201213480 jy4U4pif 六、發明說明： 【發明所屬之技術領域】 本發明是有關於例如在電路基板或電子零件中用於形 成絕緣性接著劑層的接著劑樹脂組成物、其硬化物 麵。 镬者 【先前技術】 環氧樹脂的接著性、機械強度及電氣絕緣性優異，並 且藉由樹脂、硬化劑、改質劑等的組合而可具有適;於各 種用途的功月b。因此，％氧樹脂例如大多用作電路基板材 料、電子零件用接著劑、密封劑等。近年來，隨著電氣、 電子設備往咼性能化、高密度化發展，而要求針對來^捭 載於電路基板的電子零件的發熱的對策。因此，用以提^ 電路基板的散熱性的技術已提出，在電路基板用環氧樹= 組成物中填充控制了粒徑分布的高導熱性無機填料（例^ 專利文獻1、專利文獻2)。 ° 但是’對於電氣、電子材料領域的環氧樹脂組成物中 通常使用預先分散於組成财、並藉由加齡解而開始硬 化的潛伏性硬化劑。此種潛伏性硬化劑通常使用二氛^一 醯胺。二氰基二醯胺的適用期長，並具有優異的潛伏 另一方面，硬化溫度較高，且加熱時的硬化速度亦較慢， 因此通常併用硬化促進劑。硬化促進劑通常使用胺類二味 唑化合物等（例如參照專利文獻2)。 ’、 另外’亦提出了使用冻唾化合物作為環氧樹脂的硬化 劑的提案。例如在專利文獻3中揭示，包含使用2種以上 4 201213480 裱氧當量不同的環氣掠 上]500以下，且^月^並且表觀的環氧當量為250以 當量為2000以上大的環氧當量的環氧樹脂的環氧 合物的接著劑組成物。但=下旨混合物與咪唾化 物由於所使用的環^:二此專:文獻3的接著劑組成 玻璃轉移溫度（Tg)較：^當重幸父大’因此硬化物的 250以下的㈣⑻$低°另外揭示，表觀的環氧當量為 物作為比較例，味唾化合物加以組合的組成 (加熱後的耐電壓性、柔軟性、蝴^ [先前技術文獻] [專利文獻] 丨2文獻1]日本專利特開靈_348488號公報 文獻2]日本專利特開2〇〇7_246861號公報 [專利文獻3]日本專利第3洲63號公報 作、二二氰基二醯胺在環氧樹脂組成物中大多用 但是’在使用含有二氰基二_的環氧 的電路Ϊ成與配料金屬層接觸的絕緣性接著劑廣 赤去怨t板或電子零件巾’存在接著綱賴著力降低、 ;ι題的=降低而引起絕緣不良的情況’而要求針對所述 问題的對策。 【發明内容】 本發明的目的是提供一種硬化物具有優異的導執性， '且難以產生接著力或絕雜降低的接著麟缝成物。 本發明者等人獲得如下發現：在使用二氰基二酿胺作 201213480 jyn\jHpi{ 為硬化劑的環氧樹脂的接著劑層中， 敍離子成為遷移干預因子，而對電路基板等=二_的 成不良影響。並且發現，自咪唑類中選擇接著劑樹:!性f 的，劑’並將硬化物懷離子的 4而可解决上述問題，從而完成了本發明。 Ρ本發明的接著劑樹脂組成物含有下述成 樹腊=)，：含有下述成分⑷〜成分⑷的環氧系接著 (a) 環氧樹脂、 (b) 包含咪唑化合物的硬化劑、及 (c) 苯氧樹脂， 右50[其ft ^上Ϊ⑷成分是相對於環氧樹脂的總量而含 冰18内重置百分比）以上的環氧當量為150〜220的 氧樹脂的成分，氧系接著樹脂原料中的㈨ =的=相對於環氧系接著樹脂原料中的固體成分ι〇〇 重里伤而為2重量份〜；1〇重量份的範圍内】； 滿足下述條件a)〜條件〇的氧化錄末， a)最大粒控為120 μηι以下， 如㈣粉末f的結晶性球狀氧魅的比例為 的條^上述結晶性球狀氧化峰徑分布滿足以下〇 6 〜111 201213480 〇平均粒徑DSQ為35 μηι〜50 μιη、且[體積平均粒 徑]/[個數平均粒徑]為U〜2.0的範圍内的結晶性球狀氣 化銘在結晶性雜氧魅巾的含量為30 wt%〜50 wt%的 範圍内， 7 11)平均粒徑Dm為5 μιη〜15 、且[體積平均粒 徑]/[個數平均粒徑]為2.G〜35的範圍⑽晶性球狀氧化 鋁在、、、σ aa f生球狀氧化銘中的含量為糾％〜wt〇/。的 圍内，及 m)平均粒徑D%為〇 i μιη〜2的範圍内的結晶性 球狀氧化銘在結晶性球狀氧化針的含量為1()加％〜3〇 wt%的範圍内。 〇本發明的接著劑樹脂組成物中，上述咪唑化合物可為 2·苯基-4,5-二羥基甲基咪唑。 本發明的接著劑樹脂組成物中，上述⑻成分的含 量相對於接著㈣敵成物_體成分i⑻重量份可 重量份〜95重量份的範圍内。 ’ 本發明的硬化物是使上述接著麟脂組成物硬 成0 劑樹脂組成物在半硬 本發明的接著劑膜是將上述接著 化狀態下成形為膜狀而成。 [發明的效果] 本發明賴著·愧㈣物可形餘 =，、且能維持耐_的接著劑:者: 且使本發_接·樹敝絲硬化而韻硬化物具有優 7 201213480 異導熱性’ B階段成形品的柔軟性、可挽性得到改善，並 且可防止表面破裂。因此本發明的接著劑樹脂組成&可 佳，應用於例如電路基板、f子零件等的絕緣性接著劑層。 【實施方式】 3 以下，對本發明的實施形態進行說明。本發明 劑樹脂組賴含社述⑷成分的環㈣接著樹脂原料 =及^成分的氧化崎末<A)成分含有（a)環氧樹 :)硬化劑及（c)苯氧樹脂，並且接著劑樹脂組成物 硬化而成的硬化物中的銨離子為5〇重量卯瓜以下。 [(a)成分的環氧樹脂] 物制if明中的（a)成分的環氧樹脂在由接著劑樹脂組成 物1作、、色緣性接著劑層或接著劑膜時，賦予充 性、密接性、耐熱性、機械強度、加工性等。此（心成八 的環氧樹脂可無特別關地使用，例如可例示：雙齡^ 環氧樹脂、雙紛F型環氧樹脂、雙紛s型環氧樹脂、 型壤氧樹脂、萘型環氧樹脂、苯齡祕清漆型環氧 鄰甲=祕清漆型環氧樹脂、聯苯祕清漆型環氧樹^、 =甲烧型環氧樹脂、二環戊二婦型環氧樹脂、脂環式 衣乳树脂、溴化環氧樹脂等分子中具有2個以上 環氧樹脂。該些環氧樹脂可使用1種或2種以上^另$，、 關於環氧樹脂的純度’就提高耐電壓特性、耐 ，點而言’較佳為離子性雜質或水解性氣較少的環氧樹 f °而且’就防止製成B階段狀態的接著劑_的破裂的 觀點而言’相對於⑷成分的環氧樹脂100重量份，較佳 8 201213480 =c〇重量份以上，更佳為調 環負格!·日11 4 〕液體。藉由調配液態 机作為⑷成分的環氧樹脂，而可使B階乂 ：: 的接者劑膜的軟化點降低，並抑制表面的破裂。心 内、較=:°以上的環氧當量為， 車乂佳為i50〜綱的範圍内的環氧樹脂。此環氧 ^構成U)成分的全部環氧樹脂中佔5G wt%以 上的裱巩樹脂的環氧當量低於15〇 , 變高，溶劑溶解性降低，而難 η、 曰.、、、〇日日性 的全部㈣咖若在制（a)成分 f於22(i，目^位—5〇 Wt%以上的環氧樹月旨的環氧當量 ^ . ㈣魏組絲在硬化制朗轉移溫 度（Tg)降低的傾向。並且，在環 : =環的含量相對於環氧樹脂而小於5〇 情況下’亦產生與上述相同的問題。 谅鐘= Ϊ著㈣脂組成物硬化而成的硬化物的玻 璃轉移>皿度較佳為10(rc以上，更佳為剛。c〜i7〇ec的範 圍。硬化後的硬化物的玻璃轉移溫度小於1〇〇 心度以下，而有使抑制來自金屬配線 的金屬離子的產生的作用（耐遷移性）降低的傾向。另外， 硬化物的玻璃轉移溫度的測定例如可藉由以下方式實施。 201213480 首先，將料劑樹脂纟域物轉紅基酿劑製 wt%接者劑溶液後，塗佈於縱厚度⑼咖⑽ 1 mm魏樹郎上，於肌下乾燥5分鐘使溶劑蒸 Ϊ 接著劑塗佈面上重叠相同形狀的其他I樹脂 i樣下進行真空加熱壓製1小時，而製備出成為 者制硬化物膜。可使用動態黏彈性測定裝置，於 tt^^^1'®'1500^20000 ' 線，並將所^^述方式製備的試樣的溫度分散_曲 ^ (I) 度彻δ曲線的峰值溫度作為麵轉移溫 ㈣备(1\成分的環氧樹脂的含有糊如相對於⑷成分 =氧系接著樹脂原料的固體成分_量份^成刀 = i〜9G重量份_内，更佳為40重量份=重旦 2=多内於含量相餅上顧體成分二 階段狀態的作孝性降：刀貝:產生接者劑樹脂組成物的Β 埶性降低/降或硬化物變脆，接著力降低或耐 的'=對性降低等。另-方面，若環氧:脂 重量份， 耐熱性降低。 硬化衫分，喊生接著力降低或 [(b)成分的硬化劑】 分 ’由接化:彳是為了使環氧樹脂硬化而調配的成 時，賦予== = _乍絕緣性接著劑層或接著細 的絕緣性、密接性、耐熱性、機械強度等。 201213480 本發明中’硬化劑僅由咪唑化合物構成。咪唑化合物即便 在例如硬化時的熱處理中進行加熱亦不會使銨離子游離， 因此藉由僅使用咪唑化合物作為硬化劑，而可容易地將使 接著劑樹脂組成物硬化的硬化物中的錄離子的量抑制在 50重量ppm以下。咪唾化合物例如可列舉：2_甲基咪唑、 2-十一烷基咪唑、2-十七烷基咪唑、2_乙基_4_曱基咪唑、 :本暴_4,5·二羥基甲基 厶本基咪唑、4-曱基-2-苯基咪唑 — °米唾、2·苯基-4-曱基-5-經基曱基VI米cr坐等 上述咪唑化合物中，最佳為使用2_苯基_4,5_二羥基曱 基咪唑。通常在使用咪唑化合物作為環氧樹脂的硬化劑 時，由於料化合物的活性高而容易進行硬化反應，而有 難以控制硬化反應的情況。2_苯基_4,5_二羥基曱基咪唑在 分子内具有2個反應性較高的織，另一方面，亦有具有 因大體積官能基*抑制反紐的仙的苯基，目此可將作 劑的活性抑制在適度水平，並容易將硬化反應控制 在適度水平。另外，可藉由使用2_苯基_4,5_二羥基甲㈣ =硬化劑，而例如將接著劑樹脂組成物塗佈時的^度 s 又疋在較高水平。 又 通常在以環㈣脂為域分⑽餘成物巾，大 來作為硬化促進劑，但本發明的接著劑樹脂 制成物中，由於錢料魏合物料的物質作 ^因此可藉由環氧樹脂彼此的縮合反 劑 組成物硬化。此時認為，咪唾化合物結合 端（或環氧樹職此的縮合反射的㈣點曰 201213480 立發揮觸媒功能，而促進環氧樹脂彼此的縮合反應。根 ，此，反應特性，可使㈣化合物發揮出作為硬化劑的功 能’若與調配了加成型硬化劑成分的反應體系相比，則亦 可將作為硬化冑彳的調配量抑制在較低水平。如此_嗤化合 為觸媒型硬化劑，因此例如二氰基二醯胺或苯祕 樹料加成型魏織转糾，加成型硬化劑成 乳樹脂會優歧應，而難以引起環氧樹脂單獨的縮 产童H成分的硬化劑的含有率例如相對於⑷成分的 =氧系接者樹脂原料的固體成分刚重量份，較佳為2重 Γ二1 二重量份的範圍内，更佳為3重量份〜8重量份的 樹月匕的占右石i化劑的含置多於10重量份，則有將源自環氧 =====子的擔[另-方面，若硬化 使接菩ϊ j硬化反應不會充分地進行，而 吏接者力降低’或硬化時間變長而使用性降低。 佳：:Li(a; 2的魏樹脂與(b)成分的硬化劑的較 t較佳為2咖〜1G咖，更佳為3咖〜8 度的樹脂組成物。。出咏圍，則無法獲得具有充分機械強 [(c)成分的苯氧樹脂] 例如可列舉m型苯氧樹脂；二=氧 紛处型苯氧樹脂、雙w型苯型ϊ 12 201213480. 化雙㈣型苯氧樹脂、含财氧樹脂等。所使 脂的重量平均分子量例如較佳為1 〜 ^娜的範圍内，更佳為20，_〜100，_的範圍 苯氧樹脂的重量平均分子量小於10,000 a寺，會導致P f組成物的耐熱性、機械強度、可撓性降低。反之衣^ 土樹脂的重量平均分子量大於2〇〇，_，則除了導致：： 或與環氧胸 卜月漆時的黏度、或製成接著劑膜時的熔融· 表面狀3=接3層的加工性或接細 承透處的重量平均分子量是藉由凝膠 /曰析法（GPC)測定而得的聚苯乙稀換算的值。 成分的笨氧樹脂的含量例如相對於（A)成分的 樹;固體曰成分1〇°重量份，較佳為9。 笼备执t 更佳為15重1份〜70重量份的範圍内。若 本氧秘脂的含量多於9G重f份，則會導致在偷 溶解性降低H M h 料在有機溶劑中的 ^ (b) 劑膜時的炼轉心f卜’I成清漆時的黏度或製成接著 性、接著性降低?;二 =絕緣性接著劑層的加工 降低的情況。_ ㈣變差，*且亦有導致耐熱性 對於成物中’由於在(a)成分中相 配⑴成分的在此環氧樹脂中組合調 錢如曰作為必須成分，而可提高製作接著 13 201213480 =或接者劑膜時的可撓性，而且可彌補硬化物的耐熱性 *八ί本Γ月的接著劑樹脂組成物中，上述(a)〜（C) 或三笨基甲烷型環氧氧樹脂（多官能） Γ;220 的組合二最二== 作為㈦成分的笨氧樹脂的二(= 特:可：= ::r成=rr，可獲得優丄== 下黏度亦祕為維持在1W()pa.s V ’ '大^、 為併用環氧當量為丨5一範圍==: = 】。、與環氧當量為⑼〜220的範圍内的多 [(B)成分的氧化铭粉末] (B)成分的氧 本發明的接著劑樹脂組成物所調配的 化鋁粉末具有以下a)〜c)的特徵。 201213480 a)氧化艇粉末的最大粒後為12〇阿以下較佳為_ μιη以下。若氧化銘粉末的最大粒徑大於，卿則 ，緣性接著劑層的加雜不充分，絕緣層的表面狀態變 =處’最大粒徑是表示將氧化絲子的舰積設 100/。時’於粒徑的體積分率的分布曲線中按某粒徑以上 子的分布概率全為G時的粒㈣最小值。關於氧化 =的最大！徑的下限值’就高導熱化的觀點而言，由 卿!徑較大的氧化㈣末較為有利，因此較佳為例如55 全部氧化紹粉末中的9〇 Wt%以上為結晶性球狀氧 wt%以上為結晶性球狀氧化銘。氧她粉 貞例如可列舉結晶性氧錄、錄氧脑等，氧化 2=:?彳如可列舉球狀、破碎狀。本發明的接著劑 ί Ϊίί!，就藉由最密填充實現高導熱性的觀點而 用;=Γ氧化紹相比更加提高導熱率的效果=使 ^^ 呂而具有與破碎氧化鋁相比，更加降低f成 ==戈製成接著劑膜時的熔融上 於90王。 粉末中的結晶性球狀氧化銘的含有率少 骑則製成清漆時的黏度、或製成接著劑膜時的熔 特性、接著性降低，或表層的加工性、耐電壓 所示氧化_齡_以下〇 15 〜111 201213480 0平均粒徑D5〇為35 μηι〜50 μηι、且[體積平均較 徑]/[個數平均粒徑]為1.2〜2.0的範圍内的結晶性球狀氣 化鋁的含量為30wt°/〇〜5〇wt%的範圍内。 ii)平均粒徑Dsq為5 μπι〜15 μηι、且[體積平均粒 徑]/[個數平均粒徑]為2.0〜3.5的範圍内的結晶性球狀氧 化銘的含量為30 wt%〜50 wt%的範圍内。 y "叫议^50兩μιη〜2 的範圍, 一 球狀氧化鋁的含量為10wt〇/〇〜3〇wt%的範圍内。 ,此處，[體積平均粒徑]/[個數平均粒徑]是用作表示粒 ，分布的指標，且通常[體積平均粒徑]/[個數平均粒 徑]，此值越小則表示粒徑分布越窄，此值越大則表示 L刀布越寬。若結晶性球狀氧化紹的粒徑分布超出上述 卜則高導熱化不充分，表現不出充分的散熱性，此 製成π漆時的黏度、或製成接著劑膜時的縣黏度增 签二f作為絕緣性接著劑層的加工性、耐電壓特性、接 耆性降低’或表面狀態變差。另外，平均粒徑D 氧化鋁粒子的總體積設定為 ：：曰 累積曲線中達到累積鄕時的粒徑❾U體積/刀率在 ⑻另Γ八^上述〜e)的特徵外，在本實施形態卜 成分的t聿粉末相對於接著劑樹脂組成物的固體 固體成分_會曰t對於接著劑樹脂組成物的 圍内m 86重量份〜95重量份的範 ^ 1 尺住马88重量份〜的舌旦八 93重里份。接著劑樹腊組成物 201213480 t氧化鋁粉末的含有率越多，則越可實現高導熱化及低 ^祕化。若接著職驗成物的固體成分中的（B)成 二的氧化is粉末的含有率少於86wt%，則存在導熱性不充 刀，表現不出充分的散熱性的情況。另外，存在低熱膨脹 I1 生=充为，導致焊錫耐熱性降低的情況。另一方面，若（B) 成7刀的氧化崎末的含有率多於95wt%，則製成清漆時的 黏度增大2或製成接著繼時的㈣黏度增大，而使作為 絕緣性接著劑層的加讀、耐電壓特性、接著性降低，或 表面狀癌變差。 —另外，接著劑樹脂組成物的固體成分是指：例如在接 著劑知仏組成物為含有特定溶劑的清漆時，使用此清漆形 成絕緣性接著劑層等硬化物的過程巾，藉由祕或硬化而 去f容劑後所最終殘留的固體成分。此處，清漆為了降低 接著劑細a組成物的黏度*提高加王性而含有溶劑，最故 形成絕緣性接著·等硬化物後，藉由賴、減理而去 除溶劑。H)此，本發明的接著賴驗成物巾的成分的含 ，率使Z相對於接著觸脂組成物的固體成分的成分含有 率來規疋。另外，本發明的接著冑脂組成物除了作為必 3成刀的（A)及（B)成分外，亦有視需要調配任意成分BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive resin composition for forming an insulating adhesive layer on a circuit board or an electronic component, for example, and a cured surface thereof. [Prior Art] The epoxy resin is excellent in adhesion, mechanical strength, and electrical insulating properties, and can be suitably used by a combination of a resin, a curing agent, a modifier, and the like. Therefore, the % oxygen resin is used, for example, as a circuit board material, an adhesive for electronic parts, a sealant, and the like. In recent years, as electrical and electronic devices have become more sophisticated and higher in density, countermeasures against heat generation of electronic components mounted on circuit boards have been demanded. Therefore, in order to improve the heat dissipation of the circuit board, it has been proposed to fill a highly thermally conductive inorganic filler having a particle size distribution in the epoxy resin of the circuit board (Example Patent Document 1 and Patent Document 2). . ° However, for epoxy resin compositions in the field of electrical and electronic materials, latent curing agents which are pre-dispersed in composition and hardened by ageing are usually used. Such latent hardeners are generally used as a serotonin. Dicyanoguanamine has a long pot life and excellent latency. On the other hand, the hardening temperature is high and the hardening speed at the time of heating is also slow, so a hardening accelerator is usually used in combination. As the hardening accelerator, an amine-type dixazole compound or the like is usually used (for example, refer to Patent Document 2). The proposal to use a frozen salivary compound as a hardener for an epoxy resin has also been proposed. For example, Patent Document 3 discloses that an epoxy containing two or more kinds of 4 201213480 different oxygen equivalents is used, and the epoxy equivalent is 250 or more and the equivalent epoxy is 2000 or more. An epoxy resin binder composition of an equivalent epoxy resin. But = the mixture of the lower part and the sodium saliva due to the ring used ^: two special: the adhesive composition of the literature 3 composition glass transition temperature (Tg) compared: ^ when the weight of the father big 'so the hardened matter below 250 (4) (8) $ low Further, it is