201002771 六、發明說明： 【發明所屬之技術領域】 本發明關於一種適於形成不黏性、與基材之密著性、 耐折性、低翹曲性、焊接耐熱性、無電解鍍金耐性、電絕 緣性等優異之可撓性皮膜之熱硬化性樹脂組成物、以及由 其硬化物所成之保護膜或絕緣材料、印刷電路板之製造， 尤其是可撓性印刷電路板之製造或捲帶式封裝（Tape-Carrier Package ) 之製 造中使 用之阻 焊劑或 層間絕 緣膜等 之保護膜或絕緣層’或可用於者液晶顯示器之背光板或資 訊顯示用之顯示器等中使用之電致發光板之背面電極用保 護膜’或行動電話、時鐘、汽車音響等顯示板之保護膜、 1C或超LSI封裝材料等。 【先前技術】 可撓性印刷電路板或捲帶式封裝之製造中使用之阻焊 劑使用有將稱爲上蓋膜之聚醯亞胺薄膜對準圖型以模具衝 孔後’使用黏著劑之貼合類型，或藉由網版印刷塗佈形成 具有可撓性之皮膜之紫外線硬化型、熱硬化型之阻焊劑油 墨之類型’或形成具有可撓性皮膜之液狀光阻焊劑油墨之 類型。 然而，上蓋薄膜由於有與銅箱之追隨性之問題，因此 無法形成高精度之圖型。另一方面，紫外線硬化型阻焊劑 油墨及液狀光阻焊劑油墨與基材之聚醯亞胺之密著性不良 ，且無法獲得充分之可撓性。再者，由於阻焊劑油墨之硬 -5- 201002771 化收縮及硬化後之冷卻收縮較大最後會產生翹曲，而成爲 問題。 另外，在形成電路之基板上塗佈絕緣層，經熱硬化形 成絕緣層時，將剛熱硬化後之基板彼此重疊之步驟可提高 生產性而較佳。然而，熱硬化性樹脂之硬化溫度通常高於 該硬化塗膜之玻璃轉移溫度Tg，由於成軟化狀態，因此 剛熱硬化後重疊時會有基板彼此間貼合在一起之問題。爲 了解決該等問題，雖提出有添加無機或有機粒狀抗結塊劑 等（參照專利文獻1 )，但在形成高密度電路之印刷電路 板時，若結塊劑過大則有引起電路間之絕緣性降低，相反 地若過小有無法獲得抗結塊效果之問題。 [專利文獻1]特開2007- 1 0003 8號公報（申請專利範 圍） 【發明內容】 [發明欲解決之課題] 據此，本發明之目的係爲了可解決如上述之以往技術 上之問題而提供一種熱硬化性樹脂組成物，其適用於形成 不黏性、與基材之密著性、耐折性、低翹曲性、焊接耐熱 性、無電解鍍金耐性、電絕緣性等優異之可撓性皮膜’而 且可以較低成本提供由其硬化物構成之形成保護膜或絕緣 層之印刷電路板，尤其是可撓性印刷電路板，或捲帶式封 裝等零件或製品。 201002771 [用以解決課題之手段] 爲達成上述目的，依據本發明，提供一種熱硬化性樹 脂組成物’其特徵爲含有纖維素衍生物（A )。 較佳之樣態中，上述纖維素衍生物（A )爲溶劑可溶 性’另外’纖維素衍生物（A )之玻璃轉移溫度Tg較好爲 loot以上 更具體之樣態中，本發明之熱硬化性樹脂組成物特徵 爲含有上述纖維素衍生物（A )及熱硬化性化合物（B )。 較好，上述熱硬化性化合物（B )爲環氧樹脂（B 1 )，更 好上述熱硬化性化合物（B)包含含羧基之胺基甲酸乙酯 樹脂（B 2 )。 又，依據本發明，提供一種使上述熱硬化性樹脂組成 物硬化而成之硬化物，更好爲使上述熱硬化性樹脂組成物 在鍍錫之電路上硬化之硬化物。 再者依據本發明，提供一種印刷電路板，其爲將上述 熱硬化性樹脂組成物硬化而成之硬化皮膜被覆基板之一部 份或全部而成。又，本發明提供一種可撓性印刷電路板， 其特徵爲具有含纖維素衍生物（A)之硬化皮膜。 [發明效果] 本發明之熱硬化性樹脂組成物適於形成不黏性、與基 材之密著性、耐折性、低翹曲性、焊接耐熱性、無電解鍍 金耐性、電絕緣性等優異之可撓性皮膜。 據此，本發明之熱硬化性樹脂組成物可使用作爲於可 201002771 撓性優異之可撓性引刷電路板或捲帶式封裝之製造中使用 之阻焊劑等之保護膜或絕緣樹脂材料。再者，本發明之熱 硬化性樹脂組成物可在例如藉由捲軸對捲軸之生產步驟中 ，經熱乾燥及熱硬化後立即將基板捲取或重疊。結果，藉 由使用本發明之熱硬化性樹脂組成物，於如上述各種領域 中，可以低成本下生產性良好地製造不黏性、密著性、耐 折性、低翹曲性、無電解鍍金耐性、焊接耐熱性、電絕緣 性等諸特性優異之可撓性保護膜。 【實施方式】 如上述，本發明係爲了提供適於形成不黏性等優異之 可撓性皮膜之熱硬化性樹脂組成物，其特徵爲含有纖維素 衍生物，但本發明之熱硬化性樹脂組成物只要其硬化物可 顯示上述特性則未限定於特定構成成分，基本上認爲有含 有熱硬化性成分之各種樣態。通常，除纖維素衍生物（A )及熱硬化性化合物（B )以外，亦可含有硬化促進劑（C )，進而依據需要可含有塡充劑等，藉由組合該等各成分 之種類、調配量等，可獲得上述特性之硬化物。藉由何種 類之成分、調配量等之組合可獲得上述特性之硬化物而言 ，對熟悉本技藝者可參考後述之實施例及比較例，藉由適 宜試驗可容易地確認’因此省略詳細說明，但以下針對本 發明之熱硬化性樹脂組成物之主要構成成分加以簡單說明 -8 - 201002771 (A )纖維素衍生物 本發明中使用之纖維素衍生物（A )較好爲於有機溶 劑中可溶，且具有高的玻璃轉移溫度（Tg)者。至於纖維 素衍生物舉例爲後述之纖維素醚、羧基甲基纖維素、纖維 素酯等。 纖維素醚舉例爲乙基纖維素、羥基烷基纖維素等，乙 基纖維素之市售品舉例爲 ETOCEL (註冊商標）4、 ETOCEL 7 、 ETOCEL 10 、 ETOCEL 14 、 ETOCEL 20 、 ETOCEL 45、ETOCEL 70、ETOCEL 100、ETOCEL 200、 ETOCEL 300 (均爲陶氏化學公司製造之商品名），羥基 院基纖維素之市售品爲METOLOSE SM、METOLOSE 60SH 、METOLOSE 65SH、METOLOSE 90SH ' METOLOSE SEB 、METOLOSE SNB (均爲信越化學工業（股）製造之商品 名）等。 又’羧基甲基纖維素之市售品舉例爲CMCAB-641_0.2 (伊士曼公司製造之商品名）、SUNLOSE F、SUNLOSE A 、SUNLOSEP、SUNLOSES、SUNLOSEB(均爲日本製紙 化學（股）製造之商品名）等。 又較佳之纖維素衍生物爲藉由有機酸使纖維素所帶有 之羥基酯化而成之纖維素酯，具體而言舉例爲以下述式（ 1 )表示之化合物。 201002771 【化1】201002771 VI. Description of the Invention: [Technical Field] The present invention relates to a non-stick property, adhesion to a substrate, folding resistance, low warpage, solder heat resistance, electroless gold plating resistance, A thermosetting resin composition of a flexible film excellent in electrical insulating properties, a protective film or an insulating material formed of the cured product, and a printed circuit board, particularly a flexible printed circuit board. A protective film or insulating layer such as a solder resist or an interlayer insulating film used in the manufacture of a Tape-Carrier Package, or an electroluminescence used in a backlight of a liquid crystal display or a display for information display, etc. A protective film for the back electrode of the board or a protective film for a display panel such as a mobile phone, a clock, or a car stereo, a 1C or a super LSI package material. [Prior Art] The solder resist used in the manufacture of a flexible printed circuit board or a tape-and-reel package uses a polyimine film called an upper cover film to be aligned with a pattern and then punched with a mold. A type which is an ultraviolet curable type or a thermosetting type solder resist ink which forms a flexible film by screen printing or a liquid photoresist ink having a flexible film. However, since the upper cover film has a problem with the followability of the copper case, it is impossible to form a high-precision pattern. On the other hand, the ultraviolet curable solder resist ink and the liquid photoresist ink have poor adhesion to the polyimide of the substrate, and sufficient flexibility cannot be obtained. Furthermore, since the solder resist ink is hardened and the cooling shrinkage after hardening is large, warpage is caused, which becomes a problem. Further, when an insulating layer is coated on a substrate on which a circuit is formed and an insulating layer is formed by thermal curing, the step of superposing the substrates after the heat hardening can improve productivity and is preferable. However, the hardening temperature of the thermosetting resin is usually higher than the glass transition temperature Tg of the cured coating film, and since it is in a softened state, there is a problem that the substrates are bonded to each other when they are superposed immediately after heat hardening. In order to solve such problems, an inorganic or organic granular anti-caking agent or the like has been proposed (see Patent Document 1). However, when a printed circuit board of a high-density circuit is formed, if the agglomerating agent is too large, it may cause an inter-circuit. The insulation is lowered, and conversely, if it is too small, there is a problem that the anti-caking effect cannot be obtained. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2007- 1 0003 (Application No.) [Draft of the Invention] [Problems to be Solved by the Invention] Accordingly, the object of the present invention is to solve the problems of the prior art as described above. Provided is a thermosetting resin composition which is excellent in non-stickiness, adhesion to a substrate, folding resistance, low warpage, solder heat resistance, electroless gold plating resistance, electrical insulation, and the like. The flexible film' can also provide a printed circuit board formed of a cured material thereof to form a protective film or an insulating layer at a relatively low cost, particularly a flexible printed circuit board, or a tape-and-reel package or the like. 201002771 [Means for Solving the Problem] In order to achieve the above object, according to the present invention, there is provided a thermosetting resin composition characterized by containing a cellulose derivative (A). In a preferred embodiment, the cellulose derivative (A) is a solvent-soluble 'other' cellulose derivative (A), and the glass transition temperature Tg is preferably a loot or more. The resin composition is characterized by containing the above cellulose derivative (A) and a thermosetting compound (B). Preferably, the thermosetting compound (B) is an epoxy resin (B 1 ), and the thermosetting compound (B) preferably contains a carboxyl group-containing urethane resin (B 2 ). Moreover, according to the present invention, there is provided a cured product obtained by curing the thermosetting resin composition, and more preferably a cured product obtained by curing the thermosetting resin composition on a tin-plated circuit. According to the present invention, there is provided a printed circuit board comprising one or a part of a hardened film-coated substrate obtained by curing the thermosetting resin composition. Further, the present invention provides a flexible printed circuit board characterized by having a hardened film containing a cellulose derivative (A). [Effect of the Invention] The thermosetting resin composition of the present invention is suitable for forming non-stickiness, adhesion to a substrate, folding resistance, low warpage, solder heat resistance, electroless gold plating resistance, electrical insulation, and the like. Excellent flexible film. Thus, the thermosetting resin composition of the present invention can be used as a protective film or an insulating resin material such as a solder resist which can be used in the manufacture of a flexible brushed circuit board or a tape and reel type package which is excellent in flexibility. Further, the thermosetting resin composition of the present invention can be wound up or overlapped immediately after thermal drying and heat hardening, for example, in a production step of a reel-to-reel. As a result, by using the thermosetting resin composition of the present invention, in various fields as described above, it is possible to produce non-stickiness, adhesion, folding resistance, low warpage, and electrolessness with good productivity at low cost. A flexible protective film excellent in properties such as gold plating resistance, solder heat resistance, and electrical insulating properties. [Embodiment] The present invention provides a thermosetting resin composition suitable for forming a flexible film excellent in non-stickiness and the like, and is characterized in that it contains a cellulose derivative, but the thermosetting resin of the present invention The composition is not limited to a specific constituent component as long as the cured product exhibits the above properties, and basically has various forms including a thermosetting component. In addition to the cellulose derivative (A) and the thermosetting compound (B), the curing accelerator (C) may be contained, and if necessary, a chelating agent or the like may be contained, and by combining the types of the components, A cured product of the above characteristics can be obtained by adjusting the amount and the like. A cured product having the above characteristics can be obtained by a combination of such components, a blending amount, etc., and those skilled in the art can refer to the examples and comparative examples described later, and can be easily confirmed by a suitable test. However, the main constituents of the thermosetting resin composition of the present invention are briefly described below. 