201213493 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種例如可用於電極間之電性連接的附有 ,絕緣性粒子之導電性粒子及該附有絕緣性粒子之導電性粒 子之製造方法、以及使用有該附有絕緣性粒子之導電性粒 子的異向性導電材料及連接構造體。 【先前技術】 廣泛已知有異向性導電膏及異向性導電膜等之異向性導 電材料。於該等異向性導電材料中,於黏合樹脂中分散有 導電性粒子。 上述異向性導電材料係於IC晶片與可撓性印刷電路基板 之連接、及1C晶片與具有ITO電極之電路基板之連接等中 使用。例如,可於1C晶片之電極與電路基板之電極之間配 置異向性導電材料之後,藉由加熱及加壓而將該等電極電 性連接。 作為上述導電性粒子之一例,於下述之專利文獻丨中揭 示了 一種附有絕緣性粒子之導電性粒子,其具有:導電性 粒子、固定化於該導電性粒子之表面且具有固著性之絕緣 性粒子。上述絕緣性粒子具有硬質粒子、及包覆該硬質粒 子之表面之高分子樹脂層。此處,為了使絕緣性粒子固定 化於導電性粒子之表面,可使用物理性/機械性混成法作 為固定化方法。 於下述專利文獻2中揭示了 一種附有絕緣性粒子之導電 性粒子,其具有:於表面之至少一部分具有極性基之導電 157831.doc 201213493 性粒子、包覆該導電性粒子之表面之至少一部分且包含絕 緣性粒子之絕緣性材料。上述絕緣性材料具體而言包含: 可與上述極性基吸附之高分子電解質、及可與上述高分子 電解質吸附之無機氧化物粒子。該無機氧化物粒子係絕緣 性粒子。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特表2007-537570號公報 [專利文獻2]日本專利特開2008-120990號公報 【發明内容】 [發明所欲解決之問題] 於如專利文獻1、2中所記载之先前之附有絕緣性粒子之 導電性粒子中,導電層之至少一部分之區域露出。因此, 由於大氣中之腐蝕性氣體或異向性導電材料中之腐蝕性物 質等,容易於導電層之表面產生銹。因此,存在無法經過 長時間而充分維持高的導電性之現象。又,若使用於導電 層產生有銹之附有絕緣性粒子之導電性粒子而對電極間進 行連接,則存在電極間並未確實地電性連接,或者電極間 之連接電阻變高之現象。 進而,於先前之附有絕緣性粒子之導電性粒子中,絕緣 性粒子容易自導電性粒子之表面脫離。例如,於使附有絕 緣性粒子之導電性粒子分散於黏合樹脂中時,存在絕緣性 粒子容易自導電性粒子之表面脫離之現象。 特別是如專利文獻1所記載那樣,為了使絕緣性粒子固 157831.doc 201213493 疋化於導電性粒子之表面而使用物理性/機械性混成法之 It形時’絕緣性粒子容易自導電性粒子之表面脫離。 進而’於使用物理性/機械性混成法之情形時,亦存在 如下之問題:絕緣性粒子之高分子樹脂層亦附著於導電性 粒子之表面之附著有絕緣性粒子之部分以外的部分,於電 極間之連接後容易損及導電性。 本發明之目的在於提供一種難以於導電層產生銹,可經 長時間維持高的導電性’因此於用於電極間之連接之情形 時’可使導通可靠性提高的附有絕緣性粒子之導電性粒子 及該附有絕緣性粒子之導電性粒子之製造方法、以及使用 有該附有絕緣性粒子之導電性粒子的異向性導電材料及連 接構造體。 本發明之限定性目的在於提供一種絕緣性粒子難以自導 電性粒子之表面脫離的附有絕緣性粒子之導電性粒子及該 附有絕緣性粒子之導電性粒子之製造方法、以及使用有該 附有絕緣性粒子之導電性粒子的異向性導電材料及連接構 造體》 [解決問題之技術手段] 藉由本發明之較廣之態樣,提供一種附有絕緣性粒子之 導電性粒子,其具備:附有絕緣性粒子之導電性粒子本 體’其具有至少於表面具有導電層之導電性粒子、及附著 於該導電性粒子表面之絕緣性粒子;覆膜,其包覆所述附 有絕緣性粒子之導電性粒子本體之表面;上述覆膜由具有 碳數為6〜22之烷基之化合物而形成。 157831.doc 201213493 於本發明之附有絕緣性粒子之導電性粒子之某特定態樣 中’上述絕緣性粒子包含無機粒子。 於本發明之附有絕緣性粒子之導電性粒子之其他特定之 態樣中,上述具有碳數為6〜22之烷基之化合物係選自由磷 酸酯或其鹽、亞磷酸酯或其鹽、烷氧基矽烷、烷基硫醇及 二烧基二硫趟所構成之群之至少1種。 於本發明之附有絕緣性粒子之導電性粒子之進而其他特 定之態樣中,上述絕緣性粒子具有絕緣性粒子本體、以及 覆蓋該絕緣性粒子本體之表面之至少一部分區域且由高分 子化合物所形成之層。 於本發明之附有絕緣性粒子之導電性粒子之其他特定態 樣中,於上述導電性粒子之表面之附著有上述絕緣性粒子 之部分以外的部分’並未附著上述高分子化合物。 於本發明之附有絕緣性粒子之導電性粒子之其他特定態 樣中,上述高分子化合物具有選自由(甲基)丙烯醯基、縮 水甘油基及乙烯基所構成之群之至少丨種反應性官能基。 於本發明之附有絕緣性粒子之導電性粒子之其他特定態 樣中,上述絕緣性粒子並非藉由混成法而附著於上述導電 性粒子之表面。 於本發明之附有絕緣性粒子之導電性粒子之其他特定態 樣中,藉由以5重量%之檸檬酸水溶液對附有絕緣性粒子 之導電性粒子進行處理而將上述覆膜剝離,獲得包含所剝 離之覆膜的處理液後,對該處理液進行過濾而所得之過濾 液包含50〜10000 ppm之填元素或石夕元素。 157831.doc ⑧ • 6 - 201213493 於本發明之附有絕緣性粒子之導電性粒子之其他特定態 樣中’藉由以5重量%之檸檬酸水溶液對附有絕緣性粒子 之導電性粒子進行處理而將所述覆膜剝離,獲得包含所剝 離之覆膜的處理液後,對該處理液進行過濾而所得之過濾 液包含50〜10000 ppm之破元素》 又,藉由本發明之較廣之態樣,提供一種附有絕緣性粒 子之導電性粒子’其具備:附有絕緣性粒子之導電性粒子 本體,其具有至少於表面具有導電層之導電性粒子及附著 於該導電性粒子表面之絕緣性粒子;覆膜,其附著於所述 附有絕緣性粒子之導電性粒子本體之表面;藉由以5重量 %之擰檬酸水溶液對附有絕緣性粒子之導電性粒子進行處 理而將上述覆膜剝離,獲得包含所剝離之覆膜的處理液 後,對該處理液進行過濾而所得之過濾液包含504 〇〇〇〇 ppfti之磷元素或矽元素。於此情形時,較佳的是藉由以5重 量%之檸檬酸水溶液對附有絕緣性粒子之導電性粒子進行 處理而將上述覆膜剝離,獲得包含所剝離之覆膜的處理液 後,對該處理液進行過濾而所得之過濾液包含5〇〜1〇〇〇〇 ppm之磷元素。 本發明之連接構造體具備:第1連接對象部件、第2連接 對象部件、以及連接該第丨、第2連接對象部件之連接部; 該連接部由依照本發明而構成之附有絕緣性粒子之導電性 粒子而形成,或者由包含該附有絕緣性粒子之導電性粒子 與黏合樹脂之異向性導電材料而形成。 又,藉由本發明之較廣之態樣,提供一種附有絕緣性粒 157831.doc 201213493 子之導電性粒子之製造方法’其是於具有至少於表面具有 導電層之導電性粒子、及附著於該導電性粒子表面之絕緣 性粒子的附有絕緣性粒子之導電性粒子本體之表面,使用 具有碳數為6〜22之烷基之化合物而以包覆上述附有絕緣性 粒子之導電性粒子本體之表面之方式形成覆膜。 於本發明之附有絕緣性粒子之導電性粒子之製造方法之 某特定之態樣中,上述附有絕緣性粒子之導電性粒子本體 於表面之至少一部分之區域具有羥基,使上述附有絕緣性 粒子之導電性粒子本體之表面之羥基,與具有羥基之具有 碳數為6〜22之烷基之化合物反應,以包覆上述附有絕緣性 粒子之導電性粒子本體之表面之方式形成覆膜。 本發明之異向性導電材料包含依照本發明而構成之附有 絕緣性粒子之導電性粒子、黏合樹脂,或者包含藉由本發 明之附有絕緣性粒子之導電性粒子之製造方法而所得之附 有絕緣性粒子之導電性粒子、黏合樹脂。本發明之異向性 導電材料較佳的是異向性導電膏。 [發明之效果] 本發明之附有絕緣性粒子之導電性粒子由於附有絕緣性 沣子之導電性粒子本體之表面由覆膜所包覆,且該覆膜由 具有碳數為6〜22之烧基之化合物而形成,因此難以於導電 層產生銹。 於本發明之附有絕緣性粒子之導電性粒子之製造方法 中,於附有絕緣性粒子之導電性粒子本體之表面,使用具 有碳數為6〜22之烷基之化合物而以包覆上述附有絕緣性粒 157831 .doc 201213493 子之導電性粒子本體之表面之方式形成覆膜,因此可獲得 難以於導電層產生銹之附有絕緣性粒子之導電性粒子。 因此,於使用本發明之附有絕緣性粒子之導電性粒子, 或者使用藉由本發明之附有絕緣性粒子之導電性粒子之製 造方法而所得之附有絕緣性粒子之導電性粒子,對電極間 進行連接之情形時,可提高電極間之導通可靠性。 又,本發明之附有絕緣性粒子之導電性粒子,即使於附 有絕緣性粒子之導電性粒子本體之表面附著有覆膜,進而 藉由以5重量%之檸檬酸水溶液對該附有絕緣性粒子之導 電性粒子進行處理而將上述覆膜剝離,獲得包含所剝離之 覆膜的處理液後’對該處理液進行過濾而所得之過濾液包 含50〜10000 ppm之碟元素或石夕元素之情形時,亦難以於導 電層產生銹。因此’於使用本發明之附有絕緣性粒子之導 電性粒子,對電極間進行連接之情形時,可提高電極間之 導通可靠性。 【實施方式】 以下,藉由參照圖式對本發明之具體的實施形態及實施 例加以說明而使本發明變明瞭。 (附有絕緣性粒子之導電性粒子本體) 於圖1中,藉由剖面圖表示本發明之第以施形態之附有 絕緣性粒子之導電性粒子。 圖!所示之附有絕緣性粒子之導電性粒Η具備:附有絕 緣佳粒子之導電性粒子本體2、包覆附有絕緣性粒子之導 電性粒子本趙2之表面的覆膜3。覆膜3附著㈣有絕緣性 157831.doc •9· 201213493 粒子之導電性粒子本體2之表面。覆膜3覆蓋附有絕緣性粒 子之導電性粒子本體2之表面全體。 附有絕緣性粒子之導電性粒子本體2具備:導電性粒子 11、及附著於導電性粒子叫自之複數個絕緣性粒子15。 絕緣性粒子15由具有絕緣性之材料而形成。 覆膜3覆蓋導電性粒子“之表面與絕緣性粒子15之表 面。覆蓋導電性粒子U之表面之覆膜3部分與覆蓋絕緣性 粒子15之表面之覆膜3部分相連接。 導電性粒子11具有:基材粒子12、於基材粒子12之表面 上所設之導電層13 ^導電層13覆蓋基材粒子12之表面。導 電性粒子11係基材粒子丨2之表面由導電層13所包覆之包覆 粒子。導電性粒子U於表面具有導電層13。 於圖2中,藉由剖面圖表示本發明之第2實施形態之附有 絕緣性粒子之導電性粒子。 圖2中所示之附有絕緣性粒子之導電性粒子21具備:附 有絕緣性粒子之導電性粒子本體22、包覆附有絕緣性粒子 之導電性粒子本體22之表面之覆膜23。覆膜23附著於附有 絕緣性粒子之導電性粒子本體22之表面。 附有絕緣性粒子之導電性粒子本體22具備:導電性粒子 31、及於導電性粒子31之表面所附著之複數個絕緣性粒子 15 ° 覆膜23覆蓋導電性粒子31之表面與絕緣性粒子15之表 面。覆蓋導電性粒子31之表面之覆膜23部分與包覆絕緣性 粒子15之表面之覆膜23部分相連接。 157831.doc •10 201213493 導電性粒子31具有:基材粒子12、及於基材粒子12之表 面上所設之導電層32。導電性粒子31於基材粒子12之表面 上具有複數個芯物質33。導電層32包覆基材粒子12與芯物 質33。由於導電層32包覆芯物質33,因此導電性粒子31於 表面具有複數個突起34。由於芯物質33而使導電層32之表 面隆起,形成有複數個突起34。 於圖3中,藉由剖面圖表示本發明之第3實施形態之附有 絕緣性粒子之導電性粒子。 圖3中所示之附有絕緣性粒子之導電性粒子41具備:附 有絕緣性粒子之導電性粒子本體42、包覆附有絕緣性粒子 之導電性粒子本體42之表面的覆膜3。 附有絕緣性粒子之導電性粒子本體42具備:導電性粒子 11、及附著於導電性粒子11表面之複數個絕緣性粒子45。 亦即,除了絕緣性粒子不同以外,附有絕緣性粒子之導電 性粒子41與附有絕緣性粒子之導電性粒子1同樣地構成, 附有絕緣性粒子之導電性粒子本體42與附有絕緣性粒子之 導電性粒子本體2同樣地構成。 絕緣性粒子45具有:絕緣性粒子本體45a、及覆蓋絕緣 14粒子本體45a之表面且由南分子化合物而形成之層45b。 由於層45b之存在,可適度提高絕緣性粒子45對於導電性 粒子11之密接性。 層45b包覆絕緣性粒子本體45 a之表面全體。因此,於導 電性粒子11與絕緣性粒子本體45a之間配置有層45b »層 45b若以覆蓋絕緣性粒子本體之表面之至少一部分區域之 157831.doc 201213493 方式存在即可’亦可不覆蓋絕緣性粒子本體之表面全體。 較佳的疋層45b配置於導電性粒子與絕緣性粒子本體之 間。 於圖4中藉由剖面圖表示本發明之第4實施形態之附有 絕緣性粒子之導電性粒子。 圖4中所不之附有絕緣性粒子之導電性粒子61具備:絕 緣性粒子本體62、包覆附有絕緣性粒子之導電性粒子本體 62之表面的覆膜23。覆膜23附著於附有絕緣性粒子之導電 性粒子本體62之表面。 附有絕緣性粒子之導電性粒子本體62具備:導電性粒子 71、及附著於導電性粒子71之表面之複數個絕緣性粒子 15 〇 導電性粒子71具有:基材粒子12、及於基材粒子12之表 面上所設之導電層76。導電層76具有:於基材粒子12之表 面上所設之第1導電層76a、於第1導電層76a之表面上所設 之第2導電層76b。導電性粒子71於第1導電層76a之表面上 具有複數個芯物質33。第2導電層76b包覆第1導電層76a與 过物質33。基材粒子12與芯物質33隔著間隔而配置。於基 材粒子12與芯物質33之間存在有第1導電層76a。由於第2 導電層76b包覆芯物質33,因此導電性粒子71於表面具有 複數個突起77。由於芯物質33而使導電層76及第2導電層 76b之表面隆起,形成有複數個突起77。 較佳的是附有絕緣性粒子之導電性粒子本體2、22、 42、62之表面由覆膜3、23所包覆,該覆膜3、23由具有碳 157831.doc •12· ⑧ 201213493 數為6〜22之烷基之化合物而形成。由此,變得難以於附有 絕緣性粒子之導電性粒子1、21、41、61中之導電層13、 32 76上產生錄。覆膜3、23賦予防銹效果。因此,附有 絕緣性粒子之導電性粒子中之導電性粒子之導電性變高, 可經長時間而維持高的導電性。因此,於使用附有絕緣性 粒子之導電性粒子i、21、41、61而對電極間進行連接之 情形時,可提高導通可靠性。 又,較佳的是藉由以5重量。/。之檸檬酸水溶液對附有絕 緣性粒子之導電性粒B、21、41、61進行處理而將覆膜 3、23剝離,獲得包含所剝離之覆膜3、23的處理液後,對 該處理液進行過濾而所得之過濾液包含5〇〜1〇〇〇〇叩m之碌 元素或矽7L素。藉此,變得難以於附有絕緣性粒子之導電 性粒子1、21、41、61之導電層13、32、76產生銹。因 此,附有絕緣性粒子之導電性粒子中之導電性粒子之導電 性變高,可經長時間而維持高的導電性。因此,於使用附 有絕緣性粒子之導電性粒子丨、21、41、61而對電極間進 行連接之情形時,可提高導通可靠性。 又,自更進一步難以於導電層產生銹之觀點考慮,較佳 的疋藉由以5重量%之檸檬酸水溶液對附有絕緣性粒子之 導電性粒子1、21、41、61進行處理而將覆膜3、23剝離, 獲得包含所剝離之覆膜3、23的處理液後,對該處理液進 行過濾而所得之過濾液包含5〇〜1〇〇〇〇 ppm之磷元素。自更 進-步難以於導電層產生銹之觀點考慮,較佳的是藉由以 5重s %之擰檬酸水溶液對附有絕緣性粒子之導電性粒子 15783I.doc •13- 201213493 1、21、41、61進行處理而將覆膜3、23剝離,獲得包含所 剝離之覆膜3、23的處理液後,對該處理液進行過濾而所 得之過濾液包含50〜10000 PPm之矽元素。上述過濾液中之 矽元素或磷元素之含量更佳的是1 〇〇 ppm以上,更佳的是 5000 ppm以下’進一步更佳的是1〇〇〇 ppm以下。 上述磷元素及矽元素之含量可使用ICP發光分析裝置而 測定。作為ICP發光分析裝置之市售品,可列舉堀場製作 所公司製造之「ULTIMA2」等。 於具有覆膜3、23之附有絕緣性粒子之導電性粒子i、 21、41、61之情形時,上述破元素及上述矽元素之含量通 常由覆膜3、23而決定。亦即,上述磷元素及上述矽元素 之含量表示覆膜3、23中之磷元素及矽元素之比例。 較佳的是覆膜3、2 3附著於附有絕緣性粒子之導電性粒 子本體2、22、42、62之表面。於附有絕緣性粒子之導電 性粒子1、21、41、61中,較佳的是覆膜3、23覆蓋附有絕 緣性粒子之導電性粒子本體2、22、42、62之表面全體。 再者,覆膜3、23並無必須包覆附有絕緣性粒子之導電 性粒子本體2、22、42、62之表面全體之必要。由於覆膜 3、23包覆導電層13、32、76之表面之至少一部分區域, 因此於形成有覆膜3、23之部分中,可抑制導電層23、 32、76之銹。 進而’由於覆膜3、23之存在,於附有絕緣性粒子之導 電性粒子1、21、41、61中’絕緣性粒子15、45變得難以 自導電性粒子11、31、71之表面脫離。例如,於將附有絕 157831.doc 201213493 緣性粒子之導電性粒子丨、21、41、61添加於黏合樹脂中 而進行混練時,絕緣性粒子15、45難以自導電性粒子n、 31、71之表面脫離。進而,於複數個附有絕緣性粒子之導 電I·生粒子1、21、41、61接觸時,由於接觸時之衝擊,絕 緣性粒子15、45難以自導電性粒子u、31、71之表面脫 離。因此,於將附有絕緣性粒子之導電性粒子丨、21、 41、61用於電極間之連接之情形時,於鄰接之導電性粒子 11、31、71間存在絕緣性粒子15、45,不能連接之鄰接之 電極間難以電性連接。 以下,對覆膜3、23之詳細情況及附有絕緣性粒子之導 電性粒子本體2、22、42、62之詳細情況加以說明。 [覆膜] 為了難以於導電層產生銹,較佳的是上述覆膜由具有碳 數為6〜22之烷基之化合物(以下亦稱為化合物A)而形成。 方上述烷基之碳數未達6,則變得容易於導電層之表面產 生銹。若上述烷基之碳數超過22,則附有絕緣性粒子之導 電性粒子之導電性變低。自更進一步提高附有絕緣性粒子 之導電性粒子之導電性之觀點考慮,較佳的是上述化合物 A中之上述烷基之碳數為16以下。上述烷基可具有直鏈結 構,亦可具有分支結構。較佳的是上述烷基具有直鏈結 構》 上述化合物A若具有碳數為6〜22之烷基則並無特別之限 定。上述化合物A較佳的是選自由具有碳數為6〜22之烷基 之碟酸@θ或其鹽 '具有碳數為6〜22之烧基之亞鱗酸醋或其 157831.doc •15· 201213493 鹽、具有碳數為6〜22之烷基之烷氧基矽烷、具有碳數為 6〜22之烧基之烷基硫醇、及具有碳數為6〜22之烷基之二烷 基二硫趟所構成之群的至少1種。亦即,上述具有碳數為 6〜22之烧基之化合物a較佳的是選自由構酸酯或其鹽、亞 磷酸酯或其鹽、烷氧基矽烷、烷基硫醇及二烷基二硫醚所 構成之群之至少1種。藉由使用該等較佳之化合物A,可更 進一步難以於導電層產生銹。自更進一步難以產生銹之觀 點考慮,上述化合物A較佳的是選自由上述填酸酯或其 鹽、亞磷酸酯或其鹽及烷氧基矽烷所構成之群之至少工 種,更佳的是上述璃酸酯或其鹽及亞碟酸酯或其鹽中之至 少1釋。上述化合物A可僅使用1種,亦可併用2種以上。 較佳的是上述化合物A具有可與導電性粒子反應之反應 性官能基。較佳的是上述化合物A具有可與絕緣性粒子反 應之反應性官能基。較佳的是覆膜與附有絕緣性粒子之導 電性粒子本體化學鍵結。較佳的是覆膜與導電性粒子化學 鍵結。較佳的是覆膜與絕緣性粒子化學鍵結。更佳的是覆 膜與導電性粒子及絕緣性粒子化學鍵結^由於上述反應性 以及由於上述化學鍵結,變得難以產生覆201213493 6. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to an electrically conductive particle, such as an insulating particle, and an electrically conductive particle with an insulating particle, which can be used for electrical connection between electrodes, for example. The production method and the anisotropic conductive material and the connection structure using the conductive particles with the insulating particles. [Prior Art] An anisotropic conductive material such as an anisotropic conductive paste or an anisotropic conductive film is widely known. In the anisotropic conductive material, conductive particles are dispersed in the binder resin. The anisotropic conductive material is used for connection between an IC chip and a flexible printed circuit board, and connection of a 1C wafer to a circuit board having an ITO electrode. For example, after the anisotropic conductive material is disposed between the electrode of the 1C wafer and the electrode of the circuit substrate, the electrodes are electrically connected by heating and pressurization. As an example of the above-mentioned conductive particles, a conductive particle having insulating particles, which has conductive particles and is fixed to the surface of the conductive particles and has a fixing property, is disclosed in the following patent document. Insulating particles. The insulating particles have hard particles and a polymer resin layer covering the surface of the hard particles. Here, in order to immobilize the insulating particles on the surface of the conductive particles, a physical/mechanical mixing method can be used as the immobilization method. Patent Document 2 discloses a conductive particle having insulating particles having at least a part of a surface having a polar group of conductive 157831.doc 201213493 particles, at least a surface covering the conductive particles. An insulating material partially containing insulating particles. The insulating material specifically includes a polymer electrolyte that can be adsorbed to the polar group and inorganic oxide particles that can be adsorbed to the polymer electrolyte. The inorganic oxide particles are insulating particles. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. 2008-120990 (Patent Document 2). In the conductive particles having insulating particles attached as described in Patent Documents 1 and 2, at least a part of the conductive layer is exposed. Therefore, rust is easily generated on the surface of the conductive layer due to corrosive gas in the atmosphere or corrosive substances in the anisotropic conductive material. Therefore, there is a phenomenon that the high conductivity cannot be sufficiently maintained over a long period of time. Further, when the conductive particles are used to form rust-attached conductive particles with insulating particles and the electrodes are connected to each other, the electrodes are not reliably electrically connected to each other, or the connection resistance between the electrodes is increased. Further, in the conductive particles having the insulating particles described above, the insulating particles are easily detached from the surface of the conductive particles. For example, when the conductive particles having the insulating particles are dispersed in the binder resin, the insulating particles are likely to be detached from the surface of the conductive particles. In particular, as described in Patent Document 1, in order to reduce the insulating particle solid 157831.doc 201213493 to the surface of the conductive particle and use the It shape of the physical/mechanical mixing method, the insulating particle is easily self-conductive particles. The surface is detached. Further, when the physical/mechanical mixing method is used, there is a problem that the polymer resin layer of the insulating particles adheres to a portion other than the portion of the surface of the conductive particles to which the insulating particles are adhered. Conductivity is easily impaired after the electrodes are connected. An object of the present invention is to provide a conductive particle-attached conductive material which is difficult to generate rust in a conductive layer and can maintain high conductivity over a long period of time, so that when it is used for connection between electrodes, it can improve conduction reliability. The method for producing the particles and the conductive particles with the insulating particles, and the anisotropic conductive material and the bonded structure using the conductive particles with the insulating particles. A limited object of the present invention is to provide an insulating particle-attached conductive particle in which insulating particles are hardly detached from the surface of the conductive particle, and a method for producing the conductive particle with the insulating particle, and the method of using the same An anisotropic conductive material and a bonded structure of conductive particles having insulating particles. [Technical means for solving the problem] According to a broader aspect of the present invention, a conductive particle having insulating particles is provided, which is provided a conductive particle body having insulating particles; the conductive particles having a conductive layer at least on the surface; and insulating particles attached to the surface of the conductive particles; and a coating covering the insulation The surface of the conductive particles of the particles; the film is formed of a compound having an alkyl group having 6 to 22 carbon atoms. 157831.doc 201213493 In a specific aspect of the conductive particles with insulating particles of the present invention, the insulating particles include inorganic particles. In another specific aspect of the conductive particles with insulating particles of the present invention, the compound having an alkyl group having 6 to 22 carbon atoms is selected from the group consisting of phosphates or salts thereof, phosphites or salts thereof, At least one of the group consisting of alkoxy decane, alkyl thiol and dialkyl dithizone. In still another specific aspect of the conductive particles with insulating particles of the present invention, the insulating particles have an insulating particle body and at least a portion of a surface covering the surface of the insulating particle body and are composed of a polymer compound. The layer formed. In another specific aspect of the conductive particles with insulating particles of the present invention, the polymer compound is not adhered to a portion other than the portion where the insulating particles are adhered to the surface of the conductive particles. In another specific aspect of the conductive particles with insulating particles of the present invention, the polymer compound has at least one selected from the group consisting of a (meth) acryl fluorenyl group, a glycidyl group, and a vinyl group. Sex functional group. In another specific aspect of the conductive particles with insulating particles of the present invention, the insulating particles are not adhered to the surface of the conductive particles by a mixing method. In another specific aspect of the conductive particles with insulating particles of the present invention, the conductive particles coated with insulating particles are treated with a 5% by weight aqueous solution of citric acid to remove the film. After the treatment liquid containing the peeled coating film, the treatment liquid is filtered, and the obtained filtration liquid contains 50 to 10000 ppm of a filling element or a stone element. 