[0012] 本發明之印刷配線板形成用環氧樹脂組成物包含(a)包含式[1]所示之環氧化合物A與式[2]所示之可具有環氧基之化合物B之混合物，及(b)硬化劑。 [0013] [式[1]所示之環氧化合物A] 本發明之(a)混合物包含上述式[1]所示之環氧化合物A。 上述式[1]中，R1
至R3
係各自獨立表示氫原子或甲基，L1
至L3
係各自獨立表示碳原子數1至10之伸烷基。 [0014] 作為L1
至L3
所示之碳原子數1至10之伸烷基，可舉出例如，亞甲基、伸乙基、三亞甲基、1-甲基伸乙基、四亞甲基、1-甲基三亞甲基、1,1-二甲基伸乙基、五亞甲基、1-甲基四亞甲基、2-甲基四亞甲基、1,1-二甲基三亞甲基、1,2-二甲基三亞甲基、2,2-二甲基三亞甲基、1-乙基三亞甲基、六亞甲基、1-甲基五亞甲基、2-甲基五亞甲基、3-甲基五亞甲基、1,1-二甲基四亞甲基、1,2-二甲基四亞甲基、2,2-二甲基四亞甲基、1-乙基四亞甲基、1,1,2-三甲基三亞甲基、1,2,2-三甲基三亞甲基、1-乙基-1-甲基三亞甲基、1-乙基-2-甲基三亞甲基、環己烷-1,4-二基、七亞甲基、八亞甲基、九亞甲基、2-甲基八亞甲基、十亞甲基等。較佳為亞甲基、三亞甲基、六亞甲基。 [0015] 本發明中，式[1]所示之環氧化合物係可使用市售之環氧化合物，或可使用以公知方法製造之含異三聚氰酸酯環之環氧化合物。可使用例如，TEPIC(註冊商標) [日產化學工業(股)製、三環氧丙基異三聚氰酸酯]、參(3,4-環氧基丁基)異三聚氰酸酯、TEIC-VL(註冊商標)[日產化學工業(股)製、參(4,5-環氧基戊基)異三聚氰酸酯]、參(5,6-環氧基己基)異三聚氰酸酯、TEIC-FL(註冊商標) [日產化學工業(股)製、參(7,8-環氧基辛基)異三聚氰酸酯]等。 藉由使用含異三聚氰酸酯環之環氧化合物，可取得耐光性、耐氣侯性、耐熱性、透明性等皆優之環氧樹脂。 [0016] [式[2]所示之化合物B] 又，本發明之(a)混合物包含上述式[2]所示之可具有環氧基之化合物B。 上述式[2]中，L1
至L3
係表示與前述相同意義，X1
至X3
係各自獨立表示上述式[2a]或上述式[2b]所示之基，但，X1
至X3
之中之至少一個為式[2b]所示之基。 上述式[2a]中，R1
表示與前述相同意義，黑點表示鍵結處。 上述式[2b]中，R1
及黑點表示與前述相同意義，R4
及R5
表示可經取代之碳原子數1至20之烷基、或可經取代之碳原子數6至10之芳基。 [0017] 作為R4
及R5
所示之可經取代之碳原子數1至20之烷基，可舉出例如，甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基、十三基、十四基、十五基、十六基、十七基、十八基、十九基、二十基等之直鏈狀烷基；異丙基、異丁基、sec-丁基、tert-丁基、異戊基、新戊基、tert-戊基、sec-異戊基、異己基、叔己基(thexyl)、4-甲基己基、5-甲基己基、2-乙基戊基、庚-3-基、庚-4-基、4-甲基己-2-基、3-甲基己-3-基、2,3-二甲基戊-2-基、2,4-二甲基戊-2-基、4,4-二甲基戊-2-基、6-甲基庚基、2-乙基己基、辛-2-基、6-甲基庚-2-基、6-甲基辛基、3,5,5-三甲基己基、壬-4-基、2,6-二甲基庚-3-基、3,6-二甲基庚-3-基、3-乙基庚-3-基、3,7-二甲基辛基、8-甲基壬基、3-甲基壬-3-基、4-乙基辛-4-基、9-甲基癸基、十一-5-基、3-乙基壬-3-基、5-乙基壬-5-基、2,2,4,5,5-五甲基己-4-基、10-甲基十一基、11-甲基十二基、十三烷-6-基、十三烷-7-基、7-乙基十一烷-2-基、3-乙基十一烷-3-基、5-乙基十一烷-5-基、12-甲基十三基、13-甲基十四基、十五烷-7-基、十五烷-8-基、14-甲基十五基、15-甲基十六基、十七烷-8-基、十七烷-9-基、3,13-二甲基十五烷-7-基、2,2,4,8,10,10-六甲基十一烷-5-基、16-甲基十七基、17-甲基十八基、十九烷-9-基、十九烷-10-基、2,6,10,14-四甲基十五烷-7-基、18-甲基十九基等之分枝烷基；環丙基、環丁基、環戊基、環己基、4-tert-丁基環己基、1,6-二甲基環己基、薄荷腦基、環庚基、環辛基、雙環[2.2.1]庚-2-基、莰烷基、異莰基、1-金剛烷基、2-金剛烷基、三環[5.2.1.02,6
]癸-4-基、三環[5.2.1.02,6
]癸-8-基、環十二基等之環狀烷基。以分別係碳原子數1至10之烷基為佳，較佳為碳原子數2至10之烷基。 此等烷基係可被例如，氰基、胺基、硝基、鹵素原子等之取代基所取代。 作為鹵素原子，可舉出例如，氟基、氯基、溴基、碘基等。 [0018] 作為R4
及R5
所示之可經取代之碳原子數6至10之芳基，可舉出例如，苯基、1-萘基、2-萘基等。較佳係分別為苯基。 此等芳基係可被例如，甲基、乙基、丙基等之碳原子數1至6之烷基、氰基、胺基、硝基、鹵素原子等之取代基所取代。 [0019] 本發明中，式[2]所示之化合物係可使用市售之環氧化合物，或可使用以公知方法製造者。例如，較佳可使用使式[1]所示之環氧化合物A之環氧基之一部分或全部與酸酐反應而以式[2b]所示之基取代而成者。例如，化合物B係以對環氧化合物A之環氧基加成式[3]所示之酸酐1分子而成之化合物(1莫耳加成物)、加成2分子而成之化合物(2莫耳加成物)、加成3分子而成之化合物(3莫耳加成物)之混合物為佳。(式中，R4
及R5
表示與前述相同意義)。 [0020] 上述式[3]所示之酸酐係與所謂之由2分子之單羧酸所得之酸酐且係使用作為環氧樹脂硬化劑之由二羧酸所得之酸酐相異，故不具有作為環氧樹脂硬化劑之功能。 又，使環氧化合物與酸酐反應而得之化合物B由於不具有羥基，故即使未反應之酸酐存在，仍不會膠化等且保存安定性高。 酸酐並非係受到特別限定者，可舉出例如，無水乙酸、無水丙酸、無水丁酸、無水異丁酸、無水戊酸、無水己酸、無水辛酸、無水三氟乙酸、無水安息香酸等。 [0021] 例如，可藉由式[1]所示之環氧化合物A與式[3]所示之酸酐之反應，而取得包含未反應之環氧化合物(環氧化合物A)，與包含加成酸酐1分子而成之化合物、加成酸酐2分子而成之化合物及加成酸酐3分子而成之化合物(化合物B)之混合物。藉由調整相對於環氧化合物A之莫耳數之使其反應之酸酐莫耳數，即可調整酸酐之經加成之化合物之存在量。 [0022] 本發明之(a)混合物能使環氧化合物A：酸酐在(環氧化合物A之環氧基)：(酸酐)之莫耳比下，以1：0.1~1：1，較佳為1：0.4~1：0.8之比例進行反應而得。 [0023] 反應生成物係可藉由HPLC分析等，而求出未反應之環氧化合物A，與對環氧化合物A之環氧基加成式[3]所示之酸酐1個而成之化合物、加成2個而成之化合物、及加成3個之化合物(化合物B)之莫耳比。 [0024] 反應所使用之溶劑只要係對反應呈惰性者即可。作為此等溶劑，可舉出例如，丙酮、甲基乙基酮等之酮類；乙腈等之腈類；四氫呋喃、二噁烷等之醚類；乙酸乙酯等之酯類；氯苯、甲苯等之芳香族烴類；氯仿、二氯乙烷等之鹵素化烴類等。可單獨使用或可將此等使用作為混合溶劑，來使三環氧丙基異三聚氰酸酯等之環氧化合物A溶解。 又，因應必要，可使用三乙基胺、三丙基胺、1,8-二吖雙環[5.4.0]十一-7-烯等之3級胺類，或由溴化乙基三苯基鏻、溴化四苯基鏻等所代表之鹵素化單烷基三苯基鏻等之第4級鏻鹽、2-乙基-4-甲基咪唑等之咪唑系化合物、溴化四乙基銨等之第4級銨鹽、三苯基膦等之磷化合物等作為觸媒。 [0025] 反應溫度係例如在溶劑之迴流溫度進行，且進行直到使用0.1N過氯酸／乙酸溶液所滴定之環氧基含量成為理論值(經添加之酸酐因反應而消滅之值)為止。反應結束後，餾除溶劑而可取得(a)混合物。 [0026] ＜(a)混合物＞ 本發明之混合物中，式[1]所示之環氧化合物A與式[2]所示之化合物B之含量並無特別限制，例如，相對於1莫耳之環氧化合物A，包含0.2~20莫耳之化合物B，較佳包含0.7~4莫耳。 化合物A之環氧基與化合物B之環氧基之總和，平均係換算成1分子(總環氧基數除以總分子數)以2個以上為佳。若未滿2個則硬化物之物性，尤其係耐熱性降低而不佳。 [0027] 又，本發明之混合物在不損及本發明之效果範圍內，可併用式[1]所示之環氧化合物A及式[2]所示之化合物B，與其以外之環氧化合物。 上述式[1]所示之環氧化合物A及式[2]所示之化合物B，與其以外之環氧化合物，以環氧基之莫耳比計，能在例如1：0~1：20之範圍內使用。 作為上述其以外之環氧化合物，並未受到特別限定，可使用市售之各種多官能之環氧化合物。 [0028] 作為本發明能使用之環氧化合物，可舉出例如，1,4-丁二醇二環氧丙基醚、1,6-己二醇二環氧丙基醚、(聚)乙二醇二環氧丙基醚、(聚)丙二醇二環氧丙基醚、三羥甲基乙烷三環氧丙基醚、三羥甲基丙烷三環氧丙基醚、1,4-環己烷二甲醇二環氧丙基醚、1,2-環氧基-4-(環氧基乙基)環己烷、丙三醇三環氧丙基醚、二三醇聚二環氧丙基醚、2,6-二環氧丙基苯基=環氧丙基=醚、1,1,3-參(4-環氧丙氧基苯基)丙烷、1,2-環己烷二羧酸二環氧丙基、4,4’-亞甲基雙(N,N-二環氧丙基苯胺)、3,4-環氧基環己烷羧酸3’,4’-環氧基環己基甲基、三環氧丙基-p-胺基酚、四環氧丙基間二甲苯二胺、四環氧丙基二胺基二苯基甲烷、四環氧丙基-1,3-雙胺基甲基環己烷、雙酚A二環氧丙基醚、雙酚S二環氧丙基醚、四溴雙酚A二環氧丙基醚、氫化雙酚A二環氧丙基醚、季戊四醇二環氧丙基醚、季戊四醇四環氧丙基醚、季戊四醇聚環氧丙基醚、間苯二酚二環氧丙基醚、酞酸二環氧丙基、四氫酞酸二環氧丙基、新戊二醇二環氧丙基醚、雙酚六氟丙酮二環氧丙基醚、參(2-環氧丙氧基乙基)異三聚氰酸酯、單烯丙基二環氧丙基異三聚氰酸酯、N,N’-二環氧丙基N”-(2,3-二丙醯氧基丙基)異三聚氰酸酯、N,N’-雙(2,3-二丙醯氧基丙基)N”-環氧丙基異三聚氰酸酯、參(2,2-雙(環氧丙氧基甲基)丁基)3,3’,3”-(2,4,6-三側氧基-1,3,5-三嗪-1,3,5-三基)三丙酸酯、山梨醇聚環氧丙基醚、己二酸二環氧丙基、o-酞酸二環氧丙基、二溴苯基環氧丙基醚、1,2,7,8-二環氧基辛烷、1,6-二羥甲基全氟己烷二環氧丙基醚、4-(螺[3,4-環氧基環己烷-1,5’-[1,3]二噁烷]-2’-基)-1,2-環氧基環己烷、1,2-雙(3,4-環氧基環己基甲氧基)乙烷、4,5-環氧基-2-甲基環己烷羧酸4’,5’-環氧基-2’-甲基環己基甲基、乙二醇雙(3,4-環氧基環己烷羧酸酯)、雙(3,4-環氧基環己基甲基)己二酸酯、雙(2,3-環氧基環戊基)醚等，但並非係此等所限定者。 此等環氧化合物係可單獨使用或可使用作為二種以上之混合物。 [0029] 尚且，作為上述環氧化合物之一例，可舉出如以下之市售品。 作為液狀環氧化合物，可舉出如TEPIC(註冊商標)-UC [日產化學工業(股)製]、jER(註冊商標)828、同YX8000 [皆為三菱化學(股)製]、RikaResin(註冊商標)DME100[新日本理化(股)製]、Ceroxide 2021P[(股)戴爾製]等。 [0030] ＜(b)硬化劑＞ 本發明之印刷配線板形成用環氧樹脂組成物包含(b)硬化劑。 作為硬化劑，並非無係受到特別限定者，可使用例如酸酐、胺、酚樹脂、聚醯胺樹脂、咪唑類、聚硫醇或此等之混合物。此等之中，特別係以酸酐及胺為佳。此等硬化劑係可使用固體，亦可藉由溶解於溶劑後使用。但，因溶劑蒸發會造成硬化物之密度降低或因細孔生成而造成強度降低、耐水性降低，故以硬化劑自身在常溫、常壓下為液狀者為佳。 硬化劑係相對於環氧化合物之環氧基1當量，能在0.5~1.5當量，較佳為0.8~1.2當量之比例下含有。相對於環氧化合物之硬化劑當量係以相對於環氧基之硬化劑之硬化性基之當量比來表示。尚且，在併用上述包含式[1]所示之環氧化合物及式[2]所示之化合物之混合物(a)，與其以外之環氧化合物時，該等之相對於全部環氧化合物之環氧基的當量則仍為前述範圍。 [0031] 作為酸酐，以一分子中具有複數羧基之化合物之無水物為佳。作為該等酸酐，可舉出例如，無水酞酸、無水偏苯三甲酸、無水苯均四酸、無水二苯甲酮四羧酸、乙二醇雙偏苯三甲酸酯、丙三醇參偏苯三甲酸酯、無水馬來酸、四氫無水酞酸、甲基四氫無水酞酸、內亞甲基四氫無水酞酸、甲基內亞甲基四氫無水酞酸、甲基丁烯基四氫無水酞酸、十二烯基無水琥珀酸、六氫無水酞酸、甲基六氫無水酞酸、無水琥珀酸、甲基環己烯二羧酸酐、氯香酸(Chlorendic acid)酐等。 該等之中，以在常溫、常壓為液狀之甲基四氫無水酞酸、甲基-5-降莰烯-2,3-二羧酸酐(甲基納迪克酸酐、無水甲基降莰烯二酸(methylhimic acid anhydride))、氫化甲基納迪克酸酐、甲基丁烯基四氫無水酞酸、十二烯基無水琥珀酸、甲基六氫無水酞酸、甲基六氫無水酞酸與六氫無水酞酸之混合物為佳。此等液狀之酸酐之黏度在25℃下測量為10~1,000mPa・s程度。酸酐基中，1個酸酐基係計算當作1當量。 [0032] 作為胺，可舉出例如，哌啶、N,N’-二甲基哌嗪、三乙二胺、2,4,6-參(二甲基胺基甲基)酚、苄基二甲基胺、2-(二甲基胺基甲基)酚、二伸乙三胺、三伸乙四胺、四伸乙五胺、二乙基胺基丙基胺、N-胺基乙基哌嗪、二(1-甲基-2-胺基環己基)甲烷、薄荷烷二胺、異佛爾酮二胺、二胺基二環己基甲烷、1,3-雙(胺基甲基)環己烷、茬二胺、間苯二胺、二胺基二苯基甲烷、二胺基二苯基碸等。此等之中，較佳可使用液狀之二伸乙三胺、三伸乙四胺、四伸乙五胺、二乙基胺基丙基胺、N-胺基乙基哌嗪、雙(1-甲基-2-胺基環己基)甲烷、薄荷烷二胺、異佛爾酮 二胺、二胺基二環己基甲烷等。 [0033] 作為酚樹脂，可舉出例如，苯酚酚醛樹脂、甲酚酚醛樹脂等。 [0034] 聚醯胺樹脂係由二聚物酸與聚胺之縮合而生成者，且分子中具有一級胺與二級胺之聚醯胺胺。 [0035] 作為咪唑類，可舉出例如，2-甲基咪唑、2-乙基-4-甲基咪唑、偏苯三甲酸1-氰基乙基-2-十一基咪唑鎓、環氧基咪唑加成物等。 [0036] 聚硫醇係例如，在聚丙二醇鏈之末端存在硫醇基者，或在聚乙二醇鏈之末端存在硫醇基者，以液狀者為佳。 [0037] ＜硬化促進劑＞ 又，在從本發明之印刷配線板形成用環氧樹脂組成物取得硬化物之際，除使用硬化劑之外，亦可適宜併用硬化促進劑(亦稱為硬化助劑)。 作為硬化促進劑，可舉出如三苯基膦、三丁基膦等之有機磷化合物；溴化乙基三苯基鏻、四丁基鏻O,O-二乙基硫代二磷酸酯等之第4級鏻鹽；1,8-二吖雙環[5.4.0]十一-7-烯、1,8-二吖雙環[5.4.0]十一-7-烯與辛基酸之鹽、辛基酸鋅、溴化四丁基銨等之第4級銨鹽等。又也可將作為前述硬化劑所舉出之2-甲基咪唑、2-乙基-4-甲基咪唑等之咪唑類，或2,4,6-參(二甲基胺基甲基)酚、苄基二甲基胺等之胺類，使用作為對於其他種類硬化劑之硬化促進劑。 此等硬化促進劑係相對於硬化劑1質量份，可在0.001~0.1質量份之比例下使用。 [0038] ＜＜印刷配線板形成用環氧樹脂組成物＞＞ 本發明係藉由混合上述式[1]所示之環氧化合物A及式[2]所示之化合物B，與上述硬化劑，與根據所需之硬化促進劑，而可取得印刷配線板形成用環氧樹脂組成物。以在減壓下攪拌混合該等混合物並進行脫泡為佳。 由環氧樹脂組成物所得之硬化物係可藉由將該環氧樹脂組成物塗佈於基材，或注入已塗佈離型劑之注型板，在例如100~120℃之溫度下進行預備硬化，且在120~200℃之溫度下進行主硬化(後硬化)而得。且，由本發明之環氧樹脂組成物所得之硬化物係可適合使用於印刷配線基板。 加熱時間係根據環氧樹脂之大小或厚度來適宜調節。例如，例如預備硬化及主硬化一同分別為1~12小時，例如2~5小時程度。 [0039] 作為將本發明之環氧樹脂組成物塗佈於基材上之方法，可舉出例如，流塗法、旋轉塗佈法、噴霧塗佈法、網版印刷法、柔版印刷法、噴墨印刷法、澆鑄法、棒塗佈法、簾塗佈法、輥塗佈法、凹版塗佈法、浸漬法、狹縫塗佈法等。 [0040] ＜(c)硬化觸媒＞ 本發明中，硬化觸媒係可使用例如(c1)酸發生劑及／或(c2)鹼產生劑。藉此，即使混合本發明之環氧化合物與硬化觸媒仍不會隨即產生硬化，故可取保存安定性優異，且充分作業時間。 [0041] [(c1)酸發生劑] 作為(c1)酸發生劑，可使用光酸發生劑或熱酸發生劑。光酸發生劑或熱酸發生劑只要係因光照射或加熱而直接或間接的產生酸(路易斯酸或布氏酸)者，即無特別限定。配合有熱酸發生劑之環氧樹脂組成物係藉由加熱即能在短時間使其硬化。又，配合有光酸發生劑之環氧樹脂組成物係不因加熱，而係以光照射才會進行硬化，故可使用在耐熱性低之基板及部位。 [0042] 作為光酸發生劑之具體例，可舉出如錪鹽、鋶鹽、鏻鹽、硒鹽等之鎓鹽、茂金屬錯合物化合物、鐵芳烴錯合物化合物、二碸系化合物、磺酸衍生物化合物、三嗪系化合物、苯乙酮衍生物化合物、重氮甲烷系化合物等。 [0043] 作為上述錪鹽，可舉出例如，二苯基錪、4,4’-二氯二苯基錪、4,4’-二甲氧基二苯基錪、4,4’-二-tert-丁基二苯基錪、4-甲基苯基(4-(2-甲基丙基)苯基)錪、3,3’-二硝基苯基錪、4-(1-乙氧基羰基乙氧基)苯基(2,4,6-三甲基苯基)錪、4-甲氧基苯基(苯基)錪等之，錪之氯化物、溴化物、甲磺酸鹽、甲苯磺酸鹽、三氟甲烷磺酸鹽、四氟硼酸鹽、肆(五氟苯基)硼酸鹽、六氟磷酸鹽、六氟砷酸鹽、六氟銻酸鹽等之二芳基錪鹽等。 [0044] 作為上述鋶鹽，可舉出例如，三苯基鋶、二苯基(4-tert-丁基苯基)鋶、參(4-tert-丁基苯基)鋶、二苯基(4-甲氧基苯基)鋶、參(4-甲基苯基)鋶、參(4-甲氧基苯基)鋶、參(4-乙氧基苯基)鋶、二苯基(4-(苯硫基)苯基)鋶、參(4-(苯硫基)苯基)鋶等之，鋶之氯化物、溴化物、三氟甲烷磺酸鹽、四氟硼酸鹽、六氟磷酸鹽、六氟砷酸鹽、六氟銻酸鹽等之三芳基鋶鹽等。 [0045] 作為上述鏻鹽，可舉出例如，四苯基鏻、乙基三苯基鏻、四(p-甲氧基苯基)鏻、乙基三(p-甲氧基苯基)鏻、苄基三苯基鏻等之，鏻之、氯化物、溴化物、四氟硼酸鹽、六氟磷酸鹽、六氟銻酸鹽等之芳基鏻鹽等。 [0046] 作為上述硒鹽，可舉出例如，三苯基硒六氟磷酸鹽等之三芳基硒鹽等。 [0047] 作為上述鐵芳烴錯合物化合物，可舉出例如，雙(η5
-環戊二烯基)(η6
