TWI378920B - - Google Patents

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TWI378920B
TWI378920B TW094140725A TW94140725A TWI378920B TW I378920 B TWI378920 B TW I378920B TW 094140725 A TW094140725 A TW 094140725A TW 94140725 A TW94140725 A TW 94140725A TW I378920 B TWI378920 B TW I378920B
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Taiwan
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group
compound
oxime ester
alkyl group
photosensitive composition
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TW094140725A
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Chinese (zh)
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TW200631942A (en
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Mitsuo Akutsu
Daisuke Sawamoto
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Adeka Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials For Photolithography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Indole Compounds (AREA)
  • Polymerization Catalysts (AREA)
  • Polymerisation Methods In General (AREA)

Description

九、發明說明： 【發明所屬之技術領域】 本發明係關於-種可用於感光性組合物中作為光聚合引 發劑之新㈣醋化合物，將該化合物作為有效成分之光聚 合引發劑，以及於具有乙稀性不飽和鍵之聚合性化合物中 含有該光聚合引發劑而成之感光性組合物β 【先前技術】 感光性組合物係於具有乙烯性不飽和鍵之聚合性化合物 中添加光聚合引發劑者，藉由對該感光性組合物照射405 nm 或365 nm之光線實施聚合硬化，故而可用於光硬化性墨 水、感光性印刷板、各種光阻材料等。由於對短波長之光 源具有感度之感光性組合物可實施微細印刷，因此業者期 望開發-種尤其是對365 mm之光源具有良好感度之光聚合 引發劑。 作為用於該感光性組合物之光聚合引發劑，下述專利文 獻1中提出有使用肟醋衍生物。又，下述專利文獻2〜4中揭 不有一種肟酯化合物。然而，於將該等眾所周知之肟酯化 合物作為光聚合引發劑使用時，由於曝光時之光產生之分 解物附著於光罩，其結果引起燒灼時之圖案形狀不良，降 低收率。又，分解溫度為24〇。(3以下，於顯影處理後之熱 硬化步驟中分解光聚合引發劑，故而降低感光性組合物之 密著性以及耐鹼性。因此，業者期望開發一種熱分解溫度 較兩並且由於光照射產生之引發劑之分解物揮散不會污染 聚合物或裝置等的光聚合引發劑。 106551.doc 又，下述專利文獻5〜7中提出有一種具有較高反應性之 〇-酿基肟光引發劑。然而，該等〇_醯基肟光聚合引發劑之 光罩污染或耐熱性亦不充分，會降低耐鹼性。又，專利文 獻7中揭示有一種具有咔唑基構造之〇_醯基肟化合物，本 發明者們研究之結果發現：以類似於本發明化合物之環烷 氧基苯甲酿基取代之咔唑基化合物，其環烷醚具有二級 氫，故而無法合成。 專利文獻1 :美國專利第3558309號說明書 專利文獻2:美國專利第4255513號說明書 專利文獻3:美國專利第4590145號說明書 專利文獻4 :美國專利第4202697號說明書 專利文獻5:日本專利特開2〇〇〇_8〇〇68號公報 專利文獻6 :日本專利特開2〇〇1 _ 233842號公報 專利文獻7:國際公開02/1〇〇9〇3號手冊 [發明所欲解決之問題] 如上所述，本發明所欲解決之問題點在於：迄今為止， 還未開發出一種不會對所得聚合物著色或者不污染聚合物 或裝置等’並且具有良好之顯影性、密著性、耐鹼性、感 度的光聚合弓丨發劑。 本發明之目的在於提供一種光聚合引發劑，其為高感 度，並且不會對聚合物著色或者污染聚合物以及裝置等。 【發明内容】 本發明提供—種以下述通式⑴所表示之肟酯化合物以及 將該化合物作為有效成分之光聚合引發劑，從而實現上述 106551.doc 1378920 目的。 [化i]IX. The present invention relates to a novel (tetra) vinegar compound which can be used as a photopolymerization initiator in a photosensitive composition, a photopolymerization initiator which has the compound as an active ingredient, and Photosensitive composition β containing the photopolymerization initiator in a polymerizable compound having an ethylenically unsaturated bond. [Prior Art] The photosensitive composition is added to a polymerizable compound having an ethylenically unsaturated bond to add photopolymerization. The initiator is subjected to polymerization hardening by irradiating the photosensitive composition with light of 405 nm or 365 nm, and thus can be used for a photocurable ink, a photosensitive printing plate, various photoresist materials, and the like. Since a photosensitive composition having sensitivity to a short-wavelength light source can be subjected to fine printing, it is desired to develop a photopolymerization initiator which is excellent in sensitivity to a light source of 365 mm, in particular. As a photopolymerization initiator for the photosensitive composition, the use of an anthraquinone derivative is proposed in Patent Document 1 below. Further, Patent Documents 2 to 4 below disclose an oxime ester compound. However, when these well-known oxime ester compounds are used as a photopolymerization initiator, the decomposed product due to light at the time of exposure adheres to the reticle, and as a result, the pattern shape at the time of cauterization is poor, and the yield is lowered. Also, the decomposition temperature was 24 〇. (3) The photopolymerization initiator is decomposed in the thermal curing step after the development treatment, so that the adhesion of the photosensitive composition and the alkali resistance are lowered. Therefore, it is desired to develop a thermal decomposition temperature of two and due to light irradiation. The decomposition of the decomposition product of the initiator does not contaminate the photopolymerization initiator of the polymer or the device, etc. 106551.doc Further, in the following Patent Documents 5 to 7, a ruthenium-branched photoluminescence with higher reactivity is proposed. However, the photomask contamination or heat resistance of the ruthenium-based photopolymerization initiator is also insufficient, and the alkali resistance is lowered. Further, Patent Document 7 discloses a ruthenium-based structure having a carbazole structure. Based on the results of studies by the present inventors, it has been found that a carbazolyl compound substituted with a cycloalkoxybenzoyl group similar to the compound of the present invention has a secondary hydrogen and cannot be synthesized. 1: U.S. Patent No. 3,558,309, Patent Document 2: U.S. Patent No. 4,255,513, Patent Document 3: U.S. Patent No. 4,590,145, Patent Document 4: U.S. Patent No. 4202697 Patent Document 5: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. 2, No. 2, No. 233, 842 Patent Document No.: International Publication No. 02/1〇〇9〇3 MANUAL [Problems to be Solved by the Invention] As described above, the problem to be solved by the present invention is that, to date, a polymer which has not been colored or contaminated with a polymer or a device has been developed and has been developed. Photopolymerization hair styling agent for developability, adhesion, alkali resistance, and sensitivity. It is an object of the present invention to provide a photopolymerization initiator which is highly sensitive and which does not color or contaminate a polymer and [Invention] The present invention provides an oxime ester compound represented by the following formula (1) and a photopolymerization initiator containing the compound as an active ingredient, thereby achieving the above-mentioned 106551.doc 1378920.

