200837093 九、發明說明： 【發明所屬之技術領域】 本發明係以提供具有高耐熱性、高折射率之活性能量 •線硬化物作為㈣’且有關具有特定結構之含有不飽和= .之化合物。就其用途而言’可列舉如皮膜形成用材料、& 造印刷（配線電路）基板時之阻焊遮罩（solder mask)、電鍵阻 抗劑（platmg resist)、接著劑、透鏡、顯示器、光纖、光 波路、全像片（hologram)等。 【先前技術】 近年來，以活性能量線硬化而成為高耐熱且高折射率 之具有透明性的感光性材料開發，正向各種用途上 利文獻1至3)。 在此等用途中，除了高财熱性、高折射率以外，也要 求對基材之密著性或硬化物之硬度、對於鹼之溶解度等。 於是，依據用途，很多是在樹脂中添加單體或填料等之添 e加劑。然而，由於添加此等添加劑而導致對於基材之密著 性及折射率的下降等，由於未添加此等添加劑時之有:材 料（樹脂）本身之特性無法完全顯現，而需要具有更高的對 基材之密著性、耐熱性或折射率的樹脂。 一〜另外，於專利文獻4中，揭示一種3,3,_二苯基，仏 一搜基聯苯之雙烷二醇醚化合物之（甲基）丙烯酸酯化合 物，並記載有該化合物係可作為光學用 ^ ”單體錢。然而，該化合物由於不具有 吕旎機的早體，故有時會無法滿足密著性或鹼溶解性等物 319866 6 200837093 性。此外，所得之樹脂為 域中會有添加量受限制之考量色在4透明性之光學領 更進一步，於專利文 式（1)所干之严气 中’揭不一種含有如後述通 式u)所不之％虱樹脂、酚樹脂、 心k 的半導體封裝用環氧樹浐 進蜊及無機填充劑 特性及難燃性優里。此：、、：：，亚揭示該組成物之耐焊 由…二苯基：4,外」^ ’ 一罗工基聯笨與環聋畜h (epichl〇r〇hydrin)反應而獲^衣乳乳丙烷 _ . . ^ 于^衣乳树月日，亚提到該環羞抖 脂^色、具有高折射率、且於光學料上有^衣乳树 〔專利文獻2〕 〔專利文獻3〕 〔專利文獻4〕 〔專利文獻5〕 〔專利文獻6〕 〔專利文獻 1〕w〇2002/033447 【發明内容】 (發明欲解決之課題） 右本發明之“线提供一種透明性優異、樹脂單獨即具 的：：射ft心者性、且可賦予具有充分硬度之硬化物 令感光性樹脂及樹脂組成物。 (解決課題之方法） 本發明人等為了解決前述課題，經過精心研究之結 成物Π有特定結構之含有不鮮基的化合物以及其 為可解決上述課題者，因而完成本發明。亦即，本發 日本特開2004-29042號公報 曰本特開2005-274664號公報 曰本專利第3606615號公報 曰本特開2000-248050號公報 曰本特開2006-307011號公報 319866 7 200837093 明係關於： ⑴ 三:::=== 氧樹脂（a)與 應而得：200837093 IX. Description of the Invention: [Technical Field] The present invention provides a compound having high heat resistance and high refractive index, a linear hardened material as (4)', and a compound having a specific structure and containing unsaturated =. Examples of the use thereof include a material for forming a film, a solder mask for producing a printed circuit (wiring circuit) substrate, a platmg resist, an adhesive, a lens, a display, and an optical fiber. , light wave road, hologram, etc. [Prior Art] In recent years, photosensitive materials having high heat resistance and high refractive index which are cured by active energy rays have been developed, and documents 1 to 3 have been developed for various applications. In such applications, in addition to high heat and high refractive index, the adhesion to the substrate, the hardness of the cured product, the solubility to alkali, and the like are also required. Therefore, depending on the application, many of them are added to the resin such as a monomer or a filler. However, due to the addition of such additives, the adhesion to the substrate and the decrease in the refractive index, etc., are caused by the fact that the additives (the resin) itself cannot be completely exhibited when the additives are not added, and it is required to have a higher A resin that has adhesion to a substrate, heat resistance, or refractive index. In addition, in Patent Document 4, a (meth) acrylate compound of a bis-diol ether compound of 3,3,-diphenyl, fluorenylbiphenyl is disclosed, and the compound is described. However, since this compound does not have an early body of a lyophilizer, the compound may not satisfy the properties of adhesion or alkali solubility, etc. 319866 6 200837093. Further, the obtained resin is a domain. There is a limitation that the amount of addition is limited. In the optical collar of 4 transparency, in the rigor of the patent pattern (1), it is not necessary to disclose a resin containing % of the formula u) , phenol resin, core k for semiconductor encapsulation with epoxy resin and inorganic filler properties and flame retardancy. This:,:::, reveals the composition of the solder resistance by ... diphenyl: 4, Outside "^' A Luogongjilian stupid and the 聋 聋 h h (epichl〇r〇hydrin) reaction to get the milk of the milk _ _ ^ ^ ^ 乳 乳 月 , , 亚 亚 亚 亚 亚 ^ ^Color, has a high refractive index, and has a latex on the optical material [Patent Document 2] [Patent Document 3] [Patent Document 5] [Patent Document 5] [Patent Document 6] [Patent Document 1] W〇2002/033447 [Problem to be Solved by the Invention] The "wire of the present invention" provides an excellent transparency and a resin alone. In the present invention, the inventors of the present invention have carefully studied the composition of the photosensitive resin and the resin composition. The present invention is completed by a compound containing a non-fresh group of a specific structure and a problem which can solve the above-mentioned problems, that is, the present invention is disclosed in Japanese Laid-Open Patent Publication No. 2004-29042, No. 2005-274664, Japanese Patent No. 3606615 No. 2000-248050, 曰本特开2006-307011号 319866 7 200837093 The following is about: (1) Three:::=== Oxygen resin (a) and deserved:
(式中’ η表示〇至5之正數）； (2)如上述（1)所記載之化合物（Α)，其中，今且古7 / 不先和基之早羧酸化合物⑻係（甲基）㈣酸 丙烯酸與ε-己内酉旨之反應生成物、或是肉桂酸；土 ()如上述⑴或⑺所記載之化合物㈧，其中，液 為1.6以上； (4) —種樹脂組成物’含有上述⑴至（3)中任一項所記载 之化合物（Α)及光聚合起始劑（β); (5) —種二羧酸醋樹脂，其係由具有乙烯性不飽和基之單 羧酸化合物（b)加成於通式（1)所示之環氧樹脂（a)之環 氧基上而成： 式（1) 319866 200837093(wherein η represents a positive number of 〇 to 5); (2) The compound (Α) as described in the above (1), wherein, the present and the carboxylic acid compound (8) is not (4) a reaction product of acid acrylic acid and ε-hexidine, or cinnamic acid; soil () as described in the above (1) or (7), wherein the liquid is 1.6 or more; (4) a resin composition The compound (Α) and the photopolymerization initiator (β) according to any one of the above (1) to (3); (5) a dicarboxylic acid vinegar resin having an ethylenically unsaturated group The monocarboxylic acid compound (b) is added to the epoxy group of the epoxy resin (a) represented by the formula (1): Formula (1) 319866 200837093
(式中、’n表示〇至5之正數）； (6)如上述（5)所記載之二羧酸酉旨樹脂，其中，η係大於〇 且為1以下； ⑺如上述（5)或⑹所記載之二叛酸醋樹脂，其中，該具 有乙烯性不飽和基之單羧酸化合物（b)係： ⑴（甲基）丙稀酸、 (n)(曱基）丙埽酸與卜己内酯之反應生成物、或是 (iii)肉桂酸，· ⑻如上述（5)或⑹所記载之二叛酸酯樹脂，其中，該具 :乙烯性不飽和基之單羧酸化合物⑻係(甲基)丙烯 (9) (1〇) 種感光性樹脂組成物，含有上述⑺所記载之 酸酯樹脂及光聚合起始劑； :種二幾酸醋樹脂之製造方法，其特徵為 所不之環氧樹脂⑷中’使具有乙稀性不飽和基之() 殪酸化合師)反應並相對於該環氧_⑷之環氧基 319866 9 200837093 1當量’加成該單竣酸化合物（_.8至i當量： 式⑴In the formula (5), the dicarboxylic acid is a resin according to the above (5), wherein the η system is larger than 〇 and is 1 or less; (7) as in the above (5) or (6) The two oleic acid anhydride resins described in the above, wherein the monocarboxylic acid compound (b) having an ethylenically unsaturated group is: (1) (meth)acrylic acid, (n) (fluorenyl)propionic acid and The reaction product of caprolactone or (iii) cinnamic acid, (8) The bis-acid ester resin as described in the above (5) or (6), wherein the monocarboxylic acid compound having an ethylenically unsaturated group (8) A (meth) propylene (9) (1 Å) photosensitive resin composition comprising the acid ester resin and the photopolymerization initiator according to the above (7); and a method for producing a seed acid vinegar resin, The epoxy resin (4) is characterized by the reaction of (with a ethylenic acid anhydride) having an ethylenically unsaturated group and is equivalent to the epoxy group of the epoxy _ (4) 319866 9 200837093 1 equivalent 'addition of the single Citrate compound (_.8 to i equivalent: formula (1)
(1) (式中，η表示〇至5之正數）； (11)如上述（10)所記載之二羧酸酯樹脂之製造方法，其 中，反應係在不活性之有機溶媒及觸媒存在下、於 反應溫度6 0 C至15 0 °C中進行； ⑽-種硬化物’其係由含有上述（5)所記載之二缓酸醋 樹脂及光聚合起始劑的感光性樹脂組成物進行光 硬化而成。 (發明之效果） 本發明之化合物（A)係在分子中具有3,3，_二苯美_44, ^基聯苯骨架、乙稀性不飽和基以及感應性㈣^新賴 歧醋化合物，該化合物有難燃性，且透明性優異、為具 it射率之樹脂，含有該樹腊及光聚合起始劑：樹脂組 ==可以藉由活性能量線而曝光硬化，所得之硬化物對 '之接著性優異、其無色之透明性為優異（參照第】 319866 10 200837093 •圖）、具有高折射率、且具有充分之硬度、並具有高難燃性。 '另外，將該樹脂組成物以有機溶媒稀釋之液藉由塗佈可形 成光硬化性之塗膜，再藉由將該塗膜曝光硬化，即可賦^ ‘具有高密著性、^具有充分之硬度與可撓性（柔軟性）的硬 •化物（硬化膜）。因此，本發明之化合物⑷係適合作為皮膜 形成用材料、製造印刷（配線電路）基板時之阻焊遮 雷 鑛阻抗劑、接著劑、透鏡、顯示器、光纖、光導波路二 像片等用途之一種成分。 王 f 【實施方式】 為了製造本發明之化合物㈧所使用的以通 之環氧樹脂W，例如係可藉由使下述式^所示之紛化: Ο在驗金屬氫氧化物存在下與環氧氣㈣反 二曰 析，而可以結晶之型態獲得： 无進仃曰曰 式⑺(1) In the formula (10), the method for producing a dicarboxylic acid ester resin according to the above (10), wherein the reaction is carried out in an inactive organic solvent and a catalyst. The reaction product is carried out at a reaction temperature of 60 ° C to 150 ° C; (10) a cured product comprising a photosensitive resin composition containing the sulphuric acid vinegar resin and the photopolymerization initiator described in the above (5) It is made by light hardening. (Effect of the Invention) The compound (A) of the present invention has a 3,3,-diphenylene-44, ^-biphenyl skeleton, an ethylenically unsaturated group, and an inductive (tetra)-new lysine vine compound in the molecule. The compound is flame retardant and has excellent transparency and is a resin having an injection rate, and contains the wax and a photopolymerization initiator: the resin group == can be exposed and hardened by an active energy ray, and the obtained cured product pair 'The adhesiveness is excellent, and its colorless transparency is excellent (refer to 319866 10 200837093 • Fig.), has a high refractive index, has sufficient hardness, and has high flame retardancy. Further, by coating the resin composition with a solvent diluted with an organic solvent to form a photocurable coating film, and by subjecting the coating film to exposure curing, it is possible to have high adhesion and sufficient Hardness (flexible film) of hardness and flexibility (softness). Therefore, the compound (4) of the present invention is suitable as a material for forming a film, a solder resisting resist for a printed (wiring circuit) substrate, an adhesive, a lens, a display, an optical fiber, and an optical waveguide image. ingredient. WANG f [Embodiment] The epoxy resin W used for the production of the compound (VIII) of the present invention can be obtained, for example, by the following formula: Ο in the presence of a metal hydroxide Epoxy gas (4) anti-two decantation, and can be obtained by crystallization: no entry type (7)
