201033314 六、發明說明： 【發明所屬之技術領域】 本發明係關於對於各種塑料薄膜的接著性、或對於 銅、鋁、不銹鋼等金屬的接著性、對玻璃的接著性、耐熱 性、耐濕性、片材壽命（sheet life)等優異之樹脂組成物、 * 含有其之接著劑、接著片及含其爲接著層之印刷配線板。 ' 【先前技術】 近年來，在各式各樣的領域中使用接著劑係根據其使 © 用使用目的之多樣化，從以往能使用的接著劑進一步對於 各種塑料薄膜的接著性、或對於銅、鋁、不銹鋼等金屬的 接著性、對於玻璃增強環氧樹脂的接著性、耐熱性、耐濕 性、片材壽命等，要求進一步的高性能化。例如，作爲以 可撓性印刷配線板（以下簡稱爲FPC)爲始的電路基板用的 接著劑係使用環氧/丙烯酸丁二烯系接著劑、或環氧/聚乙 烯醇縮丁醛系接著劑等。對此等的電路基板用接著劑係要 求耐焊熱性、接著性、加工性、電特性、保存性。 特別是從最近因應於無鉛焊料之FPC的使用環境，要 求具有更高度的耐熱性之接著劑。又’從配線的高密度化、 FPC配線板的多層化、作業性，強烈要求在高濕度下的耐 焊接性、高溫高濕度下的接著性。用以往的環氧/丙烯酸丁 二烯系接著劑、或環氧/聚乙烯醇縮丁醛系接著劑，係特別 是在高溫高濕度下的接著性、加工性不良，又對於金屬或 塑料薄膜的接著性也不夠充分。另外，亦無法確保即使在 201033314 常溫亦可流通之穩定的片材壽命（參照專利文獻1、2、3、 4)。 專利文獻5中，揭示有以特定的聚酯·聚胺基甲酸酯與 環氧樹脂作爲主成分之接著劑用樹脂組成物。根據這裡所 表示的組成物，雖然有提昇片材壽命、在高溫下及高濕度 下的接著性的可能，但是無法充分地滿足在高溫且高濕度 下的接著性。 專利文獻6中亦揭示有以特定的聚酯·聚胺基甲酸酯 © 與環氧樹脂作爲主成分之接著劑用樹脂組成物。根據這裡 所表示的組成物，雖然有提昇在高溫下及高濕度下的接著 性、使用塑料薄膜於補強板之際的耐加濕焊接性的可能， 但是無法充分地滿足在高溫且高濕度下的接著性、補強金 屬於補強板之際的耐加濕焊接性。又，在常溫或40 °C保管 後的耐加濕焊接性、於高溫且高濕度下的接著性係顯著地 降低，而無法確保穩定的片材壽命。 先行技術文獻 ® 專利文獻 專利文獻1 特開200卜29 1964號公報 專利文獻2 特開2003-313526號公報 專利文獻3 特開2005-139387號公報 專利文獻4 特開2005-139391號公報 專利文獻5 特開平11-116930號公報 專利文獻6 特開2008-205370號公報 【發明內容】 201033314 發明所欲解決之課題 本發明的課題就是在於爲改良擁有此等以往的接著劑 之各問題點，而提供一種可維持對於各種塑料薄膜、或銅、 鋁、不銹鋼等的金屬、玻璃增強環氧樹脂的接著性，且能 因應於在高濕度下的無鉛焊料之高度的耐濕熱性、在高溫 高濕度下的接著性優異之接著劑，以及提供一種由前述接 著劑所得之B階段的接著片在即使於高溫高濕下流通之後 使用，亦能維持良好的接著特性之片材壽命良好的接著劑 〇 片。又，提供一種含有由前述接著劑或接著片所得之接著 層的印刷配線板。 解決課題之手段 本發明人等係爲了解決上述課題，經專心一意檢討的 結果，而終至完成本發明。亦即，本發明係由以下的構成 所組成的。 (1) 一種接著劑用樹脂組成物，係含有熱可塑性樹脂 (A)、無機塡充材（B)、溶劑（C)、環氧樹脂（D)之接著劑用樹 ® 脂組成物， 該熱可塑性樹脂（A)的酸價（單位：當量/ l〇6g)爲100以 上1 0 0 0以下， 該熱可塑性樹脂（A)的數量平均分子量爲5.0 X 103以 上l.〇xl〇5以下， 該環氧樹脂（D)係具有二聚環戊二烯骨架的環氧樹脂， 在該接著劑用樹脂組成物的含有比率中合計含有25 質量份的該熱可塑性樹脂（A)與該無機塡充材（B)，由甲基 201033314 乙基酮52質量份與甲苯23質量份所構成之混合溶劑（其 中，該熱可塑性樹脂（A)以前述的濃度在25¾中不溶解於 前述混合溶劑中的情形，變更前述混合溶劑而使用由二甲 基乙醯胺52質量份與甲苯23質量份所構成之混合溶劑） 作爲分散媒之分散液（α)在液溫251中的搖變度（TI値）爲 3以上6以下。 (2)—種二液型接著劑用樹脂組成物，樹脂組成物（冷） 係含有熱可塑性樹脂（A)、無機塡充材（B)、溶劑（C)爲必要 〇成分， 該熱可塑性樹脂（A)的酸價（單位：當量/106g)爲100以 上1 0 0 0以下， 該熱可塑性樹脂（A)的數量平均分子量爲5.0 X 103以 上1.0 X 1 0 5以下， 在該接著劑用樹脂組成物的含有比率中合計含有25 質量份的該熱可塑性樹脂（A)與該無機塡充材（B)，由甲基 乙基酮52質量份與甲苯23質量份所構成之混合溶劑（其 中，該熱可塑性樹脂（A)以前述的濃度在25C中不溶解於 前述混合溶劑中的情形，變更前述混合溶劑而使用由二甲 基乙醯胺52質量份與甲苯23質量份所構成之混合溶劑） 作爲分散媒之分散液（α )在液溫251中的搖變度（TI値）爲 3以上6以下， 樹脂組成物（r )係含有二聚環戊二烯骨架的環氧樹脂 (D)爲必要成分， 該樹脂組成物（沒）中所含有的該熱可塑性樹脂（A)的酸 201033314 價 AV(/3 )(單位：當量/ l〇6g)與摻合量 AW( )(單位：質量 份）、該樹脂組成物（r)中所含有的環氧樹脂的環氧價 EV( r )(單位：當量/ i〇6g)與摻合量EW( r )(單位：質量份） 係以滿足以下所示之式（1)的摻合比，摻合樹脂組成物（冷） 與樹脂組成物（r ): 0.7S {EV(r )xEW(r )}/{AV(yS )xAW(yS )}$ 4.0(1)。 (3) 如（1)或（2)項之接著劑用樹脂組成物，其中前述環 氧樹脂（D)係在接著劑用樹脂組成物中所含有之環氧樹脂 〇 全體的60質量％以上99.9質量％以下。 (4) 如（1)~(3)項中任一項之接著劑用樹脂組成物，其 中前述無機塡充材（B)的摻合量係相對於熱可塑性樹脂 (A) 100質量份，爲10質量份以上50質量份以下。 (5) 如（1)~ (4)項中任一項之接著劑用樹脂組成物，其 中將接著劑用樹脂組成物設爲1 00質量份時，前述溶劑（C) 的摻合量爲60質量份以上85質量份以下。 (6) 如（1)~ (5)項中任一項之接著劑用樹脂組成物，其 © 係包含具有氮原子之環氧樹脂。 (7) 如（1)~(6)項中任一項之接著劑用樹脂組成物，其 中前述具有氮原子之環氧樹脂係含有縮水甘油二胺構造。 (8) —種接著劑，係含有如（1)~(7)項中任一項之接著 劑用樹脂組成物。 (9) 一種接著片，係包含如（1)~(7)項中任一項之接著 劑用樹脂組成物中所含有之前述熱可塑性樹脂（A)、前述無 機塡充材（B)、前述環氧樹脂（D)及來自於此等的反應生成 201033314 物。 (10) —種印刷配線板’係含有使用如（8)項之接著劑 或如（9)項之接著劑片而成的接著層。 發明的效果 根據本發明，可提供一種能夠得到對於PET薄膜等的 各種塑料薄膜及銅 '銘、不銹鋼等的各種金屬有很高的接 著性、可因應於在高濕度下的無鉛焊料之高度的耐濕熱 性、在高溫高濕度下的接著性優異之接著劑，而且B階段 〇 的片即使在高溫高濕下流通之後亦可使用，可維持良好接 著特性之片材壽命良好的樹脂組成物、含有其之接著劑、 接著片及含其爲接著層之印刷配線板。又，本發明的較佳 實施態樣中，可提供一種對於各種塑料薄膜的接著性、或 對於銅、鋁、不銹鋼等金屬的接著性、對於玻璃增強環氧 樹脂的接著性亦爲優異之樹脂組成物、含有其之接著劑、 接著片及含其爲接著層之印刷配線板。另外，本發明的較 佳實施態樣中，特別是在對於鋁、不銹鋼等金屬的接著性、 ^ 耐濕熱性優異，將接著物在高溫高濕環境下長期間放置後 亦能維持高的剝離強度之點上，發揮更優異之特性。 【實施方式】 實施發明之形態 以下，詳細說明本發明。 <分散液（α )> 本發明中，分散液（α)的搖變度（ΤΙ値）係爲判定在本發 明接著劑用樹脂組成物中的熱可塑性樹脂（Α)與無機塡充 201033314 材（B)的組合及摻合比是否適合的指針。分散液（α)的搖變 度（ΤΙ値）爲3以上6以下，更佳爲3.5以上5以下。分散 液（α )中所含有的無機塡充材（Β)粒子間或熱可塑性樹脂（Α) 與無機塡充劑（Β)的相互作用很高時，分散液（α)的搖變度 有變高的傾向。搖變度低於3時，會有無機塡充材（Β)粒子 間或無機塡充材（Β)與熱可塑性樹脂（Α)的相互作用降低， 且耐熱性降低之傾向，另外會有無機塡充材容易沈降，而 得不到穩定的適用期之傾向。搖變度超過6時，會有處理 ® 性降低，變得難以平均地塗布之傾向。 分散液（α )係可藉由以在本發明接著劑用樹脂組成物 中的含有比率，用合計25質量份的熱可塑樹脂（Α)與無機 塡充材（Β)，52質量份的甲基乙基酮、23質量份的甲苯之 摻合比進行混合，進而加入約爲分散液（α)體積1/3左右 的直徑0.5-2 mm之玻璃珠，使用塗料攪拌器且在室溫 20~25t：的室内中分散4小時之後，去除玻璃珠後而進行 調製。但是，當該熱可塑性樹脂（A)以前述濃度在25 °C中 不溶解於前述溶劑之情形，變更前述混合溶劑而使用由二 甲基乙醯胺52質量份與甲苯23質量份所構成者作爲分散 液U )。 分散液（α)的搖變度（TI値）係藉由以下的方法而求 得。取分散液（α)放入容量225mL的玻璃製廣口瓶（通稱： 美乃茲瓶）內，在測定溫度25±1。〇下，使用BL型黏度計（東 機產業（股）製），測定回轉數在6rpm與60rpm的黏度（以 下係有分別簡稱爲BL(6)、BL(60)之情形。單位：dPa.s)， -10- 201033314 BL(6)爲100以下的情形係藉由下述式（2)來求得搖變度（ΤΙ 値）。 搖變度（ΤΙ 値）= BL(6)/BL(60) (2) 又，BL(6)超過100之情形係使用BH型黏度計（東機 產業（股）製），以2rptn與20rpm測定黏度（以下係有分別 簡稱爲BH(2)、BH(20)之情形。單位：dPa«s)，藉由下述式 (3)來求得搖變度（TI値）。 搖變度（TI 値）= BH(2)/BH(20) (3) 〇 此外，在利用BL型黏度計及BH型黏度計的黏度測定 之際所使用的軋輥，係按照各黏度計之操作説明書的記 載’選擇No.2~4中的任·~者。 <樹脂組成物（/3 } > 本發明中所使用的樹脂組成物（/3 )係以前述的比例， 摻合熱可塑性樹脂（A)、無機塡充材（B)、溶劑（C)、以及按 照需要的其他成分，並用壓延機、混合器、塗料攪拌器等 進行平均地混合而得到，只要是能得到充分的分散之方 ® 法’分散方法方面沒有特別地限制。另外，樹脂組成物（沒} 的固體成分濃度爲1 5質量。/。以上40質量。/。以下爲佳。固 體成分濃度低於15質量。/。時，接著劑的厚度變薄，且耐熱 性、接著強度降低，大於40質量％時，由於溶液的黏度變 得過高，會有變得難以平均地塗布的傾向。 <樹脂組成物（r )> 本發明中所使用的樹脂組成物（γ )係可僅由環氧樹脂 (D)所構成的，較佳係更含有溶劑（c)。樹脂組成物（r )中所 -11- 201033314 含有的溶劑（c)只要是可溶解樹脂組成物（r )中所含有的成 分即可，沒有特別地限制。又，樹脂組成物（τ )的固體成 分濃度係以1 5質量％以上80質量％以下爲佳、25質量％ 以上75質量。/。以下爲較佳、35質量％以上70質量％以下 爲更佳。固體成分濃度低於15質量％時，溶劑揮散後接著 劑的厚度變薄，且會有耐熱性、接著強度降低之傾向。固 體成分濃度大於80質量％時，由於接著劑用樹脂組成物的 黏度變得過高，會有變得難以平均地塗布的傾向。 © <接著劑用樹脂組成物> 本發明的接著劑用樹脂組成物可爲含有熱可塑性樹脂 (A)、無機塡充材（B)、溶劑（C)、環氧樹脂（D)的一液型接著 劑用樹脂組成物，亦可爲使用上先分成複數的溶劑後再進 行混合的複數劑混合型接著劑用樹脂組成物。藉由形成複 數劑混合型，會有變的可長期間保存的優點。另一方面， 複數劑混合型的情形，在作爲接著劑使用之際必須以正確 的摻合比且平均地混合複數劑，劑數增加越多則其步驟的 ® 困難度也變得越大。因此，在複數劑混合型之中，尤以由 含有熱可塑性樹脂（A)、無機塡充材（B)、溶劑（C)之樹脂組 成物（々）與含有環氧樹脂（D)之樹脂組成物（r )所構成之二 劑混合型爲佳，基於均一混合的容易度，以二液混合型爲 更佳。 由樹脂組成物（Θ )與樹脂組成物（r )得到接著劑用樹 脂組成物之情形中，該樹脂組成物（Θ)中所含有的該熱可 塑性樹脂（A)的酸價AV (沒）（單位：當量/1〇6g)與摻合量 -12- 201033314 AW(/S )(單位：質量份）、該樹脂組成物（7·)中所含有的環氧 樹脂的環氧價 EV(r)(單位：當量/ l〇6g)與摻合量 EW(r )(單位：質量份）係以滿足以下所示之式（1)的摻合 比，摻合樹脂組成物（Θ )與樹脂組成物（r ): 0.7$ {EV(r )xEW(r )}/{AV(/3 )xAW(召）}$ 4.0(1) {EV( r )XEW( r )}/{AV(/3 )XAW(/S )}係較佳爲 0.8 以 上3.5以下，更佳爲0.9以上3.0以下。低於0.7時，熱 可塑性樹脂（A)與環氧樹脂的交聯變得不夠充分，會有耐熱 ® 性降低之傾向，大於4 · 0時，未反應的環氧樹脂係大量殘 留，會有耐熱性、耐濕性降低之傾向。 <熱可塑性樹脂（A}> 作爲本發明中所使用的熱可塑性樹脂（A)，係可舉出聚 酯系樹脂、聚胺基甲酸酯系樹脂、苯乙烯系樹脂、聚醯胺 系樹脂、聚醯胺醯亞胺系樹脂、聚酯醯亞胺系樹脂、聚碳 酸酯系樹脂、聚苯醚系樹脂、乙烯系樹脂、烯烴系樹脂及 丙烯酸系樹脂等，較佳係可舉出聚酯系樹脂、聚胺基甲酸 ❹ 酯系樹脂.、聚醯胺醯亞胺系樹脂。此等的熱可塑性樹脂係 可一種單獨使用，倂用二種以上也沒有關係。 本發明中所使用的熱可塑性樹脂（A)的數量平均分子 量係5xl〇3以上ixio5以下。數量平均分子量如果低於 5xl〇3’則塗布之後的密合性不充分且作業性變差，數量 平均分子量超過lxl〇5時，塗布時的溶液黏度變得過高， 而無法得到均一的塗膜。較佳係下限分子量8xl03，更佳 -13- 201033314 係下限分子量1χ1〇4，較佳係上限分子量5χ104，更佳係 上限分子量3x1 04。 本發明中所使用的熱可塑性樹脂（Α)的酸價（單位：當量 /106g)係100以上1000以下。酸價如過低於1〇〇當量 / 1 〇6g，硬化後對於金屬系基材的密合性係變得不充分， 又會有交聯度低且耐熱性降低之傾向。酸價超過1000當 量/106g時，溶解於溶劑之際的清漆保存穩定性降低，又 交聯反應容易在常溫下進行，會有得不到穩定的片材壽命 〇 的傾向。又，預期對於酯鍵與胺基甲酸酯鍵等的耐久性也 會造成不良的影響。較佳係酸價的下限爲250當量/106g， 更佳係酸價的下限爲300當量/106g，更佳爲酸價的下限 爲350當量/ l〇6g。較佳的上限爲900當量/106g，更佳 的上限爲800當量/ l〇6g、尤佳的上限爲700當量/ l〇6g。 (聚酯系樹脂） 作爲本發明的熱可塑性樹脂（A)所使用之聚酯系樹脂 的玻璃轉移溫度係較佳爲-1 0 °C以上6 0 °C以下。玻璃轉移 ® 溫度若低於-1 ，則會有在高溫的接著性變得不充分的傾 向。玻璃轉移溫度超過60T：時，與基材的貼合變得不夠充 分，又在常溫的彈性模數增高，會有在常溫的接著性變得 不充分的傾向。較佳係玻璃轉移溫度的下限爲-5°C，更佳 係玻璃轉移溫度的下限爲0C，更佳爲玻璃轉移溫度的下 限爲5 °C。較佳的上限爲5 5 °C，更佳的上限爲5 0 °C、尤佳 .的上限爲4 5 °C。 -14- 201033314 該聚醋系樹脂係將組成中全酸成分的合計量設: 臭耳％時，芳香族羧酸較佳爲6 0莫耳。/。以上，更隹 莫耳％以上，尤佳爲99莫耳％以上。芳香族羧酸亦可 奠耳％。芳香族殘酸低於6 0莫耳％之情形，塗膜的 弱，觀察到對於各種基材的接著強度的降低。 作爲芳香族羧酸的例子係可例示對苯二甲酸、 甲酸、鄰苯二甲酸、萘二羧酸、聯苯二羧酸、聯苯 5-羥基間苯二甲酸等的芳香族二羧酸。又，可舉出 對苯二甲酸、5 -磺酸基間苯二甲酸、4 -磺酸基苯二 磺酸基萘-2,7-二羧酸、5(4-磺酸基苯氧基）間苯 等的具有磺酸基之芳香族二羧酸、彼等之金屬鹽、 的具有磺酸鹽基之芳香族二羧酸、P-羥基安息香酸 基苯基丙酸、P-羥基苯基乙酸、6-羥基-2-萘甲酸 雙（P-羥基苯基）戊酸等的芳香族羥酸等》此等之中 對苯二甲酸、間苯二甲酸、及其混合物從提昇塗膜 ^ 力之點而言，爲特佳。 此外，作爲其他的酸成分係可舉出1，4 -環己 酸、1,3-環己烷二羧酸、1,2-環己烷二羧酸與其酸 脂環族二羧酸、琥珀酸、己二酸、壬二酸、癸二酸 烷二酸、二聚酸等的脂肪族二羧酸。 另一方面，二醇成分較佳係由脂肪族一醇、脂 醇、含有芳香族之二醇、含有醚鍵之二醇等所構成 脂肪族二醇的例子係可舉出乙二醇、L2-丙二醇、 二醇、1,4-丁 二醇、2 -甲基-1,3，-丙二醇、1,5-戊 _ 100 :爲8 5 占1〇〇 凝集力 間苯二 甲酸、 磺酸基 甲酸、 二甲酸 銨鹽等 、P-羥 ' 4,4- ，尤以 的凝集 烷二羧 酐等的 、十二 環族二 ，作爲 1,3-丙 二醇、 -15- 201033314 新戊二醇、1,6-己二醇、3-甲基-1,5-戊二醇、1,9-壬二醇、 2-乙基-2-丁基丙二醇、羥基新戊酸新戊二醇酯、二羥甲基 庚烷、2，2,4 -三甲基-1,3 -戊二醇等，作爲脂環族二醇的例 子係可舉出1,4 -環己二醇、1,4 -環己烷二甲醇、三環癸二 醇、三環癸烷二羥甲基、螺二醇、氫化雙酚A'氫化雙酚A 的環氧乙烷加成物及環氧丙烷加成物等。作爲含有醚鍵之 二醇的例子亦可按照需要，使用二甘醇、三乙二醇、二丙 二醇、另外，聚乙二醇、聚丙二醇、聚丁二醇、新戊二醇 〇 環氧乙烷加成物、新戊二醇環氧丙烷加成物。作爲含有芳 香族之二醇的例子係可例示如對二甲苯二醇、間二甲苯二 醇、鄰二甲苯二醇、1,4-苯二醇、1,4-苯二醇的環氧乙烷 加成物、雙酚A、雙酚A的環氧乙烷加成物及環氧丙烷加 成物等的、在雙酚類的2個酚性羥基上分別加成1~數莫耳 的環氧乙烷或環氧丙烷所得之二醇類等。 又’分子構造之中，亦能例示如可使用具有羥基與羧 基之羥氧化合物作爲聚酯原料的5-羥基間苯二甲酸、p-羥 ® 基安息香酸、P-羥基苯硫酚、p-羥基苯基丙酸、p-羥基苯 基乙酸、6-羥基-2-萘甲酸、4,4-雙（P-羥基苯基）戊酸等。 在本發明所使用之聚酯系樹脂中，可按照需要以導入 分枝骨架爲目的，共聚合0.1莫耳％以上5莫耳。/。以下的3 官能以上的聚羧酸類及/或多元醇類也沒有關係。特別是與 硬化劑反應而得到硬化塗膜之情形，藉由導入分枝骨架， 可得到樹脂的末端基濃度（反應點）增加、交聯密度高且強 度的塗膜。作爲此時的3官能以上之聚羧酸的例子係可使 -16- 201033314 用偏苯三酸、均苯三酸、乙二醇雙（脫水偏苯三酸酯）、丙 三醇參（脫水偏苯三酸酯）、偏苯三酸酐、苯均四酸酐 (PMDA)' 經基二苯二甲酸二酐（〇dPA)、3,3’，4,4’-二苯基 酮四羧酸二酐（8丁〇八）、3,3，，4,4，-二苯基四羧酸二酐 (BPDA)、3,3，，4,4，-二苯颯四竣酸二酐（DSDA)' 4,4，-(六 氟異亞丙基）二苯二甲酸二酐（6FDA)'2,2，-雙[(二羧基苯氧 基）苯基]丙烷二酐（BSAA)等的化合物等，另一方面，作爲 3官能以上的多元醇的例子係可使用丙三醇、三羥甲基乙 〇 烷、三羥甲基丙烷 '季戊四醇等。使用3官能以上的聚羧 酸及/或多元醇之情形，相對於全酸成分或全二醇成分，以 在〇· 1莫耳％以上5莫耳％以下，較佳爲在〇· 1莫耳％以3 莫耳％以下的範圍內進行共聚合者爲佳，超過5莫耳％時， 塗膜的斷裂點伸度等的力學物性產生降低，又會有在聚合 中引起凝膠化的可能性》 作爲在本發明所使用之聚酯系樹脂中導入酸價之方 法’可舉出藉由在聚合後加酸而將羧酸導入於樹脂之方 © 法。加酸中使用一元羧酸、二羧酸、多官能羧氧化合物時， 經由酯交換會有引起分子量降低的可能性，較佳係使用至 少具有一個羧酸酐之化合物。作爲酸酐係可使用琥珀酸 酐、馬來酸酐、鄰苯二甲酸、2,5 -降萡烯二羧酸酐、四氫 苯二甲酸酐、偏苯三酸酐、苯均四酸酐（PMDA)、羥基二苯 二甲酸二酐（ODPA)、3,3’，4,4’-二苯基酮四羧酸二酐 (BTDA)、3,3，，4,4’-二苯基四竣酸二軒（8?0入}、3,3，，4,4，-二苯颯四羧酸二酐（DSDA)、4,4’-(六氟異亞丙基）二苯二甲 •17· 201033314 酸二酐（6FDA)、2,2’-雙[(二羧基苯氧基）苯基】丙 (BSAA}等的化合物等。將構成在本發明所使用之聚 脂的全酸成分設爲100莫耳％時，進行10莫耳％以 酸會引起凝膠化，又引起聚酯的解聚合而降低了樹 量。加酸係有在聚酯聚縮合後，以整體狀態直接進f 與溶液化聚酯而進行加成的方法。在整體狀態的反 速度快速，但是大量加成時會引起凝膠化，且由於 高溫的反應，所以有注意遮斷氧氣以防止氧化等的 Ο 另一方面，在溶液狀態的加成雖然反應緩慢，但是 地導入大量的羧基。 (聚胺基甲酸酯系樹脂） 本發明中所使用的聚胺基甲酸酯系樹脂之玻璃 度較佳爲-10°c以上 60°C以下。玻璃轉移溫度 -1 0°C，會有在高溫的接著性變得不充分的傾向。玻 溫度超過60°C時，與基材的貼合變得不夠充分，又 的彈性模數變高，會有於常溫的接著性變得不夠充 © 向。較佳係玻璃轉移溫度的下限爲-5°C，更佳係玻 溫度的下限爲0 °C，更佳爲玻璃轉移溫度的下限爲 佳的上限爲 55°C，更佳的上限爲 50°C、尤佳的 4 5尤。 本發明中所使用的聚胺基甲酸酯系樹脂，作爲 較佳係使用聚酯多元醇、聚異氰酸酯、及鏈增長劑 導入酸價的方法，係有預先對構成聚胺基甲酸酯系 烷二酐 酯系樹 上的加 脂分子 :方法， 應雖然 變成在 必要。 可穩定 轉移溫 若低於 璃轉移 在常溫 分的傾 璃轉移 51。較 上限爲 >其原料 丨。作爲 :樹脂之 -18 - 201033314 聚酯多元醇賦予酸價的方法，或使用於鏈增長劑中含有羧 酸之二醇的方法等。 本發明中所使用的聚胺基甲酸酯系樹脂作爲原料使用 的前述聚酯多元醇，除了數量平均分子量以外，較佳係與 上述之聚酯系樹脂相同。本發明中所使用的聚酯多元醇的 數量平均分子量爲5χ102以上5χ104以下。數量平均分子 量若低於5χ102，胺基甲酸酯基濃度增高，會有降低在高 溫高濕下的接著性的傾向，數量平均分子量超過5χ104， 〇 聚胺基甲酸酯的聚合性降低，而引起聚合不良。較佳係下 限分子量8Χ102，更佳係下限分子量lxl〇3、較佳係上限 分子量3.5x104，更佳係上限分子量2x104。 在本發明中所使用之聚胺基甲酸酯系樹脂的製造中所 使用的聚異氰酸酯，係可爲二異氰酸酯、其二聚物（脲基二 酮）、其三聚物（異三聚氰酸酯、三醇加成物、縮二脲）等的 一種、或彼等二種以上的混合物。例如，作爲二異氰酸酯 成分係可舉出 2，4 -甲苯二異氰酸酯、2，6 -甲苯二異氰酸 〇 酯、P-苯二異氰酸酯、二苯基甲烷二異氰酸酯、m-苯二異 氰酸酯、六亞甲基二異氰酸酯、四亞甲基二異氰酸酯、3，3’-二甲氧基-4,4’-聯苯二異氰酸酯、1,5-萘二異氰酸酯'2,6-萘二異氰酸酯、4,4’-二異氰酸酯二苯基醚、1，5_苯二甲基 二異氰酸酯、1,3-二異氰酸酯甲基環己烷、ι，4-二異氰酸 酯甲基環己烷、4,4’-二異氰酸酯環己烷、4,4’-二異氰酸酯 環己基甲烷、異佛爾酮二異氰酸酯、二聚酸二異氰酸酯、 降萡烯二異氰酸酯等，基於黃變性的問題，以脂肪族.脂環 -19- 201033314 族的二異氰酸酯爲佳。進而從入手的容易度與經濟的理 由’以六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯爲特佳。 在製造本發明中所使用的聚胺基甲酸酯系樹脂上，亦 可按照需要使用鏈增長劑。作爲鏈增長劑，可舉出作爲聚 酯多元醇的構成成分而已經記載之低分子量二醇、或二羥 甲基丙酸'二羥甲基丁酸等的具有一個羧酸與二個羥基的 化合物等。其中，從酸價導入的容易度、與對泛用溶劑的 溶解性’以二羥甲基丁酸爲佳。又，作爲導入分枝之方法， © 亦可使用三羥甲基丙烷。 作爲本發明中所使用的聚胺基甲酸酯系樹脂的製造方 法，亦可將前述聚酯多元醇及前述聚異氰酸酯、按照需要 的鏈增長劑全部一起進料製反應容器內，亦可分期進料。 總之，就系統内的聚酯多元醇、鏈增長劑的羥基價的合計， 與聚異氰酸酯之異氰酸酯基的合計而言，將異氰酸酯基/ 羥基的官能基之比率在1以下使其反應。又該反應係可藉 由在對於異氰酸酯基而言爲不活性的溶媒存在下或非存在 ® 下，使其反應而進行。作爲該溶媒，係可舉出酯系溶媒（乙 酸乙酯、乙酸丁酯、丁酸乙酯等）、醚系溶媒（二噁烷、四 氫呋喃、二乙基醚等）、酮系溶媒（環己酮、甲基乙基酮、 甲基異丁基酮等）、芳香族烴系溶媒（苯、甲苯、二甲苯等） 及此等之混合溶媒，從減低環境負荷之觀點，以乙酸乙醋 與甲基乙基酮爲佳。作爲反應裝置係不限於具有攪拌裝置 的反應罐’亦可使用如捏和機、二軸擠壓機的混合混練裝 置。 -20- 201033314 爲了促進胺基甲酸酯反應，可使用在通常的胺 酯反應中所使用的觸媒，例如可使用錫系觸媒（月桂 錫、二月桂酸二甲錫、二月桂酸二丁錫、氫氧化三 二氫氧化二甲錫、辛酸亞錫等）、鉛系觸媒（油酸鉛 乙基己酸酯等）、胺系觸媒（三乙基胺、三丁基胺、 二氮雜二環辛烷、二氮雜二環十一碳烯等）等，從有 観點而言，以胺系觸媒爲佳。 (聚醯胺醯亞胺系樹脂） Ο 本發明中所使用的聚醯胺醯亞胺系樹脂的玻璃 度係較佳爲 3〇°C以上 160¾以下。玻璃轉移溫度 30尤，會有耐熱性不足之傾向。玻璃轉移溫度超過 時，由於樹脂變硬變脆，會有接著強度變得不夠充 向。較佳係玻璃轉移溫度的下限爲40°C，更佳係玻 溫度的下限爲50°C，較佳的上限爲150尤，更佳的 1 4 0°C 〇 本發明中所使用的聚醯胺醯亞胺系樹脂係使作 ® 料之酸成分與二異氰酸酯或二胺反應所得之聚醯胺 系樹脂，酸成分較佳係使用具有芳香環之聚羧酸的 於兩末端具有羧基之丙烯腈-丁二烯橡膠。 在製造本發明中所使用的聚醯胺醯亞胺系樹脂 具有芳香環之聚羧酸的酸酐係完成醯亞胺環形成的 作爲具有芳香環之聚羧酸的酸酐係可舉出例如偏 酐、苯均四酸二酐、乙二醇雙脫水偏苯三酸酯、丙 脫水偏苯三酸酯、1,4 -丁二醇雙脫水偏苯三酸酯、 基甲酸 酸三甲 甲錫、 .錯-2 - 味啉、 害性之 轉移溫 若低於 1601 分的傾 璃轉移 上限爲 爲其原 醯亞胺 酸酐、 之際， 任務。 苯三酸 二醇雙 六亞甲 -21- 201033314 基二醇雙脫水偏苯三酸酯、聚乙二醇雙脫水偏苯三酸酯、 聚丙二醇雙脫水偏苯三酸酯等的伸烷二醇雙脫水偏苯三酸 酯、3,3’，4,4’-二苯基酮四羧酸二酐、3,3，，4,4，-聯苯四羧 酸二酐、1,2,5,6 -萘四羧酸二酐、1，4,5,8 -萘四羧酸二酐、 2,3,5,6 -吡啶四羧酸二酐、3,4,9,10 -茈四羧酸二酐、 3,3’，4,4’-二苯楓四羧酸二酐、111_聯三苯-3,3’，4,4，-四羧 酸二酐、4,4’-羥基二苯二甲酸二酐、：六氟基 -2,2-雙（2,3-或 3,4-二羧基苯基）丙烷二酐、2,2-雙（2,3-〇 或3,4_二羧基苯基）丙烷二酐、2,2 -雙[4-(2,3 -或3,4-二羧 基苯氧基）苯基]丙烷二酐、1，1，1，3,3,3-六氟基-2,2-雙 [4-(2,3-或 3,4-二羧基苯氧基）苯基]丙烷二酐、1,3-雙 (3,4-二羧基苯基）-1,1,3,3-四甲基二矽氧烷二酐等，此等 係可單獨使用，併用二種以上也沒有關係。 在兩末端具有該羧基之丙烯腈-丁二烯橡膠係爲了賦 予聚醯胺醯亞胺樹脂可撓性與接著性而使用，將全酸成分 設爲1 0 0莫耳％時，較佳係3莫耳％以上1 5莫耳％以下， © 更佳係3莫耳。/。以上1 〇莫耳％以下。共聚合量低於3莫耳 %時，不能發現可撓性與接著性，超過1 5莫耳％時，會有 溶劑溶解性降低之傾向。 作爲在本發明中所使用的聚醯胺醯亞胺系樹脂的製造 中所使用的酸成分，在無損及本發明效果的程度內，可使 用脂肪族或脂環族的酸酐與二羧酸作爲其他的酸成分。例 如，可舉出丁烷-1,2,3,4-四羧酸二酐、戊烷-1,2，4,5-四羧 酸二酐、環丁烷四羧酸二野、六氫化苯均四酸二酐、環己 -22- 201033314 -1 -稀-2，3，5，6 -四竣酸二酐、3-乙基環己-1 -燒 -3-(l，2)，5,6-四羧酸二酐、1-甲基-3-乙基環己燒 -3-(1，2)，5,6-四羧酸二酐、1-甲基-3-乙基環己-1-嫌 -3-(1，2)，5,6-四羧酸二酐、1-乙基環己烷-1-(1，2)，3,4、四 羧酸二酐、1-丙基環己烷-1-(2,3)，3,4-四羧酸二酐、1,3-二丙基環己烷-卜（2,3)，3-(2,3)-四羧酸二酐、二環己基 -3,4,3’，4’-四羧酸二酐、雙環[2_2_1]庚烷- 2,3,5,6-四羧酸 二酐、1-丙基環己烷-1-(2,3),3,4 -四羧酸二酐、1,3-二两 〇 基環己烷-1-(2,3),3-(2,3)-四羧酸二酐、二環己基 -3，4,3’，4’-四羧酸二酐、雙環[2.2.1】庚烷- 2,3,5,6-四羧酸 二酐、雙環[2.2.2]辛烷- 2,3,5,6 -四羧酸二酐、雙環[2.2.2】 辛-7-烯- 2,3,5,6-四羧酸二酐、六氫化偏苯三酸酐等的酸 酐或與聚酯系樹脂中所記載者相同的二羧酸等，此等係可 單獨使用，倂用二種以上也沒有關係。 作爲在製造本發明中所使用的聚醯胺醯亞胺系樹脂之 際所使用的二異氰酸酯或二胺，可舉出與在聚胺基甲酸酯 ® 系樹脂中所記載者相同的二異氰酸酯、或對應於此等的二 異氰酸酯之二胺，此等係可單獨使用，倂用二種以上使用 也沒有關係。 本發明中所使用的聚醯胺醯亞胺系樹脂中，以提昇耐 熱性爲目的，可聚合具有3個以上官能基之化合物。例如， 均苯三酸等的多官能羧酸；5-羥基間苯二甲酸等的具有羥 基之二羧酸；5-胺基間苯二甲酸等的具有胺基之二羧酸； 丙三醇、聚丙三醇等的具有3個以上羥基者、參（2 -胺基乙 -23- 201033314 基）胺等的具有ί 解性之觀點而言 之二羧酸、參（2 本發明中所 本發明效果的程 二聚酸、聚矽氧 接著性所謂本發 作爲本發明 〇 溶劑，可舉出例 基咪唑啶酮、二 環己酮、環戊酮 合效率而言，以 中所使用的溶劑 揮發分濃度與溶 作爲低沸點 系溶劑、己烷、 Ο 醇、丙醇、丁醇 酮、甲基異丁基 基醚、四氫呋喃 酸異丁酯等的酯 <無機塡充材（Β) 作爲本發明 散液（α )搖溶性 塡充材，例如可 ;個以上胺基者，此等之中，從反應性、溶 ，較佳係5-羥基間苯二甲酸等的具有羥基 -胺基乙基）胺等的具有3個以上胺基者。 使用的聚醯胺醯亞胺系樹脂中，在無損及 度內，可共聚合聚酯、聚醚、聚碳酸酯、 烷等。此時，爲無損及耐熱性或溶解性、 明的效果，有適當選擇共聚合量的必要。 的聚醯胺醯亞胺樹脂的聚合中能夠使用的 如Ν -甲基-2-啦略陡酮、γ-丁內酯、二甲 甲亞楓、二甲基甲醯胺、二甲基乙醯胺、 、四氫呋喃等’其中從低沸點與良好的聚 二甲基乙酿胺爲佳。又聚合後可使用聚合 或其他的低沸點溶劑進行稀釋，以調整不 液黏度。 溶劑’可舉出甲苯、二甲苯、等的芳香族 庚院、辛院等的脂肪族系溶劑；甲醇、乙 、異丙醇等的醇系溶劑；丙酮、甲基乙基 酮、環己酮、環戊酮等的酮系溶劑；二乙 等的酸系溶劑；乙酸乙醋、乙酸丁酿、乙 系溶劑等。 > 中所使用的無機塡充材（Β)，只要能賦予分 即可，沒有特別地限制。作爲這樣的無機 使用氧化鋁、二氧化矽、二氧化鈦、氧化 -24- 201033314 钽、氧化锆、氮化矽、鈦酸鋇、碳酸鋇、鈦酸鉛、鈦酸銷 酸鉛、鈦酸銷酸鑭鉛、氧化鎵、尖晶石、莫來石、堇青石、 滑石、氫氧化鋁、氫氧化鎂、鈦酸鋁、氧化釔含有氧化鉻、 矽酸鋇、氮化硼、碳酸鈣、硫酸鈣、氧化鋅、硼酸鋅、鈦 酸鎂、硼酸鎂、硫酸鋇、有機膨潤土、碳等，此等係可單 獨使用，倂用二種以上也沒有關係。從接著劑用樹脂組成 物的透明性、機械特性、耐熱性、搖溶性賦予之觀點而言， 以二氧化矽爲佳，特別是以具有3次元網目構造之煙霧狀 〇 二氧化矽爲佳。又，在賦予疏水性方面，以單甲基三氯矽 烷、二甲基二氯矽烷、六甲基二矽氮烷、辛基矽烷、矽油 等進行處理之疏水性二氧化矽者爲佳。使用作爲無機塡充 材（B)之煙霧狀二氧化矽的情形中，一次粒子的平均直徑係 以30nm以下爲佳，更佳係25nm以下。一次粒子的平均 直徑超過30nrn時，會有粒子間或與樹脂之相互作用降低 且耐熱性降低之傾向。此外，此處所謂的一次粒子的平均 .直徑，係從使用掃瞄型電子顯微鏡所得之一次粒子像，無 G 作爲抽出之粒子100個的圓相當直徑的平均値。 無機塡充材（B)的摻合量係相對於熱可塑性樹脂 (A) 100質量份，較佳爲10質量份以上50質量份以下，更 佳爲1 3質量份以上4 5質量份以下，尤佳爲1 5質量份以 上40質量份以下。低於10質量份時，會有無法發揮耐熱 性提昇之效果的情形，另外超過50質量份時，恐有產生二 氧化矽的分散不良、又溶液黏度變得過高、又產生不適合 於作業性、或是接著性降低之虞。 -25- 201033314 <溶劑（c) > 本發明中所使用的溶劑（C)係可由單一成分所構成 者、亦可由2種以上的複數成分所構成之混合溶劑。溶劑 (C)只要能溶解熱可塑性樹脂（A)及環氧樹脂（D)者即可，沒 有特別地限制。作爲這樣的溶劑，可舉出二甲基乙醯胺、 N-甲基-2-吡咯啶酮等的醯胺系溶劑、甲醇、乙醇、異丙醇 等的醇系溶劑、甲苯、二甲苯等的芳香族系溶劑、丙酮、 甲基乙基酮、環己酮等的酮系溶劑、乙酸乙酯等的酯系溶 〇 劑等，從作業性之觀點而言，較佳係可舉出二甲基乙醯胺、 乙醇、甲苯、二甲苯、甲基乙基酮、乙酸乙酯，從乾燥容 易性之觀點而言，更佳係可舉出甲苯、甲基乙基酮、乙酸 乙酯。此等的溶劑係可1種單獨使用、倂用2種以上也沒 有關係。 <環氧樹脂（D)> 本發明的接著劑樹脂組成物係含有具有二聚環戊二烯 * 骨架之環氧樹脂（D)作爲必要成分。由具有剛直的二聚環戊 ® 二烯骨架之環氧樹脂所構成的硬化塗膜，由於吸濕率非常 小，又降低硬化塗膜的交聯密度，可緩和剝離時的應力， 所以可提昇耐加濕焊接性。作爲環氧樹脂（D)的具體例，可 舉出DIC製HP7200系列。 具有二聚環戊二烯骨架之環氧樹脂（D)的摻合量係爲 接著劑用樹脂組成物中所含環氧樹脂全體的6 0質量。/。以上 爲佳，更佳係7 5質量％以上，更佳爲9 〇質量％以上。藉 -26- 201033314 由含有60質量％以上的具有二聚環戊二烯骨架之環氧樹脂 (D)，能夠發現更優異之耐加濕焊接性。 於本發明的接著劑用樹脂組成物中含有具有氮原子之 環氧樹脂作爲環氧樹脂’可用比較低溫度的加熱來B階段 化接著劑組成物的塗膜，而且會有抑制B階段薄膜的流動 性且可提昇在接著操作的作業性的傾向，另外可期待抑制 B階段薄膜發泡的效果，而爲較佳。作爲含有氮原子之環 氧樹脂，可舉出例如四縮水甘油基二胺基二苯基甲烷、三 © 縮水甘油基對胺基酚、四縮水甘油基雙胺基甲基環己酮、 Ν，Ν,Ν’，Ν’-四縮水甘油基-m-二甲苯二胺等的縮水甘油基 胺系等。含有此等氮原子之環氧樹脂的摻合量較佳係爲環 氧樹脂全體的20質量％以下。摻合量多於20質量％時， 會有變得過度提高剛直性，而接著性降低的傾向，又，會 有在接著片保存中交聯反應容易進行，而片材壽命降低之 傾向。較佳摻合量的上限爲1 0質量％，更佳爲5質量％。 亦可倂用其他的環氧樹脂作爲本發明中所使用的環氧 ® 樹脂。可舉出例如雙酚A二縮水甘油基醚、雙酚S二縮水 甘油基醚、酚醛清漆縮水甘油基醚、溴化雙酚A二縮水甘 油基醚等的縮水甘油基醚類型、六氫化苯二甲酸縮水甘油 基酯、二聚酸縮水甘油基酯等的縮水甘油基酯類型、三縮 水甘油基異三聚氰酸酯、或3,4-環氧環己基甲基羧酸酯、 環氧化聚丁二烯、環氧化大豆油等的脂環族或脂肪族環氧 化物等’可1種單獨使用、倂用二種以上也沒有關係。 本發明中所使用的環氧樹脂的硬化反應中，可使用硬 -27- 201033314 化觸媒。例如將2 -甲基咪唑或1，2 -二甲基咪唑、2 甲基咪唑或2-苯基-4-甲基咪唑或1-氰基乙基-2 甲基咪唑等的咪唑系化合物、三乙基胺、三乙二月 基- N-(2-二甲基胺基乙基）哌阱、1,8_二氮雜二環 ~\--碳烯-7、1,5-二氮雜二環（4,3,0)-壬烯-5、6- 基-1,8-二氮雜二環（5,4,0)-十一碳烯-7等的三 此等之三級胺類用酚、辛酸、四級化四苯基硼酸 以胺鹽而成之化合物，三烯丙基锍六氟基銻酸酯 © 基碘鎗六氟基亞銻酸酯等的陽離子觸媒、三苯基 等之中，從熱硬化性及耐熱性、對金屬的接著性 的保存穩定性之點而言，較佳將1,8-二氮雜二瑪 --碳烧-7、1,5 -二氮雜二環（4,3,0) -壬嫌-5、6- 基-1,8-二氮雜二環（5,4,0)-十一碳烯-7等的三 此等之三級胺類，用酚、辛酸、四級化四苯基硼 予以胺鹽而成之化合物。此時的摻合量係相對於 樹脂（A)100重量份，較佳爲〇·〇ΐ~ι.〇重量份的 © 若在該範圍内’對於熱可塑性樹脂（A)與環氧樹脂 媒效果係更爲增加，而可得到堅固的接著性能。 <其他的添加劑> 本發明的接著劑用樹脂組成物可直接這樣、 各種硬化性樹脂、添加劑以形成接著劑組成物。 性樹脂’可舉出聚矽氧樹脂、胺基樹脂、酚系樹 酸酯化合物等。 卜乙基-4-乙基-4-安、N，-甲 [(5,4,0)-二丁基胺 級胺類及 酯鹽等予 、二烯丙 膦等。此 、摻合後 I(5,4,0)-二丁基胺 級胺類及 酸酯鹽等 熱可塑性 摻合量。 反應之觸 或更摻合 作爲硬化 脂、異氰 -28- 201033314 作爲酚系樹脂可舉出例如烷基化酚類、甲酚類的甲醛 縮合物。具體而言，可舉出烷基化（例如，甲基、乙基、丙 基、異丙基、丁基）酚、p-第三戊基酚、4,4’-第二亞丁基酚、 p-第三丁基酣、〇 -甲酌、m -甲酣、P -甲酌、P-環己基酣、 4,4’-異亞丙基酚、p_壬基酚、p-辛基酚、3-十五烷基酚、 酚、苯基-〇-甲酚、p_苯基酚、二甲苯酚等的甲醛縮合物。 作爲胺基樹脂，可舉出例如尿素、三聚氰胺、苯并胍 胺等的甲醛加成物、以及由此等的碳原子數爲1~6的醇之 ❹ 烷基醚化合物。具體而言，可舉出甲氧基化羥甲基尿素、 甲氧基化羥甲基N，N-伸乙基尿素、甲氧基化羥甲基氰胍、 甲氧基化羥甲基三聚氰胺、甲氧基化羥甲基苯并胍胺、丁 氧基化羥甲基三聚氰胺、丁氧基化羥甲基苯并胍胺等，較 佳爲甲氧基化羥甲基三聚氰胺、丁氧基化羥甲基三聚氰 胺、及羥甲基化苯并胍胺，可分別單獨或合倂使用。 作爲異氰酸酯化合物係有芳香族、脂肪族的二異氰酸 酯、3價以上的聚異氰酸酯，可爲低分子化合物、高分子 © 化合物中任一者。例如，可舉出將四亞甲基二異氰酸酯、 六亞甲基二異氰酸酯、甲苯二異氰酸酯、二苯基甲烷二異 氰酸酯、氫化二苯基甲烷二異氰酸酯、苯二甲基二異氰酸 酯、氫化苯二甲基二異氰酸酯、異佛爾酮二異氰酸酯或此 等的異氰酸酯化合物的三聚物、及此等之異氰酸酯化合物 的過剩量，與例如乙二醇、丙二醇、三羥甲基丙烷、丙三 醇、山梨糖醇、乙二胺、單乙醇胺、二乙醇胺、三乙醇胺 等的低分子活性氫化合物或各種聚酯多元醇類、聚醚多元 -29- 201033314 醇類、聚醯胺類的高分子活性氫化合物等反應所得的含有 末端異氰酸酯基之化合物。 異氰酸酯化合物係亦可爲嵌段化異氰酸酯。作爲異氰 酸酯嵌段化劑，可舉出例如酚、苯硫酚、甲基苯硫酚、甲 酚、二甲苯酚、間苯二酚、硝基苯酚、氯苯酚等的酚類； 丙酮肟、甲基乙基酮肟、環己酮肟等的肟類；甲醇、乙醇、 丙醇、丁醇等的醇類；氯乙醇、1,3-二氯-2-丙醇等的鹵素 取代醇類；第三丁醇、第三戊醇等的第3級醇類；e-己內 Ο 醯胺、（5-戊內醯胺、r-丁內醯胺、冷-丙內醯胺等的內醯 胺類，另外亦可舉出芳香族胺類；醯亞胺類；乙醯丙酮、 乙醯乙酸酯、丙二酸乙基酯等的活性亞甲基化合物、硫醇 類；亞胺類；尿素類；二芳基化合物類亞硫酸氫鈉等。嵌 段化異氰酸酯係可利用以往眾所周知的適宜方法，使上述 異氰酸酯化合物、異氰酸酯化合物與異氰酸酯嵌段化劑進 行加成反應而得到。 本發明的接著劑用樹脂組成物亦可按照需要摻合矽烷 ® 偶合劑。藉由摻合矽烷偶合劑，由於可提昇對金屬的接著 性與耐熱性的特性而非常良好。作爲矽烷偶合劑係沒有特 別地限定，可舉出具有不飽和基者、具有縮水甘油基者、 具有胺基者等。作爲具有不飽和基之矽烷偶合劑，可舉出 乙烯基參（Θ-甲氧基乙氧基）矽烷、乙烯基三乙氧基矽烷、 乙烯基三甲氧基矽烷等。作爲具有縮水甘油基之矽烷偶合 劑，可舉出 r-環氧丙氧基丙基三甲氧基矽烷、点-(3,4-環氧環己基）乙基三甲氧基矽烷、-(3,4-環氧環己基）乙基 -30- 201033314 三乙氧基矽烷等。作爲具有胺基之矽烷偶合劑，可舉出 N-/3-(胺基乙基）-r-胺基丙基三甲氧基矽烷、N-/3-(胺基 乙基）-r -胺基丙基甲基二甲氧基矽烷、N-苯基-r -胺基丙 基三甲氧基矽烷等。此等之中，從耐熱性之觀點而言’以 r -環氧丙氧基丙基三甲氧基矽烷、Θ -(3，4 -環氧環己基） 乙基三甲氧基矽烷、/3 -( 3，4 -環氧環己基）乙基三乙氧基矽 烷等的具有縮水甘油基之矽烷偶合劑爲尤佳。矽烷偶合劑 的摻合量較佳係相對於熱可塑性樹脂（A) 1 0 0重量份，爲 © ‘ 0.5〜20重量份的摻合量。矽烷偶合劑的摻合量低於0.5重 量份時，會有所得之接著劑變成耐熱性不良之情形，超過 20重量份時，會有成爲耐熱性不良、接著性不良之情形。 本發明的接著劑用樹脂組成物係可按照需要，適當摻 合溴系、磷系、氮系、氫氧化金屬化合物等的難燃劑、流 平劑、顔料、染料等的添加劑。 <接著片> 本發明中’所謂的接著片係含有本發明接著劑用樹脂 ® 組成物中所含有的前述熱可塑性樹脂（A)、前述無機塡充材 (B)、前述環氧樹脂（D)及來自於此等的反應生成物者。在 本發明的接著片係含有本發明接著劑用樹脂組成物中所含 有的前述熱可塑性樹脂（Α)、前述無機塡充材（Β}、前述環 氧樹脂（D)及來自於此等的反應生成物之層單獨所構成之 片’或亦可爲含有基材與本發明接著劑用樹脂組成物中所 含有的前述熱可塑性樹脂（Α)、前述無機塡充材（Β)、前述 環氧樹脂（D)及來自於此等的反應生成物之層所構成之 -31- 201033314 片’或亦可爲由含有基材與本發明接著劑用樹脂組成物中 所含有的前述熱可塑性樹脂（A)、前述無機塡充材（B)、前 述環氧樹脂（D)及來自於此等的反應生成物之層、與脫膜基 材所構成之片。