TW201202375A - Adhesive composition, circuit connecting material, connecting structure and circuit member connecting method - Google Patents

Adhesive composition, circuit connecting material, connecting structure and circuit member connecting method Download PDF

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Publication number
TW201202375A
TW201202375A TW100112010A TW100112010A TW201202375A TW 201202375 A TW201202375 A TW 201202375A TW 100112010 A TW100112010 A TW 100112010A TW 100112010 A TW100112010 A TW 100112010A TW 201202375 A TW201202375 A TW 201202375A
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TW
Taiwan
Prior art keywords
circuit
particles
connecting material
metal
conductive
Prior art date
Application number
TW100112010A
Other languages
Chinese (zh)
Inventor
Tomomi Yokozumi
Masaki Fujii
Kenzou Takemura
Original Assignee
Hitachi Chemical Co Ltd
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Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of TW201202375A publication Critical patent/TW201202375A/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01RELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00Electrically-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
    • H01R4/04Electrically-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
    • CCHEMISTRY; METALLURGY
    • 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
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • 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
    • C09J9/00Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02Electrically-conducting adhesives
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • 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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    • H01L24/28Structure, shape, material or disposition of the layer connectors prior to the connecting process
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    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/30Assembling printed circuits with electric components, e.g. with resistor
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    • 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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Abstract

An adhesive composition is provided with an adhesive component and conductive particles (10) dispersed in the adhesive component. The conductive particle (10) is provided with a base material particle (1) constituting the center portion, a metal plating layer (3) covering at least a part of the surface of the base material particle (1), and a plurality of metal fine particles (2) arranged inside the metal plating layer (3) and on the surface of the base material particle (1).

Description

201202375 九、發明說明 【發明所屬之技術領域】 本發明係關於黏著劑組成物、電路連接材料及連接構 造、以及電路構件之連接方法。 【先前技術】 隨著電子機器之小型化、薄型化,形成於電路構件之 電路電極的高密度化及高精細化正進展者。又,電路電極 之進一步微細化,即,對於多電極化或窄間距化等微細間 距化之要求日漸升高。形成微細電路之電路構件彼此的連 接於過去焊接或橡膠連接管上難以對應,故使用具有異方 導電性之黏著劑組成物。 上述黏著劑組成物一般爲黏著劑成分與分散於此之導 電粒子所成。於經相對配置之一對電路構件之間配置該黏 著劑組成物,將黏著劑組成物於挾持方向對全體施預壓力 ,而使相對電路電極彼此成電性連接。與此同時鄰接之電 極彼此於確保電絕緣性之狀態下黏著固定一對電路構件。 過去作爲具有黏著劑組成物之導電粒子,使用具有導 電性之種種微粒子。例如金屬微粉末、或金屬薄膜下表面 經被覆之塑質微粒子等。 然而,液晶顯示器等製造步驟中,高度微細間距化及 較高連接信賴性被要求下,有時使用於表面容易形成氧化 膜之金屬材料所成的電路電極。上述金屬微粉末及金屬薄 膜下表面經被覆之塑質微粒子各爲一長一短。因此使用過 -5- 201202375 去的黏著劑組成物時,微細間距化及連接信賴性雙方無法 同時到達所需的高水準。 具體而言,作爲導電粒子使用金屬微粉末時,金屬微 粉末因具有充分髙硬度,故即使於電路電極表面形成氧化 膜,亦可突破此而連接電路電極彼此。然而,金屬微粉末 一般爲粒度分佈較爲廣,此時無法適用於微細間距化上。 又,連接電路電極彼此連接後,隨著時間經過,有時會產 生連接部分電阻値上升之現象。此原因爲隨著溫度變動或 連接構造之連接狀態緩和等情況下,電路電極間之間隔擴 大,而使金屬微粉末無法充分地配合。又,一般金屬微粉 末之線熱膨脹係數比黏著劑成分之硬化物小,故重複昇溫 降溫之熱循環試驗後有時會產生如此現象。 相對於此作爲導電粒子使用以金屬薄膜將表面被覆之 塑質微粒子時,比較容易得到狹隘粒度分佈之導電粒子。 對於此點,使用塑質微粒子之導電粒子適用於微細間距化 。又,塑質微粒子之線熱膨脹率與黏著劑成分的硬化物爲 相近値。因此,溫度變動等所引起的電路電極間之間隔擴 大下塑質微粒子可充分地配合,具有可維持當初的電阻値 之優點。然而,塑質微粒子與一般金屬微粉末相比較時硬 度較爲低。因此,於電路電極表面形成氧化膜時,有著無 法充分地突破下使得連接部分的初期電阻値比較高之問題 〇 於是檢討欲具備金屬微粉末及金屬薄膜被覆表面之塑 質微粒子的各特長。具體爲檢討以金屬薄膜被覆之塑質粒 -6- 201202375 子表面上具有突起等之導電粒子。例如,專利文獻1及2中 記載導電性薄膜表面設置突起之導電粒子。又,專利文獻 3中記載金屬薄膜表面上進一步地附著金屬粒子之導電粒 子。且,專利文獻4及5中記載對具有凹凸之塑質粒子施預 金屬鍍敷所得之導電粒子。 專利文獻1 :特開2000- 1 953 3 9號公報 專利文獻2:特開2000-243 1 32號公報 專利文獻3 :特開昭63 -3 0 1 408號公報 專利文獻4 :特開平4-36902號公報 專利文獻5 :特開平1 1 -738 1 8號公報 【發明內容】 專利文獻1及2之導電粒子爲形成金屬薄膜之無電解鍍 敷步驟中,藉由析出突起而製造。此時,突起尺寸或突起 數之控制難以充分地進行。因此,突起的不均一性而難以 達到充分之高連接信賴性。又,專利文獻3之導電粒子爲 ,金屬薄膜與附著於該表面之金屬粒子之密著性並不充分 ,該金屬粒子可能會脫落。金屬粒子若脫落,連接構造的 初期電阻値會提高、或與鄰接之電路電極的絕緣性會不充 分,難以達到充分高之連接信賴性。 又,專利文獻4及5的導電粒子爲凹凸以塑質粒子之方 式形成。因此,電路電極表面上形成氧化膜時,無法充分 地突破該氧化膜,而恐有連接構造的初期電阻値提高之現 201202375 本發明爲有鑑於以上實情所得者,以提供一種即使必 須連接之電極係由於表面容易形成氧化膜之金屬材料所成 ,亦可充分降低連接構造的初期電阻値之黏著劑組成物及 使用此之電路連接材料爲目的。 又,本發明爲以提供較低連接電阻下連接電路構件之 連接構造及欲得到此之電路構件的連接方法爲目的。 本發明黏著劑組成物爲,具備黏著劑成分、分散於該 黏著劑成分中的導電粒子者,其特徵爲該導電粒子具有構 成該導電粒子之中心部分的基材粒子、與覆蓋該基材粒子 表面之至少一部份的金屬鍍敷層、及配置於該金屬鍍敷層 內側之該基材粒子表面上的複數金屬微粒子。 且複數金屬微粒子與基材粒子之位置關係中,所謂「 配置於基材粒子表面上」爲包含金屬微粒子於基材粒子表 面上以銜接之狀態下配置、以及以未銜接的狀態下配置者 。複數金屬微粒子配置於上述位置之導電粒子爲,於基材 粒子上附著金屬微粒子後,藉由鍍敷處理形成金屬鍍敷層 而製造。 藉由控制對基材粒子所所附著之金屬微粒子的個數及 其粒子徑,可於導電粒子表面上設置所望數目及尺寸之突 起。因此,調整鍍敷步驟之條件等與設有突起之導電粒子 做比較時,本發明中金屬微粒子之附著數及粒子徑之均一 性充分地高。藉由具備均一性高之金屬微粒子之導電粒子 ,即使爲電路電極以氧化膜被覆之金屬電極,可將電極彼 此更確實地進行電性連接。其結果可充分地降低連接構造 -8 - 201202375 之初期電阻値。 又,本發明黏著劑組成物所具有的導電粒子爲具備將 基材粒子及金屬微粒子成整體化被覆之金屬鍍敷層。因此 ,金屬微粒子與基材粒子之密著性高,可充分地抑制金屬 微粒子自導電粒子的脫落。其結果,電路電極彼此可更確 實地以電性連接,且可更充分地確保與鄰接之電路電極的 絕緣性。 金屬微粒子的平均粒徑爲200〜lOOOnm時爲佳。又, 基材粒子的平均粒徑爲1〜ΙΟμηι時爲佳。這些粒子的平均 粒徑各於上述範圍內時,可更確實地達到較低初期連接電 阻値。除此以外,連接電阻値的上昇抑制及與鄰接的電路 電極之絕緣性雙方可同時達到高水準。本發明中所謂的「 平均粒徑」表示如下所測定之値。即,任意選擇之金屬微 粒子以掃描型電子顕微鏡(SEM)進行觀察,測定其最大徑 及最小徑。該最大徑及最小徑的積平方根作爲其粒子之粒 徑。對於任意選擇之50個粒子進行如上述之粒徑測定,其 平均値作爲平均粒徑。 由可有效率且確實地得到本發明的效果之觀點來看, 金屬微粒子的數目以每1個基材粒子中1〇〜40個時爲佳。 又,金屬微粒子的數目爲10〜40個時,具有連接電阻値之 上昇抑制及與鄰接之電路電極的絕緣性雙方達到高水準之 優點。每1個基材粒子之金屬微粒子的數目表示以下述測 定出之値。即,將任意選擇之導電粒子以SEM攝影後’ 觀察所得之導電粒子表面的突起數作爲金屬微粒子數而計 -9- 201202375 算出。藉此所得之計算數乘以2倍可算出1個導電粒子之金 屬微粒子數。對於任意選擇之50個導電粒子’如上述測定 出金屬微粒子數,該平均値作爲每1個基材粒子中的金屬 微粒子數。 又,基材粒子係由粒子直徑的20%壓縮變形時之壓縮 彈性率爲100〜kgf/mm2之材質所成者時爲佳。基材 粒子具有如上述之硬度時,於電路電極表面上即使形成氧 化膜,配置於金屬鍍敷層內側之金屬微粒子可更確實地突 破該氧化膜。除此以外,隨著溫度變動等,即使電路電極 間的間隔變寬,基材粒子可充分地配合電路電極間隔之擴 大。因此,可充分地抑制連接電阻値之上昇。 又,基材粒子爲,最大負載5 mN下經壓縮後之壓縮 回復率爲40%以上時爲佳。基材粒子具有如上述之壓縮回 復率時,即使隨著溫度變動等而使電路電極間的間隔變寬 ,基材粒子可充分地配合電路電極間隔之擴大。因此,可 充分地抑制連接電阻値的上昇。 本發明的電路連接材料爲上述本發明之黏著劑組成物 所成,黏著電路構件彼此之同時,電性連接具有各電路構 件之電路電極彼此者。 本發明之連接構造係由經相對配置之一對電路構件、 與上述本發明之電路連接材料的硬化物所成,具備使介在 上述一對電路構件之間具有各電路構件之電路電極彼此以 電性連接該電路構件彼此之連接部。 本發明爲一種電路構件之連接方法,其特徵爲使經相 -10- 201202375 對配置之一對電路構件間介著如申請專利範圍第7項之電 路連接材料,全體經加熱及加壓,形成由該電路連接材料 之硬化物所成,介於該一對電路構件之間,黏著該電路構 件彼此,使各電路構件所具有之電路電極彼此電性連接之 連接部,得到具備該一對電路構件及該連接部之連接結構 者。 本發明爲可提供一種必須連接之電極即使爲於表面上 容易形成氧化膜之金屬材料所成者,可充分降低連接構造 之初期電阻値的黏著劑組成物及使用此之電路連接材料》 又,本發明爲可提供較低連接電阻下連接電路構件之連接 構造、以及得到此之電路構件的連接方法。 以下參考附圖下詳細說明本發明之較佳實施形態。圖 面說明中,同一要素賦預同一符號,省略重複說明》又, 爲使圖面上便利,圖面寸法比率並非與說明內容一致。 且,本說明書中的「(甲基)丙烯酸酯」的意思爲「丙 烯酸酯」及對應此之「甲基丙烯酸酯」。 圖1表示有關本發明之黏著劑組成物作爲電路連接材 料使用,電路電極彼此經連接之連接構造的槪略截面圖。 圖1所示連接構造100爲具備相互相對之第1電路構件30及 第2電路構件40,第1電路構件30與第2電路構件4〇之間設 有連接彼等之連接部50a。 第1電路構件30爲具備電路基板(第1電路基板)31、與 電路基板31之主面31a上所形成之電路電極(第1電路電極 )32。第2電路構件40爲具備電路基板(第2電路基板)4 1、 -11 - 201202375 與電路基板41的主面41a上所形成之電路電極(第2電路電 極)42。電路基板31、41中電路電極32、42之表面爲平坦 。且,此所謂「電路電極之表面爲平坦」爲電路電極表面 之凹凸極小之意思,表面凹凸以20 nm以下時爲佳。 連接部50a爲具備含於電路連接材料之黏著劑成分的 硬化物20a、與分散於此之導電粒子10。而連接構造100中 ,呈相對電路電極32與電路電極42介著導電粒子10以電性 連接。即,導電粒子10於電路電極32,42之雙方直接接觸 〇 因此,充分地減低電路電極32、42間之連接電阻下, 可達成電路電極32、42間之良好電性連接。另一方面,硬 化物20a爲具有電絕緣性者,鄰接之電路電極彼此可確保 其絕緣性。因此,電路電極3 2、42間之電流可緩和地流動 ,可充分地發揮電路所具有的功能。 其次,對於黏著劑成分硬化前之狀態的黏著劑組成物 做詳細。圖2表示有關本發明黏著劑組成物作爲電路連接 材料使用時的較佳實施形態之槪略截面圖。圖2所示電路 連接材料50之形狀爲薄膜狀》電路連接材料50爲具備黏著 劑成分20、與分散於黏著劑成分20中之導電粒子10。 電路連接材料50係於薄膜狀支持體上使用塗佈裝置進 行含有黏著劑成分及導電粒子之黏著劑組成物的塗佈,經 所定時間熱風乾燥後製得。 對於導電粒子10之構成,參照圖3下做說明》圖3表示 有關本發明之電路連接材料所含有的導電粒子之形態顯示 -12- 201202375 截面圖。圖3所示導電粒子10係由構成中心部分之基材粒 子1、與於該基材粒子1上所設置的複數金屬微粒子2、與 如覆蓋於基材粒子1及金屬微粒子2之表面般地所形成之金 屬鍍敷層3所構成。金屬微粒子2位於金屬鍍敷層3之內側 〇 作爲基材粒子1之材質,可舉出金屬及有機高分子化 合物。作爲構成基材粒子1之金屬,例如可舉出鎳、銅、 金、銀、鈷及彼等之合金。作爲構成基材粒子1之有機高 分子化合物,例如可舉出丙烯酸樹脂、苯乙烯樹脂、苯並 鳥糞胺樹脂、聚矽氧樹脂、聚丁二烯樹脂或彼等共聚物, 亦可爲這些經交聯所得者。 作爲基材粒子1之材質,由達成較高連接信賴性之觀 點來看,電路電極彼此連接後,使用可充分配合電路電極 間隔的擴大之材質爲佳。隨著溫度變動等於電路電極間隔 的擴大上,基材粒子1若無法充分配合時,連接部分的電 阻値會有上昇之情況。由有效地防止如此電阻値的上昇之 觀點來看,作爲基材粒子1,使用有機高分子化合物所成 的粒子爲佳》 有機高分子化合物所成之粒子即使於連接電路電極彼 此時於電路電極間壓成扁平形狀,其具有由扁平形狀恢復 至原來球狀之傾向。因此,隨著溫度變動等於電路電極間 隔之擴大上導電粒子10可充分地配合。由此觀點來看,基 材粒子1的最大負載5 mN下壓縮後之壓縮回復率以40%以 上時爲佳。作爲具有如上述壓縮回復率之有機化合物所成 -13- 201202375 的粒子,例如可舉出,丙烯酸樹脂、苯乙烯樹脂、苯並鳥 糞胺樹脂、聚矽氧樹脂、聚丁二烯樹脂或彼等共聚物所成 之粒子。該壓縮回復率若未達4 0%時,對於電路電極間的 間隔擴大有著未充分配合之傾向。該壓縮回復率可由Fischer Instruments製H-100微小硬度計進行測定。 又,作爲基材粒子1之材質,粒子直徑經20%壓縮變 形時,較佳爲使用具有100〜1000 kgf/mm2,更佳爲具有 100〜800 kgf/mm2之壓縮彈性率者。作爲由具有如上述硬 度之有機化合物所成的粒子,例如可舉出丙烯酸樹脂、苯 乙烯樹脂、苯並鳥糞胺樹脂、聚矽氧樹脂、聚丁二烯樹脂 或彼等共聚物所成的粒子》 上述20%壓縮變形時的壓縮彈性率若未達1〇〇 kgf/mm2 時,與於表面形成氧化膜之金屬電路電極連接時,無法充 分地突破表面的氧化膜,會有連接部分的電阻値提高之傾 向。另一方面,壓縮彈性率若超過1 000 kgf/mm2時,加壓 相對電路電極時,會有基材粒子1不會充分變形成扁平形 狀之傾向。基材粒子1的變形若不充分下,與電路電極之 接觸面積亦會不充分,使得連接部分之電阻値提高。又, 爲使基材粒子1可充分變形成扁平形狀而施預較高壓力之 加壓時,恐怕粒子因粉碎而無法充分地連接。該壓縮彈性 率可由Fischer Instruments製Η -100微小硬度計進行測定 〇 且,基材粒子1於粒子間可爲相同或相異種類之材質 ,同一粒子中可使用單獨1種材質、或混合2種以上材質。 • 14 - 201202375 基材粒子1的平均粒徑雖配合用途等而可適宜設計’ 但以1〜10 μηι爲佳,2〜8 μιη爲較佳,3〜5 μηι爲更佳。 平均粒徑若未達1 μιη時,會產生粒子的二次凝集,與鄰 接電路之絕緣性會有不充分的傾向。另一方面,平均粒徑 若超過10 μιη時,因過大而使與鄰接電路之絕緣性會有不 充分的傾向。 作爲構成金屬微粒子2之金屬,例如可舉出Ni、Ag、 Au、Cu、Co、Zn、Al、Sb、U、Ga、Ca、Sn、Se、Fe、 Th、Be、Mg、Mn及彼等之合金。這些金屬之中,導電性 及耐腐蝕性之觀點來看,以Ni、Ag、Au、Cu爲佳’以 Ni爲較佳。這些可單獨1種、或組合2種以上使用。 金屬微粒子2之平均粒徑爲對應用途等而可做適宜設 計,但以200〜1000 nm爲佳,400〜800 nm爲較佳,400 〜500 nm爲更佳。平均粒徑若未達200 nm時,與表面上 形成氧化膜之金屬的電路電極連接時,無法充分地突破氧 化膜,會有連接部分的電阻値提高之傾向。另一方面’平 均粒徑若超過1〇〇〇 nm時,與鄰接電路之絕緣性會有不充 分的傾向。 金屬鍍敷層3的內側之基材粒子1的表面上所配置之金 屬微粒子2的數目爲,每1個基材粒子中10〜40個爲佳’ 10 〜30個爲較佳,10〜20個爲更佳。金屬微粒子2的數目若 未達10個時,連接電阻値之上昇有著無法充分抑制的傾向 。另一方面,金屬微粒子2的數目若超過40個時’有著與 鄰接電路之絕緣性不充分的傾向。 -15- 201202375 金屬鍍敷層3爲基材粒子1及金屬微粒子2表面之至少 一部經被覆者。但,欲更確實地防止金屬微粒子2的脫落 之觀點來看,實質上將基材粒子1及金屬微粒子2的所有表 面皆經被覆爲佳。 金屬鍍敷層3的膜厚以80〜200 nm爲佳,100〜150 nm爲較佳,100〜110 nm爲更佳。金屬鍍敷層3之膜厚若 未達80 nm時,會有連接部分的電阻値提高之傾向。另一 方面,金屬鍍敷層3的膜厚若超過200 nm時,會有與鄰接 電路之絕緣性不充分的傾向。 作爲製造導電粒子10之方法,可舉出於基材粒子1表 面上將金屬微粒子2以物理性附著後,進行形成金屬鍍敷 層3之鍍敷處理的方法。此時,藉由調整添加之金屬微粒 子2的量,可控制附著於基材粒子1表面之金屬微粒子2的 數目。因此,對於此施預無電解鍍敷處理後製造出導電粒 子1 0。 其次,對於分散於導電粒子1之黏著劑成分做說明。 作爲黏著劑成分20,含有(a)熱硬化性樹脂及(b)熱硬化性 樹脂用硬化劑所成之黏著劑的組成物、以及含有藉由(c) 加熱或光產生游離自由基之硬化劑及(d)自由基聚合性物 質所成之黏著劑的組成物爲佳。或上述(a)、(b)、(c)及(d) 之混合組成物爲佳。 作爲(a)熱硬化性樹脂,任意溫度範圍中可進行硬化 處理之熱硬化性樹脂即可,並無特別限定,以環氧基樹脂 時爲佳。作爲環氧基樹脂可舉出雙酚A型環氧基樹脂、 -16- 201202375 雙酚F型環氧基樹脂、雙酚S型環氧基樹脂、酚漆用酚醛 型環氧基樹脂、甲酚漆用酚醛型環氧基樹脂、雙酚A漆 用酚醛型環氧基樹脂、雙酚F漆用酚醛型環氧基樹脂、脂 環式環氧基樹脂、環氧丙基酯型環氧基樹脂、環氧丙基胺 型環氧基樹脂、海因型環氧基樹脂、異三聚氰酸型環氧基 樹脂、脂肪族鏈狀環氧基樹脂等。這些環氧基樹脂可經鹵 化,或經氫化。這些環氧基樹脂單獨1種、或組合2種以上 使用。 作爲(b)熱硬化性樹脂用硬化劑可舉出胺系、酚系、 酸酐系、咪唑系、醯胼系、二氰二醢胺、三氟化硼-胺錯 合物、鎏鹽、碘鑰鹽、胺亞胺等。這些可單獨或混合2種 以上使用,亦可混合使用分解促進劑、抑制劑等。又,將 這些硬化劑以聚尿烷系、聚酯系之高分子物質等經被覆後 使其微膠囊化者,可延長使用時間而較佳。 (b)熱硬化性樹脂用硬化劑之配合量以黏著劑成分的 總質量作爲基準時,以0.1〜60.0質量%程度爲佳、1.0〜 2 0.0質量%爲較佳。熱硬化性樹脂用硬化劑之配合量若未 達0.1質量%時,硬化反應之進行會不充分,會有難以得到 良好黏著強度或連接電阻値之傾向。另一方面,配合量若 超過60質量%時,會有黏著劑成分之流動性降低、或適用 期縮短之傾向,且連接部分之連接電阻値會有提高之傾向 〇 作爲(C)藉由加熱或光產生游離自由基之硬化劑,可 舉出過氧化化合物、偶氮系化合物等之經加熱或光分解後 -17- 201202375 產生游離自由基者。硬化劑可依據目的之連接溫度、連接 時間、適用期等而做適宜選擇。由高反應性與適用期之觀 點來看,半衰期10小時的溫度爲40°c以上,而半衰期1分 鐘的溫度爲180°c以下之有機過氧化物爲佳。此時(c)藉由 加熱或光產生游離自由基之硬化劑的配合量以黏著劑成分 的總質量爲基準時,以0.05〜10質量%爲佳,以0.1〜5質 量%爲較佳。 (c)藉由加熱或光產生游離自由基之硬化劑,具體可 選出二醯基過氧化物、過氧化二碳酸酯、過氧化酯、過氧 化縮酮、二烷基過氧化物、氫過氧化物等。欲抑制電路構 件之連接端子的腐蝕,選自過氧化酯、二烷基過氧化物、 氫過氧化物爲佳,選自可得到高反應性之過氧化酯爲較佳 〇 作爲二醯基過氧化物類例如可舉出異丁基過氧化物、 2,4-二氯苯醯基過氧化物、3,5,5-三甲基己醯基過氧化物 、辛醯基過氧化物、月桂醯基過氧化物、硬脂醯基過氧化 物、琥珀醯酵過氧化物、苯醯基過氧化甲苯、苯醯基過氧 化物等。 