201219437 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種分散有導電性粒子之異向性導電材 料及其製造方法。本申請案係基於2〇1〇年9月27日在日 本提出申請之曰本專利特願2〇1〇_215485而主張優先權 者將°亥申明案作為參照而引用至本申請案中。 【先前技術】 先前，異向性導電膜（ACF : Anisotropic C0nductive Fiim) 係用於將半導體等零件安裝於印刷基板上。 由於聚氨知（p〇lyUrethane)樹脂於硬化時之應力緩 和性方面優異，且具有極性基，故而特佳為用於進行低溫、 短時間壓接之丙烯酸系異向性導電膜（例如參照專利文獻1 〜3) 〇 聚氨醋樹脂係由多元醇（二醇）盘 呼）興录異齓酸酯之聚合所 成，夕讀先前係使用具有聚醋骨架或聚鍵”者。 但是’具有聚醋骨架之多元醇雖然可提昇接著力，作 水解耐性較低，於高溫、高 ^ ^ 條件下異向性導電膜之遠垃 可罪性降低。於下述通式、之連接 )中揭不聚酯系聚氨酯之水解機 制。聚酯部分之酯鍵與水發生 解機 生反應而分解為醇與酸。 [化1] 201219437 »h2o 11 醋鍵 o-c—〇-(〇Η2)4·-C-0· (CH2)2-0-201219437 VI. Description of the Invention: [Technical Field] The present invention relates to an anisotropic conductive material in which conductive particles are dispersed and a method for producing the same. This application is based on Japanese Patent Application No. 2 〇 〇 215 485, filed on Sep. 27, 2011, the entire disclosure of which is hereby incorporated by reference. [Prior Art] Conventionally, an anisotropic conductive film (ACF: Anisotropic C0nductive Fiim) is used to mount a component such as a semiconductor on a printed circuit board. Since the polyfluorene (p〇lyUrethane) resin is excellent in stress relaxation at the time of hardening and has a polar group, it is particularly preferably an acrylic anisotropic conductive film for performing low-temperature, short-time pressure bonding (for example, reference patent) References 1 to 3) Polyurethane resin is made up of a polyhydric alcohol (diol), which is a mixture of isophthalic acid esters. It has been previously used with a polyester skeleton or a poly bond. Although the polyol of the vinegar skeleton can improve the adhesion, the hydrolysis resistance is low, and the irritability of the anisotropic conductive film is lowered under the conditions of high temperature and high ^ ^. The hydrolysis mechanism of non-polyester polyurethane. The ester bond of the polyester part reacts with water to decompose into alcohol and acid. [Chemical 1] 201219437 »h2o 11 vinegar bond oc-〇-(〇Η2)4·-C- 0· (CH2)2-0-
胺基甲酸酯鍵 聚酯部分 (1) iHO-C-(CH2)4-C-〇h+ "ΗΟ-ίΟ^-ΟΗΗ- HO-C-N-R-N-C^o II A jl H Η II υ'' 〇 u 0 〇 另一方面，具有聚醚骨架之多元醇雖然Sg-, ’不出良好水 解耐性，但耐熱水性差，因而於高溫、高渴條 1干下同樣產 生特性劣化。 [專利文獻1]日本特開2005-322938號公報 [專利文獻2]曰本特開20094丨1327號公報 [專利文獻3]日本特表2009-508290號公報 【發明内容】 本發明係鑒於上述先前之情況而提出者， ^ ^ 捉供—種 向溫、高濕條件下之連接可靠性優異之異向' 及其製造方法。 等電膜材料 藉由使用耐 之多元醇， 可提昇於高 本件發明者等進行努力研究，結果發現： 熱性優異之聚碳酸酯二醇作為聚氨酯樹脂原料 且規定聚碳酸酯二醇與聚醚二醇之質量比， 溫、高濕條件下之連接可靠性。 即，本發明之異向性導電材料含 酯反應而得之帶盏聚異氘酸 3…9: Λ二樹脂，其特徵在於：上述多元醇係以 罝比調配聚碳酸酯二醇與聚醚二醇， 碳酸酿二醇之數量平均且聚 4 201219437 ::本發明之異向性導電材料之製造方法係製 …與聚異氛酸醋反應而得之聚氣醋樹脂的異向性導： 材料，其特徵在於：上计、夕”门’生導電 上述夕7〇醇係以3: 7〜9: 1之曾旦a 调配聚碳酸酯二醇鱼 _ 里 ，、永醚一醇，且聚叙酸酯二醇之數詈承 均分子量大於500。 广本發明之連接方法之特徵在於：於第！電子零件 :子上貼附上述異向性導電膜，於上述異向性導電膜上 日配置第2電子零件’利用加熱按壓裝置從上述第2電 零件上按H使上述第丨電子零件 電子零件之端子連接。 /、述弟2 合體又’本發明之接合體係藉由上述連接方法所製造之接 根據本發明，藉由使用耐熱性優異之聚碳酸醋二醇作 於：虱S旨樹脂原料之多元醇’進而調配聚醚二醇，可提昇 、鬲溫、高濕條件下之連接可靠性。 【實施方式】 以下，按照下述順序詳細說明本發明之實施形態。 1.異向性導電材料 2 ·異向性導電材料之製造方法 3. 連接方法 4. 實施例 < 1.異向性導電材料> 夕一作為本發明之具體例而揭示之異向性導電材料係含有 夕凡醇與聚異氰酸酯反應而得之聚氨鲳樹脂者。 201219437 聚氨酯樹脂係異氰酸酯基與醇基縮合而成之高分子量 樹脂，其骨架内具有源自原料多元醇的軟鏈段、及源自聚 異氰酸酯之硬鏈段。 本實施形態之聚氨酯樹脂係藉由使用耐熱性及耐濕性 優異之聚碳酸酿二醇作為軟鏈段之多元醇，進而調配聚醚 二醇’來提昇耐熱性及接著性者。 作為聚碟酸酿二醇，可使用具有下述通式⑺所示之基 本結構者。 [化2] HO-^ R, —~Urethane bond polyester moiety (1) iHO-C-(CH2)4-C-〇h+ "ΗΟ-ίΟ^-ΟΗΗ- HO-CNRNC^o II A jl H Η II υ'' 〇u On the other hand, the polyol having a polyether skeleton, although Sg-, does not have good hydrolysis resistance, but has poor hot water resistance, and thus exhibits deterioration in characteristics even under high temperature and high thirst. [Patent Document 1] JP-A-2005-322938 [Patent Document 2] JP-A-2009-1041 [Patent Document 3] JP-A-2009-508290 SUMMARY OF THE INVENTION The present invention is based on the foregoing In the case of the case, ^ ^ catching the supply - the kind of the opposite direction to the temperature and high humidity conditions, and the manufacturing method. The isoelectric film material can be improved by the inventors of the present invention by using a resistant polyol, and as a result, it has been found that a polycarbonate diol having excellent heat is used as a raw material of a polyurethane resin and a polycarbonate diol and a polyether are specified. The mass ratio of alcohol, the reliability of connection under warm and high humidity conditions. That is, the anisotropic conductive material of the present invention contains an ester-reactive polyisocyanuric acid 3...9: a bismuth resin, which is characterized in that the above polyol is formulated with a ruthenium ratio of a polycarbonate diol and a polyether. The average number of diols and carbonated diols and poly 4 201219437 :: The method for producing anisotropic conductive materials of the present invention is made by reacting polyisocyanate with polyisocyanuric acid: The material is characterized in that: the upper meter, the eve "gate" is electrically conductive, and the seventh sterol is a 3:7 to 9:1 Zengdan a formulated with a polycarbonate