1332027 玖、發明說明： 明所屬之拮術領诚 —本發明係有關異向性導電電路連接用黏著劑使用該 黏著劑之電路板的連接方法與電路連接構造體，更詳細= 說’係有關低溫快速硬化性優異，且： 連接電阻亦安定之-性導電電路連接㈣著劑=用 該黏著劑之電路板的連接方法以及連接構造體者。 先前拮術 近年’在半導體或液晶顯示器等範疇中 子零件，或為了進行雷政、鱼拉 ^固疋電 算用、連接而使用各種黏著材料，在此 等用途中，越來越邁向高密度化、高精細 = 也要求有高黏著力或高可信賴度。 …面 :其做為電路連接材料者，在使用 或是FPC與Tcp之連 裔與TCi 用在點著劑中分散有導電粒子與：刷配線板之連接，是使 著劑。最近在基板異向性導電電路連接用黏 統的導線連結，而是進行 才木用傳 構裝在基板上之所 A t正面朝下直接 使用異向性導電電路連 號、特開昭6G，228號;了二特開昭59—12_ 7一9〇237號公報）。 4千1 —25 1 787號、特開平 化，二 =ΪΓ子機器範嘴中，電路正邁向高密度 寬及电極間ρ南變爲技 用環氧樹脂系之電路連接用$狹此’在—向使 用黏者劑之連接條件下，會產生 5 313294D1 1332027 配線脫落、剝離、位置不吻合等問題。為了提高生產率， 強力要求連接時間需縮短在1G秒鐘以下’低溫快速硬化性 因而成為不可或缺之要求。為此，在特開平1〇_ 273636 號公報中揭示使用自由基聚合性物質之電路連接用材料。 然而，含有（甲基；）丙烯酸酯、磷酸酿化合物等之自 由基聚合性物質與導電粒子之黏著劑若放置在空氣中則 連接後之連接電阻會有上昇之問題。 發明内衮 本發明提供低溫快速硬化性優異、保存安定性良好、 連接電阻安定之電路連接用黏著劑，纟高濕度條件下之保 存期限優異之異向性導電電路連接用黏著劑，以及使用該 黏著劑之電路板連接方法與連接構造體。 本發明是有關以使導電粒子均句分散 ::電生：物中，至少是由™構成為其特徵之異向 拴導電電路連接用黏著劑： 子、⑴在表面不露出銀、金、m卜之過渡金屬的導電粒 (2) 自由基聚合性物質、 (3) 由加熱或光產生游離基之硬化劑。 薄膜二Γ明是有關以使導電粒子均勾分散而成之樹脂 向性導電=中’至少是由以下成分所構成為其特徵之異 導電电路連接用黏著劑： 子、⑴在表面不露出銀、金1以外之過渡金屬的導電粒 313294D1 6 1332027 (2) 自由基聚合性物質、 (3) 由加熱或光產生游離基之硬化劑，及 (4) 磷酸酯化合物 本發明亦有關將上述異向性導電電路連接用黏著劑 介入具有相對向電路電極的基板間，加壓具有相對向電路 電極的基板，㈣’依場合不同，照射光（活性能源）將 加屢方向之電極間以t氣連接電路板之連接方法。 八本發明又有關將上述異向性導電電路連接用黏著劑 ^具有相對向1路電極的基板間’加壓具有相對向電路 造：的基板後，將加壓方向之電極間以電氣連接之連接構 …一發明之異向性導電電路連接用黏著劑，即使放置在 度下’在連接㈣經耐濕試驗、冷熱循環等各種 ;降’：:驗後，也能夠抑制連接電阻之上昇或連接強度之 下降，顯示具有優異連接可信度。 表面電路連接用黏著齊^是在薄膜、被黏著體 形成之異向性導電樹脂。 麼4=有關介入具有相對向電路電極的基板間，加 電氣連接之異向性導電電路 ：之電極間以 以含有經由,、 ⑨制㈣劑，上述黏著劑係 化合物及至…:二由A基聚合性化合物’及（2)驗性 化合物進行表面虚¥ 化合物所成組群中至少一種 路連接用㈣％後之導電粒子為特徵之異向性導電電 β。上述異向性導電電路連接用黏著劑，係 313294D1 U32027 以含有由光或加熱產生自由基之化合物或磷酸酯化合物者 為佳。再者，本發明之異向性導電電路連接用黏著劑，係 以表面處理令使用之鹼性化合物為胺系化合物者為佳。 又，本發明之另一種形態，是將異向性導電電路連接 用黏著劑介入在具有相對向電路電極的基板間，加壓具有 相對向電路電極的基板後，將加壓方向之電極間以電氣連 接而成之連接構造體向性導電電路連接用黏著劑係有 關含有經由選自⑴自由基聚合性化合物及⑺驗性 化合物及至少冑i個環氧基之化合物所成組群中至少 化合物進行表面處理後 遙 ^ 電路連接構造體。 子电 f施方式. 本發明的異向性導電電* φ % ^ _ 連接用黏耆劑，是使用在導 電粒子表面上不露出銀、 仕导 電粒子。為了可以充八^ 之鎳等過渡金屬的導 ^ ± Φ ^ 77付彳耐濕保存期限及連接可信度， 取表面之金屬必需是銀、金、_ / 在本發明的異向性導 权住 導電粒子，σ要右叮電電路連接用黏著劑中使用之 要有可以得到電氣遠技十.s 特別限定，伸可u ” 之導電性即可，而無 屬粒子或碳等。又， :銀、鎳、鋼 '鈷、錫等之金 之非導電性之玻璃、陶：以：用:乂上迷金屬導電物質被覆 厚度，為了可_ 、膠等。此時，被覆金屬層之 在姑、鋅、鋼、錄等過渡金Hi置以上為宜。 金屬類層之缺損哎又置貝金屬類層時，因貴 w 4等電粒子 刀政時所產生之貴金屬類 8 313294D1 e缺&等所產生的氧化還原作S，會產生游離基而弓I起保 j限減紐，所以導電粒子需經表面處理。導電粒子之使 。用 '圍為相當於電路連接用黏著劑成分之〇丨至3〇體積 最好使用0· 1至2〇體積％之範圍。 做為導電粒子表面處理之化合物，以對酸性物質具有 1〜ϋ之化合物來處理為宜，依此處理可以顯著提高上述 "向性導電電路連接用黏著劑之保存安定性。 小做為導電粒子表面處理之化合物，以鹼性化合物或至 4固環氧基之化合物為宜，尤其做為鹼性化合物者 以胺系化合物為佳。 物者 解到有機：化°物者’液體、固體都可以，固體需先溶 以溶解Π1或水等然後使用。又，液體之化合物中，也 要η-劑等然後使用為宜。做為有機溶劑者，只 月“解虱系化合物而不與氨系化合 別限制，但…、乙醇、異丙醇、甲乙二者：可’無特 甲焚哲+ τ匕酮、醋酸乙酷、 專免理後能乾燥導電粒子者為宜。 處理液中所含胺系化合物之濃度， %為宜，·〇5至20重量 未滿0.05重量％時不能有效 20重量％時導 、面處理，超過 才等笔粒子表面被覆之氨系化人 電阻變高。 。物$變多，連接 做為至少具有〗個環氧基之化合物 可以，固體之場合需使溶解在有機溶:液體、固體都 又，液體之化合物也以使用；容解到有機容 < 等然後使用。 宜。做為有機溶劑者，只要能溶解至 齊1等然後使用為 ^，、有1個環氧基之 9 313294D1 不與至少具有1個環氧基之化合物反應者即可， r:特別::制，以甲醇、乙醇、異丙醇、甲乙嗣、醋酸乙 曰曱苯等表面處理後能乾燥導電粒子者為宜。 處理液中所含至少具有^固環氧基之化合物濃度，以 5至2〇重量％為宜，未滿〇 〇5重量％時不能有效進行表 超過20重量％時，導電粒子表面被覆之至少具有 固嶮氧基之化合物量變多，連接電阻變高。 表面處理時之溫度、時間等處理條件，並無特別限 1 ’但處理溫度是以室S (25。〇至1G(rc、處理時間是 以1 〇秒至1小時之範圍為宜。 又，處理後之導電粒子是經過濾後乾燥才使用，乾燥 條件隨使用之有機溶劑而作適當之選擇，但在室溫（25。〇 至10 〇 °c中進行。 本發明之表面處理所使用之驗性化合物，尤其做為氛 土化合物者可以列舉如，三乙胺、二乙胺、丁胺、乙二胺、 六甲基二胺、苯胺 '胺基丙基三甲氧基矽烷、咪唑、2 -乙 基-4-甲基味唑、2_苯基—卜氰基乙基咪唑、苯乙基味 唑、苯乙基。定等’胺系中可以列舉卜級之級、3級胺， 也可以使用混合2種類以上者。 本發明之表面處理所使用之至少具有丨個環氧基之化 合物，可以使用苯基縮水甘油醚、（甲基）丙烯酸縮水甘油 酯、r一垓氧丙氧基丙基三甲氧基矽烷、環氧丙氧基 丙基二乙氧基矽烷、r一環氧丙氧基丙基甲基二甲氧基矽 烧、7 —環氧丙氧基丙基二乙氧基石夕貌、点一（3，4環氧 10 313294D1 環己基）乙基三甲氧基矽1332027 玖 发明 发明 发明 发明 发明 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — It is excellent in low-temperature rapid hardenability, and: the connection resistance is also stabilized - the conductive circuit is connected (4) the agent = the connection method of the board using the adhesive, and the connection structure. Previously, in recent years, in the sub-components such as semiconductors or liquid crystal displays, or in order to carry out Lei Zheng, fish pull, solid use, and connection, various adhesive materials have been used. In these applications, more and more high density has been adopted. Chemical, high-precision = also requires high adhesion or high reliability. ...face: It is used as a circuit connecting material, and it is used as a connecting agent between FPC and Tcp and TCi. The conductive particles and the connection of the brush wiring board are used as a bonding agent. Recently, in the substrate anisotropic conductive circuit connection, the bonding wire of the bonding system is connected, and the A t is directly mounted on the substrate, and the anisotropic conductive circuit serial number and the special opening 6G are directly used. No. 228; the second special opening 59-12_7-9〇237 bulletin). 4 thousand 1 - 25 1 787, special Kaiping, two = ΪΓ子 machine van mouth, the circuit is moving towards high density and the electrode between the south and the technical epoxy resin circuit connection 'In the case of the connection to the adhesive, 5 313294D1 1332027 wiring, peeling, position mismatch, etc. will occur. In order to increase productivity, it is strongly required that the connection time be shortened to less than 1 Gsec, and the low-temperature rapid hardening property becomes an indispensable requirement. For this reason, a material for circuit connection using a radical polymerizable substance is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 273636. However, if the adhesive containing a free radical polymerizable substance such as a (meth;) acrylate or a phosphoric acid absorbing compound and a conductive particle is placed in the air, the connection resistance after the connection increases. The present invention provides an adhesive for connecting a circuit having excellent low-temperature rapid hardenability, good storage stability, and stable connection resistance, and an adhesive for connecting an anisotropic conductive circuit excellent in shelf life under high humidity conditions, and using the same The board connection method and the connection structure of the adhesive. The present invention relates to an adhesive for connecting conductive particles in a uniform state: an electro-optical material, at least consisting of TM, which is characterized by a metamorphic germanium conductive circuit: sub-, (1) does not expose silver, gold, m on the surface a conductive particle of a transition metal of (2) a radically polymerizable substance, (3) a hardener which generates a radical by heating or light. The film is a non-conductive circuit-connecting adhesive which is characterized in that the conductive conductive particles are dispersed in a conductive state, and at least the following components are formed: sub-, (1) no silver is exposed on the surface. Conductive particles of a transition metal other than gold 1 313294D1 6 1332027 (2) a radically polymerizable substance, (3) a hardener which generates a radical by heating or light, and (4) a phosphate compound. The present invention also relates to the above The adhesive for connecting the conductive conductive circuit is interposed between the substrates having the opposing circuit electrodes, and the substrate having the opposing circuit electrodes is pressurized, and (4) Depending on the occasion, the illuminating light (active energy source) is added between the electrodes in the repeated direction. Connection method for connecting boards. According to another aspect of the invention, the adhesive for connecting the anisotropic conductive circuit has a substrate that is pressed against the substrate of one of the electrodes, and is electrically connected to the electrodes in the pressurizing direction. The connection structure...the adhesive for connecting the anisotropic conductive circuit of the invention, even if placed under the degree of 'wet resistance test, cold and heat cycle, etc.; after the drop::, the connection resistance can be suppressed or The decrease in connection strength shows excellent connection reliability. The surface circuit is bonded to the anisotropic conductive resin formed on the film or the adherend. 