TW201315787A - 黏著劑組成物,薄膜狀黏著劑及電路構件之連接構造 - Google Patents

黏著劑組成物,薄膜狀黏著劑及電路構件之連接構造 Download PDF

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TW201315787A
TW201315787A TW101144840A TW101144840A TW201315787A TW 201315787 A TW201315787 A TW 201315787A TW 101144840 A TW101144840 A TW 101144840A TW 101144840 A TW101144840 A TW 101144840A TW 201315787 A TW201315787 A TW 201315787A
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Prior art keywords
adhesive composition
circuit
resin
adhesive
film
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TW101144840A
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English (en)
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TWI525166B (zh
Inventor
Hiroyuki Izawa
Toshiaki Shirasaka
Shigeki Katogi
Sunao Kudou
Keiko Tomizawa
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Hitachi Chemical Co Ltd
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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/30Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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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    • C09J183/00Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/10Block or graft copolymers containing polysiloxane sequences
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    • C09J9/02Electrically-conducting adhesives
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    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/22Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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Abstract

本發明之黏著劑組成物,其係含有有機微粒子,而該有機微粒子係含有至少一種選自由(a)(甲基)丙烯酸烷基酯-丁二烯-苯乙烯共聚合物或複合體、(甲基)丙烯酸烷基酯-矽酮共聚合物或複合體、及、矽酮-(甲基)丙烯酸共聚合物或複合體所構成之群。

Description

黏著劑組成物,薄膜狀黏著劑及電路構件之連接構造
本發明係關於一種黏著劑組成物、薄膜狀黏著劑及電路構件之連接構造。
在半導體元件及液晶顯示元件中,就結合元件中之各種構件之目的,自以往已使用各種之黏著劑組成物。於黏著劑組成物所要求之特性係以黏著性為首,而涵蓋於耐熱性、高溫高濕狀態之信賴性等各種。
又,於黏著所使用之被黏體係以印刷電路板、聚醯亞胺等之有機基材為首,可使用銅、鋁等之金屬、或ITO、SiN、SiO2等各式各樣的表面狀態之基材。因此,黏著劑組成物係必須符合於各被黏體之分子設計。
自以往,半導體元件或液晶顯示元件用之黏著劑組成物係可使用顯示高信賴性之環氧樹脂的環氧硬化系或使用自由基聚合性化合物之自由基硬化系的熱硬化性樹脂(例如參照專利文獻1及2)。環氧硬化系之黏著劑組成物的構成成分係一般可使用環氧樹脂、與環氧樹脂具有反應性之酚樹脂等的硬化劑、促進環氧樹脂與硬化劑之反應的熱潛在性觸媒。另外,自由基硬化系的黏著劑組成物之構成成分係可使用丙烯酸酯衍生物或甲基丙烯酸酯衍生物等之自由基聚合性化合物與自由基聚合起始劑之過氧化物。
但,伴隨最近之半導體元件的高積體化、液晶元件 之高精細化,元件間及配線間間隙狹小化,受硬化時之加熱,而出現對周邊構件有不良影嚮之虞。進一步,為了低成本化,必須提昇產量。對於此等之課題,被要求更低溫且短時間的硬化,換言之,在低溫速硬化之黏著。但,可知在短時間硬化時因硬化收縮等而內部應力變大,或黏著強度變低。又,可知以低溫硬化時,環氧樹脂或丙烯酸酯衍生物或甲基丙烯酸酯衍生物之反應不會充分地進行,而變成交聯密度不足,或信賴性降低。
又,藉由使用具有醚鍵之自由基聚合性化合物作為黏著強度的改良方法,而對黏著劑之硬化物賦予可撓性,改善黏著強度之方法(例如參照專利文獻3、4),於黏著劑中分散由橡膠系之彈性材料所構成之應力吸收粒子,改善黏著強度之方法(例如參照專利文獻5)已被提出。
專利文獻1:特開平01-113480號公報