-異丙基苯)鐵(II)六氟磷酸鹽等。 [0048] 此等光酸發生劑係可單獨使用，或可將二種以上組合使用。 [0049] 作為熱酸發生劑，可舉出如鋶鹽及鏻鹽，較佳使用鋶鹽。 作為此等之例示化合物，可舉出如上述光酸發生劑中作為各種鎓鹽之例示所例舉之化合物。 此等熱酸發生劑係可單獨使用，或可將二種以上組合使用。 [0050] 此等之中，(c1)酸發生劑係以鋶氯化合物或錪氯化合物為佳，以例如顯示強酸性之六氟磷酸鹽或六氟銻酸鹽等之具有陰離子種之化合物為佳。 本發明之環氧樹脂組成物中之(c1)酸發生劑之含量係相對於(a)環氧化合物100質量份，可作成0.1~20質量份，或0.1~10質量份，更佳作成0.5~10質量份。尚且，在併用上述式[1]所示之環氧化合物，與其以外之環氧化合物時，該等之相對於全部環氧化合物100質量份之含量仍成為前述範圍。 [0051] [(c2)鹼產生劑] 作為(c2)鹼產生劑，可使用光鹼產生劑或熱鹼產生劑。光鹼酸發生劑或熱鹼產生劑只要係因光照射或加熱而直接或間接的產生鹼(路易斯鹼或布氏鹼)者，即無特別限定。在配合有熱鹼產生劑之環氧樹脂組成物係藉由加熱而能短時間內使其硬化。又，在配合有光鹼產生劑之環氧樹脂組成物係不因加熱，而係因光照射才會進行硬化，故可使用於耐熱性低之基板及部位。 [0052] 作為光鹼產生劑，可舉出例如，9-蒽基甲基=N,N-二乙基胺甲酸酯(carbamate)等之烷基胺系光鹼產生劑；9-蒽基=N,N-二環己基胺甲酸酯、1-(9,10-蒽醌-2-基)乙基=N,N-二環己基胺甲酸酯、二環己基銨=2-(3-苄醯基苯基)丙酸酯、9-蒽基=N-環己基胺甲酸酯、1-(9,10-蒽醌-2-基)乙基=N-環己基胺甲酸酯、環己基銨=2-(3-苄醯基苯基)丙酸鹽、(E)-N-環己基-3-(2-羥基苯基)丙烯醯胺等之環烷基胺系光鹼產生劑；9-蒽基甲基=哌啶-1-羧酸酯、(E)-1-哌啶基-3-(2-羥基苯基)-2-丙烯-1-酮、(2-硝基苯基)甲基=4-羥基哌啶-1-羧酸酯、(2-硝基苯基)甲基=4-(甲基丙烯醯氧基)哌啶-1-羧酸酯等之哌啶系光鹼產生劑；胍鎓(guanidinium)=2-(3-苄醯基苯基)丙酸鹽、1,2-二異丙基-3-(雙(二甲基胺基)亞甲基)胍鎓=2-(3-苄醯基苯基)丙酸鹽、1,2-二環己基-4,4,5,5-四甲基二胍鎓=n-丁基三苯基硼酸鹽、1,5,7-三吖雙環[4.4.0]癸-5-烯鎓=2-(9-側氧基呫噸-2-基)丙酸鹽等之胍系光鹼產生劑；1-(9,10-蒽醌-2-基)乙基=咪唑-1-羧酸酯等之咪唑系光鹼產生劑等。 此等光鹼產生劑係可單獨使用一種，或可將二種以上組合使用。 又，光鹼產生劑係能取得作為市售品，可適宜使用例如，和光純藥工業(股)製之光鹼產生劑WPBG系列(WPBG-018、同027、同082、同140、同266、同300等)等。 [0053] 作為熱鹼產生劑，可舉出例如，1-甲基-1-(4-聯苯基)乙基胺甲酸酯、2-氰基-1,1-二甲基乙基胺甲酸酯等之胺甲酸酯類；脲、N,N-二甲基-N’-甲基脲等之脲類；三氯乙酸胍、苯基磺醯基乙酸胍、苯基丙炔酸胍等之胍類；1,4-二氫菸鹼醯胺等之二氫吡啶類；N-(異丙氧基羰基)-2,6-二甲基哌啶、N-(tert-丁氧基羰基)-2,6-二甲基哌啶、N-(苄氧基羰基)-2,6-二甲基哌啶等之二甲基哌啶類；苯基磺醯基乙酸四甲基銨、苯基丙炔酸四甲基銨等之四級化銨鹽；二氰二醯胺等。又，可舉出如1,8-二吖雙環[5.4.0]十一-7-烯(DBU)之鹽，即U-CAT(註冊商標)SA810、同SA831、同SA841、同SA851[以上，Sun-Apro(股)製]等。 此等熱鹼產生劑係可單獨使用一種，或可將二種以上組合使用。 [0054] 本發明之環氧樹脂組成物中之(c2)鹼產生劑之含量在相對於(a)環氧化合物100質量份，可作成0.1~20質量份，或0.1~10質量份，更佳可作成0.5~10質量份。尚且，在併用上述包含式[1]所示之環氧化合物及式[2]所示之化合物之混合物(a)，與其以外之環氧化合物時，該等之相對於全部環氧化合物100質量份之含量仍成為前述範圍。 [0055] 本發明中藉由混合上述(a)混合物與上述硬化觸媒而可取得環氧樹脂組成物。為了取得該環氧樹脂組成物之混合之操作條件係如同前述。 [0056] 本發明係可藉由將包含上述(a)混合物及光酸發生劑或光鹼產生劑之環氧樹脂組成物塗佈基板上並進行光照射來使其硬化。又在光照射之前後亦可進行加熱。 又，本發明係可藉由將包含上述(a)混合物及熱酸發生劑或熱鹼產生劑之環氧樹脂組成物塗佈於基板上進行加熱來使其硬化。 並且，可藉由將包含上述(a)混合物及熱酸發生劑與光酸發生劑或熱鹼產生劑與光鹼產生劑之環氧樹脂組成物塗佈於基板上，在加熱後進行光照射來使其硬化。 [0057] 由本發明之環氧樹脂組成物所形成之塗膜之厚度係可因應硬化物之用途，在0.01μm~10mm程度之範圍內選擇，例如，在使用於光阻時可作成0.05~10μm(尤其0.1~5μm)程度，在使用於印刷配線基板時可作成10μm ~5mm(尤其100μm~1mm)程度，在使用於光學薄膜時可作成0.1~100μm(尤其0.3~50μm)程度。 [0058] 作為在使用光酸發生劑或光鹼產生劑時之照射或曝光之光，可舉出例如，γ射線、X線、紫外線、可見光線等，通常使用可見光線或紫外線，尤其係使用紫外線之情況較多。 光之波長係例如，150~800nm，較佳為150~600nm，更佳為200~400nm，特佳為300~400nm程度。 照射光量係根據塗膜之厚度而不同，可做成例如2~20,000mJ／cm2
，較佳作成5~5,000mJ／cm2
程度。 作為光源，可因曝光之光線種類進行選擇，例如，在紫外線之情況，可使用低壓水銀燈、高壓水銀燈、超高壓水銀燈、氘燈、鹵素燈、雷射光(氦-鎘雷射、準分子雷射等)、UV-LED等。藉由此種光照射，前述組成物之硬化反應即會進行。 [0059] 在使用熱酸發生劑或熱鹼產生劑之情況，或使用光酸發生劑或光鹼產生劑且在光照射後因應必要所實施之塗膜之加熱係在例如室溫(約23℃)~250℃程度下進行。加熱時間係可選自3秒以上(例如，3秒~5小時程度)之範圍，例如，5秒~2小時程度。 [0060] 並且，在形成圖型或畫像之情況(例如，在製造印刷配線基板等之情況)，亦可對形成於基材上之塗膜進行圖型曝光。此圖型曝光係可藉由雷射光之掃描來進行，亦可藉由通過光罩進行光照射來進行。藉由使用顯像液使藉由此種圖型曝光所生成之非照射區域(未曝光部)進行顯像(或溶解)，即可形成圖型或畫像。 [0061] 作為顯像液，可使用鹼水溶液或有機溶劑。 作為鹼水溶液，可舉出例如，氫氧化鉀、氫氧化鈉、碳酸鉀、碳酸鈉等之鹼金屬氫氧化物之水溶液；氫氧化四甲基銨、氫氧化四乙基銨、膽鹼等之氫氧化四級銨之水溶液；乙醇胺、丙基胺、乙二胺等之胺水溶液等。 [0062] 前述鹼顯像液一般係使用10質量%以下之水溶液，較佳使用0.1~3質量%之水溶液等。並且，亦可對上述顯像液添加醇類或界面活性劑後使用，此等添加量係分別相對於顯像液100質量份而言，較佳為0.05~10質量份。具體而言，可使用0.1~2.38質量%之氫氧化四甲基銨水溶液等。 [0063] 又，作為顯像液之有機溶劑係能使用一般性有機溶劑，可舉出例如，甲苯等之芳香族烴類；乳酸乙酯、丙二醇單甲基醚乙酸酯(PGMEA)、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、丙二醇單丁基醚乙酸酯等之酯類；N,N-二甲基甲醯胺(DMF)等之醯胺類；乙腈等之腈類；丙酮、環己酮等之酮類；甲醇、乙醇、2-丙醇、丙二醇單甲基醚(PGME)、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚等之醇類等。此等係可使用單獨使用或可使用作為二種以上之混合物。 其中，較佳可使用乳酸乙酯、丙二醇單甲基醚乙酸酯(PGMEA)、丙二醇單甲基醚(PGME)等。 [0064] ＜溶劑＞ 上述之環氧樹脂組成物在因應必要尚可包含溶劑。 作為溶劑，可舉出例如，甲苯、茬等之芳香族烴類；乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯等之酯類；羥基乙酸甲酯、羥基乙酸乙酯、羥基乙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3-羥基丙酸甲酯、3-羥基丙酸乙酯、3-羥基丙酸丙酯、3-羥基丙酸丁酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、2-羥基-3-甲基丁酸甲酯等之羥基酯類；甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸丙酯、乙氧基乙酸丁酯、丙氧基乙酸甲酯、丙氧基乙酸乙酯、丙氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸甲酯、丁氧基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-甲氧基丙酸丁酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸丙酯、2-乙氧基丙酸丁酯、2-丁氧基丙酸甲酯、2-丁氧基丙酸乙酯、2-丁氧基丙酸丙酯、2-丁氧基丙酸丁酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸丙酯、3-乙氧基丙酸丁酯、3-丙氧基丙酸甲酯、3-丙氧基丙酸乙酯、3-丙氧基丙酸丙酯、3-丙氧基丙酸丁酯、3-丁氧基丙酸甲酯、3-丁氧基丙酸乙酯、3-丁氧基丙酸丙酯、3-丁氧基丙酸丁酯、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丙二醇單甲基醚乙酸酯(PGMEA)、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、丙二醇單丁基醚乙酸酯、丙二醇單甲基醚丙酸酯、丙二醇單乙基醚丙酸酯、丙二醇單丙基醚丙酸酯、丙二醇單丁基醚丙酸酯等之醚酯類；甲基乙基酮(MEK)、4-羥基-4-甲基-2-戊酮、環己酮等之酮類；乙二醇單甲基醚、乙二醇單乙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、丙二醇單甲基醚(PGME)、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚等之醇類；四氫呋喃(THF)、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇乙基甲基醚等之醚類等。 [0065] ＜其他硬化性單體＞ 本發明中，以調整環氧樹脂組成物之黏度或提升硬化性為目的，可使用含乙烯基化合物、含環氧丙烷基化合物等作為陽離子硬化性單體。 [0066] 作為含乙烯基化合物，只要係具有乙烯基之化合物即無特別限定，可舉出例如，2-羥基乙基乙烯基醚(HEVE)、二乙二醇單乙烯基醚(DEGV)、2-羥基丁基乙烯基醚(HBVE)、三乙二醇二乙烯基醚等之乙烯基醚化合物等。又，亦可使用在α位及／或β位具有烷基、烯丙基等之取代基之乙烯基化合物。又，可使用包含環氧基及／或環氧丙烷基等之環狀醚基之乙烯基醚化合物，可舉出例如，氧基降莰烯二乙烯基醚、3、3-二甲醇環氧丙烷二乙烯基醚等。 又，可使用具有乙烯基與(甲基)丙烯醯基之化合物，可舉出例如，(甲基)丙烯酸2-(2-乙烯基氧基乙氧基)乙基等。 此等含乙烯基化合物係可單獨使用或可將二種以上組合使用。 [0067] 作為含環氧丙烷基化合物，只要係具有環氧丙烷基之化合物即無特別限定，可舉出如3-乙基-3-(羥基甲基)環氧丙烷(OXA)、3-乙基-3-(苯氧基甲基)環氧丙烷(POX)、雙((3-乙基-3-環氧丙烷基)甲基)醚(DOX)、1,4-雙(((3-乙基-3-環氧丙烷基)甲氧基)甲基)苯(XDO)、3-乙基-3-(2-乙基己氧基甲基)環氧丙烷(EHOX)、3-乙基-3-((3-三乙氧基矽基丙氧基)甲基)環氧丙烷(TESOX)、環氧丙烷基半矽氧烷(OX-SQ)、苯酚酚醛環氧丙烷(PNOX-1009)等之環氧丙烷化合物等。 又，可使用具有環氧丙烷基與(甲基)丙烯醯基之化合物，可舉出例如，(甲基)丙烯酸(3-乙基-3-環氧丙烷基)甲基等。 此等含環氧丙烷基之化合物係可單獨使用或可將二種以上組合使用。 [0068] ＜其他成分＞ 上述組成物因應必要亦可包含慣用之添加劑。作為此種添加劑，可舉出例如，增稠劑、增感劑、消泡劑、調平劑、塗佈性改良劑、潤滑劑、安定劑(防氧化劑、熱安定劑、耐光安定劑等)、塑化劑、界面活性劑、溶解促進劑、填充劑、防帶電劑、硬化劑等。此等添加劑係可單獨使用或使用二種以上之組合。 [0069] 在提升塗佈性之目的上，本發明之環氧樹脂組成物中可添加界面活性劑。此種界面活性劑可舉出如氟系界面活性劑、聚矽氧系界面活性劑、非離子系界面活性劑等，並非係特別受到此等所限定者。前述界面活性劑係可單獨使用或可將二種類以上組合使用。 此等界面活性劑之中，在從改善塗佈性改善效果之觀點，以氟系界面活性劑為佳。作為氟系界面活性劑之具體例，可舉出例如，Eftop(註冊商標)EF-301、同EF-303、同EF-352[皆為三菱材料電子化成(股)製]、Megafac(註冊商標)F-171、同F-173、同F-482、同R-08、同R-30、同R-90、同BL-20[皆為DIC(股)製]、Fluorad FC-430、同FC-431[皆為日本3M(股)製]、Asahiguard(註冊商標)AG-710[旭硝子(股)製]、SurflonS-382、同SC-101、同SC-102、同SC-103、同SC-104、同SC-105、同SC-106[皆為AGC清美化學(股)製]等，但並非係受限於此等者。 本發明之環氧樹脂組成物中之界面活性劑之添加量在基於該環氧樹脂組成物之固體成分之含量而言，如為0.01~5質量%，以0.01~3質量%為佳，較佳為0.01~2質量%。 [0070] 在提升顯像後之與基板之密著性為目的，本發明之環氧樹脂組成物中可添加密著促進劑。作為此等密著促進劑，可舉出例如，氯三甲基矽烷、三氯(乙烯基)矽烷、氯(二甲基)(乙烯基)矽烷、氯(甲基)(二苯基)矽烷、氯(氯甲基)(二甲基)矽烷等之氯矽烷類；甲氧基三甲基矽烷、二甲氧基二甲基矽烷、二乙氧基二甲基矽烷、乙氧基(二甲基)(乙烯基)矽烷、二甲氧基二苯基矽烷、三乙氧基(苯基)矽烷、3-氯丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-環氧丙基氧基丙基三甲氧基矽烷、三甲氧基(3-(N-哌啶基)丙基)矽烷等之烷氧基矽烷類；六甲基二矽氮烷、N,N’-雙(三甲基矽基)脲、二甲基(三甲基矽基)胺、三甲基矽基咪唑等之矽氮烷類；咪唑、吲唑、苯並咪唑、苯並三唑、巰基咪唑、巰基嘧啶2-巰基苯並咪唑、2-巰基苯並噁唑、2-巰基苯並噻唑、脲唑、硫脲嘧啶等之含氮雜環化合物；1,1-二甲基脲、1,3-二甲基脲等之脲類或硫脲類等。此等密著促進劑係可單獨使用或可將二種類以上組合使用。 本發明之環氧樹脂組成物中之密著促進劑之添加量在基於該環氧樹脂組成物之固體成分之含量而言，通常為20質量%以下，以0.01~10質量%為佳，較佳為0.05~5質量%。 [0071] 本發明之環氧樹脂組成物亦可包含增感劑。作為可使用之增感劑，可舉出如蒽、Phenothiazene、苝、噻噸酮、二苯甲酮噻噸酮等。並且，作為增感色素，可例示如硫代吡喃鎓鹽系色素、部花青素系色素、喹啉系色素、苯乙烯基喹啉系色素、香豆素酮系色素、噻吨系色素、呫噸系色素、氧雜菁系色素、花青系色素、玫瑰紅系色素、吡喃鎓鹽系色素等。特佳者為蒽系之增感劑，藉由併用陽離子硬化觸媒(感放射性陽離子聚合開始劑)，感度可飛躍性提升，且同時具有自由基聚合起始功能，例如，在採用併用陽離子硬化系統與自由基硬化系統之混合型時，可使觸媒種類較為簡單。作為具體之蒽之化合物，如二丁氧基蒽、二丙氧基蒽醌等為有效者。 又，使用鹼產生劑作為硬化觸媒時之增感劑，可舉出例如，苯乙酮類、安息香類、二苯甲酮類、蒽醌類、呫噸(Xanthone)類、噻噸酮類、縮酮類、3級胺類等。 本發明之環氧樹脂組成物中之增感劑之添加量在基於該環氧樹脂組成物之固體成分之含量而言，如為0.01~20質量%，較佳為0.01~10質量%。 [產業上之可利用性] [0072] 本發明之包含(a)混合物及(b)硬化劑之環氧樹脂組成物具有光及熱硬化性，可廣泛使用於接著劑、防反射膜(液晶顯示器用之防反射膜等)之高折射率層、光學薄膜(反射板等)、電子零件用密封材、印刷配線基板、層間絕緣膜材料(增層印刷基板用層間絕緣膜材料等)等之電子材料領域。尤其係可廣泛利用作為印刷配線基板、層間絕緣膜材料等之要求低介電正切且低介電率之電子材料。 [實施例] [0073] 以下，列舉實施例更加具體說明本發明，但本發明並非係受限於下述之實施例者。 尚且，實施例中，調製試料及分析物性所使用之裝置及條件係如以下所示。 [0074] (1)氣相層析(GC) 裝置：(股)島津製作所製 GC-2010 Plus 檢出器：FID 管柱：安捷倫科技(股)製 Agilent J＆W GC管柱 HP-5(長度30m、內徑0.32mm、膜厚0.25μm) 注入量：1.0μL 注入口溫度：250℃ 管柱溫度：40℃(5分鐘)、以20℃／分升溫至300℃、300℃(12分鐘) (2)高速液體層析(HPLC) 裝置：安捷倫科技(股)製 1200 Infinity LC系統 檢出器：UV(205nm) 管柱溫度：40℃ 管柱：GL科學(股)製 Inertsil(註冊商標)ODS-4(粒徑5μm、內徑4.6mm、長度250mm) 注入量：10μL 移動相組成：乙腈／純水(體積比)=4／96~90／10(線性梯度、30分) 流量：1.5mL／分 (3)凝膠滲透層析(GPC) 裝置：東曹(股)製 HLC-8220GPC 管柱：昭和電工(股)製 Shodex(註冊商標)GPC KF-804L、同KF-805L 管柱溫度：40℃ 溶析液：四氫呋喃 檢測器：RI (4)環氧當量 裝置：京都電子工業(股)製 電位差自動滴定裝置AT-510 (5)介電正切、比介電率 裝置：是德科技公司製 E4980A精密LCR計器 試樣夾具：(股)東陽科技製 12962型室溫試夾具 (6)玻璃轉移溫度Tg 裝置：TA Instrument公司製 動態黏彈性測量裝置(DMA)Q800 變形模式：雙懸臂 頻率：1Hz 失真：0.05% 掃描溫度：30~300℃ 昇溫速度：5℃／分 (7)彎曲係數、撓度 裝置：(股)島津製作所製 桌上型精密萬能試驗機自動立體測圖儀AGS-5kNX (8)烤箱 裝置：大和科學(股)製 送風低溫恆溫器DNF400 [0075] 又，略稱表示下述意義。 BA：無水丁酸[東京化成工業(股)製] BzA：無水安息香酸[東京化成工業(股)製] iBA：無水異丁酸[東京化成工業(股)製] OA：無水辛酸[東京化成工業(股)製] PA：無水丙酸[(股)戴爾製 APA] P3EPB：溴化乙基三苯基鏻[北興化學工業(股)製] P4PB：溴化四苯基鏻[東京化成工業(股)] BPA：雙酚A型環氧樹脂[三菱化學(股)製 jER(註冊商標)828] TGIC：三環氧丙基異三聚氰酸酯[日產化學工業(股)製TEPIC(註冊商標)-S] MH700：4-甲基六氫無水酞酸／六氫無水酞酸混合物(莫耳比70：30)[新日本理化(股)製 Rikacid(註冊商標)MH-700] PX4ET：四丁基鏻O,O-二乙基硫代二磷酸酯[日本化學工業(股)製Hishicolin (註冊商標)PX-4ET] [0076] [製造例1]TGIC無水丙酸變性物(PA-TGIC)之製造 在反應燒瓶中放入TGIC 60.0g(202mmol)、及甲苯54g，使該混合物迴流，並同時滴入PA 21.2g(162mmol)、及P3EPB 0.06g(0.156mmol)之混合物。滴入結束後，再使其迴流2小時。藉由從此反應混合物減壓餾除甲苯，而取得TGIC無水丙酸變性物(PA-TGIC)作為液狀物。取得之PA-TGIC之在依據JIS K7236：2009所測量之環氧當量為181(理論值182)。又，HPLC分析之TGIC(非加成物)：1莫耳加成物：2莫耳加成物：3莫耳加成物(面積比)為33：45：19：3。 [0077] [製造例2]TGIC無水丁酸變性物(BA-TGIC)之製造 在反應燒瓶中放入TGIC 40.0g(135mmol)、及乙腈14g。使該混合物迴流，並同時滴入BA 17.0g(108mmol)、P4PB 0.026g(0.062mmol)、及乙腈0.4g之混合物。滴入結束後，再使迴流24小時。藉由從此反應混合物減壓餾除乙腈，而取得TGIC無水丁酸變性物(BA-TGIC)作為液狀物。取得之BA-TGIC之環氧當量為192(理論值193)。又，HPLC分析之TGIC(非加成物)：1莫耳加成物：2莫耳加成物：3莫耳加成物(面積比)為33：52：14：0.1。 [0078] [製造例3]TGIC無水異丁酸變性物(iBA-TGIC)之製造 除了將BA取代成iBA以外，其他與製造例2同樣地進行操作，而取得TGIC無水異丁酸變性物(iBA-TGIC)作為液狀物。取得之iBA-TGIC之環氧當量為192(理論值193)。又，HPLC分析之TGIC(非加成物)：1莫耳加成物：2莫耳加成物：3莫耳加成物(面積比)為30：52：17：1。 [0079] [製造例4]TGIC無水辛酸變性物(OA-TGIC)之製造 除了將BA取代成OA 29.1g(108mmol)以外，其他與製造例2同樣地進行操作，而取得TGIC無水辛酸變性物(OA-TGIC)作為液狀物。取得之OA-TGIC之環氧當量為234(理論值234)。又，HPLC分析之TGIC(非加成物)：1莫耳加成物：2莫耳加成物：3莫耳加成物(面積比)為29：43：24：4。 [0080] [製造例5]TGIC無水安息香酸變性物(BzA-TGIC)之製造 除了將BA取代成BzA 24.4g(108mmol)以外，其他與製造例2同樣地進行操作，而取得TGIC無水安息香酸變性物(BzA-TGIC)作為液狀物。取得之BzA-TGIC之環氧當量為217(理論值217)。又，HPLC分析之TGIC(非加成物)：1莫耳加成物：2莫耳加成物：3莫耳加成物(面積比)為15：43：35：7。 [0081] [實施例1~5、比較例1~2] 對表1記載之環氧化合物100質量份添加與環氧化合物之環氧基為等莫耳量MH700作為硬化劑，及硬化促進劑之PX4ET 1質量份。在減壓下，室溫(約23℃)中攪拌此混合物30分鐘進行脫泡而調製成環氧樹脂組成物。 使用預先受到Optool(註冊商標)DSX[大金工業(股)製]離型處理之玻璃基板2枚，將各組成物與厚度3mm之ㄈ之字型之聚矽氧橡膠製間隔器一同地挾持。將此在100℃之烤箱中加熱(預備硬化)2小時，其後升溫至150℃進行5小時加熱(主硬化)。在徐冷後，拆掉玻璃基板而取得厚度3mm之各硬化物。 對於取得之硬化物評價介電正切、比介電率、玻璃轉移溫度、吸水率、彎曲係數、及撓度。尚且，各物性值係依據以下之操作順序進行測量。將結果合併展示於表1。 [0082] [介電正切] 測量對被夾在夾具之電極間之試驗片施加1V、1MHz之電壓時之介電正切。 [0083] [比介電率] 測量對被夾在夾具之電極間之試驗片施加1V、1MHz之電壓時之靜電容量Cp，並除以在相同條件下經測量之空氣之靜電容量C0
來算出比介電率。 [0084] [玻璃轉移溫度(Tg)] 藉由DMA測量儲藏彈性係數E’及損失彈性係數E”，且將從該等所求出之tanδ(損失彈性係數E”／儲藏彈性係數E’)之值顯示最大之溫度設為Tg。 [0085] [吸水率] 根據JIS K-6911：2006進行測量。具體而言，首先作為前處理，在保持於50℃之玻璃容器中，使用油浴乾燥處理試驗片(30×30×3mm)24小時。使此試驗片在乾燥器內冷卻至20℃，並測量其之質量(W1
