TWI378745B - - Google Patents

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Publication number
TWI378745B
TWI378745B TW097117009A TW97117009A TWI378745B TW I378745 B TWI378745 B TW I378745B TW 097117009 A TW097117009 A TW 097117009A TW 97117009 A TW97117009 A TW 97117009A TW I378745 B TWI378745 B TW I378745B
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TW
Taiwan
Prior art keywords
circuit
film
connecting material
resin
circuit connecting
Prior art date
Application number
TW097117009A
Other languages
English (en)
Other versions
TW200913808A (en
Inventor
Nichiomi Mochizuki
Motohiro Arifuku
Kazuyoshi Kojima
Kouji Kobayashi
Original Assignee
Hitachi Chemical Co Ltd
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Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of TW200913808A publication Critical patent/TW200913808A/zh
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Publication of TWI378745B publication Critical patent/TWI378745B/zh

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    • 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
    • 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
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/711—Monoisocyanates or monoisothiocyanates containing oxygen in addition to isocyanate oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
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    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
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    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
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    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R12/00—Structural associations of a plurality of mutually-insulated electrical connecting elements, specially adapted for printed circuits, e.g. printed circuit boards [PCB], flat or ribbon cables, or like generally planar structures, e.g. terminal strips, terminal blocks; Coupling devices specially adapted for printed circuits, flat or ribbon cables, or like generally planar structures; Terminals specially adapted for contact with, or insertion into, printed circuits, flat or ribbon cables, or like generally planar structures
    • H01R12/50—Fixed connections
    • H01R12/51—Fixed connections for rigid printed circuits or like structures
    • H01R12/52—Fixed connections for rigid printed circuits or like structures connecting to other rigid printed circuits or like structures
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    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
    • H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive adhesives
    • 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
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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    • 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