(式中，X表示氫原子、鹵素原子或烷基，爪為2以上 時，複數個X亦可為分別不同之基，R丨、R2以及表示 R、OR、COR、SR、CONRR’ 或 CN ’ R 以及 R'表示烷基、 芳基、芳烧基或雜環基，該等亦可經鹵素原子以及/或雜 環基取代，該等中烷基以及芳烷基之伸烷基部分，亦可藉 由不飽和鍵、醚鍵、硫醚鍵、酯鍵而插入，又，R以及r, 亦可一同形成環；A表示環烷基烷基，m表示ι〜4之正 數）。 【實施方式】 以下’就本發明之肟酯化合物以及將該化合物作為有效 成分之光聚合引發劑，加以詳細說明。 上述通式（I)中，作為以X表 示之鹵素原子，可列舉氟、 氣、*/臭、碘；作為以X表示之烷基，例如可列舉甲基、乙 基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁 基、戊基、異戊基、第三戊基、己基、庚基、辛基、異辛 基、2-乙基己基、第三辛基、壬基、異壬基、癸基、異癸 基、乙烯基、烯丙基、丁烯基、乙炔基、丙炔基、甲氧基 乙基、乙氧基乙基、丙氧基乙基、甲氧基乙氧基乙基、乙 10655l.doc Ϊ378920 氧基乙氧基乙基、丙氧基乙氧基乙基、甲氧基丙基、單氟 曱基、二氟曱基、三氟曱基、三氟乙基、全氟乙基、2-(苯 幷惡唑-2’-基）乙烯基等。 作為以R以及R’表示之烷基，例如可列舉甲基乙基、 丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊 基、異戊基、第三戊基、己基、庚基、辛基、異辛基、2-乙基己基、第三辛基、壬基、異壬基、癸基、異癸基、乙 烯基、烯丙基、丁烯基、乙炔基、丙炔基、甲氧基乙基、 乙氧基乙基、丙氧基乙基、甲氧基乙氧基乙基、乙氧基乙 氧基乙基、丙氧基乙氧基乙基、甲氧基丙基、單氟甲基、 一氟甲基、三氟甲基、三氟乙基、全氟乙基、2_(苯幷惡 唑-2’-基）乙烯基等；作為以R以及R，表示之芳基，例如可 列舉苯基、甲苯基、二曱苯基、乙基苯基、氣苯基、萘 基、蒽基、菲基等，·作為以R以及表示之芳烷基，例如 了列舉基、氯苄基、α_甲基苄基、α，α·二甲基苄基、笨 基乙基、苯基乙烯基等；作為以R以及Rl表示之雜環基， 例如可列舉吡啶基、嘧啶基、呋喃基、噻吩基等；又’作 為R以及R’ 一同形成之環，例如可列舉哌啶環、嗎啉環 等。 ’Wherein X represents a hydrogen atom, a halogen atom or an alkyl group, and when the formula is 2 or more, a plurality of X may be different groups, R丨, R2 and represent R, OR, COR, SR, CONRR' or CN. 'R and R' represent an alkyl group, an aryl group, an arylalkyl group or a heterocyclic group, which may also be substituted by a halogen atom and/or a heterocyclic group, the alkyl group of the intermediate alkyl group and the aralkyl group, Alternatively, it may be inserted by an unsaturated bond, an ether bond, a thioether bond or an ester bond, and R and r may form a ring together; A represents a cycloalkylalkyl group, and m represents a positive number of ι 4). [Embodiment] Hereinafter, the oxime ester compound of the present invention and a photopolymerization initiator containing the compound as an active ingredient will be described in detail. In the above formula (I), examples of the halogen atom represented by X include fluorine, gas, */odor, and iodine; and examples of the alkyl group represented by X include methyl group, ethyl group, propyl group, and isopropyl group. Base, butyl, isobutyl, second butyl, tert-butyl, pentyl, isopentyl, third pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, Trioctyl, decyl, isodecyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxy Ethyl ethyl, methoxyethoxyethyl, B 10655l.doc Ϊ378920 Oxyethoxyethyl, propoxyethoxyethyl, methoxypropyl, monofluoroindolyl, difluoroindolyl , trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-(benzoxazole-2'-yl)vinyl, and the like. Examples of the alkyl group represented by R and R' include a methylethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group, a pentyl group, and an isopentyl group. Third amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, decyl, isodecyl, vinyl, allyl, butyl Alkenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxy Oxyethyl, methoxypropyl, monofluoromethyl, monofluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-(benzoxazole-2'-yl)vinyl Examples of the aryl group represented by R and R include, for example, a phenyl group, a tolyl group, a diphenylene group, an ethylphenyl group, a gas phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, etc. And an aralkyl group represented by, for example, an exemplified group, a chlorobenzyl group, an α-methylbenzyl group, an α,α·dimethylbenzyl group, a stupidylethyl group, a phenylvinyl group or the like; as represented by R and R1 The heterocyclic group, for example, pyridyl group, pyrimidine Group, furyl group, thienyl group and the like; and 'as R and R' together a ring formed of, for example, a piperidine ring, morpholine ring and the like. ’

作為以A表示之環烧基烧基，可列舉環丙基甲基、2•環 丙基乙基、3-環丙基丙基、環丁基甲基、2-環丁基乙基、 3-環丁基丙基、環戊基甲基、2_環戊基乙基、3_環戊基丙 基、環己基曱基、3-環己基丙基、2-氣-3-環己基丙基等。 於本發明之肟酯化合物之中，較好是上述通式⑴中’ X 106551.doc 1378920 為烷基，尤其是甲基；Rl為烷基，尤其是甲武 基，尤其是甲基；r3為貌基，尤其是乙基；‘環=燒 基，尤其是環己基甲基；m為1者。 几土烷 之 故而’作為以上述通式⑴砉千 入衣不之本發明之肟酯化合物 較好之具體例，可列舉下述化合物N〇」〜n〇32化合物 但是’本發明並非限制於下述化合物。 [化2]Examples of the cycloalkyl group represented by A include a cyclopropylmethyl group, a 2:cyclopropylethyl group, a 3-cyclopropylpropyl group, a cyclobutylmethyl group, a 2-cyclobutylethyl group, and a 3-ring group. Butylpropyl, cyclopentylmethyl, 2_cyclopentylethyl, 3-cyclopentylpropyl, cyclohexyldecyl, 3-cyclohexylpropyl, 2-cyclo-3-cyclohexylpropyl, etc. . Among the oxime ester compounds of the present invention, it is preferred that 'X 106551.doc 1378920 in the above formula (1) is an alkyl group, especially a methyl group; R1 is an alkyl group, especially a methyl group, especially a methyl group; Is a base, especially ethyl; 'ring = alkyl, especially cyclohexylmethyl; m is one. As a specific example of the oxime ester compound of the present invention which is not contained in the above formula (1), the following compounds N 〇" to n 〇 32 compounds are exemplified, but the present invention is not limited to The following compounds. [Chemical 2]

化合物No. 1Compound No. 1

化合物No.2 cr[化4]Compound No. 2 cr [Chemical 4]

化合物No.3 0Compound No.3 0

106551.doc 1378920106551.doc 1378920

以上述通式⑴表示之本發明之肟酯化合物，其通常可藉 由下述方法製造。首先，於氣化鋅存在下，同時或依次使 咔唑化合物1、碳醯氣2以及X之一個為鹵素原子之碳醯氯3 反應，獲得醯基化合物4。繼而，於第三丁氧化鉀存在 下’使醒基化合物4與醇化合物5反應，獲得醯基體6。亦 可於實施醯基化反應之前，將酵化合物附加至羧酸氯化 物。繼而，於DMF存在下，使醯基體6與鹽酸羥基胺反 應，獲得肟化合物7»繼而，使肟化合物7與酸酐8或者醯 氯8’反應，獲得以上述通式（I)表示之本發明之辟醋化合 物。例如’化合物No.l係可藉由以下述[化5]之反應式表示 之方法製造。 [化5]The oxime ester compound of the present invention represented by the above formula (1) can be usually produced by the following method. First, the mercapto compound 4 is obtained by reacting the carbazole compound 1, the carbon argon gas 2, and one of X, which are halogen atoms, in the presence or absence of zinc hydride. Then, the compound 4 is reacted with the alcohol compound 5 in the presence of potassium tributoxide to obtain a ruthenium substrate 6. The leavening compound may also be added to the carboxylic acid chloride prior to carrying out the thiolation reaction. Then, in the presence of DMF, the ruthenium substrate 6 is reacted with hydroxylamine hydrochloride to obtain the ruthenium compound 7», and then the ruthenium compound 7 is reacted with the acid anhydride 8 or ruthenium chloride 8' to obtain the invention represented by the above formula (I). The vinegar compound. For example, 'Compound No. 1 can be produced by a method represented by the following reaction formula [Chemical Formula 5]. [Chemical 5]

(XO + 人， 咔唑基化合物1 醯氯2 醯氯3(XO + human, carbazolyl compound 1 醯 chloro 2 醯 chloro 3

醯基化合物4 + Α-0Η 卜嘯 醇化合物 醯體β +s-r ο 肟化合物7 +酸軒8Mercapto compound 4 + Α-0Η Bu Xiao alcohol compound steroid β +s-r ο 肟 compound 7 + acid Xuan 8