[g])。其次，將此試驗片浸漬於已沸騰之蒸餾水中100小時後並取出，在20℃之流水中冷卻30分鐘且拭除水分，隨即測量吸水後之質量(W2
[g])。從該等之值藉由以下之式算出吸水率。 吸水率[%]=(W2
-W1
)÷W1
×100 [0086] [彎曲係數] 根據JIS K-6911：2006進行測量。具體而言，對以支點間距離64mm所支撐之試驗片(80×10×3mm)之中央使用加壓楔子加上荷重，並求出荷重-撓度曲線之直線部分之梯度F／Y[N／mm]。從該梯度，與支點間距離L[mm]、試驗片之寬W[mm]及厚度h[mm]之值，藉由以下之式算出彎曲係數。 彎曲係數[MPa]=(L3
÷4Wh3
)×(F／Y) [0087] [撓度] 斷裂點之撓度(壓入距離)。＞30係在斷裂前掉落。 [0088][0089] 如表1所示，在與印刷配線板形成用途上所廣泛使用之環氧化合物即BPA(比較例2)相比，使用本發明之環氧樹脂組成物所得之硬化物(實施例1~5)顯示極低之介電正切。其中，亦確認到包含以芳香族羧酸酐進行變性之環氧化合物之環氧樹脂組成物可維持高Tg，且實現低吸水率、低比介電率，適宜當作印刷配線板形成用之樹脂。[0012] The epoxy resin composition for forming a printed wiring board of the present invention contains (a) a mixture comprising the epoxy compound A represented by the formula [1] and the compound B which may have an epoxy group represented by the formula [2] , and (b) a hardener. [Epoxy compound A represented by formula [1]] The (a) mixture of the present invention contains the epoxy compound A represented by the above formula [1]. In the above formula [1], R 1 to R 3 each independently represent a hydrogen atom or a methyl group, and L 1 to L 3 each independently represent an alkylene group having 1 to 10 carbon atoms. As L 1 to L 3 the alkylene group having 1 to 10 carbon atoms, for example, methylene group, ethylidene group, trimethylene group, 1-methyl ethylidene group, tetramethylene group can be mentioned. Methyl, 1-methyltrimethylene, 1,1-dimethylethylidene, pentamethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-bis Methyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-ethyltrimethylene, hexamethylene, 1-methylpentamethylene, 2-methylpentamethylene, 3-methylpentamethylene, 1,1-dimethyltetramethylene, 1,2-dimethyltetramethylene, 2,2-dimethyltetramethylene Methylene, 1-ethyltetramethylene, 1,1,2-trimethyltrimethylene, 1,2,2-trimethyltrimethylene, 1-ethyl-1-methyltrimethylene base, 1-ethyl-2-methyltrimethylene, cyclohexane-1,4-diyl, heptamethylene, octamethylene, nonamethylene, 2-methyl octamethylene, Decamethylene etc. Preferred are methylene, trimethylene and hexamethylene. In the present invention, the epoxy compound shown in formula [1] can use a commercially available epoxy compound, or can use the epoxy compound containing isocyanurate ring manufactured by a known method. For example, TEPIC (registered trademark) [manufactured by Nissan Chemical Industry Co., Ltd., triglycidyl isocyanurate], sam(3,4-epoxybutyl) isocyanurate, TEIC-VL (registered trademark) [Nissan Chemical Co., Ltd., sam(4,5-epoxypentyl)isocyanurate], sams(5,6-epoxyhexyl)isotrimer Cyanate ester, TEIC-FL (registered trademark) [manufactured by Nissan Chemical Industry Co., Ltd., ginseng (7,8-epoxyoctyl) isocyanurate], etc. By using an epoxy compound containing an isocyanurate ring, an epoxy resin with excellent light resistance, weather resistance, heat resistance and transparency can be obtained. [The compound B represented by the formula [2]] In addition, the (a) mixture of the present invention contains the compound B which may have an epoxy group represented by the above formula [2]. In the above formula [2], L 1 to L 3 represent the same meanings as described above, and X 1 to X 3 each independently represent a group represented by the above formula [2a] or the above formula [2b], but X 1 to X At least one of 3 is a base represented by formula [2b]. In the above formula [2a], R 1 has the same meaning as described above, and the black dots represent the bond. In the above formula [2b], R 1 and black dots represent the same meanings as described above, and R 4 and R 5 represent a substituted alkyl group having 1 to 20 carbon atoms, or a substituted carbon atom having 6 to 10 carbon atoms. Aryl. As R 4 and R 5 can be substituted by the alkyl group of carbon number 1 to 20, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl , octyl, nonyl, decyl, undecyl, dodecyl, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty, etc. straight-chain alkyl; isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, sec-isoamyl, isohexyl, tert-hexyl ( thexyl), 4-methylhexyl, 5-methylhexyl, 2-ethylpentyl, hept-3-yl, hept-4-yl, 4-methylhexyl-2-yl, 3-methylhexyl- 3-yl, 2,3-dimethylpent-2-yl, 2,4-dimethylpent-2-yl, 4,4-dimethylpent-2-yl, 6-methylheptyl, 2-ethylhexyl, oct-2-yl, 6-methylhept-2-yl, 6-methyloctyl, 3,5,5-trimethylhexyl, nonan-4-yl, 2,6- Dimethylhept-3-yl, 3,6-dimethylhept-3-yl, 3-ethylhept-3-yl, 3,7-dimethyloctyl, 8-methylnonyl, 3 -Methylnon-3-yl, 4-ethyloct-4-yl, 9-methyldecyl, undecyl-5-yl, 3-ethylnonan-3-yl, 5-ethylnonan-5 -yl, 2,2,4,5,5-pentamethylhex-4-yl, 10-methylundecyl, 11-methyldodecyl, tridec-6-yl, tridecane- 7-yl, 7-ethylundecan-2-yl, 3-ethylundecan-3-yl, 5-ethylundecan-5-yl, 12-methyltridecyl, 13- Methyltetradecyl, pentadec-7-yl, pentadec-8-yl, 14-methylpentadecyl, 15-methylhexadecyl, heptadecan-8-yl, heptadecan- 9-yl, 3,13-dimethylpentadecan-7-yl, 2,2,4,8,10,10-hexamethylundecan-5-yl, 16-methylheptadecyl, 17-Methyloctadecyl, nonadecan-9-yl, nonadecan-10-yl, 2,6,10,14-tetramethylpentadecan-7-yl, 18-methyl nonadecyl Branched alkyl, etc.; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-tert-butylcyclohexyl, 1,6-dimethylcyclohexyl, menthol, cycloheptyl, cyclohexyl Octyl, bicyclo[2.2.1]heptan-2-yl, camphenyl, isocampanyl, 1-adamantyl, 2-adamantyl, tricyclo[5.2.1.0 2,6 ]dec-4-yl , cyclic alkyl groups such as tricyclo[5.2.1.0 2,6 ]dec-8-yl, cyclododecyl, etc. It is preferably an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 2 to 10 carbon atoms. These alkyl groups may be substituted with substituents such as cyano groups, amino groups, nitro groups, halogen atoms and the like. As a halogen atom, a fluorine group, a chlorine group, a bromine group, an iodine group etc. are mentioned, for example. [0018] Examples of the aryl group having 6 to 10 carbon atoms that can be substituted as represented by R 4 and R 5 include, for example, phenyl, 1-naphthyl, 2-naphthyl, and the like. The preferred systems are phenyl, respectively. These aryl groups may be substituted with substituents such as methyl, ethyl, propyl and the like, alkyl groups having 1 to 6 carbon atoms, cyano groups, amino groups, nitro groups, halogen atoms and the like. In the present invention, the compound shown in formula [2] can use commercially available epoxy compounds, or can use those manufactured by known methods. For example, a part or all of the epoxy groups of the epoxy compound A represented by the formula [1] can be preferably substituted with the group represented by the formula [2b] by reacting with an acid anhydride. For example, compound B is a compound obtained by adding 1 molecule of the acid anhydride represented by formula [3] to the epoxy group of epoxy compound A (1 molar adduct), and a compound obtained by adding 2 molecules (2 A mixture of compounds obtained by adding 3 molecules (3-molar adduct) is preferred. (In the formula, R 4 and R 5 have the same meanings as described above). The acid anhydride shown in the above-mentioned formula [3] is different from the acid anhydride obtained from the so-called monocarboxylic acid of 2 molecules and the acid anhydride obtained from the dicarboxylic acid used as the epoxy resin hardener, so it does not have as an epoxy resin hardener. The function of epoxy resin hardener. Moreover, since the compound B obtained by making an epoxy compound and an acid anhydride react does not have a hydroxyl group, even if an unreacted acid anhydride exists, it does not gel, etc., and it has high storage stability. The acid anhydride is not particularly limited, and examples thereof include anhydrous acetic acid, anhydrous propionic acid, anhydrous butyric acid, anhydrous isobutyric acid, anhydrous valeric acid, anhydrous caproic acid, anhydrous octanoic acid, anhydrous trifluoroacetic acid, anhydrous benzoic acid, and the like. For example, can be by the reaction of the epoxy compound A shown in formula [1] and the acid anhydride shown in formula [3], and obtain the epoxy compound (epoxy compound A) that comprises unreacted, and comprises adding A mixture of a compound formed by adding 1 molecule of acid anhydride, a compound formed by adding 2 molecules of acid anhydride, and a compound formed by adding 3 molecules of acid anhydride (compound B). By adjusting the mole number of the acid anhydride to be reacted with respect to the mole number of the epoxy compound A, the amount of the added compound of the acid anhydride can be adjusted. (a) mixture of the present invention can make epoxy compound A: acid anhydride under the molar ratio of (epoxy group of epoxy compound A): (acid anhydride), with 1:0.1～1:1, preferably It is obtained by reacting in the ratio of 1:0.4~1:0.8. The reaction product system can be analyzed by HPLC, etc., and obtains the unreacted epoxy compound A, and is formed with one acid anhydride shown in the epoxy group addition formula [3] of the epoxy compound A. The molar ratio of the compound, the compound obtained by