TWI375967B - Adhesive film, connecting method, and connected structure - Google Patents

Adhesive film, connecting method, and connected structure Download PDF

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Publication number
TWI375967B
TWI375967B TW097124788A TW97124788A TWI375967B TW I375967 B TWI375967 B TW I375967B TW 097124788 A TW097124788 A TW 097124788A TW 97124788 A TW97124788 A TW 97124788A TW I375967 B TWI375967 B TW I375967B
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Taiwan
Prior art keywords
adhesive layer
substrate
resin component
temperature
film
Prior art date
Application number
TW097124788A
Other languages
English (en)
Other versions
TW200908027A (en
Inventor
Tomoyuki Ishimatsu
Hiroki Ozeki
Original Assignee
Sony Chem & Inf Device Corp
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Publication date
Application filed by Sony Chem & Inf Device Corp filed Critical Sony Chem & Inf Device Corp
Publication of TW200908027A publication Critical patent/TW200908027A/zh
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Publication of TWI375967B publication Critical patent/TWI375967B/zh

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • C—CHEMISTRY; METALLURGY
    • 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
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Landscapes

  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Wire Bonding (AREA)
  • Non-Insulated Conductors (AREA)
  • Combinations Of Printed Boards (AREA)
  • Laminated Bodies (AREA)

Description

1375967 九、發明說明： 【發明所屬之技術領域】 本發明關於用於連接電子零件之膠膜、連接方法及接 合體。 【先前技術】 過去以來’將電子零件或配線板連接到基板上時，使 用各向異性導電性黏著劑。各向異性導電性黏著劑具有膠 黏劑及散佈在膠黏劑中的導電性粒子。 在配置有基板的端子之面與配置有電子零件的端子之 面之間，配置各向異性導電性黏著劑並予以加熱押壓，軟 化的膠黏劑則會從基板的端子與電子零件的端子之間展 開，使導電性粒子夾持在基板的端子與電子零件的端子之 間’基板與電子零件互相電連接。 但是，會有膠黏劑被展開時，導電性粒子的一部分與 膠黏劑一起展開，被展開的導電性粒子，流入到基板所相 4的子間或電子零件所相鄰的端子間’因導電性粒子而 使相鄰的端子間短路（sh〇rt)的情況。 另外，導電性粒子從基板的端子與電子零件的端子之 間展開，夾持導電性粒子的數量則會因基板的端子與電子 零件的端子而變少，造成導通的可靠度也劣化。 專利文獻1:日本專利特開2006_32335號公報 專利文獻2 :曰本專利特開平7 —230840號公報 5 > 【發明内容】 本發明的課觸解決習知的前述㈣題並達成以下的 :=p是本發明的目的係提供既不會引起短路_ 麟電子零件連接到基板之膠膜、連接方法及接合體。 用來解決前述課題的手段，如同以下所述。