「發明所欲解決之課題」 [0006] 但是專利文獻1，2所記載的材料有引起金屬導體之密著性劣化等之信賴性降低的問題。 [0007] 因此，本發明之目的係提供可得到低熱膨脹性，且與金屬導體之密著性良好之硬化物的印刷配線板用硬化性樹脂組成物、乾薄膜、硬化物及印刷配線板。 用以解決課題之手段 [0008] 本發明人等精心檢討的結果，發現藉由使用將平均纖維徑為特定之範圍，平均纖維長為特定値以下，表示平均纖維徑與平均纖維長之比的長寬比為特定之範圍之具有羧基之微細纖維素纖維經疏水化者，可解決上述課題，遂完成本發明。 [0009] 亦即，本發明之印刷配線板用硬化性樹脂組成物，其特徵係含有具有羧基之微細纖維素纖維之該羧基藉由胺化合物及四級銨化合物中之至少任一種修飾，經疏水化而成之微細纖維素纖維與硬化性樹脂的樹脂組成物， 其中前述具有羧基之微細纖維素纖維的平均纖維徑為0.1nm以上、200nm以下，平均纖維長為600nm以下，且平均長寬比為1以上、200以下。 [0010] 本發明之樹脂組成物，其係進一步含有二氧化矽為佳。又，本發明之樹脂組成物係含有熱硬化性樹脂及光硬化性樹脂中之至少任一種，作為前述硬化性樹脂為佳。 [0011] 本發明之乾薄膜，其特徵係具有將上述印刷配線板用硬化性樹脂組成物塗佈於薄膜上，經乾燥而成的樹脂層。 [0012] 本發明之硬化物，其特徵係上述印刷配線板用硬化性樹脂組成物或上述乾薄膜之前述樹脂層經硬化而成者。 [0013] 本發明之印刷配線板，其特徵係具備上述硬化物者。 發明效果 [0014] 依據本發明時，可實現可得到低熱膨脹性，且與金屬導體之密著性良好之硬化物的印刷配線板用硬化性樹脂組成物、乾薄膜、硬化物及印刷配線板。 實施發明之形態 [0015] 以下詳細說明本發明之實施形態。 本發明之印刷配線板用硬化性樹脂組成物係含有具有羧基之微細纖維素纖維之羧基藉由胺化合物及四級銨化合物中之至少任一種修飾，經疏水化而成的微細纖維素纖維與硬化性樹脂的樹脂組成物者，其中具有羧基之微細纖維素纖維，使用平均纖維徑為0.1nm以上、200nm以下，平均纖維長為600nm以下，且平均長寬比(平均纖維長/平均纖維徑)為1以上、200以下者。 在此，具有羧基之微細纖維素纖維係平均纖維徑為0.1nm以上、200nm以下，平均纖維長為600nm以下，且平均長寬比為1以上、200以下，但是具有羧基之微細纖維素纖維之羧基經修飾、疏水化所成之微細纖維素纖維也平均纖維徑為0.1nm以上200nm以下，平均纖維長為600nm以下，且平均長寬比為1以上200以下。 以下，將具有羧基之微細纖維素纖維也稱為含有羧基之微細纖維素纖維，含有羧基之微細纖維素纖維之羧基經疏水化所成之微細纖維素纖維，也稱為疏水化微細纖維素纖維。 [0016] 以往，對於通常具有300左右之平均長寬比的含有羧基之微細纖維素纖維，使鍵結各種修飾基等之進行了疏水化處理者，此微細纖維素纖維係低熱膨脹性，但是與金屬導體之密著性低。但是本發明人等發現作為包含對於平均長寬比為1以上200以下之含有羧基之微細纖維素纖維，施予疏水化處理者與硬化性樹脂的組成物時，由此組成物所得的硬化物，維持低熱膨脹性的狀態，與金屬導體之密著性優異。發揮這種效果的詳細理由雖不明，但是推測平均長寬比包含於上述範圍之含有羧基的微細纖維素纖維為因存在於天然纖維素纖維中的脆弱部分，例如非晶區域被切斷，形成短纖維化者，故全體而言結晶區域之分布比例增加，故雖短纖維但是可維持低熱膨脹性。又，認為所得之疏水化微細纖維素纖維的纖維長也較短，提高在樹脂組成物中之分散性，可充分發揮作為填料的效果，故低熱膨脹性優異，且與金屬導體之密著性優異。 [0017] 本發明之硬化性樹脂組成物，適用於形成印刷配線板的絕緣層，例如適用於形成印刷配線板之核層、層間絕緣層、阻焊劑等的表面保護層。又，本發明之硬化性樹脂組成物，可列舉例如含有熱硬化性樹脂的熱硬化性樹脂組成物、含有光硬化性樹脂的光硬化性樹脂組成物、含有光硬化性樹脂及熱硬化性樹脂的光硬化性熱硬化性樹脂組成物。 [0018] [疏水化微細纖維素纖維] 上述疏水化微細纖維素纖維係含有羧基之微細纖維素纖維之羧基藉由胺化合物及四級銨化合物中之至少任一種修飾，經疏水化而成者，如以下可得。原材料之天然纖維素纖維，可列舉例如針葉樹系木漿、闊葉樹系木漿等之木材漿料；如綿花棉絨、原綿長纖維之綿系漿料；草紙漿(straw pulp)、蔗渣漿(Bagasse pulp)等之非木材系漿；細菌性纖維素(bacteria cellulose)等，此等可單獨使用1種，或組合2種以上使用。 [0019] 上述原材料主要由纖維素、半纖維素(hemicellulose)及木質素所構成，其中，木質素之含量通常為0~40質量%左右，特別是0~10質量%左右。此等之原材料，必要時可進行木質素之除去或漂白處理，調整木質素量。又，木質素含量之測量，可藉由Klason法進行。 [0020] 植物細胞壁中，纖維素分子非單分子，而是規則性凝聚，形成具有數十條集合之結晶性的微纖絲(microfibril)，此乃是植物之基本骨架物質。因此，為了由上述原材料製造微細纖維素纖維時，對於上述原材料，藉由施予打漿或粉碎處理、高溫高壓水蒸氣處理、磷酸鹽等之處理等，可將該纖維解開至奈米尺寸。 [0021] 又，對於天然纖維素纖維，藉由進行氧化處理(例如使用後述之TEMPO的氧化處理)，將天然纖維素之葡萄吡喃糖(Glucopyranose)環中之C6位之一級羥基，選擇性氧化成羧基，可得到含有羧基之纖維素纖維。藉由進行此處理，可將纖維素纖維以比較弱的剪力，解開至奈米尺寸。 [0022] 此外，藉由將含有羧基之纖維素纖維之羧基，以胺化合物及四級銨化合物中之至少任一種修飾，進行疏水化，可得到上述疏水化微細纖維素纖維。 [0023] 以下具體記載本發明使用之疏水化微細纖維素纖維之製造方法。 (漿液(slurry)化步驟) 首先，調製將天然纖維素纖維分散於水中的漿液。漿液係相對於成為原料之天然纖維素纖維(絕對乾燥基準：使於150℃下加熱乾燥30分鐘後的天然纖維素纖維的質量)，添加約10~1000倍量(質量基準)的水，藉由混合機等處理而得。天然纖維素纖維可被施予打漿等提高表面積的處理。又，上述市售漿料的纖維素I型結晶化度，通常為80%以上。 [0024] (氧化處理步驟) 其次，將上述天然纖維素纖維在N-氧基(oxyl)化合物等之氧化劑之存在下進行氧化處理，得到含有羧基之纖維素纖維(以下有時僅稱為「氧化處理」)。 [0025] N-氧基化合物係選自具有碳數1或2之烷基的哌啶氧基化合物、吡咯烷氧基化合物、咪唑啉氧基化合物、及、氮雜金剛烷化合物之1種以上之雜環式的N-氧基化合物為佳。此等之中，從反應性的觀點，較佳為具有碳數1或2之烷基的哌啶氧基化合物，2,2,6,6-四烷基哌啶-1-氧基(TEMPO)、4-羥基-2,2,6,6-四烷基哌啶-1-氧基、4-烷氧基-2,2,6,6-四烷基哌啶-1-氧基、4-苯甲醯氧基-2,2,6,6-四烷基哌啶-1-氧基、4-胺基-2,2,6,6-四烷基哌啶-1-氧基等之二-tert-烷基硝基氧基化合物、4-乙醯胺-TEMPO、4-羧基-TEMPO、4-膦醯氧基-TEMPO等。此等之哌啶氧基化合物之中，更佳為2,2,6,6-四甲基哌啶-1-氧基(TEMPO)、4-羥基-2,2,6,6-四甲基哌啶-1-氧基、4-甲氧基-2,2,6,6-四甲基哌啶-1-氧基，又更佳為2,2,6,6-四甲基哌啶-1-氧基(TEMPO)。 [0026] N-氧基化合物之量，只要是觸媒量即可，相對於天然纖維素纖維(絕對乾燥基準)100質量份，較佳為0.001~10質量份，更佳為0.01~9質量份，又更佳為0.1~8質量份，再更佳為0.5~5質量份。天然纖維素纖維之氧化處理時，可使用N-氧基化合物以外的氧化劑。氧化劑從將溶劑調整為鹼性域時之溶解度或反應速度等的觀點，可列舉氧或空氣、過氧化物；鹵素、次亞鹵素酸、亞鹵素酸、過鹵素酸及彼等之鹼金屬鹽或鹼土金屬鹽；鹵素氧化物、氮氧化物等。此等之中，較佳為鹼金屬次亞鹵素酸鹽，具體而言，可列舉次亞氯酸鈉或次亞溴酸鈉。氧化劑之使用量可依據天然纖維素纖維之羧基取代度(氧化度)選擇即可，又，氧化反應收率因反應條件而異，無法一概決定，但是相對於原材料的天然纖維素纖維(絕對乾燥基準)100質量份，較佳為成為約1~100質量份的範圍。 [0027] 又，為了更有效率地進行氧化反應，可使用作為助觸媒之溴化鈉、溴化鉀等之溴化物或、碘化鈉、碘化鉀等之碘化物等。助觸媒之量，只要是可發揮其功能的有效量即可，無特別限制。氧化處理中之反應溫度，從反應的選擇性、副反應之抑制的觀點，較佳為50℃以下，更佳為40℃以下，又更佳為20℃以下，其下限較佳為-5℃以上。 [0028] 又，反應系之pH係配合氧化劑之特性為佳，例如氧化劑使用次亞氯酸鈉的情形，反應系之pH為鹼性為佳，較佳為pH7~13，更佳為pH10~13。此外，反應時間較佳為1~240分鐘。 [0029] 藉由進行上述氧化處理，可得到羧基含量較佳為0.1mmol/g以上之含有羧基之纖維素纖維。 [0030] (純化步驟) 上述氧化處理步驟所得之含有羧基之纖維素纖維，含有作為觸媒使用之TEMPO等的N-氧基化合物或副產鹽( byproduct salt)。在該狀態可進行下步驟，但是進行純化也可得到高純度之含有羧基之纖維素纖維。純化方法可依據氧化反應中之溶劑的種類、生成物之氧化程度、純化之程度採用最佳的方法。例如良溶劑使用水，弱溶劑使用甲醇、乙醇、丙酮等之再沉澱、在己烷等與水相分離之溶劑中之TEMPO等之萃取、及藉由鹽之離子交換、透析等之純化等。 [0031] (微細化步驟) 其次，將上述純化步驟後所得之含有羧基之纖維素纖維進行微細化的步驟。微細化步驟中，將經過上述純化步驟之含有羧基之纖維素纖維分散於溶劑中，進行微細化處理為佳。藉由進行此微細化步驟，可得到平均長寬比在上述範圍的微細纖維素纖維。 [0032] 作為分散媒的溶劑，除了水外，可列舉甲醇、乙醇、丙醇等之碳數1~6，較佳為碳數1~3之醇；丙酮、甲基乙基酮、甲基異丁基酮等之碳數3~6之酮；直鏈或分枝狀之碳數1~6之飽和烴或不飽和烴；苯、甲苯等之芳香族烴；二氯甲烷、氯仿等之鹵化烴；碳數2~5之低級烷醚；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲基亞碸、琥珀酸與三乙二醇單甲醚之二酯等的極性溶劑等。此等可單獨使用或混合2種以上使用，但是從微細化處理之操作性的觀點，較佳為水、碳數1~6之醇、碳數3~6之酮、碳數2~5之低級烷醚、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲基亞碸、琥珀酸甲基三乙二醇二酯等的極性溶劑，從環境負擔降低的觀點，更佳為水。溶劑之使用量只要是可分散含有羧基之纖維素纖維的有效量即可，無特別限制，相對於含有羧基之纖維素纖維，較佳為可使用1~500質量倍，更佳為可使用2~200質量倍。 [0033] 微細化處理使用的裝置，適宜使用習知的分散機。例如可使用離解機、打漿機、低壓均質器、高壓均質機、研磨機、切割刀機、球磨機、噴射磨機、單軸押出機、2軸押出機、超音波攪拌機、家庭用果汁機混合機等。又，微細化處理中之反應物纖維的固體成分濃度，較佳為50質量%以下。 [0034] 又，本發明中，進行上述微細化處理之前，可再進行選自生化學處理、化學處理、及機械處理之至少1個的處理。具體而言，可列舉酸水解、熱水分解、氧化分解、粉碎、酵素處理、UV處理、電子束處理等的處理方法，但是藉由此等處理使纖維素纖維之短纖維化，可更有效地進行微細化處理，特別是成為平均長寬比包含於上述範圍內者。上述處理內容，可列舉例如將經過純化步驟之含有羧基之纖維素纖維以酸迴流的方法。酸之種類及其濃度無特別限定。可列舉例如添加濃鹽酸，將鹽酸濃度為0.1~10M之含有羧基之纖維素纖維的水分散液進行加熱的方法。 [0035] 所得之微細纖維素纖維的形態，必要時可形成調整固體成分濃度的懸浮液狀(目視為無色透明或不透明的液體)、或經乾燥處理的粉末狀(但是為微細纖維素纖維凝聚的粉末狀，而非纖維素粒子)。又，形成懸浮液狀的情形，也可使用水作為分散媒，也可使用水與其他之有機溶劑(例如、乙醇等之醇類)或界面活性劑、酸、鹼等之混合溶劑。 [0036] 如上述操作後，可得到纖維素構成單位之C6位的羥基經由醛基，選擇性氧化為羧基，上述羧基含量為0.1mmol/g以上，且平均纖維徑為0.1~200nm，平均纖維長為600nm以下，平均長寬比為1以上、200以下之經微細化的纖維素，較佳為具有30%以上之結晶化度的微細纖維素纖維。 [0037] [微細纖維素纖維之平均纖維徑、平均纖維長及平均長寬比] 如下述可測量含有羧基之微細纖維素纖維之平均纖維徑、平均纖維長及平均長寬比。在含有羧基之微細纖維素纖維中添加水，調製其濃度為0.0001質量%的分散液，將此分散液滴下至雲母(mica)上，經乾燥者作為觀察試料，使用原子間力顯微鏡(AFM、Nanoscope III Tapping mode AFM、Digital instrument公司製、探針為使用Nano sensors公司製Point Probe(NCH))，測量觀察試料中之微細纖維素纖維的纖維高度。此時，可確認微細纖維素纖維的的顯微鏡圖像中，由微細纖維素纖維取出5條以上，由彼等之纖維高度算出平均纖維徑。又，藉由纖維方向的距離算出平均纖維長。藉由平均纖維長/平均纖維徑算出平均長寬比。 [0038] 本發明中，含有羧基之微細纖維素纖維之平均纖維徑為0.1nm以上200nm以下，較佳為1nm以上100nm以下，更佳為2nm以上50nm以下，又更佳為2.5nm以上20nm以下。平均纖維徑未達0.1nm者製造困難，又，平均纖維徑超過200nm時，無法得到與印刷配線板之導體密著性良好的硬化物。 [0039] 含有羧基之微細纖維素纖維之平均纖維長為600nm以下，較佳為50nm以上600nm以下，更佳為100nm以上500nm以下，又更佳為150nm以上500nm以下。平均纖維長超過600nm者，作為組成物時之分散變得困難。 [0040] 含有羧基之微細纖維素纖維之平均長寬比為1以上200以下，較佳為5以上180以下，更佳為9以上170以下，又特佳為9以上未達100。平均長寬比未達1者製造困難，平均長寬比超過200時，無法得到與金屬導體之密著性良好的硬化物。平均長寬比為200以下時，金屬導體與硬化物之密著性良好，平均長寬比越小，金屬導體與硬化物之密著性越優異，可降低組成物的黏度。 [0041] 本發明係使用將上述羧基修飾，經疏水化的微細纖維素纖維。亦即，使用將具有羧基之微細纖維素纖維，使用、胺化合物或第四級銨化合物修飾的疏水化微細纖維素纖維。 以下說明此疏水化微細纖維素纖維。 含有羧基之微細纖維素纖維之羧基被修飾，經疏水而成的微細纖維素纖維係修飾基經由醯胺鍵或胺鹽之任一者或兩者而與纖維素主鏈鍵結。 [0042] 作為修飾基只要是經由醯胺鍵或胺鹽之中之任一者或兩者而鍵結的官能基即可，可列舉例如碳數1之烴基、或碳數2~30之飽和或不飽和之直鏈狀或分枝狀之烴基。具體例可列舉以下的烴基。碳數1之烴基：甲基。碳數2~30之飽和之直鏈狀烴基：乙基、丙基、丁基、戊基、己基、辛基、壬基、癸基、十二烷基、十八烷基、廿二烷基、二十八烷基(octacosanyl)。碳數2~30之不飽和之直鏈狀烴基：油烯基、十四醯基、十六醯基、十八碳二烯醇基、十八碳三烯醇基、二十烷基。碳數2~30之飽和之分枝狀烴基：異丙基、異丁基、sec-丁基、tert-丁基、異戊基、t-戊基、異己基、2-己基、二甲基丁基、乙基丁基。 [0043] 飽和或不飽和之直鏈狀或分枝狀烴基的碳數，可依與硬化性樹脂之組合，任意選擇，較佳為1以上、特別是3以上、尤其是10以上，又，較佳為30以下、特別是20以下、尤其是18以下。例如較佳為1以上30以下，更佳為3以上20以下，又更佳為10以上18以下。藉由碳數在上述範圍，微細纖維素纖維與硬化性樹脂成為均勻的混合狀態，作為低線熱膨脹係數等樹脂組成物可得到良好的物性。 [0044] 具有上述飽和或不飽和之直鏈狀或分枝狀烴基之胺，具體而言，一級胺可列舉例如甲基胺、乙基胺、丙基胺、異丙基胺、丁基胺、己基胺、辛基胺、癸基胺、十二烷基胺、十八烷基胺、油烯基胺等的單烷基胺。第二級胺可列舉例如二甲基胺、二乙基胺、二丁基胺、二(十八烷基)胺等的二烷基胺。 [0045] 又，具有芳香族烴基之胺，只要是總碳數為6~20即可，可為一級胺、二級胺之任一，但是從與羧基之反應性的觀點，較佳為一級胺。又，胺中之芳香族烴基數，只要是總碳數成為6~20時，可為1個、2個之任一，較佳為1個。 [0046] 具有芳香族烴基之胺，可列舉具有芳基之胺、具有芳烷基之胺，從與樹脂之相溶性的觀點，較佳為具有芳基之胺。 [0047] 芳基具體而言，可列舉苯基、萘基、蒽基、菲基、聯苯基、三苯基，此等可單獨或2種以上鍵結。其中，從與樹脂之相溶性的觀點，較佳為苯基、萘基、聯苯基，更佳為苯基。 [0048] 芳烷基具體而言，可列舉苄基、苯乙基、苯基丙基、苯基戊基、苯基己基、苯基庚基，此等可單獨或2種以上鍵結。其中，從與樹脂之相溶性的觀點，較佳為苄基、苯乙基、苯基丙基、苯基戊基、苯基己基，更佳為苄基、苯乙基、苯基丙基、苯基戊基。 [0049] 又，上述芳基、芳烷基可具有取代基，其取代基可列舉例如甲基、乙基、丙基、異丙基、丁基、異丁基、sec-丁基、tert-丁基、戊基、異戊基、己基等之碳數1~6之烷基；甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、sec-丁氧基、tert-丁氧基、戊氧基、異戊氧基、己氧基等之碳數1~6之烷氧基；甲氧基羰基、乙氧基羰基、丙氧基羰基、異丙氧基羰基、丁氧基羰基、異丁氧基羰基、sec-丁氧基羰基、第三丁氧基羰基、戊氧基羰基、異戊氧基羰基等之碳數1~6之烷氧基羰基；氟原子、氯原子、溴原子、碘原子等之鹵素原子；碳數1~6之醯基、芳烷基、芳烷基氧基。 [0050] 具有上述芳香族烴基之胺，具體而言，具有芳基之胺，可列舉苯胺、甲苯胺、4-聯苯胺、二苯基胺、2-胺基萘、p-聯三苯胺、2-胺基蒽、2-胺基蒽醌。其中，從與樹脂之相溶性的觀點，較佳為苯胺、甲苯胺、4-聯苯胺、二苯基胺、2-胺基萘，更佳為苯胺。具有芳烷基之胺，可列舉苄基胺、苯乙基胺、3-苯基丙基胺、5-苯基戊基胺、6-苯基己基胺、7-苯基庚基胺、8-苯基辛基胺。其中，從同樣的觀點，較佳為苄基胺、苯乙基胺、3-苯基丙基胺、5-苯基戊基胺、6-苯基己基胺、7-苯基庚基胺，更佳為苄基胺、苯乙基胺、3-苯基丙基胺、5-苯基戊基胺、6-苯基己基胺，又更佳為苄基胺、苯乙基胺、3-苯基丙基胺、5-苯基戊基胺。本發明使用之具有芳香族烴基之胺，可依據習知的方法調製，也可為市售品。 [0051] 又，其他使所期望量之環氧乙烷、環氧丙烷加成於丙二醇烷醚後，將羥基末端進了行胺基化的胺、羥基乙基、羥基丙基等具有親水基的胺或具有乙二醇、丙二醇等之聚醚鏈或、丙交酯(lactide)、己內酯等之聚酯鏈之聚醚胺或聚酯胺、具有環戊基、環己基等之脂環式烴之胺也適合作為本發明使用之疏水化微細纖維素纖維中，經由醯胺鍵或胺鹽之任一者或兩者鍵結的化合物使用。 [0052] 作為修飾疏水化微細纖維素纖維之羧基，形成胺鹽用的第四級銨化合物，可列舉氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丁基銨、氫氧四丙基銨、四乙基銨氯化物、四丁基銨氯化物、月桂基三甲基銨氯化物、二月桂基二甲基銨氯化物、十八烷基三甲基銨氯化物、二(十八烷基)二甲基銨氯化物、十六烷基三甲基銨氯化物、烷基苄基二甲基銨氯化物。其中，從對羧基之修飾容易度的觀點，較佳為氫氧化四甲基銨、氫氧化四乙基銨、氫氧四丙基銨、氫氧化四丁基銨。 [0053] 本發明之硬化性樹脂組成物中之疏水化微細纖維素纖維的添加量係相對於硬化性樹脂之全量(固體成分基準)100質量份，較佳為0.1質量份以上30質量份以下，更佳為1質量份以上20質量份以下，又更佳為2質量份以上10質量份以下。將添加量設為0.1質量份以上時，熱膨脹性變低，設為30質量份以下時，成無低熱膨脹性與金屬導體之密著性平衡優異者。 [0054] (微細纖維素纖維之羧基之修飾方法) 本發明中之微細纖維素纖維之羧基的修飾方法，可列舉以下者。第1方法，可列舉使含有羧基之微細纖維素纖維與具有修飾基之胺化合物在溶劑中混合成為鹽的方法。上述胺化合物之使用量可依據疏水化微細纖維素纖維中之所期望之胺鹽的鍵結量來決定，但是相對於含有羧基之微細纖維素纖維所含有之羧基1mol，胺基較佳為0.1mol以上，更佳為0.5mol以上，又更佳為0.7mol以上，再更佳為1mol以上，從製品純度的觀點，較佳為使用50mol以下，更佳為20mol以下，又更佳為10mol以下的量。又，可將上述範圍所含有之量的胺一次供給鹽形成步驟，也可分次供給鹽形成步驟。 [0055] 溶劑選擇溶解使用之胺化合物的溶劑為佳，可列舉例如乙醇、異丙醇(IPA)、N,N-二甲基甲醯胺(DMF)、二甲基亞碸(DMSO)、N,N-二甲基乙醯胺、四氫呋喃(THF)、琥珀酸與三乙二醇單甲醚之二酯、丙酮、甲基乙基酮(MEK)、乙腈、二氯甲烷、氯仿、甲苯、乙酸等，此等可單獨使用1種或組合2種以上使用。此等之極性溶劑之中，較佳為琥珀酸與三乙二醇單甲醚之二酯、乙醇、DMF。 [0056] 混合時之溫度，較佳為0℃以上，更佳為5℃以上，又更佳為10℃以上。又，從疏水化微細纖維素纖維之著色的觀點，較佳為50℃以下，更佳為40℃以下，又更佳為30℃以下。混合時間可配合使用之胺及溶劑的種類適宜設定，但是較佳為0.01小時以上，更佳為0.1小時以上，又更佳為1小時以上，較佳為48小時以下，更佳為24小時以下，又更佳為12小時以下。 [0057] 上述鹽之形成後，為了除去鹽形成未使用的胺化合物，可適宜進行後處理。此後處理的方法，例如可使用過濾、離心分離、透析等。 [0058] 第2方法，可列舉使具有羧基之微細纖維素纖維與具有修飾基之胺化合物在溶劑中進行醯胺化反應的方法。具有上述修飾基之胺化合物的使用量，可藉由疏水化微細纖維素纖維中之所期望的鍵結量來決定，但是從反應性的觀點，相對於含有羧基之微細纖維素纖維所含有之羧基1mol，胺基較佳為0.1mol以上，更佳為0.5mol以上，又更佳為0.7mol以上，再更佳為1mol以上，從製品純度的觀點，較佳為使用50mol以下，更佳為20mol以下，又更佳為10mol以下的量。又，可將上述範圍所含有之量的胺一次供給反應，也可分次供給反應。 [0059] 上述含有羧基之微細纖維素纖維與具有修飾基之胺化合物之反應中，可使用習知的縮合劑。縮合劑無特別限定，可列舉合成化學系列肽合成(丸善公司)P116記載、或Tetrahedron，57,1551(2001)記載的縮合劑等，可列舉例如4-(4,6-二甲氧基-1,3,5-三嗪-2-基)-4-甲基嗎啉氯化物(以下有時僅稱為「DMT-MM」)等。 [0060] 上述縮合反應選擇溶解使用之胺化合物的溶劑為佳。上述縮合反應中之反應時間及反應溫度，可配合使用之胺及溶劑的種類等適宜選擇，從反應率及生產性的觀點，較佳為1~24小時，更佳為10~20小時。又，反應溫度從反應性的觀點，較佳為0℃以上，更佳為5℃以上，又更佳為10℃以上。又，從疏水化微細纖維素纖維之著色的觀點，較佳為200℃以下，更佳為80℃以下，又更佳為30℃以下。 [0061] 上述混合後及反應後，為了除去未反應之胺化合物或縮合劑等，可適宜進行後處理。此後處理的方法，例如可使用過濾、離心分離、透析等。 [0062] 第3方法，可列舉使具有羧基之微細纖維素纖維與具有修飾基之第四級銨化合物在溶劑中混合形成鹽的方法。上述第四級銨化合物之使用量係藉由疏水化微細纖維素纖維中之所期望的鍵結量來決定，但是相對於含有羧基之微細纖維素纖維所含有的羧基1mol，第四級銨陽離子較佳為0.1mol以上，更佳為0.5mol以上，又更佳為0.7mol以上，再更佳為1mol以上，從製品純度的觀點，較佳為使用50mol以下，更佳為20mol以下，又更佳為10mol以下的量。又，可將上述範圍所含有之量的第四級銨化合物一次供給鹽之形成步驟，也可分次供給鹽之形成步驟。 [0063] 溶劑可同樣使用與上述胺混合時使用的溶劑，此等外，也可使用水。此等可單獨使用或組合2種以上使用，其中，較佳為水、琥珀酸與三乙二醇單甲醚之二酯、乙醇、DMF。 混合時之溫度或時間及鹽形成後之後處理，可參照與上述胺化合物混合的情形，適宜設定。 [0064] [硬化性樹脂] 本發明之硬化性樹脂組成物為熱硬化性樹脂組成物、光硬化性樹脂組成物或光硬化性熱硬化性樹脂組成物。 [0065] (熱硬化性樹脂組成物) 本發明之熱硬化性樹脂組成物，較佳為包含熱硬化性樹脂、無機填料及硬化觸媒。熱硬化性樹脂組成物所使用之熱硬化性樹脂，使用具有藉由熱可硬化反應之官能基的樹脂為佳，特別是使用分子中具有1個以上之環狀(硫)醚基的化合物為佳。 [0066] 具有環狀醚基的化合物，可列舉例如雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚E型環氧樹脂、雙酚M型環氧樹脂、雙酚P型環氧樹脂、雙酚Z型環氧樹脂等之雙酚型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆環氧樹脂等之酚醛清漆型環氧樹脂、聯苯型環氧樹脂、聯苯基芳烷基型環氧樹脂、芳基伸烷基(alkylene)型環氧樹脂、四羥苯基乙烷型環氧樹脂、萘型環氧樹脂、蒽型環氧樹脂、苯氧基型環氧樹脂、二環戊二烯型環氧樹脂、降莰烯型環氧樹脂、金剛烷型環氧樹脂、茀型環氧樹脂、環氧丙基甲基丙烯酸酯共聚合系環氧樹脂、環己基馬來醯亞胺與環氧丙基甲基丙烯酸酯之聚合環氧樹脂、環氧基改質之聚丁二烯橡膠衍生物、CTBN改質環氧樹脂、三羥甲基丙烷聚環氧丙醚、苯基-1,3-二環氧丙醚、聯苯基-4,4’-二環氧丙醚、1,6-己二醇二環氧丙醚、乙二醇或丙二醇之二環氧丙醚、山梨醣醇聚環氧丙醚、三(2,3-環氧基丙基)異三聚氰酸酯、三環氧丙基三(2-羥基乙基)異三聚氰酸酯等之環氧樹脂；苯酚酚醛清漆樹脂、甲酚酚醛清漆(cresol novolac)樹脂、雙酚A酚醛清漆樹脂等之酚醛清漆型酚醛樹脂、未改質之甲階酚醛(resol phenol)樹脂、以桐油、亞麻子油、核桃油(Walnut Oil)油等進行改質的油改質甲階酚醛樹脂等之水溶性Resol型酚醛樹脂等之酚醛樹脂；苯氧基樹脂；脲(尿素)樹脂；三聚氰胺樹脂等之含有三嗪環之樹脂；不飽和聚酯樹脂、二烯丙基苯二甲酸酯樹脂、矽氧樹脂、具有苯并噁嗪環之樹脂、降莰烯系樹脂、氰酸酯樹脂、異氰酸酯樹脂、胺基甲酸酯樹脂、苯并環丁烯樹脂、馬來醯亞胺樹脂、雙馬來醯亞胺三嗪樹脂、聚偶氮甲鹼樹脂、熱硬化性聚醯亞胺、氰酸酯酯樹脂、活性酯樹脂等。 [0067] 熱硬化性樹脂包含環氧樹脂及酚樹脂為佳。藉由包含環氧樹脂及酚樹脂，可提高耐熱性、剝離強度及絕緣信賴性等。環氧樹脂之含量係相對於全熱硬化性樹脂100質量份，例如為1質量份以上90質量份以下，較佳為10質量份以上85質量份以下，更佳為20質量份以上80質量份以下。酚樹脂之含量係相對於全熱硬化性樹脂，例如為1質量份以上70質量份以下，較佳為5質量份以上60質量份以下，更佳為10質量份以上50質量份以下。