527371 A7 B7 五、發明説明（1 ) 發明所屬的技術領域 (請先閲讀背面之注意事項再填寫本頁) 本發明係有關印刷電路法，尤指於構築工法等中可用 以作爲多層印刷電路板之層間絕緣材或焊錫光阻等的光硬 化性·熱硬化性組成物。 習知技術 由於最近的半導體構件之急速進步，電子機器有小型 輕量化、高性能性、多功能化之傾向，伴隨著此等，印刷 電路板之高密度化正進展著。例如，導體電路之細線化、 高多層化、或貫穿孔、盲穿孔（blind viahole )之小徑化， 再者由小型晶片構件之表面裝配引起的高密度裝配等正進 行著，對應於此等高密度印刷電路板，多層印刷電路板之 需要正日益增加著，因此安裝施工法等新穎的多層印刷電 路板之製造方法係被倡導。此等用途同樣的被視作必要的 特性之一，係耐燃性或自行熄火性。向來，爲賦與耐燃性 或自行熄火性至層間絕緣材或軟焊光阻方面，則採用含有 鹵素之環氧樹脂作爲組成物之熱固性成分。 經濟部智慧財產局員工消費合作社印製 然而，使用含鹵素之環氧樹脂之情形，廢棄後的多層 印刷電路板在燃燒時會發生戴奧辛等有害氣體，在最近成 爲問題所在。 發明欲解決的課顆 因此，本發明係以提供在燃燒時不發生戴奧辛等有害 氣體之具有耐燃性或自熄性之無鹵素的光硬化性·熱硬化 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -4- 527371 A7 B7 五、發明説明（2 ) 性組成物爲目的。 解決課題而採的手段· 爲達成前述目的，依本發明係於（A) (a)分子中 具有二個以上的環氧基之化合物內，使（b )不飽和單羧 酸及（c )以下述一般式（1 )表示的化合物反應後，含 有以使（d )飽和或不飽和多元酸酐反應而得的樹脂化合 物，（B )光聚合引發劑，（C )分子中具有二個以上的 環氧基之化合物，及（D )稀釋劑爲特徵之具有耐燃性或 自熄性之光硬化性·熱硬化性組成物。至於稀釋劑係可採 用反應性稀釋劑及非反應性稀釋劑之任一種或二種。 (請先閲讀背面之注意事項再填寫本頁)527371 A7 B7 V. Description of the invention (1) The technical field to which the invention belongs (please read the precautions on the back before filling out this page) The present invention is related to the printed circuit method, especially the construction method, which can be used as a multilayer printed circuit board Photocurable and thermosetting composition such as interlayer insulation material or solder resist. Conventional technology Due to recent rapid advances in semiconductor components, electronic devices tend to be small, lightweight, high-performance, and multifunctional. With this, high density of printed circuit boards is progressing. For example, thinning of conductor circuits, high-level multilayers, or reduction in diameter of through holes and blind via holes, and high-density assembly due to surface mounting of small chip components are being carried out, corresponding to these. The demand for high-density printed circuit boards and multi-layer printed circuit boards is increasing. Therefore, novel manufacturing methods of multi-layer printed circuit boards such as installation and construction methods are advocated. These applications are also considered to be one of the necessary properties, either flame resistance or self-extinguishing. Conventionally, in order to impart flame resistance or self-extinguishing properties to interlayer insulation materials or soldering photoresist, an epoxy resin containing a halogen is used as a thermosetting component of the composition. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs However, in the case of the use of halogen-containing epoxy resin, hazardous gases such as dioxin may be generated during the combustion of discarded multilayer printed circuit boards, which has recently become a problem. Therefore, the present invention is to provide halogen-free light-hardening and heat-hardening that are flame-resistant or self-extinguishing without causing harmful gases such as dioxin during combustion. The paper is compliant with Chinese National Standards (CNS) A4 specification (210X297 mm) -4- 527371 A7 B7 V. Description of the invention (2) Sexual composition is for the purpose. Means for solving the problem · In order to achieve the aforementioned object, according to the present invention, (b) an unsaturated monocarboxylic acid and (c) are contained in a compound having two or more epoxy groups in a molecule of (A) (a) After reacting the compound represented by the following general formula (1), a resin compound obtained by reacting (d) a saturated or unsaturated polybasic acid anhydride, (B) a photopolymerization initiator, and (C) having two or more Epoxy-based compounds and (D) thinners are photocurable and thermosetting compositions with flame resistance or self-extinguishing properties. As for the diluent, either or both of a reactive diluent and a non-reactive diluent can be used. (Please read the notes on the back before filling this page)
〇 式中，111及112係各自表示芳香族環或烷基。 經濟部智慧財產局員工消費合作社印製 於較合適的態樣，至於供前述樹脂化合物（A )之合 成所用的分子中具有2個以上之環氧基的化合物（a)， 可採用酚酚醛型環氧樹脂或甲酚酚醛型環氧樹脂。 再者在其他的合適態樣，至於前述樹脂化合物（A ) 之合成時所用的前述一般式（1)表示的化合物（1) ’ 可採用二苯基膦酸。 發明之實施形熊 與本發明有關的光硬化性·熱硬化性組成物’係以於 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -5- 527371 A7 B7___ 五、發明説明（3 ) (A ) (a)分子中具有二個以上的環氧基之化合物中 使（b )不飽和單羧酸及（c )以下述一般式（1 )表示 的化合物反應後，含有以使（d )飽和或不飽和多元酸酐 反應而得的樹脂化合物，（B )光聚合引發劑，（C )分 子中具有二個以上的環氧基之化合物，及（D )反應性及 /或非反應性稀釋劑爲特徵。 亦即，本發明之特徵爲可採用在耐燃性或自熄性上有 效果的下述一般式（1 )之磷化合物於已導入含有羧基之 感光性樹脂化合物（上述（a )成分、（b )成分與（d )成分之反應生成物）內的樹脂化合物（A )。結果，即 使無鹵素亦可構成耐燃性或自熄性優越的光硬化性·熱硬 化性組成物。In the formula, 111 and 112 each represent an aromatic ring or an alkyl group. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has printed it in a more suitable form. As for the compound (a) having two or more epoxy groups in the molecule for the synthesis of the aforementioned resin compound (A), a phenol novolac type can be used. Epoxy or cresol novolac epoxy resin. Furthermore, in another suitable aspect, as the compound (1) 'represented by the aforementioned general formula (1) used in the synthesis of the aforementioned resin compound (A), diphenylphosphonic acid can be used. Implementation of the invention The photocurable and thermosetting composition related to the present invention is shaped according to the Chinese paper standard (CNS) A4 (210X297 mm) -5- 527371 A7 B7___. (3) (A) (a) A compound having two or more epoxy groups in a molecule is reacted with (b) an unsaturated monocarboxylic acid and (c) a compound represented by the following general formula (1), and contains A resin compound obtained by reacting (d) a saturated or unsaturated polybasic acid anhydride, (B) a photopolymerization initiator, (C) a compound having two or more epoxy groups in a molecule, and (D) reactivity and / Or non-reactive diluent. That is, the present invention is characterized in that a phosphorus compound of the following general formula (1), which is effective in flame resistance or self-extinguishing property, can be used in a photosensitive resin compound containing the carboxyl group (the (a) component, (b) ) And the resin compound (A) in the reaction product of the component and the component (d). As a result, even if it is halogen-free, a photocurable and thermosetting composition having excellent flame resistance and self-extinguishing properties can be formed.
Ri (請先閲讀背面之注意事項再填寫本頁)Ri (Please read the notes on the back before filling this page)