亦即， 於H種膠臈，鄉膜係具有第—黏著劑層、及密著 中崎減M s之弟—黏制，在前述第-黏著劑層 層成:述!::r及前述第二黏著劑 、成刀7别述弟一黏著劑層及前述第二 皿’刖述第-黏著劑層和前述第二黏著劑層中 =述副樹脂成分則會起反應，使前述第—黏著劑層及前 破Li 層硬化，其特徵為：前述第—黏著劑層含有： 轉移溫度兩於前述副樹脂成分之第一主樹脂成分，前 二第=著劑層含有：玻璃轉移溫度高於前述副樹月旨成 二且玻璃轉移溫度餘前述第—主樹脂成分之第二主樹 y分’前述第-黏著劑層和前述第二黏著劑層升溫中， =第一黏著劑層和前述.第二黏著劑層的發熱量變最大之 %顛峰溫度’低於前述第一主樹脂成分的玻璃轉移溫 -’且局於前述第二主樹脂成分的玻璃轉移溫度。 一 <2>如同前述第<!>項所述_著劑層，其中，第 1著劑層㈣厚為㈣性粒子之平均粒㈣Q5倍以 上，2.0倍以下。 13 膜，^ >如同前述第<!>至<2>項中任一項所述的膠 、/、中，弟一主樹脂成分的玻璃轉移溫度為5〇它以上， 1375967 110°C以下。 <4>如同前述第<1>至<3>項中任一項所述的膠 膜，其中，第一黏著劑層的反應顛峰溫度與第二黏著劑層 的反應顛岭溫度之差被設定為l〇°C以下。 <5>—種連接方法’該連接方法係令第一基板的電極 與第二基板的電極，隔著前述第<1>至<4>項中任—項 所述的膠膜相對向’將前述第一基板與前述第二基板予以 加熱押壓，令前述膠膜中的導電性粒子夾持在前述第一基 板的電極與前述第二基板的電極之間，以將前述第一基板 與第前述二基板相連接。 <6>-種接合體’該接合體的特徵為：具備有以前述 第<5>項所述的連接方法來相連接之第―基板及第二基 板。 依據本發明，將前述過去以來的諸問題予以解決，可 以達成前述目的，又可以提供既不會引起短路（也⑻又 能夠將電子零件連接到基板之_、連接方法及接合體。 本發明係以上述方式所構成，副樹 經 進行聚合之樹脂（例如，熱硬化性樹脂）。3力，、、、來 第一黏著劑層和第二黏著劑芦 在第-黏著劑層和第二黏著靜叫脂成分則會 反應具體上是指副樹脂成分單;進行聚f:=脂成分起 其他的成分起反應，單獨進行聚合或::聚= 情況皆會使第一黏著劑層和第二霉二何一種 則是溫度愈高則愈増加’但超過“:發熱量 7 1375967 本發明中，在令散佈有導電性粒子的狀態之第— 劑層升溫之間，將發熱量從增加轉變為減少的溫度作 一黏著劑層的反應顛♦溫度，在令第二料劑層升 間，將發熱量從增加轉變為減少的溫度作為第二^ ^應顛峰溫度。發熱量及反應顛峰溫度則是用例如咖 (熱不差掃描分析儀）來進行測定。 第-著劑層仙玻璃轉移溫度高於第—黏著劑層和 :-黏者劑層的反應顛峰溫度之第—主樹脂成分作為原 料二將該原、料和其他原料（副樹脂成分或添 ::,製::原料液體，塗佈在酬^ 層之後，將該原料予以乾燥來除去多餘的溶劑而形成。 的玻係以玻璃轉移溫度低於第-， 且低於第一黏著劑層和第二黏著劑層的 他^/溫度之第二主樹脂成分作為原料，將該原料和並 :分或添加劑)一起與溶劑混合，製作原 ^體、’㈣在剝離薄膜的表面而形成塗佈層之後，將該 ’、；斗予以乾燥來除去多餘的溶劑而形成。 ° 脂成分和第二主樹脂成分為玻 ㈤南於常溫⑽）⑽以上，更好的是听以上， 的间分子物質，化學性穩定。 原料樹脂成分的玻璃轉移溫度係即使是作為 黏著::=:=即_和乾燥後含在第-反應仍一第一黏著劑層和第二黏著劑層的 1375967 原料=在成移溫度係即使响 中之則，或％合和乾燥後含在第二黏荽旬 均矛弟一黏著劑層的反應顛峰溫度。 相η第：主，，分和第二主樹月旨成分的玻璃轉移溫度為 解。作是，太恭 第-黏考劑層會在大致同時開始熔 中，第一主樹脂成分的玻璃轉移溫度， 去笛一」月曰成分的玻璃轉移溫度’所以第—黏著劑芦 和苐—黏著劑層，開始熔解的溫卢 曰 熔解的溫度，不纽解第-黏著^層。σ 著劑層 著，:::=在端子之間予以加熱押屬時，即使第二黏 殘留著，故被散佈在第一，丄黏：劑層仍不會炫解而 端子間•殘留在第 =1:中之導電性粒子’不會從 -黏粒子不會從相對向的端子間展開，殘留在第 的數:二力曰：以相對向的端子間所捕捉的導電性粒子 里日加。另外，相_端子間不會流人導電性粒子 相鄰的端子間不會因導電性粒子而短路（short)。因 彳發㈣膠膜來與基板㈣接之連接 【實施方式】 膜係至少具有相互密著的 第一黏著劑層和 (膠膜） 本發明的膠 1375967 第二黏著劑層，還具有因應於進一步所需作適切選擇的其 他層而形成。 <第一黏著劑層> 前述第一黏著劑層，至少含有導電性粒子、副樹脂成 分、以及第一主樹脂成分，還含有因應於進一步所需作適 當選擇的其他成分。 一導電性粒子一 前述導電性粒子若為散佈在前述第一黏著劑層的話， 並沒有特別的限定，可以依照目的來作適當選擇。 具體上列舉有：以鎳、銅、钻等的金屬為主成分之金 屬粒子，或對前述金屬粒子的表面進一步施予鍍金之金屬 粒子、對有機微粒子的表面施予鍍鎳、鍍銅、鍍金、鍍錫 等的導電性覆膜之金屬粒子等。 前述導電性粒子也可單獨將一種散佈在第一黏著劑 層，還可以將二種以上散佈在相同第一黏著劑層中。被附 著體（電子零件或基板）之連接端子的表面容易氧化的情 況，也可以使用導電性粒子的表面附加有鎳等的突出物之 金屬粒子。 另外，為了要對應於前述連接端子的微距，也可以使 用將經熱會熔解的樹脂塗佈在前述導電性粒子的表面之絕 緣性覆膜粒子。 前述導電性粒子的粒徑（平均粒徑）係依照連接端子 的間距及面積來區分使用，不過本提案中最好是平均粒徑 為Ιμιη以上，50μιη以下。前述導電性粒子的平均粒徑小 1375967 &易引起/¾在—起反而會導致短路的發 本 導電性粒子的平均粒徑大於50叫的情況， 2 以微距連接為主目的的膠膜，會衰退本發明的 效果。 —副樹脂成分~~
