201030121 六、發明說明： 【發明所屬之技術領域】 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，更詳細地 說，係有關低溫快速硬化性優異，且保存安定性也良好、 連接電阻亦安定之異向性導電電路連接用黏著劑，及使用 該黏著劑之電路板的連接方法以及連接構造體者。 【先前技術】 近年，在平命餿或液曰0顯示器等範疇中，為了固定電 子零件’或為了 it行f路連接而使用各種黏著材料，在此 等用途中’祕越邁^高密度化、高精細化，黏著劑方面 也要求有局黏者力或南可信賴产。 尤其做為電路連接材料者， 或是FPC與TCP之連接 f使用液晶顯示器與仰 用在黏著劑中分散有導電=配線板之連接，是使 著劑。最近在基板上構袭：二性導電電路連接用黏 統的導線連結，而是騎時，並不是採用傳 構裝在基板上之所謂壓著晶=體以片之正面朝下直接 始使用異向性導電電路 裝’在此也開 號、特開日⑽，228號=^(特開昭Μ-1議 7—9〇237號公報）。 I開平1-251787號、特開平 又，近年在精密電子機々 化，電極幅宽及雷拉„藥器乾可中，電路正邁向高密度 用王哀氣樹m路連接_，為此，在一向使 連接用黏者劑之連接條件下，會產生 313294D1D1 4 201030121 配線脫洛、剝離、位置不吻合等問題。為了提高生產率， 強力要奉連接時間需細短在1 〇秒鐘以下，低溫快速硬化性 因而成為不可或缺之要求。為此，在特開平10-273636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、磷酸酯化合物等之自由 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。 【發明内容】 本發明提供低溫快速硬化性優異、保存安定性 著劑’在_件下以 黏著劑之電路板連接 ^連接用黏著劑，以及使用 本發明是有二二與連接構造體。 ❿ 狀生成物中，至少是由、電粒子均勻分散而成之樹脂薄旗 導電電路連接用黏著劑从下成分所構成為其特徵之異向性 U)在表面不露出報、 子、 、、金、鉑以外之過渡金屬的導電粒 ⑵自由基聚合性 (3)由加熱或先產 施 又，本發明是有關^離基之硬化劑。 薄膜狀生成物中，至少=使導電粒子均勻分散而成之樹脂 向性導電電路連接用觀著由以下成分所構成為其特徵之異 ⑴在表面不露出起香劑. 子、 、金、鉑以外之過渡金屬的導電粒 313294D1D1 5 201030121 (2) 自甴基聚合性物質、 (3) 由加熱或光產生游離基之硬化劑，及 (4) 磷酸g旨化合物 入4::=上述異向性導電電路連接用黏著劑介 ㈣料極的絲間，加壓具有㈣向電路電 方^^同時’依场合不同，照射光（活性能源）將加壓 方向之電極間以電氣連接電路板之連接方法。 本發明又有關將上述異向性導 入具有相對向電路電極的基板間， 極的基板後，將加壓方向之電極間 電電路連接用黏著劑介 加壓具有相對向電路電 以電氣連接之連接構造 室、2 ^之異向性導電㈣連接用轉劑，即使放置在 在連接初期經耐濕試驗、冷熱循環等各種 ;降也能夠抑制連接電阻之上昇或連接強度之 卜^，顯不具有優異連接可信度。 =性導電電路連接用黏著劑，是在薄膜、被黏著體 表面形成之異向性導電樹脂。 壓且又有關介人具有㈣向電路電極的基板間，加 路電極的基板後，將加壓方向之電極間以 以:導電電路連接用㈣劑，上述黏著劑係 ==選自⑴自由基聚合性化合物，及⑵驗性化合 物進行ί 2個縣基之化合物所成組群中至卜種化合 接用黏者劑。上述異向性導電電路連接用黏著劑，係以含 313294D1D1 6 201030121 有由光或加熱產生自由基之化合物或鱗酸醋化合物者為 佳。再者，本發明之異向性導電電路連接用黏著劑，係以 - 表面處理中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，異向性導電電路連接用黏著劑係有 關含有經由選自（1)自由基聚合性化合物，及（2)鹼性化合 ® 物及至少有1個環氧基之化合物所成組群中至少一種化合 物進行表面處理後之導電粒子之黏著劑的異向性導電電路 連接構造體。 【實施方式】 本發明的異向性導電電路連接用黏著劑，是使用在導 電粒子表面上不露出銀、金、鉑以外之鎳等過渡金屬的導 電粒子。為了可以充分得到耐濕保存期限及連接可信度， 參最表面之金屬必需是銀、金、始族之貴金屬，而以金較佳。 在本發明的異向性導電電路連接用黏著劑中使用之導 電粒子，只要有可以得到電氣連接之導電性即可，而無特 別限定，但可以列舉如金、銀、鎳、銅、鈷、錫等之金屬 粒子或碳等。又，也可以使用以上述金屬導電物質被覆之 非導電性之玻璃、陶瓷、塑膠等。此時，被覆金屬層之厚 度，為了可以得到充分之導電性，以10 0 A以上為宜。在銘、 鋅、銅、錄等過渡金屬上設置貴金屬I每層f時，-貴'金屬類心 層之缺損或導電粒子混合分散時所產生之貴金屬類層缺損 7 313294D1D1 201030121 等所產生的氧化還原作用，會產生游離基而引起保存期限 減短，所以導電粒子需經表面處理。導電粒子之使用範圍 為相當於電路連接用黏著劑成分之〇. 1至30體積％，最好 使用0. 1至20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 反應性之化合物來處理為宜，依此處理可以顯著提高上述 異向性導電電路連接用黏著劑之保存安定性。 做為導電粒子表面處理之化合物，以鹼性化合物或至 少具有1個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。 做為胺系化合物者，液體、固體都可以，固體需先溶 解到有機溶劑或水等然後使用。又，液體之化合物中，也 以溶解在有機溶劑等然後使用為宜。做為有機溶劑者，只 要能溶解氨系化合物而不與氨系化合物反應者即可，無特 別限制，但以曱醇、乙醇、異丙醇、甲乙酮、醋酸乙酯、 甲苯等處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，以0. 05至20重量％ 為宜，未滿0. 05重量％時不能有效進行表面處理，超過20 重量％時導電粒子表面被覆之氨系化合物量變多，連接電阻 變高。 做為至少具有1個環氧基之化合物者，液體、固體都 可以，固體之場合需使溶解在有機溶劑或水等然後使用。 又，液體之化合物也以使用溶解到有機溶劑等然後使用為 宜。做為有機溶劑者，只要能溶解至少具有1個環氧基之 8 313294D1D1 201030121 化合物而不與至少具有1個環氧基之化合物反應者即可， 無特別限制，但以曱醇、乙醇、異丙醇、甲乙酮、醋酸乙 . 酯、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1個環氧基之化合物濃度，以 0. 05至20重量％為宜，未滿0. 05重量％時不能有效進行表 面處理，超過20重量％時，導電粒子表面被覆之至少具有 1個環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，並無特別限制， — 但處理溫度是以室溫（25°C)至100°C、處理時間是以10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°C) 至100°C中進行。 本發明之表面處理所使用之鹼性化合物，尤其做為氨 系化合物者可以列舉如，三乙胺、二乙胺、丁胺、乙二胺、 ❿六曱基二胺、苯胺、胺基丙基三甲氧基矽烷、咪唑、2-乙 基-4-甲基β米β坐、2-苯基-1-氰基乙基10米α坐、苯乙基味®坐、 苯乙基啶等，胺系中可以列舉1級、2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1個環氧基之化 合物，可以使用苯基縮水甘油醚、（曱基）丙烯酸縮水甘油 酯、7-環氧丙氧基丙基三甲氧基矽烷、環氧丙氧基丙 基二乙氧基碎烧、7"-環氧丙氧基.丙^基"甲、基....二^'早"氧基碎....烧、 環氧丙氧基丙基二乙氧基矽烷、/3-(3, 4環氧環己基） 9 313294D1D1 201030121 、 乙基三$氧基矽烷、雙酚A型環氧樹月匕雔 月旨、雙齡S型環氧樹脂、齡駿清=j㈣型環氣樹 清漆型環氧樹r、餹祕 々衣氧樹脂、甲酚酚醛 醛:主㈣r — 3冑齡祕清漆型環氧樹脂、雙紛F齡 ::她㈣旨、腊環式環編、縮水甘、齡 樹脂、縮水甘油胺型環氧 尺甘油S曰型％氣 酸酯型璟查 内醯脲環氧樹脂、異氰 ::曰，樹腊、脂肪族鏈狀環氧樹脂等，此等環氧樹二 也可以齒化，也可以添加氣 ^讀知 氧化合物。 幻以併用2種以上此等環201030121 VI. Description of the Invention: [Technical Field] The present invention relates to an adhesive for connecting an anisotropic conductive circuit, a connection method of a circuit board using the adhesive, and a circuit connection structure, and more particularly, An adhesive for connecting an anisotropic conductive circuit, which has excellent low-temperature rapid hardenability, good storage stability, and a stable connection resistance, and a connection method of a circuit board using the adhesive and a connection structure. [Prior Art] In recent years, in the category of flat life or liquid helium 0 display, various adhesive materials have been used for fixing electronic parts or for f-connection, and in these applications, 'the secret is higher and higher density. High-definition, adhesives also require a sticky or South-reliable production. Especially as a circuit connection material, or the connection between FPC and TCP f. The use of a liquid crystal display and the connection of the conductive=wiring board dispersed in the adhesive is an agent. Recently, it has been attacked on the substrate: the two-conductor conductive circuit is connected with the bonding wire of the adhesive, but when riding, it is not the so-called pressing crystal body that is mounted on the substrate, and the front side of the film is directly used downward. The directional conductive circuit is also opened here, the special opening date (10), and the 228 number = ^ (Japanese Unexamined Japanese Patent Publication No. 7-9-237). I Kaiping 1-251787, special Kaiping and other, in recent years in the precision electronic machine smashing, electrode width and Leila Pharmacy dry, the circuit is moving towards high density with the king sorrow tree m road connection _, In the connection condition of the adhesive for connection, 313294D1D1 4 201030121 wiring detachment, peeling, misalignment, etc. In order to improve productivity, the connection time should be as short as 1 sec. The low-temperature rapid hardening property is indispensable, and a material for circuit connection using a radically polymerizable substance is disclosed in Japanese Laid-Open Patent Publication No. Hei 10-273636. However, it contains (meth) acrylate and phosphate. When the adhesive of a radically polymerizable substance such as a compound and an electrically conductive particle is placed in the air, the connection resistance after the connection may increase. [Invention] The present invention provides an excellent low temperature rapid hardenability and a storage stability agent. 'In the case of _ pieces, the board is connected with an adhesive, the adhesive for connection, and the use of the present invention is a two-two connection structure. In the ❿-like product, at least The resin particles are uniformly dispersed, and the adhesive for connecting the conductive circuit of the resin is formed from the lower component to have the characteristic anisotropy. U) The conductive particles of the transition metal other than the newspaper, the sub-, the gold, and the platinum are not exposed on the surface. (2) Free radical polymerizability (3) The present invention relates to a hardening agent for a base, and at least a resin-formed conductive circuit for forming a resin-based conductive product. It is characterized by the following components: (1) Conductive particles of a transition metal other than a lightening agent. Substrate, gold, or platinum. 