含有本發明接著劑用樹脂組成物中所含有 的前述熱可塑性樹脂（A)、前述無機塡充材（B)、前述環氧 樹脂（D)及來自於此等的反應生成物之層，係可形成於基材 的單面、亦可在兩面上形成。又，接著片亦可含有微量或 少量的溶劑（C)。接著性片係具有藉由接著劑組成物使基材 〇 接著於被接著材的功能。接著性片的基材係就有在接著 後，成爲被接著材之保護層的功能。另外，使用脫膜性基 材作爲接著性片的基材時，可將脫膜性基材脫膜，進而將 接著劑層轉印至其他被接著材上。 本發明的接著劑組成物係按照常用方法，藉由塗布至 各種基材上，除去溶劑的至少一部分並使其乾燥，可得到 本發明的接著片。另外，在除去溶劑的至少一部分使其乾 燥之後，將脫膜基材貼合至接著劑層上時，由於不會引起 © 對基材的內移而變得可以卷取，且操業性優異的同時，接 著劑層受到保護，所以保存性優異，使用也容易。又’塗 布於脫膜基材上使其乾燥之後，若按照需要貼附其他的脫 膜基材，亦可將接著劑層本身轉印至其他的基材上。 這裡，作爲塗布本發明組成物之基材係沒有特別地限 定，可舉出薄膜狀樹脂、金屬板、金屬箔、紙類等。作爲 薄膜狀樹脂，可例示聚酯樹脂、聚醯胺樹脂、聚醯亞胺樹 脂、聚醯胺醯亞胺樹脂、烯烴系樹脂等。作爲金屬板及金 -32- 201033314 屬箔的素材，可例示sus、銅、鋁、鐵、鋅等的各種金屬、 及各自的合金、電鍍品等，紙類可例示如高級紙、牛皮紙、 卷筒紙、玻璃紙等。又，複合素材係可例示如玻璃增強環 氧樹脂等。從與接著劑組成物的接著力、耐久性而言，作 爲塗布本發明的組成物之基材，較佳爲聚酯樹脂、聚醯胺 樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、S U S鋼板、銅 箔、鋁箔、玻璃增強環氧樹脂。 另外，作爲塗布本發明組成物之脫膜基材係沒有特別 © 地限定，可舉出例如在高級紙、牛皮紙、卷筒紙、玻璃紙 等紙的兩面上，設置黏土、聚乙烯、聚丙烯等的塡充劑的 塗布層，然後在其各塗布層上塗布聚矽氧系、氟系、醇酸 系的脫膜劑者’及在聚乙烯、聚丙烯、乙烯-α-烯烴共聚 物、丙烯-α-烯烴共聚物等的各種烯烴薄膜單獨、及在聚 對苯二甲酸乙二酯等的薄膜上，塗布上述脫膜劑者，惟基 於與被塗布之接著劑層的脫膜力、聚矽氧會賦予電性不良 影響等的理由，較佳係使用在高級紙的兩面上進行聚丙烯 © 塡充處理且於其上使用醇酸系脫膜劑者、於聚對苯二甲酸 乙二酯上使用醇酸系脫膜劑者。 此外’本發明中作爲塗布接著劑組成物於基材上之方 法’沒有特別地限定’可舉出刮刀式塗布機（Comma coater)、逆向輥塗布機等。或者，亦可按照需要，設置印 刷配線板構成材料之壓延銅箱、或以直接或轉印法在聚醯 亞胺薄膜上設置接著劑薄膜層。乾燥後的接著劑薄膜厚度 係可按照需要做適宜變更，較佳係5~200；am的範圍。接 -33- .201033314 著薄膜厚低於5ym的話，接著強度不充分。爲200#m 以上的話乾燥不充分，且殘留溶劑增多，會有例如在印刷 配線板製造的壓制時產生鼓泡的問題點。乾燥條件係沒有 特別地限定，乾燥後的殘留溶劑率爲4質量％以下爲佳、1 質量％以下爲較佳。地於4質量％時，會有產生在印刷配線 板壓制時殘留溶劑發泡，且產生鼓泡的問題之情形。 <印刷配線板> 在本發明的印刷配線板係含有由形成導體電路之金屬 箔與樹脂層所形成之積層體作爲構成要素者。印刷配線板 係例如使用覆金屬積層體，利用減法等的以往眾所周知的 方法而製造的。可按照需要使用覆蓋薄膜、絲網印刷油墨 等部分、或是全面地被覆由金屬箔所形成之導體電路，總 稱爲所謂的可撓性電路板（FPC)、扁平電纜、帶式自動焊接 (TAB)用的電路板等。 本發明的印刷配線板係可形成作爲印刷配線板所採用 獲得之任意積層構成。例如’可形成由基材薄膜層、金屬 © 箔層、接著劑層、及覆蓋薄膜層的4層所構成之印刷配線 板。另外，例如可形成由基材薄膜層、接著劑層、金屬箱 層、接著劑層、及覆蓋薄膜層的5層所構成之印刷配線板。 印刷配線板係可按照需要用增強材料進行補強，此時，增 強材料、接著劑層係設置在基材薄膜層的下方。 另外’亦可按照需要形成積層2或3層以上的上述印 刷配線板之構成。 -34- .201033314 本發明的樹脂組成物係可適當使用於印刷配線板的各 接著劑層。特別是本發明的樹脂組成物作爲接著劑使用 時’對於構成印刷配線板之基材具有很高的接著性，且具 有可因應於無鉛焊料之高度的耐熱性，以及即使在高溫高 濕度下亦可維持高的接著性。特別是在評價耐焊接性的高 溫領域中’藉由均衡良好地賦予樹脂與樹脂的化學交聯以 及樹脂與無機塡充材的物理交聯，在加濕狀態下耐焊接性 試驗中不會因水分蒸發所引起的衝撃而膨脹或變形，可以 Ο 緩和應力’適合於金屬箔層與覆蓋薄膜層間的接著劑、及 基材薄膜層與增強材料層間的接著。特別是在使用如SUS 板、鋁板的金屬增強材料之情形中，由於在加濕狀態下進 行焊接之際’從增強材料側水分無發蒸發，所以波及基材 薄膜層與增強材料層間的接著劑層的衝撃特別強大，適合 作爲像這樣情形下用於接著的樹脂組成物。 本發明的印刷配線板中，作爲基材薄膜係可使用迄今 作爲印刷配線板基材使用的任意樹脂薄膜。作爲基材薄膜 〇 的樹脂係可使用含有鹵素的樹脂，亦可使用不含有鹵素的 樹脂。基於環境問題之觀點，較佳係不含有鹵素的樹脂， 基於難燃性之觀點的話，亦可使用含有鹵素的樹脂。基材 薄膜係較佳爲聚醯亞胺薄膜或聚醯胺醯亞胺薄膜。 作爲本發明中所使用的金屬箔，可使用於電路基板中 可使用之任意的以往眾所周知的導電性材料。作爲材質可 舉出例如銅箔、鋁箔、鋼箔、及鎳箔等，對於複合此等之 -35- 201033314 複合金屬箔、用鋅、鉻化合物等其他金屬處理之金屬箔亦 可使用。較佳係銅箔。 關於金屬箔的厚度係沒有特別地限制，較佳爲lym 以上，更佳爲3ym以上，尤佳爲10ym以上。又，較佳 爲50ym以下，更佳爲30/zm以下，尤佳爲20//m以下。 厚度過薄之情形中，會有電路得不到充分的電性能之情 形，另一方面，厚度過厚之情形中，會有電路製作時的加 工能率等降低之情形。 〇 金屬箔通常係以軋輥狀的形態而提供的。製造本發明 印刷配線板之際所使用的金屬箔的形態，沒有特別地限 定。使用軋輥狀形態的金屬箔之情形，其長度係沒有特別 地限定。又，其寬度也沒有特別地限定，較佳爲 250~1000mm 左右者。 覆蓋薄膜係可使用以往眾所周知的任意絶緣薄膜作爲 印刷配線板用的絶緣薄膜。例如，可使用聚醯亞胺、聚酯、 聚苯硫醚、聚醚颯、聚醚醚酮、芳族聚醯胺、聚碳酸酯、 ® 聚芳酯、聚醯亞胺、聚醯胺醯亞胺等的由各種聚合物所製 造之薄膜。較佳係聚醯亞胺薄膜或聚醯胺醯亞胺薄膜，更 佳爲聚醯亞胺薄膜。 聚醯亞胺薄膜係以作爲其樹脂成分之聚醯亞胺樹脂爲 主成分。樹脂成分之中，90重量％以上爲聚醯亞胺爲佳、 95重量％以上爲聚醯亞胺爲較佳、98重量％以上爲聚醯亞 胺爲更佳、99重量％以上爲聚醯亞胺爲特佳。作爲聚醯亞 胺樹脂，可使用以往眾所周知的任意樹脂。 -36- 201033314 作爲覆蓋薄膜的素材樹脂可使用含有鹵素的樹脂、亦 可使用不含有鹵素的樹脂。基於環境問題之觀點，較佳係 不含有鹵素的樹脂，基於難燃性之觀點的話，亦可使用不 含有鹵素的樹脂。 作爲增強材料，可使用SUS板、鋁板等的金屬板、聚 醯亞胺薄膜、用環氧樹脂硬化玻璃繊維的板（玻璃增強環氧 樹脂板）等》特別是本發明的樹脂組成物係對於SUS板或 銘板與聚醯亞胺薄膜的接著能發揮極大的性能，其接著 〇 性、耐熱性係顯示肥常優異之性能。 本發明的印刷配線板係除了使用上述各層的材料以 外’可使用以往眾所周知的任意製程來進行製造。 在較佳的實施態樣方面，製造在覆蓋薄膜層上積層接 著劑層之半成品（以下，稱爲「覆蓋薄膜側半成品」）。另 外’製造在基材薄膜層上積層金屬箔層以形成所期望的電 路圖案的半成品（以下，稱爲「基材薄膜側2層半成品」）、 或在基材薄膜層上積層接著劑層，於其上積層金屬箔層， ❿ 以形成所期望的電路圖案的半成品（以下，稱爲「基材薄膜 側3層半成品」）（以下，一倂將貼合基材薄膜側2層半成 品與基材薄膜側3層半成品稱爲「基材薄膜側半成品」）。 藉由貼合如此所得之覆蓋薄膜側半成品、與基材薄膜側半 成品，可得到4層或5層的印刷配線板。而且，製造在增 強材料層上積層接著劑層之半成品（以下，稱爲「增強材料 側半成品」），並可按照需要對印刷配線板的基材薄膜層進 行貼合補強。又，將在增強材料與基材薄膜間所使用的接 -37- 201033314 著劑塗布至脫膜基材上，並轉印至印刷配線板的基材薄膜 裏面，亦可與增強材料貼合在一起。 基材薄膜側半成品係例如可藉由含有下述之製造法而 得到： (A) 在前述金屬箔上塗布形成基材薄膜之樹脂溶液，並 初期乾燥塗膜之步驟 (B) 將在（A)所得之金屬箔與初期乾燥塗膜的積層物進 行熱處理·乾燥之步驟（以下，稱爲「熱處理.脫溶劑步驟」）。 〇 在形成金屬箔層的電路上係可使用以往眾所周知的方 法。可使用有源法，亦可使用減法。較佳係減法。 所得之基材薄膜側半成品係可直接這樣與覆蓋薄膜側 半成品貼合而使用，又亦可在與脫膜薄膜貼合且保管之 後，與覆蓋薄膜側半成品貼合而使用。 覆蓋薄膜側半成品係例如將接著劑塗布至覆蓋薄膜上 而製造的。可按照需要在經塗布之接著劑中進行交聯反 應。較佳的實施態樣係使接著劑層半硬化。 © 所得之覆蓋薄膜側半成品係可直接這樣與基材側半成 品貼合而使用，又亦可在與脫膜薄膜貼合且保管之後，與 基材薄膜側半成品貼合而使用。 基材薄膜側半成品與覆蓋薄膜側半成品係分別例如以 軋輥的形態保管之後，貼合以製造印刷配線板。作爲貼合 的方法係可使用任意的方法，例如可使用壓力機或軋輥等 使其貼合。又，亦可利用加熱加壓、或加熱軋輥裝置等的 方法，一邊進行加熱、一邊使其兩者貼合。 -38- 201033314 增強材料側半成品例如爲像聚醯亞胺薄膜般柔軟且可 卷取之增強材料的情形下，將接著劑塗布至增強材料上而 製造爲適宜。又，例如爲像使SUS、鋁等的金屬板、玻璃 繊維經環氧樹脂硬化之板等般堅硬且不能卷取之補強板的 情形下，預先藉由將經塗布之接著劑轉印塗布至脫膜基材 上而製造爲適宜。又，可按照需要在塗布之接著劑中進行 交聯反應。較佳的實施態樣係使接著劑層半硬化。 所得之增強材料側半成品係可直接這樣與印刷配線板 〇 裏面貼合而使用，又亦可與脫膜薄膜貼合且保管之後，與 基材薄膜側半成品貼合而使用。 基材薄膜側半成品、覆蓋薄膜側半成品、補強劑側半 成品係均爲本發明的印刷配線板用積層體。 實施例 列舉以下的實施例以詳細說明本發明，惟本發明係不 受限於實施例。此外，在實施例中僅記’載爲「份」者係表 示質量份。又，沒有特別記載而記述爲環氧樹脂摻合率之 © 情形中，係指{EV(r )xEW(r )}/{AV(/5 )XAW(/S )}之値。 又，在表中，例如若爲「>40」係表示超過40,若爲「<230_ 係表示低於2 3 0。 (物性評價方法） (1)熱可塑性樹脂的組成 將熱可塑性樹脂溶解於重氯仿，並藉由1H-NMR分析 以求得各成分的莫耳比。但是，在該熱可塑性樹脂不溶解 -39- 201033314 於重氯仿之情形’係將其溶解於重二甲亞颯以進行 1 Η - N M R 分析。 (2) 數量平均分子量Μη 將試料溶解或稀釋於四氫呋喃中以使得樹脂濃度成爲 0.5 %左右，將經孔徑〇.5/ζιη的聚四氟乙烯製薄膜過濾器 過濾者作爲測定用試料，四氫呋喃作爲移動相，並利用微 差折射計爲檢出器之凝膠滲透層析法來測定分子量。流速 設爲lmL/分、管柱溫度設爲30Ί〇。管柱係使用昭和電工 Ο 製KF_802、8〇4L、806L。分子量標準係使用單分散聚苯 乙烯。但是’試料不溶解於四氫呋喃之情形則變更四氫呋 喃而改使用n，n -二甲基甲醯胺。 (3) 玻璃轉移溫度 聚酯樹脂及聚胺基甲酸酯樹脂的情形係使用微差掃瞄 熱量計（DSC)，並以20°C /分的昇溫速度來測定。 聚醯胺醯亞胺樹脂的情形係對於寬度1 0mm、厚度 30# m的短冊狀試料，使用IT計測控制公司製的動態黏彈 〇 性測定裝置DVA-220，以頻率1 10Hz來進行動態黏彈性 的測定，並將該儲藏彈性模數的變曲點做爲玻璃轉移點。 此外，短冊狀試料係可經由將聚醯胺醯亞胺的聚合溶液塗 布至聚丙烯製薄膜上，在1~ lOmmHg的減壓狀態下，在 1 201乾燥10小時以得到去除溶劑之薄膜。 (4) 酸價 將試料〇.2g溶解於20ml的氯仿中，使用酚酞做爲指 示劑，在只有0.1N的氫氧化鉀乙醇溶液、聚醯胺醯亞胺 -40- 201033314 系樹脂的情形用甲醇鈉甲醇溶液進行滴定，並算出每樹脂 l〇6g 的當量（eq/l〇6g)。 (5)環氧價 按照JISK7236，使用高氯酸滴定法，從所得之環氧 當量（含1當量環氧基的樹脂質量）算出每樹脂l〇6g的當量 (eq/ 1 〇6g) 〇 (特性評價方法） (1)耐焊接性、剝離強度 © (1)-1評價用試樣1作成方法 將後述之接著劑組成物塗布至厚度25#m的聚醯亞 胺薄膜（ΚΑΝΕ KA股份有限公司製、APICAL)上，以使得乾 燥後的厚度爲30ym’在1301使其乾燥3分鐘。將如此 所得之接著性薄膜（B階段品）與30/z m的壓延銅箔貼合之 際，以壓延銅箔的光澤面與接著劑接觸的方式，在16〇t： 中3 5kgf/ cm2的加壓下加壓30秒鐘，使其接著。接著， 在1 4 0 °C熱處理4小時使其硬化，以得到耐焊接性及剝離 © 強度評價用試樣1(初期評價用）。 又’將接著性薄膜（B階段品）在4 0 °C、8 0 %加濕下放 置14天後’用上述條件與壓延銅箱壓合，進行熱處理使其 硬化，以得到經時評價用的試樣1。 (1)-2評儐用試樣2作成方法 將後述之接著劑組成物塗布至厚度50# m的聚丙稀 薄膜（東洋紡績股份有限公司製、RYLEN)上，以使得乾燥 後的厚度爲30#ηι，在130°C中乾燥3分鐘以得到接著性 -41- 201033314 薄膜（B階段品）。評價用基板係藉由以通常的電路製作步驟 (穿孔、電鍍、乾膜光阻（以下簡稱爲DFR)積層、曝光·顯 像·蝕刻、DFR剝離）製作、硬化單面覆銅積層版（25a m聚 醯亞胺薄膜、18/zm壓延銅箔），以得到評價用基板。將前 述接著性薄膜（B階段品）暫時壓延至如此所得之評價用基 板上之後，剝離聚丙烯薄膜，將作爲補強板之500/zm的 SUS304板在160°C、35kgf/cm2的加壓下進行加壓30 秒鐘使其接著。其次，在140°C中熱處理4小時使其硬化， Ο 以得到耐焊接性及剝離強度評價用試樣2(初期評價用）。 又，將接著性薄膜（B階段品）在40Ό、80%加濕下放 置14天後，用上述條件與壓延銅箔壓合，進行熱處理使其 硬化，以得到經時評價用的試樣2。 各特性的評價係用以下的方法來進行： 耐焊接性（加濕）：將試樣在40°C、80%加濕下放置2天 後，在經加熱的金屬熔化浴漂浮1分鐘，以1 0尤的間距測 定不會產生膨脹之上限溫度。在該試驗中，測定値高的一 ® 方表示具有良好的耐熱性，且也有抑制因各基材、接著劑 層中所含有水蒸氣蒸發所引起之衝撃的必要，所以要求比 乾燥狀態更嚴格的耐熱性。從實用的性能考慮時，較佳爲 250^以上，更佳爲260*C以上。 剝離強度：在25°C中，用拉伸速度 50mm/min進行 9 0°剝離試驗，以測定剝離強度。該試驗係表示在常溫的接 著強度。從實用的性能考慮時，較佳爲1 ON/cm以上，更 佳爲15N/cm_以上。 -42- 201033314 (2) 蠕變特性 使用前述之評價試樣2，在60°Cx90%環境下，懸掛 200g的錘並測定在30分鐘中剝落的距離。此外懸掛錘的 一方，其剝離形態係以成爲1 8 0。剝離的方式來實施。該試 驗係表示在高溫高濕下的接著強度，所以沒有剝離者爲 佳，剝離距離越大，接著強度越低。從實用的性能考慮時， 較佳爲l〇mm以下，更佳爲4mm以下。 (3) 高溫高濕環境試驗 〇 將前述之耐焊接性及剝離強度評價用試樣2 (初期評價 用）放置在85°C、85%加濕環境下，測定經過500小時後 及經過1 0 0 0小時後的剝離強度。該試驗係以確認實際使 用時的可靠性爲目的，評價在高溫且高濕環境下的耐久性 者，從實際使用時的可靠性，較佳爲5N/cm以上，更佳爲 ΙΟΝ/cm 以上。 聚酯樹脂A的聚合例 在裝備有攪拌器、溫度計、流出用冷却器之反應罐内， ® 進料對苯二甲酸243份、間苯二甲酸237份、己二酸107 份、偏苯三酸酐7份、2-甲基-1,3-丙二醇455份、1，4-丁二醇205份、鈦酸四丁酯0.3份，花4小時緩緩昇溫至 2 50 °C，一面將餾出的水排出至系統外且一面進行酯化反 應。酯化反應結束後花 30分鐘進行減壓初期聚合至 lOmmHg的同時，將溫度昇溫至250°C，進而在ImmHg 以下進行1小時的後期聚合。然後’用氮回復至常壓，投 入偏苯三酸酐28份，藉由在220 °C中反應30分鐘，以得 -43- 201033314 到聚酯樹脂A »將如此所得之聚酯樹脂A的組成、特性値 表示於表1中。各測定評價項目係按照前述之方法。 聚酯樹脂B的聚合例 在裝備有攪拌器、溫度計、流出用冷却器之反應罐内， 進料對苯二甲酸99.6份、間苯二甲酸229.1份、偏苯三 酸酐3.8份、2-甲基-1,3-丙二醇54.0份、1,6-己二醇 401_2份、鈦酸四丁酯0.2份，花4小時緩緩昇溫至250 °C，一面將餾出的水排出至系統外且一面進行酯化反應。 〇 酯化反應結束後花30分鐘進行減壓初期聚合至lOmmHg 的同時，將溫度昇溫至250°C，進而在ImmHg以下進行1 小時的後期聚合。將1〇〇份的所得樹脂進料至具備有攪拌 器、溫度計、迴流式冷却管及蒸餾管之反應容器中，加入 甲苯182份且溶解後，蒸餾甲苯70份，利用甲苯/水的共 沸使反應系統脫水。冷卻至後，加入甲基乙基酮112 份、3,3’，4,4’-二苯基酮四羧酸二酐7份，藉由在70°C中 反應3小時，以得到聚酯樹脂B的溶液。將如此所得之聚 © 酯樹脂B的組成、特性値表示於表1中。 使用於聚胺基甲酸酯樹脂之聚酯多元醇C~I的聚合例 與聚酯樹脂A的聚合例同樣地，使用表1中所示之原 料，製得使用於聚胺基甲酸酯樹脂之聚酯多元醇C~I。將 該樹脂的組成、特性値表示於表1中。 -44- 201033314201033314 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to adhesion to various plastic films, or adhesion to metals such as copper, aluminum, stainless steel, adhesion to glass, heat resistance, and moisture resistance. An excellent resin composition such as sheet life, * an adhesive containing the same, a back sheet, and a printed wiring board including the adhesive layer. [Prior Art] In recent years, the use of an adhesive in various fields has been used to further improve the adhesion of various plastic films from the adhesives that have been used in the past, or to copper. Further, the adhesion of a metal such as aluminum or stainless steel, the adhesion to a glass-reinforced epoxy resin, heat resistance, moisture resistance, sheet life, and the like are required to be further improved. For example, an epoxy/acrylic butadiene-based adhesive or an epoxy/polyvinyl butyral based adhesive is used as an adhesive for a circuit board starting from a flexible printed wiring board (hereinafter abbreviated as FPC). Agents, etc. Such an adhesive for a circuit board requires solder heat resistance, adhesion, workability, electrical properties, and preservability. In particular, an adhesive having a higher heat resistance is required from the use environment of FPC which is recently required for lead-free solder. Further, from the viewpoint of increasing the density of wiring, multilayering of FPC wiring boards, and workability, it is strongly required to have solder resistance under high humidity and adhesion under high temperature and high humidity. The conventional epoxy/acrylic butadiene-based adhesive or epoxy/polyvinyl butyral-based adhesive is particularly excellent in adhesion and workability under high temperature and high humidity, and is also suitable for metal or plastic film. The continuity is not sufficient. In addition, it is not possible to ensure a stable sheet life that can be circulated even at room temperature at 201033314 (see Patent Documents 1, 2, 3, and 4). Patent Document 5 discloses a resin composition for an adhesive having a specific polyester-polyurethane and an epoxy resin as main components. According to the composition shown here, there is a possibility that the sheet life is improved, and the adhesion at high temperature and high humidity is not sufficient, but the adhesion at high temperature and high humidity cannot be sufficiently satisfied. Patent Document 6 also discloses a resin composition for an adhesive having a specific polyester/polyurethane/epoxy resin as a main component. According to the composition shown here, there is a possibility of improving the adhesion at high temperatures and high humidity, and the use of a plastic film to enhance the wettability of the reinforcing plate, but it is not sufficiently satisfied under high temperature and high humidity. The adhesion and the adhesion of the metal to the reinforced plate during the humidification resistance. Further, the moisture-resistant solderability after storage at normal temperature or 40 °C and the adhesion at high temperature and high humidity are remarkably lowered, and stable sheet life cannot be ensured. Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. 2005-139387. Patent Publication No. 2005-139387. [Problem to be Solved by the Invention] 201033314 SUMMARY OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to provide a problem for improving the problems of possessing such conventional adhesives. It can maintain the adhesion of various plastic films, or metal, glass reinforced epoxy resin of copper, aluminum, stainless steel, etc., and can withstand the heat and humidity resistance of high-humidity lead-free solder at high humidity, under high temperature and high humidity. An adhesive having excellent adhesion and an adhesive sheet which provides a B-stage adhesive sheet obtained from the above-mentioned adhesive agent and which can be used after being circulated even under high temperature and high humidity, and which can maintain good adhesive properties and has a good sheet life. . Further, a printed wiring board comprising an adhesive layer obtained from the above-mentioned adhesive or adhesive sheet is provided. MEANS FOR SOLVING THE PROBLEMS The present inventors have completed the present invention by focusing on the results of the review in order to solve the above problems. That is, the present invention is composed of the following constitutions. (1) A resin composition for an adhesive comprising a thermoplastic resin (A), an inorganic cerium (B), a solvent (C), and an epoxy resin (D) The acid value (unit: equivalent/l〇6g) of the thermoplastic resin (A) is 100 or more and 100% or less, and the number average molecular weight of the thermoplastic resin (A) is 5.0 X 103 or more and 1.0 〇 xl 〇 5 or less. The epoxy resin (D) is an epoxy resin having a dicyclopentadiene skeleton, and the thermoplastic resin (A) and the inorganic component are contained in a total amount of 25 parts by mass of the resin composition of the adhesive. The cerium (B) is a mixed solvent of 52 parts by mass of methyl 201033314 ethyl ketone and 23 parts by mass of toluene (wherein the thermoplastic resin (A) is insoluble in the aforementioned mixed solvent at a concentration of 253⁄4 in the aforementioned concentration. In the case of the above-mentioned mixed solvent, a mixture of 52 parts by mass of dimethylacetamide and 23 parts by mass of toluene is used as a dispersion medium (α) as a dispersion medium (α) in the liquid temperature 251 ( TI値) is 3 or more and 6 or less. (2) A resin composition for a two-liquid type adhesive, and a resin composition (cold) containing a thermoplastic resin (A), an inorganic cerium (B), and a solvent (C) as essential components, and the thermoplasticity The acid value (unit: equivalent/106 g) of the resin (A) is 100 or more and 100% or less, and the number average molecular weight of the thermoplastic resin (A) is 5.0 X 103 or more and 1.0 X 1 5 5 or less. The thermoplastic resin (A) and the inorganic cerium (B) in a total amount of 25 parts by mass of the resin composition, and a mixed solvent of 52 parts by mass of methyl ethyl ketone and 23 parts by mass of toluene. (When the thermoplastic resin (A) is not dissolved in the mixed solvent at 25 C in the above-mentioned concentration, the mixed solvent is changed and 52 parts by mass of dimethylacetamide and 23 parts by mass of toluene are used. Mixed solvent) The degree of turbulence (TI値) of the dispersion (α) as a dispersion medium in the liquid temperature 251 is 3 or more and 6 or less, and the resin composition (r) is an epoxy containing a dicyclopentadiene skeleton. Resin (D) is an essential component and is contained in the resin composition (not) The acid of the thermoplastic resin (A) 201033314 is valence AV (/3 ) (unit: equivalent / l 〇 6 g) and the blending amount AW ( ) (unit: parts by mass), and the resin composition (r) is contained The epoxy resin EV(r) (unit: equivalent/i〇6g) and the blending amount EW(r) (unit: parts by mass) of the epoxy resin satisfy the blending ratio of the formula (1) shown below , blending resin composition (cold) and resin composition (r ): 0.7S {EV(r )xEW(r )}/{AV(yS )xAW(yS )}$ 4.0(1). (3) The resin composition for an adhesive according to (1) or (2), wherein the epoxy resin (D) is 60% by mass or more of the entire epoxy resin contained in the resin composition for an adhesive. 99.9 mass% or less. (4) The resin composition for an adhesive according to any one of (1) to (3), wherein the inorganic inorganic filler (B) is blended in an amount of 100 parts by mass based on the thermoplastic resin (A). It is 10 parts by mass or more and 50 parts by mass or less. (5) The resin composition for an adhesive according to any one of (1) to (4), wherein, when the resin composition for the adhesive is 100 parts by mass, the blending amount of the solvent (C) is 60 parts by mass or more and 85 parts by mass or less. (6) The resin composition for an adhesive according to any one of (1) to (5), wherein the resin comprises an epoxy resin having a nitrogen atom. (7) The resin composition for an adhesive according to any one of (1) to (6), wherein the epoxy resin having a nitrogen atom contains a glycidyl diamine structure. (8) An adhesive composition comprising the resin composition for a binder according to any one of (1) to (7). (9) The thermoplastic resin (A), the inorganic ruthenium filler (B), and the inorganic ruthenium filler (B) contained in the resin composition for an adhesive according to any one of the above items (1) to (7), The epoxy resin (D) and the reaction derived therefrom generate 201033314. (10) A printed wiring board' includes an adhesive layer obtained by using the adhesive of (8) or the adhesive sheet of (9). Advantageous Effects of Invention According to the present invention, it is possible to provide a high degree of adhesion to various plastic films such as PET films and various metals such as copper, stainless steel, and the like, and can be used in accordance with the height of lead-free solder under high humidity. An adhesive which is excellent in wet heat resistance and excellent adhesion under high temperature and high humidity, and can be used after the B-stage ruthenium sheet is circulated even under high temperature and high humidity, and can maintain a good resin composition with good adhesive properties. The adhesive, the subsequent sheet, and the printed wiring board including the adhesive layer are contained. Further, in a preferred embodiment of the present invention, it is possible to provide a resin which is excellent in adhesion to various plastic films, or adhesion to metals such as copper, aluminum, and stainless steel, and adhesion to glass-reinforced epoxy resins. The composition, the adhesive containing the same, the subsequent sheet, and the printed wiring board including the adhesive layer. Further, in a preferred embodiment of the present invention, in particular, it is excellent in adhesion to metals such as aluminum and stainless steel, and heat and humidity resistance, and high adhesion can be maintained even after the laminate is placed in a high-temperature and high-humidity environment for a long period of time. At the point of strength, it exerts superior characteristics. [Embodiment] Mode for Carrying Out the Invention Hereinafter, the present invention will be described in detail. <Dispersion (α)> In the present invention, the degree of turbulence (ΤΙ値) of the dispersion (α) is determined as a thermoplastic resin (Α) and an inorganic charge in the resin composition for an adhesive of the present invention. 