專利文獻2:特開2002-203427號公報
專利文獻3:特許第3522634號公報
專利文獻4:特開2002-285128號公報
專利文獻5:特許第3477367號公報
發明之揭示
但,使用如記載於上述專利文獻3及4之具有醚鍵的自由基聚合性化合物的黏著劑,有如下問題:以低溫 硬化時,具有醚鍵之丙烯酸酯衍生物或甲基丙烯酸酯衍生物之反應不會充分地進行,而變成交聯密度不足。進一步,即使為使用於上述專利文獻5記載之應力吸收粒子的黏著劑時,應力吸收粒子之玻璃轉移溫度(Tg)高達80℃~120℃,故有無法得到充分的應力緩和效果之問題。因此,使此等之黏著劑使用於以高溫高濕條件(例如85℃/85%RH)長時間曝露後亦要求有安定的性能之半導體元件或液晶顯示元件的黏著劑時,信賴性試驗(高溫高濕試驗)後會產生黏著力或連接電阻等之特性惡化的問題。
本發明係有鑑於上述習知技術具有之課題而成者,目的在於提供一種顯示優異之黏著強度,即使在信賴性試驗(例如85℃/85%RH放置)後,亦可維持安定的性能之黏著劑組成物、使用其之薄膜狀黏著劑及電路構件之連接構造。
為達成上述目的,本發明係提供一種黏著劑組成物,其特徵係含有有機微粒子,而該有機微粒子係含有至少一種選自由(a)(甲基)丙烯酸烷基酯-丁二烯-苯乙烯共聚合物或複合體、(甲基)丙烯酸烷基酯-矽酮共聚合物或複合體、及、矽酮-(甲基)丙烯酸共聚合物或複合體所成之群。
如此之黏著劑組成物係藉由含有上述(a)有機微粒子,俾可得到應力緩和性及與樹脂組成物之相容性的 提昇效果,可得到優異之黏著強度,同時並可充分地降低連接電路構件間之時的連接電阻,進一步,即使在信賴性試驗(例如85℃/85%RH放置)後,亦可維持安定的性能。
本發明之黏著劑組成物係宜為含有(b)自由基聚合性化合物、及(c)自由基聚合起始劑者。如此之樹脂組成物係藉由含有(b)自由基聚合性化合物、及(c)自由基聚合起始劑,反應活性種之自由基富於反應性,故可短時間硬化。又,可得到優異之黏著強度,同時並於信賴性試驗(高溫高濕試驗)後亦發揮優異之特性。
又,本發明之黏著劑組成物係亦宜為含有(d)環氧樹脂、及(e)潛在性硬化劑者。如此之黏著劑組成物係藉由含有(d)環氧樹脂、及(e)潛在性硬化劑,俾可得到優異之黏著強度,同時並於信賴性試驗(高溫高濕試驗)後亦可發揮優異之特性。
在本發明之黏著劑組成物中,上述(a)有機微粒子的Tg,宜為-100℃~70℃。(a)有機微粒子之Tg超過70℃時,因無法充分緩和黏著劑內部之應力,故有黏著強度降低之傾向。又,若(a)有機微粒子之Tg不足-100℃,無法得到充分的凝集力,而有降低黏著劑組成物物性之傾向。又,於上述專利文獻5所記載之應力吸收粒子係Tg高達80℃~120℃,應力緩和效果會不充分。
又,於本發明之黏著劑組成物中,上述(a)有機微粒子宜為含有具有三維交聯構造之聚合物的粒子。藉此,可藉交聯構造而顯現充分的礙集力,可得到優異之黏著強度,同時並於信賴性試驗(高溫高濕試驗)後亦發揮優異之特性。
又,在本發明之黏著劑組成物中,上述(a)有機微粒子宜為含有重量平均分子量100萬~300萬之聚合物的粒子。藉此,以分子鏈的糾纏顯現充分的凝集力,可得到優異之黏著強度,同時並於信賴性試驗(高溫高濕試驗)後亦發揮優異之特性。
又,在本發明之黏著劑組成物中,上述(a)有機微粒子之含有量係宜以黏著劑組成物之固形分全量作為基準而為5~80質量%。(a)有機微粒子之含有量不足5質量%時,擔心耐熱性、凝集力的不足,超過80質量%時,恐流動性降低。
又,在本發明之黏著劑組成物中,上述(a)有機微粒子係宜為具有核殼構造之粒子。藉此,(a)有機微粒子間相互作用被緩和,構造黏性(非牛頓黏性)變低,故於樹脂中之分散性提高,可有效地得到(a)有機微粒子之性能。
又,本發明之黏著劑組成物係宜含有於(f)分子內具有1個以上之磷酸基之乙烯基化合物。藉此,黏著劑組成物係可得到對於基材尤其金屬優異之黏著強度。
又,本發明之黏著劑組成物係宜含有(g)熱塑性 樹脂。黏著劑組成物係藉由含有上述(g)熱塑性樹脂,俾薄膜性提高,處理性良好。
又,在本發明之黏著劑組成物中,上述(g)熱塑性樹脂係宜含有至少1種選自由苯氧樹脂、聚酯樹脂、聚胺酯樹脂(polyurethane resin)、聚酯胺酯樹脂(polyester urethane)、縮丁醛樹脂、丙烯酸樹脂、及、聚醯亞胺樹脂所成之群者。
又,本發明之黏著劑組成物宜含有(h)導電性粒子。
本發明係又,提供一種使上述本發明之黏著劑組成物形成薄膜狀而成之薄膜狀黏著劑。
本發明係進一步提供一種電路構件之連接構造,其特徵在於具備:呈對向配置的一對電路構件、與設置於上述一對電路構件之間,且將上述一對電路構件彼此黏接的連接構件,以使上述一對電路構件具有之電路電極相互電連接;上述連接構件係由上述本發明之黏著劑組成物的硬化物所構成者。
如此之電路構件的連接構造係連接一對的電路構件之連接構件藉由上述本發明之黏著劑組成物的硬化物所構成,故可充分提高電路構件間之黏著強度,同時並可充分地降低電氣連接之電路電極間的連接電阻,進一步,即使在信賴性試驗(例如85℃/85%RH放置)後,亦可維持安定的性能。
若依本發明,可提供一種顯示優異之黏著強度,即使在信賴性試驗(例如85℃/85%RH放置)後,亦可維持安定的性能之黏著劑組成物、使用其之薄膜狀黏著劑及電路構件之連接構造。
為讓本發明之上述特徵和優點能更明顯易懂,下文特舉實施例,並配合所附圖式作詳細說明如下。
用以實施發明之最佳形態
以下,視情形,一邊參照圖面,一邊詳細說明有關本發明之適當的實施形態。又,圖面中,同一或相當部分係賦予同一符號,重複之說明係省略。又,於本發明中,所謂Tg意指依動態黏彈性測定所得到之損失正切(tanδ)的譜峰頂的溫度。又,在本發明中,所謂(甲基)丙烯酸係表示丙烯酸或對應於其之(甲基)丙烯酸,(甲基)丙烯酸酯意指丙烯酸酯或對應於其之甲基丙烯酸酯,所謂(甲基)丙烯醯基(acryloyl)基意指丙烯醯基或甲基丙烯醯基。
