200427811 玖、發明說明： 【發明所屬之技術領域】 本發明涉及用於電路基板之間或者ic b 令什同佈線基板之間連接的電路連接用黏結劑。年電子 【先前技術】 當電路基板之間或者IC晶片等電子零件和電路美 反之間進订電路連接時，使用將黏結劑或 / 分數的各向異性的導電黏处亦彳。 — 電粒子 劑塗覆於相對設立的兩電極之間，經加熱、加 極之間連接後，再通過在加壓方向使 ^ f接。例，’在曰本特許公開公報平3-16147 :…，提出使用環氧樹脂作爲主要成分的電路 黏結劑的方案。 連接用 …’然而’以環氧樹脂作爲主姜成分的黏結劑 衝擊試驗和PCT等試驗 几，，，、 非1王4 ^〒，基於連接 土板的熱膨脹率的不同所産生的内部應力，容易在連 接處産生連接阻抗的增大以及黏結劑的剝離。 另外在通過黏結劑將晶片直接連接到基板上時， 作爲連接基板若使用FR4基體材料等的印刷基板，、使 用聚酿亞胺及聚脂等高分子薄膜作爲基體材料的撓性 電路板或者玻璃基板，連接後，源於同晶 率的不同而產生的内部應力，容易産生晶片和基板I 撓曲。再有’當將晶片向基板壓接使黏結劑流動的情 兄下泎夕孔隙發生在連接介面，存在耐濕性降低等 200427811 問題。 【發明内容】 ::明的目的在於提供一種電路連接用 可抑制由於源於熱膨脹率的不同所産生的内部 連接處的連接阻抗增大，黏結劑的剝離和 的撓曲。 々夂I扳 本么明的電路連接用黏結劑是將相對的電路電極 經加熱、加壓，使加壓方向的電極間實現電連接的熱 黏結性黏結劑中，上述黏結劑具有以下特徵，即：它 含有分散的平均粒徑爲10" m以下的橡膠粒子和熱固 化的反應性樹脂，該黏結劑的Dsc (差式掃描熱分析） 的發熱開始溫度爲6(rc以上，而固化反應❾8〇:的結 束溫度爲260°C以下。 另外，本發明的黏結劑在從發熱開始溫度到固化反 應的80%結束的溫度，用Dsc測得的發熱量最好爲 50-140焦耳/克。 再有，本發明的黏結劑用DSC測得的固化反應的 6 〇 %結束溫度最好在16 0 °C以下。 再有，反應性樹脂最好含有環氧樹脂和潛在性固化 劑0 再有，潛在性固化劑最好是銕鹽。 另外，本發明的黏結劑也可以含有以分散狀態存在 的〇·1-30體積％的導電粒子。 本發明的黏結劑意在包含薄膜狀的黏結劑和糊狀 黏結劑兩者’但最好是薄膜狀黏結劑。 在將本發明的黏結劑做成薄膜狀的情況下，可以含 有形成薄膜的高分子物質。 另外，本發明的薄膜在25 〇c時的彈性率最好爲 50-lOOGMPa，若使用本發明，可以吸收在抗熱衝擊試 驗及PCT試驗等的可靠性試驗中所産生的内部應力， 即使在可罪性試驗後也沒有連接處的連接阻抗增大及 黏結劑剝離的現象，可以得到連接可靠性提高的黏結 劑。另外，若使用本發明，在將晶片實際安裝在LCD 板時’由於降低了基板的撓曲可以抑制其對顯示質量 的不良影響。即，可以抑制由於撓曲的發生帶來的顯 示面的間隙的變化而産生顯示斑點的現象。 因此，本發明的電路連接用黏結劑最適用於僅僅將 LCB板和TAB，TAB和印刷基板，LCD板和1C晶片， IC晶片和印刷基板在連接時的加壓方向進行電連接。 【實施方式】 具體實施方式 本發明的黏結劑在黏結劑中以分散狀態含有平均 粒徑爲10 // m以下的橡膠粒子。含有橡膠粒子的目的 是爲了緩解可靠性試驗中所産生的内部應力，防止黏 結劑的剝離，降低基板的撓曲。 橡膠粒子的平均粒徑最好是〇 · 1 _ 1 〇 # m，尤其好的 疋0·1-5μ m。另外，特別好的是橡膠粒子 一 |、/ ^ ’弓赤立和4 下的粒子占粒徑分佈的8〇%以上。 作爲本發明的橡膠粒子只要是玻璃化轉化m 25 C以下的橡膠粒子均可，沒有特別限定，例如又 以使用丁二稀橡膠，聚丙烯橡膠，丁笨橡膠，… 膠’矽橡膠等。 丁腈橡 在上述的橡膠粒子中，最好使用矽橡膠粒子，因爲 :除了耐溶劑性優良外，分散性也很好。石夕橡膠粒； ::使用以下方法製得，即：將石夕院化合物或甲基三 2虱基矽烷及/或其部分水解縮合物加到使用苛性納或 氣等驗性物質將PH值調整到9以上的乙醇水溶液中之 2 ’再使其水解縮聚的方法或者使其與有㈣氧燒共 、方法另外，爲了提高反應性樹脂的分散性，最 f使用在分子端部或者分子内支鏈中含有氫氧基或環 氧基酮亞胺，羧基，巯基等官能團的矽微粒子。 在用偶σ剤對橡膠粒子表面進行處理的情況下，更 好的是提高對反應性樹脂的分散性。 橡4粒子在室溫（25 °C )下的彈性率最好是 1 lOOMpa，考慮到橡膠粒子的分散性或降低連接時介 面的應力更好 匕 士 的疋U0 MPa 0但是，當選擇反應性樹 月曰的呤候’應考慮黏結劑的反應性和發熱量決定。 橡膠粒子相對於黏結劑組合物的使用量最好是相 對於黏結劑纟且么^ % δ Λ Γ\ ^ 、、、σ物爲100重量份時其爲1〇1〇〇重量份。 士匕作爲本發明所使用的反應性樹脂可以是例如，環氧 曰# ’曰在性固化劑的混合物，自由基反應性樹脂和 有機過氧化物的混合物。 作马％氧樹脂可以使用以下例子中的單獨一種或 將兩種以上混人蚀 匕。使用’但不受這些例子的限制。例如： 由氣曱基夤％ P 4 70和双酚A，F或AD衍生的双酚型環氧 w脂；由氣甲1 $ 、、一 ” 土氣丙燒和線性齡盤清漆樹脂（7二y a 、、一 · 可〉谷性盼酸清漆樹脂（夕b 乂、'— ；]y /木7夕夕）衍生的環氧酚醛清漆樹脂， ;的蔡系環氧樹脂，以及在縮水甘油氨絡合物二水 甘油醚，聯笨或者 一 曰衣式等的一個分子中具有二個以 上的縮水甘油基的環氧化合物。 ϋ這些環氧樹脂，爲了防止電子遷移最好使用將 30二 Μ，CK或者水解性氣的濃度降低到 3〇〇PPM以下的高純度品。 子MPP⑹ j舉例如下，但不受這些具體例 子的限制。例如：咪唑系， 一 故入^ 馱肼系，二亂化硼-醯胺的 、、各合物，銃鹽，胺化醯 胺化騐亞胺，聚胺的鹽以及雙氰胺等。 在這些潛在性固化劑中，、^ ^ ^200427811 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to an adhesive for circuit connection used for connection between circuit substrates or IC substrates. Nintendo Electronics [Previous Technology] When circuit connections are made between circuit boards or electronic components such as IC chips and circuit boards, anisotropic conductive adhesives that use adhesives or / fractions are also used. — Electron particles are applied between two electrodes that are set up oppositely, and after heating and connecting between the electrodes, they are connected in the direction of pressure. For example, "In Japanese Patent Laid-Open Publication No. Hei 3-16147: ..., a circuit adhesive using epoxy resin as a main component is proposed. For connection ... 'However', the binder impact test using epoxy resin as the main ginger component, and PCT and other tests are based on the internal stress caused by the different thermal expansion coefficients of the connecting soil plates. An increase in connection resistance and peeling of the adhesive easily occur at the connection. In addition, when the wafer is directly connected to the substrate through an adhesive, if a printed circuit board such as a FR4 base material is used as the connection substrate, or a flexible circuit board or glass using a polymer film such as polyimide and polyester as a base material, After the substrates are connected, the internal stress caused by the difference in isomorphism is likely to cause the wafer and the substrate I to flex. Another problem is that when the wafer is pressed against the substrate to make the adhesive flow, the next pores occur at the connection interface, and there are problems such as a decrease in moisture resistance 200427811. [Summary of the Invention]: The object of the invention is to provide a circuit connection for suppressing an increase in connection resistance at an internal connection due to a difference in thermal expansion coefficient, peeling of an adhesive, and deflection. 