〇 式內，Ri及R2各自表示芳香族環或烷基。 經濟部智慧財產局員工消費合作社印製 至於前述樹脂化合物（A )之合成所用的分子中具有 二個以上的環氧基之化合物（a )，可爲公知慣用的各種 環氧樹脂，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、氫化雙酚A型環氧樹脂、雙酚型環氧 樹脂、雙甲苯酚型環氧樹脂、酚酚醛型環氧樹脂、甲酣酸 醛型環氧樹脂、二環戊二烯型環氧樹脂、雙酚A之酚醒型 環氧樹脂等的縮水甘油基醚化合物；對苯二甲酸二縮水甘 油基酯、六氫苯二甲酸二縮水甘油基酯、二元酸二縮水甘 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -6- 527371 A7 B7 五、發明説明（4 ) 油基酯等的縮水甘油基酯化合物、三聚異氰酸三縮水甘油 基酯、N，N，—四縮水甘油基伸甲基二甲苯 二胺，Ν，Ν，Ν— ，N>-四縮水甘油基雙胺基甲基環 已烷、N，N -二縮水甘油基苯胺等縮水甘油基胺化合物 等，單獨採用或組合二種以上採用，此等環氧樹脂之中較 宜者，可舉出高靈敏度化或磷之導入率容易調整的酚酚醛 型環氧樹脂或甲酚酚醛型環氧樹脂。 至於前述樹脂化合物（A )之合成所用的不飽和單羧 酸單羧酸（b)，可舉出有：（甲基）丙烯酸、或於含有 羥基之（甲基）丙烯酸酯內加成以多元酸酐之化合物，例 如單（2 -丙烯醯，氧基乙基）琥珀酸、單（2 -丙烯醯氧 基乙基）苯二甲酸、單（2 -丙烯醯氧基乙基）六氫苯二 甲酸、單（2 -丙烯醯氧基丙基）琥珀酸、單（2 -丙烯 醯氧基丙基）苯二甲酸、單（2 -丙烯醯氧基丙基）六氫 苯二甲酸、單（2 —甲基丙烯醯氧基乙基）琥珀酸、單（ 2 —甲基丙烯醯氧基乙基）苯二甲酸、單（2 —甲基丙烯 醯氧基乙基）六氫苯二甲酸、單（2 -甲基丙烯醯氧基丙 基）琥珀酸、單（2 -甲基丙烯醯氧基丙基）苯二甲酸、 單（2 -甲基丙烯醯氧基丙基）六氫苯二甲酸等。此等的 不飽和單羧酸、可單獨採用或組合二種以上使用。且，於 本說明書中，（甲基）丙烯酸係指丙烯酸、甲基丙烯酸及 此等混合物之總稱用語，至於其他類似的表現亦係相同的 〇 至於前述樹脂化合物（A )之合成所用的前述一般式 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公酱） (請先閲讀背面之注意事項再填寫本頁) 、τ 經濟部智慧財產局員工消費合作社印製 7- 527371 A7 B7 五、發明説明（ 5 經 濟 部 智 慧 財 產 局 消 費 合 作 社 印 製 (1)表示的化合物（C)，可採用二甲基膦酸 膦酸、二苯基膦酸等的膦酸衍生物等。至於較宜 用無毒性、安定性良好的二苯基膦酸。 至於前述樹脂化合物（A )之合成所用的飽 和多元酸酐（d)，可舉出苯二甲酸、四氫苯二 氫苯二甲酸、琥珀酸、苯偏三甲酸、苯均四甲酸 或不飽和多鹼基酸之酸酐。此等之中亦以四氫苯 六氫苯二甲酸及琥珀酸之酸酐內硬化塗膜之特性 爲尤宜者。此等飽和或不飽和多元酸酐，可單獨 合二種以上採用。 前述一般式（1 )表示的化合物（c )之反 對於前述分子中具有二個以上的環氧基之化合物 環氧基1當量，以〇 . 2〜0 · 8當量之比例爲 般式（1 )表示的化合物（1 )若較上述範圍少 與耐燃性之效果變小，並不合適。另一方面若超 圍時，則所得的樹脂化合物（A )之不飽和單羧 變小，由上述組合物而得的光硬化膜之耐鹼顯影 用鹼水溶液之顯影（以下稱鹼顯影）的耐性）較 故並不合適。 又，前述樹脂化合物（A )之酸價以5 0〜1 mgK〇H/g爲宜。酸價未達5 OmgKOH 上述組成物之塗膜係變成較難獲得鹼顯影性，故 。另一方面，酸價較150mgK〇H/g大時 膜之耐顯影性變成較難獲得，並不適合。 、二丁基 者，可採 和或不飽 甲酸、六 等的飽和 二甲酸、 之點而言 採用或組 應比例， (a )之 宜。以一 時，則賦 過上述範 酸含有率 性（對利 難獲得，5 0 / g時， 並不合適 ，光硬化 _______________丁______------up- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇x297公釐） 8 527371 A7 B7 五、發明説明（6 ) 至於前述光聚合引發劑（B )，可用公知慣用的各種 光聚合引發劑，例如苯偶因（benzoin )、苯偶因甲基醚、 苯偶因乙基醚、苯偶因異丙醚等苯偶因及苯偶因院基醚類 ，本乙嗣、2 ’ 2 —一甲氧基—2 -苯基苯乙嗣、2 ，2 一二乙氧基—2 —苯基苯乙酮、1 ，1 一二氯苯乙酮等苯 乙酮類、2 —甲基一 1—〔4 一（甲基硫代）苯基〕一 2 一嗎啉基胺基丙酮—1 ，2 -苄基一 2 -二甲基胺基一 1 一（4 一嗎啉基苯基）一 丁酮一 1等胺基苯乙酮類；2-甲基蒽酮醌、2 -乙基蒽醌、2 -第三丁基蒽醌、1 -氯 蒽醌等蒽醌類；2，4 一二甲基硫雜蒽酮、2 ，4 一二乙 基硫雜蒽酮、2 -氯硫雜蒽酮、2，4 - 異丙基硫雜蒽 酮等硫雜蒽酮類；苯乙酮二甲基縮酮、苄基二甲基縮酮等 縮酮類；二苯酮等二苯酮類；或雜蒽酮類等。此等公知慣 用的光聚合引發劑，係可單獨採用或組合二種以上採用， 又可單獨使用或組合二種以上使用第三級胺類公知慣用的 光增感劑。 此等光聚合引發劑之配合比例（合倂使用光增感劑時 此等的合計量），係對每1 0 0重量分之前述樹脂化合物 (A) 1〇〇重量分爲1〜30重量分，宜爲5〜25重 量分。光聚合引發劑之使用量較上述範圍少時，組成物之 光硬化性變差，另一方面，較多時，由於光聚合引發劑本 身之吸收，塗膜在成爲厚膜時，光硬化性變差，故並不適 宜。 至於前述環氧化合物（C )，可採用與前述樹脂化合 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 __ 經濟部智慧財產局員工消費合作社印製 -9 527371 A7 B7 五、發明説明（7 ) 物（A )之合成所用的環氧化合物（a )同樣的公知慣用 的多種環氧樹脂。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 至於環氧化合物（C)之具體例，可列舉有：日本化 藥股份有限公司製造的EBP S - 2 0 0、旭電化工業股 份有限公司製造的EPX - 3 0、大日本油墨化學工業股 份有限公司製造的Epiclon EXA— 1514等雙酚8型 環氧樹脂；日本油脂股份有限公司製造的Plemer - D G T 等苯二甲酸二縮水甘油基酯樹脂；日產化學股份有限公司 製造的T E P I C系列，Ciha Geigy公司製造的Araldite P T 8 1 0等雜環式環氧樹脂；油化蜆殼環氧股份有限公 司製造的YL - 6 0 6 5等之雙酚型環氧樹脂；東都化成 股份有限公司製造的EX - 1 〇 6 3等四縮水甘油基二甲 基苯酚型環氧樹脂.；油化蜆殼環氧股份有限公司製造的 YL - 6 0 6 5等的雙酚環氧樹脂；東都化成股份有限公 司製造的EX - 1 〇 6 3等之四縮水甘油基二甲苯酚乙烷 樹脂等的稀釋劑難溶性環氧樹脂、油化蜆殻環氧股份有限 公司製造的Epikote 1009、1031、大日本油墨化 學工業股份有限公司製造的Epiclon 3050、7 0 5 0 、9050、旭化成工業股份有限公司製造的AER-664、AER - 667、AER— 669、東都化成股 份有限公司製造的YD — 0 12、YD - 0 14、YD — 017、YD — 020、YD — 002、Giba Geigy 公司製 造的 XAC — 5005、GT — 7004、6484T、 6099，陶化學公司製DER — 642U、DER - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -10- 527371 A7 _______B7 五、發明説明（8 ) (請先閲讀背面之注意事項再填寫本頁) 6 7 3MF、旭電化工業股份有限公司製造的EP — 54〇〇、EP — 5900等雙酚A型環氧樹脂；東都化 成公司製ST-2004、 ST2007等氫化雙酚A型 環氧樹脂；東都化成股份有限公司製造的Y D F -2004、YDF — 2007等的雙酚F型環氧樹脂；日 本化藥股份有限公司製造的EPPN— 20 1、EOCN 一 103、 EOCN — 1020、 EOCN-1025. 旭化成工業股份有限公司製造的ECN— 2 7 8、ECN —292、ECN— 299、Ciba Geigy 公司製造的 ECN—1273、 ECN—1299、東都化成股份有 限公司製造的YDCN-200L、 YDCN— 經濟部智慧財產局員工消費合作社印製 220HN、YDCN- 702、YDCN-704、 YDPN — 601、YDPN— 602、大日本油墨化學 工業股份有限公司製造的Epic Ion N - 673、N— 680 、N—695、N— 770、N775等的酚醛型環氧樹 月旨；旭電化工業股份有限公司製造的E P X — 8 0 0 1、 EPX-8002> EOOX8060. E P P X - 8 0 6 1、大日本油墨化學工業股份有限公司製造的Epiclon N - 8 8 0等的雙酚A之酚醛型環氧樹脂；旭電化工業股 份有限公司製造的EPX — 4 9 — 6 0、EPX — 4 9 — 3 0等整合物型環氧樹脂·，東都化成股份有限公司製造的 Y D G - 4 1 4等乙二醛型環氧樹脂·，東都化成股份有限 公司製造的YH-1402、 ST-11〇、油化蜆殼環 氧股份有限公司製造的71^-9 3 1、丫1^ — 9 3 3等含 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -11 - 527371 A7 B7 五、發明説明（9 ) (請先閱讀背面之注意事項再填寫本頁) 胺基環氧樹脂；大日本油墨化學工業股份有限公司製造的 Epiclon TSR— 6 0 1、旭電化工業股份有限公司製 EPX— 84 - 2、EPX— 406 1等橡膠改質環氧樹 月旨；山陽國策紙漿股份有限公司製造的D C E — 4 0 0等 二環戊二烯酚醛型環氧樹脂；旭電化工業股份有限公司製 造的X - 1 3 5 9等矽氧改質環氧樹脂；Daicel化學工業 股份有限公司製造的Plaxel G — 402、G710等ε -已內酯改質環氧樹脂等稀釋劑可溶性的環氧樹脂等。 經濟部智慧財產局員工消費合作社印製 此等環氧樹脂係可單獨採用或組合2種以上使用，惟 以在組成物中使以微粒狀分散爲尤宜。因此，在常溫以固 形或本固形之環氧樹脂爲宜，又混煉時不溶解於前述樹脂 化合物（A )及使用的稀釋劑（D )者，及/或對所得的 光硬化性·熱硬化性組成物之感光性及顯影性無惡劣影響 之範圍的溶解性即可。亦即，於稀釋劑內採用難溶性之微 粒狀的環氧樹脂、或組合使用難溶性之環氧樹脂及可溶性 環氧樹脂爲宜。此時，稀釋劑內可溶的環氧樹脂之摻合量 ，以熱硬化性成分之對全環氧化合物環氧當量之未達5 0 莫耳％的比例爲宜。稀釋劑可溶的環氧樹脂之摻合比例若 成爲5 0莫耳％以上（稀釋劑內難溶性環氧樹脂之摻合比 例未達5 0莫耳％ )時，塗膜之暫時乾燥後的指觸乾燥性 或顯影壽命會降低，故並不合適。又大量合倂使用可溶於 稀釋劑的環氧樹脂時，所得的光硬化性·熱硬化性組成物 係在塗布至印刷電路板前或多或少變成容易增黏，故組成 以前述樹脂化合物（A )爲主成分之主劑及以環氧化合物 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12- 527371 Μ Β7 五、發明説明（10 ) (C )爲主成分之硬化劑之二液形態’在使用之際混合兩 者使用爲佳。 又上述環氧化合物（c )之使用量之合適的範圍’對 前述樹脂化合物（A)之羧基1當量而言，前述環氧化合 物（C)之環氧基爲0·6〜2.0當量’更宜爲1.〇 〜1 . 6當量之比例。在超過上述範圍之環氧化合物（c )之配合量，利用鹼水溶液對塗膜之未曝光部分之顯影性 、塗膜特性會降低，故並不合適。另一方面，環氧化合物 (C )之配合量若較上述範圍小時，則硬化塗膜之交聯密 度降低，較難獲得耐熱性等必需的特性，故並不合適。 至於用作前述稀釋劑（D )之反應性稀釋劑之代表性 者，可舉出有：丙烯酸2 -羥乙酯、丙烯酸2 -羥丁酯等 丙烯酸羥烷酯類；乙二醇、甲氧基四乙二醇、聚乙二醇、 丙二醇等二醇之單或二丙烯酸酯類；N，N -二甲基丙烯 醯胺、N -羥甲基丙烯醯胺等丙烯醯胺類；丙烯酸N，N 一二甲基胺基乙基酯等之丙烯酸胺基烷酯類；六二醇、三 羥甲基丙烷、季戊四醇、二季戊四醇、三聚異氰酸羥乙基 酯等多元醇或此等環氧乙烷加成物或兩二醇加成物之多元 丙烯酸酯類；丙烯酸苯氧酯、雙酚A二丙烯酸酯及此等酚 類之環氧乙烷加成物等的丙烯酸酯類；丙三醇縮水甘油基 _、三羥甲基丙烷三縮水甘油基醚、三聚異氰酸三縮水甘 油基酯等縮水甘油基醚之丙烯酸酯類；及三聚氰胺丙烯酸 酉旨=及/或對應於上述丙烯酸酯類之甲基丙烯酸酯類等之 %聚合性單體等。上述的反應性稀釋劑係可單獨採用或組 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 __ 經濟部智慧財產局員工消費合作社印製 -13- 527371 A7 B7 五、發明説明（Μ ) 合二種以上使用。反應性稀釋劑之使用量之合適的範圍， 爲前述樹脂化合物（Α)每1 〇 〇重量分1 〇〜3 0重量 分。反應性稀釋劑之配合比例若超過上述範圍時，塗膜之 指觸乾燥性會降低，故並不合適。 另一方面，至於用作前述稀釋劑（D )之非反應性稀 釋劑之代表性者，可舉出有：乙基甲基酮、環己酮等酮類 ;甲苯、二甲苯、四甲基苯等的芳香族烴類；乙氧基乙醇 、甲氧基乙醇、丁氧基乙醇、卡必醇、甲基卡必醇、丁基 卡必醇、丙二醇單甲醚、二丙二醇單甲醚、二丙二醇二乙 醚、三丙二醇單甲醚等二醇醚類；醋酸乙酯、醋酸丁酯、 乳酸丁酯、乙氧基乙醇乙酯、丁氧基乙醇乙酯、卡必醇乙 酯、丁基卡必醇乙酯、丙二醇單甲醚乙酯、二丙二醇單甲 醚乙酯、碳酸丙烯酯等的酯類；辛烷、癸烷等的脂肪族烴 類；石油醚、石油腦、溶劑石油腦等石油系溶劑等公知f貫 用的有機溶劑。上述的非反應性稀釋劑，可單獨採用或組 合二種以上使用。非反應性稀釋劑之使用量之較合適的範 圍雖依塗布方法而異，惟前述樹脂化合物（A )每1 0 0 重量分爲2 0〜3 0 0重量分，宜爲3 0〜2 0 0重量分 〇 本發明之光硬化性·熱硬化性組成物，係爲使耐燃性 或自熄性提高，可合倂公知常用的耐燃劑。例如可採用三 聚氰胺磷酸鹽；磷酸酯系化合物；聚磷酸鹽化合物；紅磷 ;氫氧化鋁、氫氧化鎂、硼酸鋅、鉻系化合物、鉬系化合 物等無機耐燃性之一種或二種以上。又由本發明之樹脂化 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 4 訂 經濟部智慧財產局員工消費合作社印製 -14 - 經濟部智慧財產局員工消費合作社印製 527371 A7 B7 五、發明説明（12 ) 合物（A )之含磷化合物，係藉由與三聚氰胺、乙醯基鳥 糞胺、苯並鳥糞胺、尿素、二氰二醯胺等含氮化合物合倂 使用，可提高耐燃性或自行熄火性。再者，亦可添加具有 耐燃性之熱硬化性樹脂之三聚氰胺樹脂、苯并鳥糞胺樹脂 、脲樹脂、矽氧樹脂、光氣樹脂等。此等耐燃劑或耐燃性 樹脂，係在不使塗膜特性降低的範圍內可予使用。 