前述副樹脂成分並沒有特別的限定，可以依照目的來 作適當選擇，例如列舉魏_脂及結晶性樹脂等。 前述副樹脂成分是-種玻璃轉移溫度低於後述的第一 主樹脂成分和第二主_旨成分的麵轉移溫度，到達特定 的硬化溫度以上則會聚合之樹脂’對黏著劑層賦予硬化性。 前述液狀樹脂是-種玻璃轉移溫度低於常溫（3〇τ：)， 常溫（30°C)時為㈣’但加熱到高於常溫（贼）之特 疋的硬化溫度以上則會聚合之樹月旨。常溫（3〇。〇時該聚 合物為固體。
於1 μιη的情泥， 生。 前述結晶性樹脂是一種即是常溫（3(rc)時為固體（結 晶），-旦加熱到高於常溫（3(rc)的特定轉溫度致使熔 解之後’回到常溫（30。〇仍會維持液狀之樹脂。溶解過 後的結晶性樹脂，加熱到特定的硬化開始溫度以上則會進 行聚合。常溫C 30 C )時該聚合物為固體。 具體上，前述結晶性樹脂列舉有：環氧樹脂、丙稀酸 酯、甲基丙烯酸酉旨、矽烷耦合劑、三聚氰胺樹脂、以及酚 樹脂等。 前述的第一黏著劑層和後述的第二黏著劑層，可以含 1375967 有相同種類的副樹脂成分，也可以含有不同種類的副樹脂 成分，不過為了要提高第一黏著劑層和第二黏著劑層之黏 著劑層的密著性，最好是含有相同種類的副樹脂成分。 —第一主樹脂成分— 第一主樹脂成分若為玻螭轉移溫度高於前述副樹脂成. 分的話並缘有特別的限定，可以依照目的來作適當選擇。 例如，列舉有.苯氧基樹脂、聚胺基甲酸乙酯樹脂、飽和 聚酯、丙烯酸橡膠、NBR(nitrile_butadiene rubber ; 丁腈橡- 膠）' 聚丁二稀橡膠、聚苯乙稀、聚乙浠、聚醋酸乙稀酉旨和 · 這些共聚物等。這些樹脂為熱可塑性樹脂。 常溫（30C )時，前述第—主樹脂成分為固體的固態 樹脂。即疋第一主樹脂成分的玻璃轉移溫度，高於常溫 (30t：)。 前述第一主樹脂成分所擔負重要任務係作為用來變成 薄片狀的膜成分。
•刖述第一主樹脂成分是一種以玻璃轉移溫度為界線在 A 固體與液體間進行變化之樹脂，若為玻璃轉移溫度高於常. 溫（30°C)的話，並不侷限於熱可塑性樹脂，例如可以使 用玻璃轉移溫度低於聚合開始溫度，且高於常溫 (30°C ) : 之熱硬化性樹脂。前述熱硬化性樹脂列舉有：主骨幹的末 端結合了壤氧基之高分子環氧樹脂、或將末端環氧基予以 丙烯K匕之壤氧丙歸酸醋等。作為前述第一主樹脂成分來 使用之熱硬化性樹脂，分子量高於副樹脂成分所使用的熱 硬化性樹脂。 12 1375967 —其他成分一 前述其他成分並沒有特別的限定，可以依照目的來作 適當選擇，如列舉有：無機充填物、有機充填物等。 <第二黏著劑層> 前述第二黏著劑層係至少含有副樹脂成分和第二主樹 脂成分，且含有依照目的作適當選擇之其他成分而形成。 此外，前述.第二黏著劑層之副樹脂成分，如同前述第一黏 著劑層中的記載。 —第二主樹脂成^ 第二主樹脂成分若為玻璃轉移溫度高於前述副樹脂成 分，且玻璃轉移溫度低於前述第一主樹脂成分的話，並沒 有特別的限定，可以依照目的來作適當選擇。例如，列舉 有：苯氧基樹脂、聚胺基甲酸乙酯樹脂、飽和聚酯、丙烯 酸橡膠·、NBR(nitrile-butadiene rubber ; 丁腈橡膠）、聚丁二 烯橡膠、聚苯乙烯、聚乙烯、聚醋酸乙烯酯和這些共聚物 等。這些樹脂為熱可塑性樹脂。 常溫（30°C)時，前述第二主樹脂成分為固體的固態 樹脂。即是第二主樹脂成分的玻璃轉移溫度，高於常溫 (30°C ) ° 前述第二主樹脂成分所擔負重要任務係作為用來變成 薄片狀的膜成分。 前述第二主樹脂成分是一種以玻璃轉移溫度為界線在 固體與液體間進行變化之樹脂，若為玻璃轉移溫度高於常 溫（30°C)的話，並不侷限於熱可塑性樹脂，例如可以使 13 丄J/ 用玻璃轉移’皿度低於聚合開始溫度，且高於常溫（3〇。。） 之,、、、硬化H樹脂。Μ熱硬化性樹脂列舉有：主骨幹的末 端結合了環氧基之高分子環氧樹脂 、或將末端環氧基予以 ^化之％氧丙烯_旨等。作為前述第二主樹脂成分來 用之…、硬化性树脂，分子量高於副樹脂成分所使用的熱 硬化性樹脂。 一二主樹脂成分和第二车樹脂成分，分別可以將 、種:在别述第—黏著劑層和前述第二黏著劑層中，也可 .、♦二種以上含在第一黏著劑層和前述第二黏著劑層中。 