4=About the intervening conductive circuit between the substrates having the opposite circuit electrodes and the electrical connection: the electrodes are interposed between the electrodes to contain the vias, the above-mentioned adhesives, and the above-mentioned adhesive compounds and The polymerizable compound 'and the (2) test compound are characterized by an anisotropic conductive electric β characterized by at least one type of conductive particles in a group of surface-defining compounds. The above-mentioned anisotropic conductive circuit-bonding adhesive is preferably 313294D1 U32027, which contains a compound or a phosphate compound which generates a radical by light or heat. Further, in the adhesive agent for connecting an anisotropic conductive circuit of the present invention, it is preferred that the basic compound used for the surface treatment is an amine compound. Further, in another aspect of the present invention, the anisotropic conductive circuit-connecting adhesive is interposed between the substrates having the opposing circuit electrodes, and the substrate having the opposing circuit electrodes is pressurized, and then the electrodes in the pressing direction are interposed. The connection structure for electrically connecting the electrically conductive circuit-connecting adhesive is a compound containing at least a compound selected from the group consisting of a compound selected from the group consisting of (1) a radically polymerizable compound and (7) a test compound and at least one epoxy group. After the surface treatment, the remote circuit is connected to the structure. The electric conductivity of the present invention is the same as that of the conductive material of the present invention. In order to be able to charge the transition metal of the transition metal such as nickel, the corrosion-resistant shelf life and the reliability of the connection, the metal of the surface must be silver, gold, _ / anisotropic power in the present invention. The conductive particles are used, and the σ is required to be used in the adhesive for connecting the right electric circuit. The electric telescope can be obtained. The conductivity of the electric ray can be obtained without any particles or carbon. : silver, nickel, steel, cobalt, tin, etc., non-conductive glass, ceramic: to: use: the thickness of the metal conductive material coated on the enamel, in order to _, glue, etc. At this time, the coated metal layer It is advisable to set the transitional gold Hi such as Zn, Zinc, Steel, and Recording. When the metal layer is defective and the shell metal layer is placed, the precious metal 8 313294D1 e lack & The oxidation-reduction produced by S, etc., will generate free radicals and the electrons will be subjected to surface treatment. Therefore, the conductive particles are required to be used. The volume of 〇丨 to 3 最好 is preferably in the range of 0.1 to 2 vol%. The sub-surface-treated compound is preferably treated with a compound having 1 to 酸性 of an acidic substance, and the treatment can significantly improve the storage stability of the above-mentioned adhesive for directional conductive circuit connection. The compound is preferably a basic compound or a compound having a 4-epoxy group, and particularly preferably a basic compound is an amine compound. The solution is organic: the liquid can be liquid or solid. The solid needs to be dissolved first to dissolve hydrazine 1 or water, etc. Further, in the liquid compound, it is also preferred to use η-agent, etc., as an organic solvent, only "resolving lanthanide compounds and not combining with ammonia systems" Do not limit, but ..., ethanol, isopropyl alcohol, A and B: can be 'no special armor burning zh + τ ketone, acetic acid B cool, can be used to dry conductive particles after special treatment. The concentration of the amine compound contained in the treatment liquid is preferably %, and when the weight of 5 to 20 is less than 0.05% by weight, the amount of the amine compound is not effective at 20% by weight, and the surface treatment is carried out. The resistance becomes high. . The amount of material is increased, and the connection is made as a compound having at least one epoxy group. In the case of a solid, it needs to be dissolved in an organic solvent: liquid, solid, and liquid compound are also used; and the organic solvent is allowed to be used. Then use. should. As an organic solvent, as long as it can be dissolved to 1 and then used as a ^, there is an epoxy group 9 313294D1 does not react with a compound having at least one epoxy group, r: special:: It is preferred to dry the conductive particles after surface treatment with methanol, ethanol, isopropanol, methyl ethyl hydrazine or ethyl acetate. The concentration of the compound having at least an epoxy group contained in the treatment liquid is preferably 5 to 2% by weight, and when the amount is less than 5% by weight, the surface of the conductive particles is at least 20% by weight. The amount of the compound having a solid methoxy group increases, and the connection resistance becomes high. The processing conditions such as temperature and time during surface treatment are not particularly limited to 1 'but the treatment temperature is chamber S (25. 〇 to 1G (rc, processing time is preferably in the range of 1 sec to 1 hr. The treated conductive particles are used after being dried by filtration, and the drying conditions are appropriately selected depending on the organic solvent to be used, but are carried out at room temperature (25 to 1010 ° C. The surface treatment of the present invention is used. The test compound, especially as an organic compound, may, for example, be triethylamine, diethylamine, butylamine, ethylenediamine, hexamethyldiamine, aniline 'aminopropyltrimethoxydecane, imidazole, 2 -ethyl-4-methyl oxazole, 2-phenyl-cyanoethylimidazole, phenethyl sulphonazole, phenethyl. The determinate 'amine system can be listed as a grade, a grade 3 amine, It is also possible to use a mixture of two or more types. The compound having at least one epoxy group used in the surface treatment of the present invention may be a phenyl glycidyl ether, a glycidyl (meth)acrylate or a rhodium oxyfluoride. Propyl trimethoxydecane, glycidoxypropyl diethoxy decane, R-glycidoxypropylmethyldimethoxy oxime, 7-glycidoxypropyldiethoxylate, point one (3,4 epoxy 10 313294D1 cyclohexyl) ethyltrimethyl Oxyquinone