8-201002771 (A) Cellulose Derivative The cellulose derivative (A) used in the present invention is preferably in an organic solvent. Soluble and have a high glass transition temperature (Tg). The cellulose derivative is exemplified by a cellulose ether, a carboxymethyl cellulose, a cellulose ester or the like which will be described later. The cellulose ether is exemplified by ethyl cellulose, hydroxyalkyl cellulose, etc., and the commercial products of ethyl cellulose are exemplified by ETOCEL (registered trademark) 4, ETOCEL 7, ETOCEL 10, ETOCEL 14, ETOCEL 20, ETOCEL 45, ETOCEL. 70, ETOCEL 100, ETOCEL 200, ETOCEL 300 (both trade names manufactured by The Dow Chemical Company), and commercially available products of hydroxy-based cellulose are METOLOSE SM, METOLOSE 60SH, METOLOSE 65SH, METOLOSE 90SH 'METOLOSE SEB, METOLOSE SNB (All are the trade names manufactured by Shin-Etsu Chemical Co., Ltd.) and so on. Further, a commercial product of carboxymethyl cellulose is exemplified by CMCAB-641_0.2 (trade name manufactured by Eastman Co., Ltd.), SUNLOSE F, SUNNOSE A, SUNLOSEP, SUNLOSES, and SUNLOSEB (all manufactured by Nippon Paper Chemical Co., Ltd.). Product name) and so on. Further, a cellulose derivative which is a cellulose ester obtained by esterifying a hydroxyl group of cellulose with an organic acid is specifically exemplified by a compound represented by the following formula (1). 201002771 【化1】
(式中，R表示氫或有機酸酯基，由選自氫及有 酯中之至少兩種以上所構成，η爲1以上之整數，其 係由後述之分子量所限制）。 以上述式（1 )表示之纖維素酯中，相對於纖維 脂之羥基含量爲0〜6 wt%，作爲有機酸酯，乙醯基含 0〜40wt%，丙醯基或/及丁醯基含量爲0〜55wt%之範圍 。此處所謂[wt%]爲相對於纖維素之重量之氫或有機 之重量％。 該等纖維素酯之市售品，至於纖維素乙酸酯舉 CA-3 9 8-3、CA-3 9 8 -6、CA-3 9 8- 1 0、CA-3 9 8 -3 0、CA-60S等，至於纖維素乙酸酯丁酸酯舉例爲CAB-551-0. CAB-551-0.2 ' CAB-5 5 3 -0.4 ' CAB-531-1 ' CAB-500 CAB-3 8 1-0.1、CANB-381-0.5、CAB-38 1-2、CAB-38 、CAB-3 8 1 -20BP ' CAB-321-0.1、CAB-171-15 等，至 維素乙酸酯丙酸酯舉例爲 CAP-504-0.2、CAP-482-0 CAP-4 82-20 (上述纖維素衍生物均爲伊士曼公司製造 品名）等。該等中，就對溶劑之溶解性之觀點而言較 機酸 上限 素樹 量爲 較佳 酸酯 例爲 3 94 -01、 -5、 1-20 於纖 .5、 之商 好爲 -10- 201002771 纖維素乙酸酯丁酸酯、纖維素乙酸酯丙酸酯，另外就臭味 之觀點而言較好爲纖維素乙酸酯丙酸酯。 纖維素衍生物之數平均分子量並無特別限制，但較好 爲5000〜500,〇〇〇，更好爲10,〇〇〇〜100,000。分子量小於上 述範圍時’難以獲得乾燥後塗膜之不黏性，另一方面，大 於上述範圍時，對溶劑之溶解性、相溶性容易變差而不佳 〇 又’纖維素衍生物之玻璃轉移溫度Tg較好爲7〇t:以 上、未達20CTC，更好爲loot：以上、未達18〇t。玻璃轉 移溫度未達70°c時，難以獲得充分之不黏性。另一方面， 當爲2 00°C以上時，會有損及硬化塗膜之耐折性之虞。 又’本說明書之玻璃轉移溫度Tg意指以熱機械分析 (DSC) ’依據 JIS C648 1 :1 996 之「5. 17_5 DSC 法」中 所述之方法測定之玻璃轉移溫度。 本發明中使用之纖維素衍生物爲源自天然物者，此就 石化燃料枯竭之方面而言較佳。再者，本發明之纖維素衍 生物中使用之起始原料亦可由再生紙漿等回收物品製造， 可提供就C〇2減量之環境面而言較佳之組成物。 如上述之纖維素衍生物（A)可單獨使用亦可混合兩 種以上使用。纖維素衍生物（A )之調配量相對於1 0 0質 量份之後述熱硬化性化合物（B )爲1〜5 0質量份，較好， 以2〜4 0質量份之範圍較適當。當纖維素衍生物（a)之調 配量未達1質量份時’難以形成不黏性等優異之可撓性硬 化皮膜’另一方面，當超過50質量份時容易造成其硬化 -11 - 201002771 物之機械特性降低而不佳。 (B )熱硬化性化合物 本發明中使用之熱硬化性化合物（B )可使用環氧樹 脂、胺基甲酸乙酯樹脂、聚酯樹脂、含有羥基、胺基或殘 基之聚胺基甲酸乙酯、聚酯、聚碳酸酯類、多元醇、酚樹 脂、丙烯酸系共聚合樹脂、乙烯樹脂、聚醯胺、聚醯胺醯 亞胺、噁嗪樹脂、氰酸酯等習知慣用之熱硬化性樹脂。又 ，作爲對應於此等之硬化劑可使用（封端）異氰酸酯類、 胺類、酚類等。 該等熱硬化性化合物中，就密著性、絕緣信賴性之觀 點而言，較好組合使用環氧樹脂（B 1 )及與環氧樹脂反應 之硬化劑。再者，環氧樹脂（B1)與含有羧基之胺基甲酸 乙酯樹脂（B2 )之組合，就低翹曲性、絕緣信賴性而言爲 較佳。 (B 1 )環氧樹脂 環氧樹脂之具體例爲例如二官能基環氧樹脂舉例爲雙 酚A型環氧樹脂、氫化雙酚A型環氧樹脂、溴化雙酚A 型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙 二甲酚型環氧樹脂、聯酚型環氧樹脂等，三官能基以上之 多官能基環氧樹脂舉例爲酚醛清漆型環氧樹脂、酚酚醛清 漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、N-縮水甘油基 型環氧樹脂、雙酚A之酚醛清漆型環氧樹脂、聯二甲酚型 -12- 201002771 環氧樹脂、聯酚酚醛清漆型環氧樹脂、螯合型環氧樹脂、 乙二醛型環氧樹脂'含有胺基之環氧樹脂、橡膠改質之環 氧樹脂、二環戊二烯酚型環氧樹脂、二縮水甘油基苯二甲 酸酯樹脂、雜環系環氧樹脂、四縮水甘油基二甲苯醯基乙 院樹脂、砂氧改質之環氧樹脂、ε -己內醋改質之環氧樹 脂等。又更好之易於獲得高Tg之硬化物之環氧樹脂舉例 爲N-縮水甘油基型環氧樹脂、聯二甲酚型環氧樹脂、聯 酚型環氧樹脂、四縮水甘油基二甲苯醯基乙烷樹脂、肆酚 乙烷型環氧樹脂、二環戊二烯酚型環氧樹脂、含有萘骨架 之環氧樹脂等。具體而言，肆酚乙烷型環氧樹脂舉例爲 GTR- 1800(日本化藥（股）製造）、二環戊二烯酚型環氧 樹脂舉例爲HP-7 200H (大日本油墨化學工業（股）製造 )、具有萘骨架之環氧樹脂舉例爲HP-4032D、EXA-7240 、EXA-4700、EXA-4770 (均爲大日本油墨化學工業（股 )製造）、具有氧雜蒽（Xanthene )骨架之環氧樹脂舉例 爲EXA-73 3 5 (大日本油墨化學工業（股）製造）、聯酚 酚醛清漆環氧樹脂舉例爲NC-3000 (日本化藥（股）製造 )’藉由使用該等多官能基環氧樹脂或其他三官能基及四 官能基環氧樹脂，可提高焊接耐熱性等特性。該等環氧樹 脂中’最好爲固態環氧樹脂。 又爲了賦予難燃性，亦可使用於其構造中導入氯、溴 等鹵素或磷等原子之環氧樹脂。 (B2)含有羧基之胺基甲酸乙酯樹脂 -13- 201002771 本發明中可使用之含有羧基之胺基甲酸乙酯樹脂（B2 )舉例爲二異氰酸酯化合物（a )與多元醇化合物（b )， 及一分子中具有一個羧基與兩個醇性羥基之化合物（c) 之反應獲得者。此時亦可使用反應停止劑使末端安定化者 。至於反應停止劑可使用脂肪族醇或單羥基單（甲基）丙 烯酸酯化合物等之單羥基化合物，或具有與醇性羥基、胺 基、硫醇基等之與異氰酸酯基加成反應或縮合反應獲得之 官能基之單羧酸等之以往已知之各種反應停止劑。又，上 述反應時，使亦作爲反應停止劑功能之一分子中具有一個 醇性羥基及一個以上之酚性羥基之化合物（d )反應，具 有於末端導入之酧性羥基之含有羧基之胺基甲酸乙酯樹脂 ，由於除羧基以外會引起可期待耐熱性之環氧樹脂與酚基 之反應，故在要求焊接耐熱等之情況下最佳。 本發明中可使用之含有羧基之胺基甲酸乙酯樹脂（B2 )之構成成分之二異氰酸酯化合物（a)可使用慣用已知 之二異氰酸酯，但就低翹曲性之觀點而言較好使用不具有 芳香環之異氰酸酯化合物。 不具有芳香環之異氰酸酯化合物之具體例舉例爲例如 六亞甲基二異氰酸酯等之脂肪族二異氰酸酯、三甲基六亞 甲基二異氰酸酯等之分支脂肪族二異氰酸酯、異佛爾酮二 異氰酸酯' (鄰、間或對）-氫化二甲苯二異氰酸酯、亞 甲基雙（環己基異氰酸酯）、環己烷-1,3-二亞甲基二異氰 酸酯、環己烷-1,4-二亞甲基二異氰酸酯等之脂環式二異氰 酸酯。該等中，較好爲脂肪族二異氰酸酯之六亞甲基二異 -14- 201002771 氰酸酯、分支脂肪族二異氰酸酯之三甲基六亞甲基二異氰 酸酯。該等不具有芳香環之二異氰酸酯化合物可單獨使用 或混合兩種以上使用。使用該等二異氰酸酯化合物時，可 獲得低翹曲性優異之硬化物。又，在不損及塗膜特性之範 圍內，亦可使用芳香族二異氰酸酯。 本發明中可使用之含有羧基之胺基甲酸乙酯樹脂（B2 )之構成成分之多元醇成分（b)可使用以往已知之各種 多元醇，且並不限於特定之化合物，但較好使用聚碳酸酯 二醇等之聚碳酸酯系多元醇，聚醚系多元醇、聚酯系多元 醇、聚烯烴系多元醇、聚丁二烯系多元醇、聚異戊間二烯 系多元醇、氫化聚丁二烯系多元醇、氫化異戊間二烯系多 元醇、丙烯酸系多元醇、雙酚A系環氧烷加成物二醇、含 磷之多元醇等。聚碳酸酯二醇舉例爲含有源自一種或兩種 以上之直鏈狀脂肪族二醇之重複單位作爲構成單位之聚碳 酸酯二醇（b-Ι)，含有源自一種或兩種以上之脂環式二 醇之重複單位作爲構成單位之聚碳酸酯二醇（b-2)，或 含有源自直鏈狀脂肪族二醇與脂環式二醇兩者之二醇之重 複單位作爲構成單位之聚碳酸酯二醇（b-3 )。 上述含有源自一種或兩種以上之直鏈狀脂肪族二醇之 重複單位作爲構成單位之聚碳酸酯二醇（b-Ι)之具體例 舉例爲例如由1，6-己二醇衍生之聚碳酸酯二醇、由1,5-戊 二醇與1,6-己二醇衍生之聚碳酸酯二醇、由1，4-丁二醇與 1，6-己二醇衍生之聚碳酸酯二醇、由3-甲基-1，5-戊二醇與 1,6_己二醇衍生之聚碳酸酯二醇、由1,9 -壬二醇與2 -甲基- -15- 201002771 1 8 -辛二醇衍生之聚碳酸酯一醇等。 上述含有源自一種或兩種以上之脂環式二醇之重複單 位作爲構成單位之聚碳酸酯二醇（b-2 )之具體例舉例爲 例如由I，4-環己烷二甲醇衍生之聚碳酸醋二醇。 上述含有源自直鏈狀脂肪族二醇與脂環式二醇兩者之 二醇之重複單位作爲構成單位之聚碳酸酯二醇（b_3)之 具體例舉例爲例如由1，6 -己二醇與1,4 -環己院甲醇衍生之 聚碳酸酯二醇等。 含有由上述直鏈狀脂肪族二醇之重複單位作爲構成單 位之聚碳酸酯二醇具有低翹曲性及可撓性優異之傾向。另 外，含有源自脂環式二醇之重複單位作爲構成單位之聚碳 酸酯二醇具有耐鍍錫性、焊接耐熱性優異之傾向。就以上 觀點，該等聚碳酸酯二醇可組合兩種以上使用，或者可使 用含有源自直鏈狀脂肪族二醇與脂環式二醇兩者之二醇之 重複單位作爲構成單位之聚碳酸酯二醇。就展現低翹曲性 或可撓性、與焊接耐熱性或耐鍍錫性均衡之觀點而言，較 好使用直鏈狀脂肪族二醇與脂環式二醇之共聚合比例以質 量比計爲3·· 7〜7:3之聚碳酸酯二醇。 上述聚碳酸酯二醇較好爲數平均分子量200〜5,000者 ’但於含有源自以聚碳酸酯二醇作爲構成單位之直鏈狀脂 肪族二醇與脂環式二醇之重複單位，其直鏈狀脂肪族二醇 與脂環式二醇之共聚合比例以質量比計爲3 : 7〜7 : 3之情況 下，數平均分子量較好爲400〜2,〇〇〇。 上述雙酚A系環氧烷加成物二醇舉例爲雙酚a之環 -16- 201002771 氧乙院加成物、環氧丙院加成物、環氧丁垸加成物等’但 該等中較佳者爲雙酚A之環氧丙烷加成物。 上述含磷之多元醇之具體例舉例爲FC-450 (旭電化 工業（股）製造）、M-Ester (三光（股）製造）、M-Ester-HP (三光（股）製造）等。藉由使用該等含磷之多 元醇可將磷化合物導入胺基甲酸乙酯樹脂中，可賦予難燃 性。 本發明中可使用之爲含羧基之胺基甲酸乙酯樹脂（B2 )之構成成分，且一分子中具有一個羧基與兩個醇性羥基 之化合物（c )之具體例舉例爲二羥甲基丙酸、二羥甲基 丁酸等。藉由使用該等具有羧基及兩個以上醇性羥基之化 合物，可輕易的將羧基導入胺基甲酸乙酯樹脂中。 其次，作爲上述停止劑之具有一個醇性羥基之化合物 可使用以往已知之各種單羥基化合物。例如，甲醇、乙醇 、正-丙醇、異丙醇、正丁醇、異丁醇、第二丁醇、第三 丁醇、戊醇、己醇、辛醇、（甲基）丙烯酸2-羥基乙酯、 (甲基）丙烯酸羥基丙酯、（甲基）丙烯酸羥基丁酯、單 (甲基）丙烯酸環己二甲醇酯、上述各（甲基）丙烯酸酯 之內酯或環氧烷加成物、二（甲基）丙烯酸甘油酯、三羥 甲基二（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯 、二季戊四醇五（甲基）丙烯酸酯、二（三羥甲基）丙烷 三（甲基）丙烯酸酯、烯丙基醇、烯丙氧基乙醇、乙醇酸 、羥基丙酮酸等，但並不限於該等。 再者，上述一分子中具有一個醇性羥基與一個以上酚 -17- 201002771 性羥基之化合物（d )其使用目的係將酚性羥基導入聚胺 基甲酸乙酯中’具有作爲聚胺基甲酸乙酯之末端封端劑之 功能，尤其是若與分子中之異氰酸酯反應獲得之具有一個 醇性羥基及酚性羥基之化合物即可作爲反應停止劑之功能 。該等化合物（d )之具體例舉例爲例如羥基甲基酚、羥 基甲基甲酚、羥基甲基-二-第三丁基酚、對-羥基苯基- 2-甲醇、對-羥基苯基-3 -丙醇、對-羥基苯基· 4 - 丁醇、羥基 乙基甲酚、2,6 -二甲基-4-羥基甲基酚、2,4 -二甲基-6-羥基 甲基酚、2,3,6 -三甲基-4-羥基甲基酚' 2 -環己基-4-羥基甲 基-5-甲基酚、4-甲基-6-羥基甲基苯-1,2-二醇、4- (1,1-二 甲基乙基）-6-羥基甲基苯-1,2-二醇等之羥基烷基酚，或 羥基烷基甲酚；羥基苯甲酸、羥基苯基苯甲酸或羥基苯氧 基苯甲酸等之含有羧基取代基之酚，及乙二醇、丙二醇、 二乙二醇、三乙二醇、二丙二醇、三丙二醇等之酯化物； 雙酚之單環氧乙烷加成物、雙酚之單環氧丙烷加成物、 對-羥基苯乙基醇等，但並不限於該等者。該等化合物（d )可單獨使用或混合兩種以上使用。 上述含有羧基之胺基甲酸乙酯樹脂（B2)之重量平均 分子量較好爲5 00〜1 00,000，更好爲8,000〜50,〇〇〇。其中 ’重量平均分子量係以凝膠滲透層析測定換算成聚苯乙嫌 之値。含有羧基之胺基甲酸乙酯樹脂（B2)之重量平均分 子量未達5 0 0時，有損及硬化膜之伸長度、可燒性以及強 度之情況，另一方面，超過1 0 0，0 0 0時對溶劑之溶解性下 降，即使溶解黏度亦過高，故就使用面而言限制較大。 -18- 201002771 另外，上述含有羧基之胺基甲酸乙酯樹脂（B2)之酸 價較好爲 10〜120mgKOH/g 之範圍，更好爲 20〜80mg KOH/g。當酸價未達10mgKOH/g時，與熱硬化性成分之 反應性下降，有損及耐熱性之情況。另一方面，當酸價超 過120mgKOH/g時，有硬化膜之耐鹼性、電特性等之作爲 抗蝕劑之特性下降之情況。又，樹脂酸價係以JIS K5407 爲準測定之値。 本發明之熱硬化性樹脂組成物中，與上述含有羧基之 胺基甲酸乙酯樹脂（B2 ) —起調配之熱硬化性化合物（B )除上述環氧樹脂（B1)以外，亦可使用一分子中具有兩 個以上與上述含有羧基之胺基甲酸乙酯樹脂（B2)之羧基 (或者酚性羥基）反應獲得之氧雜環丁烷基等之氧雜環丁 烷樹脂（B 3 )等。 如上述之熱硬化性化合物（B )可單獨使用或混合兩 種以上使用。熱硬化性化合物（B )之調配量以組成物總 量之20〜99質量％，較好爲30〜95質量％之範圍較適宜。 又，組合使用環氧樹脂（B1)與含有羧基之胺基甲酸乙酯 樹脂（B2 )時，相對於1 00質量份之環氧樹脂，含有羧基 之胺基甲酸乙酯樹脂較適宜爲5 0~2 000質量份，較好爲 100〜1 000質量份之範圍。 本發明中使用之硬化促進劑（C )爲促進熱硬化反應 者，且使用以更進一步提升密著性、耐藥品性、耐熱性等 特性。該硬化促進劑之具體例舉例爲例如咪唑及其衍生物 (例如四國化成工業（股）製造之2MZ、2E4MZ、C11Z、 -19- 201002771 C17Z、2PZ、1B2MZ、2MZ-CN、2E4MZ-CN、C11Z-CN、 2PZ-CN、2PHZ-CN、2MZ - CN S、2E4 Μ Z - CN S、2PZ-CNS、 2MZ-AZINE、2E4MZ-AZINE、C1 1Z-AZINE、2MA-OK、 2P4MHZ、2PHZ > 2P4BHZ等）；乙醯狐胺、苯并胍胺等 胍胺類；二胺基二苯基甲烷、間-苯二胺、間-二甲苯二胺 、二胺基二苯基楓、二胺基二醯胺、尿素、尿素衍生物、 三聚氰胺、多鹼基醯肼等聚胺類；該等之有機酸鹽及/或 環氧加成物；三氟化硼之胺錯合物；乙二胺-S-三嗪、2,4-二胺基-S-三嗪、2,4-二胺基-6-二甲苯基-S-三嗪等三嗪衍 生物類；三甲胺、三乙醇胺、Ν,Ν -二甲基辛基胺、N -苄基 二甲基胺、吡啶、Ν-甲基嗎啉、六（Ν-甲基）三聚氰胺、 2,4,6-參（二甲胺基酚）、肆甲基胍、間-胺基酚等胺類； 聚乙烯基酚、聚乙烯基酚溴化物、酚酚醛清漆樹脂、烷基 酚酚醛清漆樹脂等多酚類；三丁基膦、三苯基膦、參-2 -氰 基乙基膦等有機膦類；三-正丁基（2,5 -二羥基苯基）溴化 鐵、十六烷基三丁基氯化錢等錢鹽類；苄基三甲基氯化銨 、苯基三丁基氯化銨等四級銨鹽；上述多鹼基酸酐；二苯 基碘鑰四氟硼酸鹽 '三苯基锍六氟銻酸鹽、2,4,6·三苯基 硫代吡啶鑰六氟磷酸鹽、汽巴·特用化學品公司製造之 IRUGACURE (註冊商標）261 > ADEKA (股）製造之 OPTOMER-SP-170等之光陽離子聚合觸媒；苯乙烯-馬來 酸酐樹脂；苯基異氰酸酯及二甲胺之等莫耳反應物，或甲 苯二異氰酸酯、異佛爾酮二異氰酸酯等有機聚異氰酸酯與 二甲胺之等莫耳反應物等之已知慣用之硬化促進劑或硬化 -20- 201002771 劑類。 該等硬化促進劑（C )可單獨使用或混合兩種以上使 用。硬化促進劑（C )之使用並非必要，但在尤其促進硬 化之清況下，相對於1 〇〇質量份上述熱硬化性化合物（B )，較好可以0.1~25質量份之範圍使用。超過25質量份 時，由於自其硬化物之昇華性成分變多而不佳。 本發明之熱硬化性樹脂組成物可使用混練機例如分散 機、捏合機、三軸輥硏磨機、珠粒硏磨機等，使纖維素衍 生物（A )、熱硬化性化合物（B )(環氧樹脂（B 1 )、 含有羧基之胺基甲酸乙酯樹脂（B 2 )等）及視情況之硬化 促進劑（C )、塡充劑等溶解或分散而獲得。此時，亦可 使用對於環氧基或酚性羥基爲惰性之溶劑。該等惰性溶劑 較好爲有機溶劑。 有機溶劑係爲了使上述纖維素衍生物（A )、熱硬化 性化合物（B )(環氧樹脂（B 1 )、含有羧基之胺基甲酸 乙酯樹脂（B2)等）容易溶解或分散，或者調整成適於塗 佈之黏度而使用。有機溶劑可舉例爲例如甲苯、二甲苯、 乙基苯、硝基苯、環己烷、異佛爾酮、二乙二醇二甲基醚 、乙二醇二乙基醚、卡必醇乙酸酯、丙二醇甲基醚乙酸酯 、丙二醇乙基醚乙酸酯、二丙二醇甲基醚乙酸酯、二乙二 醇乙基醚乙酸酯、甲氧基丙酸甲酯、甲氧基丙酸乙酯、乙 氧基丙酸甲酯、乙氧基丙酸乙酯、乙酸乙酯、乙酸正丁酯 、乙酸異戊酯、乳酸乙酯、丙酮、甲基乙基酮、環己酮、 N，N-二甲基甲醯胺、N,N_二甲基乙醯胺、N-甲基吡咯啶酮 -21 - 201002771 、r-丁內酯、二甲基亞碾、氯仿及二氯甲烷等。有機溶 劑之調配量可依據所需黏度適當設定。 