本發明之黏著劑組成物係含有(a)有機微粒子,而該有機微粒子係含有至少一種選自由(甲基)丙烯酸烷基酯-丁二烯-苯乙烯共聚合物或複合體、(甲基)丙烯酸烷基酯-矽酮共聚合物或複合體、及、矽酮-(甲基)丙烯酸共聚合物或複合體所成之群。又,所謂上述複合體係各成分不共聚合而形成複合化(混合)者。
此處,上述(甲基)丙烯酸烷基酯係表示丙烯酸烷 酯、甲基丙烯酸烷酯及其等之混合物,(甲基)丙烯酸表示丙烯酸、甲基丙烯酸及其等之混合物。
又,本發明之黏著劑組成物係宜含有上述(a)有機微粒子的同時,含有(b)自由基聚合性化合物、及(c)自由基聚合起始劑,或,含有(d)環氧樹脂、及(e)潛在性硬化劑。
進一步,於本發明之黏著劑組成物所含有的成分較佳係可舉例如(f)於分子內具有1個以上之磷酸基的乙烯基化合物、(g)熱塑性樹脂、及、(h)導電性粒子。以下詳細地說明有關各成分。
在本發明中,(a)有機微粒子係含有至少一種選自由(甲基)丙烯酸烷基酯-丁二烯-苯乙烯共聚合物或複合體、(甲基)丙烯酸烷基酯-矽酮共聚合物或複合體、及、矽酮-(甲基)丙烯酸共聚合物或複合體所成之群的粒子。
(a)有機微粒子之Tg宜為-100℃~70℃。
(a)有機微粒子係宜為含有具三維交聯構造之聚合物的粒子、及/或、含重量平均分子量100萬以上之聚合物的粒子。又,構成(a)有機微粒子之聚合物的重量平均分子量係更宜為100萬~300萬。
又,從於黏著劑組成物之分散性的觀點,(a)有機微粒子係宜為於核材之表面形成玻璃轉移溫度高於該核材表面之玻璃轉移溫度的表面層者,或於核材之表面使樹脂接枝聚合而形成接枝層者等之核殼型之粒子。
在本發明之黏著劑組成物中,(a)有機微粒子之含有量係宜以黏著劑組成物之固形分全量作為基準而宜為5~80質量%,更宜為10~70質量%。(a)有機微粒子之含有量不足5質量%時,擔心耐熱性、凝集力的不足,超過80質量%時,恐流動性降低。
在本發明中所使用的(b)自由基聚合性化合物並無特別限制,可使用公知者。又,(b)自由基聚合性化合物係亦可以單體、寡聚物之任一者的狀態使用,亦可混合單體與寡聚物而使用。
(b)自由基聚合性化合物具體上可舉例如環氧(甲基)丙烯酸酯寡聚物、胺基甲酸乙酯(甲基)丙烯酸酯寡聚物、聚醚(甲基)丙烯酸酯寡聚物、聚酯(甲基)丙烯酸酯寡聚物等之寡聚物、三羥甲基丙烷三(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚烷撐基二醇二(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、二環戊烯氧乙基(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三聚異氰酸改性2官能(甲基)丙烯酸酯、三聚異氰酸改性3官能(甲基)丙烯酸酯、雙酚芴二縮水甘油基醚之縮水甘油基加成(甲基)丙烯酸之環氧(甲基)丙烯酸酯、雙酚芴二縮水甘油基醚之縮水甘油基加成乙二醇或丙二醇之化合物中導入(甲基)丙烯醯氧基之化合物、以下述通式(1)及(2)所示之化合物等。此等之化合物係可1種單獨或混合2種以上而使用。
〔式中,R1及R2係各別獨立地表示氫原子或甲基,k及l分別獨立地表示1~8之整數。又,式中,R1間及R2間分別為同一亦可相異〕。
〔式中,R3及R4係各別獨立地表示氫原子或甲基,m及n分別獨立地表示0~8之整數。又,式中,R3間及R4間分別為同一亦可相異〕。
在本發明之黏著劑組成物中,(b)自由基聚合性化合物之含有量係宜以黏著劑組成物之固形分全量作為基準而宜為15~70質量%,更宜為25~60質量%。此含有量不足15質量%時,係擔心硬化後之耐熱性降低, 超過60質量%時,恐薄膜形成性降低。
在本發明所使用之(c)自由基聚合起始劑係可使用自以往所知之過氧化物或偶氮化合物等之公知的化合物。從安定性、反應性、相溶性之觀點,宜使用(c)自由基聚合起始劑係1分鐘半衰期溫度為90~175℃,且分子量為180~1000之過氧化物。此處,「1分鐘半衰期溫度」謂半衰期成為1分鐘的溫度,「半衰期」謂化合物之濃度減少至初期值之一半的時間。
(c)自由基聚合起始劑具體上可舉例如1,1,3,3-四甲基丁基過氧化新癸酸酯、二(4-第三丁基環己基)過氧化二碳酸酯、二(2-乙基己基)過氧化二碳酸酯、枯基過氧化新癸酸酯、1,1,3,3-四甲基丁基過氧化新癸酸酯、二月桂醯基過氧化物、1-環己基-1-甲基乙基過氧化新癸酸酯、第三己基過氧化新癸酸酯、第三丁基過氧化新癸酸酯、第三丁基過氧化三甲基乙酸酯、1,1,3,3-四甲基丁基過氧化-2-乙基己酸酯、2,5-二甲基-2,5-二(2-乙基己醯基過氧化)己烷、第三己基過氧化-2-乙基己酸酯、第三丁基過氧化-2-乙基己酸酯、第三丁基過氧化新庚酸酯、第三戊基(amyl)過氧化-2-乙基己酸酯、二第三丁基過氧化六氫對酞酸酯、第三戊基過氧化-3,5,5-三甲基己酸酯、3-羥基-1,1-二甲基丁基過氧化新癸酸酯、1,1,3,3-四甲基丁基過氧化-2-乙基己酸酯、第三戊基過氧化新癸酸酯、第三戊基過氧化-2-乙基己酸酯、3-甲基苯甲醯基過氧化物、4-甲基苯甲醯基過氧化 物、二(3-甲基苯甲醯基)過氧化物、二苯甲醯基過氧化物、二(4-甲基苯甲醯基)過氧化物、2,2’-偶氮雙-2,4-二甲基戊腈、1,1’-偶氮雙(1-乙醯氧-1-苯基乙烷)、2,2'-偶氮雙異丁腈、2,2’-偶氮雙(2-甲基丁腈)、二甲基-2,2’-偶氮雙異丁腈、4,4’-偶氮雙(4-氰基戊酸)、1,1’-偶氮雙(1-環己烷甲腈)、第三己基過氧化異丙基單碳酸酯、第三丁基過氧化馬來酸、第三丁基過氧化-3,5,5-三甲基己酸酯、第三丁基過氧化月桂酸酯、2,5-二甲基-2,5-二(3-甲基苯甲醯基過氧化)己烷、第三丁基過氧化-2-乙基己基單碳酸酯、第三己基過氧化苯甲酸酯、2,5-二甲基-2,5-二(苯甲醯基過氧化)己烷、第三丁基過氧化苯甲酸酯、二丁基過氧化三甲基己二酸酯、第三戊基過氧化正辛酸酯、第三戊基過氧化異壬酸酯、第三戊基過氧基苯甲酸酯等。此等之化合物係可1種單獨使用外,亦可混合2種以上而使用。