201033314 The combination of material (B) and the blending ratio are suitable for the pointer. The degree of turbulence (ΤΙ値) of the dispersion (α) is 3 or more and 6 or less, more preferably 3.5 or more and 5 or less. When the interaction between the inorganic cerium (Β) particles contained in the dispersion (α) or the thermoplastic resin (Α) and the inorganic cerium (Β) is high, the shaking degree of the dispersion (α) is The tendency to become higher. When the degree of sag is less than 3, the interaction between the inorganic cerium (Β) particles or the inorganic cerium (Β) and the thermoplastic resin (Α) is lowered, and the heat resistance tends to decrease, and inorganic The ruthenium material is easy to settle, and there is no tendency to obtain a stable pot life. When the degree of swaying exceeds 6, there is a tendency that the handling property is lowered and it becomes difficult to apply evenly. The dispersion (α) can be a total of 25 parts by mass of a thermoplastic resin (Α) and an inorganic ruthenium (Β) by a content ratio in the resin composition for an adhesive of the present invention, 52 parts by mass of A Mixing ratio of base ethyl ketone and 23 parts by mass of toluene, and adding about 0.5 to 2 mm of glass beads having a volume of about 1/3 of the dispersion (α), using a paint stirrer and at room temperature 20 After dispersing for 4 hours in a room of ~25t:, the glass beads were removed and prepared. However, when the thermoplastic resin (A) is not dissolved in the solvent at 25 ° C, the mixed solvent is used, and 52 parts by mass of dimethylacetamide and 23 parts by mass of toluene are used. As a dispersion U). The degree of shaking (TI値) of the dispersion (α) was determined by the following method. The dispersion (α) was placed in a glass jar (commonly known as: Menez bottle) having a capacity of 225 mL, and the temperature was measured at 25 ± 1. Under the armpit, the viscosity of the number of revolutions at 6 rpm and 60 rpm was measured using a BL type viscometer (manufactured by Toki Sangyo Co., Ltd.) (hereinafter referred to as BL(6) and BL(60), respectively. Unit: dPa. s), -10- 201033314 When BL(6) is 100 or less, the degree of rocking (ΤΙ 値) is obtained by the following formula (2). Shake degree (ΤΙ 値) = BL(6)/BL(60) (2) In addition, when BL(6) exceeds 100, a BH type viscometer (made by Toki Sangyo Co., Ltd.) is used, and 2rptn and 20 rpm are used. The viscosity (hereinafter referred to as BH(2) and BH(20), respectively: unit: dPa«s), the degree of rocking (TI値) was obtained by the following formula (3). Shake degree (TI 値) = BH(2)/BH(20) (3) 〇 In addition, the rolls used in the viscosity measurement using the BL type viscometer and the BH type viscometer are in accordance with each viscosity meter. The description of the operation manual 'Select any one of No. 2 to 4. <Resin Composition (/3 } > The resin composition (/3) used in the present invention is blended with the thermoplastic resin (A), the inorganic ruthenium (B), and the solvent (C) in the above ratio. And the other components which are required to be uniformly mixed by a calender, a mixer, a paint shaker or the like, and are not particularly limited as long as they are capable of obtaining a sufficient dispersion. The solid content concentration of the composition (none) is 15 mass%. / 40 mass% or more. Preferably, the solid content concentration is less than 15 mass%, the thickness of the adhesive is thin, and heat resistance is followed. When the strength is lowered, when the viscosity is more than 40% by mass, the viscosity of the solution becomes too high, and it tends to be difficult to apply evenly. <Resin Composition (r)> The resin composition (γ) used in the present invention may be composed only of the epoxy resin (D), and more preferably contains the solvent (c). The solvent (c) contained in the resin composition (r) is not particularly limited as long as it is a component contained in the soluble resin composition (r). Further, the solid content concentration of the resin composition (τ) is preferably 15% by mass or more and 80% by mass or less, and preferably 25% by mass or more and 75% by mass. /. The following is preferable, and it is more preferably 35% by mass or more and 70% by mass or less. When the solid content concentration is less than 15% by mass, the thickness of the adhesive becomes thin after the solvent is volatilized, and the heat resistance and the subsequent strength tend to be lowered. When the solid content concentration is more than 80% by mass, the viscosity of the resin composition for an adhesive tends to be too high, and it tends to be difficult to apply evenly. © <Resin Composition for Resin> The resin composition for an adhesive of the present invention may be one containing a thermoplastic resin (A), an inorganic ruthenium (B), a solvent (C), and an epoxy resin (D). The resin composition for a liquid type adhesive may be a resin composition for a plurality of mixed type adhesives which is mixed with a plurality of solvents and then mixed. By forming a multi-component mixing type, there is an advantage that it can be preserved for a long period of time. On the other hand, in the case of a mixed type of a plurality of agents, when used as an adhesive, it is necessary to mix a plurality of agents at an appropriate blending ratio, and the more the number of the agents increases, the greater the difficulty of the steps becomes. Therefore, among the plurality of mixed types, a resin composition containing a thermoplastic resin (A), an inorganic cerium (B), a solvent (C), and a resin containing an epoxy resin (D) are particularly preferable. The two-component mixing type consisting of the composition (r) is preferred, and the two-liquid mixing type is more preferable because of the ease of uniform mixing. In the case where the resin composition (Θ) and the resin composition (r) are used to obtain a resin composition for an adhesive, the acid value of the thermoplastic resin (A) contained in the resin composition (A) is AV (not). (Unit: equivalent/1〇6g) and blending amount -12-201033314 AW(/S) (unit: parts by mass), epoxy resin EV of epoxy resin contained in the resin composition (7·) r) (unit: equivalent / l〇6g) and the blending amount EW(r) (unit: parts by mass) satisfy the blending ratio of the formula (1) shown below, blending the resin composition (Θ) with Resin composition (r ): 0.7$ {EV(r )xEW(r )}/{AV(/3 )xAW(call)}$ 4.0(1) {EV( r )XEW( r )}/{AV( /3) XAW(/S)} is preferably 0.8 or more and 3.5 or less, more preferably 0.9 or more and 3.0 or less. When the ratio is less than 0.7, the crosslinking of the thermoplastic resin (A) and the epoxy resin is insufficient, and the heat resistance property is lowered. When the temperature is more than 4 · 0, the unreacted epoxy resin remains in a large amount. The tendency to reduce heat resistance and moisture resistance. <The thermoplastic resin (A)> The thermoplastic resin (A) used in the present invention may, for example, be a polyester resin, a polyurethane resin, a styrene resin or a polyamine. a resin, a polyamidoximine resin, a polyester quinone resin, a polycarbonate resin, a polyphenylene resin, an ethylene resin, an olefin resin, an acrylic resin, etc., preferably A polyester resin, a urethane resin, and a polyamidoximine resin are used. These thermoplastic resins may be used singly or in combination of two or more kinds. The number average molecular weight of the thermoplastic resin (A) to be used is 5xl 〇 3 or more and ixio 5 or less. If the number average molecular weight is less than 5xl 〇 3', the adhesion after coating is insufficient and the workability is deteriorated, and the number average molecular weight exceeds lxl. When 〇5, the viscosity of the solution at the time of coating becomes too high, and a uniform coating film cannot be obtained. It is preferably a lower molecular weight of 8x10, more preferably -13 to 201033314, and a lower molecular weight of 1χ1〇4, preferably an upper molecular weight of 5χ104, more preferably High limit Sub-quantity 3x1 04. The acid value (unit: equivalent/106g) of the thermoplastic resin (Α) used in the present invention is 100 or more and 1000 or less. The acid value is as low as 1 〇〇 equivalent / 1 〇 6 g, after hardening The adhesiveness of the metal base material is insufficient, and the degree of crosslinking tends to be low, and the heat resistance tends to be lowered. When the acid value is more than 1000 equivalents/106 g, the storage stability of the varnish dissolved in the solvent is lowered. Further, the crosslinking reaction tends to proceed at a normal temperature, and a stable sheet life tends not to be obtained. Further, it is expected that the durability of the ester bond and the urethane bond or the like may be adversely affected. The lower limit of the acid value is 250 equivalents/106 g, more preferably the lower limit of the acid value is 300 equivalents/106 g, more preferably the lower limit of the acid value is 350 equivalents/l 6 g. The preferred upper limit is 900 equivalents/106 g, more The upper limit is preferably 800 equivalent / l 6g, and the upper limit is preferably 700 equivalent / l 6g. (Polyester resin) The glass transition temperature of the polyester resin used as the thermoplastic resin (A) of the present invention. It is preferably -10 ° C or more and 60 ° C or less. Glass transfer ® temperature is lower than -1, In the case where the glass transition temperature exceeds 60T: the adhesion to the substrate is insufficient, and the modulus of elasticity at room temperature increases, and the adhesion at room temperature changes. The lower limit of the glass transition temperature is preferably -5 ° C, more preferably the lower limit of the glass transition temperature is 0 C, more preferably the lower limit of the glass transition temperature is 5 ° C. The preferred upper limit is 5 The upper limit is 5 ° C, the upper limit is 50 ° C, and the upper limit is 45 ° C. -14- 201033314 The polyester resin is a combination of the total acid components in the composition: The aromatic carboxylic acid is preferably 60 moles. /. The above is more than 5% by mole, and more preferably 99% by mole or more. Aromatic carboxylic acids can also be used at %. In the case where the aromatic residual acid is less than 60% by mole, the coating film is weak, and a decrease in the adhesion strength to various substrates is observed. Examples of the aromatic carboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, formic acid, phthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, and biphenyl 5-hydroxyisophthalic acid. Further, examples thereof include terephthalic acid, 5-sulfonic acid isophthalic acid, 4-sulfonic acid benzenesulfonic acid naphthalene-2,7-dicarboxylic acid, and 5 (4-sulfonic acid phenoxy group). An aromatic dicarboxylic acid having a sulfonic acid group such as benzene, a metal salt thereof, an aromatic dicarboxylic acid having a sulfonate group, P-hydroxybenzoic acid phenylpropionic acid, P-hydroxybenzene Aromatic hydroxy acid such as acetic acid or 6-hydroxy-2-naphthoic acid bis(P-hydroxyphenyl)pentanoic acid, etc., such as terephthalic acid, isophthalic acid, and mixtures thereof ^ In terms of strength, it is especially good. Further, examples of other acid components include 1,4-cyclohexanoic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, acid alicyclic dicarboxylic acid, and amber. An aliphatic dicarboxylic acid such as an acid, adipic acid, sebacic acid, sebacic acid diacid or dimer acid. On the other hand, the diol component is preferably an aliphatic diol composed of an aliphatic monool, a fatty alcohol, an aromatic diol, or an ether bond-containing diol, and examples thereof include ethylene glycol and L2. -propanediol, diol, 1,4-butanediol, 2-methyl-1,3,-propanediol, 1,5-pentyl-100: 8 5 occupies 1 〇〇 cohesive isophthalic acid, sulfonic acid a carboxylic acid, an ammonium dicarboxylate or the like, a P-hydroxy ' 4,4-, especially a condensed alkane dicarboxylic anhydride, a tetracyclic ring 2, as a 1,3-propanediol, -15-201033314 neopentyl glycol 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, neopentyl glycol hydroxypivalate , dimethylol heptane, 2,2,4-trimethyl-1,3-pentanediol, etc., and examples of the alicyclic diol include 1,4-cyclohexanediol and 1, Ethylene oxide adduct of 4-cyclohexanedimethanol, tricyclodecanediol, tricyclodecane dimethylol, spiro diol, hydrogenated bisphenol A' hydrogenated bisphenol A, and propylene oxide addition Things and so on. As an example of the diol having an ether bond, diethylene glycol, triethylene glycol, dipropylene glycol, or polyethylene glycol, polypropylene glycol, polytetramethylene glycol, neopentyl glycol, epoxy B, may be used as needed. Alkane adduct, neopentyl glycol propylene oxide adduct. Examples of the aromatic-containing diol include epoxy bromide such as p-xylene glycol, m-xylene glycol, o-xylene glycol, 1,4-benzenediol, and 1,4-benzenediol. An alkane adduct, bisphenol A, an ethylene oxide adduct of bisphenol A, and a propylene oxide adduct, each of which is added to the two phenolic hydroxyl groups of bisphenols in an amount of 1 to several moles A diol or the like obtained by ethylene oxide or propylene oxide. Further, among the molecular structures, 5-hydroxyisophthalic acid, p-hydroxy® benzoic acid, P-hydroxythiophenol, p, which can use a hydroxyl group having a hydroxyl group and a carboxyl group as a raw material of a polyester, can also be exemplified. - hydroxyphenylpropionic acid, p-hydroxyphenylacetic acid, 6-hydroxy-2-naphthoic acid, 4,4-bis(P-hydroxyphenyl)pentanoic acid, and the like. In the polyester-based resin used in the present invention, it is possible to copolymerize 0.1 mol% or more and 5 mols for the purpose of introducing a branch skeleton as needed. /. The following trifunctional or higher polycarboxylic acids and/or polyhydric alcohols may also be used. In particular, when a hardened coating film is obtained by reacting with a curing agent, a coating film having an increased terminal group concentration (reaction point) of the resin and a high crosslinking density and strength can be obtained by introducing a branching skeleton. As an example of the trifunctional or higher polycarboxylic acid at this time, it is possible to use -13-201033314 with trimellitic acid, trimesic acid, ethylene glycol bis(hydrogen trimellitate), and glycerin (dehydration). Trimellitic acid ester, trimellitic anhydride, pyromellitic anhydride (PMDA) 'transbasic phthalic acid dianhydride (〇dPA), 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride ( 8丁〇8),3,3,,4,4,-diphenyltetracarboxylic dianhydride (BPDA), 3,3,,4,4,-diphenylfluorene tetraphthalic acid dianhydride (DSDA) 4,4,-(hexafluoroisopropylidene)dicarboxylic acid dianhydride (6FDA) '2,2,-bis[(dicarboxyphenoxy)phenyl]propane dianhydride (BSAA), etc. On the other hand, as an example of the trifunctional or higher polyhydric alcohol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol or the like can be used. When a trifunctional or higher polycarboxylic acid and/or a polyhydric alcohol is used, the total acid component or the total diol component is at most 5 mol% or less, preferably at 〇·1 Mo, in terms of 全·1 mol% or more. When the amount of the ear is more than 3 mol%, it is preferable to carry out copolymerization. When the amount is more than 5 mol%, the mechanical properties such as the elongation at break of the coating film are lowered, and gelation occurs in the polymerization. Possibility As a method of introducing an acid value into the polyester resin used in the present invention, a method in which a carboxylic acid is introduced into a resin by adding an acid after polymerization can be mentioned. When a monocarboxylic acid, a dicarboxylic acid or a polyfunctional carboxyoxy compound is used in the acid addition, there is a possibility that the molecular weight is lowered by transesterification, and a compound having at least one carboxylic anhydride is preferably used. As the acid anhydride, succinic anhydride, maleic anhydride, phthalic acid, 2,5-norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride (PMDA), hydroxydicarboxylic acid can be used. Diacid anhydride (ODPA), 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride (BTDA), 3,3,4,4'-diphenyltetradecanoic acid dixanthine (8? 