又於本發明之光硬化性·熱硬化性組成物內，在提高 塗膜之附著性、硬度等的特性之目的，可配合硫酸鋇、滑 石粉、二氧化矽、氧化鋁、氫氧化鋁等公知慣用的無機塡 充劑。此等無機塡充劑之配合比例對前述樹脂化合物（A )每1 0 0重量分，以在1 0 0重量分以下爲適合，宜爲 在5 0重量分以下。無機塡充劑之配合比率較上述範圍多 時，會生成塗膜強度之降低，靈敏度降低等，故並不適合 。再者，因應需要時，可添加公知慣用的著色顏料、著色 染料、熱聚合物抑制劑、增黏劑、消泡劑、均展劑、偶合 劑、耐燃助劑等。又以提高靈敏度爲目的，視必要時可配 合吩噻啡系、蒽系、六苯並苯系、苯並蒽系、茈系、芘系 、份菁系、酮基香豆素、硫雜蒽酮系之增感色素。兩者視 必要時，可添加咪唑鹽類或三氟化硼錯合物、有機金屬鹽 等作爲潛在性的硬化觸媒。再者印刷電路板之電路，亦即 防止銅之氧化的目的，可添加腺嘌呤、乙烯基三畊、二氰 基二醯胺、正甲苯基雙胍、三聚氰胺等的化合物、或此等 鹽。此等化合物之配合比例，係對前述樹脂化合物（A ) 每1 0 0重量分在2 0重量分以下爲較適宜，藉由添加此 本紙張尺度適用中國國家標準（ CNS ) A4規格（210X 297公釐丁 ---------______丁____________ (請先閱讀背面之注意事項再填寫本頁) -15- 527371 A7 B7 五、發明説明（1;3 ) 等’可使硬化塗膜之耐藥品性或與銅箔間之接著性提高。 (請先閲讀背面之注意事項再填寫本頁) 本發明之光硬化性·熱硬化性組成物係利用網版印刷 法、簾幕塗布法、噴布法、輥塗法等的方法予以塗布於經 予形成電路的印刷電路板上，例如藉由在6 0〜1 0 0 °C 之溫度使含於組成物中的有機溶劑揮發乾燥（暫時乾燥） ’可形成指觸乾燥性優越、顯影壽命較長的塗膜。其後通 過已形成圖案之光罩掩膜利用活性光線選擇性的曝光，利 用稀鹼水溶液將未曝光部顯影，可形成光阻圖案，再者例 如加熱至1 4 0〜1 8 0 t之溫度使硬化，可形成附著性 、硬度、軟焊耐熱性、耐藥品性、耐溶劑性、電氣絕緣性 、耐電蝕性優越的絕緣塗膜。 至於上述稀鹼水溶液，可使用氫氧化鉀、氫氧化鈉、 碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等的稀鹼水 溶液。 經濟部智慧財產局員工消費合作社印製 又至於爲使塗膜光硬化而用的照射光源，以低壓水銀 燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、氙氣燈或 鹵化金屬燈等較合適。其他亦可利用雷射光線作爲曝光用 活性光線。 以下表示合成例、實施例及比較例，具體的說明本發 明，惟以下的實施例僅係供本發明之例示目的而用者，並 非限定本發明者’且以下「份」及「％」，若未予特別限 定時，均係指重量基準。 合成例1 本紙張尺度適用中國國家標準（CNS)A4規格（210x 297公釐） -16- 527371 A7 B7 五、發明説明（14 ) 將二甲酚酚醛淸漆型環氧樹脂（Epiclon N - 6 8 0 、大日本油墨化學工業股份有限公司製造、環氧當量= 2 1 0 ) 2 1 0份放入附有攪拌機及迴流冷却器之四頸燒 瓶內，加入卡必醇乙酯3 0 4份，加熱溶解。其次加入三 苯基膦2 · 0分及二苯基膦酸109份，在9 0〜100 °C使反應8小時。再者，加入氫醌0 · 1份作爲聚合抑制 劑後，徐徐滴下丙烯酸3 6份，使反應1 6小時。冷却此 反應物至8 0〜9 ，加入四氫苯二甲酸酐1 〇 1份， 使反應8小時，冷却後取出。 如此而得的感光性樹脂係含有磷3 · 4 %、不揮發分 60%、固形物之酸價爲82mgK〇H/g。以下將此 反應溶液稱爲A淸漆。 比較合成例1 將甲酚酚醛型環氧樹脂（Epiclon N — 6 9 5、大日 本油墨化學工業股份有限公司製造、環氧當量=2 2 〇 ) 2 2 0份放入附有擾梓機及迴流冷却器之四頸燒瓶內，加 入卡必醇乙酯2 1 4分，加熱溶解。其次加入氫醌〇 · 1 份作爲聚合抑制劑’三苯基膦酸2 · 〇份作爲反應觸媒。 將此混合物加熱至9 5〜1 〇 5 °C ’徐徐滴下丙烯酸7 2 份，使反應1 6小時。將此反應物冷却至8 〇〜9 0 °C， 加入四氫苯二甲酐1 〇 6份，使反應8小時，冷却後取出 〇 如此而得的乙烯性不飽和鍵結及合倂具有羧基之感光 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 、*?<» 經濟部智慧財產局員工消費合作社印製 -17- 527371 A7 B7 五、發明説明（15 ) 性樹脂，係不揮發分65%、固形物之酸價10Omg K〇H/g。以下稱此反應溶液爲B淸漆。 (請先閱讀背面之注意事項再填寫本頁) 實施例1 各以三支輥磨機混練採用前述合成例1而得的下述A 淸漆之摻合成分，而得A成分及B成分。混合此A成分 6 0份及B成分1 6 . 5份而得光硬化性·熱硬化性組成 物。 A成分 A淸漆 3 0份 IRGACURE 907 3 份 (Ciba Specialty chemicals股份有限公司製造的光聚合引發 劑） KS-66 0.5 份 (信越化學工業股份有限公司製造的矽氧系消泡劑） 酞菁藍 0 · 2份 經濟部智慧財產局員工消費合作社印製 二氧化矽 2 1份 滑石粉 3 · 3份 二丙二醇單甲醚 2份 合計 6 0份 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -18- 527371 A7 B7 五、發明説明（ 16 B成分 三聚異氰酸三縮水甘油基酯 _六丙烯酸二季戊四醇酯 合計In the formula, Ri and R2 each represent an aromatic ring or an alkyl group. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the compound (a) having more than two epoxy groups in the molecule used for the synthesis of the aforementioned resin compound (A) may be various commonly known epoxy resins, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol type epoxy resin, biscresol type epoxy resin, phenol novolac type ring Glycidyl ether compounds such as oxyresin, formic acid aldehyde-type epoxy resin, dicyclopentadiene-type epoxy resin, phenolic epoxy resin of bisphenol A; diglycidyl terephthalate, Hexahydrophthalic acid diglycidyl ester, diacid diglycidyl paper standard applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -6- 527371 A7 B7 V. Description of the invention (4) Oil-based ester And other glycidyl ester compounds, triglycidyl isocyanate, N, N, —tetraglycidyl methylidylene diamine, Ν, Ν, Ν—, N > -tetraglycidyl bis Aminomethylcyclohexane, N, N -diglycidylaniline Glycidylamine compounds and the like are used singly or in combination of two or more kinds. Among these epoxy resins, phenol novolac type epoxy resins or formic acid epoxy resins which are more sensitive or whose phosphorus introduction rate can be easily adjusted are mentioned Phenolic novolac epoxy resin. As for the unsaturated monocarboxylic acid monocarboxylic acid (b) used in the synthesis of the aforementioned resin compound (A), there may be mentioned (meth) acrylic acid, or addition of a poly (meth) acrylate to a hydroxyl group-containing (meth) acrylic acid ester to multiply Acid anhydride compounds such as mono (2-propenyloxy, ethoxyethyl) succinic acid, mono (2-propenyloxyethyl) phthalic acid, and mono (2-propenyloxyethyl) hexahydrobenzene Formic acid, mono (2-propenyloxypropyl) succinic acid, mono (2-propenyloxypropyl) phthalic acid, mono (2-propenyloxypropyl) hexahydrophthalic acid, mono ( 2-methacryloxyethyl) succinic acid, mono (2-methacryloxyethyl) phthalic acid, mono (2-methacryloxyethyl) hexahydrophthalic acid, Mono (2-methacryloxypropyl) succinic acid, Mono (2-methacryloxypropyl) phthalic acid, Mono (2-methacryloxypropyl) hexahydrobenzene Formic acid and so on. These unsaturated monocarboxylic acids may be used singly or in combination of two or more kinds. In addition, in the present specification, (meth) acrylic acid refers to a general term of acrylic acid, methacrylic acid, and these mixtures, and other similar expressions are also the same. 0 As for the aforementioned general used for the synthesis of the aforementioned resin compound (A) This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 male sauce) (Please read the precautions on the back before filling this page), τ Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs 7- 527371 A7 B7 V. DESCRIPTION OF THE INVENTION (5) The compound (C) represented by (1) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs may use phosphonic acid derivatives such as dimethylphosphonic acid, diphenylphosphonic acid, and the like. Non-toxic and stable diphenylphosphonic acid. Examples of the saturated polybasic acid anhydride (d) used in the synthesis of the resin compound (A) include phthalic acid, tetrahydrobenzenedihydrophthalic acid, succinic acid, The anhydrides of trimellitic acid, pyromellitic acid or unsaturated polybasic acids. Among them, the characteristics of the internal hardening coating film of tetrahydrobenzenehexahydrophthalic acid and succinic acid anhydride are Those preferred. These saturated or unsaturated polybasic acid anhydrides may be used alone or in combination of two or more. The compound (c) represented by the aforementioned general formula (1) is opposed to the epoxy compound having two or more epoxy groups in the aforementioned molecule. The compound (1) represented by the general formula (1) with a ratio of 0.2 to 0. 