又,(c)自由基聚合起始劑係可使用藉波長150~750nm之光照射而產生自由基之化合物。如此之化合物並無特別限制,可使用公知之化合物,但例如於Photoinitiation,Photopolymerization,and Photocuring,J.-P.Fouassier,Hanser Publishers(1995年)、p17~p35所記載之α-胺基苯乙酮(acetaminophenone)衍生物或氧化磷衍生物對於光照射之感度高,故佳。此等之化合物係1種單獨使用之外,亦可與上述過氧化物或偶氮化合物混合物而使用。
在本發明之黏著劑組成物中,(c)自由基聚合起始劑之含有量係宜以黏著劑組成物之固形分全量作為基準而宜為0.1~50質量%,更宜為1~30質量%。此含有量不足0.1質量%時,擔心硬化不足,超過50質量%時係恐放置安定性降低。
在本發明中所使用之(d)環氧樹脂係可舉例如由表氯醇與雙酚A或F、AD等所衍生之雙酚型環氧樹脂;由表氯醇與酚酚醛清漆或甲酚酚醛清漆所衍生之環氧酚醛清漆樹脂;具有含萘環之骨架的萘系環氧樹脂;縮水甘油基胺、縮水甘油基醚、聯苯基、脂環式等之1分子內具有2個以上之縮水甘油基之各種環氧化合物等。此等係可1種單獨使用,亦可混合2種以上而使用。此等之環氧樹脂係為防止電子遷移性,宜使用雜質離子(Na+、Cl-等)或水解性氯等降低至300ppm以下之高純度品。
在本發明所使用之(e)潛在性硬化劑,可舉例如咪唑系硬化劑、醯肼(hydrazide)系硬化劑、三氟化硼-胺錯合物、硫鎓鹽、胺醯亞胺、二胺基馬來腈、三聚氰胺及其衍生物、聚胺之鹽、二氰二胺(dicyandiamide)等、及此等之改性物。此等係可1種單獨使用,亦可混合2種以上而使用。此等係陰離子或陽離子聚合性的觸媒型硬化劑,易得到速硬化性,又,化學當量的考量少,故佳。(e)潛在性硬化劑係上述者之外,亦可使用聚胺類、聚硫醇、多酚(polyphenol)、酸酐等加成聚合 型的硬化劑。又,亦可與複加成型硬化劑與觸媒型硬化劑之併用。
陰離子聚合型的觸媒型硬化劑宜為第3胺類或咪唑類。陽離子聚合型的觸媒型硬化劑係藉能量線照射使環氧樹脂硬化時,宜為芳香族重氮(diazonium)鎓鹽、芳香族硫鎓鹽等之感光性鎓鹽。又,能量線照射以外即使藉加熱而活性化使環氧樹脂硬化時係宜為脂肪族硫鎓鹽。此等之硬化劑係具有速硬化性之特徵,故佳。
於本發明中之(f)於分子內具有1個以上之磷酸基的乙烯基化合物,可舉例如以下述通式(3)~(5)所示之化合物。
〔式中,R5表示(甲基)丙烯醯基,R6係表示氫原子或甲基,w及x分別獨立地表示1~8之整數。又,式中,R5間、R6間、w間及x間係可分別相同,亦可相異〕。
〔化4〕
〔式中,R7表示(甲基)丙烯醯基,y及z分別獨立地表示1~8之整數。又,式中,R7間、y間及z間係可分別相同,亦可相異〕。
〔式中,R8表示(甲基)丙烯醯基,R9係表示氫原子或甲基,a及b分別獨立地表示1~8之整數。又,式中,R9間及a間係可分別相同,亦可相異〕。
(f)於分子內具有1個以上之磷酸基的乙烯基化合物具體上可舉例如酸式(acid)磷氧乙基甲基丙烯酸酯、酸式(acid)磷氧乙基丙烯酸酯、酸式(acid)磷氧丙基甲基丙烯酸酯、酸式(acid)磷氧聚氧乙二醇單甲基丙烯酸酯、酸式(acid)磷氧聚氧丙二醇單甲基丙烯酸酯、2,2’-二(甲基)丙烯醯氧二乙基磷酸酯、EO改性磷酸二甲基丙烯酸酯、磷酸改性環氧丙烯酸酯、磷酸乙烯酯等。
在本發明之黏著劑組成物中,(f)於分子內具有1 個以上之磷酸基的乙烯基化合物的含有量係以黏著劑組成物之固形分全量作為基準,宜為0.1~15質量%,更宜為0.5~10質量%。此含有量不足0.1質量%時係有很難得到高的黏著強度之傾向,超過15質量%時係易造成硬化後之黏著劑組成物的物性降低,恐信賴性降低。
本發明之(g)熱塑性樹脂並無特別限制,可使用公知者。如此之(g)熱塑性樹脂係可使用苯氧樹脂類、聚(甲基)丙烯酸酯類、聚醯亞胺類、聚醯胺類、聚胺基甲酸乙酯類、聚酯類、聚酯胺基甲酸乙酯類、聚乙烯縮丁醛類等。此等之中,(g)熱塑性樹脂係宜使用苯氧樹脂、聚酯樹脂、聚胺酯樹脂、聚酯胺基甲酸乙酯樹脂、縮丁醛樹脂、丙烯酸樹脂、聚醯亞胺樹脂等。此等係可1種單獨使用,亦可混合2種以上而使用。
進一步,於此等熱塑性樹脂中亦可含有矽氧烷鍵或氟取代基。混合此等熱塑性樹脂之2種類以上而使用時,可選擇混合之樹脂間完全相溶,或產生微相分離而成為白濁之狀態的2種類以上之樹脂而使用。又,此等之熱塑性樹脂係分子量愈大,薄膜形成性愈容易得到,又,可使對作為黏著劑組成物或薄膜狀黏著劑之流動性影嚮之熔融黏度設定於廣範圍。
(g)熱塑性樹脂之分子量係無特別限定,但一般的重量平均分子量係宜為5000~150000,尤宜為10000~80000。此值不足5000時,有薄膜形成性差之傾向,若超過150000,與其他之成分的相溶性有變差之 傾向。
在本發明之黏著劑組成物中,(g)熱塑性樹脂之含有量係宜以黏著劑組成物之固形分全量作為基準而宜為5~80質量%,更宜為15~70質量%。此含有量不足5質量%時,薄膜形成性有降低之傾向,若超過80質量%,有黏著劑組成物之流動性有降低之傾向。
在本發明中之(h)導電性粒子可舉例如Au、Ag、Ni、Cu、焊料(solder)等之金屬粒子或碳粒子等。又,(h)導電性粒子係亦可使非導電性之玻璃、陶瓷、塑膠等作為核,於此核上被覆上述金屬、金屬粒子、碳等。(h)導電性粒子為以塑膠作為核,於此核上被覆上述金屬、金屬粒子、碳等者,或,為熱熔融金屬粒子時,藉加熱加壓具有變形性,故連接電路構件間之時,導電性粒子與電極之接觸面積會增加而信賴性提高,故佳。
又,使此等之導電性粒子的表面進一步以高分子樹脂等被覆的微粒子,係可抑制增加導電性粒子的調配量時之粒子間接觸造成的短路,並可提昇電路電極間之絕緣性。以高分子樹脂等被覆導電性粒子的表面之粒子,係可本身單獨或與其他之導電性粒子混合而使用。
(h)導電性粒子之平均粒徑從良好的分散性及導電性觀點,宜為1~18μm。