々 夂 I The bonding adhesive for circuit connection is a thermal bonding adhesive that heats and presses the opposite circuit electrodes to achieve electrical connection between the electrodes in the pressing direction. The above adhesive has the following characteristics. That is: it contains dispersed rubber particles with an average particle diameter of 10 " m or less and a thermosetting reactive resin, and the Dsc (Differential Scanning Thermal Analysis) of the adhesive has a heating start temperature of 6 (rc or more, and the curing reaction ❾80: The end temperature is below 260 ° C. In addition, in the adhesive of the present invention, at a temperature from the start of heating to the end of the curing reaction at 80%, the calorific value measured by Dsc is preferably 50-140 J / g Moreover, the end temperature of 60% of the curing reaction measured by DSC of the adhesive of the present invention is preferably below 160 ° C. Furthermore, the reactive resin preferably contains an epoxy resin and a latent curing agent. The latent curing agent is preferably a sulfonium salt. In addition, the adhesive of the present invention may also contain conductive particles in a dispersed state of 0.1-30% by volume. The adhesive of the present invention is intended to include a film-like adhesive Agent and paste sticky Both of the agents are preferably film-shaped adhesives. When the adhesive of the present invention is made into a film, it may contain a film-forming polymer substance. In addition, the film of the present invention has an elasticity at 25 ° C. The rate is preferably 50-100 GMPa. If the present invention is used, the internal stress generated in reliability tests such as thermal shock test and PCT test can be absorbed. Even after the guilty test, the connection resistance of the connection is not increased. The phenomenon of large and peeling of the adhesive can obtain an adhesive with improved connection reliability. In addition, when the present invention is used, when the wafer is actually mounted on the LCD panel, the deflection of the substrate can be reduced to reduce the deterioration of the display quality. In other words, it is possible to suppress the phenomenon of display speckle caused by the change in the gap of the display surface caused by the occurrence of deflection. Therefore, the adhesive for circuit connection of the present invention is most suitable for only LCB board, TAB, TAB, and printing. The substrate, the LCD panel and the 1C chip, and the IC chip and the printed substrate are electrically connected in a direction of pressure during connection. [Embodiment] DETAILED DESCRIPTION OF THE INVENTION Adhesion of the present invention The adhesive contains rubber particles with an average particle diameter of 10 // m or less in a dispersed state. The purpose of containing the rubber particles is to alleviate internal stress generated in the reliability test, prevent the peeling of the adhesive, and reduce the deflection of the substrate. The average particle diameter of the rubber particles is preferably 0.1-1 〇 # m, particularly good 疋 0 · 1-5 μm. In addition, rubber particles 1 and 2 are particularly preferred. The particles occupy 80% or more of the particle size distribution. The rubber particles of the present invention are not particularly limited as long as they are rubber particles having a glass transition m 25 C or less. For example, butadiene rubber, polypropylene rubber, Butadiene rubber,… rubber 'silicone rubber, etc. Among the above rubber particles, nitrile rubber is best to use silicon rubber particles, because in addition to excellent solvent resistance, the dispersion is also very good. Shixi rubber granules; :: Prepared using the following method, that is: adding Shixiyuan compound or methyltrisylsilane and / or its partially hydrolyzed condensate to pH value using caustic soda or gas A method of adjusting 2 ′ in an ethanol aqueous solution of 9 or more and hydrolyzing and polycondensing it, or co-oxidizing it with aerobic sintering. In addition, in order to improve the dispersibility of the reactive resin, it is used at the end of the molecule or in the molecule. Silicon particles containing functional groups such as hydroxyl or epoxyketimine, carboxyl, and mercapto in the branch chain. In the case where the surface of the rubber particles is treated with even σ 剤, it is more preferable to improve the dispersibility of the reactive resin. The elasticity of rubber 4 particles at room temperature (25 ° C) is preferably 1 lOOMpa. Considering the dispersion of rubber particles or reducing the stress on the