上述式⑺所示之⑽b合物⑷，例 3606615號公報（前述專利文獻4)記载之方^日本專利第 在獲得上述環氧樹脂⑷之反應中用而合成。 化物可使用其固形物、亦可使用 I用之驗金屬氫氧 亦可為如下述之方法··將 田使用水溶液時， 屬風半飞化物之水溶液連續 319866 11 200837093 地添加至反應系統中，同時於減壓下或常壓下連續地使水 及環氧i丙烷（epihalohydrin)流出’更進行分液而去除水， 再連續地使環氧齒丙烷流回到反應系統内。相對於式（2) =示之酚化合物（c)之羥基丨當量，鹼金屬氫氧化物之使用 量通常為0.9至2.5當量，較佳為〇 95至2 〇當量。 就驗金屬氫氧化物而言，可列舉如氳氧化納、氮氧化 鉀及氫氧化鋰等。 f 在獲得上述環氧樹脂⑷之反應中，為了使反應更簡便 =進彳，可添加讀銨鹽作為觸媒。可用之喊銨鹽係列 :乳化四甲基銨、廣化四甲基銨、氯化三甲基I基 =四低級絲銨或心三低級·τ基銨。就㈣化物 於式⑺所/之化合;=//// r Μ基。相對 用量通常為…重量；二 佳。 忉又以〇.2至10重量份為更 &得上述環氧樹脂（a)之反應一 化合物之經基J當量#A，Μ ^相對於式⑺所不之 。…當量(莫耳)，又以。;至、4=Γ為 所使用之環4 Λw， 田里（莫耳）為更佳。 容易使用。此日：業上而言’係以環氧齒丙烷比較 較佳為添力/甲提，斤示之化合物之溶 基亞石風、四Λ“酵、兴丙醇等醇類、二甲基石風、二甲 反應。' d亏烧等非質子性極性溶劑等來進行 319866 12 200837093 當是使用醇類時， 於 .使用量通常為2至5G奮旦㈣“燒之量，該醇類之 重里/>’又以4至30重量％為更佳。 另外，當使用非質子椹技α 垔里/。為更仫 .旦θ、s二 極性溶劑時，相對於環氧鹵丙烷之 .里，其使用1通常為5至1πη舌旦〇/ …％為更佳。 100重Κ又以Η)至80重量 ,„為3〇至錢，又以35至8吖為更佳， :又可'、、、C1 &亦可使其經時性地變化。反應時間通 〇·5至1Μ、時’又以1至8小時為更佳。 因應需要而在反應結束後，將反應液進行水洗及/或將 f應液〜αΡ至室/Ja，然後藉由過遽所析出之鹽而去除反應 ?成之鹽。當析出環氧樹脂時，由於恐怕鹽可能會混入 衣氧树月曰之、、、口曰曰中’故本操作較佳為藉由水洗反應液而先 去除反應時生成之鹽。 從所得之環氧樹脂反應液進行晶析之方法，雖然並無 特另指定，但可利用例如經一次濃縮後使用溶劑並進行^ 、、、°曰曰之手法、或者是添加貧溶劑而進行再沉殿之手法等各 種手法’但本發明中係以下述手法為佳。 將含有反應生成物、環氧鹵丙烷等之反應混合物於加 熱減壓下蒸餾去除過量之環氧鹵丙烷等（步驟d)。此時，析 出結晶’並在變成泥漿狀時就停止減壓回收（步驟e)，於其 中添加丙酮、甲基乙基嗣(MEK)、環戊酮（CP)、環己酮等 酮類或乙酸乙酯、乙酸丁酯、丁酸乙酯、7 -丁内酯、卡必 醇乙酸酯等酯類、二噚烷、THF等爾類、甲醇、乙醇、丙 醇、丁醇、乙二醇、丙二醇等醇類等有機溶劑，使其分散 319866 13 200837093 後（步驟f)，更進—步據 ?醇、乙醇、丙醇;二“要而 等嗣類等有機溶劑（步驟〇，一；1、^^等奋醇類、丙酮 •幻。藉由將所得之結晶過滅、乾焊地滴下娜 .目的物之結晶性環氧樹脂（㈣h)，而可獲得作為 之中，條件以及所使用之溶劑量係依據使用 之=不心不同，無法—致地限定範圍，但例如當步驟 驟f,使用甲醇广 步驟“吏用丙酮，步 —才，在步驟d中以加熱到50至1 〇〇。〇，並使 =度設為―Μ聰至—_職左右為宜。相對^ Γη生成Γ。之理論收量，步驟f中使用之丙嗣量係以20至 0重量％為佳’又以5〇至重量％為更佳。相對於咳 7論收量，步驟f，中使用之甲醇量係以2〇至5〇〇重量％為 么又以50至2〇〇重量％為更佳。相對於該理論收量，步 驟g中使用之水係以4〇至1〇〇〇重量％為佳。（步驟〇及（步 )中使用之有機溶劑以及（步驟g)中使用之水的比率（重 1比率）較佳為（步驟f之溶媒）：（步驟f，之溶媒）：（步驟g 1至3.1至3:1至9左右。另外，在步驟h中， 較佳為將經過濾之結晶以曱醇、乙醇等醇類或水進行洗淨。 進订如上操作而得之樹脂（a )，雖然因依據反應條件等 不同而兴，恶法稱為一致，但在以上述較佳條件合成時， 一般係以於通式（1)所示之化合物中n=0之化合物作為主 體’獲得含有少量n= 1至5之化合物的混合物。因此，通 式（1)中之η係表示該等混合物之平均值，且n表示〇至$ 319866 14 200837093 正二=:n之值(平均值)之計算方法可列舉 貝I不/貝J里J衣氧當1，鱼理给 的方法.赤3、 /、理哪上之分子1比較後計算出 漆，3疋以GPC分析分子量分布’計算出各η數之波 k峰面積後，再計算平均值之方法。 波 ^明之化合物㈧’係可藉由使前述環氧樹脂⑷盘 (以^；^乙~性不飽和基之單羧酸化合物⑻反應而製得 (以下亦稱為羧酸酯化反應）。 本發明之化合物⑷係由前述單羧酸化合物 =成於前述環氧樹脂⑷之環氧基上而成㈣_，雖^ 化合物⑼之使用量等亦可獲得單或二幾酸 (:)之;;在本發明中，較佳為相對於環㈣ ()之㈣基！ η，加成有單羧酸化合 :=(a)1莫耳，酸化一莫耳)： —當使用為原料之前述環氧樹脂⑷之單一化合物（例如 η-0或1寺整數之化合物）時，雖亦可能獲得單一之 醋化合物’但通常如上所述，由於環氧樹脂⑷係以通式（1 所示之環氧化合物之混合物而得，並直接使用該混合物， 故本發明之化合物（Α)亦得到相對應之幾酸醋化合物之、、曰 :物。因此’基本上，本申請案之化合物⑷係由前述單： 酉夂化合物（b)之羧基加成於前述環氧樹脂⑷之環氧基上 成的㈣⑽脂’更佳為相對於環氧基i當量，前^單_ 酸化合物⑻加成0.8至！當量而成的幾酸醋樹脂。、 用以製造本發明化合物⑷之具有乙稀性不飽和基之 319866 15 200837093 單敌S义化合物（b)，可列舉如· 氛基肉桂酸或巴豆酸1 丁左ΑΧ# 矛或不飽和之二元酸盘今古 環二環氧丙基化合物(含有乙烯性不飽和基之單 ::如二if)的反應物。較佳之該單羧酸化合物⑻可 稀西1w °就丙婦酸類而言，可列舉如··（甲基）丙 喊ϋ乙稀基丙烯酸K喃甲基丙稀⑽彻㈣ ( :::::d)、(-甲基)丙烯酸與ε 己内§旨之反應生成物、飽 八S ϋ之一7^酸酐(馬來酸酐、四氫鄰苯二甲酸酐）與i 刀子中/、有1個！基之（曱基）丙烯酸酯衍生物的等莫耳反 應物的半_、飽和或不餘和二元酸與單環氧丙基(、甲基） 丙細酸s旨衍生物類的等莫耳反應物的半g|類等。更佳之化 合物之一例可列舉如：以下述式（3)所示之化合物 式（3)The (10)b compound (4) represented by the above formula (7), and the method disclosed in Japanese Patent No. 3606615 (Patent Document 4) are synthesized for the reaction of the above epoxy resin (4). The solid matter can be used as the solid matter, and the metal hydroxide can also be used. The method can be as follows. When an aqueous solution is used in the field, the aqueous solution of the semi-flying compound is continuously added to the reaction system at 319866 11 200837093. At the same time, the water and the epihalohydrin are continuously discharged under reduced pressure or under normal pressure to further remove the water, and the epoxidized propane is continuously flowed back into the reaction system. The alkali metal hydroxide is usually used in an amount of from 0.9 to 2.5 equivalents, preferably from 95 to 2 equivalents, based on the oxime equivalent of the formula (2) = the phenol compound (c). Examples of the metal hydroxides include sodium ruthenium oxide, potassium oxynitride, and lithium hydroxide. f In the reaction for obtaining the above epoxy resin (4), in order to make the reaction easier, a read ammonium salt may be added as a catalyst. Available ammonium salt series: emulsified tetramethylammonium, broadened tetramethylammonium chloride, trimethylsilyl chloride = tetra-lower ammonium or tris-lower. (4) Compounds of formula (7); =//// r thiol. The relative amount is usually ... weight; preferably. Further, from 2 to 10 parts by weight, the reaction of the above epoxy resin (a) is obtained by the base J equivalent #A, Μ ^ relative to the formula (7). ...equivalent (mole), again. ; to, 4 = Γ is the ring used 4 Λ w, Tian Li (Mor) is better. easy to use. This day: in terms of industry, it is better to use epoxidized propane to add force/methyl, the compound of the compound is the base of the sulphur, the sulphur, the alcohol, the dimethyl alcohol, etc. Stone wind, dimethyl reaction. 'd low-burning aprotic polar solvent, etc. to 319866 12 200837093 When using alcohol, the amount used is usually 2 to 5G Fendan (four) "burning amount, the alcohol It is more preferably 4 to 30% by weight. In addition, when using the aprotic technique α 垔 /. In the case of a more quaternary θ, s dipolar solvent, it is more preferably used in the range of 5 to 1 πη 〇 / / / relative to the epoxy halopropane. 100 heavy Κ Η Η) to 80 weight, „3〇 to money, and 35 to 8吖 is better, : can also ',,, C1 & can also make it change over time. Reaction time It is better to use 1 to 8 hours when the temperature is 5 to 1 。. If necessary, after the reaction is finished, the reaction solution is washed with water and/or the solution of f should be ~αΡ to the chamber/Ja, and then by The salt is removed and the reaction is removed. When the epoxy resin is precipitated, it is preferable that the salt may be mixed into the sputum, the sputum, and the sputum. The salt formed by the reaction is removed first. The method of crystallization from the obtained epoxy resin reaction liquid is not particularly specified, but may be carried out by, for example, concentrating once, using a solvent, and performing, In the present invention, it is preferred to use a method of adding a poor solvent to a method of re-sinking. However, in the present invention, the following method is preferred. The reaction mixture containing a reaction product, an epihalopropane, and the like is distilled under heating and reduced pressure. Excess epoxy halogen propane or the like is removed (step d). At this time, crystals are precipitated and become When the slurry is used, the pressure recovery is stopped (step e), and acetone, methyl ethyl hydrazine (MEK), cyclopentanone (CP), cyclohexanone or the like is added thereto, or ethyl acetate, butyl acetate, butyric acid is added. An organic solvent such as an ester such as ethyl ester, 7-butyrolactone or carbitol acetate, a dioxane or THF, or an alcohol such as methanol, ethanol, propanol, butanol, ethylene glycol or propylene glycol. After dispersing 319866 13 200837093 (step f), further step-by-step according to alcohol, ethanol, propanol; two "to be equal to the organic solvent such as hydrazine (step 〇, one; 1, ^ ^ and other alcohols, Acetone • Magical. By using the crystal obtained by extruding the crystal and dry-welding the crystalline epoxy resin ((4) h), the conditions and the amount of solvent used are based on the use. Inconsistent, it is impossible to limit the range, but for example, when step f, use the methanol wide step "吏 acetone, step - only, in step d to heat to 50 to 1 〇〇. 〇, and make = It is better to set it as “Μ聪至—_左右左右。 