8 equivalents is less than the above range, and the effect of flame resistance becomes small, which is not suitable. In this case, the unsaturated monocarboxylic acid of the obtained resin compound (A) becomes smaller, and the alkali-resistant development of the light-cured film obtained from the composition described above is less resistant to development by an alkali aqueous solution (hereinafter referred to as alkali development). Suitable. The acid value of the resin compound (A) is preferably 50 to 1 mgKOH / g. If the acid value is less than 5 OmgKOH, the coating film of the above composition becomes difficult to obtain alkali developability, so it is difficult to obtain. On the other hand, when the acid value is larger than 150 mgKOH / g, the development resistance of the film becomes difficult to obtain, which is not suitable. For dibutyl and dibutyl, formic or unsaturated formic acid, sixth-grade saturated dicarboxylic acid, etc. can be adopted, or the proportion should be adopted, (a) is preferred. For a while, the above-mentioned content of vanillic acid was given (it is difficult to obtain, at 50 / g, it is not suitable, light hardening ____________) (Please read the back Note: Please fill in this page again.) This paper size is in accordance with Chinese National Standard (CNS) A4 (21 × 297 mm) 8 527371 A7 B7 V. Description of the invention (6) As for the aforementioned photopolymerization initiator (B), it can be used commonly known Various photopolymerization initiators, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isopropyl ethers, Benzoin Samarium, 2 '2-methoxy-2-2-phenylacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 1, 1-dichloroacetophenone and other acetophenones , 2-methyl-1— [4-mono (methylthio) phenyl] -2 2-morpholinylaminoacetone-1, 2-benzyl-1 2-dimethylamino-1 1-1 (4-1 Morpholinyl phenyl) monobutanone-1 and other aminoacetophenones; anthracenes such as 2-methylanthone quinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone Quinones; 2,4-dimethylthioanthracene , 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-isopropylthioxanthone and other thioanthrones; acetophenone dimethyl ketal, benzyl Acetals such as dimethyl ketal; benzophenones such as benzophenone; or heteroanthrones, etc. These well-known and commonly used photopolymerization initiators can be used alone or in combination of two or more, and can also be used alone Use or combine two or more light sensitizers that are commonly known and used as tertiary amines. The blending ratio of these photopolymerization initiators (the total amount when using photosensitizers in combination) is 10 per 10 100 parts by weight of the aforementioned resin compound (A) 100 parts by weight is preferably 1 to 30 parts by weight, preferably 5 to 25 parts by weight. When the amount of the photopolymerization initiator used is less than the above range, the photohardenability of the composition is changed. Poor, on the other hand, when there are many, the photopolymerization initiator itself absorbs, and when the coating film becomes a thick film, the photohardenability is deteriorated, so it is not suitable. As for the aforementioned epoxy compound (C), it can be used in combination with The paper size of the aforementioned resin compound is applicable to China National Standard (CNS) A4 (210X297 mm) (please read the back first) Please fill in this page again before ordering) Order __ Printed by the Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -9 527371 A7 B7 V. Description of the invention (7) The same epoxy compound (a) used in the synthesis of the object (A) A variety of epoxy resins are commonly known. (Please read the precautions on the back before filling out this page.) Specific examples of epoxy compounds (C) printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs include: Co., Ltd. EBP S-200, EPX-30 manufactured by Asahi Chemical Industry Co., Ltd., Epiclon EXA-1514 and other bisphenol 8 epoxy resins manufactured by Dainippon Ink Chemical Industry Co., Ltd .; Japan Grease Co., Ltd. Co., Ltd. Plemer-DGT and other diglycidyl phthalate resins; TEPIC series manufactured by Nissan Chemical Co., Ltd., Araldite PT 8 1 0 and other heterocyclic epoxy resins manufactured by Ciha Geigy Company; Bisphenol type epoxy resins such as YL-6 0 6 5 manufactured by Oxygen Co., Ltd .; tetraglycidyl dimethyl etc. manufactured by Todo Chemical Co., Ltd. EX-1 06 Phenol-based epoxy resins; bisphenol epoxy resins such as YL-6 0 6 5 manufactured by Sinopec Epoxy Resin Co., Ltd .; tetraglycidyl glyceride such as EX-1 0 6 manufactured by Todo Chemical Co., Ltd. Diluents such as xylenol ethane resin, hardly soluble epoxy resins, Epikote 1009, 1031 manufactured by Petrochemicals Epoxy Co., Ltd., Epiclon 3050, 7 0 5 0 manufactured by Dainippon Ink Chemical Industry Co., Ltd. , 9050, AER-664, AER-667, AER-669, manufactured by Asahi Kasei Industrial Co., Ltd., YD — 0 12, YD-0 14, YD — 017, YD — 020, YD — 002 manufactured by Todo Chemical Co., Ltd. , XAC — 5005, GT — 7004, 6484T, 6099 manufactured by Giba Geigy, DER — 642U, DER made by Tao Chemical Co. — This paper size applies to China National Standard (CNS) A4 (210X297 mm) -10- 527371 A7 _______B7 V. Description of the invention (8) (Please read the notes on the back before filling in this page) 6 7 3MF, EP — 5400, EP — 5900 and other bisphenol A epoxy resins manufactured by Asahi Chemical Industry Co., Ltd. Dongduhua ST-2004, ST2007 and other hydrogenated bisphenol A type epoxy resins; manufactured by Todo Chemical Co., Ltd .; YDF-2004 and YDF — 2007 bisphenol F type epoxy resins; manufactured by Nippon Kayaku Co., Ltd. EPPN—20 1. EOCN—103, EOCN—1020, EOCN-1025. ECN—2 7 8 manufactured by Asahi Kasei Co., Ltd., ECN—292, ECN—299, ECN—1273 manufactured by Ciba Geigy, ECN—1299 , YDCN-200L, YDCN manufactured by Todo Chemical Co., Ltd. — Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy 220HN, YDCN-702, YDCN-704, YDPN — 601, YDPN — 602, Dainippon Ink Chemical Industry Co., Ltd. Epic Ion N-673, N-680, N-695, N-770, N775 and other phenolic epoxy resins; EPX-8 0 0, EPX-8002 > manufactured by Asahi Chemical Industry Co., Ltd. EOOX8060. EPPX-8 0 6 1. Epiclon N-8 8 0 and other phenolic epoxy resins made by Dainippon Ink Chemical Industry Co., Ltd .; EPX made by Asahi Chemical Industry Co., Ltd. — 4 9 — 6 0, EP X — 4 9 — 3 0 and other integrated epoxy resins, YDG-4 1 4 and other glyoxal epoxy resins, manufactured by Tohto Kasei Co., Ltd., YH-1402, ST manufactured by Tohto Chemicals Co., Ltd. -11〇, 71 ^ -9 3 made by Petrochemical Co., Ltd. Epoxy Co., Ltd. 1, 1 ^ — 9 3 3, etc. The paper containing this paper is applicable to China National Standard (CNS) A4 (210X297 mm) -11- 527371 A7 B7 V. Description of the invention (9) (Please read the precautions on the back before filling out this page) Amine-based epoxy resin; Epiclon TSR — 6 0 manufactured by Dainippon Ink Chemical Industry Co., Ltd. 1. Asahi Denki Chemical Co., Ltd. Co., Ltd. EPX— 84-2, EPX — 406 1 and other rubber modified epoxy tree month purpose; DCE — 4 0 0 and other dicyclopentadiene phenolic epoxy resin manufactured by Shanyang Guoce Pulp Co., Ltd .; Asahi Denka X-1 3 5 9 and other silicon modified epoxy resins manufactured by Industrial Co., Ltd .; Plaxel G — 402, G710 and other ε-caprolactone modified epoxy resins manufactured by Daicel Chemical Industry Co., Ltd. are soluble. Epoxy. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs These epoxy resins can be used alone or in combination of two or more, but it is particularly suitable to disperse the composition in particulate form. Therefore, it is suitable to use a solid or solid epoxy resin at room temperature, and it does not dissolve in the resin compound (A) and the diluent (D) used during kneading, and / or the obtained photohardenability and heat It is only necessary that the photosensitivity and developability of the curable composition have solubility in a range that does not adversely affect. That is, it is preferable to use a hardly-soluble fine-grained epoxy resin in a diluent, or to use a hard-soluble epoxy resin and a soluble epoxy resin in combination. At this time, the blending amount of the soluble epoxy resin in the diluent is preferably a ratio of the thermosetting component to the epoxy equivalent of the total epoxy compound of less than 50 mol%. If the blending ratio of the diluent-soluble epoxy resin is 50 mol% or more (the blending ratio of the poorly soluble epoxy resin in the diluent is less than 50 mol%), the It is not suitable because the touch-drying property or development life are reduced. When a large amount of diluent-soluble epoxy resin is used in combination, the obtained photo-curable and thermosetting composition becomes more or less easily thickened before being applied to a printed circuit board. Therefore, the composition is based on the aforementioned resin compound ( A) The main component of the main component and the epoxy compound The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -12- 527371 Μ B7 V. Description of the invention (10) (C) The main component The two-liquid form of the hardener is preferably used by mixing the two at the time of use. In addition, an appropriate range of the amount of the epoxy compound (c) used is 'for 1 equivalent of the carboxyl group of the resin compound (A), the epoxy group of the epoxy compound (C) is 0.6 to 2.0 equivalents'. It should be a ratio of 1.0 to 1.6 equivalents. When the compounding amount of the epoxy compound (c) exceeds the above range, the developability and coating film characteristics of the unexposed portion of the coating film using the aqueous alkali solution are lowered, which is not suitable. On the other hand, if the blending amount of the epoxy compound (C) is smaller than the above range, the crosslinking density of the cured coating film is reduced, and it is difficult to obtain necessary characteristics such as heat resistance, which is not suitable. Representative examples of the reactive diluent used as the aforementioned diluent (D) include: hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; ethylene glycol and methoxy Mono- or diacrylates of diols such as tetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide, N-hydroxymethacrylamine and other acrylamides; acrylic acid N , N-dimethylaminoethyl acrylates and other amine alkyl acrylates; hexadiols, trimethylolpropane, pentaerythritol, dipentaerythritol, trimeric hydroxyethyl isocyanate and other polyols or these Polyacrylates of ethylene oxide adducts or two glycol adducts; phenoxy acrylates, bisphenol A diacrylates, and acrylates of ethylene oxide adducts of these phenols; Glycidyl glycidyl_, trimethylolpropane triglycidyl ether, triglycidyl isocyanate, and other glycidyl ether acrylates; and melamine acrylic acid == and / or corresponds to % Polymerizable monomers such as the acrylates and methacrylates. The above-mentioned reactive diluents can be used alone or in combination. The paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) (please read the precautions on the back before filling this page). Order __ Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Employee Consumption Cooperatives-13- 527371 A7 B7 V. Description of Invention (M) Use more than two types. A suitable range of the amount of the reactive diluent to be used is 100 to 30 parts by weight per 100 parts by weight of the resin compound (A). If the blending ratio of the reactive diluent exceeds the above range, the finger touch dryness of the coating film will be reduced, which is not suitable. On the other hand, as representative examples of the non-reactive diluent used as the diluent (D), ketones such as ethyl methyl ketone and cyclohexanone; toluene, xylene, and tetramethyl Aromatic hydrocarbons such as benzene; ethoxyethanol, methoxyethanol, butoxyethanol, carbitol, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol diethyl ether and tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, ethoxyethanol ethyl, butoxyethanol ethyl, carbitol ethyl, butyl Carbitol ethyl ester, propylene glycol monomethyl ether ethyl ester, dipropylene glycol monomethyl ether ethyl ester, propylene carbonate and other esters; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum brain, solvent petroleum brain Well-known organic solvents such as petroleum-based solvents. These non-reactive diluents can be used alone or in combination of two or more. Although a more suitable range of the amount of the non-reactive diluent varies depending on the coating method, the aforementioned resin compound (A) is divided into 20 to 3 0 0 weight parts per 100 0 weight, preferably 30 to 2 0 0 parts by weight. The photocurable and thermosetting composition of the present invention can be combined with a commonly-known flame retardant to improve flame resistance or self-extinguishing property. For example, one or two or more kinds of inorganic flame resistance such as melamine phosphate, phosphate compound, polyphosphate compound, red phosphorus, aluminum hydroxide, magnesium hydroxide, zinc borate, chromium compound, and molybdenum