interface when connecting, it is better to use U0 MPa 0. However, when reactivity is selected Shuyue's purine should be determined by considering the reactivity and calorific value of the binder. The use amount of the rubber particles with respect to the adhesive composition is preferably 100% by weight with respect to the adhesive%% δ Δ Γ \ ^, when the amount of σ is 100 parts by weight. As the reactive resin used in the present invention, a dagger can be, for example, a mixture of epoxy resins and curing agents, a mixture of radical reactive resins and organic peroxides. As the horsetail oxygen resin, one of the following examples can be used alone or two or more of them can be mixed. Use 'is not limited by these examples. For example: Bisphenol-type epoxy resins derived from airborne hydrazone-based P 4 70 and bisphenol A, F, or AD; from 1%, 1 "rustic acrylic and linear ageing varnish resin (72%) ya ，、 一 · can> glutamic acid varnish resin (Yu b 乂, '—;] y / wood 7 Xixi) derived epoxy novolac resin,; Cai series epoxy resin, and glycidyl ammonia Complex diglycidyl ether, biben or yiyi type epoxy compounds with two or more glycidyl groups in one molecule. Ϋ These epoxy resins, in order to prevent electron migration, it is best to use 30 mM CK or high-purity products whose concentration of hydrolyzable gas is reduced to less than 300 PPM. Examples of sub-MPP ⑹ j are as follows, but are not limited by these specific examples. For example: imidazole series, hydrazine system Boron-ammonium, compounds, sulfonium salts, amidated ammonium amines, imines, polyamine salts, dicyandiamide, etc. Among these potential curing agents, ^ ^ ^
的固化溫度在60〇C 而^固化反應完成6〇%的溫度在16〇亡以 低溫反應性優良，有妄入 因，、 4± 民 可〒長而最適用。作爲铲豳， 特別適用的以—般式⑴表示的㈣ ^ 427811 R3 (i) 、/疋在式（1)中，Rl爲電子吸水性的基，例如： 亞3硝基，碳基，後基，氰基三烧基兹，甲氟基；R2及 R爲電子供給性的基，例如：氨基，氫氧基，甲基；γ 爲非求核性陰離子，例如：六氟砷酸鹽，六氟銻酸鹽。 銷1鹽相對於環氧樹脂的使用量最好是2-20重量 份。 在本發明的黏結劑中最好-混入分散導電粒子，其目 的&爲了彌補晶片的凸緣或基板電極的高度誤差而使 黏結劑具有各向異性的異電性。 ★反應性樹脂相對於黏結劑的使用量最好是相對於 黏結劑100重量份爲20_1〇〇重量份。 作爲本發明的導電粒子可以使用例如Au，Ag， 焊料等金屬粒子，❻不受這些例子的限制。最好 的是在聚苯乙烯等高分子球形芯材的表面設置Ni， CU，AU，焊料等導電層，另外，在導電粒子的表面， 還可以形成Sn，Au焊料等表面層。進一步形成表面層 的目的是爲了通過同底層（導電層）的結合提高導電 200427811 性。導電粒子的 還小。另外，在電：：1頁比基板上的電極的最小間隔 的粒徑最好比娛向度誤差的情況下，導電粒子 扣阿度誤差要大，且 外’分散在黏結割中 ，、體的-㈣“。另 口 d甲的導電粒子詈 β %，尤其好的是η 9 1C 里取好疋〇·Uo體積 丁 π 疋 0.2-15 體積 ％。 在本發明的黏結劑中 .. 了以此入分散無機充填材料。 马本發明中可使用 材料，作 、丄 …、機充填材料可列舉如 t不叉廷些材料的限制 矽、晶體二4朴μ J如.炫μ的二氧化 化夕、氧化銘、碳酸料粉末。 物二i:真=的：用量最好是相對於黏結劑組合 量广爲1〇·200重量份。尤其好的是20-90重 ^ 4 了降低熱膨脹係數，盔機充填；^ # 越大效果越好；铁而，田旦、 填材枓的使用量 ^ ^ W 里蟫大有産生黏結性降低戋 者電極間導雷I @ M ^ ^ ^ 柄备咏 電不良的傾向’用量過小則有不能充分降 低熱膨脹係數的傾向。 無機充填材料的平均粒徑從防止連接處導 ，親點來看最好在3" 。另外，從防止在連接^ 樹月曰的机動性降低的觀點和防止對晶片的純化膜的損 傷的觀點來看’最好使用球狀填料作爲無機充填材 料。無機充填材料無論黏結劑是否含有導電粒子都可 混入、分散。 爲了更容易形成薄膜，還可以將苯氧基樹脂，聚脂 樹脂，聚醯胺樹脂等熱塑性樹脂（以下稱爲薄膜形成性 高分子）加入到本發明的黏結劑中。這些薄膜形成性高 11 分子具有緩解反應性樹脂固化時的應力的效果。尤其 、疋^其具有氫氧基等官能團時，薄膜形成性高分 子有利於提高黏結性。 爲了將本發明的黏結劑做成薄膜形狀可以採用以 下的方法進行’即··將至少由這些反應性樹脂，潛在 2固化劑組成的黏結劑組合物溶解或者分散在有機溶 J中使其成液體狀，然後塗覆在可以剝離的基體材料 上，在固化劑的活性溫度以下除去溶劑即可。這時所 用的溶劑最好是有利於提高材料溶解性的芳香族烴系 和含氧系的混合溶劑。 ，本發明的黏結薄膜可以通過調整反應性樹脂，橡膠 r子薄膜形成性高分子材料等的使用量使薄膜的彈 ，率（25。〇 爲 5(M〇〇〇MPa，最好是 7〇5〇〇Mpa。黏結 薄膜的彈诠率-超過100〇MPa就不能將薄膜黏貼到電 一反上在將薄膜按規定的寬度切斷加工時存在黏結 薄膜由基體材料薄膜上剝離的傾向。另外，若彈性率 不足5〇MPa，當同基體材料薄膜一起捲成10M以上的 、’狀物呀，存在黏結薄膜黏貼在基體材料薄膜的背面 、於進行將黏結薄膜黏貼到電路基板上的作業的傾 向。另外，芦# , 夕 。寸’由於低分子的反應性樹脂的含量增 ^ 在壓接時存在産生許多孔隙的傾向。再有，黏結 薄膜的彈性率(儲存彈性率：測定用帛膜厚& : 10 # III) 可以用黏彈性測定裝置（升溫速度：10°c /分，頻率：1Hz) 200427811 點結劑的反應性可以用DSC(升溫速度：i〇°c /分） ’則疋。本發明的黏結劑使用DSC的發熱開始溫度是60 C以上’黏結劑的固化反應的80%的結束溫度在260 C以下。通過選擇加入黏結劑中的反應性樹脂進行調 整使其達到這些溫度。再有，固化反應的6〇%的結束 溫度最好在160°C以下。 基於本發明的黏結劑的固化反應的發熱量也可以 用DSC(升溫速度：1(rc/分）求得。發熱量最好爲5〇_14〇 焦耳/克，尤其好的是60_120焦耳/克，特別好的是鲁 60-100焦耳/克，通過改變反應性樹脂，橡膠粒子，薄 膜形成性高分子等的使用量進行調整。黏結劑的發熱 1右超過140焦耳/克，則由於黏結劑的固化收縮力及 彈性率的增大等因素使内部應力增大，電路之間連接 時，存在電路基板撓曲導致連接可靠性降低或者電子 零件的特性降低等傾向。另外，在發熱量不足5〇焦耳 /克犄存在由於黏結劑的固化不充分，導致黏結性及 連接可靠性降低的傾向。 ^ DSC是將供給或除去熱量的零位法作爲測定原理 使得在測定溫度範圍内不斷地消除同沒有發熱、吸熱 的標準試樣的溫度差，也可以使用市售的測定裝置進 行測定。黏結劑的反應是發熱反應，若以一定的升溫 速度升溫’試樣反應就産生熱量。將該發熱量輸出到 圖表中，將基線作爲基準，由發熱曲線和基線求得所 圍的面積，將其作爲發熱量。以i〇°c/分的升溫速度從 至溫（25 C )到300°C左右進行測定，求得上述的發熱 13 200427811 量。這些都是完全自動地進行的，若使用它可以很容 易地進行。另外，固化反應的80%的結束溫度可以由 發熱量的面積求得。 貫施例一 將苯氧基樹脂（聯合碳化物公司（Union Carbide Ltd.)製’ PKHC) 50克溶解在醋酸乙酯115克中，得到 30重量％的苯氧基樹脂溶液。 作爲石夕mere將甲基三甲氧基矽烷加入到以 300轉/分鐘授拌的12的乙醇水溶液中使盆水 解、縮合，製得25t的儲存彈性率爲8Mpa，平均粒徑 爲2 // m的球形微粒子。 將含有笨氧基樹脂溶液（以固態重量比苯氧基樹脂 C克）硅酮微粒子3〇克，微膠囊型潛在性固化劑的液 體環氧樹脂（環氧當量185,旭化成工業股份有限公司 製，諾瓦卡（N0vacul) HX_3941)2〇克，双酚A型環氧 :脂（環氧當* 180)50克混合’將在聚笨乙稀系核芯（直 徑：5 # m)的表面形成Au層的導電粒子以6體積％分 散在其中從而製得薄膜塗覆用溶液。隨後，用塗覆裝 字該’合液塗覆到對厚度爲5〇#m的薄膜的單面進行 ^面處理的PET(聚對苯二甲酸乙醋，基體材料薄膜， 分離器）薄膜上，經70°C熱風乾燥10分鐘，得到黏結 又马45 // m的薄膜狀黏結劑。