Relative to Γη generate Γ. The theoretical yield, the amount of 嗣 使用 used in step f is 20 to 0 The weight % is preferably 'more preferably 5 〇 to wt%. The amount of methanol used in step f, relative to the cough 7 is 2 〇 to 5 〇〇 wt% and 50 to 2 〇. The % by weight is more preferably. The water used in the step g is preferably 4 to 1% by weight relative to the theoretical amount. (Steps (steps) and organic solvents used in (step) and (step g) The ratio of the water used (weight ratio 1) is preferably (the solvent of step f): (step f, the solvent): (steps g 1 to 3.1 to 3: 1 to 9 or so. In addition, in step h Preferably, the filtered crystal is washed with an alcohol such as decyl alcohol or ethanol or water. The resin (a) obtained by the above operation is preferred because it is different depending on reaction conditions and the like. However, when it is synthesized under the above preferred conditions, a compound having a small amount of n = 1 to 5 is obtained by using a compound of n = 0 as a host in the compound of the formula (1). Therefore, η in the general formula (1) represents the average value of the mixtures, and n represents 〇 to $ 319866 14 200837093. The calculation method of the value of the n (the average value) (average value) can be cited as J clothing oxygen as 1, the method of fish management. Red 3, /, Lie on the molecule 1 after the calculation of the paint, 3 疋 GPC analysis of the molecular weight distribution 'calculated the η number of wave k peak area, and then The method of calculating the average. The compound (8) of the invention can be obtained by reacting the above-mentioned epoxy resin (4) disk (the monocarboxylic acid compound (8) which is an ethylenically unsaturated group (hereinafter also referred to as a carboxylic acid esterification reaction). The compound (4) of the present invention is obtained by forming the above-mentioned monocarboxylic acid compound = (4) in the epoxy group of the epoxy resin (4), and obtaining a mono- or di-acid (:) although the amount of the compound (9) used; In the present invention, it is preferred to add a monocarboxylic acid compound with respect to the (four) group of the ring (tetra) (), η: = (a) 1 mole, acidified one mole): - when used as a raw material When a single compound of the epoxy resin (4) (for example, a compound of η-0 or 1 temple integer), it is also possible to obtain a single vinegar compound 'but generally as described above, since the epoxy resin (4) is represented by the formula (1) The compound of the present invention is obtained by directly using the mixture of the epoxy compound, so that the compound (Α) of the present invention also obtains the corresponding acid vinegar compound, so that 'substantially, the compound (4) of the present application is From the foregoing single: the carboxyl group of the hydrazine compound (b) is added to the epoxy group of the aforementioned epoxy resin (4) The (4) (10) fat is more preferably an acid vinegar resin which is added to the epoxy group i equivalent, and the former mono-acid compound (8) is added in an amount of 0.8 to ! equivalent. The ethylene compound used in the production of the compound (4) of the present invention is ethylene. Unsaturated group 319866 15 200837093 Single enemy S compound (b), for example, aryl cinnamic acid or crotonic acid 1 butyl sulphate # spear or unsaturated dibasic acid plate of this ancient ring diepoxy propyl compound (Resin containing an ethylenically unsaturated group: such as two if). Preferably, the monocarboxylic acid compound (8) can be dilute to 1 W ° for the case of the bupropionic acid, and may be exemplified by (. K-methyl propyl methacrylate (10) (4) ( :::::d), (-meth)acrylic acid and ε hexene § reaction product, one of the eight saponins Maleic anhydride, tetrahydrophthalic anhydride) and i knives, half-, saturated or non-dicarboxylic acids of a molar reaction of a (meth) acrylate derivative And a semi-g| class of a monomoric reactant of a monoepoxypropyl (meth)-propionic acid s derivative, etc. An example of a more preferable compound is exemplified by the following formula (3) The compound of formula (3)
Rl - CH= CH- COOH (式中’R1表示氫原子、甲基或苯基，較佳為氫原子或曱 I基）或丽述（甲基）丙烯酸與£_己内酯之反應生成物。 k製成感光性樹脂組成物時之感度觀點來看，尤以（曱 基）丙烯酸、（甲基）丙烯酸與£-己内酯之反應生成物、或是 肉桂酸為特佳。 另外’在本發明中，「（甲基）丙烯酸」之用語係表示丙 烯酸或甲基丙烯酸。 本叛酸酯化反應可於無溶劑下反應，亦可以溶劑稀釋 而使其反應。通常係以於溶劑存在下進行反應為較佳。在 此，就可使用之溶劑而言，只要是對於羧酸酯化反應為不 16 319866 200837093 活性之溶劑即可，* a ， 亚I 4寸別限定。較佳之一例係可列舉如 不具有醇性羥基之溶劑。 ♦，合S,1之使用量係可依據所得之樹脂之黏度或用途而適 *虽：整二例如，當旨化反應中之固形成分與溶劑成分 -=合計設為100重量％時，溶劑之使用量以成為9〇至〇重 量％、較佳為60至5重量％之方式使用溶劑。 f 上述不具有醇性羥基之溶劑，可列舉如：丙酮、乙基 甲基酮、環己酮等酉同類；苯、甲苯、二 1香族煙類；乙二醇二甲絲、乙二醇二乙基縫、二丙: 醇一曱基醚、二丙二醇二乙基醚、三乙二醇二甲基醚、三 乙二醇=乙基ϋ等二醇乙酸乙醋、乙酸丁醋、乙酸 甲赛璐蘇（methyl celiosolve acetate)、乙酸乙賽璐蘇、乙酸 :赛璐蘇、卡必醇乙酸酯、丙二醇單甲基醚乙酸酯、戊二 酉欠一烷S曰、丁二酸二烷酯、己二酸二烷酯等酯類；γ _丁内 酯等環狀醋類；石油醚、石油腦（petr〇leum卿心）、加氩 石油知、溶劑油（solvent naphtha)等石油系溶劑。更可列舉 如作為各種單體與多羧酸化合物之酸酐的反應物的半酯， 例如，含有羥基之（甲基）丙烯酸酯（如（甲基）丙烯酸2-羥乙 酯、（甲基）丙烯酸2_羥丙酯、1,4_ 丁二醇單（甲基）丙稀酸 酉曰卡必醇（f基）丙婦酸酯等）與多幾酸化合物之酸肝的反 應物的半酯，以及丙烯醯基嗎啉與多羧酸化合物之酸酐的 反應物的半酯（此等半酯用的多叛酸化合物之酸酐，可列舉 士丁 一酉欠酐、馬來酸酐、鄰苯二P酸if、四氫鄰苯二甲酸 肝、六氫鄰苯二甲酸酐等）。 319866 17 200837093 此外，其他亦可列舉如：苯基酚之環氧乙烷加成物 之末端丙稀酸醋化合物（例如日本化藥股份公司製之 OPP-l、OPP-2)、聚乙二醇二（甲基）丙烯酸酯、三丙二醇二 •(曱基）丙烯酸酯、二羥甲基丙烷三（曱基）丙烯酸酯、三羥甲 ，基丙烷聚乙氧基二（甲基）丙烯酸酯、甘油聚丙氧基三（甲基） 丙烯酸酯、新戊二醇羥基三曱基乙酸酯（neopentylglycol hydr〇Xypivalate)2 ε _己内酯加成物之二（甲基）丙烯酸酯 (例如日本化藥股份公司製之KAYARADrtm、ΗΧ_22〇、 f ΗΧ·620等）、季戊二醇四（甲基）丙烯酸酯、二季戊二醇與 己内酯之反應物的聚（甲基）丙烯酸酯、二季戊二醇聚（甲 基）丙烯酸酉旨、單或聚環氧丙基化合物（例如丁基環氧丙基 醚^基環氧丙基_、聚乙二醇二環氧丙基鍵、聚丙二醇 :氧丙基醚、1,6-己二醇二環氧丙基醚、六氫鄰苯二甲 =二環氧丙醋、甘油聚環氧丙基_、甘油聚乙氧基環氧丙 =、三羥甲基丙烧聚環氧丙基趟、三經甲基丙院聚乙氧 I ^環氧丙基料）與（甲基）丙_之反應物的環氧 基）丙稀酸等。 ⑩士另Γ包括上述溶劑，絲可使用之溶媒更具體地分 二：：列ί如烴溶劑、醋系溶劑、醚系溶劑、酮系溶 :茉右：該寻具體地分類並例示，則烴溶劑可列舉如： 烷、辛二甲苯、乙基苯、四甲基苯等芳香族系烴溶劑；己 =/、癸烧等脂肪族系烴溶劑；以及該等之混合物的 /醚、白汽油（white gasoline)、溶劑油等。 、 又，就醋系溶劑而言，可列舉如：乙酸乙顆、乙酸丙 319866 18 200837093 酉曰、乙酸丁酯等乙酸烷酯類；r _ 丁内酯等環狀酯類；乙二 醇單甲基醚乙酸酯、二乙二醇單曱基醚單乙酸酯、二乙二 醇單乙基單乙酸g旨、三乙單乙基醚單乙酸§旨、二乙 一知單丁基醚單乙酸酯、丙二醇單甲基醚乙酸酯、丁二醇 =甲基醚乙酸酯等單或多烷二醇單烷基醚單乙酸類；戊二 酸二烷酯、丁二酸二烷酯、己二酸二烷酯等多羧酸烷酯類。 就_糸’谷劑而δ，可列舉如：二乙基_、乙基丁 基醚等烷基醚類；乙二醇二曱基醚、乙二醇二乙基趟、二 一醇一甲基醚、一丙二醇二乙基醚、三乙二醇二甲基醚、 乙醇—乙基醚等二醇醚類；四氫呋喃等環狀驗類等。 μ又，就酮系溶劑而言，可列舉如丙酮、甲基乙基酮、 環己酮、異佛爾酮等。 除此之外，亦可在上述反應中，以不活性的乙烯性不 2和化合物（C)(除了本發明之化合物(Α)以外）等的單獨或 此口口有機溶媒進行。此時，由於不需將反應生成物分離， 即可直接將反應液作為硬化型域物錢，故為較佳。 、…上述乙烯性不飽和化合物（C)之具體例，係可列舉如雖 =於前㈣酸酯化反應為不活性、但在㈣ 更化反應中可反應的自由基反應型丙烯酸酯類等所謂之 反應性單體或反應性寡聚物類。 )來就該丙烯酸酯類而言，可列舉如單官能（甲基）丙烯酸 、'官能（甲基）丙烯酸酯類、其他之環氧基丙烯酸酯、 a -，蝉g夂g曰、丙稀酸胺酯（urdhaneacryiate)等。 單此（甲基）丙烯酸酯類，係可列舉如：（甲基）丙烯酸 19 319866 200837093 甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丁酯、（甲基）丙烯 酸月桂酯、聚乙二醇（甲基）丙烯酸酯單甲基醚、（甲基）丙烯 酸苯基乙酯、（甲基）丙烯酸異莰酯（is〇b〇rnyl加^比） • acrylate)、（甲基）丙烯酸環己酯、（甲基）丙烯酸苄酯、（甲基） •丙烯酸四氫吱喃甲酉旨、聯苯氧基乙基（甲基）丙稀酸醋等。 多官能（甲基）丙烯酸酯類，可列舉如··丁二醇二（甲基） 丙烯酸酯、己二醇二（甲基）丙烯酸酯、新戊二醇二（甲 丙烯酸酯、壬二醇二（曱基）丙稀酸醋、乙二醇二（甲羞）丙土婦 酸酯、二乙二醇二（甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯 酸醋、三（甲基）丙稀酿基氧基乙基異氯酸醋、聚丙二醇二 (甲基）丙烯酸酯、己二酸環氧基二(甲基）丙烯酸酯、雙齡環 氧乙燒二（甲基）丙烯酸醋、氫化雙齡環氧乙烧（甲基）丙稀酸 酯、雙齡二（甲基）丙稀酸醋、新戊二醇經基三甲基乙酸酯 之r ·己内酯加成物之二（甲基)丙蝉酸醋、二季戊二醇盘^ -己内醋之反應物之聚（甲基）丙烯酸酯、二季戊二醇聚（甲基 丙婦酸酉旨、三經T基丙燒三（甲基）丙稀酸酉旨、三經乙基^ 烷三（甲基）丙稀酸酉旨、及其環氧乙烧加成物 二二四 (甲基）丙稀酸醋、二季戊二醇六（甲基)丙烯酸酯、及 乙烷加成物等。 ，、衣虱 上述溶媒可作為單獨或混合有機溶媒使用。 士反解之原料加人比率，相對於環氧樹脂⑷之夷 1 g量，以前述單羧酸化合物（b)成為08至12告旦ς 120當量%)為佳。當超出此範圍時，反應中恐怕田會引起膠 化’或會使最後所得之化合物（Α)的熱安定性降低。- 319866 20 200837093 反應時’為了促造及處 ^ + 選反應而以使用觸媒為佳，告祛田辟 。媒觸媒之使用量係以相對於反應物為〇1至'〇重： 二反應溫度為6。至。c，此外， 為5至6小時。所使用之觸媒的具體例，可列舉如.: 崎基…銨I;/: Τ基三甲基銨、 η 、 * 一 —本基膦、三苯基銻（triphenyl s 1 me)、甲基二苯基銻、辛酸絡、辛酸錯等。 厂。：：’可使用熱聚合抑制劑，其具體例可列舉如：氡 …基越、2岬基氫酉昆、氫叫二第三丁 ： ，苯基—苦基肼Piphenyl咖ylh咖㈣、二苯基胺、Μ· 一-弟二丁基-4-羥基甲苯等，使用時之使用量較佳係相對 於反應物為使用0.1至10重量％。 以上述較佳範圍來使用前述單幾酸化合物⑻時，較户 為一邊將反應液適當地取樣，一邊使樣品之酸價成^ 5mg . KOH/g以下（更佳為3mg . K〇H/g左右或以下）為止”、、， 並以此時作為反應之終點。反應生成物之分離，係可從反 應液藉由減壓蒸餾等常法而去除溶媒，以進行分離。 此時，所得之本發明目的化合物（A)(羧酸酯化合物）係 能以下述形式獲得化合物：相對於原料環氧樹脂（a)之環氧 基1當量，使單羧酸化合物（b)以〇·8至i當量（更佳為〇 9 至1當夏）加成而成的化合物。 另外，上述反應液係可依據情形而不需分離目的化合 物，並於其中添加光聚合起始劑，亦可作為本發明中之樹 脂組成物使用。 丑、 319866 21 200837093 由於本發明之化合物（A)係樹脂單獨就使液折射率 而、且液折射料h6以上者，故為較佳。在本發明中， 液折射率係指硬化前之化合物之折射率，雖然測定波長為 二各式各樣，但例如可使用D線（589nm)。本說明書中广所 «己載之折射率皆為以D線（589nm)之測定值。 測定如此之折射率的裝置係為 λτα” 1刈羋例如 fAGO股份公司製之多波長阿貝折射計。測定方法係例如 直接塗佈硬化前之液狀化合物，而可敎光源之透射光之 折射角度。 本發明之化合物⑷係如前述，將前述單綾酸化合物 加成於前述環氧樹脂⑻之環氧基上而成的賴酉旨樹脂，彰 佳之竣酸㈣脂之情形，係於分子中平均具有^至7値 (m^8至3個）經基。基本上，該二羧酸醋樹脂係為 料早幾酸化合物⑻分別加成於通式⑴之2個環氧基 上而成的結構，且基本上n之值亦與原料環氧樹脂相同。 本發明之化合物㈧係與光聚合起始劑或熱感應性之 始劑(如偶氮雙異丁腈等）等—起制，而可利用於前 本㈣中’含有本發明化合物⑷與光聚 々（）的U性的樹腊組成物係較佳之態樣之一。 取士：明之樹脂組成物含有上述本發明之化合物⑷與 先♦ 5起始劑（B)。本發明之樹脂組成物 100重量份中之化 合物㈧含量較佳為5至98重量份，更佳為】〇至96重量 伤，更進一步依據情形而為1〇至94重量份。 殘餘部分為光聚合起始劍與任意之添加成分。為了發 319866 22 200837093 揮本發明之樹脂特性，相對於樹脂組成物之固形成分全 體，較佳為含有本發明之樹脂2〇i 98%(以下若無特別限 定’「％」即同樣地意指「重量％」）左右，更佳為3〇至98%， 依據情形而為40至98%或50至98% ;另外，其他情妒# 較佳為含有20至94%(以下若無特別限定，「%」丄= 意指「重量。/。」）左右，更佳為3〇至94%，依據情形而為 40 至 94%或 50 至 94%。 ^ 作為本發明之樹脂組成物中所含有之光聚合起始劑（B) "者，只要疋能作為光聚合起始劑使用者皆可利用。