又，熱硬化性樹脂使用活性酯樹脂的情形時，使用二甲基胺基吡啶時，可提高硬化性。 [0068] 本案發明之硬化性樹脂組成物，藉由併用微細纖維素纖維與無機填料，硬化物之線膨脹係數減低效果優異。無機填料可列舉硫酸鋇、鈦酸鋇、無定形二氧化矽、結晶性二氧化矽、熔融二氧化矽、球狀二氧化矽、滑石、黏土、碳酸鎂、碳酸鈣、氧化鋁、氫氧化鋁、氮化矽、氮化鋁等。此等之無機填料之中，比重低，且可以高比例調配於組成物中，從低熱膨脹性優異的觀點，較佳為二氧化矽，其中更佳為球狀二氧化矽。本案發明之硬化性樹脂組成物，較佳為微細纖維素纖維與二氧化矽之組合，此時，對於硬化物之線膨脹係數之減低效果更優異，與金屬導體之密著性更佳。無機填料之平均粒徑，較佳為3μm以下，更佳為1μm以下。又，無機填料之平均粒徑，可藉由雷射繞射式粒徑分布測量裝置求得。無機填料之調配量係相對於組成物之固體成分，例如為25~90質量%，較佳為30~90質量%，更佳為35~85質量%。藉由將無機填料之調配量設為上述範圍內，可良好確保硬化後之硬化物的塗膜性能。 [0069] 硬化觸媒在硬化性樹脂之中，主要是使熱硬化性樹脂硬化者，可列舉例如咪唑、2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、4-苯基咪唑、1-氰基乙基-2-苯基咪唑、1-(2-氰基乙基)-2-乙基-4-甲基咪唑等之咪唑衍生物；雙氰胺、苄基二甲基胺、4-(二甲基胺基)-N,N-二甲基苄基胺、4-甲氧基-N,N-二甲基苄基胺、4-甲基-N,N-二甲基苄基胺等之胺化合物、己二酸二醯肼、癸二酸二醯肼等之肼化合物；三苯基膦等之磷化合物、二甲基胺基吡啶等。又，市售品可列舉例如2MZ-A、2MZ-OK、2PHZ、2P4BHZ、2P4MHZ(四國化成工業(股)製)、U-CAT3503N、U-CAT3502T、DBU、DBN、U-CATSA102、U-CAT5002(san-apro(股)製)等，可單獨使用或混合2種以上使用。又，同樣也可使用胍胺、乙醯胍胺、苯胍胺、三聚氰胺、2,4-二胺基-6-甲基丙烯醯氧基乙基-S-三嗪、2-乙烯基-2,4-二胺基-S-三嗪、2-乙烯基-4,6-二胺基-S-三嗪･異三聚氰酸加成物、2,4-二胺基-6-甲基丙烯醯氧基乙基-S-三嗪･異三聚氰酸加成物等之S-三嗪衍生物。 [0070] 硬化觸媒較佳為鹼性觸媒。特佳為咪唑類，藉由使用咪唑類，可兼具組成物之硬化性與安定性，可提高耐熱性。硬化觸媒之含量係相對於熱硬化性樹脂100質量份，例如為0.01質量份以上20質量份以下，較佳為0.05質量份以上15質量份以下，更佳為0.1質量份以上15質量份以下。 [0071] 本發明之熱硬化性樹脂組成物中，除了疏水化微細纖維素纖維、熱硬化性樹脂、無機填料及硬化觸媒外，依其用途，可適宜調配慣用之其他的調配成分。 [0072] 慣用之其他的調配成分，可列舉例如著色劑、有機溶劑、分散劑、消泡劑･平坦劑、觸變劑、偶合劑、難燃劑等。 [0073] 著色劑作為、著色顏料或染料等，可使用色彩索引(color index)表示之習知慣用者。可列舉例如Pigment Blue 15、15：1、15：2、15：3、15：4、15：6、16、60、Solvent Blue 35、63、68、70、83、87、94、97、122、136、67、70、Pigment Green 7、36、3、5、20、28、Solvent Yellow 163、Pigment Yellow 24、108、193、147、199、202、110、109、139、179、185、93、94、95、128、155、166、180、120、151、154、156、175、181、1、2、3、4、5、6、9、10、12、61、62、62：1、65、73、74、75、97、100、104、105、111、116、167、168、169、182、183、12、13、14、16、17、55、63、81、83、87、126、127、152、170、172、174、176、188、198、Pigment Orange 1、5、13、14、16、17、24、34、36、38、40、43、46、49、51、61、63、64、71、73、Pigment Red1、2、3、4、5、6、8、9、12、14、15、16、17、21、22、23、31、32、112、114、146、147、151、170、184、187、188、193、210、245、253、258、266、267、268、269、37、38、41、48：1、48：2、48：3、48：4、49：1、49：2、50：1、52：1、52：2、53：1、53：2、57：1、58：4、63：1、63：2、64：1、68、171、175、176、185、208、123、149、166、178、179、190、194、224、254、255、264、270、272、220、144、166、214、220、221、242、168、177、216、122、202、206、207、209、Solvent Red 135、179、149、150、52、207、Pigment Violet 19、23、29、32、36、38、42、Solvent Violet 13、36、Pigment Brown 23、25、Pigment Black 1、7等。 著色劑之含量在全組成物中，例如為0.01質量%以上3質量%以下，較佳為0.05質量%以上1質量%以下，更佳為0.1質量%以上0.5質量%以下。又，使用氧化鈦等，得到白色硬化膜的情形時，在全組成物中，例如為1質量%以上65質量%以下，較佳為3質量%以上60質量%以下，更佳為5質量%以上50質量%以下。 [0074] 有機溶劑可列舉甲基乙基酮、環己酮等之酮類；甲苯、二甲苯、四甲基苯等之芳香族烴類；甲基溶纖劑、乙基溶纖劑、丁基溶纖劑、甲基卡必醇、丁基卡必醇、丙二醇單甲醚、二乙二醇單***、二丙二醇單***、三乙二醇單***等之乙二醇醚類；乙酸乙酯、乙酸丁酯、溶纖劑乙酸酯、二乙二醇單***乙酸酯及上述乙二醇醚類之酯化物等的酯類；乙醇、丙醇、乙二醇、丙二醇等之醇類；二甲基甲醯胺、二甲基乙醯胺等之醯胺類、辛烷、癸烷等之脂肪族烴類；石油醚、石油腦、氫化石油腦、溶劑石油腦等之石油系溶劑等。 [0075] 分散劑可使用聚羧酸系、萘磺酸福馬林縮合系、聚乙二醇、聚羧酸部分烷基酯系、聚醚系、聚伸烷基聚胺(polyalkylene polyamine)系等之高分子型分散劑、烷基磺酸系、四級銨系、高級醇環氧烷系、多元醇酯系、烷基多胺系等之低分子型分散劑等。 [0076] 消泡劑･平坦劑，可使用聚矽氧、改質聚矽氧、礦物油、植物油、脂肪族醇、脂肪酸、金屬皂、脂肪酸醯胺、聚氧烷二醇、聚氧伸烷基烷醚、聚氧伸烷基脂肪酸酯等的化合物等。 [0077] 觸變劑可使用微粒子二氧化矽、矽凝膠、不定形無機粒子、聚醯胺系添加劑、改質脲系添加劑、蠟系添加劑等。 [0078] 偶合劑可使用作為烷氧基之甲氧基、乙氧基、乙醯基等，作為反應性官能基之乙烯基、甲基丙烯醯基、丙烯醯基、環氧基、環狀環氧基、巰基、胺基、二胺基、酸酐、脲基、硫基(sulfide)、異氰酸酯等之矽烷偶合劑，例如乙烯基乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基･三(β-甲氧基乙氧基)矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷等之乙烯基系矽烷化合物、γ-胺基丙基三甲氧基矽烷、N-β-(胺基乙基)γ-胺基丙基三甲氧基矽烷、N-β-(胺基乙基)γ-胺基丙基甲基二甲氧基矽烷、γ-脲基丙基三乙氧基矽烷等之胺基系矽烷化合物、γ-環氧丙氧基丙基三甲氧基矽烷、β-(3,4-環氧基環己基)乙基三甲氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷等之環氧系矽烷化合物、γ-巰基丙基三甲氧基矽烷等之巰基系矽烷化合物、N-苯基-γ-胺基丙基三甲氧基矽烷等之苯基胺基系矽烷化合物等之矽烷偶合劑、異丙基三異硬脂醯化鈦酸酯、四辛基雙(二(十三烷基)亞磷酸酯)鈦酸酯、雙(二辛基焦磷酸酯)氧基乙酸酯鈦酸酯、異丙基三十二烷基苯磺醯基鈦酸酯、異丙基三(二辛基焦磷酸酯)鈦酸酯、四異丙基雙(二辛基亞磷酸酯)鈦酸酯、四(1,1-二烯丙氧基甲基-1-丁基)雙-(二-十三烷基)亞磷酸酯鈦酸酯、雙(二辛基焦磷酸酯)伸乙基鈦酸酯、異丙基三辛醯基鈦酸酯、異丙基二甲基丙烯醯基異硬脂醯基鈦酸酯、異丙基硬脂醯基二丙醯基鈦酸酯、異丙基三(二辛基磷酸酯)鈦酸酯、異丙基三枯基苯基鈦酸酯、二枯基苯氧基乙酸酯鈦酸酯、二異硬脂醯基乙烯鈦酸酯等之鈦酸酯系偶合劑、含有乙烯性不飽和鋯酸鹽的化合物、含有新烷氧基鋯酸鹽的化合物、新烷氧基三新癸醯基鋯酸鹽、新烷氧基三(十二烷基)苯磺醯基鋯酸鹽、新烷氧基三(二辛基)磷酸酯鋯酸鹽、新烷氧基三(二辛基)焦磷酸酯鋯酸鹽、新烷氧基三(乙烯二胺基)乙基鋯酸鹽、新烷氧基三(m-胺基)苯基鋯酸鹽、四(2,2-二烯丙氧基甲基)丁基，二(二-十三烷基)亞磷酸酯鋯酸鹽、新戊基(二烯丙基)氧基，三新癸醯基鋯酸鹽、新戊基(二烯丙基)氧基，三(十二烷基)苯-磺醯基鋯酸鹽、新戊基(二烯丙基)氧基，三(二辛基)磷酸酯鋯酸鹽、新戊基(二烯丙基)氧基，三(二辛基)焦磷酸酯鋯酸鹽、新戊基(二烯丙基)氧基，三(N-乙烯二胺基)乙基鋯酸鹽、新戊基(二烯丙基)氧基，三(m-胺基)苯基鋯酸鹽、新戊基(二烯丙基)氧基，三甲基丙烯醯基鋯酸鹽、新戊基(二烯丙基)氧基，三丙烯醯基鋯酸鹽、二新戊基(二烯丙基)氧基，二對胺基苯甲醯基鋯酸鹽、二新戊基(二烯丙基)氧基，二(3-巰基)丙酸酯鋯酸鹽、鋯(IV)2,2-雙(2-丙氧基甲基)丁氧基，環二[2,2-(雙2-丙氧基甲基)丁氧基]焦磷酸酯-O,O等之鋯酸鹽系偶合劑、二異丁基(油基)乙醯乙醯基鋁酸酯、烷基乙醯乙酸酯二異丙醇鋁等之鋁酸酯系偶合劑等。 [0079] 難燃劑可使用氫氧化鋁、氫氧化鎂等之水和金屬系、紅磷(red phosphorus)、磷酸銨、碳酸銨、硼酸鋅、錫酸鋅、鉬化合物系、溴化合物系、氯化合物系、磷酸酯、含磷多元醇、含磷胺、三聚氰胺三聚氰酸酯、三聚氰胺化合物、三嗪化合物、胍化合物、矽聚合物等。 [0080] (光硬化性樹脂組成物) 本發明之光硬化性樹脂組成物，包含光硬化性樹脂、無機填料、光聚合起始劑及著色劑等為佳。光硬化性樹脂使用具有藉由活性能量線照射可硬化反應之官能基的樹脂為佳，可為自由基聚合性或陽離子聚合性。可列舉例如分子中具有1個以上之乙烯性不飽和鍵的化合物、脂環環氧化合物、氧雜環丁烷化合物，較佳為使用分子中具有1個以上之乙烯性不飽和鍵的化合物。 [0081] 具有乙烯性不飽和鍵之化合物，可使用習知慣用的光聚合性寡聚物、及光聚合性乙烯基單體等。上述光聚合性寡聚物，可列舉不飽和聚酯系寡聚物、(甲基)丙烯酸酯系寡聚物等。(甲基)丙烯酸酯系寡聚物，可列舉苯酚酚醛清漆環氧(甲基)丙烯酸酯、甲酚酚醛清漆環氧(甲基)丙烯酸酯、雙酚型環氧(甲基)丙烯酸酯等之環氧(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯、環氧基胺基甲酸酯(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯、聚丁二烯改質(甲基)丙烯酸酯等。又，本說明書中，(甲基)丙烯酸酯係指丙烯酸酯、甲基丙烯酸酯及彼等之混合物統稱的用語，其他類似的敘述也同樣。 [0082] 上述光聚合性乙烯基單體，有習知慣用者，可列舉例如苯乙烯、氯苯乙烯、α-甲基苯乙烯等之苯乙烯衍生物；乙酸乙烯酯、丁酸乙烯基或苯甲酸乙烯基等之乙烯基酯類；乙烯基異丁醚、乙烯基-n-丁醚、乙烯基-t-丁醚、乙烯基-n-戊醚、乙烯基異戊醚、乙烯基-n-十八烷醚、乙烯基環己醚、乙二醇單丁基乙烯醚、三乙二醇單甲基乙烯醚等之乙烯醚類；丙烯醯胺、甲基丙烯醯胺、N-羥基甲基丙烯醯胺、N-羥基甲基甲基丙烯醯胺、N-甲氧基甲基丙烯醯胺、N-乙氧基甲基丙烯醯胺、N-丁氧基甲基丙烯醯胺等之(甲基)丙烯醯胺類；三烯丙基異三聚氰酸酯、鄰苯二甲酸二烯丙基、間苯二甲酸二烯丙基等之烯丙基化合物；2-乙基己基(甲基)丙烯酸酯、月桂基(甲基)丙烯酸酯、四氫糠基(甲基)丙烯酸酯、異莰基(甲基)丙烯酸酯、苯基(甲基)丙烯酸酯、苯氧基乙基(甲基)丙烯酸酯等之(甲基)丙烯酸之酯類；羥基乙基(甲基)丙烯酸酯、羥基丙基(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯等之羥基烷基(甲基)丙烯酸酯類；甲氧基乙基(甲基)丙烯酸酯、乙氧基乙基(甲基)丙烯酸酯等之烷氧基伸烷二醇單(甲基)丙烯酸酯類；乙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯類、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等之伸烷基多元醇聚(甲基)丙烯酸酯；二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、乙氧基化三羥甲基丙烷三丙烯酸酯、丙氧基化三羥甲基丙烷三(甲基)丙烯酸酯等之聚氧烷二醇聚(甲基)丙烯酸酯類；羥基新戊酸(pivalic acid)新戊二醇酯二(甲基)丙烯酸酯等之聚(甲基)丙烯酸酯類；三[(甲基)丙烯醯氧基乙基]異三聚氰酸酯等之異三聚氰酸酯型聚(甲基)丙烯酸酯類等。 [0083] 脂環環氧化合物，可列舉3,4,3’,4’-二環氧基雙環己基、2,2-雙(3,4-環氧基環己基)丙烷、2,2-雙(3,4-環氧基環己基)-1,3-六氟丙烷、雙(3,4-環氧基環己基)甲烷、1-[1,1-雙(3,4-環氧基環己基)]乙基苯、雙(3,4-環氧基環己基)己二酸酯、3,4-環氧基環己基甲基(3,4-環氧基)環己烷羧酸酯、(3,4-環氧基-6-甲基環己基)甲基-3’,4’-環氧基-6-甲基環己烷羧酸酯、乙烯-1,2-雙(3,4-環氧基環己烷羧酸)酯、環己烯氧化物、3,4-環氧基環己基甲基醇、3,4-環氧基環己基乙基三甲氧基矽烷等之具有環氧基的脂環環氧化合物等。市售品可列舉例如DAICEL化學工業公司製之CELLOXID 2000、CELLOXID 2021、CELLOXID 3000、EHPE3150；三井化學公司製之Epomic VG-3101；油化Shell epoxy公司製之E-1031S；三菱氣體化學公司製之TETRAD-X、TETRAD-C；日本曹達公司製之EPB-13、EPB-27等。 [0084] 氧雜環丁烷化合物，可列舉雙[(3-甲基-3-氧環丁基甲氧基)甲基]醚、雙[(3-乙基-3-氧環丁基甲氧基)甲基]醚、1,4-雙[(3-甲基-3-氧環丁基甲氧基)甲基]苯、1,4-雙[(3-乙基-3-氧環丁基甲氧基)甲基]苯、(3-甲基-3-氧環丁基)甲基丙烯酸酯、(3-乙基-3-氧環丁基)甲基丙烯酸酯、(3-甲基-3-氧環丁基)甲基甲基丙烯酸酯、(3-乙基-3-氧環丁基)甲基甲基丙烯酸酯或彼等之寡聚物或共聚物等之多官能氧雜環丁烷類外，可列舉氧雜環丁烷醇(oxetane alcohol)與酚醛清漆樹脂、聚(p-羥基苯乙烯)、cardo型雙酚類、杯芳烴類、杯間苯二酚芳烴類、或倍半矽氧烷等之具有羥基之樹脂之醚化物、具有氧雜環丁烷環之不飽和單體與烷基(甲基)丙烯酸酯之共聚物等之氧雜環丁烷化合物。市售品可列舉宇部興產公司製之ETERNACOLLOXBP、OXMA、OXBP、EHO、亞二甲苯基雙氧雜環丁烷、東亞合成公司製之Aron Oxetane OXT-101、OXT-201、OXT-211、OXT-221、OXT-212、OXT-610、PNOX-1009等。 [0085] 光聚合起始劑係在硬化性樹脂之中，使光硬化性樹脂硬化者，可為光自由基聚合起始劑，也可為光陽離子聚合起始劑。光自由基聚合起始劑，可列舉例如苯偶姻、苯偶姻甲醚、苯偶姻***、苯偶姻異丙醚等之苯偶姻與苯偶姻烷醚類；苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、1,1-二氯苯乙酮等之苯乙酮類；2-甲基-1-[4-(甲基硫基)苯基]-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮-1,2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮等之胺基烷基苯酮類；2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、1-氯蒽醌等之蒽醌類；2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2-氯噻噸酮、2,4-二異丙基噻噸酮等之噻噸酮類；苯乙酮二甲基縮醛、苄基二甲基縮醛等之縮醛類；二苯甲酮等之二苯甲酮類；或呫噸酮類；(2,6-二甲氧基苯甲醯基)-2,4,4-戊基氧化磷、雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物、2,4,6-三甲基苯甲醯基二苯基膦氧化物、乙基-2,4,6-三甲基苯甲醯基苯基膦酸酯(phosphonate)等之膦氧化物類；各種過氧化物類、二茂鈦系起始劑等。此等可與如N,N-二甲基胺基苯甲酸乙酯、N,N-二甲基胺基苯甲酸異戊酯、戊基-4-二甲基胺基苯甲酸酯、三乙基胺、三乙醇胺等之三級胺類的光增感劑等併用。 [0086] 光陽離子聚合起始劑，可列舉例如重氮鎓鹽、錪鹽、溴鎓鹽、氯鎓鹽、鋶鹽、硒鎓鹽、嘧啶鎓鹽、硫胺嘧啶鎓鹽、吡啶鎓鹽等之鎓鹽；三(三鹵甲基)-s-三嗪及其衍生物等之鹵化化合物；磺酸之2-硝基苄基酯；亞胺基磺酸鹽；1-側氧-2-重氮萘醌-4-磺酸鹽衍生物；N-羥基醯亞胺=磺酸鹽；三(甲烷磺醯氧基)苯衍生物；雙磺醯基重氮甲烷類；磺醯基羰基烷烴類；磺醯基羰基重氮甲烷類；二碸化合物等。此等之光聚合起始劑可單獨使用或組合2種以上使用。 [0087] 光聚合起始劑之調配量係以固體成分換算，相對於光硬化性樹脂100質量份，例如為0.05~20質量份，較佳為0.1~15質量份，更佳為0.5~10質量份。藉由以此範圍調配光聚合起始劑，銅上之光硬化性變得充分，塗膜之硬化性變得良好，提高耐藥品性等的塗膜特性，也提高深部硬化性。 [0088] 無機填料可使用與上述熱硬化性樹脂組成物中使用者同樣者，且調配量也可同樣。 [0089] 著色劑可使用與上述熱硬化性樹脂組成物使用者同樣者。藉由含有著色劑，在光硬化性樹脂組成物中，即使照射過剩的積算光量，也可防止密著性降低。又，也可提高塗膜之辨識性。 [0090] 本發明之光硬化性樹脂組成物中，除了疏水化微細纖維素纖維、光硬化性樹脂、無機填料、光聚合起始劑及著色劑外，配合其用途，可適宜調配慣用之其他的調配成分。慣用之其他的調配成分，可列舉例如有機溶劑、分散劑、消泡劑･平坦劑、觸變劑、偶合劑、難燃劑等。此等有機溶劑、分散劑、消泡劑･平坦劑、觸變劑、偶合劑、難燃劑，可使用與熱硬化性樹脂組成物同樣者。 [0091] (光硬化性熱硬化性樹脂組成物) 本發明之光硬化性熱硬化性樹脂組成物為包含光硬化性樹脂及熱硬化性樹脂者，特別是將本發明之光硬化性熱硬化性樹脂組成物作為使用鹼水溶液之顯影型的情形時，含有作為硬化性樹脂之含羧基之樹脂為佳。含羧基之樹脂可使用具有1個以上之感光性之不飽和雙鍵之感光性的含羧基之樹脂、及不具有感光性之不飽和雙鍵之含羧基之樹脂之任一，不限定於特定者。特別是適合使用以下所列舉的樹脂。 [0092] (1)藉由不飽和羧酸與具有不飽和雙鍵之化合物之共聚合所得的含羧基之樹脂、及將其改質調整分子量或酸價的含羧基之樹脂。 (2)使含羧基之(甲基)丙烯酸系共聚樹脂與1分子中具有環氧乙烷環與乙烯性不飽和基的化合物反應所得之含羧基之感光性樹脂。 (3)使1分子中分別具有1個環氧基與不飽和雙鍵的化合物與具有不飽和雙鍵的化合物之共聚物，與不飽和單羧酸反應，藉此反應生成之第2級羥基與飽和或不飽和多元酸酐反應所得之含羧基之感光性樹脂。 (4)含有羥基之聚合物與飽和或不飽和之多元酸酐反應後，藉此反應生成之羧酸與1分子中分別具有1個環氧基與不飽和雙鍵的化合物反應所得之含羥基及羧基的感光性樹脂。 (5)使多官能環氧化合物與不飽和單羧酸反應，藉此反應生成之第2級羥基，以一部分或全部與多元酸酐反應所得之含羧基的感光性樹脂。 (6)使多官能環氧化合物與、1分子中具有2個以上之羥基與環氧基反應之羥基以外之1個反應基的化合物與、含有不飽和基之單羧酸反應所得之反應生成物，與多元酸酐反應所得之含羧基之感光性樹脂。 (7)使具有酚性羥基之樹脂與環氧烷烴(alkylene oxide)之反應生成物，與含不飽和基之單羧酸反應所得之反應生成物，與多元酸酐反應所得之含羧基的感光性樹脂。 (8)使多官能環氧化合物與1分子中具有至少1個醇性羥基與1個酚性羥基的化合物與含不飽和基之單羧酸反應所得之反應生成物的醇性羥基，與多元酸酐之酸酐基反應所得之含羧基的感光性樹脂。 [0093] 本發明之光硬化性熱硬化性樹脂組成物所使用之光硬化性樹脂及熱硬化性樹脂，可使用與上述光硬化性樹脂及熱硬化性樹脂同樣者。本發明之光硬化性熱硬化性樹脂組成物，除上述外，包含上述無機填料、硬化觸媒及光聚合起始劑為佳，配合其用可適宜調配慣用其他之調配成分。 [0094] 慣用其他之調配成分，可列舉例如上述著色劑、有機溶劑、分散劑、消泡劑･平坦劑、觸變劑、偶合劑、難燃劑等。 [0095] 本發明之硬化性樹脂組成物，可乾膜化使用亦可作為液狀使用。作為液狀使用時，可為1液性亦可為2液性以上。2液性組成物也可為例如分成疏水化微細纖維素纖維與硬化性樹脂的組成物。 [0096] 其次，本發明之乾薄膜係具有藉由將本發明之硬化性樹脂組成物塗佈於載體薄膜上，經乾燥所得的樹脂層。形成乾薄膜時，首先，將本發明之硬化性樹脂組成物以上述有機溶劑稀釋，調整為適當的黏度，藉由缺角輪塗佈機、刮刀塗佈機、唇模塗佈機、桿塗佈機、擠壓塗佈機、逆輥塗佈機、轉移輥塗佈機、凹版塗佈機、噴霧塗佈機等，在載體薄膜上塗佈成均勻的厚度。然後，使塗佈的組成物，通常以50~130℃之溫度乾燥1~30分鐘，可形成樹脂層。關於塗佈膜厚並無特別限制，但一般乾燥後的膜厚可在3~150μm，較佳為5~60μm之範圍適當選擇。 [0097] 載體薄膜可使用塑膠薄膜，例如聚對苯二甲酸乙二酯(PET)等之聚酯薄膜、聚醯亞胺薄膜、聚醯胺醯亞胺薄膜、聚丙烯薄膜、聚苯乙烯薄膜等。載體薄膜之厚度，無特別限制，一般可在10~150μm之範圍適宜選擇。更佳為15~130μm之範圍。 [0098] 載體薄膜上形成由本發明之硬化性樹脂組成物所成的樹脂層後，為了避免在樹脂層表面附著塵埃之目的，進一步在樹脂層表面層合可剝離之覆蓋薄膜(cover film)為佳。可剝離之覆蓋薄膜，可使用例如聚乙烯薄膜、聚四氟乙烯薄膜、聚丙烯薄膜、經表面處理後的紙等。覆蓋薄膜只要是當剝離覆蓋薄膜時，與樹脂層間的接著力小於樹脂層與載體薄膜的接著力者即可。 [0099] 又，本發明可為藉由將本發明之硬化性樹脂組成物塗佈於上述覆蓋薄膜上，經乾燥形成樹脂層，其表面層合載體薄膜者。亦即，本發明中，製造乾薄膜時，塗佈本發明之硬化性樹脂組成物的薄膜，可使用載體薄膜及覆蓋薄膜之任一。 [0100] 本發明之印刷配線板為具有由本發明之硬化性樹脂組成物或乾薄膜的樹脂層所得的硬化物者。本發明之印刷配線板之製造方法，首先，例如將本發明之硬化性樹脂組成物，使用上述有機溶劑調整為適合塗佈方法的黏度，藉由浸漬塗佈法、淋塗法、輥塗法、塗佈棒法、網版印刷法、淋幕式塗佈法等的方法塗佈於基材上，以60~100℃之溫度使組成物中所含有之有機溶劑揮發乾燥(暫時乾燥)，形成不黏手(tack-free)的樹脂層。又，乾薄膜的情形，藉由層合機等，使樹脂層與基材接觸，以貼合於基材上後，剝離載體薄膜，在基材上形成樹脂層。 [0101] 上述基材，除了預先藉由銅等形成電路之印刷配線板或可撓性印刷配線板外，可列舉使用利用紙酚、紙環氧樹脂、玻璃布環氧樹脂、玻璃聚醯亞胺、玻璃布/不織布環氧樹脂、玻璃布/紙環氧樹脂、合成纖維環氧樹脂、氟樹脂/聚乙烯/聚苯醚、聚苯醚/異氰酸酯等之高頻電路用貼銅層合板等的材質，可列舉全部等級(FR-4等)的貼銅層合板，其他有金屬基板、聚醯亞胺薄膜、PET薄膜、聚萘二甲酸乙二酯(PEN)薄膜、玻璃基板、陶瓷基板、晶圓板等。 [0102] 塗佈本發明之硬化性樹脂組成物後進行的揮發乾燥，可使用熱風循環式乾燥爐、IR爐、加熱板、對流烘箱等(使用具備利用蒸氣之空氣加熱方式的熱源者，使乾燥機內之熱風對流接觸的方法及由噴嘴吹至支撐體的方式)進行。 [0103] 本發明之組成物為熱硬化性樹脂組成物的情形時，基材上塗佈組成物形成塗膜或、層合乾薄膜形成樹脂層後，例如藉由加熱至約100~180℃的溫度使熱硬化，可形成耐熱性、耐藥品性、耐吸濕性、密著性、電特性等之諸特性優異的硬化膜(硬化物)。 [0104] 本發明之組成物為光硬化性樹脂組成物的情形時，基材上塗佈組成物形成塗膜或層合乾薄膜形成樹脂層後，照射活性能量線形成硬化膜(硬化物)。又，必要時，可在活性能量線之照射前，將塗膜加熱。本發明之組成物為鹼顯影型的光硬化性熱硬化性樹脂組成物的情形時，在印刷配線板上形成樹脂層後，透過形成有特定圖型的光罩，以活性能量線選擇性曝光，未曝光部藉由希鹼水溶液(例如0.3~3質量%碳酸鈉水溶液)顯影，形成硬化物的圖型。此外，藉由對硬化物照射活性能量線後，進行加熱硬化(例如100~220℃)、或加熱硬化後，照射活性能量線或、僅加熱硬化，進行最終硬化(本硬化)，形成密著性、硬度等之諸特性優異的硬化膜。又，本發明之組成物可為含有上述熱硬化性樹脂與光硬化性樹脂，不顯影處理或非顯影型的光硬化性熱硬化性樹脂組成物。 [0105] 上述活性能量線照射所用的曝光機，只要是搭載高壓水銀燈、超高壓水銀燈、金屬鹵素燈、水銀短弧燈等，以350~450nm的範圍照射紫外線的裝置即可，此外，也可使用直接描繪裝置(例如藉由電腦之CAD數據直接雷射描繪圖像的雷射直接顯像裝置)。直接描繪機之燈光源或雷射光源，只要最大波長為350~450nm的範圍即可。圖像形成用的曝光量係因膜厚等而異，但一般為10~1000mJ/cm2
，較佳為20~800mJ/cm2