關於該黏結劑， 〜碣始％間，反應結束時間，固化反應的6 〇 %和 80%的結束溫度，直到固化反應@ 80%結束的dsc的 14The curing temperature is 60 ° C and the curing reaction is completed at 60%. The temperature is 160 ° C. The low temperature reactivity is excellent. As a shovel, 适用 427811 R3 (i), which is particularly suitable for the general formula 疋 In formula (1), R1 is an electron-absorptive group, for example: 3nitroso, carbon, and R2 and R are electron-donating groups, for example: amino, hydroxyl, methyl; γ is a non-nucleating anion, for example: hexafluoroarsenate, Hexafluoroantimonate. The amount of the pin 1 salt to the epoxy resin is preferably 2 to 20 parts by weight. In the adhesive of the present invention, it is preferable that the dispersed conductive particles are mixed. The purpose of the adhesive is to make the adhesive have anisotropic heteroelectricity in order to compensate for the height error of the wafer flange or the substrate electrode. ★ The amount of the reactive resin used with respect to the binder is preferably 20 to 100 parts by weight relative to 100 parts by weight of the binder. As the conductive particles of the present invention, metal particles such as Au, Ag, solder, etc. can be used, and ❻ is not limited to these examples. It is preferable that a conductive layer such as Ni, CU, AU, and solder be provided on the surface of a polymer spherical core material such as polystyrene. In addition, a surface layer such as Sn and Au solder may be formed on the surface of the conductive particles. The purpose of further forming the surface layer is to improve the electrical conductivity by combining with the bottom layer (conductive layer). The conductive particles are still small. In addition, in the case where the diameter of the smallest interval of the electrode on the substrate is better than the error of the orientation, the error of the conductive particle is larger, and the outer part is dispersed in the bonding cut. -㈣ ". In addition, the conductive particles 甲 β%, especially η 9 1C, 疋 〇 · Uoo 丁丁 π 0.2-15 vol%. In the adhesive of the present invention. This is used to disperse the inorganic filling material. The materials that can be used in the present invention include, for example, the limited silicon of some materials such as t, etc., and the crystals. Huaxi, oxidized salt, carbonic acid powder. Material II: True =: The dosage is preferably 10 · 200 parts by weight relative to the combined amount of the binder. Especially preferred is 20-90 weight ^ 4 to reduce thermal expansion Coefficient, helmet machine filling; ^ # The greater the effect, the better; iron and, Tian Dan, the amount of filling material used ^ ^ W has a large adhesion to reduce the lightning between the electrodes I @ M ^ ^ ^ handle Tendency of bad electric performance 'If the amount is too small, the thermal expansion coefficient may not be sufficiently reduced. The average particle size is preferably from the point of view of preventing the connection, and from the point of view. In addition, from the viewpoint of preventing the decrease in mobility at the connection ^ Shuyue said and the point of preventing damage to the purified membrane of the wafer, 'most It is good to use spherical fillers as inorganic fillers. Inorganic fillers can be mixed and dispersed regardless of whether the binder contains conductive particles. In order to form films more easily, phenoxy resins, polyester resins, polyamide resins and other thermoplastics can be used. A resin (hereinafter referred to as a thin film-forming polymer) is added to the adhesive of the present invention. These 11 thin-film-forming molecules have the effect of alleviating the stress when the reactive resin is cured. In particular, it has functional groups such as hydroxyl groups In order to make the adhesive of the present invention into a thin film shape, the following methods can be used: that is, an adhesive composed of at least these reactive resins and 2 latent curing agents can be used. The composition is dissolved or dispersed in an organic solvent to make it liquid, and then coated on a substrate material that can be peeled off. It is sufficient to remove the solvent at a temperature lower than the temperature. The solvent used at this time is preferably a mixed solvent of an aromatic hydrocarbon type and an oxygen-containing type which is helpful for improving the solubility of the material. The adhesive film of the present invention can be adjusted by reactive resin and rubber. The amount of film-forming polymer material used makes the film elastic, and the ratio (25.0 is 5 (MPa), preferably 7500 MPa. The elastic modulus of the adhesive film-more than 100 MPa When