313294D1D1 5 201030121 (2) Self-polymerizable materials, (3) a curing agent that generates a radical by heating or light, and (4) a phosphoric acid to a compound: 4:: = an anisotropic conductive circuit connecting adhesive (4) between the filaments of the material, and having a (four) direction circuit electric ^^At the same time, depending on the occasion, the irradiation light (active energy source) is used to electrically connect the electrodes between the electrodes in the pressurizing direction. The present invention further relates to introducing the above anisotropy into the substrate having the opposite circuit electrodes, After the substrate The inter-electrode circuit for connecting the electrodes in the pressurizing direction is pressurized with an adhesive having a connection structure chamber electrically connected to the circuit, and an anisotropic conductive (four) connecting agent for the connection, even if placed in the initial stage of the connection. Moisture resistance test, cold and heat cycle, etc.; drop can also suppress the rise of the connection resistance or the connection strength, and it does not have excellent connection reliability. The adhesive for the connection of the conductive circuit is on the surface of the film and the adherend. The anisotropic conductive resin is formed, and the substrate is provided between the substrates having the (four)-direction circuit electrodes and the substrate of the addition electrode, and the electrodes in the pressing direction are connected to each other by the conductive circuit (four) agent. The system is selected from the group consisting of (1) a radically polymerizable compound, and (2) an organic compound to be used in a group of compounds of the two county-based compounds. The above-mentioned anisotropic conductive circuit-bonding adhesive is preferably a compound containing 303294D1D1 6 201030121 which generates a radical or a scaly acid compound by light or heat. Further, in the adhesive for connecting an anisotropic conductive circuit of the present invention, it is preferred that the basic compound used in the surface treatment is an amine compound. Further, in another aspect of the present invention, the anisotropic conductive circuit is connected to each other between the substrates having the opposing circuit electrodes by the adhesive, and the electrodes having the opposing circuit electrodes are pressed, and the electrodes in the pressing direction are interposed. In the connection structure electrically connected, the adhesive for the anisotropic conductive circuit connection is selected from the group consisting of (1) a radically polymerizable compound, and (2) a basic compound and at least one epoxy. An anisotropic conductive circuit-connecting structure of an adhesive of a conductive particle obtained by surface-treating at least one compound in a group of compounds. [Embodiment] The adhesive for connecting an anisotropic conductive circuit of the present invention is a conductive particle which does not expose a transition metal such as nickel other than silver, gold or platinum on the surface of the conductive particles. In order to fully obtain the moisture-resistant shelf life and the reliability of the connection, the metal of the most surface must be a precious metal of silver, gold, and the first group, and gold is preferred. The conductive particles used in the adhesive for connecting an anisotropic conductive circuit of the present invention are not particularly limited as long as they have electrical conductivity capable of electrical connection, and examples thereof include gold, silver, nickel, copper, and cobalt. Metal particles such as tin or carbon. Further, a non-conductive glass, ceramic, plastic or the like coated with the above-mentioned metal conductive material may be used. In this case, the thickness of the metal layer to be coated is preferably 100 A or more in order to obtain sufficient conductivity. When precious metal I is provided on each layer f of transition metals such as Ming, Zinc, copper, and recording, the oxidation of the noble metal layer or the loss of the noble metal layer produced by the dispersion of the conductive particles 7 313294D1D1 201030121 The reduction action causes a radical to be generated and the shelf life is shortened, so the conductive particles are subjected to surface treatment. The range of the use of the conductive particles is in the range of from 0.1 to 20% by volume, preferably from 0.1 to 20% by volume. It is preferable to treat the compound which is a surface treatment of the conductive particles with a compound which is reactive with an acidic substance, and the treatment stability of the above-mentioned anisotropic conductive circuit-bonding adhesive can be remarkably improved. The compound to be surface-treated with conductive particles is preferably a basic compound or a compound having at least one epoxy group, and particularly preferably a basic compound. As the amine compound, liquid or solid can be used, and the solid needs to be dissolved in an organic solvent or water and then used. Further, in the liquid compound, it is preferably dissolved in an organic solvent or the like and then used. As the organic solvent, it is not particularly limited as long as it can dissolve the ammonia compound without reacting with the ammonia compound, but can be dried after treatment with decyl alcohol, ethanol, isopropanol, methyl ethyl ketone, ethyl acetate, toluene or the like. Conductive particles are preferred. The concentration of the amine compound contained in the treatment liquid is preferably from 0.05 to 20% by weight, and the surface treatment is not effective when it is less than 0.05% by weight, and the amount of the ammonia compound coated on the surface of the conductive particles is more than 20% by weight. More, the connection resistance becomes higher. As the compound having at least one epoxy group, a liquid or a solid may be used, and in the case of a solid, it may be dissolved in an organic solvent or water and then used. Further, the liquid compound is preferably dissolved in an organic solvent or the like and then used. As the organic solvent, as long as it can dissolve the 8 313294D1D1 201030121 compound having at least one epoxy group and is not reacted with a compound having at least one epoxy group, it is not particularly limited, but is decyl alcohol, ethanol, or different. It is preferred to dry the conductive particles after surface treatment such as propanol, methyl ethyl ketone, ethyl acetate, or benzene. - The concentration of the compound having at least one epoxy group in the treatment liquid is preferably from 0.05 to 20% by weight, and the surface treatment is not effective when it is less than 0.05% by weight, and the conductive particles are more than 20% by weight. The amount of the compound having at least one epoxy group coated on the surface is increased, and the connection resistance is increased. The treatment conditions such as temperature and time at the time of surface treatment are not particularly limited, but the treatment temperature is preferably from room temperature (25 ° C) to 100 ° C, and the treatment time is in the range of from 10 seconds to 1 hour. Further, 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 ° C) to 100 ° C. The basic compound used in the surface treatment of the present invention, particularly as an ammonia compound, may, for example, be triethylamine, diethylamine, butylamine, ethylenediamine, hexamethylenediamine, aniline or aminopropyl. Trimethoxy decane, imidazole, 2-ethyl-4-methyl β m β sit, 2-phenyl-1-cyanoethyl 10 m α sit, phenethyl taste® sit, phenethyl pyridine, etc. The amine system may be a primary, secondary or tertiary amine, or a mixture of two or more. As the compound having at least one epoxy group used in the surface treatment of the present invention, phenyl glycidyl ether, glycidyl (meth) acrylate, 7-glycidoxypropyl trimethoxy decane, and a ring can be used. Oxypropoxypropyl diethoxy calcination, 7"-glycidoxy. propyl group " A, base .... 2 ^ 'early " oxy broken .... burning, ring Oxypropoxypropyldiethoxydecane, /3-(3,4 epoxycyclohexyl) 9 313294D1D1 201030121 , Ethyl triethoxy decane, bisphenol A epoxy tree Age S-type epoxy resin, age Junqing = j (four) type ring tree varnish type epoxy tree r, 餹 secret 々 々 epoxy resin, cresol phenolic aldehyde: main (four) r - 3 years old secret varnish type epoxy resin, double F age:: she (four) purpose, wax ring type ring, shrinking water, age resin, glycidylamine type epoxy glycerin S 曰 type % gas ester type 璟 check urem urea epoxy resin, isocyanide:: 曰, tree wax, aliphatic chain epoxy resin, etc., these epoxy trees can also be toothed, or add gas to read oxygen compounds. Magical use of two or more of these rings