0,},3,3,,4,4,-diphenylfluorene tetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroisopropylidene)diphenyl dimethyl•17· 201033314 acid dianhydride (6FDA), a compound such as 2,2'-bis[(dicarboxyphenoxy)phenyl]propene (BSAA), etc. The total acid component constituting the polyester used in the present invention is set to 100 mol%. At the time of 10 mol%, the acid causes gelation, which causes depolymerization of the polyester to reduce the amount of the tree. The acid addition is carried out directly after the polycondensation of the polyester, and the solution is directly fed into the solution of the polyester. The method of addition is carried out. The reverse speed in the overall state is rapid, but gelation occurs when a large amount of addition occurs, and due to the reaction at a high temperature, attention is paid to blocking oxygen to prevent oxidation, etc. On the other hand, in the solution State bonus However, the reaction is slow, but a large amount of carboxyl groups are introduced. (Polyurethane-based resin) The glass of the polyurethane resin used in the present invention preferably has a glass degree of -10 ° C or more and 60 ° C or less. When the glass transition temperature is -10 ° C, the adhesion at high temperature tends to be insufficient. When the glass temperature exceeds 60 ° C, the adhesion to the substrate becomes insufficient, and the elastic modulus becomes high. There is a tendency for the adhesion at room temperature to become insufficient. The lower limit of the glass transition temperature is preferably -5 ° C, the lower limit of the glass temperature is preferably 0 ° C, and more preferably the lower limit of the glass transition temperature is A preferred upper limit is 55 ° C, a more preferred upper limit is 50 ° C, and particularly preferably 45. In particular, the polyurethane resin used in the present invention is preferably a polyester polyol or a poly The method of introducing an acid value into an isocyanate and a chain extender is a method of preliminarily forming a fatliquoring molecule on a polyalkane alkane dianhydride tree: it is necessary. In the glass transfer, the glass transfer at normal temperature is 51. The upper limit is > It is: a resin -18 - 201033314 A method of imparting an acid value to a polyester polyol, or a method of using a diol containing a carboxylic acid in a chain extender, etc. The polyurethane resin used in the present invention is used as The polyester polyol used as the raw material is preferably the same as the polyester resin described above except for the number average molecular weight. The polyester polyol used in the present invention has a number average molecular weight of 5 χ 102 or more and 5 χ 104 or less. When the concentration is less than 5χ102, the concentration of the carbamate group increases, and there is a tendency to lower the adhesion under high temperature and high humidity. The number average molecular weight exceeds 5χ104, and the polymerizability of the ruthenium polycarboxylate decreases, resulting in poor polymerization. . Preferably, the lower molecular weight is 8Χ102, more preferably the lower molecular weight lxl〇3, preferably the upper limit molecular weight is 3.5x104, and more preferably the upper limit molecular weight is 2x104. The polyisocyanate used in the production of the polyurethane resin used in the present invention may be a diisocyanate, a dimer thereof (ureidodione), or a terpolymer thereof (isocyanato) One of an acid ester, a triol adduct, a biuret, or the like, or a mixture of two or more thereof. For example, examples of the diisocyanate component include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, P-phenyl diisocyanate, diphenylmethane diisocyanate, m-benzene diisocyanate, and Methylene diisocyanate, tetramethylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 1,5-naphthalene diisocyanate '2,6-naphthalene diisocyanate, 4 , 4'-diisocyanate diphenyl ether, 1,3-benzenedimethyl diisocyanate, 1,3-diisocyanate methylcyclohexane, iota, diisocyanate methylcyclohexane, 4,4' - diisocyanate cyclohexane, 4,4'-diisocyanate cyclohexylmethane, isophorone diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, etc., based on the problem of yellow denaturation, with aliphatic alicyclic -19- 201033314 Group of diisocyanates is preferred. Further, it is particularly preferable to start with hexamethylene diisocyanate or isophorone diisocyanate. A chain extender may also be used as needed in the production of the polyurethane resin used in the present invention. Examples of the chain extender include a low molecular weight diol which is a constituent component of the polyester polyol, or a carboxylic acid and two hydroxyl groups such as dimethylolpropionic acid 'dimethylol butyric acid. Compounds, etc. Among them, the ease of introduction of the acid value and the solubility in a general-purpose solvent are preferably dimethylolbutanoic acid. Further, as a method of introducing the branch, © trimethylolpropane can also be used. As a method for producing the polyurethane resin used in the present invention, the polyester polyol, the polyisocyanate, and the chain extender as required may be all fed into a reaction container, or may be staged. Feeding. In short, in the total of the hydroxyl groups of the polyester polyol and the chain extender in the system, the ratio of the isocyanate group/hydroxy group functional group is 1 or less in total in combination with the isocyanate group of the polyisocyanate. Further, the reaction can be carried out by reacting in the presence or absence of a solvent which is inactive to the isocyanate group. Examples of the solvent include ester-based solvents (such as ethyl acetate, butyl acetate, and ethyl butyrate), ether-based solvents (such as dioxane, tetrahydrofuran, and diethyl ether) and ketone-based solvents (cyclohexane). Aromatic hydrocarbon-based solvent (benzene, toluene, xylene, etc.) and a mixed solvent thereof Methyl ethyl ketone is preferred. The reaction apparatus is not limited to a reaction tank having a stirring apparatus. A mixing and kneading apparatus such as a kneader or a two-axis extruder can also be used. -20- 201033314 In order to promote the urethane reaction, a catalyst used in a usual amine ester reaction can be used, for example, a tin-based catalyst (lauric tin, dimethyl tin dilaurate, dilauric acid) can be used. Ding tin, dimethyl tin hydroxide dihydrate, stannous octoate, etc.), lead-based catalyst (lead oleate ethyl hexanoate, etc.), amine-based catalyst (triethylamine, tributylamine, An aza-based catalyst is preferable from the viewpoint of a diazabicyclooctane, a diazabicycloundecene, or the like. (Polyacrylamide-based imide resin) The glass-based system of the polyamidoximine-based resin used in the present invention is preferably 3 ° C or more and 1603⁄4 or less. The glass transition temperature of 30 is particularly high, and there is a tendency for heat resistance to be insufficient. When the glass transition temperature exceeds, the resin becomes hard and becomes brittle, and the bonding strength becomes insufficient. Preferably, the lower limit of the glass transition temperature is 40 ° C, the lower limit of the preferred glass temperature is 50 ° C, and the preferred upper limit is 150, more preferably 140 ° C. The polyfluorene used in the present invention. The amine quinone-based resin is a polyamine-based resin obtained by reacting an acid component of a material with a diisocyanate or a diamine, and the acid component is preferably a propylene having a carboxyl group at both terminals using a polycarboxylic acid having an aromatic ring. Nitrile-butadiene rubber. The polyamidoximine-based resin used in the production of the polyacrylamide-based resin having an aromatic ring is an acid anhydride of a polycarboxylic acid having an aromatic ring, which is formed of an aromatic ring, and is an acid anhydride having an aromatic ring. , pyromellitic dianhydride, ethylene glycol double dehydrated trimellitate, propane dehydrated trimellitate, 1,4-butanediol bis-dehydrated trimellitate, trimethyltin thioformate, . False-2 - The transfer temperature of the porphyrin and the harmful phase is less than 1601. The upper limit of the shift of the glass is the original bismuth imidate, at the time of the task. Trimethylene phthalate bis-hexamethylene-21- 201033314 diol bis-dehydrated trimellitic acid ester, polyethylene glycol double-dehydrated trimellitic acid ester, polypropylene glycol double-dehydrated trimellitic acid ester, etc. Alcoholic double-dehydrated trimellitate, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 3,3,4,4,-biphenyltetracarboxylic dianhydride, 1,2 , 5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10 - Terpene tetracarboxylic dianhydride, 3,3',4,4'-diphenyl maple tetracarboxylic dianhydride, 111_bitriphenyl-3,3',4,4,-tetracarboxylic dianhydride, 4, 4'-hydroxydiphthalic dianhydride, hexafluoro-2,2-bis(2,3- or 3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3- Bismuth or 3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis[4-(2,3 - or 3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 1,1, 1,3,3,3-hexafluoro-2,2-bis[4-(2,3- or 3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 1,3-double (3 , 4-dicarboxyphenyl)-1,1,3,3-tetramethyldioxane dianhydride, etc. These may be used singly or in combination of two or more. The acrylonitrile-butadiene rubber having the carboxyl group at both ends is used to impart flexibility and adhesion to the polyamidoximine resin, and when the total acid component is 100% by mole, the system is preferably 3 moles above 1 5 mole%, © better 3 moles. /. Above 1% of the moles are below. When the amount of copolymerization is less than 3 mol%, flexibility and adhesion cannot be found, and when it exceeds 15 mol%, solvent solubility tends to be lowered. As the acid component used in the production of the polyamidoximine-based resin used in the present invention, an aliphatic or alicyclic acid anhydride and a dicarboxylic acid can be used as long as the effect of the present invention is not impaired. Other acid components. For example, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, cyclobutane tetracarboxylic acid di-field, hexahydrogenation Pyromellitic dianhydride, cyclohexene-22- 201033314 -1 - dilute-2,3,5,6-tetradecanoic acid dianhydride, 3-ethylcyclohexyl-1 -burn-3-(l,2) ,5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexanol-3-(1,2),5,6-tetracarboxylic dianhydride, 1-methyl-3-B Cyclohexan-1-iso-3-(1,2),5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1-(1,2),3,4,tetracarboxylic acid Anhydride, 1-propylcyclohexane-1-(2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-b (2,3), 3-(2 , 3)-tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo[2_2_1]heptane-2,3,5,6-tetracarboxylic dianhydride , 1-propylcyclohexane-1-(2,3), 3,4-tetracarboxylic dianhydride, 1,3-diammonium cyclohexane-1-(2,3), 3-( 2,3)-tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylate Acid dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid An acid such as dianhydride or hexahydrotrimellitic anhydride The anhydride or the same dicarboxylic acid as that described in the polyester resin may be used singly or in combination of two or more kinds. The diisocyanate or diamine used in the production of the polyamidoximine resin used in the present invention is the same as the diisocyanate described in the polyurethane® resin. Or the diamine of the diisocyanate corresponding to these, these can be used individually, and it does not matter if it uses two or more types. In the polyamidoximine-based resin used in the present invention, a compound having three or more functional groups can be polymerized for the purpose of improving heat resistance. For example, a polyfunctional carboxylic acid such as trimesic acid; a dicarboxylic acid having a hydroxyl group such as 5-hydroxyisophthalic acid; a dicarboxylic acid having an amine group such as 5-aminoisophthalic acid; and glycerin And a dicarboxylic acid or a ginseng having a solubility of three or more hydroxyl groups such as polyglycerol or a ginseng (2-aminoethyl-23-201033314)-amine, etc. (2 in the present invention) The effect of the invention is that the dimer acid and the polyoxynium sulfonate are the solvents of the present invention, and the solvent is used in the case of the combination of the imidazolidinone, the dicyclohexanone and the cyclopentanone. Concentration and solubility as a low boiling point solvent, hexane, decyl alcohol, propanol, butanolone, methyl isobutyl ether, isobutyl tetrahydrofuranate, etc. <Inorganic sputum filling material (Β) As the dispersion liquid (α) of the present invention, for example, one or more amine groups may be used, and among them, from the viewpoint of reactivity and dissolution, it is preferably a 5-hydroxy group. A hydroxy-aminoethylamine or the like having phthalic acid or the like having three or more amine groups. In the polyamidoximine-based resin to be used, a polyester, a polyether, a polycarbonate, an alkane or the like can be copolymerized in a non-destructive manner. In this case, it is necessary to appropriately select the amount of copolymerization for the purpose of non-destructiveness, heat resistance, solubility, and clarity. For the polymerization of polyamidoximine resins, such as Ν-methyl-2-la-s-done, γ-butyrolactone, dimethylformin, dimethylformamide, dimethylethyl Indoleamine, tetrahydrofuran, etc. are preferred from low boiling point to good polydimethyl ethanoamine. After polymerization, it can be diluted with a polymerization or other low boiling point solvent to adjust the liquid viscosity. Examples of the solvent include aliphatic solvents such as aromatic Gengyuan and Xinyuan, such as toluene and xylene; alcohol solvents such as methanol, ethylene, and isopropyl alcohol; acetone, methyl ethyl ketone, and cyclohexanone. A ketone solvent such as cyclopentanone; an acid solvent such as diethyl ether; an ethyl acetate, a butyl acetate, a solvent, and the like. The inorganic ruthenium (Β) used in the > is not particularly limited as long as it can impart a component. As such inorganic use, alumina, ceria, titania, oxidized-24-201033314 bismuth, zirconium oxide, hafnium nitride, barium titanate, barium carbonate, lead titanate, lead titanate, barium titanate Lead, gallium oxide, spinel, mullite, cordierite, talc, aluminum hydroxide, magnesium hydroxide, aluminum titanate, cerium oxide containing chromium oxide, barium strontium silicate, boron nitride, calcium carbonate, calcium sulfate, Zinc oxide, zinc borate, magnesium titanate, magnesium borate, barium sulfate, organic bentonite, carbon, etc., these may be used singly or in combination of two or more. From the viewpoint of transparency, mechanical properties, heat resistance, and thixotropic property of the resin composition for an adhesive, cerium oxide is preferred, and particularly smog cerium dioxide having a three-dimensional mesh structure is preferred. Further, in terms of imparting hydrophobicity, it is preferred that the hydrophobic cerium oxide is treated with monomethyltrichlorosilane, dimethyldichlorosilane, hexamethyldiazepine, octyl decane, eucalyptus or the like. In the case of using the fumed cerium oxide as the inorganic cerium (B), the average diameter of the primary particles is preferably 30 nm or less, more preferably 25 nm or less. When the average diameter of the primary particles exceeds 30 nrn, the interaction between the particles or the resin tends to decrease and the heat resistance tends to decrease. In addition, the average diameter of the primary particles herein is a primary particle image obtained by using a scanning electron microscope, and there is no G as the average diameter of a circle having a diameter of 100 extracted particles. The blending amount of the inorganic ceramium filler (B) is preferably 10 parts by mass or more and 50 parts by mass or less, more preferably 13 parts by mass or more and 4 5 parts by mass or less, based on 100 parts by mass of the thermoplastic resin (A). It is particularly preferably 15 parts by mass or more and 40 parts by mass or less. When the amount is less than 10 parts by mass, the effect of improving the heat resistance may not be exhibited. When the amount is more than 50 parts by mass, the dispersion of cerium oxide may occur, the viscosity of the solution may become too high, and workability may be unsuitable. Or the continuation of the reduction. -25- 201033314 <Solvent (c) > The solvent (C) used in the present invention may be a single component or a mixed solvent of two or more plural components. The solvent (C) is not particularly limited as long as it can dissolve the thermoplastic resin (A) and the epoxy resin (D). Examples of such a solvent include a guanamine solvent such as dimethylacetamide or N-methyl-2-pyrrolidone, an alcohol solvent such as methanol, ethanol or isopropyl alcohol, toluene or xylene. The aromatic solvent, a ketone solvent such as acetone, methyl ethyl ketone or cyclohexanone, or an ester solvent such as ethyl acetate, etc., from the viewpoint of workability, preferably Methyl acetamide, ethanol, toluene, xylene, methyl ethyl ketone, and ethyl acetate are more preferable from the viewpoint of easiness of drying, and toluene, methyl ethyl ketone, and ethyl acetate are mentioned. These solvents may be used singly or in combination of two or more. <Epoxy Resin (D)> The adhesive resin composition of the present invention contains an epoxy resin (D) having a dicyclopentadiene* skeleton as an essential component. A hardened coating film composed of an epoxy resin having a rigid dicyclopentadiene® diene skeleton can reduce the stress at the time of peeling because the moisture absorption rate is extremely small and the crosslinking density of the cured coating film is lowered. Resistance to humidification solderability. Specific examples of the epoxy resin (D) include the DIC HP7200 series. The blending amount of the epoxy resin (D) having a dicyclopentadiene skeleton is 60% by mass of the entire epoxy resin contained in the resin composition for the subsequent agent. /. The above is preferable, and more preferably 75 mass% or more, more preferably 9 mass% or more. By -26-201033314, an epoxy resin (D) having a dicyclopentadiene skeleton containing 60% by mass or more can be found to have superior moisturizing weldability. In the resin composition for an adhesive of the present invention, an epoxy resin having a nitrogen atom is used as an epoxy resin, and a coating film of a B-staged adhesive composition which can be heated at a relatively low temperature can be used, and a film of a B-stage film can be suppressed. The fluidity tends to increase the workability in the subsequent operation, and it is preferable to suppress the effect of the B-stage film foaming. Examples of the epoxy resin containing a nitrogen atom include tetraglycidyldiaminediphenylmethane, tri-glycidyl-p-aminophenol, tetraglycidylbisaminomethylcyclohexanone, and anthracene. A glycidylamine system such as hydrazine, Ν', Ν'-tetraglycidyl-m-xylylenediamine or the like. The blending amount of the epoxy resin containing these nitrogen atoms is preferably 20% by mass or less based on the entire epoxy resin. When the blending amount is more than 20% by mass, the rigidity is excessively increased, and the adhesion tends to decrease. Further, the crosslinking reaction tends to proceed during the storage of the sheet, and the sheet life tends to decrease. The upper limit of the preferable blending amount is 10% by mass, and more preferably 5% by mass. Other epoxy resins may also be used as the epoxy resin used in the present invention. For example, a glycidyl ether type such as bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, novolak glycidyl ether, brominated bisphenol A diglycidyl ether, or hexahydrobenzene can be mentioned. Glycidyl ester type of glycidyl dicarboxylate, glycidyl dimerate, triglycidyl isocyanurate, or 3,4-epoxycyclohexylmethylcarboxylate, epoxidation The alicyclic or aliphatic epoxide such as polybutadiene or epoxidized soybean oil may be used singly or in combination of two or more kinds. In the hardening reaction of the epoxy resin used in the present invention, a hard catalyst of -27-201033314 can be used. For example, an imidazole compound such as 2-methylimidazole or 1,2-dimethylimidazole, 2-methylimidazole or 2-phenyl-4-methylimidazole or 1-cyanoethyl-2-methylimidazole, Triethylamine, triethylenediamine-N-(2-dimethylaminoethyl)piped, 1,8-diazabicyclo~\-carbene-7, 1,5-di Azabicyclo(4,3,0)-nonene-5,6-yl-1,8-diazabicyclo(5,4,0)-undecene-7, etc. a cation contact of a tertiary amine with a phenol, a caprylic acid, a tetrabasic tetraphenylboronic acid as an amine salt, a triallyl hexafluoro decanoate, a thiol hexafluoroantimonate, etc. Among the media, triphenylene, etc., from the viewpoints of thermosetting property, heat resistance, and storage stability to the metal, it is preferred to use 1,8-diazabicarb-carbocarb-7. 