作爲過氧化二碳酸酯類例如可舉出二-N-丙基過氧化 二碳酸酯、二異丙基過氧化二碳酸酯、雙(4-第三丁基環 己基)過氧化二碳酸酯、二-2-乙氧基甲氧基過氧化二碳酸 酯、二(2-乙基己基過氧化)二碳酸酯、二甲氧基丁基過氧 化二碳酸酯、二(3-甲基-3-甲氧基丁基過氧化)二碳酸酯等 -18- 201202375 作爲過氧化酯類例如可舉出’枯烯基過氧化新癸酸酯 、1,1,3,3 -四甲基丁基過氧化新癸酸酯、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 基過氧化特戊酸醋、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-雙(2-乙基己醯基過氧化)己烷、1-環己基-1-甲基乙基過氧化-2-乙基己酸酯、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 丁基過氧化異丁酸酯、1,卜雙(第三丁基過氧化)環己烷、 第三己基過氧化異丙基單碳酸酯、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-雙(間甲苯醯基過氧化)己烷、第三丁基過氧化異丙基 單碳酸酯、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、第三丁基過氧化乙酸酯等。 作爲過氧化縮酮類例如可舉出1,1-雙(第三己基過氧 化)-3,5,5-三甲基環己烷、1,1_雙(第三己基過氧化)環己烷 、1,1-雙(第三丁基過氧化)-3,5,5-三甲基環己烷、1,1-(第 三丁基過氧化)環十二烷' 2,2-雙(第三丁基過氧化)癸烷 等。 作爲二烷基過氧化物類例如可舉出α,α’-雙(第三丁基 過氧化)二異丙基苯、二枯烯基過氧化物、2,5 -二甲基-2,5 -二(第三丁基過氧化)己烷、第三丁基枯烯基過氧化物 等。 作爲氫過氧化物類例如可舉出二異丙基苯氫過氧化物 、枯烯氫過氧化物等》 -19- 201202375 這些(C)藉由加熱或光產生游離自由基之硬化劑可單 獨使用1種或混合2種以上,亦可混合分解促進劑、抑制劑 等使用》 (d)自由基聚合性物質爲具有藉由自由基聚合之官能 基的物質,例如可舉出(甲基)丙烯酸酯、馬來酸酐縮亞胺 化合物等。 作爲(甲基)丙烯酸酯例如可舉出,尿烷(甲基)丙烯酸 酯、甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、異丙基( 甲基)丙烯酸酯、異丁基(甲基)丙烯酸酯、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、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲 基甲烷四(甲基)丙烯酸酯、2-羥基-1,3-二(甲基)丙烯氧基 丙烷、2,2-雙〔4-((甲基)丙烯氧基甲氧基)苯基〕丙烷、 2,2-雙〔4-((甲基)丙烯氧基聚乙氧基)苯基〕丙烷、二環 戊烯基(甲基)丙烯酸酯、三環癸醯基(甲基)丙烯酸酯、雙 ((甲基)丙烯氧基乙基)異三聚氰酸、ε-己內酯變性參((甲 基)丙烯氧基乙基)異三聚氰酸、參((甲基)丙烯氧基乙基) 異三聚氰酸等。 如此自由基聚合性物質可單獨使用1種或組合2種以上 。黏著劑成分爲至少含有25 t之黏度爲100000〜1 000000 mPa· s之自由基聚合性物質爲特佳,特別爲含有具有 1 00000〜5 00000 mPa . s之黏度(25 °C)的自由基聚合性物 質爲佳。自由基聚合性物質之黏度的測定使用販賣的E型 黏度計進行測定。 -20- 201202375 自由基聚合性物質之中,由黏著性的觀點來看,使用 尿烷丙烯酸酯或尿烷甲基丙烯酸酯爲佳。又,欲提高耐熱 性與所使用的有機過氧化物進行交聯後,單獨下並用顯示 loot以上之Tg的自由基聚合性物質時爲特佳。作爲如此 自由基聚合性物質可使用分子內具有二環戊烯基、三環癸 醯基及/或三嗪環者。特別適合使用分子內具有三環癸醯 基或三嗪環之自由基聚合性物質。 作爲馬來酸酐縮亞胺化合物以分子中至少含有2個以 上的馬來酸酐縮亞胺基者爲佳,例如可舉出1-甲基-2,4-雙 馬來酸酐縮亞胺苯、N,N’-間伸苯基雙馬來酸酐縮亞胺、 N,N’-對伸苯基雙馬來酸酐縮亞胺、N,N’-間伸甲苯基雙馬 來酸酐縮亞胺、N,N’-4,4·雙伸苯基雙馬來酸酐縮亞胺、 N,N’-4,4-(3,3’-二甲基-雙伸苯基)雙馬來酸酐縮亞胺、 Ν,Ν’-4,4-(3,3’-二甲基二苯基甲烷)雙馬來酸酐縮亞胺、 Ν,Ν’-4,4-(3,3’-二乙基二苯基甲烷)雙馬來酸酐縮亞胺、 !^少’-4,4-二苯基甲烷雙馬來酸酐縮亞胺、:^:^-4,4-二苯 基丙烷雙馬來酸酐縮亞胺、Ν,Ν’-4,4-二苯基醚雙馬來酸酐 縮亞胺、Ν,Ν’-3,3’-二苯基楓雙馬來酸酐縮亞胺、2,2-雙 〔4-(4-馬來酸酐縮亞胺苯氧基)苯基〕丙烷、2,2-雙〔3-第二丁基-4,8-(4-馬來酸酐縮亞胺苯氧基)苯基〕丙烷、 1,1-雙〔4-(4-馬來酸酐縮亞胺苯氧基)苯基〕癸烷、4,4’-環亞己基-雙〔1-(4-馬來酸酐縮亞胺苯氧基)-2-環己基〕 苯、2,2-雙〔4-(4-馬來酸酐縮亞胺苯氧基)苯基〕六氟丙 烷等。這些可單獨使用1種或並用2種以上,可並用烯丙基 -21 - 201202375 酚、烯丙基苯基醚、安息香酸烯丙基等烯丙基化合物。 又,若必要可使用氫醌、甲基醚氫醌類等聚合禁止劑 0 黏著劑成分20可含有薄膜形成性高分。以黏著劑成分 20之全質量爲基準,薄膜形成性高分子的含有量以2〜80 質量%爲佳,5〜70質量°/。爲較佳,10〜60質量%爲更佳。 作爲薄膜形成性高分子可舉出聚苯乙烯、聚乙烯、聚乙烯 丁縮醛、聚乙烯甲縮醛、聚亞胺、聚醯胺、聚酯、聚氯化 乙烯、聚伸苯基氧化物、尿素樹脂、蜜胺樹脂、酚樹脂、 二甲苯樹脂、聚異氤酸酯樹脂、苯氧基樹脂、聚亞胺樹脂 、聚酯尿烷樹脂等》 上述薄膜形成性高分子之中具有水酸基等官能基之樹 脂可提高黏著性,故較佳。又,亦可使用這些高分子以自 由基聚合性官能基進行變性者。薄膜形成性高分子之重量 平均分子量以10000〜10000000爲佳》 且,電路連接材料50可含有塡充材料、軟化劑、促進 劑、老化防止劑、著色劑、難燃化劑、觸變劑、偶合劑、 酚樹脂、蜜胺樹脂、異氰酸酯類等。 含有塡充材料時可得到連接信賴性等提高而較佳。塡 充材料僅爲該最大徑未達到導電粒子之粒徑者即可使用, 嘍5〜60體積%之範圍爲佳。若超過60體積%時信賴性提高 之效果已達飽和。 作爲偶合劑已含有1種以上選自乙烯、丙烯基、胺基 、環氧基及異氰酸酯基所成群之基的化合物,其由黏著性 -22- 201202375 提高之觀點來看爲佳。 電路連接材料50中,導電粒子10之含有量對於100體 積份的電路連接材料50之全體積而言,以0·5〜60體積份 爲佳,該含有量可依據用途而有不同之使用方式。 圖4表示有關本發明之電路連接材料50.設置於薄膜狀 支持體60上之狀態顯示截面圖。作爲支持體60例如可使用 聚乙烯對苯二甲酸薄膜、聚乙烯萘酸酯薄膜、聚乙烯異酞 酸酯薄膜、聚丁烯對苯二甲酸薄膜、聚烯烴系薄膜、聚乙 酸酯薄膜、聚碳酸酯薄膜、聚伸苯基硫化物薄膜、聚醯胺 薄膜、乙烯-酢酸乙烯共聚物薄膜、聚氯化乙烯薄膜、聚 氯化亞乙烯基薄膜、合成橡膠系薄膜、液晶聚合物薄膜等 之各種薄膜。對於上述薄膜表面,若必要可使用施預電暈 放電處理、增黏塗層處理、帶電防止處理等的支持體。 使用電路連接材料50時,欲由電路連接材料50容易剝 離支持體60,若必要支持體60表面上可塗佈剝離處理劑而 使用。作爲剝離處理劑可使用聚矽氧樹脂、聚矽氧與有機 系樹脂之共聚物、醇酸樹脂、胺醇酸樹脂、具有長鏈烷基 之樹脂、具有氟烷基之樹脂、蟲膠樹脂等各種剝離處理劑 支持體60之膜厚並無特別限定,但考慮到製作之電路 連接材料50之保管、使用時的便利性等以4〜200 μιη爲佳 。且,支持體60的膜厚若考慮到材料成本或生產性時以15 〜75 μηι爲佳。 電路連接材料並未如電路連接材料50—般限定於單層 -23- 201202375 構造,可層合複數層之多層構造。多層構造之電路連接材 料可由黏著劑成分及導電粒子之種類或這些含有量之相異 層經複數層合而製造。例如電路連接材料爲可具備含有導 電粒子之導電粒子含有層、與於該導電粒子含有層之至少 一面上設置未含導電粒子之導電粒子非含有層亦可。 圖5表示二層構造之電路連接材料由支持體所支持之 狀態顯示截面圖。圖5所示電路連接材料70係由含有導電 粒子之導電粒子含有層70a及未含導電粒子之導電粒子非 含有層7〇b所構成。電路連接材料70之兩最外面各設有支 持體60a,60b。電路連接材料70爲支持體60a表面上形成 導電粒子含有層70a,另一方面,支持體6 0b表面上形成 導電粒子非含有層7 0b,這些層使用過去公知之層壓機等 進行貼合而製造出。使用電路連接材料70時,可剝離適宜 支持體60a,60b使用。 電路連接材料70爲電路構件彼此接合時,黏著劑成分 之流動所引起的電路電極上導電粒子個數之減少可充分受 到抑制。因此,例如將1C晶片裝入基板上時,可充分確 保1C晶片之金屬凸塊(連接端子)上的導電粒子個數。此 時,具備1C晶片之金屬凸塊的面與導電粒子非含有層7 Ob ’另一必須裝入1C晶片之基板與導電粒子含有層70a各 可銜接下配置電路連接材料70爲佳。 (連接方法) 圖6表示有關本發明之電路構件之連接方法的一實施 -24- 201202375 形態槪略截面圖所示步驟圖,將電路連接材料50經熱硬化 後製造出連接構造之一連串步驟。 首先,準備上述第1電路構件30、與薄膜狀之電路連 接材料50。電路連接材料50係由含有導電粒子10之黏著劑 組成物所成。 電路連接材料50之厚度以5〜50 μιη時爲佳。電路連 接材料50之厚度若未達5 μιη時,第1及第2電路電極32, 42間電路連接材料5 0會有塡充不足之傾向。另一方面,厚 度若超過50 μιη時,第1及第2電路電極32,42間的導通有 難確保之傾向。 其次,將電路連接材料5 0載持於形成第1電路構件30 之電路電極32的面上。而將電路連接材料50往圖6(a)之箭 頭Α及Β方向加壓,將電路連接材料5 0於第1電路構件30 上進行假連接(圖6(b))。 此時的壓力僅不會傷害到電路構件之範圔即可,並無 特別限定,一般以0.1〜30.0 Mpa爲佳。又,可一邊加熱 一邊加壓,加熱溫度爲實質上不使電路連接材料50硬化之 溫度。加熱溫度一般以50〜190 °C爲佳。這些加熱及加壓 於0.5〜120秒範圍內進行爲佳。 其次,如圖6(c)所示,將第2電路構件40可使第2電路 電極42往第1電路構件30之方向而載持於電路連接材料50 上。然後加熱薄膜狀電路連接材料50下,往圖6(c)的箭頭 A及B方向做全體加壓。 此時的加熱溫度爲可硬化電路連接材料50之溫度。加 -25- 201202375 熱溫度以60〜180 °C爲佳,70〜170 °C爲較佳,80〜160 °C爲 更佳。加熱溫度若未達60°C時,會有硬化速度過慢的傾向 ,若超過1 80°C時會有容易進行不佳副反應之傾向。加熱 時間以0.1〜180秒爲佳,以0.5〜180秒爲較佳,以1〜180 秒爲更佳。 藉由電路連接材料50之硬化形成黏著部50a,得到如 圖1所示之連接體1 00。連接之條件依使用用途、黏著劑組 成物、電路構件而做適宜選擇。且,作爲電路連接材料50 之黏著劑成分,使用經光可硬化者時,對於電路連接材料 5〇適宜照射活性光線或能量線即可。作爲活性光線可舉出 、紫外線、可見光、紅外線等。作爲能量線可舉出電子線 、X線、γ線、微波等。 以上對於本發明的較佳實施形態做說明,但本發明並 未限定於上述實施形態。本發明以不脫離該要旨之範圍下 可做種種變化。 【實施方式】 實施例 以下藉由實施例對本發明內容做更具體說明,但本發 明未限定於這些實施例。 (實施例1) 混合作爲薄膜形成性高分子之苯氧基樹脂溶液(苯氧 基樹脂/甲苯/乙酸乙酯= 40/3 0/30質量份)100質量份、作 -26- 201202375 爲環氧基樹脂與潛在性硬化劑之混合物的含有微膠囊型潛 在性硬化劑之液狀環氧基(旭化成股份公司製,商品名: 諾巴奎亞394 1 )60質量份、作爲導電粒子的Ni/Au鍍敷聚 苯乙烯粒子10質量份、及矽烷偶合劑(東麗· Dow Corning 聚矽氧股份公司製、商品名:SZ6030)1 0質量份,調製出 電路連接用之黏著劑組成物。且作爲苯氧基樹脂使用FX-293 (商品名、東都化成股份公司製)。 上述Ni/Au鍍敷聚苯乙烯粒子爲平均粒徑3μιη之聚苯 乙烯粒子(基材粒子)表面上,附著平均粒徑400nm之Ni 微粒子(金屬微粒子)後,經無電解鍍敷形成Ni層,最後 形成Au層而製作出。將鍍敷處理後的導電粒子經SEM使 其成爲倍率6000倍後觀察結果,Ni微粒子所引起的突起 數(配置於金屬鍍敷層內側之金屬微粒子數)爲32個。聚苯 乙烯粒子的20%壓縮變形時之壓縮彈性率爲750 kgf/mm2, 最大負載5 mN下壓縮後之壓縮回復率爲70%。 PET(聚乙烯對苯二甲酸)所成之支持體(膜厚50 μπι)上 塗佈上述黏著劑組成物。其後將此於70°C下乾燥10分鐘, 得到設置於支持體上導電粒子含有層(膜厚25 μπι)。 另一方面,取代黏著劑組成物之溶液使用苯氧基樹脂 溶液(苯氧基樹脂/甲苯/乙酸乙酯=40/30/30質量份)1 〇〇質 量份及作爲環氧基樹脂與潛在性硬化劑混合物之含有微膠 囊型潛在性硬化劑之液狀環氧基(旭化成股份公司製,商 品名:諾巴奎亞3 94 1 )60質量份所成之黏著劑成分溶液塗 佈於PET所成之支持體(膜厚50 μιη)上。其後,將此於 -27- 201202375 70 °c下乾燥10分鐘,得到設置於支持體上之導電粒子非含 有層(膜厚25 μηι)。 將上述導電粒子含有層與導電粒子非含有層使用過去 公知的層壓機進行貼合。藉此得到圖5所示狀態之二層構 成的電路連接材料》將此切成帶狀,製造出電路連接材料 (實施例2) 將Ni/Au鍍敷聚苯乙烯粒子如下述製作以外,與實施 例1同樣地得到電路連接材料。Ni/Au鍍敷聚苯乙烯粒子 與實施例1所使用者於同一聚苯乙烯粒子表面上,以平均 粒徑200 nm之Ni微粒子附著後,經無電解鍍敷形成Ni 層,最後形成Au層製作出。將鍍敷處理後的導電粒子經 SEM使其成爲倍率6000倍後觀察其結果,Ni微粒子所引 起的突起數爲20個。 (實施例3) 將Ni/Au鍍敷聚苯乙烯粒子如下述製作以外,與實施 例1同樣地得到電路連接材料。Ni/Au鍍敷聚苯乙烯粒子 與實施例1所使用者於同一聚苯乙烯粒子表面上,平均粒 徑8 00 nm之Ni微粒子附著後,經無電解鍍敷形成Ni層 ,最後形成Au層製作出。將鍍敷處理後的導電粒子經 SEM使其成爲倍率6000倍後觀察其結果,Ni微粒子所引 起的突起數爲15個》 -28- 201202375 (實施例4) 將Ni/Au鍍敷聚苯乙烯粒子如下述製作以外,與實施 例1同樣地得到電路連接材料。Ni/Au鍍敷聚苯乙烯粒子 於20%壓縮變形時之壓縮彈性率爲3 00 kgf/mm2之聚苯乙烯 粒子表面上,以平均粒徑400 nm的Ni微粒子附著後,經 無電解鍍敷形成Ni層,最後形成Au層製作出。將鍍敷 處理後的導電粒子經SEM使其成爲倍率6000倍後觀察其 結果,Ni微粒子所引起的突起數爲3 0個。 (實施例5) 將Ni/Au鍍敷聚苯乙烯粒子如下述製作以外,與實施 例1同樣地得到電路連接材料。Ni/Au鍍敷聚苯乙烯粒子 於20%壓縮變形時的壓縮彈性率爲600 kgf/mm2,且最大負 載5 mN下經壓縮後之壓縮回復率爲40%的聚苯乙烯粒子 表面上,以平均粒徑400 rim的Ni微粒子附著後,經無電 解鍍敷形成Ni層,最後形成Au層製作出。將鍍敷處理 後的導電粒子經SEM使其成爲倍率6000倍後觀察其結果 ,Ni微粒子所引起的突起數爲30個。 (實施例6) 將Ni/Au鍍敷聚苯乙烯粒子如下述製作以外,與實施 例1同樣地得到電路連接材料。Ni/Au鍍敷聚苯乙烯粒子 於平均粒徑爲4 μιη,且20%壓縮變形時的壓縮彈性率爲 -29- 201202375 700 kgf/mm2的聚苯乙烯粒子表面上,以平均粒徑400 nm 的Ni微粒子附著後,經無電解鍍敷形成Ni層,最後形成 Au層製作出。將鍍敷處理後的導電粒子經SEM使其成爲 倍率6000倍後觀察其結果,Ni微粒子所引起的突起數爲 32個。 (參考例7) 將Ni/Au鍍敷聚苯乙烯粒子如下述製作以外,與實施 例1同樣地得到電路連接材料。Ni/Au鍍敷聚苯乙烯粒子 於平均粒徑爲3 μιη,且20%壓縮變形時的壓縮彈性率爲 45 0 kgf/mm2的聚苯乙烯粒子表面上,以平均粒徑160 nm 之Ni微粒子附著後,經無電解鍍敷形成Ni層,最後形成 Au層製作出。將鍍敷處理後的導電粒子經SEM使其成爲 倍率6000倍後觀察其結果,Ni微粒子所引起的突起數爲8 個。 (參考例8) 將Ni/Au鍍敷聚苯乙烯粒子如下述製作以外,與實施 例1同樣地得到電路連接材料。Ni/Au鍍敷聚苯乙烯粒子 於平均粒徑爲3 μιη,且20%壓縮變形時的壓縮彈性率爲 500 kgf/mm2之聚苯乙烯粒子表面上,以平均粒徑230 nm 的Ni微粒子附著後,經無電解鍍敷形成Ni層,最後形成 Au層製作出。將鍍敷處理後的導電粒子經SEM使其成爲 倍率6000倍後觀察其結果,Ni微粒子所引起的突起數爲 -30- 201202375 47個。 (參考例9) 將Ni/Au鍍敷聚苯乙烯粒子如下述製作以外,與實施 例1同樣地得到電路連接材料。Ni/Au鍍敷聚苯乙烯粒子 於平均粒徑爲3μιη,且20%壓縮變形時的壓縮彈性率爲90 kgf/mm2的聚苯乙烯粒子表面,以以平均粒徑200 nm之Ni 微粒子附著後,經無電解鍍敷形成Ni層,最後形成Au 層製作出。將鍍敷處理後的導電粒子經SEM使其成爲倍 率6 0〇〇倍後觀察其結果,Ni微粒子所引起的突起數爲23 個。 (參考例10) 將Ni/Au鍍敷聚苯乙烯粒子如下述製作以外,與實施 例1同樣地得到電路連接材料。Ni/Au鍍敷聚苯乙烯粒子 於最大負載5mN下經壓縮後的壓縮回復率爲25%,且20% 壓縮變形時的壓縮彈性率爲700 kgf/mm2的聚苯乙烯粒子 表面’以平均粒徑400 nm的Ni微粒子附著後,經無電解 鍍敷形成Ni層,最後形成Au層製作出。將鍍敷處理後 的導電粒子經SEM使其成爲倍率6000倍後觀察其結果, Ni微粒子所引起的突起數爲30個。 (比較例1) 取代Ni/Au鍍敷聚苯乙烯粒子使用如下述製造之Au -31 - 201202375 鍍敷聚苯乙烯粒子以外,與實施例1同樣地得到電路連接 材料。與實施例1所使用者於同一聚苯乙烯粒子表面上’ 經無電解鍍敷形成Au層,製造出Au鍍敷聚苯乙烯粒子 (比較例2) 將Ni/Au鍍敷聚苯乙烯粒子如下述製作以外,與實施 例1同樣地得到電路連接材料。Ni/Au鍍敷聚苯乙烯粒子 與實施例1所使用者於同一聚苯乙烯粒子表面上,施預無 電解鎳鍍敷形成Ni層之同時析出Ni塊,其後將Αιι層進 行鍍敷製作出。將鍍敷處理後的導電粒子經SEM使其成 爲倍率6000倍後觀察其結果,Ni塊所引起的突起數爲35 個。 其次對於上述實施例、參考例及比較例所製作的電路 連接材料進行各種評估。 (初期連接電阻的評估) 準備具備凸塊尺寸50 μιηχ50 μπι、間距100 μιη、高度 2〇 μιη之金凸塊之1C晶片與表面上形成鋁電極之玻璃基 板(厚度0.7 mm)。鋁電極與金凸塊以電路連接材料以電性 連接製造出連接構造,測定該電阻値來進行連接部分之初 期連接的電阻値評估。 具體爲,首先剝離導電粒子含有層側之支持體,使導 電粒子含有層可銜接玻璃基板下將電路連接材料配置於玻 -32- 201202375 璃基板上,進行預備壓著。然後剝離導電粒子非含有層側 之支持體後,使金凸塊與導電粒子非含有層銜接下載持 1C晶片。配置1C晶片後’一邊加熱一邊將電路連接材料 往挾持方向進行加壓並連接。預備壓著之條件爲溫度70°C ,壓力0.5 MPa(凸塊面積換算),保持時間爲1秒。另一方 面,連接條件爲溫度21〇°C、壓力70 MPa(凸塊面積換算) 、保持時間爲5秒。 測定如此經連接之連接構造的電阻値(R〇)。初期連接 電阻之評估以下述基準進行。 A : R〇未達 1 Ω、 B : R〇爲 1 〜2Ω、 C: R〇 超過 2Ω。 作爲電路連接材料使用上述實施例、參考例及比較例 的電路連接材料,該各情況的初期連接電阻的評估結果如 表1及表2所示。 (熱循環試驗後之連接電阻之評估) 進行上述初期連接電阻之評估後,對於連接構造進行 重複昇溫降溫之熱循環試驗後進行熱循環試驗後之連接電 阻的評估。熱循環試驗爲,重複20次將連接構造自室溫昇 溫至1〇〇 °C,其次再降溫-40 °C後昇溫至室溫之步驟。測定 熱循環試驗後的連接構造之電阻値(RJ。 熱循環試驗後之連接電阻的評估依據以下基準進行。 A : Ri 未達 3Ω、 -33- 201202375 B : R1 爲 3 〜4 Ω、 C : R1 超過 4 Ω β 作爲電路連接材料使用上述實施例、參考例及比較例 的電路連接材料,該各情況的初期連接電阻的評估結果如 表1及表2所示。 (絕緣性的評估) 準備具備凸塊尺寸50 μιηχΙΟΟ μηι、間距15 μιη、高度 20 μπι之金凸塊之1C晶片與ΙΤΟ基板。將ΙΤΟ基板與複 數金凸塊以電路連接材料做電性連接製造出連接構造,測 定鄰接之金凸塊間的電阻値而進行連接部分之鄰接金凸塊 間的電氣絕緣性之評估。且,ΙΤΟ基板爲於玻璃基板(厚 度0.7 mm)上上蒸鍍銦-錫氧化物(ΙΤΟ),形成ΙΤΟ電極(表 面電阻$20 Ω/C])。 首先剝離導電粒子含有層側之支持體,使導電粒子含 有層與ITO基板銜接下,將電路連接材料配置於ITO基 板上,進行預備壓著。然後,剝離導電粒子非含有層側之 支持體後,使金凸塊與導電粒子非含有層銜接下’載持 1C晶片。配置1C晶片後,一邊加熱一邊將電路連接材料 往挾持方向進行加壓並連接。預備壓著之條件爲溫度70 °c 、壓力0.5 MPa(凸塊面積換算)、保持時間爲1秒。另一方 面,連接條件爲溫度210 °C、壓力70 MPa(凸塊面積換算) 、保持時間爲5秒。 如此經連接之連接構造的鄰接金凸塊間’外加5 0V電 -34- 201202375 壓1分鐘後,測定該金凸塊間之絕緣電阻値(r2)。絕緣性 之評估依據以下基準進行。 A : R2爲 1χ1〇1()Ω 以上、 B : R2爲 1 X 1 09 〜1 X 1 Ο10Ω、 C : R2爲達1 χ109Ω未満。 作爲電路連接材料使用上述實施例、參考例及比較例 之電路連接材料,該各情況之絕緣性評估結果如表1及表2 所示。 -35- 201202375 【一嗽】 實施例6 寸 700 _ . ο 400 CN cn < < < 實施例5 m 600 ο 400 < < < 實施例4 m 300 ο 400 < < < 實施例3 m 750 ο 800 < < < 實施例2 m 750 ί_ ο 200 < < < 實施例1 750 ο 400 (Ν m < < < 平均粒徑,μπι (Ν 1 s -觐 樹·糴 担幽 1¾ i ii d ^ gs ε 掛S 鹏獅 1 « y 4< Μ E睦 mm 金屬微粒子之平均粒徑,nm 導電粒子表面的突起數 初期連接電阻 熱循環試驗後之連接電阻 絕緣性 基材 粒子 評估 結果 -36- 201202375 E 比較例2 m 750 Ο 300 m m υ PQ 比較例1 m 750 ο 1 ο m υ < 參考例10 CO 700 <Ν Ο 寸 沄 < PQ c 參考例9 m ο Ο m <N PQ < 參考例8 m 500 ο 230 < CQ PQ 參考例7 m 450 ο s 1-H 00 < PQ < 平均粒徑,μιη (N 1 § ^ m 幽Ci - g 糊·设 鹏 w ra Λ y -κ s酿 wm <3 金屬微粒子之平均粒徑,nm 導電粒子表面的突起數 初期連接電阻 熱循環試驗後之連接電阻 絕緣性 基材 粒子 評估 結果 -37- 201202375 如表1所示,實施例1〜6的電路連接材料於所有評估 項目皆顯示A。因此,由此得知實施例1〜6之電路連接材 料爲,較低初期連接電阻及與鄰接的電路電極之良好絕緣 性雙方可達到高水準。除此以外,熱循環試驗後之連接電 阻的評估爲A,此表示連接電阻値的上昇可充分地受到抑 制。 又,未設置Ni微粒子所引起的突起之比較例1的電路 連接材料,其初期連接電阻之評估爲B,熱循環試驗後之 連接電阻的評估爲C。 由上述結果得知,本發明爲提供一種連接被要求較高 微細間距化之電路電極彼此時,即使電路電極爲表面容易 形成氧化膜之金屬材料所成,連接構造之初期電阻値可充 分降低之電路連接材料。 產業上之利用可能性 本發明爲提供一種連接電極即使爲表面容易形成氧化 膜之金屬材料所成,連接構造之初期電阻値可充分降低的 黏著劑組成物及使用其之電路連接材料》又,本發明爲提 供一種較低連接電阻下電路構件經連接之連接構造、以及 得到此之電路構件的連接方法。 【圖式簡單說明】 [圖1]表示關於本發明的電路連接材料使用於電路電 極間’連接電路電極彼此之狀態截面圖。 -38- 201202375 [圖2]表示關於本發明的電路連接材料之一實施形態 截面圖。 [圖3]表示關於本發明之含於電路連接材料的導電粒 子之一形態截面圖。 [圖4]表示關於本發明之電路連接材料設置於支持體 上之狀態截面圖。 [圖5]表示關於本發明之電路連接材料由支持體支持 之狀態截面圖。 [圖6]表示關於本發明的電路構件之連接方法的一實 施形態槪略截面圖之步驟圖。 