diol fish _ 里, a long ether monool, and The polyanthracene diol has a number average molecular weight of more than 500. The connection method of the present invention is characterized in that the anisotropic conductive film is attached to the electronic component: on the anisotropic conductive film. The second electronic component is disposed on the second electric component by a heating pressing device, and the terminal of the electronic component of the second electronic component is connected by H. /, the two brothers and the joint system of the present invention are connected by the above connection method. Manufactured according to the present invention, by using a polymer having excellent heat resistance Carbonic acid diol is used as the polyol of the resin raw material, and the polyether diol is blended to improve the connection reliability under conditions of high temperature and high humidity. [Embodiment] Hereinafter, the details will be described in the following order. Embodiments of the present invention 1. Anisotropic conductive material 2 · Method for producing anisotropic conductive material 3. Connection method 4. Example < 1. Anisotropic conductive material > 夕一 as a specific example of the present invention The disclosed anisotropic conductive material is a polyurethane resin obtained by reacting an oxime alcohol with a polyisocyanate. 201219437 A polyurethane resin is a high molecular weight resin obtained by condensing an isocyanate group with an alcohol group, and has a skeleton derived from the raw material. a soft segment of a polyhydric alcohol and a hard segment derived from a polyisocyanate. The polyurethane resin of the present embodiment is prepared by using a polylactic acid diol having excellent heat resistance and moisture resistance as a polyol of a soft segment. The polyether diol is used for the purpose of improving the heat resistance and the adhesion. As the poly-dissolved diol, a basic structure having the following general formula (7) can be used. [Chemical 2] HO-^ R, —~
⑵ [式⑺中’ Rl、R2表示碳數1〜18之伸烷基，各自可相 同亦可不同；又，n表示聚碳酸酯之聚合度]。 作為上述通式（2)所示之聚碳酸酯二醇，例如可列舉： :，二聚(六亞甲基碳酸醋)二醇、α，ω-聚(五亞甲基碳_) 一醇等；市售者可列舉：Daicel化學股份有限公司製造之商 品名：CD2〇5、CD22〇等。於本實施形態中，該等可單獨使 用’或組合使用2種以上。 又，聚碳酸酯二醇之數量平均分子量Mn較佳為大於 5〇〇 ’更佳為1〇〇〇以上、5_以下。於聚碳酸賴多元醇之 數量平均分子量Mn為500以下之情形時，聚氨酯之交聯密 度增兩，接著強度降低。又，於聚碳酸酯多元醇之數旦、， 均分子量Μη超出5000之情形時，於藉由增加伸長率 6 201219437 線加工後會發生滲出，並且聚氨酯樹 低。再者，聚碳酸酯二醇之數量平均 冷*丨’合解性降 .,( Ί 子里Mn係藉由利用 例如GPC測定而預先製作標準試樣之校準曲線所得。 聚醚二醇例如可列舉··聚乙二醇、 寸 _ 叶眾丙二醇、聚1，4- 丁二醇（poly(tetramethylene glyc〇1))、聚甲基 ^ 等，該等可單獨使用，或組合使用2種以上。，扣丁一醇 •於本實施形態中，係以(聚碳酸酿二醇m(2) [In the formula (7), R1 and R2 represent an alkylene group having 1 to 18 carbon atoms, and each may be the same or different; and n is a degree of polymerization of the polycarbonate]. Examples of the polycarbonate diol represented by the above formula (2) include dimer (hexamethylene carbonate) diol and α, ω-poly (pentamethylene carbon _) monool. The market name can be exemplified by the product name: CD2〇5, CD22〇, etc. manufactured by Daicel Chemical Co., Ltd. In the present embodiment, these may be used singly or in combination of two or more. Further, the number average molecular weight Mn of the polycarbonate diol is preferably more than 5 Å ', more preferably 1 Å or more and 5% or less. When the number average molecular weight Mn of the polylactic acid lanthanum polyol is 500 or less, the crosslinking density of the polyurethane is increased by two, and then the strength is lowered. Further, in the case where the polycarbonate polyol is several denier and the average molecular weight Μη exceeds 5,000, bleeding occurs after the wire is processed by increasing the elongation 6 201219437, and the polyurethane tree is low. Further, the amount of the polycarbonate diol is on average lower than that of the condensing property. (The Mn in the scorpion is obtained by preliminarily preparing a calibration curve of a standard sample by, for example, GPC measurement. Illustratively, polyethylene glycol, indole propylene glycol, poly(tetramethylene glycoside), polymethyl^, etc., may be used alone or in combination of two or more. In this embodiment, it is (polycarbonated diol)