the film is cut to a predetermined width, there is a tendency for the adhesive film to peel off from the base material film. In addition, if the elastic modulus is less than 50 MPa, it is rolled together with the base material film. If the thickness is more than 10M, there is a tendency that the adhesive film is adhered to the back surface of the base material film to perform the operation of adhering the adhesive film to the circuit board. In addition, Lu #, Xi. As the content of the low-molecular reactive resin increases, there is a tendency that many pores are generated during crimping. In addition, the elastic modulus of the adhesive film (storage elastic modulus: film thickness for measurement &: 10 # III) can be measured with a viscoelasticity device (temperature rise rate: 10 ° c / min, frequency: 1Hz) 200427811 Reactivity can be measured by DSC (temperature rise rate: 10 ° C / min). The temperature at which the adhesive of the present invention uses DSC to start is 60 C or higher. 80% of the curing reaction of the adhesive is to be completed at 260 C or lower. Adjust to reach these temperatures by selecting the reactive resin added to the binder. The end temperature of 60% of the curing reaction is preferably 160 ° C or lower. The calorific value of the curing reaction based on the adhesive of the present invention can also be obtained by DSC (temperature rise rate: 1 (rc / min). The calorific value is preferably 50-14 joules / gram, particularly preferably 60-120 joules / gram. Grams, particularly preferably Lu 60-100 Joules / gram, adjusted by changing the amount of reactive resin, rubber particles, film-forming polymers, etc. The heat of the adhesive 1 exceeds 140 Joules / gram, but due to adhesion Factors such as the curing shrinkage force and the increase of the elastic modulus increase the internal stress. When connecting circuits, there is a tendency that the circuit board is deflected to reduce the connection reliability or the characteristics of the electronic components. In addition, the heat generation is insufficient. 50 Joules / gram, there is a tendency that the adhesiveness and connection reliability are reduced due to insufficient curing of the adhesive. ^ DSC uses the zero method of supplying or removing heat as the measuring principle to continuously eliminate within the measuring temperature range. The temperature difference with a standard sample that does not generate heat or endotherm can also be measured using a commercially available measuring device. The reaction of the adhesive is a fever reaction, and it will rise at a constant temperature increase rate. Heat is generated when the sample is warmed. The heat output is output to the graph, and the baseline is used as the reference. The area around the heat curve and the baseline is used as the heat output. The temperature is raised at i0 ° c / min. The speed is measured from the temperature (25 C) to about 300 ° C, and the above-mentioned amount of heat generation 13 200427811 is obtained. These are fully automatic, and it can be easily performed if it is used. In addition, 80% of the curing reaction The end temperature can be obtained from the area of heat generation. Example 1 50 grams of a phenoxy resin ('PKHC manufactured by Union Carbide Ltd.) was dissolved in 115 grams of ethyl acetate to obtain 30 weights. % Phenoxy resin solution. As Shi Ximere, methyltrimethoxysilane was added to an aqueous ethanol solution of 12 at 300 rpm to hydrolyze and condense the pot to obtain a 25t storage elasticity rate of 8Mpa. Spherical microparticles with an average particle size of 2 // m. Liquid epoxy resin containing 30 grams of silicone microparticles containing a stupid oxy resin solution (solid weight ratio of phenoxy resin C) and a microcapsule-type latent curing agent. (Epoxy equivalent 185, Made by Chemical Industry Co., Ltd., Novavac (HX_3941) 20 grams, 50 grams of bisphenol A epoxy: grease (epoxy when * 180) will be mixed in a polystyrene core (diameter: 5 # m) The conductive particles forming the Au layer were dispersed therein at 6 vol% to prepare a thin film coating solution. Subsequently, the coating was coated with the coating material to a thickness of 5 0 #m. On one side of the film, PET (polyethylene terephthalate, base material film, separator) film was treated with 70 ° C hot air for 10 minutes to obtain a film-like adhesion of 45 // m. Regarding the adhesive, ~~% of the beginning, the end of the reaction time, 60% of the curing reaction and 80% of the curing temperature, until the curing reaction @ 80% of the end of the dsc 14