其3之異向性導電電路連接用黏著射使用之自^ 土…’生化合物’係具有由自由基誘發聚合之官能基之化 合物’有（甲基）丙烯酸醋樹脂、馬來酸酐縮亞胺樹脂、寧 康醯亞胺樹脂、萘酚二亞胺樹脂等，也可以使用2種類二 上之混合物。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，也可以使用單體與寡聚合物之混 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。The three-way anisotropic conductive circuit is connected with an adhesive film, which is a compound having a functional group which is induced by a radical, and has a (meth)acrylic acid resin, maleic anhydride imide. A resin, a Ningkang imine resin, a naphthol diimine resin, or the like may be used. Further, a radical polymerizable compound may be used in any of a monomer or an oligomer, or a mixture of a monomer and an oligomer, and "(meth)acrylate" means an acrylate and a phase thereof. Corresponding to methacrylate.
做為（甲基）丙烯酸酯樹脂者，是使（甲基）丙烯酸酯進 行自由基聚合而传者，做為（甲基）丙烯酸醋者，可列舉如 (甲基）丙烯酸曱酯、（曱基）丙烯酸乙酯、（曱基）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（甲基）丙烯酸三甲醇丙烷 酯、四（甲基）丙烯酸四曱基乙二醇酯、2-羥基-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-(丙稀醯乙氧基）笨基]丙烷、（曱基）丙烯酸二環戊烯 10 313294D1D1 201030121 酯、（甲基）丙烯酸三環癸烷、異氰酸三（丙烯醯乙基）酯、（甲 基）丙烯酸胺酯、異氰酸環乙烷改質二氰酸等，可單獨使用 也可以使用兩種以上混合者。又，由於必要，在不損及硬 ·-化性範圍下也可以使用氫醌、甲基醚氫醌等之自由基聚合 禁止劑。 土 σ 再者，使用磷酸酯化合物做為自由基聚合性化合物之 場合，針對金屬等無機物可以提高接著力。此磷酸酯化合 ❿物之使用量是相對於接著劑成分1〇〇重量份的〇. i至1〇重 1伤，較佳為0. 5至5重量份。磷酸酯化合物是由無水磷 酸和（甲基）丙烯酸2-經基乙酯之反應生成物而得。具體的 有單（甲基丙婦醯乙基）酸罐酸、二（甲基丙婦酿乙基）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’例如苯基馬來酸肝縮亞胺、卜甲基 -U-馬來酸野縮亞胺隻苯、N，N’f苯基雙馬來酸酐縮亞 ❹胺、N’N -P-苯基雙馬來酸酐縮亞胺、义^^-雙苯基雙 馬來酸軒縮亞胺、U，-4, 4-(3, 3-二甲基二苯基）雙馬來酸 軒縮亞胺、Ν，Ν’ -4, 4-(3, 3-二甲基二苯基甲烧）雙馬來酸酐 縮亞胺、Ν’Ν’-4, 4-(3, 3-二乙基雙苯基曱烷）雙馬來酸酐縮 亞胺、Ν’ Ν -4, 4-二苯基乙烷雙馬來酸酐縮亞胺、Ν，Ν，_4, 4_ 一苯基丙烷雙馬來酸酐縮亞胺、Ν，Ν’ _4,4_雙苯基乙醚雙馬 來酋夂針縮亞胺、Ν，Ν，-4, 4-雙苯基橫基雙馬來酸酐縮亞胺、 2, 2-雙（4-(4-馬來酸酐縮亞胺苯氧基）苯基）两烧、义2_雙挪 (3-s-丁基-3’4-(4~馬來酸酐縮亞胺苯氧基）苯基）丙烷、 11 313294D1D1 201030121 1，1-雙（4-(4-馬來酸酐縮亞胺苯氧基）苯基）癸烷、4, 4-環 亞己基-雙（1-(4-馬來酸酐縮亞胺苯氧基）苯氧基）-2-環己 基苯、2,2-雙（4-(4-馬來酸酐縮亞胺笨氧基）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，是將分子中至少含有1個寧 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, Ν’-m-苯基雙寧康醯亞胺苯、Ν, Ν’ -p-苯基 雙寧康醯亞胺苯、N，N’-4,4-雙苯基雙寧康醯亞胺、 二曱基二苯基）雙寧康醯亞胺、 N, N’-4,4-(3,3-二曱基二笨基曱烷）雙寧康醯亞胺、N，^Γ-4,4-(3,3-二乙基 二苯基甲烷）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’ -4, 4-二苯基乙醚雙寧康醯亞胺、Ν, Ν’ -4, 4-雙苯基磺基雙寧康醯 亞胺、2,2-雙（4-(4-寧康醯亞胺苯氧基）苯基）丙烷、2,2-雙（3-s-丁基-3, 4-(4-寧康醢亞胺苯氧基）苯基）丙烷、1，1-雙（4-(4-寧康醯亞胺苯氧基）笨基）癸烷、4,4-環亞己基-雙（1-(4-寧康醯亞胺苯氧基）苯氧基）-2-環己基苯、2,2-雙（4-(4-寧康醯亞胺苯氧基）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，做為萘酚二亞胺 化合物者，例如有萘酚二亞胺、卜曱基-2, 4-雙萘酚二亞 胺、N，Ν’-m-苯基雙萘酚二亞胺、Ν, Ν’ -p-苯基雙萘酚二亞 12 313294D1D1 201030121 胺苯、Ν，Ν’-4, 4-雙苯基雙萘酚二亞胺、Ν，Ν’-4, 4-(3,3-二曱基二苯基）雙萘酚二亞胺、Ν，Ν’ -4, 4-(3, 3-二甲基二苯 基甲烷）雙萘酚二亞胺、N，Ν’ -4, 4-(3, 3-二乙基二苯基甲烷） • 雙萘酚二亞胺、Ν，Ν’ -4, 4-二苯基曱烷雙萘酚二亞胺、Ν，Ν’ -. 4, 4-二苯基丙烷雙萘酚二亞胺、Ν，Ν’ -4, 4-二苯基乙醚雙萘 酚二亞胺、Ν，Ν’ -4, 4-雙苯基磺基雙萘酚二亞胺、2, 2-雙 (4-(4-萘酚二亞胺苯氧基）苯基）丙烷、2,2-雙（3-s-丁基 -3, 4-(4-萘酷二亞胺苯氧基）苯基）丙烧、1,1-雙（4-(4-萘 ® 酚二亞胺苯氧基）笨基）癸烷、4, 4-環亞己基-雙（1-(4-萘酚 二亞胺苯氧基）苯氧基）-2-環己基苯、2, 2-雙（4-(4-萘酚二 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。 使用上述自由基聚合性化合物之場合，是使用聚合起 始劑作為由加熱或光產生游離基之硬化劑。做為聚合起始 劑者，只要能由加熱或光產生自由基之化合物即可，而無 _特別限制。有過氧化物、偶氮化合物等，可隨接著溫度、 接著時間、保存安定性等目的適當選擇，但從高反應性和 保存安定性之觀點來看，以半衰期為10小時之溫度為40 °C以上，半衰期為1分鐘之溫度為180°C以下之有機過氧 化物為佳。半衰期為10小時之溫度為40°C以上，半衰期 為1分鐘之溫度為170°C以下之有機過氧化物尤佳。接著 時間為10秒之場合，為了得到充分反應率之聚合起始劑的 配合量，相對於接著劑之總量，以1至20重量％為佳，以 2至15重量％為特佳。做為具體使用之有機過氧化物者， 13 313294D1D1 201030121 可以選自二醯過氧化物、二碳酸過氧化物、過氧化物酯、 過氧化物_縮醇、二燒基過氧化物、氫過氧化物、甲石夕院 基過氧化物等，但是過氧化物酯、二院基過氧化物、氫過 氧化物、曱矽院基過氧化物等，因為起始劑中之氯離子或 有機酸在5000 ppm以下，分解後產生之有機酸很少，可以 抑制電路構材之接著端子之腐蝕，所以特佳。由可得高反 應性之過氧化物酯來選定更佳，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_三曱基己醯過氧化物、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、苯醯過氧化物曱笨、苯醯過氧化 物等。 做為二碳酸過氧化物類者，可列舉如二丙基過氧化 物二碳酸鹽、二異丙基二碳酸鹽過氧化物二碳酸鹽、雙（4_ 二級-丁基ί辰己基）過氧化物_ 過氧化物二碳酸鹽、二（2^^7二_2—乙氧基曱氧基 二甲氧基丁基二碳酸過氧化乙物基二己^過臨氧化物）二碳酸鹽、 氧基丁基過氧化物)二碳酸鹽等广一二(3-甲基-3-乙 做為過氧化物酯者，可 醋、u，3,3-四甲基丁基過氧化;^氧化物新癸酸 甲基乙基過氧化物新癸酸酯、三开力IS曰、1-環己基-1-醋、三級-丁基過氧化物新癸酸=、/己基過氧化物新癸酸 氧化物-2-乙基己酸酯、2 9 i，I 3, 3-四曱基丁基過 過氧化物）己烷、1-環己美_1曱基〜2, 二（2-乙基己醯基 甲基己基過氧化-2-乙基己酸 313294D1D1 14 201030121 酯、三級-己基過氧化物_2-乙基已酸酯、三級—丁基過氧化 物一2-乙基已酸酯、三級-丁基過氧化物異丁酸酯、丨，(三 級過氧化物）環己烷、三級-已基過氧化物異丙單碳酸鹽、 一’及丁基過氧化物一3, 5’ 5-二曱基己酸酯、三級_丁基過氧 化物錄酸酯、2, 5-二甲-2, 5-二甲苯醯過氧化物）已 烧一級丁基過氧化物異丙燒單碳酸酯、三級—丁基過氧 化物-2-乙基己基單碳酸醋、三級_己基過氧化物苯酸醋、 三級-丁基過氧化物乙酸酯等。 做為過氧化輔醇類者，可列舉如^卜（三級_己基過 ^化物）-3,3,5-三甲基環己燒]，卜（三級_己基過氧化物） %己烷、1，1-(二級-丁基過氧化物）_3,3,卜三曱基環己 烷、1，1-(三級-丁基過氧化物）環癸院、2, 2_雙（三級—丁美 過氧化物）癸烧等。 土 ❹ 做為二院基過氧化物類者可列舉如ϋ-雙（三級_ 丁基過氧化物）二異丙苯、二異苯丙基過氧化物、2, 5-二甲 過氧化物）—級-丁基異苯丙基 異丙基苯氫過氧化 ，二 15又砀虱過虱化物類者可列舉如 物、異苯丙烷氫過氧化物等。 做為甲残基過氧化物類者可列舉如， 基甲矽烷基過氧化物、雙（二 —甲 化物、三級-丁基：乙烯丁基）二甲基甲石夕烧基過氧 榼其田— 甲矽烷基過氧化物、雙（三級一 丁基）一乙烯基甲錢基過氧化物 基甲矽烷基過氧化物、：級 1一、級了基）一乙烯 —观〜丁基三丙烯基甲矽烷基過氧化 313294D1D1 15 201030121 物又（一級丁基）二丙烯基曱矽烷基過氧化物、三（三級〜 丁基）丙烯基曱矽烷基過氧化物等。 又，為了抑制電路構材之連接端子之腐蝕，游離基發 生劑化劑）中所含之氣離子或有機酸是以在漏卿以 下為且再者力口熱分解後產生之有機酸以少者為佳。又， 在提高製成電路連接材料之安定性上，以室溫（25。〇、常 壓下開放放置24 /丨、0主Μ θ 寺後仍具有20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 解促進劑、抑制劑等混合使用。 游離基發生劑以聚胺§旨系、聚㈣之高 物質等覆蓋後使之微膠囊化產 間，所以較佳。 自，基聚合性化合物以外，也可㈣人做為敎 樹脂^㈣樹脂。做為環氧樹脂者，有雙紛a型環氧 雙酚购乳樹脂、雙紛s型環氧樹月旨曰、 樹脂、f驗_清漆型環氧樹脂、雙紛 樹脂、雙齡F齡磐清漆型環氧樹脂、腊環式環=樹，環氧 水甘油酯型環氧樹脂、縮水甘油胺型環氧樹腊曰、如 環氧樹腊、異氰酸醋型環氧樹腊、脂肪族鍵 内酿脲 此等環氧樹脂也可以歯素化、也可以加歲。此腊等’ 也可以併用2種以上。 展氧樹脂 又’做為上述環氧樹脂之硬化劑者 _、酸_，類'二氣二酿胺等通常做=: 3i3294DlDl 16 201030121 硬化劑者。再者’做為硬化促進劑者，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法者，在使用上述硬化 … 劑以外’也可以使用四價硫（sulfonium ;硫鏺）鹽、碘鍚鹽 *· 等，使陽離子聚合也可以。 癱 ❿ 社w <电路接著用黏著劑或異向性導電樹脂薄膜 狀生成物中’為了賦與薄膜形成性、黏著性、硬化時之應 力缓和性’一般要使用聚乙烯丁縮醛樹脂、聚乙烯甲縮醛 樹脂、聚酯樹脂、聚醯胺樹脂、聚亞醯胺樹脂、二曱苯樹 脂、聚胺酯樹脂、尿素樹脂等高分子成分，此等高分 分是以分子量為10,000至1〇 〇〇〇 〇〇〇者為宜。刀 樹脂’也可以是自由基聚合性之官能基所 ’此等 耐熱性提高。再者，也可以是用自由絲，此場合 環氧基，齡等所變成，在此場合賴性會提基或 成分之配合1為2至8G重量％，以5至7():阿分子 1〇至60趟最好。不滿2 宜’以 不足，超過80重量％時流動性下降。力緩和或黏著力 本發明之異向性導電電路 加適當之充填劑、軟化 -者种，也可以添 難燃劑、偶合劑。 、刈、老化防止劑、著色劑、As the (meth) acrylate resin, those which are subjected to radical polymerization of (meth) acrylate are used as the (meth) acrylate vinegar, and examples thereof include decyl (meth) acrylate. Ethyl acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, ethylene glycol di(meth) acrylate, diethylene glycol di(meth) acrylate, tris Base) trimethylolpropane acrylate, tetradecyl ethylene glycol tetra(meth)acrylate, 2-hydroxy-1,3-dipropene oxime, 2,2-bis[4-(acryloxy) Phenyl]propane, 2,2-bis[4-(acrylic ethoxy)phenyl]propane, (cyclo)acrylic acid dicyclopentene 10 313294D1D1 201030121 ester, tricyclodecane (meth)acrylate, Tris(propylene sulfonium ethyl) isocyanate, amine (meth) acrylate, isocyanate modified by diisocyanate, etc., may be used singly or in combination of two or more. Further, if necessary, a radical polymerization inhibiting agent such as hydroquinone or methyl ether hydroquinone may be used without impairing the hard acidity. Soil σ Further, when a phosphate compound is used as the radical polymerizable compound, the adhesion can be improved for an inorganic substance such as a metal. 