::9二量比:配聚碳酸醋二醇與聚喊二醇作為軟 鏈&之夕凡醉。於以（聚碳酸醋二醇）：（聚峻二醇）H 〜2 ’ 8之質量比調配聚碳酸酯二醇與聚醚二醇之情形時， 異向性導電㈣之㈣性會降低，並且接著性亦降低。又， :二亀二醇):(聚峻二醇)=1。：。之質量比調配聚 反H醇與聚喊二醇之情形時，異向性導電材料之耐散 =，但接著性降低。更佳之聚碳酸醋二醇與聚醚二醇 之質里比為（聚碳酸酯二醇）：（聚醚二醇）=3 : 7〜7 . 3，艮 高溫、高濕環境後亦可獲得良好之連接電阻值及: 考強度。 作為硬鏈段之聚異氰酸醋，可使用先前用於製造聚氨 酿者。例如可列舉：脂肪族聚異氰酸醋(六亞甲基二異氰酸 ::二甲基六亞甲基二異氰酸醋等)、脂環族二異氰酸醋 ，-%己烷二異氰酸酯、異佛酮二異氰酸酯等卜 :氰酸崎二異氰酸醋、2，"苯二異氰酸酿等），該等可 早獨使用’或組合使用2種以上。 軟鏈段之多元醇與硬鏈段之聚異氰酸酯之添加質量比 201219437 較佳為（多元醇）：（聚異氰酸酯）=1〇〇〇 : 1〇〇〜讀：彻。 於聚異氰酸酿相對於多元醇1000質量份未達ι〇〇質量份之 ::時’及聚異氰酸酯相對於多元醇1〇〇〇質量份超出_ 置份之情形時，硬化時無法獲得聚氨㈣脂之良好之應 力綠和性C> 又，本實施形態之異向性導電材料含有自由基聚合性 物質、硬化劑、及導電性粒子。 自由基聚合性物質係具有利用自由基進行聚合之官能 ;的物質。例如可列舉：丙稀酸醋、甲基丙烯酸酿、馬來 醯亞胺化合物等。該等可單獨使用任一種，或併用2種以 上。又，自由基聚合性物質可在單體及募聚物之任—狀態 下使用，亦可併用單體與寡聚物。 用=實施形態中’作為自由基聚合性物質，較佳為使 °、行低咖紐時間壓接之丙烯酸酯。丙烯酸酯例如可 :舉：丙埽酸甲醋、丙稀酸乙醋、丙烯酸異丙酿'丙稀酸 異丁醋、環氧丙稀酸S旨、乙二醇：㈣酸醋、二乙二醇二 _歸H二㈣基丙院三丙稀酸酯、二經甲基三環癸烷 :烯“、Μ·丁二醇四丙烯酸酯、2_羥基·二丙烯醯 土丙烧、2’2_雙[4-(丙烯醯氧基曱氧基）苯基]丙烷、2 2 :[4_(丙稀醯氧基乙氧基）苯基]丙烧、丙稀酸二環戊稀酿' ^二環癸@旨、異氰尿酸三（丙烯酿氧基乙_)、丙締酸教 曰專。該等可單獨使用1種，亦可併用2種以上。 硬化劑係藉由加熱發生分解而產生游離自由基者，例 如可列舉：過氧化合物、偶氮系化合物等。於本實施形態 201219437 中，較佳為使用有機過氧化物。 有機過氧化物例如可列舉：二醢基過氡化物 Γ二)·、Γ化二機、過氧醋、過氧縮酮、二貌基過 d yl peroxide)、過氧化氫、石夕貌基過氧化物（silyl —e)等。該等可單獨使用4，亦可併用2種以上。又， 將㈣微膠囊化而成者由於使使用壽命延長，&而較佳。 同，==分之調配量與通常之異向性導電材料相 其中聚Μ曰樹脂為2〜75質量份，自由基聚合 為〜6〇質量份，硬化劑為〜3〇質量份。 調配量可於上述範圍内適宜決定。 玖刀之 導電樹脂之調配量未達2質量份，則缺乏異向性 ’硬化時、熱負載時等之應力緩和效果，接著強 超出75重量份’則有連接可靠性降低之虞。 組成物，較佳為添力，偶合劑。 吏用％氧糸、胺系、巯基-硫醚系、脲基系等。 曰此可提升有機材料與無機材料之界面之接著性。又， 2加無機填充材料。作為無機填充材料，可使用石夕土、、 2、氧化鈦、碳_、氧化料，無機填充材料 :無特別限定。藉由無機填充材料之含量，可控制流動性鎖 提昇粒子捕班盘 J^ * 合體之應力_1’亦可適宜制橡膠成分等，以使接 列舉導：性粒子只要為電性良好之導體則可使用，例如可 脂所槿1'、銀、鎳等金屬之粉末或利用上述金屬包覆由樹 曰所構成之粒子而成者。又，亦可使用以絕緣性之皮膜包 201219437 覆導電ί生粒子之整個表面而成者。又，其調配量較佳為設 $相對於接著劑成分而A 〇· 1〜30體積％，可根據用途適宜 決定。 < 2，異向性導電材料之製造方法> 、八人’對上述異向性導電材料之製造方法進行說明。 ^ 以3 · 7〜9 : 1之質量比調配聚碳酸酯二醇與聚醚二 醇作為聚氨酯樹脂之軟鏈段之多元醇，以使軟鏈段（多元醇） ，、硬鏈段（聚異氰酸酯）之添加質量比在（多元醇广（聚異氰酸 ®d= 1000: 1〇〇〜100〇: 4〇〇之範圍内之方式調配軟鏈段與 硬鏈段。使該等於反應爐内、氮氣流下、3〇〜1〇〇七下反應， 而獲得異氰酸酯封端氨酯預聚物。 其次，為了獲得水性氨酯樹脂分散液，將異氰酸酯封 鳊氨酯預聚物添加於胺類中，於3〇〜i 〇(rc下使之反應使 鏈延伸而獲得聚碳酸酯聚氨酯樹脂溶液（聚氨酯樹脂）。 私類例如可列舉：異佛酮二胺、二正丁胺 '乙二胺、 1，2_丙二胺等，該等可單獨使用1種，亦可併用2種以上。 其次，使用甲苯、乙酸乙酯、或該等之混合溶劑 '其 他各種有機溶劑’以2〜75: 30〜60: 0.1〜30之質量比調 配聚氰S曰樹脂、自由基聚合性物質、及硬化劑，而製作絕 緣性黏合劑（接著劑成分）。繼而，相對於絕緣性黏合劑，以 體積比率〇.丨〜30%分散導電性粒子，而獲得異向性導電材 料。 於製作片狀之異向性導電膜之情形時，於塗佈有聚石夕 氧等剝離劑的PET等之剝離基材上塗佈上述異向性導電材 10 201219437 離基材上之異向性 料，使用熱烘箱、加熱乾燥裝置等使剝 導電材料乾燥，而形成規定厚度之層。 < 3.連接方法> /、k ,對使用上述異向性導電M U + 方法進行說明。本實施形態之/子電接子方零件之連接 電子零件之端子上貼附上述異向 #方法係於第1 向性導電材料，於異向性導 雷^上暫時配置第2電子零件，利用加熱 Γ零件上㈣，而^丨電子零件之料與上述第2電 子零件之端子連接。藉此，可# 電 第1電子零件之端子與 第2電子零件之端子隔著分散於異向性導電材料中之導電 性粒子而連接而成之連接體。 。本實施形‘％之異向性導電材料係使用耐熱性優異之聚 碳酸酯二醇作為聚氧酷樹脂原料之多元醇，進而調配聚醚 -醇’因此即便於高溫、高濕條件下亦可防止連接電阻及 接著強度降低。 [實施例] < 4 _實施例> 以下，對本發明之實施例進行說明，但本發明並不限 定於該等實施例。此處，使用實施例1〜9及比較例卜7 之片狀連接㈣製作安裝冑，敎安裝體之料電阻及接 著強度，並進行評價。 [實施例1] 首先，於具備攪拌機 '溫度計、冷卻器、及氮氣導入 官之四口燒瓶中調配聚碳酸酯二醇（Μη = 2000，商品名： 201219437::9 two ratio: with polycarbonate diol and poly diol as soft chain & When the polycarbonate diol and the polyether diol are blended in a mass ratio of (polycarbonate diol): (poly diol) H 〜 2 '8, the (iv) property of the anisotropic conduction (four) is lowered, And the adhesion is also reduced. Also: diterpenediol): (polythioglycol) = 1. :. When the mass ratio is adjusted to the case of the poly-H alcohol and the poly diol, the resistance of the anisotropic conductive material is reduced, but the adhesion is lowered. More preferably, the ratio of polycarbonate to polyether diol is (polycarbonate diol): (polyether diol) = 3: 7~7. 3, can also be obtained after high temperature and high humidity environment Good connection resistance value and: test strength. As the polyisocyanate of the hard segment, it can be used previously for the manufacture of polyurethanes. For example, aliphatic polyisocyanuric acid (hexamethylene diisocyanate: dimethyl hexamethylene diisocyanate, etc.), alicyclic diisocyanate, -% hexane Diisocyanate, isophorone diisocyanate, etc.: cyanic acid diisocyanate, 2, " phenyl diisocyanate, etc., these may be used alone or in combination of two or more. The mass ratio of the soft segment of the polyol to the hard segment of the polyisocyanate is preferably 201219437 (polyol): (polyisocyanate) = 1 〇〇〇 : 1 〇〇 ~ read: Che. When the polyisocyanate is blended with respect to 1000 parts by mass of the polyol, less than 1 part by mass of the polyol: and the polyisocyanate is not more than 1 part by mass relative to the polyol, it is not obtained when hardened. Further, the stress green of the polytetrazide (tetra) grease and the property C> The anisotropic conductive material of the present embodiment contains a radical polymerizable substance, a curing agent, and conductive particles. The radically polymerizable substance is a substance having a function of polymerization by a radical. For example, acrylic acid vinegar, methacrylic acid brewing, maleimide compound, and the like can be mentioned. These may be used alone or in combination of two or more. Further, the radical polymerizable substance may be used in the state of any of a monomer and a polymer, and a monomer and an oligomer may be used in combination. In the embodiment of the invention, as the radical polymerizable substance, it is preferred to use an acrylate which is pressure-bonded at a low time. Acrylates can be, for example: methyl acetonate, ethyl acetoacetate, isopropyl acrylate, isopropyl acetonate, propylene acrylate, ethylene glycol: (iv) vinegar, diethylene glycol Alcohol _ _ H bis (tetra) propyl propylene triacrylate, di-methyl tricyclodecane: ene ", Μ · butanediol tetraacrylate, 2 - hydroxy · propylene propylene terephthalate, 2 ' 2_bis[4-(acryloxymethoxyoxy)phenyl]propane, 2 2 :[4_(acrylic ethoxyethoxy)phenyl]propane, acrylic acid dicyclopentene ^二环癸@致, isocyanuric acid three (acrylic acid ethoxylate), and propionic acid teaching. These may be used alone or in combination of two or more. The hardener is decomposed by heating. Examples of the radical generating radicals include a peroxy compound and an azo compound. In the embodiment 201219437, an organic peroxide is preferably used. Examples of the organic peroxide include diterpene-based perylene. Γ2)·, Γ化二机, peroxy vinegar, peroxy ketal, dimorphic dyl peroxide), hydrogen peroxide, sulphate-based peroxide (silyl-e), etc. Use 4 alone, Two or more kinds may be used in combination. Further, the microencapsulation of (4) is preferred because it prolongs the service life, and the ratio of the === is divided into the usual anisotropic conductive material phase. 