revealed that the apparent epoxy equivalent is a comparative example, and the composition of the salivary compound is combined (voltage resistance after heating, flexibility, and butterfly) [Prior Art Document] [Patent Literature] 丨 2 Document 1] Japanese Patent Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 2-246861 (Patent Document 3) Japanese Patent No. 3, No. 63, and didicyanodiamine in an epoxy resin composition Most of them are used but 'in the use of a circuit containing a dicyano-based epoxy to form an insulating adhesive in contact with the metal layer of the compound, and the red plate is used to reduce the number of plates or electronic parts. The problem is that the case where the problem is lowered and the insulation is poor is required. The present invention aims to provide a cured product having excellent conductability, and it is difficult to generate an adhesion force or a reduction in impurities. Then the sew is stitched into objects. The inventors obtained the following findings: in the adhesive layer of epoxy resin using dicyandiamide as 201213480 jyn\jHpi{ as a hardener, the sigma ion becomes a migration intervention factor, and on a circuit substrate, etc. It has been found that the above problem can be solved by selecting an adhesive tree from the imidazole class and selecting the adhesive agent, and the hardening agent is 4, thereby completing the present invention. The resin composition contains the following wax:), an epoxy-based (a) epoxy resin containing the following components (4) to (4), (b) a hardener containing an imidazole compound, and (c) a phenoxy resin. The composition of the oxygen resin having an epoxy equivalent of 150 to 220 or more in the right 50 [its ft ^ upper (4) component is a replacement percentage in the ice 18 with respect to the total amount of the epoxy resin), and the oxygen is followed by the resin raw material (9) = = is in the range of 2 parts by weight to 1 part by weight relative to the solid content of the epoxy-based resin raw material, and the oxidation condition is as follows: a) The maximum grain size is below 120 μηι, such as (four) the knot of powder f The ratio of the spherical oxidized glaze is the above-mentioned crystalline spherical oxidized peak diameter distribution satisfying the following 〇6 to 111 201213480 〇the average particle diameter DSQ is 35 μηι to 50 μιη, and [volume average particle diameter]/[number The average particle diameter is a crystal spherical gasification in the range of U to 2.0. The content of the crystalline heteroxia charm is in the range of 30 wt% to 50 wt%, and 7 11) the average particle diameter Dm is 5 μm. 〜15, and [volume average particle size] / [number average particle diameter] is in the range of 2.G to 35 (10) crystalline spherical alumina in the content of σ aa f globular oxidation %~wt〇/. Within the circumference, and m) the average particle diameter D% is in the range of 〇i μιη~2, and the content of the crystalline spherical oxidized needle is in the range of 1 () plus % to 3 〇 wt%. Inside. In the adhesive resin composition of the present invention, the imidazole compound may be 2,phenyl-4,5-dihydroxymethylimidazole. In the adhesive resin composition of the present invention, the content of the component (8) is in a range of from 95 parts by weight to the weight of the (iv) component (i) component (i). The cured product of the present invention is obtained by hardening the above-mentioned lining composition into a resin composition of a semi-hardening agent. The adhesive film of the present invention is formed into a film shape in the above-mentioned adhesive state. [Effects of the Invention] The present invention has an adhesive capable of maintaining the resistance of the 四(四), and is capable of maintaining the resistance of the _:: and the hair of the hair stalk is hardened and the sclerosing material has an excellent 7 201213480 The thermal conductivity 'B-stage molded article is improved in flexibility and manageability, and prevents surface cracking. Therefore, the adhesive resin composition of the present invention is preferably applied to an insulating adhesive layer such as a circuit board or a f-part. [Embodiment] 3 Hereinafter, an embodiment of the present invention will be described. The agent resin group of the present invention contains the ring of the component (4) (4), and then the resin raw material = and the component of the oxidized slag <A) component contains (a) an epoxy tree: a hardener and (c) a phenoxy resin, and The ammonium ion in the cured product obtained by curing the resin composition of the subsequent agent is 5 ounces or less. [Epoxy Resin of Component (a)] The epoxy resin of the component (a) in the composition of the present invention is used as the epoxy resin composition 1 as a binder, a color-based adhesive layer or an adhesive film. , adhesion, heat resistance, mechanical strength, processability, etc. This kind of epoxy resin can be used without special use. For example, it can be exemplified: double age ^ epoxy resin, double F type epoxy resin, double s type epoxy resin, type oxy-resin, naphthalene type Epoxy resin, benzene age varnish type epoxy phthalate = secret varnish type epoxy resin, biphenyl secret varnish type epoxy tree ^, = burnt type epoxy resin, dicyclopentane type epoxy resin, grease Two or more epoxy resins are contained in a molecule such as a ring-type latex resin or a brominated epoxy resin. These epoxy resins can be used in one type or two or more types, and the purity of the epoxy resin can be improved. In terms of voltage characteristics, resistance, and point, it is preferable that the epoxy resin f ° having less ionic impurities or hydrolyzable gas and 'in terms of cracking of the adhesive _ which is formed in the B-stage state are relative to (4) 100 parts by weight of the epoxy resin of the component, preferably 8 201213480 = c 〇 by weight or more, more preferably a ring-regulating granule! · Day 11 4 〕 liquid. By blending a liquid machine as the epoxy resin of the component (4), The softening point of the film of the B-stage 乂:: is lowered, and the crack of the surface is suppressed. Intracardiac, more than =: ° The oxygen equivalent is an epoxy resin in the range of i50~. The epoxy equivalent of 5g wt% or more of the epoxy resin constituting the U) component has an epoxy equivalent of less than 15〇. , becomes higher, solvent solubility is reduced, and it is difficult to η, 曰,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Epoxy equivalent of epoxy tree ^ (4) The tendency of the Wei group filament to decrease in the hardening temperature (Tg), and in the case of the ring: = ring content relative to the epoxy resin and less than 5 ' The same problem. The bell = the glass transition of the cured product obtained by hardening the (4) fat composition. The degree of the dish is preferably 10 (rc or more, more preferably the range of c~i7〇ec. The glass transition temperature of the cured product is less than 1 〇〇 centimeter, and the effect of suppressing the generation of metal ions from the metal wiring (migration resistance) tends to decrease. Further, the measurement of the glass transition temperature of the cured product can be performed, for example. It is implemented as follows: 201213480 First, the material resin is converted into a red broth. After the t% adapter solution, it was applied to a vertical thickness (9) coffee (10) 1 mm Wei Shulang, and dried under the muscle for 5 minutes to evaporate the solvent. The other coated surface of the same shape was coated on the coated surface to carry out vacuum heating. Pressing for 1 hour, and preparing a cured film of the product. The dynamic viscoelasticity measuring device can be used to measure the temperature of the sample prepared by the method of tt^^^1'®'1500^20000'. Dispersion_曲^(I) The peak temperature of the δ curve is used as the surface transfer temperature (4). (1) The content of the epoxy resin is as shown in the component (4) = the solid content of the oxygen-based resin material. Knife = i ~ 9G parts by weight _, more preferably 40 parts by weight = heavy denier 2 = more than the content of the phase cake on the two-stage state of the body composition of the filial drop: knife shell: the production of the resin composition The Β property is reduced/decreased or the hardened material becomes brittle, and then the force is reduced or the resistance is reduced. On the other hand, if epoxy: fat parts by weight, heat resistance is lowered. Sclerotherapy shirt, shouting force reduction or [(b) component hardener] Minutes: 彳 is the time to prepare for hardening the epoxy resin, giving == = _乍 insulating adhesive layer Or followed by fine insulation, adhesion, heat resistance, mechanical strength, and the like. 201213480 In the present invention, the hardener is composed only of an imidazole compound. The imidazole compound does not cause ammonium ions to be released even when heated, for example, in heat treatment at the time of hardening, so that by using only an imidazole compound as a hardener, the recording ion in the hardened body which hardens the adhesive resin composition can be easily obtained. The amount is suppressed to 50 ppm by weight or less. Examples of the stilbene compound include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-indolyl imidazole, and violent _4,5·dihydroxyl Methyl decyl imidazole, 4-mercapto-2-phenylimidazole-[R), 2, phenyl-4-mercapto-5- via fluorenyl VI mcr, etc. 2-Phenyl-4,5-dihydroxydecyl imidazole was used. In general, when an imidazole compound is used as a curing agent for an epoxy resin, a hardening reaction is easily performed due to a high activity of a compound, and it is difficult to control a hardening reaction. 