TWI752101B - Photosensitive composition, manufacturing method of photosensitive composition, photopolymerization initiator, and preparation method of photopolymerization initiator - Google Patents

Photosensitive composition, manufacturing method of photosensitive composition, photopolymerization initiator, and preparation method of photopolymerization initiator Download PDF

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TWI752101B
TWI752101B TW106136151A TW106136151A TWI752101B TW I752101 B TWI752101 B TW I752101B TW 106136151 A TW106136151 A TW 106136151A TW 106136151 A TW106136151 A TW 106136151A TW I752101 B TWI752101 B TW I752101B
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山口尚人
野田国宏
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日商東京應化工業股份有限公司
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    • 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
    • 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
    • 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
    • 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

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Abstract

本發明提供一種感光性組合物、該感光性組合物之製造方法、可較佳地調配於該感光性組合物中之光聚合起始劑、及該光聚合起始劑之調製方法，上述感光性組合物含有光聚合性化合物(A)、含有於與肟基(＞C=N-O-)中之C=N鍵鄰接之位置具有羰基之特定結構之肟酯化合物的光聚合起始劑(B)、及溶劑(S)，且經時性之感度之降低受到抑制。 本發明係於好感度但另一方面容易發生感度之經時性降低之感光性組合物中，將水分之量、及特定結構之羧酸之含量限制為特定之值以下，上述感光性組合物含有光聚合性化合物(A)、含有於與肟基(＞C=N-O-)中之C=N鍵鄰接之位置具有羰基之特定結構之肟酯化合物的光聚合起始劑(B)、及溶劑(S)。The present invention provides a photosensitive composition, a method for producing the photosensitive composition, a photopolymerization initiator that can be preferably formulated into the photosensitive composition, and a method for preparing the photopolymerization initiator, wherein the photosensitive composition is described above. A photopolymerizable composition containing a photopolymerizable compound (A), a photopolymerization initiator (B) containing an oxime ester compound having a specific structure of a carbonyl group at a position adjacent to the C=N bond in an oxime group (>C=NO-). ), and the solvent (S), and the decrease in sensitivity over time was suppressed. In the present invention, the amount of water and the content of carboxylic acid having a specific structure are limited to a specific value or less in a photosensitive composition in which the sensitivity is likely to decrease with time, and the above-mentioned photosensitive composition A photopolymerization initiator (B) containing a photopolymerizable compound (A), an oxime ester compound having a specific structure having a carbonyl group at a position adjacent to the C=N bond in an oxime group (>C=NO-), and Solvent (S).

Description

感光性組合物、感光性組合物之製造方法、光聚合起始劑及光聚合起始劑之調製方法Photosensitive composition, manufacturing method of photosensitive composition, photopolymerization initiator, and preparation method of photopolymerization initiator

本發明係關於一種感光性組合物、感光性組合物之製造方法、光聚合起始劑及光聚合起始劑之調製方法。The present invention relates to a photosensitive composition, a method for producing the photosensitive composition, a photopolymerization initiator, and a method for preparing the photopolymerization initiator.