别^ 夕烷、雙酚A型環氧樹脂、雙酚F 里辰氧樹脂、雙齡§型環氧樹 衣乳樹月日、酚醛清漆型環氧樹脂、 清漆型環氧樹脂、” A _清漆型環氧樹脂、 g:二齡Π漆型環氧樹脂、脂環式環氧樹脂、縮水甘油 -曰i環氧树脂、縮水甘油胺型 1衣乳树月日、乙内醯脲環氧樹 曰、異氰酸S旨型環氧樹脂、脂肪族鏈狀環氧樹脂等，此等 核氧樹脂也可以“，也可以添加氫。也可以併用2種以 上此等環氧化合物。 本發明之異向性導電電路連接用黏著劑中使用之自 由基聚合性化合物’係具有由自由基誘發聚合之官能基之 化口物有（曱基）丙稀酸醋樹脂、馬來酸野縮亞胺樹脂、 寧康醯亞胺樹脂、萘齡二亞胺樹脂等，也可以使用2種類 、上之混δ物又自由基聚合性化合物也可以使用單體、 寡聚合物中之任一種狀態，也可以使用單體與募聚合物之 扣合物，在此『（甲基）丙烯酸酯』是指丙烯酸酯及其相對 應之甲基丙烯酸酯。 做為（曱基）丙烯酸酯樹脂者，是使（曱基）丙烯醆 酯進行自由基聚合而得者，做為（甲基）丙烯酸酯者，可 列舉如（曱基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基） 丙烯酸異丙酯、（甲基）丙烯酸異丁酯 '二（曱基）丙烯酸 乙二醇酯、二（甲基）丙烯酸二乙二醇酯、三（曱基）丙 烯酸二甲醇丙從酯 '四（曱基）丙烯酸四甲基乙二醇酯、2 —羥基一 1，3 -二丙烯醯丙烷、2, 2—雙[4—(丙烯醯曱氧 基）苯基]丙烷、2, 2—雙[4 一（丙烯醯乙氧基）苯基]丙烷' 11 313294D1 -舻：）丙烯駄—％戊烯酯、（曱基）丙烯酸三環癸烷、異 乳二二（丙烯醯乙基）酿、（甲基 酸胺 Γ:改質二氛酸等，可單獨使用也可以使用兩種以上混合 西曰又’由於必要，在不損及硬化性範圍下也可以使用氫 I、曱基醚氫醌等之自由基聚合禁止劑。 β八者使用磷酸酯化合物做為自由基聚合性化合物之 0十對金屬等無機物可以提高接著力。此麟酸g旨化合 ::使用量是相對於接著劑成分100重量份的(M至丨0重 里伤車乂佳為〇·5至5重量份。磷酸酯化合物是由無水磷 酉文矛（曱基）丙烯酸2 —經基乙酷之反應生成物而得。具 體的有單（曱基丙稀醯乙基）酸磷酸、i (曱基丙稀酿乙 基）酸磷酸等’可單獨或混合使用。 做為馬來酸酐縮亞胺樹脂者，是分子中至少含有1個 馬來酸酐縮亞胺者，例如苯基馬來酸酐縮亞胺、丨_曱基— 2’4 —馬來酸酐縮亞胺隻苯、N，N，— m_苯基雙馬來酸酐縮 亞胺、Ν，Ν’ 一 p —苯基雙馬來酸酐縮亞胺、N，N，_ 4, 4 一 雙苯基雙馬來酸酐縮亞胺、N，N，一4,4- (3，3 —二曱基 二苯基）雙馬來酸酐縮亞胺、N，N，一4, 4— (3, 3 —二甲 基二苯基曱烷）雙馬來酸酐縮亞胺、N，N，一4, 4- (3, 3 —二乙基雙苯基曱烷）雙馬來酸酐縮亞胺、N，N，一 4, 4-二苯基乙烷雙馬來酸酐縮亞胺、Ν, Ν’一 4, 4 —二苯基丙烷 雙馬來酸酐縮亞胺' Ν，Ν’一4,4 —雙苯基乙謎雙馬來酸酐 縮亞胺、Ν，Ν’一 4, 4-雙苯基磺基雙馬來酸酐縮亞胺、2, 2 —雙（4— (4 —馬來酸針縮亞胺苯氧基）苯基）丙烧、2,2 12 313294D1 1332027 一雙（3 — s— 丁基一3, 4— (4 —馬來酸酐縮亞胺苯氧基） 苯基）丙炫·、1,1—雙（4— (4一馬來酸肝縮亞胺苯氧基） 苯基）癸烷、4, 4 一環亞己基-雙（1 — ( 4 一馬來酸酐縮 亞胺本氧基）苯氧基）一2 —環己基苯、2,2 —雙（4— (4 —馬來酸酐縮亞胺苯氧基）苯基）六氟丙烷等，可單獨使 用也可以使用兩種以上混合。 做為寧康醯亞胺樹脂者，是將分 一， 4 康醯亞胺基之寧康醯亞胺化合物聚合而成者，做為寧康醯 亞胺化合物者，例如有苯基寧康醯亞胺、1 —曱基—2, 4 — 雙寧康醯亞胺苯、N，N，—m—苯基雙寧康醯亞胺苯、n，n， —P—苯基雙寧康醯亞胺苯、N，N，_4,4-雙苯基雙寧康醯 亞胺、Ν，Ν’-4, 4— ( 3, 3一二甲基二苯基）雙寧康醯亞 胺、Ν，Ν，一 4, 4— (3, 3—二甲基二苯基甲烧）雙寧康醯 亞胺、Ν，Ν’-4, 4— (3, 3 -二乙基二笨基甲烷）雙寧康 醯亞胺、Ν，Ν’—4, 4—二苯基甲烷雙寧康醯亞胺、ν，ν， —4,4 —二苯基丙烷雙寧康醯亞胺、Ν, Ν，一 4, 4 —二苯美 ㈣雙寧康醯亞胺、Ν，Ν，—4,4—雙苯基續基雙寧康：亞 胺、2,2—雙（4— (4 一寧康醯亞胺苯氧基）苯基）丙烷、 ，雙（3 s — 丁基一 3, 4— (4 —寧康醯亞胺苯氧基 苯基）丙院、1 1 一雒（4 ( λ a ，1又（4一（4~寧康醯亞胺苯氧基）笨 基）癸院' 4, 4 —環亞己基一雙（丨〜 金志狀 # (4 —寧康醯亞胺笨 氧基）本氧基）一2 —環？其贫、〇 η %己基本、2,2~雙（4— (4—宝 醯亞胺苯氧基）苯基）六氟丙烷等，可單彳' 用兩種了早獨使用也可以使 13 313294D1 1332027 做為萘酚二亞胺樹脂者，是將分子中至少含有1個萘 酚二亞胺基之萘酚二亞胺化合物聚合者，做為蔡酚二亞胺 化合物者，例如有萘盼二亞胺、1—甲基一2，4_雙萘紛二 亞胺、N，N， — · 萘酚二亞胺苯、Ν，Ν’一 4, 4 -雙苯基雙萘酚二亞胺、Ν, Ν’ -4,4— (3, 3—二曱基二笨基）雙萘酚二亞胺、Ν，Ν’一4, 4— (3, 3 —二甲基二苯基曱烷）雙萘酚二亞胺、Ν,Ν’一4, 4_ (3, 3 —二乙基二苯基曱烷）雙萘酚二亞胺、ν，Ν’一4, 4 一二笨基曱炫·雙萘酌二亞胺、Ν，Ν’一 4，4 —二苯基丙院雙 萘酚二亞胺、Ν, Ν’一 4, 4 -二苯基***雙萘酚二亞胺、Ν， Ν’一4, 4 —雙苯基磺基雙萘酚二亞胺、2, 2 -雙（4— (4 —蔡齡二亞胺苯氧基）苯基）丙烷、2,2_雙（3_s 一丁 基一 3, 4— (4一萘酚二亞胺苯氧基）苯基）丙烷、丨，^ 雙（4— (4—萘酚二亞胺苯氧基）苯基）癸烷、4, 4—環 亞己基雙（1_ (4 一萘酚二亞胺苯氧基）苯氧基）_2 2己基m雙（4— (4 —蔡紛二亞胺苯氧基）笨 基）六氟丙烧等，可單獨使用也可以使用兩種以上混人 使用上述自由基聚合性化合物之場合，是使用聚合：始 :為由加熱或光產生游離基之硬化劑。做為聚合起始劑 :只要能由加熱或光產生自由基之化合物即可…別 、制。有過氧化物、偶氮化合物等，可隨接著溫产“士 間、保存安定性等目的適當選擇 Λ 者捋 定，14 4〜 攸呵反應性和保存容 之硯點來看，以半衰期為10小時 t 半笋细了 皿度為4〇°C以上， 裒d為1分鐘之溫度為i 8(rc 下之有機過氧化物為 14 313294D1 丄JJZUZ/ 佳。半农期為10小時之溫度為4〇。。以上 鐘之溫度為17〇t以^七 +哀d為1分 1Λ 41 下之有機過氧化物尤佳。接著& 10秒之場合，為 接者呀間為 传到充分反應率之聚合起始劑的阳八 相對於接著劑之總量，以^20重量%為：的配合 15重量％為特佳 里為佳，以2至 選自用之有機過氧化物者，可以 ^目—酿過氣化物、__ 化物酮縮醇、-”：乳化物、過氧化物醋、過氧 氧化物等化物、氫過氧化物、甲錢基過 乳化物酯、二烷基過氧化物、氫過氧化 酸在SO:基過氧化物等’因為起始劑中之氣離子或有機 -义在5000 PPm以下’分解後產生之有機酸很少， 制電路構材之接著端子之腐姓，所以特佳。由可得高反應 性之過氣化物S旨來選定更佳，此等可以適當混合使用。 做為二醯過氧化物類者，可列舉如異丁基過氧化物、 2,4—二氯苯醯過氧化物、3,5, 5—三甲基己醯過氧化物、 辛醯過氧化物、十二基醯過氧化物、硬脂醯過氧化物、琥 珀醯過氧化物、過氧化物、苯醯過氧化物甲#、苯醯過‘ 化物等。 做為二碳酸過氧化物類者，可列舉如二一 η _丙基過 氧化物二碳酸鹽、二異丙基二碳酸鹽過氧化物二碳酸鹽、 雙（4 —三級一丁基環己基）過氧化物二碳酸鹽、二—2 — 乙氧基甲氧基過氧化物二碳酸鹽、二（2_乙基己基過氧化 物）一碳酸鹽、二甲氧基丁基二碳酸過氧化物二碳酸鹽、 一（3—甲基_3—乙氧基丁基過氧化物）二碳酸鹽等。 做為過氧化物酯者，可列舉如丙基過氧化物新癸酸 15 313294D1 1332027 賴、1，1，3，3 —四曱基丁基過氧化物新癸酸酯、1 一環己烏 ~ 1 一甲基乙基過氧化物新癸酸酯、三級一己基過氧化物^ 癸酸醋、三級_ 丁基過氧化物新癸酸g旨、1，1，3 3 —四甲 基丁基過氧化物一2 —乙基己酸醋、2，5 —二甲基—2 5 二（2—乙基己醯基過氧化物）己烷、1 —環己基—丨—甲式 乙基過氧化一2 —乙基己酸酯、三級—己基過氧化物一2〜 乙基己酸酯、三級一丁基過氧化物—2~乙基己酸酯、三級 —丁基過氧化物異丁酸酯、1，1—(三級過氧化物）環己 烧、三級—己基過氧化物異丙單碳酸鹽、三級一丁基過氧 化物一3，5，5 —三曱基己酸酯、三級—丁基過氧化物月桂 酸酯、2, 5 -二甲一2, 5 —二（m—曱苯醯過氧化物）己烷、 二級'•丁基過氧化物異丙烷單碳酸酯、三級—丁基過氧化 物一2 -乙基己基單碳酸酯、三級—已基過氧化物苯酸酯、 二級一丁基過氧化物乙酸酯等。 做為過氧化酮縮醇類者，可列舉如丨，1 三級—己 基過氧化物）一3, 3, 5—三曱基環己烷、1，1—(三級—己 基過氧化物）環己烷、丨，丨_ (三級一 丁基過氧化物）_ 3，5 —曱基環己院、1，1—(三級一丁基過氧化物）環癸 炫、2, 2 —雙（三級一丁基過氧化物）癸烷等。 做為二烷基過氧化物類者可列舉如，α，α，一雙（三 級 丁基過氧化物）二異丙苯、二異苯丙基過氧化物、2, 5 —一曱基一25 —二（三級一丁基過氧化物）己烷、三級— 丁基異笨丙基過氧化物等。 做為氫過氧化物類者可列舉如，二異丙基苯氫過氧化 16 313294D1 1332027 物、異苯丙烷氫過氧化物等。 做為甲石夕烧基過氧化物類者可列舉如，三級一 丁基三 甲基甲石夕院基過氧化物、雙（三級一丁基）二$基曱矽烷 基過氧化物、三級一丁基三乙烯基曱矽烷基過氧化物、雙 (二級一丁基）二乙烯基甲矽烷基過氧化物、三（三級_ 丁基）二乙烯基甲矽烷基過氧化物、三級—丁基三丙烯基 曱矽烷基過氧化物、雙（三級一丁基）二丙烯基甲矽烷基 過氧化物、三（三級—丁基）丙烯基甲矽烷基過氧化物等。 又’為了抑制電路構材之連接端子之腐蝕，游離基發 生劑（硬化劑）中所含之氯離子或有機酸是以在5〇〇〇 以下為宜’再者’加熱分解後產生之有機酸以少者為佳。 又在長：尚製成電路連接材料之安定性上，以室溫（2 $ )、 吊壓下開放放置24小時後仍具有2〇重量％以上之重量保 持率者為宜’此等可適當混合使用。 此等游離基發生劑可以單獨或混合使用，也可以與分 解促進劑、抑制劑等混合使用。 又，此等游離基發生劑以聚胺酯系、聚酯系之高分子 物處等覆蓋後使之微膠囊化之產物，因能延長可使用時 間’所以較佳。 ^自由基聚合性化合物以外，也可以配入做為熱硬化性樹 之環氧树知。做為環氧樹脂者，有雙酚A型環氧樹脂、雙 :F型％氧樹脂 '雙酚S型環氧樹脂、酚醛清漆型環氧樹 =、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹 月曰、雙酚F酚醛清漆型環氧樹脂、脂環式環氧樹脂 '縮水 17 313294D1 1332027 甘油酉旨型環氧樹脂、縮水甘油胺型環氧樹脂、乙内 氧樹脂、異氰酸酿型環氧樹脂、脂肪族鍵狀 乂 二等環氧樹脂也可以W化、也可以加氫。此等環氧^ 也可以併用2種以上。 又，做為上述環氧樹脂之硬化劑者，可使用如胺類、 酉分類、酸針類、P米。全麵 _ g _ 坐類-亂-醯胺等通常做為環氧樹脂 1者。再者’冑為硬化促進劑者，通常可以適當使用 3級胺、有機磷系化合物。 、又，做為使環（氧樹脂反應之方㈣，在使用上述硬化 d X外也可以使用四價硫（sulf〇nium ;硫鑰）鹽、碘鐯 鹽等’使陽離子聚合也可以。 本發月之電路接著用黏著劑或異向性導電樹脂薄 膜狀；成物中，為了賦與薄膜形成性、黏著性、硬化時之 應：緩和性’一般要使用聚乙烯丁縮醛樹脂、聚乙烯甲縮 酸樹月a聚酉旨樹脂、& gi胺樹脂、聚亞醯胺樹脂、二甲苯 樹：、聚胺酯樹脂、尿素樹脂等高分子成分，&等高分子 成刀疋以分子量為1(M〇〇 S 10,000,000者為宜。又，此 等树月曰’也可以是自由基聚合性之官能基所變成，在此場 口耐熱性提两。再者’也可以是用自由基聚合性之官能基 或％氧基’綾基等所變成，在此場合耐熱性會提高。高分 子成刀之配合量為2至80重量％，以5至70重量％為宜， :1 〇至6〇重量％最好。不S 2重量％時，應力緩和或黏 著力不足，超過8〇重量％時流動性下降。 00 少- x <呉向性導電電路連接用黏著劑中，也可以添 18 313294D1 1332027 加適當之充填劑、軟化劑、侦 „ , „ 促進劑、老化防止劑、著色劑、 難燃劑、偶合劑。 含有充填劑之場合，因可 』以钗円黏者可信度等，所以 k好，填充材之最大粒徑只要 不超過導電粒子之粒徑就可 以使用，以5至6〇體積％範圍為宜，超過60體積％時， I信度提高效果就達到飽和。做為偶合劑者，以含有乙稀 基/稀基、胺基、環氧基、酸胺基及異氛酸基者，因可 以提向黏著性所以較佳。 化時：τ將广發明之異向性導電電路連接用黏著劑做為硬 =Tg (玻璃轉移度)，也可以為不同之2種類以上之 層所成之多層構造。 a板吏ϋ明之異向性導電電路連接用黏著劑之黏著 觸二必要之電氣點接電極者就可以，而無特 =塑=:在液晶顯示器中使用…形成電極之 刷配線板'土& pdp平板、el平板等畫像顯示基板、印 陶究配線板、可撓配線板、半導體晶片、申阻 =半：Γ晶片等晶片組件、磁帶包裝、C〇F等之電路 零件+導體砂晶片等，必要時可以組合使用。 ::時之條件並無特別限制，但點接溫度為9〇至250 二:ΤΓ1秒鐘至10分鐘之間，使用之用途可以依 不同而作適當選擇，視需要也可以使用熱 月匕源，例如光、超音波、電磁波等。 實施例 、 、貝她例來具體说明本發明，但本發明之範圍 19 313294D1 1332027 並不限定於該等實施例。 (實施例1) 將50g之苯氧樹脂（union carbide公司製，商品名 PKHC，平均分子量45,〇〇〇 )溶解於MEK (曱乙酮，沸點 79_6°C ) ’成為固形分5〇重量％之溶液。 自由基聚合性物質使用異氰酸環氧乙烷改質之二丙 烯酸酯（東亞合成公司製，商品名Μ — 2 1 5 )及磷酸酯型 丙烯酸酯（共榮社油脂株式公司製、商品名Ρ — 2Μ ) » 加熱或光產生游離基之硬化劑，使用2, 5 —二甲基一 2, 5—雙（2 —乙基己醯基過氧化物）己烷之5〇重量。/。碳化 氫溶液（日本油脂公司製，品名Perhexa 250 )。 導電粒子係使用在以聚苯乙烯當作核心的粒子（壓縮 彈性率480 kg/mm2)表面上，設置厚度為〇.〇9 /z m之銀 層而成之平均粒子徑5 # m之導電粒子。 固形重量比係以苯氧基樹脂50g，異氰酸環氧乙烷改 質之二丙烯酸酯50g，磷酸酯型丙烯酸酯2 g，2, 5 ~二曱 基_2,5—雙（2 —乙基己醯基過氧化物）己烷5g之模式 配入’再將導電粒子3體積％配入分散，再以塗抹裝置塗 布於單面經表面處理之厚度的PET (聚對苯二甲酸 乙酯）薄膜，經701'1 〇分鐘之熱風乾燥，可得黏著劑層 厚度為35/zm之異向性導電電路連接用黏著劑。 (實施例2) 導電粒子係使用在以聚苯乙烯當作核心的粒子（屢縮 彈性率366 kg/mm2)表面上，設置厚度〇1(αηΐ2銀層而 20 313294D1 U^2027 成之平均粒子徑6·15 # m之導電粒子，與實施例1相同處 理後可得異向性導電電路連接用黏著劑。 (實施例3) 。。導電粒子係使用在以聚苯乙烯當作核心的粒子（壓縮 單〖生率480 kg/ mm2 )表面上，設置厚度〇1"爪之銀層， 在：銀層之外側，設置厚度〇·〇—之金層而成之平均粒 / 5以m之導電粒子，經與實施例丨相同處理後可得異 向性導電電路連接用黏著劑。 " (實施例4) 。。導電粒子係使用在以聚苯乙烯當作核心的粒+(壓縮 彈性率480 kg/mm2)表面上，設置厚度〇」心之鎳層， 在7此錄層之外側’設置厚度〇 〇5〆m之銀層而成之平均粒 子徑5 # m之導電粒子’經與實施例1相同處理後可得里 向性導電電路連接用黏著劑。 " (比較例1) 導電粒子係使用在以聚笨乙烯當作核心的粒子（壓縮 :性率彻^馳2)表面上，設置厚度〇.2…錄層而 成之平均粒子徑5心之導電粒子，經與實施例"目同處 理後可得異向性導電電路連接用黏著齊卜 (比較例2) :電粒子係使用在以聚笨乙烯當作核心的粒子 弹性率撕g/lw)表面上，設置厚度02…鎳層， 在此鎳層之外側，設置厚度〇.〇—之金層而成之平均粒 子控5Mm之導電粒子，經與實施例1相同處理後可得昱 313294D1 1332027 向性導電連接用黏著劑β (電路之連接） 使用上述異向性導電樹脂薄膜狀形成物，對具有5〇 條線寬30μ m、間距30# m、厚度18 # m之銅電路的磁帶 套、’且（TCP )和ITO玻璃（Di〇merteck公司製，表面電阻 2〇至30歐姆/每平方米⑴/口），厚度i丨爪叫以14〇。〔， 3MPa加熱加壓15秒鐘，可得連接寬2mm之連接構造體。 此時，預先在ITO玻璃上，將異向性導電電路連接用黏著 劑之連接面貼付後’在8(rc , Q 5MPa加熱加壓3秒鐘使 連接，之後，將PET薄膜剝離即與TCp完成連接。 (連接電阻之測定） 將製成之異向性導電電路連接用黏著劑，於―抓保 存及在3(TC、85%RH之恒溫恒濕槽中分別保存_小 時後’進行上述之電路連接，含 ^ 3上述連接部之TCP的鄰接 電路間之連接電阻值，以多功能 θ ,t ^^ ^測心測定，連接電阻值 疋指鄰接電路間之電阻之i 50 私一 〇點+均值，測定結果如表1 所不。