157831.doc 8 • 6 - 201213493 In other specific aspects of the conductive particles with insulating particles of the present invention, 'the conductive particles with insulating particles are treated with a 5% by weight aqueous solution of citric acid After the coating film is peeled off to obtain a treatment liquid containing the peeled coating film, the filtration liquid obtained by filtering the treatment liquid contains 50 to 10000 ppm of broken elements, and by the broader aspect of the present invention Provided is a conductive particle with insulating particles, comprising: a conductive particle body having insulating particles, having conductive particles having a conductive layer at least on the surface, and insulating layer attached to the surface of the conductive particles a film which adheres to the surface of the main body of the conductive particles with the insulating particles; and the conductive particles coated with the insulating particles are treated with a 5% by weight aqueous solution of citric acid After the film is peeled off and a treatment liquid containing the peeled film is obtained, the treatment liquid is filtered, and the obtained filtrate contains 504 ppfti of phosphorus or strontium.In this case, it is preferred that the coating film is peeled off by treating the conductive particles coated with the insulating particles with a 5% by weight aqueous citric acid solution to obtain a treatment liquid containing the peeled coating film. The filtrate obtained by filtering the treatment liquid contains 5 〇 to 1 〇〇〇〇 ppm of a phosphorus element. The connection structure of the present invention includes: a first connection target member, a second connection target member, and a connection portion that connects the second and second connection target members; and the connection portion is made of an insulating particle according to the present invention. The conductive particles are formed or formed of an anisotropic conductive material containing the conductive particles with insulating particles and a binder resin. Further, according to a broader aspect of the present invention, there is provided a method for producing conductive particles having an insulating particle 157831.doc 201213493, which is characterized in that it has conductive particles having a conductive layer at least on the surface, and is attached to On the surface of the conductive particles on the surface of the conductive particles, the conductive particles having the carbon atoms of 6 to 22 are coated on the surface of the conductive particles, and the conductive particles with the insulating particles are coated. A film is formed in the form of the surface of the body. In a specific aspect of the method for producing conductive particles with insulating particles according to the present invention, the conductive particles having the insulating particles have a hydroxyl group in at least a part of the surface, and the insulating layer is insulated. The hydroxyl group on the surface of the conductive particle body of the particles is reacted with a compound having a hydroxyl group having an alkyl group having 6 to 22 carbon atoms, and is formed to cover the surface of the conductive particle body having the insulating particles. membrane. The anisotropic conductive material of the present invention comprises conductive particles having an insulating particle formed according to the present invention, a binder resin, or a method comprising the production method of the conductive particles with insulating particles of the present invention. Conductive particles with insulating particles and binder resin. The anisotropic conductive material of the present invention is preferably an anisotropic conductive paste. [Effects of the Invention] The conductive particles with insulating particles of the present invention are coated with a film on the surface of the conductive particle body with insulating braids, and the film has a carbon number of 6 to 22 It is formed by the compound of the base, and thus it is difficult to generate rust on the conductive layer. In the method for producing conductive particles with insulating particles according to the present invention, a compound having an alkyl group having a carbon number of 6 to 22 is used on the surface of the conductive particle body having the insulating particles to coat the above. Since the coating film is formed so as to have the surface of the conductive particles of the insulating particles 157831.doc 201213493, it is possible to obtain conductive particles with insulating particles which are less likely to cause rust in the conductive layer. Therefore, the conductive particles with insulating particles of the present invention or the conductive particles with insulating particles obtained by the method for producing conductive particles with insulating particles of the present invention are used. When the connection is made between, the conduction reliability between the electrodes can be improved. Further, the conductive particles with insulating particles of the present invention have a coating adhered to the surface of the conductive particle body having the insulating particles, and are further insulated by a 5% by weight aqueous solution of citric acid. The conductive particles of the particles are treated to peel off the film to obtain a treatment liquid containing the peeled film, and the filtrate obtained by filtering the treatment liquid contains 50 to 10000 ppm of a dish element or a stone element. In the case of this, it is also difficult to generate rust on the conductive layer. Therefore, when the conductive particles having the insulating particles of the present invention are used to connect the electrodes, the conduction reliability between the electrodes can be improved. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the specific embodiments and examples of the invention. (Electrically conductive particle body with insulating particles) In Fig. 1, conductive particles with insulating particles attached to the first embodiment of the present invention are shown in cross section. The conductive particles with insulating particles shown in Fig. include a conductive particle body 2 with excellent insulating particles, and a coating 3 covering the surface of the conductive particles Ben Zhao 2 with insulating particles. Adhesion of the film 3 (4) Insulation 157831.doc •9· 201213493 The surface of the conductive particle body 2 of the particles. The film 3 covers the entire surface of the conductive particle body 2 to which the insulating particles are attached. The conductive particle main body 2 with insulating particles is provided with conductive particles 11 and a plurality of insulating particles 15 attached to the conductive particles. The insulating particles 15 are formed of a material having an insulating property. The film 3 covers the surface of the conductive particles and the surface of the insulating particles 15. The portion of the film 3 covering the surface of the conductive particles U is connected to the portion of the film 3 covering the surface of the insulating particles 15. Conductive particles 11 The substrate particle 12 has a conductive layer 13 provided on the surface of the substrate particle 12. The conductive layer 13 covers the surface of the substrate particle 12. The surface of the conductive particle 11-based substrate particle 丨2 is covered by the conductive layer 13. The coated particles are coated. The conductive particles U have a conductive layer 13 on the surface. In Fig. 2, the conductive particles with insulating particles according to the second embodiment of the present invention are shown in cross section. The conductive particles 21 with insulating particles are provided with a conductive particle body 22 with insulating particles and a coating film 23 covering the surface of the conductive particle body 22 with insulating particles. The film 23 is attached. The surface of the conductive particle body 22 to which the insulating particles are attached is provided. The conductive particle body 22 with the insulating particles is provided with the conductive particles 31 and a plurality of insulating particles 15 attached to the surface of the conductive particles 31. ° Cover 23 The surface of the conductive particles 31 and the surface of the insulating particles 15 are covered. The portion of the film 23 covering the surface of the conductive particles 31 is connected to the portion of the film 23 covering the surface of the insulating particles 15. 157831.doc •10 201213493 The conductive particles 31 have a substrate particle 12 and a conductive layer 32 provided on the surface of the substrate particle 12. The conductive particle 31 has a plurality of core materials 33 on the surface of the substrate particle 12. The conductive layer 32 is provided. The substrate particles 12 and the core material 33 are coated. Since the conductive layer 32 covers the core material 33, the conductive particles 31 have a plurality of protrusions 34 on the surface. The surface of the conductive layer 32 is embossed by the core material 33, and a plurality of layers are formed. In the third embodiment of the present invention, the electrically conductive particles with insulating particles according to the third embodiment of the present invention are shown in Fig. 3. The electrically conductive particles 41 with insulating particles shown in Fig. 3 are provided with: a conductive particle body 42 having insulating particles, and a coating film 3 covering the surface of the conductive particle body 42 with insulating particles. The conductive particle body 42 with insulating particles is provided with conductive particles 11 and Attached to A plurality of insulating particles 45 on the surface of the conductive particles 11. In other words, the conductive particles 41 with insulating particles are formed in the same manner as the conductive particles 1 with insulating particles, except that the insulating particles are different. The conductive particle body 42 of the insulating particles is configured in the same manner as the conductive particle body 2 with the insulating particles. The insulating particles 45 have an insulating particle body 45a and a surface covering the insulating body 14a and a south molecule. The layer 45b formed of the compound can appropriately improve the adhesion of the insulating particles 45 to the conductive particles 11 by the presence of the layer 45b. The layer 45b covers the entire surface of the insulating particle body 45a. Therefore, the layer 45b is disposed between the conductive particles 11 and the insulating particle body 45a. The layer 45b may be formed so as to cover at least a part of the surface of the insulating particle body. The entire surface of the particle body. A preferred ruthenium layer 45b is disposed between the conductive particles and the body of the insulating particles. Fig. 4 is a cross-sectional view showing conductive particles with insulating particles according to a fourth embodiment of the present invention. The conductive particles 61 to which the insulating particles are not attached in Fig. 4 include an insulating particle body 62 and a coating film 23 covering the surface of the conductive particle body 62 to which the insulating particles are attached. The film 23 is attached to the surface of the conductive particle body 62 to which the insulating particles are attached. The conductive particle body 62 with insulating particles includes conductive particles 71 and a plurality of insulating particles 15 attached to the surface of the conductive particles 71. The conductive particles 71 have substrate particles 12 and a substrate. A conductive layer 76 is provided on the surface of the particle 12. The conductive layer 76 has a first conductive layer 76a provided on the surface of the substrate particle 12, and a second conductive layer 76b provided on the surface of the first conductive layer 76a. The conductive particles 71 have a plurality of core materials 33 on the surface of the first conductive layer 76a. The second conductive layer 76b covers the first conductive layer 76a and the dopant 33. The substrate particles 12 and the core material 33 are arranged at intervals. The first conductive layer 76a is present between the substrate particles 12 and the core material 33. Since the second conductive layer 76b covers the core material 33, the conductive particles 71 have a plurality of protrusions 77 on the surface. The surface of the conductive layer 76 and the second conductive layer 76b is raised by the core material 33, and a plurality of protrusions 77 are formed. Preferably, the surface of the conductive particle bodies 2, 22, 42, 62 with insulating particles is covered by a film 3, 23 having carbon 157831.doc •12·8 201213493 It is formed by a compound of 6 to 22 alkyl groups. Thereby, it becomes difficult to produce a recording on the conductive layers 13, 32 76 of the conductive particles 1, 21, 41, and 61 to which the insulating particles are attached. The coatings 3 and 23 impart an anti-rust effect. Therefore, the conductivity of the conductive particles in the conductive particles with the insulating particles is increased, and high conductivity can be maintained over a long period of time. Therefore, when the electrodes are connected using the conductive particles i, 21, 41, and 61 with the insulating particles, the conduction reliability can be improved. Also, it is preferred to use 5 weights. /. The citric acid aqueous solution treats the conductive particles B, 21, 41, and 61 with insulating particles, and peels off the coatings 3 and 23 to obtain a treatment liquid containing the peeled coatings 3 and 23, and then treats the treatment. The filtrate obtained by filtering the liquid contains 5 〇 to 1 〇〇〇〇叩m of the element or 矽 7L of the element. Thereby, it becomes difficult to generate rust on the conductive layers 13, 32, and 76 of the conductive particles 1, 21, 41, and 61 to which the insulating particles are attached. Therefore, the conductivity of the conductive particles in the conductive particles with the insulating particles is increased, and high conductivity can be maintained over a long period of time. Therefore, when the electrodes are connected by using the conductive particles 丨, 21, 41, and 61 with insulating particles, the conduction reliability can be improved. Further, from the viewpoint that it is further difficult to generate rust in the conductive layer, it is preferred that the conductive particles 1, 21, 41, and 61 with insulating particles are treated with a 5% by weight aqueous citric acid solution. After the coating films 3 and 23 are peeled off and the treatment liquid containing the peeled coatings 3 and 23 is obtained, the treatment liquid is filtered to obtain a phosphorus element of 5 〇 to 1 〇〇〇〇 ppm. From the viewpoint that it is difficult to generate rust in the conductive layer from the further step, it is preferred to pass the conductive particles with insulating particles with a 5 s % aqueous solution of citric acid 15783I.doc • 13-201213493 1, 21, 41, and 61 are treated to peel off the coatings 3 and 23, and the treatment liquid containing the peeled coatings 3 and 23 is obtained, and the filtration liquid obtained by filtering the treatment liquid contains 50 to 10000 ppm of ruthenium element. . The content of the lanthanum element or the phosphorus element in the above filtrate is more preferably 1 〇〇 ppm or more, more preferably 5000 ppm or less, and still more preferably 1 〇〇〇 ppm or less. The content of the above phosphorus element and cerium element can be measured using an ICP luminescence analyzer. As a commercial item of the ICP luminescence analyzer, "ULTIMA2" manufactured by Horiba, Ltd., and the like can be cited. In the case of the conductive particles i, 21, 41, and 61 having the insulating particles coated with the coatings 3 and 23, the content of the breaking element and the cerium element is usually determined by the coatings 3 and 23. That is, the content of the above-mentioned phosphorus element and the above-mentioned lanthanum element means the ratio of the phosphorus element and the lanthanum element in the coating films 3 and 23. Preferably, the films 3, 23 are attached to the surface of the conductive particles 2, 22, 42, 62 to which the insulating particles are attached. In the conductive particles 1, 21, 41, and 61 with insulating particles, it is preferable that the coatings 3 and 23 cover the entire surface of the conductive particles 2, 22, 42, and 62 to which the insulating particles are attached. Further, it is not necessary for the coating films 3 and 23 to cover the entire surface of the conductive particle bodies 2, 22, 42, and 62 to which the insulating particles are attached. Since the coatings 3, 23 cover at least a part of the surface of the conductive layers 13, 32, 76, the rust of the conductive layers 23, 32, 76 can be suppressed in the portions where the coatings 3, 23 are formed. Further, 'the insulating particles 15 and 45 become difficult to form from the surface of the conductive particles 11, 31, 71 in the conductive particles 1, 21, 41, and 61 with the insulating particles present due to the presence of the coatings 3 and 23. Get rid of. For example, when the conductive particles 丨, 21, 41, and 61 containing the 156831.doc 201213493 rim particles are added to the binder resin and kneaded, the insulating particles 15 and 45 are less likely to be self-conductive particles n and 31. The surface of 71 is detached. Further, when a plurality of conductive I·green particles 1, 21, 41, and 61 having insulating particles are in contact with each other, the insulating particles 15 and 45 are hard to be self-contained from the surfaces of the conductive particles u, 31, and 71 due to the impact at the time of contact. Get rid of. Therefore, when the conductive particles 丨, 21, 41, and 61 with the insulating particles are used for the connection between the electrodes, the insulating particles 15 and 45 are present between the adjacent conductive particles 11, 31, and 71. It is difficult to electrically connect between adjacent electrodes that cannot be connected. Hereinafter, the details of the coatings 3 and 23 and the details of the conductive particle bodies 2, 22, 42, and 62 to which the insulating particles are attached will be described. [Coated film] In order to make it difficult to generate rust on the conductive layer, it is preferred that the film be formed