前述第-主樹脂成分和前述第二主樹脂成分，可以使 用相同種類的樹脂，也可以使用不同種類的樹脂嗜用相 _類的樹脂來作為第—主樹脂成分和前述第二主樹脂成 '刀的若為將分子量高於前述第二主樹脂成分的樹脂 作為刖述第-主樹㈣分的話，前述第―主樹脂成分的玻 多里度咼於别述第一主樹脂成分的玻璃轉移溫度。 别述第一主樹脂成分係使用玻璃轉移溫度高於第一反 應顛峰溫度（第—黏著騎的反應跡溫度）和第二反應 顛峰溫度（第二黏著劑層的反應顛峰溫度）的樹脂。〜 相對於此，如述第二主樹脂成分係使用玻璃轉移溫度 低於别述第一主樹脂成分的玻璃轉移溫度，且低於第一反 應顛峰溫度和第二反應顛峰溫度的樹脂。 前述反應顛峰溫度係指進行熱示差掃描分析儀測定 (DSC)時，所獲得之DSC曲線的發熱顛峰為最大的溫度。 前述第一反應顛峰溫度和前述第二反應顛峰溫度^，&分 14 別最好是60°C以。 乂上’ 140°C以下的範圍。 前述第一 5腐 〜'顛峰溫度和前述第二反應顛峰溫度低於 、2則在，膠賤暫固定在基板等的被附著體時，會有前 述第·^著d層和前述第二黏著劑層開始^反應的 性，故並不理想。 度高=。=;〜應颠峰溫度和前述第二反應颠蜂溫
月况，在以2個附著體來夾持膠膜後進行 加^押壓之主屋合步驟，令前述第-黏著劑層和前述第二 々著:^層更化所而_^的時間超過2()秒鐘，導致無法在短時 間内相連接，惡化量產性。另外，即使會在2G秒鐘以下的 短日^間内相連接’該情況，必須以2机的高溫來相連接， 對附著體的破壞過大，故並不理想。
月ί述第反應顛峰溫度與前述第二反應顛峰溫度的差 超過10C ’刖述第一黏著劑層和前述第二黏著劑層當中， 反應顛峰狐度t低的—方會先硬化，故不僅在主壓合步驟 會受到壓人速度的限制，完成連接時間也會發生差距，所 以不適於短時間内相連接，故缺乏實用性。 使用玻璃轉移溫度為3代以下的樹脂，作為前述第一 主樹脂成分和刖述第二主樹脂成分，則會在賴成捲輪狀 變成製品時放置在常溫⑼。C)以上，料引起黏著劑滲 出’成為結塊（無法捲出）的原因，故並不理想。 —其他成分一 其他成分並沒有特別的限制，例如列舉有：導電性粒 子、無機充填物、有機充填物等。 15 1375967 <其他層> 的來作適當遽 一個例子，以 其他層並沒有特別的限制，可以依照目 擇。 此處’有關製造本發明的膠膜之步驟的 下參考圖面來進行說明。
將副樹脂成分、第一主樹脂成分、導I 电性粒子、耦合 劑或硬牝劑等的添加劑及溶劑予以混合，制从结 灰作第一原料浪 玻璃轉#溫度低於副樹赌成分、第—主樹脂成分之第 二主樹脂成分、耦合劑或硬化劑等的添加劑及溶劑予以混 合，製作第二原料液體。 a 為了要促進前述第一黏著劑層和第二黏著劑層中之副 樹脂成分的聚合反應，第一原料液體和第二原料液體，分 別最好是含有硬化劑。 前述硬化劑，若為會令前述第一黏著劑層和前述第二 黏者劑層中的副樹脂成分硬化的話，並沒有特別的限制， 可以依照目的來作適當選擇。例如，列舉有：令這些聚胺、 聚酿胺、咪嗤（imidazole)、令這些予以微膠囊化之胺系硬 化劑、錄鹽（onium salt)或鎮鹽（suif〇nium salt)等的陽 離子（cation)系硬化劑、有機化氧化物等的自由基起始劑 (Radical Initiator)、酸酐（acid anhydride)、以及硫醇（thiol) 系硬化劑等。 前述硬化劑可以單獨添加在第一原料液體和第二原料 液體中，也可以令二種以上含在第一原料液體和第二原料 16
1375967 V 液體中 另外，最好是將第—主樹k 以下
化劑組合在一起來製作原料液體，使前述 第一反應顛峰溫度與前述第二反應顛峰溫度之差變成KTC
第- Α圖和第一 Β圖中’在剝離薄膜21和剝離薄膜 22的表面分別塗佈第—原料液體和第二原料液體而形成塗 佈層之後，將塗佈層予以乾燥，除去多餘的溶劑，形成薄 膜狀的第一黏著劑層11和第二黏著劑層12。 如同上述，第一原料液體中含有導電性粒子15，第一 A圖則是導電性粒子15散佈在第一黏著劑㉟u巾。另外， 導電性粒子15並沒有散佈在第二黏著劑層12中，即使有 加以散佈的話，該粒子密度仍小於第一黏著劑層u。
令第-黏著劑層11和第二黏著劑層12之沒有剝離薄 膜的面相互密著，用押壓滾輪等進行押壓，將第一黏著劑 層11與第一黏著劑層12相黏貼在一起，以獲得本發明的 膠膜10 (第一 C圖）。 · 此外，膠膜10的製造方法，並不侷限於將第一黏著劑 層11與第一黏著劑層12相黏貼在一起的方式，也可以在 薄臈狀之第一黏著劑層11的表面塗佈第二原料液體之後 予以乾燥，形成第二黏著劑層12，還可以在薄膜狀之第二 黏著劑層12的表面塗佈第一原料液體之後予以乾燥，形成 第一黏著劑層11。 膠膜10係在第一黏著劑層11和第二黏著劑層丨2的表 17 面任方或雙方張貼剥離薄膜21和剝離薄膜22，以這樣 的狀態進行捲取，獲得膠膜1G的膜卷18 (第四圖’ Λ八第一黏著劑層11和第二黏著劑層12軟化，則敕化的 Ρ刀滲出，膠膜10彼此間相連接，導致膠膜10無法從膜 卷18捲出（結塊）。 ^ 、 、使用破璃轉移溫度為30°C上的樹脂來作為第一主樹月t ，分和第二主樹脂成分的話，常溫（30°C )下，第〜黏^ 悧層11和第二黏著劑層12不會軟化也不會炫解，所以艮 使在常溫（30°C)下長時間保管膜卷18仍不會弓|結换： 卷U的存放時間增長。 、 其次’利用本發明的膠膜10來說明基板與電你 連接之步驟的—個例子。 十令件相 使用本發明的膠膜10來加以連接之被附著體，並沒有 特別的限制，例如電子零件4 (第二基板）列舉有：半導 體晶片’其他還有電阻元件、COF (ChipOnFilm)褒置、 (Tape Automated Bonding)裝置等。 基板3 (第一基板）並不侷限於玻璃基板，列舉有： 硬質基板、軟性配線板等。 第二A圖中，被附著體也就是基板3 (LCD面板等） 具有如同玻璃板之基板本體31、及隔著特定間隔配置在基 板本體31的表面上之複數個第一端子35 (電極）。 將剝離薄膜21從第一黏著劑層u剝離，使第一黏著 劑層11表面露出’將膠膜10的第一黏著劑層U露出的面， 密著於基板3的第一端子35露出的面並予以暫黏貼（第二 18 1375967 B圖）〇 剝離薄膜2 2密著於第二黏著劑芦 貼前或暫黏貼後，將剝離薄膜 月/一黏= 12表面露出。 雕7弟一黏耆劑層 連接在第二C圖中的基板3之 =小於基板3之電子零件，電子零件^零Γ本體41 3配置在零件本體41的—面之複數個第二端子45(電 第-ΪΓ:子Γ之中心位置間的距離(間距)、及與各 之中心位置間的距離（凸塊間空間）變成相 的方4 2子45分別位於各第—端子35的正上面位置 的方式，將電子零件4予以對準位置，如第二㈣所示， 有電子零件4的第二端子45之側的面密著於第二黏 者知彳層12表面並予以暫固定。 第-黏著劑層U和第二黏著劑層12的反應颠峰溫 X均低於第-主樹脂成分的玻璃轉移溫度，且高於第二 主樹脂成分的玻璃轉移溫度。 、τ加熱手& 51升溫到高於第—主樹脂成分的玻璃轉 移溫度的溫度’再將該加熱手段51抵觸在被暫固定的基板 3與電子料4的任—方或雙方（第二d圖）。 、第黏著;^層11和第二黏著劑層12藉由傳導熱來逐 靳升mL首先田達到第二主樹脂成分的玻璃轉移溫度的 話’第一黏著劑層12熔解，藉由押壓來使第二端子45的 刖端展開熔解的第二黏著劑層12。 被展開的第二黏著劑層12流入 間，不過因導電性粒子未散佈在第 5 的篦-# 2 " 今茶剧層12，故相鄰 弟-好45間不會短路（short)。 因弟-主樹脂成分的玻璃轉移溫度高於 刀的玻璃轉移溫度，故第―黏著 主树月曰成 著劑層η 香^層11不會熔解，第一黏 hi赝11不會從苐一端子 此，導雷柯如m ”弟—绞子:45之間流出。因 ;子15並未從第一端子35盒第— 流出而餘留在第—黏著劑層„。 ”弟―〜子衫之間 溫度和第二黏著劑層12達到反應颠峰 月·) 從弟一端子45的前端决展pq每· 再令兮^“展開第二黏著劑層12， 丹亥别端接觸到第一黏著劑層 *香月彳層U來進一步押壓（第三 以上，反應顛峰溫 不會熔解也不會硬 在第二主樹脂成分的玻璃轉移溫度 度以下的溫度範圍，第一黏著劑層U 化，並沒有流動性，但有彈性變形可能 第—黏著_ Η的膜厚薄到導電性粒子^ :=倍以上，2·。倍以下，在第二端子45接觸到二 ;= 狀態下進一步加熱押歷，第-點著劑層η ^祕變形，第—端子35與第二端子45夹持導電性粒 于15而相電連接。 至少第一黏著劑層11位於導電性粒子15之間，不僅 導％ ! 生粒子15，就連第一端子35與第二端子45的前端， 也接觸到第一黏著劑層U。 持續加熱押廢，在第一端子35與第二端子45夹持導 20 1375967 2性粒子15之後，令第一黏著劑層u ::到反應颠峰温度，則第一黏著劑層„和第二:：2 〜中的3靖脂成分進行聚合反應，使第— ^ 弟二黏著劑層！2硬化，第—端子3 ^ 則藉由硬化的第一黏著劑層n予以固定一 45的别端 此外，經由押壓而流人到第二端子45間
與第二端子45的周園及相互間相鄰的第二= 間所路出之零件本體41相密著的狀態下予以硬化。 μ 一第一黏著劑層11在加熱押壓時不會從第一_子％與 =二端子45之間流出，但會變形而在與相互間相鄰之第二 端子35間的基板本體31相密著的狀態下予以固化。因此， 不僅第-端子35和第二端子45的前端’就連該周圍部分 ，以硬化的第-黏著劑層U和第二黏著劑層12來予以固 定，電子零件4則機械性地連接到基板3。 此外，第一黏著劑層11 一旦硬化，則即使達到第一主 樹脂成分的玻璃轉移溫度仍不會熔解。即是第一黏著劑層 11即使硬化前或硬化後都不會熔解，因不會讓導電性粒子 15從第一端子35上流出，所以第一端子35與第二端子牦 之間之不僅導電性粒子15仍維持在高密度，相鄰的第一端 子35間之導電性粒子15的密度不會變高。因此，利用本 發明的膠膜10相連接之電子零件4及基板3，連接可靠性 很高。 將形成在相鄰的端子間之凹部的深度設定為端子的高 度’則與第一黏著劑層11相密著侧的被附著體（例如，基 21 板3)之第—端+ γ 固定後或真正壓合後，成 子45的向度，暫 附著體的接觸面積變大，故連接體的與被 、·♦糸明亚不侷限於下述實施例。 