之範圍內。 [0106] 上述顯影方法，可藉由浸漬法、噴灑法、噴霧法、刷毛法等，顯影液可使用氫氧化鉀、氫氧化鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等的鹼水溶液。"Problems to be Solved by the Invention" [0006] However, the materials described in Patent Documents 1 and 2 have a problem in that the reliability of the metal conductor is deteriorated, such as deterioration in adhesion. [0007] Therefore, an object of the present invention is to provide a curable resin composition for a printed wiring board, a dry film, a cured product, and a printed wiring board that can obtain a cured product with low thermal expansion and good adhesion to a metal conductor. Means to Solve the Problem [0008] As a result of careful review by the present inventors, it was found that by using the average fiber diameter to a specific range and the average fiber length to a specific range or less, the ratio of the average fiber diameter to the average fiber length was expressed. The fine cellulose fiber having a carboxyl group having a specific aspect ratio and being hydrophobized can solve the above-mentioned problems and complete the present invention. [0009] That is, the curable resin composition for a printed wiring board of the present invention is characterized in that the carboxyl group containing fine cellulose fibers having a carboxyl group is modified by at least one of an amine compound and a quaternary ammonium compound, Hydrophobized fine cellulose fibers and a resin composition of a hardening resin, wherein the average cellulose fiber diameter of the fine cellulose fibers having a carboxyl group is 0. 1 nm or more and 200 nm or less, the average fiber length is 600 nm or less, and the average aspect ratio is 1 or more and 200 or less. [0010] The resin composition of the present invention preferably further contains silicon dioxide. The resin composition of the present invention contains at least one of a thermosetting resin and a photocurable resin, and is preferably used as the curable resin. [0011] The dry film of the present invention is characterized by having a resin layer obtained by coating the film with a curable resin composition for a printed wiring board and drying the film. [0012] The cured product of the present invention is characterized in that the curable resin composition for a printed wiring board or the resin layer of the dry film is cured. [0013] A printed wiring board according to the present invention is characterized by having the above-mentioned cured product. ADVANTAGEOUS EFFECTS OF INVENTION According to the present invention, a curable resin composition, a dry film, a cured product, and a printed wiring board for a printed wiring board that can obtain a cured product with low thermal expansion and good adhesion to a metal conductor can be realized. . Embodiments of the Invention [0015] Embodiments of the present invention will be described in detail below. The curable resin composition for a printed wiring board of the present invention is a fine cellulose fiber containing a fine cellulose fiber having a carboxyl group, which is modified with at least one of an amine compound and a quaternary ammonium compound, and is hydrophobicized. A resin composition of a curable resin, in which fine cellulose fibers having a carboxyl group, use an average fiber diameter of 0. 1 nm or more and 200 nm or less, an average fiber length of 600 nm or less, and an average aspect ratio (average fiber length / average fiber diameter) of 1 or more and 200 or less. Here, the average fiber diameter of the fine cellulose fiber having a carboxyl group is 0. Above 1nm and below 200nm, average fiber length is below 600nm, and average aspect ratio is above 1 and below 200, but fine cellulose fibers formed by carboxyl groups of modified and hydrophobicized carboxyl groups are also average fibers The diameter is 0. 1 nm to 200 nm, the average fiber length is 600 nm or less, and the average aspect ratio is 1 to 200. Hereinafter, a fine cellulose fiber having a carboxyl group is also referred to as a fine cellulose fiber containing a carboxyl group, and a fine cellulose fiber obtained by hydrophobicizing a carboxyl group of a fine cellulose fiber containing a carboxyl group is also referred to as a hydrophobic fine cellulose fiber. . [0016] In the past, carboxyl-containing fine cellulose fibers having an average aspect ratio of about 300 were generally subjected to hydrophobic treatment by bonding various modification groups, etc. The fine cellulose fibers have low thermal expansion properties, but Low adhesion to metal conductors. However, the present inventors have found that when a hydrophobizing treatment and a hardening resin are applied to a composition containing fine cellulose fibers containing a carboxyl group with an average aspect ratio of 1 to 200, the hardened product obtained from the composition is applied. It maintains a low thermal expansion state and is excellent in adhesion with a metal conductor. Although the detailed reason for this effect is unknown, it is presumed that the fine cellulose fibers containing a carboxyl group whose average aspect ratio is included in the above range are formed by the fragile portions existing in the natural cellulose fibers, such as the amorphous region being cut and formed. Those who are short-fiberized increase the distribution ratio of the crystalline region as a whole, so they can maintain low thermal expansion properties despite short fibers. In addition, it is considered that the fiber length of the obtained hydrophobicized fine cellulose fibers is also short, which improves the dispersibility in the resin composition and can fully exert the effect as a filler, so it has excellent low thermal expansion and adhesion to metal conductors. Excellent. [0017] The curable resin composition of the present invention is suitable for forming an insulating layer of a printed wiring board, for example, it is suitable for forming a surface protective layer such as a core layer, an interlayer insulating layer, and a solder resist of a printed wiring board. Examples of the curable resin composition of the present invention include a thermosetting resin composition containing a thermosetting resin, a photocurable resin composition containing a photocurable resin, a photocurable resin and a thermosetting resin. Photocurable thermosetting resin composition. [Hydrophobized fine cellulose fiber] The above-mentioned hydrophobicized fine cellulose fiber is a fine cellulose fiber containing a carboxyl group, and the carboxyl group is modified by at least one of an amine compound and a quaternary ammonium compound, and is hydrophobized. , As available below. The natural cellulose fibers of the raw materials include, for example, wood pulp of coniferous wood pulp and broadleaf wood pulp; such as cotton velvet, raw cotton long-fiber cotton pulp; straw pulp, bagasse pulp pulp) and other non-wood based pulps; bacterial cellulose and the like. These can be used alone or in combination of two or more. [0019] The above raw materials are mainly composed of cellulose, hemicellulose, and lignin, wherein the content of lignin is usually about 0 to 40% by mass, especially about 0 to 10% by mass. These raw materials can be removed or bleached to adjust the amount of lignin if necessary. The measurement of the lignin content can be performed by the Klason method. [0020] In the cell wall of a plant, cellulose molecules are not single molecules, but are regularly aggregated to form crystalline microfibrils with dozens of sets, which is the basic skeleton substance of plants. Therefore, in order to produce fine cellulose fibers from the above raw materials, the fibers may be unraveled to a nanometer size by applying a pulping or pulverizing treatment, a high-temperature and high-pressure steam treatment, a phosphate treatment, or the like to the raw materials. [0021] With regard to natural cellulose fibers, by performing an oxidation treatment (for example, an oxidation treatment using TEMPO described later), the C6 first hydroxyl group in the Glucopyranose ring of natural cellulose is selectively Oxidation to carboxyl groups results in cellulose fibers containing carboxyl groups. By performing this treatment, the cellulose fibers can be unraveled to a nanometer size with a relatively weak shear force. [0022] In addition, the carboxyl group of the cellulose fiber containing a carboxyl group is modified with at least one of an amine compound and a quaternary ammonium compound to be hydrophobized to obtain the above-mentioned hydrophobicized fine cellulose fiber. [0023] A method for producing the hydrophobized fine cellulose fibers used in the present invention will be specifically described below. (Slurrying step) First, a slurry in which natural cellulose fibers are dispersed in water is prepared. The slurry is based on the natural cellulose fibers used as raw materials (absolute drying standard: the mass of natural cellulose fibers after being dried by heating at 150 ° C for 30 minutes). It is obtained by processing by a mixer and the like. The natural cellulose fibers may be subjected to treatments such as beating to increase the surface area. The cellulose I-type crystallinity of the commercially available slurry is usually 80% or more. [0024] (Oxidation Treatment Step) Next, the above-mentioned natural cellulose fibers are subjected to an oxidation treatment in the presence of an oxidant such as an N-oxyl compound to obtain cellulose fibers containing carboxyl groups (hereinafter sometimes referred to simply as " Oxidation treatment "). [0025] The N-oxyl compound is one or more selected from the group consisting of a piperidinyloxy compound, a pyrrolidinyloxy compound, an imidazolinyloxy compound, and an azaadamantane compound having an alkyl group having 1 or 2 carbon atoms. A heterocyclic N-oxy compound is preferred. Among these, from the viewpoint of reactivity, a piperidinyloxy compound having an alkyl group having 1 or 2 carbon atoms, and 2,2,6,6-tetraalkylpiperidine-1-oxyl (TEMPO ), 4-hydroxy-2,2,6,6-tetraalkylpiperidine-1-oxy, 4-alkoxy-2,2,6,6-tetraalkylpiperidine-1-oxy, 4-benzyloxy-2,2,6,6-tetraalkylpiperidine-1-oxy, 4-amino-2,2,6,6-tetraalkylpiperidine-1-oxy Etc.-tert-alkylnitrooxy compounds, 4-acetamido-TEMPO, 4-carboxy-TEMPO, 4-phosphino-oxy-TEMPO, etc. Among these piperidyloxy compounds, 2,2,6,6-tetramethylpiperidin-1-oxy (TEMPO), 4-hydroxy-2,2,6,6-tetramethyl Piperidine-1-oxy, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxy, and more preferably 2,2,6,6-tetramethylpiperidine Pyridin-1-oxy (TEMPO). [0026] The amount of N-oxyl compound may be a catalyst amount, and is preferably 0. 0 with respect to 100 parts by mass of natural cellulose fibers (absolutely dry basis). 001 ~ 10 parts by mass, more preferably 0. 01 ~ 9 parts by mass, and more preferably 0. 1 ~ 8 parts by mass, more preferably 0. 5 to 5 parts by mass. In the oxidation treatment of natural cellulose fibers, oxidizing agents other than N-oxyl compounds can be used. Examples of the oxidizing agent include oxygen, air, and peroxides from the viewpoints of solubility or reaction rate when the solvent is adjusted to a basic region; halogens, hypohalous acids, halogenous acids, perhalonic acids, and alkali metal salts thereof Or alkaline earth metal salts; halogen oxides, nitrogen oxides, etc. Among these, an alkali metal hypohalite is preferable, and specifically, sodium hypochlorite or sodium hypobromite is mentioned. The amount of oxidant can be selected according to the degree of carboxyl substitution (degree of oxidation) of the natural cellulose fiber. The yield of the oxidation reaction varies depending on the reaction conditions and cannot be determined in general. (Standard) 100 parts by mass, preferably in a range of about 1 to 100 parts by mass. [0027] In order to perform the oxidation reaction more efficiently, a bromide such as sodium bromide, potassium bromide, etc., or an iodide such as sodium iodide, potassium iodide, or the like can be used as a catalyst. The amount of the promoter is not particularly limited as long as it is an effective amount capable of exerting its function. The reaction temperature in the oxidation treatment is preferably 50 ° C or lower, more preferably 40 ° C or lower, and still more preferably 20 ° C or lower, and the lower limit thereof is preferably -5 ° C from the viewpoints of reaction selectivity and suppression of side reactions. the above. [0028] In addition, the pH of the reaction system is better when it is mixed with an oxidant. For example, when sodium hypochlorite is used as the oxidant, the pH of the reaction system is alkaline, preferably pH 7 to 13, and more preferably pH 10 to 13. The reaction time is preferably 1 to 240 minutes. [0029] By performing the above-mentioned oxidation treatment, the carboxyl group content is preferably 0. 