of a compound having an alkyl group having 6 to 22 carbon atoms (hereinafter also referred to as Compound A). When the carbon number of the above alkyl group is less than 6, it becomes easy to cause rust on the surface of the conductive layer. When the carbon number of the alkyl group exceeds 22, the conductivity of the conductive particles with the insulating particles is lowered. From the viewpoint of further improving the conductivity of the conductive particles having the insulating particles, it is preferred that the alkyl group of the compound A has a carbon number of 16 or less. The above alkyl group may have a linear structure or a branched structure. It is preferred that the above alkyl group has a linear structure. The above compound A is not particularly limited as long as it has an alkyl group having a carbon number of 6 to 22. The above compound A is preferably an oleic acid vinegar selected from the group consisting of a disc acid @θ or a salt thereof having an alkyl group having a carbon number of 6 to 22 and having a carbon number of 6 to 22 or a 157831.doc •15 · 201213493 salt, alkoxy decane having an alkyl group having 6 to 22 carbon atoms, alkyl mercaptan having a carbon number of 6 to 22, and dialkyl having an alkyl group having 6 to 22 carbon atoms At least one of the groups consisting of bismuth sulfonium. That is, the above compound a having a carbon group of 6 to 22 is preferably selected from the group consisting of a structuring acid ester or a salt thereof, a phosphite or a salt thereof, an alkoxydecane, an alkylthiol and a dialkyl group. At least one of the group consisting of disulfides. By using these preferred compounds A, it is further difficult to produce rust on the conductive layer. The compound A is preferably at least selected from the group consisting of the above-mentioned acid ester or a salt thereof, a phosphite or a salt thereof and an alkoxydecane, and more preferably, from the viewpoint of further rust-prone rust generation. At least one of the above-mentioned phosic acid ester or a salt thereof and a sulfite acid ester or a salt thereof. The above-mentioned compound A may be used alone or in combination of two or more. It is preferred that the above compound A has a reactive functional group reactive with conductive particles. It is preferred that the above compound A has a reactive functional group reactive with insulating particles. Preferably, the film is chemically bonded to the conductive particles in the form of insulating particles. Preferably, the film is chemically bonded to the conductive particles. Preferably, the film is chemically bonded to the insulating particles. More preferably, the coating is chemically bonded to the conductive particles and the insulating particles. Due to the above reactivity and the above chemical bonding, it becomes difficult to form a coating.
作為上述具有碳數為6〜22之烧基之鱗酸自旨或其鹽例如 官能基之存在,以石 膜之剝離。其結果, 可列舉:磷酸己基酯、麟 單壬基酯、磷酸單癸基酯 、磷酸庚基酯、磷酸單辛基酯、磷酸 !·酯、碌酸單十一貌基酯、破酸單十 157831.doc 201213493 二烷基酯、鱗酸單十三烷基酯、磷酸單十四烷基酯、填酸 單十五烷基酯、磷酸單己基酯單鈉鹽、磷酸單庚基酯單鈉 鹽、磷酸單辛基酯單鈉鹽、磷酸單壬基酯單鈉鹽、磷酸單 癸基酯單鈉鹽、磷酸單十一烧基酯單鈉鹽、磷酸單十二烷 基酯單鈉鹽、磷酸單十三烷基酯單鈉鹽、磷酸單十四烷基 酯單鈉鹽及磷酸單十五烷基酯單鈉鹽等。亦可使用上述磷 酸酯之钟鹽。 作為上述具有碳數為6〜22之烷基之亞磷酸酯或其鹽’例 如可列舉亞磷酸己基酯、亞磷酸庚基酯、亞磷酸單辛基 酯、亞碟酸單壬基酯、亞鱗酸單癸基酯、亞鱗酸單十一院 基酯、亞磷酸單十二院基酯、亞鱗酸單十三烧基酯、亞鱗 酸單十四烷基酯、亞磷酸單十五烷基酯、亞磷酸單己基酯 單鈉鹽、亞磷酸單庚基酯單鈉鹽、亞磷酸單辛基酯單鈉 鹽、亞磷酸單壬基酯單鈉鹽、亞磷酸單癸基酯單鈉鹽、亞 磷酸單十一烷基酯單鈉鹽、亞磷酸單十二烷基酯單鈉鹽、 亞磷酸單十三烷基酯單鈉鹽、亞磷酸單十四烷基酯單鈉鹽 及亞磷酸單十五烷基酯單鈉鹽等。亦可使用上述亞磷酸酯 之鉀鹽。 作為上述具有碳數為6〜22之烷基之烷氧基矽烷,例如可 列舉己基三甲氧基矽烷、己基三乙氧基矽烷、庚基三甲氧 基石夕烧、庚基三乙氧基矽烷、辛基三甲氧基矽烷、辛基三 乙氧基石夕烧、壬基三曱氧基矽烷、壬基三乙氧基矽烷、癸 基三甲氧基矽烷、癸基三乙氧基矽烷、十一烷基三甲氧基 梦烧、十一院基三乙氧基矽烷、十二烷基三甲氧基矽烷、 157831.doc •17- 201213493 十二烷基三乙氧基矽烷、十三烷基三甲氧基矽烷、十三烷 基三乙氧基矽烷、十四烷基三甲氧基矽烷、十四烷基三乙 氧基矽烷、十五烷基三甲氧基矽烷及十五烷基三乙氧基矽 烷等。 作為上述具有碳數為6〜22之烷基之烷基硫醇,例如可列 舉己基硫醇、庚基硫醇、辛基硫醇、壬基硫醇、癸基硫 醇、十一烷基硫醇、十二烷基硫醇、十三烷基硫醇、十四 烷基硫醇、十五烷基硫醇及十六烷基硫醇等。上述烷基硫 醇較佳的是於炫基鏈之末端具有疏基。 作為上述具有碳數為6〜22之烷基之二烷基二硫醚,例如 可列舉二己基二硫醚、二庚基二硫醚、二辛基二硫醚、二 壬基二硫醚、二癸基二硫醚、二·十一烷基二硫醚、二-十 院基一硫ϋ 一-十二院基二硫驗、二-十四院基二硫 醚一-十五烧基二硫喊及二-十六烧基二硫趟等。 [附有絕緣性粒子之導電性粒子本體] 上述導電性粒子若至少於表面具有導電層即可。導電性 粒子可為具有基材粒子及於基材粒子之表面上所設之導電 層的導電性粒子’亦可為全體為導電層之金屬粒子。其 中,自減低成本,提高導電性粒子之柔軟性而提高電極間 之導通可靠性之觀點考慮’較佳的是具有基材粒子及於基 材粒子之表面上所設之導電層的導電性粒子。 作為上述基材粒子,可列舉樹脂粒子、無機粒子、有機 無機混合粒子及金屬粒子等。 上述基材粒子較佳的是由樹脂所形成之樹脂粒子。於使 157831.doc 201213493 用附有絕緣性粒子之導電性粒子而對電極間進行連接時, 將附有絕緣性粒子之導電性粒子配置於電極間,其後進行 壓接而使附有絕緣性粒子之導電性粒子壓縮。若基材粒子 為樹脂粒子,則於上述壓接時導電性粒子容易變形,且可 增大導電性粒子與電極之接觸面積。因此,可提高電極間 之導通可靠性。 作為用以形成上述樹脂粒子之樹脂,例如可列舉聚稀烴 樹脂、丙烯酸樹脂、酚樹脂、三聚氰胺樹脂、笨代三聚氮 胺樹脂、脲樹脂、環氧樹脂、不飽和聚酯樹脂、飽和聚醋 樹脂、聚對苯二甲酸乙二酯、聚砜、聚苯醚、聚縮路、聚 醢亞胺、聚醯胺醯亞胺、聚醚醚酮及聚醚砜等。為了可容 易地將基材粒子之硬度控制為適宜之範圍,用以形成上述 樹脂粒子之樹脂較佳的是使1種或2種以上之具有乙稀性不 飽和基之聚合性單體聚合而成之聚合物。 作為用以形成上述無機粒子之無機物,可列舉二氧化石夕 及碳黑等。作為上述有機無機混合粒子,例如可列舉藉由 交聯之坑氧基碎烧基聚合物與丙稀酸樹脂而形成之有機無 機混合粒子等。 於上述基材粒子為金屬粒子之情形時,作為用以形成該 金屬粒子之金屬,可列舉銀、銅、鎳、矽、金及鈦等。 用以形成上述導電層之金屬並無特別之限定。進而,於 導電性粒子係全體為導電層之金屬粒子之情形時,用以形 成該金屬粒子之金屬並無特別之限定。作為該金屬,例如 可列舉金、銀、鈀、銅、鉑、鈀、鋅、鐵、錫 '鉛、鋁、 157831.doc •19· 201213493 姑、銦、鎳、鉻、鈦、銻、鉍、鉈、鍺、鎘、矽及該等之 合金等。又,作為上述金屬,可列舉摻雜 (曝焊锡等。,中,為了可更進一步降低電丄: 接電阻,較佳的是包含錫之合金、鎳、鈀、銅或金,較佳 的是錄或纪。 於構成上述導電層之金屬中越容易產⑽,則越顯著地 獲得上述覆膜之包覆效果。於由鎳、銅或錫而形成之導電 層中,於導電層之表面比較容易產生銹。藉由以覆膜而包 覆此種導電層之表面,可有效地抑制於導電層之表面產生 銹。為了有效地獲得上述覆膜之包覆效果,上述導電層亦 可包含錄、銅或锡。 再者,於導電層之表面,多由於氧化而存在氫氧根。一 般情況下’於由鎳所形成之導電層之表面,由於氧化而存 在氫氧根。此種具有氫氧根之導電層與覆膜化學鍵結。 上述導電層由1層而形成。導電層亦可由複數層而形 成。亦即,導電層亦可具有2層以上之積層結構。於導電 層由複數層而形成之情形時,最外層較佳的是金層鎳 層、鈀層、銅層或包含錫與銀之合金層,更佳的是金層。 於最外層係該等之較佳之導電層之情形時,可更進一步降 低電極間之連接電阻。又,於最外層為金層之情形時,可 更進一步提高耐腐蝕性。 於上述基材粒子之表面形成導電層之方法並無特別之限 疋。作為形成導電層之方法,例如可列舉:利用無電鍍之 方法、利用電鍍之方法、利用物理蒸鍍之方法、亦即將金 157831 .doc 201213493 1表::二含金屬粉末與黏合劑之焊錫膏塗佈於基材粒子 之表面之方法等。装由 刊租于 a&mr,為了簡便地形成導電層,較佳的 是利用無電鍍之方法敉隹的 列舉真-暴餹施 料上述利用物理蒸鍍之方法,可 舉真工蒸链、離子電鍵及離子濺鍍等方法。 内上ίΓ性粒子之平均粒徑較佳的是〇.5〜100师之範圍 2〇 粒子之平均粒徑更佳的是1 μ威上,更佳的是 _以下。若導電性粒子之平均粒徑為上述下限以上及 述上限以下’則於使用附有絕緣性粒子之導電性粒子而 ί電極間進行連接之情形時,可充分增大導電性粒子與電 極之接觸面積,且於形成導電層時變得難以形成凝聚之導 電h粒子又,經由導電性粒子而連接之電極間之間隔並 不過於變大,且導電層變得難以自基材粒子之表面剝離。 上述導電性粒子之「平均粒徑」係表示算數平均粒徑。 導電性粒子之平均粒徑係藉由電子顯微鏡或光學顯微鏡而 觀察50個任意之導電性粒子,算出平均值而求出。 上述導電層之厚度較佳的是0.005〜1 μπι之範圍内。導電 層之厚度更佳的是0.01 μιη以上,更佳的是〇 3㈣以下。若 導電層之厚度為上述下限以上及上述上限以下則可獲得 充分之導電性,且導電性粒子並不過於變硬地於電極間之 連接時使導電性粒子充分地變形。 於上述導電層由複數層而形成之情形時,最外層之導電 層之厚度、特別是最外層為金層之情形時金層之厚度較佳 的是0.001〜0.5 μπι之範圍内。上述最外層之導電層之厚度 之更佳之下限為〇.〇1 μιη,更佳之上限為〇.1 μιη。若上述最 157831.doc -21- 201213493 外層之導電層之厚度為上述下限以上及上述上限以下則 可使最外層之導電層之包覆均一,可充分提高对腐钱性, 且可充分降低電極間之連接電阻。又,上述最外層為金層 之情形時的金層之厚度越薄,則成本越變低。 上述導電層之厚度例如可藉由使用穿透式電子顯微鏡 (TEM) ’對導電性粒子或附有絕緣性粒子之導電性粒子之 剖面進行觀察而測定。 導電性粒子較佳的是於導電層之表面具有突<,較佳的 疋該突起為複數個。於藉由附有絕緣性粒子之導電性粒子 而進行連接之電極之表面’多形成有氧化覆膜。於使用於 導電層之表面具有突起之附有絕緣性粒子之導電性粒子之 情形時,可藉由於電極間配置導電性粒子而進行壓接,藉 由突起而有效地排除上述氧化覆膜。因此,可使電極與導 電層更進一步確實地接觸,可減低電極間之連接電阻。進 而’於電極間之連接時,可藉由導電性粒子之突起而有效 地排除導電性粒子與電極之間的絕緣性粒子。因此,可提 高電極間之導通可靠性。 作為於導電性粒子之表面形成突起之方法,可列舉·使 芯物質附著於基材粒子之表面後,藉由無電鑛而形成導電 層之方法;以及藉由無電鍵而於基材粒子之表面形成導電 層後,使芯物質附著於其上,進而藉由無電鍍而形成導電 層之方法等。 作為使芯物質附著於基材粒子之表面之方法,例如可列 舉:於基材粒子之分散液中添加成為芯物質之導電性物 157831.doc -22· 201213493 質’藉由例如凡得瓦力而使芯物質積體、附著於基材粒子 之表面之方法,·以及於放入有基材粒子之容器中添加成為 芯物質之導電性物質,藉由容器之旋轉等之機械性作用而 使芯物質附著於基材粒子之表面的方法等。其中,為了容 易控制所附著之芯物質之量’較佳的是使芯物質積體、: 著於分散液中之基材粒子之表面的方法。 上述導電性粒子亦可於基材粒子之表面上具有第丨導電 層’且於該第1電層上具有第2導電層。於此情形時,亦 可使芯物質附著於第i導電層之表面。芯物質較佳的是由 第2導電層而包覆。上述第1導電層之厚度較佳的是 〇·05〜〇·5μπ^範圍内。導電性粒子較佳的是藉由如下方式 而獲得:於基材粒子之表面上形成第1電層其次使芯 物質附著於該第!導電層之表面上後,於第】導電層及芯物 質之表面上形成第2導電層。 作為構成上述芯物質之導電性物質,例如可列舉金屬、 金屬之氧化物、石墨等導電性非金屬及導電性聚合物等。 作為導電性聚合物,可列舉聚乙块等。其中,為了提高導 電性’較佳的是金屬。 L作為上述金屬’例如可列舉金、銀、銅、鉑、鋅、鐵、 厘錫#8、銘、銦、鎳、鉻、欽、録、叙 '錯及録等金 ’以及錫-錯合金、錫鋼合金、錫-銀合金及錫-錯-銀合 金等由2種以上金屬所構成之合金等。其中較佳的是錄、 鋼銀或金。構成上述芯物質之金屬可與構成上述導電層 之金屬相同,亦可不同。 157831.doc -23- 201213493 上述芯物質之形狀並無特別之限定。芯物質之形狀較佳 的是塊狀。作為芯物質’例如可列舉粒子狀之塊、複數個 微小粒子凝聚而成之凝聚塊、及不定形之塊等。 上述絕緣性粒子係具有絕緣性之粒子。絕緣性粒子較導 電性粒子更小。若使用附有絕緣性粒子之導電性粒子對電 極間進行連接’則可藉由絕緣性粒子而防止鄰接之電極間 之短路。具體而言,於複數個附有絕緣性粒子之導電性粒 子接觸時,於複數個附有絕緣性粒子之導電性粒子中之導 電性粒子間存在有絕緣性粒子,因此可防止並非上下之電 極間’而是於橫方向上鄰接之電極間之短路。再者,於電 極間之連接時,藉由以2個電極對附有絕緣性粒子之導電 性粒子進行加壓,可容易地排除於導電層與電極之間的絕 緣性粒子。於導電性粒子之表面設有突起之情形時,可更 進一步容易地排除導電層與電極之間的絕緣性粒子。 作為構成上述絕緣性粒子之材料,可列舉絕緣性樹脂、 及絕緣性無機物等。作為上述絕緣性樹脂,可列舉作為用 以形成可用作基材粒子之樹脂粒子的樹脂而列舉之上述樹 脂。作為上述絕緣性之無機物,可列舉作為用以形成可用 作基材粒子之無機粒子的無機物而列舉之上述無機物。 作為上述絕緣性粒子之材料的絕緣性樹脂之具體例可 列舉聚烯烴類、(甲基)丙烯酸酯聚合物、(甲基)丙烯酸酯 共聚物、嵌段聚合物、熱塑性樹脂、熱塑性樹脂之交聯 物、熱硬化性樹脂及水溶性樹脂等。 作為上述聚烯烴類’可列舉聚乙烯、乙烯_乙酸乙烯酯 157831.doc •24· 201213493 共聚物及乙烯-丙烯酸酯共聚物等。作為上述(甲基)丙烯酸 酯聚合物’可列舉聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸 乙酯及聚(甲基)丙烯酸丁酯等。作為上述嵌段聚合物可 列舉聚笨乙稀、苯乙烯-丙稀酸酯共聚物、SB型苯乙稀丁 二烯嵌段共聚物、及SBS型苯乙烯-丁二烯嵌段共聚物、以 及該等之氫化物等。作為上述熱塑性樹脂,可列舉乙烯系 聚合物及乙烯系共聚物等。作為上述熱硬化性樹脂可列 舉環氧樹脂、酚樹脂及三聚氰胺樹脂等。作為上述水溶性 樹脂’可列舉聚乙烯醇、聚丙烯酸、聚丙烯酿胺、聚乙烯 吡咯啶酮、聚環氧乙烷及甲基纖維素等。其中,較佳的是 水溶性樹脂’更佳的是聚乙烯醇。 自更進一步提高熱壓接時之絕緣性粒子之脫離性之觀點 考慮,較佳的是絕緣性粒子包含無機粒子,較佳的是二氧 化梦粒子。於絕緣性粒子於表面並不具有由上述高分子化 合物所形成之層之情料,較佳的是絕緣性粒子為無機粒 子,較佳的是二氧化矽粒子。於使用絕緣性粒子本體之表 面覆蓋有由上述高分子化合物所形成之層的絕緣性粒子之 情形時’ &佳的是絕緣性粒子本體為無機粒+,較佳的是 二氧化矽粒子。作為上述無機粒子,可列舉白砂粒子、羥 碌石灰粒子、氧化鎂粒子、氧化錯粒子及二氧化碎粒子 更進步長1尚熱壓接時之絕緣性粒子之脫離性之觀 :考慮’較佳的是上述絕緣性粒子包含無機粒子,較佳的 述無機粒子為二氧化矽粒子。作為二氧化矽粒子,可 舉粉碎一氧切、球形二氧化梦較佳的是使用球形二 157831.doc -25· 201213493 氧化石夕。又’二氧化梦粒子較佳的是於表面具有例如叛 基、經基等可化學鍵結之官能基,更佳的是具有經基。無 機粒子比較硬,特別是二氧化矽粒子比較硬。於使用具有 此種硬的絕緣性粒子之附有絕緣性粒子之導電性粒子本體 之情形時,於對附有絕緣性粒子之導電性粒子本體與黏合 樹脂進行混練時,硬的絕緣性粒子容易自導電性粒子之表 面脫離。然而,於使用本發明之附有絕緣性粒子之導電性 粒子之情形時,即使使用硬的絕緣性粒子,亦可於上述混 練時抑制硬的絕緣性粒子自覆膜脫離。藉由上述高分子化 合物而形成之層例如起到作為柔軟層之作用。 作為由上述高分子化合物所形成之層中的高分子化合物 或藉由聚合等而成為該高分子化合物之化合物較佳的是 具有可聚合之反應性官能基的化合物。該可聚合之反應性 官能基較佳的是不飽和雙鍵。例如,可於絕緣性粒子本體 之表面上使具有不飽和雙鍵之化合物(成為高分子化合物 之化合物)進行聚合反應,且亦可使高分子化合物與絕緣 性粒子本體之表面之反應纟官能基反冑。作為上述高分子 化合物或成為該高分子化合物之化合物,可列舉具有(甲 基)丙烯醯基之化合物、具有環氧基之化合物及具有乙烯 基之化合物等。於對附有絕緣性粒子之導電性粒子進行分 散時等,自抑制絕緣性粒子自導電性粒子之表面脫離之觀 點考慮’較佳的是上4高分子化合物或成為該高分子化合 物之化合物具有選自由(甲基)丙烯醯基、縮水甘油基及= 烯基所構成之群之至少丨種反應性官能基。其中自更進 157831.doc ⑧ 201213493 一步抑制絕緣性粒子之脫離之觀點考慮,較佳的是上述高 分子化合物或成為該高分子化合物之化合物具有(甲基)丙 稀酿基。 作為上述具有(甲基)丙稀酿基之化合物之具體例,可列 舉甲基丙烯酸、丙烯酸羥乙酯及乙二醇二甲基酸酯 等。 作為上述環氧化合物之具體例,可列舉雙酚A型環氧樹 脂及間苯二紛縮水甘油醚等。 作為上述具有乙烯基之化合物之具體例,可列舉苯乙烯 及乙酸乙烯酯等。 上述高分子化合物之重量平均分子量較佳的是1〇〇〇以 上。上述高分子化合物之重量平均分子量之上限並無特別 之限疋,較佳的是上述高分子化合物之重量平均分子量為 20000以下。該重量平均分子量表示藉由凝膠滲透層析法 (GPC)而測定之聚苯乙烯換算之值。 於絕緣性粒子之表面形成藉由上述高分子化合物而形成 之層的方法並無特別限定。較佳的是以覆蓋絕緣性粒子本 體之表面之至少一部分區域之方式’使用高分子化合物或 成為高分子化合物之化合物,形成藉由高分子化合物而形 成之層,獲得絕緣性粒子。作為藉由上述高分子化合物而 形成之層的形成方法之一例,可列舉:使具有反應性雙鍵 及羥基之化合物表面與具有乙烯基等反應性官能基之絕緣 性粒子本體於絕緣性粒子本體之表面上進行聚合之方法 等。但是,亦可使用該形成方法以外之方法。 157831.doc •27· 201213493 較佳的是上述絕緣性粒子本體與上述層化學鍵社。談化 學鍵包括共價鍵、氫鍵、離子鍵及配位鍵等。其中,較佳 的是共價鍵,較佳的使用反應性官能基之化學鍵。 作為形成上述化學鍵之反應性官能基,例如可列舉乙稀 基、(甲基)丙烯醯基、矽烷基、矽醇基、綾基、胺基、敍 基、硝基、羥基、羰基、疏基、磺酸基、銃基、硼酸基、 噁唑啉基、吡咯啶酮基、磷酸基及腈基等。其中,較佳的 是乙烯基、(甲基)丙烯醯基。 自更進一步抑制絕緣性粒子之脫離,更進—步提高連接 構造趙之絕緣可靠性之觀點考慮,作為上述絕緣性粒子本 體,較佳的是使用於表面具有反應性官能基之絕緣性粒子 本趙。自更進一步抑制絕緣性粒子之脫離,更進一步提高 連接構造體之絕緣可靠性之觀點考慮,作為上述絕緣性粒 子本體,較佳的是使用使用具有反應性官能基之化合物而 進行了表面處理之絕緣性粒子本體。自更進一步抑制絕緣 性粒子之脫離,更進一步提高連接構造體之絕緣可靠性之 觀點考慮,較佳的是使用於表面具有反應性官能基之上述 絕緣性粒子本體及高分子化合物或成為該高分子化合物之 化合物,使藉由上述高分子化合物而形成之層與上述絕緣 性粒子本體之表面之反應性官能基化學鍵結,由此而獲得 上述絕緣性粒子本體與上述層化學鍵結著的上述絕緣性粒 子。 作為上述絕緣性粒子本體於表面所具有之上述反應性官 能基,可列舉(甲基)丙烯醯基、縮水甘油基、羥基、乙烯 157831.doc 28 ⑧ 201213493 基及胺基等。上述絕緣性粒子本體於表面所具有之上述反 應性官能基較佳的是選自由(甲基)丙烯醯基、縮水甘油 基、經基、乙稀基及胺基所構成之群之至少1種反應性官 能基。 作為用以於上述絕緣性粒子本體之表面導入上述反應性 官能基之化合物(表面處理物質),可列舉具有(甲基)丙烯 醯基之化合物、具有環氧基之化合物及具有乙烯基之化合 物等。 作為用以於上述絕緣性粒子本體之表面導入作為上述反 應性S成基之乙稀基的化合物(表面處理物質),可列舉具 有乙稀基之石夕烧化合物、及具有乙稀基之鈦化合物、及具 有乙稀基之填酸化合物等。上述表面處理物質較佳的是具 有乙烯基之石夕统化合物。作為上述具有乙烯基之石夕烧化合 物,可列舉乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、 乙烯基三乙醯氧基矽烷及乙烯基三異丙氧基矽烷等。 作為用以於上述絕緣性粒子本體之表面導入作為上述反 應性官能基之(甲基)丙烯醯基的化合物(表面處理物質), 可列舉具有(甲基)丙烯醯基之矽烷化合物、及具有(甲基) 丙婦酿基之鈦化合物、及具有(甲基)丙稀醯基之填酸化合 物等。上述表面處理物質較佳的是具有(甲基)丙烯醯基之 石夕烧化合物。作為上述具有(曱基)丙烯醯基之矽烷化合 物’可列舉(甲基)丙烯醯氧基丙基三乙氧基矽烷、(曱基) 丙稀酿氧基丙基三f氧基矽烷及(甲基)丙烯醯氧基丙基二 甲氧基矽烷等。 157831.doc •29· 201213493 上述絕緣性粒子較佳的是並非藉由使用上述絕緣性粒子 本體與南分子化合物或成為該高分子化合物之化合物之混 合所產生之摩擦而形成。又,較佳的是上述絕緣性粒子本 體之表面並非使用混成法而由上述層所包覆。於使用混合 所產生之摩擦或混成法而形成絕緣性粒子之情形時,層變 得容易自絕緣性粒子本體之表面上脫離。又,變得容易於 絕緣性粒子之表面附著混練時所形成之層之破片。因此存 在如下之傾向:於附有絕緣性粒子之導電性粒子的導電層 之表面上附著所脫離之層或層之破片,從而造成連接構造 體之導通可靠性容易降低。因此,自更進一步抑制絕緣性 粒子之脫離,更進一步提高連接構造體之絕緣可靠性及導 通可靠性的觀點考慮,較佳的是並未藉由混合所產生之摩 擦而形成絕緣性粒子’較佳的是並未使用混成法。 於獲得上述絕緣性粒子時,上述高分子化合物或成為該 高分子之化合物相對於上述絕緣性粒子本體1〇〇重量份之 使用量較佳的是30重量份以上,更佳的是50重量份以上, 較佳的是500重量份以下,更佳的是300重量份以下。若上 述高分子化合物之使用量為上述下限以上及上述上限以 下,則可形成良好之層。 作為藉由上述高分子化合物而形成之層的具體製造條件 之一例’可列舉以下之製造條件。 首先’於水等溶劑100〜500重量份中,添加於表面具有 反應性§能基之絕緣性粒子本體1 ~3重量份、具有反應性 雙鍵與羥基之化合物0.1〜20重量份(較佳的是〇1〜1重量 157S31.doc -30· 201213493 的是0.01〜1重量份)、分散 重量份)及熱聚合起始劑 份)、交聯劑0.01〜5重量份(較佳 劑0.1〜5重量份(較佳的是〇The scaly acid having a carbon group of 6 to 22 or the like, or a salt thereof, for example, a functional group, is peeled off by a stone film. As a result, hexyl phosphate, linolenic acid ester, monodecyl phosphate, heptyl phosphate, monooctyl phosphate, phosphoric acid ester, monoester phthalate, and acid-killing acid may be mentioned.十157831.doc 201213493 Dialkyl ester, monotridecyl sulphate, monotetradecyl phosphate, monopentadecyl acid ester, monohexyl phosphate monosodium salt, monoheptyl phosphate mono Sodium salt, monooctyl phosphate monosodium salt, monodecyl phosphate monosodium salt, monodecyl phosphate monosodium salt, monodecyl phosphate monosodium salt, monododecyl phosphate monosodium salt Salt, monotridecyl phosphate monosodium salt, monotetradecyl phosphate monosodium salt and monopentadecyl phosphate monosodium salt. The above-mentioned phosphate salt can also be used. Examples of the phosphite having a carbon number of 6 to 22 or a salt thereof include hexyl phosphite, heptyl phosphite, monooctyl phosphite, and monodecyl sulfite. Monodecyl succinate, sulphate monodecyl ester, sulphate monodecyl ester, sulphate monotridecyl ester, sulphate monotetradecyl citrate, phosphite mono Pentaalkyl ester, monohexyl phosphite monosodium salt, monoheptyl phosphite monosodium salt, monooctyl phosphite monosodium salt, monodecyl phosphite monosodium salt, monodecyl phosphite Monosodium salt, monoundecyl monophosphate of phosphite, monosodium salt of monododecyl phosphite, monosodium salt of monotridecyl phosphite, monosodium monotetradecyl phosphite Salt and monopentadesyl monopentaphosphate and the like. The potassium salt of the above phosphite may also be used. Examples of the alkoxydecane having an alkyl group having 6 to 22 carbon atoms include hexyltrimethoxydecane, hexyltriethoxydecane, heptyltrimethoxycarbazide, and heptyltriethoxydecane. Octyltrimethoxydecane, octyltriethoxyxanthene, decyltrimethoxy decane, decyltriethoxydecane, decyltrimethoxydecane,decyltriethoxydecane,undecane Trimethoxymethane, eleven yards of triethoxydecane, dodecyltrimethoxydecane, 157831.doc •17- 201213493 dodecyltriethoxydecane, tridecyltrimethoxy Decane, tridecyltriethoxydecane, tetradecyltrimethoxydecane, tetradecyltriethoxydecane, pentadecyltrimethoxydecane, and pentadecyltriethoxydecane . Examples of the alkylthiol having an alkyl group having 6 to 22 carbon atoms include hexyl mercaptan, heptyl mercaptan, octyl mercaptan, mercapto mercaptan, mercapto mercaptan, and undecyl sulfur. Alcohol, dodecyl mercaptan, tridecyl mercaptan, tetradecyl mercaptan, pentadecyl mercaptan and cetyl mercaptan. The above alkylthiol preferably has a sulfhydryl group at the end of the thiol chain. Examples of the dialkyl disulfide having an alkyl group having 6 to 22 carbon atoms include dihexyl disulfide, diheptyl disulfide, dioctyl disulfide, and dimercapto disulfide. Dimercapto disulfide, di-undecyl disulfide, di-ten yard based monothiol 1- 12 yards disulfide test, two-fourteen yard disulfide mono-pentadecene Disulfide and di-hexadecyldithiopurine. [Electroconductive particle body with insulating particles] The conductive particles may have a conductive layer at least on the surface. The conductive particles may be conductive particles having a substrate particle and a conductive layer provided on the surface of the substrate particle, or metal particles entirely of a conductive layer. Among them, from the viewpoint of reducing the cost, improving the flexibility of the conductive particles, and improving the conduction reliability between the electrodes, it is preferable that the conductive particles having the substrate particles and the conductive layer provided on the surface of the substrate particles are preferable. . Examples of the substrate particles include resin particles, inorganic particles, organic-inorganic hybrid particles, and metal particles. The substrate particles are preferably resin particles formed of a resin. When 157831.doc 201213493 is used to connect electrodes between conductive particles with insulating particles, conductive particles with insulating particles are placed between the electrodes, and then pressure-bonded to provide insulation. The conductive particles of the particles are compressed. When the substrate particles are resin particles, the conductive particles are easily deformed at the time of the pressure bonding, and the contact area between the conductive particles and the electrode can be increased. Therefore, the conduction reliability between the electrodes can be improved. Examples of the resin for forming the above resin particles include a polyolefin resin, an acrylic resin, a phenol resin, a melamine resin, a stupa triamine resin, a urea resin, an epoxy resin, an unsaturated polyester resin, and a saturated poly Vinegar resin, polyethylene terephthalate, polysulfone, polyphenylene ether, polycondensation, polyimine, polyamidoximine, polyetheretherketone and polyethersulfone. In order to easily control the hardness of the substrate particles to a suitable range, it is preferred that the resin for forming the resin particles polymerize one or two or more kinds of polymerizable monomers having an ethylenically unsaturated group. The polymer. Examples of the inorganic material for forming the inorganic particles include carbon dioxide and carbon black. Examples of the organic-inorganic hybrid particles include organic inorganic mixed particles formed by crosslinking a pit-based oxyalkylene-based polymer and an acrylic resin. In the case where the substrate particles are metal particles, examples of the metal for forming the metal