、將主樹脂成分溶解在甲苯和醋酸乙酯（ethylacetate) ^ 1 1的比例予以混合之混合溶媒中，獲得固態分（主樹 月曰成分）含有30重量％之溶解液體。 、以下述第-表所述之調配比率（重量比），將副樹脂成 分、導電性粒子、輕合劑混合在各溶液中，製作第一原料 液體和第二原料液體各4種。 將各第一原料液體和第二原料液體塗佈在剝離薄膜2玉 和剝離薄膜22，以60°C經10分鐘予以乾燥，製作第一黏 著劑層A1〜A4和第二黏著劑層N1〜N4。 將用於第一黏著劑層A1〜A4和第二黏著劑層N1〜N4 的原料液體之固態成分的調配比率記载下述第一表中。 ^_一表：第一、第二的黏著劑層的組成 品名 Tg點 第一黏著劑J 1 第一黏著劑^ 庵· A1 A2 A3 A4 N1 N2 mj N4 50 9 硬化劑 HX3941HP 一 39 50 50 50 9 50 50 副樹脂 成分 EP828 ' 0 9 9 9 9 9 9 主樹脂 SG708-6T -8°C 60 0 0 0 90 0 0 0 YDF2001 54〇C 0 0 0 0 0 40 0 0 YP70 84°C 0 40 0 0 0 0 40 0 22 1375967
此外，上述第-表中，玻璃轉移溫度（Tg點） 的「一」代表室溫下為液態。 爛中 硬化劑（.日本旭化成化工公司製造，商。 「HX3941HP」）為胺系硬化劑被微膠囊化過之微膠囊名 系環氧硬化劑。副樹脂成分（日本環氧樹脂公司制膝 品名「ΕΡ828」）為雙紛（bisphenc)1) Α型液狀環=以商 也疋常溫（30 C)下液狀的熱硬化性樹脂。 主樹脂成分當中，商品名「ΥΡ70」為破璃轉移溫度 點）84〇C ’分子量5.5 ^，日本東都化成公5Ί製造的苯氧 基樹脂；商品名「YDF2001」為玻璃轉移溫度（巧點）， 曰本東都化成公司製造的固態雙F型環氧樹脂' 商品名 「FX293」為玻璃轉移溫度（Tg點）163°C，分子量4 5萬， 日本東都化成公司製造的苯氧基樹脂；商品名「^p425〇」 為玻璃轉移溫度（Tg點）l〇8°C，分子量6萬，曰本環^ 樹脂公司製造的苯氧基樹脂；商品名「SG7〇8 —6丁」為玻 璃轉移溫度（Tg點）一8〇C，分子量5〇萬，固態^量15 % (甲苯：醋酸乙酯=1 : 1)’日本長瀨化工科技公司製造 的丙烯酸橡膠。 商品名「KBE403」為曰本信越化學工業公司製、土 s 氧矽烷。 ^、衣 23 1375967 商品名「AUL704」為曰本積水化學工業公司製造的 Nl//Au電鍍樹脂粒子（平均粒徑為4μιη)。 使用TA Instrument公司製造的DSC Q100，在第一黏 著劑層11和第二黏著劑層12的升溫速度為1〇。〇/分的條 件下，進行各第一黏著劑層Ai〜A4和第二黏著劑層N1〜N4 , 的DSC測定，求出反應顛峰溫度。將所獲得之第一黏著劑 層A4的DSC曲線與主樹脂成分（商品名「γρ7〇」及商品 名「FX293」）的DSC曲線，顯示在第五圖中。 '、 .第五圖中’縱軸表示熱流量，橫軸表示溫度。第五圖 _ 則是表示第一黏著劑層A4的DSC曲線Ld、商品名「FX293」 的DSC曲線La、商品名「YP70」的DSC曲線Lb。 第五圖中表示的第一黏著劑層A4在121。(：時熱流量最 大，即是副樹脂成分的聚合反應所形成的熱流量變最大， 第一黏著劑層A4的反應顛峰溫度為i21°C。 此外，「FX293」的DSC曲線La及「YP70」的DSC 曲線Lb係表示因在163 C及84°C下因熔解所導致的吸熱而 鲁 使熱流量變低，「FX293」及「YP70」的玻璃轉移溫度分別. 為 163°C、84°C。 ^ 其次，將第一黏著劑層Α1〜Α4和第二黏著劑層 - N1〜N4，依據下述第二表的組合，以橡膠卷來進行貼合， 獲得膜厚20μπι的實施例X4、Y1〜Y3以及比較例XI〜X3 的膠膜10。 24 1375967 if*表：第一、第二黏著劑層的組合 一......... _ 一 · *-----------——-- 〜1. II — ·ΙΓ· 比較例 實施例 i電性黏著薄片 XI Χ2 Χ3 Χ4 Υ1 Υ2 Υ3 導電，ΙΪ~~ 黏著層 笫〆黏著 劍潘 Α1 Α2 A3 Α4 Α4 Α4 Α4 —-- 4 4 4 10 4 4 4 絕緣性 黏著層 第二黏著 劑層 Ν1 Ν3 Ν3 Ν3 Ν2 Ν3 Ν4 厚度〔μη»〕 16 16 16 10 16 16 16 子密度f個/mm J 30000 30000 30000 30000 30000 30000 30000 以光學顯微鏡，觀察實施例X4、Y1〜Y3以及比較例 XI〜X3的膠·膜10，測定每1 mm2的導電性粒子密度，結果 如上述第二表所示，各膠膜10的導電性粒子相同密度。 其次，使用實施例X4、Y1〜Y3以及比較例XI〜X3的 膠膜10 ’經由下述所示的組裝步驟，進行電子零件（IC晶 片）與基板的連接。 <組裝步驟> 準備評估測試用的1C晶片（材質：矽：平面面積1.8 mm X 20 mm、厚度：0.5 mm ;金凸塊、凸塊高度：15μιη ;凸 塊面積：2〇μιη X 85μιη、凸塊間空間ΙΟμπι ;凸塊中心間距 離（間距）：30μιη)以及評估測試用的ΙΤΟ圖案玻璃（基 板本體：Corning公司製造，品名「1737F」，玻璃尺寸：50 111111><3〇111111><〇.7 111111、1丁0導電片（端子）尺寸2(^111>< 85μιη ’導電片中心間距離（間距）：3〇pm)，作為評估基材。 利用預壓合機（工具尺寸2.0 mm X 50 mm)，將切割成 縱2.0 mm X橫25 mm的長方形形狀之比較例XI〜X3和實 施例X4、Y1〜γ3的膠膜10，隔著膜厚7〇μιη的鐵弗龍（登 錄商標）緩衝材，暫黏貼在ΙΤΟ圖案玻璃。暫黏貼是在預 25 1375967 壓合機溫度80°C、預壓合機的押壓力1 MPa下進行2秒鐘。 剝離薄膜21和剝離薄膜22從各膠膜10剝離之後，將 1C晶片予以對準，載置在膠膜10上，暫固定在玻璃基板 上。 接著，隔著膜厚50μπι的鐵弗龍（登錄商標）緩衝材， 將主壓合裝置（工具尺寸30 mm X 50 mm)抵觸到1C晶片 予以加熱押壓，獲得7種的連接體（主壓合）。主壓合條件 則是在主壓合裝置的溫度190°C、主壓合裝置的押壓力3 MPa下進行10秒鐘。 <捕捉效率> 在上述組裝步驟，測定：暫固定後位於1C晶片的1個 凸塊的下方之導電性粒子的數量、及主壓合後被1C晶片的 1個凸塊及ITO圖案玻璃的1個ITO導電片所夹持之導電 性粒子的數量（粒子捕捉數量）。 測定係針對100個凸塊進行，將粒子捕捉數量的最大 值、最小值、平均值、以及捕捉效率（單位：％)記載在 下述第三表中。 第三表：捕捉效率 比較分 實施例 XI X2 X3 X4 Y1 Y2 Y3 粒子捕捉 數量 (單位 Bump) 〔個〕 最大 值 24 23 27 33 45 44 40 最小 值 4 3 5 10 26 26 22 平均 12 10 14 22 36 36 32 捕捉效率〔％〕 23.5 19.6 27.5 43.1 70.6 70.6 62.8 26 1375967 導通電阻 最大 值 0.67 0.73 0.62 0.70 0.63 0.62 0.62 最小 值 0.42 0.42 0.42 0.44 0.41 0.41 0.41 平均 0.53 0.64 0.52 0.67 0.51 0.51 0.51 (連接面積=1700 μπι2、測定數量N = 100) 此外，捕捉效率是指針對將1C晶片予以暫固定時在凸 塊下所存在的粒子數，以百分比來表示主壓合後有多少個 粒子被捕捉之值，利用下述式子（1)來求出。 捕捉效率（％)=(主壓合後的粒子捕捉數量）/ (暫 固定後凸塊下所存在的粒子數量）X 100 ——式子（1) 實施例X4、Y1〜Y3，獲得高捕捉效率的值（43%〜71 % )。這當中，實施例Y1〜Y3出現60%以上的捕捉效率， 得知更加理想。 <導通電阻> 主壓合後，測定相對向的1個凸塊與1個端子之間的 導通電阻。測定是針對100處所進行，將導通電阻的最小 值、最大值、平均值記載在上述第三表中。 從上述第三表能明白，實施例Y1〜Y3的粒子捕捉數量 多於比較例XI〜X3，有導通電阻也很低的傾向，將本發明 的膠膜10用於連接電子零件的話，確認會提高黏接可靠 性。 <短路發生率> 除了 1C晶片的凸塊及ITO圖案玻璃的配線（ITO導電 片），以橫向偏離7 mm的方式，進行誤對準以外，在上述 27 組裝步驟所述的條件下，將Ic 製作連接體。 晶片連接到ITO圖案玻璃 在連接體所相鄰的1TO導電片之間施加3GV的電麼， 測定絕緣電阻。短路發生基準係將l.GxHTh以下判定為 ^路’ 短路發生次數。進而，維持連接體通電直接在 二度85C、溼度85。/。的高溫高濕環境下放置5〇〇小時之 後’測定4GG處所的短路發生次數，求出短路發生率。將 測定結果記載在下述第四表中。
Xl 較1 Χ2 V/I 實方 &例 短路發生次 數〔％〕 初期 1.00 1.00 1.00 入4 0.25 X 1 0.00 Y2 0.00 Y3 0.25 85 C /85%/ 500hr 2.00 2.00 2.00 0.50 0.25 0.25 0.25 (相鄰端子間空間=7μιη，測定次數N == 400) 從上述第四表能明白，即使是初期且是在高溫高濕環 境下放置後，短路發生率仍是實施例χ4、γι~γ3低於比較 例XI〜Χ3。 <結塊> 將實施例Χ4、Υΐ〜Υ3以及比較例χι〜χ3的膠膜1〇分 別擷取寬度1.5 mm，長度1〇〇 m，再將擷取的膠膜捲取到 捲輪，進行是否發生結塊的確認。此外，膠膜1〇係在剝離 薄膜黏貼在其中一面的狀態下，捲取到捲輪中。 結塊的確認方法係首先在所捲取之導電性膠膜的末端 28 1375967 部二垂予3〇g的重錘，再在3〇。〇氛圍中（推定壓合裝置内 的風圍）放置2小時。之後，在常溫氛圍t拉拉看導電性 膠膜，檢查是否引起膠膜無法捲出的現象（結塊）。 第一黏著劑層11和第二黏著劑層12引起滲出，滲出 的部分黏著而無法捲出則判斷為X ，能正常捲出則判斷為 〇。將該結果記载在下述第五表中。