compound can be used. The paper size of the resinized paper of the present invention is also applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling out this page) 4 Order printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs- 14-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 527371 A7 B7 V. Description of the invention (12) Phosphorus compounds of the compound (A) are produced by combining with melamine, ethinoguanamine, and benzoguanamine , Urea, dicyandiamide and other nitrogen-containing compounds used together, can improve flame resistance or self-extinguishing. Furthermore, a melamine resin, a benzoguanamine resin, a urea resin, a silicone resin, a phosgene resin, or the like, which is a thermosetting resin having flame resistance, may be added. These flame retardants or flame retardant resins can be used as long as they do not reduce the characteristics of the coating film. In addition, in the photocurable and thermosetting composition of the present invention, in order to improve the adhesion and hardness of the coating film, barium sulfate, talc, silicon dioxide, aluminum oxide, aluminum hydroxide, and the like can be blended. Known and customary inorganic fillers are known. The mixing ratio of these inorganic fillers is preferably 100 parts by weight or less per 100 parts by weight of the aforementioned resin compound (A), and preferably 50 parts by weight or less. When the compounding ratio of the inorganic filler is more than the above range, it may cause a decrease in the strength of the coating film and a decrease in sensitivity, etc., so it is not suitable. Furthermore, if necessary, known coloring pigments, coloring dyes, thermal polymer inhibitors, tackifiers, defoamers, leveling agents, coupling agents, flame retardants, etc. may be added. For the purpose of improving sensitivity, if necessary, it can be combined with phenothiaphne, anthracene, hexabenzobenzo, benzoanthracene, fluorene, hydrazone, cyanine, ketocoumarin, and thiathracene Ketone-sensitized pigment. If necessary, imidazole salts, boron trifluoride complexes, organic metal salts, etc. can be added as potential hardening catalysts. Furthermore, the circuit of the printed circuit board, that is, for the purpose of preventing the oxidation of copper, compounds such as adenine, vinyl tripine, dicyanodiamide, n-tolylguanidine, melamine, or the like may be added. The compounding ratio of these compounds is more suitable for the aforementioned resin compound (A) to be less than 20 weight points per 100 weight points. By adding this paper, the Chinese National Standard (CNS) A4 specification (210X 297) is applicable. D-mm ---------______ D____________ (Please read the notes on the back before filling this page) -15- 527371 A7 B7 V. Description of the invention (1; 3) etc. The chemical resistance of the coating film or the adhesion to the copper foil is improved. (Please read the precautions on the back before filling in this page.) The photocurable and thermosetting composition of the present invention uses screen printing and curtains. The coating method, spraying method, roll coating method and the like are applied to a printed circuit board on which a circuit has been formed. For example, the organic solvent contained in the composition is volatilized at a temperature of 60 to 100 ° C. Drying (temporary drying) 'It is possible to form a coating film with excellent finger-drying property and long development life. After that, a patterned photomask is used to selectively expose active light, and an unexposed part is developed with a dilute aqueous alkali solution. , Can form a photoresist pattern, and for example, heated to 1 It is hardened at a temperature of 40 ~ 180 ° to form an insulating coating film with excellent adhesion, hardness, soldering heat resistance, chemical resistance, solvent resistance, electrical insulation, and electrical corrosion resistance. Dilute alkali aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. can be used. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy As the light source for light hardening, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a metal halide lamp is suitable. Other laser light can also be used as the active light for exposure. The synthesis examples are shown below. , Examples and Comparative Examples to specifically describe the present invention, but the following examples are only for the purpose of exemplification of the present invention, and are not limited to the inventor's and the following "parts" and "%", unless otherwise specified When it is limited, it refers to the basis of weight. Synthesis Example 1 This paper size applies the Chinese National Standard (CNS) A4 (210x 297 mm) -16- 527371 A7 B7 V. Description of the invention (14 ) Put xylenol novolac epoxy paint type epoxy resin (Epiclon N-6 8 0, manufactured by Dainippon Ink Chemical Industry Co., Ltd., epoxy equivalent = 2 1 0) 2 10 parts are put in a mixer and reflux cooling In a four-necked flask, add 304 parts of carbitol ethyl ester and heat to dissolve. Next, add 3.0 points of triphenylphosphine and 109 parts of diphenylphosphonic acid, and make the reaction 8 at 90 ~ 100 ° C. After adding 0.1 parts of hydroquinone as a polymerization inhibitor, 36 parts of acrylic acid was slowly added to the reaction for 16 hours. The reaction was cooled to 80-9 and tetrahydrophthalic anhydride was added. One part was allowed to react for 8 hours, and it was taken out after cooling. The photosensitive resin thus obtained contained 3.4% of phosphorus, 60% of nonvolatile matter, and had an acid value of 82 mgKOH / g as a solid. This reaction solution is hereinafter referred to as A lacquer. Comparative Synthesis Example 1 2 2 0 parts of a cresol novolac epoxy resin (Epiclon N — 6 9 5; manufactured by Dainippon Ink Chemical Industry Co., Ltd., epoxy equivalent = 2 2 〇) In a four-necked flask with a reflux cooler, add carbitol ethyl ester 2 to 4 minutes, and heat to dissolve. Next, 0.1 part of hydroquinone was added as a polymerization inhibitor, and 3.0 parts of triphenylphosphonic acid was used as a reaction catalyst. This mixture was heated to 95 to 105 ° C, and 72 parts of acrylic acid was slowly dropped, and the reaction was allowed to proceed for 16 hours. This reaction product was cooled to 80 ° to 90 ° C, 106 parts of tetrahydrophthalic anhydride was added, and the reaction was allowed to proceed for 8 hours. After cooling, it was taken out. The ethylenically unsaturated bond thus obtained had a carboxyl group. The paper size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling out this page), *? ≪ »Printed by the Employees’ Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-17 -527371 A7 B7 5. Description of the invention (15) Resin, which is 65% non-volatile content, and the acid value of the solid is 100 mg KOH / g. This reaction solution is hereinafter referred to as B lacquer. (Please read the precautions on the back before filling this page) Example 1 Each of the three roller mills was used to mix the following A lacquer blending ingredients obtained from the above Synthesis Example 1 to obtain A and B components. 