5至五重量份。 The amount of the phosphate compound is used in an amount of from 1 to 1 part by weight, preferably from 0.5 to 5 parts by weight. The phosphate compound is obtained by reacting anhydrous phosphoric acid with 2-ethylidene ethyl (meth)acrylate. Specific examples include methacrylic acid ethyl acrylate acid and bis(methyl propyl hydroxy) acid phosphate, which may be used singly or in combination. As a maleic anhydride imide resin, it is a molecule containing at least one maleic anhydride imide in the molecule, such as phenyl maleic acid hemiacetin, methyl-U-maleic acid, iminoacetic acid, and only benzene. , N, N'f phenyl bismaleic acid linoleamide, N'N-P-phenyl bismaleimide imide, Yi^-diphenyl dimaleic acid acetin, U ,-4,4-(3,3-dimethyldiphenyl)bismaleate, hydrazine, Ν'-4,4-(3,3-dimethyldiphenylcarbamate) Bimaleic anhydride imide, Ν'Ν'-4, 4-(3,3-diethyl bisphenyldecane) bis-maleic anhydride imide, Ν' Ν -4, 4-diphenyl Ethane double maleic anhydride imipenem, hydrazine, hydrazine, _4, 4_ phenylpropane double maleic anhydride imipenem, hydrazine, Ν' _4,4_ bisphenylether double emale acesulfame , hydrazine, hydrazine, -4, 4-bisphenylyl bis-bis-maleic acid imide, 2,2-bis(4-(4-maleic anhydride) phenyloxy)phenyl),义2_双动(3-s-butyl-3'4-(4~maleic anhydride acetoxyphenoxy)phenyl)propane, 11 313294D1D1 201030121 1,1-double (4-(4-horse Anhydride acetal phenoxy)phenyl)indole Alkane, 4, 4-cyclohexylene-bis(1-(4-maleic anhydride) phenoxy)-2-cyclohexylbenzene, 2,2-bis(4-(4-ma) The acid anhydride imide oxyalkyl) phenyl) hexafluoropropane or the like may be used singly or in combination of two or more. As a Ningkang imine resin, a compound containing at least one Ningkang imino group in the molecule is polymerized as a Ningkang imine compound, for example, a phenyl group. Ningkang imine, 1-mercapto-2, 4-shuangning Kangxiuylidene benzene, N, Ν'-m-phenyl bis-quinone quinone amide, hydrazine, Ν'-p-phenyl bis Ningkang imine benzene, N, N'-4,4-bisphenyl bis-quinone quinone, dimercaptodiphenyl) bispyretinium, N, N'-4,4-( 3,3-dimercapto-p-nonyl decane) shuangning quinone imine, N, Γ-4,4-(3,3-diethyldiphenylmethane) bispyretinium, hydrazine ,Ν'-4, 4-diphenylmethane bispyrene, Ν, Ν'-4, 4-diphenylpropane, bis, quinone, hydrazine, Ν'-4, 4-diphenyl Ethyl ether, succinimide, hydrazine, Ν'-, 4-bisphenyl sulfo bispyramine, 2,2-bis(4-(4-Ningkang iminophenoxy) Phenyl)propane, 2,2-bis(3-s-butyl-3,4-(4-Ningkangimine phenoxy)phenyl)propane, 1,1-bis(4-(4- Ningkang imine phenoxy) phenyl) decane, 4,4-cyclohexylene-bis(1-(4-Ningkangimine phenoxy) Phenoxy) -2-cyclohexylbenzene, 2,2-bis (4- (4-citraconic imide acyl) phenyl) hexafluoropropane and the like, can be used alone or two or more may be used mixed. As a naphthol diimine resin, a naphthol diimine compound containing at least one naphthol diimine group in a molecule is polymerized as a naphthol diimine compound, for example, naphthol di Amine, dimercapto-2, 4-bis-naphthol diimine, N, Ν'-m-phenyl bis-naphthol diimine, hydrazine, Ν'-p-phenyl bis-naphthol diol 12 313294D1D1 201030121 Aminobenzene , Ν, Ν '-4, 4-bisphenyl bis-naphthol diimine, hydrazine, Ν '-4, 4-(3,3-dimercaptodiphenyl) bis naphthol diimine, hydrazine, Ν' -4, 4-(3, 3-dimethyldiphenylmethane) bis-naphthol diimine, N, Ν' -4, 4-(3, 3-diethyldiphenylmethane) • Bis-naphthol diimine, hydrazine, Ν'-4, 4-diphenyldecane bis-naphthol diimine, hydrazine, Ν'-. 4, 4-diphenylpropane bis-naphthol diimine, hydrazine ,Ν' -4, 4-diphenylethyl ether bis-naphthol diimine, hydrazine, Ν' -4, 4-bisphenyl sulfonabisnaphthol diimine, 2, 2- bis (4-(4 -naphthol diimine phenoxy)phenyl)propane, 2,2-bis(3-s-butyl-3, 4-(4-naphthalene diimide phenoxy)phenyl)propane, 1,1-bis(4-(4-naphthalene® phenol diimine phenoxy) phenyl) decane, 4, 4-cyclohexylidene-bis(1-(4-naphthol diimine phenoxy)phenoxy)-2-cyclohexylbenzene, 2,2-bis(4-(4-naphthol dimethylene) Aminophenoxy)phenyl)hexafluoropropane or the like may be used singly or in combination of two or more. In the case of using the above radical polymerizable compound, a polymerization initiator is used as a curing agent which generates a radical by heating or light. As the polymerization initiator, as long as the compound capable of generating radicals by heating or light can be used, it is not particularly limited. There are peroxides, azo compounds, etc., which can be appropriately selected for the purpose of temperature, subsequent time, storage stability, etc., but from the viewpoint of high reactivity and storage stability, the temperature at a half-life of 10 hours is 40 °. Above C, an organic peroxide having a half-life of 1 minute and a temperature of 180 ° C or less is preferred. An organic peroxide having a half-life of 10 hours and a temperature of 40 ° C or more and a half-life of 1 minute and a temperature of 170 ° C or less is particularly preferable. When the time is 10 seconds, the amount of the polymerization initiator to be sufficiently reacted is preferably from 1 to 20% by weight, particularly preferably from 2 to 15% by weight, based on the total amount of the adhesive. As a specific organic peroxide, 13 313294D1D1 201030121 may be selected from the group consisting of diterpene peroxide, dicarbonate peroxide, peroxide ester, peroxide-polyhydric alcohol, dialkyl peroxide, hydrogen peroxide Oxide, methyl sulphate-based peroxide, etc., but peroxide esters, second-compartment peroxides, hydroperoxides, sputum-based peroxides, etc., because of the chloride ion or organic in the initiator When the acid is at most 5,000 ppm, the organic acid generated after decomposition is small, and it is possible to suppress corrosion of the subsequent terminals of the circuit member, which is particularly preferable. It is preferably selected from the highly reactive peroxide esters, and these can be suitably mixed. As the dioxane peroxide, for example, isobutyl peroxide, 2'4-dichlorophenylhydrazine peroxide, 3,5,5-tridecylhexyl peroxide, and bismuth Oxide, dodecyl peroxide, stearic acid peroxide, amber peroxide, peroxide, phenyl peroxide peroxide, benzoquinone peroxide, and the like. As the dicarbonate peroxide, there may be mentioned, for example, dipropyl peroxide dicarbonate, diisopropyl dicarbonate peroxide dicarbonate, bis(4_di-butyl butyl hexyl) Oxide _ peroxide bicarbonate, di(2^^7二_2-ethoxymethoxy dimethoxybutyl dicarbonate peroxyethylene dihexyl oxide) dicarbonate , oxybutyl peroxide) dicarbonate and the like a wide range of two (3-methyl-3-ethyl as a peroxide ester, vinegar, u, 3,3-tetramethylbutyl peroxidation; ^Oxide neodecanoic acid methyl ethyl peroxide neodecanoate, three-opening IS曰, 1-cyclohexyl-1-acetate, tertiary-butyl peroxide neodecanoic acid =, / hexyl peroxidation Neodecanoate oxide-2-ethylhexanoate, 2 9 i, I 3, 3-tetradecyl butyl per peroxide) hexane, 1-cyclohexyl-1 fluorenyl~2, two (2-ethylhexylmethylhexylperoxy-2-ethylhexanoic acid 313294D1D1 14 201030121 ester, tertiary-hexyl peroxide 2 - ethyl hexanoate, tertiary butyl peroxide 2-ethyl hexanoate, tertiary butyl peroxide isobutyrate, hydrazine, (tertiary peroxidation) Cyclohexane, tertiary-hexyl peroxide isopropyl monocarbonate, a 'and butyl peroxide-3,5' 5-didecyl hexanoate, tertiary _butyl peroxide Acid ester, 2, 5-dimethyl-2, 5-xylene oxime peroxide) calcined primary butyl peroxide isopropyl monocarbonate, tertiary butyl peroxide-2-ethylhexyl Monocarbonic acid, tertiary _ hexyl peroxide benzoic acid vinegar, tertiary butyl peroxide acetate, and the