2_Phenyl-4,5-dihydroxydecylimidazole has two highly reactive woven fabrics in the molecule, and on the other hand, there is also a phenyl group having a strong functional group* This can suppress the activity of the agent to a moderate level and easily control the hardening reaction to a moderate level. Further, by using 2_phenyl_4,5-dihydroxymethyl(tetra)-hardener, for example, when the adhesive resin composition is applied, the degree s is further increased. In addition, it is usually used as a hardening accelerator in the form of a ring (tetra) grease, which is used as a hardening accelerator. However, in the adhesive resin product of the present invention, since the material of the material of the weed material can be used, it can be used by the ring. The condensation resin composition of the oxyresin is hardened. At this time, it is considered that the binding end of the stilbene compound (or the condensed reflection of the epoxy tree (4) point 曰201213480 plays a catalytic function, and promotes the condensation reaction of the epoxy resins with each other. Root, this, the reaction characteristics can make (4) The compound functions as a curing agent. When compared with a reaction system in which a curing hardener component is blended, the amount of the hardening enthalpy can be suppressed to a low level. Thus, 嗤 嗤 is a catalytic hardening. Agent, for example, dicyanoguanamine or benzene secret tree material plus molding Wei weaving rectification, adding a molding hardener into a milk resin will be superior, but it is difficult to cause the epoxy resin alone to shrink the child H component hardener The content of the component is, for example, in the range of 2 parts by weight to 2 parts by weight, more preferably 3 parts by weight to 8 parts by weight, per part by weight of the solid content of the oxygen-based resin raw material of the component (4). If the content of the sputum of the sputum is more than 10 parts by weight, there will be a burden derived from the epoxy ===== sub-[in addition, if the hardening causes the hardening of the sputum j The ground is carried out, and the strength of the splicer is reduced or the hardening time is lengthened. The use of Li: a; 2 of the Wei resin and (b) component of the hardener is preferably 2 coffee ~ 1G coffee, more preferably 3 coffee ~ 8 degrees resin composition. However, it is impossible to obtain a phenoxy resin having a sufficient mechanical strength [(c) component], for example, an m-type phenoxy resin; a second-oxygen phenoxy resin; a double w-type benzene type ϊ 12 201213480. (4) a phenoxy resin, a hydroxy-containing resin, etc. The weight average molecular weight of the lipid is, for example, preferably in the range of 1 to Mn, more preferably 20, _ to 100, and the weight average molecular weight of the phenoxy resin. Less than 10,000 a temple will result in lower heat resistance, mechanical strength, and flexibility of the composition of P f. Conversely, the weight average molecular weight of the coating resin is greater than 2 〇〇, _, in addition to causing:: or with an epoxy chest The viscosity at the time of the lacquer or the melting at the time of forming the adhesive film. The surface shape 3 = the workability of the three layers or the weight average molecular weight at the fine penetration is determined by gel/decantation (GPC). The value of the obtained polystyrene conversion. The content of the component of the epoxy resin is, for example, relative to the tree of the component (A); Preferably, it is 9. The cage is preferably in the range of 15 parts by weight to 70 parts by weight. If the content of the oxygen secreted fat is more than 9 parts by weight, it may result in a decrease in the solubility of the HM h material. When the (b) film in an organic solvent is used, the viscosity at the time of varnishing or the adhesion and the adhesion are lowered. The second is the case where the processing of the insulating adhesive layer is lowered. (4) Variation, * and also cause heat resistance for the product "Because the compound (1) in the (a) component is combined with the money in the epoxy resin as a necessary component, and can be improved by the subsequent 13 201213480 = Or the flexibility of the film, and can compensate for the heat resistance of the cured product. In the adhesive composition of the month, the above (a) to (C) or the three stupid methane type epoxy oxide Resin (multi-functional) Γ; combination of two of 220 is the second most == as the (seven) component of the stupid resin of the second (= special: can be: = ::r into = rr, can get excellent 丄 == lower viscosity is also secret to maintain In 1W() pa.s V ' 'large ^, the combined epoxy equivalent is 丨5 a range ==: = 】. In the range of (9) to 220 in which the epoxy equivalent is in the range of (9) to 220, the oxygen of the component (B) is the oxygen of the component (B). The aluminum compound powder of the present invention has the following a) to c. )Characteristics. 201213480 a) The maximum grain size of the oxidation boat powder is 12 〇 or less, preferably _ μηη or less. If the maximum particle size of the oxidized powder is greater than that, the addition of the edge adhesive layer is insufficient, and the surface state of the insulating layer becomes = where the maximum particle size indicates that the oxidized filament is 100/. In the distribution curve of the volume fraction of the particle diameter, the particle (four) minimum value when the distribution probability of a certain particle size or more is all G. About oxidation = the biggest! From the viewpoint of high thermal conductivity, it is advantageous from the end of the oxidation (4) having a large diameter, and therefore, for example, it is preferable that, for example, all of the oxidized powders of 9 〇Wt% or more are crystalline globular The oxygen wt% or more is a crystalline spherical oxidation. Examples of the oxygen-containing powders include crystalline oxygen recording, oxygen recording brain, and the like, and oxidation 2 =: ?, for example, a spherical shape or a broken shape. The adhesive ί Ϊίί! of the present invention is used by the viewpoint of achieving the high thermal conductivity by the densest packing; the effect of further improving the thermal conductivity compared with the bismuth oxide = having a higher affinity than the broken alumina Further reduce the f ===g to the melting of the adhesive film on the 90th king. The content of the crystalline spherical oxide in the powder is less than that of the varnish when the varnish is formed, or the melting property and the adhesion at the time of forming the adhesive film are lowered, or the surface layer is processed and the voltage is resistant to oxidation. _The following 〇15 ～111 201213480 0The average particle diameter D5〇 is 35 μηι~50 μηι, and the [volume average diameter]/[number average particle diameter] is in the range of 1.2 to 2.0. The content is in the range of 30 wt ° / 〇 ~ 5 〇 wt%. Ii) the content of the crystalline spherical oxide in the range of the average particle diameter Dsq of 5 μπι to 15 μηι and the [volume average particle diameter] / [number average particle diameter] of 2.0 to 3.5 is 30 wt% to 50 Within the range of wt%. y " is called ^50 two μιη~2 range, a spherical alumina content of 10wt〇/〇~3〇wt%. Here, [volume average particle diameter] / [number average particle diameter] is used as an index indicating the distribution of particles, and generally [volume average particle diameter] / [number average particle diameter], the smaller the value Indicates that the narrower the particle size distribution, the larger the value indicates the wider the L-knife. If the particle size distribution of the crystalline spherical oxide is higher than the above, the thermal conductivity is insufficient, and sufficient heat dissipation is not exhibited. The viscosity when the π lacquer is formed or the county viscosity increase when the adhesive film is formed is used. The workability, the withstand voltage characteristics, and the joint property of the second f as the insulating adhesive layer are deteriorated or the surface state is deteriorated. In addition, the total volume of the average particle diameter D of the alumina particles is set to be: in the 曰 accumulation curve, the particle diameter when the cumulative enthalpy is reached ❾U