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1378745 九、發明說明 【發明所屬之技術領域】 本發明係關於一種薄膜狀電路連接材料及電 連接構造。 【先前技術】 近年，於半導體或液晶顯示器等之領域爲固 件，或進行電路連接，可使用各種之連接材料。 用途中，漸漸進行高密度化、高精細化，黏著劑 之黏著力或信賴性。 尤其，在液晶顯示器與TCP之連接、FPC # 連接、或FPC與印刷電路板之連接上係可使用於 已分散導電性粒子之異方導電性黏著劑作爲電路 。又’最近，即使使半導體矽晶片封裝於基板時 知之導線黏合而直接使半導體矽晶片以面朝下封 上，所謂覆晶封裝，此處亦開始適用異方導電性; 進而，近年在精密電子機器之領域中，進行 密度化’電極寬及電極間隔變極窄。因此，在使 環氧樹脂系的電路連接材料之連接條件中，係易 之脫落、剝離、偏位。 又’爲提昇生產效率，期望連接時間之縮短 求可以10秒以下連接的電路連接材料。因此， 種低溫速硬化性優，且可使用時間長之電氣電子 連接材料（例如參照專利文獻1)。 路構件的 定電子零 在此等之 亦尋求高 ! TCP 之 黏著劑中 連接材料 ，取代習 裝於基板 諮著劑。 電路的高 用習知之 產生配線 化，並尋 開發出一 用的電路 1378745 專利文獻1:特開平11-97825號公報 【發明內容】 .發明之揭示 發明卻解決之課題 ' 然而，上述電路連接材料係黏著強度依連接之電路構 件的材質而異。尤其，電路構件表面以氮化矽、聚酮樹脂 • 或聚醯亞胺樹脂塗佈，或此等之樹脂附著於電路構件表面 時’黏著強度有降低之傾向，因此，期盼一種不依電路構 件之材質而黏著性優，且具有非常長之可使用時間的電路 連接材料。 • 本發明係有鑑於上述事情者，目的在於提供一種不依 電路構件之材質而顯示非常高之黏著性，且具有非常長之 可使用時間的薄膜狀電路連接材料及使用其之電路構件的 連接構造。 用以解決課題之手段 -本發明係提供一種薄膜狀電路連接材料，其係將於第 . 1電路基板之主面上形成有第1電路電極之第1電路構件 、與於第2電路基板之主面上形成有第2電路電極之第2 電路構件，以使第1及第2電路電極呈對向狀態進行電連 接用’其特徵係含有薄膜形成材料、自由基聚合性化合物 、經加熱產生游離自由基之自由基聚合起始劑及含異氰酸 酯基化合物，該含異氰酸酯基化合物之含有比例，相對於 -6- 1378745 薄膜形成材料與自由基聚合性化合物之合計100質量份， 爲0.09〜5質量份。 藉具備上述構成，本發明之薄膜狀電路連接材料係不 依電路構件之材質而顯示非常高之黏著性，且具有非常長 之可使用時間者。可顯現如此之效果的理由係不定，但本 發明人等係如以下般推測。 一般，爲延長電路連接材料的可使用時間係必須控制 電路連接材料的反應性。但，若完全控制電路連接材料的 反應性，因被黏體之種類有很難顯現充分黏著性之傾向。 另外，認爲上述含有含異氰酸酯基化合物係在電路連接時 之溫度條件下反應性優，但在較其低溫下安定，因此，認 爲本發明之薄膜狀電路連接材料係藉含有特定量之含異氰 酸酯基化合物與上述其他之成分，俾可使良好的黏著性與 充分長之可使用時間倂存。 上述薄膜狀電路連接材料宜含有含氟有機化合物。如 此之薄膜狀電路連接材料係黏著性可更提昇，同時並發揮 轉印性亦優之效果。 又本發明之薄膜狀電路連接材料係宜含有具有重量平 均分子量10000以上之尿烷鍵結的有機化合物作爲薄膜形 成材料。藉此’薄膜狀電路連接材料之柔軟性會提高，可 發揮與各種電路構件之黏著性優即所謂更有效發揮本發明 之效果。 本發明之薄膜狀電路連接材料係宜更含有導電性粒子 。藉此，電路連接材料係可容易地具有其本身導電性。因 1378745 此，此電路連接材料係在電路電極或半導體等 或電子工業之領域中使用來作爲導電性黏著劑 此時，因電路連接材料具有導電性，故可更降 連接電阻。 本發明係提供一種電路構件之連接構造， 第1電路基板之主面上形成有第1電路電極之 件，與被設置成於第2電路基板之主面上形成 電極、且第2電路電極與第1電路電極相對設 路構件，以及設置於第1電路基板及第2電路 連接第1電路構件與第2電路構件，使第1及 極電連接之電路連接部，其特徵爲電路連接部 之薄膜狀電路連接材料之硬化物所形成的。 如此之電路構件的連接構造係電路構件爲 優異，且可使用時間爲非常長之本發明的薄膜 材料之硬化物來形成，故可在同一電路構件上 電路電極間的絕緣性，同時並降低對向之電路 阻値。 本發明之電路構件之連接構造中，第1及 路電極中至少1者係其表面由含從金、銀、錫 金屬及銦-錫氧化物所成群中選出之至少1種 所成。如此之電路構件的連接構造係可在同一 維持相鄰之電路電極間的絕緣性，同時並進一 之電路電極間的電阻値。 本發明之電路構件之連接構造中，第1及 之電氣工業 。進一步， 低硬化後之 其係具有於 第1電路構 有第2電路 置之第2電 基板之間， 第2電路電 爲藉由上述 黏著性充分 狀電路連接 維持相鄰之 電極間的電 該第2之電 、白金族之 物質之材料 電路構件上 步降低對向 該第2之電 -8- 1378745 路基板中至少1者係由含從聚對苯二甲酸乙二酯、聚醚颯 '環氧樹脂、丙烯酸樹脂、聚醯亞胺樹脂及玻璃所成群中 選出之至少1種之材料所成之基板。上述本發明之電路連 接材料係硬化而形成電路連接部時，在以此等的材料所構 成的基板之間可顯現更高的黏著性。 進一步在上述電路構件之連接構造中，第1及該第2 之電路構件中至少1者與上述電路連接部間形成含由氮化 矽、聚酮樹脂、聚醯亞胺樹脂及丙烯酸樹脂所成群中選出 之至少1種材料之層。藉此，相較於未形成上述層者，可 更進一步提昇電路構件與電路連接部之黏著性。 • 發明之效果 若依本發明，可提供一種不依電路構件之材質而顯示 非常高之黏著性，且具有非常長之可俊用時間的薄膜狀電 路連接材料及使用其等之電路構件的連接構造。 用以實施發明之最佳形態 • 以下，依需要而一邊參照圖面一邊詳細說明有關本發 .明之較佳實施形態。又，圖面中，於同一要素係賦予同一 符號，省略重複之說明。又，上下左右等之位置關係只要 無特別聲明，依據圖面所示之位置關係者。進一步圖面之 尺寸比率係不限定於圖示之比率。又，所謂本說明書之「 (甲基）丙烯酸」係「丙烯酸」及對應於其之「甲基丙烯 酸」’所謂「（甲基）丙烯酸酯」係「丙烯酸酯」及對應 -9- 1378745 於其之「甲基丙烯酸酯」， 「丙烯醯基」及對應於其之 (薄膜狀電路連接材料） 本發明之薄膜狀電路連 )，係將於第1電路基板之 第1電路構件與於第2電路 電極之第2電路構件，以使 態進行電連接。本發明之薄 形成材料、自由基聚合性化 之自由基聚合起始劑及含異 分，含異氰酸酯基化合物之 料與自由基聚合性化合物之 質量份。 薄膜形成材料係使液狀 膜形狀時，其薄膜容易處理 黏之機械特性等者，可以一 膜形成材係可舉例如聚乙烯 乙烯丁縮醛樹脂、聚酯樹脂 、聚尿烷樹脂、聚醯胺醯亞 本樹脂、苯氧樹脂。又，薄 性之官能基改性。 本發明之薄膜狀電路連 點’宜含有具尿烷鍵之有機 所謂「（甲基）丙烯醯基」係 「甲基丙烯醯基」。 接材料（電路連接用黏著薄膜 主面上形成有第1電路電極之 基板之主面上形成有第2電路 第1及第2電路電極呈對向狀 膜狀電路連接材料係含有薄膜 合物、經加熱產生游離自由基 氰酸酯基化合物作爲黏著劑成 含有比例’相對於薄膜形成材 合計100質量份，爲0.09〜5 物固形化，當構成組成物爲薄 ’賦予不容易破裂或龜裂或沾 般之狀態以薄膜來處理者。薄 甲醛樹脂、聚苯乙烯樹脂、聚 、聚酯尿烷樹脂、聚醯胺樹脂 胺樹脂、聚醯亞胺樹脂、二甲 膜形成材係亦可被自由基聚合 接材料係從以黏著性更優之觀 化合物（以下有時稱爲「尿烷 -10- 1378745 化合物」）作爲薄膜形成材。又，尿烷化合物係宜於其主 鍵中具有尿烷鍵，更宜具有尿烷鍵以及酯鍵。 此尿烷化合物係藉聚酯多元醇與二異氰酸酯之反應來 得到。以此反應所得到之尿烷化合物一般係有時稱爲聚酯 尿烷樹脂。 二異氰酸酯基係可適宜使用2，4-甲苯撐基二異氰酸酯 (TDI ) 、4,4’-二苯基甲烷二異氰酸酯（MDI ) 、1，6-六亞 甲基二異氰酸酯（HDI)、異氟爾酮二異氰酸酯（IP DI) 等之芳香族、脂環族或脂肪族的二異氰酸酯。 聚酯多元醇係例如藉二羧酸與二元醇之反應來得到。 二羧酸宜爲對酞酸、異酞酸、己二酸、癸二酸等之芳香族 或脂肪族二羧酸。二元醇宜爲乙二醇、丙二醇、1,4-丁二 醇、己二醇、新戊二醇、二乙二醇、三乙二醇之甘醇類。 尿烷化合物宜重量平均分子量爲1 0000以上。若尿烷 化合物之重量平均分子量不足1 0000，薄膜形成性有降低 之傾向。又，尿烷化合物之重量平均分子量之上限値無特 別限定，但若重量平均分子量太高，於溶劑之溶解性或相 溶性會降低，要調製用以成形爲薄膜狀之塗佈液有很難之 傾向，故宜爲約200000。 在本說明書中之重量平均分子量係依表1所示之條件 而藉凝膠滲透色層分析（GPC)分析來測定’使用標準聚 苯乙烯之檢量線而換算來求出。又’ GPC條件1係測定聚 醯亞胺樹脂之重量平均分子量時之條件’ GPC之條件2係 測定聚醯亞胺樹脂以外之重量平均分子量時之條件。 -11 - 1378745 [表i] GPC條件1 GPC條件2 使用機器 高速液體色層分析-C-R4A 日立L-6000型 (曰立製作所製、商品名） 檢測器 L-4200 (日立製作所公司製） L-3300RI (曰立製作所公司製、商品名） 管柱 G6000HXL G4000HXL G2000HXL (東曹公司製、商品名） Geel Pack GL-R420 Geel Pack GL-R430 Geel Pack GL-R440 (日立化成工業公司製、商品名） 溶離液 溴化鋰（LiBr) Ν,Ν-二甲基甲醯胺（DMF) (0.03mol/L) 磷酸（0.06mol/L) 六氬咲喃 測定溫度 30°C 40°C 流量 l.Oml/min 1.75ml/min