本發明之熱硬化樹脂組成物可依據需要含有已知慣用 之硫醇化合物以提升與聚醯亞胺等基材之密著性。硫醇化 合物舉例爲2-锍基丙酸、三羥甲基丙烷參（2-硫基丙酸酯 )、2-巯基乙醇、2-胺基硫酚、3-锍基-1，2,4-三唑、3-锍 基丙基三甲氧基矽烷等含有锍基之矽烷偶合劑等。該等可 分別單獨使用，亦可兩種以上組合使用。其調配量每100 質量份之上述熱硬化性化合物（B )以1 0質量份以下之範 圍較適當。硫醇化合物之調配量超過上述範圍時，會消耗 交聯反應所必需之上述環氧樹脂之環氧基（與環氧基反應 )，造成交聯密度下降而不佳。 本發明之熱硬化性樹脂組成物可進而依據需要，就提 升密著性、硬度、耐熱性等特性之目的，而含有選自由無 機塡充劑及有機塡充劑組成之組群之至少一種塡充劑。無 機塡充劑舉例爲硫酸鋇、碳酸15、鈦酸鋇、氧化砍、無定 型氧化矽、滑石、灰石、雲母粉等，有機塡充劑舉例爲聚 矽氧粉、尼龍粉、氟粉等。上述塡充劑中，低吸濕性、低 體積膨脹性最佳者爲氧化砂。氧化砂不論是熔融、結晶性 ’或是該等之混合物均可’但尤其是以偶合劑等表面處理 之氧化矽之情況下’由於可提升電絕緣性者故而較佳。塡 充劑之平均粒徑爲25//m以下，更好爲i〇#m以下，又 更好爲3^m以下較適宜。該等無機及/或有機塡充劑之調 配量每1 0 0質量份之上述熱硬化性化合物（B )以3 0 0質 -22- 201002771 量份以下較適當，且較好爲5〜1 5 0質量份之比例。塡充劑 之調配量超過上述比例時，硬化皮膜之耐折性下降而不適 當。 再者本發明之熱硬化性樹脂組成物中，只要不損及本 發明之效果，亦可添加上述成分以外之其他添加劑、著色 劑。添加劑舉例爲石棉、有機膨潤土、蒙脫土等增黏劑， 聚矽氧系、氟系消泡劑，平流劑、玻璃纖維、碳纖維、氮 化硼纖維等纖維強化材料等，至於著色劑舉例爲酞菁.藍 、酞菁·綠、碘·綠、二偶氮黃、氧化鈦、碳黑等。再者 可依據需要添加已知慣用之熱聚合抑制劑、紫外線吸收劑 、矽烷偶合劑、可塑劑、發泡劑、難燃劑、抗靜電劑、抗 老化劑、抗菌·防黴劑等。 具有如上述組成之熱硬化性樹脂組成物除可以簾塗法 、輥塗法、噴塗法及浸塗法等以往已知之各種方法塗佈於 印刷基板上以外，亦可使用於乾膜或預漬物等各種形態、 用途中。依據其使用方法或用途可使用各種溶劑，但依據 狀況不僅可使用良溶劑使用弱溶劑亦無妨。 另外’本發明之熱硬化性樹脂組成物可藉由網版印刷 法塗佈於形成電路之可撓性電路板或捲帶式封裝或電致發 光面板上’例如藉由加熱至120〜18(TC之溫度，且藉由硬 化收縮及冷卻收縮，而形成無翹曲、對基材之密著性、耐 折性、低翹曲性、無電解鍍金耐性、焊接耐熱性、電絕緣 性等優異之阻焊劑膜或保護膜。 -23- 201002771 [實施例] 以下以實施例及比較例對本發明具體說明，但本發明 並不受以下實施例之限制。又，以下之[份]及[%]若未特別 說明則全部爲質量基準。 合成例1<熱硬化性樹脂（含有羧基之聚胺基甲酸乙 酯）之合成> 於配置攪拌裝置、溫度計、冷凝器之反應容器中注入 360克（〇.45莫耳）由l，5-戊二醇與1，6 -己二醇衍生之聚 碳酸酯二醇（數平均分子量8 00 )作爲具有兩個以上醇性 羥基之化合物、81.4克（0.55莫耳）二羥甲基丁酸、及 1 1 _ 8克（〇 . 1 6莫耳）正丁醇作爲分子量調節劑（反應停止 劑）。接著，注入200.9克（1_08莫耳）三甲基六亞甲基 二異氰酸酯作爲不具有芳香環之異氰酸酯化合物，邊攪拌 邊加熱至60°C後停止，於反應容器內之溫度開始下降時再 度加熱且於80 °C下繼續攪拌，且以紅外線吸收光譜確認異 氰酸酯基之吸收光譜（2 28 OcnT1 )消失作爲反應結束。接 著，添加卡必醇乙酸酯使固體成分成爲6 0 wt%，獲得含有 稀釋劑之黏稠液體之含有羧基之聚胺基甲酸乙酯。所得含 有羧基之聚胺基甲酸乙酯之固體成分之酸價爲 49.8 mgKOH/g 0 實施例1〜5及比較例1 以表1中所示之各成分及調配比例’在室溫下通過三 -24- 201002771 軸輥混練三次，藉此調製熱硬化性樹脂,組成物 「夷 1 1 __—- 組成 (質量份） 實施迴一_~— 比較例 1 一---- 1 2 3 4 5 纖維素 衍生物 CAB-553-0.4*l 100 ----- CAP-504-0 2*2 100 CAP-482-0 5*3 100 CAP-482-20*4 100 ------- CAB-551-0.01*5 100 環氣樹β 旨*6 40 40 40 40 40 40 含有羧基之聚胺基甲酸乙 酯(合成例1) 167 167 167 167 167 167 消泡劑*7 4 4 4 4 4 4 ----- 三聚氰胺 2 2 2 2 2 2 1------- 熔融二氧化矽 100 100 100 100 100 100 —- — 卡必醇乙酸酯 20(In the formula, R represents hydrogen or an organic acid ester group, and is composed of at least two or more selected from the group consisting of hydrogen and an ester, and η is an integer of 1 or more, which is limited by the molecular weight described later). The cellulose ester represented by the above formula (1) has a hydroxyl group content of 0 to 6 wt% with respect to the fiber fat, and as the organic acid ester, the ethyl ketone group contains 0 to 40% by weight, and the acrylonitrile group and/or the butyl group content is A range of 0 to 55 wt%. Here, [wt%] is the weight % of hydrogen or organic relative to the weight of cellulose. Commercial products of such cellulose esters, as for cellulose acetate, CA-3 9 8-3, CA-3 9 8 -6, CA-3 9 8- 1 0, CA-3 9 8 -3 0 , CA-60S, etc., as for cellulose acetate butyrate, for example, CAB-551-0. CAB-551-0.2 ' CAB-5 5 3 -0.4 ' CAB-531-1 ' CAB-500 CAB-3 8 1-0.1, CANB-381-0.5, CAB-38 1-2, CAB-38, CAB-3 8 1 -20BP 'CAB-321-0.1, CAB-171-15, etc., to vegan acetate propionate The esters are exemplified by CAP-504-0.2, CAP-482-0 CAP-4 82-20 (the above cellulose derivatives are all manufactured by Eastman Company) and the like. In the above, from the viewpoint of solubility of the solvent, the amount of the upper limit of the organic acid is preferably 3 94 -01, -5, 1-20 in the fiber. 5, the good value is -10- 201002771 Cellulose acetate butyrate, cellulose acetate propionate, and cellulose acetate propionate is preferred from the viewpoint of odor. The number average molecular weight of the cellulose derivative is not particularly limited, but is preferably from 5,000 to 500, more preferably from 10, 〇〇〇 to 100,000. When the molecular weight is less than the above range, it is difficult to obtain the non-stickiness of the coating film after drying. On the other hand, when it is larger than the above range, the solubility and compatibility of the solvent are likely to be deteriorated, and the glass transition of the cellulose derivative is not preferable. The temperature Tg is preferably 7 〇 t: or more, less than 20 CTC, more preferably loot: above, less than 18 〇t. When the glass transfer temperature is less than 70 ° C, it is difficult to obtain sufficient non-stickiness. On the other hand, when it is 200 ° C or more, the folding resistance of the cured coating film may be impaired. Further, the glass transition temperature Tg of the present specification means a glass transition temperature measured by a thermomechanical analysis (DSC) ' according to the method described in "5. 17_5 DSC method" of JIS C648 1 : 996. The cellulose derivative used in the present invention is derived from a natural product, which is preferable in terms of depletion of the fossil fuel. Further, the starting materials used in the cellulose derivative of the present invention can also be produced from recycled articles such as recycled pulp, and can provide a composition which is preferable in terms of environmental aspects of C〇2 reduction. The cellulose derivative (A) as described above may be used singly or in combination of two or more. The amount of the cellulose derivative (A) is preferably from 1 to 50 parts by mass, more preferably from 2 to 40 parts by mass, per 100 parts by mass of the thermosetting compound (B). When the amount of the cellulose derivative (a) is less than 1 part by mass, it is difficult to form a flexible hardened film excellent in non-stickiness and the like. On the other hand, when it exceeds 50 parts by mass, it is liable to cause hardening -11 - 201002771 The mechanical properties of the material are not well reduced. (B) Thermosetting compound The thermosetting compound (B) used in the present invention may be an epoxy resin, a urethane resin, a polyester resin, or a polyaminocarbamate having a hydroxyl group, an amine group or a residue. Conventional thermosetting of esters, polyesters, polycarbonates, polyols, phenol resins, acrylic copolymer resins, vinyl resins, polyamides, polyamidolimides, oxazine resins, cyanates, etc. Resin. Further, as the curing agent corresponding to these, an isocyanate, an amine, a phenol or the like can be used (blocked). Among these thermosetting compounds, an epoxy resin (B 1 ) and a curing agent reactive with an epoxy resin are preferably used in combination in terms of adhesion and insulation reliability. Further, the combination of the epoxy resin (B1) and the carboxyl group-containing urethane resin (B2) is preferable in terms of low warpage and insulation reliability. (B 1 ) Specific examples of the epoxy resin epoxy resin are, for example, a difunctional epoxy resin, such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a brominated bisphenol A type epoxy resin, Bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisxylenol type epoxy resin, biphenol type epoxy resin, etc., and a trifunctional or higher polyfunctional epoxy resin is exemplified by a novolak type ring Oxygen resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol type-12- 201002771 Epoxy resin, phenolic novolac type epoxy resin, chelating epoxy resin, glyoxal epoxy resin 'amine-containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenol Epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylene fluorene based resin, sand oxide modified epoxy resin, ε - hexamethylene vinegar Epoxy resin, etc. Further preferred epoxy resins which are easy to obtain a cured product of high Tg are N-glycidyl epoxy resin, bisphenol phenol epoxy resin, biphenol phenol epoxy resin, tetraglycidyl xylene oxime A ethane resin, a nonyl ethane type epoxy resin, a dicyclopentadiene phenol type epoxy resin, an epoxy resin containing a naphthalene skeleton, and the like. Specifically, the indophenol type epoxy resin is exemplified by GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.), and the dicyclopentadiene phenol type epoxy resin is exemplified by HP-7 200H (Daily Ink Chemical Industry ( Epoxy resin having a naphthalene skeleton, such as HP-4032D, EXA-7240, EXA-4700, EXA-4770 (all manufactured by Dainippon Ink Chemical Industry Co., Ltd.), with xanthene The epoxy resin of the skeleton is exemplified by EXA-73 3 5 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), and the biphenol novolac epoxy resin is exemplified by NC-3000 (manufactured by Nippon Kayaku Co., Ltd.) Polyfunctional epoxy resins or other trifunctional and tetrafunctional epoxy resins can improve solder heat resistance and the like. Among these epoxy resins, 'preferably a solid epoxy resin. Further, in order to impart flame retardancy, an epoxy resin in which a halogen or a phosphorus atom such as chlorine or bromine is introduced into the structure may be used. (B2) Carbamate-containing urethane resin-13-201002771 The carboxyl group-containing urethane resin (B2) which can be used in the present invention is exemplified by a diisocyanate compound (a) and a polyol compound (b). And a reaction of a compound (c) having one carboxyl group and two alcoholic hydroxyl groups in one molecule. At this time, it is also possible to use a reaction stopper to stabilize the terminal. As the reaction stopper, a monohydroxy compound such as an aliphatic alcohol or a monohydroxy mono(meth)acrylate compound may be used, or an isocyanate group addition reaction or condensation reaction with an alcoholic hydroxyl group, an amine group, a thiol group or the like may be used. Various reaction stop agents known in the art such as a monocarboxylic acid obtained as a