可列舉 例如ι_羥基環己基苯基酮（Ciba Specialty Chemicais公司 製之Irgacure 184)、2,2_二曱氧基_2_苯基乙醯苯（CibaRl - CH=CH-COOH (wherein R1 represents a hydrogen atom, a methyl group or a phenyl group, preferably a hydrogen atom or a ruthenium I group) or a reaction product of a sample of (meth)acrylic acid and £_caprolactone . k From the viewpoint of sensitivity in the case of forming a photosensitive resin composition, a reaction product of (meth)acrylic acid, (meth)acrylic acid and £-caprolactone, or cinnamic acid is particularly preferable. Further, in the present invention, the term "(meth)acrylic acid" means acrylic acid or methacrylic acid. The reductive acidification reaction can be carried out without a solvent or by solvent dilution. It is usually preferred to carry out the reaction in the presence of a solvent. Here, as the solvent which can be used, as long as it is a solvent which is not reactive with the carboxylic acid esterification reaction, * a , sub-I 4 inch is not limited. A preferred example is a solvent which does not have an alcoholic hydroxyl group. ♦, the amount of S, 1 can be used depending on the viscosity or use of the obtained resin. Although: For example, when the solid component and the solvent component in the reaction are -100% by weight, the solvent is used. The amount of use is such that it is 9 〇 to 〇 by weight, preferably 60 to 5% by weight. f The above solvent having no alcoholic hydroxyl group may, for example, be acetone, ethyl methyl ketone or cyclohexanone; benzene, toluene, bis 1 scented tobacco; ethylene glycol dimethyl wire, ethylene glycol Diethyl sulphide, dipropylene: alcohol monodecyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol = ethyl hydrazine, etc. glycol acetic acid vinegar, acetic acid butyl vinegar, acetic acid Methyl celiosolve acetate, ethyl acesulfame acetate, acetic acid: celecoxib, carbitol acetate, propylene glycol monomethyl ether acetate, pentane oxime, succinic acid Esters such as dialkyl esters and dialkyl adipates; cyclic vinegars such as γ-butyrolactone; petroleum ether, petroleum brain (petr〇leum qingxin), argon petroleum, solvent naphtha, etc. Petroleum solvent. Further, there may be mentioned, for example, a half ester of a reactant as an acid anhydride of various monomers and a polycarboxylic acid compound, for example, a hydroxyl group-containing (meth) acrylate (e.g., 2-hydroxyethyl (meth) acrylate, (methyl)) A half ester of a reaction of 2-hydroxypropyl acrylate, 1,4-butanediol mono(methyl) acrylate decyl alcohol (f-based) proacetate, etc. with a fatty acid of a polyacid compound And a half ester of a reaction product of an acryloyl morpholine and an acid anhydride of a polycarboxylic acid compound (an acid anhydride of a polyhedoic acid compound for such a half ester, and examples thereof include an anhydride, a maleic anhydride, and an phthalic acid. If, tetrahydrophthalic acid liver, hexahydrophthalic anhydride, etc.). 319866 17 200837093 In addition, other examples include: a terminal acetoacetate compound of an ethylene oxide adduct of phenylphenol (for example, OPP-1 and OPP-2 manufactured by Nippon Kayaku Co., Ltd.), and polyethylene. Alcohol di(meth)acrylate, tripropylene glycol di((mercapto) acrylate, dimethylolpropane tris(decyl) acrylate, trimethylolpropane polyethoxy di(meth) acrylate , glycerol polypropoxy tri(meth) acrylate, neopentyl glycol hydroxy hydrazide acetate (neopentylglycol hydr〇 Xypivalate) 2 ε-caprolactone adduct bis(meth) acrylate (eg Japan Poly (meth) acrylate of the reaction of penta diol tetra(meth) acrylate, dipentadiol diol and caprolactone, manufactured by Chemical Pharmaceutical Co., Ltd., KAYARADrtm, ΗΧ_22〇, f ΗΧ·620, etc.) Dipentaerythritol poly(meth)acrylate hydrazine, mono or polyepoxypropyl compound (eg butyl epoxypropyl ether oxime propyl propyl group), polyethylene glycol diepoxy propyl bond, poly Propylene glycol: oxypropyl ether, 1,6-hexanediol diepoxypropyl ether, hexahydrophthalic acid = bicyclic Oxypropyl vinegar, glycerol polyepoxypropyl _, glycerol polyethoxy epoxide =, trimethylol propyl polyepoxypropyl hydrazine, trimethyl propyl propylene polyoxyl I ^ -propyl propyl An epoxy group such as a reaction with (meth)propene), acrylic acid or the like. 10 士 Γ Γ 上述 上述 上述 上述 , , , , , , , , , , , , , , , , , , , , , , 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as an alkane, octylene, ethylbenzene, and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexanol and oxime; and ethers and whites of the mixtures thereof. White gasoline, solvent oil, etc. Further, examples of the vinegar solvent include, for example, ethyl acetate, acrylic acid 319866 18 200837093 hydrazine, butyl acetate, and the like; alkyl esters such as r-butyrolactone; ethylene glycol single Methyl ether acetate, diethylene glycol monodecyl ether monoacetate, diethylene glycol monoethyl monoacetic acid g, triethylene monoethyl ether monoacetic acid §, diyi monobutyl ether Mono or polyalkylene glycol monoalkyl ether monoacetic acid such as monoacetate, propylene glycol monomethyl ether acetate, butanediol = methyl ether acetate; dialkyl glutarate, succinic acid A polycarboxylic acid alkyl ester such as an alkyl ester or a dialkyl adipate. δ 谷 谷 而 δ δ δ δ δ , , , , , , , , , δ δ δ δ δ δ δ δ δ δ δ 谷 δ 谷 δ 谷 烷基 烷基 烷基 烷基 烷基 烷基 烷基Glycol ethers such as monoether, monopropylene glycol diethyl ether, triethylene glycol dimethyl ether, and ethanol-ethyl ether; and cyclic test such as tetrahydrofuran. Further, examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone. In addition, in the above reaction, the inactive ethylenic acid (2) and the compound (C) (other than the compound of the present invention) may be used alone or in an oral organic solvent. In this case, since it is not necessary to separate the reaction product, the reaction liquid can be directly used as a hardening type, so that it is preferable. Specific examples of the ethylenically unsaturated compound (C) include a radical reactive acrylate which is inactive in the (4) acidification reaction, but which is reactive in the (iv) reforming reaction. Reactive monomers or reactive oligomers. The acrylates may, for example, be monofunctional (meth)acrylic acid, 'functional (meth) acrylates, other epoxy acrylates, a -, 蝉g夂g曰, propylene An acid amine (urdhaneacryiate) and the like. Examples of the (meth) acrylates include (meth)acrylic acid 19 319866 200837093 methyl ester, ethyl (meth)acrylate, butyl (meth)acrylate, and lauryl (meth)acrylate. Polyethylene glycol (meth) acrylate monomethyl ether, phenyl ethyl (meth) acrylate, isodecyl (meth) acrylate (is〇b〇rnyl plus ratio) • acrylate), (methyl) Cyclohexyl acrylate, benzyl (meth) acrylate, (meth) • tetrahydrofurfuryl acrylate, biphenyloxyethyl (meth) acrylate vinegar, and the like. Examples of the polyfunctional (meth) acrylates include, for example, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(methacrylate), decanediol. Di(indenyl) acrylate vinegar, ethylene glycol di(meth) dipropionate, diethylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate vinegar, three ( Methyl) propylene methoxyethyl isochlorate, polypropylene glycol di(meth) acrylate, adipic acid bis(meth) acrylate, double aged epoxy bromide (methyl) Acrylic vinegar, hydrogenated double-aged ethylene bromide (meth) acrylate, double-aged di(meth) acrylate vinegar, neopentyl glycol via trimethyl acetate, r · caprolactone a poly(meth) acrylate of a reactant of a di(meth)propionic acid vinegar, a dipentadiol diol, a dipentadiol diol, a dipentaerythritol poly(methyl acetoacetate), T-based propyl trimethyl (meth) acrylate, triethyl ethoxide tris(methyl) acrylate, and its epoxy Ethylene adduct 224 (methyl) Acetic acid vinegar, second season Diol hexa(meth) acrylate, ethane adduct, etc., and the above solvent can be used as a single or mixed organic solvent. The ratio of raw materials added by the anti-solution is relative to that of the epoxy resin (4). The amount of 1 g is preferably such that the above-mentioned monocarboxylic acid compound (b) is from 08 to 12 ς 120% by weight. When it is outside this range, the reaction may cause gelation or may result in the finally obtained compound (热) The thermal stability is reduced. - 319866 20 200837093 During the reaction, it is better to use the catalyst for the purpose of promoting and selecting the reaction. The use of the medium is relative to the reactants. 〇1 to '〇重: The two reaction temperatures are from 6. to c, and further, from 5 to 6 hours. Specific examples of the catalyst to be used include, for example,: akiji...ammonium I;/: sulfhydryl III Methylammonium, η, *--benylphosphine, triphenyl s 1 me, methyl diphenyl hydrazine, octanoic acid, octanoic acid, etc. Plant:: 'Can use thermal polymerization inhibitors, Specific examples thereof may be exemplified by: 氡 基 基 、, 2 岬 酉 酉 、 、 氢 氢 氢 氢 氢 , , , , , , , , , , , , , , , Coffee (tetra), diphenylamine, hydrazine-di-dibutyl-4-hydroxytoluene, etc., preferably used in an amount of 0.1 to 10% by weight based on the reactants. In the case of the above-mentioned monoacid compound (8), the acid value of the sample is set to be 5 mg. KOH/g or less (more preferably 3 mg. K〇H/g or less) until the reaction liquid is appropriately sampled. In this case, the reaction product is separated, and the solvent is removed from the reaction solution by a conventional method such as distillation under reduced pressure to carry out the separation. In this case, the obtained target compound of the present invention (A) (Carboxylic acid ester compound) is a compound which can be obtained in such a form that the monocarboxylic acid compound (b) is 〇8 to i equivalent (more preferably 1 equivalent to the epoxy group of the raw material epoxy resin (a)). 