volume/knife rate is (8) the other characteristics of the above-mentioned e), in this embodiment The solid content of the t聿 powder of the component with respect to the adhesive resin composition is 86t to the inner resin of the adhesive resin composition, 86 parts by weight to 95 parts by weight, and the weight of the horse is 88 parts by weight. The tongue is eighty-three. Next, the agent wax composition 201213480 t The higher the content of the alumina powder, the higher the thermal conductivity and the lower the secret. When the content of the (B) oxidized is powder in the solid content of the subsequent test product is less than 86% by weight, the thermal conductivity may not be filled, and sufficient heat dissipation may not be exhibited. In addition, there is a case where the low thermal expansion I1 is generated and the charge is lowered, resulting in a decrease in solder heat resistance. On the other hand, if the content of the osmium-containing slag of (B) is 7 knives is more than 95% by weight, the viscosity at the time of making the varnish is increased by 2 or the viscosity of the subsequent (4) is increased to be used as the insulating property. The addition of the agent layer, the withstand voltage characteristics, the adhesion, or the surface cancer are deteriorated. In addition, the solid content of the adhesive resin composition is, for example, a process towel obtained by using the varnish to form a cured material such as an insulating adhesive layer when the adhesive composition is a varnish containing a specific solvent, by secret or The solid component that is finally left after being hardened and removed. Here, the varnish contains a solvent in order to reduce the viscosity of the composition of the fine agent a, and the solvent is added to the varnish. The varnish is formed into a resin, and the like, and the cured material is removed. H) Here, the content ratio of the component of the present invention to the finished towel is such that Z is proportional to the component content ratio of the solid component following the lipophobic composition. Further, in addition to the components (A) and (B) which are required to be knives, the adhesive composition of the present invention may be formulated with optional components as needed.
的情況，此時，純括其他途徑調_任意成分而計算固 體成分量即可。 U 本實轭形恝的接著劑樹脂組成物除了上述（A)及（b) 的必須成分外，視需要還可調配例如溶劑、橡膠成分、复 他任意成分。. /、 17 201213480 jy^fu^pif [橡膠成分] +另外，本發明中的接著劑樹脂組成物中，就實現製成 接著劑膜或具備接著麵的銅箱時的膜支樓性提高或作為 絕緣性接著劑層的低彈性化的觀點而言，視需要可添加橡 膠成分。此種橡膠成分例如可列舉：聚丁二烯橡膠、丙烯 f-丁^二烯橡膠、改質丙稀腈·丁二烯橡膠、丙婦酸系橡膠 ，、。,该些橡膠可使用1種或2種以上。所使用的橡膠的重 量平均分子量例如可設定為10,〇〇〇〜1〇〇〇 〇〇〇，較佳為設 定為20,000〜500，_。此處，重量平均分子量是藉由Gpc 測，而得的聚苯乙稀換算的值。若橡膠成分的重量平均分 子量小於10,000,則會導致硬化物（接著劑層）的耐熱性、 機械強度、可撓性降低，並且亦有導致硬化前階段的膜支 撐性降低的情況。若橡膠成分的重量平均分子量大於 1，000,000，則於有機溶劑中的溶解性、與環氧樹脂及硬化 劑的相溶性降低’並且導致作#性降低，另外，製成清漆 時的黏度、或製成接著舰時的熔_度 絕緣性接麵的加工性、接著性降低，^面狀:^為 另外，關於时橡膠成分的橡膠的純度，就提^電壓特 I·生、耐濕可罪性的觀點而言，較佳為離子性雜質較少的橡 膠0 [其他任意成分] 另外’本發明的接著雜驗祕 低 ，提高等的觀點而言，視需要例如可添加氣= 氧系專的如包劑、均化劑等。並且就與金屬基板、銅配線 18 201213480 J構件的密?性提高的觀點w，例如可添加雜偶合 Μ、熱塑性寡聚物等密接性賦悄。而且 ::樹==’視需要可添力柄以外的無機填充 : W作為⑻成分的氧化铭粉末以外的填充 t無機填充劑例如可列舉：二氧切、氮㈣、氮化紹、 =化石夕、碳_、碳_等。料，有機填充劑例如可列 =·石夕粉末、域粉末、_腈_了二烯纟 =些填細，可使们種或2種以上。另外，本發明= 接者劑樹脂組成物卜視需要可調配 黑等著色劑。 月丁职貢監石反 上述任意成分中，就降低硬化物中的銨離子 為使用分子結構中不含胺基，或者胺』 [組成物、清漆] 士發_接著麵驗·可藉心合上述必 及任思成分而製備。此時，較佳為製成含 H即本發明的接著劑樹脂組成物可溶解或分散 ^谷刮而形成清漆。此處可使用的溶劑可例示：νν· 2酿胺⑽F )、Ν，Ν_二甲基乙酿胺、Ν_甲基心二比:： 等嶋溶劑’ 甲氧基_2_丙醇等驗系‘ _洛劑’甲苯、二甲苯等芳香族系溶劑等的i種或^ =加以混合而得的溶劑。關於（b)成分的硬化 成/刀的氧化崎末、視需要响加的任意成分中的無) 19 201213480 ^^-τυ-rpif 機填充劑、有機填充劑、著色劑等，若會均勻地分散 劑中，則可不必溶解於溶劑。 ' 清漆例如可根據以下所示的順序製備。首先 備授拌機的容器檀拌（c)成分的笨氧樹脂並溶解於^當^ ，劑。接著，在此溶液中混合（a)成分的環氧樹脂、㈦ 成为的硬化劑、還有任意成分’進行獅並溶解。另外， 根據（a)成分的環氧樹脂的種類，可另 I溶解了環氧顏的狀_溶液，並將該些 二f著’在此混合溶液中舰⑻成分的氧化銘粉末 清漆的黏度較佳為l_Pa.s〜2_〇Pa.s的範圍内， 更佳為2000 Pa · s〜10_ Pa · s的範圍内。在清漆的黏产 小於1000 Pa · s時，科產生氧她粉末的崎並且^ ^生塗佈時的不均或收縮等。另一方面，在清漆的黏度 於20000 Pa · s時，由於流動性降低，而塗佈性降低， 而難以製作均勻的塗膜。由於（B)成分的氧化崎末具 備遂& ) C)的特徵，因此容易將清漆的黏度調節至上 述範圍内。 [接著劑膜、具備接著劑膜的銅箔] 本發明中’將上述清漆塗佈於作為支禮材料的基礎膜 上’並進行乾燥’藉此可形成8階段狀態的接著劑膜。並 且’將上述清漆塗佈於銅羯上並進行乾燥，藉此亦可形成 具備接著劑臈的銅羯。此處，接著劑膜的厚度並無特別限 201213480 設定為刚μΓη〜3°〇 _的範圍内°Β階段狀 L的接者綱（具備接著麵_)若在f折時在表面 ^生，裂（龜裂）’則作為製品的價值會受損。此種B階 的表面破裂藉由在常溫下調配大量的固體樹脂成分 而谷易發生。就降低硬化物中的銨離子的含量的觀點而 '，亦考慮制苯騎料漆系硬·，但由於通常苯驗 祕清漆系硬化劑為固體，因此容易產生表面破裂。但是， 本發明的接著劑膜（具備接著劑膜的銅箱）中，由於僅使 m物作為硬化劑，因而可將固體樹脂成分在環氧 、、“者^月曰原料中所佔的比例抑制在較低水平。另外，至 2唾化合物’若與魏例如純祕清漆系硬化劑成分 的情形相比，則由於亦可將作為硬化劑的調配量抑制在較 且能於常溫下調配更多的液態或半固體成分， ^可^兩β階段狀態的柔軟性、可撓性，並防止表面破 聚0 另外’關於接著劑膜、或具備接著劑膜的銅箱（硬化 二）的，支撐性’溶劑殘存率越高則膜支擇性越良好的傾 y但是’若溶劑殘存率過高’則接著劑膜、或具備接著 f膜的銅箱（硬化前）會產生赦糟、或於硬化時產生氣泡。 =’溶劑殘存率較佳為5 wt%以下。另外，溶劑殘存率 j i8iC環境下進行賴6G分鐘時藉由接著綱部分的 貫質重里減少率的測定而求得的值。 另外二上述接著劑膜及具備接著劑臈的銅羯可藉由以 式而得：將不含溶劑的接著劑樹脂組成物於加熱炫融 21 201213480 狀癌作為支撐材料的基礎膜上’然後進行冷卻。 料，例如可:】:膜膜的鋼箱時所用的支撐材 钔噹4 聚十本—曱酉欠乙二酯（PET)、聚乙烯、 =〜、=、脫模紙等。支撐材料的厚度例如可設定為1〇 時，金屬使用軸、銘料金屬_作為支撐材料 $此今解法、壓延料而製造。另外， 就提高與概層的接紐峨點而言，較 佳為對與絕緣層接觸之_面進行粗化處理。 ’接著舰或具備接著舰的㈣在貼合於作為 ff材料的基礎膜上後，亦可使⑽為保護材料的膜覆蓋 的;早觸的另一個面，捲繞成輥狀而保存。此時所用 :呆:土材料例如可列舉聚對苯二甲酸乙二酯、聚乙烯、脫 、、”氏專。㈣保護材料的厚度例如可設定為⑺卿〜刚 [硬化物] 本發明的硬化物例如可藉由在由接著劑樹脂組成物製 備上述B階段狀態的接著劑膜（或具備接著劑膜的銅笛） 後’加熱至例如150。(：〜2坑的範圍内的溫度並進行硬化 而製造。以此種方式獲得的硬化物可抑制銨離子（NH/) 的含量。即本發明的硬化物中的銨離子的含量為5〇 ^量 ppm以下’更佳為25重量ppm以下。藉由將絲子抑制 在50重量pPm以下，而即便在使用硬化物作為與金屬配 線接觸的接著劑層時，亦不會誘導金屬離子的產生，而可 有效地抑制導致接著不良或絕緣不良的遷移。 22 201213480 jynuHpif —另外，硬化物十的銨離子的含量可藉由在純水中加熱 卒5將？化物粉’而成的粉末’並供於離子層析法而測定 所知·的萃取水的銨離子濃度。銨離子的含量以相對於硬化 物的銨離子的重量分率（重量ppm)表示。 、另外，本發明的硬化物的導熱率例如較佳為7 w/mK 以上，更佳為10 W/mK以上。通常若硬化物的導熱率小於 I W/mK’則為了散熱蝴如必触法在基板上形成熱通道 荨，藉由使硬化物的導熱率大於7 w/mK，而使散熱特性 優異而可應用於南溫環境下所使用的電路基板等。此種 優異的導熱率可藉由以滿足上述&)〜e)的方式控制（B) 成分的氧化鋁粉末的粒徑分布與含量而獲得。 [金屬基礎電路基板的製造方法] 接著，對使用本發明的接著劑樹脂組成物製造金屬基 礎電路基板的方法的—舰行說明。此處，例示使用銘基 板的紹基j電路基板。首先，祕著雜脂組成物獲得上 述具備接著鑛的銅驗，使祕次絲空壓製機將此具 備接著劑膜的銅箔於鋁基板上於例如溫度15(TC〜 25^C、壓力ι·〇 MPa〜3〇 Mpa的條件下接著。此時，使 接著劑膜面触基板面接觸，在將作為 為上面的㈣下精加熱、加壓，藏職樹脂硬化； 貼附於!g基板上。如此可獲得將接著劑膜作為絕緣性接 Γ劑層而介隔存在於銅㈣與絲板之間的積層體。接 著藉由I虫刻去除特定部位的銅箱而形成電路配線，而最 終獲得IS基礎電路基板。另外，關_基板的厚度，並無 23 201213480 jy^fu^pif 特別限制，通常例如可設定為0.5 mm〜3.0 mm。 為了使用本發明的接著劑樹脂組成物而獲得 5的導體層、絕紐接著_及@層的喊礎電路 除了上述方法外，亦可採用：於銘基板二， ^接著劑層上載置_進行加熱、减並硬化$層·， 或者於銘基板面形成絕緣性接著劑層 = :形f銅導體層的方法。另外，關於此時的接著 你使用.塗佈清漆後藉由加熱使溶劑揮發的方法、塗 =了糾]_料的方法或貼合接著綱的方法的任—種方 在以上述方式製造的金屬基礎電路基板中， 與銅箱的剝離強度例如較佳4G5 kN/m以上，更^層 kWm以上。此種練離強度可藉由完全献上述（b) 为的硬化劑的含量及與⑻成分的氧化歸末有關的= ^ ^條件而獲得。在不滿足⑴成分的硬化劑的含量 成分的氧化崎末的a)〜e)的條件任一種時， =_與_關離強度會小於…驗 基板等料所㈣密接力不足。 ^夂電路 [作用] 在壤氧樹脂組成物中大多用作潛伏性硬化劑的 二醯胺’例如具有會因麵使用時的元件的發熱而 ^中發Ϊ掘2基游離’而容易產生銨離子的性質。因此 氰基二醯胺作為環氧樹脂組成物的硬化劑形成電 土板或電子零件的接著劑層時，由二氰基二醯胺生成的 24 201213480 子在製品:使τ 銨鹽而將陰離子併入“:::機:：與 上，并入至接著劑層中的陰離子在反覆高溫高濕 认下會逐漸游離，而誘導產生來自金屬配線的金 屬離子，iHI起導致_不良的遷移。 在本發明的接著劑樹脂組成物中，由於僅使时嗤化 =勿作為硬化劑’因而可將硬化物巾成為遷移干預因子的 ，離子的里抑制在5〇重量ppm以下，因此即便是在用作 與金屬配線接_接著㈣時，亦不會料金屬離子的產 生，而可有效地抑制導致絕緣不良的遷移。 實例 、=了，藉由實例對本發明進行具體地說明，但本發明 並不乂η亥些實例任何限定。另外，以下實例中，只要無特 別說明，各制^是依據如下所述。 、 [清漆黏度] 清漆黏度是設定為使用Β型黏度計4號轉子於23ΐ、 6 rpm下測定所得的接著冑_旨喊物的清漆的黏度時的 測定值（Pa· s；)。 [清漆中的沈降] 清漆的沈降是將400 g接著劑樹脂組成物的清漆於 500 ml二角燒瓶中於23°C放置7日及1個月，並確認三角 燒瓶底有無氧化鋁粉末的沈降物，將有高度為1〇 mm以上 的沈降物的情形評價為「有」，將沈降物的高度小於 10 mm 25 201213480 的情形評價為「無」。但即便在沈降物的高度小於i〇咖 時’將沈澱物變硬且藉由搜拌亦恢復不到原來的狀態的情 形亦判定為「有」。 [銨離子（NH4+)] 藉由歷縮壓製成型機將B P皆段的接著劑膜於18〇。〔加 熱硬化1小時而獲得硬化物。將粉碎此硬化物而得的粉末 1 g於50 cc的純水中加壓並於加熱溫度12Γ(：萃取2〇小 寺—藉由DIONEX公司製造的離子層析測定裝置DX_3〇〇 對萃取水進行處理而測定銨離子濃度。銨離子的含量設定 為相對於硬化物的銨離子的重量分率（重量ppm)。 [塗佈性] 藉由刀塗機以乾燥後的厚度為130 μηι的方式將接著 劑樹脂組成物的清漆塗佈於Ρ Ε τ膜上，將塗佈面均勻的情 形評價為「良」，將產生條紋或不均等外觀缺陷的情形評價 為「不良」。 [導熱率] 使用特疋篁的Β階段的接著劑膜，藉由壓縮壓製成形 機於180°C加熱1〇分鐘，自壓製機取出後，再於乾燥機中 於180°C加熱50分鐘，藉此獲得直徑50 mm、厚度5 mm 的圓盤狀試驗片。使用英弘精機製造的導熱率測定裝置 HC-110 ’猎由一慣的方法測定此試驗片的導熱率（谓瓜· K)。 [剝離強度] 將B階段的接著劑膜重合於銅箔上，使用批次式真空 26 201213480^ 壓製機，於壓力10MPa、最高溫度18叱維持】小時的溫 度刀布中’壓製於厚度丨5 mm的紹基板上並進行硬化。 此時，使接著_面油基板面接觸，在將銅羯設定為上 面的狀態下進行加壓而貼附於紹基板上。料，根據瓜〇 續（剝離強度）實施試驗。即將如上述方式製作的試驗 片切取成基於上述標準的形狀，使用TENSIL〇N試驗機 (Onentec製造的RTA_25〇)，將銅箔成9〇度方向以速度 50 mm/分鐘的條件拉伸，藉此測定9〇度銅箔剝離強度 (kN/m )。 [B階段破裂] 將B階段的接著劑膜沿著直徑5 mm的圓棒彎曲丨⑽。 時，將膜表面無異常的情形評價為「無」，將確認到產生龜 裂的情形評價為「破裂」。 [耐濕可靠性] 在作為試驗基板的B階段的接著劑膜的兩面重合銅 箔’使用批次式真空壓製機，於壓力1〇 MPa、最高溫度 180°C維持1小時的溫度分布中進行熱壓接，而製作兩面銅 箔的積層板。藉由蝕刻於此積層板的單面形成線寬2〇〇 μπι、間隔200 μιη的網格圖案。將此積層板切割成2 em見 方後，於上下的銅箔部分安裝偏壓施加用配線。對此試驗 基板於122°C、2大氣壓、濕度100%的壓力鍋試驗機中施 加72小時的直流50 V的電壓。將初始的電阻值作為基準， 將試驗後的電阻值降低20%以上的情形評價為「不良」， 將試驗後的電阻值的降低小於20%的情形評價為「良」。 27 201213480 jy^unpif [實例1〜實例6、及比較例1〜比較例13] 接著劑樹脂組成物、及用於製作接著劑膜的原料及其 簡稱如以下所述。 (A )環氧系接著樹脂原料 (a) 環氧樹脂 環氧樹脂（1) ··雙酚A型環氧樹脂（東都化成製造、 YD128、環氧當量W9、液態） 環氧樹脂（2) ·雙盼F型環氧樹脂（東都化成製造、 YDF-170、環氧當量170、液態） 環氧樹脂（3):鄰甲酚酚醛清漆環氧樹脂（日本化藥 製造、EOCN-1020-55、環氧當量2〇〇、軟化點55。〇) 環氧樹脂（4):三苯基曱烷型環氧樹脂（曰本化藥製 造、EPPN-501H、環氧當量no、半固體） %氧樹脂（5):雙酚A型環氧樹脂（新日鐵化學製造、 YD-011、環氧當量470、固體） (b) 硬化劑 硬化劑（1广2-乙基-4-曱基咪唑 硬化劑（2) : 2-苯基咪唑 硬化劑（3) : 2-曱基咪唑 硬化劑（4):苯酚酚醛清漆（群榮化學工業製造、 PSM-4261、酚性羥基當量1〇5、軟化點8〇艺） 硬化劑（5):二氰基二醯胺 硬化劑（6) : 2-苯基-4,5-二羥基曱基咪唑 (c) 笨氧樹脂 28 201213480 苯氧樹脂（1):雙酚A型苯氧樹脂（東都化成製造、 YP-50 ) 苯氧樹脂（2):雙酚AF型苯氧樹脂（東都化成製造、 YP-70 ) 苯氧樹脂（3):雙酚S型苯氧樹脂（東都化成製造、 YPS-007 ) (B)氧化鋁粉末 氧化鋁粉末（1): 球狀、結晶性、最大粒徑：100 μηι、平均粒徑D5〇: 45 μηι、體積平均粒徑MV : 49 μιη '個數平均粒徑MN : 38 μιη、MV/MN : 1.3 氧化鋁粉末（2): 球狀、結晶性、最大粒徑：68 μηι、平均粒徑d5〇 : 11 μιη、體積平均粒徑MV : 12 μιη、個數平均粒徑MN : 4 3 μιη ' MV/MN ： 2.8 氧化鋁粉末（3): 球狀、結晶性、最大粒徑：7 μπι、平均粒徑d5〇:〇 4 μπ1、 體積平均粒徑MV : 0.7 μιη、個數平均粒徑ΜΝ : 」μιη、 MV/MN ： 6.7 [氧化铭粉末的粒徑分布參數] ，測定對象的氧化紹粉末以試樣濃度為〇 〇4 wt%的方 式稱里並混合於作為分散介質的〇 2 wt%六偏磷酸鈉溶液 中’使用超音波均化ϋ分散3分鐘。使錄度分布測定裝 置MiCrotrac ΜΤ3300ΕΧ (曰機裝製造），利用藉由波長78〇 29 201213480 nm的半導體雷射的照射而得的散射光測定此氧化紹分散 液的粒徑分布。 最大粒徑是表示在藉由上述測定法而得的粒徑分布中 將粒子的總體積設定為100%時，於粒徑的體積分率的分 布曲線中，按某粒徑以上計，粒子的分布概率全為〇時的 粒徑的最小值。 平均粒控D5〇是表示在藉由上述測定法而得的粒徑分 布中’將粒子的總體積設定為100%時，於粒徑的體積分 率的累積曲線中達到累積50%時的粒徑。 