醯氯8’Chlorine 8'

(月亏脂化合物） 106551.doc -11 - 本發明之肟酯化合物，苴可诂β I Α β丄 式 具可使用作為具有乙烯性不飽和 鍵之聚合性化合物之光聚合引發劑。 其次’京尤本發明之感光性組合物加以說明。 至於具有乙烯性不飽和鍵之上述聚合性化合物為過去 於感光性組合物中所使用者。即，作為具有乙烤性不飽和 鍵之上述聚合性化合物，例如可列舉苯乙稀、α_甲基苯乙 烯、氣苯乙稀等之苯乙稀系化合物；將（甲基）丙烯酸甲 酯、（甲基）丙烯酸乙醋、（甲基）丙烯酸正丙醋、（甲基）丙烯 酸異丙酯、（曱基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯、 (曱基）丙烯酸第二丁酯、（甲基）丙烯酸第三丁酯、（甲基）丙 烯酸四氫呋喃酯、（甲基）丙烯酸2_乙基己酯、（甲基）丙烯 酸月桂醋、（甲基）丙烯酸硬脂酯、（甲基）丙烯酸環己酯、 (甲基）丙烯酸羥基乙酯、（甲基）丙烯酸苯氧基乙酯、（甲基） 丙烯酸甲氧基乙酯、（甲基）丙烯酸乙氧基乙酯、（甲基）丙 稀酸聚（乙氧基）乙酯、（甲基）丙婦酸丙氧基乙酯、（甲基）丙 烯酸丁氧基乙酯、（甲基）丙烯酸丁氧基乙氧基乙酯、（甲 基）丙烯酸聚（丙氧基）丙酯、（甲基）丙烯酸乙烯酯、二（甲 基）丙烤酸乙二醇醋、二（曱基）丙稀酸二乙二醇醋、二（甲 基）丙烯酸三乙二醇酯、二（甲基）丙烯酸聚乙二醇酯、二 (甲基）丙烯酸丙二醇酯、二（甲基）丙烯酸聚丙二醇酯、二 (甲基）丙烯酸1，4-丁二醇酯、二（曱基）丙烯酸新戊二醇酯、 二（甲基）丙烯酸1,6-己二醇酯、三（曱基）丙烯酸三（羥甲基） 丙烷酯、三（甲基）丙烯酸三（羥甲基）乙烷酯，三（2-丙烯醯 基乙基）異氰尿酸醋、（曱基）丙稀酸季戊四醇醋、四（甲基） 106551.doc -12· 1378920 丙稀酸季戊四醇酯等之多價醇，以α，ρ·不飽和羧酸實施酯 化所獲得之化合物；丙烯腈、（甲基）丙烯醯胺、Ν_取代（甲 基）丙烯酸酯；乙酸乙烯酯、異丁基乙烯基醚、Ν_乙烯基 吼哈烷酮、乙稀氣、偏氯乙烯、二乙烯基苯、二乙烯基琥 轴酸醋、鄰笨二甲酸二烯丙酯、三烯丙基磷酸酯、三丙烯 基異氰尿酸酯等。該等之中，將本發明之肟酯化合物作為 有效成分之光聚合引發劑適合於苯乙烯、（甲基）丙烯酸甲 醋、（甲基）丙烯酸正丁酯、（甲基）丙烯酸羥基乙酯。 又，亦可藉由使用具有乙烯性不飽和鍵之上述聚合性化 合物與熱可塑性有機聚合物，從而改善硬化物之特性。作 為該熱可塑性有機聚合物，例如可列舉聚苯乙烯、聚曱基 丙烯酸甲酯、曱基丙烯酸甲酯-丙烯酸乙酯共聚物、聚（甲 基）丙烯酸、笨乙烯_(甲基）丙烯酸共聚物、（曱基）丙烯酸_ 甲基丙烯酸甲酯共聚物、聚乙烯縮丁醛、纖維酯、聚丙烯 醯胺、飽和聚酯、環氧樹脂等，該等之中，較好是聚苯乙 烯、（甲基）丙烯酸-甲基丙烯酸甲酯共聚物、環氧樹脂。 又，於本發明之感光性組合物中，作為光聚合引發劑， 除本發明之肟酯化合物以外，亦可相應需要併用其他光聚 合引發劑，有時亦可藉由併用其他光聚合引發劑，發揮顯 著相乘效果之情形。 作為可與本發明之肟酯化合物併用之光聚合引發劑可 使用先前既知孓化合物，例如可列舉二苯甲酮、苯基聯苯 酮、1-羥基-1-苯甲醯環己烷、苯偶醯、苯偶醯二甲基縮 網、1-节基-1-二曱胺基+(41-嗎啉基苯甲醯）丙烷、2_嗎啉 106551.doc 13 1378920 基-2-(4’-甲基巯基）苯甲醯丙烷、硫雜蒽酮、1-氣-4-丙氧基 硫雜蒽酮、異丙基硫雜蒽酮、二乙基硫雜蒽嗣、乙基貧 醗、4-苯甲醯-4’-甲基二苯硫醚、安息香丁醚、2_羥基·2·(Monthly fat-reducing compound) 106551.doc -11 - The oxime ester compound of the present invention, which is a photopolymerization initiator which is a polymerizable compound having an ethylenically unsaturated bond, can be used as the oxime 诂β I Α β丄. Next, the photosensitive composition of the present invention will be described. The above polymerizable compound having an ethylenically unsaturated bond is a user who has been used in a photosensitive composition. In other words, examples of the polymerizable compound having an ethylenically unsaturated bond include a styrene compound such as styrene, α-methylstyrene or styrene; and methyl (meth)acrylate; , (meth)acrylic acid ethyl vinegar, (meth)acrylic acid n-propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (mercapto) acrylic acid Second butyl ester, tert-butyl (meth)acrylate, tetrahydrofuran (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauric acid (meth)acrylate, stearic acid (meth)acrylate Ester, cyclohexyl (meth)acrylate, hydroxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxylate (meth)acrylate Ethyl ester, poly(ethoxy)ethyl (meth)acrylate, propoxyethyl (meth)propionate, butoxyethyl (meth)acrylate, butoxy (meth)acrylate Ethyl ethoxyethyl ester, poly(propoxy)propyl (meth)acrylate, (methyl) propyl Vinyl olefinate, ethylene glycol acetonate, di(indenyl) acrylate diethylene glycol vinegar, triethylene glycol di(meth)acrylate, di(meth)acrylic acid Polyethylene glycol ester, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(indenyl)acrylate Ester, 1,6-hexanediol di(meth)acrylate, tris(hydroxymethyl)propane tris(meth)acrylate, tris(hydroxymethyl)ethane tris(meth)acrylate, three ( 2-propenylethyl)isocyanuric acid vinegar, (mercapto)acrylic acid pentaerythritol vinegar, tetrakis(methyl) 106551.doc -12· 1378920 polyvalent alcohol such as pentaerythritol acrylate, with α, ρ - a compound obtained by esterification of an unsaturated carboxylic acid; acrylonitrile, (meth) acrylamide, hydrazine-substituted (meth) acrylate; vinyl acetate, isobutyl vinyl ether, hydrazine - vinyl hydrazine Halanone, ethylene, vinylidene chloride, divinylbenzene, divinyl succinic acid, diallyl phthalate, triallyl , Tris-propenyl isocyanurate and the like. Among these, the photopolymerization initiator containing the oxime ester compound of the present invention as an active ingredient is suitable for styrene, methyl methacrylate, n-butyl (meth) acrylate, and hydroxyethyl (meth) acrylate. . Further, the properties of the cured product can be improved by using the above polymerizable compound having an ethylenically unsaturated bond and the thermoplastic organic polymer. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, and stupid ethylene-(meth)acrylic acid copolymer. , (mercapto)acrylic acid _ methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polypropylene decylamine, saturated polyester, epoxy resin, etc., among these, preferably polystyrene , (meth)acrylic acid-methyl methacrylate copolymer, epoxy resin. Further, in the photosensitive composition of the present invention, as the photopolymerization initiator, in addition to the oxime ester compound of the present invention, other photopolymerization initiators may be used in combination, and other photopolymerization initiators may be used in combination. , to play a significant synergy effect. As the photopolymerization initiator which can be used in combination with the oxime ester compound of the present invention, previously known ruthenium compounds can be used, and examples thereof include benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoguanidine hexane, and benzene. Even oxime, benzoin dimethyl condensed network, 1-mercapto-1-diamino group + (41-morpholinyl benzamidine) propane, 2-morpholine 106551.doc 13 1378920 base-2-( 4'-Methyl-mercapto) benzamidine propane, thioxanthone, 1-aluminum-4-propoxy thioxanthone, isopropyl thioxanthone, diethyl thiazepine, ethyl poor醗, 4-benzylidene-4'-methyldiphenyl sulfide, benzoin butyl ether, 2_hydroxy·2·