adding two, and the compound (compound B) adding three. As long as the solvent used in the reaction is inert to the reaction. Examples of such solvents include ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate; chlorobenzene and toluene Aromatic hydrocarbons such as chloroform; halogenated hydrocarbons such as chloroform, dichloroethane, etc. These can be used alone or as a mixed solvent to dissolve epoxy compounds A such as triglycidyl isocyanurate. In addition, if necessary, tertiary amines such as triethylamine, tripropylamine, 1,8-diazbicyclo[5.4.0]undec-7-ene, etc. can be used, or ethyl triphenyl bromide can be used. Fourth-order phosphonium salts such as halogenated monoalkyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, etc., imidazole-based compounds such as 2-ethyl-4-methylimidazole, tetraethyl bromide, etc. Fourth-order ammonium salts such as ammonium chloride, phosphorus compounds such as triphenylphosphine, etc., are used as catalysts. The reaction temperature is, for example, carried out at the reflux temperature of the solvent, and is carried out until the epoxy group content titrated using 0.1N perchloric acid/acetic acid solution becomes the theoretical value (the value at which the added acid anhydride is destroyed by the reaction). After completion of the reaction, the solvent can be distilled off to obtain the (a) mixture. <(a) mixture> In the mixture of the present invention, the content of epoxy compound A represented by formula [1] and compound B represented by formula [2] is not particularly limited, for example, relative to 1 mole The epoxy compound A contains 0.2-20 mol of compound B, preferably 0.7-4 mol. The sum of the epoxy groups of compound A and the epoxy groups of compound B is preferably 2 or more in terms of the average conversion to one molecule (the total number of epoxy groups divided by the total number of molecules). If it is less than two, the physical properties of the cured product, especially the heat resistance, are not good. In addition, the mixture of the present invention can be used in combination with the epoxy compound A shown in formula [1] and the compound B shown in formula [2], and epoxy compounds other than them within the scope of the effect of the present invention. . The epoxy compound A represented by the above formula [1] and the compound B represented by the formula [2] and other epoxy compounds can be, for example, 1:0 to 1:20 in molar ratio of epoxy groups. use within the range. The epoxy compound other than the above is not particularly limited, and various commercially available polyfunctional epoxy compounds can be used. As the epoxy compound that can be used in the present invention, for example, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, (poly) ethylene glycol Glycol Diglycidyl Ether, (Poly)Propylene Glycol Diglycidyl Ether, Trimethylolethane Triglycidyl Ether, Trimethylolpropane Triglycidyl Ether, 1,4-Cyclic Hexanedimethanol Diglycidyl Ether, 1,2-Epoxy-4-(epoxyethyl)cyclohexane, Glycerol Triglycidyl Ether, Ditriol Polydiglycidyl base ether, 2,6-diglycidylphenyl=glycidyl=ether, 1,1,3-para(4-glycidoxyphenyl)propane, 1,2-cyclohexanedi Carboxylic acid diepoxypropyl, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexanecarboxylic acid 3',4'-epoxy cyclohexylmethyl, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine, tetraglycidyldiaminodiphenylmethane, tetraglycidyl-1, 3-Bisaminomethylcyclohexane, Bisphenol A Diglycidyl Ether, Bisphenol S Diglycidyl Ether, Tetrabromobisphenol A Diglycidyl Ether, Hydrogenated Bisphenol A Diepoxy propyl ether, pentaerythritol diglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol polyglycidyl ether, resorcinol diglycidyl ether, diglycidyl phthalate, tetrahydrophthalate Acid Diglycidyl, Neopentyl Glycol Diglycidyl Ether, Bisphenol Hexafluoroacetone Diglycidyl Ether, Gins(2-glycidoxyethyl)isocyanurate, Mono Allyl diglycidyl isocyanurate, N,N'-diglycidyl N"-(2,3-dipropyloxypropyl) isocyanurate, N, N'-bis(2,3-dipropyloxypropyl) N"-glycidyl isocyanurate, ginseng (2,2-bis(glycidoxymethyl)butyl) 3,3',3"-(2,4,6-Tri-oxy-1,3,5-triazine-1,3,5-triyl) tripropionate, sorbitol polyglycidyl Ether, Diglycidyl Adipate, Diglycidyl O-phthalate, Dibromophenylglycidyl Ether, 1,2,7,8-Diepoxyoctane, 1,6- Dimethylol perfluorohexane diglycidyl ether, 4-(spiro[3,4-epoxycyclohexane-1,5'-[1,3]dioxane]-2'-yl )-1,2-epoxycyclohexane, 1,2-bis(3,4-epoxycyclohexylmethoxy)ethane, 4,5-epoxy-2-methylcyclohexane Carboxylic acid 4',5'-epoxy-2'-methylcyclohexylmethyl, ethylene glycol bis(3,4-epoxycyclohexanecarboxylate), bis(3,4-epoxy cyclohexylmethyl) adipate, bis(2,3-epoxycyclopentyl) ether, etc., but not limited thereto. These epoxy compounds may be used alone or may be used as two More than one kind of mixture.Also, as an example of above-mentioned epoxy compound, can enumerate such as the following commercial product.As liquid epoxy compound, can enumerate such as TEPIC (registered trademark)-UC [Nissan Chemical Industry (stock) system], jER (registered trademark) 828, same as Y X8000 [all manufactured by Mitsubishi Chemical Corporation], RikaResin (registered trademark) DME100 [Shin Nippon Rika Corporation], Ceroxide 2021P [(stock) Dell], etc. <(b) Hardener> The epoxy resin composition for printed wiring board formation of this invention contains (b) hardener. As the curing agent, there is no particular limitation, and for example, acid anhydrides, amines, phenol resins, polyamide resins, imidazoles, polythiols, or a mixture of these can be used. Among these, acid anhydrides and amines are particularly preferred. A solid can be used for these hardeners, and it can also be used by dissolving in a solvent. However, the density of the cured product will decrease due to evaporation of the solvent, or the strength and water resistance will decrease due to the formation of pores, so the curing agent itself is preferably liquid at normal temperature and normal pressure. The hardener can be contained in a ratio of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, relative to 1 equivalent of epoxy groups of the epoxy compound. The equivalent weight of the hardener with respect to the epoxy compound is represented by the equivalent ratio of the hardening group of the hardener with respect to the epoxy group. Furthermore, when the above-mentioned mixture (a) comprising the epoxy compound represented by the formula [1] and the compound represented by the formula [2] is used in combination with epoxy compounds other than these, these are relative to the rings of all epoxy compounds. The equivalent weight of the oxy group is still within the aforementioned range. As acid anhydride, it is better to have the anhydrate of the compound of plural carboxyl groups in one molecule. As these acid anhydrides, for example, anhydrous phthalic acid, anhydrous trimellitic acid, anhydrous pyromellitic acid, anhydrous benzophenone tetracarboxylic acid, ethylene glycol bis-trimellitic acid ester, glycerol paraffinic acid can be mentioned. trimellitic acid ester, anhydrous maleic acid, tetrahydro anhydrous phthalic acid, methyl tetrahydro anhydrous phthalic acid, endomethylene tetrahydro anhydrous phthalic acid, methyl endomethylene tetrahydro anhydrous phthalic acid, methyl butene Tetrahydro anhydrous phthalic acid, dodecenyl anhydrous succinic acid, hexahydro anhydrous phthalic acid, methyl hexahydro anhydrous phthalic acid, anhydrous succinic acid, methyl cyclohexene dicarboxylic acid anhydride, Chlorendic acid anhydride Wait. Among them, methyl tetrahydro anhydrous phthalic acid, methyl-5-norbornene-2,3-dicarboxylic acid anhydride (methyl nadic anhydride, anhydrous methyl norbornene anhydride, etc.) Camphenedioic acid (methylhimic acid anhydride), hydrogenated methyl nadic anhydride, methyl butenyl tetrahydro anhydrous phthalic acid, dodecenyl anhydrous succinic acid, methyl hexahydro anhydrous phthalic acid, methyl hexahydro anhydrous A mixture of phthalic acid and hexahydroanhydrophthalic acid is preferred. The viscosity of these liquid acid anhydrides is about 10 to 1,000 mPa·s measured at 25°C. Among acid anhydride groups, 1 acid anhydride group is calculated as 1 equivalent. As the amine, for example, piperidine, N,N'-dimethylpiperazine, triethylenediamine, 2,4,6-para(dimethylaminomethyl)phenol, benzyl Dimethylamine, 2-(Dimethylaminomethyl)phenol, Diethylenetriamine, Triethylenetetramine, Tetraethylenepentamine, Diethylaminopropylamine, N-aminoethylamine piperazine, bis(1-methyl-2-aminocyclohexyl)methane, menthanediamine, isophoronediamine, diaminodicyclohexylmethane, 1,3-bis(aminomethyl) ) cyclohexane, stubble diamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl benzene and the like. Among these, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, bis( 1-methyl-2-aminocyclohexyl)methane, menthanediamine, isophoronediamine, diaminodicyclohexylmethane, etc. [0033] As the phenol resin, for example, phenol novolac resin, cresol novolac