於如液晶顯示裝置之顯示裝置中，如絕緣膜之材料必須使從如背光裝置之光源發出之光效率良好地透過。因此，為了形成絕緣膜，要求能夠形成透明性優異之膜之材料。 通常此種透明絕緣膜於基板上被圖案化。作為形成經圖案化之透明絕緣膜之方法，已知有例如使用含有具有氧雜環丁烷環之鹼溶性樹脂、聚合性多官能化合物、及α-胺基烷基苯酮系光聚合起始劑之負型感光性組合物之方法(參照專利文獻1)。 此外，近年來，隨著液晶顯示器之生產台數增大，彩色濾光片之生產量亦不斷增大。因此，就進一步提高生產性之觀點而言，期待能夠以低曝光量形成圖案之高感度之感光性組合物。 然而，專利文獻1所記載之負型感光性組合物於感度方面要求進一步改良。 於此種狀況下，本申請人提出有一種含有於與肟基(＞C=N-O-)中之C=N鍵鄰接之位置具有羰基之特定結構之肟酯化合物作為光聚合起始劑的感光性組合物作為高感度之感光性組合物(專利文獻2)。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2012-173678號公報 [專利文獻2]日本專利特開2013-148872號公報In a display device such as a liquid crystal display device, a material such as an insulating film must efficiently transmit light emitted from a light source such as a backlight device. Therefore, in order to form an insulating film, a material capable of forming a film with excellent transparency is required. Usually such a transparent insulating film is patterned on a substrate. As a method of forming a patterned transparent insulating film, it is known to use, for example, an alkali-soluble resin having an oxetane ring, a polymerizable polyfunctional compound, and an α-aminoalkylphenone-based photopolymerization initiator. The method of the negative photosensitive composition of an agent (refer patent document 1). In addition, in recent years, with the increase in the number of production units of liquid crystal displays, the production volume of color filters is also increasing. Therefore, from the viewpoint of further improving productivity, a high-sensitivity photosensitive composition capable of forming a pattern with a low exposure amount is expected. However, the negative photosensitive composition described in Patent Document 1 is required to be further improved in terms of sensitivity. Under such circumstances, the applicant proposes a photosensitive photopolymer containing an oxime ester compound having a specific structure with a carbonyl group at the position adjacent to the C=N bond in the oxime group (>C=NO-) as a photopolymerization initiator. The photosensitive composition is a high-sensitivity photosensitive composition (Patent Document 2). [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2012-173678 [Patent Document 2] Japanese Patent Laid-Open No. 2013-148872