1 mmol / g or more of carboxyl-containing cellulose fibers. (Purification step) The carboxyl group-containing cellulose fiber obtained in the above-mentioned oxidation treatment step contains an N-oxyl compound such as TEMPO used as a catalyst or a byproduct salt. The next step can be performed in this state, but purification can also obtain cellulose fibers containing carboxyl groups with high purity. The purification method can be based on the type of solvent in the oxidation reaction, the degree of oxidation of the product, and the degree of purification. For example, water is used as a good solvent, reprecipitation using methanol, ethanol, acetone, etc. as a weak solvent, extraction of TEMPO, etc. in a solvent separated from the water phase, such as hexane, and purification by ion exchange of salts, dialysis, and the like. [0031] (Refinement step) Next, a step of refining the carboxyl group-containing cellulose fiber obtained after the purification step described above is performed. In the refining step, it is preferable that the cellulose fiber containing a carboxyl group that has been subjected to the purification step is dispersed in a solvent, and the refining treatment is performed. By performing this miniaturization step, fine cellulose fibers having an average aspect ratio in the above range can be obtained. [0032] As the solvent of the dispersing medium, in addition to water, alcohols having a carbon number of 1 to 6, such as methanol, ethanol, and propanol, are preferred, and alcohols having a carbon number of 1 to 3; acetone, methyl ethyl ketone, and methyl Isobutyl ketones with 3 to 6 carbons; linear or branched saturated or unsaturated hydrocarbons with 1 to 6 carbons; aromatic hydrocarbons such as benzene and toluene; methylene chloride and chloroform Halogenated hydrocarbons; lower alkyl ethers with 2 to 5 carbon atoms; N, N-dimethylformamide, N, N-dimethylacetamide, dimethylmethylene, succinic acid, and triethylene glycol monomethyl Polar solvents such as ether diesters. These can be used singly or in combination of two or more, but from the viewpoint of the operability of the miniaturization treatment, water, alcohols having 1 to 6 carbons, ketones having 3 to 6 carbons, and 2 to 5 carbons are preferred. Polar solvents such as lower alkyl ethers, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfine, methyltriethylene glycol succinate, etc. A reduced viewpoint, more preferably water. The amount of the solvent used is not particularly limited as long as it is an effective amount for dispersing cellulose fibers containing carboxyl groups. It is preferably 1 to 500 times the mass of cellulose fibers containing carboxyl groups, and more preferably 2 ~ 200 times the mass. [0033] The apparatus used for the miniaturization process is preferably a conventional disperser. For example, disintegrator, beater, low-pressure homogenizer, high-pressure homogenizer, grinder, cutting knife, ball mill, jet mill, single-shaft extruder, 2-axis extruder, ultrasonic mixer, household juicer mixer Wait. In addition, the solid content concentration of the reactant fiber in the miniaturization treatment is preferably 50% by mass or less. [0034] In the present invention, before performing the aforementioned miniaturization treatment, at least one treatment selected from the group consisting of biochemical treatment, chemical treatment, and mechanical treatment may be further performed. Specifically, treatment methods such as acid hydrolysis, hot water decomposition, oxidative decomposition, pulverization, enzyme treatment, UV treatment, and electron beam treatment may be mentioned. However, short-fibrillation of cellulose fibers by such treatments can be more effective. Refinement treatment is carried out, especially when the average aspect ratio is included in the above range. The content of the treatment includes, for example, a method of refluxing cellulose fibers containing a carboxyl group after the purification step with an acid. The type of acid and its concentration are not particularly limited. Examples include the addition of concentrated hydrochloric acid, the concentration of hydrochloric acid is 0. A method for heating an aqueous dispersion of cellulose fibers containing 1 to 10 M of carboxyl groups. [0035] The morphology of the obtained fine cellulose fibers may be in the form of a suspension (adjusted as a colorless transparent or opaque liquid), or a powdered form (but fine cellulose fibers agglomerated) after adjusting the solid content concentration, if necessary. Powder, not cellulose particles). When a suspension is formed, water may be used as a dispersion medium, and a mixed solvent of water and other organic solvents (for example, alcohols such as ethanol) or surfactants, acids, and alkalis may be used. [0036] After the above operation, a hydroxyl group at the C6 position of the cellulose constituent unit can be selectively oxidized to a carboxyl group through an aldehyde group, and the content of the carboxyl group is 0. 1mmol / g or more, and the average fiber diameter is 0. 1 to 200 nm, fine cellulose fibers having an average fiber length of 600 nm or less and an average aspect ratio of 1 or more and 200 or less, preferably fine cellulose fibers having a crystallinity of 30% or more. [Average fiber diameter, average fiber length, and average aspect ratio of the fine cellulose fibers] The average fiber diameter, average fiber length, and average aspect ratio of the fine cellulose fibers containing a carboxyl group can be measured as described below. Water is added to the fine cellulose fibers containing carboxyl groups to adjust the concentration to 0. 0001% by mass of dispersion liquid, this dispersion liquid was dropped onto mica, and the dried sample was used as an observation sample, and an atomic force microscope (AFM, Nanoscope III Tapping mode AFM, manufactured by Digital Instrument Co., Ltd.) was used. The probe was made of Nano. Point Probe (NCH), manufactured by sensors company, measures the fiber height of the fine cellulose fibers in the sample. At this time, it was confirmed that in the microscopic image of the fine cellulose fibers, five or more fine cellulose fibers were taken out, and the average fiber diameter was calculated from their fiber heights. The average fiber length was calculated from the distance in the fiber direction. The average aspect ratio was calculated from the average fiber length / average fiber diameter. [0038] In the present invention, the average fiber diameter of the fine cellulose fibers containing a carboxyl group is 0. 1nm to 200nm, preferably 1nm to 100nm, more preferably 2nm to 50nm, and even more preferably 2. 5nm to 20nm. The average fiber diameter is less than 0. It is difficult to manufacture at 1 nm, and when the average fiber diameter exceeds 200 nm, a cured product having good adhesion to the conductor of the printed wiring board cannot be obtained. [0039] The average fiber length of the fine cellulose fibers containing a carboxyl group is 600 nm or less, preferably 50 nm or more and 600 nm or less, more preferably 100 nm or more and 500 nm or less, and still more preferably 150 nm or more and 500 nm or less. When the average fiber length exceeds 600 nm, dispersion when used as a composition becomes difficult. [0040] The average aspect ratio of the fine cellulose fibers containing a carboxyl group is 1 or more and 200 or less, preferably 5 or more and 180 or less, more preferably 9 or more and 170 or less, and particularly preferably 9 or more and less than 100. It is difficult to manufacture the average aspect ratio of less than 1, and when the average aspect ratio exceeds 200, a hardened material having good adhesion to a metal conductor cannot be obtained. When the average aspect ratio is 200 or less, the adhesion between the metal conductor and the cured product is good. The smaller the average aspect ratio, the better the adhesion between the metal conductor and the cured product, and the viscosity of the composition can be reduced. [0041] The present invention uses a fine cellulose fiber modified with the carboxyl group and hydrophobized. That is, a fine cellulose fiber having a carboxyl group and a hydrophobicized fine cellulose fiber modified with an amine compound or a quaternary ammonium compound is used. The hydrophobicized fine cellulose fibers will be described below. The carboxyl group of the fine cellulose fiber containing a carboxyl group is modified, and the finely modified cellulose fiber-based modification group which is hydrophobic is bonded to the cellulose main chain via one or both of an amidine bond or an amine salt. [0042] The modification group may be a functional group which is bonded via any one or both of a amine bond or an amine salt, and examples thereof include a hydrocarbon group having 1 carbon atom or a saturated group having 2 to 30 carbon atoms. Or unsaturated linear or branched hydrocarbon group. Specific examples include the following hydrocarbon groups. Hydrocarbyl group having 1 carbon atom: methyl group. Saturated straight-chain hydrocarbon groups with 2 to 30 carbon atoms: ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, octadecyl, fluorenyldialkyl Octacosanyl. Unsaturated straight chain hydrocarbon groups with 2 to 30 carbon atoms: oleyl, tetradecyl, hexadecyl, octadecadienyl, octadecadienol, eicosyl. Saturated branched hydrocarbon groups with 2 to 30 carbon atoms: isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, t-pentyl, isohexyl, 2-hexyl, dimethyl Butyl, ethylbutyl. [0043] The carbon number of the saturated or unsaturated linear or branched hydrocarbon group may be selected arbitrarily depending on the combination with the hardening resin, preferably 1 or more, particularly 3 or more, especially 10 or more, and, It is preferably 30 or less, particularly 20 or less, and especially 18 or less. For example, it is preferably 1 or more and 30 or less, more preferably 3 or more and 20 or less, and even more preferably 10 or more and 18 or less. When the carbon number is within the above range, the fine cellulose fibers and the curable resin are uniformly mixed, and good physical properties can be obtained as a resin composition such as a low linear thermal expansion coefficient. [0044] An amine having the above-mentioned saturated or unsaturated linear or branched hydrocarbon group, and specifically, the primary amine includes, for example, methylamine, ethylamine, propylamine, isopropylamine, and butylamine , Hexylamine, octylamine, decylamine, dodecylamine, octadecylamine, oleylamine, etc. Examples