苯甲醯丙烷、2-羥基_2·(4，-異丙基）苯甲醯丙烷、4_丁基苯 甲醯三氣甲烷、4·苯氧基苯甲醯二氯甲烷、苯曱醯甲酸甲 酯、1，7-雙（9·-吖啶基）庚烷、9·正丁基_3,6_雙（2、嗎啉基異 丁醯基）咔唑、2-甲基-4,6-雙（三氯甲基）_s_三嗪、2_苯基· 4’6-雙（二氯甲基）_s_三嗓、2-萘基·4,6_雙（三氣甲基）$-二 嗪、2,2-雙（2-氯苯基）-4,5,4'，5'-四苯基_1-2'-聯咪唑等。 又，於本發明之感光性組合物中，亦可相應需要添加對 笨甲醚、對苯二酚、焦兒茶酚、第三丁基兒茶酚、吩噻嗪 等之熱聚合抑制劑；可塑劑；接著促進劑；填充劑等之慣 用添加物。Benzopyrene propane, 2-hydroxy-2·(4,-isopropyl)benzimidazole, 4-butylbenzylidene tri-methane, 4-phenoxybenzidine dichloromethane, benzoquinone Methyl formate, 1,7-bis(9--acridinyl)heptane, 9-n-butyl-3,6-bis(2, morpholinylisobutyl) carbazole, 2-methyl-4, 6-bis(trichloromethyl)_s_triazine, 2_phenyl·4'6-bis(dichloromethyl)_s_triterpene, 2-naphthyl-4,6-bis (trimethylmethyl) )--Diazine, 2,2-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1-2'-biimidazole, and the like. Further, in the photosensitive composition of the present invention, a thermal polymerization inhibitor such as methyl ether, hydroquinone, pyrocatechol, t-butyl catechol, phenothiazine or the like may be added as needed; A plasticizer; followed by an accelerator; a conventional additive such as a filler.

通常，於本發明之感光性組合物中，亦可相應需要添加 可4解或分散上述各成分（本發明之肟酯化合物以及具有 乙烯性不飽和鍵之聚合性化合物）之溶劑，例如丙酮、甲 基乙基酮、甲基異丁基酮、曱基溶纖劑、乙基溶纖劑、氯 仿、二氣甲烷、己烷、庚烷 '辛烷、環己烷、苯、甲笨' 二甲苯、曱醇、乙醇、異丙醇。 可藉由较塗機、淋幕式塗裝機、各種印刷 '浸潰等眾所 周知之方法’將本發明之感光性組合物適用於金屬、紙、 塑膠等之支持基體上。X，亦可暫時實施於薄膜等之支持 基體上後’轉印至其他支持基體上，對於其翻方法並未 加以限制。 106551.docIn general, in the photosensitive composition of the present invention, a solvent which can dissolve or disperse the above components (the oxime ester compound of the present invention and a polymerizable compound having an ethylenically unsaturated bond), for example, acetone, may be added as needed. Methyl ethyl ketone, methyl isobutyl ketone, thiol cellosolve, ethyl cellosolve, chloroform, di-methane, hexane, heptane 'octane, cyclohexane, benzene, methyl stupid Toluene, decyl alcohol, ethanol, isopropanol. The photosensitive composition of the present invention can be applied to a support substrate of metal, paper, plastic or the like by a coater, a curtain coater, various printing methods such as 'impregnation'. X may be temporarily applied to a supporting substrate such as a film and then transferred to another supporting substrate, and the method of turning it is not limited. 106551.doc

•14· 本發明之感先性組合物，其可用於光硬化性塗料、光硬 化眭墨水、光硬化性接著劑、印刷板、印刷配線板用光阻 材料等各種用途，對於其用途並未加以特別限制。 又’作為硬化含有本發明之肟酯化合物之感光性組合物 時使用之活性光之光源’可使用發出波長為300〜450 nm之 光線者’例如可使用超高壓水銀、水銀蒸汽電弧、碳電 弧、氙氣電弧等。 再者’對於本發明之感光性組合物中之光聚合引發劑之 添加量並未加以特別限定，但本發明之肟酯化合物相對於 具有乙烯性不飽和鍵之上述聚合性化合物1〇〇重量份，較 好是1〜50重量份，更好是5〜30重量份。 實施例 以下’列舉實施例等進而詳細說明本發明，但本發明並 非限定於該等實施例。 [實施例1]化合物No.l之製造 <步騾1 >4-氟-2-甲基苯甲醯氣之製造 如下方式製造具有下述構造之4-氟-2-甲基苯甲醯氣。 [化6] 丨 於氮環境下，裝入20.0 g(0.13莫耳）之4-氟-2-甲基苯甲 酸、〇.1〇 g(l.3微莫耳）之N，N-二曱基曱醯胺以及134 g之曱 苯’室溫下滴加23.2 g(〇.20莫耳）之亞硫醯氯，升溫至 106551.doc 15 1378920 60〜65°c後攪拌1小時。餾去溶劑，減壓下50°C下乾燥，從 而獲得19.7 g之褐色液體（收率88%、GC純度99%)。 所獲得之褐色液體之IR測定之結果為如下所示，確認該 褐色液體為目的物。 IR測定：（cm-i) 2985、2931、1766、1606、1579、1486、1450、1384、 1240、1189、11〇5、964、869、823 <步驟2>醯基體之製造 如下方式製造下述醯基體。 [化7] 醯基體14. The prior composition of the present invention can be used for various applications such as photocurable paints, photocurable inks, photocurable adhesives, printing plates, and photoresists for printed wiring boards, and is not used for its purposes. Special restrictions are imposed. Further, 'the source of the active light used for hardening the photosensitive composition containing the oxime ester compound of the present invention' can be used for emitting light having a wavelength of 300 to 450 nm, for example, ultrahigh pressure mercury, mercury vapor arc, carbon arc can be used. , Xenon arc, etc. In addition, the amount of the photopolymerization initiator to be added to the photosensitive composition of the present invention is not particularly limited, but the weight of the above-described polymerizable compound having an ethylenically unsaturated bond of the oxime ester compound of the present invention is 1 〇〇. The portion is preferably from 1 to 50 parts by weight, more preferably from 5 to 30 parts by weight. EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and the like, but the present invention is not limited to the Examples. [Example 1] Production of Compound No. 1 <Step 1 > Production of 4-fluoro-2-methylbenzhydrazine Gas The following structure was used to produce 4-fluoro-2-methylbenzoic acid having the following structure. Helium. 2, 6 g (0.13 mol) of 4-fluoro-2-methylbenzoic acid, 〇.1〇g (l.3 micromolar) of N, N-di Hydrylamine and 134 g of hydrazine were added dropwise 23.2 g (〇.20 mol) of sulfinium chloride at room temperature, and the temperature was raised to 106551.doc 15 1378920 60 to 65 ° C and stirred for 1 hour. The solvent was distilled off, and dried under reduced pressure at 50 ° C to obtain 19.7 g of a brown liquid (yield 88%, GC purity: 99%). The IR measurement of the obtained brown liquid was as follows, and it was confirmed that the brown liquid was the object. IR measurement: (cm-i) 2985, 2931, 1766, 1606, 1579, 1486, 1450, 1384, 1240, 1189, 11〇5, 964, 869, 823 <Step 2> The manufacture of the ruthenium substrate was carried out as follows Describe the matrix. [Chemical 7] 醯 matrix