2 to 75 parts by mass, the radical polymerization is ～6 〇 parts by mass, and the hardener is 〜3 〇 parts by mass. The amount of the compound can be appropriately determined within the above range. The amount of the conductive resin of the boring tool is less than 2 parts by mass. In the absence of an anisotropic stress relaxation effect such as hardening or heat load, and then exceeding 75 parts by weight, the connection reliability is lowered. The composition is preferably a force, a coupling agent.糸, amine, thiol-thioether, urea-based, etc. 曰 This can improve the interface between the organic material and the inorganic material. In addition, 2 plus inorganic filler material. As an inorganic filler, you can use Shi Xi soil, 2. Titanium oxide, carbon_, oxidized material, inorganic filler: no special limitation. By the content of inorganic filler, the fluidity lock can be controlled to enhance the particle trapping plate J^ * The stress of the joint _1' can also be suitable Rubber composition, etc. The particles may be used as long as they are electrically conductive, and may be used, for example, a powder of a metal such as a fat, or a metal such as silver or nickel, or a particle composed of a tree raft by the metal. The insulating film is coated with the entire surface of the conductive particles of 201219437. Further, the blending amount is preferably set to be 〇1 to 30% by volume based on the adhesive composition, and can be appropriately determined depending on the use. < 2, Method for producing anisotropic conductive material>, eight people's description of the method for producing the above anisotropic conductive material. ^Polymerized with a mass ratio of 3 · 7 to 9 : 1 The polyether diol is used as the polyol of the soft segment of the polyurethane resin to increase the mass ratio of the soft segment (polyol) and the hard segment (polyisocyanate) (polyol is widely used (polyisocyanate®d= 1000: 1〇〇~100〇: The soft and hard segments are blended in a range of 4〇〇. The reaction was carried out in the same manner as in the reaction furnace under a nitrogen stream at a temperature of 3 Torr to 1 Torr to obtain an isocyanate-terminated urethane prepolymer. Next, in order to obtain an aqueous urethane resin dispersion, an isocyanate-terminated urethane prepolymer is added to an amine, and the chain is extended to obtain a polycarbonate urethane resin solution at 3 〇 i 〇 (rc) The urethane resin may be exemplified by isophorone diamine, di-n-butylamine 'ethylenediamine, 1,2-propylenediamine, etc., and these may be used alone or in combination of two or more. , using a mixture of toluene, ethyl acetate, or a mixture of the solvents 'other various organic solvents' at a mass ratio of 2 to 75: 30 to 60: 0.1 to 30 to prepare a polycyanide resin, a radical polymerizable substance, and hardening. An insulating adhesive (adhesive component) is prepared, and then the conductive binder is dispersed in a volume ratio of 丨.30% with respect to the insulating adhesive to obtain an anisotropic conductive material. In the case of an anisotropic conductive film, the anisotropic conductive material 10 201219437 is applied to a release substrate such as PET coated with a release agent such as polysulfide, and the anisotropic material on the substrate is used. Drying and peeling conductive materials in an oven, heating and drying device And forming a layer having a predetermined thickness. <3. Connection method> /, k, the method of using the above-described anisotropic conductive MU + will be described. The terminal of the electronic component of the sub-electrical component of the present embodiment is connected. The above-mentioned anisotropic method is attached to the first conductive material, and the second electronic component is temporarily placed on the anisotropic guide, and the second electronic component is heated (4), and the electronic component material and the second component are The terminal of the electronic component is connected, whereby the terminal of the first electronic component and the terminal of the second electronic component are connected by a conductive particle dispersed in the anisotropic conductive material. The '% anisotropic conductive