resin, etc. can be mentioned. [0034] The polyamide resin is generated by the condensation of dimer acid and polyamine, and has a polyamide amine of primary amine and secondary amine in the molecule. As imidazoles, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitic acid, epoxy imidazole adducts, etc. [0036] The polythiol is, for example, a thiol group at the end of a polypropylene glycol chain, or a thiol group at the end of a polyethylene glycol chain, preferably in a liquid state. <Curing Accelerator> Furthermore, when obtaining a cured product from the epoxy resin composition for forming a printed wiring board of the present invention, in addition to using a curing agent, a curing accelerator (also referred to as curing auxiliaries). Examples of the curing accelerator include organophosphorus compounds such as triphenylphosphine, tributylphosphine, etc.; ethyltriphenylphosphonium bromide, tetrabutylphosphonium O,O-diethylthiodiphosphate, etc. Phosphonium salts of the fourth grade; salts of 1,8-diazbicyclo[5.4.0]undec-7-ene, 1,8-diazbicyclo[5.4.0]undec-7-ene and octyl acid , 4th grade ammonium salts of zinc octylate, tetrabutylammonium bromide, etc. In addition, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, etc. mentioned as the above-mentioned curing agent, or 2,4,6-sam(dimethylaminomethyl) Amines such as phenol and benzyldimethylamine are used as hardening accelerators for other types of hardeners. These hardening accelerators can be used in a ratio of 0.001 to 0.1 part by mass with respect to 1 part by mass of the hardener. <<Epoxy resin composition for printed wiring board formation>> The present invention is achieved by mixing the epoxy compound A represented by the above formula [1] and the compound B represented by the formula [2], and the above-mentioned curing agent. , and according to the required hardening accelerator, an epoxy resin composition for forming a printed wiring board can be obtained. Preferably, these mixtures are stirred and mixed under reduced pressure and defoamed. The hardened product obtained from the epoxy resin composition can be carried out by coating the epoxy resin composition on the substrate, or injecting the mold plate with the release agent coated, for example, at a temperature of 100~120°C. It is obtained by pre-hardening and main hardening (post-hardening) at a temperature of 120~200°C. Moreover, the hardened|cured material system obtained from the epoxy resin composition of this invention can be used suitably for a printed wiring board. The heating time is appropriately adjusted according to the size or thickness of the epoxy resin. For example, the preliminary hardening and the main hardening are each about 1 to 12 hours, for example, about 2 to 5 hours, respectively. As the method for coating the epoxy resin composition of the present invention on the substrate, for example, flow coating method, spin coating method, spray coating method, screen printing method, flexographic printing method can be enumerated. , inkjet printing method, casting method, bar coating method, curtain coating method, roll coating method, gravure coating method, dipping method, slit coating method, etc. <(c) Hardening catalyst> In this invention, as a hardening catalyst system, for example, (c1) acid generator and/or (c2) alkali generator can be used. Thereby, even if the epoxy compound of the present invention and the curing catalyst are mixed, curing does not occur immediately, so it is desirable that the storage stability is excellent and the working time is sufficient. [(c1) Acid generator] As the (c1) acid generator, a photoacid generator or a thermal acid generator can be used. The photoacid generator or the thermal acid generator is not particularly limited as long as it directly or indirectly generates an acid (Lewis acid or Brookfield acid) by light irradiation or heating. The epoxy resin composition compounded with the thermal acid generator can be hardened in a short time by heating. In addition, the epoxy resin composition containing the photoacid generator is not heated but cured by light irradiation, so it can be used on substrates and parts with low heat resistance. Specific examples of the photoacid generator include onium salts such as iodonium salts, peronium salts, phosphonium salts, selenium salts, etc., metallocene complex compounds, iron arene complex compounds, and diarene-based compounds. , sulfonic acid derivative compounds, triazine compounds, acetophenone derivative compounds, diazomethane compounds, etc. As the above-mentioned iodonium salt, for example, diphenyl iodonium, 4,4'-dichlorodiphenyl iodonium, 4,4'-dimethoxydiphenyl iodonium, 4,4'-diphenyl iodonium, -tert-butyldiphenyl iodonium, 4-methylphenyl (4-(2-methylpropyl)phenyl) iodonium, 3,3'-dinitrophenyl iodonium, 4-(1-ethyl) Oxycarbonylethoxy) phenyl (2,4,6-trimethylphenyl) iodo, 4-methoxyphenyl (phenyl) iodo, etc., iodonium chloride, bromide, methanesulfonic acid Diaryl of salt, tosylate, trifluoromethanesulfonate, tetrafluoroborate, tetra(pentafluorophenyl)borate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, etc. Chili salt, etc. As the above-mentioned periconium salt, for example, triphenyl peri 4-Methoxyphenyl) peri -(Phenylthio)phenyl) peri salt, hexafluoroarsenate, hexafluoroantimonate, triaryl perionate, etc. As above-mentioned phosphonium salt, for example, tetraphenylphosphonium, ethyl triphenylphosphonium, tetrakis (p-methoxyphenyl) phosphonium, ethyl tris (p-methoxyphenyl) phosphonium , benzyl triphenyl phosphonium, etc., phosphonium, chloride, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate and other arylphosphonium salts, etc. [0046] As the selenium salt, for example, triaryl selenium salts such as triphenylselenide hexafluorophosphate, etc. can be mentioned. As the above-mentioned iron aromatic complex compound, for example, bis(n 5 -cyclopentadienyl)(n 6 -isopropylbenzene) iron(II) hexafluorophosphate and the like can be mentioned. These photoacid generators can be used alone, or can be used in combination of two or more. [0049] As the thermal acid generator, for example, perylene salts and phosphonium salts can be cited, and perylene salts are preferably used. As these exemplary compounds, the compounds exemplified as examples of various onium salts in the above-mentioned photoacid generators can be mentioned. These thermal acid generators may be used alone or in combination of two or more. Among these, (c1) acid generating agent is preferably with pericynium chloride compound or iodochloride compound, with the compound with anion species such as hexafluorophosphate or hexafluoroantimonate showing strong acidity for example good. The content of the (c1) acid generator in the epoxy resin composition of the present invention is 0.1 to 20 parts by mass, or 0.1 to 10 parts by mass, more preferably 0.5 parts by mass relative to 100 parts by mass of the (a) epoxy compound. ~10 parts by mass. In addition, when the epoxy compound represented by the said formula [1] is used together with the epoxy compound other than it, the content with respect to 100 mass parts of all epoxy compounds remains in the said range. [(c2) Base generator] As the (c2) base generator, a photobase generator or a thermal base generator can be used. The photobase acid generator or the thermal base generator is not particularly limited as long as it directly or indirectly generates a base (Lewis base or Brinell base) by light irradiation or heating. The epoxy resin composition containing the thermal alkali generator can be hardened in a short time by heating. Moreover, since the epoxy resin composition which mix|blended the photobase generator is not heated by heating, but hardened by light irradiation, it can be used for the board|substrate and the site|part with low heat resistance. As photobase generator, for example, can enumerate, 9-anthracenyl methyl=N, the alkylamine system photobase generator of N-diethylcarbamate (carbamate) etc.; 9-anthracenyl =N,N-dicyclohexylcarbamate, 1-(9,10-anthraquinone-2-yl)ethyl=N,N-dicyclohexylcarbamate, dicyclohexylammonium=2-( 3-benzylphenyl)propionate, 9-anthryl=N-cyclohexylcarbamate, 1-(9,10-anthraquinone-2-yl)ethyl=N-cyclohexylcarbamate Ester, cyclohexyl ammonium = 2-(3-benzyl phenyl) propionate, (E)-N-cyclohexyl-3-(2-hydroxyphenyl) acrylamide, etc. cycloalkylamine light Base generator; 9-anthrylmethyl=piperidine-1-carboxylate, (E)-1-piperidinyl-3-(2-hydroxyphenyl)-2-propen-1-one, (2 -Nitrophenyl)methyl=4-hydroxypiperidine-1-carboxylate, (2-nitrophenyl)methyl=4-(methacryloyloxy)piperidine-1-carboxylate Piperidine-based photobase generators such as; guanidinium (guanidinium) = 2-(3-benzyl phenyl) propionate, 1,2-diisopropyl-3-(bis(dimethylamino) ) methylene)guanidinium=2-(3-benzylphenyl)propionate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium=n-butyl Guanidine-based light such as triphenylborate, 1,5,7-triazabicyclo[4.4.0]dec-5-enium=2-(9-oxyxanthene-2-yl)propionate, etc. Base