含有如此之(h)導電性粒子時,黏著劑組成物係可適宜地使用來作為異方導電性黏著劑組成物。
本發明之黏著劑組成物中的(h)導電性粒子之含有量係無特別限制,但宜以黏著劑組成物之固形分全體積作為基準而為0.1~30體積%,更宜為0.1~10體積%。若此含有量不足0.1體積%,有導電性差之傾向,若超過30體積%,有易產生電路電極間之短路的傾向。又,(h)導電性粒子之含有量(體積%)係依據23℃之硬化前的各成分之體積來決定。又,各成分之體積係可利用比重而使質量換算成體積來求取。又,不溶解欲測定體積之成分,也不使之膨潤,而可使其成分充分潤濕其成分之適當溶劑(水、醇等)置入於量筒等內,再投入測定對象之成分而增加之體積求出作為其成分體積。
本發明之黏著劑組成物係以硬化速度的控制或貯存安定性之賦予作為目的而亦可添加安定劑。如此之安定化劑無特別限定,可使用公知之化合物,但宜為苯醌或氫醌等之醌衍生物、4-甲氧基酚或4-第三丁基兒茶酚等之酚衍生物、2,2,6,6-四甲基六氫化吡啶-1-氧基或4-羥基-2,2,6,6-四甲基六氫化吡啶-1-氧基等之胺氧衍生物、四甲基六氫化吡啶基甲基丙烯酸酯等之阻胺衍生物。
安定化劑之添加量係以黏著劑組成物之固形分全量作為基準,宜為0.01~30質量%,更宜為0.05~10質量%。此添加量不足0.01質量%時,有無法充分得到添加效果之傾向,超過30質量%時係恐與其他成分之相溶性降低。
本發明之黏著劑組成物係亦可添加以烷氧基矽烷衍生物或矽氮烷衍生物為代表之偶合劑或密著提昇劑、流平劑等之黏著助劑。如此之黏著助劑具體上宜為以下述通式(6)所示之化合物。此等之黏著助劑係可1種單獨或混合2種以上而使用。
〔式中,R10、R11及R12係分別獨立地表示氫原子、碳數1~5之烷基、碳數1~5之烷氧基、碳數1~5之烷氧基羰基、或、芳基,R13係表示(甲基)丙烯醯基、乙烯基、異氰酸酯基、咪唑基、氫硫基、胺基、甲基胺基、二甲基胺基、苯甲基胺基、苯基胺基、環己基胺基、嗎啉基、六氫化吡嗪基、脲基、或縮水甘油基,c表示1~10之整數〕。
於本發明之黏著劑組成物中係以應力緩和及黏著性提昇作為目的,亦可添加橡膠成分。就橡膠成分而言可舉例如聚異戊二烯、聚丁二烯、羧基末端聚丁二烯、羥基末端聚丁二烯、1,2-聚丁二烯、羧基末端1,2-聚丁二烯、羥基末端1,2-聚丁二烯、丙烯酸橡膠、苯乙烯-丁二烯橡膠、羥基末端苯乙烯-丁二烯橡膠、丙烯腈-丁二烯橡膠、於聚合物末端含有羧基、羥基、(甲基)丙 烯醯基或嗎啉基之丙烯腈-丁二烯橡膠、羧基化腈橡膠、羥基末端聚(氧亞丙烯)、烷氧基甲矽烷基末端聚(氧亞丙烯)、聚(氧四亞甲基)二醇、聚烯烴二醇、聚-ε-己內酯。
上述橡膠成分係從黏著性提昇之觀點,宜為於側鏈或末端含有高極性基之氰基、羧基之橡膠成分,進一步從流動性提昇之觀點,宜為液狀橡膠。橡膠成分具體上可舉例如液狀丙烯腈-丁二烯橡膠、於聚合物末端含有羧基、羥基、(甲基)丙烯醯基或嗎啉基之液狀丙烯腈-丁二烯橡膠、液狀羧基化腈橡膠。在此等之橡膠成分中,極性基之丙烯腈含有量宜為5~60質量%。此等之化合物係可1種單獨或混合2種以上而使用。
本發明之黏著劑組成物的使用形態並無特別限制,但例如可使用來作為使上述各成分溶解及/或分散於溶劑之塗佈液。溶劑並無特別限制,但可舉例如甲苯、甲乙酮(MEK)、醋酸乙酯、醋酸異丙酯等。
又,本發明之黏著劑組成物係使含有上述各成分之組成物塗佈於氟樹脂薄膜、聚對苯二甲酸乙二酯薄膜、離型紙等之剝離性基材上,或,可使用來作為含浸於不織布等之基材而載置於剝離性基材上之薄膜狀黏著劑。
圖1係表示本發明之薄膜狀黏著劑的一實施形態之模式截面圖。圖1所示之薄膜狀黏著劑1係使含有上述各成分之黏著劑組成物形成為薄膜狀而成者。若依此薄膜狀黏著劑1,很容易處理,可容易地設置於被黏體 ,可容易地進行連接作業。又,薄膜狀黏著劑1係亦可具有由2種以上之層所構成的多層構成(未圖示)。又,薄膜狀黏著劑1含有上述(h)導電性粒子(未圖示)時係可適宜使用來作為異方導電性薄膜。
本發明之黏著劑組成物及薄膜狀黏著劑1係一般可併用加熱及加壓而黏著被黏體間。加熱溫度無特別限定,但宜為100~250℃之溫度。壓力係只要為不對被黏體造成損傷之範圍,無特別限制,但一般宜為0.1~10MPa。此等之加熱及加壓宜在0.5秒~120秒的範圍進行。本發明之黏著劑組成物及薄膜狀黏著劑1係可於低溫且短時間之硬化,例如以140~200℃、3MPa之條件,即使以10秒鐘之短時間的加熱及加壓,亦可充分黏著被黏體間。
又,本發明之黏著劑組成物及薄膜狀黏著劑1係可使用來作為熱膨脹係數相異的異種被黏體之黏著劑。具體上係可使用來作為異方導電性黏著劑、銀漿、銀薄膜等為代表之電路連接材料、CSP用彈性體、CSP用底部填充材、LOC膠帶等為代表之半導體元件黏著材料。
以下,說明有關使用本發明之薄膜狀黏著劑作為異方導電性薄膜,於電路基板上之主面上連接形成電路電極之電路構件間之時的一例。亦即,使異方導電性薄膜配置於電路基板上相對峙之電路電極間,加熱加壓,俾進行對向之電路電極間之電氣連接與電路基板間之黏著,可連接電路構件。此處,形成電路電極之電路基板 係可使用半導體、玻璃、陶瓷等之無機物所構成的基板、由聚醯亞胺、聚碳酸酯等之有機物所構成之基板、玻璃等之無機物與環氧等之有機物之組合之基板等。又,於作為如此之電路連接材料之用途使用本發明之薄膜狀黏著劑時,此等係宜為含有導電性粒子。又,使用本發明之黏著劑組成物取代薄膜狀黏著劑,亦可直接塗佈於電路基板上。
圖2係表示本發明之電路連接構造體(電路構件的連接構造)之一實施形態的概略截面圖。如圖2所示般,本實施形態之電路構件的連接構造係具備相互對向之第一電路構件20及第二電路構件30,第一電路構件20與第二電路構件30之間設有連接此等之電路連接構件10。
第1電路構件20係具備電路基板(第一電路基板)21、與形成於電路基板21之主面21a上之電路電極(第一電路電極)22。又,於電路基板21之主面21a上係視情況亦可形成絕緣層(未圖示)。