^ 、, bisphenol A type epoxy resin, bisphenol F lining oxygen resin, double age § type epoxy tree lacquer tree day, novolak type epoxy resin, varnish type epoxy resin, "A _ Varnish type epoxy resin, g: two-year-old lacquer type epoxy resin, alicyclic epoxy resin, glycidol-曰i epoxy resin, glycidylamine type 1 clothing milk tree, day, urethra urea epoxy Tree scorpion, isocyanic acid S-type epoxy resin, aliphatic chain epoxy resin, etc., and these nucleating oxygen resins may also be "may be added with hydrogen." It is also possible to use two or more of these epoxy compounds in combination. The radically polymerizable compound used in the adhesive for connecting an anisotropic conductive circuit of the present invention has a functional group having a radical-induced polymerization, and has a (mercapto) acrylic acid vinegar resin and a maleic acid field. For the imide resin, the Nykine imine resin, the naphthyl diimide resin, or the like, it is also possible to use two kinds of the above-mentioned mixed delta and radically polymerizable compounds, and any of a monomer and an oligomer. In the state, it is also possible to use a monomer and a polymer-binding compound. Here, "(meth) acrylate" means acrylate and its corresponding methacrylate. As the (fluorenyl) acrylate resin, those obtained by radical polymerization of (fluorenyl) propylene phthalate are mentioned, and as (meth) acrylate, methyl (meth) acrylate, ( Ethyl methyl acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate bis (mercapto) acrylate, diethylene glycol di(meth) acrylate, three ( Mercapto) Dimethyl propylene acrylate from ester 'tetrakis(yl) methacrylate tetramethyl glycol ester, 2-hydroxy-1,3-dipropene oxime propane, 2, 2-bis[4-(propylene oxyhydroxide) Phenyl]propane, 2,2-bis[4-(acryloyloxy)phenyl]propane ' 11 313294D1 -舻:) propylene fluorene-% pentene ester, trimethyl decane (mercapto) acrylate , Isomilk II (propylene oxime ethyl) brewing, (methyl amide hydrazine: modified quaternary acid, etc., can be used alone or in combination of two or more kinds of sputum and 'because necessary, without compromising hardenability A radical polymerization inhibitor such as hydrogen I or mercaptoether hydroquinone may also be used in the range. The inorganic compound such as a metal compound can improve the adhesion force. The linonic acid g is a compound: the amount used is 100 parts by weight relative to the adhesive component (M to 丨0 is a good car 乂 〇·5 to 5 parts by weight. The phosphate compound is obtained from the reaction product of anhydrous phosphonium (mercapto)acrylic acid 2 - by the reaction of thioethyl amide. Specifically, it is mono(mercapto propyl sulfonate) acid phosphoric acid, i ( "Mercaptopropyl propylene ethyl) acid phosphate, etc. can be used singly or in combination. As a maleic anhydride imide resin, it contains at least one maleic anhydride imide in the molecule, such as phenyl maleic anhydride. Imine, 丨 曱 — - 2 '4 - maleic anhydride imine benzene, N, N, - m phenyl bis maleic anhydride imimine, hydrazine, Ν ' a p - phenyl double horse Anhydride, N, N, _ 4, 4 bis-phenyl bis-maleic acid imide, N, N, a 4,4-(3,3-didecyldiphenyl) double horse Anhydride imide, N,N,-4,4-(3,3-dimethyldiphenylnonane) bismaleimide, N,N,-4,4- (3, 3 — Diethyl bis phenyl decane) double maleic anhydride Amine, N, N, 4, 4-diphenylethane bis-maleic anhydride imide, hydrazine, Ν'-4, 4-diphenylpropane double maleic anhydride imipenem Ν, Ν '1 4,4 —Diphenyl-bi-mystery double maleic anhydride imide, hydrazine, Ν'-4, 4-bisphenylsulfobismaleic acid imide, 2, 2 — double (4—(4 — Maleic acid acetal phenoxy)phenyl)propane, 2,2 12 313294D1 1332027 a pair (3 — s — butyl — 3 , 4 — (4 — maleic anhydride acetimidate phenoxy) Phenyl)-propanol, 1,1-bis (4-(4-monomaleimide phenoxy)phenyl)decane, 4, 4-cyclohexylene-double (1 - (4 one horse) Anhydride acetonitrile, oxy)phenoxy)-2-cyclohexylbenzene, 2,2-bis(4-(4-maleic acid acetimidate)phenyl)hexafluoropropane, etc. It is also possible to use two or more types of mixing alone. As a Ningkang imine resin, it is a kind of polymerized from Ningkangimine compound which is divided into 4, and is a kind of Ningkang imine compound, for example, Phenyl Ning Kang Imine, 1 - fluorenyl-2, 4 - Shuangning Kangxiuylidene benzene, N, N, -m-phenyl bispyrene quinone amide benzene, n, n, -P-phenyl shuangning Kangxi Iminobenzene, N,N,_4,4-bisphenyl bis-quinone quinone imine, hydrazine, Ν'-4, 4-(3,3-dimethylphenyl) phenyl quinone Ν,Ν,4,4-(3,3-dimethyldiphenylmeth) Shuangning Kangxiimine, Ν,Ν'-4, 4-(3,3-diethyldiphenyl) Methane) Shuangning Kangxiuyimine, hydrazine, Ν'-4, 4-diphenylmethane bis-quinone quinone, ν, ν, -4,4 - diphenylpropane bispyrene, hydrazine , Ν, a 4, 4 - diphenylene (tetra) quinine quinone imine, hydrazine, hydrazine, -4,4-bisphenyl hydrazine Shuang Ningkang: imine, 2,2-bis (4- (4宁康醯iminophenoxy)phenyl)propane, bis(3 s-butyl-3,4-(4-Ningkangimine phenoxyphenyl)propyl, 1 1 雒( 4 ( λ a , 1 again (4 (4~Ningkang imine phenoxy) stupid base) 癸院' 4, 4 - Cyclohexylene hexyl double (丨~金志状# (4 —Ningkang 醯iamine phenyloxy) oxy) a 2 - ring? Its lean, 〇η% basic, 2,2~ bis (4-(4-b. quinone) phenyloxy) phenyl) hexafluoropropane, etc., can be used alone It is also possible to use 13 313294D1 1332027 as a naphthol diimine resin, and to polymerize a naphthol diimine compound having at least one naphthol diimine group in the molecule as a doxy phenol diimine compound. For example, there are naphthene diimine, 1-methyl-2,4-bisnaphthalene diimine, N,N, —naphthol diimine benzene, anthracene, Ν'-4,4-diphenyl double Naphthol diimine, anthracene, Ν'-4,4-(3,3-dimercapto-diphenyl) bis-naphthol diimine, anthracene, Ν'-4, 4-(3,3-dimethyl Bis-phenyl decane) bis-naphthol diimine, hydrazine, Ν '- 4, 4_ (3, 3-diethyldiphenyl decane) bis-naphthol diimine, ν, Ν '-4 4 one or two stupid base 曱 · 双 双 双 双 双 双 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一-diphenylether bis-naphthol diimine, anthracene, Ν'-4,4-bisphenylsulfobisnaphthol diimine, 2,2-bis(4-(4-Cailing diimine benzene) Oxy)phenyl)propane, 2,2_bis(3_s-butyl-3,4-(4-naphthyldiimidephenoxy)phenyl)propane, hydrazine, ^bis (4-(4- Naphthol diimine phenoxy)phenyl)decane, 4,4-cyclohexylene bis(1_(4-naphthol diimine phenoxy)phenoxy)_2 2 hexyl m bis (4-( 4—Caidi diimine phenoxy) stupyl) hexafluoropropane, etc., may be used singly or in combination of two or more kinds of the above-mentioned radical polymerizable compound, using polymerization: starting: heating Or light produces a free radical hardener. As a polymerization initiator: as long as the compound can generate free radicals by heating or light. There are peroxides, azo compounds, etc., which can be appropriately selected according to the purpose of the temperature production, such as the inter-study, preservation stability, etc., 14 4~ 反应 反应 reactivity and preservation capacity, the half-life is 10 hours t half a bamboo shoots with a dish size of 4 ° ° C or more, 裒 d for 1 minute at a temperature of i 8 (the organic peroxide under rc is 14 313294D1 丄JJZUZ / good. Half-agricultural period is 10 hours It is 4 〇. The temperature of the above clock is 17 〇t to ^7 + dd is 1 minute 1 Λ 41 organic peroxide is especially good. Then & 10 seconds, the receiver is full The polymerization rate of the polymerization initiator is preferably 8% by weight relative to the total amount of the binder, and 15% by weight of the polymerization initiator is preferably used, and 2 to the organic peroxide selected from the group. ^目—Boiled gasification, __ ketal ketal,-”: emulsion, peroxide vinegar, peroxy oxide, etc., hydroperoxide, methicone over emulsion ester, dialkyl peroxidation Substance, hydroperoxy acid in SO:-based peroxide, etc. 