functional group. Further, in the above reaction, the compound (d) having one alcoholic hydroxyl group and one or more phenolic hydroxyl groups in the molecule as a function of the reaction terminator is reacted, and the carboxyl group-containing amine group having an inert hydroxyl group introduced at the terminal is further reacted. Since the ethyl formate resin causes a reaction between the epoxy resin and the phenol group which are expected to have heat resistance in addition to the carboxyl group, it is preferable in the case where welding heat resistance or the like is required. The diisocyanate compound (a) which is a constituent component of the carboxyl group-containing urethane resin (B2) which can be used in the present invention can be a conventionally known diisocyanate, but it is preferably used from the viewpoint of low warpage. An isocyanate compound having an aromatic ring. Specific examples of the isocyanate compound having no aromatic ring are, for example, an aliphatic diisocyanate such as hexamethylene diisocyanate or a branched aliphatic diisocyanate such as trimethylhexamethylene diisocyanate or isophorone diisocyanate. (o-, m- or p-)-hydroxylene diisocyanate, methylene bis(cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-diene An alicyclic diisocyanate such as a diisocyanate. Among these, hexamethylene diiso-14-201002771 cyanate ester of aliphatic diisocyanate and trimethylhexamethylene diisocyanate of branched aliphatic diisocyanate are preferred. These diisocyanate compounds having no aromatic ring may be used singly or in combination of two or more. When these diisocyanate compounds are used, a cured product excellent in low warpage can be obtained. Further, an aromatic diisocyanate can also be used insofar as the properties of the coating film are not impaired. The polyol component (b) which is a constituent component of the carboxyl group-containing urethane resin (B2) which can be used in the present invention can be various conventionally known polyols, and is not limited to a specific compound, but is preferably used. Polycarbonate-based polyol such as carbonate diol, polyether-based polyol, polyester-based polyol, polyolefin-based polyol, polybutadiene-based polyol, polyisoprene-based polyol, hydrogenation A polybutadiene-based polyol, a hydrogenated iso-pentadiene-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a phosphorus-containing polyol, or the like. The polycarbonate diol is exemplified by a polycarbonate diol (b-fluorene) containing a repeating unit derived from one or two or more kinds of linear aliphatic diols as a constituent unit, and one or more kinds thereof are contained. The repeating unit of the alicyclic diol is used as a constituent unit of the polycarbonate diol (b-2), or a repeating unit containing a diol derived from both a linear aliphatic diol and an alicyclic diol as a constituent Unit of polycarbonate diol (b-3). Specific examples of the above-mentioned polycarbonate diol (b-fluorene) containing a repeating unit derived from one or two or more kinds of linear aliphatic diols as constituent units are exemplified by, for example, 1,6-hexanediol. Polycarbonate diol, polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol, polycarbonate derived from 1,4-butanediol and 1,6-hexanediol Ester diol, polycarbonate diol derived from 3-methyl-1,5-pentanediol and 1,6-hexanediol, from 1,9-nonanediol and 2-methyl--15- 201002771 1 8 - Octanediol-derived polycarbonate monool. Specific examples of the above-mentioned polycarbonate diol (b-2) containing a repeating unit derived from one or two or more kinds of alicyclic diols as constituent units are exemplified by, for example, I,4-cyclohexanedimethanol. Polycarbonate diol. Specific examples of the polycarbonate diol (b_3) containing the repeating unit derived from the diol of the linear aliphatic diol and the alicyclic diol as the constituent unit are exemplified by, for example, 1,6-hexane. Alcohol and 1,4 -cyclohexanyl methanol-derived polycarbonate diol, and the like. The polycarbonate diol containing the repeating unit of the above linear aliphatic diol as a constituent unit tends to have low warpage and excellent flexibility. Further, the polycarbonate diol containing a repeating unit derived from an alicyclic diol as a constituent unit tends to have excellent tin plating resistance and solder heat resistance. In view of the above, these polycarbonate diols may be used in combination of two or more kinds, or a repeating unit containing a diol derived from both a linear aliphatic diol and an alicyclic diol may be used as a constituent unit. Carbonate diol. From the viewpoint of exhibiting low warpage or flexibility, balance with solder heat resistance or tin plating resistance, it is preferred to use a copolymerization ratio of a linear aliphatic diol and an alicyclic diol in terms of a mass ratio. A polycarbonate diol of 3·7 to 7:3. The polycarbonate diol is preferably a number average molecular weight of from 200 to 5,000', but contains a repeating unit derived from a linear aliphatic diol and an alicyclic diol having a polycarbonate diol as a constituent unit. When the copolymerization ratio of the linear aliphatic diol and the alicyclic diol is 3:7 to 7:3 by mass ratio, the number average molecular weight is preferably 400 to 2, 〇〇〇. The above bisphenol A-based alkylene oxide adduct diol is exemplified by a ring of bisphenol a-16-201002771 oxyethylene compound, a propylene oxide adduct, an epoxy butyl hydride adduct, etc. Preferred among these are propylene oxide adducts of bisphenol A. Specific examples of the above phosphorus-containing polyol are exemplified by FC-450 (manufactured by Asahi Kasei Co., Ltd.), M-Ester (manufactured by Sanko Co., Ltd.), and M-Ester-HP (manufactured by Sanko Co., Ltd.). By using these phosphorus-containing polyols, a phosphorus compound can be introduced into the urethane resin to impart flame retardancy. In the present invention, a constituent component of a carboxyl group-containing urethane resin (B2), and a compound (c) having one carboxyl group and two alcoholic hydroxyl groups in one molecule is exemplified as a dimethylol group. Propionic acid, dimethylol butyric acid, and the like. The carboxyl group can be easily introduced into the urethane resin by using these compounds having a carboxyl group and two or more alcoholic hydroxyl groups. Next, as the compound having an alcoholic hydroxyl group as the above-mentioned stopper, various conventionally known monohydroxy compounds can be used. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, pentanol, hexanol, octanol, 2-hydroxyl (meth)acrylate Ethyl ester, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, lactone or alkylene oxide addition of each of the above (meth)acrylates , glyceryl di(meth)acrylate, trimethylol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, bis(trimethylol)propane Tris(meth)acrylate, allyl alcohol, allyloxyethanol, glycolic acid, hydroxypyruvate, etc., but are not limited thereto. Further, the compound (d) having one alcoholic hydroxyl group and one or more phenol-17-201002771 hydroxyl groups in the above molecule is used for introducing a phenolic hydroxyl group into the ethyl urethane, and has a polyaminocarboxylic acid. The function of the terminal blocking agent for ethyl ester, especially a compound having an alcoholic hydroxyl group and a phenolic hydroxyl group obtained by reacting with an isocyanate in a molecule, functions as a reaction stopper. Specific examples of the compound (d) are exemplified by, for example, hydroxymethylphenol, hydroxymethylcresol, hydroxymethyl-di-tert-butylphenol, p-hydroxyphenyl-2-methanol, p-hydroxyphenyl group. -3 -propanol, p-hydroxyphenyl-4-butanol, hydroxyethyl cresol, 2,6-dimethyl-4-hydroxymethylphenol, 2,4-dimethyl-6-hydroxyl Phenol, 2,3,6-trimethyl-4-hydroxymethylphenol '2-cyclohexyl-4-hydroxymethyl-5-methylphenol, 4-methyl-6-hydroxymethylbenzene-1 , 2-diol, 4-(1,1-dimethylethyl)-6-hydroxymethylbenzene-1,2-diol, etc., hydroxyalkylphenol, or hydroxyalkyl cresol; hydroxybenzoic acid a phenol having a carboxyl group substituent such as hydroxyphenylbenzoic acid or hydroxyphenoxybenzoic acid, and an esterified product of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol or the like; The monoethylene oxide adduct of phenol, the monopropylene oxide adduct of bisphenol, p-hydroxyphenylethyl alcohol, etc., but it is not limited to these. These compounds (d) may be used singly or in combination of two or more. The weight average molecular weight of the above carboxyl group-containing urethane resin (B2) is preferably from 50,000 to 1,00,000, more preferably from 8,000 to 50, 〇〇〇. Wherein the weight average molecular weight is converted to polystyrene by gel permeation chromatography. When the weight average molecular weight of the carboxyl group-containing urethane resin (B2) is less than 50,000, the elongation, burnability, and strength of the cured film are impaired, and on the other hand, it exceeds 100%. At 0 0, the solubility in the solvent is lowered, and even if the dissolved viscosity is too high, the use of the surface is greatly restricted. Further, the acid value of the carboxyl group-containing urethane resin (B2) is preferably in the range of 10 to 120 mgKOH/g, more preferably 20 to 80 mg KOH/g. When the acid value is less than 10 mgKOH/g, the reactivity with the thermosetting component is lowered to impair the heat resistance. On the other hand, when the acid