TW200837503A - Phototool for solder resist exposure and solder resist pattern forming method in which exposure processing is performed using the same - Google Patents

Phototool for solder resist exposure and solder resist pattern forming method in which exposure processing is performed using the same Download PDF

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TW200837503A
TW200837503A TW96142700A TW96142700A TW200837503A TW 200837503 A TW200837503 A TW 200837503A TW 96142700 A TW96142700 A TW 96142700A TW 96142700 A TW96142700 A TW 96142700A TW 200837503 A TW200837503 A TW 200837503A
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Taiwan
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group
film
solder resist
resist pattern
carbon atoms
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TW96142700A
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Chinese (zh)
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TWI426351B (en
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Yoko Shibasaki
Kenji Kato
Masao Arima
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Taiyo Ink Mfg Co Ltd
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Priority claimed from JP2006309100A external-priority patent/JP5079310B2/en
Priority claimed from JP2006309101A external-priority patent/JP2008122845A/en
Application filed by Taiyo Ink Mfg Co Ltd filed Critical Taiyo Ink Mfg Co Ltd
Publication of TW200837503A publication Critical patent/TW200837503A/en
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Publication of TWI426351B publication Critical patent/TWI426351B/en

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Abstract

To provide a phototool for exposure processing of solder resist with which a high-resolution resist pattern can be formed with good reproducibility regardless of the thickness of a solder resist layer and the influence of a blue pigment, and to provide a solder resist pattern forming method in which exposure processing is performed using the phototool, and a photosensitive composition suitable for use in the forming method. The phototool is used in exposure processing in pattern formation of solder resist and has a photomask, wherein the phototool has a protective film which cuts off ≥ 50% of light of ≤ 370 nm and transmits ≥ 80% of light of ≥ 400 nm on the resist face side of the photomask.