号务、 “、、里’以及直到固化反應完全結束的DSC的發熱量 及彈性率進行測定，其結果示於表1。 其-人’使用所得的薄膜狀黏結劑如以下所示地將帶 金凸緣（面積80Χ80//Π1，間隔30//m，高度15//m，二 緣數288)的晶片（10xl0mm，厚度5〇〇" m)同具 Η ^ 曰曰 的電極相對應的電路電極的鍍Ni/All的Cu電路印刷 板進行連接。 將薄膜狀黏結劑（12又12111111)在80。(：，1.〇]^3(1〇公 斤力/屋米2)的壓力下黏貼在鑛Ni/Au的Cu電路印刷 板（電極高度20mm，厚度〇.8inm)，剝離分離器，使晶 片的凸緣和鍍Ni/Au的Cu電路印刷板（厚度〇8mm)的 位置吻合。隨後’在180°C，75克/每個凸緣，2〇秒的 條件下由晶片上方進行加熱、加壓，從而實現本連接。 本連接後晶片的撓曲爲1 // m (向晶片方向凸起的 撓曲）。另外’本連接後的連接阻抗，每個凸緣爲最高 15 Μ Ω，平均爲8M Ω，絕緣阻抗在j 88 〇以上。這些 值即使在進行-55-125 C的抗熱衝擊試驗JQQ0次迴圈 處理’ PCT試驗（121 C ’ 0.2Mpa(2個大氣壓））2〇〇小時， 260°C釺焊浴中浸潰1〇秒鐘後也沒有變化，表明其良 好的連接可靠性。 f施例二 除了將10體積％的導電粒子分散在黏結劑中外， 15 其餘同實關—相同H胃The calorific value and elasticity of the DSC, ",, and li" and DSC until the curing reaction was completely completed were measured, and the results are shown in Table 1. The film-adhesive obtained by using the obtained film adhesive as described below was used as follows. Circuits with gold flanges (area 80 × 80 // Π1, spacing 30 // m, height 15 // m, two edges 288) (10xl0mm, thickness 500) and the corresponding circuit with the electrode Η ^ The electrode was plated with a Ni / All-plated Cu circuit printed circuit board. A thin film adhesive (12 and 12111111) was attached under a pressure of 80. (:, 1.0) ^ 3 (10 kgf / m2). On a Cu circuit printed board (electrode height 20mm, thickness 0.8inm) of the Ni / Au mine, the separator was peeled off, so that the position of the flange of the wafer and the Ni / Au plated Cu circuit printed board (thickness 0.8mm) matched. 'This connection is achieved by heating and pressing from above the wafer at 180 ° C, 75 g / each flange, 20 seconds. The wafer deflection after this connection is 1 // m (toward the wafer) Convex deflection). In addition, the connection impedance after this connection, each flange is a maximum of 15 megaohms, the average is 8 megaohms, the insulation resistance in j 88 〇 or more. These values are even after the thermal shock test of -55-125 C. JQQ 0 cycles. PCT test (121 C '0.2Mpa (2 atmospheres)) 200 hours, 260 ° C brazing There was no change after immersion in the bath for 10 seconds, indicating good connection reliability. FExcept for the second embodiment, except that 10% by volume of the conductive particles were dispersed in the adhesive, the rest was the same as the real one—the same stomach
Ik後’使用塗覆裝置將該溶液塗覆在對厚度 "m的薄膜的單面進行. 馬50 進仃表面處理的PET薄膜上，經 C熱風乾燥10分鐘，桿 /0 ^ u 侍到黏結劑層厚度爲10/zm的薄 膜狀黏結劑a。 J /辱 隨後，在上述製作塗覆用溶液的過裎中，除了产 將形成Au層的導電離+八 又 〒电雖子刀散在溶液中這—點外， 與上相同的方法製作薄膜塗覆用溶液，使用 將該溶液塗覆在對厚度爲50一薄膜的單面二 面處理的PET薄膜上，‘經7代熱風乾燥iq分鐘^ 到黏結劑層厚度爲15 ”的薄膜狀黏結劑b。再將 得到的薄膜狀黏結劑b在机_邊加熱，一邊 耗式層μ裝置製成層壓的二層結構的各向導性的 薄膜。， * 斧¥ 關於這種黏結劑，同實施例一同樣地進行測定，其 結果示於表1。 /、 其次，使用所製得的各向異向導電薄膜，如以下所 示地將帶金凸緣（面積·· 5〇x5〇//m，間隔·· 2〇#m，高 m凸緣數362)的晶片（1.7x17mm，厚度：500After Ik ', the solution was applied on one side of a film with a thickness of "m" using a coating device. Ma 50 was treated on a surface-treated PET film and dried by hot air in C for 10 minutes. Film-shaped adhesive a having an adhesive layer thickness of 10 / zm. J / In the following, in the above process for preparing a coating solution, a thin film coating was produced in the same manner as above except that the conductive layer that would form the Au layer + the Yatsuzaki battery was scattered in the solution. Cover the solution, and apply the solution on a one-sided and two-sided PET film with a thickness of 50 and a film. 'Dried with 7 generations of hot air for iq minutes ^ to a film-like adhesive with a thickness of 15 ” b. Then the obtained film-like adhesive b is heated on the machine, while the consumable layer μ device is used to make a laminated two-layer structure of each guide film., * AX ¥ The same implementation of this adhesive The measurement was performed in the same manner as in Example 1. The results are shown in Table 1. Next, using the obtained anisotropic conductive film, a gold flange (area ·· 50 × 50 // m, Interval · · 20 # m, height m flange number 362) wafer (1.7x17mm, thickness: 500