【主要元件符號說明】 1 :基材粒子 2 :金屬微粒子 3 ’·金屬鍍敷層 1 〇 :導電粒子 2〇 :黏著劑成分 30 :第1電路構件 31 :電路基板(第1電路基板) 32:電路電極(第1電路電極) 40 :第2電路構件 41 :電路基板(第2電路基板) 42:電路電極(第2電路電極) 50,70 :電路連接材料 -39- 201202375 60,60a,60b :支持體 100 :連接構造 -40201202375 IX. Description of the Invention [Technical Field] The present invention relates to an adhesive composition, a circuit connecting material and a connection structure, and a connection method of a circuit member. [Prior Art] As the size and thickness of the electronic device are reduced, the density and high definition of the circuit electrodes formed in the circuit member are progressing. Further, the circuit electrode is further miniaturized, that is, the demand for fine pitch such as multi-electrode or narrow pitch is increasing. It is difficult to correspond to the connection of the circuit members forming the fine circuits to the past welding or the rubber connecting pipe, so that an adhesive composition having an anisotropic conductivity is used. The above adhesive composition is generally composed of an adhesive component and conductive particles dispersed therein. The adhesive composition is disposed between the circuit members via one of the opposing arrangements, and the adhesive composition is pre-stressed in the holding direction to electrically connect the opposing circuit electrodes to each other. At the same time, the adjacent electrodes are adhered to each other to secure the pair of circuit members while ensuring electrical insulation. In the past, as the conductive particles having the adhesive composition, various kinds of fine particles having conductivity were used. For example, a metal fine powder or a plastic fine particle coated on the lower surface of a metal film. However, in the manufacturing steps such as a liquid crystal display, a highly fine pitch and a high connection reliability are required, and a circuit electrode formed of a metal material having an oxide film formed on the surface may be used. The metal micropowder and the plastic microparticles coated on the lower surface of the metal film are each long and short. Therefore, when the adhesive composition of -5-201202375 is used, both the fine pitch and the connection reliability cannot reach the required high level at the same time. Specifically, when the metal fine powder is used as the conductive particles, since the metal fine powder has sufficient ruthenium hardness, even if an oxide film is formed on the surface of the circuit electrode, the circuit electrodes can be connected to each other. However, metal fine powders generally have a wide particle size distribution and cannot be applied to fine pitch at this time. Further, when the connection circuit electrodes are connected to each other, a phenomenon in which the resistance of the connection portion rises may occur as time passes. The reason for this is that the gap between the circuit electrodes is enlarged as the temperature changes or the connection state of the connection structure is relaxed, and the metal fine powder cannot be sufficiently matched. Further, in general, the coefficient of thermal expansion of the metal micropowder is smaller than that of the adhesive component, and this phenomenon may occur after the thermal cycle test of repeating the temperature rise and the temperature drop. In contrast, when a plastic fine particle having a surface coated with a metal thin film is used as the conductive particle, it is relatively easy to obtain a conductive particle having a narrow particle size distribution. For this, the conductive particles using the plastic fine particles are suitable for fine pitching. Further, the linear thermal expansion coefficient of the plastic fine particles is similar to that of the cured material of the adhesive component. Therefore, the interval between the circuit electrodes due to temperature fluctuation or the like is widened, and the plastic fine particles can be sufficiently matched, and the advantage of maintaining the original resistance 値 can be obtained. However, the plastic microparticles have a lower hardness when compared with the general metal micropowder. Therefore, when an oxide film is formed on the surface of the circuit electrode, there is a problem that the initial resistance 连接 of the connection portion is not sufficiently broken, and the characteristics of the plastic fine particles to be provided with the metal fine powder and the metal film coating surface are reviewed. Specifically, it is a review of conductive particles having protrusions and the like on the surface of the plastic plasmid -6-201202375 coated with a metal film. For example, Patent Documents 1 and 2 disclose conductive particles in which protrusions are provided on the surface of a conductive film. Further, Patent Document 3 describes conductive particles in which metal particles are further adhered to the surface of the metal thin film. Further, in Patent Documents 4 and 5, conductive particles obtained by subjecting a plastic particle having irregularities to pre-metal plating are described. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000- 1 953 No. PCT Publication No. JP-A No. 2000-243 No. In the electroless plating step of forming a metal thin film, the conductive particles are produced by depositing protrusions in the electroless plating step of forming a metal thin film. At this time, it is difficult to sufficiently control the protrusion size or the number of protrusions. Therefore, the unevenness of the protrusions makes it difficult to achieve a sufficiently high connection reliability. Further, in the conductive particles of Patent Document 3, the adhesion between the metal thin film and the metal particles adhering to the surface is insufficient, and the metal particles may fall off. When the metal particles are detached, the initial resistance 连接 of the connection structure is increased, or the insulation of the adjacent circuit electrodes is insufficient, and it is difficult to achieve a sufficiently high connection reliability. Further, the conductive particles of Patent Documents 4 and 5 are formed by forming a concavity and convexity in a manner of molding a particle. Therefore, when an oxide film is formed on the surface of the circuit electrode, the oxide film cannot be sufficiently broken, and the initial resistance of the connection structure is increased. 201202375 The present invention has been made in view of the above facts to provide an electrode that must be connected even if it is necessary. It is formed by a metal material which is easy to form an oxide film on the surface, and it is also possible to sufficiently reduce the adhesive composition of the initial resistance of the connection structure and the circuit connecting material using the same. Further, the present invention has an object of providing a connection structure for connecting a circuit member with a lower connection resistance and a connection method for obtaining the circuit member. The adhesive composition of the present invention is a conductive particle having an adhesive component and dispersed in the adhesive component, wherein the conductive particle has a substrate particle constituting a central portion of the conductive particle, and covers the substrate particle. At least a portion of the surface of the metal plating layer and a plurality of metal fine particles disposed on the surface of the substrate particle inside the metal plating layer. In the positional relationship between the plurality of metal fine particles and the substrate particles, the "distribution on the surface of the substrate particles" is such that the metal fine particles are placed in contact with each other on the surface of the substrate particles, and are disposed in an unjoined state. The conductive particles in which the plurality of fine metal particles are disposed at the above position are produced by adhering metal fine particles to the substrate particles and then forming a metal plating layer by a plating treatment. By controlling the number of metal fine particles attached to the substrate particles and the particle diameter thereof, a desired number and size of protrusions can be formed on the surface of the conductive particles. Therefore, when the conditions of the plating step and the like are compared with the conductive particles provided with the protrusions, the number of adhesion of the metal fine particles and the uniformity of the particle diameter in the present invention are sufficiently high. By providing the conductive particles of the metal fine particles having high uniformity, the electrodes can be electrically connected to each other more reliably, even if the metal electrodes are coated with an oxide film on the circuit electrodes. As a result, the initial resistance 连接 of the connection structure -8 - 201202375 can be sufficiently reduced. Further, the conductive particles of the adhesive composition of the present invention are metal plating layers having integrated substrate particles and metal fine particles. Therefore, the adhesion between the metal fine particles and the substrate particles is high, and the fall of the metal fine particles from the conductive particles can be sufficiently suppressed. As a result, the circuit electrodes can be electrically connected to each other more surely, and the insulation with the adjacent circuit electrodes can be more sufficiently ensured. It is preferred that the average particle diameter of the metal fine particles is 200 to 100 nm. Further, it is preferred that the average particle diameter of the substrate particles is from 1 to ΙΟμηι. When the average particle diameter of these particles is within the above range, the lower initial connection resistance 値 can be more reliably achieved. In addition, both the rise suppression of the connection resistance 及 and the insulation of the adjacent circuit electrodes can simultaneously achieve a high level. The "average particle diameter" as used in the present invention means the enthalpy measured as follows. Namely, the arbitrarily selected metal microparticles were observed by a scanning electron microscope (SEM), and the maximum diameter and the minimum diameter were measured. The square root of the product of the maximum diameter and the minimum diameter is taken as the particle diameter of the particle. For the 50 particles arbitrarily selected, the particle diameter was measured as described above, and the average enthalpy was taken as the average particle diameter. From the viewpoint of efficiently and surely obtaining the effects of the present invention, the number of metal fine particles is preferably from 1 to 40 per one substrate particle. Further, when the number of the metal fine particles is 10 to 40, there is an advantage that both the rise of the connection resistance 抑制 and the insulation of the adjacent circuit electrode are high. The number of metal fine particles per one substrate particle indicates the enthalpy measured as follows. That