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200837503 九、發明說明 【發明所屬之技術領域】 本發明爲關於印刷配線板抗焊阻劑圖型形成時之曝光 處理技術。 【先前技術】 一般來說,印刷配線板爲於其最外層形成抗焊阻劑層 。此抗焊阻劑層爲於形成配線電路之基材上塗佈感光性組 成物後,將所得到之塗膜經由光罩選擇性曝光,使未曝光 部分顯像形成圖型後,經過藉由加熱使熱硬化之步驟而形 成。 於此般抗焊阻劑層之形成中,光罩素材方面,使用聚 對苯二甲酸乙二酯(PET )薄膜或玻璃。其中,PET薄膜 爲價廉、有柔軟性’又可使300nm以上紫外線區域之光 有90 %以上透過,可在感光性組成物照射充分紫外線量 ,故廣泛用作光罩(如,參考專利文獻1 )。 而’係爲者色系’厚膜(〜100//m程度)硬化必要 之印刷配線板用抗焊阻劑中’因使用於紫外線區域3 0 0〜 4OOnm有大吸收之酞菁藍顏料,無法有效利用特地透過光 罩之3 00〜40 Onm之光,有細線及因厚膜易產生光暈或凹 槽等解像性問題。 又,根據被加工基材之形成電路基板,其電路厚有 2 5 // m〜105 // m之大差異,光阻膜厚依部位可能有大差 異。此時,以同一光阻要得到相同光阻形狀係困難的。對 -5- 200837503 於此,以往在膜厚爲厚的情況下,爲得到更深之硬化深度 ,以比一般高之曝光量進行照射。而,此般處理有表層部 產生光暈、線寬比設計値粗、導通孔徑比設計値小等眾多 不期望問題產生。另一方面,低曝光量無法得到充分硬化 深度,有凹槽產生之問題。 因此,印刷配線板所用之光阻圖型方面,正尋求厚膜 且可形成高精細圖型形成之技術。 [專利文獻1]特開平9-23 05 8 0號公報 【發明內容】 [發明所欲解決之課題] 本發明以提供不受抗焊阻劑層膜厚及藍色顏料之影響 ,再現性佳可形成高解像度光阻圖型之抗焊阻劑曝光處理 技術爲目的。 又,本發明其他目的爲提供使用上述曝光處理技術所 得之抗焊阻劑圖型及印刷配線板。 [解決課題之方法] 發明者們,爲解決上述課題努力硏究,發現在調節光 源光波長之相對強度有醒目之結果,發現藉由使用令曝光 光之波長之相對強度最適化用之具特定光吸收特性的薄膜 ,可達成上述目的,完成本發明。 也就是,本發明之光具爲用於抗焊阻劑圖型形成之曝 光處理,係具備光罩之光具,其特徵係在該光罩之光阻面 -6- 200837503 側具備阻斷5 0 %以上3 7 0 n m以下之光,且使8 0 %以上 400nm以上之光透過之薄膜。 在此,上述薄膜可爲熱可塑性薄膜(如,聚萘二甲酸 乙二醇酯),此時該熱可塑性薄膜可含紫外線吸收劑。或 ,上述薄膜可由熱可塑性薄膜與於該熱可塑性薄膜上所層 合之紫外線吸收劑含有層所構成。 本發明之抗焊阻劑圖型形成方法的一樣態爲,介由上 述光具使感光性組成物乾燥膜構成之抗焊阻劑進行選擇性 曝光,使未曝光部分顯像形成圖型後,經加熱使熱硬化而 得到硬化膜。 其他樣態方面,本發明之抗焊阻劑的圖型形成方法爲 介由光罩將由感光性組成物之乾燥膜所成之抗焊阻劑選擇 性曝光,使未曝光部分顯像形成圖型後,經加熱使熱硬化 後得到硬化膜之抗焊阻劑圖型之形成方法,其中於產生曝 光光之光源與光罩間,存在有阻斷50%以上3 70nm以下 之光且使80%以上400nm以上之光透過的薄膜。 在此,上述薄膜可爲熱可塑性薄膜(如,聚萘二甲酸 乙二醇酯),此時該熱可塑性薄膜可含紫外線吸收劑。或 ,上述薄膜可爲熱可塑性薄膜與於該熱可塑性薄膜上所層 合之紫外線吸收劑含有層所構成。 本發明之抗焊阻劑的圖型形成方法中,該抗焊阻劑可 由可鹼顯像之感光性組成物或具有可鹼顯像之感光性組成 物的塗膜之乾薄膜所形成。 該感光性組成物可爲其乾燥塗膜波長405 nm時,吸 200837503 光度係每膜厚25 // m爲0.2〜1.2之感光性組成物。 又,上述感光性組成物爲可含有由後述之含一般式( I )所示之構造部分之肟酯系光聚合起始劑、含一般式( II )所示之構造部分之胺基苯乙酮系光聚合起始劑、含一 般式(III )所示之構造部分之醯基膦氧化物系光聚合起 始劑,及一般式(IV )所示之二茂鈦系光聚合起始劑所成 群所選出之1種或2種以上之光聚合起始劑。 進一步,上述含一般式(I)所示之構造部分之膀酯 系光聚合起始劑可爲後述式(I-1 )所示之化合物,或後 述一般式(1-2 )所示之化合物。 又,上述感光性組成物可含作爲增感劑之由二乙基噻 噸酮、二乙基胺基二苯甲酮及香豆素類所選出之至少1種 ,或酞菁藍系顏料。 又,本發明之一態樣中,上述硬化膜可爲綠色或藍色 〇 進一步,根據本發明,提供藉由上述抗焊阻劑圖型之 形成方法所得之硬化膜。 又,藉由本發明,提供藉由上述抗焊阻劑圖型之形成 方法所得之具備硬化膜之印刷配線板。 [發明效果] 根據本發明之光阻圖型的形成技術,可提供不受酞菁 藍系顏料之紫外線光吸收之影響,厚膜且具備高精細之抗 焊阻劑圖型之印刷配線板。 -8- 200837503 [實施發明之最佳形態] 以下,詳細說明本發明。 本發明爲於被加工基板上所形成之抗焊阻劑層上介著 光罩曝光所期望圖型之曝光處理技術中,其特徵爲爲使曝 光光波長之相對強度最適化,使用具有特定之光吸收特性 的薄膜。 接著,本發明圖型曝光所用之具有特定之光吸收特性 的薄膜,係使用具有阻斷紫外線中3 70nm以下之光的50 %以上且使400nm以上之光的80%以上透過功能的薄膜 〇 本發明中,有使相關薄膜貼附於光罩之光阻面側的光 具之態樣,與使相關薄膜介在光源與光罩間之態樣。任一 之態樣,皆容易預想在使用高壓水銀燈之曝光中係可使 3 65nm之光大幅被阻斷之低感度,故爲調節光阻圖型曝光 時曝光光波長之相對強度,使用此般薄膜係常識推論上不 可行的。本發明中,特別是乾燥塗膜之波長405 nm時, 相對吸光度每膜厚25 // m爲0.2〜1.2之可鹼顯像之感光 性組成物而言,本發明者們硏究發現可厚膜且形成高解像 度之光阻圖型。 又,本發明中「乾燥塗膜之波長405 nm時吸光度係 每膜厚25// m爲0.2〜1.2」在後述實施例中詳述,其係指 製作塗佈•乾燥感光性組成物糊料後所得之塗膜膜厚與各 膜厚中波長405iim時吸光度之圖表,由其近似式算出膜 200837503 厚25/zm之乾燥塗膜吸光度後所得之吸光度在〇.2〜K2 之範圍。 在此,本發明之光具中可用之上述薄膜(亦作爲保護 薄膜),或使介在光源與光罩間之上述薄膜係具有上述光 吸收特性者即可,並未特別限制,如,可使用熱可塑性薄 膜,其中聚萘二甲酸乙二醇酯薄膜因滿足上述光吸收特性 故宜用於本發明光具中。又,熱可塑性薄膜本身不滿足上 述光吸收特性時,進而可藉由層合紫外線吸收劑含有層使 滿足上述光吸收特性爲用作爲層合薄膜。進而可使用在薄 膜本身含有紫外線吸收劑者。在此,紫外線吸收劑方面可 使用慣用公知者,具體上,可使用二苯甲酮系、苯並三唑 系、水楊酸系、香豆素系、羥基苯基三嗪系等。就算如保 護薄膜之薄膜爲得到充分吸收效果,使用羥基苯基三嗪系 之 TINUVIN460 或 TINUVIN479 ( CIba Specialty C h e m I c a 1 s I n c .製)等係有效的,乳化分散之紫外線吸收 劑方面,以 TINUVIN477DW 或 TINUVIN1130 (CIba Specialty Chemicals Inc·製)等爲有效。 此含紫外線吸收劑之薄膜,如,於聚對苯二甲酸乙二 酯(PET )薄膜製作時藉由混練入紫外線吸收劑而製作。 具有紫外線吸收層之熱可塑性薄膜,如’於PET薄 膜塗佈紫外線吸收劑而成。 更進一步,可於聚乙烯基醇或醋酸纖維系之親水性熱 可塑性薄膜含浸乳化分散紫外線吸收劑使吸著或浸透而成 -10- 200837503 作爲於光罩之光阻側貼合之保護薄膜功能之薄膜的情 況,可使用於其薄膜接著層或黏著層含紫外線吸收劑者。 熱可塑性薄膜爲聚萘二甲酸乙二醇酯時,因其化學構 造而有紫外線吸收領域,可直接使用。 此般薄膜之厚度,在用作於光罩光阻側貼合之保護薄 膜之機能薄膜時,在5//m〜50/zm,較佳爲10//m〜30 // m。此因未滿5 // m則紫外線吸收效果弱,超過5 0 // m 則因光散射而光阻形狀變不安定而不宜。 又,介在光罩與光源間之薄膜的情況,爲1 〇 // m〜 1 m m,較佳爲2 5 /z m〜1 0 0 // m。此因未滿1 0 // m則操作 變困難,紫外線吸收效果變弱。另一方面,超過1 mm則 4 OOnm以上之光無法有80%以上之透過,且薄膜重量變 重而不宜。 使用本發明之上述曝光處理技術進行光阻圖型曝光處 理,就算作爲抗焊阻劑層使用之感光性組成物含有多量酞 菁藍系顏料,亦不受該酞菁藍影響紫外線吸收,可以厚膜 形成高解像度之光阻圖型。 以下,說明關於使用本發明之曝光處理技術曝光處理 之抗焊阻劑圖型之形成方法中,所適用之感光性組成物。 本發明抗焊阻劑圖型之形成方法中所適用之感光性組 成物,其乾燥塗膜波長40 5nm時吸光度每膜厚25// m爲 0.2〜1.2,較佳爲0.3〜0.8之可鹼顯像之光硬化性,或光 硬化性•熱硬化性樹脂組成物,可含有(A )含羧酸樹脂 ,(B )含一般式(I )所示之構造部分之肟酯系光聚合起 -11 - 200837503 始劑,含一般式(II )所示之構造部分之胺基苯乙酮系光 聚合起始劑,含一般式(III )所示之構造部分之醯基膦 氧化物系光聚合起始劑,及一般式(IV )所示之二茂鈦系 光聚合起始劑所成群所選出之1種或2種以上之光聚合起 始劑,(C )於分子中有2個以上乙烯性不飽和基之化合 物,(D )熱硬化性成分,(E )酞菁藍系顏料及(F )二 乙基噻噸酮、二乙基胺基二苯甲酮及香豆素類所選出之1 種或2種以上之增感劑。特別是藉由適當地選擇光聚合起 始劑(B )及藍色顏料(E ),可調整其乾燥塗膜波長 405 nm時吸光度在每膜厚25//m爲0.2〜1.2,較佳爲0.3 〜0.8。波長405nm時吸光度比每25//m爲0.2低時,無 法防止感度降低,另一方面,比1 · 2大時產生凹槽難以獲 得高精細圖型。 如上述般,一般使用高壓水銀燈之曝光,使用3 65nm ,405nm,433nm波長之光,但如本發明般介由具有特定 之光吸收特性的薄膜之曝光處理,阻斷了 3 6 5nm之光, 感度變低。而,使用其塗膜波長4 0 5 nm時吸光度在每膜 厚25 // m爲0.2〜1.2之特定光聚合起始劑之可鹼顯像之 感光性組成物爲對於單獨4 0 5 nm之光,有高感度,可賦 予與以往以3 65nm,405nm,43 3nm等複合光線曝光之市 售組成物幾乎相同之感度。 以下,詳細說明有關各構成成分。 本發明方法所適用之感光性組成物所含之含羧酸樹脂 (A )方面,可使用於分子中含羧基之公知慣用的樹脂化 -12- 200837503 合物。進而於分子中有乙烯性不飽和雙鍵之含羧酸感光性 樹脂由光硬化性及耐顯像性方面來看更佳。 具體上,有下列之樹脂。 (1) 藉由(甲基)丙烯酸等不飽和羧酸與其以外之 具不飽和雙鍵化合物之1種類以上進行共聚合所得之含羧 酸樹脂, (2) (甲基)丙烯酸等不飽和羧酸與其以外具不飽 和雙鍵化合物之1種類以上之共聚合物,藉由縮水甘油基 (甲基)丙烯酸酯及3,4一環氧環己基甲基(甲基)丙烯 酸酯等環氧基與具不飽和雙鍵之化合物及(甲基)丙烯酸 氯化物等,使乙烯性不飽和基作爲懸掛基進行加成所得之 含羧酸感光性樹脂, (3) 縮水甘油基(甲基)丙烯酸酯及3,4 一環氧環己 基甲基(甲基)丙烯酸酯等環氧基與具不飽和雙鍵之化合 物與其以外之具不飽和雙鍵化合物之共聚合物,和(甲基 )丙烯酸等不飽和羧酸進行反應,使生成之二級羥基與多 元酸酐反應所得之含羧酸感光性樹脂, (4 )具有馬來酸酐等不飽和雙鍵之酸酐與,其以外 之具不飽和雙鍵化合物之共聚合物,和2 —羥基乙基(甲 基)丙烯酸酯等羥基與具不飽和雙鍵化合物進行反應所得 之含羧酸感光性樹脂, (5 )使多官能環氧化合物與(甲基)丙烯酸等不飽 和單殘酸進行反應,於生成羥基與飽和或不飽和多元酸酐 反應所得之含羧酸感光性樹脂, -13- 200837503 (6 )聚乙烯基醇衍生物等含羥基聚合物,與飽和或 不飽和多元酸酐反應後,生成之羧酸與於一分子中有環氧 基及不飽和雙鍵之化合物進行反應所得之含羥基之含羧酸 感光性樹脂, (7)多官能環氧化合物與(甲基)丙烯酸等不飽和 單羧酸與於一分子中至少1個醇性羥基,與環氧基反應之 醇性羥基以外之具1個反應性基之化合物(如,二羥甲基 丙酸等)之反應生成物再與飽和或不飽和多元酸酐進行反 應所得之含羧酸感光性樹脂, (8 )於一分子中至少有2個氧雜環丁烷環之多官能 氧雜環丁烷化合物與(甲基)丙烯酸等不飽和單羧酸反應 ,對所得之改性氧雜環丁烷樹脂中第一級羥基,和飽和或 不飽和多元酸酐進行反應所得之含羧酸感光性樹脂,及 (9 )多官能環氧樹脂(如,甲酚醛型環氧樹脂等) 與不飽和單羧酸(如,(甲基)丙烯酸等)反應後,與多 元酸酐(如,四氫苯二甲酸酐等)反應所得之含羧酸感光 性樹脂,進一步,與分子中有1個環氧乙烷環與有1個以 上乙烯性不飽和基之化合物(如,縮水甘油基(甲基)丙 烯酸酯等)進行反應所得之含羧酸感光性樹脂等,但於此 並無限定。 此等例示中偏好者方面,爲上述(2 ) 、 ( 5 ) 、(7 )、(9 )之含羧酸感光性樹脂,特別上述(9 )之含羧酸 感光性樹脂,由光硬化性’硬化塗膜特性面來看爲佳。 又,本說明書中,(甲基)丙烯酸酯爲丙烯酸酯、甲 -14- 200837503 基丙烯酸酯及彼等混合物之總稱,亦有其他類似表達。 如上般含羧酸樹脂(A )爲於主幹•聚合物側鏈有多 量遊離之羧基,故可經由稀鹼水溶液顯像。 又,上述含羧酸樹脂(A )之酸價在 40〜 200mgKOH/g之範圍,較佳爲45〜120mgKOH/g之範圍。 含羧酸樹脂之酸價未滿40mgKOH/g則鹼顯像變困難,另 一方面,超過200mgKOH/g則爲使藉由顯像液曝光部進行 溶解,需要在必要以上之細線,依狀況而有曝光部與未曝 光部無法區分,而以顯像液溶解剝離之情形,正常光阻圖 型之描畫變困難,故不宜。 又,上述含羧酸樹脂(A )之重量平均分子量依樹脂 骨架而異,一般在2,000〜1 50,000,以5,000〜1 00,000之 範圍之者爲佳。重量平均分子量未滿2,0 0 0,則不黏性能 差,曝光後塗膜之耐濕性差,於顯像時產生膜減薄,解像 度大幅劣化。另一方面,重量平均分子量超過1 5 0,000則 顯像性明顯變差,貯藏安定性差。 此般含羧酸樹脂(A )之搭配量爲,全組成物中,爲 20〜60質量%,較佳爲30〜50質量%。較上述範圍少時 ,因塗膜強度降低,故不宜。另一方面’較上述範圍多時 ,因黏性變高,塗佈性等降低,故不宜。 本發明中所用之感光性組成物所含之光聚合起始劑( B )方面,以含有二苯甲酮系、乙醯苯系、胺基苯乙酮系 、苯偶因醚系、苄基縮酮系、醯基膦氧化物系、肟醚系、 肟酯系、二茂鈦系等公知慣用之自由基光聚合起始劑,但 -15- 200837503 以含有含下述含一般式(I)所示之構造部分之肟酯系光 聚合起始劑、含下述一般式(π)所示之構造部分之胺基 苯乙酮系光聚合起始劑、含下述一般式(111)所示之構 造部分的醯基膦氧化物系光聚合起始劑,及下述一般式( IV )所示之二茂鈦系光聚合起始劑所成群所選出之1種或 2種以上爲佳。 [化1]200837503 IX. Description of the Invention [Technical Field] The present invention relates to an exposure processing technique for forming a resistive resist pattern of a printed wiring board. [Prior Art] Generally, a printed wiring board has a solder resist layer formed on its outermost layer. The solder resist layer is formed by applying a photosensitive composition on a substrate on which a wiring circuit is formed, and selectively removing the obtained coating film through a photomask to form an unexposed portion to form a pattern. Heating is carried out by the step of thermally hardening. In the formation of the solder resist layer as described above, a polyethylene terephthalate (PET) film or glass is used as the mask material. Among them, the PET film is inexpensive and flexible, and more than 90% of the light in the ultraviolet region of 300 nm or more can be transmitted, and the photosensitive composition can be irradiated with a sufficient amount of ultraviolet rays, so it is widely used as a photomask (for example, reference patent document) 1 ). And the 'system color' thick film (~100//m degree) hardens the necessary solder resist for printed wiring boards. 'Because of the phthalocyanine blue pigment which has a large absorption in the ultraviolet region of 300 to 400 nm, It is impossible to effectively use the light of 300 to 40 Onm which is specially transmitted through the mask, and there are problems such as thin lines and resolution problems such as halo or grooves due to thick film. Further, according to the circuit substrate on which the substrate to be processed is formed, the circuit thickness is as large as 2 5 // m to 105 // m, and the thickness of the photoresist film may vary greatly depending on the portion. At this time, it is difficult to obtain the same photoresist shape with the same photoresist. In the case where the film thickness is thick, in order to obtain a deeper depth of hardening, irradiation is performed at a higher exposure amount than usual. However, there are many undesired problems such as surface halation, wide line width design, and small on-hole size design. On the other hand, the low exposure amount cannot be sufficiently hardened, and there is a problem that a groove is generated. Therefore, in terms of the photoresist pattern used for printed wiring boards, a thick film is being sought and a technique for forming a high-definition pattern can be formed. [Problem to be Solved by the Invention] The present invention provides a reproducibility without being affected by the film thickness of the solder resist layer and the blue pigment. The anti-weld resist exposure processing technology of the high resolution photoresist pattern can be formed. Further, another object of the present invention is to provide a solder resist pattern and a printed wiring board which are obtained by the above exposure processing technique. [Means for Solving the Problem] In order to solve the above problems, the inventors have found that the relative intensity of the wavelength of the light source is adjusted to be conspicuous, and it has been found that the use of the relative intensity of the wavelength of the exposure light is optimized. The film of the light absorbing property can achieve the above object and complete the present invention. That is, the optical device of the present invention is an exposure process for forming a resistive resist pattern, and is an optical device having a photomask, which is characterized in that it has a blocking on the photoresist surface -6-200837503 side of the photomask. A film having a light of 0% or more and 30.7 nm or less, and transmitting light of 80% or more and 400 nm or more. Here, the above film may be a thermoplastic film (e.g., polyethylene naphthalate), and in this case, the thermoplastic film may contain an ultraviolet absorber. Alternatively, the film may be composed of a thermoplastic film and a UV absorber-containing layer laminated on the thermoplastic film. In the same manner as the method for forming a solder resist pattern according to the present invention, the solder resist formed of the dried film of the photosensitive composition is selectively exposed by the optical device to form an unexposed portion to form a pattern. The film is hardened by heating to obtain a cured film. In other aspects, the pattern of the solder resist of the present invention is formed by selectively exposing the anti-solder resist formed by the dried film of the photosensitive composition through a photomask to form an unexposed portion to form a pattern. Then, after heat-hardening, a method of forming a resistive resist pattern of the cured film is obtained, wherein between the light source that generates the exposure light and the mask, there is a light that blocks 50% or more and 3 70 nm or less and makes 80% A film that transmits light above 400 nm or more. Here, the above film may be a thermoplastic film (e.g., polyethylene naphthalate), and in this case, the thermoplastic film may contain an ultraviolet absorber. Alternatively, the film may be composed of a thermoplastic film and a UV absorber-containing layer laminated on the thermoplastic film. In the pattern forming method of the solder resist according to the present invention, the solder resist may be formed of a photosensitive film which can be alkali-developed or a dry film of a coating film having a photosensitive composition which can be alkali-developed. The photosensitive composition can be a photosensitive composition having a dry film temperature of 405 nm and a density of 0.2 to 1.2 per film thickness of 200837503. In addition, the photosensitive composition may be an oxime-based photopolymerization initiator containing a structural moiety represented by the general formula (I), and an aminophenyl group containing a structural moiety represented by the general formula (II). a ketone photopolymerization initiator, a mercaptophosphine oxide photopolymerization initiator containing a structural moiety represented by the general formula (III), and a titanocene photopolymerization initiator represented by the general formula (IV) One or two or more photopolymerization initiators selected in the group. Further, the urethane-based photopolymerization initiator containing the structural moiety represented by the general formula (I) may be a compound represented by the following formula (I-1) or a compound represented by the following general formula (1-2). . Further, the photosensitive composition may contain at least one selected from the group consisting of diethyl thioxanthone, diethylaminobenzophenone, and coumarin as a sensitizer, or a phthalocyanine blue pigment. Further, in one aspect of the invention, the cured film may be green or blue. Further, according to the present invention, a cured film obtained by the above-described method for forming a solder resist pattern is provided. Moreover, according to the present invention, there is provided a printed wiring board having a cured film obtained by the above-described method for forming a solder resist pattern. [Effect of the Invention] According to the technique for forming a photoresist pattern of the present invention, it is possible to provide a printed wiring board which is not affected by ultraviolet light absorption of a phthalocyanine blue pigment, and which has a thick film and a high-precision solder resist pattern. -8- 200837503 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The present invention is an exposure processing technique in which a resist pattern of a mask is formed on a resistive resist layer formed on a substrate to be processed, and is characterized in that the relative intensity of the wavelength of the exposure light is optimized, and the use is specific. A film of light absorbing properties. Next, a film having a specific light absorbing property for use in the pattern exposure of the present invention is a film constituting a film having a function of blocking 50% or more of light of 3 70 nm or less and 80% or more of light of 400 nm or more in ultraviolet rays. In the invention, there is a state in which the relevant film is attached to the light-receiving surface side of the photomask, and the related film is interposed between the light source and the photomask. In any aspect, it is easy to predict that in the exposure using a high-pressure mercury lamp, the low sensitivity of the light of 3 65 nm can be greatly blocked, so that the relative intensity of the wavelength of the exposure light when adjusting the photoresist pattern is used. Thin film system common sense is not feasible. In the present invention, in particular, when the wavelength of the dried coating film is 405 nm, the inventors have found that the photosensitive composition having an absorbance of 25 // m per film thickness of 0.2 to 1.2 can be thick. The film forms a high resolution photoresist pattern. Further, in the present invention, "the absorbance at a wavelength of 405 nm of the dried coating film is 0.2 to 1.2 per film thickness of 25/m", which is described in detail in the later-described examples, and refers to the preparation of a coating/drying photosensitive composition paste. The graph of the obtained film thickness and the absorbance at a wavelength of 405 μm in each film thickness was calculated from the approximation formula, and the absorbance of the dried coating film of the film 200837503 thick 25/zm was in the range of 〇.2 to K2. Here, the film (also used as a protective film) usable in the optical device of the present invention, or the film having the light absorption property between the light source and the photomask may be used, and is not particularly limited, and may be used. A thermoplastic film in which a polyethylene naphthalate film is suitable for use in the optical device of the present invention because it satisfies the above-mentioned light absorbing characteristics. Further, when the thermoplastic film itself does not satisfy the above-described light absorption characteristics, it is also possible to use the layer of the ultraviolet absorber-containing layer to satisfy the above-mentioned light absorption characteristics as a laminate film. Further, it can be used in the film itself which contains an ultraviolet absorber. Here, as the ultraviolet absorber, a conventionally known one can be used. Specifically, a benzophenone type, a benzotriazole type, a salicylic acid type, a coumarin type, a hydroxyphenyl triazine type, or the like can be used. Even if the film of the protective film is sufficiently absorbed, the hydroxyphenyl triazine-based TINUVIN 460 or TINUVIN 479 (manufactured by CIba Specialty C hem I ca 1 s I nc.) is used as an effective, emulsified and dispersed ultraviolet absorber. It is effective as TINUVIN 477DW or TINUVIN 1130 (manufactured by CIba Specialty Chemicals Inc.). The film containing the ultraviolet absorber, for example, is produced by kneading a polyethylene absorbent in the production of a polyethylene terephthalate (PET) film. A thermoplastic film having an ultraviolet absorbing layer, such as a coating of a UV absorber on a PET film. Furthermore, it can be immersed or soaked in a hydrophilic thermoplastic film impregnated with a polyvinyl alcohol or a cellulose-based hydrophilic thermoplastic film to form a protective film function as a photoresist layer on the photoresist side of the photomask. In the case of a film, it can be used for a film having an adhesive layer or an adhesive layer containing an ultraviolet absorber. When the thermoplastic film is polyethylene naphthalate, it has a chemical structure and is in the field of ultraviolet absorption, and can be used as it is. The thickness of the film is 5/m to 50/zm, preferably 10/m to 30 // m, which is used as a functional film for the protective film to be bonded to the photoresist side. If the reason is less than 5 // m, the ultraviolet absorption effect is weak. When the temperature exceeds 50 // m, the shape of the photoresist is unstable due to light scattering. Further, in the case of a film interposed between the photomask and the light source, it is 1 〇 // m to 1 m m, preferably 2 5 /z m to 1 0 0 // m. If the reason is less than 1 0 // m, the operation becomes difficult and the ultraviolet absorption effect becomes weak. On the other hand, when it exceeds 1 mm, light of 400 nm or more cannot be transmitted by 80% or more, and the weight of the film becomes heavy and unsuitable. By performing the photoresist pattern exposure treatment using the above-described exposure processing technique of the present invention, even if the photosensitive composition used as the solder resist layer contains a large amount of phthalocyanine blue pigment, it is not affected by the phthalocyanine blue, and can be thick. The film forms a high resolution photo resistive pattern. Hereinafter, a photosensitive composition to be applied to the method for forming a solder resist pattern by exposure treatment using the exposure processing technique of the present invention will be described. The photosensitive composition for use in the method for forming a solder resist pattern of the present invention has a dry film thickness of 45 5 nm and an absorbance of 25 to 0.2 m per film thickness of 0.2 to 1.2, preferably 0.3 to 0.8. The photocurable or photocurable thermosetting resin composition of the developing image may contain (A) a carboxylic acid-containing resin, and (B) an oxime-based photopolymerization containing a structural moiety represented by the general formula (I) -11 - 200837503 Starting agent, an amino acetophenone-based photopolymerization initiator containing a structural moiety represented by the general formula (II), and a mercaptophosphine oxide-based light containing a structural moiety represented by the general formula (III) One or two or more photopolymerization initiators selected from the group consisting of a polymerization initiator and a titanocene-based photopolymerization initiator represented by the general formula (IV), (C) having 2 in the molecule More than one ethylenically unsaturated group compound, (D) thermosetting component, (E) phthalocyanine blue pigment and (F) diethyl thioxanthone, diethylaminobenzophenone and coumarin One or more sensitizers selected from the class. In particular, by appropriately selecting the photopolymerization initiator (B) and the blue pigment (E), the absorbance at a wavelength of 405 nm of the dried coating film can be adjusted to 0.2 to 1.2 per film thickness of 25/m, preferably 0.3 to 0.8. When the absorbance at a wavelength of 405 nm is lower than 0.2 per 25/m, it is not possible to prevent the sensitivity from being lowered. On the other hand, it is difficult to obtain a high-definition pattern when the groove is larger than 1/2. As described above, the exposure of a high-pressure mercury lamp is generally used, and light of a wavelength of 3 65 nm, 405 nm, and 433 nm is used, but the exposure treatment of a film having a specific light absorption property as in the present invention blocks light of 365 nm. The sensitivity is low. However, the photo-sensitizing composition of the specific photopolymerization initiator having an absorbance at a film thickness of 45 μm of 25 // m of 0.2 to 1.2 is used for the individual 4500 nm. The light has a high sensitivity and can impart almost the same sensitivity as a commercially available composition which has been conventionally exposed to composite light of 3 65 nm, 405 nm, and 43 3 nm. Hereinafter, each constituent component will be described in detail. The carboxylic acid-containing resin (A) contained in the photosensitive composition to which the method of the present invention is applied can be used for a resinous -12-200837503 compound which is conventionally used for a carboxyl group in a molecule. Further, the carboxylic acid-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is more preferable from the viewpoint of photocurability and development resistance. Specifically, there are the following resins. (1) A carboxylic acid-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with one or more kinds of unsaturated double bond compounds, and (2) an unsaturated carboxylic acid such as (meth)acrylic acid One or more kinds of copolymers of an acid and an unsaturated double bond compound thereof, and an epoxy group such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate a carboxylic acid-containing photosensitive resin obtained by adding an ethylenically unsaturated group as a pendant group to a compound having an unsaturated double bond, a (meth)acrylic acid chloride or the like, (3) glycidyl (meth)acrylic acid a copolymer of an epoxy group such as an ester and a 3,4-epoxycyclohexylmethyl (meth) acrylate with a compound having an unsaturated double bond and a compound having an unsaturated double bond, and (meth)acrylic acid a carboxylic acid-containing photosensitive resin obtained by reacting an unsaturated carboxylic acid with a secondary hydroxy group and a polybasic acid anhydride, (4) an acid anhydride having an unsaturated double bond such as maleic anhydride, and an unsaturated double Copolymer of bond compound And a carboxylic acid-containing photosensitive resin obtained by reacting a hydroxyl group such as 2-hydroxyethyl (meth) acrylate with an unsaturated double bond compound, and (5) unsaturated polyfunctional epoxy compound and (meth)acrylic acid a single residual acid is reacted to form a carboxylic acid-containing photosensitive resin obtained by reacting a hydroxyl group with a saturated or unsaturated polybasic acid anhydride, a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative, and saturated or unsaturated. After the polybasic acid anhydride is reacted, the resulting carboxylic acid is reacted with a compound having an epoxy group and an unsaturated double bond in one molecule to obtain a hydroxyl group-containing carboxylic acid-containing photosensitive resin, (7) a polyfunctional epoxy compound and (a) a compound having one reactive group other than an unsaturated monocarboxylic acid such as acrylic acid and at least one alcoholic hydroxyl group in one molecule and an alcoholic hydroxyl group reactive with an epoxy group (eg, dimethylolpropionic acid, etc.) a carboxylic acid-containing photosensitive resin obtained by reacting a reaction product with a saturated or unsaturated polybasic acid anhydride, (8) a polyfunctional oxetane compound having at least two oxetane rings in one molecule With (methyl) a carboxylic acid-containing photosensitive resin obtained by reacting an unsaturated monocarboxylic acid such as acrylic acid, a first-stage hydroxyl group in the obtained modified oxetane resin, and a saturated or unsaturated polybasic acid anhydride, and (9) polyfunctional An epoxy resin (for example, a cresol type epoxy resin or the like) is reacted with an unsaturated monocarboxylic acid (for example, (meth)acrylic acid) to be reacted with a polybasic acid anhydride (for example, tetrahydrophthalic anhydride or the like). The carboxylic acid-containing photosensitive resin is further obtained by reacting a compound having one oxirane ring and one or more ethylenically unsaturated groups (for example, glycidyl (meth) acrylate) in the molecule. The carboxylic acid-containing photosensitive resin or the like is not limited thereto. The carboxylic acid-containing photosensitive resin of the above (2), (5), (7), and (9), particularly the carboxylic acid-containing photosensitive resin of the above (9), is photocurable. 'The surface of the hardened coating film is better. Further, in the present specification, (meth) acrylate is a general term for acrylate, methyl-14-200837503 acrylate, and the like, and other similar expressions are also available. As described above, the carboxylic acid-containing resin (A) has a large amount of free carboxyl groups in the backbone/polymer side chain, so that it can be imaged through a dilute aqueous alkali solution. Further, the acid value of the carboxylic acid-containing resin (A) is in the range of 40 to 200 mgKOH/g, preferably 45 to 120 mgKOH/g. When the acid value of the carboxylic acid-containing resin is less than 40 mgKOH/g, the alkali development becomes difficult. On the other hand, when it exceeds 200 mgKOH/g, it is necessary to dissolve it by the exposure portion of the developing liquid, and it is necessary to use fine lines or more depending on the situation. When the exposed portion and the unexposed portion are indistinguishable, and the developing solution is dissolved and peeled off, the drawing of the normal photoresist pattern becomes difficult, which is not preferable. Further, the weight average molecular weight of the carboxylic acid-containing resin (A) varies depending on the resin skeleton, and is usually from 2,000 to 150,000, preferably from 5,000 to 1,000,000. When the weight average molecular weight is less than 2,0 0, the non-stick property is poor, and the moisture resistance of the coating film after exposure is poor, and film thinning occurs at the time of development, and the resolution is largely deteriorated. On the other hand, when the weight average molecular weight exceeds 1,500,000, the developability is remarkably deteriorated, and the storage stability is poor. The amount of the carboxylic acid-containing resin (A) to be used is, in the total composition, 20 to 60% by mass, preferably 30 to 50% by mass. When it is less than the above range, it is not preferable because the film strength is lowered. On the other hand, when it is more than the above range, the viscosity is high, and the coatability and the like are lowered, which is not preferable. The photopolymerization initiator (B) contained in the photosensitive composition used in the present invention contains a benzophenone type, an acetophenone type, an amino acetophenone type, a benzoin ether type, and a benzyl group. a conventionally used radical photopolymerization initiator such as a ketal system, a mercaptophosphine oxide system, an oxime ether system, an oxime ester system or a titanocene system, but the -15-200837503 contains the following general formula (I) The oxime ester photopolymerization initiator of the structural moiety shown, the aminoacetophenone photopolymerization initiator containing the structural moiety represented by the following general formula (π), and the following general formula (111) One or more selected from the group consisting of a mercaptophosphine oxide photopolymerization initiator of the structural moiety and a titanocene photopolymerization initiator represented by the following general formula (IV) It is better. [Chemical 1]