particles include silver, copper, nickel, rhodium, gold, titanium, and the like. The metal for forming the above conductive layer is not particularly limited. Further, in the case where the entire conductive particles are metal particles of the conductive layer, the metal for forming the metal particles is not particularly limited. Examples of the metal include gold, silver, palladium, copper, platinum, palladium, zinc, iron, tin 'lead, aluminum, 157831.doc •19·201213493, indium, nickel, chromium, titanium, lanthanum, cerium, Antimony, bismuth, cadmium, antimony and the like. Further, examples of the metal include doping (exposure soldering, etc.), in order to further reduce the electric enthalpy: the electric resistance, preferably an alloy containing tin, nickel, palladium, copper or gold, preferably The more easily the film (10) is formed in the metal constituting the conductive layer, the more remarkable the coating effect of the film is obtained. In the conductive layer formed of nickel, copper or tin, it is easier on the surface of the conductive layer. Rust is generated. By coating the surface of the conductive layer with a film, rust can be effectively suppressed from occurring on the surface of the conductive layer. In order to effectively obtain the coating effect of the film, the conductive layer may also include Copper or tin. Further, on the surface of the conductive layer, hydroxide is often present due to oxidation. In general, on the surface of the conductive layer formed of nickel, hydroxide is present due to oxidation. The conductive layer of the root is chemically bonded to the coating film. The conductive layer is formed by one layer. The conductive layer may also be formed by a plurality of layers, that is, the conductive layer may have a laminated structure of two or more layers, and the conductive layer is composed of a plurality of layers. In the case of formation Preferably, the outermost layer is a gold layer nickel layer, a palladium layer, a copper layer or an alloy layer containing tin and silver, more preferably a gold layer. In the case where the outermost layer is such a preferred conductive layer, it may be more Further, the connection resistance between the electrodes is further reduced. Further, when the outermost layer is a gold layer, the corrosion resistance can be further improved. The method of forming the conductive layer on the surface of the substrate particles is not particularly limited. Examples of the layer method include: an electroless plating method, a plating method, a physical vapor deposition method, and a gold paste 157831. The method of the surface of the substrate particles, etc. The article is rented from a&mr, and in order to form the conductive layer simply, it is preferable to use the electroless plating method to cite the true-violent application. The method may be a method such as a real steaming chain, an ion bond, or an ion sputtering. The average particle diameter of the inner particles is preferably in the range of 5 to 100 divisions, and the average particle diameter of the particles is better. 1 μ Wei, better When the average particle diameter of the conductive particles is equal to or higher than the lower limit and lower than the upper limit, the conductive particles can be sufficiently increased when the electrodes are connected by using the conductive particles with the insulating particles. The contact area with the electrode, and the conductive h particles which become difficult to form agglomerate when the conductive layer is formed, the interval between the electrodes connected via the conductive particles is not excessively large, and the conductive layer becomes difficult to be self-substrate particles The "average particle diameter" of the conductive particles is an arithmetic mean particle diameter. The average particle diameter of the conductive particles is obtained by observing 50 arbitrary conductive particles by an electron microscope or an optical microscope, and calculating an average value. The thickness of the conductive layer is preferably in the range of 0.005 to 1 μm, and the thickness of the conductive layer is more preferably 0.01 μm or more, and more preferably 〇3 (four) or less. When the thickness of the conductive layer is not less than the above lower limit and not more than the above upper limit, sufficient conductivity can be obtained, and the conductive particles are not sufficiently hardened to sufficiently deform the conductive particles when they are connected between the electrodes. In the case where the above-mentioned conductive layer is formed of a plurality of layers, the thickness of the outermost conductive layer, particularly in the case where the outermost layer is a gold layer, is preferably in the range of 0.001 to 0.5 μm. A more preferred lower limit of the thickness of the outermost conductive layer is 〇.1 μιη, and a more preferred upper limit is 〇.1 μιη. If the thickness of the outermost conductive layer of the above-mentioned 157831.doc -21 - 201213493 is more than the above lower limit and less than the above upper limit, the coating of the outermost conductive layer can be uniform, and the corrosion resistance can be sufficiently improved, and the electrode can be sufficiently reduced. Connection resistance between. Further, the thinner the thickness of the gold layer in the case where the outermost layer is a gold layer, the lower the cost. The thickness of the conductive layer can be measured, for example, by observing a cross section of conductive particles or conductive particles with insulating particles using a transmission electron microscope (TEM). Preferably, the conductive particles have protrusions on the surface of the conductive layer. Preferably, the protrusions are plural. An oxide film is formed on the surface of the electrode to which the conductive particles having the insulating particles are attached. In the case where the conductive particles are provided on the surface of the conductive layer with the conductive particles coated with the insulating particles, the conductive particles are disposed between the electrodes, and the oxide film can be effectively removed by the protrusions. Therefore, the electrode can be further reliably contacted with the conductive layer, and the connection resistance between the electrodes can be reduced. Further, when the electrodes are connected, the insulating particles between the conductive particles and the electrodes can be effectively removed by the protrusions of the conductive particles. Therefore, the conduction reliability between the electrodes can be improved. As a method of forming a protrusion on the surface of the conductive particle, a method of forming a conductive layer by electroless ore after attaching a core substance to a surface of the substrate particle, and a surface of the substrate particle by no electric bond After the conductive layer is formed, a core material is attached thereto, and a conductive layer is formed by electroless plating. As a method of attaching a core material to the surface of the substrate particle, for example, a conductive material to be a core material is added to the dispersion of the substrate particles. 157 831.doc -22 201213493 Further, a method of depositing a core material and adhering to the surface of the substrate particles, and adding a conductive material to be a core material to a container in which the substrate particles are placed is caused by mechanical action such as rotation of the container. A method in which a core substance adheres to the surface of a substrate particle or the like. Among them, in order to easily control the amount of the core material to be attached, it is preferable to integrate the core material with the surface of the substrate particles in the dispersion. The conductive particles may have a second conductive layer on the surface of the substrate particles and a second conductive layer on the first electrical layer. In this case, the core material can also be attached to the surface of the i-th conductive layer. Preferably, the core material is coated by the second conductive layer. The thickness of the first conductive layer is preferably in the range of 〇·05 〇·5 μπ. Preferably, the conductive particles are obtained by forming a first electric layer on the surface of the substrate particle, and then attaching the core material to the surface of the first conductive layer, and then the conductive layer and the core material. A second conductive layer is formed on the surface. Examples of the conductive material constituting the core material include a metal, a metal oxide, a conductive non-metal such as graphite, and a conductive polymer. Examples of the conductive polymer include a polyethylene block and the like. Among them, in order to improve conductivity, metal is preferred. L as the above metal 'for example, gold, silver, copper, platinum, zinc, iron, PCT #8, Ming, indium, nickel, chromium, 钦, 录, 叙's wrong and recorded gold' and tin-alloy An alloy composed of two or more kinds of metals such as a tin steel alloy, a tin-silver alloy, and a tin-wrong-silver alloy. Among them, preferred is steel, steel or gold. The metal constituting the core material may be the same as or different from the metal constituting the above-mentioned conductive layer. 157831.doc -23- 201213493 The shape of the above core material is not particularly limited. The shape of the core material is preferably a block shape. Examples of the core material ' include a particulate block, agglomerates in which a plurality of fine particles are aggregated, and an amorphous block. The insulating particles are insulating particles. The insulating particles are smaller than the conductive particles. When the electrodes are connected by using conductive particles with insulating particles, the short-circuit between the adjacent electrodes can be prevented by the insulating particles. Specifically, when a plurality of conductive particles having insulating particles are in contact with each other, insulating particles are present between the plurality of conductive particles having insulating particles with insulating particles, so that electrodes that are not up and down can be prevented. The 'between' is a short circuit between the adjacent electrodes in the lateral direction. Further, when the electrodes are connected to each other, the conductive particles having the insulating particles are pressed against the two electrodes, whereby the insulating particles between the conductive layer and the electrodes can be easily removed. When the protrusion is provided on the surface of the conductive particles, the insulating particles between the conductive layer and the electrode can be more easily removed. Examples of the material constituting the insulating particles include an insulating resin and an insulating inorganic material. The above-mentioned insulating resin is exemplified as the above-mentioned resin which is used as a resin for forming resin particles which can be used as the substrate particles. The above-mentioned inorganic substance exemplified as the inorganic substance for forming the inorganic particles which can be used as the substrate particles can be mentioned as the insulating inorganic material. Specific examples of the insulating resin as the material of the insulating particles include a polyolefin, a (meth) acrylate polymer, a (meth) acrylate copolymer, a block polymer, a thermoplastic resin, and a thermoplastic resin. A combination, a thermosetting resin, a water-soluble resin, and the like. Examples of the polyolefins include polyethylene, ethylene-vinyl acetate 157831.doc • 24·201213493 copolymer, and ethylene-acrylate copolymer. Examples of the (meth) acrylate polymer' include poly(methyl) acrylate, poly(meth) acrylate, and poly(meth) acrylate. Examples of the block polymer include polystyrene, styrene-acrylic acid ester copolymer, SB-type styrene-butadiene block copolymer, and SBS-type styrene-butadiene block copolymer. And such hydrides and the like. Examples of the thermoplastic resin include a vinyl polymer and an ethylene copolymer. The thermosetting resin may, for example, be an epoxy resin, a phenol resin or a melamine resin. Examples of the water-soluble resin' include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, and methyl cellulose. Among them, preferred is a water-soluble resin, and more preferably polyvinyl alcohol. From the viewpoint of further improving the detachment property of the insulating particles during thermocompression bonding, it is preferred that the insulating particles contain inorganic particles, preferably oxidized dream particles. In the case where the insulating particles do not have a layer formed of the above polymer compound on the surface, it is preferred that the insulating particles are inorganic particles, and preferably cerium oxide particles. In the case where the insulating particles of the layer formed of the polymer compound are coated on the surface of the insulating particle body, it is preferable that the insulating particles are inorganic particles +, preferably cerium oxide particles. Examples of the inorganic particles include white sand particles, hydroxylithium particles, magnesium oxide particles, oxidized particles, and oxidized particles. The detachment property of the insulating particles at the time of thermocompression bonding is considered: The insulating particles include inorganic particles, and preferably the inorganic particles are cerium oxide particles. As the cerium oxide particles, it is preferable to use a spheroidal oxygen-cutting, spherical oxidizing dream. It is preferable to use spherical two 157831.doc -25·201213493. Further, the dioxide dioxide particles preferably have a chemically bondable functional group such as a ruthenium or a thiol group on the surface, and more preferably have a warp group. The inorganic particles are relatively hard, especially the cerium oxide particles are relatively hard. In the case of using a conductive particle body having such insulating particles as the insulating particles, when the conductive particle body with the insulating particles and the binder resin are kneaded, the hard insulating particles are easy. Detach from the surface of the conductive particles. However, when the conductive particles with insulating particles of the present invention are used, even if hard insulating particles are used, the hard insulating particles can be prevented from being detached from the film during the above-mentioned kneading. The layer formed by the above polymer compound functions, for example, as a soft layer. The polymer compound in the layer formed of the above polymer compound or the compound which is a polymer compound by polymerization or the like is preferably a compound having a polymerizable reactive functional group. The polymerizable reactive functional group is preferably an unsaturated double bond. For example, a compound having an unsaturated double bond (a compound which becomes a polymer compound) can be polymerized on the surface of the insulating particle body, and the reaction between the polymer compound and the surface of the insulating particle body can also be carried out. Counterattack. Examples of the polymer compound or a compound which is the polymer compound include a compound having a (meth)acryl fluorenyl group, a compound having an epoxy group, and a compound having a vinyl group. From the viewpoint of suppressing the separation of the insulating particles from the surface of the conductive particles when the conductive particles having the insulating particles are dispersed, it is preferable that the upper polymer compound or the compound which is the polymer compound has At least one of the reactive functional groups of the group consisting of (meth) acryloyl group, glycidyl group and = alkenyl group is selected. From the viewpoint of further suppressing the detachment of the insulating particles in one step, it is preferred that the above-mentioned polymer compound or a compound which is the polymer compound has a (meth) acryl base. Specific examples of the compound having a (meth) propylene-based base include methacrylic acid, hydroxyethyl acrylate, and ethylene glycol dimethyl ester. Specific examples of the epoxy compound include bisphenol A type epoxy resin and m-phenylene diglycidyl ether. Specific examples of the compound having a vinyl group include styrene and vinyl acetate. The weight average molecular weight of the above polymer compound is preferably at least 1 Å. The upper limit of the weight average molecular weight of the polymer compound is not particularly limited, and it is preferred that the polymer compound has a weight average molecular weight of 20,000 or less. The weight average molecular weight represents a value in terms of polystyrene measured by gel permeation chromatography (GPC). The method of forming the layer formed of the above polymer compound on the surface of the insulating particles is not particularly limited. It is preferable to form a layer formed of a polymer compound by using a polymer compound or a compound which is a polymer compound so as to cover at least a part of the surface of