is, the number of protrusions on the surface of the conductive particles observed by SEM after the SEM imaging was arbitrarily measured was calculated as the number of metal fine particles -9 - 201202375. The number of metal particles of one conductive particle can be calculated by multiplying the calculated number by two times. The number of metal fine particles was determined as described above for the 50 conductive particles arbitrarily selected, and the average enthalpy was used as the number of metal fine particles per one substrate particle. Further, it is preferable that the substrate particles are composed of a material having a compression modulus of 100 to kgf/mm 2 when the particle diameter is 20% compression-deformed. When the substrate particles have the hardness as described above, even if an oxide film is formed on the surface of the circuit electrode, the metal fine particles disposed inside the metal plating layer can more reliably break the oxide film. In addition, as the temperature varies or the like, even if the interval between the circuit electrodes is widened, the substrate particles can sufficiently match the increase in the interval between the circuit electrodes. Therefore, the rise of the connection resistance 値 can be sufficiently suppressed. Further, it is preferred that the substrate particles have a compression recovery ratio of 40% or more after compression at a maximum load of 5 mN. When the substrate particles have the compression recovery ratio as described above, even if the interval between the circuit electrodes is widened in accordance with temperature fluctuation or the like, the substrate particles can sufficiently match the increase in the interval between the circuit electrodes. Therefore, the rise of the connection resistance 値 can be sufficiently suppressed. The circuit connecting material of the present invention is formed by the above-described adhesive composition of the present invention, and the circuit members are electrically connected to each other with the circuit electrodes of the respective circuit members. The connection structure of the present invention is formed by a pair of a circuit member and a cured material of the circuit connecting material of the present invention, and is provided with a circuit electrode having a circuit member interposed between the pair of circuit members. The connecting portions of the circuit members are connected to each other. The invention relates to a method for connecting circuit members, which is characterized in that a phase connecting material between a pair of circuit components and a pair of circuit components, such as the circuit connecting material of claim 7 of the patent application scope, is heated and pressurized. a pair of circuits formed by the cured material of the circuit connecting material, interposed between the pair of circuit members, and bonded to the circuit members so that the circuit electrodes of the circuit members are electrically connected to each other The member and the connection structure of the connecting portion. According to the present invention, it is possible to provide an electrode composition which is required to be connected to an electrode which is easy to form an oxide film on the surface, and an adhesive composition which can sufficiently reduce the initial resistance of the connection structure and a circuit connecting material using the same. The present invention is a connection structure for connecting a circuit member under a lower connection resistance, and a connection method for obtaining the circuit member. Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and the repeated description is omitted. In order to facilitate the drawing, the ratio of the aspect ratio is not consistent with the description. Further, "(meth)acrylate" in the present specification means "acrylic acid ester" and "methacrylate" corresponding thereto. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a structure in which an adhesive composition of the present invention is used as a circuit connecting material and a circuit electrode is connected to each other. The connection structure 100 shown in Fig. 1 includes a first circuit member 30 and a second circuit member 40 that face each other, and a connection portion 50a that connects them is provided between the first circuit member 30 and the second circuit member 4A. The first circuit member 30 is provided with a circuit board (first circuit board) 31 and a circuit electrode (first circuit electrode) 32 formed on the main surface 31a of the circuit board 31. The second circuit member 40 is a circuit electrode (second circuit electrode) 42 formed on the principal surface 41a of the circuit board 41 including the circuit board (second circuit board) 4 1 and -11 - 201202375. The surfaces of the circuit electrodes 32, 42 in the circuit boards 31, 41 are flat. Further, the term "the surface of the circuit electrode is flat" means that the unevenness of the surface of the circuit electrode is extremely small, and it is preferable that the surface unevenness is 20 nm or less. The connecting portion 50a is a cured product 20a having an adhesive component contained in a circuit connecting material, and conductive particles 10 dispersed therein. In the connection structure 100, the opposite circuit electrode 32 and the circuit electrode 42 are electrically connected via the conductive particles 10. That is, the conductive particles 10 are in direct contact with both of the circuit electrodes 32, 42. Therefore, the electrical connection between the circuit electrodes 32, 42 can be achieved by sufficiently reducing the connection resistance between the circuit electrodes 32, 42. On the other hand, if the carbide 20a is electrically insulating, the adjacent circuit electrodes can ensure insulation therebetween. Therefore, the current between the circuit electrodes 3, 42 can be gently flowed, and the function of the circuit can be sufficiently exerted. Next, the adhesive composition in the state before the adhesive component is hardened is detailed. Fig. 2 is a schematic cross-sectional view showing a preferred embodiment of the adhesive composition of the present invention as a circuit connecting material. The circuit connecting material 50 shown in Fig. 2 has a film shape. The circuit connecting material 50 is provided with an adhesive component 20 and conductive particles 10 dispersed in the adhesive component 20. The circuit connecting material 50 is obtained by coating a film-form support on an adhesive composition containing an adhesive component and conductive particles using a coating device, and drying it by hot air for a predetermined period of time. The configuration of the conductive particles 10 will be described with reference to Fig. 3. Fig. 3 is a cross-sectional view showing the form of the conductive particles contained in the circuit connecting material of the present invention, -12-201202375. The conductive particles 10 shown in FIG. 3 are composed of the substrate particles 1 constituting the central portion, the plurality of metal fine particles 2 provided on the substrate particles 1, and the surface of the substrate particles 1 and the metal fine particles 2, for example. The formed metal plating layer 3 is formed. The metal fine particles 2 are located inside the metal plating layer 3. As the material of the substrate particles 1, a metal and an organic polymer compound are exemplified. Examples of the metal constituting the substrate particle 1 include nickel, copper, gold, silver, cobalt, and alloys thereof. Examples of the organic polymer compound constituting the substrate particle 1 include an acrylic resin, a styrene resin, a benzoguanamine resin, a polyfluorene oxide resin, a polybutadiene resin, or a copolymer thereof. Those who have been cross-linked. As the material of the substrate particle 1, in order to achieve high connection reliability, it is preferable to use a material which can sufficiently expand the interval between the circuit electrodes after the circuit electrodes are connected to each other. When the temperature fluctuation is equal to the increase in the interval between the electrode electrodes, if the substrate particles 1 are not sufficiently matched, the electrical resistance of the connected portion may increase. From the viewpoint of effectively preventing such an increase in the resistance 値, it is preferable that the particles of the organic polymer compound are used as the substrate particles 1. The particles of the organic polymer compound are formed on the circuit electrode even when the circuit electrodes are connected to each other. It is pressed into a flat shape and has a tendency to return to the original spherical shape from a flat shape. Therefore, the conductive particles 10 can be sufficiently fitted as the temperature fluctuation is equal to the expansion of the circuit electrode interval. From this point of view, it is preferable that the compression recovery ratio after compression of the base material particle 1 at a maximum load of 5 mN is 40% or more. Examples of the particles of the organic compound having the above-mentioned compression recovery ratio of -13 to 201202375 include acrylic resin, styrene resin, benzoguanamine resin, polyoxyn resin, polybutadiene resin or the like. a particle formed by a copolymer. If the compression recovery ratio is less than 40%, there is a tendency that the interval between the circuit electrodes is not sufficiently matched. The compression recovery rate can be measured by an H-100 micro hardness tester manufactured by Fischer Instruments. Further, as the material of the substrate particle 1, when the particle diameter is 20% compression-deformed, it is preferred to use a compression modulus of 100 to 1000 kgf/mm2, more preferably 100 to 800 kgf/mm2. Examples of the particles formed of the organic compound having the above hardness include, for example, an acrylic resin, a styrene resin, a benzoguanamine resin, a polyoxyxylene resin, a polybutadiene resin or a copolymer thereof. Particles: When the compression modulus at the 20% compression deformation is less than 1 〇〇kgf/mm2, when it is connected to a metal circuit electrode having an oxide film formed on the surface, the oxide film on the surface cannot be sufficiently broken, and there is a connection portion. The tendency of resistance 値 to increase. On the other hand, when the compression modulus is more than 1 000 kgf/mm2, the substrate particles 1 tend to be not formed into a flat shape when pressed against the circuit electrode. If the deformation of the substrate particles 1 is insufficient, the contact area with the circuit electrodes is also insufficient, so that the resistance 连接 of the connection portion is improved. Further, in order to sufficiently pressurize the substrate particles 1 to