式中,R1爲氫原子、苯基(以碳數1〜6之烷基、苯 基或鹵原子取代亦可)、碳數1〜20之院基(可以1個以 上羥基取代,烷基鏈中間可有1個以上之氧原子)、碳數 5〜8之環烷基、碳數2〜20之烷醇基或苯醯基(碳數爲 可以1〜6之烷基或苯基取代)。R2爲苯基(以碳數1〜6 之烷基、苯基或鹵原子取代亦可)、碳數1〜20之烷基( 可以1個以上羥基取代,烷基鏈中間可有1個以上之氧原 子)、碳數5〜8之環烷基、碳數2〜20之烷醇基或苯醯 基(碳數爲可以1〜6之烷基或苯基取代)。R3、R4爲各 自獨立,表示碳數1〜12之烷基或芳基烷基,R5、R6爲 各自獨立,表示氫原子、或碳數1〜6之院基’或可2個 200837503 鍵結形成環狀垸基。R7、R8爲各自獨立,表示碳數1〜6 之烷基、環己基、環戊基、芳基,或鹵原子,烷基或以烷 氧基所取代之芳基,或碳數1〜20之羰基(但,除兩者爲 碳數1〜20之羰基之情形以外)。R9、R1G爲各自獨立, 表示鹵原子、芳基、鹵化芳基、含雜環之鹵化芳基。 該含一般式(I)所示之構造部分之肟酯系光聚合起 始劑方面,有1,2 —辛烷二酮一 1—〔4一(苯基硫)—2-/ (〇—苯醯基肟)〕、乙酮一1— 〔9 —乙基一 6 — (2—甲 基本釀基)一 9H—味哇一 3-基〕—1— (〇 —乙釀聘)、 下述式(1-1)所示之化合物、2—(乙醯氧基亞胺甲基) 硫二苯並喃一 9 一酮,及下述一般式(1-2)所示之化合物 等。 [化2]In the formula, R1 is a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or a group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, and an alkyl chain There may be one or more oxygen atoms in the middle), a cycloalkyl group having 5 to 8 carbon atoms, an alkanol group having 2 to 20 carbon atoms or a phenylhydrazine group (the number of carbon atoms may be 1 to 6 or substituted by a phenyl group) . R2 is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom) or an alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, and one or more alkyl chains may be present in the middle). The oxygen atom), a cycloalkyl group having 5 to 8 carbon atoms, an alkylol group having 2 to 20 carbon atoms or a phenylhydrazine group (having a carbon number of 1 to 6 or a phenyl group). R3 and R4 are each independently, and represent an alkyl group or an arylalkyl group having 1 to 12 carbon atoms, and R5 and R6 are each independently represented by a hydrogen atom or a hospital group having a carbon number of 1 to 6 or 2 may be bonded to 200837503. A cyclic sulfhydryl group is formed. R7 and R8 are each independently and represent an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or a halogen atom, an alkyl group or an aryl group substituted with an alkoxy group, or a carbon number of 1 to 20 A carbonyl group (except that in the case where the two are a carbonyl group having 1 to 20 carbon atoms). R9 and R1G are each independently and represent a halogen atom, an aryl group, a halogenated aryl group, and a halogenated aryl group having a hetero ring. In the aspect of the oxime ester photopolymerization initiator containing the structural moiety represented by the general formula (I), there are 1,2-octanedione-1-[4-(phenylthio)-2-(( Phenylhydrazinium)], Ethylketone-1 - [9-Ethyl-6-(2-methyl-branched)- 9H------------------------ The compound represented by the formula (1-1), 2-(ethenoxyiminomethyl)thiodibenzofuran-9-one, and the compound represented by the following general formula (1-2). [Chemical 2]

[化3][Chemical 3]

式(1-2)中,R11爲與一般式(I)中R1同義,R -17- 200837503 及R14爲各自獨立,與一般式(I)中R2同義。R13爲表 示氫原子、鹵原子、碳數1〜12之烷基、環戊基、環己基 '苯基、爷基、苯醯基、碳數2〜12之院醇基、碳數2〜 12之烷氧基羰基(構成烷氧基之烷基碳數爲2以上時, 烷基可以1個以上羥基所取代,於烷基鏈中間可有1個以 上之氧原子)或苯氧基羧基。 此等之中,上述式(I-1 )所示之化合物,以2 —(乙 醯氧基亞胺甲基)硫二苯並喃一 9 一酮、及一般式(I 一 2 )所示之化合物爲特佳。上述化合物之市售品方面,有 CIba Specialty Chemicals Inc.製之 CGI-3 25、IRGACURE-OXEOl、IRGACURE-OXE02。 含該一般式(II)所示之構造部分的胺基苯乙酮系光 聚合起始劑方面,有2—甲基一 1 一〔4一(甲基硫)苯基 〕一2-嗎啉基丙烷一 1酮、2-苄基一 2 —二甲基胺基一 1 一(4一嗎啉基苯基)一丁烷—1 一酮、2-(二甲基胺基 )—2— 〔 (4 —甲基苯基)甲基〕一 1— 〔4— (4 —嗎啉 基)苯基〕—1— 丁酮、N,N —二甲基胺基苯乙酮等。市 售品方面,有 CIba Specialty Chemicals Inc.製 IRGACURE-907、IRGACURE-3 69、IRGACURE-3 79 等。 含該一般式(III)所示之構造部分之醯基膦氧化物 系光聚合起始劑方面,有2,4,6-三甲基苯醯基二苯基膦 氧化物、雙(2,4,6 —三甲基苯醯基)一苯基膦氧化物、 雙(2,6—二甲氧基苯醯基)一 2,4,4 —三甲基—戊基膦氧 化物等。市售品方面,有 BASF公司製之 LucIrlnTPO, -18 - 200837503 CIba Specialty Chemicals Inc·製之 IRGACURE-819 寺 該一般式(IV)所示之二茂紘系光聚合起始劑方 有雙(/75— 2,4 —環戊二烯—1—基)一雙(2,6 —二 3 - ( 1Η —吡咯一 1 一基)—苯基)鈦。市售品方面 CIba Specialty Chemicals Inc.製之 IRGACURE-784 等 此般光聚合起始劑(B )之搭配率,相對於該含 樹脂(A ) 100質量份,爲0.01〜30質量份,較佳爲 〜1 5質量份之比例。光聚合起始劑(B )之搭配率, 該含羧酸樹脂(A) 10 0質量份爲未滿0.0 1質量份則 上之光硬化性不足,塗膜會剝離,耐藥品性等塗膜特 低,故不宜。另一方面,光聚合起始劑(B )之搭配 相對該含羧酸樹脂(A ) 1 00質量份,超過3 0質量份 光聚合起始劑(B )之光吸收,深部硬化性降低而不:^ 又,爲該式(I-1 )所示之肟酯系光聚合起始劑 其搭配率,相對於該含羧酸樹脂(A ) 1 00質量份, 爲0.01〜20質量份,更佳爲〇.〇1〜5質量份之比例 用此般肟酯系光聚合起始劑時,在與銅箔之界面與銅 反應,因作爲光聚合起始劑之功能有失活之情形,故 該S女基本乙醒系光聚合起始劑等併用爲佳。 本發明中所用之感光性組成物可含有之於分子中 個以上乙烯性不飽和基之化合物(c )係經紫外線照 光硬化,使該含羧酸樹脂(A )不溶於鹼水溶液或幫 不溶化者。此般化合物方面,有乙二醇、甲氧基四乙 、聚乙二醇、丙二醇等乙二醇之二丙烯酸酯類;己二 面, 氟一 ,有 〇 羧酸 0.5 相對 在銅 性降 率, 則因 [° 時, 較佳 。使 原子 以與 有2 射而 助其 二醇 醇、 -19- 200837503 三羥甲基丙烷、季戊四醇、二季戊四醇、三一羥基乙基異 氰脲酸酯等多價醇或此等之乙烯氧化物加成物或丙烯氧化 物加成物等多價丙烯酸酯類;苯氧基丙烯酸酯、雙酚A二 丙烯酸酯,及此等之酚類之乙烯氧化物加成物或丙烯氧化 物加成物等多價丙烯酸酯類;甘油二縮水甘油基醚、甘油 三縮水甘油基醚、三羥甲基丙烷三縮水甘油基醚、三縮水 甘油基異氰脲酸酯等縮水甘油基醚之多價丙烯酸酯類;及 三聚氰胺丙烯酸酯,及/或對應上述丙烯酸酯之各甲基丙 烯酸酯類等。 另外,有甲酚醛型環氧樹脂等多官能環氧樹脂與丙烯 酸反應之環氧丙烯酸酯樹脂及進一步其環氧丙烯酸酯樹脂 之羥基與季戊四醇三丙烯酸酯等羥基丙烯酸酯及異佛爾酮 二異氰酸酯等二異氰酸酯之半尿烷化合物反應之環氧尿烷 丙烯酸酯化合物等。此般環氧丙烯酸酯系樹脂,不降低指 觸乾燥性,可提升光硬化性。 此般於分子中有2個以上乙烯性不飽和基之化合物( C )之搭配率,相對於該含羧酸樹脂(A ) 1 00質量份,較 佳爲5〜100質量份,更佳爲1〜70質量份之比例。該搭 配率未滿5質量份時,光硬化性降低,藉由紫外線照射後 之鹼顯像,圖型形成變困難,故不宜。另一方面,超過 1 〇〇質量份時,對鹼水溶液之溶解性降低,塗膜變脆,故 不宜。 本發明所用之熱硬化性成分(D )方面,可使用三聚 氰胺樹脂、苯並鳥糞胺樹脂等胺基樹脂、嵌段異氰酸酯化 -20- 200837503 合物、環碳酸酯化合物、多官能環氧化合物、多官能氧雜 環丁烷化合物、環氧硫化物樹脂等公知慣用之熱硬化性樹 脂。此等之中,以多官能環氧化合物(D-1 )、多官能氧 雜環丁烷化合物(D-2 )、環氧硫化物樹脂等於分子中有 2個以上環狀醚基及/或環狀硫醚基之熱硬化性成分(以 下,略稱爲環狀(硫)醚化合物)係特別佳。 該多官能性環氧化合物(D-1 )方面,如,JaPan Epoxy Resins Co.,Ltd.製之 EPIKOTE828,EPIKOTE83 4, EPIKOTE1001,EPIKOTE1004,大日本油墨化學工業公司 製之 EPICLON840 、 EPICLON8 5 0 、 EPICLON 1 05 0 、 EPICLON2055,東都化成公司製之 E POTOHTOYD-Oll、 YD-013、YD-127、YD-128,The Dow Chemical Company 製之 D.E.R.317、D.E.R.331、D.E.R.661、D.E.R.664、 CIba Specialty Chemicals Inc.之 Araldlte607 1 、In the formula (1-2), R11 is synonymous with R1 in the general formula (I), and R-17-200837503 and R14 are each independently and synonymous with R2 in the general formula (I). R13 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl 'phenyl group, a aryl group, a benzoyl group, a carbon number of 2 to 12, and a carbon number of 2 to 12 The alkoxycarbonyl group (when the alkyl group number of the alkoxy group is 2 or more, the alkyl group may be substituted by one or more hydroxyl groups, and one or more oxygen atoms may be contained in the middle of the alkyl chain) or a phenoxycarboxy group. Among these, the compound represented by the above formula (I-1) is represented by 2-(ethoxyindoliminemethyl)thiodibenzofuran-9-one, and the general formula (I-2) The compound is particularly good. Commercially available products of the above compounds include CGI-3 25, IRGACURE-OXEO1, and IRGACURE-OXE02 manufactured by CIba Specialty Chemicals Inc. In the aspect of the aminoacetophenone-based photopolymerization initiator containing the structural moiety represented by the general formula (II), 2-methyl-l-[4-(methylthio)phenyl]-2-morpholine Propane- 1 ketone, 2-benzyl- 2,2-dimethylamino-1 - (4-morpholinophenyl)-butane- 1 ketone, 2-(dimethylamino)-2 [(4-Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone and the like. Commercially available, IRGACURE-907, IRGACURE-3 69, IRGACURE-3 79, etc., manufactured by CIba Specialty Chemicals Inc. The mercaptophosphine oxide photopolymerization initiator containing the structural moiety represented by the general formula (III) has 2,4,6-trimethylphenylnonyldiphenylphosphine oxide and bis (2, 4,6-trimethylphenylhydrazino)-phenylphosphine oxide, bis(2,6-dimethoxyphenylhydrazine)-2,4,4-trimethyl-pentylphosphine oxide, and the like. For commercial products, there are LucIrlnTPO manufactured by BASF Corporation, -18 - 200837503 IRGACURE-819 Temple manufactured by CIba Specialty Chemicals Inc. The diruthenium photopolymerization initiator represented by the general formula (IV) has a double (/ 75-2,4-cyclopentadienyl-l-yl)-double (2,6-di- 3 -(1Η-pyrrole-l-yl)-phenyl)titanium. The collocation ratio of the photopolymerization initiator (B), such as IRGACURE-784 manufactured by CIba Specialty Chemicals Inc., is 0.01 to 30 parts by mass, preferably 0.01 to 30 parts by mass, based on 100 parts by mass of the resin (A). For a ratio of ~15 parts by mass. When the carboxylic acid-containing resin (A) is used in an amount of less than 0.01 part by mass, the photocuring property of the carboxylic acid-containing resin (A) is insufficient, and the coating film is peeled off, and the coating film is resistant to chemicals. Very low, so it is not appropriate. On the other hand, the photopolymerization initiator (B) is more than 100 parts by mass of the carboxylic acid-containing resin (A), and more than 30 parts by mass of the photopolymerization initiator (B) absorbs light, and the deep hardenability is lowered. The ratio of the oxime ester photopolymerization initiator represented by the formula (I-1) is 0.01 to 20 parts by mass based on 100 parts by mass of the carboxylic acid-containing resin (A). More preferably, the ratio of 1 to 5 parts by mass of the oxime ester-based photopolymerization initiator is reacted with copper at the interface with the copper foil, and the function as a photopolymerization initiator is deactivated. Therefore, it is preferred that the S female basic wake-up photopolymerization initiator is used together. The photosensitive composition used in the present invention may contain the compound (c) having more than one ethylenically unsaturated group in the molecule, which is cured by ultraviolet light, so that the carboxylic acid-containing resin (A) is insoluble in an aqueous alkali solution or insoluble. . In terms of such compounds, there are ethylene glycol diacrylates such as ethylene glycol, methoxytetraethylene, polyethylene glycol, and propylene glycol; and two-sided, fluorine-containing, ruthenium carboxylic acid 0.5 relative copper reduction rate. , because [°, it is better. a polyvalent alcohol such as a diol, a -19-200837503 trimethylolpropane, pentaerythritol, dipentaerythritol, trishydroxyethyl isocyanurate or the like, or an ethylene oxide thereof a polyvalent acrylate such as an adduct or a propylene oxide adduct; a phenoxy acrylate, a bisphenol A diacrylate, and an ethylene oxide adduct or a propylene oxide adduct of the phenols Multivalent acrylates such as polyvalent acrylates; glycidyl ethers such as glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc. An ester; and a melamine acrylate, and/or a methacrylate corresponding to the above acrylate. Further, an epoxy acrylate resin having a polyfunctional epoxy resin such as a cresol novolac epoxy resin and acrylic acid, and a hydroxyl group such as an epoxy acrylate resin and a hydroxy acrylate such as pentaerythritol triacrylate and isophorone diisocyanate An epoxy urethane acrylate compound or the like which is reacted with a hemiurethane compound of a diisocyanate. Such an epoxy acrylate-based resin can improve photocurability without lowering the dryness of the touch. The collocation ratio of the compound (C) having two or more ethylenically unsaturated groups in the molecule is preferably from 5 to 100 parts by mass, more preferably from 1 to 100 parts by mass, based on the carboxylic acid-containing resin (A). A ratio of 1 to 70 parts by mass. When the blending ratio is less than 5 parts by mass, the photocurability is lowered, and the formation of a pattern by alkali irradiation after ultraviolet irradiation becomes difficult, which is not preferable. On the other hand, when the amount is more than 1 part by mass, the solubility in the aqueous alkali solution is lowered, and the coating film becomes brittle, which is not preferable. In the thermosetting component (D) used in the present invention, an amine-based resin such as a melamine resin or a benzoguanamine resin, a block isocyanate-20-200837503 compound, a cyclic carbonate compound, or a polyfunctional epoxy compound can be used. A known thermosetting resin such as a polyfunctional oxetane compound or an epoxy sulfide resin. Among these, the polyfunctional epoxy compound (D-1), the polyfunctional oxetane compound (D-2), and the epoxy sulfide resin have two or more cyclic ether groups in the molecule and/or The thermosetting component of the cyclic thioether group (hereinafter, abbreviated as a cyclic (thio)ether compound) is particularly preferable. In terms of the polyfunctional epoxy compound (D-1), for example, EPIKOTE 828, EPIKOTE 83 4, EPIKOTE 1001, EPIKOTE 1004 manufactured by JaPan Epoxy Resins Co., Ltd., EPICLON 840, EPICLON 8 5 0, EPICLON manufactured by Dainippon Ink and Chemicals Co., Ltd. 1 05 0 , EPICLON 2055, E POTOHTOYD-Oll, YD-013, YD-127, YD-128, manufactured by Dongdu Chemical Co., Ltd., DER317, DER331, DER661, DER664, CIba Specialty Chemicals Inc, manufactured by The Dow Chemical Company .Araldlte607 1 ,