所謂自由基聚合性化合物係具有可自由基聚合之官能 基者。自由基聚合性化合物係可適宜使用（甲基）丙烯酸 化合物、馬來醯亞胺化合物或苯乙烯衍生物。此等之自由 基聚合性化合物係可爲聚合性單體及聚合性寡聚物之任一 者'，亦可倂用聚合性單體及聚合性寡聚物。聚合性寡聚物 一般爲高黏度，故使用聚合性寡聚物時，宜倂用低黏度之 聚合性多官能（甲基）丙烯酸酯等的聚合性單體來調整黏 度。 (甲基）丙烯酸化合物係可舉例如環氧（甲基）丙烯 酸酯寡聚物、尿烷（甲基）丙烯酸酯寡聚物、聚醚（甲基 -12- 1378745 )丙烯酸酯寡聚物及聚酯（甲基）丙烯酸酯寡聚 聚合性寡聚物、三羥甲基丙烷三（甲基）丙烯酸 二醇二（甲基）丙烯酸酯、聚烷撐基甘醇二（甲 酸酯、二環戊烯基（甲基）丙烯酸酯、二環戊烯 (甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸 戊四醇六（甲基）丙烯酸酯、三聚異氰酸改性2 基）丙烯酸酯、三聚異氰酸改性3官能（甲基） 、2,2’-二（甲基）丙烯醯氧二乙基磷酸酯及2_( 烯醯氧基乙基酸磷酸酯等之多官能（甲基）丙烯 物、季戊四醇（甲基）丙烯酸酯、2_氰基乙基（ 烯酸酯、環己基（甲基）丙烯酸酯、2-(2-乙氧 )乙基（甲基）丙烯酸酯、2-乙氧基乙基（甲基 酯、2-乙基己基（甲基）丙烯酸酯、正己基（甲 酸酯、2-羥基乙基（甲基）丙烯酸酯、羥基丙基 丙烯酸酯、異冰片基（甲基）丙烯酸酯、異癸基 丙烯酸酯、異辛基（甲基）丙烯酸酯、正月桂基 丙烯酸酯、2-甲氧基乙基（甲基）丙烯酸酯、2-基（甲基）丙烯酸酯、四氫糠基（甲基）丙烯酸 二醇二（甲基）丙烯酸酯、第三丁基胺基乙基（ 烯酸酯、環己基（甲基）丙烯酸酯、二環戊烯氧 甲基）丙烯酸酯、2-羥基乙基（甲基）丙烯酸酯 基（甲基）丙烯酸酯、異癸基（甲基）丙烯酸酯 基（甲基）丙烯酸酯、硬酯基（甲基）丙烯酸酯 基（甲基）丙烯酸酯、以及縮水甘油基（甲基） 物等之光 酯、聚乙 基）丙烯 氧基乙基 酯、二季 官能（甲 丙烯酸酯 甲基）丙 酸酯化合 甲基）丙 基乙氧基 )丙烯酸 基）丙烯 (甲基） (甲基） (甲基） 苯氧基乙 酯、新戊 甲基）丙 基乙基（ 、異冰片 、正月桂 、十三碳 丙烯酸酯 -13- 1378745 (甲基）丙烯酸化合物係可1種單獨或組合2種以上 而使用。爲抑制電路連接材料的硬化收縮，賦予柔軟性， 宜調配尿烷（甲基）丙烯酸酯寡聚物。 馬來醯亞胺化合物宜於分子中具有馬來醯亞胺基2個 以上者。其具體例可舉例如1-甲基-2,4-雙馬來醯亞胺苯、 N，N’-間苯撐基雙馬來醯亞胺、N，N’-對苯撐基雙馬來醯亞 胺、Ν,Ν’-間二甲苯撐基雙馬來醯亞胺' N，N’-4,4_聯苯撐 基雙馬來醯亞胺' N，N’-4,4- (3,3’-二甲基-聯苯撐基）雙 馬來醯亞胺、1^，>1’-4,4-(3,3’-二甲基二苯基甲烷）雙馬來 醯亞胺、：^川’-4,4-(3,3’-二乙基二苯基甲烷）雙馬來醯亞 胺、N，N’-4,4-二苯基甲烷雙馬來醯亞胺、N，N’-4,4-二苯基 丙烷雙馬來醯亞胺、N,N’-4,4-二苯基醚雙馬來醯亞胺、 N，N’-3,3’-二苯基颯雙馬來醯亞胺、2,2-雙[4- (4-馬來醯 亞胺苯氧基）苯基]丙烷、2,2-雙[3-第二丁基-4- (4-馬來 醯亞胺苯氧基）苯基]丙烷、1，1_雙[4- (4-馬來醯亞胺苯氧 基）苯基]癸烷、4，4’-環己叉基·雙[1-(4-馬來醯亞胺苯氧 基）-2-環己基苯]及2,2-雙[4-(4-馬來醯亞胺苯氧基）苯 基]六氟丙烷。 馬來醯亞胺化合物係可1種單獨或組合2種以上而使 用。 本發明之薄膜狀電路連接材料係就提昇黏著性之目的 。宜含有磷酸酯型（甲基）丙烯酸酯作爲自由基聚合性化 合物。藉由含有磷酸酯型（甲基）丙烯酸酯，薄膜狀電路 -14- 1378745 連接材料係特別地與金屬等之無機材料的黏著性會提高。 磷酸酯型（甲基）丙烯酸酯係無特別限制，可使用公知者 。其具體例可舉例如以下過通式（2 )所示之化合物。 [化1]
Γ ch3 I ——och2ch2 〇choc=ch (2)
此處，η表示之整數。 一般磷酸酯型（甲基）丙烯酸酯係形成磷酸酐與2 -羥 乙基（甲基）丙烯酸酯之反應物來得到。磷酸酯型（甲基 )丙烯酸酯具體上可舉例如單（2 -甲基丙烯醯氧乙基）酸 磷酸酯、二（2 -甲基丙烯醯氧乙基）酸磷酸酯。此等係可 一種單獨使用或組合兩種以上而使用。
本發明之薄膜狀電路連接材料係從以黏著性更優之觀 點’可含有烯丙基（甲基）丙烯酸酯。烯丙基（甲基）丙 烯酸酯之調配比率係相對於薄膜形成材與自由基聚合性化 合物之合計100質量份宜爲0.1〜10質量份，更宜爲0.5〜5 質量份。 又，以加熱產生游離自由基之自由基聚合起始劑係可 使用以往所知之過氧化化合物（有機過氧化物）及偶氮化 合物。 有機過氧化物及偶氮化合物係主要以加熱產生游離自 由基。使用此等之化合物作爲自由基聚合起始劑時，依目 -15- 1378745 的之連接溫度、連接時間、可使用時間（以下，有時稱爲 「操作時間」）等從有機過氧化物及偶氮化合物適當選擇 1種或2種以上。 有機過氧化物係使高的反應性與長的操作時間倂存之 觀點，宜爲10小時半衰期溫度爲40 °c以上且1分鐘半衰 期溫度爲1 80°C以下之有機過氧化物，更宜爲10小時半衰 期溫度爲60°C以上且1分鐘半衰期溫度爲170 °C以下之有 機過氧化物。又有機過氧化物係爲防止電路構件的電路電 極（連接端子）的腐蝕，宜氯離子或有機酸之含量爲5000 質量ppm以下。進一步，有機過氧化物係更宜爲加熱分解 後產生之有機酸少者。 有機過氧化物係具體上適宜爲一種以上選自由過氧化 二醯基、過氧化二碳酸酯、過氧化酯、過氧化縮酮、過氧 化二烷基、過氧化氫及過氧化甲矽烷基所構成之群中的有 機過氧化物。此等之中從保存時高的保存安定性與使用時 高的反應性倂存的觀點，更宜爲一種以上選自由過氧化酯 、過氧化縮酮、過氧化二烷基、過氧化氫及過氧化甲矽烷 基所構成之群中的有機過氧化物》進一步就可得到更高之 反應性的觀點，更宜有機過氧化物爲過氧化酯及/或過氧 化縮酮。 過氧化二醯基係可舉例如過氧化異丁基、過氧化2,4-二環甲醯基、過氧化3，5,5-三甲基己醯基、過氧化辛醯基 、過氧化月桂醯基、過氧化硬酯醯基、過氧化琥珀醯基、 苯甲醯基過氧化甲苯及過氧化苯甲醯基。此等係可一種單 -16- 1378745 獨使用或組合兩種以上而使用。 過氧化二烷基係可舉例如α，α ’ -雙 )二異丙基苯、過氧化二枯基、2,5-二 化第三丁基）己烷及過氧化第三丁基枯 單獨使用或組合兩種以上而使用。 