generators; imidazole-based photobase generators such as 1-(9,10-anthraquinone-2-yl)ethyl=imidazole-1-carboxylate and the like. These photobase generators may be used alone or in combination of two or more. In addition, photobase generators can be obtained as commercial products, and for example, photobase generators WPBG series (WPBG-018, same 027, same 082, same 140, same 266 manufactured by Wako Pure Chemical Industries, Ltd.) can be suitably used. , the same as 300, etc.) and so on. As the thermal base generator, for example, 1-methyl-1-(4-biphenyl)ethylcarbamate, 2-cyano-1,1-dimethylethylamine Urethanes such as formate; ureas such as urea, N,N-dimethyl-N'-methylurea; guanidine trichloroacetate, guanidine phenylsulfonylacetate, guanidine phenylpropiolate Guanidines such as guanidines; dihydropyridines such as 1,4-dihydronicotinamide; N-(isopropoxycarbonyl)-2,6-dimethylpiperidine, N-(tert-butoxy Carbonyl)-2,6-dimethylpiperidine, N-(benzyloxycarbonyl)-2,6-dimethylpiperidine and other dimethylpiperidines; tetramethylammonium phenylsulfonyl acetate , quaternary ammonium salts of tetramethylammonium phenylpropiolate, etc.; dicyandiamide, etc. In addition, salts such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), that is, U-CAT (registered trademark) SA810, the same SA831, the same SA841, the same SA851 [above , Sun-Apro (stock) system] and so on. These thermal alkali generators can be used individually by 1 type, or can be used in combination of 2 or more types. The content of (c2) alkali generator in the epoxy resin composition of the present invention is relative to 100 parts by mass of (a) epoxy compound, can be made into 0.1～20 parts by mass, or 0.1～10 parts by mass, more Preferably, it can be made into 0.5 to 10 parts by mass. Furthermore, when the mixture (a) containing the epoxy compound represented by the formula [1] and the compound represented by the formula [2] and other epoxy compounds are used together, these are based on 100 mass of the total epoxy compounds. The content of parts remains within the aforementioned range. In the present invention, an epoxy resin composition can be obtained by mixing the above-mentioned (a) mixture and the above-mentioned hardening catalyst. The operating conditions for obtaining the mixing of the epoxy resin composition are the same as described above. [0056] The present invention can be cured by applying the epoxy resin composition comprising the above-mentioned (a) mixture and a photoacid generator or a photobase generator onto a substrate and irradiating it with light. Furthermore, heating may be performed before and after light irradiation. Moreover, this invention can harden it by apply|coating the epoxy resin composition containing the said (a) mixture and a thermal acid generator or a thermal base generator on a board|substrate, and heating. In addition, the epoxy resin composition comprising the above-mentioned (a) mixture, a thermal acid generator and a photoacid generator or a thermal base generator and a photobase generator can be coated on the substrate, and light irradiation can be performed after heating to harden it. [0057] The thickness of the coating film formed by the epoxy resin composition of the present invention can be selected in the range of 0.01 μm to 10 mm according to the application of the hardened material, for example, it can be made 0.05 to 10 μm when used in photoresist (especially 0.1~5μm), when used in printed wiring boards, it can be made into about 10μm~5mm (especially 100μm~1mm), and when used in optical films, it can be made into about 0.1~100μm (especially 0.3~50μm). As the light of irradiation or exposure when using the photoacid generator or the photobase generator, for example, gamma rays, X-rays, ultraviolet rays, visible rays, etc., are usually used visible rays or ultraviolet rays, especially the use of UV rays are more common. The wavelength of light is, for example, 150 to 800 nm, preferably 150 to 600 nm, more preferably 200 to 400 nm, and particularly preferably about 300 to 400 nm. The amount of irradiation light varies depending on the thickness of the coating film, but can be, for example, 2 to 20,000 mJ/cm 2 , preferably about 5 to 5,000 mJ/cm 2 . As the light source, it can be selected according to the type of exposure light. For example, in the case of ultraviolet rays, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, deuterium lamps, halogen lamps, laser light (helium-cadmium laser, excimer laser can be used) etc.), UV-LED, etc. By such light irradiation, the hardening reaction of the aforementioned composition proceeds. In the case of using a thermal acid generator or a thermal base generator, or using a photoacid generator or a photobase generator and after light irradiation, the heating of the coating film performed as necessary is, for example, at room temperature (about 23°C). ℃)~250℃. The heating time can be selected from the range of 3 seconds or more (eg, about 3 seconds to about 5 hours), for example, about 5 seconds to about 2 hours. [0060] In addition, in the case of forming a pattern or an image (for example, in the case of manufacturing a printed wiring board, etc.), pattern exposure can also be performed on the coating film formed on the substrate. This pattern exposure can be performed by scanning with laser light, or by light irradiation through a mask. A pattern or an image can be formed by developing (or dissolving) a non-irradiated area (unexposed portion) generated by such pattern exposure using a developing solution. [0061] As the developer, an aqueous alkaline solution or an organic solvent can be used. Examples of the alkaline aqueous solution include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate; aqueous solutions of tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, and the like. Aqueous solution of quaternary ammonium hydroxide; amine aqueous solution of ethanolamine, propylamine, ethylenediamine, etc. [0062] The above-mentioned alkaline developing solution generally uses an aqueous solution of 10% by mass or less, preferably an aqueous solution of 0.1 to 3% by mass. In addition, alcohols or surfactants may be added to the developing solution before use, and these addition amounts are preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the developing solution, respectively. Specifically, 0.1-2.38 mass % of tetramethylammonium hydroxide aqueous solution etc. can be used. Also, as the organic solvent system of the developer, general organic solvents can be used, for example, aromatic hydrocarbons such as toluene; ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol Esters of monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc.; amides such as N,N-dimethylformamide (DMF); acetonitrile Nitriles, etc.; ketones, such as acetone, cyclohexanone, etc.; methanol, ethanol, 2-propanol, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and other alcohols. These can be used alone or as a mixture of two or more. Among them, ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) and the like can be preferably used. <Solvent> The above-mentioned epoxy resin composition may contain a solvent according to necessity. Examples of the solvent include aromatic hydrocarbons such as toluene and stubble; esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; methyl glycolate, ethyl glycolate, and glycolic acid. Butyl, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate , 2-hydroxy-2-methyl propionate methyl ester, 2-hydroxy-2-methyl propionate ethyl ester, 2-hydroxy-3-methyl butyric acid methyl ester and other hydroxy esters; methyl methoxyacetate Ester, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate , methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, Butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2-ethyl acetate Methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, Propyl 2-ethoxypropionate, Butyl 2-ethoxypropionate, Methyl 2-butoxypropionate, 2-Butyl Ethyl oxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methylpropionate Propyl oxypropionate, Butyl 3-methoxypropionate, Methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, Propyl 3-ethoxypropionate, 3-ethylpropionate Butyl oxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3-butane methyl oxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, methyl cellosolve acetate, ethyl cellosolve Acetate, Propylene Glycol Monomethyl Ether Acetate (PGMEA), Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monopropyl Ether Acetate, Propylene Glycol Monobutyl Ether Acetate, Propylene Glycol Monomethyl Ether Propyl ether esters of acid esters, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, etc.; methyl ethyl ketone (MEK), 4-hydroxy-4- Ketones such as methyl-2-pentanone and cyclohexanone; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Alcohols such as propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.; tetrahydrofuran (THF), diethylene glycol