'because the gas ion or organic-sense in the initiator is 'under 5,000 PPm' The organic acid produced is rare, and the circuit member is followed by the rot of the terminal, so it is particularly preferable. It is preferably selected from the highly reactive pervaporation S, and these can be appropriately mixed and used. Examples of the peroxides include isobutyl peroxide, 2,4-dichlorophenylhydrazine peroxide, 3,5,5-trimethylhexyl peroxide, octyl peroxide, and ten. Dibasic peroxide, stearyl peroxide, amber peroxide, peroxide, benzoquinone peroxide #, benzoquinone, etc. As a dicarbonate, Listed as two η _ propyl peroxide bicarbonate, diisopropyl dicarbonate peroxide dicarbonate, bis (4-tri-tert-butylcyclohexyl) peroxide dicarbonate, two - 2 — ethoxymethoxy peroxide dicarbonate, bis(2-ethylhexyl peroxide) monocarbonate, dimethoxybutyl dicarbonate dicarbonate, one (3-A) Base _3-ethoxybutyl peroxide) dicarbonate, etc. As a peroxide ester, for example, propyl peroxide neodecanoic acid 15 313 294D1 1332027 La, 1,1,3,3 - Tetradecyl butyl peroxide neodecanoate, 1 Cyclohexanone ~ 1 monomethylethyl peroxide neodecanoate, tertiary monohexyl peroxidation ^ 癸 vinegar, tertiary _ butyl peroxide neodecanoic acid g, 1,1,3 3 -tetramethylbutyl peroxide 2-ethylhexanoic acid vinegar, 2,5-dimethyl Base - 2 5 bis(2-ethylhexyl peroxide) hexane, 1-cyclohexyl-hydrazine-methyl ethyl peroxy-2-ethylhexanoate, tertiary hexyl peroxide 2~ Ethyl hexanoate, tertiary monobutyl peroxide - 2 - ethyl hexanoate, tertiary butyl peroxide isobutyrate, 1, 1 - (tertiary peroxide) ring Benzene, tertiary-hexyl peroxide isopropyl monocarbonate, tertiary monobutyl peroxide-3,5,5-tridecyl hexanoate, tertiary butyl peroxide laurate, 2,5-Dimethyl-2,5-di(m-nonylphenylhydrazine peroxide) hexane, secondary '•butyl peroxide isopropane monocarbonate, tertiary-butyl peroxide-2 -ethylhexyl monocarbonate, tertiary-hexyl peroxide benzoate A two-butyl peroxide acetate. As the ketone ketals, for example, hydrazine, 1 tertiary hexyl peroxide, 3, 3, 5 -trimethylcyclohexane, 1,1 - (tris-hexyl peroxide) ) cyclohexane, hydrazine, hydrazine _ (tri-tert-butyl peroxide) _ 3,5 - fluorenyl ring, 1,1 - (tri-tert-butyl peroxide) ring 癸, 2, 2 - bis (tertiary monobutyl peroxide) decane and the like. Examples of the dialkyl peroxides include α, α, a bis(tertiary butyl peroxide) diisopropylbenzene, diisophenylpropyl peroxide, and 2,5-fluorenyl. A 25-bis (tri-tert-butyl peroxide) hexane, a tertiary-butyl isopropyl propyl peroxide, and the like. Examples of the hydroperoxides include diisopropylbenzene hydroperoxide 16 313294D1 1332027, isophenylpropane hydroperoxide and the like. As the methacrylate peroxide, for example, tertiary monobutyl trimethyl methacrylate peroxide, bis (tertiary monobutyl) bis- fluorenyl peroxide , tertiary monobutyltrivinyl decyl peroxide, bis(di-butyl-butyl)divinylcarbenyl peroxide, tris(tertiary-butyl)divinylformamido peroxidation , tertiary butyl tripropenyl decyl peroxide, bis(tri-tert-butyl)dipropenylmethyl decyl peroxide, tris(tertiary-butyl) propylene methacrylate alkyl peroxidation Things and so on. Further, in order to suppress the corrosion of the connection terminal of the circuit member, the chloride ion or the organic acid contained in the radical generator (hardener) is organically produced after being decomposed and decomposed by 5 Å or less. It is better to use less acid. In addition, in the long-term stability of the circuit-connected material, it is appropriate to have a weight retention rate of 2% by weight or more after being left open for 24 hours at room temperature (2$). Mixed use. These radical generators may be used singly or in combination, or may be used in combination with a decomposition accelerator, an inhibitor, or the like. In addition, it is preferred that the radical generating agent is coated with a polyurethane-based or polyester-based polymer or the like to form a microencapsulated product, since the usable time can be extended. In addition to the radically polymerizable compound, it can also be incorporated into an epoxy tree which is a thermosetting tree. As epoxy resin, there are bisphenol A type epoxy resin, double: F type % oxygen resin 'bisphenol S type epoxy resin, novolak type epoxy tree =, cresol novolak type epoxy resin, double Phenol A novolak type epoxy tree sap, bisphenol F novolac type epoxy resin, alicyclic epoxy resin 'shrinkage 17 313294D1 1332027 glycerin 酉 type epoxy resin, glycidylamine type epoxy resin, B The oxygen resin, the isocyanate-type epoxy resin, and the aliphatic bond-type bismuth-based epoxy resin may be either hydrogenated or hydrogenated. These epoxy resins may be used in combination of two or more kinds. Further, as the hardener of the above epoxy resin, for example, an amine, a hydrazine classification, an acid needle, or a P meter can be used. Comprehensive _ g _ sitting class - chaotic - guanamine, etc. usually used as epoxy resin. Further, as the hardening accelerator, a tertiary amine or an organic phosphorus compound can be usually used as appropriate. Further, in order to make the ring (the oxygen resin reaction side (4), it is also possible to use a tetravalent sulfur (sulfonium salt), an iodonium salt or the like to polymerize the cation in addition to the above-mentioned hardening d X . The circuit of the moon is followed by an adhesive or an anisotropic conductive resin film; in order to impart film formability, adhesion, and hardening properties in the product: temperability 'Generally use polyvinyl butyral resin, poly Polymers such as vinyl acetal, giamine resin, polyamido resin, xylene tree, polyurethane resin, urea resin, etc. 1 (M〇〇S 10,000,000 is suitable. Also, these tree 曰 曰 ' can also be a radical polymerizable functional group, in this field heat resistance two. In addition, 'can also use free radicals The polymerizable functional group or the %oxy 'indenyl group or the like is formed, and in this case, the heat resistance is improved. The amount of the polymer forming blade is 2 to 80% by weight, preferably 5 to 70% by weight, and 1 : 1 to 6〇% by weight is the best. When S 2% by weight, stress relaxation or adhesion Insufficient, the fluidity decreases when it exceeds 8% by weight. 00 Less - x <Adhesive for the connection of the conductive conductive circuit, it is also possible to add 18 313294D1 1332027 plus appropriate filler, softener, detective, „ accelerator , anti-aging agent, coloring agent, flame retardant, coupling agent. In the case of filling agent, because of the credibility of the adhesive, so k, the maximum particle size of the filler as long as it does not exceed the conductive particles The particle size can be used, preferably in the range of 5 to 6 vol%, and when it exceeds 60 vol%, the I reliability improvement effect is saturated. As a coupling agent, it contains an ethylene group/thin group, an amine group, The epoxy group, the acid amine group and the ionic acid group are preferred because they can be improved in adhesion. When τ: τ will be widely used as an anisotropic conductive circuit connecting adhesive as hard = Tg (glass transition degree) ), it can also be a multi-layer structure made up of two or more different layers. A plate 吏ϋ 明 anisotropic conductive circuit connection adhesive bonding can be used to connect the necessary electrical points to the electrode, and no special = Plastic =: used in liquid crystal displays... forming electrodes Wiring board 'soil & pdp flat panel, el flat panel, etc., such as a substrate, a printed circuit board, a flexible wiring board, a semiconductor wafer, a semiconductor chip, a semiconductor chip, a tape package, a circuit pack, and a C〇F circuit. Parts + conductor sand wafers, etc., can be used in combination if necessary. :: The conditions are not particularly limited, but the junction temperature is 9〇 to 250 2: ΤΓ 1 second to 10 minutes, the use can be different As appropriate, a hot moon source such as light, ultrasonic wave, electromagnetic wave, or the like may be used as needed. The present invention is specifically described by way of examples, but the scope of the present invention is not limited to such a range of 19 313294D1 1332027. Example. (Example 1) 50 g of phenoxy resin (manufactured by Union Carbide Co., Ltd., trade name: PKHC, average molecular weight: 45, 〇〇〇) was dissolved in MEK (anthraquinone, boiling point: 79-6 ° C) to become a solid content of 5 〇% by weight. Solution. The radically polymerizable material is a diacrylate modified with isocyanate oxirane (manufactured by Toagosei Co., Ltd., trade name 2 - 2 15 ) and a phosphate ester acrylate (manufactured by Kyoeisha Oil Co., Ltd., trade name) Ρ — 2Μ ) » Heat or light to generate a free radical hardener, using 5 〇 by weight of 2,5-dimethyl- 2,5-bis(2-ethylhexyl peroxide) hexane. /. Hydrogenated hydrogen solution (manufactured by Nippon Oil & Fat Co., Ltd., product name Perhexa 250). Conductive particles are used on the surface of particles with polystyrene as the core (compression elastic modulus: 480 kg/mm2), and conductive particles with an average particle diameter of 5 #m are formed by a silver layer having a thickness of 〇.