過氧化二碳酸酯可舉例如二正丙基 二異丙基過氧化二碳酸酯、雙（4-第三 氧化二碳酸酯、二-2-乙氧基甲氧基過氧 2-乙基己基過氧化）二碳酸酯、二甲氧 酸酯及雙（3-甲基-3-甲氧基丁基過氧化 係可一種單獨使用或組合兩種以上而使 過氧化酯可舉例如枯基過氧化新多 甲基丁基過氧化新癸酸酯、1-環己基-1-癸酸酯、第三己基過氧化新癸酸酯、第 基乙酸酯、1，1，3,3-四甲基丁基過氧化 2,5-二甲基-2,5-雙（2-乙基己醯基過氧 基-1-甲基乙基過氧化-2-乙基己酸酯、J 乙基己酸酯、第三丁基過氧化-2-乙基己 氧化異丁酸酯、1,1-雙（第三丁基過氧 己基過氧化異丙基單碳酸酯、第三丁基 基己酸酯、第三丁基過氧化月桂酸酯、 (間甲苯醯基過氧化）己烷、第三丁基 酸酯、第三丁基過氧化-2-乙基己基單碳 氧化苯甲酸酯、第三丁基過氧化乙酸酯 (過氧化第三丁基 甲基-2,5-二（過氧 基。此等係可一種 過氧化二碳酸酯、 .丁基環己基）過 化二碳酸酯、雙（ 基丁基過氧化二碳 )二碳酸酯。此等 用。 I 酸酯、1，1，3,3-四 甲基乙基過氧化新 三丁基過氧化三甲 ,-2-乙基己酸酯、 化）己烷、1-環己 奪三己基過氧化-2-酸酯、第三丁基過 化）環己烷 '第三 過氧化-3,5,5-三甲 2,5-二甲基-2,5-雙 過氧化異丙基單碳 酸酯、第三己基過 及雙（過氧化第三 -17-
1378745 丁基）六氫對酞酸酯。此等係可一種單獨使用或箱 以上而使用。 過氧化縮酮可舉例如1，1 -雙（過氧化第三： 3，3, 5-三甲基環己烷、1，1-雙（過氧化第三己基）環 1，1_雙（過氧化第三丁基）-3,3,5-三甲基環己院 過氧化第三丁基）環十二碳院及' 2,2 -雙（過氧化 基）癸烷。此等係可一種單獨使用或組合兩種以上 〇 氫過氧化物可舉例如氫過氧化二異丙基苯及蕾 枯基。此等係可一種單獨使用或組合兩種以上而使 過氧化甲矽烷基可舉例如過氧化第三丁基三甲 烷基、過氧化雙（第三丁基）二甲基甲矽烷基、遇 三丁基三乙烯基甲矽烷基、過氧化雙（.第三丁基） 基甲矽烷基、過氧化三（第三丁基）乙烯基甲矽燒 氧化第三丁基三烯丙基甲矽烷基、過氧化雙（第三 二烯丙基甲矽烷基及過氧化三（第三丁基）烯丙基 基。此等係可一種單獨使用或組合兩種以上而使用 使用此等之有機過氧化物時，亦可進一步組合 進劑、抑制劑等。又，此等之有機過氧化物係若爲 烷系、聚酯系之高分子物質等被覆而微膠囊化者， 可使用時間，故佳。 又偶氮化合物可舉例如2,2’-偶氮雙-2,4-二甲 、1，1’-偶氮雙（1-乙醯氧-卜苯基乙烷）、2,2’-偶 丁腈、2,2’-偶氮雙（2-甲基丁腈）、二甲基-2,2’. i合兩種 己基）-i己烷、 ' 1,1-( ;第三丁 :而使用 L過氧化 用。 I基甲矽 丨氧化第 二乙烯 :基、過 .丁基） 丨甲矽烷 〇 •分解促 ，以聚尿 可延長 基戊腈 氮雙異 •偶氮雙 -18- 1378745 具有異氰酸酯基的化合物。二異氰酸酯化合物係可取自市 售品，例如，可使用日本Polurethane工業公司製之商品 名「Coronate L」、「Milionate MR」、「Coronate EH」 . 、「Coronate HLj 。又，從更進一步提昇對被黏體之黏 著性，宜含異氰酸酯基化合物於末端具有羥基、腈基、羧 基等之反應性高的極性基。進一步，若含異氰酸酯基化合 物具有三甲氧基甲矽烷基、三乙氧基甲矽烷基等之烷氧基 φ 甲矽烷基，此等之基係與被黏體表面之吸附水形成化學鍵 ，可牢固地黏著，故更佳。 上述含異氰酸酯基化合物之調配比率係相對於薄膜形 成材料與自由基聚合性化合物之合計100質量份，爲0.09 ' 〜5質量份，宜爲〇·1〜5質量份，更宜爲0.5〜3質量份 。含異氰酸酯基化合物之含有比率不足0.09質量份時， 很難得充分的黏著性，若超過0.5質量份，有可使用時間 有變短之傾向。 ® 又’本發明之薄膜狀電路連接材料係宜含有含氟有機 化合物作爲黏著劑成分。含氟有機化合物係只需要於分子 • 中具有氟之化合物即可，亦可爲公知者，上述薄膜形成材 .或自由基聚合性化合物亦可具有氟原子。具體上，可舉例 如含氣聚乙稀基丁縮醒樹脂、含氟聚乙稀基甲醒樹脂、含 氟聚醯亞胺樹脂、含氟聚醯胺樹脂、含氟聚醯胺醯亞胺樹 脂、含氟聚酯樹脂、含氟酚樹脂、含氟環氧樹脂' 含氟苯 氧樹脂、含氟聚尿烷樹脂、含氟聚酯尿烷樹脂 '含氟聚芳 酸醋樹脂、含氟苯乙烯樹脂、含氟聚酮樹脂、含氟丙烯酸 -20- 1378745 橡膠、含氟腈橡膠、含氟NBR、含氟SBS。此等 使用或混合兩種以上而使用。若薄膜狀電路連接 此等之含氟有機化合物，可成爲不依電路構件的 示更良好的黏著性，並可抑制轉印性之隨時間變 性亦優者。 含氟有機化合物之重量平均分子量係從硬化 緩和性優，黏著性更進一步提昇的觀點 5000〜1000000，更宜爲 20000-200000。含氟有 之重量平均分子量不足5000，薄膜形成性有不充 ，若重量平均分子量超過1000000，與其他之成 性有差的傾向。 進而’本發明之薄膜狀電路連接材料係爲形 和優者，可含有丙烯酸橡膠。丙烯酸橡膠係可使 、（甲基）丙烯酸酯或丙烯腈之中至少一種的丙 體聚合之聚合物或共聚物。丙烯酸橡膠亦可爲使 與具有縮水甘油基醚之縮水甘油基（甲基）丙烯 合者。丙烯酸橡膠之重量平均分子量係從提高薄 連接材料之凝集力的點，宜爲2 00000以上。 本發明之薄膜狀電路連接材料係除上述者以 依使用目的而添加另外的材料作爲黏著劑成分。 膜狀電路連接材料係亦可適當添加偶合劑、密著 、流平劑等之黏著助劑。藉此，可進一步賦予良 性或處理性》 偶合劑係從黏著性之提昇而言，較佳係可使 係可單獨 材料含有 材質而顯 化，轉印 時之應力 t ，宜爲 機化合物 分的傾向 分的相溶 成應力緩 用丙烯酸 烯酸系單 上述單體 酸酯共聚 膜狀電路 外，亦可 例如，薄 性提昇劑 好的黏著 用酮亞胺 -21 - 1378745 、乙烯基、丙烯基、胺基、環氧基及含異 體上，具有丙烯基之矽烷偶合劑係可舉例 氧丙基）三甲氧基矽烷、（3-丙烯氧丙基 、（3-甲基丙烯氧丙基）二甲氧基甲基砂 丙基）三甲氧基甲基矽烷、具有胺基之砂 如Ν-Θ (胺基乙基）r-胺基丙基三甲 (胺基乙基）7-胺基丙基甲基二甲氧3 丙基三乙氧基矽烷、N-苯基-r-胺基丙基. 具有酮亞胺之矽烷偶合劑可舉例如於 矽烷偶合劑與丙酮、甲乙酮、甲基異丁基 反應所得到者。又，具有環氧基之矽烷 r-縮水甘油基氧丙基三甲氧基矽烷、r-基三乙氧基矽烷、r-縮水甘油基氧丙基-烷、r-縮水甘油基氧丙基-甲基二乙氧基1 偶合劑之調配比率係相對於電路連接 配物之合計1〇〇質量份宜爲〇.1〜2〇質量 配比率不足〇. 1質量份時，有無法得到實 向。偶合劑之調配比率超過20質量份時 形成由電路連接材料所構成的黏著層時之 成性會降低，膜厚強度有降低之傾向。 本發明之薄膜狀電路連接材料係即使 子，藉由連接時相對向之電路電極間或直 接。但，若薄膜狀電路連接材料含有導電 更安定之電路電極間的連接’故佳。 氰酸酯基物。具 如（3 -甲基丙烯 )三甲氧基矽烷 烷、（3-丙烯氧 烷偶合劑可舉例 氧基矽烷、N- /5 I矽烷、r -胺基 Ξ甲氧基矽烷。 具有上述胺基之 酮等之酮化合物 偶合劑可舉例如 縮水甘油基氧丙 甲基二甲氧基矽 坎烷。 材料中其他的調 份。偶合劑之調 質添加效果之傾 ，於支撐基材上 黏著層之薄膜形 不含有導電性粒 接接觸可得到連 性粒子，可得到 -22- 1378745 在本發明中依需要所含有之導電性粒子係只有爲具有 可得到電性連接之導電性者，無特別限制。導電性粒子可 舉例如Au、Ag、Ni、Cu及焊錫等之金屬粒子或碳。又， .導電性粒子係使成爲核之粒子以1層或2層以上之層進行 被覆，亦可爲其最外層具有導電性者。此時，從可得到更 ' 優之操作時間之觀點，最外層與其爲Ni、Cu等之過渡金 屬，不如宜以Au、Ag及/或鈾族金屬等之貴金屬作爲主成 φ 分，更宜爲由此等之貴金屬的至少一種以上所構成。此等 之貴金屬之中最宜爲Au。 