〇9 to 1 when added in summer). Further, the above reaction liquid may be used without depending on the case, and the photopolymerization initiator may be added thereto, or may be used as the resin composition in the present invention. Ugly, 319866 21 200837093 The compound (A)-based resin of the present invention is preferred because it has a refractive index of liquid and a liquid refractive index h6 or higher. In the present invention, the liquid refractive index means the refractive index of the compound before curing, and although the measurement wavelength is two, for example, a D line (589 nm) can be used. In this specification, the refractive index of the self-contained group is measured by the D line (589 nm). The apparatus for measuring such a refractive index is λτα"1", for example, a multi-wavelength Abbe refractometer manufactured by fAGO Co., Ltd. The measurement method is, for example, direct application of a liquid compound before hardening, and refraction of transmitted light by a light source The compound (4) of the present invention is a ruthenium resin obtained by adding the above-mentioned monodecanoic acid compound to the epoxy group of the epoxy resin (8) as described above, and in the case of the bismuth citrate (tetra) lipid, it is attached to the molecule. The average medium has a radical of from 7 to 7 (m^8 to 3). Basically, the dicarboxylic acid vinegar resin is added to the two epoxy groups of the general formula (1). The structure is formed, and the value of n is also the same as that of the raw material epoxy resin. The compound (8) of the present invention is combined with a photopolymerization initiator or a heat-inducing initiator (such as azobisisobutyronitrile). It can be used in the above-mentioned (4), which is one of the preferred aspects of the U-containing wax composition containing the compound (4) of the present invention and the photopolymerization. The resin composition of the present invention contains the above-mentioned present invention. Compound (4) and first ♦ 5 initiator (B). Resin composition of the present invention The content of the compound (VIII) in 100 parts by weight is preferably from 5 to 98 parts by weight, more preferably from 〇 to 96 parts by weight, still further from 1 to 94 parts by weight depending on the case. The residual portion is a photopolymerization starting sword and In the case of the resin composition of the present invention, the resin composition of the present invention is preferably contained in the resin composition of the present invention, which is preferably 98% (hereinafter, unless otherwise specified as '%). That is, the same means "% by weight" or so, more preferably 3 to 98%, depending on the situation, 40 to 98% or 50 to 98%; in addition, other conditions # preferably contain 20 to 94% ( Unless otherwise specified, "%" 丄 = means "weight. /."), preferably 3〇 to 94%, depending on the situation, 40 to 94% or 50 to 94%. ^ As the photopolymerization initiator (B) contained in the resin composition of the present invention, it can be used as a photopolymerization initiator. For example, iota-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicais Co., Ltd.), 2,2-dimethoxy-2-phenyl phenyl benzene (Ciba)
Specialty Chemicals 公司製之 irgacure 651)、2-經基甲 基1本基-丙文元-1-酮（Ciba Specialty Chemicals公司製之 Dar〇Cure 1173)、2_甲基〔 ‘（甲基硫代）苯基〕_2_嗎啉基 丙烧]·酮（Ciba Specialty Chemicals 公司製之 irgacure (907)、2-卞基-2-二甲基胺基-i_(4_嗎啉基苯基卜丁烷酮、 2-氯硫雜蒽酮（2-Chlorothioxanthone)、2,4-二甲基硫雜葱 酮、2,4-二異丙基硫雜蒽酮、異丙基硫雜蒽酮、2,4,6_三甲 基卞醯基二苯基膦氧化物、雙（2,6-二曱氧基苄醯基）_2,4,4_ 二甲基戊基膦氧化物等。此等光聚合起始劑能以單獨1種 或炎數種、並能以任意比例混合而使用，亦可與胺類等光 聚合起始助劑併用。此等光聚合起始劑中，以酮系之聚合 起始劑較佳。 本發明之樹脂組成物（100重量份）中之光聚合起始劑 319866 23 200837093 為更佳3。里:二〇.5f20重量份為佳，又以1至ι〇重量份 旦^八， 了本發明之化合物（A)之含量為99.5至10重 分。 、9至2〇重里份為更佳，而任意成分為殘餘部 旦 々據丨月开>，光聚合起始劑（B)之含量為1至20 ，又以2至10重量份為較佳，再以4至1〇重量份 二，土、此吩，本發明之化合物（A)之含量為98至5重量 立、至1 〇重1份為更佳，而任意成分為殘餘部分。 ，壬1分而言，較佳為下述之乙稀性不飽和化合物⑹。 本發明之樹脂組成物可因應需要而含有各種之任意成 分0 人1要之該任意成分而言，如下所述，可列舉如光聚 始助劑、& 了本發明 <匕合物⑷以外之乙烯性不飽和化 δ物（C)、其他之添加劑及稀釋劑等。 本鲞月中可使用之胺類等光聚合起始助劑，可列舉 如·一乙醇胺、2-二甲基胺基苯甲酸乙酯、二曱基胺基苯 =酮、對_二甲基胺基苯曱酸乙酯、對_二▼基胺基苯曱酸 /、戊自曰專。本發明之樹脂組成物（1⑽重量份）中之光聚合起 :助劑之含量為〇至5重量份，當有併用光聚合起始助劑 時，該助劑在本發明之樹脂組成物中之含量係以〇 〇5至5 重量份為佳，又以（U至3重量份為更佳。 本發明之樹脂組成物中，因應需要而可添加之乙稀性 不飽和化合物（除了本發明化合物（Α)以外之乙烯性不飽和 化a物（C))之較佳者可列舉如：（甲基）丙稀酸酯單體、（甲 319866 24 200837093 基）丙烯酸醋寡聚物等，亦可任意地使用該等。 作為乙稀性不飽和化合物之（甲基）丙婦酸醋單體可分 類為.在分子中具有1個(甲基)丙烯酸醋基之單宫能單體、 以及在刀子中具有2個以上（甲基）丙稀酸醋基之多官能單 •體。 在刀子中具有1個（甲基）丙烯酸酯基之單官能單體係 可列舉如三環癸院（甲基）丙稀酸酉旨、二環戊二婦氧基乙基 (甲基）丙稀酸酯、（甲基）丙婦酸二環戊酯（此㈣叩她㈣ (meth)ACrylate)、（甲基）丙稀酸異茨酯、（甲基）丙婦酸金剛 烷醋\(甲基）丙烯酸苯基氧基乙酯、（甲基）丙烯酸节酯、（甲 基）丙烯酸四氫呋喃甲酯、嗎啉（甲基）丙烯酸酯、（甲基）丙 稀酸苯基環氧丙酯、（甲基）丙賴2音乙醋、（甲基）丙烯 酸2-羥丙酯、乙基卡必醇（甲基）丙烯酸酯等。 另外·，在分子中具有2個以上（甲基）丙烯酸酯基之（甲 基）丙烯酸酯單體係可列舉如：新戊二醇二（曱基）丙烯酸 酉曰一環六烧一备甲基一（甲基）丙稀酸酯、經基三甲基乙 醛改質二羥甲基丙烷二（甲基）丙烯酸酯、羥基三曱基乙酸 新戊一醇二（曱基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、 一％戊基二（曱基）丙烯酸酯、匕卜己二醇二（甲基）丙烯酸 醋、聚丙二醇二（甲基）丙烯酸酯、環氧乙烷改質雙酚A二 (甲基）丙烯酸酯、環氧乙烷改質三羥曱基丙烷三（曱基）丙烯 酉欠酉曰、環氧乙烷改質季戊二醇四（曱基）丙烯酸酯、參〔（曱 基）丙烯酿氧乙基〕異氰酸酯、環氧乙烷啤質二季戊二醇六 (曱基）丙烯酸酯等。 25 319866 200837093 • 此等（甲基）丙烯酸酯單體能以工種或2種以上、並能 以任意比例混合而使用。本發明之樹脂組成物（1GG重量份） 中之该(曱基)丙烯酸酯單體之含量係〇至9〇重量份，當是 —使用（曱基）丙烯酸酯單體時，係以1至90重量份為佳，尤 “以5至85重量份為更佳。 作為乙烯性不飽和化合物之（曱基）丙烯酸酯寡聚物者 可列舉如分子量400至10000之胺酯（曱基）丙烯酸酯、分 f子量500至100〇〇之環氧基（甲基）丙烯酸酯。 刀子里400至10000之胺酯（甲基）丙稀酸酯，係藉由 下述多兀醇與有機聚異氰酸酯與（甲基）丙烯酸羥基酯化合 物的反應而獲得。 夕元醇可列舉如：新戊二醇、3-甲基-1，5-戊二醇、乙 一醇、丙二醇、匕4-丁二醇、1，6-己二醇、三羥甲基丙烷、 季戊二醇、三環癸烷二羥曱基、雙_(羥基甲基環己烷等多 疋酵；由前述多元醇與多元酸（例如丁二酸、鄰苯二曱酸、 c ’、氯鄰苯二甲酸酐、對苯二曱酸、己二酸、壬二酸、四氫 鄰苯二甲酸酐等）之反應所得之聚酯多元醇；由前述多元醇 與e -己内酯之反應所得之己内酯醇；聚碳酸酯多元醇(例 如由1，6-己二醇與碳酸二苯酯之反應所得之聚碳酸酯二醇 等）；以及聚醚多元醇（例如聚乙二醇、聚丙二醇、聚四亞 节二醇、環氧乙烷改質雙酚A等）。 就有機聚異氰酸醋而言，可列舉如：異佛爾酮二異氰 酸醋、六亞甲基二異氰酸酯、甲苯二異氰酸酯、二甲苯二異 亂酸酷、二苯基甲烷_4,4_二異氰酸酯、二環戊基異氰酸酯 26 319866 200837093 等。 (曱基）丙細酸輕基s曰化合物可列舉如（甲基）丙稀酸經 乙酯、（甲基）丙細酸輕丙酯、（甲基）丙稀經丁醋、單（甲 -基）丙烯酸二羥曱基環己醋、己内酯（曱基）丙烯酸羥基醋 ‘等。 本發明之樹脂組成物（100重量份）中該分子量4〇〇至 10000之胺酯（甲基）丙烯酸酯之含量係〇至重量份，當 疋使用该胺g旨（甲基）丙細酸酯時，係以1至9 〇重量份為 C 佳，尤以3至85重量份為更佳。 前述分子量500至10000之環氧基丙烯酸酯雖然並無 特別限制，但以使用雙酚型環氧基丙烯酸酯為佳，可列舉 如：由油化Shell環氧股份公司製之Epik〇teRTM8〇2、1〇〇卜 1004等雙酚A型環氧樹脂、以及Epik〇teRTM4〇〇ip、4〇〇^、 4003=等又酌f型裱氧樹脂與（甲基）丙烯酸的反應而獲得 的環氧基丙烯酸酯（上述所附之RTM係表示註冊商標）。另 (外亦可使用經加氫之脂環式環氧基丙稀酸醋作為上述 者。本發明之樹脂組成物（1〇〇重量份）中之該分子量 至二1000j之裱氧基丙烯酸酯之含量係〇至卯重量份，當使 ，該環氧基丙烯酸酯時，其於本發明之樹脂組成物中:含 系、、隹至90重里份為佳，尤以3至85重量份為更佳。 更進步，本發明之掛脂組成物可因應用途而適當使 ，，反應性化合物、無機填充劑、有機填充劑、偶合劑、 :占Γ賦：^、消泡劑、調平劑、塑化劑、抗氧化劑、紫外 、、在吸收劑、難燃劑、顏料、染料等。 ” 319866 27 200837093 :前述非反應性化合物之具體例係反應性低或無反應性 之液體或固體狀之寡聚物或樹脂，可列舉如（甲基）丙稀酸 烷酯共聚物、環氧樹脂、液狀聚丁二烯、二環戊二烯衍生 .物、飽和聚醋寡聚物、二甲苯樹脂、聚胺心合：、：樹 -脂、鄰苯二甲酸二烯丙醋聚合物(diallyi ㈣ymer，DAP樹脂)、石油樹脂、松香樹脂、氟系寡聚物、 矽系寡聚物等，但並不限定此等。 前述無機填充劑可列舉如：二氧化石夕、氧化石夕、碳酸 鈣、梦酸舞、碳酸鎂、氧化鎂、滑石、高嶺土黏土、燒成 黏土、氧化辞、硫酸鋅、氫氧化鋁、氧化鋁、玻璃、雲母、 硫酸鋇、蓉土白（Alumina white)、沸石、石夕石氣球（& ballon)、玻璃氣球（GlassBall〇〇n)等。此等無機填充劑亦 可藉由添加矽烷偶合劑、鈦酸系偶合劑、鋁系偶合劑、錘 酸鹽系偶合劑等，使反應等方法而具有齒素基、環氧基、 羥基、硫醇基之官能基。 前述有機填充劑可列舉如苯.并胍胺（benz〇guanamine) 樹脂' 聚石夕氧樹脂、低密度聚乙稀、高密度聚乙婦、聚稀 烴樹脂、乙烯.丙烯酸共聚物、聚苯乙烯、丙烯醯基共聚 物、聚甲基丙烯酸甲酯樹脂、氟樹脂、尼龍12、尼龍 6/66、 酚樹脂、環氧樹脂、聚胺酯樹脂、聚醯亞胺樹脂等。 产偶合劑可列舉如r _環氧丙氧基丙基三甲氧基矽烷或 r -氯丙基二甲氧基矽烷等矽烷偶合劑；四（2,2_二烯丙氧基 甲基小丁基）雙（二（十三烷基））亞磷酸醋鈦酸酯、雙（焦磷酸 二辛酯）鈦酸伸乙酯等鈦酸酯系偶合劑；二異丙酸乙醯基烷 28 319866 200837093 氧基鋁（acetoalkoxy aiuminum diis〇pr〇pylate)等鋁系偶合 劑，乙醯丙酮·鍅錯合物等鍅系偶合劑等。 本發明之樹脂組成物中可使用之黏著賦予劑、消泡 ^凋平训塑化劑、抗氧化劑、紫外線吸收劑、難燃劑、 顏料、染料只要是習知慣用者，無論是哪一種，於不損其 硬化性、樹脂特性之範圍内皆可使用，即無特別之限制。 f 若欲獲得本發明之樹脂組成物，只要將上述各成分混 合即可，並未特別限定混合之順序或方法。 、本發明之樹脂組成物亦可以稀釋劑稀釋而作為塗佈用 組成物等使用。稀釋劑係列舉如有機溶劑，例如··甲基乙 二 :甲基異丁基銅等酮類；乙酸乙醋、乙酸丁醋等Ξ酸 二ί、甲苯、二甲苯等芳香族烴；其他—般常用之有機 η於較佳之溶媒之—為_溶媒。在該塗佈用組成物 中，有機溶劑以外之樹脂組成物成分含量為2〇%至8 右，又以30¾至70%左右為更佳 工 本發明之塗佈用組成物之較佳例之—係如下述所構 成·· 20 至 80% 8〇 至 20% 重1份_，本發明之樹 5至99重量份 1至20重量份 本發明之樹脂組成物 有機溶劑 而在本發明之樹脂組成物1〇〇 脂組成物係由下述之組成所構成·· 本發明之化合物（A) 光聚合起始劑（B) 319866 29 200837093 • 任意成分（較佳為乙烯性 殘餘部分（〇至 不飽和化合物（C)) 94重量份） 本發明之樹脂組成物係可藉由照射18〇至5〇〇nm之波 ，長的紫外線或或可見光線等活性能量線而聚合（交聯硬 -化）。另外，本發明之樹脂組成物亦可藉由照射紫外線以外 之能量線、或是藉由使熱感應性起始劑（例如偶氮二異丁腈 (azobisisobutyronitrile))因熱而硬化。 , 波長180至500nm之紫外線或可見光線之光產生源， f係可列舉如低壓水銀燈、高壓水銀燈、超高壓水銀燈、金 屬鹵素燈、化學燈、黑光燈、水銀_氙氣燈、準分子燈、短 弧燈（Short arc lamp)、氦·鎘雷射、氬雷射、準分子雷射、 太陽光。 本發明中之活性能量線係可列舉如紫外線、可見光 線、紅外線、X線〜^線彳以㈤^叮^雷射光線等電磁波； 阿爾發射線、貝他射線、電子線等粒子線等。但是，若考 、慮到本發明之較佳用途，則以包含雷射之紫外線、可見光 線、或電子線為較佳。 本發明之樹脂組成物係可使用於皮膜形成用材料、製 造印刷（配線電路）基板時之阻焊遮罩（solder mask)、電鍵阻 抗劑、接著劑、透鏡、顯示器、光纖、光導波路、全像片 等方面。皮膜形成用材料係指以被覆基板表面為目的而使 用者。就其具體之用途而言，相當於凹版印墨（gravure ink)、軟版印刷油墨（fiexso ink)、絲網印墨、平版印墨等 印墨材料；硬塗佈、頂塗佈、套印清漆（〇verprint varnish)、 319866 30 200837093 •透明塗佈（cIear coat)等塗佈材料等。此外，亦可使用於抗 *焊劑（S〇lder resist)、抗蝕刻劑（etching resist)、微機器用阻 抗劑等阻抗劑（resist)材料；積層用之其他各種接著劑、黏 '著劑等接著材料；LED用接著劑等各種接著劑；菲淫耳透 …鏡、雙凸透鏡（Lenticular lens)等各種透鏡；光纖之芯材、 殼材、光導波路、全像片等各種光學材料等。更進一步， 將樹脂組成物塗佈於暫時剝離性基材上並經薄膜化後，貼 合於原本作為目的物之基材上而形成皮膜，則也可作為所 ( 謂之乾膜（dry film)使用。 斤形成各種塗膜之方法雖未特別限定，但可適用於凹版 等凹版印刷方式、軟版等凸版印刷方式、絲網等孔版印刷 f式、平版等平版印刷方式、輥塗器、刀塗器、模具塗器、 簾塗裔、旋塗器等各種塗佈方式。 (實施例） 以下，依據參考例及實施例而更加具體地說明本發 I明，但本發明並不受下述實施例所限定。 參考例1 通式（1)之環氧樹脂（a)之合成 〜在附有溫度計、冷卻管、授拌器之燒瓶中，一邊施予 =:，一邊加入下述式(2)所示之紛化合物⑷(三光股 =二衣之D〇Q-〇) 169份、環氧氯丙院463份、以及甲醇 ^使前兩者溶解於甲醇中。