混合33.1 g之單氣苯、21. 及1.40 gH0傲望 5 g(〇.ll莫耳）之N-乙基咔唑以Mixing 33.1 g of monogas, 21. and 1.40 gH0 of 5 g (〇.ll mol) of N-ethylcarbazole

10〜15°〇。在1〇〜2〇1，滴加9.9〇 g °於所獲得之單氣苯溶液 h 4〇·〇 g之氣化鋁冷卻至 1 g((M3莫耳）之乙醯氯，室 10655l.doc -16 - I378920 溫下攪拌1小時。於224 g之二氯乙烷以及134 g之冰水混合 物中，在25〜3 〇C滴加反應液。分離油層後’依次以4〇 g之 5% HC1水溶液.、40 g之水' 40 g之2% NaOH水溶液洗淨。 德去二氣乙烷’自74.6 g之乙酸正丙酯實施再結晶。經由 過濾、使用乙酸正丙酯/正庚烷混合溶劑之洗淨，獲得22,4 g之淡黃色固體（收率60%、HPLC純度98%)。 所獲得之淡黃色結晶熔點為175。(：，W-NMR之化學位移 以及IR之測定結果為如下所示’可確認其為目的物之醯基 體。 i-NMR測定：（ppm) 8.70(s:lH)、8.52(s:lH)、8.17(d:lH)、8.09(d:lH)、 7.50(s:lH) 、 7.48(d:lH) 、 7.39(d:lH) 、 7.05(d:lH)、 7.00(d:lH)、4.45(d:2H)、2.73(s:3H)、2.37(s:3H)、 1.49(t:3H) IR測定：（cm·1) 3448、3054、2064、1662、1625、1589、1567、1484、 1386 、 1305 、 1245 、 1153 、 1124 、 1022 、 809 <步驟3>化合物No.l之製造 於氮氣流下，裝入57.1 g(0.5莫耳）之環己烷甲醇以及 66.0 g之1,3-二甲基-2-咪唑啉酮，30~40°C下添加8.4 g(0.075莫耳）之第三丁氧化鉀後升溫至73〜75〇c。繼而，添 加18.7 g(0.05莫耳）之步驟2中獲得之醯基體後，攪拌1小 時。添加6.3 g(〇.〇9莫耳）之鹽酸羥胺，73〜75°C下攪拌m、 時後，冷卻至室溫。添加48.2 g之乙酸正丙酯以及24.1 g之 106551.doc •17· 1378920 4%氫氧化鉀水溶液分離油層，分兩次添加75 g之水洗淨油 層。分離油層實施脫水後，60〜70°C下添加6.1 g(〇.〇6莫耳） 之乙酸酐，80〜9(TC下攪拌1小時。當冷卻至室溫時，析出 淡黃色固體。經由過遽、使用己酸正丙酯/正庚烧洗淨， 獲得淡黃色结晶10 g(收率38%、HPLC純度99% < )。分析 該淡黃色結晶時，確認該淡黃色結晶為目的物之化合物 No.l »以下表示分析結果。 (分析結果） (1)熔點：148.2°C P^H-NMR測定：（ppm) 8.50(d:lH)、8.44(d:lH)、8.08(dd:lH)、7.98(dd:lH)、 7.47(d:lH)、7.45(d:lH)、7.37(d:lH) > 6.86(d:lH)、 6.78(dd:lH)、4.43(q:2H)、3-84(d:2H)、2.52(s:3H)、 2_40(s:3H)、2.30(s:3H)、1.92-1.71(m:6H)、1.48(t:3H)、 1.38-1.04(m:5H) (3) IR測定：（cm·1) 2927、2853、1751、1649、1626、1605、1590、1568、 1488、1450、1376、1308、1275、1244、1149、1129、 1044、1009、983、941、894、812、772 (4) UV光譜測定（乙腈：水=9 : 1)10~15°〇. At 1〇~2〇1, add 9.9〇g ° to the obtained single gas benzene solution h 4〇·〇g of vaporized aluminum to 1 g ((M3 mole) of bismuth chloride, room 10655l. Doc -16 - I378920 Stir for 1 hour under temperature. Add the reaction solution at 25~3 〇C in 224 g of dichloroethane and 134 g of ice-water mixture. After separating the oil layer, '4 in 5 % HC1 aqueous solution, 40 g of water '40 g of 2% aqueous NaOH solution. De-di-ethane ethane' is recrystallized from 74.6 g of n-propyl acetate. Filtered, using n-propyl acetate / n-glycol The mixture was washed with an alkane mixed solvent to obtain 22,4 g of pale yellow solid (yield: 60%, HPLC purity: 98%). The obtained pale yellow crystals had a melting point of 175. (:, chemical shift of W-NMR and IR The measurement results are as follows: 'The ruthenium substrate can be confirmed as the target. i-NMR measurement: (ppm) 8.70 (s: 1H), 8.52 (s: 1H), 8.17 (d: 1H), 8.09 (d: lH), 7.50 (s:lH), 7.48 (d:lH), 7.39 (d:lH), 7.05 (d:lH), 7.00 (d:lH), 4.45 (d:2H), 2.73 (s:3H) ), 2.37 (s: 3H), 1.49 (t: 3H) IR measurement: (cm·1) 3448, 3054, 2064, 1662, 1625, 1589, 1567, 1484 1386, 1305, 1245, 1153, 1124, 1022, 809 <Step 3> Compound No. 1 was prepared under a nitrogen stream, and charged with 57.1 g (0.5 mol) of cyclohexane methanol and 66.0 g of 1,3- Dimethyl-2-imidazolidinone, after adding 8.4 g (0.075 mol) of potassium dibutoxide at 30 to 40 ° C, the temperature was raised to 73 to 75 ° C. Then, 18.7 g (0.05 m) was added. After the ruthenium substrate obtained in the step 2, the mixture was stirred for 1 hour. 6.3 g (〇.〇9 mol) of hydroxylamine hydrochloride was added, and m was stirred at 73 to 75 ° C, and then cooled to room temperature. 48.2 g of acetic acid was added. N-propyl ester and 24.1 g of 106551.doc •17· 1378920 4% potassium hydroxide aqueous solution to separate the oil layer, add 75 g of water to wash the oil layer twice. Separate the oil layer for dehydration, add 6.1 g at 60~70 °C (〇.〇6mol) acetic anhydride, 80~9 (stirred for 1 hour under TC. When cooled to room temperature, a pale yellow solid precipitated. After passing through hydrazine, using n-propyl hexanoate / n-glycolate , 10 g of pale yellow crystals were obtained (yield 38%, HPLC purity 99% <). When the pale yellow crystal was analyzed, it was confirmed that the pale yellow crystal was the target compound No. l » The analysis results are shown below. (Analysis results) (1) Melting point: 148.2 ° CP^H-NMR measurement: (ppm) 8.50 (d: 1H), 8.44 (d: 1H), 8.08 (dd: 1H), 7.98 (dd: 1H), 7.47 (d:lH), 7.45 (d:lH), 7.37(d:lH) > 6.86(d:lH), 6.78(dd:lH), 4.43(q:2H), 3-84(d:2H) , 2.52 (s: 3H), 2_40 (s: 3H), 2.30 (s: 3H), 1.92-1.71 (m: 6H), 1.48 (t: 3H), 1.38-1.04 (m: 5H) (3) IR Determination: (cm·1) 2927, 2853, 1751, 1649, 1626, 1605, 1590, 1568, 1488, 1450, 1376, 1308, 1275, 1244, 1149, 1129, 1044, 1009, 983, 941, 894, 812 , 772 (4) UV spectrometry (acetonitrile: water = 9: 1)