Araldlte6084、AraldIteGY250、AraldIteGY260,住友化 學工業公司製之 Sumi-Epoxy ESA-011、ESA-014、ELA-115、ELA-128,旭化成工業公司製之 A.E.R.3 3 0、 A.E.R.331、A.E.R.661、A.E.R.664 等(皆商品名)之雙 酉分A型環氧樹脂;Japan Epoxy Resins Co.,Ltd.製之 EPIKOTEYL903 ,大曰本油墨化學工業公司製之 EPICLON152 、 EPIC L ON 1 6 5 , 東都化成公司製之 EPOTOHTOYDB-400、YDB-5 00,The Dow Chemical Company 製之 D.E.R.542,CIba Specialty Chemicals Inc. 製之 Araldlte8011,住友化學工業公司製之 Sumi-Epoxy -21 - 200837503 ESB-400、ESB-700,旭化成工業公司製之A.E.R·711、 A.E.R.714等(皆商品名)之溴化環氧樹脂;JaPan ΕΡοχΥ Resins Co·,Ltd·製之 EPIKOTE152、EPIKOTE154,The Dow Chemical Company 製之 D.E.N.431、D.E.N.43 8 ’ 大 曰本油墨化學工業公司製之EPICLONN-73 0、EPICLONN-770、EPICLONN-865,東都化成公司製之 EPOTOHTOYDCN-701、YDCN-704,CIba Specialty Chemicals Inc.製之 A r a 1 d 11 e E C N 1 2 3 5、A r a 1 d 11 e E C N 1 2 7 3 、AraldIteECN 1 299、AraldIteXPY3 07,曰本化藥公司製 之 EPPN-201、EOCN- 1 025、EOCN- 1 020、EOCN-104S、 RE-3 06,住友化學工業公司製之 Sumi-Epoxy ESCN-195X 、ESCN-220,旭化成工業公司製之 A.E.R.ECN-23 5、 ECN-299等(皆商品名)之酚醛清漆型環氧樹脂;大日本 油墨化學工業公司製之 EPICLON 83 0,Japan Epoxy Resins Co.,Ltd·製EPIKOTE807,東都化成公司製之 EPOTOHTO YDF-1 70、YDF-1 75、YDF-2004,CIba Specialty Chemicals Inc.製之 AraldIteXPY3 06 等(皆商品 名)之雙酚F型環氧樹脂;東都化成公司製之 EPOTOHTOST-2004、ST-2007、ST-3 000 (商品名)等氫 化雙酣 A 型 3¾¾ 樹脂;Japan Epoxy Resins Co.,Ltd·製之 EPIKOTE604,東都化成公司製之 EPOTOHTOYH-434, CIba Specialty Chemicals Inc.製之 AraldIteMY720,住友 化學工業公司製之Sumi-Epoxy ELM-120等(皆商品名) 縮水甘油基胺型環氧樹脂;CIba Specialty Chemicals Inc. -22- 200837503 製之Aral dlteC Υ-3 5 0 (商品名)等乙內醯脲型環氧樹脂; DAICEL CHEMICAL INDUSTRIES,LTD.製之 CELLOXIDE202 1, CIba Specialty Chemicals Inc·製之 AraldIteCY175,CY179等(皆商品名)脂環式環氧樹脂 ;Japan Epoxy Resins Co·,L t d ·製之 Y L - 9 3 3,T h e D o w Chemical Company 製之 T.E.N.、EPPN-501、EPPN-5 02 等 (皆商品名)三經基苯基甲院型環氧樹脂;Japan Epoxy Resins Co.,Ltd·製之 YL-605 6、YX-4000、YL-6121 (皆 商品名)等雙二甲苯酚型或雙酚型環氧樹脂或彼等之混合 物;日本化藥公司製EBPS-200,旭電化工業公司製EPX-30,大日本油墨化學工業公司製之EXA-15 14 (商品名) 等雙酚S型環氧樹脂;Japan Epoxy Resins Co.,Ltd.製之 EPIKOTE157S (商品名)等雙酚A酚醛清漆型環氧樹脂; Japan Epoxy Resins Co.,Ltd.製之 EPIKOTEYL-931,CIba Specialty Chemicals Inc.製之 Araldltel63 等(皆商品名 )tetraphenylolethane 型環氧樹脂;CIba Specialty Chemicals Inc.製之 AraldItePT810,日產化學工業公司製 之TEPIC等(皆商品名)雜環式環氧樹脂;日本油脂公 司製Bremmer DGT等二縮水甘油基鄰苯二甲酸酯樹脂; 東都化成公司製ZX- 1 063等四縮水甘油基xylenoyl乙烷 樹脂;新日鐵化學公司製 ESN-190、ESN-3 60,大日本油 墨化學工業公司製 HP-403 2、EXA-4750、EXA-4700等含 萘基環氧樹脂;大日本油墨化學工業公司製HP-7200、 HP-7200H等具二環戊二烯骨架之環氧樹脂;日本油脂公 -23- 200837503 司製CP-50S、CP-5 0M等縮水甘油基甲基丙烯酸酯共聚合 系環氧樹脂;環己基馬來酸酐縮亞胺與縮水甘油基甲基丙 烯酸酯之共聚合環氧樹脂;環氧改性之聚丁二烯橡膠衍生 物(如,DAICEL CHEMICAL INDUSTRIES, LTD·製 PB-3 600等),CTBN改性環氧樹脂(如,東都化成公司製之 YR-102,YR-450等)等,但並不限於此等。此等之環氧 樹脂可單獨或2種以上組合使用。此等之中,特別以酚醛 清漆型環氧樹脂、雜環式環氧樹脂、雙酚A型環氧樹脂或 彼等之混合物爲佳。 該多官能氧雜環丁烷化合物(D-2 )方面,有雙〔(3 —甲基一 3—氧雜環丁烷基甲氧基)甲基〕醚、雙〔(3 — 乙基一 3—氧雜環丁烷基甲氧基)甲基〕醚、1,4 一雙〔( 3 —甲基一 3 —氧雜環丁烷基甲氧基)甲基〕苯、1,4 一雙 〔(3 —乙基一 3 —氧雜環丁烷基甲氧基)甲基〕苯、(3 一甲基一 3—氧雜環丁烷基)甲基丙烯酸酯、(3—乙基— 3 —氧雜環丁烷基)甲基丙烯酸酯、(3 -甲基一 3 -氧雜 環丁烷基)甲基甲基丙烯酸酯、(3 —乙基一 3—氧雜環丁 烷基)甲基甲基丙烯酸及彼等之寡聚物或共聚合物等多官 能氧雜環丁烷類以外,尙有氧雜環丁烷與酚醛清漆樹脂、 聚(P —羥基苯乙烯)、cardo type雙酚類、杯芳烴類、 CALIXRESORCINARENE類,或與矽倍半氧烷等具羥基之 樹脂之醚化物等。其他,亦有具有氧雜環丁烷環之不飽和 單體與烷基(甲基)丙烯酸酯之共聚合物等。 於該分子中有2個以上環狀硫醚基之化合物方面,如 -24- 200837503 ,Japan Epoxy Resins Co.,Ltd.製之雙酸A型環氧硫化物 樹脂YL7000等。又,使用同樣合成方法,亦可用將酚醛 清漆型環氧樹脂之環氧基的氧原子取代爲硫原子之環氧硫 化物樹脂等。 此般環狀(硫)醚化合物之搭配率’相對於該含乙烯 性不飽和基之含羧酸樹脂的羧基1當量’環狀(硫)醚基 爲0.6〜3.0當量,較佳爲0.8〜2.5當量之範圍。環狀( 硫)醚化合物之搭配量,較上述範圍少時,羧基殘留、耐 熱性、耐鹼性、電絕緣性等降低,故不宜。另一方面,超 過上述範圍時,因殘留低分子量環狀(硫)醚基,塗膜強 度等降低,故不宜。 使用上述環狀(硫)醚化合物時,以含有熱硬化觸媒 爲佳。該等熱硬化觸媒方面,如,咪唑、2-甲基咪唑、2 —乙基咪唑、2—乙基一 4 —甲基咪唑、2 —苯基咪唑、4 — 苯基咪唑、1 一氰基乙基一 2-苯基咪唑、1 一(2 -氰基乙 基)一 2-乙基一 4 一甲基咪唑等咪唑衍生物;二氰基二醯 胺、苄基二甲基胺、4—(二甲基胺基)一 N,N —二甲基 苄基胺、4 —甲氧基一 N,N—二甲基苄基胺、4 —甲基一 N,N—二甲基苄基胺等胺化合物、己二酸肼、癸二酸肼等 聯氨化合物;三苯基膦等磷化合物等,市售者方面,如, 四國化成工業公司製之 2MZ-A、2MZ-0K、2PHZ、 2P4BHZ、2P4MHZ (皆爲咪唑系化合物商品名),SAN-APRO Ltd·製之 U-CAT3503N、U-CAT3502T (皆二甲基胺 嵌段異氰酸酯化合物之商品名)、DBU、DBN、U- -25- 200837503 CATSA102、U-CAT5 0 02 (皆二環式脉化合物及其鹽)等 。特別不限於此等,可爲環氧樹脂及氧雜環丁烷化合物之 熱硬化觸媒,或促進環氧基及/或氧雜環丁烷基與羧基反 應者皆可,可單獨或2種以上混合使用。又,亦可使用有 密著性賦予劑機能之鳥糞胺、乙醯基鳥糞胺、苯並鳥糞胺 、二聚氰胺、2,4一二胺基一 6 -甲基丙嫌酸氧乙基一 S-三嗪、2 —乙烯一4,6 —二胺基一 S —三嗪、2 —乙烯一 4,6 —二胺基—S-三嗪•氰尿酸加成物、2,4 一二胺基—6_ 甲基丙烯醯氧乙基一 S-三嗪•氰尿酸加成物等S-三嗪 衍生物,較佳爲將此等有密著性賦予劑機能化合物與該熱 硬化觸媒倂用。 熱硬化觸媒之搭配率爲通常使用之比例即可,如,相 對於含羧酸樹脂(A )或熱硬化性成分(D ) 1 0 0質量份, 可使用0.1〜20質量份,較佳爲〇·5〜15.0質量份之比例 〇 本發明之光阻圖型形成方法所用之感光性組成物中含 酞菁藍系顏料(E )係重要的。本發明者們發現對於 405 nm單獨之光,添加酞菁藍系顏料(E)者,可以較低 曝光量得到光澤感度。此酞菁藍系顏料之增感效果理由仍 未明瞭,如,於每膜厚25 // m吸光度未滿0.2之樹脂組成 物中,添加酞菁藍,僅使吸光度在0 · 2以上即可以低曝光 量同時得到充分之表面硬化性與硬化深度。又,此增感效 果有改善表面反應性(光澤改善),而硬化深度反而變差 。也就是,進行反射曝光光的運作。此運作有安定光阻形 -26- 200837503 狀之效果。 如’看到光阻圖型斷面形狀時,不含酞菁藍,吸光度 比0.2低時,光阻斷面形狀爲底部大且廣之形狀,而塗膜 表面部爲亦無光澤之狀況。又,不含酞菁藍,吸光度超過 1 · 2時’有表層部大且廣底部爲細之狀況。但,吸光度於 0·2〜1.2之範圍內,含上述光聚合起始齊彳(b),及鈦菁 染料系顏料(Ε )時,光阻膜厚在5〜1 00 // m之範圍內, 發現可得到具有與光罩負尺寸幾乎相同之尺寸的底部之光 阻形狀且可得到表面光澤。 此般鈦菁染料系顏料(E )之合適之添加量爲可在使 乾燥塗膜405nm波長時,吸光度在每25//m,0.2〜1.2範 圍內任意添加,如,相對含羧酸樹脂(A ) 1 00質量份, 可在〇 . 0 1〜5質量份之範圍添加。 鈦菁染料系顏料(E )方面,有α型銅鈦菁染料•藍 、α型單氯代銅鈦菁染料•藍、/5型銅鈦菁染料•藍、ε 型銅鈦菁染料•藍、鈷鈦菁染料•藍、無金屬鈦菁染料· 藍等。 本發明中所適用之感光性組成物除上述光聚合起始劑 以外,亦可含其他之光聚合起始劑、光起始助劑及增感劑 ,如,苯偶因化合物、乙醯苯化合物、蒽醌化合物、噻噸 酮化合物、縮酮化合物、二苯甲酮化合物、咕噸酮化合物 ,及3級胺化合物等。 苯偶因化合物具體例,如,苯偶因、苯偶因甲基醚、 苯偶因乙基醚、苯偶因異丙基醚。 -27- 200837503 乙醯苯化合物之具體例,如,乙醯苯、2,2—二甲氧 基一2 —苯基乙醯苯、2,2-二乙氧基—2 —苯基乙醯苯、 1,1 —二氯乙醯苯。 蒽醌化合物具體例,如,2 —甲基蒽醌、2 -乙基蒽醌 、2— t — 丁基蒽驅、1—氯蒽醌。 噻噸酮化合物之具體例,如,2,4 一二甲基噻噸酮、 2,4 一二乙基噻噸酮、2 -氯噻噸酮、2,4 一二異丙基噻噸 酮。 縮酮化合物之具體例,如,乙醯苯二甲基縮酮、苄基 二甲基縮酮。 二苯甲酮化合物之具體例,如,二苯甲酮、4 一苯醯 基二苯基硫化物、4一苯醯基一 4’一甲基二苯基硫化物、4 一苯醯基一 4’ 一乙基二苯基硫化物、4一苯醯基一 4’ 一丙 基二苯基硫化物。 3級胺化合物之具體例,如,乙醇胺化合物、有二烷 基胺基苯構造之化合物,如,4,4’ -二甲基胺基二苯甲酮 (曰本曹達公司製 NISSO CURE-MABP ) 、4,4,一二乙基 胺基二苯甲酮(HODOGAYA化學公司製EAB)等二烷基 胺基二苯甲酮I、7—( 一乙基胺基)—4 —甲基一 2H— 1 -苯並吡喃一 2—酮、7— (二乙基胺基)一 4 —甲基香豆素 )等含二烷基胺基香豆素化合物、4 -二甲基胺基安息香 酸乙酯(日本化藥公司製 Kayacure-EPA) 、2 —二甲基 胺基安息香酸乙酯(International Bio-Synthetics公司製 Quantacure DMB)、4 —二甲基胺基安息香酸(n — 丁氧基 -28- 200837503 )乙酯(International Bio-Synthetics 公司製 Quantacure BE A)、p —二甲基胺基安息香酸異戊基乙基酯(曰本化藥 公司製 Kayacure -DMBI) 、4—二甲基胺基安息香酸2 — 乙基己酯(Van Dyk公司製Esolol 5 07 ) 、4,4’一二乙基 胺基二苯甲酮(HODOGAYA化學公司製EAB )。 上述中,以噻噸酮化合物及3級胺化合物爲佳。本發 明組成物中,由深部硬化性觀點來看以含噻噸酮化合物爲 佳,其中,以2,4 —二甲基噻噸酮、2,4 —二乙基噻噸酮、 2 -氯噻噸酮、2,4 -二異丙基噻噸酮等噻噸酮化合物爲佳 此般噻噸酮化合物搭配率方面,對於上述含羧酸樹脂 (A) 100質量份,較佳爲20質量份以下,更佳爲10質 量份以下之比例。噻噸酮化合物搭配量過多則厚膜硬化性 降低,涉及製品造價提高,故不宜。 3級胺化合物方面,以具二烷基胺基苯構造之化合物 爲佳,其中,以二烷基胺基二苯甲酮化合物,最大吸收波 長在3 5 0〜410nm之含二烷基胺基香豆素化合物爲特別佳 。二烷基胺基二苯甲酮化合物方面,4,4’ -二乙基胺基二 苯甲酮因毒性亦低而佳。最大吸收波長在3 5 0〜4 1 Onm之 含二烷基胺基香豆素化合物,因最大吸收波長在紫外線區 域,不僅可提供著色少,無色透明之感光性組成物,且提 供使用著色顏料,反應著色顏料本身顏色之著色抗焊阻劑 膜。特別是7 —(二乙基胺基)一 4 —甲基一2H - 1 一苯並 吡喃—2-酮係對波長 400〜410nm雷射光有優異增感效 -29- 200837503 果,故佳。 此般3級胺化合物之搭配率方面,相對上述含羧酸樹 脂(A) 100質量份,較佳爲0.1〜20質量份,更佳爲0.1 〜1 〇質量份之比例。3級胺化合物搭配量未滿0 . 1質量份 則有無法獲得充分之增感效果之傾向。超過2 0質量份, 則因3級胺化合物在乾燥抗焊阻劑塗膜表面之光吸收變強 ,有降低深部硬化性傾向。 此等之光聚合起始劑、光起始助劑及增感劑可以單獨 或2種類以上混合物使用。 此般光聚合起始劑、光起始助劑,及增感劑總量,相 對該含羧酸樹脂(A ) 1 0 0質量份,以3 5質量份以下範圍 爲佳。超過3 5質量份,則有因此等之光吸收而降低深部 硬化性之傾向。 本發明中可用之感光性組成物中,爲提升塗膜之物理 強度等,依必要,可搭配塡充料。此般塡充料方面,可使 用公知慣用之無機或有機塡充料,但特別以使用硫酸鋇, 球狀二氧化矽及滑石爲佳。另外,亦可使用在前述之於分 子中有2個以上乙烯性不飽和基之化合物(C )及該多官 能環氧樹脂(D-1)中分散奈米二氧化矽之Hanse-Chemie 公司製之 NANOCRYL(商品名)χρ 〇396、XP 0596、XP 0733 、 XP 0746 、 XP 0765 、 XP 0768 、 XP 0953 、 XP 0954 、XP 1045 (皆爲製品等級名)及,Hanse-Chemie公司製 之 NANOPOX(茼品名)χρ 〇516、χρ 〇525、XP 0314( 皆爲製品等級名)。此等可單獨或2種以上搭配使用。 -30- 200837503 此等塡充料之搭配率,相對於該含羧酸樹脂(A ) 100質量份,以300質量份以下爲佳,較佳爲0.1〜300質 量份,更佳爲0·1〜15〇質量份之比例。該塡充料之搭配 率,超過3 00質量份時,組成物黏度變高而印刷性降低, 硬化物變脆,故不宜。 另外,本發明中可使用之感光性組成物,爲了該含羧 酸樹脂(A )之合成及組成物之調整,或塗佈於基板及載 體薄膜用之黏度調整,可使用有機溶劑。 此般有機溶劑方面,有酮類、芳香族烴類、乙二醇醚 類、乙二醇醚乙酸酯類、酯類、醇類、脂肪族烴、石油系 溶劑等。更具體上,有甲基乙基酮、環己酮等酮類;甲苯 、二甲苯、四甲基苯等芳香族烴類;溶纖劑、甲基溶纖劑 、丁基溶纖劑、卡必醇、甲基卡必醇、丁基卡必醇、丙二 醇單甲基醚、二丙二醇單甲基醚、二丙二醇二乙基醚、三 乙二醇單乙基醚等乙二醇醚類;醋酸乙酯、醋酸丁酯、二 丙二醇甲基醚乙酸酯、丙二醇甲基醚乙酸酯、丙二醇乙基 醚乙酸酯、丙二醇丁基醚乙酸酯等酯類;乙醇、丙醇、乙 二醇、丙二醇等醇類;辛烷、癸烷等脂肪族烴;石油醚、 石油精、氫化石油精、溶劑油等石油系溶劑等。 此般有機溶劑可單獨或以2種以上混合物使用。 又,本發明之感光性組成物在不造成解像性等負面影 響範圍內,可添加藍色顏料以外之著色顏料。 本發明中可使用之感光性組成物,進一步依必要,可 搭配對苯二酚、對苯二酚單甲基醚、t- 丁基兒茶酚、焦 -31 - 200837503 掊酚、吩噻嗪等公知慣用之熱聚合防止劑、微粉二氧化砂 、有機巷土、蒙脫石等公知慣用之增黏劑、砍酮系、氟系 、高分子系等消泡劑及/或調平劑、咪唑系、噻Π坐系、三 唑系等矽烷偶合劑等公知慣用之添加·劑類。 又,在不賦予解像性等負面影響範圍內,可添加酞菁 藍系顏料以外之藍色顏料及藍色顏料以外之著色顏料。 本發明中可使用之感光性組成物,如,以該有機溶劑 調整至適合塗佈方法之黏度,於電路形成基板上,藉由浸 漬塗佈法、流延塗佈法、輥塗佈法、棒塗佈法、網板印刷 法、簾式塗佈法等方法塗佈,在約60〜loot:溫度,藉由 使組成物中所含之有機溶劑揮發乾燥(假乾燥),可形成 不黏塗膜。又,使上述組成物塗佈於載體薄膜上,藉由使 乾燥後捲取爲薄膜之乾薄膜貼合於電路形成基板上,可形 成樹脂絶緣層。之後,介著形成圖型之光罩選擇性地藉由 紫外線曝光,使未曝光部分用稀鹼水溶液(如,0.3〜3 % 碳酸鈉水溶液)顯像形成光阻圖型。另外,含熱硬化性成 分時’如,藉由於約140〜18(TC溫度加熱後熱硬化,該 含殘酸樹脂(A)之羧基與在分子中有2個以上環狀醚基 及/或環狀(硫)醚基之熱硬化性成分(D )反應,可形 成耐熱性、耐藥品性、耐吸濕性、密著性、電特性等諸特 性優異之硬化塗膜。 於上述基板所用之基材方面,有使用以用紙酚、環氧 紙、環氧玻璃布、玻璃聚醯亞胺、玻璃布/環氧不纖布、 玻璃布/環氧紙、環氧合成纖維、氟·聚乙烯· PPO ·氰 -32- 200837503 酸酯等之高周波電路用貼銅層合板等材質者之全 FR-4等)之貼銅層合板、其他聚醯亞胺薄膜、 、玻璃基板、陶瓷基板、晶圓板寺。 本發明中,於塗佈感光性組成物後進行之揮 可使用具備熱風循環式乾燥爐、IR爐、加熱板 烤箱等(使用以蒸氣進行空氣加熱方式之熱源者 機內熱風流向使接觸之方法及藉由噴嘴吹向支持 )進行。 上述紫外線照射所用之曝光機方面,爲產生 曝光裝置即可,其光源方面有高壓水銀燈、超高 、金鹵燈等爲佳。上述曝光裝置方面,如,ORC MANUFACTURING CO·,LTD.製 HMW-680GW Engineering C ο ·,L t d ·製 A D E X 6 0 0 P 等,可使用於 ο 該顯像方法方面,有浸漬塗裝法、shower 噴霧法、手刷法等,顯像液方面,可使用氫氧化 化鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、銨、 氧化錢等驗水溶液。 【實施方式】 [實施例] 以下,以實施例及比較例具體說明本發明 不爲下述實施例所限定。 部等級( PET薄膜 發乾燥爲 、對流式 ,使乾燥 體之方式 紫外線之 壓水銀燈 ,ADTEC 本發明中 method、 鉀、氫氧 四曱基氫 但本發明 -33- 200837503 合成例1 於具備攪拌機、溫度計、迴流冷卻管、滴 導入管之2公升之可拆式燒瓶中,加入甲酣醒 (日本化藥(股)製,EOCN-104S,軟化點 當量= 220g/當量)660g、卡必醇乙酸酯421. 油180.6g,於90°C加熱•攪拌,溶解。接著 6〇°C後,添加丙烯酸216g、三苯基膦4.0g、 酚1.3g,在100°C反應12小時,得到酸價爲 之反應生成物。於此添加四氫苯二甲酸酐2 4 1 至9(TC,進行6小時反應。藉此得到不揮發: %,固形分酸價= 77mgKOH/g,雙鍵當量(每 莫耳之樹脂之g重量)=40 0g/當量,重量平 7,〇〇〇之含羧酸感光性樹脂(A )之溶液。& 羧酸感光性樹脂溶液稱清漆Α。 (感光性組成物No. 1〜10之調製) 使用上述合成例1所得之清漆A,如表1 成分以同一表所示比例(質量份)進行搭配, 行預備混合後,以3輥筒硏磨機混練,調製抗 感光性組成物。在此,使所得之感光性組成物 ERICHSEN公司製GRINDOMETER進行粒度測 一之試料皆在1 5 // m以下。 液漏斗及氮 型環氧樹脂 92°C,環氧 3 g,及溶劑 ,一冷卻至 甲基對苯二 0.2mgKOH/g • 7 g,加熱 分=65質量 不飽和基1 均分子量= 下,將此含 所示種種之 用攪拌機進 焊阻劑用之 之分散度以 定評估,任 -34- 200837503 [表i] 搭配例 1 2 3 4 5 6 7 8 9 10 清漆A 155 155 155 155 155 155 155 155 155 155 聚合起始劑(B-1)” 2 2 - - - 1 4 0.5 2 2 聚合起始劑(B-2)+2 6 6 12 - - 6 6 6 6 6 聚合起始劑(B-3f - - - 10 響 - - - - - 聚合起始劑(B-4广 - - - - 5 - - - - - 增感劑(F-1)*5 1 - 1 1 1 - 1 0.5 1 1.5 增感劑(F-2)+6 - 0.25 - 增感劑(F-3f - - - - - 0.3 - - - - 酞菁藍(E) 0.9 0.9 0.9 0.9 0.9 0.9 0.9 - - - 黃色顏料*8 2.3 - 2.3 2.3 2.3 2.3 2.3 - 2.3 - 化合物(C-2)*9 20 20 20 20 20 20 20 20 20 20 化合物(C-3)”0 10 10 10 10 10 10 10 10 10 10 塡充料*U 130 130 130 130 130 130 130 130 130 130 熱硬化成分(D-1-1)”2 15 15 15 15 15 15 15 15 15 15 熱硬化成分(D-W/13 30 30 30 30 30 30 30 30 30 30 微粉三聚氰胺 3 3 3 3 3 3 3 3 3 3 矽酮系消泡劑 3 3 3 3 3 3 3 3 3 3 DPM*14 5 5 5 5 5 5 5 5 5 5 #150*15 5 5 5 5 5 5 5 5 5 5 備註 * 1:2-(乙醯氧基亞胺甲基)硫二苯並喃-9-酮 *2:2-甲基-1-[4-(甲基硫)苯基]-2-嗎啉基丙院小酮 *3:2,4,6-三甲基苯醯基二苯基膦氧化物 *4:雙(η5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1Η-耻略-1-基)-苯基)鈦 *5:2,4-二乙基噻噸酮 *6:二乙基胺基二苯甲酮 *7:7-(二乙基胺基)-4-甲基苯並吡喃-2-酮 蒽醌系黃色顏料 *9:二季戊四醇六丙烯酸酯 * 10:三羥甲基丙烷三丙烯酸酯 * 11:硫酸鋇(堺化學工業公司製Β-30) *12:苯酚酚醛清漆型環氧樹脂(日本化藥公司製ΕΡΡΝ-201) *13:雙二甲苯酉分型環氧樹脂(Japan Epoxy Resins Co_,Ltd.製 ΥΧ-4000) *14:二丙二醇甲基醚乙酸酯 *15:出光石油化學公司製芳香族系有機溶劑 -35- 200837503 光阻性能評估= <吸光度> 吸光度測定,係使用紫外可見分光光度計(日本分光 股份公司製Ubest-V-570DS),及積分球裝置(日本分光 股份公司製ISN-470 )。使搭配例1〜10之光硬化性•熱 硬化性樹脂組成物塗佈於玻璃板進行塗佈器塗佈後,使用 熱風循環式乾燥爐,80 °C,乾燥30分鐘,製作光硬化性 •熱硬化性樹脂組成物之乾燥塗膜於玻璃板上。使用紫外 可見分光光度計及積分球裝置,在與塗佈光硬化性•熱硬 化性樹脂組成物之同一玻璃板,測定500〜3 00nm時吸光 度基線。測定製作之附乾燥塗膜玻璃板之吸光度,從基線 可算出乾燥塗膜之吸光度,得到目的光波長4 0 5 n m時之 吸光度。爲防止塗佈膜厚偏差造成吸光度偏差,使此作業 以塗佈器塗佈厚分4階段改變進行,製作塗佈厚度與 40 5nm時吸光度之圖表,由其近似式算出膜厚25 // m之 乾燥塗膜吸光度,爲其各自之吸光度。 其吸光度評估結果如表2所示。 [表2] 搭配例 1 2 3 4 5 6 7 8 9 10 405nm吸光度 (25//m 厚) 0.59 0.59 0.48 0.46 0.51 0.34 1.25 0.18 0.25 0.54 <斷面形狀> 將搭配例1〜1 0之感光性組成物藉由拋光輥硏磨線/ -36- 200837503 空隙係300/300//m,銅厚18//111及7〇/zm之電 基板後’水洗進行乾燥後之網板印刷法進行塗佈 °C熱風循環式乾燥爐進行3 〇分鐘乾燥。乾燥後, 備高壓水銀燈之曝光裝置進行曝光。曝光圖型爲使 隙部描畫50/60/70/80/90/100/zm線之圖型 量爲以下述合適曝光量評估而得之曝光量。曝光後 碳酸鈉水溶液進行顯像形成圖型,以高壓水銀 1 000mJ/cm2紫外線後,藉由1 5 0。(:,6 0分鐘熱硬 硬化塗膜。觀察硬化塗膜之設計値1 〇〇 # m線部之 〇 此斷面形狀如圖1記載之模式圖般,分爲A〜 階段進行評估。圖1中,評估A〜E爲以下現象產 模式圖。特別是A評價時,與設計値之偏差係線 下部皆在5 # m以內者。其結果如表2所示。於此 評價爲E。 A評價:同設計寬之理想狀態 B評價:因耐顯像性不足等產生表面層之腐蝕 C評價:凹槽狀態 D評價:因光暈等產生粗線 E評價:產生表面層之粗線及凹槽。 在此,不限於A評價、C評價,D評價亦爲抗 方面可使用之程度。相對於此,B評價、E評價之 、凹槽部易剝離,在用作抗焊阻劑方面係困難的, 評價爲不能使用之程度。 路圖型 ,在80 使用配 用於空 。曝光 ,藉由 燈照射 化得到 橫斷面 E之5 生時之 上部、 最差的Araldlte6084, AraldIteGY250, AraldIteGY260, Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Industries, AER3 3 0, AER331, AER661, AER664, etc., manufactured by Asahi Kasei Kogyo Co., Ltd. (All of the trade names) are made of A-type epoxy resin; EPIKOTEYL903 manufactured by Japan Epoxy Resins Co., Ltd., EPICLON152, EPIC L ON 1 6 5 manufactured by Otsuka Ink Chemical Industry Co., Ltd., manufactured by Dongdu Chemical Co., Ltd. EPOTOHTOYDB-400, YDB-5 00, DER542 manufactured by The Dow Chemical Company, Araldlte 8011 manufactured by CIBA Specialty Chemicals Inc., Sumi-Epoxy -21 - 200837503 manufactured by Sumitomo Chemical Industries Co., Ltd. ESB-400, ESB-700, Asahi Kasei Industry Brominated epoxy resin of AER·711, AER714, etc. (all trade names) manufactured by the company; EPIKOTE 152, EPIKOTE 154 manufactured by Resins Co., Ltd., manufactured by The Dow Chemical Company, DEN431, DEN43 8 'large EPICLONN-73 0, EPICLONN-770, EPICLONN-865, manufactured by Sakamoto Ink Chemical Industry Co., Ltd., ETOOHTOYDCN-701, YDCN-704, CIBA Specialty Chemic, manufactured by Dongdu Chemical Co., Ltd. A ra 1 d 11 e ECN 1 2 3 5, A ra 1 d 11 e ECN 1 2 7 3 , AraldIteECN 1 299, AraldIte XPY3 07, EPPN-201, EOCN-1 manufactured by Sakamoto Chemical Co., Ltd. 025, EOCN- 1 020, EOCN-104S, RE-3 06, Sumi-Epoxy ESCN-195X manufactured by Sumitomo Chemical Industries, Inc., ESCN-220, AERECN-23 5, ECN-299, etc., manufactured by Asahi Kasei Kogyo Co., Ltd. A novolac type epoxy resin of the trade name; EPICLON 83 0 manufactured by Dainippon Ink Chemical Industry Co., Ltd., EPIKOTE 807 manufactured by Japan Epoxy Resins Co., Ltd., EPOTOHTO YDF-1 70, YDF-1 75 manufactured by Dongdu Chemical Co., Ltd. YDF-2004, bisphenol F-type epoxy resin of Arald Ite XPY3 06 (all trade names) manufactured by CIBA Specialty Chemicals Inc.; ETOHTOST-2004, ST-2007, ST-3 000 (trade name), etc. manufactured by Dongdu Chemical Co., Ltd. Hydrogenated biguanide type A 33⁄43⁄4 resin; EPIKOTE604 manufactured by Japan Epoxy Resins Co., Ltd., EPOTOHTOYH-434 manufactured by Tosho Kasei Co., Ltd., AraldIteMY720 manufactured by CIba Specialty Chemicals Inc., Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Industries, Ltd. Etc. (all trade names) glycidylamine type Oxygen resin; CIBA Specialty Chemicals Inc. -22- 200837503 Aral dlteC Υ-3 5 0 (trade name) and other urethane type epoxy resin; DAICEL CHEMICAL INDUSTRIES, LTD. CELLOXIDE202 1, CIba Specialty Chemicals Inc · AraldIteCY175, CY179, etc. (all trade names) alicyclic epoxy resin; Japan Epoxy Resins Co., L td · YL - 9 3 3, T he D ow Chemical Company TEN, EPPN-501, EPPN-5 02, etc. (all trade names) tri-phenyl-based epoxy resin; YL-605 6 by Japan Epoxy Resins Co., Ltd., YX-4000, YL-6121 (all trade names), etc. Bis-xylenol type or bisphenol type epoxy resin or a mixture thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., EXA-15 14 manufactured by Dainippon Ink Chemical Industry Co., Ltd. Name) bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin such as EPIKOTE 157S (trade name) manufactured by Japan Epoxy Resins Co., Ltd.; EPIKOTEYL-931 manufactured by Japan Epoxy Resins Co., Ltd. , Araldltel63, etc. manufactured by CIba Specialty Chemicals Inc. ) tetraphenylolethane type epoxy resin; AraldIte PT810 manufactured by CIba Specialty Chemicals Inc., TEPIC (trade name) heterocyclic epoxy resin manufactured by Nissan Chemical Industries Co., Ltd.; diglycidyl phthalate such as Bremmer DGT manufactured by Nippon Oil & Fats Co., Ltd. Formate resin; tetraglycidyl xylenoyl ethane resin such as ZX- 1 063 manufactured by Dongdu Chemical Co., Ltd.; ESN-190, ESN-3 60 manufactured by Nippon Steel Chemical Co., Ltd., HP-403 manufactured by Dainippon Ink Chemical Industry Co., Ltd. 2 Naphthalene-based epoxy resin such as EXA-4750 and EXA-4700; epoxy resin with dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink Chemical Industry Co., Ltd.; Japan Oils and Fats -23-200837503 Glycidyl methacrylate copolymerized epoxy resin such as CP-50S, CP-5 0M; copolymerized epoxy resin of cyclohexyl maleic anhydride and glycidyl methacrylate; Polybutadiene rubber derivatives (for example, PB-3 600 manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.), CTBN modified epoxy resin (for example, YR-102, YR-450, etc. manufactured by Dongdu Chemical Co., Ltd.) , but not limited to this. These epoxy resins may be used singly or in combination of two or more kinds. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable. In the polyfunctional oxetane compound (D-2), there are bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3 -ethyl-) 3-oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxecycloalkylmethoxy)methyl]benzene, 1,4 Bis[(3-ethyl-3-oxobutanealkylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl) — 3 —oxetanyl”methacrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetane In addition to polyfunctional oxetane such as methyl methacrylic acid and their oligomers or copolymers, oxetane and novolak resins, poly(P-hydroxystyrene), Cardo type bisphenols, calixarenes, CALIXRESORCINARENE, or etherates of hydroxyl-containing resins such as sesquises. Further, there are also copolymers of an oxetane ring-unsaturated monomer and an alkyl (meth) acrylate. In the case of a compound having two or more cyclic thioether groups in the molecule, for example, -24-200837503, a double acid type A epoxy sulfide resin YL7000 manufactured by Japan Epoxy Resins Co., Ltd., or the like. Further, an epoxy sulfide resin obtained by substituting an oxygen atom of an epoxy group of a novolac type epoxy resin with a sulfur atom may be used in the same synthesis method. The collocation ratio of the cyclic (thio)ether compound is from 0.6 to 3.0 equivalents, preferably from 0.8 to 3.0 equivalents per 1 equivalent of the carboxyl group of the carboxylic acid-containing carboxyl group containing the ethylenically unsaturated group. A range of 2.5 equivalents. When the amount of the cyclic (thio)ether compound is less than the above range, the residual carboxyl group, heat resistance, alkali resistance, electrical insulation, and the like are lowered, which is not preferable. On the other hand, when the above range is exceeded, the low molecular weight cyclic (thio)ether group remains, and the coating film strength or the like is lowered, which is not preferable. When the above cyclic (thio)ether compound is used, it is preferred to contain a thermosetting catalyst. For such thermosetting catalysts, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoquinone Imidazole derivatives such as 2-ethyl-2-phenylimidazole, 1-(2-cyanoethyl)- 2-ethyl-4-methylimidazole; dicyanodiamine, benzyldimethylamine, 4-(Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethyl An amine compound such as benzylamine, a hydrazine compound such as bismuth adipate or bismuth sebacate; a phosphorus compound such as triphenylphosphine, and the like, and a commercially available person, for example, 2MZ-A, 2MZ-made by Shikoku Chemical Industry Co., Ltd. 0K, 2PHZ, 2P4BHZ, 2P4MHZ (all are imidazole compound trade names), U-CAT3503N, U-CAT3502T (trade name of dimethylamine block isocyanate compound) manufactured by SAN-APRO Ltd., DBU, DBN, U- -25- 200837503 CATSA102, U-CAT5 0 02 (all bicyclic compounds and their salts). In particular, it may be a thermosetting catalyst for epoxy resins and oxetane compounds, or a catalyst for promoting the reaction of an epoxy group and/or an oxetane group with a carboxyl group, either alone or in combination. The above is mixed. Further, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino- 6-methylpropionic acid, which has the function of adhesion imparting agent, can also be used. Oxyethyl-S-triazine, 2-ethylene-4,6-diamino-S-triazine, 2-ethylene-4,6-diamino-S-triazine-cyanuric acid adduct, 2 An S-triazine derivative such as a 4-diamino-6-methacryloyloxyethyl-S-triazine-cyanuric acid addition product, preferably such a binding agent-functional compound Thermally hardened catalyst. The ratio of the heat-hardening catalyst is usually in the range of 0.1 to 20 parts by mass, preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the carboxylic acid-containing resin (A) or the thermosetting component (D). The ratio of 〇·5 to 15.0 parts by mass is important in the photosensitive composition used in the method for forming a photoresist pattern of the present invention. The phthalocyanine-based pigment (E) is important. The present inventors have found that a phthalocyanine blue pigment (E) is added to 405 nm alone light, and gloss sensitivity can be obtained at a lower exposure amount. The reason for the sensitization effect of the phthalocyanine blue pigment is still unclear. For example, in a resin composition having a film thickness of 25 // m and an absorbance of less than 0.2, phthalocyanine blue is added, and only the absorbance is 0 or more. The low exposure amount simultaneously gives sufficient surface hardenability and hardening depth. Moreover, this sensitizing effect has an improved surface reactivity (improvement in gloss), and the depth of hardening is rather deteriorated. That is, the operation of reflecting exposure light is performed. This operation has the effect of stable photoresist shape -26- 200837503. For example, when the shape of the cross-sectional shape of the photoresist pattern is observed, the phthalocyanine blue is not contained, and when the absorbance is lower than 0.2, the shape of the light blocking surface is a large and wide shape at the bottom, and the surface portion of the coating film is also dull. Further, when phthalocyanine blue is not contained, when the absorbance exceeds 2.6, the surface portion is large and the wide bottom portion is fine. However, when the absorbance is in the range of 0. 2 to 1.2, including the photopolymerization initiation (b), and the titanium cyanine dye (Ε), the photoresist film is in the range of 5 to 100 // m. Inside, it was found that a photoresist shape having a bottom portion having a size almost the same as that of the negative mask size was obtained and surface gloss was obtained. The titanium oxide dye-based pigment (E) is suitably added in an amount such that the absorbance is 0.25 nm, and the absorbance is arbitrarily added in the range of 0.2 to 1.2 per 25/m, for example, relative to the carboxylic acid-containing resin ( A) 1 00 parts by mass, which can be added in the range of 1. 0 1 to 5 parts by mass. For the titanium cyanine dye-based pigment (E), there are α-type copper phthalocyanine dyes • Blue, α-type monochloro copper phthalocyanine dyes • Blue, /5 type copper phthalocyanine dyes • Blue, ε-type copper phthalocyanine dyes • Blue , cobalt phthalocyanine dyes • blue, metal-free phthalocyanine dyes, blue, etc. The photosensitive composition to which the present invention is applied may contain, in addition to the above photopolymerization initiator, other photopolymerization initiators, photoinitiating aids, and sensitizers, such as benzoin compounds and acetophenone. A compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a xanthone compound, a tertiary amine compound, and the like. Specific examples of the benzoin compound, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether. -27- 200837503 Specific examples of acetophenone compounds, such as acetophenone, 2,2-dimethoxy-2-phenylethenzene, 2,2-diethoxy-2-phenylacetamidine Benzene, 1,1-dichloroacetamidine. Specific examples of the hydrazine compound are, for example, 2-methyl hydrazine, 2-ethyl hydrazine, 2-t-butyl hydrazine, and 1-chloropurine. Specific examples of thioxanthone compounds, such as 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone . Specific examples of the ketal compound are, for example, acetophenone ketal and benzyl dimethyl ketal. Specific examples of the benzophenone compound are, for example, benzophenone, 4-phenylphenyldiphenyl sulfide, 4-phenylhydrazin-4'-methyldiphenyl sulfide, 4-phenylphenyl group 4'-Ethyldiphenyl sulfide, 4-phenylphenyl- 4'-propyldiphenyl sulfide. Specific examples of the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4'-dimethylaminobenzophenone (NISSO CURE-MABP manufactured by Sakamoto Soda Co., Ltd.) , 4,4, monoethylamino benzophenone (EAB, manufactured by HODOGAYA Chemical Co., Ltd.), dialkylaminobenzophenone I, 7-(ethylamino)-4-methyl Dialkylamine-based coumarin compound, 4-dimethylamino group, etc., 2H-1 -benzopyran-2-one, 7-(diethylamino)-4-methylcoumarin Ethyl benzoate (Kayacure-EPA, manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino benzoic acid ethyl ester (Quantacure DMB manufactured by International Bio-Synthetics Co., Ltd.), 4-dimethylamino benzoic acid (n-butyl) Ethoxy-28-200837503) Ethyl ester (Quantacure BE A, manufactured by International Bio-Synthetics Co., Ltd.), p-dimethylamino benzoic acid isoamylethyl ester (Kayacure -DMBI, manufactured by Sakamoto Chemical Co., Ltd.), 4 Dimethylamino benzoic acid 2-ethylhexyl ester (Esolol 5 07 manufactured by Van Dyk Co., Ltd.), 4,4'-diethylaminobenzophenone (HODOGAY) A chemical company made EAB). Among the above, a thioxanthone compound and a tertiary amine compound are preferred. In the composition of the present invention, a thioxanthone-containing compound is preferred from the viewpoint of deep hardenability, wherein 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chloro The thioxanthone compound such as thioxanthone or 2,4-diisopropylthioxanthone is preferably a thioxanthone compound having a tyrosolone compound ratio of 100 parts by mass, preferably 20 parts by mass, of the above-mentioned carboxylic acid-containing resin (A). The ratio is preferably 10 parts by mass or less. If the amount of the thioxanthone compound is too large, the thick film hardenability is lowered, and the product cost is increased, so it is not suitable. In the case of the tertiary amine compound, a compound having a dialkylaminobenzene structure, wherein a dialkylaminobenzophenone compound and a dialkylamine group having a maximum absorption wavelength of from 350 to 410 nm is preferred. The coumarin compound is particularly preferred. As for the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is also low in toxicity. A dialkylamine-based coumarin compound having a maximum absorption wavelength of 3 5 0 to 4 1 Onm, which provides a photosensitive composition having less coloration, colorlessness and transparency, and providing a coloring pigment because the maximum absorption wavelength is in the ultraviolet region. A color resistive resist film that reacts to the color of the coloring pigment itself. In particular, 7-(diethylamino)-4-methyl-2H-1pybenzopyran-2-one has excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm. -29-200837503 . The collocation ratio of the tertiary amine compound is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the above-mentioned carboxylic acid-containing resin (A). When the amount of the tertiary amine compound is less than 0.1 part by mass, there is a tendency that a sufficient sensitizing effect cannot be obtained. When the amount is more than 20 parts by mass, the light absorption of the third-order amine compound on the surface of the dry resist resist coating film becomes strong, and the tendency of deep-hardening tends to be lowered. These photopolymerization initiators, photoinitiating aids, and sensitizers may be used singly or in combination of two or more kinds. The photopolymerization initiator, the photoinitiator, and the total amount of the sensitizer are preferably in the range of 35 parts by mass or less based on 100 parts by mass of the carboxylic acid-containing resin (A). When the amount is more than 35 parts by mass, there is a tendency that the light is absorbed and the deep hardenability is lowered. In the photosensitive composition which can be used in the present invention, in order to enhance the physical strength of the coating film, etc., it is possible to mix with the ruthenium. For the purpose of the ruthenium filling, it is possible to use a conventionally known inorganic or organic hydrazine filler, but it is particularly preferable to use barium sulfate, spherical cerium oxide and talc. Further, a compound (C) having two or more ethylenically unsaturated groups in the molecule and a Hanse-Chemie company in which the nano-sized cerium oxide is dispersed in the polyfunctional epoxy resin (D-1) can also be used. NANOCRYL (trade name) χρ 〇396, XP 0596, XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all product grade names) and NANOPOX (made by Hanse-Chemie)茼 〇 〇 〇 516, χρ 〇 525, XP 0314 (all are product grade names). These can be used alone or in combination of two or more. -30- 200837503 The collocation ratio of the ruthenium-containing resin is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, more preferably 0·1, based on 100 parts by mass of the carboxylic acid-containing resin (A). ~15〇 parts by mass. When the ratio of the enamel charge is more than 300 parts by mass, the viscosity of the composition becomes high and the printability is lowered, and the cured product becomes brittle, which is not preferable. Further, in the photosensitive composition which can be used in the present invention, an organic solvent can be used for the adjustment of the synthesis and composition of the carboxylic acid-containing resin (A) or the viscosity adjustment applied to the substrate and the carrier film. Examples of the organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, there are ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, and carbitol. , methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; Esters such as ester, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate; ethanol, propanol, ethylene glycol Alcohols such as propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum spirit, hydrogenated petroleum spirit, and solvent oil. These organic solvents can be used singly or in combination of two or more. Further, the photosensitive composition of the present invention may contain a coloring pigment other than a blue pigment in a range which does not cause adverse effects such as resolution. The photosensitive composition usable in the present invention may further be combined with hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, coke-31 - 200837503 indophenol, phenothiazine, if necessary Or known conventionally used thermal polymerization inhibitors, fine powdered silica sand, organic road soil, montmorillonite, and other known tackifiers, chopping ketones, fluorine-based, polymer-based antifoaming agents and/or leveling agents, A conventionally-added additive such as an imidazole-based, a thiazide-based or a triazole-based decane coupling agent. In addition, a blue pigment other than the phthalocyanine blue pigment and a color pigment other than the blue pigment may be added in a range in which negative effects such as resolution are not provided. The photosensitive composition which can be used in the present invention, for example, is adjusted to a viscosity suitable for the coating method by the organic solvent, and is applied to a circuit-formed substrate by a dip coating method, a cast coating method, a roll coating method, Coating by bar coating method, screen printing method, curtain coating method, etc., at a temperature of about 60 to loot: by drying the organic solvent contained in the composition (false drying), forming a non-sticky Coating film. Further, the composition is applied onto a carrier film, and a resin film is formed by bonding a dry film which is taken up as a film after drying to a circuit-formed substrate. Thereafter, the photomask formed by patterning is selectively exposed to ultraviolet light to develop an unexposed portion with a dilute aqueous alkali solution (e.g., 0.3 to 3% aqueous sodium carbonate solution) to form a photoresist pattern. Further, when the thermosetting component is contained, for example, by about 140 to 18 (the thermosetting of the TC temperature after heating, the carboxyl group containing the residual acid resin (A) has two or more cyclic ether groups in the molecule and/or The thermosetting component (D) of the cyclic (thio)ether group reacts to form a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. For the substrate, it is used for paper phenol, epoxy paper, epoxy glass cloth, glass polyimide, glass cloth/epoxy fiber cloth, glass cloth/epoxy paper, epoxy synthetic fiber, fluorine/polyethylene. · PPO · Cyanide - 32 - 200837503 High-frequency circuit for high-frequency circuits, such as copper-clad laminates, etc., all of FR-4, etc.), copper-clad laminates, other polyimide films, glass substrates, ceramic substrates, crystals Round plate temple. In the present invention, after the application of the photosensitive composition, a hot air circulation type drying furnace, an IR furnace, a hot plate oven, or the like (using a method of using a steam to perform air heating in a heat source) And by blowing the nozzle to the support). The exposure machine used for the above ultraviolet irradiation may be an exposure device, and a high-pressure mercury lamp, an ultra-high, a metal halide lamp or the like is preferable as the light source. For the above-mentioned exposure apparatus, for example, HMW-680GW Engineering C ο, manufactured by ORC MANUFACTURING CO·, LTD., ADDX 650 P, etc., can be used for the development method, and has a dip coating method, Shower Spray method, hand brush method, etc., in the case of a developing solution, an aqueous solution of sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonium, or oxidized money can be used. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, which are not limited by the following examples. Part grade (PET film is dry, convection, dry type, UV-pressure mercury lamp, ADTEC, method, potassium, hydrogen oxytetrahydrogen, in the present invention, but the present invention - 33 - 200837503 Synthesis Example 1 is equipped with a mixer, 2 liters of separable flask of thermometer, reflux cooling tube and drop introduction tube, adding 甲酣醒 (made by Nippon Chemical Co., Ltd., EOCN-104S, softening point equivalent = 220g/eq) 660g, carbitol Acid ester 421. 180.6 g of oil, heated, stirred and dissolved at 90 ° C. After 6 ° C, 216 g of acrylic acid, 4.0 g of triphenylphosphine and 1.3 g of phenol were added, and reacted at 100 ° C for 12 hours to obtain an acid. The reaction product was obtained by adding a tetrahydrophthalic anhydride 2 4 1 to 9 (TC for 6 hours), thereby obtaining a nonvolatile content: %, a solid acid value = 77 mgKOH/g, and a double bond equivalent ( a weight of the resin per mole of the resin = 40 g / equivalent, a weight of 7, a solution of the carboxylic acid-containing photosensitive resin (A). & carboxylic acid photosensitive resin solution is called varnish Α. Modification of Composition No. 1 to 10) The varnish A obtained in the above Synthesis Example 1 was used as the composition of Table 1. The ratios (mass parts) shown in the same table were mixed, and after preliminary mixing, the mixture was kneaded by a 3-roller honing machine to prepare a photosensitive composition. Here, the obtained photosensitive composition, GRINDOMETER, manufactured by ERICHSEN Co., Ltd. was subjected to particle size measurement. The sample is all below 1 5 // m. The liquid funnel and nitrogen epoxy resin 92 ° C, epoxy 3 g, and solvent, once cooled to methyl p-phenylene 0.2 mg KOH / g • 7 g, heating points =65 mass unsaturation 1 average molecular weight = lower, this dispersion with the indicated variety of mixers used for solder resists is evaluated, any -34-200837503 [Table i] with example 1 2 3 4 5 6 7 8 9 10 Varnish A 155 155 155 155 155 155 155 155 155 155 Polymerization initiator (B-1)” 2 2 - - - 1 4 0.5 2 2 Polymerization initiator (B-2) + 2 6 6 12 - - 6 6 6 6 6 Polymerization initiator (B-3f - - - 10 ring - - - - - Polymerization initiator (B-4 wide - - - - 5 - - - - - Sensitizer (F -1)*5 1 - 1 1 1 - 1 0.5 1 1.5 Sensitizer (F-2) +6 - 0.25 - Sensitizer (F-3f - - - - - - 0.3 - - - - Phthalocyanine Blue (E ) 0.9 0.9 0.9 0.9 0.9 0.9 0.9 - - - Yellow pigment *8 2.3 - 2.3 2.3 2.3 2.3 2. 3 - 2.3 - Compound (C-2)*9 20 20 20 20 20 20 20 20 20 20 Compound (C-3)"0 10 10 10 10 10 10 10 10 10 10 塡Filling*U 130 130 130 130 130 130 130 130 130 130 Thermosetting component (D-1-1)” 2 15 15 15 15 15 15 15 15 15 15 Thermosetting component (DW/13 30 30 30 30 30 30 30 30 30 30 Micronized melamine 3 3 3 3 3 3 3 3 3 3 Anthrone defoamer 3 3 3 3 3 3 3 3 3 3 DPM*14 5 5 5 5 5 5 5 5 5 5 #150*15 5 5 5 5 5 5 5 5 5 5 Remarks * 1:2-(ethoxyninimidomethyl)thiodibenzofuran-9-one*2:2-methyl-1-[4-(methylthio)phenyl]-2-morpholine Propyl ketone*3: 2,4,6-trimethylphenylnonyldiphenylphosphine oxide *4: bis(η5-2,4-cyclopentadien-1-yl)-bis (2 ,6-difluoro-3-(1Η-disc-1-yl)-phenyl)titanium*5:2,4-diethylthioxanthone*6:diethylaminobenzophenone*7 :7-(Diethylamino)-4-methylbenzopyran-2-one anthraquinone yellow pigment*9: Dipentaerythritol hexaacrylate* 10: Trimethylolpropane triacrylate* 11: Barium sulfate (Β-30, manufactured by Nippon Chemical Industry Co., Ltd.) *12: Phenolic novolac type epoxy resin (ΕΡΡΝ-201, manufactured by Nippon Kayaku Co., Ltd.) *13: bis-xylene Bismuth type epoxy resin (ΥΧ-4000, manufactured by Japan Epoxy Resins Co., Ltd.) *14: Dipropylene glycol methyl ether acetate*15: Aromatic organic solvent manufactured by Idemitsu Petrochemical Co., Ltd. -35- 200837503 Photoresistive properties Evaluation = <Absorbance> The absorbance was measured using an ultraviolet-visible spectrophotometer (Ubest-V-570DS manufactured by JASCO Corporation) and an integrating sphere device (ISN-470 manufactured by JASCO Corporation). The photocurable/thermosetting resin composition of the collocation examples 1 to 10 was applied onto a glass plate to coat the applicator, and then dried in a hot air circulating drying oven at 80 ° C for 30 minutes to prepare photocurability. The dried coating film of the thermosetting resin composition is applied to a glass plate. The absorbance baseline at 500 to 300 nm was measured using an ultraviolet-visible spectrophotometer and an integrating sphere device on the same glass plate as the photocurable/thermosetting resin composition. The absorbance of the dried glass film to be coated was measured, and the absorbance of the dried coating film was calculated from the baseline to obtain the absorbance at a wavelength of the target light of 4 0 5 n m. In order to prevent the deviation of the absorbance caused by the deviation of the coating film thickness, the operation was carried out in a four-stage change of the applicator coating thickness, and a graph of the coating thickness and the absorbance at 40 5 nm was prepared, and the film thickness was calculated by the approximate formula of 25 // m. The dry film absorbance is its respective absorbance. The results of the absorbance evaluation are shown in Table 2. [Table 2] Matching Example 1 2 3 4 5 6 7 8 9 10 405 nm absorbance (25//m thick) 0.59 0.59 0.48 0.46 0.51 0.34 1.25 0.18 0.25 0.54 <Sectional shape > Pairing example 1~1 0 The photosensitive composition is dried by a polishing roll honing line / -36- 200837503 gap 300/300 / / m, copper thickness of 18 / / 111 and 7 〇 / zm after the substrate is washed with water and dried. It was dried in a coating °C hot air circulating drying oven for 3 minutes. After drying, the exposure apparatus of the high pressure mercury lamp is exposed. The exposure pattern is such that the pattern of the 50/60/70/80/90/100/zm line of the gap is the exposure amount obtained by evaluating the appropriate exposure amount described below. After the exposure, an aqueous solution of sodium carbonate was subjected to development of a pattern, and after high-pressure mercury of 1 000 mJ/cm 2 of ultraviolet light, by 150. (:, 60 minutes thermosetting hardening film. Observe the design of the hardened coating film 値1 〇〇# m line part 〇 This section shape is as shown in the pattern diagram of Figure 1, and is divided into A~ stage for evaluation. In the first evaluation, A to E are the following pattern of production patterns. Especially in the case of A evaluation, the deviation from the design 系 is below 5 #m. The results are shown in Table 2. The evaluation is E. A evaluation: ideal state of design width B evaluation: corrosion of surface layer due to insufficient development resistance C evaluation: evaluation of groove state D: thick line E due to halo, etc. evaluation: generation of thick lines of surface layer and Here, it is not limited to the A evaluation, the C evaluation, and the D evaluation is also an extent that can be used for the resistance. In contrast, the B evaluation, the E evaluation, the groove portion is easily peeled off, and it is used as a solder resist. If the system is difficult, the evaluation is not applicable. The road pattern is used at 80. The exposure is used, and the illumination is illuminated by the lamp to obtain the cross section E.