更進—步，將該溶液之 至，於其中耗費90分鐘分割添加薄片狀之 納41份髮再於Μ反應分鐘。反應結束後， 319866 31 200837093 Γ ，將反應液以水150份進行2次洗淨並去除所生成之鹽等 •後，於加熱減壓下（至7〇t：為止，―山⑽馗以至—化的旭〜） 一邊攪拌一邊以3小時蒸餾去除過量之環氧氯丙烷等。當 ，反應液變成泥漿狀態時，開放減壓，於其中添加丙酮3〇W〇 份，以回流狀態攪拌3〇分鐘後，添加甲醇i5〇〇份並攪拌 15分鐘，其次緩緩地添加水3〇〇份。將析出之結晶藉由減 Μ過遽而分離，即獲得作為目的物之結晶狀環氧樹脂一 0.01(平均值））。更進—步，將此結晶以Τ醇獅份洗淨、 再以水200份充分洗淨，經由乾燥，而以白色至淡白色之 粉末狀結晶獲得作為目的物之環 二環氧樹脂(a)之環氧當量為227却 攸此刀析值计异出通式（1)之 氧樹脂⑷之折射率時，[為0.01。此外’測定此環 艰中，以3_定料射==^65。_於二甲基 股份公司製之多波長阿貝折予;^算。測定裝置^ago 589nm(D線））。 十DR-M2，測疋波長： 式⑺Igacure 651), 2-methylmethyl 1 keto-propyl-1-one (Dar Cure 1173, manufactured by Ciba Specialty Chemicals, Inc.), 2-methyl [ '(methylthio) )phenyl]_2_morpholinylpropanone]·ketone (irgacure (907), 2-mercapto-2-dimethylamino-i_(4_morpholinylphenyl), manufactured by Ciba Specialty Chemicals Alkanone, 2-Chlorothioxanthone, 2,4-dimethylthiaxanone, 2,4-diisopropylthiaxanone, isopropylthioxanthone, 2 , 4,6-trimethyldecyldiphenylphosphine oxide, bis(2,6-dimethoxybenzylbenzyl)-2,4,4-dimethylpentylphosphine oxide, etc. The starting agent can be used alone or in combination in an arbitrary ratio, and can be used in combination with a photopolymerization initiator such as an amine. Among these photopolymerization initiators, ketone polymerization is used. Preferably, the photopolymerization initiator 319866 23 200837093 in the resin composition (100 parts by weight) of the present invention is more preferably 3. It is preferably used in an amount of from 2 to 20 parts by weight.旦^8, the compound of the invention (A) The content is 99.5 to 10 parts by weight. The weight of 9 to 2 parts is more preferred, and the optional component is the residual part. According to the opening of the month, the photopolymerization initiator (B) is 1 to 20, and Preferably, the amount of the compound (A) of the present invention is from 98 to 5 parts by weight to 1 part by weight, preferably from 2 to 10 parts by weight, more preferably from 4 to 1 part by weight, of the earth, the phenone. And the optional component is a residue. In terms of 壬1, the following ethylenically unsaturated compound (6) is preferred. The resin composition of the present invention may contain various optional components as needed. Examples of the optional component include, as described below, a photopolymerization aid, an ethylenically unsaturated δ (C) other than the conjugate (4) of the present invention, other additives, a diluent, and the like. Photopolymerization start-up aids such as amines which can be used in the present month, such as monoethanolamine, ethyl 2-dimethylaminobenzoate, dinonylaminobenzene = ketone, p-dimethyl Ethyl phthalic acid ethyl ester, p-dih-ylamino phenyl phthalic acid / pentane oxime. Photopolymerization in the resin composition (1 (10) parts by weight) of the present invention: The content of the agent is from 〇 to 5 parts by weight, and when the photopolymerization initiation auxiliary is used in combination, the content of the auxiliary agent in the resin composition of the invention is preferably from 5 to 5 parts by weight, and further More preferably, it is more than 3 parts by weight. In the resin composition of the present invention, an ethylenically unsaturated compound (except for the ethylenically unsaturated a substance (C) other than the compound of the present invention) may be added as needed. Preferred examples thereof include (meth) acrylate monomer and (A 319866 24 200837093) acrylate oligopolymer, and these may be used arbitrarily. The (meth) propyl acetoacetate monomer which is an ethylenically unsaturated compound can be classified into a mono-energy monomer having one (meth)acrylic acid acrylate group in the molecule, and two or more in the knives. (Methyl) acrylate acrylate based polyfunctional monomer. A monofunctional single system having one (meth) acrylate group in the knives may, for example, be a tricyclic brothel (methyl) acrylate, or a dicyclopentanyloxyethyl (meth) propyl group. Dilute ester, dicyclopentanyl (meth)propionate (this (four) 叩 her (four) (meth) ACrylate), (meth) isopropyl methacrylate, (methyl) propyl acetoin vinegar vinegar \ ( Phenyloxyethyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofuran (meth)acrylate, morpholine (meth)acrylate, phenylglycidyl (meth)acrylate , (methyl) propylene 2 ketone, 2-hydroxypropyl (meth) acrylate, ethyl carbitol (meth) acrylate, and the like. In addition, a (meth) acrylate single system having two or more (meth) acrylate groups in a molecule may, for example, be neopentyl glycol bis(indenyl) ruthenium sulfonate Mono(methyl) acrylate, trans-trimethylacetaldehyde modified dimethylolpropane di(meth) acrylate, hydroxytrimethyl acetic acid pentaerythritol di(decyl) acrylate, poly Ethylene glycol di(meth)acrylate, monopentyl bis(indenyl) acrylate, bismuth hexane di(meth)acrylate vinegar, polypropylene glycol di(meth) acrylate, ethylene oxide Modified bisphenol A di(meth) acrylate, ethylene oxide modified trihydroxy decyl propane tris(fluorenyl) propylene oxime, ethylene oxide modified pentaerythritol tetra(sulfonyl) Acrylate, ginseng (oxycarbonylethyl) isocyanate, ethylene oxide dipentaerythritol hexa(meth) acrylate, and the like. 25 319866 200837093 • These (meth) acrylate monomers can be used in the form of a work type or two or more types and can be mixed in any ratio. The content of the (fluorenyl) acrylate monomer in the resin composition (1 GG parts by weight) of the present invention is 〇 to 9 Å by weight, and when it is - using (fluorenyl) acrylate monomer, it is 1 to 90 parts by weight is preferable, particularly preferably 5 to 85 parts by weight. As the (fluorenyl) acrylate oligomer of the ethylenically unsaturated compound, an amine ester (mercapto) acrylic acid having a molecular weight of 400 to 10,000 may be mentioned. An ester, an epoxy group (meth) acrylate having a mass of 500 to 100 Å. An amine (meth) acrylate of 400 to 10,000 in a knife, which is organically polymerized by the following polyterpene alcohol. The isocyanate is obtained by a reaction with a hydroxy (meth) acrylate compound. Examples of the oxime alcohol include neopentyl glycol, 3-methyl-1,5-pentanediol, ethyl alcohol, propylene glycol, and fluorene 4-butene. Alcohol, 1,6-hexanediol, trimethylolpropane, pentanyl glycol, tricyclodecane dihydroxyindenyl, bis-(hydroxymethylcyclohexane, etc.; from the aforementioned polyols and polyhydric alcohols Acid (eg succinic acid, phthalic acid, c ', chlorophthalic anhydride, terephthalic acid, adipic acid, sebacic acid, tetrahydrogen a polyester polyol obtained by the reaction of dicarboxylic anhydride or the like; a caprolactone obtained by reacting the aforementioned polyol with e-caprolactone; a polycarbonate polyol (for example, 1,6-hexanediol and carbonic acid) a polycarbonate diol obtained by the reaction of diphenyl ester, etc.; and a polyether polyol (for example, polyethylene glycol, polypropylene glycol, polytetraethylene diol, ethylene oxide modified bisphenol A, etc.). The organic polyisocyanate may, for example, be isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, xylene diisophoric acid, diphenylmethane_4,4 _Diisocyanate, dicyclopentyl isocyanate 26 319866 200837093, etc. (fluorenyl) propionate light s oxime compound can be exemplified by (meth) acrylic acid by ethyl ester, (meth) propyl benzoate light propyl ester , (meth) propyl butyl vinegar, mono (methyl meth) hydroxy hydroxy hydroxy vinegar, caprolactone (mercapto) hydroxy vinegar vinegar, etc. The resin composition of the present invention (100 parts by weight) The content of the amino acid (meth) acrylate having a molecular weight of 4 to 10,000 is 〇 to parts by weight, when used When the amine g is a (meth)propionate, it is preferably 1 to 9 parts by weight, more preferably 3 to 85 parts by weight, more preferably an epoxy acrylate having a molecular weight of 500 to 10,000. It is not particularly limited, but a bisphenol type epoxy acrylate is preferably used, and examples thereof include bisphenol A type epoxy such as Epik〇teRTM 8 〇 2, 1 〇〇 100 1004 manufactured by Oiled Shell Epoxy Co., Ltd. Epoxy acrylate obtained by the reaction of resin, and Epik〇teRTM4〇〇ip, 4〇〇^, 4003=, etc., and the reaction of f-type oxirane resin with (meth)acrylic acid (the attached RTM system is registered Trademark). Alternatively (hydrogenated alicyclic epoxy acrylates may also be used as the above). The content of the methoxy acrylate in the resin composition (1 part by weight) of the present invention to the molecular weight of 2,000 Å is 〇 to 卯 by weight, and when the epoxy acrylate is used, it is in the present invention. In the resin composition, it is preferable to contain a system, and a hydrazine to 90 parts by weight, more preferably 3 to 85 parts by weight. Further, the fat-hanging composition of the present invention can be