form a flat shape and to apply a higher pressure, the particles may not be sufficiently joined by pulverization. The compression modulus can be measured by a Η100 microhardness tester manufactured by Fischer Instruments, and the substrate particles 1 can be made of the same or different types of materials, and a single material or a mixture of two can be used for the same particle. The above materials. • 14 - 201202375 The average particle size of the substrate particles 1 can be appropriately designed for use in use, etc., but preferably 1 to 10 μηι, 2 to 8 μηη is preferable, and 3 to 5 μηι is more preferable. If the average particle diameter is less than 1 μm, secondary aggregation of the particles occurs, and the insulation with the adjacent circuit tends to be insufficient. On the other hand, when the average particle diameter exceeds 10 μm, the insulation property with an adjacent circuit tends to be insufficient due to an excessively large particle size. Examples of the metal constituting the metal fine particles 2 include Ni, Ag, Au, Cu, Co, Zn, Al, Sb, U, Ga, Ca, Sn, Se, Fe, Th, Be, Mg, Mn, and the like. Alloy. Among these metals, Ni, Ag, Au, and Cu are preferred from the viewpoints of conductivity and corrosion resistance, and Ni is preferred. These may be used alone or in combination of two or more. The average particle diameter of the metal fine particles 2 can be appropriately designed for the purpose of use, etc., but it is preferably 200 to 1000 nm, more preferably 400 to 800 nm, and more preferably 400 to 500 nm. When the average particle diameter is less than 200 nm, when it is connected to a circuit electrode of a metal on which an oxide film is formed on the surface, the oxide film is not sufficiently broken, and the electric resistance of the connected portion tends to increase. On the other hand, when the average particle diameter exceeds 1 〇〇〇 nm, the insulation property with the adjacent circuit tends to be insufficient. The number of the metal fine particles 2 disposed on the surface of the substrate particle 1 on the inner side of the metal plating layer 3 is preferably 10 to 40 per one substrate particle, preferably 10 to 30, preferably 10 to 20 One is better. If the number of the metal fine particles 2 is less than 10, the increase in the connection resistance 値 tends to be insufficiently suppressed. On the other hand, when the number of the metal fine particles 2 exceeds 40, the insulation property with the adjacent circuit tends to be insufficient. -15- 201202375 The metal plating layer 3 is at least one of the surface of the substrate particle 1 and the metal fine particle 2 coated. However, from the viewpoint of more reliably preventing the detachment of the metal fine particles 2, it is preferable that substantially all of the surface of the substrate particles 1 and the metal fine particles 2 are coated. The thickness of the metal plating layer 3 is preferably 80 to 200 nm, more preferably 100 to 150 nm, and more preferably 100 to 110 nm. If the film thickness of the metal plating layer 3 is less than 80 nm, the resistance 连接 of the connection portion tends to increase. On the other hand, when the film thickness of the metal plating layer 3 exceeds 200 nm, the insulation property with the adjacent circuit tends to be insufficient. As a method of producing the conductive particles 10, a method of forming a metal plating layer 3 by plating the metal fine particles 2 on the surface of the substrate particle 1 may be employed. At this time, by adjusting the amount of the added metal fine particles 2, the number of the metal fine particles 2 adhering to the surface of the substrate particle 1 can be controlled. Therefore, the conductive particles 10 are produced after the pre-electroless plating treatment. Next, the adhesive component dispersed in the conductive particles 1 will be described. The adhesive component 20 contains a composition of an adhesive composed of (a) a thermosetting resin and (b) a curing agent for a thermosetting resin, and a hardening agent containing free radicals by (c) heating or light generation. The composition of the adhesive and the (d) radical polymerizable substance are preferably the composition of the adhesive. Or a mixed composition of the above (a), (b), (c) and (d) is preferred. The (a) thermosetting resin may be a thermosetting resin which can be subjected to a curing treatment in any temperature range, and is not particularly limited, and is preferably an epoxy resin. Examples of the epoxy resin include bisphenol A epoxy resin, -16-201202375 bisphenol F epoxy resin, bisphenol S epoxy resin, and phenolic epoxy resin for phenol paint. Phenolic epoxy resin for phenol paint, phenolic epoxy resin for bisphenol A paint, phenolic epoxy resin for bisphenol F paint, alicyclic epoxy resin, epoxypropyl ester epoxy A base resin, a epoxypropylamine type epoxy resin, a hydantotype epoxy resin, an iso-cyanuric acid type epoxy resin, an aliphatic chain epoxy resin, or the like. These epoxy resins may be halogenated or hydrogenated. These epoxy resins are used singly or in combination of two or more. Examples of the curing agent for thermosetting resin (b) include an amine system, a phenol system, an acid anhydride system, an imidazole system, an anthraquinone system, a dicyandiamide, a boron trifluoride-amine complex, a phosphonium salt, and an iodine. Key salt, amine imine, etc. These may be used alone or in combination of two or more kinds, and a decomposition accelerator, an inhibitor, or the like may be used in combination. Further, when these curing agents are coated with a polyurethane-based or polyester-based polymer material or the like and then microencapsulated, the use time can be prolonged. (b) When the amount of the hardener for the thermosetting resin is based on the total mass of the adhesive component, it is 0. 1~60. 0% by mass is better, 1. 0~ 2 0. 0% by mass is preferred. The amount of the hardening agent for the thermosetting resin is less than 0. When the amount is 1% by mass, the progress of the hardening reaction may be insufficient, and it may be difficult to obtain good adhesion strength or connection resistance 値. On the other hand, when the blending amount is more than 60% by mass, the fluidity of the adhesive component may be lowered or the pot life may be shortened, and the connection resistance of the joint portion may be improved. (C) by heating The curing agent which generates free radicals by light may, for example, be a peroxy compound or an azo compound which is heated or photodecomposed to generate free radicals after -17 to 201202375. The hardener can be suitably selected depending on the connection temperature of the purpose, the connection time, the pot life, and the like. From the viewpoint of high reactivity and pot life, an organic peroxide having a half-life of 10 hours is 40 ° C or more, and a half-life of 1 minute is preferably 180 ° C or less. At this time, (c) the amount of the hardener which generates free radicals by heating or light is based on the total mass of the adhesive component, and is 0. 05~10% by mass is better, with 0. A mass ratio of 1 to 5 is preferred. (c) a hardening agent for generating free radicals by heating or light, specifically selecting a decyl peroxide, a peroxydicarbonate, a peroxyester, a peroxyketal, a dialkyl peroxide, a hydrogen peroxide Oxide, etc. In order to suppress corrosion of the connection terminal of the circuit member, it is preferably selected from the group consisting of a peroxy ester, a dialkyl peroxide, and a hydroperoxide, and is preferably selected from a peroxy ester which can obtain high reactivity as a dimercapto group. Examples of the oxides include isobutyl peroxide, 2,4-dichlorophenylhydrazine peroxide, 3,5,5-trimethylhexyl peroxide, octyl peroxide, and laurel A base peroxide, a stearyl peroxide, an amber fermentation peroxide, a benzoyl peroxide toluene, a phenylhydrazine peroxide, or the like. Examples of the peroxydicarbonate include di-N-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, and bis(4-t-butylcyclohexyl)peroxydicarbonate. Di-2-ethoxymethoxy peroxydicarbonate, di(2-ethylhexylperoxy)dicarbonate, dimethoxybutyl peroxydicarbonate, di(3-methyl-3) -Methoxy butyl peroxy)dicarbonate, etc. -18 - 201202375 Examples of the peroxyesters include ' cumenyl peroxy neodecanoate and 1,1,3,3 -tetramethylbutyl Peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, third hexyl peroxy neodecanoate, tert-butyl peroxypivalic acid vinegar, 1,1, 3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexane, 1-ring Hexyl-1-methylethylperoxy-2-ethylhexanoate, third hexylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, third Butyl peroxyisobutyrate, 1, bis (tert-butyl peroxy) cyclohexane, third hexyl Isopropyl monocarbonate, tert-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5- Bis(m-tolylthioperoxide)hexane, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexylmonocarbonate, third hexylperoxybenzoate , tert-butyl peroxyacetate, and the like. Examples of the peroxy ketals include 1,1-bis(Third-hexylperoxy)-3,5,5-trimethylcyclohexane and 1,1-bis (trihexylperoxy)cyclohexane. Alkane, 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-(t-butylperoxy)cyclododecane' 2,2- Bis(t-butyl peroxy) decane, and the like. Examples of the dialkyl peroxides include α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, and 2,5-dimethyl-2. 5-bis(t-butylperoxy)hexane, tert-butylcumenyl peroxide, and the like. Examples of the hydroperoxides include diisopropylbenzene hydroperoxide and cumene hydroperoxide. -19-201202375 These (C) hardeners which generate free radicals by heating or light can be used alone. (1) The radically polymerizable substance is a substance having a functional group by radical polymerization, and may be mentioned, for example, (meth), or a mixture of two or more kinds thereof. Acrylate, maleic anhydride imide compound, and the like. Examples of the (meth) acrylate include urethane (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and the like. Butyl (meth) acrylate, ethylene glycol di(meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, tetramethylol methane tetra(meth) acrylate, 2-hydroxy-1,3-bis(methyl) propylene oxypropane, 2,2- bis [4-((methyl) , propyleneoxymethoxy)phenyl]propane, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, dicyclopentenyl (meth) acrylate , tricyclodecyl (meth) acrylate, bis((meth) propylene oxyethyl) isocyanuric acid, ε-caprolactone denaturing ginseng ((meth) propylene oxyethyl) Cyanuric acid, ginseng ((meth)acryloxyethyl) isocyanuric acid, and the like. These radically polymerizable substances may be used alone or in combination of two or more. The adhesive component is preferably a radical polymerizable substance having a viscosity of at least 25 t and a viscosity of 100,000 to 1,000,000 mPa·s, particularly containing 1,000,000 to 500,000 mPa.  