焊阻劑 者,線 特別E 37- 200837503 &lt;殘存感度&gt; 使搭配例1〜1 0感光性組成物,藉由拋光輥硏磨貼銅 層合板後’水洗進行乾燥後以網板印刷法塗佈,在8 (TC 之熱風循環式乾燥爐乾燥3 0分鐘。乾燥後,使用配備有 高壓水銀燈之曝光裝置進行曝光。曝光方法爲於乾燥塗膜 上放置Step Tablet ( Kodak No.2 ),進而於其上放置熱可 塑性薄膜進行曝光。曝光量爲藉由下述合適曝光量評估所 得之曝光量。曝光後,進行顯像(30°C,0.2MPa,1質量 %碳酸鈉水溶液)60秒描畫圖型,經1 50°C X60分鐘熱硬 化得到硬化塗膜。評估如此所得之硬化塗膜的殘存感度段 數。 &lt;合適曝光量&gt; 使搭配例1〜1 0之感光性組成物於各評估基板全面藉 由網板印刷進行塗佈。其後,使以熱風循環式乾燥機乾燥 後之塗膜,介著形成50〜130//m之線的負圖型的光罩, 使用配備高壓水銀燈之曝光裝置進行曝光。其後,以1.0 質量%碳酸鈉水溶液進行6 0秒鐘顯像處理。使此時能得 到6 0 // m解像性之最少曝光量爲合適曝光量。 (比較例1 :使用PET系薄膜作爲保護薄膜/光阻膜厚i 8 β m ) 使用銅厚20//m電路圖型之光阻形成中,在曝光時 38- 200837503 使用於光罩(負圖型)貼合聚對苯二甲酸乙二酯系薄膜( tackwelll55)之光具時,所得之抗焊阻劑圖型斷面形狀之 評估結果如表3。此時之抗焊阻劑層的膜厚皆爲1 8 // m。 [表3]For the solder resist, the wire is particularly E 37-200837503 &lt;Residual sensitivity&gt; The photosensitive composition of the matching examples 1 to 10 is honed by a polishing roll, and then dried by water washing and then screen-printed. Coating, drying in a hot air circulating drying oven of 8 (TC) for 30 minutes. After drying, exposure is performed using an exposure apparatus equipped with a high-pressure mercury lamp. The exposure method is to place a Step Tablet (Kodak No. 2) on the dried coating film. Further, a thermoplastic film was placed thereon for exposure. The exposure amount was evaluated by the appropriate exposure amount described below, and after exposure, development (30 ° C, 0.2 MPa, 1% by mass aqueous sodium carbonate solution) was carried out for 60 seconds. The pattern was drawn, and the hardened coating film was obtained by heat hardening at 150 ° C for 60 minutes. The number of residual sensitivity of the hardened coating film thus obtained was evaluated. <Appropriate exposure amount> The photosensitive composition of the matching examples 1 to 10 was used. The evaluation substrate is entirely coated by screen printing. Thereafter, the coating film dried by the hot air circulation dryer is passed through a mask having a negative pattern of 50 to 130/m. Exposure unit with high pressure mercury lamp Thereafter, the development treatment was carried out for 60 seconds with a 1.0% by mass aqueous sodium carbonate solution, and the minimum exposure amount at which the resolution of 60 // m was obtained at this time was a suitable exposure amount. (Comparative Example 1: Using PET The film is used as a protective film/thickness film thickness i 8 β m ) in the formation of a photoresist having a copper thickness of 20//m circuit pattern, and is used in a mask (negative pattern) for bonding poly(p-phenylene) at the time of exposure 38-200837503. When the optical film of the ethylene diester film (Tackwelll 55) is used, the evaluation results of the cross-sectional shape of the resistive resist pattern obtained are shown in Table 3. The film thickness of the solder resist layer at this time is 1 8 // m. [Table 3]