of the secondary amine include dialkylamines such as dimethylamine, diethylamine, dibutylamine, and bis (octadecyl) amine. [0045] The amine having an aromatic hydrocarbon group may have a total carbon number of 6 to 20, and may be any of a primary amine and a secondary amine. However, from the viewpoint of reactivity with a carboxyl group, a primary amine is preferred. amine. The number of aromatic hydrocarbon groups in the amine may be one or two, as long as the total carbon number is 6 to 20, and preferably one. [0046] The amine having an aromatic hydrocarbon group includes an amine having an aryl group and an amine having an aralkyl group. From the viewpoint of compatibility with a resin, an amine having an aryl group is preferred. [0047] Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a triphenyl group. These may be bonded alone or in combination of two or more kinds. Among these, from the viewpoint of compatibility with resins, phenyl, naphthyl, and biphenyl are preferred, and phenyl is more preferred. [0048] Specific examples of the aralkyl group include benzyl, phenethyl, phenylpropyl, phenylpentyl, phenylhexyl, and phenylheptyl, and these may be bonded alone or in combination of two or more. Among these, from the viewpoint of compatibility with resins, benzyl, phenethyl, phenylpropyl, phenylpentyl, and phenylhexyl are preferred, and benzyl, phenethyl, phenylpropyl, Phenylpentyl. [0049] The aryl group and the aralkyl group may have a substituent. Examples of the substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert- Butyl, pentyl, isopentyl, hexyl and other alkyl groups having 1 to 6 carbon atoms; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec- Butoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, etc. 1 to 6 carbon alkoxy groups; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, iso Alkoxy having 1 to 6 carbon atoms such as propoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, third butoxycarbonyl, pentoxycarbonyl, isopentoxycarbonyl, etc. Carbonyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; fluorenyl group, aralkyl group, aralkyloxy group having 1 to 6 carbon atoms. [0050] The amine having the above-mentioned aromatic hydrocarbon group, specifically, the amine having an aryl group includes aniline, toluidine, 4-benzidine, diphenylamine, 2-aminonaphthalene, p-terphenylamine, 2-aminoanthracene, 2-aminoanthraquinone. Among these, from the viewpoint of compatibility with the resin, aniline, toluidine, 4-benzidine, diphenylamine, and 2-aminonaphthalene are preferred, and aniline is more preferred. Examples of the amine having an aralkyl group include benzylamine, phenethylamine, 3-phenylpropylamine, 5-phenylpentylamine, 6-phenylhexylamine, 7-phenylheptylamine, 8 -Phenyloctylamine. Among these, from the same viewpoint, benzylamine, phenethylamine, 3-phenylpropylamine, 5-phenylpentylamine, 6-phenylhexylamine, and 7-phenylheptylamine are preferred, More preferred are benzylamine, phenethylamine, 3-phenylpropylamine, 5-phenylpentylamine, 6-phenylhexylamine, and even more preferred are benzylamine, phenethylamine, 3- Phenylpropylamine, 5-phenylpentylamine. The amine having an aromatic hydrocarbon group used in the present invention may be prepared according to a conventional method or may be a commercially available product. [0051] In addition, after adding a desired amount of ethylene oxide or propylene oxide to a propylene glycol alkyl ether, amines having a hydroxyl end group which are aminated, hydroxyethyl, hydroxypropyl, and the like have a hydrophilic group. Amine or polyetheramine or polyesteramine having a polyether chain of ethylene glycol, propylene glycol, etc., or a polyester chain of lactide, caprolactone, etc., or a lipid having cyclopentyl, cyclohexyl, etc. The amine of a cyclic hydrocarbon is also suitably used as a compound which is bonded via either or both of an amine bond or an amine salt in the hydrophobic fine cellulose fiber used in the present invention. [0052] Examples of the quaternary ammonium compound for modifying the carboxyl group of the hydrophobicized fine cellulose fiber to form an amine salt include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and hydroxide Tetrapropylammonium, tetraethylammonium chloride, tetrabutylammonium chloride, lauryltrimethylammonium chloride, dilauryldimethylammonium chloride, octadecyltrimethylammonium chloride, two (Octadecyl) dimethylammonium chloride, cetyltrimethylammonium chloride, alkylbenzyldimethylammonium chloride. Among these, from the viewpoint of the ease of modification to the carboxyl group, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide are preferred. [0053] The amount of the hydrophobic fine cellulose fibers in the curable resin composition of the present invention is 100 parts by mass relative to the total amount of the curable resin (based on the solid content), preferably 0. 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 2 to 10 parts by mass. Set the amount of addition to 0. When it is 1 part by mass or more, the thermal expansion property becomes low, and when it is 30 parts by mass or less, there is no excellent balance between low thermal expansion property and adhesion of the metal conductor. (Method for Modifying Carboxylic Group of Fine Cellulose Fiber) The method for modifying the carboxyl group of fine cellulose fiber in the present invention includes the following. The first method includes a method in which a fine cellulose fiber containing a carboxyl group and an amine compound having a modifying group are mixed in a solvent to form a salt. The amount of the above-mentioned amine compound can be determined based on the amount of bonding of the desired amine salt in the hydrophobicized fine cellulose fibers, but the amine group is preferably 0 relative to 1 mol of the carboxyl group contained in the fine cellulose fibers containing the carboxyl group . 1mol or more, more preferably 0. 5mol or more, and more preferably 0. 7 mol or more, and more preferably 1 mol or more. From the viewpoint of product purity, it is preferable to use an amount of 50 mol or less, more preferably 20 mol or less, and still more preferably 10 mol or less. In addition, the amine contained in the above range may be supplied to the salt formation step at one time, or may be supplied to the salt formation step in portions. [0055] The solvent is preferably selected as a solvent for dissolving the amine compound to be used, and examples thereof include ethanol, isopropyl alcohol (IPA), N, N-dimethylformamide (DMF), dimethylmethane (DMSO), N, N-dimethylacetamide, tetrahydrofuran (THF), diesters of succinic acid and triethylene glycol monomethyl ether, acetone, methyl ethyl ketone (MEK), acetonitrile, dichloromethane, chloroform, toluene , Acetic acid, etc. These can be used alone or in combination of two or more. Among these polar solvents, diesters of succinic acid and triethylene glycol monomethyl ether, ethanol, and DMF are preferred. [0056] The temperature during mixing is preferably 0 ° C or higher, more preferably 5 ° C or higher, and even more preferably 10 ° C or higher. From the viewpoint of coloring of the hydrophobized fine cellulose fibers, the temperature is preferably 50 ° C or lower, more preferably 40 ° C or lower, and even more preferably 30 ° C or lower. Mixing time can be appropriately set according to the type of amine and solvent used, but it is preferably 0. More than 01 hours, more preferably 0. 1 hour or more, and more preferably 1 hour or more, preferably 48 hours or less, more preferably 24 hours or less, and still more preferably 12 hours or less. [0057] After the formation of the above-mentioned salt, in order to remove the salt to form an unused amine compound, a post-treatment may be appropriately performed. As a method for the subsequent treatment, for example, filtration, centrifugation, dialysis, and the like can be used. [0058] The second method includes a method in which a fine cellulose fiber having a carboxyl group and an amine compound having a modifying group are subjected to amidation reaction in a solvent. The amount of the amine compound having the above-mentioned modification group can be determined by the desired amount of bonds in the hydrophobicized fine cellulose fibers, but from the viewpoint of reactivity, it is relative to the amount contained in the fine cellulose fibers containing carboxyl groups. Carboxyl 1mol, amine group is preferably 0. 1mol or more, more preferably 0. 5mol or more, and more preferably 0. 7 mol or more, and more preferably 1 mol or more. From the viewpoint of product purity, it is preferable to use an amount of 50 mol or less, more preferably 20 mol or less, and still more preferably 10 mol or less. In addition, the amount of the amine contained in the above range may be supplied to the reaction at one time, or may be supplied to the reaction in portions. [0059] A conventional condensing agent can be used in the reaction between the above-mentioned carboxyl group-containing fine cellulose fibers and an amine compound having a modification group. The condensing agent is not particularly limited, and examples include the condensing agent described in Synthetic Chemistry Series Peptide Synthesis (Maruzen Corporation) P116, or the condensing agent described in Tetrahedron, 57,1551 (2001), and examples thereof include 4- (4,6-dimethoxy- 1,3,5-triazin-2-yl) -4-methylmorpholine chloride (hereinafter sometimes referred to simply as "DMT-MM") and the like. [0060] The solvent for the amine compound used in the condensation reaction is preferably selected and dissolved. The reaction time and reaction temperature in the above-mentioned condensation reaction can be appropriately selected according to the type of amine and solvent to be used. From the viewpoint of reaction rate and productivity, it is preferably 1 to 24 hours, and more preferably 10 to 20 hours. From the viewpoint of reactivity, the reaction temperature is preferably 0 ° C or higher, more preferably 5 ° C or higher, and even more preferably 10 ° C or higher. From the viewpoint of coloring of the hydrophobized fine cellulose fibers, the temperature is preferably 200 ° C or lower, more preferably 80 ° C or lower, and even more preferably 30 ° C or lower. [0061] After the above-mentioned mixing and after the reaction, in order to remove unreacted amine compounds, condensing agents, and the like, a post-treatment may be performed as appropriate. As a method for the subsequent treatment, for example, filtration, centrifugation, dialysis, and the like can be used. [0062] The third method includes a method of mixing a fine cellulose fiber having a carboxyl group and a fourth-order ammonium compound having a modifying group in a solvent to form a salt. The amount of the above-mentioned fourth-order ammonium compound is determined by the desired amount of bonding in the hydrophobicized fine cellulose fibers, but the fourth-order ammonium cation is 1 mol of carboxyl groups contained in the fine cellulose fibers containing carboxyl groups. It is preferably 0. 1mol or more, more preferably 0. 5mol or more, and more preferably 0. 