A free radical polymerizable substance having a viscosity of s (25 ° C) is preferred. The viscosity of the radically polymerizable substance was measured using a commercially available E-type viscometer. -20- 201202375 Among the radical polymerizable substances, urethane acrylate or urethane methacrylate is preferred from the viewpoint of adhesion. Further, in order to improve the heat resistance and the organic peroxide to be used for crosslinking, it is particularly preferable to use a radically polymerizable substance having a Tg or more of loot or more. As the radical polymerizable substance, those having a dicyclopentenyl group, a tricyclodecanyl group and/or a triazine ring in the molecule can be used. A radical polymerizable substance having a tricyclic fluorenyl group or a triazine ring in the molecule is particularly preferably used. The maleic anhydride imide compound is preferably one containing at least two maleic anhydride imide groups in the molecule, and examples thereof include 1-methyl-2,4-bismaleuric acid imide benzene. N,N'-meta-phenyl bis-maleic anhydride imide, N,N'-p-phenylene bismaleimide, N,N'-m-tolyl-bis-maleic anhydride imide ,N,N'-4,4·Bistyl phenyl bismaleimide, N,N'-4,4-(3,3'-dimethyl-biphenyl) bismaleic anhydride Imine, hydrazine, Ν'-4,4-(3,3'-dimethyldiphenylmethane) bis-maleic anhydride imide, hydrazine, Ν'-4,4-(3,3'- Diethyldiphenylmethane) bis-maleic anhydride imide, less than 4,4-diphenylmethane bismaleimide, :^:^-4,4-diphenylpropane Bimaleic anhydride imide, hydrazine, Ν'-4,4-diphenyl ether bis-maleic anhydride imide, hydrazine, Ν'-3,3'-diphenyl maple bis-maleic anhydride imide , 2,2-bis[4-(4-maleic anhydride acetimidate) phenyl]propane, 2,2-bis[3-t-butyl-4,8-(4-maleic anhydride) Imine phenoxy)phenyl]propane, 1,1-bis[4-(4-horse Anhydride-imine phenoxy)phenyl]decane, 4,4'-cyclohexylene-bis[1-(4-maleic anhydride acetimidate)-cyclohexyl]benzene, 2, 2-bis[4-(4-maleic anhydride)-imidophenoxy)phenyl]hexafluoropropane. These may be used alone or in combination of two or more. Allyl compounds such as allyl-21 - 201202375 phenol, allyl phenyl ether, and benzoic acid allyl may be used in combination. Further, if necessary, a polymerization inhibiting agent such as hydroquinone or methyl ether hydroquinone may be used. The adhesive component 20 may contain a film forming high score. The content of the film-forming polymer is preferably 2 to 80% by mass, and 5 to 70% by mass based on the total mass of the adhesive component 20. Preferably, 10 to 60% by mass is more preferable. Examples of the film-forming polymer include polystyrene, polyethylene, polyvinyl butyral, polyvinyl formal, polyimine, polyamine, polyester, polyvinyl chloride, and polyphenylene oxide. , urea resin, melamine resin, phenol resin, xylene resin, polyisophthalate resin, phenoxy resin, polyimine resin, polyester urethane resin, etc.) The above-mentioned film-forming polymer has a water acid group or the like The functional group resin is preferred because it improves adhesion. Further, it is also possible to use these polymers to be denatured by a radical polymerizable functional group. The weight average molecular weight of the film-forming polymer is preferably 10,000 to 10,000,000. Further, the circuit connecting material 50 may contain a chelating material, a softening agent, an accelerator, an aging preventing agent, a coloring agent, a flame retarding agent, a thixotropic agent, A coupling agent, a phenol resin, a melamine resin, an isocyanate or the like. When the filler is contained, it is preferable to improve the connection reliability and the like. The 塡 filling material can be used only if the maximum diameter does not reach the particle diameter of the conductive particles, and the range of 喽 5 to 60% by volume is preferable. When the amount exceeds 60% by volume, the effect of improving the reliability is saturated. The coupling agent contains one or more compounds selected from the group consisting of ethylene, propylene, amine, epoxy, and isocyanate groups, and is preferably improved from the viewpoint of adhesion -22 to 201202375. In the circuit connecting material 50, the content of the conductive particles 10 is preferably 0.5 to 60 parts by volume for 100 parts by volume of the entire circuit connecting material 50, and the content may be different depending on the use. . Figure 4 shows the circuit connecting material 50 of the present invention. A cross-sectional view is shown in a state of being placed on the film-like support 60. As the support 60, for example, a polyethylene terephthalate film, a polyethylene naphthalate film, a polyethylene isocyanate film, a polybutylene terephthalate film, a polyolefin film, a polyacetate film, or the like can be used. Polycarbonate film, polyphenylene sulfide film, polyamide film, ethylene-ethylene phthalate copolymer film, polyvinyl chloride film, polyvinyl chloride film, synthetic rubber film, liquid crystal polymer film, etc. Various films. For the surface of the above film, a support such as a pre-corona discharge treatment, a tackifying coating treatment, a charge prevention treatment, or the like can be used if necessary. When the circuit connecting material 50 is used, the support 60 is easily peeled off by the circuit connecting material 50, and if necessary, a peeling treatment agent can be applied to the surface of the support 60. As the release treatment agent, a polyoxyxylene resin, a copolymer of polyoxymethylene and an organic resin, an alkyd resin, an amine alkyd resin, a resin having a long-chain alkyl group, a resin having a fluoroalkyl group, a shellac resin, or the like can be used. The film thickness of the various release treatment agent supports 60 is not particularly limited, but it is preferably 4 to 200 μm in consideration of convenience in storage and use of the circuit connecting material 50 to be produced. Further, the film thickness of the support 60 is preferably 15 to 75 μηι in consideration of material cost or productivity. The circuit connecting material is not limited to the single layer -23-201202375 structure as the circuit connecting material 50, and the multilayer structure of the plurality of layers can be laminated. The circuit connecting material of the multilayer structure can be produced by laminating a plurality of layers of the adhesive component and the conductive particles or the different layers of these contents. For example, the circuit connecting material may be provided with a conductive particle-containing layer containing conductive particles, and a conductive particle-free layer containing no conductive particles on at least one surface of the conductive particle-containing layer. Fig. 5 is a cross-sectional view showing the state in which the circuit connecting material of the two-layer structure is supported by the support. The circuit connecting material 70 shown in Fig. 5 is composed of a conductive particle-containing layer 70a containing conductive particles and a conductive particle-containing layer 7〇b containing no conductive particles. The outermost portions of the circuit connecting material 70 are each provided with supporting bodies 60a, 60b. The circuit connecting material 70 is formed by forming the conductive particle-containing layer 70a on the surface of the support 60a, and on the other hand, the conductive particle non-containing layer 70b is formed on the surface of the support 60b, and these layers are bonded using a conventionally known laminator or the like. Made out. When the circuit connecting material 70 is used, the suitable support bodies 60a, 60b can be peeled off. When the circuit connecting material 70 is joined to each other by the circuit members, the decrease in the number of conductive particles on the circuit electrodes caused by the flow of the adhesive component can be sufficiently suppressed. Therefore, for example, when a 1C wafer is mounted on a substrate, the number of conductive particles on the metal bumps (connection terminals) of the 1C wafer can be sufficiently ensured. In this case, it is preferable that the surface of the metal bump having the 1C wafer and the conductive particle non-containing layer 7 Ob ′ are disposed on the substrate on which the 1C wafer is to be mounted and the conductive particle-containing layer 70a. (Connection method) Fig. 6 shows an embodiment of the connection method of the circuit member according to the present invention. The step shown in the schematic cross-sectional view of Fig. 24 is a series of steps for manufacturing the connection structure by thermally hardening the circuit connecting material 50. First, the first circuit member 30 and the film-like circuit connecting material 50 are prepared. The circuit connecting material 50 is formed of an adhesive composition containing the conductive particles 10. The thickness of the circuit connecting material 50 is preferably 5 to 50 μm. If the thickness of the circuit connecting material 50 is less than 5 μm, the circuit connecting material 50 between the first and second circuit electrodes 32 and 42 tends to be insufficiently charged. On the other hand, when the thickness exceeds 50 μm, the conduction between the first and second circuit electrodes 32 and 42 tends to be difficult to ensure. Next, the circuit connecting material 50 is carried on the surface of the circuit electrode 32 on which the first circuit member 30 is formed. On the other hand, the circuit connecting material 50 is pressed in the direction of the arrow Α and the 图 in Fig. 6(a), and the circuit connecting material 50 is erroneously connected to the first circuit member 30 (Fig. 6(b)). The pressure at this time is not harmful to the circuit components, and is not particularly limited, generally 0. 1~30. 0 Mpa is better. Further, it is possible to pressurize while heating, and the heating temperature is a temperature at which the circuit connecting material 50 is not substantially hardened. The heating temperature is usually 50 to 190 ° C. These heat and pressure are at 0. It is better to carry out within 5 to 120 seconds. Next, as shown in Fig. 6(c), the second circuit member 40 can carry the second circuit electrode 42 to the circuit connecting material 50 in the direction of the first circuit member 30. Then, the film-like circuit connecting material 50 is heated, and the entire pressure is applied to the directions of arrows A and B in Fig. 6(c). The heating temperature at this time is the temperature of the hardenable circuit connecting material 50. Add -25- 201202375 The hot temperature is preferably 60 to 180 ° C, 70 to 170 ° C is preferred, and 80 to 160 ° C is more preferred. If the heating temperature is less than 60 ° C, the curing rate tends to be too slow, and if it exceeds 180 ° C, the side reaction tends to be poor. Heating time is 0. 1 to 180 seconds is better, with 0. 