Xmax= 273、299、341 nmXmax= 273, 299, 341 nm

(5) 分解溫度測定（氮環境下，升溫速度l〇°C/分鐘，5%重量 減少溫度）241.2°C 106551.doc -18· 1378920 [實施例2]感光性組合物No. 1之製造 對於14 g之丙烯酸系共聚物，添加59 g之三（羥甲基）丙 院三丙烯酸酯、2.7g之實施例1中獲得之化合物Νο·ι以及 79 g之乙基溶纖劑加以充分攪拌’從而獲得感光性組合物 No. 1。 再者’上述丙烯酸系共聚物係藉由下述方式獲得：將甲 基丙稀酸20質量份、甲基丙稀酸羥基乙酯丨5質量份、甲基 丙烯酸甲酯10質量份以及甲基丙烯酸丁酯55質量份溶解於 乙基溶纖劑300質量份，於氮環境下添加〇 75質量份之偶 氮二異丁腈，70。(：下反應5小時。 [實施例3]感光性組合物No.2之製造 對於7_2 g之丙烯酸系共聚物’添加4.3 g之三（經甲基）丙 烧三丙烯酸酯、2.0 g之實施例1中獲得之化合*Ν〇.ι以及 87 g之乙基溶纖劑加以充分攪拌’從而獲得感光性組合物 Νο·2。 [實施例4]感光性組合物No.3之製造 對於14 g之苯乙烯-丙烯酸系感光性共聚物，添加6〇 g 之六丙烯酸二季戊四醇酯、1.3 g之實施例1中獲得之化合 物No.l、1.3 g之2,2_雙（2_氯苯基）_4,5,4，，5，·四苯基-丨·〗,·聯 _唾以及83 g之乙基溶纖劑加以充分攪拌，從而獲得感光 性組合物No.3 9 再者’上述苯乙烯·丙烯酸系感光性共聚物係藉由下述 方式獲得：將苯乙烯26.3質量份、曱基丙烯酸2•羥基乙酯 43.8質量份、甲基丙烯酸35質量份以及甲基丙烯酸乙酯7〇 106551.doc •19- 1378920 質量份溶解於乙基溶纖劑175質量份，於氮環境下添加偶 氮二異丁腈0.75質量份，90°C下反應5小時，繼而花費1〇分 鐘滴下將23.5質量份之甲基丙烯酸異氰酸乙酯、〇ai質量 份之辛酸錫溶解於乙基溶纖劑20質量份者，滴下後反應2 小時。 [實施例5]感光性組合物ν〇.4之製造 對於12 g之苯乙烯-丙烯酸系感光性共聚物，添加81 g 之二季戊四醇五及六丙烯酸酯、2.5 g之實施例1中獲得之 化合物No. 1、47 g之乙基溶纖劑以及30 g之環己酮加以充 分擾拌，從而獲得感光性組合物No.4。 [實施例6]感光性組合物No.5之製造 對於20 g之丙稀酸系共聚物，添加8·7 g之三（經甲基）丙 烷三丙烯酸酯、2.2 g之實施例1中獲得之化合*N〇1、4 6 g之雙酚A型環氧樹脂以及65 g之乙基溶纖劑加以充分擾 拌，從而獲得感光性組合物No.5。 [比較例1]感光性組合物No.6之製造 對於14 g之實施例2中使用之丙烯酸系共聚物，添加5 9 g之二季戊四醇五及六丙烯酸酯、2.1 g之比較化合物丨（下 述[化8])以及78 g之乙基溶纖劑加以充分攪拌，從而獲得 感光性組合物N 〇. 6。 [化8] 比較化合物1 106551.doc •20· 0(5) Decomposition temperature measurement (temperature increase rate l〇°C/min, 5% weight reduction temperature in a nitrogen atmosphere) 241.2 ° C 106551.doc -18· 1378920 [Example 2] Production of photosensitive composition No. 1 For 14 g of the acrylic copolymer, 59 g of tris(hydroxymethyl)propyl triacrylate, 2.7 g of the compound obtained in Example 1 and 79ο·ι and 79 g of ethyl cellosolve were added and thoroughly stirred. 'The photosensitive composition No. 1 was obtained. Further, the above acrylic copolymer was obtained by 20 parts by mass of methyl acrylate, 5 parts by mass of hydroxyethyl methacrylate, 10 parts by mass of methyl methacrylate, and methyl group. 55 parts by mass of butyl acrylate was dissolved in 300 parts by mass of ethyl cellosolve, and 75 parts by mass of azobisisobutyronitrile, 70, was added under a nitrogen atmosphere. (: The next reaction was carried out for 5 hours. [Example 3] Production of photosensitive composition No. 2 The addition of 4.3 g of tris(methyl)propane triacrylate and 2.0 g to 7_2 g of the acrylic copolymer ' The compound *Ν〇.ι obtained in Example 1 and 87 g of ethyl cellosolve were thoroughly stirred to obtain a photosensitive composition Νο. 2 [Example 4] Production of photosensitive composition No. 3 for 14 G styrene-acrylic photosensitive copolymer, 6 g of dipentaerythritol hexaacrylate, 1.3 g of compound No. 1 obtained in Example 1, 1.3 g of 2,2_bis (2-chlorobenzene) Base)_4,5,4,5,·tetraphenyl-anthracene, ···_sal and 83 g of ethyl cellosolve were thoroughly stirred to obtain a photosensitive composition No. 3 9 The styrene-acrylic photosensitive copolymer was obtained by the following means: 26.3 parts by mass of styrene, 43.8 parts by mass of 2, hydroxyethyl methacrylate, 35 parts by mass of methacrylic acid, and ethyl methacrylate 7 〇106551.doc •19- 1378920 parts by mass dissolved in 175 parts by mass of ethyl cellosolve, adding azobisisobutyronitrile 0.7 under nitrogen 5 parts by mass, reacted at 90 ° C for 5 hours, and then dripped 23.5 parts by mass of ethyl methacrylate isocyanate, and 〇ai parts by mass of tin octylate was dissolved in 20 parts by mass of ethyl cellosolve. After the dropwise addition, the reaction was carried out for 2 hours. [Example 5] Production of photosensitive composition ν〇.4 For 12 g of the styrene-acrylic photosensitive copolymer, 81 g of dipentaerythritol penta and hexaacrylate, 2.5 g was added. The compound No. 1, 47 g of ethyl cellosolve obtained in Example 1, and 30 g of cyclohexanone were sufficiently scrambled to obtain a photosensitive composition No. 4. [Example 6] Photosensitive combination Production of No. 5 For 20 g of the acrylic acid copolymer, 8·7 g of tris(methyl)propane triacrylate, 2.2 g of the compound obtained in Example 1 *N〇1, 4 were added. 6 g of bisphenol A type epoxy resin and 65 g of ethyl cellosolve were sufficiently scrambled to obtain photosensitive composition No. 5. [Comparative Example 1] Production of photosensitive composition No. 6 for 14 g of the acrylic copolymer used in Example 2, adding a mixture of 5 9 g of dipentaerythritol penta and hexaacrylate, 2.1 g Shu (described below under [Chemical 8]) and 78 g of ethyl cellosolve to be sufficiently stirred to obtain photosensitive composition billion N 6. [Formula 8] Comparative Compound 1 106551.doc • 20 · 0

^78920^78920

分解溫度測定（氮環境下，升溫速度10°c/分鐘，5%重量 減少溫度）191.2°CDecomposition temperature measurement (temperature increase rate 10 ° c / min, 5% weight reduction temperature) 191.2 ° C

[比較例2]感光性組合物No.7之製造 除代替丙烯酸系共聚物而使用實施例4中使用之苯乙烯-丙烯酸系感光性共聚物以外，其餘以與比較例1相同之條 件下獲得感光性組合物No.7。 [比較例3]感光性組合物No.8之製造 對於7.2 g之實施例2中使用之丙烯酸系共聚物，添加4.3 g之三（羥曱基）丙烷三丙烯酸酯、1.5 g之比較化合物2(下述 [化9])以及87 g之乙基溶纖劑加以充分攪拌，從而獲得感 光性組合物No.8。 [化9] 比較化合物2[Comparative Example 2] Production of the photosensitive composition No. 7 was carried out under the same conditions as in Comparative Example 1, except that the styrene-acrylic photosensitive copolymer used in Example 4 was used instead of the acrylic copolymer. Photosensitive composition No. 7. [Comparative Example 3] Production of photosensitive composition No. 8 For 7.2 g of the acrylic copolymer used in Example 2, 4.3 g of tris(hydroxyindenyl)propane triacrylate and 1.5 g of Comparative Compound 2 were added. (The following [Chem. 9]) and 87 g of ethyl cellosolve were thoroughly stirred to obtain a photosensitive composition No. 8. Comparative Compound 2