like. As a peroxy alcohol auxiliary, it can be exemplified as ^ (di- _ hexyl peroxy) -3,3,5-trimethylcyclohexanol], di (tri- _ hexyl peroxide) % Alkane, 1,1-(secondary-butyl peroxide)_3,3,ditridecylcyclohexane, 1,1-(tertiary-butyl peroxide) ring broth, 2, 2_ Double (three-stage - Dingmei peroxide) simmered and so on. As a kind of peroxide in the second hospital, such as bismuth-bis(tris-butyl peroxide) diisopropylbenzene, diisophenylpropyl peroxide, 2, 5-dimethylperoxide The product is a per- butyl isophenyl propyl benzene hydroperoxide, and the bismuth hexyl isopropyl benzene is hydrolyzed. Examples of the methyl peroxide-based peroxides include, for example, a mercaptoalkyl peroxide, a bis(di-formate, a tertiary-butyl group: an ethylene butyl group), a dimethyl ketone-based peroxy oxime. Field - methyl ketone alkyl peroxide, bis (tertiary butyl) monovinyl ketone peroxide methyl methacrylate peroxide, grade 1 , grade base) - ethylene - butyl ~ butyl Tripropylene methacrylate alkyl peroxidation 313294D1D1 15 201030121 Further (first-order butyl) dipropenyl decyl peroxide, tris(terta- to butyl) propylene decyl peroxide, and the like. Further, in order to suppress corrosion of the connection terminal of the circuit member, the gas ion or the organic acid contained in the radical generating agent is less than the organic acid which is generated after the thermal decomposition of the resin. It is better. Moreover, in order to improve the stability of the circuit-connecting material, it is preferable to have a weight retention ratio of 20% by weight or more after being placed at room temperature (25 〇, under normal pressure, 24/丨, 0 main θ θ temple) These radical generators may be used singly or in combination, or may be used in combination with a promoter, an inhibitor, etc. The radical generator is covered with a polyamine §, a poly(tetra) substance, or the like. It is preferred to make it microencapsulated in the production room. In addition to the base polymerizable compound, it can also be used as a resin (4) resin. As an epoxy resin, there are double a type epoxy bisphenols. Latex resin, double s-type epoxy tree moon 曰, resin, f test _ varnish type epoxy resin, double bismuth resin, double age F 磐 varnish type epoxy resin, wax ring ring = tree, epoxy water Glyceryl ester type epoxy resin, glycidylamine type epoxy resin wax, such as epoxy wax, isocyanate type epoxy wax, and aliphatic bond urea, etc. It is also possible to add years. This wax can also be used in combination of two or more. Oxygen-expanding resin is also used as the above ring. Resin hardener _, acid _, class 'diqi urethane, etc. usually do =: 3i3294DlDl 16 201030121 hardener. In addition, as a hardening accelerator, usually can use appropriate grade 3 amine, organic phosphorus In addition, as a method of reacting an epoxy resin, a sulfonium sulfonium salt or an iodonium salt* may be used in addition to the above-mentioned hardening agent, and cationic polymerization may be carried out.瘫❿ 社 w < circuit followed by adhesive or anisotropic conductive resin film-like product 'in order to impart film formability, adhesion, stress relaxation during hardening' generally use polyvinyl butyral resin, a polymer component such as a polyvinyl acetal resin, a polyester resin, a polyamide resin, a polyamidene resin, a diphenyl benzene resin, a polyurethane resin, or a urea resin, and the high molecular weight is 10,000 to 1 分子量. The squeegee resin may be a radical polymerizable functional group, and the heat resistance is improved. Further, a free yarn may be used. In this case, an epoxy group or the like may be used. Become here The compatibility of the base or the component 1 is 2 to 8 G weight%, and 5 to 7 (): the A molecule is preferably 1 to 60. The less than 2 is less than, and the fluidity is decreased when it exceeds 80% by weight. Force relaxation or adhesion The anisotropic conductive circuit of the present invention is added with a suitable filler, softening type, and may also be added with a flame retardant, a coupling agent, a cockroach, an aging preventive agent, a coloring agent,
含有充填劑之場合， I 較好，填充材之最士乂楗南黏著可信度等，所以 以使用，以5 $ 粒徑只要不超過導電粒子 以使用以5至6〇體積 千之杻從就可 信度提高效果就達 圍為且，超過60體積％時 相餘和。做為偶合劑者，以含有乙;基: 313294〇1Di 17 201030121 丙烯基、胺基、環氧基、醯胺基及異氰酸基者，因可以提 高黏著性所以較佳。 又，將本發明之異向性導電電路連接用黏著劑做為硬 化時之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。 使用本發明之異向性導電電路連接用黏著劑之黏著基 板，只要有形成必要之電氣黏接電極者就可以，而無特別 限制，例如有在液晶顯示器中使用之ΙΤ0等形成電極之玻 璃或塑膠基板、PDP平板、EL平板等晝像顯示基板、印刷 配線板、陶瓷配線板、可撓配線板、半導體晶片、申阻晶 片、電容器晶片等晶片組件、磁帶包裝、⑶F等之電路零 件半導體矽晶片等，必要時可以組合使用。 黏著時之條件並無特別限制，但黏接溫度為90至250 °C、黏著時間為1秒鐘至10分鐘之間，使用之用途可以依 黏著劑、基板之不同而作適當選擇，視需要也可以使用熱 以外之能源，例如光、超音波、電磁波等。 實施例 以下，以實施例來具體說明本發明，但本發明之範圍 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, 000)溶解於MEK(曱乙酮，沸點79. 6 °C)，成為固形分50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 18 313294D1D1 201030121 酸酯（東亞合成公司製，商品名M-215)及磷酸酯型丙烯酸 酯（共榮社油脂株式公司製、商品名P-2M)。 加熱或光產生游離基之硬化劑，使用2, 5-二甲基-2, 5-雙（2-乙基己醯基過氧化物）己烷之50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0. 09/im之銀層 而成之平均粒子徑5 μ 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5(^，磷酸酯型丙烯酸酯2舀，2,5-二甲基 -2, 5-雙（2-乙基己酿基過氧化物）己烧5 g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80/im的PET(聚對苯二曱酸乙酯）薄膜， 經7(TC、10分鐘之熱風乾燥，可得黏著劑層厚度為35/i m 之異向性導電電路連接用黏著劑。 0 (實施例2) 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366 kg/匪2)表面上，設置厚度0. 1 // m之銀層而成 之平均粒子徑6. 15/im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 彈性率480 kg/匪2)表面上，設置厚度Ο.ΐμπι之銀層，在 此銀層之外側，設置厚度0. 04//m之金層而成之平均粒子 19 313294D1D1 201030121 徑5 // m之導電粒子，經與實施例1相同處理後可得異向性 導電電路連接用黏著劑。 、 (實施例4) 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，設置厚度〇· 1从^之錄層，在 此鎳層之外側，設置厚度0.05 之銀層而成之平均粒子 徑5 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。 (比較例1) 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0 2/zm之鎳層而成 之平均粒子徑5//m之導電粒子，經與實施例1相同處理後 可得異向性導電電路連接用黏著劑。 (比較例2) 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，設置厚度〇·2以m之鎳層，在 此鎳層之外侧，設置厚度0.04/zm之金層而成之平均粒子 徑5# m之導電粒子，經與實施例丨相同處理後可得異向性 導電連接用黏著劑。 (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30Am、間距3〇Am、厚度18//m之銅電路的磁帶套組 (TCP)和ITO玻璃（Di〇merteck公司製，表面電阻2〇至3〇 歐姆/每平方米⑴/口），厚度1. 1咖）以HC，3MPa加 3I3294D1D1 20 201030121 熱加壓15秒鐘’可得連接寬2丽之連接構造體。此時， 預先在ΙΤ0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8CTC，〇.5MPa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） ❹ 及在電電路連接用黏著劑，於保存 進行上述之電路連接^恒濕槽中，分別保存⑽小時後， 之連接電阻值，以/含上述連接部之TCP的鄰接電路間 接電路間之夕功能測試_定，連接電阻值是指鄰 之150點平均值，測定結果如表！所示。In the case of a filler, I is better, and the filler is the most reliable. It is used in a size of 5 $ as long as it does not exceed the conductive particles to be used in a volume of 5 to 6 〇. As far as the credibility improvement effect is reached, the balance is more than 60% by volume. As the coupling agent, it is preferred to contain B; group: 313294〇1Di 17 201030121 propylene group, amine group, epoxy group, decylamino group and isocyanate group, since adhesion can be improved. Further, the Tg (glass transition degree) at the time of hardening the adhesive for connecting an anisotropic conductive circuit of the present invention may be a multilayer structure of two or more different layers. The adhesive substrate to which the anisotropic conductive circuit of the present invention is bonded is used as long as it forms a necessary electrode for electrical bonding, and is not particularly limited. For example, there is a glass for forming an electrode such as ΙΤ0 used in a liquid crystal display or A semiconductor substrate such as a plastic substrate, a PDP panel, or an EL panel, such as a display substrate, a printed wiring board, a ceramic wiring board, a flexible wiring board, a semiconductor wafer, a resist wafer, a capacitor chip, and the like, a magnetic tape package, and a circuit component semiconductor such as (3)F Wafers, etc., can be used in combination if necessary. The conditions for adhesion are not particularly limited, but the bonding temperature is 90 to 250 ° C, and the adhesion time is between 1 second and 10 minutes. The use can be appropriately selected depending on the adhesive and the substrate, as needed. It is also possible to use energy sources other than heat, such as light, ultrasonic waves, electromagnetic waves, and the like. EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the scope of the present invention is not limited to the examples. (Example 1) 50 g of a phenoxy resin (manufactured by Union Carbide, trade name: PKHC, average molecular weight: 45,000) was dissolved in MEK (anthraquinone, boiling point: 79. 