1,5-diazabicyclo(4,3,0)-壬-5,6-yl-1,8-diazabicyclo(5,4,0)-undecene-7 A third of these tertiary amines, a compound of phenol, octanoic acid, and tetrabasic boron tetrachloride. The blending amount at this time is preferably 100 parts by weight of the resin (A), preferably 〇·〇ΐ~ι.〇 by weight, if within this range, for the thermoplastic resin (A) and the epoxy resin medium. The effect is even more increased, and a solid next performance is obtained. <Other Additives> The resin composition for an adhesive of the present invention can be directly formed into various adhesive resins and additives to form an adhesive composition. The resin "is a polyoxyxylene resin, an amine resin, a phenolic resin compound, etc.". Butyl-4-ethyl-4-an, N,-methyl [(5,4,0)-dibutylamine amines and ester salts, etc., diallyl phosphine. The blending amount of the thermoplasticity such as I(5,4,0)-dibutylamine amines and ester salts after blending. In the case of the phenolic resin, a formaldehyde condensate of an alkylated phenol or a cresol is exemplified as the hardening grease or the isocyanide -28-201033314. Specific examples thereof include alkylation (for example, methyl, ethyl, propyl, isopropyl, butyl) phenol, p-third amyl phenol, 4,4'-second butylene phenol, P-tert-butyl hydrazine, hydrazine-method, m-formamidine, P-method, P-cyclohexyl fluorene, 4,4'-isopropylidene phenol, p-nonyl phenol, p-octyl A formaldehyde condensate of phenol, 3-pentadecylphenol, phenol, phenyl-hydrazine-cresol, p-phenylphenol, xylenol or the like. The amine-based resin may, for example, be a formaldehyde adduct such as urea, melamine or benzoguanamine, or a decyl alkyl ether compound of an alcohol having 1 to 6 carbon atoms. Specific examples thereof include methoxylated methylol urea, methoxylated methylol N,N-extended ethyl urea, methoxylated methylol cyanide, methoxylated methylol melamine Methoxylated hydroxymethylbenzoguanamine, butoxylated methylol melamine, butoxylated hydroxymethylbenzoguanamine, etc., preferably methoxylated methylol melamine, butoxy The methylol melamine and the methylolated benzoguanamine can be used singly or in combination. The isocyanate compound may be an aromatic or aliphatic diisocyanate or a trivalent or higher polyisocyanate, and may be any of a low molecular compound and a polymer © compound. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, benzodimethyl diisocyanate, and hydrogenated phthalic acid can be mentioned. a dimer of a bis-isocyanate, an isophorone diisocyanate or such an isocyanate compound, and an excess amount of such an isocyanate compound, for example, ethylene glycol, propylene glycol, trimethylolpropane, glycerol, sorbitol Low molecular weight active hydrogen compounds such as sugar alcohol, ethylene diamine, monoethanolamine, diethanolamine, triethanolamine or various polyester polyols, polyether polyols -29- 201033314 Alcohols, polyamines, polymer active hydrogen compounds The terminal isocyanate group-containing compound obtained by the reaction. The isocyanate compound may also be a blocked isocyanate. Examples of the isocyanate blocking agent include phenols such as phenol, thiophenol, methyl thiophenol, cresol, xylenol, resorcin, nitrophenol, and chlorophenol; Anthraquinones such as ethyl ketoxime and cyclohexanone oxime; alcohols such as methanol, ethanol, propanol and butanol; halogen-substituted alcohols such as chlorohydrin and 1,3-dichloro-2-propanol; a third-order alcohol such as a third butanol or a third pentanol; an internal enthalpy of e-caprolactam, (5-valeroinamide, r-butyrolactone, cold-propionamide, etc.) Examples of the amines include aromatic amines; quinone imines; active methylene compounds such as acetamidineacetone, acetamidine acetate, and ethyl malonate; thiols; imines; A urea-based compound, a diaryl compound such as sodium hydrogen sulfite, etc. The blocked isocyanate can be obtained by subjecting an isocyanate compound, an isocyanate compound, and an isocyanate blocking agent to an addition reaction by a conventionally known method. The resin composition for the subsequent agent may also be blended with a decane® coupling agent as needed. By blending the decane coupling agent, It is excellent in the characteristics of the adhesion to the metal and the heat resistance. The decane coupling agent is not particularly limited, and examples thereof include those having an unsaturated group, those having a glycidyl group, and those having an amine group. Examples of the decane coupling agent include vinyl quinone (methoxy-methoxyethoxy) decane, vinyl triethoxy decane, vinyl trimethoxy decane, etc. As a decane coupling agent having a glycidyl group, R-glycidoxypropyltrimethoxydecane, p-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, -(3,4-epoxycyclohexyl)ethyl- 30- 201033314 Triethoxy decane, etc. As a decane coupling agent having an amine group, N-/3-(aminoethyl)-r-aminopropyltrimethoxydecane, N-/3- (Aminoethyl)-r-aminopropylmethyldimethoxydecane, N-phenyl-r-aminopropyltrimethoxydecane, etc. Among these, from the viewpoint of heat resistance 'R-glycidoxypropyltrimethoxydecane, Θ-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, /3 -( 3,4-epoxycyclohexyl) A decane coupling agent having a glycidyl group such as triethoxysilane or the like is preferred. The blending amount of the decane coupling agent is preferably from 0.5 to 20 parts by weight based on 100 parts by weight of the thermoplastic resin (A). When the blending amount of the decane coupling agent is less than 0.5 part by weight, the resulting adhesive may be inferior in heat resistance, and when it exceeds 20 parts by weight, the heat resistance may be poor and the adhesion may be poor. In the resin composition for an adhesive agent of the present invention, an additive such as a flame retardant, a leveling agent, a pigment, or a dye such as a bromine-based, phosphorus-based, nitrogen-based or metal hydroxide compound may be appropriately blended as needed. <Bottom Sheet> In the present invention, the above-mentioned thermoplastic sheet (A), the inorganic ceramium filler (B), and the epoxy resin contained in the resin composition for an adhesive of the present invention are contained. (D) and those from the reaction products. The adhesive sheet of the present invention contains the thermoplastic resin (Α), the inorganic ruthenium (、), the epoxy resin (D), and the like contained in the resin composition for an adhesive of the present invention. The sheet composed of the layer of the reaction product alone may be the thermoplastic resin (Α), the inorganic ruthenium (Β), and the ring contained in the resin composition containing the substrate and the adhesive of the present invention. The -31-201033314 sheet composed of the layer of the oxygen resin (D) and the reaction product derived therefrom, or may be the aforementioned thermoplastic resin contained in the resin composition containing the substrate and the adhesive of the present invention. (A), the inorganic cerium filling material (B), the epoxy resin (D), a layer derived from the reaction product, and the like, and a sheet composed of the release substrate. The layer of the thermoplastic resin (A), the inorganic chelating material (B), the epoxy resin (D), and the reaction product derived therefrom may be formed on one side of the substrate. It can also be formed on both sides. There is a trace amount or a small amount of a solvent (C). The adhesive sheet has a function of causing the substrate to be bonded to the substrate by the adhesive composition, and then the substrate of the tablet is subsequently used as the substrate. When the release substrate is used as the substrate of the adhesive sheet, the release substrate can be removed, and the adhesive layer can be transferred to another member to be bonded. The subsequent composition is obtained by applying to at least a part of the solvent and drying it according to a usual method, and removing the at least a part of the solvent, and obtaining the adhesive sheet of the present invention. Further, after removing at least a part of the solvent and drying it, When the release film is bonded to the adhesive layer, it can be wound up without causing the internal movement of the substrate, and the workability is excellent, and the adhesive layer is protected, so that the storage property is excellent and the use is excellent. It is also easy. After applying to the release substrate to dry it, if the other release substrate is attached as needed, the adhesive layer itself may be transferred to another substrate. Invention group The substrate of the material is not particularly limited, and examples thereof include a film-like resin, a metal plate, a metal foil, and paper. Examples of the film-like resin include a polyester resin, a polyamide resin, a polyimide resin, and a poly An amidoxime resin, an olefin resin, etc. As a material of a metal plate and a gold-32-201033314 foil, various metals, such as sus, copper, aluminum, iron, and zinc, and each alloy, electroplating, etc. are illustrated. The paper may be exemplified by a high-grade paper, a kraft paper, a roll paper, a cellophane, etc. Further, the composite material may be, for example, a glass reinforced epoxy resin, etc., as a coating from the adhesive force and durability of the adhesive composition. The substrate of the composition of the present invention is preferably a polyester resin, a polyamide resin, a polyimide resin, a polyamide amide resin, a SUS steel plate, a copper foil, an aluminum foil, or a glass reinforced epoxy resin. The release substrate to which the composition of the present invention is applied is not particularly limited, and examples thereof include clay, polyethylene, polypropylene, and the like on both sides of paper such as fine paper, kraft paper, web paper, and cellophane. Supplement The coating layer is then coated with a polyfluorene-based, fluorine-based or alkyd-based release agent on each of the coating layers, and in polyethylene, polypropylene, ethylene-α-olefin copolymer, propylene-α-olefin. Each of the olefin films such as a copolymer and the film of the polyethylene terephthalate or the like are coated on the film of the polyethylene terephthalate or the like, and the release agent is applied to the adhesive layer to be applied, and the polysiloxane is imparted thereto. For reasons of electrical adverse effects, etc., it is preferred to use polypropylene on both sides of a high-grade paper, and to use an alkyd-based release agent thereon, and to use an alcohol on polyethylene terephthalate. Acid-based release agent. In the present invention, the method of applying the composition of the adhesive to the substrate is not particularly limited. A Comma coater, a reverse roll coater, or the like can be given. Alternatively, a rolled copper box which is a constituent material of the printed wiring board may be provided as needed, or an adhesive film layer may be provided on the polyimide film by a direct or transfer method. The thickness of the adhesive film after drying can be appropriately changed as needed, and is preferably in the range of 5 to 200; am. When the thickness of the film is less than 5 μm, the strength is not sufficient. When the thickness is 200 #m or more, the drying is insufficient, and the residual solvent is increased, which may cause problems such as bubbling during pressing of the printed wiring board. The drying conditions are not particularly limited, and the residual solvent ratio after drying is preferably 4% by mass or less, preferably 1% by mass or less. When the content is 4% by mass, there is a problem in that residual solvent foaming occurs when the printed wiring board is pressed, and bubbling occurs. <Printed wiring board> The printed wiring board of the present invention includes a laminate formed of a metal foil forming a conductor circuit and a resin layer as a constituent element. The printed wiring board is produced by, for example, a conventionally known method such as subtraction using a metal-clad laminate. A cover film, a screen printing ink or the like may be used as needed, or a conductor circuit formed of a metal foil may be completely covered, which is collectively referred to as a so-called flexible circuit board (FPC), a flat cable, and a tape automatic soldering (TAB). ) Used circuit boards, etc. The printed wiring board of the present invention can be formed into any laminated structure obtained as a printed wiring board. For example, a printed wiring board composed of a base film layer, a metal foil layer, an adhesive layer, and a cover film layer can be formed. Further, for example, a printed wiring board composed of a base film layer, an adhesive layer, a metal case layer, an adhesive layer, and a cover film layer can be formed. The printed wiring board can be reinforced with a reinforcing material as needed. At this time, the reinforcing material and the adhesive layer are disposed under the base film layer. Further, it is also possible to form a laminate 2 or more layers of the above-described printed wiring board as needed. -34-.201033314 The resin composition of the present invention can be suitably used for each of the subsequent layers of the printed wiring board. In particular, when the resin composition of the present invention is used as an adhesive, it has high adhesion to a substrate constituting a printed wiring board, and has heat resistance which is compatible with the height of lead-free solder, and even under high temperature and high humidity. Can maintain high adhesion. In particular, in the high-temperature field in which the solder resistance is evaluated, 'the chemical cross-linking of the resin and the resin and the physical cross-linking of the resin and the inorganic ruthenium are imparted in a well-balanced manner, and the solder resistance test is not caused in the humidification state. The swelling or deformation caused by evaporation of water can relax the stress 'adapted between the metal foil layer and the cover film layer, and the adhesion between the base film layer and the reinforcing material layer. In particular, in the case of using a metal reinforcing material such as a SUS plate or an aluminum plate, since the water is not evaporated from the reinforcing material side when the welding is performed in a humidified state, the adhesive between the base film layer and the reinforcing material layer is affected. The layer is particularly strong and suitable for use as a resin composition for the subsequent case. In the printed wiring board of the present invention, any resin film which has hitherto been used as a substrate for a printed wiring board can be used as the base film. As the resin of the base film 〇, a halogen-containing resin or a halogen-free resin can be used. From the viewpoint of environmental problems, a resin containing no halogen is preferable, and a halogen-containing resin can also be used from the viewpoint of flame retardancy. The substrate film is preferably a polyimide film or a polyimide film. The metal foil used in the present invention can be used for any conventionally known conductive material which can be used in a circuit board. The material may, for example, be a copper foil, an aluminum foil, a steel foil, or a nickel foil. For the composite metal foil of -35-201033314, or a metal foil treated with other metals such as zinc or a chromium compound, it may be used. It is preferably a copper foil. The thickness of the metal foil is not particularly limited, but is preferably lym or more, more preferably 3 ym or more, and still more preferably 10 ym or more. Further, it is preferably 50 μm or less, more preferably 30/zm or less, and still more preferably 20//m or less. In the case where the thickness is too thin, there is a case where the circuit does not have sufficient electrical performance. On the other hand, in the case where the thickness is too thick, there is a case where the processing energy at the time of circuit fabrication is lowered. 