搭配例 1 2 3 4 5 6 7 8 9 10 曝光量 (mJ/cm ) 80 80 180 160 150 100 50 80 70 70 斷面形狀 A A A A A A A A或D A或D A或D (實施例1 :使用PEN系薄膜作爲保護薄膜/光阻膜厚 1 8 // m ) 使用聚萘二甲酸乙二醇酯薄膜取代聚對苯二甲酸乙二 酯系薄膜作爲保護薄膜以外與比較例1進行同樣試驗。所 得之抗焊阻劑圖型斷面形狀之評估結果如同表3。又,光 罩爲無損傷及光阻之附著係爲乾淨之狀態。 (比較例2 :使用PET系薄膜作爲保護薄膜/光阻膜厚45 tJL m ) 於使用銅厚5 0 // m之電路圖型的光阻形成中,於曝 光時使用在光罩(負圖型)貼合聚對苯二甲酸乙二酯系薄 膜(tackwelll55)之光具時,所得之抗焊阻劑圖型斷面形 狀之評估結果如同表4。此時之抗焊阻劑膜厚爲4 5 // m。 根據表4 ’關於不被藍色及綠色著色之搭配例8〜1 〇 ’光阻圖型斷面形狀方面爲比較良好之者,被藍色及綠色 -39- 200837503 著色之搭配例1〜7有凹槽及粗線 [表4]Matching Example 1 2 3 4 5 6 7 8 9 10 Exposure (mJ/cm) 80 80 180 160 150 100 50 80 70 70 Sectional shape AAAAAAAA or DA or DA or D (Example 1: Using PEN film as protection Film/Thick Film Thickness 1 8 // m ) The same test as in Comparative Example 1 was carried out except that a polyethylene naphthalate film was used instead of the polyethylene terephthalate film as a protective film. The evaluation results of the shape of the resist resist pattern obtained are shown in Table 3. Further, the reticle is in a state of no damage and the adhesion of the photoresist is clean. (Comparative Example 2: Using a PET-based film as a protective film/thickness film thickness of 45 tJL m ) In the formation of a photoresist pattern using a copper pattern of 50 +/- m, it is used in a mask at the time of exposure (negative pattern) When the optical device of the polyethylene terephthalate film (tackwelll 55) was attached, the evaluation results of the cross-sectional shape of the obtained solder resist pattern are as shown in Table 4. At this time, the film thickness of the solder resist is 4 5 // m. According to Table 4 'About the coloring pattern of the 8th to 1st 〇' photoresist pattern which is not colored by blue and green, it is better to match the blue and green -39-200837503 color matching examples 1 to 7. Grooved and thick lines [Table 4]