60 parts of component A and 16.5 parts of component B were mixed to obtain a photocurable and thermosetting composition. A component A lacquer 30 parts IRGACURE 907 3 parts (photopolymerization initiator manufactured by Ciba Specialty chemicals Co., Ltd.) KS-66 0.5 parts (silicone defoamer manufactured by Shin-Etsu Chemical Industry Co., Ltd.) Phthalocyanine blue 0 · 2 copies of silicon dioxide printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 1 part of talc 3 · 3 parts of dipropylene glycol monomethyl ether 2 parts total 60 parts This paper size applies Chinese National Standard (CNS) A4 specifications ( 210X297 mm) -18- 527371 A7 B7 V. Description of the invention (16 B component triglycidyl isocyanate triglyceride_dipentaerythritol hexaacrylate total
88iL 份 份 實施例2 各以三支輥磨機混練採用前述合成例1而得的下@ A 淸漆之摻合成分，而得A成分及B成分。混合此A成分 6 0份及B成分1 8份而得光硬化性·熱硬化性組成物。 (請先閱讀背面之注意事項再填寫本頁) d 經濟部智慧財產局員工消費合作社印製 A成分 A淸漆 IRGACURE 907 K S - 6 6 酞菁藍 二氧化矽 滑石粉 二丙二醇單甲醚88iL parts parts Example 2 Each of the three roller mills was used to knead the blending ingredients of the lower @ A 淸 lacquer obtained in the above Synthesis Example 1 to obtain component A and component B. 60 parts of component A and 18 parts of component B were mixed to obtain a photocurable and thermosetting composition. (Please read the notes on the back before filling out this page) d Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A component A lacquer IRGACURE 907 K S-6 6 Phthalocyanine blue Silica Talc powder Dipropylene glycol monomethyl ether
本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 訂 ir 19 527371 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（17 ) B成分 三聚異氰酸三縮水甘油基酯 8.5份 六丙烯酸二季戊四醇酯 8份 ___三聚氰胺__1.51 合計 1 8份 比較例1 各以三支輥磨機混練採用前述比較合成例1而得的下 述B淸漆之摻合成分，而得A成分及B成分。混合此A成 分6 〇份及B成分1 6 · 5份而得光硬化性·熱硬化性組 成物。 A成分 B淸漆 3 0份 IRGACURE 907 3 份 K S - 6 6 0.5 份 献靑藍 0 . 2份 二氧化矽 2 1份 滑石粉 3 . 3份 二丙二醇單甲醚 _2份 合計 6 0份 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I ---I--- I _ _ n I n T I I I n _ n - (請先閱讀背面之注意事項再填寫本f ) -20 - 527371 A7 B7 五、 B成分 發明説明（18 ) Η聚異氰酸三縮水甘油基酯 _六丙烯酸二季戊四醇酯 8 · 5份 8份 合計 • 5份 比較例2 各以三支輥磨機混練採用前述比較合成例1而得的下 述Β淸漆之摻合成分，而得Α成分及Β成分。混合此Α成 分6 〇份及B成分1 6 . 5份而得光硬化性·熱硬化性組 成物。 A成分 經濟部智慧財產局員工消費合作社印製 B 淸漆 3 0 份 IRGACURE 907 3 份 K S — 6 6 0 • 5份 酞 円監 0 • 2份 二 氧化矽 2 1 份 滑 石粉 3 • 3份 二 丙二 醇單甲醚 2 份 6 0 份 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---------______丁______------ (請先閱讀背面之注意事項存填寫本頁) 21 - 527371 A7 B7 五、發明説明（彳9 ) B成分 三聚異氰酸三縮水甘油基酯 8 • 5份 六丙烯酸二季戊四醇酯 8 份 二聚氰胺 1 • 5份 合計 1 8份 比較例3 各以三支輥磨機混練採用前述比較合成例1而得的B 淸漆之摻合成分，而得A成分及B成分。混合此A成分 6 0份及B成分4 0份而得光硬化性·熱硬化性組成物。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A成分 B淸漆 3 0份 IRGACURE 907 3 份 KS — 66 0.5 份 酞菁藍 0 . 2份 二氧化矽 2 1份 滑石粉 3 . 3份 二丙二醇單甲醚_2份 合計 6 0份 訂 — 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -22- 527371 A7 _ —_B7_ 五、發明説明（2〇 ) B成分 溴化酚醛淸漆型環氧樹脂 (請先閲讀背面之注意事項再填寫本頁) (環氧當量283，含溴量35 · 5%) 32份 _六丙烯酸二季戊四醇酯_8份 合計 4 0份 比較例4 各以三支輥磨機混練採用前述比較合成例1而得的B 淸漆之摻合成分，而得A成分及B成分。混合此A成分 6 0份及B成分4 2份而得光硬化性·熱硬化性組成物。 A成分 B淸漆 3 0份 IRGACURE 907 3 份 KS-66 0.5 份 酞菁藍 0 . 2份 二氧化矽 2 1份 經濟部智慧財產局員工消費合作社印製 滑石粉 3 . 3份 二丙二醇單甲醚_2份 合計 6 0份 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -23- 527371 A7 B7 五、發明説明（21 ) B成分 溴化酚醛淸漆型環氧樹脂 (環氧當量283，含溴量35 · 5%) 32份 六丙烯酸二季戊四醇酯 8份 _ 三聚氰胺_2份 合計 4 2份 性能評估： 將前述各實施例及比較例而得的光硬化性·熱硬化性 組成物全面塗布於基板上，在8 0 °C乾燥2 0分鐘後，介 由光罩掩膜進行曝光，以鹼水溶液顯影。在1 5 0 °C熱硬 化此基板6 0分鐘，製作評估基板。 (1 )軟焊耐熱性 將已塗布松香系焊劑之基板浸漬於已事先設定於 2 6 0 °C之軟燥槽內3 0秒鐘，以丙二醇單甲醚乙酯淸洗 焊劑後’以目視方式評估光阻層之膨脹、剝離、變色。評 估基準係如下述般。 〇：完全未發現有變化者 △:僅少許變化者 X :光阻層上有膨脹、剝離者 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -24- 527371 A7 B7 五、發明説明（22 ) (2 )絕緣特性 採用I PC B - 25之梳子型電極B試棒，以上述 條件製作評估基板，對此梳子型電極施加D C 5 Ο Ο V之 偏壓，測定絕緣電阻値。 (3 )自熄性 將前述各實施例及比較例而得的光硬化性·熱硬化性 組成物全面塗布於基板上，在8 0 °C乾燥1 5分鐘後，背 面亦予全面塗布，在8 0 °C乾燥2 0分鐘後，進行兩面曝 光，以鹼水溶液予以顯影。在1 5 0 °C熱硬化此基板6 0 分鐘，製作硬化塗膜之厚度約8 0 // m之評估基板。將此 基板裁切成長度1 2 5mm，寬度1 3mm，使由下方與 燃氣器之光焰接觸，保持1 0秒鐘後，撤離火焰，測定其 後試料燃燒的時間。 所得的結果示於表1。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇Χ297公釐） -25- 527371 A7 B7 五、發明説明（ 23 表1 特性 實施例 比較例 1 2 1 2 3 4 軟焊耐熱性 〇 〇 〇 〇 〇 〇 絕緣特性(絕緣 抵抗Ω) 1012以上 1012以上 1012以上 1012以上 1012以上 1012以上 自熄®秒） 4.1 3.8 16.5 15.3 3.9 1.8 (請先閲讀背面之注意事項再填寫本頁) 發明之功效 如上述，藉由採用本發明之光硬化性·熱硬化性組成 物作爲印刷電路板之軟焊光阻或建構施工法等中之多層印 刷電路板之層間絕緣材，可得具有自熄性，又燃燒時不產 生有毒氣體的硬化物。而且，若於印刷電路板上形成由本 發明之光硬化性·熱硬化性組成物而成的塗膜時，則曝光 後成爲可鹼顯影，又曝光硬化部可形成自熄性優越的軟焊 光阻。再者，可用於印刷電路板關聯的永久保護光阻、感 光性接著劑、塗料、塑膠浮凸、塑膠之硬塗劑、作爲平板 印刷板之P S板、網版印刷用之感光液及光阻油墨等，可 用於廣泛領域方面。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 訂 經濟部智慧財產局員工消費合作社印製 -26-This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) Order ir 19 527371 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy A7 B7 V. Description of the invention (17) B component trimeric isocyanate triglycidyl Base ester 8.5 parts dipentaerythritol hexaacrylate 8 parts _ melamine __1.51 total 1 8 parts Comparative Example 1 Each was kneaded with a three-roll mill using the aforementioned Comparative Synthesis Example 1 The components are synthesized to obtain component A and component B. 60 parts of this A component and 16 · 5 parts of the B component were mixed to obtain a photocurable and thermosetting composition. A component B lacquer 30 parts IRGACURE 907 3 parts KS-6 6 0.5 parts Xanthine blue 0.2 parts silicon dioxide 2 1 part talc 3. 3 parts dipropylene glycol monomethyl ether _2 parts total 60 parts Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) I --- I --- I _ _ n I n TIII n _ n-(Please read the notes on the back before filling in this f) -20 -527371 A7 B7 V and B Ingredients Explanation (18) ΗPolyglycidyl isocyanate_dipentaerythritol hexaacrylate 8 · 5 parts 8 parts in total • 5 parts Comparative Example 2 Each is kneaded with three roller mills By using the blending ingredients of the following bismuth lacquer obtained in Comparative Synthesis Example 1, the A component and the B component were obtained. 