Am)同帶IT〇電路的玻璃基板（厚度·· 進行連 接。將各向異性導電薄膜（2x20mm)在8(TC，lMpa(10 公斤力/釐米2)的壓力下黏貼到帶IT0電路的玻璃基板 上後，剝離分離器，使晶片的凸緣和帶ΙΤ〇電路的玻 璃基板的位置吻合。隨後，在190°C，40克/每個凸緣， 16 200427811 ι〇秒的條件下由晶片上方進行加熱，加壓，從而實現 本連接。本連接後晶片的撓曲爲2·5//ιη。另外，連接 阻抗每一個凸緣爲最高80ΜΩ，平均爲30ΜΩ，絕緣 阻抗在108Ω以上。這些值即使在進行_4〇-1〇(rc的抗 熱衝擊试驗X000次迴圈處理，高溫，高濕（85。〇， 85%RH’ 1〇00小時）試驗後也沒有變化，表明其良好的 連接可靠性。 實施例三 將笨氧基樹脂（聯合碳化物公司（Uni〇n CarbideAm) Connected to the glass substrate with IT0 circuit (thickness ...). Anisotropic conductive film (2x20mm) was stuck to the glass with IT0 circuit under a pressure of 8 (TC, 1Mpa (10 kgf / cm2)). After the substrate was peeled off, the separator was peeled to match the position of the wafer's flange with the glass substrate with the ITO circuit. Subsequently, the wafer was removed from the wafer at 190 ° C, 40 g / flange, 16 200427811 μm. The upper part is heated and pressurized to achieve this connection. The deflection of the chip after this connection is 2.5 // ιη. In addition, each flange of the connection resistance is up to 80MΩ, the average is 30MΩ, and the insulation resistance is above 108Ω. These The value did not change even after carrying out the thermal shock test of _4〇-10 (rc for X000 cycles, high temperature, high humidity (85. 0, 85% RH '1000 hours) test, indicating that it Good connection reliability. The third embodiment is a bonoxy resin (Union Carbide
Ltd·)製，PKHC)50克，溶解在醋酸乙酯115克中，製 得3 0 %的溶液。 將具有固態重量比的苯氧基樹脂6〇克，2〇重量％ 的平均粒徑爲0.2// m的丙蟬酸粒子（儲存彈性率爲 3Mpa)分散在其中的雙酚a型環氧樹脂（環氧當量 180)25克，雙酚a型固態環氧樹脂（環氧當量· 185)5 克，P-醋酸苯基甲磺酸鹽（非求核性陰離 鹽)3克混合，再將在聚笨乙稀系核芯(直徑：二 表面形成金層的10體積％的導電粒子分散混合於其中 而製得薄膜塗覆用溶液。 ik後，使用塗覆裝置將該溶液塗覆在將厚度爲 A m的薄膜的單面進行表面處理後的PET薄膜上，在 7(TC經熱風乾燥1〇分鐘，從而製得黏結劑層的厚度爲 1 〇 m的薄膜狀黏結劑c。 隨後，在上述製作薄膜塗覆用溶液的過程中，除了 17 200427811 =有將形成Au層的導電粒子分散在溶液中這一點外， ’、餘用同上相同的方法製得薄膜塗覆用溶液，使用塗 覆裝置將該溶液塗覆到對厚度爲50 // m的薄膜的單面 進行表面處理後的pET薄膜上，在7〇它經熱風乾燥1〇 刀鐘，k π製得黏結劑層的厚度爲i5 v爪的薄膜狀黏 結劑d。 將所製得的薄膜狀黏結劑c和d在4〇它一邊加 熱’ 一邊用輥式層壓裝置製作層壓成二層結構的各向 異眭導電薄膜。關於該黏結薄膜同實施例一同樣地進· 行測定。其結果示於表1。 其-人，使用所製得的各向異性導電薄膜，如以下所 示將页金凸緣（面積：5〇χ5〇 “ m，間隔：2〇 # m，高度： “m’凸緣數362)的晶片（]_7xi7mm，厚度：500// 叫同帶1丁0電路的玻璃基板（厚度·· ilmm)進行連接。 將各向異性導電薄膜（2x2〇mm)在80°C，以1ΜΡΑ(1〇公 斤力/厘米2)的壓力黏貼到帶IT〇電路的玻璃基板上， 到離分離器’使晶片的凸緣和帶ΙΤ〇電路的玻璃基板馨 的位置吻合。隨後，在15(rc，4〇克/每個凸緣，1〇秒 的條件下由晶片上方進行加熱、加壓，從而實現本連 接。本連接後晶片的撓曲爲。另外，連接阻抗 每一個凸緣最高爲50ΜΩ，平均爲20ΜΩ，飽緣阻抗 在108Ω以上，這些值即使經-4〇-1〇〇〇c抗熱衝擊試驗 1〇〇〇次迴圈處理，高溫、高濕（85t /85%RH，1〇〇〇小 時）試驗後也沒有變化，表明良好的連接可靠性。 18 200427811 比較例一 使用沒有混合橡膠粒子的各向異性導電薄膜 FC-110A(曰立化成工業工股份有限公司製，膜厚·· 45# m)同實施例一進行比較試驗，其結果示於表1。 其次’使用上述薄膜狀黏結劑，如以下所示，將帶 金凸緣（面積：80x80//m，間隔：3〇em，高度：a# m’凸緣數288)的晶片（10x10mm，厚度：5〇〇"m)同鑛 Ni/Au的Cu電路印刷板進行連接。將薄膜黏結劑 (12x12mm)在80C，lMpa(10公斤/釐米2)的壓力下黏 貼到M Ni/Aii的Cu電路印刷板上（電極高度：2〇 # ^， 厚度：0.8mm)，剝離分離器後，使晶片的凸緣同鍍Ni/Au 的C u電路印刷板的位置吻合。隨後，在19 〇 ，7 5克 /每個凸緣，10秒的條件下由晶片上方進行加熱，加 壓，從而實現本連接。本連接後晶片的撓曲爲7.2// m(向晶片方向凸起的撓曲）。另外，本連接後的連接阻 抗爲每一個凸緣最高爲20ΜΩ，平均爲ι〇ΜΩ，絕緣 阻抗在108 Ω以上。連接阻抗經25。〇的抗熱衝擊 試驗1〇〇〇次迴圈處理，PCT試驗（121t，2MpA(2個 大氣壓））200小時，26〇°C的釺焊浴浸潰10秒鐘後除了 增大之外還産生一些連接不良的情況。 比較例二 使用將由厚度爲8//m的含有導電粒子的薄膜層和 19 200427811 厚度爲15// m的不含導電粒子的薄膜層構成的兩層結 構的不含橡膠粒子的各向異性導電薄膜AC%84〇1(日立 化成工業股份有限公司製，膜厚：23 # m)相對實施例 二進行比較試驗，其結果示於表i。 其-人’使用该各向異性導電薄膜，如以下所述將帶 金凸緣（面積：50x50 // m，間隔20// m，高度：15// m， 凸緣數362)的晶片（1.7x17mm，厚度：500 // m)和帶IT〇 電路的玻璃基板（厚度：進行連接。將各向異性 導電薄膜（2x20mm)在80°C，以IMPa的壓力黏貼到帶 ITO電路的玻璃基板上後，剝離分離器，使晶片的凸緣 和帶ITO電路的玻璃基板的位置吻合。隨後，在19〇 °C，40克/每個凸緣，10秒的條件下由晶片上方進行加 熱、加壓，實現本連接。本連接的晶片的撓曲爲8·2“ m，同實施例二相比撓曲增大-。Ltd.), 50 g of PKHC), dissolved in 115 g of ethyl acetate to prepare a 30% solution. 60 g of phenoxy resin having a solid weight ratio and 20% by weight of propionic acid particles having an average particle diameter of 0.2 // m (a storage elasticity rate of 3 MPa) were dispersed in the bisphenol a type epoxy resin (Epoxy equivalent 180) 25 g, bisphenol a solid epoxy resin (epoxy equivalent · 185) 5 g, 3 g of P-phenylacetic acid mesylate (non-nucleating anion salt), and mix A thin film coating solution was prepared by dispersing and mixing a polystyrene core (diameter: 10% by volume of conductive particles forming a gold layer on the two surfaces). After ik, the solution was coated on a coating device using a coating device. A PET film having a surface of a film having a thickness of A m was surface-treated and dried at 70 ° C. for 10 minutes with hot air to obtain a film-shaped adhesive c having a thickness of 10 m. In the process of making the above-mentioned thin-film coating solution, except for the point that 17 200427811 = dispersing the conductive particles forming the Au layer in the solution, ', and using the same method to obtain the thin-film coating solution, use The coating device applies this solution to the surface of one side of a film having a thickness of 50 // m On the treated pET film, it was dried by hot air for 10 knife minutes at 70, and k π was used to prepare a film-shaped adhesive d with a thickness of i5 v claw. The obtained film-shaped adhesive c and d It was heated at 40 °, and an anisotropic conductive film laminated into a two-layer structure was produced by a roll laminating apparatus. The adhesive film was measured and measured in the same manner as in Example 1. The results are shown in the table. 