搭配例 1 2 3 4 5 6 7 8 9 10 曝光量 Λ (mJ/cm ) 100 100 200 180 170 120 70 100 80 80 斷面形狀 c或E c或E C或E C或E C或E C或E E A A A (實施例2 :使用P EN系薄膜作爲保護薄膜/光阻膜厚4 5 // m ) 使用聚萘二甲酸乙二醇酯薄膜取代聚對苯二甲酸乙二 酯系薄膜作爲保護薄膜外,與比較例2進行同樣試驗。所 得之抗焊阻劑圖型(膜厚4 5 // m )斷面形狀之評估結果如 同表5。又’光罩爲無損傷及光阻之附著係爲乾淨之狀態 〇 根據表5,使用本發明之光具進行曝光處理時,光阻 層膜厚就算在45 // m之厚膜,知道感光性組成物之吸光 度在合適範圍內,可得到無凹槽等高精細之圖型。此特別 在感光性樹脂被藍色及綠色著色時更明顯。 [表5]Matching example 1 2 3 4 5 6 7 8 9 10 Exposure amount Λ (mJ/cm) 100 100 200 180 170 120 70 100 80 80 Section shape c or E c or EC or EC or EC or EC or EEAAA (Example 2: Using a P EN film as a protective film/thickness film thickness of 4 5 // m ) using a polyethylene naphthalate film instead of a polyethylene terephthalate film as a protective film, and a comparative example 2 Carry out the same test. The evaluation results of the cross-sectional shape of the resistive resist pattern (film thickness of 4 5 // m) are shown in Table 5. In addition, the mask is in a state of no damage and the adhesion of the photoresist is clean. According to Table 5, when the exposure is performed using the optical device of the present invention, the film thickness of the photoresist layer is even thick film of 45 // m, and the photosensitive film is known. The absorbance of the composition is within a suitable range, and a high-definition pattern such as a groove can be obtained. This is especially noticeable when the photosensitive resin is colored by blue and green. [table 5]

搭配例 1 2 3 4 5 6 7 8 9 10 曝光量 (mJ/cm2) 100 100 200 180 170 120 70 180 80 80 斷面形狀 A A A A A A C B B B (實施例3 :使用於PET製光罩上設置紫外線吸收處理之 -40- 200837503 薄膜而成者作爲保護薄膜/光阻膜厚45//m) 作爲保護薄膜,藉由於聚對苯二甲酸乙二酯製光罩上 層合紫外線吸收處理之薄膜,取代調節爲具本發明之光吸 收特性之層合薄膜以外與比較例2進行同樣試驗。所得之 抗焊阻劑圖型斷面形狀之評估結果如同表5。 根據以上,使用令405nm時吸光度在0.2〜1.2之範 圍內之感光性組成物調整爲3 70nm以下光有50%以上遮 蔽且400nm以上之光透過80%以上之保護薄膜貼合於光 罩所成之本發明之光具之步驟,不因光阻層厚度影響,可 賦予斷面形狀優異之光阻圖型。 (比較例3 ··無薄膜之存在/銅厚18 // m ;光阻膜厚20 β m ) 在使用銅厚之電路圖型的光阻圖型形成中, 於曝光時在光源與光罩間不介在紫外線遮蔽薄膜時,可得 如表6的任一條件皆好之斷面形狀。此時之抗焊阻劑膜厚 爲2 0 // m。又,本比較例中,光罩之保護薄膜方面,係使 用PET系保護薄膜。 [表6]Matching example 1 2 3 4 5 6 7 8 9 10 Exposure amount (mJ/cm2) 100 100 200 180 170 120 70 180 80 80 Cross-sectional shape AAAAAACBBB (Example 3: UV absorbing treatment is applied to a PET mask -40- 200837503 The film is made of a protective film/resist film thickness of 45//m). As a protective film, the film is laminated with UV-absorbing film on the mask made of polyethylene terephthalate. The same test as in Comparative Example 2 was carried out except for the laminated film of the light absorption property of the present invention. The evaluation results of the obtained resistive resist pattern cross-sectional shape are shown in Table 5. According to the above, the photosensitive composition in which the absorbance at 405 nm is in the range of 0.2 to 1.2 is adjusted to be 3 70 nm or less, the light is blocked by 50% or more, and the light having 400 nm or more is transmitted through 80% or more. The step of the optical device of the present invention can impart a photoresist pattern excellent in cross-sectional shape without being affected by the thickness of the photoresist layer. (Comparative Example 3··No film presence/copper thickness 18 // m; photoresist film thickness 20 β m ) In the formation of a resist pattern using a copper thick circuit pattern, between the light source and the mask during exposure When it is not in the ultraviolet shielding film, a cross-sectional shape which is excellent in any of the conditions of Table 6 can be obtained. At this time, the film thickness of the solder resist is 2 0 // m. Further, in the comparative example, a PET-based protective film was used as the protective film for the photomask. [Table 6]

搭配例 1 2 3 4 5 6 7 8 9 10 曝光量 (mJ/cm2) 80 80 180 160 150 100 50 80 70 70 斷面形狀 A A A A A A A A或D A或D A或D -41 - 200837503 (比較例4 :無薄膜之存在/銅厚70 # m ;光阻膜厚6〇 β m) 接著使用銅厚70//m之電路圖型之光阻圖型形成中 ’於曝光時在光源與光罩間不介在紫外線遮蔽薄膜時,如 表7所示般,含藍色顏料之搭配例1〜7係使曝光量增大 亦無畫像殘留,另外,搭配例8〜1 0,畫像雖可形成,但 斷面形狀係最差的E。此時之抗焊阻劑厚度爲約6〇//m。 又,本比較例中,作爲光罩保護薄膜係使用p e T系保護 薄膜。 [表7]Matching Example 1 2 3 4 5 6 7 8 9 10 Exposure (mJ/cm2) 80 80 180 160 150 100 50 80 70 70 Sectional shape AAAAAAAA or DA or DA or D-41 - 200837503 (Comparative Example 4: No film Existence / copper thickness 70 # m; photoresist film thickness 6 〇 β m) Then use a copper pattern 70 / / m circuit pattern of the photoresist pattern formation in the exposure between the light source and the reticle without UV shielding In the case of the film, as shown in Table 7, the blending examples 1 to 7 containing the blue pigment did not cause an increase in the amount of exposure, and the examples 8 to 10, although the portraits were formed, the cross-sectional shape was Worst E. The thickness of the solder resist at this time is about 6 Å/m. Further, in the comparative example, a p e T protective film was used as the photomask protective film. [Table 7]

搭配例 1 2 3 4 5 6 7 8 9 10 曝光量 (mJ/cm2) 100 100 200 180 170 120 70 100 80 80 斷面形狀 c或E c或E C或E C或E C或E C或E E A A A (實施例4 :有PEN薄膜存在/銅厚70 // m ;光阻膜厚60 β m ) 使用銅厚70 // m電路圖型之抗焊阻劑圖型形成中, 於曝光時使用PEN薄膜作爲紫外線遮蔽薄膜,如表8所 示般,含藍色顏料之搭配例1〜7可得良好斷面形狀。此 爲不介在PEN薄膜之該比較例4中,相較於搭配例1〜7 中畫像不被形成,本發明之效果極優。又,不含藍色顏料 之搭配例8〜1 0,相較於比較例4之搭配例8〜1 0斷面形 狀有被改善,可知本發明爲於不含藍色顏料之感光性組成 -42- 200837503 物中’亦有光阻圖型厚膜化之效果。 [表8]Matching Example 1 2 3 4 5 6 7 8 9 10 Exposure (mJ/cm2) 100 100 200 180 170 120 70 100 80 80 Sectional shape c or E c or EC or EC or EC or EC or EEAAA (Example 4 : PEN film exists / copper thickness 70 / m; photoresist film thickness 60 β m ) Using a copper thickness of 70 / m m circuit pattern resistive resist pattern formation, using PEN film as UV shielding film during exposure As shown in Table 8, the blending examples 1 to 7 containing the blue pigment gave a good cross-sectional shape. In the comparative example 4 which is not in the PEN film, the effect of the present invention is excellent as compared with the case where the image is not formed in the collocation examples 1 to 7. Further, in the case of the combination of Examples 8 to 10 which did not contain the blue pigment, the cross-sectional shape of the matching examples 8 to 10 of Comparative Example 4 was improved, and it was found that the present invention is a photosensitive composition containing no blue pigment - 42- 200837503 'There is also the effect of thick film formation of photoresist pattern. [Table 8]

搭配例q 1 2 3 4 5 6 7 8 9 10 曝光量 (mJ/cm2) 100 100 200 180 170 120 70 180 80 80 斷面形狀 A A A A A A C B B B (實施例5 :有薄膜存在/銅厚7〇 # m ;光阻膜厚60 // m ) 取代實施例4所使用之ΡΕΝ薄膜,使用以市售紫外 線遮蔽薄膜(於HOME CENTER購入)且係滿足本發明所 規定之光吸收特性之紫外線遮蔽薄膜以外,與實施例4同 樣條件進行實驗,可得與實施例4同樣之結果。 又’ PET薄膜、PEN薄膜及市售紫外線遮蔽薄膜之譜 圖如圖2。 【圖式簡單説明】 [圖1 ]由感光性組成物硬化塗膜所成圖型之斷面形狀 模式圖。 [圖2]表不薄膜之光透過譜圖,(a)爲pet薄膜, (b )爲PEN薄膜,及(c )爲市售紫外線遮蔽薄膜之譜 圖。 【主要元件符號說明】 1 a :線寬之設計値 -43- 200837503 1 b :曝光·顯像後之樹脂組成物 1 c :基板 •44-Matching example q 1 2 3 4 5 6 7 8 9 10 Exposure amount (mJ/cm2) 100 100 200 180 170 120 70 180 80 80 Section shape AAAAAACBBB (Example 5: film presence / copper thickness 7 〇 # m; Photoresist film thickness: 60 // m ) In place of the ruthenium film used in Example 4, a commercially available ultraviolet shielding film (purchased at HOME CENTER) and an ultraviolet ray shielding film satisfying the light absorbing characteristics specified in the present invention are used. The experiment was carried out under the same conditions as in Example 4, and the same results as in Example 4 were obtained. Further, the spectrum of PET film, PEN film and commercially available ultraviolet shielding film is shown in Fig. 2. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] A cross-sectional shape pattern of a pattern formed by curing a photosensitive composition. [Fig. 2] shows the light transmission spectrum of the film, (a) is a pet film, (b) is a PEN film, and (c) is a spectrum of a commercially available ultraviolet shielding film. [Explanation of main component symbols] 1 a : Design of line width 値 -43- 200837503 1 b : Resin composition after exposure and development 1 c : Substrate • 44-