[發明所欲解決之問題] 然而，如專利文獻2所記載之含有於與肟基(＞C=N-O-)中之C=N鍵鄰接之位置具有羰基之特定結構之肟酯化合物作為光聚合起始劑的感光性組合物之感度優異，另一方面存在屢次發生經時性之感度降低之問題。 本發明係鑒於上述課題而完成者，其目的在於提供一種感光性組合物、該感光性組合物之製造方法、可較佳地調配於該感光性組合物中之光聚合起始劑及該光聚合起始劑之調製方法，該感光性組合物含有光聚合性化合物(A)、含有於與肟基(＞C=N-O-)中之C=N鍵鄰接之位置具有羰基之特定結構之肟酯化合物的光聚合起始劑(B)、及溶劑(S)，且經時性之感度之降低受到抑制。 [解決問題之技術手段] 本發明者等人發現，於含有光聚合性化合物、含有於與肟基(＞C=N-O-)中之C=N鍵鄰接之位置具有羰基之特定結構之肟酯化合物的光聚合起始劑(B)、及溶劑(S)且好感度但另一方面容易發生感度之經時性降低之感光性組合物中，藉由將水分之量、及特定結構之羧酸之含量限制為特定之值以下，而能夠抑制感度之經時性之降低，從而完成本發明。具體而言，本發明提供以下者。 本發明之第1態樣係一種感光性組合物，其係含有光聚合性化合物(A)、光聚合起始劑(B)、及溶劑(S)者，且 光聚合起始劑(B)含有下述式(1)： [化1]

Figure 02_image001
(式(1)中，R1 、R2 、及R3 分別獨立為具有與碳原子鍵結之鍵結鍵之一價有機基) 所表示之化合物， 感光性組合物中之下述式(2)： R3 COOH・・・(2) (式(2)中，R3 與上文所述相同) 所表示之羧酸之含量相對於光聚合起始劑(B)之質量與式(2)所表示之羧酸之質量之合計為550質量ppb以下， 上述感光性組合物中之水分之量相對於上述感光性組合物整體為0.1質量%以下。 本發明之第2態樣係一種感光性組合物之製造方法，其包括將光聚合性化合物(A)與光聚合起始劑(B)溶解於溶劑(S)中，且 光聚合起始劑(B)為下述式(1)： [化2]
Figure 02_image003
(式(1)中，R1 、R2 、及R3 分別獨立為具有與碳原子鍵結之鍵結鍵之一價有機基) 所表示之化合物， 溶解於上述溶劑(S)中之光聚合起始劑(B)所附帶之水分之量相對於光聚合起始劑(B)之質量與水分之質量之合計為1質量%以下。 本發明之第3態樣係一種光聚合起始劑，其係含有下述式(1)： [化3]
Figure 02_image005
(式(1)中，R1 、R2 、及R3 分別獨立為具有與碳原子鍵結之鍵結鍵之一價有機基) 所表示之化合物者，且 光聚合起始劑所附帶之水分之量相對於光聚合起始劑之質量與水分之質量之合計為1質量%以下， 光聚合起始劑所附帶之下述式(2)： R3 COOH・・・(2) (式(2)中，R3 所表示之羧酸之含量相對於光聚合起始劑之質量與式(2)所表示之羧酸之質量之合計為550質量ppb以下。 本發明之第4態樣係第3態樣之光聚合起始劑之調製方法，其 包括於不會將光聚合起始劑(B)熱分解之溫度下在遮光下進行乾燥。 [發明之效果] 根據本發明，可提供一種感光性組合物、該感光性組合物之製造方法、可較佳地調配於該感光性組合物中之光聚合起始劑、及該光聚合起始劑之調製方法，該感光性組合物含有光聚合性化合物(A)、含有於與肟基(＞C=N-O-)中之C=N鍵鄰接之位置具有羰基之特定結構之肟酯化合物的光聚合起始劑(B)、及溶劑(S)，且經時性之感度之降低受到抑制。[Problems to be Solved by the Invention] However, as described in Patent Document 2, an oxime ester compound containing a specific structure having a carbonyl group at a position adjacent to a C=N bond in an oxime group (>C=NO-) is used as a photopolymerizable compound. The sensitivity of the photosensitive composition of the initiator is excellent, but on the other hand, there is a problem that the sensitivity of the time-dependent decrease frequently occurs. The present invention has been accomplished in view of the above-mentioned problems, and its object is to provide a photosensitive composition, a method for producing the photosensitive composition, a photopolymerization initiator that can be preferably formulated in the photosensitive composition, and the photosensitive composition. A method for preparing a polymerization initiator comprising a photopolymerizable compound (A), an oxime having a specific structure of a carbonyl group at a position adjacent to a C=N bond in an oxime group (>C=NO-) The photopolymerization initiator (B) of the ester compound and the solvent (S) suppress the decrease in sensitivity over time. [Technical Means for