分解溫度測定（氮環境下，升溫速度10°C/分鐘’ 5。/。重量 減少溫度）232.2°CDecomposition temperature measurement (temperature increase rate 10 ° C / min in a nitrogen atmosphere 5 / / weight reduction temperature) 232.2 ° C

[比較例4]感光性組合物No.9之製造 除代替丙烯酸系共聚物而使用實施例4中使用之苯乙烯- 106551.doc -21 - 1378920 丙烯酸系感光性共聚物以外，其餘以與比較例3相同之條 件下獲得感光性組合物No. 9。 如下評估所獲得之感光性組合物。即，基板上旋塗γ縮 水甘油氧基丙基甲基乙氧基矽烷加以充分旋塗乾燥後，旋 塗（1300 r.p.m、50秒）上述感光性組合物ν〇. 1〜9後使其乾 燥。70C下烘烤20分鐘後，塗層聚乙烯醇5質量％溶液製成 氧氣阻隔膜。70°C下乾燥20分鐘後，使用特定光罩且使用 _ 超高壓水銀燈作為光源實施曝光後，25°C下、於2.5❶/。碳酸 鈉溶液中浸潰30秒實施顯影且充分水洗。水洗乾燥後， 230 C下烘烤1小時固定成圖案。再者，曝光量為8〇 mJ/cm2。如下評估所獲得之圖案。將各感光性組合物中使 用之光聚合引發劑與其分解溫度以及各種評估結果表示於 表1 〇 <密著性> 根據JIS D 0202之試驗方法曝光顯影後，在2〇〇 下加熱 籲 30刀鐘之塗膜予以橫切成棋盤狀，繼而藉由玻璃膠帶實施 剝離測試，目視評估棋盤之剝離狀態。將確認為全部未剝 離者設為〇，將確認剝離者設為X。 <耐驗性> 顯影曝光後，20(TC下加熱處理30分鐘。將加熱處理後[Comparative Example 4] Production of photosensitive composition No. 9 The styrene-106551.doc -21 - 1378920 acrylic photosensitive copolymer used in Example 4 was used instead of the acrylic copolymer, and the others were compared and compared. Photosensitive composition No. 9 was obtained under the same conditions as in Example 3. The photosensitive composition obtained was evaluated as follows. That is, the substrate was spin-coated with γ-glycidoxypropylmethylethoxysilane and sufficiently spin-dried, and then spin-coated (1300 rpm, 50 seconds) to expose the photosensitive composition ν〇. 1 to 9 and dried. . After baking at 70 C for 20 minutes, the coated polyvinyl alcohol 5 mass% solution was made into an oxygen barrier film. After drying at 70 ° C for 20 minutes, the exposure was carried out at 25 ° C using a specific mask and using an _ ultrahigh pressure mercury lamp as a light source. Development was carried out by dipping in a sodium carbonate solution for 30 seconds and sufficiently washed with water. After washing with water, it was baked at 230 C for 1 hour and fixed in a pattern. Furthermore, the exposure amount was 8 〇 mJ/cm 2 . The pattern obtained was evaluated as follows. The photopolymerization initiator used in each photosensitive composition and its decomposition temperature and various evaluation results are shown in Table 1. 〇 <Adhesiveness> After exposure and development according to the test method of JIS D 0202, heating under 2 〇〇 The film of 30 knives was cut into a checkerboard shape, and then a peeling test was performed by a glass tape, and the peeling state of the board was visually evaluated. It is confirmed that all of the unpeeled persons are set to 〇, and it is confirmed that the peeling is set to X. <Testability> After development exposure, 20 (heat treatment at TC for 30 minutes. After heat treatment)

之塗膜，於a)5% NaOHaq.中 24小時，b)4% KOHaq.中 50°C 下1〇分鐘，c)l% NaOHaq.中80T：下5分鐘之條件下浸潰， 目視評估浸潰後之外觀。將無任何外觀變化且完全未剝離 光阻材料者設為〇，將可確認光阻材料之浮動者設為△， 106551.doc -22- 1378920 將確認光阻材料剝離者設為χ。 <感度> 除以曝光量5 0 mJ/cm2實施以外，其餘以與上述顯影性 之試驗相同之方式，分為如下五個階段評估：將曝光部之 形狀與光罩形狀一致者設為5，將對於光罩形狀面積為5% 以下可確認缺損者設為4，將面積5〜20%缺損者設為3，將 面積20〜50%缺損者設為2，將面積大於50%缺損者設為1。 將結果表示於表1。 [表1] 光聚合.引發劑 熱分解溫度 密著性 财驗性 感度 實施例2 化合物No. 1 241.2〇C 〇 〇 5 實施例3 化合物No.l 241.2〇C 〇 〇 5 實施例4 化合物No. 1 241.2〇C 〇 〇 5 實施例5 化合物No.l 241.2。。 〇 〇 5 實施例6 化合物No.l 241.2。。 〇 〇 5 比較例1 比較化合物1 191.2〇C X X 3 比較例2 比較化合物1 191.2〇C X X 3 比較例3 比較化合物2 232.2〇C 〇 Δ 5 比較例4 比較化合物2 232.2〇C 〇 Δ 5 自實施例1〜6以及比較例1〜4顯示，使用本發明之將酯化 合物之感光性組合物之密著性，其與眾所周知之肟酯化合 物之情形相同或優良，耐鹼性較為優良。尤其是與比較例 1以及2相比，密著性、耐鹼性優良，與比較化合物1具有 基本性能差，比較化合物1之性财熱性較低，於2 3 0 °C下之 熱硬化處理中比較化合物1分解，故而認為感光性組合物 之性能有所下降。本發明之肟酯化合物，其分解溫度高於 106551.doc -23 - 1378920 240°C，比眾所周知之肟酯化合物高9〜5〇<t，為耐熱性優 良、在熱硬化處理溫度為穩定者。 [實施例7]曝光處理之昇華性評估 將0.5 g之化合物N〇1之引發劑溶解於1〇 g之丙二醇單甲 醚乙酸酯，添加〇_5 g之丙烯酸系聚合物（與實施例2相同）The film was coated in a) 5% NaOH aq. for 24 hours, b) 4% KOHaq. at 50 ° C for 1 minute, c) 1% NaOH aq. 80T: under 5 minutes of impregnation, visual evaluation The appearance after the dipping. It is assumed that the photoresist of the photoresist material is 〇, and the float of the photoresist is Δ, 106551.doc -22- 1378920. <Sensitivity> Except for the exposure amount of 50 mJ/cm2, the evaluation was carried out in the following five stages in the same manner as the above-described developability test: the shape of the exposure portion was matched with the shape of the mask. 5, for the mask shape area of 5% or less, it can be confirmed that the defect is 4, the area 5 to 20% defect is 3, the area 20 to 50% defect is 2, and the area is greater than 50% defect. Set to 1. The results are shown in Table 1. [Table 1] Photopolymerization. Initiator Thermal Decomposition Temperature Adhesion Sensitivity Example 2 Compound No. 1 241.2〇C 〇〇5 Example 3 Compound No. 1 241.2〇C 〇〇5 Example 4 Compound No. 1 241.2 〇C 〇〇5 Example 5 Compound No. 1 241.2. . 〇 〇 5 Example 6 Compound No. 1 241.2. . 〇〇5 Comparative Example 1 Comparative Compound 1 191.2〇CXX 3 Comparative Example 2 Comparative Compound 1 191.2〇CXX 3 Comparative Example 3 Comparative Compound 2 232.2〇C 〇Δ 5 Comparative Example 4 Comparative Compound 2 232.2〇C 〇Δ 5 Self-Example 1 to 6 and Comparative Examples 1 to 4 show that the adhesion of the photosensitive composition of the ester compound of the present invention is the same as or excellent in the case of the known oxime ester compound, and the alkali resistance is excellent. In particular, compared with Comparative Examples 1 and 2, the adhesion and alkali resistance were excellent, and the basic compound was inferior to the comparative compound 1, and the comparative compound 1 was low in heat and heat hardening treatment at 203 °C. In Comparative Example 1, the compound 1 was decomposed, and it was considered that the performance of the photosensitive composition was lowered. The oxime ester compound of the present invention has a decomposition temperature higher than 106551.doc -23 - 1378920 240 ° C, which is 9 to 5 Å higher than the well-known oxime ester compound, and is excellent in heat resistance and stable at a heat curing temperature. By. [Example 7] Sublimation evaluation of exposure treatment 0.5 g of the initiator of the compound N〇1 was dissolved in 1 g of propylene glycol monomethyl ether acetate, and 〇5 g of the acrylic polymer was added (with the example) 2 same)