the surface of the insulating particle body, thereby obtaining insulating particles. An example of a method for forming a layer formed of the polymer compound is an insulating particle body having a surface of a compound having a reactive double bond and a hydroxyl group and an insulating particle having a reactive functional group such as a vinyl group. A method of performing polymerization on the surface or the like. However, methods other than the formation method can also be used. 157831.doc • 27· 201213493 Preferably, the insulating particle body and the layer chemical bond are used. Chemical bonds include covalent bonds, hydrogen bonds, ionic bonds, and coordination bonds. Among them, a covalent bond is preferred, and a chemical bond of a reactive functional group is preferably used. Examples of the reactive functional group forming the above chemical bond include an ethylene group, a (meth)acryl fluorenyl group, a decyl group, a decyl group, a fluorenyl group, an amine group, a succinyl group, a nitro group, a hydroxyl group, a carbonyl group, and a thiol group. Sulfonic acid group, mercapto group, boric acid group, oxazolinyl group, pyrrolidinone group, phosphoric acid group and nitrile group. Among them, a vinyl group or a (meth) acrylonitrile group is preferred. From the viewpoint of further suppressing the detachment of the insulating particles and further improving the insulation reliability of the connection structure, it is preferable that the insulating particle body is used for an insulating particle having a reactive functional group on the surface. Zhao. From the viewpoint of further suppressing the detachment of the insulating particles and further improving the insulation reliability of the bonded structure, it is preferred that the insulating particle body is surface-treated using a compound having a reactive functional group. Insulating particle body. From the viewpoint of further suppressing the detachment of the insulating particles and further improving the insulation reliability of the bonded structure, it is preferable to use the insulating particle body and the polymer compound having a reactive functional group on the surface or to be high. a compound of a molecular compound, wherein a layer formed by the polymer compound is chemically bonded to a reactive functional group on a surface of the insulating particle body, thereby obtaining the insulating material in which the insulating particle body and the layer are chemically bonded Sex particles. Examples of the reactive functional group which the insulating particles are mainly present on the surface include (meth)acryl fluorenyl group, glycidyl group, hydroxyl group, ethylene 157831.doc 28 8 201213493 group, and an amine group. The reactive functional group which is present on the surface of the insulating particles is preferably at least one selected from the group consisting of a (meth) acryl fluorenyl group, a glycidyl group, a trans group, an ethylene group, and an amine group. Reactive functional group. Examples of the compound (surface-treating substance) for introducing the reactive functional group on the surface of the insulating particle main body include a compound having a (meth)acryl fluorenyl group, a compound having an epoxy group, and a compound having a vinyl group. Wait. Examples of the compound (surface-treating material) for introducing the ethylene group as the reactive S-form on the surface of the insulating particle main body include a silicon-based compound having a vinyl group and titanium having a vinyl group. a compound, an acid-filling compound having a vinyl group, and the like. The above surface treating material is preferably a compound having a vinyl group. Examples of the above-mentioned vinyl group-containing compound include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl triethoxy decane, and vinyl triisopropoxy decane. The compound (surface-treating substance) which introduces the (meth)acryl fluorenyl group which is the above-mentioned reactive functional group on the surface of the said insulating particle main body, the decane compound which has a (meth) acryl A (meth) propylene-based titanium compound, and an acid-filled compound having a (meth) acrylonitrile group. The above surface-treating substance is preferably a sulphur-burning compound having a (meth) acrylonitrile group. Examples of the decane compound having a (fluorenyl) acrylonitrile group include (meth) propylene oxypropyl triethoxy decane, (fluorenyl) propylene oxypropyl tri-foxy decane and ( Methyl) propylene methoxy propyl dimethoxy decane or the like. 157831.doc • 29· 201213493 It is preferable that the insulating particles are formed not by friction generated by mixing the main body of the insulating particles with a compound of a south molecular compound or a compound which is a polymer compound. Further, it is preferable that the surface of the insulating particle body is not covered by the layer by a mixing method. In the case where insulating particles are formed by friction or mixing by mixing, the layer becomes easily detached from the surface of the insulating particle body. Further, it is easy to adhere to the fragments of the layer formed at the time of kneading on the surface of the insulating particles. Therefore, there is a tendency that the detached layer or the layer of the layer is adhered to the surface of the conductive layer on which the conductive particles of the insulating particles are attached, and the conduction reliability of the bonded structure is liable to be lowered. Therefore, from the viewpoint of further suppressing the detachment of the insulating particles and further improving the insulation reliability and the conduction reliability of the connection structure, it is preferable that the insulating particles are not formed by the friction generated by the mixing. The best is that the blending method is not used. When the insulating particles are obtained, the polymer compound or the compound which is the polymer is preferably used in an amount of 30 parts by weight or more, more preferably 50 parts by weight, per part by weight of the insulating particles. The above is preferably 500 parts by weight or less, more preferably 300 parts by weight or less. When the amount of the polymer compound used is at least the above lower limit and below the upper limit, a favorable layer can be formed. An example of the specific production conditions of the layer formed by the above polymer compound is exemplified by the following production conditions. First, it is added to 100 to 500 parts by weight of a solvent such as water, and is added in an amount of 1 to 3 parts by weight based on the surface of the insulating particles having a reactive carbon atom, and 0.1 to 20 parts by weight of a compound having a reactive double bond and a hydroxyl group. 〇1~1 weight 157S31.doc -30·201213493 is 0.01~1 parts by weight), dispersed parts by weight) and thermal polymerization initiator part), cross-linking agent 0.01~5 parts by weight (preferred agent 0.1~) 5 parts by weight (preferably 〇
\ J 〇.刚量份(較佳的是(U〜3重量份卜其次,—面藉由三 一馬達進㈣拌1於油浴中升溫至熱聚合起始劑之反應 溫度以上’開始m持該狀態5小時以上而使其反 應。其後,使用離心分離機,除去未反應之化合物獲得 由上述層覆蓋絕緣性粒子本體之表面的絕緣性粒子。 作為於上述導電性粒子及上述導電層之表面附著絕緣性 粒子之方法,可列舉化學性方法、及物理性或機械性方法 等。作為上述化學性方法,例如可列舉介面聚合法、於粒 子存在下之懸浮聚合法及乳化聚合法等。作為上述物理性 或機械性方法,可列舉利用喷霧乾燥、混成、靜電附著 法、喷霧法、浸潰及真空蒸鍍之方法等。其中,於混成法 中’存在谷易產生絕緣性粒子之脫離之傾向,因此於上述 導電性粒子及上述導電層之表面附著絕緣性粒子之方法較 佳的是混成法以外之方法。其中,自絕緣性粒子難以脫離 之方面考慮’較佳的是於導電層之表面,經由化學鍵而附 著絕緣性粒子之方法。 於本發明之附有絕緣性粒子之導電性粒子中,較佳的是 絕緣性粒子並非藉由混成法而附著於導電性粒子之表面。 再者’如圖6所示,於使用混成法之先前之附有絕緣性 粒子之導電性粒子1〇1中,於導電性粒子1〇2之表面之附著 有絕緣性粒子103之部分1〇2a以外的部分l〇2b上亦附著有 高分子化合物104。其原因在於:於混成法中,施加壓縮 157831.doc -31, 201213493 剪力,反覆產生絕緣性粒子之附著與脫離, 緣性粒子。由㈣縮剪力,絕隸粒子之由高分子== 所形成之層剝落,剝落之高分子化合物附著於導電性粒子 之表面之附著有絕緣性粒子之部分以外的部分。附著於導 電性粒子之表面之附著有絕緣性粒子之部分以外之部分的 高分子化合物可提高導電性粒子之體積電阻率’減低電極 間之連接電阻。又,即使於藉由覆膜而包㈣6中所示之 附有絕緣性粒子之導電性粒子101之表面之情形時導電 性亦變低,電極間之連接電阻亦容易變低。 作為使絕緣性粒子附著於上述導電性粒子及上述導電層 之表面的方法之一例,可列舉以下之方法。 首先,於水等溶劑3 L中放入導電性粒子,一面攪拌一 面緩緩添加絕㈣粒子4㈣拌後,將时絕緣性粒子 之導電性粒子分離’藉由真空乾燥機等加以乾燥,獲得附 有絕緣性粒子之導電性粒子。 上述導電層較佳的是於表面具有可與絕緣性粒子反應之 反應性官能基,較佳的是具有可與覆膜反應之反應性官能 基粒子較佳的是於表面具有可與導電層反應之反 應性官能基’較佳的是具有可與覆膜反應之反應性官能 基。上述覆膜較佳的是於表面具村與導電層反應之反應 性官能基,較佳的是具有可與絕緣性粒子反應之官能基。 由於該等反應性g能基,絕緣性粒子意想不到地變得難以 自導電性粒子之表面脫離,冑而覆膜變得難以自導電性粒 子之表面及絕緣性粒子之表面剝離。進而,可藉由覆膜而 157831.doc ⑧ •32· 201213493 充分地包覆導電層之表面,進而可藉由覆膜而充分地包覆\ J 〇. Just the amount (preferably (U~3 parts by weight, secondly, the surface is heated by the Trinity motor (4) in the oil bath to the temperature above the reaction temperature of the thermal polymerization initiator] The reaction is carried out for 5 hours or more in this state. Thereafter, the unreacted compound is removed by a centrifugal separator to obtain insulating particles covering the surface of the insulating particle body with the layer. The conductive particles and the conductive layer are used as the conductive particles. Examples of the method for adhering the insulating particles to the surface include a chemical method, a physical or mechanical method, etc. Examples of the chemical method include an interface polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method. Examples of the physical or mechanical method include spray drying, mixing, electrostatic adhesion, spraying, dipping, and vacuum vapor deposition. Among them, in the mixing method, the presence of moisture tends to cause insulation. Since the particles are detached, the method of attaching the insulating particles to the surface of the conductive particles and the conductive layer is preferably a method other than the mixing method. In view of the fact that the particles are difficult to be detached, it is preferable to use a method of attaching the insulating particles to the surface of the conductive layer via a chemical bond. Among the conductive particles with insulating particles of the present invention, insulating particles are preferred. It is not attached to the surface of the conductive particles by the mixing method. Further, as shown in Fig. 6, in the conductive particles 1〇1 with the insulating particles previously used in the hybrid method, the conductive particles 1〇 The polymer compound 104 is also adhered to the portion l〇2b other than the portion 1〇2a of the surface of the insulating particle 103. The reason is that in the mixing method, the compression is applied 157831.doc -31, 201213493 shear force The adhesion and detachment of the insulating particles are repeated, and the edge particles are peeled off by the (4) shrinkage force, the layer formed by the polymer == of the absolute particles, and the adhesion of the peeled polymer compound to the surface of the conductive particles A portion other than the portion of the insulating particles, and a polymer compound adhering to a portion of the surface of the conductive particle to which a part other than the insulating particle adheres can improve the body of the conductive particle. The resistivity 'decreases the connection resistance between the electrodes. Further, even when the surface of the conductive particles 101 with insulating particles shown in (4) 6 is covered by the film, the conductivity is lowered, and the connection between the electrodes is made. An example of the method of attaching the insulating particles to the surface of the conductive particles and the conductive layer is as follows. First, conductive particles are placed in a solvent such as water (3 L). After the addition of the (four) particles 4 (four) is stirred, the conductive particles of the insulating particles are separated and dried by a vacuum dryer or the like to obtain conductive particles with insulating particles. The conductive layer is preferably Having a reactive functional group reactive with the insulating particles on the surface, preferably having a reactive functional group reactive with the coating, preferably having a reactive functional group reactive with the conductive layer on the surface It is preferred to have a reactive functional group reactive with the coating. The above-mentioned coating film is preferably a reactive functional group which reacts with the conductive layer on the surface, and preferably has a functional group reactive with the insulating particles. Due to these reactive g-energy groups, the insulating particles are unexpectedly prevented from being detached from the surface of the conductive particles, and the film is less likely to be peeled off from the surface of the conductive particles and the surface of the insulating particles. Further, the surface of the conductive layer can be sufficiently covered by the film 157831.doc 8 •32·201213493, and the film can be sufficiently coated by the film.
絕緣性粒子之表面D 作為上述反應性官能基,可考慮反應性而選擇適宜之 基°作為上述反應性官能基,可列舉羥基、乙烯基及胺基 等。為了使反應性優異,上述反應性官能基較佳的是羥 基。較佳的是上述附有絕緣性粒子之導電性粒子本體於表 面之至少一部分區域具有羥基。較佳的是上述導電性粒子 於表面具有羥基。較佳的是上述絕緣性粒子於表面具有羥 基。較佳的是上述覆膜於表面具有羥基。 於絕緣性粒子之表面與導電性粒子之表面具有羥基之情 形時,藉由脫水反應而使絕緣性粒子與導電性粒子之附著 力適度變高》 作為上述具有羥基之化合物’可列舉含有p_〇H基之化 合物及含有Si-OH基之化合物等。作為用以於絕緣性粒子 之表面導入經基之具有經基之化合物’可列舉含有ΡΟΗ 基之化合物及含有Si-OH基之化合物等。 作為上述含有P-OH基之化合物之具體例,可列舉磷酸 一氫根乙基甲基丙稀酸醋(acid ph〇sphoxy ethyl methacrylate)、磷酸二氫根丙基曱基丙烯酸酯、磷酸二氫 根聚乙二醇單甲基丙稀酸酯及碟酸二氫根聚丙二醇單甲基 丙烯酸酯等。上述含有P_〇H基之化合物可僅使用丨種,亦 可併用2種以上。 作為上述含有Si-OH基之化合物之具體例,可列舉乙烯 基三羥基矽烷、及3-甲基丙烯醯氧基丙基三羥基矽烷等。 157831.doc -33- 201213493 上述含有Si-OH基之化合物可僅使用丨種,亦可併用2種以 上。 例如’於表面具有羥基之絕緣性粒子可藉由使用梦院偶 合劑之處理而獲得。作為上述矽烷偶合劑,例如可列舉羥 基三甲氧基矽烷等。 (附有絕緣性粒子之導電性粒子之製造方法) 於本發明之附有絕緣性粒子之導電性粒子之製造方法 中,於附有絕緣性粒子之導電性粒子本體之表面,使用具 有碳數為6〜22之烷基之化合物(化合物A)而以包覆上述附 有絕緣性粒子之導電性粒子本體之表面之方式形成覆膜。 作為使用上述化合物A而於附有絕緣性粒子之導電性粒 子本體之表面形成覆膜之方法,並無特別之限定,可列舉 使包含上述化合物A之溶液附著於附有絕緣性粒子之導電 性粒子本體之表面的方法等。 包含上述化合物A之溶液中的溶劑較佳的是水。包含上 述化合物A之溶液中的溶劑亦可包含四氫呋喃、以及甲 醇、乙醇及丙醇等醇等有機溶劑。於使上述溶液附著於附 有絕緣性粒子之導電性粒子本體之表面之後,視需要而除 去溶劑。 包含上述化合物Α之溶液中的上述化合物a之含量可進 行適宜調整以獲得所期望之覆膜。於包含上述化合物八之 溶液100重量°/。中,較佳的是上述化合物A之含量為〇 5〜3 重量%之範圍内。 例如’於導電層之表面或絕緣性粒子之表面存在可與上 157831.doc -34· ⑧ 201213493 述化合物A反應之反應性官能基之情形時,可使該反應性 官能基與上述化合物A反應,使上述化合物A化學鍵結於 上述導電層之表面及絕緣性粒子之表面。 較佳的是附有絕緣性粒子之導電性粒子本體於表面之至 少一部分區域具有羥基’使具有羥基之具有碳數為6〜22之 院基之化合物(以下亦稱為化合物Ai)與附有絕緣性粒子之 導電性粒子本體之表面之羥基反應,以包覆附有絕緣性粒 子之導電性粒子本體之表面之方式形成覆膜。又,較佳的 是導電性粒子於表面具有羥基,使上述化合物幻與該導電 性粒子之表面之羥基反應,以包覆附有絕緣性粒子之導電 性粒子本體之表面之方式形成覆膜。較佳的是絕緣性粒子 於表面具有羥基,使上述化合物八丨與絕緣性粒子之表面之 羥基反應,以包覆附有絕緣性粒子之導電性粒子本體之表 面之方式形成覆膜。進而,較佳的是導電性粒子之表面及 絕緣性粒子之表面分別具有羥基,使上述化合物入丨與導電 性粒子之表面及絕緣性粒子之表面之歸反應,以包覆附 有絕緣性粒子之導電錄子本體之表面之方式形成覆膜。 藉由以該等較佳之態樣形成覆膜,可藉由覆膜而充分地包 覆導電層之表©’進而可藉由覆膜而充分地包覆絕緣性粒 子之表面,’變得更進一步難以於導電層產生錄覆 膜變得難以剝離,進而絕緣性鈕;咅 琢迮粒子意想不到地變得難以脫 離。 (異向性導電材料) 本發明之異向性導電材料包含本 I乃之附有絕緣性粒子 157831.doc -35· 201213493 之導電性粒子及黏合樹脂,或者包含藉由本發明之附有絕 緣性粒子之導電性粒子之製造方法而所得之附有絕緣性粒 子之導電性粒子及黏合樹脂。 於使用上述附有絕緣性粒子之導電性粒子之情形時,絕 緣性粒子與導電性粒子之表面由覆膜所包覆,因此於使附 有絕緣性粒子之導電性粒子分散於黏合樹脂中時等,絕緣 性粒子難以自導電性粒子之表面脫離。 上述黏合樹脂並無特別之限定。作為上述黏合樹脂,通 常使用絕緣性樹脂。作為上述黏合樹脂,例如可列舉乙稀 系樹脂、熱塑性樹脂、硬化性樹脂、熱塑性嵌段共聚物及 彈性體等。上述黏合樹脂可僅使用1種,亦可併用2種以 上。 作為上述乙稀系樹脂,例如可列舉乙酸乙缔酯樹脂、丙 稀酸樹月曰及本乙浠樹脂等。作為上述熱塑性樹脂,例如可 列舉聚烯烴樹脂、乙烯-乙酸乙烯酯共聚物及聚醯胺樹脂 等。作為上述硬化性樹脂,例如可列舉環氧樹脂、胺酯樹 脂、聚醯亞胺樹脂及不飽和聚酯樹脂等。再者,上述硬化 性樹I曰亦可為常溫硬化型樹脂、熱硬化型樹脂光硬化型 樹脂或濕氣硬化型樹脂。上述硬化性樹脂亦可與硬化劑併 用。作為上述熱塑性嵌段共聚物,例如可列舉苯乙烯-丁 二烯-苯乙烯嵌段共聚物、苯乙烯_異戊二烯·苯乙烯嵌段共 聚物、苯乙烯-丁二烯-苯乙浠嵌段共聚物之氫化物、及苯 乙烯-異戊二烯-苯乙烯嵌段共聚物之氫化物等。作為上述 彈性體’例如可列舉苯W·丁三料聚樹膠、及丙稀腈· 157831.doc ⑧ •36- 201213493 苯乙烯嵌段共聚樹膠等。 上述異向性導電材料除了上述附有絕緣性粒子之導電性 粒子及上述黏合樹脂以外’例如亦可包含填充劑、增量 劑、軟化劑、塑化劑、聚合觸媒、硬化觸媒、著色劑、抗 氧化劑、熱穩定劑、光穩定劑、紫外線吸收劑、潤滑劑、 靜電防止劑及阻燃劑等各種添加劑。 使上述时絕緣性粒子之導電性粒子分散於上述黏合樹 脂中之方法可使用先前公知之分散方法,並無特別之限 定。作為使附有絕緣性粒子之導電性粒子分散於黏合樹脂 中之方法’例如可列舉:於黏合樹脂令添加附有絕緣性粒 子之導電性粒子之後,藉由行星式混合機等進行混練而使 其分散之方法;使用均質器等而使附有絕緣性粒子之導電 性粒子均-地分散於水或有機溶财之後添加於黏合樹 脂中’藉由行星式混合機等進行昆練而使其分散之方法. 以及以水或有機溶㈣將黏合樹脂稀釋後,添加附有絕緣 =粒子之導電性粒子,藉由行星式混合機等進行混練而使 其分散之方法等。 本發明之異向性導電材料可作為異向性導電膏或異向性 導電膜而使用。本發明之異向性導電材料作為異向性導電 膜而使用之情形時’於包含該導電性粒子之異向性導電膜 上亦可積層未包含導電性粒子之膜。 本發明之異向性導電材料較佳的是異向性導電膏。異向 性導電膏之使用性及電路填充性優異。於獲得異向性導電 膏時,雖然賦予附有絕緣性粒子之導電性粒子比較大之 157831.doc -37· 201213493 力’但由於上述覆膜之存在而可抑制絕緣性粒子自導電性 粒子之表面脫離。 於上述異向性導電材料100重量%中,上述黏合樹脂之 含量較佳的是10〜99.99重量%之範圍内。黏合樹脂之含量 更佳的是30重量❶/❶以上,進而更佳的是5〇重量%以上特 佳的是70重量%以上,更佳的是99 9重量%以上。若黏合 樹脂之含量為上述下限以上及上述上限以下,則可有效率 地於電極間配置附有絕緣性粒子之導電性粒子,可更進一 步提高藉由異向性導電材料而連接之連接對象部件之導通 可靠性。 於上述異向性導電材料100重量%中,上述附有絕緣性 粒子之導電性粒子之含量較佳的是〇〇1〜2〇重量%之範圍 内。上附有絕緣性粒子之導電性粒子之含量更佳的是〇】 重量/。以上’更佳的疋2〇重量%以下’進而更佳的是1 $重 量%以下。若附有絕緣性粒子之導電性粒子之含量為上述 下限以上及上述上限以下’則可更進一步提高電極間之導 通可靠性。 (連接構造體) 使用本發明之附有絕緣性粒子之導電性粒子,或者使用 包含該附有絕緣性粒子之導電性粒子與黏合樹脂之異向性 導電材料’對連接對象部件進行連接,藉此可獲得連接構 造體。進而’使用藉由本發明之附有絕緣性粒子之導電性 粒子之製造方法而所得之附有絕緣性粒子之導電性粒子, 或者使用包含該附有絕緣性粒子之導電性粒子與黏合樹脂 157831.doc ⑧ 201213493 之異向性導電材料,對連接對象部件進行連接,藉此可獲 得連接構造體。 上述連接構造體具備:第!連接對象部件、第㉘接對象 部件α及對第1、第2連接對象部件進行電性連接之連接 ’較佳的是該連接部由上述附有絕緣性粒子之導電性粒 子而形成’或者由包含該附有絕緣性粒子之導電性粒子與 黏口樹月曰之異向性導電材料而形成的連接構造體。於使用 附有絕緣性粒子之導電性粒子之情形時,連接部自身由附 有絕緣性粒子之導電性粒子而形成。亦即,第i、第2連接 對象部件由时絕㈣粒子之導電絲子巾之導電性粒子 而電性連接。 圖5係模式性表不使用有圖丨所示之附有絕緣性粒子之導 電性粒子1之連接構造體的剖面圖。 圖5中所示之連接構造體51具備:第丨連接對象部件52、 第2連接對象部件53、及連接第丨、第2連接對象部件52、 53之連接部54 »連接部54由包含附有絕緣性粒子之導電性 粒子1與黏合樹脂之異向性導電材料而形成。於圖5中,為 了方便圖示,略圖性表示附有絕緣性粒子之導電性粒子 1。除了附有絕緣性粒子之導電性粒子1之外,亦可使用附 有絕緣性粒子之導電性粒子21、41、61。 第1連接對象部件52於上表面52a上具有複數個電極 52b ^第2連接對象部件53於下表面53&具有複數個電極 53b。電極52b與電極53b藉由i個或複數個附有絕緣性粒子 之導電性粒子1而電性連接。因此,第1、第2連接對象部 157831.doc -39- 201213493 件52、53藉由附有絕緣性粒子之導電性粒子1而電性連 接。 上述連接構造體之製造方法並無特別之限定。作為連接 構造體之製造方法之一例,可列舉:於第1連接對象部件 與第2連接對象部件之間配置上述異向性導電材料,獲得 積層體後,對該積層體進行加熱及加壓之方法等。上述加 Μ之壓力為9.8M04〜4.9X106 Pa左右。上述加熱之溫度為 120〜220°C左右》 對上述積層體進行加熱及加壓時,可排除於導電性粒子 11與電極52b、53b之間所存在之絕緣性粒子15,例如,於 上述加熱及加壓時,導電性粒子U與電極52b、53b之間所 存在之絕緣性粒子15熔融、變形,導電性粒子丨丨之表面部 分性地露出。再者,於上述加熱及加壓時,賦予較大之 力’因此亦存在一部分絕緣性粒子丨5自導電性粒子I丨之表 面剝離,導電性粒子丨丨之表面部分性露出之現象。導電性 粒子11之表面露出之部分與電極52b、53b接觸,因此可經 由導電性粒子11而將電極52b、53b電性連接。 作為上述連接對象部件,具體而言可列舉··半導體晶 片、電容器及二極體等電子零件、以及印刷基板、可撓性 印刷基板及玻璃基板等電路基板等電子零件等。