value exceeds 120 mgKOH/g, the properties of the resist such as alkali resistance and electrical properties of the cured film may be lowered. Further, the resin acid value is measured in accordance with JIS K5407. In the thermosetting resin composition of the present invention, the thermosetting compound (B) blended with the carboxyl group-containing urethane resin (B2) may be used in addition to the epoxy resin (B1). An oxetane resin (B 3 ) having two or more oxetane groups obtained by reacting a carboxyl group (or a phenolic hydroxyl group) of the above-mentioned carboxyl group-containing urethane resin (B2) in a molecule . The thermosetting compound (B) as described above may be used singly or in combination of two or more. The compounding amount of the thermosetting compound (B) is preferably in the range of 20 to 99% by mass, preferably 30 to 95% by mass based on the total amount of the composition. Further, when the epoxy resin (B1) and the carboxyl group-containing urethane resin (B2) are used in combination, the carboxyl group-containing urethane resin is preferably 50 with respect to 100 parts by mass of the epoxy resin. ~2 000 parts by mass, preferably in the range of 100 to 1 000 parts by mass. The hardening accelerator (C) used in the present invention is a member which promotes a thermosetting reaction and is used to further improve the properties such as adhesion, chemical resistance, and heat resistance. Specific examples of the hardening accelerator are, for example, imidazole and derivatives thereof (for example, 2MZ, 2E4MZ, C11Z, -19-201002771 C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, manufactured by Shikoku Kasei Kogyo Co., Ltd.). C11Z-CN, 2PZ-CN, 2PHZ-CN, 2MZ - CN S, 2E4 Μ Z - CN S, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C1 1Z-AZINE, 2MA-OK, 2P4MHZ, 2PHZ > 2P4BHZ, etc.; decylamine such as acesulfame and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, m-xylylenediamine, diaminodiphenyl maple, diamine Polyamines such as diamine, urea, urea derivatives, melamine, polybasic hydrazine; organic acid salts and/or epoxy adducts; amine complexes of boron trifluoride; ethylenediamine a triazine derivative such as -S-triazine, 2,4-diamino-S-triazine or 2,4-diamino-6-dimethylphenyl-S-triazine; trimethylamine, triethanolamine, Ν,Ν-dimethyl octylamine, N-benzyldimethylamine, pyridine, Ν-methylmorpholine, hexa-(methyl) melamine, 2,4,6-gin (dimethylamino) Amines such as phenol), hydrazine methyl hydrazine, m-amino phenol, etc.; polyvinyl phenol, polyethylene Polyphenols such as phenol bromide, phenol novolac resin, alkylphenol novolak resin; organic phosphines such as tributylphosphine, triphenylphosphine, gin-2-cyanoethylphosphine; tri-n-butyl ( 2,5-dihydroxyphenyl) iron bromide, cetyl tributyl chloride, etc.; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride The above polybasic acid anhydride; diphenyl iodine tetrafluoroborate 'triphenylsulfonium hexafluoroantimonate, 2,4,6·triphenylthiopyridine hexafluorophosphate, Ciba special use IRUGACURE (registered trademark) 261 manufactured by Chemicals Co., Ltd. Photocationic polymerization catalyst of OPTOMER-SP-170 manufactured by ADEKA Co., Ltd.; styrene-maleic anhydride resin; phenyl isocyanate and dimethylamine An auricular reactant, or a conventionally used hardening accelerator such as an organic polyisocyanate such as toluene diisocyanate or isophorone diisocyanate, or a molar reaction such as dimethylamine or a hardening -20-201002771 agent. These hardening accelerators (C) may be used singly or in combination of two or more. The use of the hardening accelerator (C) is not essential, but it is preferably used in an amount of 0.1 to 25 parts by mass based on 1 part by mass of the thermosetting compound (B), particularly in the case of promoting hardening. When it exceeds 25 parts by mass, it is not preferable because the sublimation component of the hardened material is increased. The thermosetting resin composition of the present invention can be a cellulose derivative (A) or a thermosetting compound (B) using a kneading machine such as a disperser, a kneader, a triaxial roll honing machine, a bead honing machine or the like. (Epoxy resin (B 1 ), carboxyl group-containing urethane resin (B 2 ), etc.), and, if appropriate, a curing accelerator (C), a chelating agent, or the like, are obtained by dissolving or dispersing. In this case, a solvent inert to the epoxy group or the phenolic hydroxyl group may also be used. These inert solvents are preferably organic solvents. The organic solvent is such that the cellulose derivative (A), the thermosetting compound (B) (epoxy resin (B 1 ), a carboxyl group-containing urethane resin (B2), etc.) are easily dissolved or dispersed, or It is adjusted to be suitable for coating viscosity. The organic solvent can be exemplified by, for example, toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, carbitol acetic acid Ester, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, methyl methoxypropionate, methoxy propyl Ethyl acetate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone-21 - 201002771, r-butyrolactone, dimethyl argon, chloroform and dichloro Methane, etc. The amount of the organic solvent to be formulated can be appropriately set depending on the desired viscosity. The thermosetting resin composition of the present invention may contain a conventionally used thiol compound as needed to enhance the adhesion to a substrate such as polyimide. Examples of thiol compounds are 2-mercaptopropionic acid, trimethylolpropane ginseng (2-thiopropionate), 2-mercaptoethanol, 2-aminothiophenol, 3-mercapto-1, 2, 4 a decane coupling agent containing a mercapto group such as triazole or 3-mercaptopropyltrimethoxydecane. These may be used singly or in combination of two or more. The compounding amount is preferably in the range of 10 parts by mass or less per 100 parts by mass of the above thermosetting compound (B). When the amount of the thiol compound is more than the above range, the epoxy group (reacting with the epoxy group) of the above epoxy resin necessary for the crosslinking reaction is consumed, which causes a decrease in the crosslinking density. The thermosetting resin composition of the present invention may further contain at least one selected from the group consisting of an inorganic chelating agent and an organic hydrazine for the purpose of improving properties such as adhesion, hardness, and heat resistance as needed. Filling. The inorganic chelating agent is exemplified by barium sulfate, carbonic acid 15, barium titanate, oxidized chopping, amorphous cerium oxide, talc, limestone, mica powder, etc., and organic cerium filling agent is exemplified by polyoxyn powder, nylon powder, fluorine powder, etc. . Among the above squeezing agents, those having a low moisture absorption property and a low volume expansion property are preferably oxidized sand. The oxidized sand can be either melted or crystallized or a mixture of these, but in particular, in the case of cerium oxide which is surface-treated with a coupling agent or the like, it is preferred because it can improve electrical insulation. The average particle diameter of the 塡 filler is 25/m or less, more preferably i〇#m or less, and more preferably 3^m or less. The amount of the inorganic and/or organic chelating agent to be added is preferably from 30,000 to -22 to 201002771 parts per 100 parts by mass of the above thermosetting compound (B), and preferably from 5 to 1. The ratio of 50 parts by mass. When the blending amount of the hydrating agent exceeds the above ratio, the folding resistance of the hardened film is lowered and it is not suitable. Further, in the thermosetting resin composition of the present invention, other additives or coloring agents other than the above components may be added as long as the effects of the present invention are not impaired. Examples of additives include asbestos, organic bentonite, montmorillonite and other tackifiers, polyfluorene-based, fluorine-based defoamers, advection agents, glass fibers, carbon fibers, boron nitride fibers and other fiber-reinforced materials. Phthalocyanine. Blue, phthalocyanine, green, iodine, green, diazo yellow, titanium oxide, carbon black, and the like. Further, a conventionally used thermal polymerization inhibitor, ultraviolet absorber, decane coupling agent, plasticizer, foaming agent, flame retardant, antistatic agent, anti-aging agent, antibacterial and antifungal agent may be added as needed. The thermosetting resin composition having the above composition may be applied to a printed substrate, or may be used for a dry film or a prepreg, in addition to various methods known in the art such as a curtain coating method, a roll coating method, a spray coating method, and a dip coating method. In various forms and uses. Various solvents may be used depending on the method of use or use, but it is also possible to use not only a good solvent but also a weak solvent depending on the conditions. Further, the thermosetting resin composition of the present invention can be applied to a circuit-formed flexible circuit board or a tape-and-reel package or an electroluminescence panel by screen printing, for example, by heating to 120 to 18 ( The temperature of TC is excellent in warpage, adhesion to the substrate, folding resistance, low warpage, electroless gold plating resistance, solder heat resistance, electrical insulation, etc. by hardening shrinkage and cooling