另外,第二電路構件30係具備電路基板(第二電路基板)31、與形成於電路基板31之主面31a上之電路電極(第二電路電極)32。又,於電路基板31之主面31a上係視情況亦可形成絕緣層(未圖示)。
第一及第二電路構件20、30係只要為形成必須電氣連接之電極者即可,並無特別限制。具體上係可舉例如以於液晶顯示器所使用之ITO等形成電極之玻璃或 塑膠基板、印刷線路板、陶瓷電路板、可撓性電路板、半導體矽晶片等,此等係依需要而組合使用。如此地,本實施形態中,係以由印刷電路板或聚醯亞胺等之有機物所構成之材質為首,如銅、鋁等之金屬或ITO(Indium tin oxide)、氮化矽(SiNx)、二氧化矽(SiO2)等的無機材質般可使用具有各式各樣的表面狀態之電路構件。
電路連接構件10係由本發明之黏著劑組成物或薄膜狀黏著劑之硬化物所構成者。此電路連接構件10係含有絕緣性物質11及導電性粒子7。導電性粒子7係不僅對向之電路電極22與電路電極32之間,亦配置於主面21a、31a之間。電路構件之連接構造中係電路電極22、32介由導電性粒子7而電氣連接。亦即,導電性粒子7直接接觸於電路電極22、32之雙方者。
此處,導電性粒子7係先前所說明之(h)導電性粒子,絕緣性物質11係構成本發明之黏著劑組成物及薄膜狀黏著劑之絕緣性的各成分之硬化物。
在此電路構件之連接構造中係如上述般,對向之電路電極22與電路電極32介由導電性粒子而電氣連接。因此,可充分降低電路電極22、32間之連接電阻。因此,可使電路電極22、32間之電流流動順利地進行。可充分發揮電路具有之功能。又,電路連接構件10不含有導電性粒子7時,係以電路電極22與電路電極32直接接觸電氣連接。
電路連接構件10係以本發明之黏著劑組成物或薄 膜狀黏著劑之硬化物所構成,故電路連接構件10對電路構件20或30之黏著強度變成非常高,即使在信賴性試驗(高溫高濕試驗)後亦可維持安定之性能(黏著強度或連接電阻)。
其次,說明有關上述之電路構件的連接構造的製造方法之一例。首先,準備上述之第1電路構件20、與薄膜狀黏著劑(薄膜狀電路連接材料)40(參照圖3(a))。薄膜狀電路連接材料40係使本發明之黏著劑組成物(電路連接材料)形成為薄膜狀者,含有導電性粒子7與黏著劑成分5。又,電路連接材料為不含有導電性粒子7時,其電路連接材料係可作為絕緣性黏著劑而使用於異方導電性黏著,尤其有時亦稱為NCP(Non-Conductive Paste)。又,電路連接材料為含有導電性粒子7時,係其電路連接材料係有時亦稱為ACP(Anisotropic Conductive Paste)。
薄膜狀電路連接材料40之厚度宜為10~50μm。薄膜狀電路連接材料40之厚度不足10μm,係於電路電極22、32間電路連接材料有成為填充不足之傾向。另外,若超過50μm,無法充分排除盡電路電極22、32間之黏著劑組成物,電路電極22、32間之導通的確保有變困難之傾向。
其次,使薄膜狀電路連接材料40載置於形成第一電路構件20的電路電極22之面上。又,薄膜狀電路連接材料40附著於支撐體(未圖示)上之情形,係以使 薄膜狀電路連接材料40側面向第一電路構件20,而載置於第一電路構件20上。此時,薄膜狀電路連接材料40為薄膜狀,容易處理。因此,於第一電路構件20與第二電路構件30之間可容易地介入薄膜狀電路連接材料40,可容易地進行第一電路構件20與第二電路構件30之連接作業。
繼而,使薄膜狀電路連接材料40朝圖3(a)之箭號A及B方向加壓,使薄膜狀電路連接材料40暫連接於第一電路構件20(參照圖3(b))。此時,也可以一邊加熱一邊加壓。但,加熱溫度係低於薄膜狀電路連接材料40中之黏著劑組成物不硬化之溫度,亦即,比自由基聚合起始劑產生自由基之溫度低的溫度。
繼而,如圖3(c)所示般,以使第二電路電極30朝向第一電路構件20之方式於薄膜狀電路連接材料40上載置第二電路構件。又,薄膜狀電路連接材料40附著於支撐體(未圖示)上時係剝離支撐體後使第二電路構件30載置於薄膜狀電路連接材料40上。
繼而,一邊加熱薄膜狀電路連接材料40,一邊朝圖3(c)之箭號A及B方向介由第一及第二電路構件20、30而加壓。此時之加熱溫度係形成自由基聚合起始劑可產生自由基之溫度。藉此,於自由基聚合起始劑中產生自由基,開始自由基聚合性化合物之聚合。如此一來,薄膜狀電路連接材料40被硬化處理而進行本連接,可得到如圖2所示之電路構件的連接構造。
此處,連接條件如先前敘述般,宜為加熱溫度100~250℃,壓力0.1~10MPa,連接時間0.5秒~120秒。此等之條件係可依所使用之用途、黏著劑組成物、電路構件而適當選擇,依需要而進行後硬化。
藉由如上述般做法而製造電路構件之連接構造,俾於所得到之電路構件的連接構造中,可使導電性粒子7接觸於對向之電路電極22、32之兩者,可充分降低電路電極22、32間之連接電阻。
又,藉由薄膜狀電路連接材料40之加熱,以充分減少電路電極22與電路電極32之間的距離之狀態,黏著劑成分5硬化而成為絕緣性物質11,第一電路構件20與第二電路構件30介由電路連接構件10而牢固地連接。亦即,在所得到之電路構件的連接構造中係藉電路連接構件10由本發明之薄膜狀黏著劑所構成之電路連接材料的硬化物所構成,故電路連接構件10對電路構件20或30之黏著強度非常高,同時並可充分地降低電氣連接之電路電極間的連接電阻。
又,在上述實施形態中係就黏著劑成分5而言,可使用含有至少藉加熱產生自由基之自由基聚合起始劑者,但亦可使用只以光照射產生自由基之自由基聚合起始劑取代此自由基聚合起始劑。此時,當薄膜狀電路連接材料40之硬化處理時,只要進行光照射取代加熱即可。又,在上述實施形態中係使用薄膜狀電路連接材料40而製造電路構件的連接構造,但亦可使用未形成薄 膜狀之電路連接材料取代薄膜狀電路連接材料40。此時,使電路連接材料溶解於溶劑中,只要使其溶液塗佈於第一電路構件20或第二電路構件30的任一者,乾燥即可,可於第一及第二電路構件20、30間介入電路連接材料。
又,在電路構件之連接構造的製造方法中係除了藉加熱或光照射產生自由基之自由基聚合起始劑外,依需要而亦可使用藉超音波、電磁波等產生自由基之自由基聚合起始劑。又,黏著劑成分5亦可使用環氧樹脂及其潛在性硬化劑。