material is a polycarbonate diol having excellent heat resistance as a polyoxyl resin raw material polyol, and further blended with a polyether-alcohol', thereby preventing connection even under high temperature and high humidity conditions. [Embodiment] <4_Examples> Hereinafter, examples of the present invention will be described, but the present invention is not limited to the examples. Here, Examples 1 to 9 and Comparative example (4) The mounting resistance, the material resistance and the subsequent strength of the mounting body were measured and evaluated. [Example 1] First, a polycarbonate was prepared in a four-necked flask equipped with a stirrer 'thermometer, a cooler, and a nitrogen introduction officer. Alcohol (Μη = 2000, trade name: 201219437
Placcel CD220’ Daicel化學股份有限公司製造）300質量份、 聚越二醇（Mn= 2000，商品名：Exenol 2020，旭硝子聚氨醋 股份有限公司製造）700質量份、及異佛酮二異氰酸酯2〇〇 質量份，於氮氣流下、於80°C下反應5小時，獲得異氰酸 酯封端氨酯預聚物。於其中加入曱苯5 12質量份，製成氨 酯預聚物溶液。 其次’於由異佛酮二胺31.2質量份、二正丁胺12.8質 量份、甲苯279質量份、甲基乙基酮579質量份及二丙酮 醇5 79質量份所構成之混合物中’添加氧酯預聚物溶液丨〇〇〇 質量份，於50°C下反應3小時，獲得固形物成分為30〇/〇之 聚碳酸酯聚氨酯樹脂溶液（聚氨酯樹脂）。 以00 : 38 : 2之質量比調配該合成之聚氨酯樹脂、自 由基5^合性物質（商品名：EB600 ’ Daicel Cytec股份有限公 司製造）、及硬化劑（商品名：perhexa c，日本油脂股份有限 么司製造），製作絕緣性黏合劑。繼而，於絕緣性黏合劑中 以體積比率10。/。分散導電性粒子（商品名：AUL7〇4，積水化 學工業股份有限公司製造），塗佈至PET膜上並乾燥，而製 作厚度為20 v m之片狀連接材料。 [實施例2] 將聚碳酸酯二醇（Mn=2〇〇〇,商品名：piaccelCD22〇， Daicel化學股份有限公司製造）設為4〇〇質量份、及聚醚二 •° ( 2000，商品名.Exen〇l 2020 ’旭硝子聚氨酯股份有 限公司製造）設為600質量份，除此以外，以與實施例i相 同之方式製作片狀連接材料。 12 201219437 [實施例3] 將聚碳酸酯二醇（Mn= 2000，商品名：Placcei CD220， Daicel化學股份有限公司製造）設為500質量份、及聚醚二 醇（Μη— 2000，商品名：Exen〇i 2〇2〇，旭硝子聚氨酯股份有 限a司製造）s免為5〇〇質量份，除此以外，以與實施例^相 同之方式製作片狀連接材料。 [實施例4] 將聚碳酸醋二醇（Mn=2〇〇〇,商品名：piaccelCD220， Daicel化學股份有限公司製造）設為6〇〇質量份、及聚醚二 醇（Μη - 2000，商品名：Exen〇i 2〇2〇，旭硝子聚氨酯股份有 限么司製造）设為4〇〇質量份，除此以外，以與實施例J相 同之方式製作片狀連接材料。 [實施例5] 將聚碳酸酯二醇（Mn= 2000，商品名：Placcei CD220， Daicel化學股份有限公司製造）設為7〇〇質量份、及聚醚二 醇（Mn= 2000，商品名：Exenol 2020，旭硝子聚氨酯股份有 限公司製造）設為3〇〇質量份’除此以外’以與實施例1相 同之方式製作片狀連接材料。 [實施例6] 將聚碳酸酯二醇（Mn= 2000，商品名：Placcei CD220， Daicel化學股份有限公司製造）設為8〇〇質量份、及聚醚二 醇（Mn= 2000，商品名：Exen〇i 2〇2〇，旭硝子聚氨酯股份有 限公司製造）設為200質量份，除此以外，以與實施例1相 同之方式製作片狀連接材料。 13 201219437 [實施例7] 將聚碳酸酯二醇（Mn= 1000，商品名：Placcel CD210， Daicel化學工業股份有限公司製造）設為5〇〇質量份、及聚 醚二醇（Mn= 2000 ’商品名：Exen〇i 2020，旭硝子聚氨酯股 份有限公司製造）設為500質量份，除此以外，以與實施例 1相同之方式製作片狀連接材料。 [實施例8] 將聚碳酸醋一醇（Mn=5000，商品名：Kuraray Polyol C-5 090 ’ Kuraray股份有限公司製造）設為"ο質量份、及聚 醚二醇（Mn= 2000，商品名：Exenol 2020，旭硝子聚氨酯股 份有限公司製造）設為500質量份，除此以外，以與實施例 1相同之方式製作片狀連接材料。 [實施例9] 將聚碳酸酯二醇（Mn= 2000，商品名：piaccel CD220，Placcel CD220' Manufactured by Daicel Chemical Co., Ltd., 300 parts by mass, polyglycol diol (Mn = 2000, trade name: Exenol 2020, manufactured by Asahi Glass Co., Ltd.), 700 parts by mass, and isophorone diisocyanate 2〇 The mass fraction of the crucible was reacted at 80 ° C for 5 hours under a nitrogen stream to obtain an isocyanate-terminated urethane prepolymer. 12 parts by mass of toluene 5 was added thereto to prepare a urethane prepolymer solution. Next, 'adding oxygen to a mixture of 31.2 parts by mass of isophorone diamine, 12.8 parts by mass of di-n-butylamine, 279 parts by mass of toluene, 579 parts by mass of methyl ethyl ketone, and 579 parts by mass of diacetone alcohol The ester prepolymer solution was subjected to a reaction at 50 ° C for 3 hours to obtain a polycarbonate urethane resin solution (polyurethane resin) having a solid content of 30 Å/〇. The synthetic polyurethane resin, free radical compound (trade name: EB600 'made by Daicel Cytec Co., Ltd.), and hardener (trade name: perhexa c, Nippon Oil and Fats Co., Ltd.) are blended at a mass ratio of 00:38:2. Made by limited company, made of insulating adhesive. Then, in a volume ratio of 10 in the insulating adhesive. /. The conductive particles (trade name: AUL7〇4, manufactured by Sekisui Chemical Co., Ltd.) were dispersed, coated on a PET film, and dried to prepare a sheet-like connecting material having a thickness of 20 m. [Example 2] Polycarbonate diol (Mn = 2 〇〇〇, trade name: piaccel CD22, manufactured by Daicel Chemical Co., Ltd.) was set to 4 parts by mass, and polyether 2 (°, 2000) A sheet-shaped connecting material was produced in the same manner as in Example i except that the amount of the product was changed to 600 parts by mass. 12 201219437 [Example 3] A polycarbonate diol (Mn = 2000, trade name: Placcei CD220, manufactured by Daicel Chemical Co., Ltd.) was used as 500 parts by mass, and a polyether diol (Μη-2000, trade name: Exe〇i 2〇2〇, manufactured by Asahi Glass Co., Ltd., manufactured by Asahi Glass Co., Ltd.), was prepared in the same manner as in Example 2 except that the mass was 5 parts by mass. [Example 4] Polycarbonate diol (Mn = 2 〇〇〇, trade name: piaccel CD220, manufactured by Daicel Chemical Co., Ltd.) was set to 6 parts by mass, and polyether diol (Μη - 2000, commercial product) A sheet-like connecting material was produced in the same manner as in Example J except that Exen〇i 2〇2〇, manufactured by Asahi Glass Co., Ltd.) was used in an amount