5 to 180 seconds is preferred, preferably 1 to 180 seconds. The bonding portion 50a is formed by hardening of the circuit connecting material 50 to obtain the connecting body 100 as shown in Fig. 1. The conditions of the connection are appropriately selected depending on the intended use, the adhesive composition, and the circuit member. Further, when the photo-curable member is used as the adhesive component of the circuit connecting material 50, the active light or the energy ray may be suitably applied to the circuit connecting material 5?. Examples of the active light include ultraviolet light, visible light, and infrared light. Examples of the energy line include an electron beam, an X-ray, a γ-ray, a microwave, and the like. The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments. The present invention can be variously modified without departing from the spirit and scope of the invention. [Embodiment] Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples. (Example 1) 100 parts by mass of a phenoxy resin solution (phenoxy resin/toluene/ethyl acetate = 40/30/30 parts by mass) as a film-forming polymer was mixed, and -26-201202375 was used as a ring. A liquid epoxy group (manufactured by Asahi Kasei Co., Ltd., trade name: Nobakiya 394 1) containing a microcapsule-type latent curing agent, a mixture of an oxy resin and a latent curing agent, 60 parts by mass, Ni as a conductive particle 10 parts by mass of the /Au plated polystyrene particles and 10 parts by mass of a decane coupling agent (manufactured by Toray Dow Corning Co., Ltd., trade name: SZ6030) were used to prepare an adhesive composition for circuit connection. FX-293 (trade name, manufactured by Tohto Kasei Co., Ltd.) was used as the phenoxy resin. The Ni/Au-plated polystyrene particles are on the surface of polystyrene particles (substrate particles) having an average particle diameter of 3 μm, and Ni fine particles (metal fine particles) having an average particle diameter of 400 nm are attached, and then a Ni layer is formed by electroless plating. Finally, the Au layer is formed and produced. The conductive particles after the plating treatment were subjected to SEM at a magnification of 6000 times, and the number of protrusions (the number of metal fine particles disposed inside the metal plating layer) caused by the Ni fine particles was 32. The compression modulus of the 20% compression deformation of the polystyrene particles was 750 kgf/mm2, and the compression recovery after compression at a maximum load of 5 mN was 70%. The above adhesive composition was applied onto a support made of PET (polyethylene terephthalate) (film thickness: 50 μm). Thereafter, the film was dried at 70 ° C for 10 minutes to obtain a conductive particle-containing layer (film thickness: 25 μm) provided on the support. On the other hand, the solution of the adhesive composition is replaced with a phenoxy resin solution (phenoxy resin / toluene / ethyl acetate = 40 / 30 / 30 parts by mass) 1 〇〇 by mass and as an epoxy resin and potential A liquid epoxy group containing a microcapsule-type latent curing agent (manufactured by Asahi Kasei Co., Ltd., trade name: Nobakiya 3 94 1 ) 60 parts by mass of an adhesive component solution is applied to PET The resulting support (film thickness 50 μιη). Thereafter, this was dried at -27 - 201202375 70 °c for 10 minutes to obtain a non-containing layer (film thickness 25 μηι) of the conductive particles provided on the support. The conductive particle-containing layer and the conductive particle-containing layer are bonded together using a conventionally known laminator. Thus, a circuit connecting material having a two-layer structure in the state shown in FIG. 5 was obtained, and this was cut into a strip shape to produce a circuit connecting material (Example 2). Ni/Au plated polystyrene particles were produced as follows, and In the first embodiment, a circuit connecting material was obtained in the same manner. Ni/Au plated polystyrene particles were adhered to the surface of the same polystyrene particles as in Example 1, and were adhered to Ni fine particles having an average particle diameter of 200 nm, and then a Ni layer was formed by electroless plating, and finally an Au layer was formed. Made out. The conductive particles after the plating treatment were subjected to SEM at a magnification of 6000 times, and the results were observed. The number of protrusions caused by the Ni fine particles was 20. (Example 3) A circuit connecting material was obtained in the same manner as in Example 1 except that the Ni/Au plated polystyrene particles were produced as follows. Ni/Au plated polystyrene particles were adhered to the surface of the same polystyrene particles on the same polystyrene particle surface as in Example 1, and Ni particles having an average particle diameter of 800 nm were attached, and then a Ni layer was formed by electroless plating, and finally an Au layer was formed. Made out. The conductive particles after the plating treatment were subjected to SEM at a magnification of 6000 times, and the results were observed. The number of protrusions caused by the Ni fine particles was 15" -28 - 201202375 (Example 4) Ni/Au plated polystyrene The circuit connecting material was obtained in the same manner as in Example 1 except that the particles were produced as follows. The Ni/Au plated polystyrene particles have a compressive modulus of 300 00 kgf/mm2 on the surface of the polystyrene particles at 20% compression deformation, and are adhered to the Ni particles having an average particle diameter of 400 nm, and then electrolessly plated. A Ni layer was formed, and finally an Au layer was formed. The conductive particles after the plating treatment were subjected to SEM at a magnification of 6000 times, and the results were observed. The number of protrusions caused by the Ni fine particles was 30. (Example 5) A circuit-connecting material was obtained in the same manner as in Example 1 except that the Ni/Au-plated polystyrene particles were produced as follows. The compressive modulus of Ni/Au coated polystyrene particles at 20% compression set is 600 kgf/mm2, and the compression recovery after compression at a maximum load of 5 mN is 40% on the surface of polystyrene particles. After the Ni fine particles having an average particle diameter of 400 rim adhered, the Ni layer was formed by electroless plating, and finally an Au layer was formed. The conductive particles after the plating treatment were subjected to SEM at a magnification of 6000 times, and the results were observed. The number of protrusions caused by the Ni fine particles was 30. (Example 6) A circuit connecting material was obtained in the same manner as in Example 1 except that the Ni/Au plated polystyrene particles were produced as follows. Ni/Au plated polystyrene particles have an average particle size of 4 μηη and a compression modulus of 20% compression deformation on the surface of polystyrene particles of -29-201202375 700 kgf/mm2 with an average particle diameter of 400 nm. After the Ni fine particles were attached, the Ni layer was formed by electroless plating, and finally an Au layer was formed. The conductive particles after the plating treatment were subjected to SEM at a magnification of 6000 times, and the results were observed. The number of protrusions caused by the Ni fine particles was 32. (Reference Example 7) A circuit connecting material was obtained in the same manner as in Example 1 except that the Ni/Au-plated polystyrene particles were produced as follows. Ni/Au plated polystyrene particles have a mean particle size of 3 μηη, and a compressive modulus of 20 0 kgf/mm 2 on the surface of the polystyrene particles at 20% compression deformation, with Ni particles having an average particle diameter of 160 nm. After the adhesion, the Ni layer was formed by electroless plating, and finally an Au layer was formed. The conductive particles after the plating treatment were subjected to SEM at a magnification of 6000 times, and the results were observed. The number of protrusions caused by the Ni fine particles was eight. (Reference Example 8) A circuit connecting material was obtained in the same manner as in Example 1 except that the Ni/Au plated polystyrene particles were produced as follows. The Ni/Au plated polystyrene particles are attached to the surface of the polystyrene particles having an average particle diameter of 3 μηη and a compressive modulus of 500 kgf/mm 2 at 20% compression deformation, and are adhered to Ni particles having an average particle diameter of 230 nm. Thereafter, a Ni layer was formed by electroless plating, and finally an Au layer was formed. The conductive particles after the plating treatment were subjected to SEM at a magnification of 6000 times, and the results were observed. The number of protrusions caused by the Ni fine particles was -30 - 201202375 47. (Reference Example 9) A circuit connecting material was obtained in the same manner as in Example 1 except that the Ni/Au plated polystyrene particles were produced as follows. The Ni/Au plated polystyrene particles have an average particle diameter of 3 μm and a compressive modulus of 20 kg/mm2 on the surface of the polystyrene particles at 20% compression deformation, and are adhered to the Ni microparticles having an average particle diameter of 200 nm. The Ni layer is formed by electroless plating, and finally an Au layer is formed. The conductive particles after the plating treatment were subjected to SEM to a magnification of 60 〇〇, and the results were observed. The number of protrusions caused by the Ni fine particles was 23. (Reference Example 10) A circuit connecting material was obtained in the same manner as in Example 1 except that the Ni/Au plated polystyrene particles were produced as follows. The compression recovery ratio of Ni/Au plated polystyrene particles after compression at a maximum load of 5 mN is 25%, and the compressive modulus at 20% compression deformation is 700 kgf/mm2 of the surface of the polystyrene particles. After the Ni fine particles having a diameter of 400 nm adhered, the Ni layer was formed by electroless plating, and finally an Au layer was formed. The conductive particles after the plating treatment were subjected to SEM at a magnification of 6000 times, and the results were observed. The number of protrusions caused by the Ni fine particles was 30. (Comparative Example 1) A circuit-connecting material was obtained in the same manner as in Example 1 except that the Au/31 - 201202375-plated polystyrene particles produced as described below were used instead of the Ni/Au-plated polystyrene particles. On the same polystyrene particle surface as the user of Example 1, the Au layer was formed by electroless plating to produce Au-plated polystyrene particles (Comparative Example 2). The Ni/Au-plated polystyrene particles were as follows. A circuit connecting material was obtained in the same manner as in Example 1 except for the production. The Ni/Au plated polystyrene particles were coated on the same polystyrene particles as in Example 1, and the Ni layer was deposited by electroless nickel plating to form a Ni layer, and then the Α1 layer was plated. Out. The conductive particles after the plating treatment were subjected to SEM at a magnification of 6000 times, and the results were observed. The number of protrusions caused by the Ni block was 35. Next, various evaluations were made for the circuit connecting materials produced in the above examples, reference examples and comparative examples. (Evaluation of initial connection resistance) A 1C wafer having gold bumps having a bump size of 50 μm χ 50 μm, a pitch of 100 μm, and a height of 2 μm was prepared, and a glass substrate on which aluminum electrodes were formed on the surface (thickness: 0. 