體積平均粒徑（MV)是表示根據藉由上述測定法而 得的粒徑分布而求出的「體積加權平均粒徑」。Mv由式（丄） 表示。 Μν = Σ (di^Vi) (l) 門二中粒徑分布用直方圖表示，山為直方圖的第1受 M曰的代表粒徑，Vi為屬於第丨號區間的粒子的體積分率 的敕平均粒把（MN)表示根據藉由上述測定法而率 叙it布而求出的「個數加權平均粒徑」。此處將假想备 ’王冲假定為球形，並根據式（2)求出MN。 ΜΝ==Σ (VM2) /Σ (Wd，）...... (2) 其中，4為直方圖的第丨號區間的代表粒徑，％為屬 201213480 於第1號區間的粒子的體積分率。 & [體積平均粒技]/[個數平均粒徑]用作表示粒徑分布的 指標。通常[體積平均粒徑]/[個數平均粒徑⑷，此值越小 則表示粒齡布鱗，此錢賴表雜徑分布越寬。 (C)硬化促進劑 硬化促進劑（1): 2_乙基_4•曱基咪唑 以表1〜表5所示的比例調配上述原料。首先，藉由 具備搜摔機的容器僅將苯氧樹脂於曱基異丁基酮（mIBK) 中攪拌、溶解。（其中，於存在環氧樹脂（2)時，與苯氧 ，脂的MIBK溶液不同，僅準備環氧樹月旨⑺的MIBK 溶液，並於苯氧樹脂的MIBK溶液中混合）接著，於此 溶液巾調配環氧獅⑴或⑵（其巾在調配環氧 樹月曰（3)〜環氧樹脂（5)的情況下，亦調配環氧樹脂（3) 〜環氧樹脂（5))、硬化劑（其中，在調配硬化促進劑〇) 的情況下，亦調配硬化促進劑（1 ))，並授拌、溶解。然後， 於此混合溶液中調配氧化鋁粉末，進行攪拌、分散，而製 作接著劑樹脂組成物的清漆。將此清漆以乾燥後的樹脂層 的厚度為ΙΟΟμιη的方式塗佈於厚度50μηι的脫模處理ρΕΤ 膜（三菱化學製造、MR-50)上，於i1(^c乾燥5分鐘， 藉此製作B階段的接著劑膜。 將結果示於表1〜表5。另外’表中環氧樹脂、硬化劑、 硬化促進劑、苯氧樹脂、氡化鋁粉末、及溶劑（mibk) 的調配量以重量份表示’氧化銘含有率以相對於接著劑樹 脂組成物的總固體成分的重量百分比表示。 31 201213480 [表1] 實例 1 2 3 4 5 6 環氧樹脂（1) 50.0 50.0 50.0 50.0 55.0 環氧樹脂（2) 50.0 環氧樹脂（3) 25.0 25.0 25.0 25.0 25.0 25.0 硬化劑（1) 5.0 5.0 5.0 5.0 硬化劑（2) 5.0 硬化劑（3) 5.0 硬化劑（4) 硬化劑（5) 硬化促進劑（1) 苯氧樹脂（1) 20.0 20.0 20.0 20.0 笨氧樹脂（2) 20.0 苯氧樹脂（3) 15.0 氧化鋁粉末（1) 532 532 532 532 532 532 氧化鋁粉末（2) 532 532 532 532 532 532 氧化鋁粉末（3) 266 266 266 266 266 266 氧化鋁含有率wt% 93 93 93 93 93 93 MIBK 160 160 160 160 180 160 清漆黏度Pa · s 2400 3100 2400 2100 4200 2200 清漆中的沈降（7曰） 無 無 無 無 無 無 清漆中的沈降（1個月） 有 有 有 有 無 有 NH4+ wtppm 21 20 20 22 20 21 塗佈性 良 良 良 良 良 良 導熱率W/m · K 10.3 10.5 10.3 10.6 10.0 11.3 剝離強度kN/m 1.0 1,1 1.0 1.0 1.2 1.1 B階段破裂 無 無 無 無 無 無 耐濕可靠性 良 良 良 良 良 良 32 201213480 [表2] 實例 7 8 9 10 11 環氧樹脂（1 ) 50.0 50.0 50.0 環氧樹脂（2) 50.0 50.0 環氧樹脂（3) 25.0 25.0 環氧樹脂（4) 25.0 25.0 環氧樹脂（5) 25.0 硬化劑（6) 5.0 5.0 5.0 5.0 5.0 硬化促進劑（1) 苯氧樹脂（1) 20.0 20.0 20.0 20.0 20.0 苯氧樹脂（2) 苯氧樹脂（3) 氧化鋁粉末（1) 532 532 532 532 532 氡化鋁粉末（2) 532 532 532 532 532 氧化鋁粉末（3) 266 266 266 266 266 氧化鋁含有率wt°/〇 93 93 93 93 93 MIBK 160 160 160 160 160 清漆黏度Pa · s 3800 3200 4000 3400 2800 清漆中的沈降（7曰） 無 無 無 無 無 清漆中的沈降（1個月） 無 無 無 無 有 NH4+ wtppm 21 21 20 19 21 塗佈性 良 良 良 良 良 導熱率W/m . K 10.1 10.3 10.2 10.3 10.3 剝離強度kN/m 1.0 1.0 1.0 1.0 1.0 B階段破裂 無 無 無 無 無 耐濕可靠性 良 良 良 良 良 33 201213480 [表3] 比較例 1 2 3 4 5 6 環氧樹脂（1 ) 50.0 50.0 50,0 54.8 54.0 環氧樹脂（2) 50.0 環氧樹脂（3) 25.0 25.0 25.0 25.0 25.0 25.0 硬化劑（0 5.0 5.0 5.0 0.2 1.0 硬化劑（2) 5.0 硬化劑（3) 硬化劑（4) 硬化劑（5) 硬化促進劑（1) 苯氧樹脂（1) 20.0 20.0 20.0 20.0 20.0 20.0 苯氧樹脂（2) 苯氧樹脂（3) 氧化鋁粉末（1) 665 665 665 532 532 氧化4S粉來（2) 665 665 1064 665 532 532 氧化鋁粉末（3) 266 266 266 氧化鋁含有率wt% 93 93 93 93 93 93 MIBK 160 160 160 160 160 160 清漆黏度Pa · s 700 500 4500 1300 1900 2000 清漆中的沈降（7曰） 沈降 沈降 無 無 無 無 清漆中的沈降（1個月） 沈降 沉鋒 沈降 沈降 沈降 沈降 NH: wtppm 20 21 21 20 19 24 塗佈性 不良 不良 良 良 良 良 導熱率W/m · K 6.5 6.5 6.8 6.8 8.5 8.9 剝離強度kN/m 0.3 0.3 1.0 0.3 0.0 0.1 B階段破裂 無 無 無 無 無 無 耐濕可靠性 良 良 良 良 良 良 34 201213480 [表4] 比較例 7 8 9 10 11 12 13 環氧樹脂（1) 54.8 39.3 39.3 49.9 環氧樹脂（2) 54.8 54.8 38.7 環氧樹脂（3) 25.0 25.0 25.0 19.6 19.6 19.5 25.0 硬化劑（1) 0.2 0.2 硬化劑（2) 0.2 硬化劑（3) 硬化劑（4) 20.9 20.9 21.6 硬化劑（5) 4.9 硬化促進劑（1) 0.2 0.2 0.2 0.2 苯氧樹脂（1) 20.0 20.0 20.0 20.0 20.0 苯氧樹脂（2) 20.0 20.0 苯氧樹脂（3) 氧化鋁粉末（1 ) 532 532 532 532 532 532 532 氧化鋁粉末（2) 532 532 532 532 532 532 532 氧化鋁粉末（3) 166 166 166 166 166 166 166 氧化Is含有率wt°/〇 93 93 93 93 93 93 93 MIBK 160 160 160 160 160 160 160 清漆黏度Pa · s 1700 1400 1600 5300 5000 4800 2100 清漆中的沈降（7曰） 無 無 無 無 無 無 無 清漆中的沈降（1個月） 沈降 沈降 沈降 沈降 沈降 沈降 沈降 NH4+ wtppm 20 20 21 18 18 19 210 塗佈性 良 良 良 良 良 良 良 導熱率W/m · K 8.5 8.5 8.2 9.8 10.0 9.9 9.9 剝離強度kN/m 0.0 0.1 0.0 0.9 0.9 0.9 1.0 B階段破裂 無 無 無 破裂 破裂 破裂 無 财濕可靠性 良 良 良 良 良 良 不良 35 201213480 39404pif [表5] 比較例 14 15 16 17 環氧樹脂（1) 35.0 35.0 環氧樹脂（2) 35.0 35.0 環氧樹脂（3) 環氧樹脂（4) 環氧樹脂（5) 40.0 40.0 40.0 40.0 硬化劑（1) 5.0 5.0 硬化劑（2) 硬化劑（3) 硬化劑（4) 硬化劑（5) 硬化劑（6) 5.0 5.0 硬化促進劑（1) 笨氧樹脂（1) 20.0 20.0 20.0 20.0 苯氧樹脂（2) 笨氧樹脂（3) 氧化鋁粉末（1) 532 532 532 532 氧化鋁粉末（2) 532 532 532 532 氧化鋁粉末（3) 266 266 266 266 氧化鋁含有率wt% 93 93 93 93 MIBK 160 160 160 160 清漆黏度Pa · s 5200 6100 4800 5400 清漆中的沈降（7曰） 有 無 有 無 清漆t的沈降（1個月） 有 有 有 有 NH4+ wtppm 21 21 22 21 塗佈性 不良 良 不良 良 導熱率W/m · K 9.6 9.5 9.6 9.4 剝離強度kN/m 1.0 1.0 0.9 0.9 B階段破裂 有 有 有 有 对濕可靠性 不良 不良 不良 不良 根據表1〜表5，本發明的實例1〜實例11的接著劑 樹脂組成物，除了考慮到實用性而為相當嚴格的評價項目 的「清漆中的沈降（1個月）」外，可獲得總體良好的結果。 特別是在採用較佳成分（a')〜成分（c’）的組合作為環氧 系接著樹脂原料的實例7〜實例10中，包括「清漆中的沈 降（1個月）」的全部評價項目均獲得良好的結果。相對於 36 201213480 此，在氧化鋁粉末的粒徑分布與含量不滿足上述a)〜c) 的條件的比較例1〜比較例4、硬化劑的調配量為規定外的 比較例5〜比較例9、使用苯酚酚醛清漆樹脂作為硬化劑的 比較例10〜比較例12、使用二氰基二醯胺作為硬化劑的比 ，例13、環氧當量為150〜220的範圍内的環氧樹脂的含 量於全部環氧樹脂中小於50 wt%的比較例14〜比較例17 中’任一項目均未獲得令人滿意的評價。 如以上所述，本發明的接者劑樹脂組成物相對於接著 劑，脂組成物的固體成分100重量份，而於2重量份〜1〇 重量份的範圍内僅使用咪唑化合物作為硬化劑，而可將硬 化物中的銨離子的量抑制在5〇重量ppm以下因此形成 接著劑層時的接著力及絕緣性難以降低，並且可唯 =耐電壓特性。另外，使本發明的接著劑樹脂組成物硬二 的硬化物由於含有具有特定粒徑分布的 優異的導熱性。另外，由本發 ’ _末而具有 唾化合物的作用:改二作 了撓!·生Jl可防止表面破裂。因此，本發明 ;i:r雅地用作例如電路基板、電子零件等的师: 但本本發明的實施形態， 【圖式簡單說明】 【主要元件符號說明】 無0 37In this case, it is sufficient to calculate the amount of the solid component by simply adjusting the _ arbitrary component by other means. In addition to the essential components of the above (A) and (b), the adhesive composition of the U-shaped yoke-shaped enamel may further contain, for example, a solvent, a rubber component, and a plurality of optional components. /,,,,,,,,,,,,, From the viewpoint of low elasticity of the insulating adhesive layer, a rubber component may be added as needed. Examples of such a rubber component include polybutadiene rubber, propylene f-butadiene rubber, modified acrylonitrile-butadiene rubber, and propylene glycol rubber. These rubbers may be used alone or in combination of two or more. The weight average molecular weight of the rubber to be used can be, for example, 10, 〇〇〇 1 〇〇〇 〇〇〇, preferably 20,000 to 500 Å. Here, the weight average molecular weight is a value converted from polystyrene measured by Gpc. If the weight average molecular weight of the rubber component is less than 10,000, the heat resistance, mechanical strength, and flexibility of the cured product (adhesive layer) may be lowered, and the film support property at the stage before hardening may be lowered. When the weight average molecular weight of the rubber component is more than 1,000,000, the solubility in an organic solvent, the compatibility with an epoxy resin and a hardener is lowered, and the viscosity is lowered, and the viscosity at the time of making a varnish, or The processability and adhesion of the melted-degree insulating joint when the ship is made into a ship are reduced, and the surface shape is: ^ is the purity of the rubber of the rubber component, and the voltage is particularly high. From the viewpoint of sin, rubber 0 having less ionic impurities is preferable. [Other optional components] In addition, from the viewpoint of low complexity and improvement of the present invention, for example, gas can be added as needed. Specialized as a package, leveling agent, etc. Further, from the viewpoint of improving the adhesion between the metal substrate and the copper wiring 18 201213480 J member, for example, adhesion such as a heterocouple or a thermoplastic oligomer can be added. Further::: === Inorganic filling other than the handle can be added as needed: W as the filler of the (8) component, other than the oxide-filled inorganic filler, for example, dioxane, nitrogen (tetra), nitriding, and fossil Xi, carbon _, carbon _ and so on. For example, the organic filler may be listed as follows: • Shi Xi powder, domain powder, _ nitrile _ adiene 纟 = some fillers, and may be used in two or more types. Further, the present invention = the resin composition of the carrier is required to be blended with a coloring agent such as black. In the case of any of the above-mentioned components, the ammonium ion in the hardened material is reduced in the hardened matter, and the molecular structure does not contain an amine group, or an amine. [Composition, varnish] It is prepared by the above-mentioned ingredients. In this case, it is preferred that the composition of the adhesive containing the H, i.e., the adhesive of the present invention, be dissolved or dispersed to form a varnish. The solvent which can be used here can be exemplified by: νν· 2 tyrosine (10)F), hydrazine, hydrazine dimethyl ethanoamine, hydrazine-methyl heart ratio:: isomer solvent methoxy __propanol, etc. A solvent obtained by mixing one type or the like of an aromatic solvent such as toluene or xylene. For the hardening of the component (b), the oxidized slag of the knives, and the arbitrarily added arbitrarily. 