of 4 parts by mass. [Example 5] Polycarbonate diol (Mn = 2000, trade name: Placcei CD220, manufactured by Daicel Chemical Co., Ltd.) was set to 7 parts by mass, and polyether diol (Mn = 2000, trade name: Exenol 2020, manufactured by Asahi Glass Co., Ltd.) was prepared in the same manner as in Example 1 except that the amount of the mixture was changed to 3 parts by mass. [Example 6] Polycarbonate diol (Mn = 2000, trade name: Placece CD220, manufactured by Daicel Chemical Co., Ltd.) was set to 8 parts by mass, and polyether diol (Mn = 2000, trade name: A sheet-shaped connecting material was produced in the same manner as in Example 1 except that the amount of the product was changed to 200 parts by mass, except that Exen〇i 2〇2〇, manufactured by Asahi Glass Co., Ltd.). 13 201219437 [Example 7] Polycarbonate diol (Mn = 1000, trade name: Placcel CD210, manufactured by Daicel Chemical Industry Co., Ltd.) was set to 5 parts by mass, and polyether diol (Mn = 2000 ' A sheet-shaped connecting material was produced in the same manner as in Example 1 except that the product name: Exen〇i 2020, manufactured by Asahi Glass Co., Ltd.) was 500 parts by mass. [Example 8] Polycarbonate monool (Mn = 5000, trade name: Kuraray Polyol C-5 090 'manufactured by Kuraray Co., Ltd.) was set to < ο mass parts, and polyether diol (Mn = 2000, A sheet-shaped connecting material was produced in the same manner as in Example 1 except that the product name: Exenol 2020 (manufactured by Asahi Glass Co., Ltd.) was 500 parts by mass. [Example 9] A polycarbonate diol (Mn = 2000, trade name: piaccel CD220,
Daicel化學股份有限公司製造）設為5〇〇質量份、聚醚二醇 (Mn= 2000 ’商品名：Exenol 2020，旭硝子聚氨酯股份有限 公司製造）设為500質里份、及異佛綱二異氰酸酯設為4〇〇 質量份，除此以外，以與實施例1相同之方式製作片狀連 接材料。 [比較例1] s周配聚醋·一醇（Kurapol P201 〇，Kuraray股份有限公1 製造）1000質量份，代替聚碳酸酯二醇及聚醚二醇，除此以 外，以與實施例1相同之方式製作片狀連接材料。 [比較例2 ] 14 201219437 不調配聚碳酸醋二醇_，調配聚喊二醇（Μη == 20〇〇，商品 名：Exenol 2020，旭硝子聚氨酯股份有限公司製造）1〇〇〇質 量份，除此以外，以與實施例1相同之方式製作片狀連接 材料。 [比較例3] 調配聚碳酸酯二醇（Μη = 2000 ’商品名：placcel CD220 ’ Daicel化學股份有限公司製造）1〇〇〇質量份，不調 配I鍵一醇，除此以外，以與實施例1相同之方式製作片 狀連接材料。 [比較例4] 將聚碳酸酯二醇（Μη = 2000，商品名：Placcei c如20， Daicel化學股份有限公司製造）設為2〇〇質量份、及聚醚二 醇（Mn= 2000，商品名：Exenol 2〇2〇，旭硝子聚氨酯股份有 限公司製造）設為800質量份，除此以外，以與實施例丄相 同之方式製作片狀連接材料。 [比較例5] 調配聚碳酸酯二醇（Mn = 2000，商品名：piaccei cduo ’ Daicel化學股份有限公司製造）5〇〇質量份，不調配 聚醚二醇，調配聚酯二醇（Kurap〇1 p2〇1〇 ’ Kuraray股份有 限公司製造）500質量份’除此以外，以與實施例丄相同之 方式製作片狀連接材料。 [比較例6] 不凋配聚碳酸酯二醇，調配聚醚二醇（Mn = 2〇〇〇，商品 名.Exen〇l 2〇2〇 ’旭硝子聚氨醋股份有限公司製造⑽質 15 201219437 量份、及聚醋二醇（Kurapol P20 10，Kuraray股份有限公司 製造）5 00質量份’除此以外，以與實施例i相同之方式製 作片狀連接材料。 [比較例7] 將聚碳酸S旨二醇（Μη = 500’商品名：Placcel CD205， Daicel化學股份有限公司製造）設為5〇〇質量份、及聚醚二 醇（Μπ= 2000，商品名：Exenol 2020，旭硝子聚氨酯股份有 限公司製造）設為500質量份，除此以外，以與實施例1相 同之方式製作片狀連接材料。 <評價> 將實施例1〜9及比較例1〜7之片狀連接材料分別切 成寬度1.5 mm，利用使用緩衝材料厚度為15〇 # m之鐵氟 龍的工具寬度為1.5 mm之暫時壓接機，於70^ < sec 之條件下，將其暫時壓接於玻璃基板（IZ0,厚度250 nm)上。 其後，將 COF(Chip On Film 用膜，50 // mP(L/S= 1/1)，Made from Daicel Chemical Co., Ltd.), 5 parts by mass, polyether diol (Mn = 2000 'trade name: Exenol 2020, manufactured by Asahi Glass Co., Ltd.), 500 parts, and isophora diisocyanate A sheet-shaped connecting material was produced in the same manner as in Example 1 except that the amount was 4 parts by mass. [Comparative Example 1] 1000 parts by mass of vinegar monool (Kurapol P201®, manufactured by Kuraray Co., Ltd.) was used in place of polycarbonate diol and polyether diol, and Example 1 was used. A sheet-like connecting material was produced in the same manner. [Comparative Example 2] 14 201219437 Unmixed polycarbonate _, formulated with poly diol (Μη == 20〇〇, trade name: Exenol 2020, manufactured by Asahi Glass Co., Ltd.) 1 〇〇〇 mass part, except Otherwise, a sheet-like connecting material was produced in the same manner as in Example 1. [Comparative Example 3] A polycarbonate diol (Μη = 2000 'trade name: placcel CD220 'manufactured by Daicel Chemical Co., Ltd.) was blended in an amount of 1 part by mass, and an I bond monool was not formulated, and In the same manner as in Example 1, a sheet-like connecting material was produced. [Comparative Example 4] A polycarbonate diol (Μη = 2000, trade name: Placcei c such as 20, manufactured by Daicel Chemical Co., Ltd.) was used as 2 parts by mass, and a polyether diol (Mn = 2000, commercial product) A sheet-shaped connecting material was produced in the same manner as in Example 除 except that the amount of the product was changed to 800 parts by mass, except that Exenol 2〇2〇, manufactured by Asahi Glass Co., Ltd.). [Comparative Example 5] A polycarbonate diol (Mn = 2000, trade name: piaccei cduo 'manufactured by Daicel Chemical Co., Ltd.) was blended in an amount of 5 parts by mass, and a polyether diol was not formulated to prepare a polyester diol (Kurap〇). 