dimethyl ether, diethylene glycol diethylene glycol Ethers such as ethyl ether, diethylene glycol ethyl methyl ether, etc. <Other curable monomer> In the present invention, for the purpose of adjusting the viscosity of the epoxy resin composition or improving the curability, a vinyl-containing compound, a propylene oxide group-containing compound, etc. can be used as the cationic curable monomer. . As the vinyl-containing compound, as long as it is a compound having a vinyl group, there is no particular limitation, for example, 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), Vinyl ether compounds such as 2-hydroxybutyl vinyl ether (HBVE), triethylene glycol divinyl ether, etc. Moreover, the vinyl compound which has a substituent, such as an alkyl group, an allyl group, in an (alpha)-position and/or (beta)-position can also be used. In addition, vinyl ether compounds containing cyclic ether groups such as epoxy groups and/or propylene oxide groups can be used, and examples thereof include oxynorbornene divinyl ether, 3,3-dimethanol epoxy Propane divinyl ether, etc. Moreover, the compound which has a vinyl group and a (meth)acryloyl group can be used, for example, (meth)acrylic acid 2-(2-vinyloxyethoxy)ethyl etc. are mentioned. These vinyl-containing compounds may be used alone or in combination of two or more. As the propylene oxide group-containing compound, as long as it is a compound having a propylene oxide group, it is not particularly limited, such as 3-ethyl-3-(hydroxymethyl) propylene oxide (OXA), 3- Ethyl-3-(phenoxymethyl)propylene oxide (POX), bis((3-ethyl-3-epoxypropylene)methyl)ether (DOX), 1,4-bis((( 3-Ethyl-3-oxiranyl)methoxy)methyl)benzene (XDO), 3-ethyl-3-(2-ethylhexyloxymethyl)propylene oxide (EHOX), 3 -Ethyl-3-((3-triethoxysilylpropoxy)methyl)propylene oxide (TESOX), propylene oxide semisiloxane (OX-SQ), phenol novolac propylene oxide ( PNOX-1009) and other propylene oxide compounds, etc. Moreover, the compound which has a propylene oxide group and a (meth)acryloyl group can be used, for example, (meth)acrylic acid (3-ethyl-3-epoxypropylene group) methyl etc. are mentioned. These propylene oxide group-containing compounds may be used alone or in combination of two or more. <Other components> The above-mentioned composition may contain conventional additives as necessary. Examples of such additives include thickeners, sensitizers, antifoamers, levelers, coatability improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.) , plasticizers, surfactants, dissolution accelerators, fillers, anti-charge agents, hardeners, etc. These additives can be used alone or in combination of two or more. On the purpose of improving coatability, surfactant can be added to the epoxy resin composition of the present invention. Such surfactants include, for example, fluorine-based surfactants, polysiloxane-based surfactants, nonionic surfactants, and the like, but are not particularly limited to these. The aforementioned surfactants may be used alone or in combination of two or more. Among these surfactants, fluorine-based surfactants are preferred from the viewpoint of improving the effect of improving coatability. Specific examples of fluorine-based surfactants include, for example, Eftop (registered trademark) EF-301, Tong EF-303, Tong EF-352 [all manufactured by Mitsubishi Materials Electronics Co., Ltd.], Megafac (registered trademark) ) F-171, same as F-173, same as F-482, same as R-08, same as R-30, same as R-90, same as BL-20 [all made by DIC (stock)], Fluorad FC-430, same as FC-431 [all made by Japan 3M Co., Ltd.], Asahiguard (registered trademark) AG-710 [made by Asahi Glass Co., Ltd.], SurflonS-382, the same SC-101, the same SC-102, the same SC-103, the same SC-104, the same SC-105, the same SC-106 [all are manufactured by AGC Qingmei Chemical Co., Ltd.], etc., but not limited to these. The addition amount of the surfactant in the epoxy resin composition of the present invention is based on the solid content of the epoxy resin composition, such as 0.01-5 mass %, preferably 0.01-3 mass %, preferably Preferably it is 0.01-2 mass %. [0070] For the purpose of improving the adhesion to the substrate after developing, an adhesion promoter can be added to the epoxy resin composition of the present invention. Examples of such adhesion promoters include chlorotrimethylsilane, trichloro(vinyl)silane, chloro(dimethyl)(vinyl)silane, and chloro(methyl)(diphenyl)silane. , Chloro(chloromethyl)(dimethyl)silane and other chlorosilanes; methoxytrimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, ethoxy(dimethyl)silane Methyl)(vinyl)silane, dimethoxydiphenylsilane, triethoxy(phenyl)silane, 3-chloropropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, trimethoxy(3-(N-piperidinyl)propyl)silane, etc. alkoxysilanes; hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyl(trimethylsilyl)amine, trimethylsilylimidazole, etc. Silazane; imidazole, indazole, benzimidazole, benzotriazole, mercaptoimidazole, mercaptopyrimidine 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, ureaazole, sulfur Nitrogen-containing heterocyclic compounds such as uracil; ureas or thioureas such as 1,1-dimethylurea and 1,3-dimethylurea. These adhesion promoters may be used alone or in combination of two or more. The addition amount of the adhesion promoter in the epoxy resin composition of the present invention is generally 20 mass % or less, preferably 0.01 to 10 mass % based on the solid content of the epoxy resin composition, preferably 0.01 to 10 mass %. Preferably it is 0.05-5 mass %. [0071] The epoxy resin composition of the present invention may also contain a sensitizer. As a sensitizer which can be used, anthracene, Phenothiazene, perylene, thioxanthone, benzophenone thioxanthone, etc. are mentioned, for example. In addition, examples of the sensitizing dye include thiopyrylium salt-based dyes, merocyanin-based dyes, quinoline-based dyes, styrylquinoline-based dyes, coumarin ketone-based dyes, and thioxanthene-based dyes. , Xanthene pigments, oxocyanine pigments, cyanine pigments, rose bengal pigments, pyrylium salt pigments, etc. The particularly preferred one is anthracene-based sensitizer. By using a cationic hardening catalyst (radioactive cationic polymerization initiator), the sensitivity can be dramatically improved, and at the same time, it has the function of starting radical polymerization. When the system is a hybrid type of the radical hardening system, the type of catalyst can be simplified. As specific anthracene compounds, such as dibutoxyanthracene, dipropoxyanthraquinone and the like are effective. In addition, as a sensitizer when an alkali generator is used as a curing catalyst, for example, acetophenones, benzoins, benzophenones, anthraquinones, xanthones, and thioxanthones can be mentioned. , ketals, tertiary amines, etc. The addition amount of the sensitizer in the epoxy resin composition of the present invention is 0.01 to 20 mass %, preferably 0.01 to 10 mass %, based on the solid content of the epoxy resin composition. [Industrial Applicability] [0072] The epoxy resin composition comprising (a) a mixture and (b) a curing agent of the present invention has light and thermosetting properties, and can be widely used in adhesives, antireflection films (liquid crystal Antireflection films for displays, etc.), high refractive index layers, optical films (reflectors, etc.), sealing materials for electronic parts, printed wiring boards, interlayer insulating film materials (interlayer insulating film materials for build-up printed circuit boards, etc.), etc. field of electronic materials. In particular, it can be widely used as electronic materials requiring low dielectric tangent and low dielectric constant, such as printed wiring boards, interlayer insulating film materials, and the like. [Examples] [0073] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. In addition, in the Examples, the apparatus and conditions used for preparing the properties of the samples and analytes are as follows. (1) Gas chromatography (GC) device: (stock) GC-2010 Plus detector made by Shimadzu Corporation: FID column: Agilent J&W GC column HP-5 (length 30m) manufactured by Agilent Technologies (stock) , inner diameter 0.32mm, film thickness 0.25μm) Injection volume: 1.0μL Injection port temperature: 250°C Column temperature: 40°C (5 minutes), 20°C/min to 300°C, 300°C (12 minutes) ( 2) High-speed liquid chromatography (HPLC) apparatus: 1200 Infinity LC system manufactured by Agilent Technologies Co., Ltd. Detector: UV (205 nm) Column temperature: 40°C Column: Inertsil (registered trademark) ODS manufactured by GL Scientific Co., Ltd. -4 (particle size 5μm, inner diameter 4.6mm, length 250mm) Injection volume: 10μL Mobile phase composition: acetonitrile/pure water (volume ratio) = 4/96~90/10 (linear gradient, 30 minutes) Flow rate: 1.5mL /min (3) Gel permeation chromatography (GPC) apparatus: HLC-8220GPC manufactured by Tosoh