7 mol or more, and more preferably 1 mol or more. From the viewpoint of product purity, it is preferable to use an amount of 50 mol or less, more preferably 20 mol or less, and still more preferably 10 mol or less. In addition, the amount of the quaternary ammonium compound contained in the above range may be supplied to the salt formation step at one time, or may be supplied to the salt formation step in portions. [0063] As the solvent, a solvent used when mixing with the above-mentioned amine may be used in the same manner, and in addition, water may be used. These can be used singly or in combination of two or more kinds. Among them, water, a diester of succinic acid and triethylene glycol monomethyl ether, ethanol, and DMF are preferred. The temperature or time during mixing and the post-treatment after salt formation can be appropriately set by referring to the case of mixing with the above amine compound. [Curable resin] The curable resin composition of the present invention is a thermosetting resin composition, a photocurable resin composition, or a photocurable thermosetting resin composition. (Thermosetting resin composition) The thermosetting resin composition of the present invention preferably contains a thermosetting resin, an inorganic filler, and a curing catalyst. The thermosetting resin used in the thermosetting resin composition is preferably a resin having a functional group that undergoes a thermosetting reaction, and in particular, a compound having one or more cyclic (thio) ether groups in the molecule is used. good. [0066] Examples of the compound having a cyclic ether group include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol E-type epoxy resin, and bisphenol M-type epoxy resin. Epoxy resin, bisphenol P-type epoxy resin, bisphenol Z-type epoxy resin, bisphenol-type epoxy resin, bisphenol A novolac-type epoxy resin, phenol novolac-type epoxy resin, cresol novolac Novolac epoxy resin, biphenyl epoxy resin, biphenylaralkyl epoxy resin, arylalkylene epoxy resin, tetrahydroxyphenylethane ring, etc. Oxygen resin, naphthalene type epoxy resin, anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type Epoxy resin, epoxy methacrylate copolymer epoxy resin, cyclohexyl maleimide and epoxy propylene methacrylate polymer epoxy resin, epoxy modified polybutadiene Ene rubber derivative, CTBN modified epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-glycidyl ether, biphenyl-4, 4'-glycidyl ether, 1,6-hexanediol diglycidyl ether, glycol or propylene glycol diglycidyl ether, sorbitol polyglycidyl ether, tris (2,3-cyclo (Oxypropyl) isotricyanate, triglycidyl (2-hydroxyethyl) isotricyanate, etc .; phenol novolac resin, cresol novolac Novolac-type phenolic resins such as resins, bisphenol A novolac resins, unmodified resol phenol resins, modified oils such as tung oil, linseed oil, and walnut oil Phenolic resins such as high-quality resol-type phenolic resins; water-soluble Resol phenolic resins; phenoxy resins; urea (urea) resins; resins containing triazine rings such as melamine resins; unsaturated polyester resins, diallyl resins Phthalate resin, silicone resin, resin with benzoxazine ring, norbornene-based resin, cyanate resin, isocyanate resin, urethane resin, benzocyclobutene resin, malay Perylene imine resin, bismaleimide imine triazine resin, polyazomethine resin, thermosetting polyimide resin, cyanate ester tree Grease, active ester resin, etc. [0067] The thermosetting resin preferably contains an epoxy resin and a phenol resin. By including an epoxy resin and a phenol resin, heat resistance, peel strength, and insulation reliability can be improved. The content of the epoxy resin is 100 parts by mass of the total thermosetting resin, and is, for example, 1 part by mass or more and 90 parts by mass, preferably 10 parts by mass or more and 85 parts by mass or less, and more preferably 20 parts by mass or more and 80 parts by mass or less. the following. The content of the phenol resin is, for example, 1 part by mass or more and 70 parts by mass or less with respect to the all-thermosetting resin, preferably 5 parts by mass or more and 60 parts by mass or less, and more preferably 10 parts by mass or more and 50 parts by mass or less. When an active ester resin is used as the thermosetting resin, when dimethylaminopyridine is used, the curability can be improved. [0068] The curable resin composition of the present invention has an excellent effect of reducing the linear expansion coefficient of the cured product by using a fine cellulose fiber and an inorganic filler in combination. Examples of the inorganic filler include barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, and aluminum hydroxide , Silicon nitride, aluminum nitride, etc. Among these inorganic fillers, the specific gravity is low, and a high proportion can be blended in the composition. From the viewpoint of excellent low thermal expansion, silicon dioxide is preferred, and spherical silicon dioxide is more preferred. The curable resin composition of the present invention is preferably a combination of fine cellulose fibers and silicon dioxide. At this time, the effect of reducing the linear expansion coefficient of the cured product is more excellent, and the adhesiveness with the metal conductor is better. The average particle diameter of the inorganic filler is preferably 3 μm or less, and more preferably 1 μm or less. The average particle diameter of the inorganic filler can be obtained by a laser diffraction type particle size distribution measuring device. The blending amount of the inorganic filler is 25 to 90% by mass, preferably 30 to 90% by mass, and more preferably 35 to 85% by mass with respect to the solid content of the composition. By setting the compounding amount of the inorganic filler within the above range, the coating film performance of the cured product after curing can be well ensured. [0069] Among the hardening resins, the hardening resin is mainly a hardening resin, and examples thereof include imidazole, 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole. , 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc. Derivatives; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzyl Amines, amine compounds such as 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as dihydrazine adipate, dihydrazine sebacate, and phosphorus compounds such as triphenylphosphine, diamine Methylaminopyridine and the like. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (made by Shikoku Chemical Industries, Ltd.), U-CAT3503N, U-CAT3502T, DBU, DBN, U-CATSA102, U- CAT5002 (san-apro) can be used alone or in combination of two or more. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, and 2-vinyl-2 can also be used in the same manner. 2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine ･ isocyanuric acid adduct, 2,4-diamino-6-formaldehyde S-triazine derivatives such as propylene propyl ethoxyethyl-S-triazine isoisocyanuric acid adduct. [0070] The hardening catalyst is preferably an alkaline catalyst. Particularly preferred are imidazoles. By using imidazoles, both the hardening properties and the stability of the composition can be improved, and the heat resistance can be improved. The content of the curing catalyst is 100 parts by mass relative to the thermosetting resin, for example, 0. 01 parts by mass or more and 20 parts by mass or less, preferably 0. 05 parts by mass or more and 15 parts by mass or less, more preferably 0. 1 part by mass or more and 15 parts by mass or less. [0071] In the thermosetting resin composition of the present invention, in addition to the hydrophobized fine cellulose fibers, the thermosetting resin, the inorganic filler, and the hardening catalyst, other conventionally-used blending ingredients can be suitably blended depending on the application. [0072] Other commonly used formulation ingredients include, for example, a coloring agent, an organic solvent, a dispersant, a defoaming agent, a flattening agent, a thixotropic agent, a coupling agent, and a flame retardant. [0073] As the colorant, a coloring pigment, a dye, or the like, a conventional user represented by a color index can be used. Examples include Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122 , 136, 67, 70, Pigment Green 7, 36, 3, 5, 20, 28, Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, 110, 109, 139, 179, 185, 93 , 94, 95, 128, 155, 166, 180, 120, 151, 154, 156, 175, 181, 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1 , 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183, 12, 13, 14, 16, 17, 55, 63, 81, 83, 87 , 126, 127, 152, 170, 172, 174, 176, 188, 198, Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51 , 61, 63, 64, 71, 73, Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, 37, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68, 171, 175, 176,185,208,123,149,166,178,179,190,194,224,254,255,264,270,272,220,144,166,214,220,221,242,168,177, 216, 122, 202, 206, 207, 209, Solvent Red 135, 179, 149, 150, 52, 207, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, Pigment Brown 23, 25, Pigment Black 1, 7, etc. The content of the colorant is in the entire composition, for example, 0. 01 mass% or more and 3 mass% or less, preferably 0. 05 mass% or more and 1 mass% or less, more preferably 0. 1% by mass or more 5 mass% or less. When titanium oxide or the like is used to obtain a white cured film, the total composition is, for example, 1% by mass or more and 65% by mass or less, preferably 3% by mass or more and 60% by mass or less, and more preferably 5% by mass. Above 50% by mass. [0074] Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, and butyl solvent Fiber agents, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, Esters of butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate, and esters of the above-mentioned glycol ethers; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; Dimethylformamide, dimethylacetamide and other amines, octane, decane and other aliphatic hydrocarbons; petroleum ether, petroleum brain, hydrogenated petroleum brain, solvent petroleum brain and other petroleum solvents . [0075] As the dispersant, a polycarboxylic acid system, a formalin naphthalenesulfonic acid condensation system, a polyethylene glycol, a polycarboxylic acid partially alkyl ester system, a polyether system, a polyalkylene polyamine system, or the like can be used. Polymer-based dispersants, alkyl sulfonic acid-based, quaternary ammonium-based, higher alcohol alkylene oxide-based, polyol ester-based, and alkyl polyamine-based low-molecular dispersants. [0076] As an antifoaming agent and a flattening agent, polysiloxane, modified polysiloxane, mineral oil, vegetable oil, aliphatic alcohol, fatty acid, metal soap, fatty acid amine, polyoxyalkylene glycol, and polyoxyalkylene can be used. Compounds such as alkyl ethers, polyoxyalkylene fatty acid esters, and the like. [0077] As the thixotropic agent, fine particles of silicon dioxide, silica gel, amorphous inorganic particles, polyamine-based additives, modified urea-based additives, wax-based additives, and the like can be used. [0078] As the coupling agent, a methoxy group, an ethoxy group, an ethano group, etc. as an alkoxy group, a vinyl group, a methacryl group, an acryl group, an epoxy group, or a cyclic group as a reactive functional group can be used. Silane coupling agents such as epoxy, mercapto, amine, diamine, anhydride, urea, sulfide, isocyanate, etc., such as vinyl ethoxy silane, vinyl trimethoxy silane, vinyl sulfonate (β-methoxyethoxy) silanes, vinyl-based silane compounds such as γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β- ( Aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxy Amine-based silane compounds such as silane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxy Epoxy-based silane compounds such as propylmethyldiethoxysilane, mercapto-based