6 ° C) to obtain a solid content of 50% by weight. Solution. The radically polymerizable material is a dipropylene propylene modified with isocyanate oxime 18 313294D1D1 201030121 acid ester (manufactured by Toagosei Co., Ltd., trade name: M-215) and a phosphate ester type acrylate (manufactured by Kyoeisha Oil Co., Ltd.) Product name P-2M). Heating or photo-generated free radical hardener, using 2, 5-dimethyl-2, 5-bis(2-ethylhexyl peroxide) hexane 50% by weight of hydrocarbon solution, (Japan Oil Company) System, name Perhexa 250). The conductive particles were used on a surface of a particle having a polystyrene as a core (compressive modulus of elasticity: 480 kg/mm 2 ), and a conductive particle having an average particle diameter of 5 μm and having a thickness of 0.99 μm. ® solid weight ratio is 50g of phenoxy resin, diacrylate acrylate modified by isocyanate oxime 5 (^, phosphate ester acrylate 2舀, 2,5-dimethyl-2, 5-double (2-ethylhexanyl peroxide) is blended in a 5 g mode, and then 3 vol% of the conductive particles are dispersed, and then coated on a single-sided surface-treated 80/mm PET by a coating device. (Poly(trimethylene terephthalate) film) After 7 (TC, 10 minutes hot air drying, an adhesive for connecting an anisotropic conductive circuit with an adhesive layer thickness of 35/im can be obtained. 0 (Example 2) 1 / / / The conductive particles are used on the surface of the particles with a polystyrene as the core (compressive modulus of 366 kg / 匪 2), the thickness of the layer of 0. 1 / m silver layer of the average particle diameter of 6. 15 / im The conductive particles were obtained in the same manner as in Example 1 to obtain an anisotropic conductive circuit-bonding adhesive. (Example 3) Conductive particles were used in a particle having a polystyrene as a core (compression elastic modulus: 480 kg/匪2) On the surface, a silver layer having a thickness of Ο. πμπι is disposed, and on the outer side of the silver layer, an average particle of a thickness of 0.04//m is formed. 19 313294D1D1 20 1030121 Conductive particles having a diameter of 5 // m were subjected to the same treatment as in Example 1 to obtain an adhesive for connecting an anisotropic conductive circuit. (Example 4) Conductive particles were used as particles having polystyrene as a core. (Compression elastic modulus: 480 kg/mm2) On the surface, a thickness 〇·1 is set from the recording layer, and on the outer side of the nickel layer, a conductive particle having an average particle diameter of 5 and a silver layer of 0.05 is provided. For example, an adhesive for connecting an anisotropic conductive circuit can be obtained by the same treatment. (Comparative Example 1) Conductive particles are used on a surface of a particle having a polystyrene as a core (compression elastic modulus: 480 kg/mm 2 ), and a thickness is set. The conductive particles having an average particle diameter of 5/m from the nickel layer of 0 2 /zm were subjected to the same treatment as in Example 1 to obtain an adhesive for connecting an anisotropic conductive circuit. (Comparative Example 2) Use of conductive particles On the surface of particles (compression elastic modulus: 480 kg/mm2) with polystyrene as the core, a nickel layer having a thickness of 〇·2 is provided, and a gold layer having a thickness of 0.04/zm is provided on the outer side of the nickel layer. The conductive particles having an average particle diameter of 5# m are treated in the same manner as in the embodiment An adhesive for anisotropic conductive connection can be obtained. (Connection of circuit) Using the above-mentioned anisotropic conductive resin film-like formation, a copper circuit having a line width of 30 Am, a pitch of 3 〇 Am, and a thickness of 18//m is used. Tape set (TCP) and ITO glass (made by Di〇merteck, surface resistance 2 〇 to 3 〇 ohm / per square meter (1) / mouth), thickness 1. 1 coffee) to HC, 3MPa plus 3I3294D1D1 20 201030121 Pressing for 15 seconds can be used to connect a wide connection structure. In this case, the bonding surface of the anisotropic conductive circuit connecting adhesive is attached to the ΙΤ0 glass in advance, and then heated and pressurized at 8 CTC, 〇5 MPa for 3 seconds to be connected, and then the PET film is peeled off and completed with Tcp. connection. (Measurement of connection resistance) ❹ and the adhesive for electrical circuit connection, and store the above-mentioned circuit connection in the constant humidity chamber, and store the resistance value for (10) hours, respectively, and the TCP adjacent to the connection portion. The function test between the circuit indirect circuits _ fixed, the connection resistance value refers to the 150 point average of the neighbor, the measurement results are as shown! Shown.
313294D1D1 21 201030121 相對於此，比較例1及2，在-20°C保存之連接構造體 中，雖可得良好連接可信度，但在30°C、85%RH之恒溫恒 濕槽中保存者，連接電阻大幅上昇到10Ω以上。 (連接強度之測定） 在實施例1至3中，於-20°C或在30°C、85% RH之恒 溫恒濕槽中保存者，任一者個都可得1000 N/m左右之良 好連接強度。另一方面，比較例1及2中，連接強度於-20 °C或在30°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 互交叉配置250條線寬50//m、間距100//m、厚度18//m 之銅電路的櫛形電路印刷電路基板，和具有500條線寬50 // m、間距100/z m、厚度18 // m之銅電路的磁帶套組（TCP)， 以14 0 °C，3MPa加熱加壓15秒鐘，連接幅寬2mm。此連接 體之櫛形電路外加100V之電壓，在85°C、85% RH之高溫 高濕下試驗500小時後測定絕緣電阻值。 任一者都可得到109Ω以上之良好絕緣性，觀察不出有 絕緣性下降現象。 (流動性之評估） 使用厚度35 // m、5mm x5mm之異向性導電電路連接用 黏著劑，將其夾持於厚度0. 7 /z m、15πιπι xl5mm之玻璃中， 在140°C，3MPa下進行加熱加Μ 15秒鐘，使用勒期之面積 (Α)和加熱加Μ後面積（Β)，求得流動性（Β)/(Α)值時，實 22 313294D1D1 201030121 施例1至3是h 9至2 〇之範圍内，另一方面，比 及2則為1. 8及1. 9。 (硬化後之彈性率） 測疋貫施例丨之異向性導電電路連接用黏著劑在 、後40°C之彈性率，為15Gpa。 由上述之連接強度、絕緣性、流動性、硬化 率等翻之士 斤1王 、—，本發明之實施例之值和比較例之值，雖顯示幾 由表1所示般’連接電阻值有很大之差里。 子Ν之特&觀之，導電粒子表面兩丁有 對連接電阻有明顯之影響。如本發明，/被認為極薄，但 金翻以外之過渡金屬的導電粒子中表面並不露出銀、 促進自由基聚合性物質之聚合現象導電粒子表面並無 良好數值。如實施例4使用錦等 ^連接電阻極低之 側覆蓋500Α以上之銀、金、鈕望4金屬時，只要在其外 魯 出，則雖經溫度或溫濕度處理均具過渡，不露 連接電阻不會增如。 異之保存安定性， (表面處理粒子Α之製作） 二乙胺之1重量％甲醇溶液中， 心之粒子表面上，設置G 2/^厚^聚苯乙埽為核 側，設置〇.〇4_厚度之金層而成鎳層，在此錄層外 粒子，於肌授拌10分鐘，過據=徑之導電 乾燥15分鐘，得到表面處理粒子A〜電麵子，在肌下 (表面處理粒子B之製作） 313294D1D3 23 201030121 乙=三魏之3重量％甲醇溶液中，放人在以聚苯 核心之粒子表面上，設置G.2//m厚度之錄層，在此 =側’設置叫4度之金層而成之平均粒徑一 ^電粒子’於5(TC攪拌5分鐘’過濾料電粒子，在8〇 L下乾紐5分鐘，得到表面處理粒子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抑之i重量％甲醇 溶液中’放人在以聚苯乙烯為核心、之粒子表面上，設置〇 2 ”厚度之錄層’在此錄層外側，設置G. 厚度之金 層而成之平均粒徑4⑽之導電粒子，於饥攪拌^鐘， 過處出導電粒子，在5Gt下乾燥15分鐘，得到表面處理 (表面處理粒子D之製作） “雙齡A型環氧樹脂之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/zm厚度之鎳層，在 此錄層外側，設置請，厚度之金層喊之平均粒徑5 導電粒子’於阶㈣5分鐘，顧出導電粒子， 在80 C下乾燥5分鐘，得到表面處理粒子D。 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(聚對笨二甲酸乙酯）薄膜單面上塗佈厚 度，在70°c、經1〇分鐘之熱風乾燥，製成電路連接用黏 著劑。 (實施例5) 313294D1D1 24 201030121 將苯氧基樹脂（PKHC，Union carbide公司製商品名、 平均分子量45, 000)5Og，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，2，5-二甲基-2, - 5-雙（2-乙基己醯過氧化物）己烷3g，溶解在做為溶劑之曱 · 乙酮中，再將3體積％之表面處理粒子A配入分散，在表面 處理過之聚對苯二甲酸乙酯薄膜單面上，以簡易塗工機塗 佈50//m厚度，在70°C、經10分鐘之熱風乾燥，製得厚 度為30/im之異向性導電電路連接用黏著劑。 ® (實施例6) 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 468，磷酸酯丙烯酸酯4运，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酮中，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 對苯二曱酸乙酯薄膜單面上以簡易塗工機塗佈50/zm厚 參度，在70°C、經10分鐘之熱風乾燥，製得厚度為30/zm 之異向性導電電路連接用黏著劑。 (實施例7) 將苯氧基樹脂（PKHC，Union carbide公司製商品名、 平均分子量45, 000)25g，聚胺酯樹脂25g，甲基丙稀酸二 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，溶解配入做為溶劑之曱乙酮 中，再將3體積％之表面處理粒子B配入分散，在表面處理 過之聚對苯二甲酸乙酯薄膜單面上以簡易塗工機塗佈50// 25 313294D1D1 201030121 m厚度，在70°C、經10分鐘之熱風乾燥，製得厚度為30 /z m之異向性導電電路連接用黏著劑。 (實施例8) 將笨氧基樹脂（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C配入分散，在表面 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/zm厚度，在70°C、經10分鐘之熱風乾燥，製得厚度為 30/zm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，鱗酸醋丙稀酸醋4g，2, 5-二曱基-2, 5-雙（2-乙基已 醯過氧化物）已烷3g，溶解配入做為溶劑之曱乙酮中，再 將3體積％之表面處理粒子D配入分散，在表面處理過之聚 對苯二曱酸乙酯薄膜單面上以簡易塗工機塗佈50 /z m厚 度，在70°C、經10分鐘之熱風乾燥，製得厚度為30/zm 之異向性導電電路連接用黏著劑。 (實施例10) 將苯氧基樹脂（PKHC，Union carbide公司製商品名、 平均分子量45, 000)25g，聚胺酯樹脂25g，曱基丙烯酸二 環己酯48g，磷酸酯丙烯酸酯2g，2, 5-二曱基-2, 5-雙（2- 26 313294D1D1 201030121 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D配入分散，在表面處理 過之聚對苯二曱酸乙酯薄膜單面上以簡易塗工機塗佈50# m厚度，在70°C、經10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。 (比較例3) 除了將實施例5之表面處理粒子A改為未處理粒子以 外，其餘與實施例5同樣處理，製得異向性導電電路連接 馨用黏著劑。 (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. 5mm 幅寬，在已形成ΙΤ0電極之玻璃基板上，於80°C、5秒、 IMPa之條件下暫時連接，剝離PET支持基材，將此對齊電 極寬50/im、間距50/ζπι之TCP電極位置，在150°C、20 秒、4MPa之條件下，製成本連接電路連接構造體。 ⑬(特性評估方法） 連接電阻：使用ADVANTEST公司製多功能測試儀 TR6848，以1mA之定電流測定電路間之電阻。連接電阻是 測定連接後之初期與30°C、60% RH、放置100小時後之值。 其結果在表2中表不。 27 313294D1D1 201030121 表2 連接抗阻（Ω ) 初期 30°C，60%RH，放置1〇〇小時後 實施例5 2. 1 2. 4 實施例6 2. 8 2. 5 實施例7 3. 2 3. 1 實施例8 2.2 2. 5 實施例9 2.4 2.4 實施例10 2. 8 3. 1 比較例3 2. 4 34. 7 本發明之實施例5至10中，連接電阻值於放置後亦低 而良好，但不使用表面處理粒子之比較例3，於放置後連 接電阻值大幅上昇，又，異向性導電電路連接用黏著劑製 造後，在25。(：放置30天後與實施例同樣製成電路連接構 造體，結果含有經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導電電路連接用黏著劑，在實 施例5至10之配合下，連接電阻（初期）為21至3 8ω， ::有良好之保存安定性。然而’比較例3之使用未經具 環氧基之化合物表面處理之導電粒子的連 接構仏體之連接電阻為20至200ω， [產業上之可利用性] 表不保存安定性很差。 依本發明，可以製得於s 著劑之後，放…：：向性導電電路連接用黏313294D1D1 21 201030121 In contrast, in Comparative Examples 1 and 2, in the connection structure stored at -20 ° C, good connection reliability was obtained, but it was stored in a constant temperature and humidity chamber at 30 ° C and 85% RH. The connection resistance is greatly increased to 10 Ω or more. (Measurement of joint strength) In Examples 1 to 3, those stored in a constant temperature and humidity chamber at -20 ° C or at 30 ° C and 85% RH can obtain about 1000 N/m. Good connection strength. On the other hand, in Comparative Examples 1 and 2, the connection strength was maintained at -20 ° C or in a constant temperature and humidity chamber of 30 ° C and 85% RH, and any one obtained a good connection strength of about 1000 N/m. . (Evaluation of Insulation) Using the obtained anisotropic conductive circuit-bonding adhesive, a 栉-shaped circuit having 250 copper lines having a line width of 50//m, a pitch of 100//m, and a thickness of 18//m is disposed to cross each other. a printed circuit board, and a tape set (TCP) having 500 copper circuits with a line width of 50 // m, a pitch of 100/zm, and a thickness of 18 // m, heated and pressurized at 14 ° C, 3 MPa for 15 seconds, The connection width is 2mm. The junction of the connector was subjected to a voltage of 100 V, and the insulation resistance value was measured after 500 hours of test at 85 ° C and 85% RH under high temperature and high humidity. Either one of them can obtain a good insulating property of 109 Ω or more, and no insulation degradation can be observed. (Evaluation of fluidity) Use an adhesive for connecting an anisotropic conductive circuit with a thickness of 35 // m and 5 mm x 5 mm, and clamp it in a glass having a thickness of 0.7/zm, 15πιπι xl5 mm, at 140 ° C, 3 MPa. Heat and twist for 15 seconds, use the area of the period (Α) and the area after heating (Μ) to obtain the fluidity (Β) / (Α) value, real 22 313294D1D1 201030121 Examples 1 to 3 It is in the range of h 9 to 2 ,, on the other hand, the ratio is 2. 8 and 1. 9. (Elassability after hardening) The elastic modulus of the adhesive for the anisotropic conductive circuit connection of the anisotropic conductive circuit was measured at a temperature of 40 °C at 15 GPa. From the above-mentioned connection strength, insulation, fluidity, hardening rate, etc., the values of the examples of the present invention and the values of the comparative examples show the connection resistance values as shown in Table 1. There is a big difference. The special characteristics of the Ν , 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 According to the present invention, / is considered to be extremely thin, but the surface of the conductive particles other than the gold transition metal does not expose silver, and the polymerization of the radical polymerizable substance is promoted. The surface of the conductive particles does not have a good value. As in the case of using the silver, gold, and button metal of 500 Α or more on the side where the connection resistance is extremely low, as in the case of using the galvanized metal, etc., as long as it is ruined out, the temperature or temperature and humidity treatment has a transition, and the connection is not exposed. The resistance will not increase. Different storage stability (production of surface treated particles) In a 1% by weight methanol solution of diethylamine, on the surface of the core particles, G 2 / ^ thick ^ polystyrene is set as the nucleus side, and 〇.〇 4_ thickness of the gold layer into a nickel layer, in this layer outside the particles, in the muscles for 10 minutes, according to the diameter = conductive drying for 15 minutes, to obtain surface treated particles A ~ electric surface, under the muscle (surface treatment Manufacture of particle B) 313294D1D3 23 201030121 B = 3 Wei of 3 wt% methanol solution, placed on the surface of the particle of polyphenylene core, set the recording layer of G.2 / / m thickness, in this = side 'set The average particle size of the gold layer of 4 degrees is made of 5 (the TC is stirred for 5 minutes) and the filter particles are dried at 8 〇L for 5 minutes to obtain surface-treated particles b. Production of C) 7-glycidoxypropylmethyldimethoxy group i weight% methanol solution in the 'putting on the surface of the particles with polystyrene as the core, set the thickness of 〇2" The layer 'on the outside of this recording layer, set the G. thickness of the gold layer to form an average particle size of 4 (10) of conductive particles, stirring in the hunger bell, The conductive particles were passed through and dried at 5 Gt for 15 minutes to obtain a surface treatment (production of surface-treated particles D). "In a 3 wt% methanol solution of a double-age A type epoxy resin, it was placed in a polystyrene-based solution. On the surface of the particle, set the thickness of the nickel layer of 〇.2/zm. On the outside of the recording layer, set the thickness of the gold layer to shout the average particle size of 5 conductive particles 'in the order (four) for 5 minutes, taking care of the conductive particles, at 80 C After drying for 5 minutes, the surface-treated particles D were obtained. The conductive particles