shrinkage. The solder resist film or the protective film. -23- 201002771 [Examples] Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited by the following examples. Further, the following [parts] and [%] Unless otherwise specified, all of them are based on mass. Synthesis Example 1 <Synthesis of Thermosetting Resin (Polyurethane Group Containing Carboxyl Group)> Injection of 360 g into a reaction vessel in which a stirring device, a thermometer, and a condenser are placed (〇.45 mol) a polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol (number average molecular weight 800) as a compound having two or more alcoholic hydroxyl groups, 81.4 g (0.55 mol) dimethylol butyric acid, and 1 1 _ 8 g (〇.16 mol) n-butanol as a molecular weight regulator (reaction stop agent). Next, 200.9 g (1_08 mol) of trimethylhexamethylene diisocyanate was injected as an isocyanate compound having no aromatic ring After heating to 60 ° C with stirring, the mixture was stopped. When the temperature in the reaction vessel began to decrease, the temperature was again heated and stirring was continued at 80 ° C, and the absorption spectrum of the isocyanate group (2 28 OcnT1 ) disappeared by infrared absorption spectrum. The reaction is completed. Then, carbitol acetate is added to make the solid content 60% by weight, and a carboxyl group-containing polyurethane having a viscous liquid containing a diluent is obtained. The resulting carboxyl group-containing polyurethane is obtained. The acid value of the solid component was 49.8 mgKOH/g. 0 Examples 1 to 5 and Comparative Example 1 The components shown in Table 1 and the blending ratio were kneaded three times at room temperature by a three-four-201002771 shaft roll. Modification of thermosetting resin, composition "I1 __-- composition (parts by mass) was carried out back to _~ - Comparative Example 1 - 1 - 1 2 3 4 5 Cellulose derivative CAB-553-0.4*l 100 ----- CAP-504-0 2*2 1 00 CAP-482-0 5*3 100 CAP-482-20*4 100 ------- CAB-551-0.01*5 100 Cyclone β **6 40 40 40 40 40 40 Polycarboxy group Ethyl urethane (Synthesis Example 1) 167 167 167 167 167 167 Antifoaming agent *7 4 4 4 4 4 4 ----- Melamine 2 2 2 2 2 2 1------- Melt oxidizing矽100 100 100 100 100 100 —- — carbitol acetate 20
備*1伊士曼公司製造之CAB-553-0_4(乙醯基含量·2·〇/°，丁醯基含量 註：46.0%，經基含量:4·8%，Tg:l36°C , M.W_ 2〇,〇〇〇)之 20wt%DPM 溶液 *2伊士曼公司製造之CAP-5〇4_0.2(乙醯基含量…·6%，丙醯基含量 :42.5%，羥基含量:5.0%，Tg:159〇C，M.W. 15,〇〇〇)之2〇加％況1^彳谷液 *3伊士曼公司製造之CAP-482-0.5(乙醯基含量:2.5% ’丙酿基含量 :45.0%，羥基含量:2.6% ’ Tg:142〇C，M.W_ 25,000)之 20wt%DPM 溶液 *4伊士曼公司製造之CAP-482-20(乙醯基含量:2.5% ’丙醯基含量:46·〇% ’羥基含量:1.8%，Tg__147°C ’ M.W. 75,000)之 20wt°/〇DPM 溶液 *5伊士曼公司製造之CAB-551-0.01(乙醯基含量:2.0%，丁醯基含量 :53.0%，羥基含量:1.5%，Tg:85〇C，M.W· 16,000)之 20wt%DPM 溶液 *6二環戊二烯型環氧樹脂(大日本化學工業(股)製造之HP-7200L)之 90wt%卡必醇乙酸酯溶液 *7共榮社化學(股)製造之FLOWREN AC300HF 對上述各熱硬化性樹脂組成物之硬化皮膜，以下述方 -25- 201002771 法評價以下各種特性。結果示於表2。 (1 )不黏性 將上述實施例1〜5及比較例1之各熱硬化性樹 物以網版印刷分別全面印刷在KAPTON 1 00ΕΝ (東 邦（股）製造之聚醯亞胺薄膜’厚度25#m)上’ °匚下熱硬化60分鐘（乾燥膜厚15/zm)。使該硬 朝上，載置於加熱至指定溫度之加熱板上。於 KAPTON 100EN，於其上載置100克之錘30秒後， 錘與塗膜間之狀態舉起KAPTON。觀察此時發生貼 痕之溫度，且以下列基準評價。 ◎:即使於8 0 °C亦未貼附、無黏痕。 〇：於6 0 °C無貼附、黏痕。於8 0°C貼附。 △:於40 °C下未貼附、黏痕。於60 °C貼附。 X :於40°C以下發生貼附、黏痕。 (2 )密著性 將上述實施例1〜5及比較例1之各熱硬化性樹 物以網版印刷分別全面印刷在KAPTON 1 00ΕΝ (東 邦（股）製造之聚醯亞胺薄膜，厚度25/zm)上， °C下熱硬化6 0分鐘後，在1 2 5 °C下進行熱硬化7.5 乾燥膜厚1 5 // m )。其硬化皮膜之密著性，係使用 黏著膠帶進行剝離試驗，確認阻焊層剝離之有無， 基準予以評價。 脂組成 麗·杜 在 120 化皮膜 其上之 以夾於 附或黏 脂組成 麗·杜 在 120 小時（ 賽璐吩 以下列 -26- 201002771 〇：完全未剝離。 △:少許剝離。 X :有剝離。 (3 )耐折性 將上述實施例1〜5及比較例1之各熱硬化性樹脂組成 物以網版印刷分別全面印刷在KAPTON 1 00ΕΝ (東麗·杜 邦（股）製造之聚醯亞胺薄膜，厚度25 //m)上，在120 °C下熱硬化6 0分鐘後，在1 2 5 °C下進行熱硬化7.5小時（ 乾燥膜厚1 5 # m )。將所得硬化皮膜彎折1 8 0°，以下列基 準予以評價。 〇：硬化皮膜無龜裂者。 △:硬化皮膜有少許龜裂者。 X :硬化皮膜有龜裂者。 (4 )低翹曲性 將上述實施例1〜5及比較例1之各熱硬化性樹脂組成 物以網版印刷分別全面印刷在KAPTON 100EN (東麗·杜 邦（股）製造之聚醯亞胺薄膜，厚度25//m)上’在120 °C下熱硬化6 0分鐘後，在1 2 5 °C下進行熱硬化7.5小時（ 乾燥膜厚15/zm)。冷卻後，將所得硬化皮膜切成50x50 mm，測定四角之翹曲求得平均値’且以下列基準評價。 ◎:翹曲未達1 mm者。 〇：翹曲1mm以上，未達4mm者。 -27- 201002771 △:翹曲4mm以上，未達7mm者。 X :翹曲7mm以上者。 (5 )無電解鍍金耐性 將上述實施例1 ~5及比較例1之各熱硬化性樹脂組成 物分別以圖型印刷在聚醯亞胺基板（新日鐵（股）製造之 ESPERNEX )之銅上，且在120 °C下熱硬化60分鐘獲得試 驗片（乾燥膜厚1 5 // m )。使用所得試驗片，以後述之步 驟進行無電解鍍金，以下列基準評價無電解鍍金之耐性° 〇：硬化皮膜未鼓起、剝離、變色者。 △:硬化皮膜稍微鼓起、剝離、變色者。 X:硬化皮膜鼓起、剝離、變色者。 無電解鑛金步驟： 1 .脫脂：將試驗片浸漬在3 0 °C之酸性脫脂液（日本 MAC DERMID (股）製造，Metex L-5B 之 20vol%水溶液 )中3分鐘。 2 .水洗：將試驗片浸漬於流水中3分鐘。 3 ·軟蝕刻：將試驗片在室溫下浸漬於1 4.3 wt%之過 硫酸銨水溶液中1分鐘。 4 .水洗：將試驗片浸漬在流水中3分鐘。 5. 酸浸漬：將試驗片在室溫下浸漬於lOvol%之硫酸 水溶液中1分鐘。 6. 水洗：將試驗片浸漬於流水中30秒〜1分鐘。 -28- 201002771 7.觸媒賦予：將試驗片浸漬於3 0°C之觸媒液體（ MELTEX (股）製造之金屬板活化劑3 5 0之lOvol%水溶液 )中3分鐘。 8 .水洗：將試驗片浸漬在流水中3分鐘。 9. 無電解鍍鎳：將試驗片浸漬於851、pH = 4.6之鎳 電鍍液（MELTEX (股）製造之 MELUPLATE ΝΪ-8 65Μ ' 20vol%水溶液）中30分鐘。 10. 酸浸漬：將試驗片在室溫下浸漬於lOvol%之硫 酸水溶液中1分鐘。 1 1 .水洗：將試驗片浸漬於流水中3 0秒〜1分鐘。 12.無電解鍍金：將試驗片浸漬於85°c、pH = 6之鍍 金液體（MELTEX (股）製造之歐羅列克斯UP 15v〇l% ’ 氰化金鉀3wt%水溶液）中30分鐘。 1 3 .水洗：將試驗片浸漬在流水中3分鐘。 14.熱水洗·_將試驗片浸漬於60°C之溫水中，充分水 洗3分鐘後，充分除水且乾燥。 (6 )電絕緣性 將上述實施例1〜5及比較例1之各熱硬化性樹脂組成 物分別在L/S (線/空間比）=15/15 // m之鍍錫處理之聚醯 亞胺基板（住友金屬礦山（股）製造之S’PERFLEX上經 錫處理而成之基板）上作成塗膜，在120 °C下熱硬化60分 鐘後’在125 °C下進行熱硬化7.5小時（乾燥膜厚15/z m )。以下列條件及基準評價所得硬化皮膜之電絕緣性。 -29- 201002771 加濕條件：溫度120°C、溼度85%RH、施加電壓60V 、1 0 0小時 試驗條件：測定時間60秒，施加電壓60V、在室溫 下測定 ◎:加濕後之絕緣電阻値1 01 2 Ω以上，未發生移行。 〇：加濕後之絕緣電阻値未達 1 〇 1 2 Ω、1 0 9 Ω以上， 未發生移行。 △:加濕後之絕緣電阻値1 09 Ω以上，發生移行。 X :加濕後之絕緣電阻値1 〇 8 Ω以下’發生移行。 (7 )耐藥品性 將上述實施例1 ~ 5及比較例1之各熱硬化性樹脂組成 物分別在L / S (線/空間比）=1 5 /1 5 # m之鍍錫處理之聚醯 亞胺基板（住友金屬礦山（股）製造之S’PERFLEX上經 錫處理而成之基板）上作成塗膜’在I20°C下熱硬化60分 鐘後，在1 2 5 t下進行熱硬化7 · 5小時（乾燥膜厚1 5 // m )。將所得硬化皮膜浸漬在N -甲基吡咯啶酮中3 0分鐘’ 擦掉溶劑後，藉由使用賽璐吩黏著膠帶進行剝離試驗’確 認阻焊層剝離之有無，以下列基準予以評價。 〇：完全未剝離。 △:有少許剝離。 X :有剝離。 評價結果示於下表2。 -30 - 201002771 [表2] 特性 實施例 比較例 1 1 2 3 4 5 不黏性 ◎ ◎ ◎ ◎ 〇 X 密著性 〇 〇 〇 〇 〇 〇 耐折性 〇 〇 〇 〇 〇 〇 低翹曲性 〇 〇 〇 〇 ◎ ◎ 無電解鍍金耐性 〇 〇 〇 〇 〇 〇 電絕緣性 ◎ ◎ ◎ ◎ ◎ 〇 耐藥品性 〇 〇 〇 〇 〇 〇 由上表2中所示之結果可清楚看出，由本發明之含有 纖維素衍生物之熱硬化性絕緣組成物形成之硬化皮膜之不 黏性、對基材之密著性、耐折性、低翹曲性、無電解鍍金 耐性、絕緣信賴性優異。相對於此’由不含纖維素衍生物 之比較例1之熱硬化性絕緣組成物形成硬化皮膜時，對基 材之密著性、耐折性、無電解鍍金耐性、電絕緣性並無問 題，但不黏性差。 本發明之含有纖維素衍生物之熱硬化性絕緣組成物可 於低溫硬化且不黏性優異，無電解鍍金耐性優異，且由於 先前經鍍錫處理之微小電路基板中之絕緣信賴性良好，因 此適用於可撓性電路板用，尤其是COF (薄膜覆晶）用絕 緣性保護膜。 實施例6〜10及比較例2 以表3所示之各成分及調配比例，在室溫通過三輥混 練3次調製熱硬化性樹脂組成物。 -31 - 201002771 [表3]Prepare *1 CAB-553-0_4 manufactured by Eastman Company (ethyl ketone content · 2 · 〇 / °, butyl sulfhydryl content Note: 46.0%, warp content: 4 · 8%, Tg: l36 ° C, M. W_ 2〇,〇〇〇) 20wt% DPM solution*2 CAP-5〇4_0.2 manufactured by Eastman Company (ethyl ketone content...·6%, propylene group content: 42.5%, hydroxyl content: 5.0 %, Tg: 159 〇 C, MW 15, 〇〇〇) 2 〇 plus % condition 1 ^ 彳谷液 * 3 CAP-482-0.5 manufactured by Eastman Company (ethyl ketone content: 2.5% ' propylene Base content: 45.0%, hydroxyl content: 2.6% 'Tg: 142〇C, M.W_ 25,000) 20wt% DPM solution *4 CAP-482-20 manufactured by Eastman Company (Ethyl thiol content: 2.5% ' Propyl sulfhydryl content: 46·〇% 'hydroxyl content: 1.8%, Tg__147 °C 'MW 75,000) 20 wt ° / 〇 DPM solution * 5 Eastman's CAB-551-0.01 (acetonitrile content: 2.0 %, butyl sulfonate content: 53.0%, hydroxyl content: 1.5%, Tg: 85 〇 C, MW · 16,000) 20 wt% DPM solution * 6 dicyclopentadiene type epoxy resin (manufactured by Dainippon Chemical Industry Co., Ltd.) 90 wt% carbitol acetate solution of HP-7200L) *FLOWREN AC300HF manufactured by Kyoeisha Chemical Co., Ltd. For the hardened film of the product, the following various characteristics were evaluated by the following method -25-201002771. The results are shown in Table 2. (1) Non-adhesiveness Each of the thermosetting trees of the above Examples 1 to 5 and Comparative Example 1 was screen-printed and printed on KAPTON 1 00 (the film of the polyimine film manufactured by Toho). #m) Thermal hardening for 60 minutes (dry film thickness 15/zm). Place the hard face up on a hot plate heated to the specified temperature. At KAPTON 100EN, after placing a 100-gram hammer for 30 seconds, the state between the hammer and the coating film lifted KAPTON. The temperature at which the sticking occurred at this time was observed and evaluated on the following basis. ◎: No sticking or sticking at 80 °C. 〇: No attachment or sticking at 60 °C. Attached at 80 °C. △: No adhesion or sticking at 40 °C. Attached at 60 °C. X: Attachment and sticking occur below 40 °C. (2) Adhesiveness Each of the thermosetting trees of the above Examples 1 to 5 and Comparative Example 1 was screen-printed and printed on KAPTON 1 00 (a film manufactured by Toho Co., Ltd., thickness 25). /zm), after hot hardening at ° C for 60 minutes, heat hardening at 1.25 ° C 7.5 dry film thickness of 1 5 // m ). The adhesion of the hardened film was measured by peeling test using an adhesive tape, and the presence or absence of peeling of the solder resist layer was confirmed. The fat composition of Li Du is on the 120-film, which is sandwiched with or attached to the composition of Li Du in 120 hours (the following -26- 201002771 璐: completely unpeeled. △: a little peeling. X: Yes (3) Folding resistance Each of the thermosetting resin compositions of the above Examples 1 to 5 and Comparative Example 1 was screen-printed and printed on KAPTON 1 00 ΕΝ (Toray Dupont Co., Ltd.) An imide film having a thickness of 25 //m) was thermally hardened at 120 ° C for 60 minutes, and then thermally hardened at 1 25 ° C for 7.5 hours (dry film thickness of 15 # m ). The resulting hardened film The bending was 180 ° and was evaluated on the basis of the following criteria: 〇: The hardened film has no cracks. △: The hardened film has a few cracks. X: The hardened film has cracks. (4) Low warpage will be the above Each of the thermosetting resin compositions of Examples 1 to 5 and Comparative Example 1 was screen-printed and printed on KAPTON 100EN (polyamide film manufactured by Toray Dupont Co., Ltd., thickness 25/m). ' After hot curing at 120 ° C for 60 minutes, heat hardening at 152 ° C for 7.5 hours (dry film thickness 15 / zm). Cold Thereafter, the obtained hardened film was cut into 50×50 mm, and the warpage of the four corners was measured to obtain an average 値′ and evaluated on the following basis: ◎: The warpage was less than 1 mm. 