又,圖4係表示使用本發明之薄膜狀黏著劑所製造之半導體裝置的一實施形態之模式截面圖。如圖4所示般,半導體裝置2係具備半導體元件50與成為半導體的支撐構件之基板60,於半導體元件50及基板60之間係設有電氣連接此等之半導體元件連接構件80。又,半導體元件連接構件80係層合於基板60之主面60a上,半導體元件50係進一步層合於其半導體元件連接構件80上。
基板60係具備電路圖型61,電路圖型61係於基板60之主面60a上介由半導體連接構件80或直接與半導體元件50電氣連接。繼而,其等藉密封材70密封,形成半導體裝置2。
半導體元件50之材料並無特別限制,但可使用矽、鍺之4族半導體元件、GaAs、InP、GaP、InGaAs、 InGaAsP、AlGaAs、InAs、GaInP、AlInP、AlGaInP、GaNAs、GaNP、GaInNAs、GaInNP、GaSb、InSb、GaN、AlN、InGaN、InNAsP等之Ⅲ-V族化合物半導體元件、HgTe、HgCdTe、CdMnTe、CdS、CdSe、MgSe、MgS、ZnSe、ZeTe等之Ⅱ-Ⅵ族化合物半導體元件、繼而,CuInSe(ClS)等之各種者。
半導體元件連接構件80係含有絕緣性物質11及導電性粒子7。導電性粒子7係不僅半導體元件50與電路圖型61之間,亦配置於半導體元件50與主面60a之間。於半導體裝置2中係半導體元件50與電路圖型61介由導電性粒子7而電氣連接。因此,半導體元件50及電路圖型61間之連接電阻可充分地降低。因此,可使半導體元件50及電路圖型61間之電流流動順利地進行,可充分地發揮半導體具有的功能。
又,半導體元件連接構件80不含有導電性粒子7時係以所希望的量之電流的方式使半導體元件50及電路圖型61直接接觸,或充分地接近以電氣連接。
半導體元件連接構件80係藉由上述本發明之薄膜狀黏著劑的硬化物所構成。從此事,半導體元件連接構件80對半導體元件50及基板60之黏著強度係非常高,且半導體元件50及電路圖型61間之連接電阻變成非常小。又,半導體元件連接構件80係可藉由低溫短時間之加熱處理來形成者。因而,半導體裝置2係可具有高於以往之信賴性。
又,半導體裝置2係在上述電路構件的連接構造的製造方法中之第一及第二電路構件20、30使用基板60及半導體元件50,可以上述電路構件之連接構造的製造方法同樣之方法來製造。
【實施方式】
實施例
以下,依據實施例及比較例而更具體地說明本發明,但本發明係不限定於以下之實施例。
(苯氧樹脂之準備)
使苯氧樹脂(商品名:YP-50,東都化成公司製)40g溶解於甲乙酮60g,而形成固形分40質量%之溶液。
(聚酯胺基甲酸乙酯樹脂之準備)
使聚酯胺基甲酸乙酯樹脂(商品名:UR-1400,東洋紡公司製)係使用固形分30質量%之甲乙酮與甲苯之1:1(質量比)混合溶劑溶解品。
(自由基聚合性化合物之準備)
三聚異氰酸EO改性二丙烯酸酯(商品名:M-215、東亞合成股份公司製)。
(胺基甲酸乙酯丙烯酸酯之合成)
於具備攪拌機、溫度計、具有氯化鈣乾燥管之回流冷卻管、及、氮氣導入管之反應容器中,投入數目平均分子量860之聚(六亞甲基碳酸酯)二醇(Aldrich公司製)860g(1.00莫耳)、及二丁基錫二月桂酸酯(Aldrich公司製)5.53g。於反應容器內充分地導入氮氣後,加熱至70~75℃,花3小時均一地滴下異氟爾酮二異氰酸酯(Aldrich公司製)666g(3.00莫耳),反應。
滴下終了後,繼續反應10小時。再投入2-羥乙基丙烯酸酯(Aldrich公司製)238g(2.05莫耳)、及、氫醌單甲基醚(Aldrich公司製)0.53g,進而反應10小時,藉IR測定確定異氰酸酯消失而終止反應,得到胺基甲酸乙酯丙烯酸酯(UA)。所得到之UA的數目平均分子量為3700。
(含磷酸基之乙烯基化合物的準備)
準備2-(甲基)丙烯醯氧乙基磷酸酯(商品名:Light-ester P-2M、共榮社股份公司製)。
(環氧樹脂之準備)
準備PO改性BisA型環氧樹脂(商品名:Adeka Resin EP-4010S、股份公司ADEKA製)作為環氧樹脂。
(有機微粒子之準備)
就有機微粒子而言,分別準備具有三維交聯構造之甲基丙烯酸烷酯-丁二烯-苯乙烯共聚合物(商品名:Metaprene C-223 A:三菱Rayon公司製:Tg:-70℃、平均粒徑:400nm)、及、丙烯酸-矽酮共聚合物(商品名:CHALINE R-210、日信化學工業公司製、Tg:-80℃、平均粒徑:200nm)。
(交聯聚丁二烯粒子之準備)
於不銹鋼製高壓鍋中置入純水,再添加聚乙烯醇(關東化學公司製)作為懸濁劑而溶解。於此中置入丁二烯(Aldrich公司製),進行攪拌而分散。進一步,置入過氧化苯甲醯(商品名:Cadox CH-50L、化藥AKZO公司製)作為自由基聚合起始劑,攪拌而溶解。
然後,使高壓鍋昇溫至60~65℃,一邊攪拌一邊聚合45分鐘。其後,釋出未反應之單體後,過濾所生成之交聯聚丁二烯粒子,水洗淨,乙醇洗淨。在真空中乾燥洗淨後之交聯聚丁二烯粒子,得到平均粒徑500nm之交聯聚丁二烯粒子(BR)。
(自由基聚合起始劑之準備)
準備第三己基過氧化-2-乙基己酸酯(商品名:Perhexyl O,日本油脂股份公司製)作為自由基聚合起始劑。
(潛在性硬化劑之準備)
準備硫鎓鹽(商品名:San-aid SI-60L、三新化成工業股份公司製)作為潛在性硬化劑。
(導電性粒子之製作)
於聚苯乙烯粒子之表面上,以成為厚0.2μm之方式設有由鎳所構成之層,進一步於由鎳所構成之層的表面上,以成為厚0.02μm之方式設有由金所構成之層。如此做法而製作平均粒徑4μm、比重2.5之導電性粒子。
(實施例1~10、比較例1~5)
使上述之各材料就固形質量比以下述表1所示之比例(單位:質量份)進行調配,進一步,調配分散上述導電性粒子使其成為所得到之黏著劑組成物的固形分全體積之1.5體積%,得到黏著劑組成物。所得到之黏著劑組成物,使用塗佈裝置塗佈成厚80μm之氟樹脂薄膜,在70℃下進行10分鐘之熱風乾燥,俾得到黏著劑層厚為20μm之薄膜狀黏著劑。