導電性粒子係亦可使以作爲核之過渡金屬作爲主成分 ' 之粒子或以核經被覆之過渡金屬作爲主成分之層的表面， * 進一步以貴金屬作爲主成分的層進行被覆而成者。又，導 電性粒子係以非導電性之玻璃、陶瓷、塑膠等作爲主成分 之絕緣性粒子爲核，於此核之表面以上述金屬或碳作爲主 成分之層被覆而成者。 # 導電性粒子爲以導電層被覆絕緣性粒子之核而成者時 ，絕緣性粒子爲以塑膠作爲主成分者，宜爲最外層以貴金 -屬作爲主成分者。藉此，薄膜狀電路連接材料中之導電性 .粒子可對於加熱及加壓而良好地變形。而且，於電路等之 連接時，導電性粒子之電路電極或連接端子之接觸面積會 增加。因此，可進一步提昇薄膜狀電路連接材料之連接信 賴性。從同樣之觀點，導電性粒子宜爲含有以上述加熱熔 融之金屬作爲主成分之粒子。 導電性粒子爲以導電層被覆絕緣性粒子之核而成者時 -23- 1378745 ，爲得到更良好的導電性，導電層之厚度宜爲100A ( l〇nm)以上。又，導電性粒子係亦可使以作爲核之過渡金 屬作爲主成分之粒子或以核經被覆之過渡金屬作爲主成分 之層的表面，進一步以貴金屬作爲主成分的層進行被覆而 成者之時，以成爲最外層之貴金屬作爲主成分的層之厚度 宜爲30〇A(30nm)以上。若此厚度低於300A，最外層易 破裂。其結果，所露出之過渡金屬與黏著劑成分接觸，受 過渡金屬之氧化還原作用易產生游離自由基，故操作時間 有容易降低之傾向。另外，若上述導電層之厚度變厚，其 等之效果會飽和，故宜使其厚度爲Ιμιη以下。 薄膜狀電路連接材料含有導電性粒子時，導電性粒子 的調配比例無特別限制，但相對於薄膜狀電路連接材料中 之黏著劑成分1〇〇體積份宜爲0.1〜30體積份，更宜爲 〇 . 1〜1 〇體積份。此値若不足0 · 1體積份，有很難得到良好 的導電性之傾向，若超過30體積份，有易產生電路等之 短路的傾向。又’導電性粒子之調配比率（體積份）係依 據23 °C中之薄膜狀電路連接材料硬化前的各成分之體積來 決定。各成分之體積係利用比重而從重量換算成體積之方 法’或溶解其成分’或不膨潤而置入充分潤濕其成分之適 當溶劑（水、醇等）之針筒等的容器中投入其成分，從已 增加之體積算出之方法來求出。又，使薄膜狀電路連接材 料分割成2層以上，分割成含有自由基聚合起始劑之層與 含有導電性粒子之層時，可得到操作時間的提高。 本發明之薄膜狀電路連接材料係亦可含有橡膠。藉此 -24- 1378745 ’可提高應力之緩和及黏著性。橡膠微粒子係粒子之平均 粒徑爲所調配之導電性粒子的平均粒徑之2倍以下，且只 要在室溫（25°C )的貯存彈性率爲導電性粒子及電路連接 材料在室溫的貯存彈性率的1/2以下者即可。尤其，橡膠 微粒子之材質爲聚矽氧、丙烯酸乳液、SBR、NBR、聚丁 二烯橡膠之微粒子係適宜單獨或混合2種以上而使用。3 次元交聯之此等橡膠微粒子係耐溶劑性優，易分散於薄膜 狀電路連接材料中。 以上述成分所構成之薄膜狀電路連接材料係電路構件 的連接時電路連接材料中之黏著劑成分會熔融、流動，連 接對向之電路構件後，硬化而保持連接者。因此，薄膜狀 電路連接材料之流動性爲很重要的因子。 例如，於厚 〇.7mm、15mmxl5mm之玻璃板上，挾住 厚35μιη、5mmx5mm之電路連接材料，以150°C、2MPa之 條件加熱及加壓1 〇秒鐘時，使用初期之面積（A )與加熱 及加壓後之面積（B )所示之流動性（B ) / ( A )之値宜爲 1.3〜3.0，更宜爲1.5〜2.5。（B) / (A)之値不足1.3時， 流動性差，有無法得到良好的電路構件連接之傾向。另外 ，（B) / (A)之値超過3.0時係易產生氣泡，有連接信 賴性差之傾向。 薄膜狀電路連接材料硬化後在40°C之彈性率，從在高 溫高濕時之連接電阻的安定化及保持連接信賴性之觀點， 宜爲 100〜3 0 00Mpa，更宜爲 5 00〜2000Mpa° 進一步，於此薄膜狀電路連接材料中係爲賦予硬化速 -25-
1378745 度的控制或貯存安定性，故可添加安定 於薄膜狀電路連接材料中調配塡充劑、 抗老化劑、著色劑、耐燃劑、搖變劑、 樹脂等。 薄膜狀電路連接材料係含有塡充材 可得到連接信賴性等之提昇，故佳。塡充 者，其最大徑若爲導電性粒子的平均粒徑 。塡充劑之調配比率相對於黏著劑成分 5〜6 0體積份。若塡充劑之調配比率超過 性提昇之效果有飽和的傾向，不足5體® 添加效果有變小之傾向。 本發明之薄膜狀電路連接材料係使含 電路連接材料形成薄膜狀而得到》此薄膜 係使於電路連接材料中加入溶劑等之混合 材上，或於不織布等之基材中含浸上述混 撐基材上，可除去溶劑等而得到。 所使用之支撐基材宜爲片狀或薄膜狀 材係亦可爲層合2層以上之形狀者。支撐 對苯二甲酸乙二酯（PET )薄膜、配向靠 膜、聚乙烯（PE)薄膜及聚醯亞胺薄膜。 寸精度的提昇與成本降低而言，宜爲PET 上述之薄膜狀電路連接材料係亦可使 係數相異之異種被黏體的電路連接材料。 使用來作爲異方導電黏著劑薄膜、銀薄膜 :劑。進一步亦可 :化劑、促進劑、 丨樹脂、三聚氰胺 (Filler )之時， ;材係具有絕緣性 :以下，則可使用 1〇〇體積份宜爲 60體積份，信賴 〖份時，塡充材之 有上述各成分之 狀電路連接材料 液塗佈於支撐基 合液而載置於支 者。又，支搏基 :基材可舉例如聚 :丙烯（OPP )薄 其等之中，就尺 薄膜。 用來作爲熱膨脹 具體上，係亦可 等爲代表之薄膜 -26- 1378745 狀電路連接材料外，CSP用彈性體、CSP用底部塡充材、 LOC膠帶爲代表之半導體元件黏著材料。 (電路構件的連接構造） 圖1係表示本發明之電路構件的連接構造之一實施形 態的槪略截面圖。圖1所示之電路構件的連接構造1係具 備相互對向之第1電路構件20及第2電路構件30，第1 電路構件20與第2電路構件30之間係設有連接此等之電 路連接部10。 第1電路構件20係具有第1電路基板21、與形成於 第1電路基板21之主面21a上的第1電路電極22»第2 電路構件30係具有第2電路基板31、與形成於第2電路 基板31之主面31a上的第2電路電極32。於第1電路基 板21之主面21a上及/或於第2電路基板31之主面31a上 視情況亦可形成絕緣層（未圖示）。亦即，絕緣層係形成 於第1電路構件20與第2電路構件30之中至少一者與電 路連接部1 0之間。 第1及第2電路基板21、31係可舉例如半導體、玻 璃、陶瓷等之無機物、TCP、FPC、COF爲代表之聚醯亞 胺基材、聚碳酸酯、聚對苯二甲酸乙二酯、聚酸楓、環氧 樹脂、丙烯酸樹脂等之有機物、此等之無機物或有機物複 合化之材料所構成的基板。從進一步提高與電路連接部1〇 之黏著性的觀點，第1及第2電路基板之中至少一者，宜 爲由含有至少一種選自聚對苯二甲酸乙二酯、聚醚颯、環 -27-