60 parts of the A component and 16.5 parts of the B component were mixed to obtain a photocurable and thermosetting composition. A Ingredient Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, B. Lacquer 30 30 parts IRGACURE 907 3 parts KS — 6 6 0 • 5 parts phthalocyanine 0 • 2 parts silicon dioxide 2 1 part talc 3 • 3 parts 2 Propylene glycol monomethyl ether 2 parts 60 parts This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) ---------______ 丁 ______------ (Please read first Note on the back, please fill in this page) 21-527371 A7 B7 V. Description of the invention (彳 9) B component triglycidyl isocyanate 8 • 5 parts dipentaerythritol hexaacrylate 8 parts melamine 1 • 5 parts total 18 parts Comparative Example 3 Each was blended with a three-roll mill using the blending ingredients of B lacquer obtained in Comparative Synthesis Example 1 above to obtain component A and component B. 60 parts of this A component and 40 parts of the B component were mixed to obtain a photocurable and thermosetting composition. (Please read the precautions on the back before filling out this page) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A component B lacquer 30 30 parts IRGACURE 907 3 parts KS — 66 0.5 parts phthalocyanine blue 0.2 parts silicon dioxide 2 1 part of talc 3. 3 parts of dipropylene glycol monomethyl ether_2 parts of 60 parts in total — This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) -22- 527371 A7 _ —_B7_ V. Description of the invention (20) B-brominated phenolic lacquer epoxy resin (please read the precautions on the back before filling this page) (epoxy equivalent 283, bromine content 35 · 5%) 32 parts_six Dipentaerythritol acrylate_8 parts total 40 parts Comparative Example 4 Each of the three roller mills was used to knead the blending ingredients of the B varnish obtained in the aforementioned Comparative Synthesis Example 1 to obtain A component and B component. 60 parts of this A component and 42 parts of the B component were mixed to obtain a photocurable and thermosetting composition. A ingredient B lacquer 3 0 parts IRGACURE 907 3 parts KS-66 0.5 parts phthalocyanine blue 0.2 parts silicon dioxide 2 1 part printed talcum powder by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3.3 parts dipropylene glycol monoformate Ether_2 parts total 60 parts This paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) -23- 527371 A7 B7 V. Description of the invention (21) B component brominated phenolic lacquer type epoxy resin ( Epoxy equivalent 283, bromine content 35 · 5%) 32 parts dipentaerythritol hexaacrylate 8 parts _ melamine _2 parts total 4 2 parts Performance evaluation: Photohardenability and heat obtained by each of the foregoing examples and comparative examples The curable composition was completely coated on the substrate, dried at 80 ° C for 20 minutes, and then exposed through a photomask and developed with an alkaline aqueous solution. This substrate was thermally hardened at 150 ° C for 60 minutes to produce an evaluation substrate. (1) Soldering heat resistance The substrate coated with rosin-based flux was immersed in a soft-drying tank set at 250 ° C for 30 seconds, and the flux was washed with propylene glycol monomethyl ether ethyl ester. Method to evaluate the expansion, peeling and discoloration of the photoresist layer. The evaluation criteria are as follows. 〇: No change is found at all △: Only a few changes X: Photoresist layer has swelling and peeling This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back first Fill out this page again) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives-24- 527371 A7 B7 V. Description of the invention (22) (2) Insulation characteristics use I PC B-25 comb-shaped electrode B test rod, as described above An evaluation substrate was prepared under conditions, and a DC bias voltage of 5 OO V was applied to this comb-type electrode to measure the insulation resistance 値. (3) Self-extinguishing property The photocurable and thermosetting composition obtained in each of the foregoing examples and comparative examples was fully coated on a substrate, and after drying at 80 ° C for 15 minutes, the back surface was also fully coated. After drying at 80 ° C for 20 minutes, both sides were exposed and developed with an aqueous alkali solution. This substrate was thermally cured at 150 ° C for 60 minutes, and an evaluation substrate with a thickness of about 8 0 // m was produced. This substrate was cut into a length of 125 mm and a width of 13 mm, and brought into contact with the flame of the gas burner from the bottom. After holding for 10 seconds, the flame was evacuated and the time after which the sample was burned was measured. The obtained results are shown in Table 1. (Please read the notes on the back before filling out this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 (21〇 × 297 mm) -25- 527371 A7 B7 5. Description of the invention (23 Table 1 Characteristic example Comparative example 1 2 1 2 3 4 Soldering heat resistance 0.000 0000 Insulation characteristics (insulation resistance Ω) 1012 or more 1012 or more 1012 or more 1012 or more 1012 or more 1012 or more 1012 or more self-extinguishing® seconds ) 4.1 3.8 16.5 15.3 3.9 1.8 (Please read the precautions on the back before filling in this page) The effect of the invention is as described above. By using the photo-hardenable and thermo-hardenable composition of the present invention as the solder resist of the printed circuit board Or the interlayer insulation material of the multilayer printed circuit board in the construction method and the like, a hardened material having self-extinguishing property and no toxic gas when burning can be obtained. In addition, when a coating film made of the photocurable and thermosetting composition of the present invention is formed on a printed circuit board, it becomes alkali developable after exposure, and the exposed hardened portion can form a soft solder with excellent self-extinguishing properties. Resistance. Furthermore, it can be used for permanent protective photoresist, photosensitive adhesive, paint, plastic embossing, plastic hard coating agent related to printed circuit board, PS board as lithographic printing board, photosensitive liquid for screen printing and photoresist Inks, etc. can be used in a wide range of areas. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -26-