較佳的是 上述異向性導電材料為糊狀,以糊劑之狀態塗佈於連接對 象部件上。上述附有絕緣性粒子之導電性粒子及異向性導 電材料較佳的是用於作為電子零件之連接對象部件之連 接》 157831.doc 201213493 本發明之附有絕緣性粒子之導電性粒子特別是可適宜使 用於以玻璃基板與半導體晶片為連接對象部件之COG、或 者以玻璃基板與可撓性印刷基板(FPC)為連接對象部件之 FOG中。本發明之附有絕緣性粒子之導電性粒子可用於 COG中,亦可用於FOG中》於本發明之連接構造體中,上 述第1、第2連接對象部件較佳的是玻璃基板與半導體晶 片’或者玻璃基板與可撓性印刷基板。上述第1、第2連接 對象部件可為玻璃基板與半導體晶片,亦可為玻璃基板與 可撓性印刷基板。 較佳的是於以玻璃基板與半導體晶片為連接對象部件之 COG中所使用之半導體晶片中設置凸塊。該凸塊尺寸較佳 的是1000 μιη2以上、10000 μηι2以下之電極面積。設有該 凸塊(電極)之半導體晶片中之電極空間較佳的是3〇 μιη以 下,更佳的是20 μιη以下’進而更佳的是10 μιη以下。於此 種COG用途中,可適宜地使用本發明之附有絕緣性粒子之 導電性粒子《於以玻璃基板與可撓性印刷基板為連接對象 部件之FOG中所使用之FPC中,電極空間較佳的是3〇 μιη# 下,更佳的是20 μιη以下。 作為設於上述連接對象部件上之電極,可列舉金電極、 鎳電極、錫電極、鋁電極、銅電極、鉬電極及鎢電極等金 屬電極《於上述連接對象部件為可撓性印刷基板之情形 時,上述電極較佳的是金電極、鎳電極、錫電極或銅電 極。於上述連接對象部件為玻璃基板之情形時,上述電極 較佳的是鋁電極、銅電極、鉬電極或鎢電極。再者,於上 157831.doc •41· 201213493 述電極為銘電極之情形時,可為僅由銘而形成之電極,亦 可為於金屬氧化物層之表面積層有鋁層之電極。作為上述 金屬氧化物,可列舉摻雜有3價金屬元素之氧化銦及摻雜 有3價金屬元素之氧化鋅等。作為上述3價金屬元素,可列 舉Sn、A1及〇£等。 以下,列舉實施例及比較例’對本發明加以具體之說 明。本發明並不僅僅限定於以下之實施例。 (實施例1) 準備在二乙烯基苯樹脂粒子之表面具有形成有鍍鎳層之 金屬層的導電性粒子(平均粒徑為3·〇1 μιη、導電層之厚度 為 0.2 μιη) 〇 又’藉由羥基三乙氧基矽烷包覆使用溶膠凝膠法而製作 之二氧化矽粒子(平均粒徑為200 nm)之表面,獲得於表面 具有羥基之絕緣性粒子。將該絕緣性粒子分散於純水3〇 mL中’獲得包含絕緣性粒子之分散液。 於1 L之可分離式燒瓶中放入純水25〇 mL、乙醇5〇 mL、 上述導電性粒子15重量份而進行充分攪拌,獲得包含導電 性粒子之液體。於該包含導電性粒子之液體中,一面施加 超音波一面以10分鐘滴加包含絕緣性粒子之分散液。其 後’進行過濾’藉由真空乾燥機而於1 〇〇。〇下乾燥8小時, 獲得附有絕緣性粒子之導電性粒子本體。 於純水25 g與乙醇25 g之混合液中放入上述附有絕緣性 粒子之導電性粒子本體10重量份與磷酸單己基酯〇 5重量 份’於50°C下攪拌1小時。其後,進行過濾,藉由真空乾 157831.doc •42· ⑤ 201213493 燥機於100°c下使其乾燥8小時,獲得於附有絕緣性粒子之 導電性粒子本體之表面具有藉由上述磷酸單己基酯而形成 之覆膜的附有絕緣性粒子之導電性粒子。上述覆膜包覆導 電性粒子之表面與絕緣性粒子之表面。包覆導電性粒子之 表面的覆膜部分與包覆絕緣性粒子之表面的覆膜部分相連 接。 (實施例2) 準備與實施例1相同之導電性粒子(平均粒徑為3 .〇 i μιη、 導電層之厚度為0.2 μιη)。 又’藉由乙烯基三乙氧基矽烷包覆使用溶膠凝膠法而製 作之二氧化矽粒子(平均粒徑為200 nm)之表面,獲得於表 面具有乙烯基之絕緣性粒子作為絕緣性粒子本體。 一面於水200 mL中’藉由三一馬達而充分攪拌上述絕緣 性粒子本體1重量份、甲基丙烯酸0.22重量份、乙二醇二 甲基丙烯酸酯0.05重量份、起始劑(和光純藥工業公司製造 之「V-50」)0.5重量份,一面升溫至7〇〇c,於7〇〇c下保持6 小時,使上述單體聚合。 其後,加以冷卻’藉由離心分離機進行2次固液分離, 藉由清洗除去多餘之單體’獲得表面全體由高分子化合物 所包覆之絕緣性粒子。其次’將所得之絕緣性粒子分散於 純水3 0 mL中,獲得絕緣性粒子之分散液。 於1 L之可分離式燒瓶中放入純水25〇 mL、乙醇50 mL、 上述導電性粒子15重量份而進行充分攪拌,獲得包含導電 性粒子之液體。於該包含導電性粒子之液體中,一面施加 157831.doc •43· 201213493 超音波一面以1 〇分鐘滴加上述絕緣性粒子之分散液,然後 升溫至40°C而進行1小時之授拌。其後,進行過濾,藉由 真空乾燥機而於100°C下乾燥8小時,獲得附有絕緣性粒子 之導電性粒子本體》 除了使用所得之附有絕緣性粒子之導電性粒子本體以 外’與實施例1同樣地進行而獲得附有絕緣性粒子之導電 性粒子》上述覆膜包覆導電性粒子之表面與絕緣性粒子之 表面。包覆導電性粒子之表面的覆膜部分與包覆絕緣性粒 子之表面的覆膜部分相連接。 (實施例3) 對樹脂粒子10 g進行蝕刻處理後,加以水洗。其次,於 樹脂粒子中添加硫酸鈀,使鈀離子吸附於樹脂粒子上。將 附著有鈀之樹脂粒子於離子交換水3〇〇 mL中攪拌3分鐘, 使其分散而獲得分散液。其次,將金屬錄粒子漿料(三井 金屬公司製造之「2020SUS」、平均粒徑為2〇〇g&3 分鐘添加於上述分散液中,獲得附著有芯物質之樹脂粒 子於附著有心物質之樹脂粒子之表面,藉由無電鑛鎳而 形成鎳層。如此而獲得於樹脂粒子之表面附著有芯物質, 且樹脂粒子與芯物質之表面由鎳層而包覆之導電性粒子。 該導電性粒子之平均粒徑為3〇2 μιη,導電層之厚度為〇2 μηι。該導電性粒子於表面具有突起。 除了使用所得之導電性粒子以外,與實施例1同樣地進 行而獲得附有絕緣性粒子之導電性粒子。 (實施例4) 157831.doc 201213493 將碟酸单己基酯變 尺為磷酸单辛基酯,除此以外與實旛 例1同樣地進行而獾 耳施 獲伸附有絕緣性粒子之導電性粒子。 (實施例5) 將磷酸單己基酯變 實施例1同樣地進行 子。 更為磷酸單十二烷基酯,除此以外與 而獲得附有絕緣性粒子之導電性粒 (貫施例6) 將磷酸單己基酷辙宙1 ^ 變更為磷酸單十六烷基酯,除此以外與 貫施例1同樣地進杆而從 疋订而獲得附有絕緣性粒子之導電性粒 子0 (實施例7) 將碟酸單己基酯轡 更為己基三乙氧基石夕烧,除此以外與 實施例1同樣地推私工 、 订而獲得附有絕緣性粒子之導電性粒 (實施例8) 將麟酸單己基酯變_ 雙更為辛基三乙氧基矽烧,除此以外與 實施例1同樣地進杆 延仃而獲得附有絕緣性粒子之導電性粒 子。 (實施例9) 將磷酸單己基_變更為十二烧基三乙氧基㈣,除此以 外與實施例1同樣地進行而獲得附有絕緣性粒子之導電性 粒子。 (實施例10) 絕緣性粒子之製作: 157831.doc -45· 201213493 藉由乙烯基三乙氧基矽烷包覆使用溶膠凝膠法而製作之 二氧化矽粒子(平均粒徑為2〇〇 nm)之表面,獲得於表面具 有反應性官能基亦即乙烯基的絕緣性粒子作為絕緣性粒子 本體。具體而言,使用三一馬達使二氧化發粒子1〇重量份 分散於水與乙醇以L9之重量比混合而成之液體4〇〇 mL 中,獲得第1分散液。其次,使乙烯基三乙氧基矽烷01重 量份分散於水與乙醇以1:9之重量比混合而成之液體1〇〇 mL中,獲得第2分散液。其後,將上述第2分散液以1〇分 鐘滴加至上述第1分散液中,獲得混合液。於滴加後,將 所得之混合液授拌3 0分鐘。其後’對混合液進行過濾,於 100 C下乾燥2小時後,藉由篩子進行篩選,獲得絕緣性粒 子本體。 於水200 mL中,調配上述絕緣性粒子本體!重量份、作 為成為高分子化合物之化合物的甲基丙烯酸2重量份、作 為成為尚分子化合物之化合物的乙二醇二甲基丙稀酸醋1 重量份、起始劑(和光純藥工業公司製造之「V_5〇」)〇.5重 量份、作為乳化劑之聚氧乙烯月桂醚(花王公司製造之 「EMULGEN 106」)1重量份,使用超音波照射機使其充 分乳化。其後,一面藉由三一馬達充分授拌一面升溫至 70°C,於70°C下保持6小時,使上述單體聚合。 其後,加以冷卻,藉由離心分離機進行2次之固液分 離’藉由清洗除去多餘之單體’獲得表面全體經高分子化 合物包覆之絕緣性粒子。其次’將所得之絕緣性粒子分散 於純水30 mL中,獲得包含絕緣性粒子之分散液。再者, I57831.doc -46 - 201213493 於上述絕緣性粒子之分散液之狀態下,由高分子化合物所 包覆之絕緣性粒子之平均粒徑為 324 nm 〇 附有絕緣性粒子之導電性粒子之製作: 使用包含所得之絕緣性粒子的分散液作為包含絕緣性粒 +之刀散液’ S此以外與實施例!同樣地進行而獲得附有 絕緣性粒子之導電性粒子。 (實施例11) 將成為高分子化合物之化合物變更為甲基丙烯酸“重 量份與二乙烯基苯L2重量份,除此以外與實施例1〇同樣 地進行而獲得包含絕緣性粒子之分散液。再者於上述絕 緣性粒子之分散液之狀態下,由高分子化合物所包覆之絕 緣性粒子的平均粒徑為33 5 nm。 使用包含所得之絕緣性粒子的分散液作為包含絕緣性粒 子之分散液,除此以外與實施例丨同樣地進行而獲得附有 絕緣性粒子之導電性粒子。 (實施例12) 藉由甲基丙烯醯氧基丙基三乙氧基矽烷包覆二氧化矽粒 子之表面,獲得表面具有甲基丙烯醯基之絕緣性粒子作為 . 絕緣性粒子本體,以及將成為高分子化合物之化合物變更 . 為乙酸乙烯酯2.2重量份、ν,Ν-亞甲基雙丙烯醯胺1〇重量 份,除此以外與實施例1〇同樣地進行而獲得包含絕緣性粒 子之分散液。 再者’於獲得絕緣性粒子本體時,使用二氧化矽粒子1〇 重量份與曱基丙婦酿氧基丙基三乙氧基石夕炫0.1重量份, 157831.doc • 47· 201213493 除此以外藉由與實施例10同樣之方法而獲得絕緣性粒子本 體。又,於上述絕緣性粒子之分散液之狀態下,由高分子 化合物所包覆之絕緣性粒子之平均粒徑為326 nm。 使用包含所得之絕緣性粒子的分散液作為包含絕緣性粒 子之分散液,除此以外與實施例1同樣地進行而獲得附有 絕緣性粒子之導電性粒子。 (實施例13) 作為導電性粒子,使用於二乙烯基苯樹脂粒子之表面附 著有作為芯物質之鎳粉體(1〇〇 nm),且於附著有鎳粉體之 二乙稀基苯粒子之表面上形成有鍍鎳層(導電層)的導電性 粒子(平均粒徑為3.03 μιη、導電層之厚度為0.21 μιη),除 此以外與實施例1同樣地進行而獲得附有絕緣性粒子之導 電性粒子。 (實施例14) 將成為高分子化合物之化合物變更為甲基丙烯酸〇4重 量份與乙二醇二甲基丙烯酸酯0.05重量份,除此以外與實 施例10同樣地進行而獲得包含絕緣性粒子之分散液。 再者’於上述絕緣性粒子之分散液之狀態下,由高分子 化合物所包覆之絕緣性粒子之平均粒徑為248 nm。 使用包含所得之絕緣性粒子的分散液作為包含絕緣性粒 子之分散液’除此以外與實施例1同樣地進行而獲得附有 絕緣性粒子之導電性粒子。 (實施例15) 使用混成法而獲得附有絕緣性粒子之導電性粒子本體, 157831.doc -48· ⑧ 201213493 除此以外與實施例2同樣地進行而獲得附有絕緣性粒子之 導電性粒子。 (比較例1) 作為實施例1中所得之附有絕緣性粒子之導電性粒子本 體的附有絕緣性粒子之導電性粒子。亦即,於比較例工 中,並未於實施例1中所得之附有絕緣性粒子之導電性粒 子本體上形成覆膜,將實施例丨中所得之附有絕緣性粒子 之導電性粒子本體自身用作附有絕緣性粒子之導電性粒 子’進行以下之評價。 (比較例2) 作為實施例2中所得之附有絕緣性粒子之導電性粒子本 體的附有絕緣性粒子之導電性粒子。亦即,於比較例2 中,並未於實施例2中所得之附有絕緣性粒子之導電性粒 子本體上形成覆膜,將實施例2中所得之附有絕緣性粒子 之導電性粒子本體自身用作附有絕緣性粒子之導電性粒 子’進行以下之評價。 (比較例3) 將麟酸單己基醋變更為磷酸單戊基酯(烷基之碳數為 5) ’除此以外與實施例丨同樣地進行而獲得附有絕緣性粒 子之導電性粒子。 (比較例4) 將麟酸單己基醋變更為磷酸單二十三烷基酯(烷基之碳 數為23) ’除此以外與實施例1同樣地進行而獲得附有絕緣 性粒子之導電性粒子。 157831.doc -49- 201213493 (評價) (υ附有絕緣性粒子之導電性粒子中之磷元素或矽元素 之含量之評價 將實施例及比較例之附有絕緣性粒子之導電性粒子i重 量份放入至5重量%之檸檬酸水溶液(於95重量%之水中溶 有5重量%之檸檬酸的液體)1〇〇重量份中,使其為而進 行30分鐘之攪拌,獲得處理液後,藉由濾紙對該處理液進 行過濾而獲得過濾液。於實施例丨〜9之附有絕緣性粒子之 導電性粒子中,於擦檬酸水溶液之處理後,附有絕緣性粒 子之導電性粒子本體之表面所附著之覆膜剝離。 使用ICP發光分析裝置(堀場製作所公司製造之 「ULTIMA2」),測定所得之過濾液中之磷元素或矽元素 之含量。 (2)連接構造體之製作 將實施例及比較例之附有絕緣性粒子之導電性粒子以含 量成為10重量%之方式而添加於三井化學公司製造之 「STRUCTBOND ΧΝ-5Α」)中,使其分散而獲得異向性導 電膏。 準備於上表面形成有L/S為30 μιη/30 μιη之ΙΤΟ電極圖案 的透明玻璃基板。又,準備於下表面形成有L/S為30 μπι/30μιη之銅電極圖案的半導體晶片。 於上述透明玻璃基板上塗佈所得之異向性導電膏以使厚 度成為30 μιη,形成異向性導電膏層。其次,於異向性導 電膏層上,以電極彼此對向之方式積層有上述半導體晶 157831.doc •50· 201213493 片。其後,一面以異向性導電膏層之溫度成為185乞之方 式調整頭之溫度,-面於半導體晶片之上表面載置加廢加 熱頭,施加1 MPa之壓力而使異向性導電膏層於185C>c下完 全硬化,獲得連接構造體。 (3)導通評價(上下電極間) 藉由四端子法分別測定所得之連接構造體之上下電極間 之連接電阻。算出2個連接電阻之平均值。再者,可根據 電壓=電流X電阻之關係,#由測定流通固定電流時之電 壓而求出連接電阻。將連接電阻之平均值為2 () Ω以下, 且於導電性粒子之表面之附著有絕緣性粒子之部分以外的 部分未附著高分子化合物之情形記為「〇」;將雖然連接電 阻之平均值為2Ω以下,但於導電性粒子之表面之附著有 絕緣性粒子之部分以外的部分存在有附著有高分子化合物 之地方的情況記為「△」;將連接電阻之平均值超過2 情況記為「X」,將結果示於下述表1中。 (4) 絕緣§平價(於橫方向上鄰接之電極間) 於所得之連接構造體中,藉由以測試器測定電阻而評價 鄰接之電極間之漏電之有&。於冑阻超過5〇〇 μω之情形 時判疋為無漏電而將結果記為「〇」,於電阻為5〇〇⑽ 以下之情形時,判定為有漏電而將結果記為「χ」,於下述 表1中。 (5) 防銹評價 將上述絕緣評價巾所製作之連接構造體於8rc及相對濕 度85%之條件下進行放置。自放置開始,1GG小時後而與 157831.doc -51- 201213493 上述同樣地藉由四端子法測定電極間之連接電阻。與上述 導通評價時之連接電阻(放置前)之平均值相比而言,將連 接電阻(放置後)之平均值未達150%之情形記為「〇」,將連 接電阻(放置後)之平均值上升150%以上之情形記為「X」, 將結果示於下述表1中。 將結果示於下述表1中。 [表1] 鱗元素之含量 梦元素之含量 H坪僧 絕緣評價 防銹評價 ppm ppm 守項1«「Ί只 實施例1 380 0 〇 〇 〇 實施例2 260 0 〇 〇 〇 實施例3 330 0 〇 〇 〇 實施例4 420 0 〇 〇 0 實施例5 340 0 〇 〇 〇 實施例6 410 0 〇 〇 〇 實施例7 0 290 〇 〇 〇 實施例8 0 390 〇 〇 〇 實施例9 0 260 〇 〇 〇 實施例10 390 0 〇 〇 〇 實施例11 360 0 〇 〇 〇 實施例12 370 0 〇 〇 〇 實施例13 370 0 〇 〇 〇 實施例14 380 0 〇 〇 〇 實施例15 320 0 Δ 〇 〇 比較例1 0 0 〇 X X 比較例2 0 0 〇 X X 比較例3 530 0 0 X X 比較例4 210 0 X 〇 〇 如上述表1所示,於使用比較例1、2之附有絕緣性粒子 157831.doc -52- ⑧ 201213493 之導電性粒子的防銹評價中,電阻值上升150%以上。其 原因在於:於導電層之表面產生銹。 又,於實施例1〜14之附有絕緣性粒子之導電性粒子中, 確認於導電性粒子之表面之附著有絕緣性粒子之部分以外 的部分並未附著高分子化合物。再者,於實施例15中,使 用了物理性/機械性混成法,因此於導電性粒子之表面之 附著有絕緣性粒子之部分以外的部分存在附著有高分子化 合物之地方。如上所述,若於導電性粒子之表面的附著有 絕緣性粒子之部分以外的部分附著有高分子化合物則根 據情況而具有導通可靠性變低之可能性。 (6)絕緣性粒子之脫離 又,於絕緣評價中所得之異向性導電膏中,觀察絕緣性 粒子是否自導電性粒子之表面脫離。 其結果,於使用實施例1〜15之附有絕緣性粒子之導電性 粒子的異向性導電膏中’與使用比較例卜2之附有絕緣性 粒子之導電性粒子的異向性導電膏相比而言,自導電性粒 子之表面所脫離的絕緣性粒子之比例極其少。特別是於使 用實施例1之附有絕緣性粒子之導電性粒子的異向性導電 膏中,與使用比較例1之附有絕緣性粒子之導電性粒子的 異向性導電膏相比而言’自導電性粒子之表面所脫離之絕 緣性粒子之比例極其少。進而,於使用實施例2之附有絕 緣性粒子之導電性粒子的異向性導電膏中,與使用比較例 2之附有絕緣性粒子之導電性粒子的異向性導電膏相比而 言’自導隸粒子之表輯麟之絕緣性好之比例極其 157831.doc •53- 201213493 少。認為其原因在於:於實施例丨〜15之附有絕緣性粒子之 導電性粒子中形成有覆膜,因此絕緣性粒子之脫離得到抑 制。 進而’於使用實施例2之附有絕緣性粒子之導電性粒子 的異向性導電膏中,於使用實施例丨之附有絕緣性粒子之 導電性粒子的異向性導電膏相比而言,自導電性粒子之表 面所脫離之絕緣性粒子之比例少。認為其原因在於:於實 施例2之絕緣性粒子甲’絕緣性粒子之表面由高分子化合 物所形成之柔軟之層而包覆,因此絕緣性粒子之脫離得到 抑制。 【圖式簡單說明】 圖1係表示本發明之第1實施形態之附有絕緣性粒子之導 電性粒子的剖面圖。 圖2係表示本發明之第2實施形態之附有絕緣性粒子之導 電性粒子的剖面圖。 圖3係表示本發明之第3實施形態之附有絕緣性粒子之導 電性粒子的剖面圖。 圖4係表示本發明之第4實施形態之附有絕緣性粒子之導 電性粒子的剖面圖。 圖5係模式性表示使用有圖1所示之附有絕緣性粒子之導 電性粒子之連接構造體的正面剖面圖。 圖6係表示使用混成法之先前之附有絕緣性粒子之導電 性粒子之剖面圖。 【主要元件符號說明】 157831,doc • 54- ⑧ 201213493 1 、 21 、 41 、 61 、 101 附有絕緣性粒子之導電性粒子 2 ' 22 、 42 、 62 附有絕緣性粒子之導電性粒子 本體 3 ' 23 覆膜 11 、 31 、 71 、 102 導電性粒子 12 基材粒子 13 、 32 、 76 導電層 15 、 35 、 45 、 103 絕緣性粒子 33 芯物質 34、77 突起 45a 絕緣性粒子本體 45b 層 51 連接構造體 52 第1連接對象部件 52a 上表面 52b ' 53b 電極 53 第2連接對象部件 53a 下表面 54 連接部 76a 第1導電層 76b 第2導電層 102a 於導電性粒子102之表面之附著 有絕緣性粒子103之部分 102b 於導電性粒子102之表面之附著 157831.doc -55- 201213493 有絕緣性粒子103之部分102a以 外的部分 104 高分子化合物 157831.doc •56· ⑧On the surface D of the insulating particles, as the reactive functional group, a suitable group can be selected as the reactive functional group in consideration of reactivity, and examples thereof include a hydroxyl group, a vinyl group, and an amine group. In order to make the reactivity excellent, the above reactive functional group is preferably a hydroxyl group. It is preferable that the conductive particles having the insulating particles have a hydroxyl group in at least a part of the surface of the surface. It is preferred that the above conductive particles have a hydroxyl group on the surface. It is preferred that the insulating particles have a hydroxyl group on the surface. It is preferred that the above film has a hydroxyl group on the surface. When the surface of the insulating particles and the surface of the conductive particles have a hydroxyl group, the adhesion between the insulating particles and the conductive particles is moderately increased by the dehydration reaction. The compound having a hydroxyl group 'is exemplified as p_ A compound based on a H group and a compound containing a Si-OH group. The compound having a radical group introduced into the surface of the insulating particles may be a compound containing a mercapto group or a compound containing a Si-OH group. Specific examples of the P-OH group-containing compound include acid ph〇sphoxy ethyl methacrylate, dihydrogen propyl methacrylate, and dihydrogen phosphate. Root polyethylene glycol monomethyl acrylate and disc hydrogen dipropylene glycol monomethacrylate. The above-mentioned compound containing a P_〇H group may be used alone or in combination of two or more. Specific examples of the Si-OH group-containing compound include vinyl trihydroxy decane and 3-methacryloxypropyl trihydroxy decane. 157831. Doc-33-201213493 The above-mentioned Si-OH group-containing compound may be used alone or in combination of two or more. For example, insulating particles having a hydroxyl group on the surface can be obtained by treatment using a Dreaming Agent. The decane coupling agent may, for example, be hydroxytrimethoxydecane or the like. (Manufacturing Method of Conductive Particles with Insulating Particles) In the method for producing conductive particles with insulating particles of the present invention, the carbonaceous surface is used on the surface of the conductive particle body with insulating particles. The compound (compound A) having an alkyl group of 6 to 22 is formed into a coating film so as to coat the surface of the main body of the conductive particles having the insulating particles. The method of forming a coating film on the surface of the conductive particle body with the insulating particles by using the above-mentioned compound A is not particularly limited, and the solution containing the compound A described above is adhered to the conductivity with insulating particles. The method of the surface of the particle body, etc. The solvent in the solution containing the above compound A is preferably water. The solvent in the solution containing the above compound A may also contain an organic solvent such as tetrahydrofuran or an alcohol such as methanol, ethanol or propanol. After the solution is attached to the surface of the conductive particle body with the insulating particles, the solvent is removed as needed. The content of the above compound a in the solution containing the above compound hydrazine can be appropriately adjusted to obtain a desired film. The solution containing the above compound VIII is 100% by weight. Preferably, the content of the above compound A is in the range of 〇 5 to 3 % by weight. For example, 'the surface of the conductive layer or the surface of the insulating particles can exist with the upper 157831. Doc -34· 8 201213493 In the case of the reactive functional group of the compound A reaction, the reactive functional group may be reacted with the above compound A to chemically bond the compound A to the surface of the conductive layer and the surface of the insulating particle. . It is preferable that the conductive particles having the insulating particles have a hydroxyl group in at least a part of the surface of the surface, and a compound having a hydroxyl group having a carbon number of 6 to 22 (hereinafter also referred to as a compound Ai) is attached The hydroxyl group on the surface of the conductive particle body of the insulating particles reacts to form a coating film so as to coat the surface of the conductive particle body with the insulating particles. Further, it is preferable that the conductive particles have a hydroxyl group on the surface, and the compound reacts with the hydroxyl group on the surface of the conductive particles, and forms a coating film so as to coat the surface of the conductive particle body with the insulating particles. It is preferable that the insulating particles have a hydroxyl group on the surface, react the above-mentioned compound gossip with the hydroxyl group on the surface of the insulating particles, and form a film so as to coat the surface of the conductive particle body with the insulating particles. Further, it is preferable that the surface of the conductive particles and the surface of the insulating particles each have a hydroxyl group, and the compound is reacted with the surface of the conductive particles and the surface of the insulating particles to coat the insulating particles. The surface of the conductive recording body forms a film. By forming the film in such a preferred manner, the surface of the conductive layer can be sufficiently covered by the film, and the surface of the insulating particles can be sufficiently covered by the film. Further, it is difficult to produce a recording film on the conductive layer, which makes it difficult to peel off, and further, the insulating button; the ruthenium particles unexpectedly become difficult to be detached. (Anisotropic conductive material) The anisotropic conductive material of the present invention comprises the insulating particles 177831. Doc-35·201213493 conductive particles and a binder resin, or conductive particles with an insulating particle and a binder resin obtained by the method for producing conductive particles with insulating particles according to the present invention. When the conductive particles having the insulating particles are used, the surface of the insulating particles and the conductive particles are coated with the coating film. Therefore, when the conductive particles with the insulating particles are dispersed in the adhesive resin, The insulating particles are less likely to be detached from the surface of the conductive particles. The above binder resin is not particularly limited. As the above-mentioned binder resin, an insulating resin is usually used. Examples of the above-mentioned binder resin include an ethylene resin, a thermoplastic resin, a curable resin, a thermoplastic block copolymer, and an elastomer. The above-mentioned adhesive resin may be used alone or in combination of two or more. Examples of the above-mentioned ethylene-based resin include a vinyl acetate resin, a lauric acid, and a acetal resin. Examples of the thermoplastic resin include a polyolefin resin, an ethylene-vinyl acetate copolymer, and a polyamide resin. Examples of the curable resin include an epoxy resin, an amine ester resin, a polyimide resin, and an unsaturated polyester resin. Further, the curable tree I may be a room temperature curing resin, a thermosetting resin photocurable resin or a moisture curing resin. The above curable resin may also be used in combination with a curing agent. Examples of the thermoplastic block copolymer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, and styrene-butadiene-phenethyl hydrazine. a hydride of a block copolymer, a hydride of a styrene-isoprene-styrene block copolymer, and the like. Examples of the above elastomers include benzene W. butyl tripoly gum and acrylonitrile 157831. Doc 8 •36- 201213493 Styrene block copolymer gum, etc. The anisotropic conductive material may contain, in addition to the conductive particles with insulating particles and the above-mentioned binder resin, a filler, a bulking agent, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, and a coloring. Various additives such as agents, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, lubricants, static inhibitors, and flame retardants. The method of dispersing the conductive particles of the insulating particles described above in the above-mentioned binder resin can be carried out by a conventionally known dispersion method, and is not particularly limited. The method of dispersing the conductive particles with the insulating particles in the binder resin is exemplified by adding a conductive particle with