應用或使用。由本發明的硬化性組成物形成的伸縮性樹脂層就高濕度環境下的長期可靠性的方面而言亦可具有優異的性能。
1‧‧‧可撓性基板
2‧‧‧電路零件
3‧‧‧伸縮性樹脂層
100‧‧‧半導體裝置
圖1是表示伸縮恢復率的測定例的應力-應變曲線。 圖2是表示半導體裝置的一實施形態的剖面圖。 圖3是表示可撓性基板以及電路零件的一實施形態的剖面圖。 圖4是表示獲得多個半導體裝置的步驟的一實施形態的剖面圖。
Claims (7)
- 一種伸縮性樹脂層形成用硬化性組成物,其含有: (A)具有聚苯乙烯鏈的彈性體、 (B)單官能的直鏈烷基(甲基)丙烯酸酯、 (C)具有脂環基的單官能的(甲基)丙烯酸酯、 (D)具有2個以上的乙烯性不飽和基的2官能以上的化合物、以及 (E)聚合起始劑。
- 如申請專利範圍第1項所述的伸縮性樹脂層形成用硬化性組成物,其中(A)具有聚苯乙烯鏈的彈性體為進而具有氫化聚二烯鏈的共聚物。
- 如申請專利範圍第1項或第2項所述的伸縮性樹脂層形成用硬化性組成物,其中(E)聚合起始劑為光自由基聚合起始劑。
- 如申請專利範圍第1項至第3項中任一項所述的伸縮性樹脂層形成用硬化性組成物,其中(B)單官能的直鏈烷基(甲基)丙烯酸酯的直鏈烷基的碳數為12以下。
- 如申請專利範圍第1項至第4項中任一項所述的伸縮性樹脂層形成用硬化性組成物,其中相對於(A)成分、(B)成分、(C)成分及(D)成分的總量,(D)具有2個以上的乙烯性不飽和基的2官能以上的化合物的含量為0.3質量%~20質量%。
- 一種伸縮性樹脂層,其為如申請專利範圍第1項至第5項中任一項所述的伸縮性樹脂層形成用硬化性組成物的硬化物。
- 一種半導體裝置,其具備如申請專利範圍第6項所述的伸縮性樹脂層。
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JP (1) | JP7127542B2 (zh) |
KR (1) | KR102389076B1 (zh) |
CN (1) | CN109863180B (zh) |
TW (1) | TWI749089B (zh) |
WO (1) | WO2018079608A1 (zh) |
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JP7141873B2 (ja) * | 2018-03-28 | 2022-09-26 | 株式会社日本触媒 | 共重合体および樹脂組成物 |
JP2022068382A (ja) * | 2019-03-12 | 2022-05-10 | 積水ポリマテック株式会社 | 光硬化性組成物及び電子基板 |
JP7332378B2 (ja) * | 2019-07-25 | 2023-08-23 | デンカ株式会社 | 組成物及び補修方法 |
US20220081571A1 (en) * | 2020-09-11 | 2022-03-17 | Canon Kabushiki Kaisha | Energy ray-curable resin compositions and its cured products |
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JPS5747308A (en) * | 1980-07-07 | 1982-03-18 | Sebunemu Kootengusuuakademii O | Pressure sensitive adhesives |
JPS6013861A (ja) * | 1983-07-02 | 1985-01-24 | Nitto Electric Ind Co Ltd | 硬化性被覆用組成物 |
JPS60118653A (ja) * | 1983-11-30 | 1985-06-26 | Nitto Electric Ind Co Ltd | 光フアイバ−被覆用組成物 |
JPH0717721B2 (ja) * | 1992-05-12 | 1995-03-01 | 三菱油化株式会社 | 塗料用樹脂組成物 |
JP3664262B2 (ja) * | 1993-04-28 | 2005-06-22 | 日本ゼオン株式会社 | 紫外線硬化性組成物、それを用いた接着方法、及び接着物 |
JP3493241B2 (ja) * | 1994-03-09 | 2004-02-03 | 三井化学株式会社 | 環状オレフィン系重合体組成物およびそれに用いるコア・シェルエラストマー |
JP5188669B2 (ja) | 2003-12-05 | 2013-04-24 | 日立化成株式会社 | 防湿絶縁塗料および絶縁処理された電子部品の製造法 |
JP5162893B2 (ja) | 2006-04-18 | 2013-03-13 | 日立化成株式会社 | 光硬化性樹脂組成物の製造方法、実装回路板用光硬化性防湿絶縁塗料、実装回路板及び実装回路板の製造方法 |
JP5747308B2 (ja) * | 2011-06-27 | 2015-07-15 | 株式会社Cics | リチウムターゲット自動再生装置、中性子源、及びリチウムターゲット自動再生方法 |
JP2013168575A (ja) * | 2012-02-16 | 2013-08-29 | Univ Of Tokyo | 伸縮性回路基板 |
JP6192350B2 (ja) * | 2012-06-21 | 2017-09-06 | キヤノン株式会社 | ズームレンズ及びそれを有する撮像装置 |
FI20145907A (fi) | 2014-10-16 | 2016-04-17 | Savo Solar Oy | Aurinkolämpökeräin |
CN106663638B (zh) * | 2014-11-18 | 2020-04-07 | 日立化成株式会社 | 半导体装置及其制造方法和挠性树脂层形成用树脂组合物 |
JP6789496B2 (ja) * | 2016-04-05 | 2020-11-25 | 昭和電工マテリアルズ株式会社 | 硬化性樹脂シート、電気回路用可撓性基材、可撓性電気回路体及び半導体装置 |
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- 2017-10-25 US US16/344,493 patent/US20190241694A1/en not_active Abandoned
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KR102389076B1 (ko) | 2022-04-22 |
JP7127542B2 (ja) | 2022-08-30 |
TWI749089B (zh) | 2021-12-11 |
JPWO2018079608A1 (ja) | 2019-09-19 |
WO2018079608A1 (ja) | 2018-05-03 |
CN109863180B (zh) | 2022-03-18 |
KR20190075941A (ko) | 2019-07-01 |
CN109863180A (zh) | 2019-06-07 |
US20190241694A1 (en) | 2019-08-08 |
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