Claims (1)

200837503 十、申請專利範圍 1. 一種光具(Phototool ),其特徵係用於抗焊阻劑 圖型形成之曝光處理,具備光罩之光具中,在該光罩之光 阻面側具備阻斷50%以上3 70nm以下之光,且使80%以 上400nm以上之光透過之薄膜。 2·如申請專利範圍第1項之光具(Phototool ),其 中該薄膜爲熱可塑性薄膜。 3.如申請專利範圍第2項之光具(Phototool ),其 中該熱可塑性薄膜含有紫外線吸收劑。 4·如申請專利範圍第1項之光具(Phototool ),其 中該薄膜爲具有紫外線吸收層之薄膜。 5. 如申請專利範圍第1項之光具(Phototool ),其 中該保護薄膜爲聚萘二甲酸乙二醇酯薄膜。 6. —種抗焊阻劑圖型之形成方法,其特徵係介由申 請專利範圍第1項之光具,使感光性組成物乾燥膜所成之 抗焊阻劑選擇性曝光,再使未曝光部分顯像形成圖型後, 經加熱使熱硬化而得到硬化膜。 7 ·如申請專利範圍第6項之抗焊阻劑圖型之形成方 法,其中該抗焊阻劑爲由可鹼顯像之感光性組成物或具有 可鹼顯像之感光性組成物塗膜之乾薄膜形成而成。 8 . —種抗焊阻劑圖型之形成方法,其係介由光罩將 由感光性組成物之乾燥膜所成之抗焊阻劑選擇性曝光,再 使未曝光部分顯像形成圖型後,經加熱使熱硬化後得到硬 化膜之抗焊阻劑圖型之形成方法,其特徵係於產生曝光之 -45- 200837503 光源與光罩間,存在有阻斷50%以上3 70nm以下之光且 使80%以上40 Onm以上之光透過的薄膜。 9 ·如申請專利範圍第8項之抗焊阻劑圖型之形成方 法,其中該抗焊阻劑爲由可鹼顯像之感光性組成物或具有 可鹼顯像之感光性組成物塗膜之乾薄膜形成而成。 1 〇·如申請專利範圍第8項之抗焊阻劑圖型之形成方 法,其中該薄膜爲熱可塑性薄膜。 1 1 ·如申請專利範圍第1 0項之抗焊阻劑圖型之形成 方法,其中該熱可塑性薄膜含有紫外線吸收劑。 1 2 ·如申請專利範圍第8項之抗焊阻劑圖型之形成方 法,其中該薄膜爲由熱可塑性薄膜與於該熱可塑性薄膜上 所層合之紫外線吸收劑含有層所構成。 1 3 ·如申請專利範圍第8項之抗焊阻劑圖型之形成方 法,其中該薄膜爲聚萘二甲酸乙二醇酯薄膜。 1 4 ·如申請專利範圍第6項之抗焊阻劑圖型之形成方 法,其中該感光性組成物爲於該感光性組成物之乾燥塗膜 的波長405nm時,吸光度爲每膜厚25//m,爲〇.2〜1.2 之感光性組成物。 1 5 ·如申請專利範圍第8項之抗焊阻劑圖型之形成方 法,其中該感光性組成物爲於該感光性組成物之乾燥塗膜 的波長40 5nm時,吸光度爲每膜厚25//m,爲0·2〜1.2 之感光性組成物。 1 6 .如申請專利範圍第6項之抗焊阻劑圖型之形成方 法,其中該感光性組成物含有含以下述一般式(I )所示 -46- 200837503 之構造部分之肟酯系光聚合起始劑,含以下述一般式(j j )所示之構造部分之α -胺基苯乙酮系光聚合起始劑,含 以下述一般式(III )所示之構造部分之醯基膦氧化物系光 聚合起始劑’及以下述〜般式(IV)所示之二茂鈦系光聚 σ起μ!Ι所成群运出之1種或2種以上之光聚合起始劑: [化1]200837503 X. Patent application scope 1. A phototool (Phototool), which is characterized by exposure processing for formation of a resistive resist pattern, in a light fixture having a photomask, and having a resistance on the photoresist surface side of the photomask A film that cuts light of 50% or more and 3 70 nm or less and transmits light of 80% or more and 400 nm or more. 2. Photonics as claimed in claim 1 wherein the film is a thermoplastic film. 3. The phototool of claim 2, wherein the thermoplastic film contains an ultraviolet absorber. 4. The phototool of claim 1, wherein the film is a film having an ultraviolet absorbing layer. 5. The phototool of claim 1, wherein the protective film is a polyethylene naphthalate film. 6. A method for forming a solder resist pattern, characterized by selectively exposing a solder resist formed by a dry film of a photosensitive composition to an optical device of the first application of the patent scope, and then After the exposed portion is developed into a pattern, it is thermally cured by heating to obtain a cured film. 7. The method for forming a solder resist pattern according to item 6 of the patent application, wherein the solder resist is a photosensitive composition which can be developed by a base or a photosensitive composition having a base image. The dry film is formed. 8. A method for forming a solder resist pattern by selectively exposing a solder resist formed by a dried film of a photosensitive composition to a mask, and then developing an unexposed portion to form a pattern a method for forming a resistive resist pattern obtained by heating to obtain a cured film after heat curing, characterized in that between -45-200837503 light source and a mask are exposed, light having a blocking ratio of 50% or more and 3 70 nm or less is present. And a film that transmits 80% or more of light of 40 Onm or more. 9. The method for forming a solder resist pattern according to item 8 of the patent application, wherein the solder resist is a photosensitive composition which can be developed by alkali or a photosensitive composition having a base image. The dry film is formed. 1 〇· The method of forming a solder resist pattern according to item 8 of the patent application, wherein the film is a thermoplastic film. 1 1 The method of forming a solder resist pattern according to claim 10, wherein the thermoplastic film contains an ultraviolet absorber. 1 2 The method of forming a solder resist pattern according to claim 8 wherein the film is composed of a thermoplastic film and a UV absorber-containing layer laminated on the thermoplastic film. 1 3 . The method of forming a solder resist pattern according to item 8 of the patent application, wherein the film is a polyethylene naphthalate film. 1 4 The method for forming a solder resist pattern according to claim 6, wherein the photosensitive composition is at a wavelength of 405 nm of the dried coating film of the photosensitive composition, and the absorbance is 25/per film thickness. /m, which is a photosensitive composition of 〇.2 to 1.2. The method for forming a solder resist pattern according to Item 8 of the patent application, wherein the photosensitive composition is at a wavelength of 40 5 nm of the dried coating film of the photosensitive composition, and the absorbance is 25 per film thickness. //m, a photosensitive composition of 0·2 to 1.2. 16. The method for forming a solder resist pattern according to claim 6, wherein the photosensitive composition contains an oxime-based light having a structural portion of -46-200837503 represented by the following general formula (I); A polymerization initiator comprising an α-aminoacetophenone photopolymerization initiator having a structural moiety represented by the following general formula (jj), and a mercaptophosphine having a structural moiety represented by the following general formula (III) One or two or more kinds of photopolymerization initiators which are transported in groups of the above-described oxide-based photopolymerization initiators and the above-described formula (IV) : [Chemical 1] 式中,R1爲氫原子、苯基(以碳數1〜6之烷基、苯 基或鹵原子取代亦可)、碳數1〜20之烷基(可以1個以 上羥基取代,烷基鏈中間可有1個以上之氧原子)、碳數 5〜8之環烷基、碳數2〜20之烷醇基或苯醯基(碳數爲可 以1〜6之烷基或苯基取代);R2爲苯基(以碳數1〜6之 烷基、苯基或鹵原子取代亦可)、碳數1〜20之烷基(可 以1個以上羥基取代,烷基鏈中間可有1個以上之氧原子 )、碳數5〜8之環烷基、碳數2〜20之烷醇基或苯醯基 (碳數爲可以1〜6之烷基或苯基取代);R3、R4爲各自 獨立,表示碳數1〜12之烷基或芳基烷基;R5、R6爲各自 獨立,表示氫原子,或碳數1〜6之烷基,或亦可2個鍵 結形成環狀烷基醚基;r7、r8爲各自獨立,表示碳數1〜 1〇之烷基、環己基、環戊基、芳基、或鹵原子、烷基或以 200837503 烷氧基取代之芳基、或碳數1〜20之羰基(但,除兩者爲 碳數1〜20之羰基之情形以外);R9、R1G爲各自獨立, 表不鹵原子、芳基、鹵化芳基、含雜丨哀之鹵化芳基。 1 7 ·如申請專利範圍第8項之抗焊阻劑圖型之形成方 法,其中該感光性組成物含有由含以下述一般式(I)所 示之構造部分之肟酯系光聚合起始劑、含以下述一般式( II )所示之構造部分之α -胺基苯乙酮系光聚合起始劑、 含以下述一般式(III )所示之構造部分之醯基膦氧化物系 光聚合起始劑,及以下述一般式(IV )所示之二茂鈦系光 聚合起始劑所成群所選出之1種或2種以上之光聚合起始 劑: [化1]In the formula, R1 is a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (may be substituted by one or more hydroxyl groups, and an alkyl chain There may be one or more oxygen atoms in the middle), a cycloalkyl group having 5 to 8 carbon atoms, an alkanol group having 2 to 20 carbon atoms or a phenylhydrazine group (the number of carbon atoms may be 1 to 6 or substituted by a phenyl group) R2 is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, and may have one in the middle of the alkyl chain) The above oxygen atom), a cycloalkyl group having 5 to 8 carbon atoms, an alkylol group having 2 to 20 carbon atoms or a phenylhydrazine group (having a carbon number of 1 to 6 or a phenyl group); R3 and R4 are Each of them is independently represented by an alkyl group or an arylalkyl group having 1 to 12 carbon atoms; R5 and R6 are each independently represented by a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or may be bonded to form a cyclic alkane. R7, r8 are each independently, and represent an alkyl group having a carbon number of 1 to 1 fluorene, a cyclohexyl group, a cyclopentyl group, an aryl group, or a halogen atom, an alkyl group or an aryl group substituted with an alkoxy group of 200837503, or a carbon number of 1 to 20 carbon atoms (but, except for two In addition to the case of a carbonyl group having 1 to 20 carbon atoms; R9 and R1G are each independently, and represent a halogen atom, an aryl group, a halogenated aryl group, and a halogenated aryl group containing a ruthenium. A method for forming a solder resist pattern according to item 8 of the patent application, wherein the photosensitive composition contains an oxime ester photopolymerization starting from a structural moiety represented by the following general formula (I) An α-aminoacetophenone photopolymerization initiator containing a structural moiety represented by the following general formula (II), and a mercaptophosphine oxide system containing a structural moiety represented by the following general formula (III) a photopolymerization initiator; and one or more photopolymerization initiators selected from the group consisting of the titanocene-based photopolymerization initiators represented by the following general formula (IV): [Chemical Formula 1] (in) (IV) 式中,R1爲氫原子、苯基(以碳數1〜6之烷基、苯 基或鹵原子取代亦可)、碳數1〜20之烷基(可以1個以 上羥基取代,烷基鏈中間可有1個以上之氧原子)、碳數 5〜8之環烷基、碳數2〜20之烷醇基或苯醯基(碳數爲可 以1〜6之烷基或苯基取代);R2爲苯基(以碳數1〜6之 烷基、苯基或鹵原子取代亦可)、碳數1〜20之烷基(可 以1個以上羥基取代,烷基鏈中間可有1個以上之氧原子 -48- 200837503 )、碳數5〜8之環院基、碳數2〜2G之院醇基或苯醯基 (碳數爲可以1〜6之烷基或苯基取代);R1 2 3、R4爲各自 獨立,表示碳數1〜12之烷基或芳基烷基;R5、R6爲各自 獨立,表示氫原子、或碳數1〜6之烷基、或亦可2個鍵 結形成環狀烷基醚基;r7、r8爲各自獨立’表示碳數1〜 10之烷基、環己基、環戊基、芳基、或鹵原子、烷基或以 烷氧基所取代之芳基、或碳數1〜20之羰基(但,除兩者 爲碳數1〜2 0之羰基之情形以外);R9、R1G爲各自獨立 ,表示鹵原子、芳基、鹵化芳基、含雜環之鹵化芳基。 1 8.如申請專利範圍第1 6或1 7項之抗焊阻劑圖型之 形成方法,其中含以一般式(I )所示之構造部分之肟酯 系光聚合起始劑爲以下述式(I-1 )所示之化合物。 [化2](in) (IV) wherein R1 is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (may be one or more) a hydroxy group substituted with one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkylol group having 2 to 20 carbon atoms or a phenylhydrazine group (having a carbon number of 1 to 6) Or a phenyl group); R2 is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, and an alkyl group; There may be more than one oxygen atom in the middle of the chain -48-200837503), a ring of 5 to 8 carbon atoms, or a phenolic group having a carbon number of 2 to 2G (the number of carbon atoms may be 1 to 6) Or phenyl substituted); R1 2 3, R4 are each independently, and represent an alkyl group or an arylalkyl group having 1 to 12 carbon atoms; and R5 and R6 are each independently, and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Or may be bonded to form a cyclic alkyl ether group; r7 and r8 are each independently ' represents an alkyl group having a carbon number of 1 to 10, a cyclohexyl group, a cyclopentyl group, an aryl group, or a halogen atom, an alkyl group or An aryl group substituted with an alkoxy group, or a carbon number The carbonyl group of 20 (but, except for the case where both of the carbonyl group having a carbon number of 1 ~ 0); R9, R1G each independently represents a halogen atom, an aryl group, a halogenated aryl group, halogenated aryl group-containing heterocycle. 1 . The method for forming a solder resist pattern according to claim 16 or 17 of the patent application, wherein the oxime ester photopolymerization initiator containing the structural moiety represented by the general formula (I) is as follows a compound of the formula (I-1). [Chemical 2] -49- 1 9 ·如申請專利範圍第1 6或1 7項之抗焊阻劑圖型之 2 形成方法,其中含以一般式(I )所示之構造部分之肟酯 3 系光聚合起始劑爲以下述式(1-2 )所示之化合物: 200837503-49- 1 9 · A method for forming a solder resist pattern according to No. 16 or 17 of the patent application, wherein the oxime ester 3 containing a structural moiety represented by the general formula (I) is photopolymerized The starting agent is a compound represented by the following formula (1-2): 200837503 式中’ R11爲與一般式(D中Ri同義,r12及Ri4爲 各自獨與〜般式(I)中R2同義,R13爲氫原子、鹵 原子、碳數1〜12之烷基、環戊基、環己基、苯基、苄基 、苯釀基、碳數2〜12之烷醇基、碳數2〜12之烷氧基羰 基(構成《完氧基之烷基之碳數爲2以上時,烷基可以1個 以± g S所取代,於烷基鏈中間可有1個以上之氧原子) 或苯氧基羧基。 串請專利範圍第6項之抗焊阻劑圖型之形成方 法’其中該感光性組成物爲含作爲增感劑之由二乙基噻噸 酮 '二乙基胺基二苯甲酮及香豆素類所選出之至少1種。 2 1 ·如申請專利範圍第8項之抗焊阻劑圖型之形成方 法’其中該感光性組成物爲含作爲增感劑之由二乙基噻噸 酮、二乙基胺基二苯甲酮及香豆素類所選出之至少1種。 22 ·如申請專利範圍第6項之抗焊阻劑圖型之形成方 法,其中該感光性組成物含酞菁藍系顏料。 23 ·如申請專利範圍第8項之抗焊阻劑圖型之形成方 法,其中該感光性組成物爲含酞菁藍系顏料。 24.如申請專利範圍第6項之抗焊阻劑圖型之形成方 法,其中該硬化膜爲綠色或藍色。 -50- 200837503 25 .如申請專利範圍第8項之抗焊阻劑圖型之形成方 法,其中該硬化膜爲綠色或藍色。 26 · —種硬化膜,其特徵係藉由申請專利範圍第6項 之抗焊阻劑圖型之形成方法所得。 27. —種硬化膜,其特徵係藉由申請專利範圍第8項 之抗焊阻劑圖型之形成方法所得。 28. 一種印刷配線板,其特徵係具備由申請專利範圍 第6項之抗焊阻劑圖型之形成方法所得之硬化膜。 29. 一種印刷配線板,其特徵係具備由申請專利範圍 第8項之抗焊阻劑圖型之形成方法所得之硬化膜。 -51 -Wherein R11 is synonymous with the general formula (R in R, r12 and Ri4 are each synonymous with R2 in the general formula (I), R13 is a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 12, and a cyclopentane. a group, a cyclohexyl group, a phenyl group, a benzyl group, a benzene ketone group, an alkylol group having 2 to 12 carbon atoms, and an alkoxycarbonyl group having 2 to 12 carbon atoms (the number of carbon atoms constituting the alkyl group of the oxy group is 2 or more When the alkyl group may be substituted by ± g S , there may be more than one oxygen atom in the middle of the alkyl chain or phenoxy carboxyl group. The formation of the anti-solder resist pattern of the sixth item of the patent scope is requested. The method wherein the photosensitive composition is at least one selected from the group consisting of diethyl thioxanthone 'diethylaminobenzophenone and coumarin as a sensitizer. 2 1 · Patent application The method for forming a solder resist pattern according to Item 8 wherein the photosensitive composition is diethyl thioxanthone, diethylaminobenzophenone and coumarin containing a sensitizer At least one selected one is selected. 22 · A method for forming a solder resist pattern according to claim 6 of the patent application, wherein the photosensitive composition contains a phthalocyanine blue pigment. The method for forming a solder resist pattern according to Item 8 of the patent scope, wherein the photosensitive composition is a phthalocyanine-containing blue pigment. 24. The method for forming a solder resist pattern according to claim 6 of the patent application scope, Wherein the hardened film is green or blue. -50-200837503 25 . The method for forming a solder resist pattern according to claim 8 wherein the cured film is green or blue. The characteristics are obtained by the method for forming the anti-solder resist pattern of claim 6 of the patent application. 27. A hardened film characterized by the anti-solder resist pattern of claim 8 The method of forming a method. 28. A printed wiring board characterized by comprising a cured film obtained by the method for forming a solder resist pattern according to claim 6 of the patent application. 29. A printed wiring board characterized by having an application A cured film obtained by the method for forming a solder resist pattern according to item 8 of the patent scope. -51 -
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