7 mm). The aluminum electrode and the gold bump are electrically connected by a circuit connecting material to form a connection structure, and the resistance 値 is measured to perform resistance 値 evaluation of the initial connection of the connection portion. Specifically, first, the support layer on the side of the conductive particle-containing layer is peeled off, and the conductive particle-containing layer can be placed under the glass substrate, and the circuit-connecting material is placed on the glass substrate to perform preliminary pressing. Then, after the conductive particles are not contained on the support side of the layer side, the gold bumps are bonded to the conductive particle non-containing layer to support the 1C wafer. After the 1C wafer is placed, the circuit connecting material is pressurized and connected while being heated while being heated. The conditions for pre-pressing are temperature 70 ° C and pressure 0. 5 MPa (bump area conversion), holding time is 1 second. On the other hand, the connection conditions were temperature 21 〇 ° C, pressure 70 MPa (bump area conversion), and holding time of 5 seconds. The resistance 値 (R〇) of the thus connected structure was measured. The initial connection resistance was evaluated on the basis of the following criteria. A : R〇 is less than 1 Ω, B: R〇 is 1 to 2 Ω, and C: R 〇 is more than 2 Ω. The circuit connecting materials of the above-described embodiments, reference examples, and comparative examples were used as the circuit connecting materials, and the evaluation results of the initial connection resistance in each case are shown in Tables 1 and 2. (Evaluation of connection resistance after thermal cycle test) After the evaluation of the initial connection resistance described above, the connection resistance was evaluated by performing a thermal cycle test after repeating the temperature rise and fall of the connection structure and then performing the thermal cycle test. The thermal cycle test was carried out by repeating the connection structure from room temperature to 1 ° C for 20 times, followed by a temperature drop of -40 ° C and then warming to room temperature. The resistance 値 of the connection structure after the heat cycle test was measured (RJ. The evaluation of the connection resistance after the heat cycle test was performed according to the following criteria: A : Ri was less than 3 Ω, -33 - 201202375 B: R1 was 3 〜 4 Ω, C: R1 exceeds 4 Ω β As the circuit connecting material, the circuit connecting materials of the above-described examples, reference examples, and comparative examples are used. The evaluation results of the initial connection resistance in each case are shown in Tables 1 and 2. (Insulation Evaluation) Preparation A 1C wafer and a germanium substrate having gold bumps having a bump size of 50 μm χΙΟΟ μηι, a pitch of 15 μm, and a height of 20 μm. The germanium substrate and the plurality of gold bumps are electrically connected by a circuit connecting material to form a connection structure, and the adjacent structure is measured. The electrical resistance between the gold bumps is evaluated by the electrical insulation between the adjacent gold bumps of the connecting portion. Moreover, the germanium substrate is on the glass substrate (thickness 0. 7 mm) The indium-tin oxide (ΙΤΟ) is deposited on top to form a tantalum electrode (surface resistance $20 Ω/C). First, the support layer on the side of the conductive particle-containing layer was peeled off, and the layer containing the conductive particles was brought into contact with the ITO substrate, and the circuit-connecting material was placed on the ITO substrate to perform preliminary pressing. Then, after the conductive particles are not contained on the support side of the layer side, the gold bumps are brought into contact with the conductive particle non-containing layer to carry the 1C wafer. After the 1C wafer is placed, the circuit connecting material is pressurized and connected while being heated while being heated. The conditions for pre-pressing are temperature 70 °c and pressure 0. 5 MPa (bump area conversion), holding time is 1 second. On the other hand, the connection conditions were a temperature of 210 ° C, a pressure of 70 MPa (contrast area conversion), and a holding time of 5 seconds. The insulation resistance 値(r2) between the gold bumps was measured by applying a 50 V electric -34 - 201202375 for 1 minute between the adjacent gold bumps of the connected structure. The evaluation of insulation is based on the following criteria. A : R2 is 1χ1〇1()Ω or more, B: R2 is 1 X 1 09 ~1 X 1 Ο10Ω, C : R2 is up to 1 χ109Ω. The circuit connecting materials of the above-described embodiments, reference examples, and comparative examples were used as the circuit connecting materials, and the results of the insulation evaluation in each case are shown in Tables 1 and 2. -35- 201202375 [一嗽] Example 6 inch 700 _ .  ο 400 CN cn <<<Example 5 m 600 ο 400 <<<Example 4 m 300 ο 400 <<<Example 3 m 750 ο 800 <<<Example 2 m 750 ί_ ο 200 <<<Example 1 750 ο 400 (Ν m <<<Average particle size, μπι (Ν 1 s - 觐 树 · 籴 幽 13 13⁄4 i ii d ^ gs ε 挂 S Peng lion 1 « y 4 < Μ E睦mm Average particle diameter of metal fine particles, nm Number of protrusions on the surface of conductive particles Initial connection resistance After heat cycle test, connection resistance Insulation substrate particle evaluation result -36- 201202375 E Comparative Example 2 m 750 Ο 300 mm υ PQ Comparative Example 1 m 750 ο 1 ο m υ < Reference Example 10 CO 700 <Ν Ο inch 沄 < PQ c Reference Example 9 m ο Ο m <N PQ <Reference Example 8 m 500 ο 230 < CQ PQ Reference Example 7 m 450 ο s 1-H 00 < PQ <Average particle size, μιη (N 1 § ^ m 幽 Ci - g paste · 立鹏 w ra Λ y -κ s brewing wm <3 Average particle diameter of metal fine particles, number of protrusions on the surface of nm conductive particles Initial connection resistance After heat cycle test, connection resistance insulating substrate particle evaluation result - 37 - 201202375 As shown in Table 1, Examples 1 to 6 The circuit connection material shows A for all evaluation items. Therefore, it was found that the circuit connecting materials of Examples 1 to 6 can achieve a high level of both the low initial connection resistance and the good insulation properties of the adjacent circuit electrodes. In addition, the evaluation of the connection resistance after the heat cycle test is A, which means that the rise of the connection resistance 値 can be sufficiently suppressed. Further, in the circuit connecting material of Comparative Example 1 in which no protrusion due to Ni fine particles was provided, the initial connection resistance was evaluated as B, and the connection resistance after the heat cycle test was evaluated as C. According to the above findings, the present invention provides an initial resistance of the connection structure which can be sufficiently reduced when a circuit electrode which is required to have a high fine pitch is connected to each other, even if the circuit electrode is formed of a metal material which is likely to form an oxide film on the surface. Circuit connection material. INDUSTRIAL APPLICABILITY The present invention provides an adhesive composition which can be sufficiently reduced in the initial structure of the connection structure, and a circuit connecting material using the same, in which the connection electrode is formed of a metal material which is easy to form an oxide film on the surface. SUMMARY OF THE INVENTION The present invention is to provide a connection structure in which a circuit member is connected under a lower connection resistance, and a connection method for obtaining the circuit member. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] Fig. 1 is a cross-sectional view showing a state in which a circuit connecting material of the present invention is used between circuit electrodes to connect circuit electrodes. -38-201202375 Fig. 2 is a cross-sectional view showing an embodiment of a circuit connecting material according to the present invention. Fig. 3 is a cross-sectional view showing one embodiment of conductive particles contained in a circuit connecting material according to the present invention. Fig. 4 is a cross-sectional view showing a state in which a circuit connecting material of the present invention is placed on a support. Fig. 5 is a cross-sectional view showing a state in which the circuit connecting material of the present invention is supported by a support. Fig. 6 is a flow chart showing a schematic sectional view of an embodiment of a method of connecting circuit members according to the present invention. [Description of main component symbols] 1 : Substrate particles 2 : Metal microparticles 3 '· Metal plating layer 1 〇 : Conductive particles 2 〇 : Adhesive component 30 : First circuit member 31 : Circuit board (first circuit board) 32 : circuit electrode (first circuit electrode) 40 : second circuit member 41 : circuit board (second circuit board) 42 : circuit electrode (second circuit electrode) 50, 70 : circuit connecting material - 39 - 201202375 60, 60a, 60b: support body 100: connection structure -40

Claims (1)

201202375 七、申請專利範圍: 1. 一種黏著劑組成物,其爲具備黏著劑成分、分散於 該黏著劑成分中的導電粒子者,其特徵爲該導電粒子具有 構成該導電粒子之中心部分的基材粒子、與覆蓋該基材粒 子表面之至少一部份的金屬鍍敷層、及配置於該金屬鍍敷 層內側之該基材粒子表面上的複數金屬微粒子。 -41 -201202375 VII. Patent application scope: 1. An adhesive composition which is a conductive particle having an adhesive component dispersed in the adhesive component, characterized in that the conductive particle has a base constituting a central portion of the conductive particle. The material particles, the metal plating layer covering at least a portion of the surface of the substrate particle, and the plurality of metal fine particles disposed on the surface of the substrate particle inside the metal plating layer. -41 -
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