19 201213480 ^^-τυ-rpif machine filler, organic filler, colorant, etc. In the dispersant, it is not necessary to dissolve in the solvent. The varnish can be prepared, for example, in the order shown below. First, prepare the mixing machine's container sandalwood (c) component of the stupid resin and dissolve it in the agent. Next, in this solution, the epoxy resin of the component (a), (7) the hardener to be added, and the optional component are mixed and lion is dissolved. In addition, according to the type of the epoxy resin of the component (a), the epoxy-like solution may be dissolved, and the viscosity of the oxidized powder varnish of the ship (8) component in the mixed solution may be added. It is preferably in the range of l_Pa.s~2_〇Pa.s, more preferably in the range of 2000 Pa·s~10_Pa·s. When the viscosity of the varnish is less than 1000 Pa · s, the family produces oxygen and the unevenness or shrinkage of the powder. On the other hand, when the viscosity of the varnish is 20,000 Pa·s, the fluidity is lowered, and the coatability is lowered, so that it is difficult to form a uniform coating film. Since the oxidized slag of the component (B) has the characteristics of 遂 & C), it is easy to adjust the viscosity of the varnish to the above range. [Binder film and copper foil provided with an adhesive film] In the present invention, the above varnish is applied onto a base film as a gift material and dried, whereby an adhesive film in an 8-stage state can be formed. Further, the varnish is applied onto a copper crucible and dried to form a copper beryllium having an adhesive crucible. Here, the thickness of the adhesive film is not particularly limited to 201213480. It is set in the range of just μΓη~3°〇_, and the contact type of the step L (with the back surface _) is generated on the surface when f is folded. Crack (cracking)' will be impaired as the value of the product. Such a B-stage surface rupture occurs easily by disposing a large amount of a solid resin component at a normal temperature. From the viewpoint of lowering the content of ammonium ions in the hardened material, it is also considered that the benzene-based paint is hard. However, since the benzene-accurate varnish-based hardener is usually a solid, surface cracking easily occurs. However, in the adhesive film (the copper case provided with the adhesive film) of the present invention, since only the m material is used as the curing agent, the proportion of the solid resin component in the epoxy resin and the "metal powder" can be used. Inhibition is at a lower level. In addition, if it is compared with the case of Wei, for example, a pure varnish-based hardener component, the amount of the compound as a hardener can be suppressed to be more suitable at room temperature. a large amount of liquid or semi-solid components, ^ can be soft and flexible in the two β-stage state, and prevent surface breakage 0. In addition, 'with respect to the adhesive film or the copper box (hardened two) having the adhesive film, The supportability 'the higher the solvent residual ratio, the better the film selectivity is, but the 'residual solvent ratio is too high', then the adhesive film or the copper box (before curing) with the f film may cause smashing, or Bubbles are generated at the time of hardening. = 'The solvent residual ratio is preferably 5% by weight or less. In addition, the solvent residual ratio is calculated in the environment of J 8iC at 6 G minutes in the environment by the measurement of the mass reduction rate of the subsequent portion. The other two of the above adhesive films and A copper ruthenium having an adhesive 羯 can be obtained by formulating a solvent-free adhesive resin composition on a base film which is heated and smashed 21 201213480 as a supporting material, and then cooled. For example, 】: The support material used in the steel box of the film is 4 聚 10 - 曱酉 乙 乙 (PET), polyethylene, = ~, =, release paper, etc. The thickness of the support material can be set, for example, to At 1 ,, the metal is made of a shaft and a metal _ as a supporting material. This is a solution and a rolling material. In addition, in order to improve the contact point of the layer, it is preferable to contact the insulating layer. The surface is roughened. 'After the ship or the ship with the ship (4), after bonding to the base film as the ff material, (10) may be covered by the film of the protective material; the other side of the early touch is wound into It is stored in the form of a roll. In this case, it is used: for example, polyethylene terephthalate, polyethylene, detached, and "special". (4) The thickness of the protective material can be set, for example, to (7) qing~gang [hardened material] The cured product of the present invention can be prepared, for example, by using an adhesive film (or copper having an adhesive film) in the B-stage state described above from the adhesive resin composition. Flute) after 'heating to, for example, 150. The temperature in the range of (2 to 2 pits) is hardened and produced. The cured product obtained in this manner can suppress the content of ammonium ions (NH/). That is, the content of ammonium ions in the cured product of the present invention is 5〇. The amount of ppm or less is more preferably 25 ppm by weight or less. By suppressing the filaments to 50 wtp or less, metal ions are not induced even when a cured product is used as an adhesive layer in contact with the metal wiring. It can effectively inhibit migration leading to poor or poor insulation. 22 201213480 jynuHpif - In addition, the content of ammonium ion in the hardened matter can be obtained by heating the powder of the product in pure water. The ammonium ion concentration of the known extraction water is measured by ion chromatography, and the content of the ammonium ion is expressed by the weight fraction (ppm by weight) of the ammonium ion with respect to the cured product, and the cured product of the present invention. The thermal conductivity is, for example, preferably 7 w/mK or more, more preferably 10 W/mK or more. Usually, if the thermal conductivity of the cured product is less than IW/mK', a heat transfer path is formed on the substrate for the purpose of heat dissipation. Heat conduction of hardened material It is more than 7 w/mK, and it has excellent heat dissipation characteristics and can be applied to a circuit board or the like used in a south temperature environment. Such excellent thermal conductivity can be controlled by satisfying the above &)~e) (B) The particle size distribution and content of the alumina powder of the component are obtained. [Method of Manufacturing Metal Base Circuit Board] Next, a description will be given of a method of manufacturing a metal base circuit board using the adhesive resin composition of the present invention. Here, a Schottky j circuit substrate using a name substrate is exemplified. First, the secret lipid composition is obtained by the copper test with the above-mentioned ore, and the copper foil having the adhesive film is applied to the aluminum substrate at a temperature of 15 (TC~25^C, pressure ι). 〇 MPa 〜 3 〇 Mpa under the conditions. At this time, the surface of the adhesive film is contacted with the surface of the substrate, and the resin is hardened and pressurized as the upper (4), and the resin is cured; attached to the !g substrate. In this way, an adhesive film can be used as an insulating binder layer to separate the layered body existing between the copper (four) and the silk plate. Then, the circuit wiring is formed by removing the copper box of the specific portion by I. Finally, the IS base circuit substrate is obtained. In addition, the thickness of the substrate is not particularly limited, and may be, for example, set to 0.5 mm to 3.0 mm, for example, in order to use the adhesive resin composition of the present invention. In addition to the above methods, the conductor layer of the 5th layer and the layer of the next layer of the _ and the @ layer can also be used: on the substrate 2, the adhesive layer is placed on the _ to heat, reduce and harden the layer, or Insulating adhesive layer on the substrate surface = : shape f copper guide The method of the layer. In addition, the method of volatilizing the solvent by heating after applying the varnish, the method of applying the correction method, or the method of bonding the subsequent method is In the metal base circuit board manufactured as described above, the peeling strength with the copper case is, for example, preferably 4 G5 kN/m or more, more preferably kWm or more. Such a peeling strength can be achieved by completely providing the hardener of the above (b). The content is obtained by the condition of the ^ ^ ^ condition related to the oxidation of the component (8). When any of the conditions of a) to e) which do not satisfy the content of the hardener of the component (1) is satisfied, =_ and _ off The strength of the separation will be less than... the substrate and other materials (4) insufficient adhesion. ^夂[Action] The diamine which is mostly used as a latent curing agent in the composition of the oxy-resin, for example, has the heat generated by the element when it is used in the surface, and it is easy to produce ammonium. The nature of the ions. Therefore, when cyanodiamine is used as a hardener for the epoxy resin composition to form an adhesive layer of an electric earth plate or an electronic component, the 24 201213480 sub-product produced by dicyanodiamine can make an anion of a tau ammonium salt. Incorporating "::: machine:: and above, the anion incorporated into the adhesive layer gradually dissipates under repeated high temperature and high humidity, and induces the generation of metal ions from the metal wiring, and iHI causes _ poor migration. In the adhesive resin composition