suitably used depending on the application, and the reactive compound, the inorganic filler, the organic filler, the coupling agent, the: endowment: ^, antifoaming agent, leveling agent, plasticizing Agents, antioxidants, ultraviolet light, in absorbents, flame retardants, pigments, dyes, etc. 319866 27 200837093: Specific examples of the aforementioned non-reactive compound are low-reactivity or non-reactive liquid or solid oligomers or resins, and examples thereof include (meth)acrylic acid alkyl ester copolymers and epoxy resins. Resin, liquid polybutadiene, dicyclopentadiene derivative, saturated polyester oligo, xylene resin, polyamine:: tree-lipid, propylene phthalate polymer (diallyi (d) ymer, DAP resin), petroleum resin, rosin resin, fluorine-based oligomer, fluorene-based oligomer, etc., but is not limited thereto. The inorganic filler may be, for example, sulphur dioxide or oxidized stone. , calcium carbonate, dream acid dance, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, oxidation, zinc sulfate, aluminum hydroxide, alumina, glass, mica, barium sulfate, Alumina white , zeolite, stone ball (& ballon), glass balloon (GlassBall〇〇n), etc. These inorganic fillers can also be added by adding a decane coupling agent, a titanic acid coupling agent, an aluminum coupling agent, and a citric acid. a salt-based coupling agent or the like, and has a reaction method or the like Functional groups of a group of an aryl group, an epoxy group, a hydroxyl group, and a thiol group. The above-mentioned organic filler may, for example, be a benz〇guanamine resin, a polyoxet, a low-density polyethylene, a high-density polymer. Ethylene, polyolefin resin, ethylene, acrylic copolymer, polystyrene, acrylonitrile-based copolymer, polymethyl methacrylate resin, fluororesin, nylon 12, nylon 6/66, phenolic resin, epoxy resin, a polyurethane resin, a polyimide resin, etc. The coupling agent may, for example, be a decane coupling agent such as r-glycidoxypropyltrimethoxydecane or r-chloropropyldimethoxydecane; four (2, 2) a titanate coupling agent such as 1,4-diallyloxymethylbutanyl)bis(di(tridecyl)phosphite vine titanate or bis(dioctylpyrophosphate)titanate; Acetyl diisopropylate 28 319866 200837093 Aluminum coupling agent such as acetoalkoxy aiuminum diis〇pr〇pylate, oxime coupling agent such as acetamidineacetone oxime complex, etc. Resin composition of the present invention Adhesive-imparting agent, defoaming, plasticizer, antioxidant, ultraviolet light The agent, the flame retardant, the pigment, and the dye may be used as long as they are conventionally used, and are not particularly limited insofar as they are not detrimental to the curability and resin properties. The resin composition is not particularly limited as long as the components are mixed, and the order or method of mixing is not particularly limited. The resin composition of the present invention may be diluted with a diluent to be used as a coating composition or the like. An organic solvent, for example, methyl ketone: a ketone such as methyl isobutyl copper; an aromatic hydrocarbon such as acetic acid, butyl acetate or the like; an aromatic hydrocarbon such as toluene or xylene; and other commonly used organic η The preferred solvent is the solvent. In the coating composition, the content of the resin composition component other than the organic solvent is from 2% to 8 right, and from about 303⁄4 to 70%, which is a preferred embodiment of the coating composition of the present invention. The composition is as follows: 20 to 80% 8 〇 to 20% by weight 1 part _, 5 to 99 parts by weight of the tree of the invention 1 to 20 parts by weight of the resin composition of the present invention, and the resin composition of the present invention The composition 1 is composed of the following composition: · The compound of the invention (A) Photopolymerization initiator (B) 319866 29 200837093 • Optional component (preferably ethylenic residue (〇 to no Saturated Compound (C)) 94 parts by weight) The resin composition of the present invention can be polymerized by irradiation of a wave of 18 Å to 5 Å nm, a long ultraviolet ray or an active energy ray such as visible light (crosslinking hardening) ). Further, the resin composition of the present invention may be cured by irradiation with an energy ray other than ultraviolet rays or by heat-sensitive initiator (e.g., azobisisobutyronitrile). The light source of ultraviolet or visible light having a wavelength of 180 to 500 nm, and the f system may be, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury lamp, a xenon lamp, an excimer lamp, and a short lamp. Short arc lamp, cesium-cadmium laser, argon laser, excimer laser, sunlight. The active energy ray line in the present invention may, for example, be an ultraviolet ray, a visible ray, an infrared ray, an X-ray ray, a ray, a (5) ray, a laser beam, or the like; or an atomic line such as an alpha ray, a beta ray, or an electron beam. However, in view of the preferred use of the present invention, it is preferred to include ultraviolet light, visible light, or electron beams including laser light. The resin composition of the present invention can be used for a material for forming a film, a solder mask for manufacturing a printed (wiring circuit) substrate, a bond resist agent, an adhesive, a lens, a display, an optical fiber, an optical waveguide, and the like. Photo and other aspects. The film forming material refers to a user who is intended to cover the surface of the substrate. For its specific use, it is equivalent to ink printing materials such as gravure ink, fiexso ink, screen printing ink, lithographic ink, etc.; hard coating, top coating, overprint varnish (〇verprint varnish), 319866 30 200837093 • Coating materials such as cIear coat. In addition, it can also be used as a resist material such as anti-flux, etching resist, and micromachine resist; other various adhesives for laminating, adhesives, etc. Next, various materials such as an adhesive for LED, various lenses such as a lens, a Lenticular lens, and various optical materials such as a core material, a shell material, an optical waveguide, and a full image. Further, after the resin composition is applied onto a temporarily peelable substrate and thinned, and then bonded to a substrate which is originally intended as a target to form a film, it can also be used as a dry film (dry film). The method of forming various coating films is not particularly limited, but can be applied to gravure printing methods such as gravure, letterpress printing methods such as soft printing, lithographic printing f-type printing such as screen printing, lithographic printing methods such as lithography, roll coaters, and the like. Various coating methods such as a knife coater, a die coater, a curtain coater, and a spin coater. (Embodiment) Hereinafter, the present invention will be more specifically described based on the reference examples and examples, but the present invention is not Reference Example 1 Synthesis of Epoxy Resin (a) of General Formula (1) - In a flask equipped with a thermometer, a cooling tube, and a stirrer, while adding =:, the following formula was added. (2) Compounds (4) (three light shares = two clothes D〇Q-〇) 169 parts, 463 parts of epoxy chlorinated propylene, and methanol ^ dissolve the former two in methanol. Further, The solution was added to it, and it took 90 minutes to divide and add 41 pieces of flakes. After the reaction is completed, 319866 31 200837093 Γ, the reaction solution is washed twice with 150 parts of water, and the salt formed is removed, and then heated and decompressed (to 7〇t: until ― (10) 馗 馗 — 化 化 ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) 过量 过量 过量 过量 过量 过量 过量 过量 过量 过量After stirring for 3 minutes in a reflux state, methanol i5 parts were added and stirred for 15 minutes, and then 3 parts of water were slowly added. The precipitated crystals were separated by deuterium reduction to obtain crystals as a target. An epoxy resin of 0.01 (average value). Further, the crystal was washed with a sterol lion and washed with 200 parts of water, and dried to obtain a white epoxy resin in a white to pale white powder. The epoxy equivalent of 227 is the same as the refractive index of the oxygen resin (4) of the general formula (1). In addition, the determination of this ring is difficult, with 3_ fixed shot ==^65. _ Multi-wavelength Abbes made by Dimethyl Co., Ltd.; The measuring device was ^ago 589 nm (D line). Ten DR-M2, measuring wavelength: (7)