從上述第五表能明白，使用玻璃轉移溫度不到3〇它的 樹脂來作為第一主樹脂成分和第二主樹脂成分之比較例 XI會^起結塊，但實施例X4、Υ1~Υ3不會引起結塊。 貫施例Χ4 Υ1〜Υ3中，第二主樹脂成分的玻璃轉移溫 I為在5(TC以上，n〇dXT的範圍，第一主樹脂成分的 玻璃轉移溫度超過11〇。〇，高於第二主樹脂成分的玻璃轉 • 移溫度。
： 因此，付知.第二主樹脂成分的玻璃轉移溫度為在50°C 以上’ 1HTC以下的範圍’第-主樹脂成分的玻璃轉移溫度 高於第二主樹脂成分的玻璃轉移溫度的話，膠膜iq實際使 用時捲取故障很少。 【圖式簡單說明】 29 第A 為說明製造本發明的膠膜的步驟之剖面圖（其 第B圖為說明製造本發明的膠膜的步驟之剖面圖（其 —* ) 〇 第0圖為說明製造本發明的膠膜的步驟之剖面圖（其 二)〇 第-A圖為說明將電子零件連接到基板的步驟之剖 (其一）。 弟-B ®為說明將電子零件連接到基板的步驟 (其二)。 第二C圖為說明將電子零件連接到基板的步驟之剖面圖 (其三）。 第一 D圖為說明將電子零件連接到基板的步驟之剖面圖 (其四）。 第二圖為說明電子零件連接到基板的狀態之剖面圖。 第四圖為表示捲取膠膜的膜卷之側面圖。 第五圖為表示第一主樹脂成分和第二主樹脂成分、及第一 黏著劑層和第二黏著劑層的DSC曲線之曲線圖。 【主要元件符號說明】 3 基板 4 電子零件 10 膠膜 11 第一黏著劑層 30

Claims (1)

  1. 十申明專利範圍： I卩吟 I. -種各向異性導電型膠膜，具 於前述第-黏著劑層之第二黏—黏著劑層、及密著 甲分佈有導電性粒子， 接層，前述第一黏著劑層 别述第一黏著劑層和前述 副樹脂成分，令前述第—黏著劑二!=，分別含有 升溫，前述第一黏著劑層 :⑴述弟一黏著劑層 副樹脂成分起反應，使前述第:黏 著劑層硬化之膠膜，其特徵為··〜層“述第二黏 前述第一黏著劑層含有：破 樹脂成分之第一主樹庐忐\ 轉私，皿度间於前述副 .、 树5成刀，前述第二黏著劑層含有： 玻璃轉移溫度高於前述副樹 八 於前计筮+ 3成刀，且玻璃轉移溫度低 於别^第：主樹脂成分之第二主樹脂成分， - 則述第-黏著劑層和前述第二黏著劑層 a Z一黏著劑層和前述第二黏著劑層的發熱量;最大： 度於前述ΐ —主樹脂成分的玻璃轉移溫 回；刖第一主樹脂成分的玻璃轉移溫度； 第一黏著劑層㈣厚為導電性粒子平均粒徑的0.5 倍以上，2. 0倍以下；以及 、第二主樹脂成分的玻璃轉移溫度為5(TC以上，i1(rc 以下。 性導電型膠膜，其中， 第二黏著劑層的反應顛 .如申請專利範圍第1項之各向異 第一黏著劑層的反應顛峰溫度與 峰溫度之差為l〇°C以下。 32 ’半i月，修正替換頁 —種恭JZL兩μ & #丨 、止版修mn12/&/24 兒子令件。基板的連接方法，其特徵為： 令第-基板的電極與第二基板的電極 =第1項所述的各向異性導電型•膜相對向’再將 k第-紐與前述第二基板Μ加熱押壓，其中該加 …押麗係以-加熱手段升溫到高於前述各向異性導電型 膠膜中第-主樹脂成分的玻璃轉移溫度，再進—步將前 述加熱手段抵觸在被暫固定的基板（第-基板或/及第二 基板）並加;t使第-基板與第二基板相連接，令前述各向 二f生導电型膝膜中的導電性粒子夾持在前述第—基板的 電極與前述第二基板的電極之間，將前述第一基板與前 述第二基板相連接。 .一種電子零件與基板之接合體，其特徵為： 具備有以申請專利範圍第3項所述的連接方法來相 連接之第一基板及第二基板，其中第一基板上具有複數 個第一端子，而第二基板上具有複數個第二端子，且各 第一端子與各第二端子之中心位置間的距離係為相等， 並各第二端子位於各第一端子之正上方。 1375967 十^一、圖式:
    12 22 第一B圖
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WO2009013968A1 (ja) 2009-01-29
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US8158887B2 (en) 2012-04-17
JP5192194B2 (ja) 2013-05-08
CN101821347B (zh) 2013-06-26
HK1144698A1 (en) 2011-03-04
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KR101150613B1 (ko) 2012-05-31
KR20100028660A (ko) 2010-03-12

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