Solving the Problem] The present inventors have found an oxime ester containing a photopolymerizable compound and having a specific structure of a carbonyl group at a position adjacent to a C=N bond in an oxime group (>C=NO-). The photopolymerization initiator (B) and the solvent (S) of the compound have good sensitivity, but on the other hand, the photosensitive composition is prone to decrease in sensitivity over time. The present invention is accomplished by limiting the content of the acid to a specific value or less to suppress the decrease in sensitivity over time. Specifically, the present invention provides the following. The first aspect of the present invention is a photosensitive composition containing a photopolymerizable compound (A), a photopolymerization initiator (B), and a solvent (S), and the photopolymerization initiator (B) Contains the following formula (1): [Chemical 1]
Figure 02_image001
(In formula (1), R 1 , R 2 , and R 3 are each independently a valent organic group having a bonding bond with a carbon atom) The compound represented by the following formula in the photosensitive composition ( 2): R 3 COOH・・・(2) (In formula (2), R 3 is the same as above) The content of the carboxylic acid represented by the mass of the photopolymerization initiator (B) is the same as the formula ( 2) The total mass of the carboxylic acid represented is 550 mass ppb or less, and the amount of water in the photosensitive composition is 0.1 mass % or less with respect to the entire photosensitive composition. A second aspect of the present invention is a method for producing a photosensitive composition, comprising dissolving a photopolymerizable compound (A) and a photopolymerization initiator (B) in a solvent (S), and the photopolymerization initiator (B) is the following formula (1): [Chemical 2]
Figure 02_image003
The compound represented by (in formula (1), R 1 , R 2 , and R 3 are each independently a valent organic group having a bond to a carbon atom) dissolved in the solvent (S) above. The amount of water attached to the polymerization initiator (B) is 1 mass % or less with respect to the total of the mass of the photopolymerization initiator (B) and the mass of the water. The third aspect of the present invention is a photopolymerization initiator, which contains the following formula (1):
Figure 02_image005