319866 32 200837093 本發明之化合物（A)之合成 在附有攪拌裝置、回流管之1L焊 、 釋劑之甲苯128.2g、與參考例1同樣i作所得==稀 ，⑷(n=0.01(平均值）)227.0g(環氧當量：丨〇告衣乳树脂 ’有乙烯性不餘和基之單幾酸化合物(b)之丙；分 印2.(^.0當量）、作為熱聚合抑制劑之2 6_二=為 丁基·對甲驗2.56g、以及作為反應觸媒之三苯基膦二^ 以100C之溫度反應24小時，而獲得含有本發明化人物 (A)70重量％的溶液。測定溶液之酸價時，其酸價為 KOH/g。 s 其次，添加甲苯570g於此溶液中，以水1〇〇g洗淨3 次，減壓濃縮有機相，而獲得淡黃色樹脂狀之化合物⑷。 =樹脂狀化合物（A)之環氧當量為62,〇〇〇g/eq。從此分析值 算出原料環氧基反鱗（丙烯酸導人率）為99 3%。測定此 樹脂於25°C之折射率時，其折射率為1616。另外，測定 質子NMR時，為如下之波峰： H-NMR 3.90 — 4.50Ppm = 10H、5.83ppm = 2H、6 15ppm = 2H、 6.42ppm= 2H > 6.90- 7.65ppm = 16H 比較例1 (H) 在氮氣環境下，於附有攪拌裝置、回流脫水裝置之2L 燒瓶中’加入上述式之酚化合物（三光股份公司製之 D0Q_0，分子量為 338.1)67.6g(0.2mol)、甲苯 600m卜碳 33 319866 200837093 酸伸乙酯（分子量：88.06)61.6g(0.70mol)。於擾掉下、9q 至l〇〇°C，在所得之液中添加無水碳酸鉀粉末8g，使其維 持该狀悲反應5小時。冷卻反應混合物並濾別析出物，再 、以水及曱醇洗淨，以7 5 C乾燥，而以白色結晶獲得上述式 ’ （2)所示之酚化合物（c)之環氧乙烷加成物71.0g。 其次’在具備回流冷卻器、攪拌機、溫度計、溫度調 節I置及水分離機的反應器中，添加上述所得之環氧乙烧 〆加成物（分子量·· 426.5)42.7g(0.10mol)、丙烯酸（分子量: ί 72.06)17.3g(0.24m〇l)、對甲苯磺酸·一水合物 〇 35g、氫 醌〇.14g、甲苯60g，並於反應溫度1〇〇。〇至115。〇中，一 邊使生成水與溶媒共濟蒸餾去除一邊進行反應’當生成水 到達3.6ml時’即作為反應之終，點。將反應混合物溶解於 io〇g甲苯中，以25%苛性鈉水溶液中和後，再以食鹽 水20g洗平3次。將溶媒減屢蒸館去除，而獲得褐色樹脂 狀之上述式(2)所示之驗化合物⑷之環氧乙㈣婦酸醋化 (合物（H)51.6g。測定此樹脂於25它之折射率時，並 為 1.614 〇 〆、 另外，以甲苯70重量％分別將實施例1、比較例1所 得=合物稀釋’測定可見光之透射率，將所料之數據 不於第1圖。 n帛目可知’本發明之化合物（A)係以波長450nm 至800nm照射，此光之诱身 古 之透射干回達70至80%且為穩定， 判疋為無者色而透明度高。 本η知例中’除了使用肉桂酸（分子量為I") 319866 34 200837093 148g替代丙烯酸以外，其餘係依照實施例i進行反應，而 可獲得由肉桂酸加成於通式（1)之環氧樹脂之環氧基上而 成的羧酸酯樹脂。 & 另外，除了使用丙烯酸與ε _己内酯之反應生成物替代 丙烯酸以外，其餘係依照實施例丨進行反應，而可獲得由 該反應生成物加成於通式（1)之環氧樹脂之環氧基上而成 的羧酸酯樹脂。 實施例2及比較例2 另外，以]VfEK(2_ 丁酮）50重量％分別將實施例i、比 較例1所得之化合物稀釋，添加作為光聚合起始劑之319866 32 200837093 The synthesis of the compound (A) of the present invention is carried out in a 1 L weld with a stirring device and a reflux tube, and 128.2 g of toluene, which is obtained in the same manner as in Reference Example 1 == lean, (4) (n = 0.01 (average Value)) 227.0 g (epoxy equivalent: 衣 衣 树脂 ' 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; 2 6_2 = butyl butyl test 2.56 g, and triphenylphosphine as a reaction catalyst were reacted at a temperature of 100 C for 24 hours to obtain 70% by weight of the person (A) containing the present invention. The acid value of the solution is determined by the acid value of KOH/g. s Next, 570 g of toluene is added to the solution, washed 3 times with water, and the organic phase is concentrated under reduced pressure to obtain a pale yellow color. Resin-like compound (4) = Resin-like compound (A) had an epoxy equivalent of 62, 〇〇〇 g / eq. From this analysis value, the raw material epoxy group anti-scale (acrylic acid introduction rate) was calculated to be 99 3%. When the resin has a refractive index at 25 ° C, its refractive index is 1616. In addition, when measuring proton NMR, it is a peak as follows: H-NMR 3.90 - 4.50 Ppm = 10H, 5.8 3ppm = 2H, 6 15ppm = 2H, 6.42ppm = 2H > 6.90- 7.65ppm = 16H Comparative Example 1 (H) In a 2 L flask equipped with a stirring device and a reflux dehydration device, the above formula was added under a nitrogen atmosphere. Phenolic compound (D0Q_0 manufactured by Sanguang Co., Ltd., molecular weight 338.1) 67.6g (0.2mol), toluene 600m, carbon 33 319866 200837093 acid ethyl ester (molecular weight: 88.06) 61.6g (0.70 mol). Under the disturbance, 9q To l 〇〇 ° C, 8 g of anhydrous potassium carbonate powder was added to the obtained liquid to maintain the sorrow reaction for 5 hours. The reaction mixture was cooled and the precipitate was filtered, and washed with water and decyl alcohol to 7 5 C was dried, and 71.0 g of an ethylene oxide adduct of the phenol compound (c) represented by the above formula (2) was obtained as a white crystal. Next, a reflux condenser, a stirrer, a thermometer, and a temperature adjustment I were provided. In the reactor of the water separator, 42.7 g (0.10 mol) of the ethylene oxide calcined adduct (molecular weight · 426.5) obtained above, and acrylic acid (molecular weight: ί 72.06) 17.3 g (0.24 m〇l), P-toluenesulfonic acid · monohydrate 〇 35g, hydroquinone. 14g, toluene 60g, and at the reaction temperature 1 〇 〇 115 115 〇 〇 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 After neutralizing with a 25% aqueous solution of caustic soda, it was washed three times with 20 g of saline. The solvent was removed by steaming, and the epoxy resin (the compound (H) 51.6 g of the test compound (4) represented by the above formula (2) was obtained as a brown resin. The resin was determined to be 25 In the case of the refractive index, the amount of the refractive index was 1.614 〇〆, and the obtained compound of Example 1 and Comparative Example 1 was diluted with 70% by weight of toluene to measure the transmittance of visible light, and the data was not shown in Fig. 1. It can be seen that the compound (A) of the present invention is irradiated at a wavelength of 450 nm to 800 nm, and the light transmission of the light is 70 to 80% and stable, and the color is high and the transparency is high. In the example, except that cinnamic acid (molecular weight I") 319866 34 200837093 148g was used instead of acrylic acid, the reaction was carried out in accordance with Example i, and an epoxy resin obtained by adding cinnamic acid to the general formula (1) was obtained. A carboxylic acid ester resin obtained by using an epoxy group. In addition, in addition to using a reaction product of acrylic acid and ε-caprolactone instead of acrylic acid, the reaction is carried out in accordance with Example ,, and the reaction product can be obtained. Ring added to epoxy resin of formula (1) Carboxylate resin obtained by oxy group. Example 2 and Comparative Example 2 Further, the compound obtained in Example i and Comparative Example 1 was diluted with 50% by weight of VfEK (2-butanone), and added as photopolymerization. Starting agent
Irgacure 184(Ciba Specialty Chemicals 公司製之經基環 己基苯基酮）3重量％，而獲得本發明之樹脂組成物之稀釋 液（塗佈用組成物）。 其次’將此等溶液使用棒塗器（No·20)塗佈於易接著處 理聚酯薄膜（東洋紡股份公司製之Α-4300,膜厚188//m)， 於80 C之乾燥爐中放置1分鐘後，在空氣環境下，一邊以 5m/分鐘之搬送速度將該薄膜搬送、一邊使用12〇 W/cm之 咼壓水銀燈從燈高度1 〇cm之距離照射紫外線並使塗膜硬 化，而獲得具有硬化皮膜（1〇至之薄膜。 對於所得之薄膜，依照JIS K 5 4 0 0，在薄膜之表面上 以1 mm之間隔切入縱、橫各11條切痕而製成100個棋盤 方格。其次，使玻璃紙膠帶密著於該表面後，一口氣將其 剝離時’並將未剝離而殘存之方格數目示於表1。 35 319866 200837093 〔表1〕 薄膜 r-^—_ 袼數目 實施例2之薄膜 (具有實施例1所得之化合物(A)之硬化膜的薄膜） 83 比較例2之薄膜 ^-—~~__ (具有比較例1所得之化合物(H)之硬化膜的薄膜） 24 --- ---- 由以上之結果，可知本發明之化合物（A)係樹脂單獨就 有透明性優異、具有高折射率，而具有包含本發明化合物（a) 之本發明樹脂組成物之硬化膜的薄膜，係具備高密著性。 (產業上之可利用性） 本發明之化合物（A)係透明性優異、具有高折射率，且 含有該化合物（A)之樹脂組成物係在藉由活性能量線曝光 硬化以形成之塗膜中具有高密著性，並且能賦予具有^分 硬度之硬化物。gj此，該感光性樹脂係適合作為皮膜形^ 用材料、製造印刷（配線電路）基板時之阻焊遮罩、電鍍抗 ，劑、接著劑、透鏡、顯示器、光纖、光導波路、全像 專用途的一種成分。 【圖式簡單說明】 〔第1圖〕 第⑶絲示分別將實施例i所得之本發明化合 與比較例1所得之化合物m 1 > 定可…夂、： 甲苯7〇重量%稀釋，再測 _ 波長之透射率並繪圖而成的曲線圖。 I主要元件符號說明】 ^\\\ 319866 36Irgacure 184 (a cyclohexyl phenyl ketone manufactured by Ciba Specialty Chemicals Co., Ltd.) was added in an amount of 3% by weight to obtain a diluted solution (coating composition) of the resin composition of the present invention. Next, these solutions were applied to a polyester film (manufactured by Toyobo Co., Ltd. Α-4300, film thickness 188/m) using a bar coater (No. 20), and placed in a drying oven of 80 C. After 1 minute, the film was conveyed at a conveying speed of 5 m/min in an air atmosphere, and a mercury lamp of 12 〇W/cm was used to irradiate ultraviolet rays from the height of the lamp at a height of 1 〇cm, and the coating film was cured. A film having a hardened film (a film of 1 Å was obtained. For the obtained film, according to JIS K 5 400, 11 cuts of vertical and horizontal are cut at intervals of 1 mm on the surface of the film to make 100 checkers. Secondly, after the cellophane tape is adhered to the surface, the number of squares which remain unpeeled and removed in one breath is shown in Table 1. 35 319866 200837093 [Table 1] Film r-^-_ 袼The film of Example 2 (film having the cured film of Compound (A) obtained in Example 1) 83 film of Comparative Example 2 - -~~__ (The cured film of Compound (H) obtained in Comparative Example 1 Film) 24 --- ---- From the above results, it is known that the compound (A) of the present invention is The film having a cured film of the resin composition of the present invention containing the compound (a) of the present invention has high adhesion, and has excellent adhesion to the resin. The compound (A) is excellent in transparency and has a high refractive index, and the resin composition containing the compound (A) has high adhesion in a coating film formed by exposure curing by active energy rays, and can be imparted with ^The hardness of the hardened material. gj This photosensitive resin is suitable as a film-shaped material, a solder mask, a plating resist, an adhesive, a lens, a display, and an optical fiber when manufacturing a printed (wiring circuit) substrate. A component of the optical waveguide and the holographic application. [Fig. 1] The (3) filament shows that the compound obtained in the example i is compounded and the compound obtained in the comparative example 1 m 1 > ...夂,: Toluene 7 〇 wt% diluted, and then measured _ wavelength transmittance and plotted. I main symbol description] ^\\\ 319866 36