〇: The warpage was 1 mm or more, and the thickness was less than 4 mm. 27-201002771 △: Warpage of 4 mm or more and less than 7 mm. X: Warpage of 7 mm or more. (5) Electroless gold plating resistance Each of the thermosetting resin compositions of the above Examples 1 to 5 and Comparative Example 1 was respectively The test piece (dry film thickness of 15 // m) was obtained by pattern printing on copper of a polyimide substrate (ESPERNEX manufactured by Nippon Steel Co., Ltd.) and thermally hardening at 120 ° C for 60 minutes. The obtained test piece was subjected to electroless gold plating in the steps described later, and the resistance to electroless gold plating was evaluated by the following criteria. 〇: The hardened film was not bulged, peeled, or discolored. △: The hardened film was slightly bulged, peeled, and discolored. : Hardened film bulging, peeling, discoloration. Electroless gold step: 1. Degreasing: The test piece is immersed in an acidic degreasing solution at 30 °C (manufactured by MAC DERMID, Japan, 20 vol% of Metex L-5B) 3 minutes in the aqueous solution. 2. Washing: immersing the test piece in running water 3 3. Soft etching: The test piece was immersed in a 14.3 wt% aqueous solution of ammonium persulfate for 1 minute at room temperature. 4. Washing: The test piece was immersed in running water for 3 minutes. 5. Acid dipping: test The sheet was immersed in a 10% by volume aqueous solution of sulfuric acid for 1 minute at room temperature. 6. Water washing: The test piece was immersed in running water for 30 seconds to 1 minute. -28- 201002771 7. Catalyst imparting: The test piece was immersed in a catalyst liquid at 30 ° C (10 vol% aqueous solution of a metal plate activator 350 manufactured by MELTEX) for 3 minutes. 8. Washing: The test piece was immersed in running water for 3 minutes. 9. Electroless nickel plating: The test piece was immersed in a 851, pH = 4.6 nickel plating solution (MELUPLATE ΝΪ-8 65 Μ '20 vol% aqueous solution manufactured by MELTEX) for 30 minutes. 10. Acid impregnation: The test piece was immersed in a 10 vol% aqueous sulfuric acid solution at room temperature for 1 minute. 1 1. Washing: The test piece was immersed in running water for 30 seconds to 1 minute. 12. Electroless gold plating: The test piece was immersed in a gold plating liquid (Eolexex UP 15v〇l% 'Cyanide gold potassium citrate 3 wt% aqueous solution manufactured by MELTEX Co., Ltd.) at 85 ° C and pH = 6 for 30 minutes. 1 3. Washing: The test piece was immersed in running water for 3 minutes. 14. Hot water washing· The test piece was immersed in warm water of 60 ° C, and after sufficiently washing with water for 3 minutes, it was sufficiently dehydrated and dried. (6) Electrical Insulating Properties Each of the thermosetting resin compositions of the above Examples 1 to 5 and Comparative Example 1 was tin-plated by L/S (line/space ratio) = 15/15 // m. The imide substrate (substrate treated with tin on S'PERFLEX manufactured by Sumitomo Metals Co., Ltd.) was coated as a coating film, and thermally cured at 120 ° C for 60 minutes and then thermally hardened at 125 ° C for 7.5 hours. (Dry film thickness 15/zm). The electrical insulation properties of the obtained hardened film were evaluated under the following conditions and criteria. -29- 201002771 Humidification conditions: temperature 120 ° C, humidity 85% RH, applied voltage 60 V, 100 hours Test conditions: measurement time 60 seconds, applied voltage 60 V, measured at room temperature ◎: insulation after humidification The resistance 値1 01 2 Ω or more did not occur. 〇: The insulation resistance after humidification is less than 1 〇 1 2 Ω, 1 0 9 Ω or more, and no migration occurs. △: The insulation resistance after humidification is 値1 09 Ω or more, and migration occurs. X: The insulation resistance 加1 〇 8 Ω or less after humidification is shifted. (7) Chemical resistance The respective thermosetting resin compositions of the above Examples 1 to 5 and Comparative Example 1 were each subjected to tin plating treatment at L / S (line/space ratio) = 15 / 1 5 # m. The yttrium imide substrate (substrate treated with tin on S'PERFLEX manufactured by Sumitomo Metal Mining Co., Ltd.) was formed into a coating film 'heat-hardened at I20 ° C for 60 minutes, and then thermally hardened at 1 2 5 t. 7 · 5 hours (dry film thickness 1 5 // m). The obtained hardened film was immersed in N-methylpyrrolidone for 30 minutes. After the solvent was wiped off, the peeling test was carried out by using a celesta adhesive tape to confirm the presence or absence of peeling of the solder resist layer, and the evaluation was performed on the following basis. 〇: Not peeled at all. △: There was a little peeling. X: There is peeling. The evaluation results are shown in Table 2 below. -30 - 201002771 [Table 2] Characteristic Example Comparative Example 1 1 2 3 4 5 Non-tacky ◎ ◎ ◎ ◎ 〇X Adhesiveness 〇〇〇〇〇〇 Folding resistance 〇〇〇〇〇〇 low warpage 〇〇〇〇 ◎ ◎ Electroless gold plating resistance 〇〇〇〇〇〇 Electrical insulation ◎ ◎ ◎ ◎ ◎ 〇 Chemical resistance 〇〇〇〇〇〇 From the results shown in Table 2 above, it is clear that the present invention The cured film formed of the thermosetting insulating composition containing a cellulose derivative has excellent non-stick properties, adhesion to a substrate, folding resistance, low warpage, electroless gold plating resistance, and excellent insulation reliability. When the cured film is formed of the thermosetting insulating composition of Comparative Example 1 containing no cellulose derivative, there is no problem in adhesion to the substrate, folding resistance, electroless gold plating resistance, and electrical insulating properties. But not sticky. The thermosetting insulating composition containing a cellulose derivative of the present invention can be cured at a low temperature and is excellent in non-stickiness, and is excellent in electroless gold plating resistance, and has excellent insulation reliability in a micro-circuit substrate which has been previously tin-plated. Suitable for flexible circuit boards, especially for COF (film over-film) insulating protective film. Examples 6 to 10 and Comparative Example 2 The thermosetting resin compositions were prepared by mixing three times at room temperature three times at the respective components and mixing ratios shown in Table 3. -31 - 201002771 [Table 3]
備註 伊士曼公司製造之CAB-553-0.4(乙醯基含量:2.0% ’ 丁醯基 基含量:4.8%，Tg:136°C，M.W. 20,000)之 2〇wt%DPM 溶液 ° ^ *2伊士曼公司製造之CAP-5〇4-0.2(乙醯基含量:〇.6°/。，丙酷基含量:42 5%，辦 基含量:5.0%，Tg:159。。，M.W. 15,0〇〇)之 2〇wt%DPM 溶液 工 *3伊士曼公司製造之CAP-482-0.5(乙醯基含量:2_5°/。，丙醯基含量:45 〇%，巧 基含量:2.6°/。，丁§:142。(：，1^.\¥.25,000)之20加％〇?河溶液 二 *4伊士曼公司製造之CAP-482-20(乙醯基含量:2_5%，丙醯基含量_46 〇%，淫 基含量:1_8% , Tg:147°C , M.W. 75,000)之20奶°/。〇卩]^溶液 *5伊士曼公司製造之CAB_551_〇.〇i(乙醯基含量:2·0%，丁醯基含量:53.0%， 羥基含量:1.5%，Tg:85°C，M.W. 16,000)之 20wt%DPM 溶液 *6 Epicoat828(日本環氧觀旨(股)製造） *7 HF-1EC65(昭和化成(股)製造） *8共榮社化學(股)製造之FLOWRENAC3〇〇HF *9 2E4MZ(四國化成工業(股)製造） 10 B-30(稱化學(肸)製浩)____ 對上述各熱硬化性樹脂組成物之硬化皮膜，以下述方 法評價以下各種特性。結果列於表4中。 -32- 201002771 (8 )不黏性 將上述實施例6〜1 0及比較例2之各熱硬化性樹脂組 成物分別圖型.印刷在印刷電路基板（厚度1.6mm )上’在 8〇t下熱乾燥30分鐘（乾燥膜厚20/zm)。接著爲進行 兩面印刷，而在乾燥之基板背側進行圖型印刷。此時’觀 察最初印刷之塗膜對鋁階之貼附或黏痕，以下列基準予以 評價。 〇：無貼附、黏痕。 X :有貼附、黏痕。 (9 )密著性 將上述實施例6〜1 0及比較例2之各熱硬化性樹脂組 成物分別圖型印刷在印刷電路基板（厚度1 · 6mm )上，在 下熱乾燥30分鐘後，在150 °C下熱硬化30分鐘（乾 燥膜厚20 μ m )。其硬化皮膜之於銅上之密著性，係使用 賽璐吩黏著膠帶，以剝離試驗確認阻焊層剝離之有無，以 下列基準予以評價。 〇：完全未剝離。 △:少許剝離。 X :有剝離。 (1 0 )焊接耐熱性 將上述實施例6〜1 0及比較例2之各熱硬化性樹脂組 -33- 201002771 成物分別圖型印刷在印刷電路基板（厚度1 · 6mm )上，在 8〇°C下熱乾燥30分鐘後，在150〇ct熱硬化30分鐘（乾 燥膜厚20 v m )。將松香系助焊劑塗佈於所得硬化皮膜上 ’且浸漬於260 °C之焊料槽中，去除助焊劑，經乾燥後， 進行膠帶剝離試驗’且以下列基準評價硬化皮膜之狀態。 〇：即使浸漬1 0秒亦無剝離者。 △:於1 〇秒稍有剝離，但浸漬5秒亦無剝離者。 X :浸漬5秒後硬化皮膜有剝離者。 [表4] 特性 實施例 比較例 2 6 7 8 9 10 不黏性 ◎ ◎ ◎ ◎ 〇 X 密著性 〇 〇 〇 〇 〇 〇 焊接耐熱性 〇 〇 〇 〇 〇 〇 實施例1 1〜1 5及比較例3 以表5中所示之各成分及調配比例，在室溫下通過三 車昆混練三次’調製熱硬化性樹脂組成物。 -34- 201002771 組成 (質量份） 實施例 比較例 3 11 12 13 14 15 纖維素 衍生物 CAB-553-0.4*l 100 CAP-504-0.2*2 100 CAP-482-0.5*3 100 CAP-482-20* 4 100 CAB-551-〇.〇l*5 100 環氧樹脂*6 100 100 100 100 100 100 環氧樹脂硬化劑*7 100 100 100 100 100 100 消泡劑*8 2 2 2 2 2 2 硬化促進劑*9 3 3 3 3 3 3 熔融二氧化矽 20 20 20 20 20 20 備註 *1伊士曼公司製造之CAB-553-0.4(乙醯基含量:2.〇% ’ 丁醯基含量:46.0%，羥 基含量:4_8°/。，Tg:136°C，M.W. 20,000)之 2〇wt°/〇DPM 溶液 *2伊士曼公司製造之CAP-504-0.2(乙醯基含量:〇·6%，丙醯基含量:42.5%，羥 基含量:5.0%，Tg:159°C，M.W. 15,000)之20加°/。〇?\1溶液 *3伊士曼公司製造之CAP-482-0.5(乙醯基含量:2·5°/。’丙醯基含量:45.0% ’羥 基含量:2.6%，Tg:142°C，M.W. 25,000)之20加％〇?^1溶液 *4伊士曼公司製造之CAP-482-20(乙醯基含量:2_5°/〇，丙醯基含量:46.0% ’羥 基含量:1.8%，Tg:147t，M.W. 75,000)之20\^%〇卩\1溶液 *5伊士曼公司製造之CAB-551-0.01(乙醯基含量:2.〇% ’ 丁醯基含量:53.0%， 羥基含量:1,5%，Tg:85°C，M.W. 16,000)之20城％〇?1^溶液 *6 EXA-4850-150(大日本化學工業(股)製造） *7 ZFR-1401H(日本化藥(股)製造） *8共榮社化學(股)製造之FLOWRENAC300HF *9 2E4MZ(四國化成工業(股)製造） 對上述各熱硬化性樹脂組成物之硬化皮膜，以下述方 法評價以下各種特性。結果示於表6。 (11 )不黏性 -35- 201002771 將上述實施例1 1〜1 5及比較例3之各熱硬化性樹脂組 成物以網版印刷分別全面印刷在KAPTON 100H (東麗· 杜邦（股）製造之聚醯亞胺薄膜，厚度25 // m)上，在80 °C下熱乾燥30分鐘（乾燥膜厚20 // m )。將1 〇片所得基 板重疊，在室溫2 5 °C下靜置1小時。剝開重疊之基板’且 觀察此時之貼附或黏痕，並以下列基準予以評價。 ◎:無貼附、黏痕。 〇：無貼附、有少許黏痕。 △:有貼附、黏痕。 X :塗膜對基板有轉印。 (1 2 )密著性 將上述實施例1 1〜1 5及比較例3之各熱硬化性樹脂組 成物分別圖型印刷在KAPTON 1 00H (東麗杜邦（股） 製造之聚醯亞胺薄膜’厚度25 "m)上’在80°C下熱乾燥 3〇分鐘後，在150 °C下熱硬化30分鐘（乾燥膜厚20//m )。其硬化皮膜之密著性係使用賽猫吩黏著膠帶藉由剝離 試驗，確認阻焊層剝離之有無’以下列基準予以評價。 〇：完全未剝離。 △:少許剝離。 X :有剝離。 (1 3 )耐折性 將上述實施例1 1〜1 5及比較例3之各熱硬化性樹脂組 -36- 201002771 成物以網版印刷分別全面印刷在KAPTON 1 0OH (東麗· 杜邦（股）製造之聚醯亞胺薄膜，厚度25/zm)上，在80 °〇下熱乾燥30分鐘後，在150 °C下進行熱硬化30分鐘（ 乾燥膜厚2 0 # m )。