〇9 /zm. . The solid weight ratio is 50 g of phenoxy resin, 50 g of diacrylate modified with isocyanate oxirane, 2 g of phosphate ester acrylate, 2,5 ~ dimercapto 2,5-double (2 - Ethylhexyl decyl peroxide) hexane 5g mode is formulated into 're-dispersing 3 % by volume of conductive particles, and then coated with a coating device on a single-sided surface-treated PET (polyethylene terephthalate) The ester film is dried by hot air at 701'1 〇 minute to obtain an adhesive for connecting an anisotropic conductive circuit having an adhesive layer thickness of 35/zm. (Example 2) Conductive particles were used on the surface of particles having a polystyrene as a core (repeated elastic modulus: 366 kg/mm2), and an average particle of thickness 〇1 (αηΐ2 silver layer and 20 313294D1 U^2027) was used. The conductive particles having a diameter of 6.15 #m were obtained by the same treatment as in Example 1 to obtain an adhesive for connecting an anisotropic conductive circuit. (Example 3) Conductive particles were used as particles having a polystyrene as a core. On the surface of the compression sheet, the thickness of 〇1"the silver layer of the claw is set. On the outer side of the silver layer, the average grain of the thickness of the gold layer of 〇·〇-/5 is set. The conductive particles were subjected to the same treatment as in Example 可 to obtain an adhesive for connecting an anisotropic conductive circuit. (Example 4) Conductive particles were used in a particle having a polystyrene as a core + (compression elasticity) On the surface of the 480 kg/mm2), a nickel layer with a thickness of 〇" is set, and a conductive particle having an average particle diameter of 5 #m is formed by setting a silver layer having a thickness of 〆5 〆m on the outer side of the recording layer. After the same treatment as in Example 1, an adhesive for connecting an intermediate conductive circuit can be obtained. Example 1) Conductive particles are used on the surface of a particle having a polystyrene as a core (compression: a rate of 2), and a conductive particle having an average particle diameter of 5 in a thickness of 〇.2... After the same treatment as in the example, the adhesion of the anisotropic conductive circuit can be obtained (Comparative Example 2): the electric particle system is used to peel the surface of the particle with the polystyrene as the core (g/lw) On the outer side of the nickel layer, a conductive particle having an average particle size of 5 Mm, which is formed by a gold layer having a thickness of 〇.〇, is disposed, and after the same treatment as in the first embodiment, 昱313294D1 1332027 is obtained. Adhesive for adhesive connection β (connection of circuit) Using the above-mentioned anisotropic conductive resin film-like formation, a tape cassette having a copper circuit having a line width of 30 μm, a pitch of 30 #m, and a thickness of 18 #m, 'And (TCP) and ITO glass (manufactured by Di〇merteck, surface resistance 2 〇 to 30 ohms / square meter (1) / mouth), thickness i 丨 claw is called 14 〇. [, 3 MPa heating and pressurization for 15 seconds, a connection structure having a width of 2 mm can be obtained. In this case, the connection surface of the adhesive for the anisotropic conductive circuit connection is attached to the ITO glass in advance, and the connection is made by heating and pressing for 8 seconds at 8 (rc, Q 5 MPa, and then peeling off the PET film and TCp). The connection is completed. (Measurement of the connection resistance) The adhesive for the connection of the anisotropic conductive circuit is prepared, and the above-mentioned adhesive is stored and stored in 3 (TC and 85% RH constant temperature and humidity chambers for _hours). The circuit connection, the connection resistance value between the adjacent circuits of the TCP including the above-mentioned connection portion is measured by the multi-function θ, t ^^ ^, and the connection resistance value i refers to the resistance between the adjacent circuits. Point + mean, the measurement results are as shown in Table 1.
22 313294D1 1332027 。實施例1所得之連接構造體，於_20。(：保存及在30 c ' 85%RH之恒溫恒濕槽中保存者’任一者都顯示在2 5 Ω以下之良好連接可信度。又，實施例2、3之連接構造體 中，也同樣顯示於一2(TC保存及在3〇°c、85%RH之恒溫 恒濕槽中保存者，任一者都得到125 Ω以下之良好連接可 信度。 相對於此，比較例i及2，在—2〇〇c保存之連接構造 體中，雖可得良好連接可信度，但在30。(：、85%RH之恒 '皿烜濕槽中保存者，連接電阻大幅上昇到10 Ω以上。 (連接強度之測定） 在實施例1至3中，於一20。(：或在30<t、85%RH之 !·旦/皿恒濕槽中保存者，任一者個都可得丨〇〇〇 N/ m左右之 良好連接強度。另一方面，比較例丨及2中，連接強度於 —20°C或在30〇C、85%RH之恒溫恒濕槽中保存者，任一 者都得到1000 N/ m左右之良好連接強度。 (絕緣性之評估） 使用所得之異向性導電電路連接用黏著劑，將具有相 互交又配置250條線寬50以m、間距1 〇〇 # m、厚度！ 8〆m 之銅電路的櫛形電路印刷電路基板，和具有5〇〇條線寬5〇 //m、間距looym、厚度18“m之銅電路的磁帶套組 (TCP)，以1401，3MPa加熱加壓15秒鐘，連接幅寬 2mm。此連接體之櫛形電路外加ι〇〇ν之電壓，在85ι、 85%RH之高溫高濕下試驗5〇〇小時後測定絕緣電阻值。 任一者都可得到1〇9Ω以上之良好絕緣性，觀察不出 23 313294D1 1332027 有絕緣性下降現象。 (流動性之評估） 使用厚度35// m、5mm X 5mm之異向性導電電路連接 用黏著劑’將其夾持於厚度0.7 " m、15mm X 15mm之破 璃中，在140 C，3MPa下進行加熱加壓丨5秒鐘，使用初 期之面積（A )和加熱加壓後面積（B )，求得流動性（b ) / ( A )值時，實施例i至3是i 9至2 〇之範圍内，另一 方面，比較例1及2則為1·8及丨9。 (硬化後之彈性率） 測疋貫施例1之異向性導電電路連接用黏著劑在硬化 後40 C之彈性率，為1 5Gpa。 由上述之連接強度、絕緣性、流動性、硬化後之彈性 率等械之，本發明之實施例之值和比較例之值，雖顯示幾 乎相同之值，但如表丨所示般，連接電阻值有报大之差 異。由實施例和比較例之連接強度、絕緣性、流動性等顯 二有相同之特性觀之，導電粒子表面之覆蓋層被認為極 但對連接電阻有明顯之影響。如本發明，在表面並不 露出銀、金鉑以外之過渡金屬的導電粒子中於導電粒子 表面並無促進自由基聚合性物質之聚合現象，顯示連接電 阻極低之良好數值。如實施例4使用錦等過渡金屬時，只 =在其外側覆蓋500A以上之銀、金、链等使内側之過渡 金屬不露出，則雖經溫度或溫濕度處理均具有優異之保存 安定性，連接電阻不會增加。 (表面處理粒子A之製作） 24 313294D1 1332027 三乙胺之1重量％曱醇溶液中，放入在以聚苯乙烯為 核心之粒子表面上，設置0 2//爪厚度之鎳層’在此鎳層 外側，設置0.04 //m厚度之金層而成之平均粒徑4#m之 導也粒子，於2 5 C攪拌1 〇分鐘，過濾出導電粒子，在5 〇 t下乾燥1 5分鐘，得到表面處理粒子a。 (表面處理粒子B之製作） 胺基丙基三矽烷之3重量％甲醇溶液中，放入在以聚 苯乙烯為核心之粒子表面上，設置〇 2" m厚度之鎳層， 在此鎳層外側’言史置0.04" m厚度之金層而成之平均粒徑 5 ^之導電粒子，於5 0 C授拌5分鐘，過濾出導電粒子， 在8 〇 C下乾燥5分鐘，得釗袅面處理粒子b。 (表面處理粒子C之製作） 7 —環氧丙氧基丙基甲基二甲氧基矽烷之i重量％甲 醇/奋液中，放入在以聚苯乙烯為核心之粒子表面上，設置 〇·2 "出厚度之鎳層，在此錄層外側，設置0.04 # m厚度之 金1而成之平均粒徑4#m之導電粒子，於Ml攪拌1〇 分釦，過濾出導電粒子’在5〇〇c下乾燥15分鐘，得到表 面處理粒子C。 (表面處理粒子D之製作） 又酚A型環氧樹脂之3重量％曱醇溶液中，放入在以 聚苯乙烯為核心之粒子表面上，設置〇 2“m厚度之鎳層， 在此錄層外側，設置G脚m厚度之金層而成之平均粒徑 5// m。之導電粒子，於5〇r攪拌5分鐘，過濾出導電粒子， 在 ◦下乾燥5分鐘，得到表面處理粒子〇。 25 313294D1 1332027 使用此等導電粒子A、B、C及D，分別配入下面所示 之配合，以簡易之塗工機（TESTER產業公司製），在表面 處理過之PET (聚對笨二曱酸乙酯）薄膜單面上塗佈5〇 # m厚度，在70°C、經10分鐘之熱風乾燥，製成電路連接 用點著劑。 (實施例5) 將本氧基樹脂（PKHC，Union carbide公司製商品名 平均分子量45,000 ) 50g，做為自由基聚合性化合物之甲 基丙烯酸二環己酯48g，磷酸酯丙烯酸酯2g，2, 5 —二曱 基~ 2, 5—雙（2—乙基己醯過氧化物）己烷3g，溶解在做為 溶劑之甲乙酮中，再將3體積％之表面處理粒子A配入分 散，在表面處理過之聚對苯二曱酸乙酯薄臈單面上，以忾 易塗工機塗佈50/zm厚度，在7(rc、經1〇分鐘之熱風^ 燥，製得厚度為30 // m之異向性導電電路連接用黏著劑。 (實施例6) ^ 將本氧基樹脂（PKHC’Unioncarbide公司製两·口名 平均分子量45,〇〇〇) 50g，異氰酸環氧己酯改質二丙烯醆 酯46g ’磷酸酯丙烯酸酯4g，2, 5 _二甲基—2, 5 —雔（欠 —乙基己醯過氧化物）己烷3g，溶解配入做為溶劑之甲乙 酮中，再將3體積。/。之表面處理粒子B配入分散，在夺 處理過之聚對苯二曱酸乙酯薄膜單面上以簡易塗工機塗佈 50以m厚度，在7〇〇c、經1〇分鐘之熱風乾燥，製得厚户 為30 # m之異向性導電電路連接用黏著劑。 