(in the formula (1), R 1 , R 2 , and R 3 are each independently a compound represented by a valent organic group having a bonding bond to a carbon atom), and the photopolymerization initiator is attached to the compound represented by The amount of water is 1 mass % or less relative to the total of the mass of the photopolymerization initiator and the mass of water, and the following formula (2) attached to the photopolymerization initiator: R 3 COOH・・・(2) (formula In (2), the total content of the carboxylic acid represented by R 3 relative to the mass of the photopolymerization initiator and the mass of the carboxylic acid represented by the formula (2) is 550 mass ppb or less. A method for preparing a photopolymerization initiator according to the third aspect, which comprises drying under light shielding at a temperature at which the photopolymerization initiator (B) is not thermally decomposed. Provided are a photosensitive composition, a method for producing the photosensitive composition, a photopolymerization initiator that can be preferably formulated in the photosensitive composition, and a method for preparing the photopolymerization initiator, the photosensitive composition The compound contains a photopolymerizable compound (A), a photopolymerization initiator (B) containing an oxime ester compound having a specific structure with a carbonyl group at a position adjacent to the C=N bond in the oxime group (>C=NO-), and solvent (S), and the decrease in sensitivity over time is suppressed.

≪感光性組合物≫ 感光性組合物含有光聚合性化合物(A)、光聚合起始劑(B)、及溶劑(S)。 光聚合起始劑(B)包含下述式(1)： [化4]

Figure 02_image007
(式(1)中，R1 、R2 、及R3 分別獨立為具有與碳原子鍵結之鍵結鍵之一價有機基) 所表示之化合物。 感光性組合物中之下述式(2)： R3 COOH・・・(2) (式(2)中，R3 與上文所述相同) 所表示之羧酸之含量相對於光聚合起始劑(B)之質量與式(2)所表示之羧酸之質量之合計為550質量ppb以下，較佳為500質量ppb，更佳為450質量ppb，尤佳為420質量ppb以下。 感光性組合物中之水分之量相對於上述感光性組合物整體為0.1質量%以下，較佳為0.08質量%以下，更佳為0.05質量%以下。 對含有式(1)所表示之化合物作為光聚合起始劑(B)之感光性組合物的經時性之感度降低之原因進行研究，結果發現感光性組合物中之水分與上述式(2)所表示之羧酸會對經時性之感度之降低造成不良影響。 即，藉由使感光性組合物滿足以上之要件，感光性組合物之經時性之感度降低受到抑制。 於感光性組合物中，為了將水分之量與式(2)所表示之羧酸之量維持於上述特定之範圍內，較佳為於低溫下將感光性組合物保管於密閉且遮光之容器中。具體而言，保管時之溫度較佳為35℃以下，更佳為25℃以下，尤佳為15℃以下，最佳為5℃以下。保管溫度之下限並無特別限定，較佳為不會發生感光性組合物之固化、或感光性組合物之成分析出的溫度。 藉由將感光性組合物保管於該條件下，可防止感光性組合物中之水分之量、及式(2)所表示之羧酸之量之增加，尤其是可防止羧酸之量之增加。 又，關於感光性組合物，較佳為含有根據下式由以下之CA0 (質量ppb)與CA48 (質量ppb)算出之羧酸增加率(%)為10質量%以下之光聚合起始劑(B)的感光性組合物，更佳為5質量%以下。 含有上述羧酸增加率(%)較小之光聚合起始劑(B)之感光性組合物有羧酸量不易經時性增加之傾向，伴隨於此，容易抑制感光性組合物之經時性之感度降低。 (羧酸增加率算出式) 羧酸增加率(%)＝(CA48 /CA0 －1.00)×100 (CA0 及CA48 之定義) CA0 ：相對於剛製造後之光聚合起始劑(B)之質量與式(2)所表示之羧酸之質量之合計的式(2)所表示之羧酸之量(質量ppb) CA48 ：相對於在35℃下保存48小時後之光聚合起始劑(B)之質量與式(2)所表示之羧酸之質量之合計的式(2)所表示之羧酸之量(質量ppb) 又，上述CA48 較佳為450質量ppb以下，更佳為430質量ppb以下，尤佳為410質量ppb以下，最佳為400質量ppm以下。 含有CA48 為上述範圍內之值之光聚合起始劑(B)的感光性組合物中羧酸量不易經時性增加，容易抑制經時性之感度降低。 感光性組合物中之式(2)所表示之羧酸之量可藉由離子層析法進行測定。 以下，對感光性組合物所含之必需或任意之成分進行說明。 ＜光聚合性化合物(A)＞ 感光性組合物含有光聚合性化合物(A)。作為光聚合性化合物(A)，並無特別限定，可使用先前公知之光聚合性化合物。其中，較佳為具有乙烯性不飽和基之樹脂或具有乙烯性不飽和基之單體。 具有乙烯性不飽和基之樹脂與具有乙烯性不飽和基之單體可組合使用。於將具有乙烯性不飽和基之樹脂與具有乙烯性不飽和基之單體組合之情形時，感光性組合物之硬化性提高，容易形成圖案。 [具有乙烯性不飽和基之樹脂] 作為具有乙烯性不飽和基之樹脂，可列舉：(甲基)丙烯酸、反丁烯二酸、順丁烯二酸、反丁烯二酸單甲酯、反丁烯二酸單乙酯、(甲基)丙烯酸2-羥基乙酯、乙二醇單甲醚(甲基)丙烯酸酯、乙二醇單***(甲基)丙烯酸酯、甘油(甲基)丙烯酸酯、(甲基)丙烯醯胺、丙烯腈、甲基丙烯腈、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸苄酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基丙烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、酚酞基環氧二丙烯酸酯等聚合而成之低聚物類；使將多元醇類與一元酸或多元酸縮合而獲得之聚酯預聚物與(甲基)丙烯酸反應而獲得之聚酯(甲基)丙烯酸酯；使多元醇與具有2個異氰酸酯基之化合物反應後與(甲基)丙烯酸反應而獲得之聚(甲基)丙烯酸胺基甲酸酯；使雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚或甲酚酚醛清漆型環氧樹脂、可溶酚醛型環氧樹脂、三苯酚甲烷型環氧樹脂、聚羧酸聚縮水甘油酯、多元醇聚縮水甘油酯、脂肪族或脂環式環氧樹脂、胺環氧樹脂、二羥基苯型環氧樹脂等環氧樹脂與(甲基)丙烯酸反應而獲得之環氧(甲基)丙烯酸酯樹脂等。進而，可適宜地使用使環氧(甲基)丙烯酸酯樹脂與多元酸酐反應而成之樹脂。再者，於本說明書中，「(甲基)丙烯酸基」意指「丙烯酸基或甲基丙烯酸基」。 於光聚合性化合物(A)為具有乙烯性不飽和基之聚合物之情形時，作為該聚合物，較佳為具有乙烯性不飽和基且含有Cardo結構之聚合物(A')。 於使用上述含有Cardo結構之聚合物(A')作為光聚合性化合物(A)之情形時，容易獲得曝光下之硬化性與顯影性之平衡性優異之感光性組合物，於感光性組合物含有著色劑(D)之情形時，容易使著色劑(D)良好地分散。 又，作為具有乙烯性不飽和基之樹脂，可適宜地使用藉由使環氧化合物與含有不飽和基之羧酸化合物之反應物進一步與多元酸酐反應而獲得之樹脂。 其中，較佳為下述式(a-1)所表示之化合物。下述式(a-1)所表示之化合物係作為上文所述之含有Cardo結構之聚合物(A')而適宜之化合物。該式(a-1)所表示之化合物就其本身之光硬化性較高之方面而言較佳。 [化5]
Figure 02_image009
上述式(a-1)中，Xa 表示下述式(a-2)所表示之基。 [化6]
Figure 02_image011
上述式(a-2)中，Ra1 分別獨立地表示氫原子、碳原子數1以上且6以下之烴基、或鹵素原子，Ra2 分別獨立地表示氫原子或甲基，Wa 表示單鍵或下述式(a-3)所表示之基。 [化7]
Figure 02_image013
又，上述式(a-1)中，Ya 表示從二羧酸酐中去除酸酐基(-CO-O-CO-)所獲得之殘基。作為二羧酸酐之例，可列舉：順丁烯二酸酐、丁二酸酐、亞甲基丁二酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基內亞甲基四氫鄰苯二甲酸酐、氯橋酸酐、甲基四氫鄰苯二甲酸酐、戊二酸酐等。 又，上述式(a-1)中，Za 表示從四羧酸二酐中去除2個酸酐基所獲得之殘基。作為四羧酸二酐之例，可列舉：均苯四甲酸二酐、二苯甲酮四羧酸二酐、聯苯四羧酸二酐、聯苯醚四羧酸二酐等。 又，上述式(a-1)中，m表示0以上且20以下之整數。 具有乙烯性不飽和基之樹脂之酸值以樹脂固形物成分計，較佳為10 mgKOH/g以上且150 mgKOH/g以下，更佳為70 mgKOH/g以上且110 mgKOH/g以下。藉由將酸值設為10 mgKOH/g以上，可獲得針對顯影液之充分之溶解性，故而較佳。又，藉由將酸值設為150 mgKOH/g以下，可獲得充分之硬化性，且可使表面性良好，故而較佳。 又，具有乙烯性不飽和基之樹脂之質量平均分子量較佳為1000以上且40000以下，更佳為2000以上且30000以下。藉由將質量平均分子量設為1000以上，可獲得良好之耐熱性、膜強度，故而較佳。又，藉由將質量平均分子量設為40000以下，可獲得良好之顯影性，故而較佳。 [具有乙烯性不飽和基之單體] 具有乙烯性不飽和基之單體有單官能單體與多官能單體。 