silane compounds such as γ-mercaptopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilanes benzene Silane coupling agents such as amine-based silane compounds, isopropyl triisostearyl halide titanate, tetraoctylbis (di (tridecyl) phosphite) titanate, bis (dioctyl coke Phosphate ester) oxyacetate titanate, isopropyl dodecylbenzenesulfonyl titanate, isopropyl tri (dioctyl pyrophosphate) titanate, tetraisopropylbis ( Dioctyl phosphite) titanate, tetra (1,1-diallyloxymethyl-1-butyl) bis- (di-tridecyl) phosphite titanate, bis (di Octyl Pyrophosphate) Ethyl Titanate, Isopropyl Trioctyl Titanate, Isopropyl Dimethylenyl Isostearyl Titanate, Isopropyl Stearyl Titanate Titanate, Isopropyltris (dioctyl phosphate) Titanate, Isopropyltricumylphenyl Titanate, Dicumylphenoxyacetate Titanate, Diisostearyl Titanate-based coupling agents such as vinyl ethylene titanate, compounds containing ethylenically unsaturated zirconate, compounds containing neoalkoxy zirconate, neoalkoxytrinedecanoyl zirconate, new Alkoxytris (dodecyl) benzenesulfonylzirconate, neoalkoxytris (dioctyl) Acid ester zirconate, neoalkoxytris (dioctyl) pyrophosphate zirconate, neoalkoxytris (ethylenediamine) ethyl zirconate, neoalkoxytris (m-amino) ) Phenyl zirconate, tetra (2,2-diallyloxymethyl) butyl, bis (di-tridecyl) phosphite zirconate, neopentyl (diallyl) oxy Base, trinedecylfluorenyl zirconate, neopentyl (diallyl) oxy, tri (dodecyl) benzene-sulfofluorenyl zirconate, neopentyl (diallyl) oxy , Tris (dioctyl) phosphate zirconate, neopentyl (diallyl) oxy, tris (dioctyl) pyrophosphate zirconate, neopentyl (diallyl) oxy, Tris (N-ethylenediamino) ethyl zirconate, neopentyl (diallyl) oxy, tris (m-amino) phenyl zirconate, neopentyl (diallyl) oxy , Trimethacrylfluorenyl zirconate, neopentyl (diallyl) oxy, tripropenylzirconate, dinepentyl (diallyl) oxy, di-p-aminobenzene Formamyl zirconate, dineopentyl (diallyl) oxy, bis (3-mercapto) propionate zirconate, zirconium (IV) 2,2-bis (2-propoxymethyl) ) Butoxy, cyclodi [2,2- (bis2-propoxymethyl) butoxy ] Zirconate-based coupling agents such as pyrophosphate-O, O, aluminates such as diisobutyl (oil-based) acetoacetate aluminate, alkylacetate acetate diisopropoxide, and the like Ester-based coupling agents and the like. [0079] As the flame retardant, water and metals such as aluminum hydroxide and magnesium hydroxide, red phosphorus, ammonium phosphate, ammonium carbonate, zinc borate, zinc stannate, molybdenum compound, bromine compound, Chlorine compounds, phosphate esters, phosphorus-containing polyols, phosphorus-containing amines, melamine melamines, melamine compounds, triazine compounds, guanidine compounds, silicon polymers, and the like. (Photo-curable resin composition) The photo-curable resin composition of the present invention preferably contains a photo-curable resin, an inorganic filler, a photopolymerization initiator, a coloring agent, and the like. The photocurable resin is preferably a resin having a functional group capable of curing reaction by irradiation with active energy rays, and may be radical polymerizable or cationic polymerizable. Examples thereof include a compound having one or more ethylenically unsaturated bonds, an alicyclic epoxy compound, and an oxetane compound in the molecule. A compound having one or more ethylenically unsaturated bonds in the molecule is preferably used. [0081] As the compound having an ethylenically unsaturated bond, conventionally known photopolymerizable oligomers, photopolymerizable vinyl monomers, and the like can be used. Examples of the photopolymerizable oligomer include unsaturated polyester-based oligomers and (meth) acrylate-based oligomers. (Meth) acrylate-based oligomers include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, bisphenol epoxy (meth) acrylate, and the like Epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meth) acrylate, polyester (meth) acrylate, polyether (formaldehyde) Group) acrylate, polybutadiene modified (meth) acrylate, and the like. In the present specification, (meth) acrylate refers to a term collectively referred to as acrylate, methacrylate, and mixtures thereof, and the same applies to other similar descriptions. [0082] The photopolymerizable vinyl monomer is a conventional one, and examples thereof include styrene derivatives such as styrene, chlorostyrene, and α-methylstyrene; vinyl acetate, vinyl butyrate, or Vinyl esters such as vinyl benzoate; vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-pentyl ether, vinyl isoamyl ether, vinyl- Vinyl ethers such as n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, and triethylene glycol monomethyl vinyl ether; acrylamide, methacrylamide, N-hydroxyl Methacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethacrylamide, N-ethoxymethacrylamide, N-butoxymethacrylamide, etc. (Meth) acrylamides; allyl compounds such as triallyl isotricyanate, diallyl phthalate, diallyl isophthalate, etc .; 2-ethylhexyl (Meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isofluorenyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (Meth) acrylic (Meth) acrylic acid esters such as esters; hydroxyalkyl (meth) acrylic acid such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate Esters; alkoxyalkylene glycol mono (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, etc .; ethylene glycol di (methyl) ) Acrylates, butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri ( Methyl acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and other alkylene polyol poly (meth) acrylates; diethylene glycol di (meth) acrylate , Triethylene glycol di (meth) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri (meth) acrylate, etc. (Meth) acrylic acid esters; poly (meth) acrylic acid esters such as hydroxypivalic acid neopentyl glycol di (meth) acrylate, etc .; tris [(meth) acrylic acid ethoxyethyl base ] Isotricyanate and other isotricyanate-type poly (meth) acrylates. Examples of the alicyclic epoxy compound include 3,4,3 ', 4'-diepoxydicyclohexyl, 2,2-bis (3,4-epoxycyclohexyl) propane, and 2,2- Bis (3,4-epoxycyclohexyl) -1,3-hexafluoropropane, bis (3,4-epoxycyclohexyl) methane, 1- [1,1-bis (3,4-epoxy Cyclohexyl)] ethylbenzene, bis (3,4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxyl Acid ester, (3,4-epoxy-6-methylcyclohexyl) methyl-3 ', 4'-epoxy-6-methylcyclohexanecarboxylate, ethylene-1,2-bis (3,4-epoxycyclohexanecarboxylic acid) ester, cyclohexene oxide, 3,4-epoxycyclohexylmethyl alcohol, 3,4-epoxycyclohexylethyltrimethoxysilane Among them are alicyclic epoxy compounds having an epoxy group and the like. Commercial products include, for example, CELLOXID 2000, CELLOXID 2021, CELLOXID 3000, and EHPE3150 manufactured by DAICEL Chemical Industry Co., Ltd .; Epomic VG-3101 manufactured by Mitsui Chemicals; E-1031S manufactured by Petrochemical Shell Epoxy; and manufactured by Mitsubishi Gas Chemical Corporation. TETRAD-X, TETRAD-C; EPB-13, EPB-27, etc. made by Japan's Soda. Examples of the oxetane compound include bis [(3-methyl-3-oxocyclomethoxy) methyl] ether, and bis [(3-ethyl-3-oxocyclomethoxy) methyl Yl] ether, 1,4-bis [(3-methyl-3-oxobutylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxocyclobutylmethoxy) methyl Phenyl] benzene, (3-methyl-3-oxobutyl) methacrylate, (3-ethyl-3-oxobutyl) methacrylate, (3-methyl-3-oxo Butyl) methyl methacrylate, (3-ethyl-3-oxobutyl) methacrylate or their oligomers or copolymers Examples include oxetane alcohol and novolac resins, poly (p-hydroxystyrene), cardo-type bisphenols, calixarene, calorificol, and silsesquioxane Oxide compounds such as ethers of hydroxy-containing resins, copolymers of unsaturated monomers having an oxetane ring and alkyl (meth) acrylates, and the like. Commercially available products include ETERNACOLLOXBP, OXMA, OXBP, EHO, xylylene dioxetane manufactured by Ube Kosan Co., Ltd., Aron Oxetane OXT-101, OXT-201, OXT-211, and OXT manufactured by Toa Kosei Corporation. -221, OXT-212, OXT-610, PNOX-1009, etc. [0085] The photopolymerization initiator is among the curable resins, and those who harden the photocurable resin may be a photoradical polymerization initiator or a photocationic polymerization initiator. Photoradical polymerization initiators include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2 , 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, Acetophenones such as 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropane-1-one, 2-benzyl Methyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl] -1-butanone and other amino alkyl phenones; 2-methylanthraquinone, 2-ethylanthraquinone, 2-third Anthraquinones such as butylanthraquinone and 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-di Thioxanthones such as isopropyl thioxanthone; acetals such as acetophenone dimethyl acetal and benzyl dimethyl acetal; benzophenones such as benzophenone; or xanthene Ketones; (2,6-dimethoxybenzyl) -2,4,4-pentyl phosphorus oxide, bis (2,4,6-trimethylbenzyl) -phenylphosphine oxidation Substance, 2,4,6-trimethylbenzyl Phosphine oxides such as phenylphosphine oxide, ethyl-2,4,6-trimethylbenzylidenephenylphosphonate (phosphonate); various peroxides, titanocene-based initiators Wait. These are compatible with, for example, ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, pentyl-4-dimethylaminobenzoate, Tertiary amine photosensitizers such as ethylamine and triethanolamine are used in combination. [0086] Examples of the photocationic polymerization initiator include diazonium salts, sulfonium salts, bromium salts, chloronium salts, sulfonium salts, selenonium salts, pyrimidinium salts, thiamine pyrimidinium salts, and pyridinium salts. Onium salts; halogenated compounds of tris (trihalomethyl) -s-triazine and its derivatives; 2-nitrobenzyl esters of sulfonic acid; iminosulfonic acid salts; 1-oxo-2- Diazonaphthoquinone-4-sulfonate derivatives; N-hydroxystilbeneimine = sulfonate; tris (methanesulfonyloxy) benzene derivatives; bissulfonyldiazomethanes; sulfonylcarbonylalkanes Class; sulfocarbonylcarbonyldiazomethanes; difluorene compounds and the like. These photopolymerization initiators can be used alone or in combination of two or more. [0087] The blending amount of the photopolymerization initiator is in terms of solid content, relative to 100 parts by mass of the photocurable resin, for example, 0. 05 ~ 20 parts by mass, preferably 0. 1 to 15 parts by mass, more preferably 0. 