又 (實施例7) 313294D1 26 1332027 將本氧基樹脂（PKHC，Union carbide公司製商品名、 平均分子量45,000 ) 25g，聚胺酯樹脂25g，曱基丙稀酸二 環己S旨48g，磷酸酯丙烯酸酯2g，2, 5 —二曱基—2, 5_雙 (2 —乙基己醯過氧化物）己烷3g，溶解配入做為溶劑之 甲乙嗣中’再將3體積％之表面處理粒子B配入分散，在 表面處理過之聚對笨二甲酸乙酯薄膜單面上以簡易塗工機 塗佈50/zm厚度，在7〇。〇、經1〇分鐘之熱風乾燥，製得 厚度為3 0 /z m之異向性導電電路連接用黏著劑。 (實施例8) 將本氧基樹脂（PKHC’Unioncarbide公司製商品名、 平均分子量45,000 ) 5 0g，做為自由基聚合性物之甲基丙 烯酸二環己酯48g，填酸酯丙烯酸酯2g，2, 5 —二甲基—2 5 —雙（2 —乙基已醯過氧化物）已烷3g，溶解配入做為溶 劑之甲乙酮中，再將3體積〇/〇之表面處理粒子c配入分散岭 在表面處理過之聚對苯二甲酸乙酯薄膜單面上以簡易塗工 機塗佈50#m厚度，在7(TC、經1〇分鐘之熱風乾燥製 得厚度為30 # m之異向性導電電路連接用黏著劑。 (實施例9) 將苯氧基樹脂（PKHC ’ Union carbide公司製商品名、 平均分子量45,000 ) 50g，異氰酸環氧己酯改質二丙烯酸 酯46g ’磷酸酯丙烯酸酯4g，2 5 —-甲A q c ， 一 1 签 —雙（2 —乙基已醯過氧化物）已烷3g，溶解配入做為溶劑之甲乙 酮中，再將3體積％之表面處理粒子〇配入分散，在表 處理過之聚對苯二曱酸乙酯薄膜單面上以簡易塗工機塗佈 27 313294D122 313294D1 1332027. The bonded structure obtained in Example 1 was at -20. (: Save and store in a constant temperature and humidity chamber of 30 c '85% RH'. Any one shows a good connection reliability of 2 5 Ω or less. In addition, in the connection structure of Examples 2 and 3, It is also shown in Fig. 2 (TC storage and storage in a constant temperature and humidity chamber of 3 ° ° C, 85% RH, either of which has a good connection reliability of 125 Ω or less. In contrast, Comparative Example i And 2, in the connection structure preserved in -2〇〇c, although good reliability of connection can be obtained, but in the case of 30. (:, 85% RH constant 'deep wet tank, the connection resistance is greatly increased Up to 10 Ω or more. (Measurement of joint strength) In Examples 1 to 3, at 20: (: or in 30 < t, 85% RH! · Dan / dish constant humidity tank, either The good connection strength is about 丨〇〇〇N/m. On the other hand, in the comparative example 2 and 2, the connection strength is -20 ° C or in a constant temperature and humidity chamber of 30 〇 C, 85% RH. The protector, either of them has a good connection strength of about 1000 N / m. (Evaluation of insulation) Using the obtained anisotropic conductive circuit connection adhesive, will have 250 pieces of mutual arrangement栉-shaped circuit printed circuit board with a line width of 50 m, a pitch of 1 〇〇# m, a thickness of 8 〆m, and a line width of 5 〇//m, pitch looym, thickness 18"m The copper circuit tape set (TCP) is heated and pressurized at 1401, 3MPa for 15 seconds, and the connection width is 2mm. The connection of the connecting body is the voltage of ι〇〇ν, high temperature and humidity at 85ι, 85% RH. The insulation resistance value was measured after 5 hours of the test. Any of them could obtain good insulation of 1 〇 9 Ω or more, and no insulation degradation was observed for 23 313294 D1 1332027. (Evaluation of fluidity) Thickness 35// m, 5mm X 5mm anisotropic conductive circuit connection adhesive 'make it in the thickness of 0.7 " m, 15mm X 15mm glass, heat and pressure at 140 C, 3MPa for 5 seconds, When the initial area (A) and the heated and pressed area (B) are used to obtain the fluidity (b) / (A) value, the examples i to 3 are in the range of i 9 to 2 ,, on the other hand, Comparative Examples 1 and 2 are 1·8 and 丨9. (Elassability after hardening) The adhesive for connecting anisotropic conductive circuits of Example 1 is measured. The modulus of elasticity after 40 C is 15 GPa. The values of the examples of the present invention and the values of the comparative examples are almost the same, depending on the above-mentioned joint strength, insulation, fluidity, and elastic modulus after hardening. The value, but as shown in Table ,, the connection resistance value has a large difference. The connection strength, insulation, fluidity, etc. of the embodiment and the comparative example have the same characteristics, and the surface of the conductive particle is covered. The layer is considered extremely but has a significant effect on the connection resistance. According to the present invention, in the conductive particles in which the transition metal other than silver or gold platinum is not exposed on the surface, the polymerization of the radical polymerizable substance is not promoted on the surface of the conductive particles, and the connection resistance is extremely low. When the transition metal such as brocade is used in the fourth embodiment, only the silver, the gold, the chain or the like of 500 A or more is covered on the outer side so that the inner transition metal is not exposed, and the storage stability is excellent after temperature or temperature and humidity treatment. The connection resistance does not increase. (Preparation of surface-treated particle A) 24 313294D1 1332027 Triethylamine in a 1% by weight decyl alcohol solution, placed on the surface of particles with polystyrene as the core, and a nickel layer of 0 2 / / claw thickness is set here On the outer side of the nickel layer, a gold layer of 0.04 //m thickness is used to form an average particle size of 4#m. The particles are stirred at 2 5 C for 1 minute, the conductive particles are filtered out, and dried at 5 〇t for 15 minutes. , surface treated particles a were obtained. (Preparation of surface-treated particle B) A 3 wt% methanol solution of aminopropyltrioxane was placed on the surface of a particle having polystyrene as a core, and a nickel layer of 〇2" m thickness was set, and the nickel layer was placed thereon. The conductive particles with an average particle size of 5 ^ on the outer side of the thickness of 0.04" m thickness are mixed for 5 minutes at 50 C, the conductive particles are filtered out, and dried at 8 ° C for 5 minutes. The surface b is processed. (Preparation of surface-treated particle C) 7 - Igoxypropylmethyldimethoxydecane in i weight% methanol/stretching liquid, placed on the surface of particles with polystyrene as the core, and set 〇 · 2 " Nickel layer of thickness, on the outside of this recording layer, set the conductive particle of average particle size 4#m of gold 1 of 0.04 # m thickness, stir 1 〇 buckle in Ml, filter out conductive particles' It was dried at 5 ° C for 15 minutes to obtain surface-treated particles C. (Preparation of surface-treated particles D) Further, a 3% by weight sterol solution of a phenol A-type epoxy resin is placed on the surface of particles having a polystyrene as a core, and a nickel layer of 〇2"m thickness is provided. On the outer side of the recording layer, an average particle size of 5/m m of a gold layer having a thickness of G feet is set. The conductive particles are stirred at 5 Torr for 5 minutes, and the conductive particles are filtered out and dried under a crucible for 5 minutes to obtain a surface treatment. 