insulating particles to the binder resin, and then kneading it by a planetary mixer or the like. a method of dispersing the conductive particles with insulating particles uniformly dispersed in water or organically dissolved in a binder resin using a homogenizer or the like, and performing a kinematic exercise by a planetary mixer or the like The method of dispersion. And a method in which the binder resin is diluted with water or an organic solvent (4), and the conductive particles having the insulating particles are added and mixed by a planetary mixer or the like to be dispersed. The anisotropic conductive material of the present invention can be used as an anisotropic conductive paste or an anisotropic conductive film. When the anisotropic conductive material of the present invention is used as an anisotropic conductive film, a film containing no conductive particles may be laminated on the anisotropic conductive film containing the conductive particles. The anisotropic conductive material of the present invention is preferably an anisotropic conductive paste. The anisotropic conductive paste is excellent in usability and circuit filling property. When the anisotropic conductive paste is obtained, the conductive particles with insulating particles are relatively large, 157,831. Doc -37· 201213493 Force' However, the presence of the above-mentioned film prevents the insulating particles from being detached from the surface of the conductive particles. The content of the above adhesive resin is preferably from 10 to 99 in 100% by weight of the above anisotropic conductive material. Within the range of 99% by weight. The content of the binder resin is more preferably 30% by weight or more, more preferably 5% by weight or more, particularly preferably 70% by weight or more, and more preferably 99% by weight or more. When the content of the binder resin is not less than the above lower limit and not more than the above upper limit, the conductive particles having the insulating particles can be efficiently disposed between the electrodes, and the connecting member to be connected by the anisotropic conductive material can be further improved. Continuity reliability. In 100% by weight of the anisotropic conductive material, the content of the conductive particles with insulating particles is preferably in the range of 〇〇1 to 2% by weight. The content of the conductive particles having the insulating particles attached thereto is more preferably 重量]. The above is more preferably 疋2〇% by weight or less and further preferably 1% by weight or less. When the content of the conductive particles with the insulating particles is not less than the above lower limit and not more than the above upper limit, the conduction reliability between the electrodes can be further improved. (Connection structure) The connection target member is connected by using the conductive particles with insulating particles of the present invention or by using an anisotropic conductive material including the conductive particles with insulating particles and an adhesive resin. This makes it possible to obtain a connection structure. Further, the conductive particles with insulating particles obtained by the method for producing conductive particles with insulating particles of the present invention or the conductive particles containing the insulating particles and the binder resin 157831 are used. Doc 8 201213493 An anisotropic conductive material that connects the connected components to obtain a connected structure. The above connection structure is provided with: The connection target member, the 28th connection target member α, and the connection for electrically connecting the first and second connection target members are preferably 'the connection portion is formed of the conductive particles with the insulating particles described above' or A connection structure comprising the electrically conductive particles with insulating particles and an anisotropic conductive material of a sticky tree. In the case of using conductive particles with insulating particles, the connecting portion itself is formed of conductive particles with insulating particles. That is, the i-th and second connection target members are electrically connected by the conductive particles of the conductive filament shawl of the (four) particles. Fig. 5 is a cross-sectional view showing a connection structure in which the conductive particles 1 with insulating particles shown in Fig. 不 are not used. The connection structure 51 shown in FIG. 5 includes a second connection target member 52, a second connection target member 53, and a connection portion 54 that connects the second and second connection target members 52 and 53. The conductive particles 1 having insulating particles and the anisotropic conductive material of the binder resin are formed. In Fig. 5, for convenience of illustration, the conductive particles 1 with insulating particles are schematically shown. In addition to the conductive particles 1 with insulating particles, conductive particles 21, 41, and 61 with insulating particles may be used. The first connection object member 52 has a plurality of electrodes 52b on the upper surface 52a. The second connection object member 53 has a plurality of electrodes 53b on the lower surface 53&. The electrode 52b and the electrode 53b are electrically connected by one or a plurality of conductive particles 1 with insulating particles. Therefore, the first and second connection object portions 157831. Doc-39-201213493 Parts 52, 53 are electrically connected by conductive particles 1 with insulating particles. The method for producing the above-described connection structure is not particularly limited. An example of the manufacturing method of the connection structure is that the anisotropic conductive material is disposed between the first connection target member and the second connection target member, and after the laminate is obtained, the laminate is heated and pressurized. Method, etc. The pressure of the above twisting is 9. 8M04~4. 9X106 Pa or so. The heating temperature is about 120 to 220 ° C. When the laminated body is heated and pressurized, the insulating particles 15 existing between the conductive particles 11 and the electrodes 52 b and 53 b can be excluded, for example, in the above heating. At the time of pressurization, the insulating particles 15 existing between the conductive particles U and the electrodes 52b and 53b are melted and deformed, and the surface of the conductive particles 部分 is partially exposed. Further, when the heating and pressurization are performed, a large force is applied. Therefore, a part of the insulating particles 丨5 is peeled off from the surface of the conductive particles I丨, and the surface of the conductive particles 部分 is partially exposed. Since the exposed portion of the surface of the conductive particles 11 is in contact with the electrodes 52b and 53b, the electrodes 52b and 53b can be electrically connected via the conductive particles 11. Specific examples of the connection target member include electronic components such as a semiconductor wafer, a capacitor, and a diode, and electronic components such as a printed circuit board, a flexible printed circuit board, and a circuit board such as a glass substrate. Preferably, the anisotropic conductive material is in the form of a paste and is applied to the connecting member in the state of a paste. The conductive particles and the anisotropic conductive material with the insulating particles described above are preferably used as a connection member for connecting electronic parts. 157831. Doc 201213493 The conductive particles with insulating particles of the present invention can be suitably used for a COG in which a glass substrate and a semiconductor wafer are connected to each other, or a glass substrate and a flexible printed circuit board (FPC). In the FOG. The conductive particles with insulating particles of the present invention can be used in COG or in FOG. In the connection structure of the present invention, the first and second connection members are preferably a glass substrate and a semiconductor wafer. 'Or a glass substrate and a flexible printed substrate. The first and second connection target members may be a glass substrate or a semiconductor wafer, or may be a glass substrate or a flexible printed substrate. Preferably, bumps are provided in the semiconductor wafer used in the COG in which the glass substrate and the semiconductor wafer are connected components. The bump size is preferably an electrode area of 1000 μm 2 or more and 10000 μη 2 or less. The electrode space in the semiconductor wafer provided with the bump (electrode) is preferably 3 Å or less, more preferably 20 μm or less, and still more preferably 10 μm or less. In such a COG application, the conductive particles with insulating particles of the present invention can be suitably used in the FPC used in the FOG in which the glass substrate and the flexible printed substrate are connected components, and the electrode space is compared. The best is 3 〇 μιη#, and the best is 20 μιη or less. Examples of the electrode provided on the connection target member include a metal electrode such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, and a tungsten electrode. The case where the connection target member is a flexible printed circuit board Preferably, the electrode is a gold electrode, a nickel electrode, a tin electrode or a copper electrode. In the case where the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode or a tungsten electrode. Furthermore, on 157831. Doc •41· 201213493 When the electrode is an electrode, it may be an electrode formed only by the name, or an electrode having an aluminum layer on the surface layer of the metal oxide layer. Examples of the metal oxide include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, A1, and ruthenium. Hereinafter, the present invention will be specifically described by way of examples and comparative examples. The invention is not limited to the following examples. (Example 1) Electroconductive particles having a metal layer on which a nickel plating layer was formed on the surface of a divinylbenzene resin particle were prepared (average particle diameter was 3·〇1 μηη, and thickness of the conductive layer was 0. 2 μιη) 〇 Further, the surface of the cerium oxide particles (having an average particle diameter of 200 nm) prepared by a sol-gel method was coated with hydroxytriethoxydecane to obtain insulating particles having a hydroxyl group on the surface. The insulating particles were dispersed in 3 〇 mL of pure water to obtain a dispersion liquid containing insulating particles. In a separable flask of 1 L, 25 〇 mL of pure water, 5 〇 mL of ethanol, and 15 parts by weight of the above-mentioned conductive particles were placed and sufficiently stirred to obtain a liquid containing conductive particles. In the liquid containing the conductive particles, a dispersion containing insulating particles was dropped over 10 minutes while applying ultrasonic waves. Thereafter, the filtration was carried out by means of a vacuum dryer at 1 Torr. The undercoat was dried for 8 hours to obtain a conductive particle body with insulating particles. Into a mixture of 25 g of pure water and 25 g of ethanol, 10 parts by weight of the conductive particles containing the insulating particles and 5 parts by weight of monohexyl phosphate ruthenium were placed at 50 ° C for 1 hour. Thereafter, filtration was carried out by vacuum drying 157831. Doc •42· 5 201213493 The dryer is dried at 100 ° C for 8 hours, and the surface of the main body of the conductive particles with insulating particles is provided with an insulating film formed by the above-mentioned monohexyl phosphate. Conductive particles of a particle. The coating film covers the surface of the conductive particles and the surface of the insulating particles. The coating portion covering the surface of the conductive particles is connected to the coating portion covering the surface of the insulating particles. (Example 2) The same electroconductive particle as that of Example 1 was prepared (the average particle diameter was 3). 〇 i μιη, the thickness of the conductive layer is 0. 2 μιη). Further, 'the surface of the cerium oxide particles (having an average particle diameter of 200 nm) prepared by a sol-gel method is coated with vinyl triethoxy decane, and insulating particles having a vinyl group on the surface are obtained as insulating particles. Ontology. 1 part by weight of the above-mentioned insulating particle body, methacrylic acid was sufficiently stirred by a three-one motor in 200 mL of water. 22 parts by weight, ethylene glycol dimethacrylate 0. 05 parts by weight, starting agent ("V-50" manufactured by Wako Pure Chemical Industries, Ltd.) 0. 5 parts by weight, the temperature was raised to 7 ° C, and kept at 7 ° C for 6 hours to polymerize the above monomers. Thereafter, the mixture was cooled, and the solid particles were separated by a centrifugal separator, and the excess monomer was removed by washing to obtain insulating particles coated with the polymer compound on the entire surface. Next, the obtained insulating particles were dispersed in 30 mL of pure water to obtain a dispersion of insulating particles. Into a 1 L separable flask, 25 mL of pure water, 50 mL of ethanol, and 15 parts by weight of the above-mentioned conductive particles were placed and sufficiently stirred to obtain a liquid containing conductive particles. In the liquid containing the conductive particles, 157831 is applied on one side. Doc •43· 201213493 Ultrasonic wave was added dropwise to the dispersion of the above insulating particles in 1 minute, and then heated to 40 ° C for 1 hour. Thereafter, the mixture was filtered and dried at 100 ° C for 8 hours by a vacuum dryer to obtain a conductive particle body with insulating particles. In addition to the obtained conductive particle body with insulating particles obtained, In the same manner as in the first embodiment, the conductive particles with insulating particles were obtained. The surface of the coating-coated conductive particles and the surface of the insulating particles. The coating portion covering the surface of the conductive particles is connected to the coating portion covering the surface of the insulating particles. (Example 3) 10 g of resin particles were subjected to an etching treatment, followed by washing with water. Next, palladium sulfate is added to the resin particles to adsorb palladium ions on the resin particles. The resin particles to which palladium was attached were stirred in 3 〇〇 mL of ion-exchanged water for 3 minutes, and dispersed to obtain a dispersion. Next, a metal recording particle slurry ("2020SUS" manufactured by Mitsui Metals Co., Ltd., an average particle diameter of 2 〇〇g & 3 minutes) was added to the dispersion liquid to obtain a resin particle to which a core substance adhered, and a resin to which a core substance adhered was obtained. On the surface of the particle, a nickel layer is formed by electroless nickel plating. Thus, a conductive material is obtained by adhering a core material to the surface of the resin particle, and the surface of the resin particle and the core material is covered with a nickel layer. The average particle diameter is 3〇2 μηη, and the thickness of the conductive layer is 〇2 μη. The conductive particles have protrusions on the surface. The insulation is obtained in the same manner as in Example 1 except that the obtained conductive particles are used. Conductive particles of particles (Example 4) 157831. Doc 201213493 In the same manner as in Example 1, except that the disc-acid monohexyl ester was changed to mono-octyl phosphate, the conductive particles in which the insulating particles were adhered were applied. (Example 5) The monohexyl phosphate was changed in the same manner as in Example 1. Further, a monododecyl phosphate is obtained, and a conductive particle having an insulating particle is obtained in addition to the above (Example 6). The monohexyl phosphate is changed to a monohexadecyl phosphate. Otherwise, in the same manner as in Example 1, the conductive particles having insulating particles were obtained from the bonding (Example 7). The monohexyl sulfonate was further hexyl triethoxylate. In the same manner as in Example 1, except that the conductive particles with insulating particles were obtained in the same manner as in Example 1 (Example 8), monohexyl cinnamate was converted into bis-octyltriethoxysulfonate. Otherwise in the same manner as in Example 1, the conductive particles having insulating particles were obtained. (Example 9) Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the monohexylphosphoric acid group was changed to the dodecyl triethoxy group (IV). (Example 10) Production of insulating particles: 157831. Doc -45· 201213493 The surface of the cerium oxide particles (average particle diameter of 2 〇〇 nm) prepared by the sol-gel method is coated with vinyl triethoxy decane to obtain reactive functional groups on the surface. That is, the insulating particles of vinyl are used as the bulk of the insulating particles. Specifically, the first dispersion liquid was obtained by dispersing 1 part by weight of the oxidized hair particles in a liquid mixture of 4 〇〇 mL of water and ethanol in a weight ratio of L9 using a tri-motor. Next, a weight portion of the vinyltriethoxydecane 01 was dispersed in 1 mL of a liquid in which water and ethanol were mixed at a weight ratio of 1:9 to obtain a second dispersion. Thereafter, the second dispersion liquid was dropwise added to the first dispersion liquid at 1 Torr to obtain a mixed liquid. After the dropwise addition, the resulting mixture was mixed for 30 minutes. Thereafter, the mixture was filtered, dried at 100 C for 2 hours, and sieved through a sieve to obtain an insulating particulate body. Dispensing the above-mentioned insulating particle body in 200 mL of water! 