of the present invention, since only the sputum is not used as a hardener, the hardened towel can be made into a migration intervention factor, and the ion is suppressed to 5 〇 or less by weight, so that even When used as a metal wiring, it is not expected to produce metal ions, and the migration which causes poor insulation can be effectively suppressed. Examples, =, the present invention will be specifically described by way of examples, but the present invention is In addition, in the following examples, unless otherwise specified, each system is based on the following. [, varnish viscosity] The varnish viscosity is set to use a Β type viscometer No. 4 rotor The measured value (Pa·s;) of the obtained varnish of the 胄 旨 旨 于 于 于 于 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 清 清 清 清 清 清 清 清 清 清 清 清 清 清 清 清 清 清 清 清 清 清 清 清 清 清The mixture was placed in a 500 ml Erkyro flask at 23 ° C for 7 days and 1 month, and it was confirmed that there was a precipitate of alumina powder at the bottom of the flask, and the sediment having a height of 1 mm or more was evaluated as "Yes". The case where the height of the sediment is less than 10 mm 25 201213480 is evaluated as "none". However, even if the height of the sinking object is less than that of the 〇 〇 ’ , the case where the sediment is hardened and the original state is restored by the search is also determined to be "Yes". [Ammonium ion (NH4+)] The adhesive film of the B P segment was 18 Å by a compression press molding machine. [Heat curing for 1 hour to obtain a cured product. 1 g of the powder obtained by pulverizing the hardened material was pressurized in 50 cc of pure water and heated at a heating temperature of 12 Torr (: 2 〇 small temples - the extracted water was performed by an ion chromatography measuring device DX_3 制造 manufactured by DIONEX) The ammonium ion concentration was measured by the treatment, and the content of the ammonium ion was set to the weight fraction (ppm by weight) of the ammonium ion with respect to the cured product. [Coating property] The thickness of the dried zinc paste was 130 μm by a knife coater. The varnish of the resin composition of the adhesive was applied to the Ρ τ 膜 film, and the case where the coated surface was uniform was evaluated as "good", and the occurrence of streaks or uneven appearance defects was evaluated as "poor". [Thermality] The adhesive film of the special crucible stage is heated by a compression press molding machine at 180 ° C for 1 minute, taken out from the press, and then heated in a dryer at 180 ° C for 50 minutes, thereby obtaining a diameter of 50. Disc-shaped test piece of mm and thickness of 5 mm. The thermal conductivity measuring device HC-110 manufactured by Yinghong Seiki was used to measure the thermal conductivity of the test piece by a conventional method (referred to as melon K). [Peel strength] B-stage adhesive film is superimposed on copper foil Using a batch vacuum 26 201213480^ press, at a pressure of 10 MPa, the maximum temperature of 18 叱, the temperature of the knives is 'pressed on a 丨5 mm thick substrate and hardened. At this time, the next _ surface oil The substrate is in surface contact, and is pressed and attached to the substrate in a state where the copper crucible is set to the upper surface. The material is subjected to a test according to the peeling strength (peeling strength). The test piece prepared as described above is cut out based on the above. The standard shape was measured by using a TENSIL® N tester (RTA_25® manufactured by Onentec) to stretch the copper foil at a speed of 50 mm/min in a 9-degree direction to determine the peel strength of the 9-inch copper foil (kN/). m) [B-stage rupture] The B-stage adhesive film is bent (10) along a round bar of 5 mm in diameter. When the film surface is not abnormal, it is evaluated as "None", and the occurrence of cracks is confirmed. The evaluation was "breaking". [Humidity resistance] The copper foil was superimposed on both sides of the B film of the test film as a test substrate. The batch vacuum press was used, and the pressure was maintained at 1 MPa and the maximum temperature was 180 °C. Hour in the temperature distribution A laminated board of double-sided copper foil is formed by crimping, and a grid pattern having a line width of 2 μm and a spacing of 200 μm is formed by etching one side of the laminated board. After the laminated board is cut into 2 em squares, A voltage application wiring was attached to the upper and lower copper foil portions. The test substrate was applied with a voltage of 50 V DC for 72 hours in a pressure cooker tester at 122 ° C, 2 atm, and 100% humidity. The initial resistance value was used as a reference. The case where the resistance value after the test was lowered by 20% or more was evaluated as "poor", and the case where the decrease in the resistance value after the test was less than 20% was evaluated as "good". 27 201213480 jy^unpif [Example 1 to Example 6, and Comparative Example 1 to Comparative Example 13] The following resin composition and raw material for producing an adhesive film and abbreviations thereof are as follows. (A) epoxy-based resin raw material (a) epoxy resin epoxy resin (1) ··bisphenol A epoxy resin (manufactured by Tohto Kasei Co., Ltd., YD128, epoxy equivalent W9, liquid) Epoxy resin (2) ·Double-F-type epoxy resin (manufactured by Dongdu Chemical, YDF-170, epoxy equivalent 170, liquid) Epoxy resin (3): o-cresol novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-1020-55 Epoxy equivalent 2 〇〇, softening point 55. 〇) Epoxy resin (4): Triphenyl decane type epoxy resin (manufactured by Sakamoto Chemicals, EPPN-501H, epoxy equivalent no, semi-solid) Oxygen resin (5): bisphenol A type epoxy resin (manufactured by Nippon Steel Chemical Co., YD-011, epoxy equivalent 470, solid) (b) Hardener hardener (1 wide 2-ethyl-4-fluorenyl) Imidazole hardener (2) : 2-phenylimidazole hardener (3) : 2-mercaptoimidazole hardener (4): phenol novolac (manufactured by Qunrong Chemical Industry, PSM-4261, phenolic hydroxyl equivalent 1〇5 , softening point 8 〇 art) Hardener (5): dicyanodiamine hardener (6): 2-phenyl-4,5-dihydroxydecyl imidazole (c) styrene resin 28 201213480 phenoxy resin (1): bisphenol A type phenoxy tree Fat (made by Dongdu Chemicals, YP-50) phenoxy resin (2): bisphenol AF type phenoxy resin (manufactured by Tohto Kasei, YP-70) phenoxy resin (3): bisphenol S type phenoxy resin (Dongdu Huacheng Manufacture, YPS-007) (B) Alumina powder Alumina powder (1): Spherical, crystalline, maximum particle size: 100 μηι, average particle size D5〇: 45 μηι, volume average particle size MV: 49 μιη ' Average number of particles MN : 38 μιη, MV/MN : 1.3 Alumina powder (2): Spherical, crystalline, maximum particle size: 68 μηι, average particle diameter d5〇: 11 μηη, volume average particle size MV: 12 μηη, number average particle size MN : 4 3 μιη ' MV/MN : 2.8 Alumina powder (3): Spherical, crystalline, maximum particle size: 7 μπι, average particle diameter d5〇: 〇4 μπ1, volume Average particle diameter MV : 0.7 μιη, number average particle diameter ΜΝ : "μιη, MV/MN : 6.7 [particle size distribution parameter of oxidized powder], and the concentration of the oxidized powder to be measured is 〇〇4 wt% The method is called and mixed in a 〇2 wt% sodium hexametaphosphate solution as a dispersion medium. 'Using ultrasonic homogenization ϋ to disperse for 3 minutes. The distribution measuring device MiCrotrac ΜΤ3300ΕΧ (manufactured by KK) was used to measure the particle size distribution of the oxidized dispersion by using scattered light obtained by irradiation of a semiconductor laser having a wavelength of 78 〇 29 201213480 nm. The maximum particle diameter is a distribution curve of the particle size fraction of the particle diameter in the particle size distribution obtained by the above-described measurement method, and the particle diameter is equal to or larger than a certain particle diameter. The distribution probability is all the minimum value of the particle size at the time of 〇. The average particle size D5 〇 is a particle at which the cumulative particle diameter of the particle diameter is 50% when the total particle volume is set to 100% in the particle size distribution obtained by the above-described measurement method. path. The volume average particle diameter (MV) is a "volumetric weighted average particle diameter" which is obtained from the particle size distribution obtained by the above measurement method. Mv is represented by the formula (丄). Μν = Σ (di^Vi) (l) The particle size distribution in the second gate is represented by a histogram, the mountain is the representative particle size of the first M曰 of the histogram, and Vi is the volume fraction of the particles belonging to the 丨 interval. The 敕 average particle size (MN) indicates the "number-weighted average particle diameter" obtained by the above-described measurement method. Here, the imaginary preparation ‘Wang Chong is assumed to be spherical, and MN is obtained according to