加以混合者，放入直徑為7〇 nm之培養皿，7〇<t下乾燥U 小時。培養皿上…〇〇xl〇〇 _之石英板作為蓋子蓋For mixing, put in a Petri dish with a diameter of 7 〇 nm and dry for 7 hours at 7 Torr. On the culture dish... 〇〇xl〇〇 _ the quartz plate as the lid cover

住，以10 mJ/cm2曝光2小時。根據附著於石英板之附著物 多少，評估㈣性。並未發現附著物1域理前後之石 英板照片表示於圖1以及圖2。 [比較例5]比較化合物之昇華性評估 除將化合物No.1替換為比較化合物2以夕卜，其餘以與實 施例7相同之方式評估附著物。附著有多數個附著物了曝 光處理前後之石英板照片表示於圖3以及圖4。Live and expose for 2 hours at 10 mJ/cm2. The (four) nature was evaluated based on how much attached to the quartz plate. It has not been found that the photographs of the stone plates before and after the attachment 1 are shown in Fig. 1 and Fig. 2. [Comparative Example 5] Evaluation of sublimation property of comparative compound The attachment was evaluated in the same manner as in Example 7 except that Compound No. 1 was replaced with Comparative Compound 2. A photograph of a quartz plate to which a plurality of adherends have been attached before and after the exposure treatment is shown in Figs. 3 and 4 .

圖1係實施例7中使用之石英板曝光前之照片，圖2係實 施例使用之石英板曝光後之照片。囷3係比較例5中使 用之石英板秦光前之照片’圖4係比較例5中使用之石英板 曝光後之照片。圖i、圖2、圖3之石英板中，並未發現附 著物。圖4中發現無數個結晶狀之附著物。 自實施例7以及比較例5,可推測本發明之化合物益曝光 後之昇華物，並且不污染光罩。另_方面，眾所周知之光 =發劑中具有大量昇耗，可推•染光罩。藉此，可連 續使用利用本發明之光引發劑之硬化性組合物，作使用先 別之光引發劑之情形時必須洗淨光罩等裝置，故而藉由使 10655 丨.docFig. 1 is a photograph before exposure of a quartz plate used in Example 7, and Fig. 2 is a photograph after exposure of a quartz plate used in the embodiment.囷3 is a photograph of the quartz plate before Qinguang used in Comparative Example 5. Fig. 4 is a photograph of the quartz plate used in Comparative Example 5 after exposure. In the quartz plates of Figs. 1, 2, and 3, no attachments were found. Numerous crystalline deposits were found in Figure 4. From Example 7 and Comparative Example 5, it was presumed that the compound of the present invention was used as a sublimate after exposure and did not contaminate the mask. Another _ aspect, the well-known light = a large amount of fuel in the hair agent, can push and dye the mask. Thereby, the curable composition using the photoinitiator of the present invention can be continuously used, and when a photoinitiator is used, it is necessary to clean the mask and the like, so that by making 10655 丨.doc

-24- 1378920 用本發明之光引發劑可提高生產性。 [產業上之可利用性] 本發明之將s旨化合物，其具有高感度且熱分解溫度較 高’不會損害感光性組合物之密著性、耐鹼性，進而光照 射下產生之分解物不會附著於光罩，從而可使用作為光聚 合引發劑。 【圖式簡單說明】 圖1係實施例7中使用之石英板曝光前的照片。 圖2係實施例7中使用之石英板曝光後的照片。 圖3係比較例.5中使用之石英板曝光前的照片。 圖4係比較例5中使用之石英板曝光後的照片。 106551.doc 25·-24- 1378920 The productivity can be improved by using the photoinitiator of the present invention. [Industrial Applicability] The compound of the present invention has high sensitivity and high thermal decomposition temperature, which does not impair the adhesion and alkali resistance of the photosensitive composition, and further decomposes under light irradiation. The object does not adhere to the photomask, and thus can be used as a photopolymerization initiator. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photograph of a quartz plate used in Example 7 before exposure. Figure 2 is a photograph of the quartz plate used in Example 7 after exposure. Fig. 3 is a photograph before exposure of a quartz plate used in Comparative Example 5. Fig. 4 is a photograph of the quartz plate used in Comparative Example 5 after exposure. 106551.doc 25·

Claims (1)

第094140725號專利申請案 中文申請專利範圍替換本(101年9月介良 十、申請專利範圍： ^ —種肟酯化合物，係以下述通式⑴表示， [化1]Japanese Patent Application No. 094140725 (Replacement of Chinese Patent Application No.) (September 101, Jieliang X. Application Patent Range: ^ - oxime ester compound, represented by the following general formula (1), [Chemical 1] (式中，X表示氫原子、卤素原子或烷基，爪為2以上時， 複數個X亦可為分別不同之基’ R]、R2以及R3表示R、 、COR、SR、C0NRR，或者CN，r以及Rl表示烷基、 芳基、芳烷基或雜環基，該等亦可經鹵素原子以及/或雜 環基取代，該等之中烷基以及芳烷基之伸烷基部分，亦 可藉由不飽和鍵、醚鍵、硫醚鍵、酯鍵插入，又R以及 π亦可一同形成環；A表示環烷基烷基，m表示卜4之正 數）。 2.如請求項1之肟酯化合物，其中χ為烷基。 3·如請求項1之肟酯化合物’其中心為烷基。 4·如請求項1之肟酯化合物，其中心為烷基。 5·如請求項1之肟酯化合物，其中化為烷基。 6. —種光聚合引發劑，係以如請求項丨〜5中任一項之肟酯 化合物作為有效成分者。 7. 一種感光性組合物，係於具有乙烯性不飽和鍵之聚合性 化合物中，含有如請求項6之光聚合引發劑而成者。 106551-1010904.doc(wherein, X represents a hydrogen atom, a halogen atom or an alkyl group, and when the claw is 2 or more, a plurality of X may be different radicals 'R], R2 and R3 represent R, COR, SR, C0NRR, or CN. And r and R1 represent an alkyl group, an aryl group, an arylalkyl group or a heterocyclic group, which may also be substituted by a halogen atom and/or a heterocyclic group, wherein the alkyl group and the alkyl group of the aralkyl group, Alternatively, it may be inserted by an unsaturated bond, an ether bond, a thioether bond or an ester bond, and R and π may form a ring together; A represents a cycloalkylalkyl group, and m represents a positive number of b). 2. The oxime ester compound of claim 1, wherein hydrazine is an alkyl group. 3. The oxime ester compound of claim 1 wherein the center is an alkyl group. 4. The oxime ester compound of claim 1, wherein the center is an alkyl group. 5. The oxime ester compound of claim 1, wherein the compound is alkyl. A photopolymerization initiator which is an oxime ester compound according to any one of claims 1 to 5 as an active ingredient. A photosensitive composition comprising a polymerizable compound having an ethylenically unsaturated bond and containing the photopolymerization initiator of claim 6. 106551-1010904.doc
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