Corporation Column: Shodex (registered trademark) GPC KF-804L manufactured by Showa Denko Corporation, same as KF-805L Column temperature : 40℃ Elution liquid: Tetrahydrofuran Detector: RI (4) Epoxy equivalent device: Potential difference automatic titration device AT-510 manufactured by Kyoto Electronics Industry Co., Ltd. (5) Dielectric tangent, specific permittivity device: Keysight Company-made E4980A precision LCR meter sample fixture: (share) Dongyang Technology's 12962 room temperature test fixture (6) Glass transition temperature Tg Device: TA Instrument company's dynamic viscoelasticity measuring device (DMA) Q800 Deformation mode: double cantilever frequency : 1Hz Distortion: 0.05% Scanning temperature: 30~300°C Heating rate: 5°C/min (7) Bending coefficient, deflection device: (stock) Shimadzu Precision Desktop Universal Testing Machine Automatic Stereo Mapper AGS-5kNX (8) Oven device: air supply cryostat DNF400 manufactured by Yamato Science (stock) [0075] Also, the abbreviation means the following. BA: Anhydrous Butyric Acid [Tokyo Chemical Industry Co., Ltd.] BzA: Anhydrous Benzoic Acid [Tokyo Chemical Co., Ltd.] iBA: Anhydrous Isobutyric Acid [Tokyo Chemical Co., Ltd.] OA: Anhydrous Caprylic Acid [Tokyo Chemical Co., Ltd.] Industrial Co., Ltd.] PA: Anhydrous propionic acid [APA made by Dale] P3EPB: Ethyltriphenylphosphonium bromide [Beixing Chemical Industry Co., Ltd.] P4PB: Tetraphenylphosphonium bromide [Tokyo Chemical Industry Co., Ltd.] (stock)] BPA: Bisphenol A epoxy resin [JER (registered trademark) 828, manufactured by Mitsubishi Chemical Corporation] TGIC: Triglycidyl isocyanurate [TEPIC (manufactured by Nissan Chemical Industries, Ltd.) Registered trademark)-S] MH700: 4-Methylhexahydroanhydrophthalic acid/hexahydroanhydrophthalic acid mixture (mol ratio 70:30) [Rikacid (registered trademark) MH-700, manufactured by Nippon Rika Co., Ltd.] PX4ET : Tetrabutylphosphonium O,O-diethyl thiodiphosphate [Hishicolin (registered trademark) PX-4ET manufactured by Nippon Chemical Industry Co., Ltd.] [0076] [Production Example 1] TGIC anhydrous propionic acid denatured (PA - Production of TGIC) TGIC 60.0 g (202 mmol) and toluene 54 g were placed in a reaction flask, the mixture was refluxed, and a mixture of PA 21.2 g (162 mmol) and P3EPB 0.06 g (0.156 mmol) was added dropwise at the same time. After completion of the dropwise addition, the mixture was refluxed for 2 hours. By depressurizingly distilling toluene from this reaction mixture, TGIC anhydrous propionic acid denatured product (PA-TGIC) was obtained as a liquid substance. The epoxy equivalent of the obtained PA-TGIC measured according to JIS K7236:2009 was 181 (theoretical value 182). In addition, TGIC (non-adduct): 1 molar adduct: 2 molar adduct: 3 molar adduct (area ratio) by HPLC analysis was 33:45:19:3. [Production Example 2] Production of TGIC anhydrous butyric acid denatured product (BA-TGIC) 40.0 g (135 mmol) of TGIC and 14 g of acetonitrile were placed in a reaction flask. The mixture was refluxed, and a mixture of BA 17.0 g (108 mmol), P4PB 0.026 g (0.062 mmol), and acetonitrile 0.4 g was added dropwise at the same time. After completion of the dropwise addition, the mixture was refluxed for another 24 hours. From this reaction mixture, acetonitrile was distilled off under reduced pressure to obtain TGIC anhydrous butyric acid denatured product (BA-TGIC) as a liquid. The epoxy equivalent of the obtained BA-TGIC was 192 (theoretical value 193). Moreover, the TGIC (non-adduct) of HPLC analysis: 1 molar adduct: 2 molar adduct: 3 molar adduct (area ratio) was 33:52:14:0.1. [Manufacture example 3] The manufacture of TGIC anhydrous isobutyric acid denatured product (iBA-TGIC) Except that BA was replaced with iBA, other operations were carried out in the same manner as manufacture example 2, and the TGIC anhydrous isobutyric acid denatured product (iBA-TGIC) was obtained. iBA-TGIC) as a liquid. The epoxy equivalent of the obtained iBA-TGIC was 192 (theoretical value 193). Moreover, TGIC (non-adduct): 1 molar adduct: 2 molar adduct: 3 molar adduct (area ratio) by HPLC analysis was 30:52:17:1. [Manufacture example 4] The manufacture of TGIC anhydrous octanoic acid denatured product (OA-TGIC) Except that BA was replaced with OA 29.1g (108mmol), other operations were carried out in the same manner as in manufacture example 2, and the TGIC anhydrous octanoic acid denatured product was obtained (OA-TGIC) as a liquid. The epoxy equivalent of the obtained OA-TGIC was 234 (theoretical value 234). In addition, the TGIC (non-adduct) of HPLC analysis: 1 molar adduct: 2 molar adduct: 3 molar adduct (area ratio) was 29:43:24:4. [Manufacture example 5] The manufacture of TGIC anhydrous benzoic acid denatured product (BzA-TGIC) Except replacing BA with BzA 24.4g (108mmol), other operations were carried out in the same manner as manufacture example 2, and TGIC anhydrous benzoic acid was obtained The denatured substance (BzA-TGIC) was used as a liquid. The epoxy equivalent of the obtained BzA-TGIC was 217 (theoretical value 217). In addition, the TGIC (non-adduct) of HPLC analysis: 1 molar adduct: 2 molar adduct: 3 molar adduct (area ratio) was 15:43:35:7. [Examples 1 to 5 and Comparative Examples 1 to 2] To 100 parts by mass of the epoxy compound described in Table 1, the epoxy group of the epoxy compound was added in an equimolar amount of MH700 as a hardener, and a hardening accelerator 1 part by mass of PX4ET. The mixture was stirred at room temperature (about 23° C.) for 30 minutes under reduced pressure, defoamed, and prepared as an epoxy resin composition. Using 2 glass substrates that had been preliminarily treated by Optool (registered trademark) DSX [Daikin Kogyo Co., Ltd.] release treatment, each composition was held together with a 3mm thick ㄈ zigzag polysiloxane rubber spacer . This was heated in an oven at 100°C (preliminary hardening) for 2 hours, and then heated to 150°C for 5 hours (main hardening). After slow cooling, the glass substrate was removed to obtain each hardened product with a thickness of 3 mm. The obtained cured product was evaluated for dielectric tangent, specific permittivity, glass transition temperature, water absorption, bending coefficient, and deflection. In addition, each physical property value was measured according to the following operation sequence. The results are combined in Table 1. [Dielectric tangent] The dielectric tangent when a voltage of 1 V and 1 MHz was applied to the test piece sandwiched between the electrodes between the jigs was measured. [Specific permittivity] Measure the electrostatic capacity Cp when a voltage of 1V, 1MHz is applied to the test piece sandwiched between the electrodes of the jig, and divide by the electrostatic capacity C0 of the air measured under the same conditions. Calculate the specific permittivity. [Glass transition temperature (Tg)] The storage elastic coefficient E' and the loss elastic coefficient E" are measured by DMA, and tanδ (loss elastic coefficient E"/storage elastic coefficient E') obtained from these The value shows that the maximum temperature is set to Tg. [Water Absorption Rate] Measured according to JIS K-6911:2006. Specifically, first, as a pretreatment, a test piece (30×30×3 mm) was dried in a glass container kept at 50° C. for 24 hours using an oil bath. This test piece was cooled to 20°C in a desiccator, and its mass (W 1 [g]) was measured. Next, this test piece was immersed in boiled distilled water for 100 hours, taken out, cooled in running water at 20°C for 30 minutes, and the water was wiped off, and then the mass (W 2 [g]) after water absorption was measured. From these values, the water absorption rate was calculated by the following formula. Water absorption [%]=(W 2 -W 1 )÷W 1 ×100 [0086] [Bending coefficient] Measured according to JIS K-6911:2006. Specifically, a load is applied to the center of a test piece (80×10×3mm) supported at a distance of 64 mm between the fulcrums using a pressure wedge, and the gradient F/Y [N/ mm]. From this gradient, the value of the distance L [mm] from the fulcrum, the width W [mm] of the test piece, and the thickness h [mm], the bending coefficient was calculated by the following formula. Bending coefficient [MPa]=(L 3 ÷ 4Wh 3 )×(F/Y) [0087] [Deflection] The deflection of the breaking point (pressing distance). >30 is dropped before breaking. [0088] As shown in Table 1, compared with BPA (Comparative Example 2), which is an epoxy compound widely used in the formation of printed wiring boards, the cured product obtained by using the epoxy resin composition of the present invention (Example 1~5) show extremely low dielectric tangent. Among them, it has also been confirmed that an epoxy resin composition containing an epoxy compound denatured with an aromatic carboxylic anhydride can maintain a high Tg, achieve low water absorption and low specific permittivity, and is suitable as a resin for forming printed wiring boards. .