〇 Metal foil is usually supplied in the form of a roll. The form of the metal foil used in the production of the printed wiring board of the present invention is not particularly limited. In the case of using a metal foil in a roll form, the length thereof is not particularly limited. Further, the width thereof is not particularly limited, but is preferably about 250 to 1000 mm. As the cover film, any conventionally known insulating film can be used as the insulating film for a printed wiring board. For example, polyimine, polyester, polyphenylene sulfide, polyether oxime, polyetheretherketone, aromatic polyamine, polycarbonate, ® polyarylate, polyimide, polyamidoxime can be used. A film made of various polymers such as an imide. Preferably, it is a polyimide film or a polyimide film, more preferably a polyimide film. The polyimide film is mainly composed of a polyimide resin as a resin component. Among the resin components, 90% by weight or more is preferably polyimine, 95% by weight or more is preferably polyimine, 98% by weight or more is more preferably polyacrylimide, and 99% by weight or more is polyfluorene. The imine is particularly good. As the polyimine resin, any conventionally known resin can be used. -36- 201033314 As the material of the cover film, a halogen-containing resin or a halogen-free resin may be used. From the viewpoint of environmental problems, a resin containing no halogen is preferable, and a resin containing no halogen can be used from the viewpoint of flame retardancy. As the reinforcing material, a metal plate such as a SUS plate or an aluminum plate, a polyimide film, a plate (glass reinforced epoxy resin plate) which is cured with an epoxy resin, or the like can be used. In particular, the resin composition of the present invention is The adhesion of the SUS plate or the nameplate to the polyimide film can exert great performance, and the subsequent enthalpy and heat resistance show excellent performance of the fertilizer. The printed wiring board of the present invention can be manufactured by any conventionally known process except that the materials of the above layers are used. In a preferred embodiment, a semi-finished product in which a layer of a primer layer is laminated on a cover film layer (hereinafter referred to as "cover film side semi-finished product") is produced. Further, a semi-finished product in which a metal foil layer is laminated on a base film layer to form a desired circuit pattern (hereinafter referred to as "substrate film side two-layer semi-finished product") or an adhesive layer is laminated on the base film layer. A semi-finished product (hereinafter referred to as "substrate film side three-layer semi-finished product") is formed by laminating a metal foil layer thereon (hereinafter, referred to as "substrate film side three-layer semi-finished product") (hereinafter, two layers of semi-finished products and bases will be bonded to the base film side) The three-layer semi-finished product on the side of the film is called "substrate film side semi-finished product"). By coating the thus obtained film-side semi-finished product and the base film-side semi-finished product, a 4-layer or 5-layer printed wiring board can be obtained. Further, a semi-finished product in which an adhesive layer is laminated on the reinforcing material layer (hereinafter referred to as "reinforcing material side semi-finished product") is produced, and the base film layer of the printed wiring board can be bonded and reinforced as needed. Further, the adhesive used in the reinforcing material and the base film is applied to the release substrate and transferred to the base film of the printed wiring board, and may be bonded to the reinforcing material. together. The base film side semi-finished product can be obtained, for example, by the following production method: (A) applying a resin solution for forming a base film on the metal foil, and initially drying the coating film (B) will be at (A) The step of heat-treating and drying the laminate of the obtained metal foil and the initial dry coating film (hereinafter referred to as "heat treatment. solvent removal step").以往 A well-known method can be used on the circuit forming the metal foil layer. An active method can be used, and subtraction can also be used. It is preferred to subtract. The obtained base film side semi-finished product can be directly bonded to the cover film side semi-finished product as it is, or can be used after being bonded to the release film and stored, and then bonded to the cover film side semi-finished product. The cover film side semi-finished product is produced, for example, by applying an adhesive to a cover film. The crosslinking reaction can be carried out in the coated adhesive as needed. A preferred embodiment is to semi-harden the adhesive layer. © The obtained cover film side semi-finished product can be used by directly bonding it to the base material side semi-finished product, or after being bonded to the release film and stored, and then bonded to the base film side semi-finished product. Each of the base film side semi-finished product and the cover film side semi-finished product is stored in the form of a roll, for example, and then bonded to manufacture a printed wiring board. As the method of bonding, any method can be used, and for example, it can be bonded by using a press or a roll. Further, it is also possible to apply a method such as heating and pressurizing or heating a roll device while heating. -38- 201033314 In the case where the reinforcing material side semi-finished product is, for example, a reinforcing material which is soft and retractable like a polyimide film, it is suitable to apply an adhesive to a reinforcing material. Further, for example, in the case of a reinforcing plate which is hard and cannot be wound up, such as a metal plate such as SUS or aluminum, or a glass plate which is cured by an epoxy resin, the applied adhesive is previously transferred to the adhesive. It is suitable to be produced on a release substrate. Further, a crosslinking reaction can be carried out in the applied adhesive as needed. A preferred embodiment is to semi-harden the adhesive layer. The obtained reinforcing material side semi-finished product can be used as it is directly bonded to the inside of the printed wiring board, or can be bonded to the release film and stored, and then bonded to the base film side semi-finished product. The base film side semi-finished product, the cover film side semi-finished product, and the reinforcing agent side semi-finished product are all laminated bodies for a printed wiring board of the present invention. EXAMPLES The following examples are given to illustrate the invention in detail, but the invention is not limited to the examples. Further, in the examples, only those who are referred to as "parts" indicate the parts by mass. Further, in the case of the epoxy resin blending ratio, which is not specifically described, it means {EV(r)xEW(r)}/{AV(/5)XAW(/S)}. In addition, in the table, for example, if ">40" means more than 40, if it is " <230_ means that it is lower than 2 3 0. (Physical property evaluation method) (1) Composition of thermoplastic resin The thermoplastic resin was dissolved in heavy chloroform, and the molar ratio of each component was determined by 1 H-NMR analysis. However, in the case where the thermoplastic resin did not dissolve -39-201033314 in the case of heavy chloroform, it was dissolved in heavy dimethyl hydrazine to carry out 1 Η - N M R analysis. (2) The number average molecular weight Μη The sample is dissolved or diluted in tetrahydrofuran so that the resin concentration becomes about 0.5%, and the membrane filter of a polytetrafluoroethylene membrane having a pore diameter of 55/ζιη is used as a sample for measurement, and tetrahydrofuran is used as a sample. The mobile phase was measured and the molecular weight was determined by gel permeation chromatography using a differential refractometer as a detector. The flow rate was set to 1 mL/min, and the column temperature was set to 30 Torr. The column is made of Showa Denko and KF_802, 8〇4L, and 806L. The molecular weight standard uses monodisperse polystyrene. However, when the sample is not dissolved in tetrahydrofuran, the tetrahydrofuran is changed and n, n-dimethylformamide is used instead. (3) Glass transfer temperature The case of the polyester resin and the urethane resin was measured using a differential scanning calorimeter (DSC) at a temperature increase rate of 20 ° C /min. In the case of a polyimide-based imide resin, a dynamic viscoelasticity measuring device DVA-220 manufactured by IT Measurement and Control Co., Ltd. was used for a short-form sample having a width of 10 mm and a thickness of 30 mm, and dynamic viscosity was performed at a frequency of 10 Hz. The elasticity is measured, and the inflection point of the storage elastic modulus is taken as a glass transition point. Further, the short sample sample can be applied to a polypropylene film by a polymerization solution of polyamidoximine, and dried at 1 201 for 10 hours under a reduced pressure of 1 to 10 mmHg to obtain a solvent-removed film. (4) Acid value The sample 〇.2g is dissolved in 20ml of chloroform, using phenolphthalein as an indicator, in the case of only 0.1N potassium hydroxide ethanol solution, polyamido sulphide-40-201033314 resin The sodium methoxide methanol solution was titrated, and an equivalent weight (eq/l 〇 6 g) per resin was calculated. (5) Epoxy Price According to JIS K7236, using the perchloric acid titration method, the equivalent epoxy equivalent (eq/ 1 〇 6g) per 树脂 (g/1 〇 6g) per oxime is calculated from the obtained epoxy equivalent (mass of resin containing 1 equivalent of epoxy group). (Characteristics Evaluation Method) (1) Solderability and Peel Strength © (1)-1 Evaluation Sample 1 Preparation Method The adhesive composition described later was applied to a polyimide film having a thickness of 25 #m. The company made, APICAL), so that the dried thickness was 30 μm' and dried at 1301 for 3 minutes. When the adhesive film (B-stage product) thus obtained was bonded to a rolled copper foil of 30/zm, the gloss surface of the rolled copper foil was brought into contact with the adhesive, and 35 kgf/cm 2 in 16 〇t: Pressurize under pressure for 30 seconds to continue. Subsequently, it was heat-treated at 140 ° C for 4 hours to be cured to obtain weldability and peeling of the sample 1 for strength evaluation (for initial evaluation). Further, 'the adhesive film (B-stage product) was left to stand at 40 ° C and 80% humidification for 14 days, and then pressed under the above conditions with a rolled copper box, and heat-treated to be cured to obtain a time-lapse evaluation. Sample 1. (1)-2 Evaluation of the sample 2 preparation method The adhesive composition described later was applied to a polypropylene film (manufactured by Toyobo Co., Ltd., RYLEN) having a thickness of 50 mm, so that the thickness after drying was 30. #ηι, dried at 130 ° C for 3 minutes to obtain an adhesive -41 - 201033314 film (B stage product). The evaluation substrate is produced by a usual circuit fabrication step (perforation, plating, dry film photoresist (hereinafter abbreviated as DFR) lamination, exposure/development, etching, DFR peeling), and hardened single-sided copper clad laminate (25a) m polyimide film, 18/zm rolled copper foil) to obtain a substrate for evaluation. After the above-mentioned adhesive film (B-stage product) was temporarily rolled onto the evaluation substrate thus obtained, the polypropylene film was peeled off, and a 500/zm SUS304 plate as a reinforcing plate was pressed at 160 ° C under a pressure of 35 kgf/cm 2 . Pressurize for 30 seconds to continue. Then, it was heat-treated at 140 °C for 4 hours to be cured, and Ο was used to obtain sample 2 for evaluation of weld resistance and peel strength (for initial evaluation). Further, the adhesive film (B-stage product) was allowed to stand under 40 Ό and 80% humidification for 14 days, and then pressed under pressure with the rolled copper foil under the above conditions, and heat-treated to obtain a sample 2 for evaluation over time. . Evaluation of each characteristic was carried out by the following method: Solderability (humidification): The sample was allowed to stand at 40 ° C, 80% humidification for 2 days, and then floated in a heated metal melting bath for 1 minute to The pitch measurement of 1 0 does not produce the upper limit temperature of expansion. In this test, it is required to have a high heat resistance and to suppress the flushing caused by evaporation of water vapor contained in each substrate or adhesive layer, so it is required to be stricter than the dry state. Heat resistance. When considering practical performance, it is preferably 250^ or more, more preferably 260*C or more. Peel strength: A 90° peel test was conducted at 25 ° C at a tensile speed of 50 mm/min to measure the peel strength. This test indicates the strength of the attachment at normal temperature. From the viewpoint of practical performance, it is preferably 1 ON/cm or more, more preferably 15 N/cm_ or more. -42- 201033314 (2) Creep property Using the above-mentioned evaluation sample 2, a hammer of 200 g was suspended in a 60 ° C x 90% environment and the distance of peeling off in 30 minutes was measured. In addition, on one side of the suspension hammer, the peeling form is set to become 180. The method of stripping is implemented. This test shows the strength at the high temperature and high humidity, so that no peeling is preferable, and the peeling distance is larger, and the strength is lower. From the viewpoint of practical performance, it is preferably l〇mm or less, more preferably 4 mm or less. (3) High-temperature and high-humidity environment test. The above-mentioned sample 2 for evaluation of weld resistance and peel strength (for initial evaluation) was placed in an environment of 85 ° C and 85% humidification, and the measurement was carried out for 500 hours and after 10 hours. Peel strength after 0 hours. This test is intended to evaluate the durability in a high-temperature and high-humidity environment for the purpose of confirming the reliability in actual use, and the reliability in actual use is preferably 5 N/cm or more, more preferably ΙΟΝ/cm or more. . Polymerization Example of Polyester Resin A In a reaction tank equipped with a stirrer, a thermometer, and a chiller for effluent, 243 parts of terephthalic acid, 237 parts of isophthalic acid, 107 parts of adipic acid, and 7 parts of trimellitic anhydride were fed. 455 parts of 2-methyl-1,3-propanediol, 205 parts of 1,4-butanediol, and 0.3 parts of tetrabutyl titanate, and the temperature was gradually raised to 2 50 °C for 4 hours, and the distilled water was distilled off. The mixture is discharged to the outside of the system and subjected to an esterification reaction. After completion of the esterification reaction, the polymerization was carried out for 30 minutes, and the initial polymerization under reduced pressure was carried out until lOmmHg, and the temperature was raised to 250 ° C, and further polymerization was carried out at 1 mmHg or less for 1 hour. Then, 'returning to normal pressure with nitrogen, and 28 parts of trimellitic anhydride were introduced, and the composition and characteristics of the polyester resin A thus obtained were obtained by reacting at 220 ° C for 30 minutes to obtain -43-201033314 to the polyester resin A. Shown in Table 1. Each measurement evaluation item is in accordance with the aforementioned method. Polymerization Example of Polyester Resin B In a reaction tank equipped with a stirrer, a thermometer, and a chiller for effluent, 99.6 parts of terephthalic acid, 229.1 parts of isophthalic acid, 3.8 parts of trimellitic anhydride, and 2-methyl-1 were fed. 54.0 parts of 3-propanediol, 401_2 parts of 1,6-hexanediol, and 0.2 parts of tetrabutyl titanate, and the temperature was gradually raised to 250 ° C for 4 hours, and the distilled water was discharged to the outside of the system and esterified. Reaction. 〇 After the end of the esterification reaction, the polymerization was carried out for 30 minutes, and the initial polymerization under reduced pressure was carried out until lOmmHg, and the temperature was raised to 250 ° C, and further polymerization was carried out for 1 hour at 1 mmHg or less. 1 part of the obtained resin was fed to a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube, and a distillation tube, and after adding 182 parts of toluene and dissolving, 70 parts of toluene was distilled, and azeotropy of toluene/water was used. The reaction system is dehydrated. After cooling, 11 parts of methyl ethyl ketone and 7 parts of 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride were added, and the mixture was reacted at 70 ° C for 3 hours to obtain a polyester. A solution of Resin B. The composition and characteristics of the poly-ester resin B thus obtained are shown in Table 1. The polymerization example of the polyester polyol C-I used for the polyurethane resin was used in the same manner as the polymerization example of the polyester resin A, and the raw materials shown in Table 1 were used to prepare a polyurethane. Resin polyester polyol C~I. The composition and characteristics of the resin are shown in Table 1. -44- 201033314