equation (2). ΜΝ==Σ(VM2) /Σ(Wd,)...... (2) where 4 is the representative particle size of the 丨 interval of the histogram, and % is the particle of the 201213480 interval Volume fraction. & [volume average particle size] / [number average particle diameter] is used as an index indicating the particle size distribution. Usually [volume average particle size] / [number average particle diameter (4), the smaller the value, the grain size cloth scale, the wider the distribution of the surface diameter. (C) Hardening accelerator Hardening accelerator (1): 2_ethyl_4•nonyl imidazole The above raw materials were prepared in the proportions shown in Tables 1 to 5. First, only the phenoxy resin was stirred and dissolved in decyl isobutyl ketone (mIBK) by a container having a search machine. (Where, in the presence of the epoxy resin (2), unlike the phenoxylate, fat MIBK solution, only the MIBK solution of the epoxy tree (7) is prepared and mixed in the MIBK solution of the phenoxy resin). The solution towel is blended with epoxy lion (1) or (2) (the towel is also formulated with epoxy resin (3) ~ epoxy resin (5) in the case of epoxy resin (3) ~ epoxy resin (5)) In the case of a hardener (in which, in the case of blending a hardening accelerator 〇), the hardening accelerator (1)) is also blended and mixed and dissolved. Then, alumina powder was blended in the mixed solution, stirred and dispersed to prepare a varnish of the adhesive resin composition. The varnish was applied to a release-treated ruthenium film (manufactured by Mitsubishi Chemical Corporation, MR-50) having a thickness of 50 μm, and dried at i1 (c) for 5 minutes to prepare B. The adhesive film of the stage. The results are shown in Table 1 to Table 5. In addition, the amount of epoxy resin, hardener, hardening accelerator, phenoxy resin, aluminum telluride powder, and solvent (mibk) in the table is by weight. The parts indicate that the 'oxidation content is expressed as a percentage by weight relative to the total solid content of the adhesive resin composition. 31 201213480 [Table 1] Example 1 2 3 4 5 6 Epoxy resin (1) 50.0 50.0 50.0 50.0 55.0 Epoxy Resin (2) 50.0 Epoxy Resin (3) 25.0 25.0 25.0 25.0 25.0 25.0 Hardener (1) 5.0 5.0 5.0 5.0 Hardener (2) 5.0 Hardener (3) 5.0 Hardener (4) Hardener (5) Hardening Promotion Agent (1) phenoxy resin (1) 20.0 20.0 20.0 20.0 oxo resin (2) 20.0 phenoxy resin (3) 15.0 alumina powder (1) 532 532 532 532 532 532 alumina powder (2) 532 532 532 532 532 532 Alumina powder (3) 266 266 266 266 266 266 Alumina content rate wt% 93 93 93 93 93 93 MIBK 160 160 160 160 180 160 Varnish viscosity Pa · s 2400 3100 2400 2100 4200 2200 Settling in varnish (7曰) Settling in no varnish (1 month) Whether there is any NH4+ wtppm 21 20 20 22 20 21 Good coatability, good thermal conductivity W/m · K 10.3 10.5 10.3 10.6 10.0 11.3 Peeling strength kN/m 1.0 1,1 1.0 1.0 1.2 1.1 B-stage rupture No no no no no no moisture resistance Reliable good good good 32 201213480 [Table 2] Example 7 8 9 10 11 Epoxy resin (1) 50.0 50.0 50.0 Epoxy resin (2) 50.0 50.0 Epoxy resin (3) 25.0 25.0 Epoxy resin (4) 25.0 25.0 Epoxy resin (5) 25.0 Hardener (6) 5.0 5.0 5.0 5.0 5.0 Hardening accelerator (1) Phenoxy resin (1) 20.0 20.0 20.0 20.0 20.0 Phenoxy resin (2) Phenoxy resin (3) Alumina powder (1) 532 532 532 532 532 Aluminized powder (2) 532 532 532 532 532 Alumina powder ( 3) 266 266 266 266 266 Aluminium content rate wt°/〇93 93 93 93 93 MIBK 160 160 160 160 160 Varnish viscosity Pa · s 3800 3200 4000 3400 2800 Settlement in varnish (7曰) No or no no varnish settlement (1 month) NO4+ wtppm 21 21 20 19 21 Good coatability, good thermal conductivity W/m. K 10.1 10.3 10.2 10.3 10.3 Peel strength kN/m 1.0 1.0 1.0 1.0 1.0 B-stage cracking No moisture resistance, good, good, good 33 201213480 [Table 3] Comparative Example 1 2 3 4 5 6 Epoxy Resin (1 ) 50.0 50.0 50,0 54.8 54.0 Epoxy Resin (2) 50.0 Epoxy Resin (3) 25.0 25.0 25.0 25.0 25.0 25.0 Hardener (0 5.0 5.0 5.0 0.2 1.0 Hardener (2) 5.0 Hardener (3) Hardener (4) Hardener (5) Hardening accelerator (1) Phenoxy resin (1) 20.0 20.0 20.0 20.0 20.0 20.0 phenoxy resin (2) phenoxy resin (3) alumina powder (1) 665 665 665 532 532 oxidized 4S powder to (2) 665 665 1064 665 532 532 alumina powder (3) 266 266 266 oxidation Aluminum content rate wt% 93 93 93 93 93 93 MIBK 160 160 160 160 160 160 Varnish viscosity Pa · s 700 500 4500 1300 1900 2000 Settlement in varnish (7曰) Settlement settlement without or without varnish settlement (1 month) Settlement sinking settlement Settlement and sedimentation NH: wtppm 20 21 21 20 19 24 Poor coating properties Good good thermal conductivity W/m · K 6.5 6.5 6.8 6.8 8.5 8.9 Peel strength kN/m 0.3 0.3 1.0 0.3 0.0 0.1 B stage cracking No or no moisture resistance, good, good, good, good 34 201213480 [Table 4] Comparative Example 7 8 9 10 11 12 13 Epoxy Resin (1) 54.8 39.3 39.3 49.9 Epoxy Resin (2) 54.8 54.8 38.7 Epoxy Resin (3) 25.0 25.0 25.0 19.6 19.6 19.5 25.0 Hardener (1) 0.2 0.2 Hardener (2) 0.2 Hardener (3) Hardener (4) 20.9 20.9 21.6 Hardener (5) 4.9 Hardening accelerator (1) 0.2 0.2 0.2 0.2 phenoxy resin (1) 20.0 20.0 20.0 20.0 20.0 phenoxy resin (2) 20.0 20.0 phenoxy resin (3) Alumina powder (1) 532 532 532 532 532 532 532 Alumina powder ( 2) 532 532 532 532 532 532 532 Alumina powder (3) 166 166 166 166 166 166 166 Oxidation Is content wt°/〇93 93 93 93 93 93 93 MIBK 160 160 160 160 160 160 160 Varnish viscosity Pa · s 1700 1400 1600 5300 5000 4800 2100 Settlement in varnish (7曰) No sedimentation in no varnish (1 month) Settlement Settlement Settlement Settlement Settlement Settlement NH4+ wtppm 20 20 21 18 18 19 210 Coating Good good good good good thermal conductivity W/m · K 8.5 8.5 8.2 9.8 10.0 9.9 9.9 Peel strength kN/m 0.0 0.1 0.0 0.9 0.9 0.9 1.0 B-stage cracking without cracks and cracks without good reliability Liang Liangliang Bad 35 201213480 39404pif [Table 5] Comparative Example 14 15 16 17 Epoxy Resin (1) 35.0 35.0 Epoxy Resin (2) 35.0 35.0 Epoxy Resin (3) Epoxy Resin (4) Epoxy Resin (5 40.0 40.0 40.0 40.0 Hardener (1) 5.0 5.0 Hardener (2) Hardener (3) Hardener (4) Hardener (5) Hardener (6) 5.0 5.0 Hardening accelerator (1) Stupid resin (1) ) 20.0 20.0 20.0 20.0 phenoxy resin (2) styrene resin (3) alumina powder (1) 532 532 532 532 alumina powder (2) 532 532 532 532 alumina powder (3) 266 266 266 266 alumina content Wt% 93 93 93 93 MIBK 160 160 160 160 Varnish viscosity Pa · s 5200 6100 4800 5400 Settling in varnish (7曰) With or without varnish t (1 month) There are some NH4+ wtppm 21 21 22 21 Good cloth quality, good thermal conductivity, W/m · K 9.6 9.5 9.6 9.4 Peel strength kN/m 1.0 1.0 0.9 0.9 B-stage cracking is not good for wet reliability. In the example of the adhesive resin composition of the example 1 to the example 11, in addition to the sedimentation (1 month) in the varnish which is a very strict evaluation item in consideration of practicality, overall good results were obtained. In particular, in the examples 7 to 10 in which the combination of the preferred component (a') to the component (c') is used as the epoxy-based resin raw material, all evaluation items including "sedimentation in varnish (1 month)" are included. Both achieved good results. In Comparative Example 1 to Comparative Example 4 in which the particle size distribution and content of the alumina powder did not satisfy the conditions of the above a) to c), Comparative Example 5 to Comparative Example in which the amount of the curing agent was defined was defined as compared with 36 201213480. 9. Comparative Example 10 to Comparative Example 12 using phenol novolak resin as a curing agent, ratio of using dicyanodiamine as a curing agent, and Example 13, epoxy resin having an epoxy equivalent of 150 to 220 In Comparative Example 14 to Comparative Example 17 in which the content was less than 50% by weight in all the epoxy resins, none of the items was satisfactorily evaluated. As described above, the adapter resin composition of the present invention uses only an imidazole compound as a hardener in a range of 2 parts by weight to 1 part by weight based on 100 parts by weight of the solid content of the fat composition with respect to the adhesive. On the other hand, the amount of ammonium ions in the cured product can be suppressed to 5 Å by weight or less. Therefore, it is difficult to reduce the adhesion and insulating properties when forming the adhesive layer, and it is possible to have only the withstand voltage characteristics. Further, the cured product of the hardener composition of the adhesive resin composition of the present invention contains excellent thermal conductivity having a specific particle size distribution. In addition, the effect of the saliva compound at the end of the present invention is: the second is made to scratch! The raw Jl prevents surface cracking. Therefore, the present invention is used as a circuit board, an electronic component, etc., but an embodiment of the present invention, [a brief description of the drawing] [Description of main component symbols] No. 0 37