A, B, c, and D were used in the following manner, and the surface was treated by a simple coating machine (manufactured by TESTER Industries, Inc.). The PET (poly(p-diethyl ester)) film was coated on one side with a thickness of 70 ° C and dried by hot air for 1 minute to form an adhesive for circuit connection. (Example 5) 313294D1D1 24 201030121 Oxygen resin (PKHC, trade name of Union Carbide Corporation, average molecular weight 45,000) 5Og, as a radical polymerizable compound, dicyclohexyl methacrylate 48g, phosphate ester acrylate 2g, 2,5-dimethyl Base-2, -5-bis(2-ethylhexyl peroxide) 3 g, dissolved in ketone and ethyl ketone as a solvent, and then 3% by volume of surface-treated particles A are dispersed and dispersed on a single surface of the surface-treated polyethylene terephthalate film by a simple coating machine The coating was applied at a thickness of 50/m, and dried at 70 ° C for 10 minutes by hot air to obtain an adhesive for connecting anisotropic conductive circuits having a thickness of 30 / im. (Example 6) A phenoxy resin ( PKHC, trade name of Union Carbide, average molecular weight 45,000) 50g, epoxy epoxidized isocyanate 468, phosphate acrylate 4, 2,5-dimercapto-2,5- 3 g of bis(2-ethylhexyl peroxide) hexane, dissolved and dissolved in methyl ethyl ketone as a solvent, and then 3% by volume of surface-treated particles B are dispersed and dispersed, and the surface-treated poly-p-benzoquinone The ethyl acetate film was coated on a single surface with a 50/zm thick parameter by a simple coating machine, and dried at 70 ° C for 10 minutes to obtain an anisotropic conductive circuit connecting adhesive having a thickness of 30/zm. . (Example 7) 25 g of phenoxy resin (PKHC, trade name, average molecular weight: 45,000 by Union Carbo), 25 g of polyurethane resin, 48 g of dicyclohexyl methacrylate, 2 g of phosphate acrylate, 2 , 5-dimercapto-2, 5-bis(2-ethylhexyl peroxide) hexane 3g, dissolved and mixed into the solvent as the solvent, and then 3% by volume of the surface treated particles B Into the dispersion, the surface of the surface treated polyethylene terephthalate film is coated with a thickness of 50// 25 313294D1D1 201030121 m by a simple coating machine, and dried at 70 ° C for 10 minutes by hot air to obtain a thickness. Adhesive for 30/zm anisotropic conductive circuit connection. (Example 8) 50 g of a styrene-based resin (PKHC, trade name, manufactured by Union Carbide Co., Ltd., average molecular weight: 45,000), 48 g of dicyclohexyl methacrylate as a radical polymerizable product, and 2 g of phosphoric acid ester acrylate , 2, 5-dimercapto-2,5-bis(2-ethylhexyl peroxide) hexane 3 g, dissolved and dissolved in methyl ethyl ketone as a solvent, and then 3% by volume of surface-treated particles C Into the dispersion, on the surface of the surface treated polyethylene terephthalate film coated with a simple coater 50 / zm thickness, dried at 70 ° C, 10 minutes hot air, to a thickness of 30 / Adhesive for connecting zm anisotropic conductive circuits. (Example 9) 50 g of a phenoxy resin (PKHC, trade name, manufactured by Union Carbide Corporation, average molecular weight: 45,000), 46 g of hexyl isocyanate modified diacrylate, and vinegar vinegar vinegar 4 g , 2, 5-dimercapto-2, 5-bis(2-ethylhexyl peroxide) hexane 3g, dissolved in acetophenone as a solvent, and then 3 vol% of surface treated particles D is dispersed, and the surface of the surface treated polyethylene terephthalate film is coated with a thickness of 50 /zm on a single surface by a simple coating machine, and dried at 70 ° C for 10 minutes by hot air to obtain a thickness of Adhesive for 30/zm anisotropic conductive circuit connection. (Example 10) 25 g of a phenoxy resin (PKHC, trade name of Union Carbo, and an average molecular weight of 45,000), 25 g of a polyurethane resin, 48 g of dicyclohexyl acrylate, 2 g of phosphoric acid acrylate, 2, 5 - Dimercapto-2, 5-bis(2- 26 313294D1D1 201030121 ethylhexyl peroxide) 3 g of hexane, dissolved and dissolved in methyl ethyl ketone as a solvent, and then 3% by volume of surface-treated particles D Disperse, the surface of the surface treated polyethylene terephthalate film is coated with a simple coating machine with a thickness of 50# m, dried at 70 ° C for 10 minutes, to obtain a thickness of 30. //m The anisotropic conductive circuit is connected with an adhesive. (Comparative Example 3) An anisotropic conductive circuit-bonding adhesive was prepared in the same manner as in Example 5 except that the surface-treated particles A of Example 5 were changed to untreated particles. (Production of circuit connection structure) The above-mentioned anisotropic conductive circuit-bonding adhesive was slit into a width of 1.5 mm, and was applied to a glass substrate on which a ΙΤ0 electrode was formed at 80 ° C, 5 seconds, and IMPa. After the temporary connection, the PET support substrate was peeled off, and the TCP electrode position of the alignment electrode width 50/im and the pitch of 50/ζπ was set, and the connection circuit connection structure was fabricated under the conditions of 150 ° C, 20 seconds, and 4 MPa. 13 (Characteristic evaluation method) Connection resistance: Using a multi-function tester TR6848 manufactured by ADVANTEST, the resistance between the circuits was measured at a constant current of 1 mA. The connection resistance was measured at the initial stage after the connection, at 30 ° C, 60% RH, and after standing for 100 hours. The results are shown in Table 2. 27 313294D1D1 201030121 Table 2 Connection Resistance (Ω) Initial 30 ° C, 60% RH, after 1 hour, Example 5 2. 1 2. 4 Example 6 2. 8 2. 5 Example 7 3. 2 3. 1 Example 8 2.2 2. 5 Example 9 2.4 2.4 Example 10 2. 8 3. 1 Comparative Example 3 2. 4 34. 7 In the embodiments 5 to 10 of the present invention, the connection resistance value was also In Comparative Example 3, which was low and good, but did not use surface-treated particles, the connection resistance value was greatly increased after standing, and after the production of the anisotropic conductive circuit connection adhesive, it was 25. (After 30 days after the placement, the circuit-connected structure was produced in the same manner as in the example, and as a result, an anisotropic conductive circuit-bonding adhesive containing conductive particles surface-treated with a compound having a basic compound or an epoxy group was used. With a combination of 5 and 10, the connection resistance (initial) is 21 to 38 ω, :: has good preservation stability. However, the structure of the conductive particles of the surface of the comparative example 3 which is not treated with the epoxy group is used. The connection resistance of the carcass is 20 to 200 ω, [industrial availability] The table is not very stable in storage stability. According to the invention, it can be obtained after the s agent is placed on the ...:: viscous conductive circuit connection adhesive
電電路著_用期）良好之異向性導 電電路連接用黏㈣。此外，亦 门性V 』衣侍相對於熱硬化性異 313294D1D1 28 201030121 向性導電電路連接用黏著劑之連接溫度170°C，可以在更 低溫之150°C連接，黏著劑保存後的連接電阻差異小之良 好連接構造體。 【圖式簡單說明】 - 無。 【主要元件符號說明】 無0The electrical circuit is _used. The good anisotropic conductive circuit is connected with the adhesive (4). In addition, the connection temperature of the Yemen V 』 侍 相对 相对 313 313 313 294 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 313 A good connection structure with small differences. [Simple description of the schema] - None. [Main component symbol description] No 0
29 313294D1D129 313294D1D1