25 313294D1 1332027 Using these conductive particles A, B, C, and D, the following combinations are shown, and the surface treated PET (poly pair) is applied to a simple coating machine (manufactured by TESTER Industries, Inc.). The epoxy resin was coated on a single side with a thickness of 5 〇 #m, and dried at 70 ° C for 10 minutes by hot air to prepare a circuit connecting dot. (Example 5) The oxy resin was used. (PKHC, trade name of Union Carbide, average molecular weight 45,000) 50g, as a radical polymerizable compound, dicyclohexyl methacrylate 48g, phosphate ester acrylate 2g, 2, 5 - dimercapto ~ 2, 5- 3 g of bis(2-ethylhexyl peroxide) hexane, dissolved in methyl ethyl ketone as a solvent Then, 3% by volume of the surface-treated particle A is dispersed and dispersed on the surface of the surface-treated polyethylene terephthalate thin layer, and coated with a thickness of 50/zm at a 涂 easy coater at 7 ( Rc, after 1 minute of hot air drying, an adhesive for connecting an anisotropic conductive circuit having a thickness of 30 // m was obtained. (Example 6) ^ This oxy resin (PKHC'Unioncarbide Co., Ltd. The average molecular weight is 45, 〇〇〇) 50g, epoxy hexyl cyanate modified dipropylene oxime ester 46g 'phosphate ester acrylate 4g, 2, 5 _ dimethyl - 2, 5 - 雔 (under-ethyl 3 g of hexane, hexane, dissolved in methyl ethyl ketone as a solvent, and 3 parts by volume of surface treated particles B were dispersed and dispersed, and the treated polyethylene terephthalate film was taken up. On one side, it is coated with a thickness of 50 m in a simple coating machine, and dried at 7 〇〇c and hot air for 1 〇 minutes to obtain an adhesive for connecting an anisotropic conductive circuit of 30 # m. Example 7) 313294D1 26 1332027 This oxy resin (PKHC, trade name, manufactured by Union Carbide Corporation, average molecular weight 45,000) 25g, polyurethane resin 25g, 曱48g of dicyclohexyl acrylate, 2g of phosphate ester acrylate, 3g of 2,5-dimercapto-2,5-bis(2-ethylhexyl peroxide) hexane, dissolved and dissolved as solvent In the methyl acetazone, 3% by volume of the surface-treated particles B are further dispersed, and the surface-treated poly(p-ethyl phthalate) film is coated on a single surface by a simple coater at a thickness of 50/zm at 7 〇. 〇, dried by hot air for 1 minute, to obtain an adhesive for connecting an anisotropic conductive circuit having a thickness of 30 / zm. (Example 8) 50 g of the oxy resin (trade name, average molecular weight: 45,000, manufactured by PKHC'Unioncarbide Co., Ltd.) was used as a radically polymerizable product, 48 g of dicyclohexyl methacrylate, and 2 g of an acid ester acrylate. 2,5-Dimethyl-25-bis(2-ethylhexanium peroxide) hexane 3g, dissolved and mixed into methyl ethyl ketone as solvent, and then 3 volumes of 〇/〇 surface treatment particles c The surface of the surface treated polyethylene terephthalate film was coated with a thickness of 50#m on a single surface, and dried at 7 (TC, dried by hot air for 1 minute to obtain a thickness of 30 # m. An adhesive for connecting an anisotropic conductive circuit. (Example 9) 50 g of a phenoxy resin (trade name, average molecular weight: 45,000 by PKHC 'General Carbide Corporation), epoxy epoxide cyanide modified diacrylate 46 g 'Phosphate acrylate 4g, 2 5 --- A A qc , 1 - 1 - bis (2-ethyl decyl peroxide) hexane 3g, dissolved in methyl ethyl ketone as a solvent, and then 3 vol% The surface treated particles are mixed and dispersed, and the surface of the polyethylene terephthalate film treated on the surface is single-sided. Coated with a simple coater 27 313294D1
5〇^m厚度，在7(rc、經1〇分鐘之熱風乾燥，製得厚度 為30 " m之異向性導電電路連接用黏著劑。 子X (實施例10) 將笨氧基樹脂（PKHC ’ Union carbide公司製商σ 平均分子量45,000 ) 25g，聚胺酯樹脂25 二名 m T巷丙稀酸二 環己酯48g ’磷酸酯丙烯酸酯2g，2, 5 —二曱義 (2—乙基己醢過氧化物）己烧3g，溶解配入做為2溶5劑： 甲乙酮中，再將3體積％之表面處理粒子d配入分散 表面處理過之聚對苯二甲酸乙酿薄膜單面上以簡易塗^ ㈣50心厚度，在70t '經1〇分鐘之熱風乾燥，製得 厚度為30 // m之異向性導電電路連接用黏著劑。 、于 (比較例3) 除了將實施例5之表面處理粒子a改A去老 又马未處理粒子以 卜，，、餘與實施例5同樣處理，製 用黏著劑。 …電電路連接 (電路連接構造體之製作） 將上述異向性導電電路連接用黏著劑，縱割成1.5麵 幅寬，在已形成ITO電極之玻璃基板上，於8〇它、5种、5 〇 ^ m thickness, at 7 (rc, dried by hot air for 1 〇 minutes, to obtain a thickness of 30 " m anisotropic conductive circuit connection adhesive. Sub X (Example 10) will be an epoxy resin (PKHC 'General carbide company manufacturer σ average molecular weight 45,000) 25g, polyurethane resin 25 two m T Lane propylene dicyclohexyl ester 48g 'phosphate ester acrylate 2g, 2, 5 - bismuth (2-ethylhexyl醢Peroxide) has been burned 3g, dissolved and dissolved as 2 dissolved 5 agents: In methyl ethyl ketone, 3 vol% of the surface treated particles d are blended into the surface of the polyethylene terephthalate film treated on the dispersed surface. The adhesive for the anisotropic conductive circuit connection having a thickness of 30 // m was obtained by simply coating (4) 50 core thickness and drying at 70t' for 1 minute hot air. (Comparative Example 3) Except for Example 5 The surface-treated particles a were changed to A, and the untreated particles were treated in the same manner as in Example 5 to prepare an adhesive. Electrical circuit connection (production of circuit connection structure) The above-mentioned anisotropic conduction The circuit is connected with an adhesive, which is slit into 1.5 widths, and the glass base of the ITO electrode has been formed. On it in 8〇, 5,
1 MPa之條件下暫時連接，剝離pET _ t 付卷材，將此對齊 電極寬50/zm、間距5〇//1„之Tcp電極位置在Hoi 秒、響a之條件τ，製成本連接電路連接構造體。、 (特性評估方法） 連接電阻：使用ADVANTEST公司fj夕丄Λμ TPAO/to J I夕功能測試儀 rR6848 ’以ImA之定電流測定電路 J <逼阻。連接電阻 313294D] 28 1332027 是測定連接後之初期與30°C ' 60%RH、放置1 00小時後之 值。其結果在表2中表示。 表 2 連接抗阻（Ω ) 初期 30°C，60%RH，放置 10 0小時後 實施例5 _ 2.1 2.4 耳施例6 實施例7 2.8 ~1 - 2.5 3.2 3.1 實施例8 2.2 2.5 實施例9 _ 2.4 2.4 貫施例1 〇 ~ 2.8 3.1 比較例3 2.4 34.7 本發明之實施例5至1〇中，連接電阻值於放置後亦 厂丨\硐衣 低而艮好 ---〜1权例j， 於放置後 連接電阻值大幅上昇，又，显& 又異向性導電電路連接用黏著劑 製造後，在25°C放置30夭絲|脊 30天後與貫細例同樣製成電路連接 構造體，結果含有6里π X b . 二具有鹼性化合物或環氧基之化合物表 面處理過之導電粒子之異向性 S · Λ ，、门注導電電路連接用黏著劑’在 貫施例5至1 〇之配合下，連 Ω m U 運接電阻（初期）為2.i至3.8 Ω表不有良好之保存安定性。然而，卜 經且有鹼性仆入鉍_+、 匕車父例3之使用未 的連接構造體之遠桩喷 表面處理之導電粒子 很差。 Ώ ’表不保存安定性 產_JLA之可利用枓： 電路連接用黏 良好之異向性 ^ 1仵於製成異向Temporarily connect under the condition of 1 MPa, peel off the pET _ t-rolled material, and make the Tcp electrode with the width of 50/zm and the pitch of 5〇//1 „ in the position of Hoi seconds and ringing a to make the connection circuit. Connection structure. (Characteristic evaluation method) Connection resistance: Use ADVANTEST company fj 丄Λ 丄Λ TPAO/to JI function tester rR6848 'ImA constant current measurement circuit J < forced resistance. Connection resistance 313294D] 28 1332027 Yes The values at the initial stage after the connection and 30 ° C '60% RH and placed for 100 hours were measured. The results are shown in Table 2. Table 2 Connection resistance (Ω) Initial 30 ° C, 60% RH, placed 10 0 After hours, Example 5 _ 2.1 2.4 Ear Example 6 Example 7 2.8 ~ 1 - 2.5 3.2 3.1 Example 8 2.2 2.5 Example 9 _ 2.4 2.4 Example 1 〇 ~ 2.8 3.1 Comparative Example 3 2.4 34.7 Implementation of the Invention In the case of Example 5 to 1〇, the connection resistance value is also low after the placement, and the clothing is low---~1, the weight of the connection is greatly increased after the placement, and the display is also anisotropic. After the conductive circuit is connected with an adhesive, place 30 turns of wire at 25 ° C for 30 days. The circuit is connected to the structure, and the result contains 6 π X b . The anisotropic S · Λ of the surface-treated conductive particles of the compound having a basic compound or an epoxy group, and the adhesive for connecting the gate conductive circuit In the case of Example 5 to 1 ,, even the Ω m U transfer resistance (initial) of 2.i to 3.8 Ω does not have good preservation stability. However, there is an alkaline servant 铋++, The conductive particles treated by the far-spray surface of the unconnected structure of the 匕 父 例 例 很 很 很 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表Make a difference
著劑之後，放置保存娈卜4 h A 仔文性（黏著劑適 313294D1 29 JJZUZ / 導電電路連接用黏著劑。 化性 可以在 d 此外，亦可製得相對於埶 異向性導電電路連接用黏婪 …、 安用黏者劑之連接溫度17CTC， 更低溫之1 50 C連著劑保存後的連接電阻差異小之 良好連接構造體。 30 313294D1After the agent is placed, it is stored and stored for 4 h A (the adhesive is suitable for 313294D1 29 JJZUZ / adhesive for connecting the conductive circuit. The chemical property can be obtained in d, and can also be used for the connection of the anisotropic conductive circuit. Adhesive..., the connection temperature of the adhesive is 17CTC, and the lower temperature of the 50 C C is a good connection structure with a small difference in connection resistance after storage. 30 313294D1