1. Its-person, using the anisotropic conductive film prepared, the sheet metal flanges (area: 50 × 50 ″ m, interval: 2〇 # m, height: “m 'flange number 362” ) Chip (] _7xi7mm, thickness: 500 // called a glass substrate (thickness · ilmm) with a 1-to-0 circuit. Connect an anisotropic conductive film (2x20mm) at 80 ° C with 1MPA ( The pressure of 10 kgf / cm2) was adhered to the glass substrate with IT0 circuit, and the flange of the wafer was aligned with the position of the glass substrate with ITO circuit to the separator. Then, at 15 (rc , 40 g / each flange, heating and pressing from above the wafer under the condition of 10 seconds, so as to realize the connection The deflection of the chip after this connection is. In addition, each flange of the connection impedance is up to 50MΩ, the average is 20MΩ, and the saturated edge impedance is above 108Ω. These values are even after the -40-1000c thermal shock test 1 There were no changes after high-temperature and high-humidity (85t / 85% RH, 10,000 hours) tests after 100,000 times of looping, indicating good connection reliability. 18 200427811 Comparative Example 1 An anisotropic conductive film FC-110A (manufactured by Li Kasei Industrial Co., Ltd., film thickness: 45 # m) was subjected to a comparison test with Example 1. The results are shown in Table 1. Next, using the above-mentioned film-shaped adhesive, as shown below, a wafer (10x10mm, thickness: 50) with gold flanges (area: 80x80 // m, interval: 30em, height: a # m 'number of flanges 288) 〇 " m) Connected to Cu circuit printed board of Ni / Au. The film adhesive (12x12mm) was adhered to a Cu printed circuit board of M Ni / Aii (electrode height: 2 ##, thickness: 0.8mm) under a pressure of 80C, 1Mpa (10 kg / cm2), and separated. After the device is placed, the flange of the wafer is aligned with the position of the Ni / Au-plated Cu circuit printed board. Subsequently, under the condition of 19,75 g / flange, heating is performed from above the wafer for 10 seconds, and pressure is applied to realize the present connection. The deflection of the wafer after this connection is 7.2 // m (the deflection protruding toward the wafer). In addition, the connection impedance after this connection is that each flange has a maximum of 20MΩ, the average is ιOMΩ, and the insulation resistance is above 108 Ω. Connection impedance via 25. 〇 Thermal shock test 10,000 cycles, PCT test (121t, 2MpA (2 atmospheres)) for 200 hours, immersion in a solder bath at 26 ° C for 10 seconds in addition to increase There are some bad connections. Comparative Example 2 uses an anisotropic conductive non-rubber particle having a two-layer structure composed of a thin film layer containing conductive particles having a thickness of 8 // m and a thin film layer containing no conductive particles having a thickness of 15 // m. The thin film AC% 84001 (made by Hitachi Chemical Co., Ltd., film thickness: 23 # m) was subjected to a comparative test with respect to Example 2, and the results are shown in Table i. Its-person 'uses this anisotropic conductive film, as described below, a wafer (1.7x17mm) with gold flanges (area: 50x50 // m, interval 20 // m, height: 15 // m, number of flanges 362) , Thickness: 500 // m) and glass substrate with IT0 circuit (thickness: connected. After anisotropic conductive film (2x20mm) is attached to the glass substrate with ITO circuit at 80 ° C, the pressure is 1 MPa. , Peel the separator to match the position of the wafer's flange with the glass substrate with ITO circuit. Then, heat and press from above the wafer at 19 ° C, 40 g / each flange, 10 seconds This connection is achieved. The deflection of the connected wafer is 8 · 2 "m, which is larger than that of the second embodiment.
20 200427811 表1 專案 實施例 1 實施例 2 實施例 3 比較例 1 比較例 2 反應開始溫度(°c) 90 90 80 90 90 反應結束溫度(°c) 190 200 240 206 205 固化反應的80%的結束 溫度(°C) 160 160 230 180 180 固化反應的60%的結束 溫度(°C) 145 145 160 160 150 直到固化反應的80%結 束的DSC的發熱量(焦耳 /克） 75 70 120 180 160 直到固化反應結束的 DSC的發熱量(焦/克） 90 85 150 200 200 '彈性率(25°C，Mpa) 600 600 200 2000 2000 21 200427811 【圖式簡單說明】 無20 200427811 Table 1 Project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Reaction Start Temperature (° c) 90 90 80 90 90 Reaction End Temperature (° c) 190 200 240 206 205 80% of the curing reaction End temperature (° C) 160 160 230 180 180 60% end temperature of curing reaction (° C) 145 145 160 160 150 150 Calorific value of DSC (Joules / gram) until 80% of curing reaction 75 70 120 180 160 Calorific value of DSC until the end of the curing reaction (joules / gram) 90 85 150 200 200 'Elasticity (25 ° C, Mpa) 600 600 200 2000 2000 21 200427811 [Brief description of the diagram] None