HH σ* (Ν 〇 1-H σι ❿ ι-Η CO 13,800 σ» rH 1 1—Η CO 00 卜 ι-Η r-H 〇 ! Ο 0 o m 1 CN ι-Η Ο Ν \〇 ϊ—1 ΙΟ LO 00 ι-Η 〇 〇 U0 寸 ϊ-Η Ο a CN 〇 τ-Η ο CO ο IN i-H 〇 〇 00" rH ΙΟ (Μ Q 〇 LO 寸 τ-Η CO 00 IN rH i—l 11,500 Ο 寸 o o 寸 〇\ C0 〇 CM τΉ 00 ΙΟ CN 寸 r-H 15,000 ο OQ σ» y〇 rH ΙΟ lO 00 Η! 600 LO < ο 寸 co 〇 <N ι-Η 00 LO CN 寸 寸 Ο ο 〇Λ \〇 τ-Η 400 ο 聚酯樹脂 對苯二甲酸 間苯二甲酸 氍 11 FI3 m 11 偏苯三酸酐 2-甲基-1，3-丙二醇 1，4-丁二醇 鮏 11 fU ώ 鮏 II Kl 新戊二醇 偏苯三酸酐 3,3、4,4 '二苯基酮四羧 酸二酐 ι-Η ί w 多元羧酸成分 多元醇成分 加成酸 數量平均分子量 (Μη) Μ 玻璃體點溫度 (°C) I μ ^ 1 I 201033314 聚胺基甲酸酯樹脂a的聚合例 在具備有溫度計、攪拌機、迴流式冷却管及 之反應容器中，進料於表1中記載之聚酯多元醇 份、甲苯7 0份且溶解後，蒸餾甲苯2 0份’利用 水的共沸使反應系統脫水。冷卻至6 0 °C後’加. 二羥甲基丁酸（DMBA)9份、甲基乙基酮50份。 溶解後，加入六亞甲基二異氰酸酯8.5份，以及 應觸媒之二月桂酸二丁錫0.4份，在80 °C使其 小時之後，投入甲基乙基酮130.2份、甲苯43 且將固體成分濃度調整成3 0重量％，以得到聚 酸酯樹脂a溶液。使用藉由將聚胺基甲酸酯樹脂 液在120 °C乾燥1小時而除去溶劑之薄膜，按照 各測定評價項目來進行測定。將聚胺基甲酸酯樹 性表示於表2中。 聚胺基甲酸酯樹脂1)~；1的聚合例 與聚胺基甲酸酯樹脂a的聚合例同樣地，使 2中所示之原料，以得到聚胺基甲酸酯樹脂 値表示於表2中。各測定評價項目係按照前述之 蒸餾管 s C 1 〇〇 !甲苯/ λ 2,2-DMBA 作爲反 反應4 •4份， 胺基甲 a的溶 前述之 脂的特 用於表 。特性 .方法。 -46- 201033314 【(N撇】 100 σ» t-H 670 4,500 5 Λ 100 CN <Ν 00 1150 〇 〇 ιτΓ ι-Η CO CO 100 σ\ 00 ο ο 〇Λ 寸 ι-Η i-H CN 9.5 700 ο ο t> o CO 0) 100 00 ΙΟ 800 ο ο ί〇" CN cs 100 630 ο ο 寸 CS| CO ο 100 4.5 4.6 390 ο ο 〇Λ co" CM IS CNJ 100 4.5 4.7 380 ο ο 〇Λ ci (Ν <N 寸 Λ 100 〇\ 8.5 650 ο ο θ' (Μ 聚胺基甲酸酯樹脂 ο Q ω ϋ X ΗΗ DMBA 新戊二醇 HDI MDI 酸價(當量/l〇6g) 數量平均分子量(Μη) 玻璃轉移溫度rc) 聚酯樹脂 (聚酯多元醇） 鏈增長劑 i 二異氰酸酯 組成 質量份 mHH σ* (Ν 〇1-H σι ❿ ι-Η CO 13,800 σ» rH 1 1—Η CO 00 卜 Η H rH 〇! Ο 0 om 1 CN ι-Η Ο Ν \〇ϊ—1 ΙΟ LO 00 ι-Η 〇〇U0 inch ϊ-Η Ο a CN 〇τ-Η ο CO ο IN iH 〇〇00" rH ΙΟ (Μ Q 〇LO τ-Η CO 00 IN rH i-l 11,500 Ο inch oo inch inch 〇 \ C0 〇CM τΉ 00 ΙΟ CN 寸rH 15,000 ο OQ σ» y〇rH ΙΟ lO 00 Η! 600 LO < ο inch co 〇<N ι-Η 00 LO CN inch inch Ο ο 〇Λ \〇τ-Η 400 ο Polyester resin terephthalic acid isophthalate isophthalate 11 FI3 m 11 trimellitic anhydride 2-methyl-1,3-propanediol 1,4-butanediol 鮏11 fU ώ 鮏II Kl neopentyl glycol trimellitic anhydride 3, 3,4,4 'diphenyl ketone tetracarboxylic acid dianhydride ι-Η ί w polycarboxylic acid component polyol component addition acid number average molecular weight (Μη) Μ vitreous point temperature (°C) I μ ^ 1 I 201033314 The polymerization example of the polyurethane resin a is provided in a reaction vessel equipped with a thermometer, a stirrer, a reflux cooling pipe, and the like. After the polyester polyol portion shown in Table 1 and 70 parts of toluene were dissolved and dissolved, 20 parts of toluene was distilled to dehydrate the reaction system by azeotropy of water. After cooling to 60 ° C, 'addition. 9 parts of acid (DMBA) and 50 parts of methyl ethyl ketone. After dissolution, 8.5 parts of hexamethylene diisocyanate and 0.4 parts of dibutyltin dilaurate should be added after the reaction at 80 ° C for one hour. The mixture was charged with 130.2 parts of methyl ethyl ketone and toluene 43 and the solid content concentration was adjusted to 30% by weight to obtain a solution of the polyacrylate resin a. It was dried by using a polyurethane resin solution at 120 ° C. The film of the solvent was removed in 1 hour, and the measurement was performed according to each measurement evaluation item. The polyurethane character is shown in Table 2. Polyurethane resin 1)~1 polymerization example and polyamine Polymerization Example of Urethane Resin A In the same manner, the raw material shown in 2 is shown in Table 2 to obtain a polyurethane resin. Each measurement evaluation item is in accordance with the aforementioned distillation tube s C 1 〇 〇! Toluene / λ 2,2-DMBA As a counter reaction 4 • 4 parts, the amino acid A is dissolved in the above-mentioned grease.Characteristics. Method. -46- 201033314 [(N撇] 100 σ» tH 670 4,500 5 Λ 100 CN <Ν 00 1150 〇〇ιτΓ ι-Η CO CO 100 σ\ 00 ο ο 〇Λ inch ι-Η iH CN 9.5 700 ο ο o> o CO 0) 100 00 ΙΟ 800 ο ο ί〇" CN cs 100 630 ο ο 寸 CS| CO ο 100 4.5 4.6 390 ο ο 〇Λ co" CM IS CNJ 100 4.5 4.7 380 ο ο 〇Λ ci ( Ν <N inch Λ 100 〇\ 8.5 650 ο ο θ' (Μ Polyurethane resin ο Q ω ϋ X ΗΗ DMBA neopentyl glycol HDI MDI acid value (equivalent / l 〇 6g) number average molecular weight ( Μη) Glass transfer temperature rc) Polyester resin (polyester polyol) Chain extender i Diisocyanate composition parts by mass m
餾經 wi(H5sffi-g^u-,i7fIapM 201033314 聚醯胺醯亞胺樹脂I的聚合例 在具備有攪拌機、冷却管、氮導入管及溫度計之4 口分離燒瓶中，進料偏苯三酸酐105.67g(0.55mol)、 癸二酸8 0.0 9 g (0.4 0 m ο 1)、兩末端爲羧基的丙烯腈丁二 烯橡膠（宇部興產（股）製 CTBN 1300 X 13)175g(0.05m〇l)、4,4，-二苯基甲烷二異氰酸酯 252.75g(l .Omol)、二甲基乙醯胺526g，在氮氣流下 昇溫至100 °C，使其反應2小時。接著，加入二甲基乙 醯胺1 17g，進而在15CTC中使其反應5小時後，加入 甲苯439g與二甲基乙醯胺I46g並稀釋，冷卻至室溫， 以得到爲褐色但沒有全部混濁的聚醯胺醯亞胺樹脂溶 液1。將如此所得之聚醯胺醯亞胺樹脂I的組成、特性 値表示於表3中。使用藉由將聚醯胺醯亞胺樹脂I的溶 液在lOmmHg以下的減壓狀態下、以 1 2 0 °C乾燥1 〇 小時以上而去除溶劑之薄膜，按照前述之各測定評價項 目來進行測定。 聚醯胺醯亞胺樹脂II~IV的聚合例 與合成例 1同樣地進行製作聚醯胺醯亞胺樹脂的 合成例II~IV。將如此所得之聚醯胺醯亞胺樹脂的組 成 '特性値表示於表3中。 -48- 201033314 【Co谳】 § ΙΟ ΙΟ 100 650 4,000 180 θ ΙΟ ΙΟ ΙΟ τ-Η 100 500 Ο Ο ο ν£Γ τ·Η § w 1〇 LO ΙΟ 400 21,000 155 HH U0 LO ο ΙΟ 100 450 Ο Ο οο" ι-Η 145 聚醯胺醯亞胺樹脂 偏苯三酸酐 趑 11 ίΠ 癸二酸 NBR TDI MDI 酸價(當量/l〇6g) 數量平均分子量(Μη) 玻璃轉移溫度rc) 酸成分 二異氰酸酯 組成 莫耳0/〇 特性 氍饀«€MSSE-糊mM-^^Ias 酸蠢m裝i您S匿HNS) _ 6寸— 201033314 <實施例1 > 摻合作爲熱可塑性樹脂（A)之聚酯樹脂A 100份（僅 固體成分的質量，以下同樣）、作爲無機塡充材（B)之 R972[日本 AEROSIL(股）製的疏水性煙霧狀二氧化 矽】20份、作爲溶劑（C)之甲基乙基酮248份、甲苯112 份，以調整固體成分濃度25%之樹脂組成物（石）。接 著，摻合作爲環氧樹脂（D)之環氧樹脂A[大日本油墨化 〇 學工業（股）製的 HP7200-H(二聚環戊二烯型環氧樹 脂）、環氧價=3540當量/ l〇6g] 1 1 ·9份、作爲溶劑（C) 之甲基乙基酮5.1份，以調整固體成分濃度70%之樹 脂組成物（r )。藉由摻合所得之樹脂組成物（Θ )與樹脂 組成物（7 )，以得到目的之接著劑用樹脂組成物。環氧 樹脂的摻合量係由算出含有聚酯樹脂的酸價總量的 1.05倍環氧基來決定。用上述方法製作接著評價試 料，且將評價之結果表示於表4。初期評價、經時評價 ® 係均顯示良好的結果》 實施例2 與實施例1同樣地’以表3所示之成分、摻合量 作成樹脂組成物並評價特性。又’在全部的實施例中， 樹脂組成物（/3 )係以固體成分濃度爲2 5 %、樹脂組成物 (r )係以固體成分濃度爲70%來進行調製。 實施例3 -50- 201033314 摻合333.3份的作爲熱可塑性樹脂（A)之聚胺基甲 酸酯樹脂溶液a、20份的作爲無機塡充材（B)之R9 72、 9 4.7份的作爲溶劑（C)之甲基乙基酮、甲苯32份’以 調整固體成分濃度2 5%之樹脂組成物（3)。接著’摻合 19.3份的作爲環氧樹脂（D)之環氧樹脂A、8.3份的作 爲溶劑（C)之甲基乙基酮，以調整固體成分濃度70%之 樹脂組成物（r)。藉由摻合所得之樹脂組成物（Θ)與樹 脂組成物（r )，以得到目的之接著劑用樹脂組成物。環 氧樹脂的摻合量係由算出含有聚酯樹脂的酸價總量的 1.05倍環氧基來決定。用上述方法製作接著評價試 料，且將評價之結果表示於表4。初期評價、經時評價 係均顯示良好的結果。 實施例4 ~ 1 1 與實施例3同樣地，以表3所示之成分、摻合量 作成接著劑用樹脂組成物並評價特性。又，在全部的實 施例中，組成物（沒）係以固體成分濃度25%、組成物（r } 係以固體成分濃度70%來進行調製。 實施例12 摻合333.3份的作爲熱可塑性樹脂（A)之聚醯胺醯 亞胺樹脂溶液I、20份的作爲無機塡充材（B)之R972、 98·5份的作爲溶劑（C)之二甲基乙醯胺、甲苯28·2份， 以調整固體成分濃度2 5%之樹脂組成物（A )。接著，摻 -51- 201033314 合13.3份的作爲環氧樹脂（D)之環氧樹脂a、5.7份的 作爲溶劑（C)之甲基乙基酮，以調整固體成分濃度7〇% 之樹脂組成物（T)。藉由摻合所得之樹脂組成物（0)與 樹脂組成物（r )’以得到目的之接著劑用樹脂組成物。 環氧樹脂的摻合量係由算出含有聚酯樹脂的酸價總量 的1·05倍環氧基來決定。用上述方法製作接.著評價試 料’且將評價之結果表示於表4。初期評價、經時評價 係均顯示良好的結果。 實施例1 3、1 4 與實施例3同樣地，以表3所示之成分、摻合量 作成接著劑用樹脂組成物並評價特性。又，在全部的實 施例中，組成物（β )係以固體成分濃度2 5%、組成物（r } 係以固體成分濃度70%來進行調製。 以下記載各成分的詳細資料。 AEROSILR8200:曰本AEROSIL(股）製疏水性煙 霧狀二氧化矽 REOLOSIL DM-10:TOKUYAMA(股）製 疏水性煙 霧狀二氧化矽 REOLOSIL HM-20L:TOKUYAMA(股）製 疏水性 煙霧狀二氧化矽 SYLOPHOBIC 200:富士 S I L Y S IA 化學（股）製疏 水性二氧化砂 -52- 201033314 HIGILITE H-42M:昭和電工（股）製氫氧化鋁 環氧樹脂 B:三菱瓦斯化學（股）製 TETRAD-X(N ,Ν,Ν ' ，Ν ’ -四縮水甘油基_ m ·二甲苯二 胺}、環氧價=10000當量/1〇6g。 環氧樹脂c:東都化成公司製 YDCN703(〇 -甲酚酚 醛清漆型環氧樹脂）、環氧價=4550當量/1〇6§。 環氧樹脂的摻合量係由算出含有熱可塑性樹脂（A) 〇 的酸價總量的0.8~1.3倍的環氧基而決定。將評價的 結果表示於表4。初期評價、經時評價均顯示良好的結 果。 ❿ •53- 201033314 【寸嗽】Distillation wi (H5sffi-g^u-, i7fIapM 201033314 Polyimine yttrium imine resin I was polymerized in a 4-point separation flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, and 105.67 g of trimellitic anhydride was fed ( 0.55mol), adipic acid 8 0.0 9 g (0.4 0 m ο 1), acrylonitrile butadiene rubber with carboxyl groups at both ends (CTBN 1300 X 13 manufactured by Ube Industries Co., Ltd.) 175g (0.05m〇l) 252.75 g (1.0 mol) of 4,4,-diphenylmethane diisocyanate and 526 g of dimethylacetamide were heated to 100 ° C under a nitrogen stream to cause a reaction for 2 hours. Then, dimethyl group B was added. 17 g of guanamine was further reacted in 15 CTC for 5 hours, and then 439 g of toluene and 46 g of dimethylacetamide were added and diluted, and cooled to room temperature to obtain a polyamidimide which was brown but not completely turbid. Resin solution 1. The composition and characteristics of the polyamidolimine resin I thus obtained are shown in Table 3. The solution of the polyamidoximine resin I was used under reduced pressure of 10 mmHg or less, The film which has been dried at 1 2 0 °C for 1 hr or more to remove the solvent, according to the above-mentioned various evaluation items The polymerization examples of the polyamidoximine resins II to IV were carried out in the same manner as in Synthesis Example 1. Synthesis Examples II to IV of the polyamidoximine resin were used. The composition of the polyamidoximine resin thus obtained was determined. 'Characteristics 値 are shown in Table 3. -48- 201033314 【Co谳】 § ΙΟ ΙΟ 100 650 4,000 180 θ ΙΟ ΙΟ ΙΟ τ-Η 100 500 Ο Ο ο ν £Γ τ·Η § w 1〇LO ΙΟ 400 21,000 155 HH U0 LO ο ΙΟ 100 450 Ο Ο οο" ι-Η 145 Polyamide amide imine resin trimellitic anhydride 趑11 ίΠ azelaic acid NBR TDI MDI acid value (equivalent/l〇6g) number average molecular weight (Μη) glass transfer Temperature rc) Acid component diisocyanate composition Mohr 0 / 〇 characteristics 氍饀 «€ MSSE- paste mM-^^Ias acid stupid m installed i you H HNS) _ 6 inch — 201033314 <Example 1 > 100 parts of the polyester resin A of the thermoplastic resin (A) (the mass of the solid component only, the same applies hereinafter), and R972 as the inorganic ceramium filler (B) [hydrophobic smoky cerium oxide manufactured by AEROSIL Co., Ltd., Japan) 20 parts, 248 parts of methyl ethyl ketone as solvent (C), 112 parts of toluene, The entire solid content concentration of 25% of the resin composition (stone). Next, an epoxy resin A blended into an epoxy resin (D) [HP7200-H (dicyclopentadiene type epoxy resin) manufactured by Dainippon Ink Chemical Industry Co., Ltd., epoxy price = 3540 Equivalent / l 〇 6g] 1 1 · 9 parts, 5.1 parts of methyl ethyl ketone as the solvent (C), to adjust the resin composition (r) having a solid concentration of 70%. The obtained resin composition (?) and the resin composition (7) are blended to obtain a desired resin composition for an adhesive. The blending amount of the epoxy resin is determined by calculating 1.05 times the epoxy group of the total acid value of the polyester resin. The evaluation sample was prepared by the above method, and the results of the evaluation are shown in Table 4. In the initial evaluation and the evaluation by time, the results were all good. Example 2 In the same manner as in Example 1, the components and the blending amounts shown in Table 3 were used to prepare a resin composition, and the properties were evaluated. Further, in all the examples, the resin composition (/3) was prepared so that the solid content concentration was 25 %, and the resin composition (r) was 70% solid content. Example 3 - 50 - 201033314 A mixture of 333.3 parts of a polyurethane resin solution a as a thermoplastic resin (A) and 20 parts of R9 72, 9 4.7 parts as an inorganic ruthenium (B) was blended. Solvent (C) methyl ethyl ketone, toluene 32 parts 'to adjust the solid content concentration of 25% of the resin composition (3). Then, 19.3 parts of epoxy resin A as epoxy resin (D) and 8.3 parts of methyl ethyl ketone as solvent (C) were blended to adjust the resin composition (r) having a solid concentration of 70%. The obtained resin composition (Θ) and the resin composition (r) are blended to obtain a desired resin composition for an adhesive. The blending amount of the epoxy resin is determined by calculating 1.05 times the epoxy group of the total acid value of the polyester resin. The evaluation sample was prepared by the above method, and the results of the evaluation are shown in Table 4. Both the initial evaluation and the elapsed time evaluation showed good results. [Examples 4 to 1 1] In the same manner as in Example 3, the components and the blending amounts shown in Table 3 were used as the resin composition for the adhesive, and the properties were evaluated. Further, in all of the examples, the composition (none) was prepared at a solid concentration of 25%, and the composition (r } was prepared at a solid concentration of 70%. Example 12 Blending 333.3 parts as a thermoplastic resin (A) Polyammonium imine resin solution I, 20 parts of R972, 98. 5 parts of inorganic chelating material (B) as solvent (C) dimethyl acetamide, toluene 28·2 To adjust the resin composition (A) having a solid concentration of 25%. Then, doping -51-201033314 and 13.3 parts of epoxy resin a as epoxy resin (D) and 5.7 parts as solvent (C) Methyl ethyl ketone to adjust the resin composition (T) having a solid concentration of 7% by weight, by blending the obtained resin composition (0) with the resin composition (r)' to obtain a desired adhesive The amount of the epoxy resin to be blended is determined by calculating the epoxy group of 1.05 times the total acid value of the polyester resin. The evaluation sample is prepared by the above method and the evaluation results are shown. In Table 4. Both the initial evaluation and the elapsed evaluation showed good results. Example 1 3, 1 4 Same as Example 3. The composition and the blending amount shown in Table 3 were used as the resin composition for the adhesive, and the properties were evaluated. Further, in all the examples, the composition (β) was a solid concentration of 25%, and the composition ( r } is prepared at a solid concentration of 70%. Details of each component are described below. AEROSILR8200: Hydrophobic smog dioxide REOLOSIL DM-10 manufactured by AEROSIL (shares): Hydrophobic smoke from TOKUYAMA二 二 矽 REOLOSIL HM-20L: TOKUYAMA (share) made of hydrophobic smog dioxide SYLOPHOBIC 200: Fuji SILYS IA chemical (share) made of hydrophobic silica sand -52- 201033314 HIGILITE H-42M: Showa Denko Aluminum hydroxide epoxy resin B: TETRAD-X (N , Ν, Ν ' , Ν '-tetraglycidyl _ m · xylylenediamine} manufactured by Mitsubishi Gas Chemical Co., Ltd., epoxy price = 10,000 equivalents /1〇6g. Epoxy resin c: YDCN703 (〇-cresol novolak type epoxy resin) made by Dongdu Chemical Co., Ltd., epoxy price = 4550 eq / 1 〇 6 §. The blending amount of epoxy resin is calculated a ring containing 0.8 to 1.3 times the total acid value of the thermoplastic resin (A) Group is determined. The results are shown in Table 4. Evaluation of the initial evaluation, the evaluation showed good results. ❿ • 53- 201033314 [inch] cough
握 κ 寸 曰 Ο ο rH § 擀 1 14.8 | n m N3 m 1.05 | in in l〇 Ο <Ν 寸 rH 〇 ν〇 <Ν 00 rH 〇 ο ΟΙ νο L0 i-H s <N v〇 CO Η Ο ο ι-Η § m K) m & II 11-9 1 1.05 in 寸· Ο <Ν ι-Η rH Ο ν〇 <Ν co »—t 〇 1〇 <Ν CO S cs in CJ h—1 Ο <τΗ 13.3 1 1.05 5.0 <N Ο Ό CS Οϊ rH Ο ν〇 (Ν 寸 f-H 〇 VO (N <Ν co i-H s <N (N <·*-* 〇 〇 fH § 擀 i m K] m El· 1 20.8 1 1.05 4.5 CO ο ο CS <N ι-Η S (Ν in Ο ν〇 (Ν Ο CO rH <N o o V 〇 〇 ι-Η 1 23.7 I 1.05 5.0 寸 rH ο <Ν i-H t-H § <Ν CO <N Ο ν〇 <Ν Ο CM 〇 VO <N o i T3 〇 rH § % 1 18-7 1 1.05 1 l〇 c6 o Ο ν〇 CN o •-H Ο νο <Ν <N t—i Ο ν£> (Ν ο o i-H 〇 VO CN 寸 i υ Ο ο in 1 11-6 1 1.05 | l〇 CO CO •—4 Ο ν£> CS (N Ο ^0 (Ν Ο ν〇 (Ν ο ¢0 (N 〇 v£) Oi o 1 ο ο ο »Ή 00 00 0.80 1 in 寸 Ο ν£> o rH S <Ν in (N Ο ν〇 <Ν ο 〇 CS o Ό (N CO VO ο ο ο ι-Η § 14-3 1 1.30 1 ΙΟ 寸 in f-H Ο 卜 CN CO r-i Ο Ο <Ν in ΟΪ Λ Ο (Ν ο in 〇 <N o m *D ο ο § o 105 1 in ¥ νϋ Ο νο CSI l〇 S <Ν ΙΟ (N Ο CS ο l〇 CN Λ 〇 o 寸 Xi ο ο ι-Η 1 11-3 1 1.05 | l〇 ο Οϊ v〇 »—4 § CN ir> <N Ο 00 (Ν ο in <N Λ o <N o c〇 ctf ο f-H § 1 19.3 | 1.05 | o (N r~< ο 〇5 o rH Ο ν〇 Οί <N S (Ν ΙΟ o r*H s <N o rH (N CQ Ο Ο ι-Η 1 16.9 1 I 0.32 I ：1.05 I lO CO co ο ν〇 <Ν CN S <Ν in pH Ο <〇 (Ν ο »—H i-H <N o < Ο ο § 1 11-9 1 105 1 in 00 (N Ο νΟ <Ν o S CN 寸 Ο ν〇 <Ν ο o S ΟΪ o 1S m 雜 画 _ ft 1 φ 豳 晅 i _ ft 1S 難 瓸 _ ft 1 R972 1 1 R8200 1 1 DM-10 1 1 HM-20L 1 1 SYLOPHOBIC 200 」 1 H-42M 1 m m 1S 難 瓸 _ m < 5 雜 Μ Φ _ ft OQ 1g 雜 B Φ iH 鲰 o 蘅 m 1 X > E m 親 ψ 百 s m m 雖 M 〇〇 I * m 1 百 υ Z m 網 凝 Μ Ρ 1 * m a i 百 m m 截 Μ Ρ 1 ft m 1 I Μ m m Si υ Z 涵 涯 鍵 Μ p m 瑯 St m a s 1 m m IMP m Si 聚胺基甲酸酯 樹脂 麵醫體亞胺 β 環氧 樹脂 卜 i X I I % i 初期評價 經時評價 初期評價 經時評價 組成物 (y3) 組成物 (r) 試樣1 試樣2 <SS®«S£®1羧赃 _®^Β--οεοΛζυαΛ 鉍陌负堪安賒嵌：υιϋ®®βΕ 拼&-:ζέ-«思扭«ϋΞ-<Ν*,Ν*Ν*Ν><-ανΗΧ3χ sifswsfr^sN觀111:mlf®®SE 201033314 實施例1 5 ~ 1 9 與實施例3同樣地，但是將對於進一步提高環氧樹 脂的摻合量之接著劑組成物的評價結果表示於表5。％ 期評價、經時評價均顯示良好的結果，而且已知剝離強 度、耐加濕焊接性爲優異的。又，將對於高溫高濕環境 試驗的評價結果表示於表6。環氧樹脂摻合量設爲 1.3~4的情形中，已知從在高溫高濕環境試驗後也可以 © 抑制剝離強度的降低之點而言爲優異的。κ 曰Ο inch ο rH § 擀1 14.8 | nm N3 m 1.05 | in in l〇Ο <Ν inch rH 〇ν〇<Ν 00 rH 〇ο ΟΙ νο L0 iH s <N v〇CO Η Ο ο ι-Η § m K) m & II 11-9 1 1.05 in inch · Ο <Ν ι-Η rH Ο ν〇<Ν co »—t 〇1〇<Ν CO S cs in CJ h —1 Ο <τΗ 13.3 1 1.05 5.0 <N Ο Ό CS Οϊ rH Ο ν〇(Ν inch fH 〇VO (N <Ν co iH s <N (N <·*-* 〇〇fH §擀im K] m El· 1 20.8 1 1.05 4.5 CO ο ο CS <N ι-Η S (Ν in Ο ν〇(Ν Ο CO rH <N oo V 〇〇ι-Η 1 23.7 I 1.05 5.0 inch rH ο <Ν iH tH § <Ν CO <N Ο ν〇<Ν Ο CM 〇VO <N oi T3 〇rH § % 1 18-7 1 1.05 1 l〇c6 o Ο ν〇CN o •-H Ο νο <Ν <N t—i Ο ν£> (Ν ο o iH 〇VO CN inch i υ Ο ο in 1 11-6 1 1.05 | l〇CO CO •—4 Ο ν£ > CS (N Ο ^0 (Ν Ο ν〇(Ν ο ¢0 (N 〇v£) Oi o 1 ο ο ο »Ή 00 00 0.80 1 In Ο Ο ν £ & o o o o o N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N CN CO ri Ο Ο <Ν in ΟΪ Λ Ο (Ν ο in 〇<N om *D ο ο § o 105 1 in ¥ νϋ Ο νο CSI l〇S <Ν ΙΟ (N Ο CS ο l〇CN Λ o inch ii ο ι Η 1 11-3 1 1.05 | l〇ο Οϊ v〇»—4 § CN ir><N Ο 00 (Ν ο in <N Λ o <N oc〇ctf ο fH § 1 19.3 | 1.05 | o (N r~< ο 〇5 o rH Ο ν〇Οί <NS (Ν ΙΟ or*H s <N o rH (N CQ Ο Ο ι-Η 1 16.9 1 I 0.32 I :1.05 I lO CO co ο ν〇<Ν CN S <Ν in pH Ο <〇(Ν ο »—H iH <N o < Ο ο § 1 11-9 1 105 1 in 00 (N Ο νΟ <Ν o S CN inchΟ ν〇<Ν ο o S ΟΪ o 1S m _ ft 1 φ 豳晅i _ ft 1S difficult _ ft 1 R972 1 1 R8200 1 1 DM- 10 1 1 HM-20L 1 1 SYLOPHOBIC 200 ” 1 H-42M 1 mm 1S difficult _ m < 5 Μ Φ _ ft OQ 1g Miscellaneous B Φ iH 鲰o m 1 X > E m relatives hundred smm although M 〇〇I * m 1 hundred υ Z m Μ Ρ 1 * mai 100 mm Μ Ρ 1 ft m 1 I Μ mm Si υ Z 涯 Μ Μ pm琅St mas 1 mm IMP m Si polyurethane resin surface imine body imine β epoxy resin i XII % i initial evaluation time evaluation initial evaluation time evaluation composition (y3) composition (r) test Sample 1 Sample 2 <SS®«S£®1carboxy 赃_®^Β--οεοΛζυαΛ 铋 负 堪 堪 υ υ:υιϋ®®βΕ 拼 &-:ζέ-«思扭«ϋΞ-< Ν*, Ν*Ν*Ν><-ανΗΧ3χ sifswsfr^sN view 111: mlf®®SE 201033314 Example 1 5 to 1 9 Same as Example 3, but for further increasing the amount of epoxy resin blended The evaluation results of the adhesive composition are shown in Table 5. The % evaluation and the evaluation by time showed good results, and it was found that the peel strength and the wet-resistant weldability were excellent. Further, the evaluation results of the high-temperature and high-humidity environment test are shown in Table 6. In the case where the epoxy resin blending amount is set to 1.3 to 4, it is known that it is excellent in the point of suppressing the decrease in peel strength after the test in the high-temperature and high-humidity environment.