1378745 氧樹脂、丙烯酸樹脂、聚醯亞胺樹脂及玻璃所構无 材料所構成之基板。 又，形成絕緣層時，絕緣層宜爲含有至少一考 氮化矽、聚酮樹脂、聚醯亞胺樹脂及丙烯酸樹脂戶 群的層。藉此，相較於形成上述層者，第1電路 及/或第2電路基板31與電路連接部10之黏著Ί 一步提高。 第1電路電極22及/或第2電路電極32之 者宜爲其表面含有至少一種選自由金、銀、錫、 屬及銦-錫氧化物所構成之群的材料。藉此，在 構件20或30上相鄰之電路電極22或32之間維 ，同時並可進一步降低對向之電路電極22及33 値。 第1及第2電路構件20、30之具體例係可 晶顯示器，以ITO等形成電路電極之玻璃基板或 、或印刷電路板、陶瓷電路板、可撓性電路板、 晶片等。此等係依需要而組合使用。 電路連接部10係從含有導電性粒子之上述薄 路連接材料的硬化物所形成。電路連接部10係由 連接材料中所含有之黏著劑成分的硬化物11、分散 劑成分的硬化物11內之導電性粒子7所構成。電 部10中之導電性粒子7係不僅對向之第1電路電4 第2電路電極32之間，而亦可配置於主面21a、3 在電路構件之連接構造1中係導電性粒子7直接連 ,之群的 :選自由 構成之 塞板21 可更進 至少一 族之金 一電路 絕緣性 之電阻 用於液 膠基板 導體矽 膜狀電 於電路 於黏著 路連接 i 22與 1 a間》 接於第 •28- 1378745 1及第2電路電極22、32之兩者。藉此’第1及If 電極22、32係介由導電性粒子7電性連接。因It! 一電路構件上相鄰之電路電極之間維持絕緣性’局 充分地降低第1電路電極22與第2電路電極325 接電阻。因此，可順利地使第1及第2電路電極 之間的電流流動，可充分發揮具電路之功能。又， 接部10不含有導電性粒子7時係以第1電路電極 2電路電極32直接接觸，俾電氣連接。 電路連接部10係如後述般，藉上述薄膜狀· 材料之硬化物來構成，故對於第1電路構件20及 路構件30的電路連接部10的黏著力非常高。 (電路構件的連接構造之製造方法） 圖2係藉槪略截面圖表示於圖1之電路構件序 造之製造方法一例的步驟圖。 • 在本實施形態中係首先準備上述第1電路構f 薄膜狀電路連接材料40。薄膜狀電路連接材料4〇 •薄膜成材、自由基聚合性化合物、以加熱產生游蘭 .的自由基聚合起始劑、含異氰酸酯基化合物之黏笔 5及導電性粒子7 ^ 又’亦可使用不含導電性粒子7之電路連接构 時，電路連接材料亦稱爲NCP(N0n C〇nductive 。另外’含導電性粒子7之電路連接材料亦稱爲 Anisotropic Conductive Paste)。 :2電路 ,，在同 時並可 間的連 22、32 電路連 22與第 路連接 第2電 I連接構 :20與 係含有 自由基 劑成分 料。此 Paste ) ACP ( -29- 1378745 薄膜狀電路連接材料40之厚度宜爲5~50μιη。薄膜狀 電路連接材料40之厚度不足5 μηι，於第1及第2之電路 電極22、32間薄膜狀電路連接材料40有成爲塡充不足之 .傾向。另外，若超過50μιη，第1及第2之電路電極22、 3 2間之導通有很難確保之傾向。 其次，使薄膜狀電路連接材料40載置於形成第1電 路構件20的電路電極22之面上。繼而，使薄膜狀電路連 φ 接材料40朝圖2(a)的箭號Α及Β方向加壓，使薄膜狀 電路連接材料40暫連接於第1電路構件20 (圖2(b)) 〇 此時之壓力只要爲不對電路構件造成損傷的範圍，無 • 特別限定，但一般宜爲0.1〜30MPa»又，亦可一邊加熱一 邊加壓’加熱溫度係薄膜狀電路連接材料40實質上不硬 化之溫度。加熱溫度一般且爲50~190。(^。此等之加熱及加 壓宜在〇.5~120秒鐘的範圍實施。 ® 然後’如圖2(c)所示般，以使第2電路電極32朝 向第1電路構件2〇之側的方式使第2電路構件30載置於 • 薄膜狀電路連接材料40上。又，薄膜狀電路連接材料40 . 密著:於支撐基材·（未Η示）±而設置時，係剝離支撐基材 後使第2電路構件30載置於薄膜狀電路連接材料4〇上。 繼而，一邊加熱薄膜狀電路連接材料4〇，_邊朝圖2(c )箭號A及B方向加壓全體。又，薄膜狀電路連接材料 40係直接設置於支撐基板上放置’亦具有非常長之可使用 時間，且保持與電路構件之非常高的黏著,性。 -30- 1378745 加熱溫度係例如爲90〜200 °C，連接時間例如爲1秒 〜10分。此等之條件係依使用之用途、薄膜狀電路連接材 料、電路構件而適當選擇，依需要，亦可進行後硬化。例 -如，薄膜狀電路連接材料含有自由基聚合性化合物時之加 熱溫度係自由基聚合起始劑爲可產生自由基之溫度。藉此 ’在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。 φ 藉由薄膜狀電路連接材料40之加熱，以充分減少第1 電路電極22與第2電路電極32之間的距離之狀態薄膜狀 電路連接材料40進行硬化，第1電路構件2〇與第2電路 構件30介由電路連接部1〇而牢固地連接。 • 藉由薄膜狀電路連接材料40之硬化以形成電路連接 部1 0 ’可得到如圖1所示般之電路構件的連接構造1。又 ’連接的條件係可依使用之用途、薄膜狀電路連接材料、 電路構件而適當選擇。 Φ 若依本實施形態，在所得到之電路構件之連接構造1 中’可接觸於使導電性粒子7對向之第1及第2電路電極 _ 22、32之兩者，在同一電路構件上相鄰之電路電極之間維 持絕緣性’同時並可充分地降低對向之第1及第2電路電 極22,32之間的連接電阻。繼而，電路連接部1〇係藉上 述薄膜狀電路連接材料之硬化物來構成，故成爲對於第！ 及第2電路構件20或30之電路連接部10的黏著力非常 商者。 以上’說明有關本發明之適當的實施形態，但本發明 -31 - 1378745 不限制於此。本發明係在不超出其要旨之範圍，可各 形。 . 【實施方式】 ' 實施例 » 以下’依據實施例而具體地說明本發明，但本發 限定於此。 (導電性粒子之製作） 於聚苯乙烯粒子之表面上，設有由厚0.2 μιη之鎳 成的層’進一步於由此鎳所構成之層的表面上，設有 0 · 0 4 pm之金所構成的層，如此做法而得到平均粒徑 之導電性粒子。 (尿烷丙烯酸酯之調整） # 使重量平均分子量800之聚丁內酯二元醇400質 、2 -羥基丙基丙烯酸酯131質量份、作爲觸媒之二 • 錫二月桂酸酯0.5質量份及作爲聚合抑制劑之氫醌單 醚1.0質量份，一邊加熱至50°C，一邊攪拌而混合。 ，滴下異佛爾酮二異氰酸酯基222質量份，進一步一 拌，一邊昇溫至80°C而進行尿烷化又應》確認異氰酸 之反應率成爲99%以上後，降低溫度而得到尿烷丙烯 種變 明不 所構 由厚 1 0 μιη 量份 丁基 甲基 然後 邊攪 酯基 酸酯 -32- 1378745 (聚酯尿烷樹脂的調製）
藉由作爲二羧酸之對酞酸、與作爲二元醇之丙二醇的 反應得到聚酯多元醇。使此聚酯多元醇溶解於甲乙酮（ Μ EK )而得到溶液。將所得到之溶液投入於具備攪拌機、 溫度§十、冷凝器及真空產生裝置與氮氣導入管的附加熱器 之不銹鋼製高壓鍋中。然後，於上述高壓鍋中投入特定量 作爲異氰酸酯基之4,4’-二苯基甲烷二異氰酸酯，使作爲 觸媒之二丁基錫月桂酸酯相對於聚酯多元醇100質量份投 入0.02質量份之量’在75t下反應10小時後，冷卻至 40°C。進一步，加入六氫化吡嗪而反應30分鐘俾鏈延長 後，以三乙基胺中和。 若將上述反應後之溶液滴下於純水中，溶劑及觸媒溶 解於水中，同時聚酯尿烷樹脂會析出。繼而，使所析出之 聚酯尿烷樹脂以真空乾燥機乾燥。藉GPC分析測定聚酯 尿烷樹脂之重量分子量後，爲2 7000。又，調製上述聚酯 尿烷樹脂時，對酞酸/丙二醇Μ，4’ -二苯基甲烷二異氰酸 酯之調配莫耳比爲1.0/1.3/0.25。 (苯氧樹脂之調整） 將苯氧樹脂（Union Carbide公司製，商品名「PKHC 」、重量平均分子量：45000) 50g，溶解於以質量比甲苯 (沸點1 10.6°C、SP値8.90) /醋酸乙酯（沸點77.1°C、 SP値9. 1 0 ) =5 0/5 0之混合溶劑，而形成固形分40質量％ 之溶液。 -33- 1378745 (含氟聚醯亞胺樹脂之調製） 準備具備Dean-Stark回流冷卻器、溫度計、攪拌器 之1000ml的分離式燒瓶中。再加入作爲二胺化合物之聚 氧丙二胺15.0mmol、2,2 -雙[4- (4 -胺基苯氧基）苯基 ]六氟丙烷lG5.0mmol、作爲非質子性極性溶劑之N-甲 基-2 -吡咯烷酮287g，在室溫（25°C )下攪拌30分鐘。 然後，加入可與水共沸之芳香族烴系有機溶劑之甲苯180g 、四羧酸二酐之4, 4’-六氟丙叉基雙酞酸二酐114.Ommol ’昇溫至50°C，而以其溫度攪拌1小時後，進一步，昇溫 至1 60 °C而回流3小時。於水分定量接受器貯存理論量之 水’確認看不出水之流出後，除去水分定量接受器中之水 與甲苯’上昇至1 80 °C而除去反應溶液中之甲苯，得到聚 醯亞胺樹脂之NMP溶液。 