5 to 10 parts by mass. By blending the photopolymerization initiator in this range, the photo-hardening property on copper becomes sufficient, the hardening property of the coating film becomes good, the coating film properties such as chemical resistance are improved, and the deep hardening property is also improved. [0088] The inorganic filler can be the same as the user in the above-mentioned thermosetting resin composition, and the amount of the filler can be the same. [0089] As the colorant, it is possible to use the same as the user of the above-mentioned thermosetting resin composition. By containing a colorant, the photocurable resin composition can prevent a decrease in adhesion even if an excessive amount of accumulated light is irradiated. Moreover, the visibility of a coating film can also be improved. [0090] In the photocurable resin composition of the present invention, in addition to the hydrophobized fine cellulose fibers, the photocurable resin, the inorganic filler, the photopolymerization initiator, and the coloring agent, according to the use thereof, other commonly used ones can be appropriately formulated. Ingredients. Examples of other commonly used formulation ingredients include organic solvents, dispersants, antifoaming agents, flattening agents, thixotropic agents, coupling agents, and flame retardants. These organic solvents, dispersants, antifoaming agents, flattening agents, thixotropic agents, coupling agents, and flame retardants can be used as the thermosetting resin composition. (Photocurable thermosetting resin composition) The photocurable thermosetting resin composition of the present invention includes a photocurable resin and a thermosetting resin, and particularly the photocurable thermosetting resin of the present invention When the developing resin composition is a developing type using an alkaline aqueous solution, it is preferable to contain a carboxyl group-containing resin as a curable resin. The carboxyl group-containing resin may be any one of a photosensitive carboxyl group-containing resin having one or more photosensitive unsaturated double bonds and a carboxyl group-containing resin having no photosensitive unsaturated double bond, and is not limited to a specific one. By. In particular, the resins listed below are suitably used. [0092] (1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and a compound having an unsaturated double bond, and a carboxyl group-containing resin modified to adjust the molecular weight or acid value. (2) A carboxyl group-containing photosensitive resin obtained by reacting a carboxyl group-containing (meth) acrylic copolymer resin with a compound having an ethylene oxide ring and an ethylenically unsaturated group in one molecule. (3) A copolymer of a compound having one epoxy group and an unsaturated double bond and a compound having an unsaturated double bond in one molecule is reacted with an unsaturated monocarboxylic acid, thereby generating a second-order hydroxyl group. Carboxyl-containing photosensitive resin obtained by reaction with a saturated or unsaturated polybasic acid anhydride. (4) After reacting a polymer containing a hydroxyl group with a saturated or unsaturated polybasic acid anhydride, the carboxylic acid produced by the reaction reacts with a compound containing one epoxy group and an unsaturated double bond in one molecule, respectively. Carboxyl photosensitive resin. (5) A carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid, and reacting a part or all of the second-stage hydroxyl group formed by the reaction with a polybasic acid anhydride. (6) A reaction product obtained by reacting a polyfunctional epoxy compound with a compound having one reactive group other than a hydroxyl group in which two or more hydroxyl groups react with an epoxy group with an unsaturated monocarboxylic acid Carboxyl group-containing photosensitive resin obtained by reaction with polybasic acid anhydride. (7) Photosensitivity of a reaction product obtained by reacting a reaction product of a resin having a phenolic hydroxyl group with an alkylene oxide with an unsaturated monocarboxylic acid and a polycarboxylic anhydride Resin. (8) An alcoholic hydroxyl group of a reaction product obtained by reacting a polyfunctional epoxy compound with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule and an unsaturated monocarboxylic acid, A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride group of an acid anhydride. [0093] The photocurable resin and the thermosetting resin used in the photocurable thermosetting resin composition of the present invention can be the same as the photocurable resin and the thermosetting resin. In addition to the above, the photocurable thermosetting resin composition of the present invention preferably contains the above-mentioned inorganic filler, a curing catalyst, and a photopolymerization initiator, and it is possible to suitably mix other conventionally-used blending ingredients according to its use. [0094] Examples of other conventionally formulated ingredients include the above-mentioned colorants, organic solvents, dispersants, antifoaming agents, flattening agents, thixotropic agents, coupling agents, and flame retardants. [0095] The curable resin composition of the present invention can be used as a dry film or as a liquid. When it is used as a liquid, it may be one liquid or two liquid or more. The two-liquid composition may be, for example, a composition divided into a hydrophobic fine cellulose fiber and a curable resin. [0096] Next, the dry film of the present invention has a resin layer obtained by applying the curable resin composition of the present invention to a carrier film and drying the carrier film. When forming a dry film, first, the hardenable resin composition of the present invention is diluted with the above-mentioned organic solvent, and adjusted to an appropriate viscosity. The cut-off wheel coater, doctor blade coater, lip mold coater, and rod coating are used. A cloth film, an extrusion coater, a reverse roll coater, a transfer roll coater, a gravure coater, a spray coater, etc. are applied to a carrier film to a uniform thickness. Then, the coated composition is usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to form a resin layer. There is no particular limitation on the coating film thickness, but generally the film thickness after drying can be appropriately selected in the range of 3 to 150 μm, preferably 5 to 60 μm. [0097] The carrier film may be a plastic film, such as a polyester film of polyethylene terephthalate (PET), a polyimide film, a polyimide film, a polypropylene film, or a polystyrene film. Wait. The thickness of the carrier film is not particularly limited, and generally can be appropriately selected in the range of 10 to 150 μm. A more preferable range is 15 to 130 μm. [0098] After the resin layer made of the curable resin composition of the present invention is formed on the carrier film, in order to avoid dust adhesion on the surface of the resin layer, a peelable cover film is further laminated on the surface of the resin layer to good. The peelable cover film can be, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, or a surface-treated paper. As for the cover film, when the cover film is peeled off, the adhesive force with the resin layer is smaller than the adhesive force between the resin layer and the carrier film. [0099] The present invention may be one in which the curable resin composition of the present invention is coated on the cover film and dried to form a resin layer, and a carrier film is laminated on the surface thereof. That is, in the present invention, when a dry film is produced, any one of a carrier film and a cover film can be used as the film for applying the curable resin composition of the present invention. [0100] The printed wiring board of the present invention is a cured product obtained from the resin layer of the curable resin composition or the dry film of the present invention. In the method for manufacturing a printed wiring board of the present invention, first, for example, the curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method by using the above-mentioned organic solvent, and a dip coating method, a shower coating method, or a roll coating method is used. , Coating rod method, screen printing method, curtain coating method and other methods are coated on the substrate, and the organic solvent contained in the composition is evaporated to dryness (temporary drying) at a temperature of 60 to 100 ° C, A tack-free resin layer is formed. In the case of a dry film, the resin layer is brought into contact with the base material by a laminator or the like to be adhered to the base material, and then the carrier film is peeled off to form a resin layer on the base material. [0101] In addition to the printed wiring board or flexible printed wiring board in which a circuit is formed by copper in advance, examples of the substrate include the use of paper phenol, paper epoxy resin, glass cloth epoxy resin, and glass polyurethane. Amine, glass cloth / non-woven epoxy resin, glass cloth / paper epoxy resin, synthetic fiber epoxy resin, fluororesin / polyethylene / polyphenylene ether, polyphenylene ether / isocyanate, etc. Materials include copper clad laminates of all grades (FR-4, etc.). Others include metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, and ceramic substrates. , Wafer board, etc. [0103] The volatilization drying performed after the application of the curable resin composition of the present invention can be performed using a hot air circulation drying furnace, an IR furnace, a heating plate, a convection oven, etc. (a person using a heat source equipped with an air heating method using steam can be used. The method of hot air convection contact in the dryer and the method of blowing from the nozzle to the support body). [0103] When the composition of the present invention is a thermosetting resin composition, after coating the composition on a substrate to form a coating film or laminating a dry film to form a resin layer, for example, by heating to about 100 to 180 ° C Temperature hardens heat and forms a cured film (hardened material) with excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. [0104] In the case where the composition of the present invention is a photocurable resin composition, the substrate is coated with the composition to form a coating film or a laminated dry film is formed to form a resin layer, and then the active energy ray is irradiated to form a cured film (cured material) . If necessary, the coating film may be heated before the irradiation with active energy rays. When the composition of the present invention is an alkali-developed photocurable thermosetting resin composition, after a resin layer is formed on a printed wiring board, a photomask having a specific pattern is formed and selectively exposed with active energy rays. , The unexposed part by the aqueous base solution (for example, 0. 3 to 3% by mass sodium carbonate aqueous solution) is developed to form a pattern of a hardened product. In addition, the hardened material is irradiated with active energy rays, and then heat-cured (for example, 100 to 220 ° C), or after heat-cured, the active energy rays are irradiated, or only heat-cured, and finally hardened (this hardening) to form adhesion Hardened film with excellent properties including hardness and hardness. In addition, the composition of the present invention may be a photocurable thermosetting resin composition that contains the above-mentioned thermosetting resin and photocurable resin, and does not undergo a development treatment or a non-developing type. [0105] The exposure machine used for the above-mentioned active energy ray irradiation may be a device equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, and the like, and irradiates ultraviolet rays in a range of 350 to 450 nm. Use a direct rendering device (for example, a laser direct imaging device that draws an image directly with CAD data from a computer). Direct drawing machine light source or laser light source, as long as the maximum wavelength is in the range of 350 ~ 450nm. The amount of exposure for image formation varies depending on film thickness, etc., but is generally 10 to 1000 mJ / cm 2 , Preferably 20 ~ 800mJ / cm 2 Within range. [0106] The development method may be a dipping method, a spray method, a spray method, a bristle method, or the like. As the developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, Aqueous alkali solutions such as amines.