-55- 201033314-55- 201033314
【表5】 mm 15 16 17 18 19 組 成 組成物 (β) 聚酯樹脂 組成 質量份個體成分1 聚胺基甲酸酯樹 脂 組成 b b b C C 質量份個體成分1 100 100 100 100 100 聚醯胺醯亞胺 樹脂 組成 質量份(固體成分1 無機塡充材 (固體成分） R972 20 20 20 20 20 R8200 DM-10 HM-20L SYLOPHOBIC 200 Η-42Μ 溶劑 甲基乙基酮/甲苯 組成物 (r) 環氧 樹脂 Α質量份個體成分) 17.2 21.5 32.2 41.9 20.0 B質量份個體成分) C質量份(固體成分1 5.7 溶劑 甲5 塞乙基酮 {EV( r) χ ew( r )}/{AV( β) ^aw( β)} 1.60 2.00 3.00 3.80 2.50 特 性 組成物ία)搖變度(τι備 4.5 4.5 4.5 4.5 4.5 _1 初期評價 剝離強度(N/cm) 16 16 16 15 15 耐加濕焊接性ra 270 270 270 270 260 經時評價 剝離強度(N/cml 16 16 16 13 13 耐加濕焊雛 260 260 260 260 260 試樣2 初期評價 剝離強度(N/cm) >25 >25 >30 >30 >25 耐加濕焊雛ra 280 280 280 270 270 蠕變特性(mml 0 0 0 0 0 經時評價 剝離強度(N/cm) >25 >25 >30 >30 >25 耐加濕焊接性rc) 270 270 270 270 270 蠕變特性(mml 0 0 0 0 0 A: ^曰本油墨工業(股)製Hp72〇〇_H(二聚環戊二稀型環氧樹脂） ΪΪΪΐ B :三菱瓦斯化學(股)製TETRAD_X(N，N，N，，N，_四縮水甘油基皆二甲苯二胺) 氧綳曰C ••東都化成公司製YDCN703(〇-甲酚酚醛清漆型環氧樹脂） -56- 201033314 【表6】 實S mi 4 5 6 7 8 15 16 17 18 19 組 成 組 成 物 (β) 聚酯樹脂 組成 質量份 個體成分） 聚胺基甲酸酯 樹脂 組成 b b C C C b b b c c 質量份 (固體成分1 100 100 100 100 100 100 100 100 100 100 聚_醯亞胺 樹脂 組成 質量份 (固體成分1 無機塡充材 (固體成分） R972 20 20 20 20 20 20 20 20 R8200 DM-10 20 HM-20L 15 SYLOPHOBIC 200 H-42M 溶劑 甲基乙基酮/甲苯 組 成 物 (r) 環氧 樹脂 A質量份 個體成分1 11.3 9.0 14.3 8.8 11.6 17.2 21.5 32.2 41.9 20.0 B質量份 個體成分） C質量份 個體成分1 1.7 5.7 溶劑 甲基乙基酮 {EV(r)xEW(r)}/{AV(^)xAW(y3)} 1.05 1.05 1.30 0.80 1.05 1.60 2.00 3.00 3.80 4.5 2.50 4.5 特 性 組成物⑷搖變度(Ή値> 4.5 4,5 4.5 4.5 3.5 4.5 4.5 4.5 試 樣 2 高溫高濕環境 試驗剝離強度 (N/cm) 經過500小時 8 8 13 5 9 18 17 14 12 15 經過1000小時 5 5 8 2 5 15 14 9 6 12[Table 5] mm 15 16 17 18 19 Composition (β) Polyester resin Composition mass parts Individual component 1 Polyurethane resin composition bbb CC mass parts Individual component 1 100 100 100 100 100 Polyamide Amine resin composition parts by mass (solid content 1 inorganic cerium filling material (solid content) R972 20 20 20 20 20 R8200 DM-10 HM-20L SYLOPHOBIC 200 Η-42Μ Solvent methyl ethyl ketone / toluene composition (r) epoxy Resin Α mass parts individual components) 17.2 21.5 32.2 41.9 20.0 B parts by mass of individual components) C parts by mass (solid content 1 5.7 Solvent A 5 ce ethyl ketone {EV( r) χ ew( r )} / {AV( β) ^aw( β)} 1.60 2.00 3.00 3.80 2.50 Characteristic composition ία)Shake degree (τι4.5 4.5 4.5 4.5 4.5 _1 Initial evaluation peel strength (N/cm) 16 16 16 15 15 Resistance to wet soldering ra 270 270 270 270 260 Peel strength evaluation over time (N/cml 16 16 16 13 13 Humidification resistant welding 260 260 260 260 260 Sample 2 Initial evaluation peel strength (N/cm) >25 >25 >30 > 30 >25 resistance to wet welding ra 280 28 0 280 270 270 Creep characteristics (mml 0 0 0 0 0 Evaluated peel strength (N/cm) >25 >25 >30 >30 >25 Humidity resistance rc) 270 270 270 270 270 Creep characteristics (mml 0 0 0 0 0 A: ^Hp72〇〇_H (dimeric cyclopentadiene epoxy resin) manufactured by 油墨本墨工业有限公司 ΪΪΪΐ B: TETRAD_X by Mitsubishi Gas Chemical Co., Ltd. (N,N,N,,N,_tetraglycidyl-xylylenediamine) Oxygen C C••DDCN703 (〇-cresol novolac type epoxy resin) manufactured by Dongdu Chemical Co., Ltd. -56- 201033314 6] Real S mi 4 5 6 7 8 15 16 17 18 19 Composition (β) Polyester resin composition mass parts individual components) Polyurethane resin composition bb CCC bbbcc parts by mass (solid content 1 100 100 100 100 100 100 100 100 100 100 Poly(indenine) resin composition parts by mass (solid content 1 inorganic cerium filling (solid content) R972 20 20 20 20 20 20 20 20 R8200 DM-10 20 HM-20L 15 SYLOPHOBIC 200 H- 42M solvent methyl ethyl ketone / toluene composition (r) Epoxy Resin A parts by mass Individual component 1 11.3 9.0 14.3 8.8 11.6 17.2 21.5 32.2 41.9 20.0 B parts by mass of individual components) C parts by weight of individual components 1 1.7 5.7 Solvent methyl ethyl ketone {EV(r)xEW( r)}/{AV(^)xAW(y3)} 1.05 1.05 1.30 0.80 1.05 1.60 2.00 3.00 3.80 4.5 2.50 4.5 Characteristic composition (4) Shake degree (Ή値> 4.5 4,5 4.5 4.5 3.5 4.5 4.5 4.5 Sample 2 High temperature and high humidity environment test peel strength (N/cm) After 500 hours 8 8 13 5 9 18 17 14 12 15 After 1000 hours 5 5 8 2 5 15 14 9 6 12
環氧樹脂A :大曰本油墨工業(股)製HP7200-H(二聚環戊二烯型環氧樹脂1 環氧樹脂B :三菱瓦斯化學(股)製TETRAD-X(N，N,N’,N’-四縮水甘油基-πl-二甲 苯二膨 環氧樹脂C :東都化成公司製YDCN703(〇-甲酚酚醛清漆型環氧樹脂） 比較例1 ~ 1 5 與實施例1〜19同樣地，以表示於表7、8之成分、 摻合量製作接著劑用樹脂組成物並評價特性。 -57- 201033314 ο οEpoxy Resin A: HP7200-H (Dicyclopentadiene Epoxy Resin 1 Epoxy Resin B: manufactured by Mitsubishi Gas Chemical Co., Ltd.) TETRAD-X (N, N, N) ', N'-tetraglycidyl-πl-xylene dimerized epoxy resin C: YDCN703 (〇-cresol novolak type epoxy resin) manufactured by Tohto Kasei Co., Ltd. Comparative Examples 1 to 1 5 and Examples 1 to 19 Similarly, a resin composition for an adhesive was prepared by using the components shown in Tables 7 and 8, and the blending amount, and the characteristics were evaluated. -57- 201033314 ο ο
卜嗽】 OJ 〇 〇 ι-Η 8 N3ffi- Ss稱 lj鱷 CO 〇\ in q r-H LO — in § (N in 8 CM ιη § CM ιη 寸 ο 寸 CM if) τ-Η rH ο ο ο »-Η 甲基乙基酮/甲苯 00 〇6 in q LO v〇 ί—1 Ο v〇 (N 寸 ί—H s (Μ ιη (Ν Λ Ο ：ν〇 (Μ ο 寸 Λ in (Ν Λ Ο ν〇 CN 〇 寸 Λ o ϋ Ο ο ι-Η o <N v〇 rH in q 1—< q τ-Η in <230 CO <230 ιη (Ν Λ Ο 00 <Ν V Ο CO cs <230! Ο ο Ο o ΟΪ v£> r-H in q i-H ό »-4 CN <230 o <230 00 § ί(Ν ；ν Ο <230 ο rH 00 υ ο r-H O CM 11.6 in q rH Ο ci in <230 00 <230 Ο 00 <Ν V ο CO <230 Ο 寸 Λ 卜 ο Ο ο rH s 11.6 ΤΗ1 BE W K] uo q tH ο ν o s CM 卜 ο 寸 ΟΙ Ο (Ν S (Ν ο VO ο 寸 (Ν Ο v〇 ο Ο ο ι-Η ~ in v〇 »—1 m fr l〇 o i-H LO τ-Η LO 〇 CO (N CO <230 ΙΟ CM Λ 0 C0 <Ν ο LO (M Λ Ο C0 <Ν V C0 in ·— Ο ο rH σ* 〇\ i-H q i-H Ο ^ί~ 00 〇 v〇 ：<N ;in S <Ν 寸 <Ν Ο ν〇 (Ν ο 寸 Λ CN (N Ο 10 CN Ο 寸 Λ 寸 Λ Ο ι-Η 容 34.1 in q ο — 〇 〇 (N o 卜 00 γΉ Ο <Ν Ο 才 Λ ： Ο CN Ο 寸 Λ Ί bi. Ο ο Τ-Η 卜 oi v〇 q i-H ιη — 00 〇 CO csi V LO <230 Ο Ο C0 (Ν V LO (Ν t> Ο C0 <Ν V Ο C0 CN ο ο r—1 § is CN v〇 q 1-^ ιο σ\ 〇 CO (N V 寸 ο 00 (Ν V 卜 Ο C0 (Ν V Ο 寸 Λ LO <230 Ο 寸 Λ Ο ο γΗ § I> o t—H ο 00 g csi V I ro Ο 00 (Ν V 00 Ο C0 CN V Ο 寸 Λ 10 V Ο 寸 Λ ί 1 u 链 m s φ in <N 1 〇 〇 CN 00 X o 1 s Q HM-20L 〇 o CS o s o ffi tx 〇 m <N 'Φ K 1 酿 酸 φ is 醒 m m 1 X 1 i Ε Μ m I ϋ u •m< 凿 s P m 细 St m a s ϋ -ttTf 锻 繼 Ρ 5 6 m □ S U <tvr 錄 Μ Ρ 0 1$ 毁 m Β S m ¢: m MP 盤 百 ϋ Z, i〇f 锻 ss s Ρ m st m _ 謹 議 m is ii I 岫 < Θ _ Λ CQ _ ϋ m 9¾ M Μ θη 5¾ te I m frgg mm » mss 麵 mm 1 驪 '― ω X *—»1 Έ I 初期評價 經時評價 擁評價 經時評價 ，晋)物 試樣1 試樣2 1 卿 思雜 tn臟 +<li« <DQO \ΊΠΤ\1ΠΤ\ΊΠΤ 1 I I '***TT^1 I I > 麵H Μ擀 ffi- II 题旱輕碧 醛扭ϋ嗽 】 OJ 〇〇ι-Η 8 N3ffi- Ss called lj crocodile CO 〇 \ in q rH LO — in § (N in 8 CM ιη § CM ιη inch ο inch CM if) τ-Η rH ο ο ο »- Η methyl ethyl ketone / toluene 00 〇 6 in q LO v〇ί—1 Ο v〇 (N inch ί—H s (Μ ιη (Ν Λ Ο :ν〇(Μ ο Λ Λ in (Ν Λ Ο ν 〇CN 〇 inch Λ o ϋ Ο ο ι-Η o <N v〇rH in q 1—< q τ-Η in <230 CO <230 ιη (Ν Λ Ο 00 <Ν V Ο CO cs <230! Ο ο Ο o ΟΪ v£> rH in q iH ό »-4 CN <230 o <230 00 § ί(Ν ;ν Ο <230 ο rH 00 υ ο rH O CM 11.6 in q rH Ο ci in <230 00 <230 Ο 00 <Ν V ο CO <230 Ο inch Λ ο Ο ο rH s 11.6 ΤΗ1 BE WK] uo q tH ο ν os CM 卜 ο inch ΟΙ Ο ( Ν S (Ν VO ο 寸 (Ν Ο v〇ο Ο ο ι-Η ~ in v〇»—1 m fr l〇o iH LO τ-Η LO 〇CO (N CO <230 ΙΟ CM Λ 0 C0 <Ν ο LO (M Λ Ο C0 <Ν V C0 in ·— Ο ο rH σ* 〇\ iH q iH Ο ^ί~ 00 〇v〇:<N ;in S <Ν 寸<Ν Ο ν〇(Ν ο Λ Λ CN (N Ο 10 CN Ο inch Λ inch Λ ι ι-Η 容 34.1 in q ο — 〇〇 (N o 00 γ Ή Ο <Ν Ο Λ Λ : Ο CN Ο Λ Λ Ί bi. Ο ο Τ-Η 卜 oi v〇q iH ιη — 00 〇CO csi V LO <230 Ο Ο C0 (Ν V LO (Ν t> Ο C0 <Ν V Ο C0 CN ο ο r—1 § is CN v〇q 1-^ ιο σ\ 〇CO (NV inch ο 00 (Ν V Ο C0 (Ν V Ο inch Λ LO <230 Ο inch Λ ο γ Η § I> ot-H ο 00 g csi VI ro Ο 00 (Ν V 00 Ο C0 CN V Ο inch Λ 10 V Ο inch Λ ί 1 u chain ms φ In <N 1 〇〇CN 00 X o 1 s Q HM-20L 〇o CS oso ffi tx 〇m <N 'Φ K 1 Brewing acid φ is awake mm 1 X 1 i Ε Μ m I ϋ u •m< Chisel s P m Fine St mas ϋ -ttTf Forged Ρ 5 6 m □ SU <tvr Record Ρ 0 1$ 毁 m Β S m ¢: m MP 盘 ϋ Z, i〇f forged ss s Ρ m St m _ mm ii I 岫< Θ _ Λ CQ _ ϋ m 93⁄4 M Μ θη 53⁄4 te I m frgg mm » mss face mm 1 骊'― ω X *—»1 Έ I Initial evaluation Elapsed evaluation Evidence evaluation Elapsed time evaluation, Jin) Substance sample 1 Sample 2 1 Qingsi miscellaneous tn dirty +<li« <DQO \ΊΠΤ\1ΠΤ \ΊΠΤ 1 II '***TT^1 II > Face H Μ擀ffi- II Dry light acetal twist
〇〇 ν〇 201033314 【00谳】 ΙΟ 〇 〇 r-H 琳 & 1 κι fr 11 64.0 | 匾 5.03 — ο 〇 CO CN o ：rH <230 1 r-H <230 1 CN Ο <230 | i-H 鎰 ii ϋ 〇 〇 »-Η § 齡 m 55.0 Ν3 猢 ffi- 4.99 in — 1 Ο CO CN o <230 m ,<N 丨Λ ο 寸 (Ν Ο <230 | o CO < 〇 〇 r-H m & 56.0 4.96 in co Ο Ο CO CN o <230 <N 1—1 <230 Ο 〇\ <230 o 1g 聽 画 i _ 链 Φ 链 幽 0 Φ 1g Φ 1S m E Φ _| 挪 R972 R8200 DM-10 HM-20L SYLOPHOBIC 200 Η-42Μ m 趣 φ 1S 豳 画 _ ft < Φ CQ Φ 链 豳 画 _ ο 罷 敏 § I X I m m i « I i υ m 瑕 繼 m 细 St m m s υ Μ m 醒 1 1 β m m St m a s 〇 ^! m 锻 醒 Ρ m 毁 m § Μ 1 Μ m IMP 11 o M 瑕 H44· 羅 g is St m 1 M 1 I δ m m iktje 驅 II 聚胺雲Γ酿 灘驪鎌 β li 初期評價 經時評價 初期評價 經時評價 組成物⑹ 組成物(r) 試樣1 — 試樣2 卿 {igut^frH-日-««扣长躍 a-<M,N2*N><-avHX3x Si{^)«-A3>^:I:瀬11!: assjatlliSE SWI^n^iffi.oo^^w ^iswiraK " < i -61? 201033314 比較例1相當於熱可塑性樹脂（A)之聚酯樹脂Η的酸價 很低，又數量平均分子量很低，在本發明的範圍外。在室 溫的剝離強度也很低，在高溫高濕度下的作爲接著性指標 的蠕變特性也不良，而且耐加濕焊接性也很低。硬化物的 交聯不夠充分，而可認爲凝集力變小。 比較例2相當於熱可塑性樹脂（Α)之聚酯樹脂I的酸價 很低，在本發明的範圍外。在室溫的剝離強度也很低，在 高溫高濕度下的作爲接著性指標的蠕變特性也不良，而且 Q 耐加濕焊接性也很低。硬化物的交聯不夠充分，而可預期 _凝集力變小。 比較例3相當於熱可塑性樹脂（Α)之聚胺基甲酸酯樹脂 g的酸價很低，在本發明的範圍外。在室溫的剝離強度也 很低，在高溫高濕度下的作爲接著性指標的蠕變特性也不 良，而且耐加濕焊接性也很低。硬化物的交聯不夠充分， 而可預期凝集力變小。 比較例4相當於熱可塑性樹脂（A)之聚胺基甲酸酯樹脂 〇 h的酸價很高，在本發明的範圍外。由於硬化物的剛直性 變得過高，所以在室溫的剝離強度也很低，而可認爲在高 溫高濕度下的作爲接著性指標的蠕變特性也不良。 比較例5相當於熱可塑性樹脂（A)之聚胺基甲酸酯樹脂 i的數量平均分子量很低，在本發明的範圍外。由於凝集力 變小’所以在室溫的剝離強度也很低，而可認爲在高溫高 濕度下的作爲接著性指標的蠕變特性也不良。 -60- 201033314 比較例6係分散液（α)的搖變度（τι値）很低，在本發 明的範圍外。樹脂與無機塡充材的相互作用變低，而可認 爲耐加濕焊接性降低。 比較例7係分散液（α )的搖變度（τι値）很高，在本發 明的範圍外。與基材的貼合變得不夠充分，而可認爲剝離 強度降低。 比較例8係分散液（α )的搖變度（ΤΙ値）很低，在本發 明的範圍外。樹脂與無機塡充材的相互作用變低，而可認 0 爲耐加濕焊接性降低，片材壽命變差且經時的特性降低。 比較例9係分散液（α )的搖變度（TI値）很低，在本發 明的範圍外。樹脂與無機塡充材的相互作用變低，而可認 爲耐加濕焊接性降低，片材壽命變差且經時的特性降低。 比較例1 0係分散液（α )的搖變度（ΤΙ値）很低，在本發 明的範圍外。樹脂與無機塡充材的相互作用變低，而可認 爲耐加濕焊接性降低。 比較例11係沒有摻合相當於環氧樹脂（D)之具有二聚 ❹ 環戊二烯骨架的環氧樹脂，在本發明的範圍外。剛直性、 低吸濕性降低，而可認爲在高溫高濕度下的作爲接著性指 標的嬬變特性降低。 比較例1 2相當於熱可塑性樹脂（Α)之聚醯胺醯亞胺樹 脂的分子量很小，在本發明的範圍外。室溫的剝離強度也 很，在高溫高濕度下的作爲接著性指標的蠕變特性也不 良。其係可認爲是因爲硬化物的凝集力變小了。 -61- 201033314 比較例13相當於環氧樹脂（D)之具有二聚環 架的環氧樹脂的慘合量很多，在本發明的範圍外 得不夠充分，而可認爲耐加濕焊接性降低。 比較例14相當於環氧樹脂之具有二聚環 架的環氧樹脂的摻合量很多，在本發明的範圍外 得不夠充分，而可認爲耐加濕焊接性降低。 比較例15相當於環氧樹脂（D)之具有二聚環 架的環氧樹脂的摻合量很多，在本發明的範圍外 0 得不夠充分，而可認爲耐加濕焊接性降低。 產業上的利用可能性 根據本發明，可提供一種能得到對於PET薄 種塑料薄膜及銅、鋁、不銹鋼等的各種金屬有很 性、可對應於高濕度下的無鉛焊料之高度的耐濕 高溫高濕度下的接著性優異之接著劑’而且8階 使在高溫高濕下流通之後亦可使用’能維持良好 的片材壽命良好的樹脂組成物、含有其之接著劑 G 及含其爲接著層之印刷配線板° 【圖式簡單說明】 無。 【主要元件符號說明】 紐。 戊二烯骨 。硬化變 戊二烯骨 。硬化變 戊二烯骨 。硬化變 膜等的各 高的接著 熱性、在 段的片即 接著特性 、接著片 -62-〇〇ν〇201033314 [00谳] ΙΟ 〇〇rH Lin & 1 κι fr 11 64.0 | 匾5.03 — ο 〇CO CN o :rH <230 1 rH <230 1 CN Ο <230 | iH 镒ii ϋ 〇〇»-Η § Age m 55.0 Ν3 猢ffi- 4.99 in — 1 Ο CO CN o <230 m ,<N 丨Λ ο 寸 (Ν Ο <230 | o CO < 〇〇rH m & 56.0 4.96 in co Ο Ο CO CN o <230 <N 1 - 1 <230 Ο 〇\ <230 o 1g Listening i _ Chain Φ Chain 幽 0 Φ 1g Φ 1S m E Φ _| R8200 DM-10 HM-20L SYLOPHOBIC 200 Η-42Μ m Interest φ 1S 豳画_ ft < Φ CQ Φ Chain 豳 _ ο 脱 敏 § IXI mmi « I i υ m 瑕 m m Fine St mms υ Μ m Wake up 1 1 β mm St mas 〇^! m Wake up Ρ m 毁 m § Μ 1 Μ m IMP 11 o M 瑕H44· 罗 g is St m 1 M 1 I δ mm iktje Drive II Polyamine cloud Γ 骊镰β li initial evaluation time-lapse evaluation initial evaluation time-dependent evaluation composition (6) composition (r) sample 1 - sample 2 qing {igut^frH-day-««扣长跃 a-<M, N2*N><-avHX3xSi{^)«-A3>^ :I:瀬11!: assjatlliSE SWI^n^iffi.oo^^w ^iswiraK "< i -61? 201033314 Comparative Example 1 The polyester resin equivalent to the thermoplastic resin (A) has a low acid value Moreover, the number average molecular weight is very low and is outside the scope of the present invention. The peel strength at room temperature is also low, and the creep property as an adhesion index under high temperature and high humidity is also poor, and the resistance to humidification weldability is also low. The crosslinking of the hardened material is insufficient, and the cohesive force is considered to be small. In Comparative Example 2, the polyester resin I corresponding to the thermoplastic resin (I) has a low acid value and is outside the scope of the present invention. The peel strength at room temperature is also low, and the creep property as an adhesion index under high temperature and high humidity is also poor, and the Q-resistant wet solderability is also low. The crosslinking of the hardened material is insufficient, and it is expected that the agglutination force becomes small. The acid value of the polyurethane resin g of Comparative Example 3, which corresponds to the thermoplastic resin (Α), was very low and was outside the scope of the present invention. The peel strength at room temperature is also low, and the creep property as an adhesion index under high temperature and high humidity is also inferior, and the resistance to humidification weldability is also low. The crosslinking of the hardened material is insufficient, and the cohesive force is expected to be small. Comparative Example 4 corresponds to a polyurethane resin of the thermoplastic resin (A). The acid value of 〇h is high and is outside the scope of the present invention. Since the rigidity of the cured product becomes too high, the peel strength at room temperature is also low, and it is considered that the creep property as an index of adhesion under high temperature and high humidity is also poor. In Comparative Example 5, the number average molecular weight of the polyurethane resin i corresponding to the thermoplastic resin (A) was low, and it was outside the scope of the present invention. Since the cohesive force is small, the peel strength at room temperature is also low, and it is considered that the creep property as an index of adhesion under high temperature and high humidity is also poor. -60-201033314 The shaking degree (τι値) of the dispersion liquid (α) of Comparative Example 6 was very low, and was outside the range of the present invention. The interaction between the resin and the inorganic ruthenium material is lowered, and it is considered that the resistance to humidification weldability is lowered. In Comparative Example 7, the degree of shaking (τι値) of the dispersion (α) was high and was outside the range of the present invention. The adhesion to the substrate becomes insufficient, and the peel strength is considered to be lowered. In Comparative Example 8, the degree of shaking (?) of the dispersion (?) was very low and was outside the range of the present invention. The interaction between the resin and the inorganic cerium material becomes low, and it is recognized that the wet-weld resistance is lowered, the sheet life is deteriorated, and the characteristics over time are lowered. In Comparative Example 9, the degree of rocking (TI値) of the dispersion (α) was very low, and it was outside the range of the present invention. The interaction between the resin and the inorganic ruthenium material is lowered, and it is considered that the resistance to humidification weldability is lowered, the sheet life is deteriorated, and the characteristics over time are lowered. Comparative Example 1 The degree of rocking (ΤΙ値) of the dispersion (α) was very low, and was outside the range of the present invention. The interaction between the resin and the inorganic ruthenium material is lowered, and it is considered that the resistance to humidification weldability is lowered. Comparative Example 11 is an epoxy resin having a dimerized quinone cyclopentadiene skeleton which is not blended with the epoxy resin (D), and is outside the scope of the present invention. The rigidity and the low hygroscopicity are lowered, and it is considered that the enthalpy characteristics as the adhesion index under high temperature and high humidity are lowered. Comparative Example 1 2 The polyamidoquinone imine resin corresponding to the thermoplastic resin (Α) has a small molecular weight and is outside the scope of the present invention. The peel strength at room temperature is also very high, and the creep property as an adhesion index under high temperature and high humidity is also poor. The system is considered to be because the cohesive force of the hardened material becomes small. -61- 201033314 Comparative Example 13 is equivalent to an epoxy resin having a dimeric ring frame of the epoxy resin (D), and has a large amount of miscellaneous amount, which is insufficient in the range of the present invention, and can be considered to be resistant to wet solderability. reduce. In Comparative Example 14, the amount of the epoxy resin having a dimeric ring structure corresponding to the epoxy resin was large, and it was insufficient in the range of the present invention, and it was considered that the wet solder resistance was lowered. In Comparative Example 15, the epoxy resin having a dimeric ring structure corresponding to the epoxy resin (D) had a large amount of blending amount, and 0 was insufficient in the range of the present invention, and it was considered that the wet solder resistance was lowered. INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a moisture-resistant high temperature which is excellent in various kinds of metals such as PET thin plastic film and copper, aluminum, stainless steel, etc., and can correspond to high-humidity lead-free solder. An adhesive which is excellent in adhesion under high humidity, and 8th order, after circulating under high temperature and high humidity, can also use a resin composition which can maintain a good sheet life, an adhesive G containing the same, and Printed wiring board of layer ° [Simple description of the diagram] None. [Main component symbol description] New Zealand. Pentadiene bone. Hardening pentadiene bone. Hardening pentadiene bone. The high thermal conductivity of the hardened film, etc., the film in the segment, that is, the next characteristic, the film -62-