1 p 2 〇 1 〇 'manufactured by Kuraray Co., Ltd.) 500 parts by mass, except that the sheet-like connecting material was produced in the same manner as in Example 。. [Comparative Example 6] Polyether diol was prepared without blending with a polycarbonate diol (Mn = 2 〇〇〇, trade name. Exen〇l 2〇2〇' manufactured by Asahi Glass Polyurethane Co., Ltd. (10) Quality 15 201219437 A sheet-shaped connecting material was produced in the same manner as in Example i except that the amount of the mixture was changed to 500 parts by mass of a polyester diol (Kurapol P20 10, manufactured by Kuraray Co., Ltd.). [Comparative Example 7] Polycarbonate S-diol (Μη = 500' trade name: Placcel CD205, manufactured by Daicel Chemical Co., Ltd.) is set to 5 parts by mass, and polyether diol (Μπ = 2000, trade name: Exenol 2020, Asahi Glass Polyurethane Co., Ltd.) A sheet-like connecting material was produced in the same manner as in Example 1 except that the amount of the sheet-like connecting material of Examples 1 to 9 and Comparative Examples 1 to 7 was respectively determined. Cut into a width of 1.5 mm, temporarily crimped to a glass substrate at 70 ° < sec using a temporary crimping machine with a width of 1.5 mm of Teflon. (IZ0, thickness 250 nm). After that, COF (Chip) Film for On Film, 50 // mP (L/S= 1/1),
Cu.8 emt’鍍錫，ρι=38 // mt)利用暫時壓接機於8〇。〇 -0.5 MPa-〇.5 sec之壓接條件下進行暫時固定，最後於2〇〇 C -5 MPa-1〇 sec之壓接條件下利用使用ι.5爪瓜工具之正式 壓接機進行壓接，而製成各安裝體。 針對如此獲得之各安裝體，測定連接電阻值及接著強 度並進行評價。將評價結果示於表1。又，連接電阻值及接 著強度之測定係藉由如下方式進行。 [連接電阻值之測定] 對各安裝體進行壓力鍋試驗（PCT, Pressure CookerlTest) 201219437 並評價連接電阻值。初始及施加85ι/85%/500 1ιγ後之連接 電阻值係使用數位萬用表（橫河電機公司製造）進行测定。測 定係使用四端子法’通入電流1 mA而進行。 [接著強度之測定] 對各安裝體進行壓力鍋試驗（PCT)並評價接著強度。初 始及施加85°C /85。/。/500 hr後之接著強度係使用拉伸試驗機 (AMD公司製造）進行測定。測定係於9〇c>c之溫度下以5〇 mm/sec之速度上拉COF而進行。 17 201219437 【1<〕 |實施例9 I in 1 1000/400 2000 1.01 1.55 寸 |實施例8 1 in in 1 1000/200 5000 S τ—Η $ 00 1實施例7 1 1000/200 1000 1.05 1 1 1.56 ； 1 00 1實施例_6j 00 (N 1 1000/200 2000 1 1.04」 1 1.75」 o 00 1實施例5 m 1 1000/200 2000 1.04 1 1.75 1 (N o 實施例4 | ν〇 寸 1 1000/200 2000 1 1.04 1 1 1.65 1 00 ro 實施例3 I in 1 1000/200 2000 1 1.01 1 1 L55 1 (N oo 卜 1實施例2 寸 1 1000/200 2000 Lr〇2 1 1—1.75 1 o 〇d 寸 |實施例1 | 卜 1 1000/200 2000 ι·〇4 ι 2.02 1 ΓΛ OO o 卜^ 聚碳酸酯二醇 聚醚二醇 聚酯二醇 二醇/異氰酸酯之質量比 聚碳酸酯二醇之分子量(Μη) 初始 85〇C ' 85% ' 500 hr 初始 85〇C ' 85% ' 500 hr 將二醇合計設為 1〇(質量比） 連接電阻值(Ω) 接著強度(N/cm) 1比較例7 I 1 1000/200 500 L—1_〇5 _ 1 I 1.56 I (N ΓΟ 比較例6 1 m 1000/200 2000 1.08 18.04 Ο) 寸 (N 比較例5 1 1000/200 2000 1.03 1 15.07 I ο 00 (N 比較例4 CN ΟΟ I 1000/200 2000 1.03 10.57 00 tn CO |比較例3 I Ο I 1 1000/200 2000 1.02 1 1.85 I (Ν ΓΟ o rn 比較例2 I I Ο 1 1000/200 1 1.05 18.07 00 <N CN 比較例1 1 I 〇 1000/200 1 1.02 | I 22.03 I ο 00 uo r-H 聚碳酸酯二醇 聚醚二醇 聚酯二醇 二醇/異氰酸酯之質量比 聚碳酸酯二醇之分子量(Μη) 初始 85°C、85%、500 hr 初始 85〇C ' 85% ' 500 hr 將二醇合計設為 1〇(質量比） 連接電阻值(Ω) 接著強度(N/cm) - 201219437 由表1得知，於僅使用聚酿二醇作為聚氨酯樹脂之軟 鏈段之情形時（比較例丨），因聚醋骨架之水解，導致經過高 溫、高濕環境後之連接電阻值及接著強度劣化。 又，於僅使用聚醚二醇作為聚氨能樹脂之軟鏈段之情 形時（比較例2)，由㈣熱性^，故而經過高溫、高濕環境 後連接電阻值及接著強度同樣劣化。 又，於僅使用聚碳酸醋二醇作為聚氨龍樹脂之軟鏈段 之情形時（比較例3)，雖然耐熱性及耐濕性優異’但是未獲 得良好之接著強度。 又，於調配聚碳酸醋^醇與聚賴^醇作為聚氨酉旨樹脂 之軟鏈段之情形時（比較例5)，因聚㈣架之水解，導致經 過高溫、高濕環境後之連接電阻值及接著強度劣化。 又，於調配聚醚二醇與聚西旨二醇作為聚氨醋樹脂之軟 =段=情形時（比較例6)’ @聚自旨骨架之水解，導致經過高 溫、高濕環境後之連接電阻值及接著強度劣化。 又，於以質量比（聚碳酸醋二醇）：（聚醚二醇）=2: 8之 比例調配聚碳酸醋二醇與聚醚二醇作為聚氨醋樹脂之敕鏈 段之情形時（比Μ 4)’經過高溫、高濕環境後之連接電阻 值及接著強度劣化。 又，於以質量比（聚碳酸醋二醇）：（聚醚二醇）=〇: 1〇 之比例調配聚碳酸S旨二醇與聚_二醇作為聚氨㈣脂之軟 鏈，之情形時（比較例3)，雖然耐熱性及•性優異，但未 獲得良好之接著強度。 另-方面，於以質量比（聚碳酸酉旨二醇）：（聚喊二醇卜 19 201219437 3 : 7〜8 : 2之比例調配聚碳酸酯二醇與聚醚二醇作為聚氨 酯樹脂之軟鏈段之情形時（實施例1〜6)，即便經過高溫、 高濕環境後亦獲得良好之連接電阻值及接著強度。 又，於調配聚碳酸酯二醇與聚醚二醇作為聚氨酷樹脂 之軟鍵段’且使用數量平均分子量Μη為500者作為聚碳酸 酯二醇之情形時（比較例7)，由於交聯密度變高，變得易碎， 故而未獲得良好之接著強度；於使用數量平均分子量Μη為 1000〜5 000者作為聚碳酸酯二醇之情形時（實施例3、7、 8)，獲得良好之接著強度。 又，多元醇與聚異氰酸酯之添加質量比為1〇〇〇 : 4〇〇 之情形時（實施例9) ’與添加質量比為1〇〇〇 : 2〇〇之情形時 (實施例3 )同樣地獲得良好之連接電阻值及接著強度。 【圖式簡單說明】 無 【主要元件符號說明】 無 20Cu.8 emt' tinned, ρι=38 // mt) using a temporary crimping machine at 8 inches. Temporary fixing under 压-0.5 MPa-〇.5 sec crimping conditions, and finally using a formal crimping machine using ι.5 claw-claw tool under pressure conditions of 2〇〇C -5 MPa-1〇sec Each of the mounting bodies is made by crimping. With respect to each of the thus obtained bodies, the connection resistance value and the subsequent strength were measured and evaluated. The evaluation results are shown in Table 1. Further, the measurement of the connection resistance value and the adhesion strength was carried out as follows. [Measurement of connection resistance value] A pressure cooker test (PCT, Pressure Cookerl Test) 201219437 was applied to each mounting body and the connection resistance value was evaluated. The connection after the initial application and application of 85 Ω/85%/500 1 γ was measured using a digital multimeter (manufactured by Yokogawa Electric Corporation). The measurement was performed using a four-terminal method with a current of 1 mA. [Measurement of Strength Next] Each of the mounted bodies was subjected to a pressure cooker test (PCT) and the subsequent strength was evaluated. Initially and apply 85 ° C / 85. /. The adhesive strength after /500 hr was measured using a tensile tester (manufactured by AMD). The measurement was carried out by pulling up the COF at a temperature of 9 〇 c > c at a rate of 5 〇 mm / sec. 17 201219437 [1<] |Example 9 I in 1 1000/400 2000 1.01 1.55 inch | Example 8 1 in in 1 1000/200 5000 S τ - Η $ 00 1 Example 7 1 1000/200 1000 1.05 1 1 1.56 ; 1 00 1 embodiment _6j 00 (N 1 1000/200 2000 1 1.04" 1 1.75" o 00 1 embodiment 5 m 1 1000/200 2000 1.04 1 1.75 1 (N o Example 4 | ν〇 inch 1 1000/200 2000 1 1.04 1 1 1.65 1 00 ro Example 3 I in 1 1000/200 2000 1 1.01 1 1 L55 1 (N oo 1 1 embodiment 2 inch 1 1000/200 2000 Lr〇2 1 1 - 1.75 1 o 〇d inch|Example 1 | Bu 1 1000/200 2000 ι·〇4 ι 2.02 1 ΓΛ OO o 卜 ^ Polycarbonate diol polyether diol polyester diol diol / isocyanate mass ratio polycarbonate Molecular weight of diol (Μη) Initial 85〇C ' 85% ' 500 hr Initial 85〇C ' 85% ' 500 hr Total diol set to 1〇 (mass ratio) Connection resistance value (Ω) Next strength (N/ Cm) 1 Comparative Example 7 I 1 1000/200 500 L—1_〇5 _ 1 I 1.56 I (N ΓΟ Comparative Example 6 1 m 1000/200 2000 1.08 18.04 Ο) Inch (N Comparative Example 5 1 1000/200 2000 1.03 1 15.07 I ο 00 (N Comparative Example 4 CN ΟΟ I 1000/200 2000 1.03 10.57 00 tn CO |Comparative Example 3 I Ο I 1 1000/200 2000 1.02 1 1.85 I (Ν ΓΟ o rn Comparative Example 2 II Ο 1 1000/200 1 1.05 18.07 00 <N CN Comparative Example 1 1 I 〇1000/200 1 1.02 | I 22.03 I ο 00 uo rH Polycarbonate diol polyether diol polyester diol diol/isocyanate mass ratio polycarbonate diol molecular weight (Μη) initial 85° C, 85%, 500 hr Initial 85 〇 C ' 85% ' 500 hr Total diol is set to 1 〇 (mass ratio) Connection resistance value (Ω) Then strength (N/cm) - 201219437 It is known from Table 1, In the case where only the polybromide diol is used as the soft segment of the urethane resin (Comparative Example), the connection resistance value and the subsequent strength deterioration after passing through a high-temperature, high-humidity environment due to hydrolysis of the vinegar skeleton. Further, when only the polyether diol was used as the soft segment of the polyaminable resin (Comparative Example 2), since (4) the heat resistance was obtained, the connection resistance value and the subsequent strength were also deteriorated after passing through the high-temperature and high-humidity environment. Further, when only polycarbonate diol was used as the soft segment of the polyurethane resin (Comparative Example 3), the heat resistance and the moisture resistance were excellent, but good adhesion strength was not obtained. Further, in the case of blending polycarbonate and polylysine as a soft segment of the polyurethane resin (Comparative Example 5), the hydrolysis after the polymerization of the poly(four) frame results in a connection after passing through a high temperature and high humidity environment. The resistance value and the subsequent strength are deteriorated. Further, when the polyether diol and the poly diol are blended as the soft squash resin of the polyurethane resin, the case of the mixture is compared with the case where the mixture is subjected to high temperature and high humidity environment. The resistance value and the subsequent strength are deteriorated. Further, when the polycarbonate diol and the polyether diol are blended as a ruthenium segment of the polyurethane resin in a ratio of mass ratio (polycarbonate diol): (polyether diol) = 2:8 ( Μ 4) 'The connection resistance value and the subsequent strength deterioration after passing through a high temperature and high humidity environment. Further, in the case of a mass ratio (polycarbonate diol): (polyether diol) = 〇: 1 调, a polyether S diol and a poly diol are blended as a soft chain of a poly(tetra) sulphate. At the time (Comparative Example 3), although heat resistance and the property were excellent, good adhesive strength was not obtained. On the other hand, in the mass ratio (polycarbonate diol): (poly diol diol 19 201219437 3 : 7~8: 2 ratio of blending polycarbonate diol and polyether diol as a polyurethane resin soft In the case of the segment (Examples 1 to 6), a good connection resistance value and subsequent strength were obtained even after a high temperature and high humidity environment. Further, the polycarbonate diol and the polyether diol were blended as a polyurethane. In the case where the soft bond segment of the resin' is used as the polycarbonate diol in the case where the number average molecular weight Μη is 500 (Comparative Example 7), since the crosslinking density becomes high, it becomes brittle, and thus a good bonding strength is not obtained; When a number average molecular weight Μη of 1000 to 5,000 is used as the polycarbonate diol (Examples 3, 7, and 8), good adhesion strength is obtained. Further, the mass ratio of the polyol to the polyisocyanate is 1 〇〇〇: In the case of 4 ( (Example 9) 'When the mass ratio of addition is 1 〇〇〇: 2 ( (Example 3), a good connection resistance value and subsequent strength are obtained. Simple description of the schema] No [main component symbolism Ming] No 20