2 parts by weight of methacrylic acid as a compound of a polymer compound, 1 part by weight of ethylene glycol dimethyl acrylate vinegar as a compound of a molecular compound, and a starter (Wako Pure Chemical Industries, Ltd.) "V_5〇"). One part by weight of a polyoxyethylene lauryl ether ("EMULGEN 106" manufactured by Kao Corporation), which is an emulsifier, was emulsified by an ultrasonic wave irradiator. Thereafter, the mixture was heated to 70 ° C while being sufficiently mixed by a triad motor, and kept at 70 ° C for 6 hours to polymerize the above monomers. Thereafter, the mixture was cooled, and the solid-liquid separation was repeated twice by a centrifugal separator to remove excess monomer by washing to obtain insulating particles coated with the polymer compound on the entire surface. Next, the obtained insulating particles were dispersed in 30 mL of pure water to obtain a dispersion containing insulating particles. Furthermore, I57831. Doc -46 - 201213493 In the state of the dispersion of the insulating particles, the average particle diameter of the insulating particles coated with the polymer compound is 324 nm. 导电 Preparation of conductive particles with insulating particles: The obtained dispersion liquid of the insulating particles is used as an example of the dispersion liquid containing the insulating particles + S and the examples! The conductive particles with insulating particles were obtained in the same manner. (Example 11) A dispersion liquid containing insulating particles was obtained in the same manner as in Example 1 except that the compound of the polymer compound was changed to a part by weight of methacrylic acid and 2 parts by weight of divinylbenzene. Further, in the state of the dispersion of the insulating particles, the average particle diameter of the insulating particles coated with the polymer compound is 33 5 nm. The dispersion liquid containing the obtained insulating particles is used as the insulating particles. In the same manner as in Example 丨, the conductive particles having insulating particles were obtained in the same manner as in Example 。. (Example 12) Coating of cerium oxide by methacryloxypropyltriethoxydecane As the surface of the particle, an insulating particle having a methacrylonitrile group on the surface is obtained. The bulk of the insulating particles and the compound to be a polymer compound are changed. For vinyl acetate 2. A dispersion liquid containing insulating particles was obtained in the same manner as in Example 1 except that 2 parts by weight of ν, Ν-methylenebisacrylamide was used in an amount of 1 part by weight. Further, when obtaining the bulk of the insulating particles, the cerium oxide particles are used in an amount of 1 part by weight and the thiopropyl ethoxylated ethoxypropyl triethoxy sulphate is used. 1 part by weight, 157831. Doc • 47·201213493 In the same manner as in Example 10, an insulating particle body was obtained. Further, in the state of the dispersion of the insulating particles, the average particle diameter of the insulating particles coated with the polymer compound was 326 nm. Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the dispersion liquid containing the obtained insulating particles was used as the dispersion liquid containing the insulating particles. (Example 13) As the conductive particles, nickel powder (1 〇〇 nm) as a core material was adhered to the surface of the divinyl benzene resin particles, and diethyl benzene particles to which nickel powder was adhered were used. A conductive layer of a nickel-plated layer (conductive layer) is formed on the surface (the average particle diameter is 3. 03 μιη, the thickness of the conductive layer is 0. Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the reaction was carried out in the same manner as in Example 1. (Example 14) The compound to be a polymer compound was changed to 4 parts by weight of ruthenium methacrylate and ethylene glycol dimethacrylate. A dispersion liquid containing insulating particles was obtained in the same manner as in Example 10 except for the above. Further, in the state of the dispersion of the insulating particles, the insulating particles coated with the polymer compound have an average particle diameter of 248 nm. Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the dispersion liquid containing the obtained insulating particles was used as the dispersion liquid containing the insulating particles. (Example 15) A conductive particle body with insulating particles was obtained by a mixing method, 157831. Doc -48·8 201213493 Other than the above, the conductive particles with insulating particles were obtained in the same manner as in Example 2. (Comparative Example 1) Conductive particles with insulating particles attached to the conductive particles of the insulating particles obtained in Example 1. That is, in the comparative work, the coating film was not formed on the body of the conductive particles with the insulating particles obtained in Example 1, and the conductive particle body with the insulating particles obtained in Example 丨 was obtained. The following was evaluated by using itself as the conductive particles with insulating particles. (Comparative Example 2) The conductive particles with insulating particles attached to the conductive particles of the insulating particles obtained in Example 2 were used. That is, in Comparative Example 2, the coating film was not formed on the main body of the conductive particles having the insulating particles obtained in Example 2, and the conductive particle body with the insulating particles obtained in Example 2 was obtained. The following was evaluated by using itself as the conductive particles with insulating particles. (Comparative Example 3) Conductive particles with insulating particles were obtained in the same manner as in Example 将 except that the linolenic acid monohexyl vinegar was changed to monopentyl phosphate (the carbon number of the alkyl group was 5). (Comparative Example 4) Conducting in the same manner as in Example 1 except that the linolenic acid monohexyl vinegar was changed to the mono-trisyl phosphate (the carbon number of the alkyl group was 23) was obtained, and the conductive particles with insulating particles were obtained. Sex particles. 157831. Doc -49-201213493 (Evaluation) (Evaluation of the content of phosphorus or antimony element in conductive particles with insulating particles) The weight of electroconductive particles i with insulating particles in the examples and comparative examples was placed. The solution was added to a 5% by weight aqueous solution of citric acid (a liquid in which 5% by weight of citric acid was dissolved in 95% by weight of water), and the mixture was stirred for 30 minutes to obtain a treatment liquid. The treatment liquid was filtered from a filter paper to obtain a filtrate. In the conductive particles having insulating particles attached to Examples 丨 to 9 after the treatment with the aqueous solution of glyceric acid, the conductive particle body with insulating particles was attached. The film adhered to the surface was peeled off. The content of the phosphorus element or the lanthanum element in the obtained filtrate was measured using an ICP luminescence analyzer ("ULTIMA2" manufactured by Horiba, Ltd.). In the example and the comparative example, the conductive particles with the insulating particles were added to the "STRUCTBOND ΧΝ-5Α" manufactured by Mitsui Chemicals Co., Ltd. as a content of 10% by weight, and dispersed. An anisotropic conductive paste. A transparent glass substrate having an electrode pattern of L/S of 30 μm / 30 μm was formed on the upper surface. Further, a semiconductor wafer having a copper electrode pattern having an L/S of 30 μm / 30 μm was formed on the lower surface. The obtained anisotropic conductive paste was applied onto the above transparent glass substrate to have a thickness of 30 μm to form an anisotropic conductive paste layer. Next, on the anisotropic conductive paste layer, the above-mentioned semiconductor crystals are laminated in such a manner that the electrodes face each other. Doc •50· 201213493 pieces. Thereafter, the temperature of the head is adjusted such that the temperature of the anisotropic conductive paste layer is 185 ,, and the waste heating head is placed on the upper surface of the semiconductor wafer, and a pressure of 1 MPa is applied to make the anisotropic conductive paste. The layer was completely hardened at 185 C > c to obtain a joined structure. (3) Conduction evaluation (between upper and lower electrodes) The connection resistance between the lower electrodes on the obtained connection structure was measured by a four-terminal method. Calculate the average of the two connection resistances. Further, the connection resistance can be obtained from the voltage at which the fixed current flows by measuring the relationship between the voltage = current X resistance and #. When the average value of the connection resistance is 2 () Ω or less, and the portion other than the portion where the insulating particles adhere to the surface of the conductive particle is not attached with a polymer compound, it is referred to as "〇"; When the value is 2 Ω or less, the portion where the insulating particles are adhered to the surface of the conductive particles is "Δ" where the polymer compound is adhered, and the average value of the connecting resistance is more than 2 The result is "X", and the results are shown in Table 1 below. (4) Insulation § parity (between electrodes adjacent in the lateral direction) In the obtained connection structure, the electric resistance between the adjacent electrodes was evaluated by measuring the resistance with a tester. When the resistance is more than 5 〇〇μω, the result is judged as no leakage, and the result is referred to as "〇". When the resistance is 5 〇〇 (10) or less, it is judged that there is leakage and the result is "χ". In Table 1 below. (5) Rust prevention evaluation The connection structure produced by the above insulation evaluation napkin was placed under conditions of 8 rc and a relative humidity of 85%. Since the beginning of the placement, 1GG hours later with 157831. Doc-51-201213493 The connection resistance between the electrodes was measured by the four-terminal method in the same manner as above. Compared with the average value of the connection resistance (before placement) in the above-mentioned conduction evaluation, the case where the average value of the connection resistance (after placement) is less than 150% is referred to as "〇", and the connection resistance (after placement) is used. The case where the average value is increased by 150% or more is referred to as "X", and the results are shown in Table 1 below. The results are shown in Table 1 below. [Table 1] Content of scale elements Content of dream elements H Ping 僧 insulation evaluation Anti-rust evaluation ppm ppm Guard 1 «" Ί only example 1 380 0 〇〇〇 Example 2 260 0 〇〇〇 Example 3 330 0 〇〇〇Example 4 420 0 〇〇0 Example 5 340 0 〇〇〇Example 6 410 0 〇〇〇Example 7 0 290 〇〇〇Example 8 0 390 〇〇〇Example 9 0 260 〇〇 〇Example 10 390 0 〇〇〇Example 11 360 0 〇〇〇Example 12 370 0 〇〇〇Example 13 370 0 〇〇〇Example 14 380 0 〇〇〇Example 15 320 0 Δ 〇〇Comparative Example 1 0 0 〇 XX Comparative Example 2 0 0 〇 XX Comparative Example 3 530 0 0 XX Comparative Example 4 210 0 X As shown in Table 1 above, the insulating particles 157831 were attached to Comparative Examples 1 and 2. Doc -52- 8 201213493 In the rust prevention evaluation of conductive particles, the resistance value increased by 150% or more. The reason is that rust is generated on the surface of the conductive layer. Further, in the conductive particles having the insulating particles of Examples 1 to 14, it was confirmed that the polymer compound was not adhered to the portion other than the portion where the insulating particles adhered to the surface of the conductive particles. Further, in the fifteenth embodiment, since the physical/mechanical compounding method is used, a portion other than the portion where the insulating particles are adhered to the surface of the conductive particles exists where the polymer compound adheres. As described above, when a polymer compound is adhered to a portion other than the portion where the insulating particles are adhered to the surface of the conductive particles, the conduction reliability may be lowered depending on the case. (6) Detachment of insulating particles Further, in the anisotropic conductive paste obtained by the evaluation of the insulation, it was observed whether or not the insulating particles were separated from the surface of the conductive particles. As a result, in the anisotropic conductive paste using the conductive particles with insulating particles of Examples 1 to 15, 'the anisotropic conductive paste using the conductive particles with insulating particles of Comparative Example 2 was used. In contrast, the ratio of the insulating particles that are detached from the surface of the conductive particles is extremely small. In particular, in the anisotropic conductive paste using the conductive particles with insulating particles of Example 1, compared with the anisotropic conductive paste using the conductive particles with insulating particles of Comparative Example 1 'The proportion of insulating particles that are detached from the surface of the conductive particles is extremely small. Further, in the anisotropic conductive paste using the conductive particles with insulating particles of Example 2, compared with the anisotropic conductive paste using the conductive particles with insulating particles of Comparative Example 2 The ratio of the self-guided particles of the series is very good. Doc •53- 201213493 Less. The reason for this is considered to be that a film is formed in the conductive particles having insulating particles attached to Examples -15 to 15, so that the separation of the insulating particles is suppressed. Further, in the anisotropic conductive paste using the conductive particles with insulating particles of Example 2, in comparison with the anisotropic conductive paste using the conductive particles with insulating particles of Example 相比The proportion of insulating particles that are detached from the surface of the conductive particles is small. The reason for this is that the surface of the insulating particle A' insulating particles of the second embodiment is coated with a soft layer formed of a polymer compound, so that the separation of the insulating particles is suppressed. [Brief Description of the Drawings] Fig. 1 is a cross-sectional view showing conductive particles with insulating particles according to a first embodiment of the present invention. Fig. 2 is a cross-sectional view showing conductive particles with insulating particles according to a second embodiment of the present invention. Fig. 3 is a cross-sectional view showing conductive particles with insulating particles according to a third embodiment of the present invention. Fig. 4 is a cross-sectional view showing conductive particles with insulating particles according to a fourth embodiment of the present invention. Fig. 5 is a front cross-sectional view schematically showing a connection structure using conductive particles with insulating particles shown in Fig. 1. Fig. 6 is a cross-sectional view showing conductive particles with insulating particles attached previously using a hybrid method. [Explanation of main component symbols] 157831,doc • 54- 8 201213493 1 , 21 , 41 , 61 , 101 Conductive particles with insulating particles 2 ' 22 , 42 , 62 Conductive particle body with insulating particles 3 ' 23 Film 11 , 31 , 71 , 102 Conductive particles 12 Base material particles 13 , 32 , 76 Conductive layers 15 , 35 , 45 , 103 Insulating particles 33 Core material 34 , 77 Projection 45 a Insulating particle body 45 b Layer 51 Connection structure 52 First connection object member 52a Upper surface 52b' 53b Electrode 53 Second connection object member 53a Lower surface 54 Connection portion 76a First conductive layer 76b Second conductive layer 102a is insulated from the surface of the conductive particle 102 The portion 102b of the particle 103 is attached to the surface of the conductive particle 102 157831. Doc -55- 201213493 Part of the portion 102a of the insulating particles 103. Polymer compound 157831. Doc •56· 8