將上述聚醯亞胺樹脂之NMP溶液投入於甲醇中，回 收析出物後，粉碎、乾燥而得到含氟聚醯亞胺樹脂。所得 到之含氟聚醯亞胺樹脂其重量平均分子量亦爲〗12〇〇〇。上 述含氣聚醯亞胺樹脂以成爲40質量％之方式溶解於甲乙酮 中 〇 以下述表2及表3所示之調配比（質量份：固形分換 算）調整實施例及比較例之電路連接材料，製作薄膜狀電 路連接材料。 (實施例1 ) -34- 1378745 混合作爲薄膜形成材之聚酯尿烷樹脂60質量份、作 爲自由基聚合性化合物之上述尿烷丙烯酸酯4〇質量份及 磷酸酯型丙烯酸酯（共榮公司油脂公司製、商品名「P2μ J ) 1質量份、作爲含異氰酸酯基化合物之甲基丙烯醯基 異氰酸酯0·5質量份、作爲自由基聚合起始劑之過氧化第 三己基-2-乙基己酸酯5質量份》其次，相對於上述成 分1〇〇體積份而調配分散上述3體積％導電性粒子，調整 電路連接材料。然後，使用塗佈裝置而使此電路連接材料 塗佈於已表面處理厚度80μπι之單面的PET薄膜而得到塗 膜。繼而’藉由使其塗膜以70 °C熱風乾燥1〇分鐘，俾得 到厚度爲20μηι之薄膜狀電路連接材料。 (實施例2 ) 除使用六亞甲基二異氰酸酯0.5質量份取代甲基丙嫌 醯基異氰酸酯0.5質量份以外，其餘係與實施例丨胃丨素{故 法而得到薄膜狀電路連接材料。 (實施例3 ) 除使用r-異氰酸酯丙基三乙氧基矽烷0.5質 甲基丙烯醯基異氰酸酯0.5質量份以外，其餘係與實施例 1同樣做法而得到薄膜狀電路連接材料。 (實施例4) 除使用r-異氰酸酯丙基三乙氧基矽院〇.1質量份_取代 -35- 1378745 甲基丙烯醯基異氰酸酯0.5質量份以外，其餘係與實施例 1同樣做法而得到薄膜狀電路連接材料。 . (實施例5) 除使用r -異氰酸酯丙基三乙氧基矽烷3質量份取代 甲基丙烯醯基異氰酸酯0.5質量份以外，其餘係與實施例 1同樣做法而得到薄膜狀電路連接材料。 (實施例6 ) 除使用r -異氰酸酯丙基三乙氧基矽烷5質量份取代 甲基丙烯醯基異氰酸酯0.5質量份以外，其餘係與實施例 • 1同樣做法而得到薄膜狀電路連接材料。 (實施例7) 除使用苯氧基60質量份取代聚酯尿烷樹脂6〇質量份 ® 以外，其餘係與實施例5同樣做法而得到薄膜狀電路連接 材料。 (實施例8 ) 除使用聚酯尿烷樹脂55質量份及含氟聚醯亞胺樹脂 50質量份取代聚酯尿烷樹脂60質量份以外’其餘係與實 施例1同樣做法而得到薄膜狀電路連接材料。 (比較例1 ) -36 - 1378745 除不使用甲基丙烯醯基異氰酸酯以外，其餘係與實施 例1同樣做法而得到薄膜狀電路連接材料。 , (比較例2) 除使用r-異氰酸酯丙基三乙氧基矽烷〇.〇5質量份取 代甲基丙烯醢基異氰酸酯〇.5質量份以外，其餘係與實施 例1同樣做法而得到薄膜狀電路連接材料。 (比較例3 ) 除使用7 -異氰酸酯丙基三乙氧基矽烷7.5質量份取代 ' 甲基丙烯醯基異氰酸酯〇.5質量份以外，其餘係與實施例 1同樣做法而得到薄膜狀電路連接材料。
[表2] 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 實施例 6 實施例 7 實施例 8 薄膜 形成材 聚酯胺基甲酸酯樹脂 60 60 60 60 60 60 • 55 苯氧樹脂 _ • • 睡 60 _ 含氟聚醯亞胺樹脂 5 自由基 聚合性 化合物 胺基甲酸酯丙烯酸酯 40 40 40 40 40 40 40 40 磷酸酯型丙烯酸酯 1 1 1 1 1 1 1 1 自由基 聚合 起始劑 t-過氧化第三己基-2-乙基己酸酯 5 5 5 5 5 5 5 5 含異氰 酸酯 化合物 甲基丙烯醯基異氰酸酯 0.5 _ _ _ _ • 六亞甲基二異氰酸酯 _ 0.5 _ • _ _ _ 7-異氰酸酯丙基三乙 氧基矽烷 - - 0.5 0.1 3 5 3 3 -37- 1378745 [表3] 比較例1 比較例2 比較例3 薄膜 形成材 聚酯胺基甲酸酯樹脂 60 60 60 苯氧樹脂 • _ • 含氟聚醯亞胺樹脂 _ • _ 自由基 聚合性 化合物 胺基甲酸酯丙烯酸酯 40 40 40 磷酸酯型丙烯酸酯 1 1 1 自由基 聚合 起始劑 t-過氧化第三己基-2-乙基己酸酯 5 5 5 含異氰 酸酯 化合物 甲基丙烯醯基 異氰酸酯 - - - 六亞甲基二異氰酸酯 _ _ 7 -異氰酸酯丙基三乙 氧基矽烷 - 0.05 7.5 <電路構件之連接構造的製作>
準備3層可撓性基板1( FPC基板1 )，其係使線寬 50μηι、線距ΙΟΟμιη及厚1 8μιη的銅電路配線500條介由黏 著劑層形成於聚醯亞胺薄膜Α (宇部興產公司製、商品名 「Upilex」、厚75μιη)上。又，準備2層可撓性基板2( FPC基板2)，其係使線寬50μπι、線距ΙΟΟμιη及厚8μπΐ 的銅電路配線50G條直接形成於聚醯亞胺薄膜Β(宇部興 產公司製、商品名「Upilexj 、厚25μηι)上。進一步，準 備玻璃基板，其係使線寬50μιη、線距ΙΟΟμτη及厚0.4μηΐ 之鉻電路配線500條直接形成於玻璃（Corning公司製、 商品「# 1 7 3 7」）上。 -38- 1378745 然後，於上述各FPC基板與玻璃基板之間配置如上述 般所得到之薄膜狀電路連接材料。繼而，使用熱壓接裝置 (加熱方式：定熱型、Toray Engineering股份公司製）， .在160 °C、3 MPa的條件下，朝其等之層合方向進行1〇秒 之加熱及加壓。如此一來，製作電路構件之連接構造，其 係使寬2mm的FPC基板與玻璃基板藉電路連接材料之硬 化物電氣連接。使如此做法所製作之電路構件的連接構造 φ 作爲初期特性評估用試樣》 [黏著性之評估] ' 黏著性係如下述所示般，如上述般做法所製作之電路 * 構件的連接構造中，進行電路間之連接電阻及黏著強度之 測定、及電路構件的連接構造中之連接外觀之觀察，以進 行評估。又，有關初期特性評估用試樣，以連接電阻、黏 著強度及連接外觀之全部良好者作爲黏著性非常優者》 <連接電阻之測定> •連接電阻係以多功能電表（Advantest公司製、商品 ，名：TR6848 )進行測定，以鄰接之電路間的電阻150點之 平均（X+ 3 σ)所示。結果表示於表4及表5中。此處’ 表4係FPC1/玻璃基板連接試樣之評估結果，表5係 FPC2/玻璃基板連接試樣之評估結果。 <黏著強度之測定> -39- 1378745 連接電阻係依據JIS - Z023 7而以90 ί 黏著強度之測定裝置係使用Tesilon UTM 50mm/分、25°C、東洋 Baldwin 公司製） 4及表5中。 <連接外觀之觀察> 使電路構件之連接構造投入於 85 85%RH之恒溫恒濕試驗裝置內2 5 0小時，： 繼而，使黏著後與耐濕試驗後之外觀從玻] 鏡觀察。在電路連接部與電路間空間界面； ，電路間之絕緣性大幅地降低，故判定爲 於表4及表5。 [可使用時間之評估] 使實施例及比較例所得到之薄膜狀電K 收容於真空包裝材中，在40°C下放置5日卷 做法而製作電路構件之連接構造，作爲可β 試樣。繼而有關可使用時間評估用試樣，功 評估黏著性。結果表示於表4及表5。在翁 ，可使用時間評估用試樣之各特性與初期转 之各特性比較，變化小，維持初期特性時， 時間長。 f剝離法測定。 - 4 (剝離速度 結果表示於表 °C 、相對濕度 I行耐濕試驗。 I基板側以顯微 L間產生剝離時 NG。結果表示 連接材料分別 ，與上述同樣 用時間評估用 與上述同樣地 著性之評估中 性評估用試樣 判定爲可使用 -40- 1378745