〔黏著強度及連接電阻之測定〕
使用於實施例及比較例所得到之薄膜狀黏著劑,使具有線寬25μm、線距50μm及厚18μm之銅電路500條之可撓性電路板(FPC)、與、形成厚0.2μm之氧化銦(ITO)的薄層之玻璃(厚1.1mm、表面電阻20Ω/□),使用熱壓接裝置(加熱方式:恆溫加熱(constant heat)型、Toray Engineering股份公司製)而以160℃之溫度、壓力3MPa之條件進行10秒鐘之加熱加壓。藉此 ,製作一涵蓋寬2mm使FPC基板與ITO基板藉薄膜狀黏著劑之硬化物連接之連接體(電路構件之連接構造)。
使此連接體之鄰接電路間的電阻值(連接電阻),黏著之後,於85℃、85%RH之高溫高濕中保持250小時後,以多功能計進行測定。電阻值係以鄰接電阻間之電阻37點的平均表示。結果表示於表2中。
又,依據JIS-Z0237而以90度剝離法測定此連接體之黏著強度,進行評估。此處,黏著強度之測定裝置係使用東洋Baldwin股份公司製之Tensilon UTM-4(剝離速度50mm/分、25℃)。結果表示於表2中。
從表2所示之結果明顯可知,實施例1~10所得到之薄膜狀黏著劑係在加熱溫度160℃,時間10秒之連接條件中,黏著之後及於85℃、85%RH之高溫高濕中保持250小時後之兩者,表示良好的連接電阻及黏著強度,確認出顯示良好的特性。
對於此等,在不使用本發明之有機微粒子的比較例1~2及4~5中,於黏著之後及高溫高濕處理後之兩者,黏著強度差,高溫高濕處理後,可看到黏著強度的降低及連接電阻之上昇。又,使用交聯聚丁二烯粒子取代本 發明之有機微粒子的比較例3中,於黏著之後及高溫高濕處理後之兩者,黏著電阻差,高溫高濕處理後,可看到黏著強度大幅的降低及連接電阻之大幅上昇。
產業中之利用可能性
如以上說明般,若依本發明,可提供一種顯示優異之黏著強度,即使在信賴性試驗(例如85℃/85%RH放置)後,亦可維持安定的性能之黏著劑組成物、使用其之薄膜狀黏著劑及電路構件之連接構造。
雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,故本發明之保護範圍當視後附之申請專利範圍所界定者為準。
1‧‧‧薄膜狀黏著劑
2‧‧‧半導體裝置
5‧‧‧黏著劑成分
7‧‧‧導電性粒子
10‧‧‧電路連接構件
11‧‧‧絕緣性物質
20‧‧‧第1電路構件
21‧‧‧電路基板(第1電路基板)
21a‧‧‧主面
22‧‧‧電路電極(第一電路電極)
30‧‧‧第二電路構件
31‧‧‧電路基板(第二電路基板)
31a‧‧‧主面
32‧‧‧電路電極(第二電路電極)
40‧‧‧薄膜狀電路連接材料
50‧‧‧半導體元件
60‧‧‧基板
61‧‧‧電路圖型
70‧‧‧密封材
80‧‧‧半導體元件連接構件
圖1係表示本發明之薄膜狀黏著劑的一實施形態之模式截面圖。
圖2係表示本發明之電路構件的連接構造之一實施形態的模式截面圖。
圖3(a)~(c)係分別連接電路構件之一連串的步驟圖。
圖4係表示半導體裝置的一實施形態之模式截面圖。
7‧‧‧導電性粒子
10‧‧‧電路連接構件
11‧‧‧絕緣性物質
20‧‧‧第1電路構件
21‧‧‧電路基板(第1電路基板)
21a‧‧‧主面
22‧‧‧電路電極(第一電路電極)
30‧‧‧第二電路構件
31‧‧‧電路基板(第二電路基板)
31a‧‧‧主面
32‧‧‧電路電極(第二電路電極)

Claims (14)

  1. 一種黏著劑組成物,其特徵係含有含由(a)(甲基)丙烯酸烷基酯-丁二烯-苯乙烯共聚合物或複合體、(甲基)丙烯酸烷基酯-矽酮共聚合物或複合體、及、矽酮-(甲基)丙烯酸共聚合物或複合體所成群所選出之至少1種的有機微粒子。
  2. 如申請專利範圍第1項之黏著劑組成物,其係含有(b)自由基聚合性化合物、及、(c)自由基聚合起始劑。
  3. 如申請專利範圍第1項之黏著劑組成物,其係含有(d)環氧樹脂、及、(e)潛在性硬化劑。
  4. 如申請專利範圍第1~3項中任一項之黏著劑組成物,其中,前述(a)有機微粒子的Tg為-100~70℃。
  5. 如申請專利範圍第1~4項中任一項之黏著劑組成物,其中,前述(a)有機微粒子係含具有三維交聯構造之聚合物之粒子。
  6. 如申請專利範圍第1~5項中任一項之黏著劑組成物,其中,前述(a)有機微粒子係含重量平均分子量100萬~300萬的聚合物之粒子。
  7. 如申請專利範圍第1~6項中任一項之黏著劑組成物,其中,前述(a)有機微粒子的含有量以黏著劑組成物的固形分全量為基準,為5~80質量%。
  8. 如申請專利範圍第1~7項中任一項之黏著劑組 成物,其中,前述(a)有機微粒子係具有核殼型構造之粒子。
  9. 如申請專利範圍第1~8項中任一項之黏著劑組成物,其係含(f)於分子內具1個以上之磷酸基的乙烯化合物。
  10. 如申請專利範圍第1~9項中任一項之黏著劑組成物,其係含(g)熱可塑性樹脂。
  11. 如申請專利範圍第10項之黏著劑組成物,其中,前述(g)熱可塑性樹脂係含選自苯氧樹脂、聚酯樹脂、聚胺酯樹脂、聚酯胺酯樹脂、縮丁醛樹脂(butyral resin)、丙烯酸樹脂、及、聚醯亞胺樹脂所成群之至少1種者。
  12. 如申請專利範圍第1~11項中任一項之黏著劑組成物,其係含有(h)導電性粒子。
  13. 一種薄膜狀黏著劑,其特徵係使申請專利範圍第1~12項中任一項之黏著劑組成物形成薄膜狀而成。
  14. 一種電路構件之連接構造,其特徵係具備呈對向配置的一對電路構件、與設置於前述一對電路構件間,且將前述一對電路構件彼此黏接,使得前述一對電路構件所具有之電路電極相互電連接的連接構件,該連接構件係由申請專利範圍第1~12中任一項之黏著劑組成物的硬化物所成者。
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