將所得硬化皮膜彎折1 8 (Γ，以下列基 準予以評價。 〇：硬化皮膜無龜裂者。 △:硬化皮膜有少許龜裂者。 X :硬化皮膜有龜裂者。 (1 4 )低翹曲性 將上述實施例1 1〜1 5及比較例3之各熱硬化性樹脂組 成物以網版印刷分別全面印刷在KAPTON 100H (東麗. 杜邦（股）製造之聚醯亞胺薄膜，厚度25 //in)上，在80 °C下熱乾燥3 0分鐘後，在1 5 (TC下進行熱硬化3 0分鐘（ 乾燥膜厚20 // m )。冷卻後，將所得硬化皮膜切成50x 5 0mm，測定四角之翹曲求得平均値，且以下歹[J基準予以 評價。 〇··翹曲0mm以上，未達4mm者。 △:翹曲4mm以上，未達7mm者。 x :題曲7mm以上者。 (1 5 )焊接耐熱性 將上述實施例1 1〜1 5及比較例3之各熱硬化性樹脂組 成物分別圖型印刷在印刷電路基板（厚度1 . 6 mm )上，在 -37- 201002771 80°C下熱乾燥3〇分鐘後，在150。(3下熱硬化30分鐘（乾 燥膜厚20 # m )。將松香系助焊劑塗佈於所得硬化皮膜上 ，且浸漬於2 6 0 °C之焊料槽中，去除助焊劑，經乾燥後， 進行膠帶剝離試驗’以下列基準評價硬化皮膜之狀態。 〇：即使浸漬1 〇秒亦無剝離者。 △:於1 0秒稍有剝離，但浸漬5秒亦無剝離者。 X :浸漬5秒後硬化皮膜有剝離者。 [表6] 特性 實施例 比較例 11 12 13 14 15 3 不黏性 ◎ ◎ ◎ 〇 X 密著性 〇 〇 〇 〇 〇 〇 耐折性 〇 〇 〇 〇 〇 〇 低翹曲性 〇 〇 〇1 〇 〇 〇 焊接耐熱性 〇 〇 〇 — 〇 〇 〇 -38-Remarks CAB-553-0.4 manufactured by Eastman Company (acetonitrile content: 2.0% 'butyl sulfonate content: 4.8%, Tg: 136 ° C, MW 20,000) 2 〇 wt% DPM solution ° ^ * 2 士CAP-5〇4-0.2 manufactured by Mann Company (ethyl ketone content: 〇.6°/., propyl group content: 42 5%, base content: 5.0%, Tg: 159., MW 15,0) 〇〇) 2〇wt%DPM solution*3 CAP-482-0.5 manufactured by Eastman Company (Ethyl thiol content: 2_5°/., propylene content: 45 〇%, QI content: 2.6°) /., Ding §: 142. (:, 1^.\¥.25,000) 20%% 〇? River solution II * 4 Eastman's CAP-482-20 (acetonitrile content: 2_5%, Propylene base content _46 〇%, mentor content: 1_8%, Tg: 147 ° C, MW 75,000) 20 milk ° /. 〇卩] ^ solution * 5 Eastman's CAB_551_〇.〇i (Ethyl thiol content: 2·0%, butyl sulfonate content: 53.0%, hydroxyl content: 1.5%, Tg: 85 ° C, MW 16,000) 20 wt% DPM solution *6 Epicoat 828 (Japan Epoxy) *7 HF-1EC65 (Manufactured by Showa Kasei Co., Ltd.) *8 FLOWRENAC3〇〇HF*9 2E4MZ manufactured by Kyoeisha Chemical Co., Ltd. (Manufactured by Shikoku Chemical Industry Co., Ltd.) 10 B-30( (Chemical) The following various characteristics were evaluated for the hardened film of each of the above thermosetting resin compositions by the following method. The results are shown in Table 4. -32 - 201002771 (8) Non-tackiness The above examples were Each of the thermosetting resin compositions of 6 to 10 and Comparative Example 2 was printed on a printed circuit board (thickness: 1.6 mm) and thermally dried at 8 Torr for 30 minutes (dry film thickness: 20/zm). Next, for the two-sided printing, the pattern printing was performed on the back side of the dried substrate. At this time, the adhesion or sticking of the first printed film to the aluminum step was observed, and the evaluation was performed on the following basis. (X) Adhesiveness Each of the thermosetting resin compositions of the above Examples 6 to 10 and Comparative Example 2 was printed on a printed circuit board (thickness of 1 · 6 mm). On the other hand, after hot drying for 30 minutes, it is thermally hardened at 150 °C for 30 minutes (dry film thickness 20 μm). The adhesion of the hardened film to copper is adhered by using celesta adhesive tape. The test confirmed the presence or absence of the solder resist peeling and evaluated it on the following basis. △: a little peeling. X: peeling. (1 0) Solder heat resistance The respective thermosetting resin groups -33 - 201002771 of the above Examples 6 to 10 and Comparative Example 2 were respectively printed on the pattern. The printed circuit board (thickness 1 · 6 mm) was thermally dried at 8 ° C for 30 minutes, and then thermally cured at 150 ° C for 30 minutes (dry film thickness 20 vm). The rosin-based flux was applied onto the obtained hardened film and immersed in a solder bath at 260 ° C to remove the flux. After drying, the tape peeling test was performed, and the state of the cured film was evaluated by the following criteria. 〇: No peeling even if immersed for 10 seconds. △: Slightly peeled off at 1 sec, but there was no peeling after immersion for 5 seconds. X: After the immersion for 5 seconds, the hardened film was peeled off. [Table 4] Characteristic Example Comparative Example 2 6 7 8 9 10 Non-tacky ◎ ◎ ◎ ◎ 〇 X Adhesive 〇〇〇〇〇〇 Soldering heat resistance 〇〇〇〇〇〇 Example 1 1 to 1 5 Comparative Example 3 The thermosetting resin composition was prepared by kneading three times at room temperature by three components at the room temperature and the mixing ratio shown in Table 5. -34- 201002771 Composition (parts by mass) Example Comparative Example 3 11 12 13 14 15 Cellulose derivative CAB-553-0.4*l 100 CAP-504-0.2*2 100 CAP-482-0.5*3 100 CAP-482 -20* 4 100 CAB-551-〇.〇l*5 100 Epoxy resin*6 100 100 100 100 100 100 Epoxy resin hardener*7 100 100 100 100 100 100 Defoamer*8 2 2 2 2 2 2 Hardening accelerator *9 3 3 3 3 3 3 Fused cerium oxide 20 20 20 20 20 20 Remarks *1 CAB-553-0.4 manufactured by Eastman Company (Ethyl thiol content: 2. 〇% ' Ding 醯 base content: 46.0%, hydroxyl content: 4_8°/., Tg: 136°C, MW 20,000) 2〇wt°/〇DPM solution*2 CAP-504-0.2 manufactured by Eastman Company (Ethyl thiol content: 〇· 6%, propylene content: 42.5%, hydroxyl content: 5.0%, Tg: 159 ° C, MW 15,000) 20 plus ° /. 〇?\1 solution*3 CAP-482-0.5 manufactured by Eastman Company (Ethyl thiol content: 2·5°/. 'Propylene content: 45.0% 'Hydroxyl content: 2.6%, Tg: 142 °C , MW 25,000) 20% by weight ^1^ solution*4 CAP-482-20 manufactured by Eastman Company (ethyl ketone content: 2_5 ° / 〇, propyl thiol content: 46.0% 'hydroxyl content: 1.8% , Tg: 147t, MW 75,000) 20\^% 〇卩 \1 solution * 5 CAB-551-0.01 manufactured by Eastman Company (ethyl ketone content: 2. 〇% ' butyl sulfhydryl content: 53.0%, hydroxyl content :1,5%, Tg: 85°C, MW 16,000) 20%%〇1^ Solution*6 EXA-4850-150 (Manufactured by Dainippon Chemical Industry Co., Ltd.) *7 ZFR-1401H (Japanese Chemicals) (manufacturing of the company) *8 FLOWRENAC300HF manufactured by Kyoritsu Chemical Co., Ltd. *9 2E4MZ (manufactured by Shikoku Chemicals Co., Ltd.) The hardened film of each of the above thermosetting resin compositions was evaluated for the following characteristics by the following method. . The results are shown in Table 6. (11) Non-tacky-35-201002771 Each of the thermosetting resin compositions of the above Examples 1 to 15 and Comparative Example 3 was screen-printed and printed on KAPTON 100H (Toray Dupont Co., Ltd.). The polyimide film was deposited on a thickness of 25 // m) and dried at 80 ° C for 30 minutes (dry film thickness 20 // m). The substrate obtained from the 1 tablet was overlapped and allowed to stand at room temperature 2 5 ° C for 1 hour. The overlapped substrates were peeled off and the attachment or sticking at this time was observed and evaluated on the following basis. ◎: No sticking or sticking. 〇: No attachment, a little sticky mark. △: There are stickers and sticky marks. X: The coating film is transferred to the substrate. (1 2) Adhesiveness Each of the thermosetting resin compositions of the above Examples 1 to 15 and Comparative Example 3 was separately printed on KAPTON 1 00H (polyamide film manufactured by Toray Dupont Co., Ltd.) 'Thickness 25 "m) was thermally dried at 80 ° C for 3 minutes, and then thermally cured at 150 ° C for 30 minutes (dry film thickness 20 / / m). The adhesion of the sclerosing film was evaluated by the peeling test using a smear-adhesive tape, and the presence or absence of peeling of the solder resist layer was evaluated by the following criteria. 〇: Not peeled at all. △: A little peeling. X: There is peeling. (13) Folding resistance Each of the thermosetting resin groups -36 to 201002771 of the above Examples 1 to 15 and Comparative Example 3 was screen-printed and printed in KAPTON 1 0OH (Toray Dupont ( The polyimide film produced by the company, thickness 25/zm), was thermally dried at 80 ° C for 30 minutes and then thermally cured at 150 ° C for 30 minutes (dry film thickness 20 0 m). The obtained hardened film was bent by 18 (Γ, and evaluated according to the following criteria. 〇: The hardened film was not cracked. △: The hardened film was slightly cracked. X: The hardened film was cracked. (1 4 ) Low Warpage property Each of the thermosetting resin compositions of the above Examples 1 to 15 and Comparative Example 3 was screen-printed and printed on KAPTON 100H (Toray DuPont). On a thickness of 25 // in), after hot drying at 80 ° C for 30 minutes, heat hardening at 1 5 (TC for 30 minutes (dry film thickness 20 // m). After cooling, the resulting hardened film is cut. 50x 50 mm, the average 値 was measured for the warpage of the four corners, and the following 歹 [J benchmark was evaluated. 〇·· warping 0 mm or more, less than 4 mm. △: warping 4 mm or more, less than 7 mm. x : The title piece is 7 mm or more. (1) Solder heat resistance The respective thermosetting resin compositions of the above Examples 1 to 15 and Comparative Example 3 were printed on a printed circuit board (thickness 1.6 mm). On, at -37- 201002771 80 ° C hot drying for 3 minutes, at 150. (3 under heat hardening for 30 minutes (dry film thickness 20 # m). Will rosin The flux was applied onto the obtained hardened film, immersed in a solder bath at 260 ° C, the flux was removed, and after drying, the tape peeling test was carried out to evaluate the state of the hardened film by the following criteria. There was no peeling in the leap seconds. △: It was slightly peeled off at 10 seconds, but it was not peeled off after immersion for 5 seconds. X: The cured film was peeled off after immersion for 5 seconds. [Table 6] Characteristic Example Comparative Example 11 12 13 14 15 3 Non-sticking ◎ ◎ ◎ 〇X Adhesiveness 〇〇〇〇〇〇 Folding resistance 〇〇〇〇〇〇 Low warpage 〇〇〇 1 〇〇〇 Welding heat resistance 〇〇〇 — 〇〇〇 -38-