[表4] 初期 40°C5曰放置後 連接電阻 (Ω) 黏著強度 (N/cm ) 連接外觀 連接電阻 (Ω) 黏著強度 (N/cm) 連接外觀 剛黏著後 耐濕試驗 後 剛黏著後 耐濕試驗 後 實施例1 0.9 11.3 良好 良好 0.9 9.3 良好 良好 實施例2 1.0 11.5 良好 良好 1.1 9.7 良好 良好 實施例3 0.9 11.6 良好 良好 1.0 9.5 良好 良好 實施例4 0.9 11.0 良好 微量剝離 0.9 8.6 良好 微量剝離 實施例5 1.0 12.2 良好 良好 1.1 9.9 良好 良好 實施例6 1.1 12.8 良好 良好 1.3 10.0 良好 良好 實施例7 0.9 10.4 良好 良好 1.0 8.3 良好 良好 實施例8 0.9 12.0 良好 良好 1.0 11.4 良好 良好 比較例1 0.9 10.8 良好 產生剝離 1.0 8.4 良好 產生剝離 比較例2 0.9 11.0 良好 產生剝離 1.0 8.6 良好 產生剝離 比較例3 1.0 12.4 良好 良好 2.9 10.2 良好 良好 [表5] 初 期 40°C5日放置後 連接電阻 (Ω) 黏著強度 (N/cm) 連接外觀 連接電阻 (Ω) 黏著強度 (N/cm) 連接外觀 剛黏著後 耐濕試驗 後 剛黏著後 耐濕試驗 後 實施例1 1.1 9.2 良好 良好 1.1 9.3 良好 良好 實施例2 1.1 9.5 良好 良好 1.2 9.7 良好 良好 實施例3 1.1 9.6 良好 良好 1.1 9.5 良好 良好 實施例4 1.1 8.9 良好 良好 1.1 8.6 良好 良好 實施例5 1.1 9.8 良好 良好 1.2 9.9 良好 良好 實施例6 1.1 10.2 良好 良好 1.4 10.0 良好 良好 實施例7 1.2 8.2 良好 良好 1.2 8.3 良好 良好 實施例8 1.1 11.3 良好 良好 1.1 11.4 良好 良好 比較例1 1.1 8.6 良好 產生剝離 1.1 8.4 良好 產生剝離 比較例2 1.1 8.8 良好 產生剝離 1.1 8.6 良好 產生剝離 比較例3 1.2 9.8 良好 良好 3.7 10.2 良好 良好 -41 - 1378745 從表4及表5可知，初期之連接電阻係實施例及比較 例均爲1 Ω左右。又，初期之黏著強度係實施例及比較例 均爲7N/cm以上。尤其在實施例5、6中係伴隨含異氰酸 酯基化合物之調配量的增加，黏著強度變高。又，在實施 例8中係使用含氟聚醯亞胺，FPC2/玻璃基板連接試樣的 黏著強度會提高》 使用於實施例1 - 3、5 - 8及比較例3所得到之薄膜 狀電路連接材料時，任一者剝離均未被觀察到，又，於實 施例4所得到之薄膜狀電路連接材料，係含異氰酸酯基化 合物之量少’故耐濕試驗後之FPC1/玻璃基板連接試樣觀 察到微量之剝離，但爲無使用上問題之程度。然而，不含 有含異氰酸酯基化合物之比較例1'含異氰酸酯基化合物 之調配量更少之比較例2中係耐濕試驗後產生剝離。 如以上述般’可確認出實施例1 ~ 8及比較例3係黏著 強度、連接電阻及連接外觀均初期特性良好，顯示非常高 之黏著性。 又，使用在4 0 °C下放置5日後的薄膜狀電路連接材料 時，可確認出實施例1~8及比較例1、2中任一者均保持 與初期特性同等之黏著性、可使用時間長。另外，含異氰 酸酯基化合物之調配量爲7.5質量份之比較例3係在401 下放置5日後之連接電阻上昇至初期連接電阻之2倍以上 ，可知可使用時間短。 從以上，實施例1〜8之薄膜狀電路連接材料係相較於 比較例1〜3的薄膜狀電路連接材料，顯示非常高的黏著性 -42- 1378745 ，且具有非常長的可使用時間。從此事可確認出，若依本 發明之薄膜狀電路連接材料，可提供—種不依電路構件之 材質而顯示非常高之黏著性，且具有非常長之可使用時間 〇 又，亦可知本發明之薄膜狀電路連接材料係具有非常 長之可使用時間，同時尤其支撐電路電極之電路基板對於 電路構件具有良好的黏著性，該電路構件係含有至少一種 選自聚對苯二甲酸乙二酯、聚醚碾、環氧樹脂、丙烯酸樹 脂、聚醯亞胺樹脂及玻璃所構成之群中之材料的電路構件 及電路基板的表面被至少一種選自由氮化矽、聚酮樹脂、 聚醯亞胺樹脂及丙烯酸樹脂所構成之群中的材料塗佈或附 著。 產業上之利用可能性 依本發明之薄膜狀電路連接材料，可提供一種不依電 路構件之材質而顯示非常高之黏著性，且具有非常長之可 使用時間的薄膜狀電路連接材料及使用其等之電路構件的 連接構造。 【圖式簡單說明】 圖1係表示本發明之電路構件的連接構造之一實施形 態的槪略截面圖。 圖2係藉槪略截面圖表示於圖1之電路構件的連接構 造之製造方法一例的步驟圖。 -43- 1378745 【主要元件符號說明】 1 :電路構件的電路連接構造、5:黏著劑成分、7: 導電性粒子、10:電路連接部、11:黏著劑成分之硬化物 、20:第i電路構件、21:第！電路基板、21a :第1電 . -Ο 路基板主面、22:第1電路電極、30:第2電路構件、 •桌 2 電路基板、31a:第 2 + . $ ^ %路基板主面、32:第2電 • 路電極、4〇:薄膜狀電路連接材料
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Claims (1)

1378745 第097117009號專利申請案中文申請專利範圍修正本 民國100年4月12日修正 十、申請專利範圍 1. _種薄膜狀電路連接材料，其係將於第1電路基板 之主面上形成有第1電路電極之第1電路構件與於第2電 路基板之主面上形成有第2電路電極之第2電路構件，以 使第1及第2電路電極呈對向狀態進行電連接用，其特徵 φ 係含有薄膜形成材料、自由基聚合性化合物、經加熱產生 游離自由基之自由基聚合起始劑及單異氰酸酯化合物，該 單異氰酸酯化合物之含有比例，相對於該薄膜形成材料與 該自由基聚合性化合物之合計1〇〇質量份，爲009〜5質 ' 量份。 2. 如申請專利範圍第1項之薄膜狀電路連接材料，其 中更含有含氟有機化合物。 3 ·如申請專利範圍第1或2項之薄膜狀電路連接材料 • ’其中該薄膜形成材料係含具有重量平均分子量1 0000以 上之尿烷鍵結的有機化合物。 4. 如申請專利範圍第1或2項之薄膜狀電路連接材料 ，其中更含有導電性粒子。 5. 如申請專利範圍第3項之薄膜狀電路連接材料，其 中更含有導電性粒子。 6. —種電路構件之連接構造，其係具有於第！電路基 板之主面上形成有第1電路電極之第1電路構件，與被設 置成於第2電路基板之主面上形成有第2電路電極、且該 1378745 第2電路電極與該第1電路電極相對設置之第2電路構件 ，以及設置於該第1電路基板及該第2電路基板間，連接 該第1電路構件與該第2電路構件，使該第1及該第2電 路電極電連接之電路連接部，其特徵爲該電路連接部爲申 請專利範圍第1〜5項中任1項之薄膜狀電路連接材料之 硬化物。 7. 如申請專利範圍第6項之電路構件之連接構造，其 中該第1及該第2之電路電極中至少1者之表面由含從金 、銀、錫、白金族之金屬及銦-錫氧化物所成群中選出之 至少1種物質之材料所成。 8. 如申請專利範圍第6或7項之電路構件之連接構造 ，其中該第1及該第2之電路基板中至少1者爲由含從聚 對苯二甲酸乙二酯、聚醚颯、環氧樹脂、丙烯酸樹脂、聚 醯亞胺樹脂及玻璃所成群中選出之至少1種之材料所成之 基板。 9. 如申請專利範圍第6或7項之電路構件之連接構造 ，其中該第1及該第2之電路構件中至少1者與該電路連 接部間形成含由氮化矽、矽酮樹脂、聚醯亞胺樹脂及丙烯 酸樹脂所成群中選出之至少1種材料之層。 10. 如申請專利範圍第8項之電路構件之連接構造，其 中該第1及該第2之電路構件中至少1者與該電路連接部 間形成含由氮化矽、矽酮樹脂、聚醯亞胺樹脂及丙烯酸樹 脂所成群中選出之至少1種材料之層。
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