作為單官能單體，可列舉：(甲基)丙烯醯胺、羥甲基(甲基)丙烯醯胺、甲氧基甲基(甲基)丙烯醯胺、乙氧基甲基(甲基)丙烯醯胺、丙氧基甲基(甲基)丙烯醯胺、丁氧基甲氧基甲基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、(甲基)丙烯酸、反丁烯二酸、順丁烯二酸、順丁烯二酸酐、亞甲基丁二酸、亞甲基丁二酸酐、甲基順丁烯二酸、甲基順丁烯二酸酐、丁烯酸、2-丙烯醯胺-2-甲基丙磺酸、第三丁基丙烯醯胺磺酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸2-苯氧基-2-羥基丙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基-2-羥基丙酯、甘油單(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、鄰苯二甲酸衍生物之半(甲基)丙烯酸酯等。該等單官能單體可單獨使用，亦可組合2種以上使用。 另一方面，作為多官能單體，可列舉：乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、2,2-雙(4-(甲基)丙烯醯氧基二乙氧基苯基)丙烷、2,2-雙(4-(甲基)丙烯醯氧基聚乙氧基苯基)丙烷、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、乙二醇二縮水甘油醚二(甲基)丙烯酸酯、二乙二醇二縮水甘油醚二(甲基)丙烯酸酯、鄰苯二甲酸二縮水甘油酯二(甲基)丙烯酸酯、甘油三丙烯酸酯、甘油聚縮水甘油醚聚(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯(即，甲苯二異氰酸酯、三甲基六亞甲基二異氰酸酯、或六亞甲基二異氰酸酯與(甲基)丙烯酸2-羥基乙酯之反應物)、亞甲基雙(甲基)丙烯醯胺、(甲基)丙烯醯胺亞甲基醚、多元醇與N-羥甲基(甲基)丙烯醯胺之縮合物等多官能單體、或三丙烯酸基縮甲醛等。該等多官能單體可單獨使用，亦可組合2種以上使用。 感光性組合物中之光聚合性化合物(A)之含量相對於感光性組合物中之下文所述之溶劑(S)以外的成分之質量之合計，較佳為10質量%以上且70質量%以下，更佳為20質量%以上且65質量%以下，尤佳為30質量%以上且60質量%以下。 以上所說明之光聚合性化合物(A)較佳為以感光性組合物中之水分之量與上文所述之式(2)所表示之羧酸之含量分別成為特定之範圍內之方式，於調製感光性組合物前實施脫水等精製。 作為從光聚合性化合物(A)中去除水之方法，可列舉利用加熱進行之乾燥。又，亦可於將光聚合性化合物(A)溶解於與水共沸之有機溶劑中後，將有機溶劑從所獲得之溶液中蒸餾去除，而減少光聚合性化合物(A)中之水分。 作為從光聚合性化合物(A)中去除羧酸之方法，可列舉利用加熱之去除、或利用經脫水之有機溶劑之洗淨等方法。 ＜光聚合起始劑(B)＞ 感光性組合物含有光聚合起始劑(B)。光聚合起始劑(B)含有下述式(1)： [化8]
Figure 02_image015
(式(1)中，R1 、R2 、及R3 分別獨立為具有與碳原子鍵結之鍵結鍵之一價有機基) 所表示之化合物。因此，感光性組合物之感度優異。 然而，含有式(1)所表示之化合物作為光聚合起始劑之先前已知之感光性組合物存在感度容易經時性降低之情形。 但於含有式(1)所表示之化合物作為光聚合起始劑之感光性組合物中，藉由水分之量與上文所述之式(2)所表示之羧酸之量分別為特定範圍內之少量，可抑制感光性組合物之感度之經時性之降低。 光聚合起始劑(B)可組合含有2種以上之式(1)所表示之化合物。 光聚合起始劑(B)亦可於不阻礙本發明之目的之範圍內含有式(1)所表示之化合物以外之光聚合起始劑。光聚合起始劑(B)中之式(1)所表示之化合物之含量較佳為70質量%以上，更佳為80質量%以上，尤佳為90質量%以上，最佳為100質量%。 式(1)中，作為適宜作為R1 之有機基之例，可列舉：烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧基羰基、飽和脂肪族醯氧基、可具有取代基之苯基、可具有取代基之苯氧基、可具有取代基之苯甲醯基、可具有取代基之苯氧基羰基、可具有取代基之苯甲醯氧基、可具有取代基之苯基烷基、可具有取代基之萘基、可具有取代基之萘氧基、可具有取代基之萘甲醯基、可具有取代基之萘氧基羰基、可具有取代基之萘甲醯氧基、可具有取代基之萘基烷基、可具有取代基之雜環基、可具有取代基之雜環基羰基、經1個或2個有機基取代之胺基、嗎啉-1-基、及哌𠯤-1-基等。 又，作為R1 ，亦較佳為環烷基烷基、芳香環上可具有取代基之苯氧基烷基、芳香環上可具有取代基之苯基硫基烷基。苯氧基烷基、及苯基硫基烷基可具有之取代基與R1 所含之苯基可具有之取代基相同。 於R1 為烷基之情形時，烷基之碳原子數較佳為1以上且20以下，更佳為1以上且6以下。又，於R1 為烷基之情形時，可為直鏈，亦可為支鏈。作為R1 為烷基之情形時之具體例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、異戊基、第二戊基、第三戊基、正己基、正庚基、正辛基、異辛基、第二辛基、第三辛基、正壬基、異壬基、正癸基、及異癸基等。又，於R1 為烷基之情形時，烷基亦可於碳鏈中含有醚鍵(-O-)。作為碳鏈中具有醚鍵之烷基之例，可列舉：甲氧基乙基、乙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙氧基乙氧基乙基、及甲氧基丙基等。 於R1 為烷氧基之情形時，烷氧基之碳原子數較佳為1以上且20以下，更佳為1以上且6以下。又，於R1 為烷氧基之情形時，可為直鏈，亦可為支鏈。作為R1 為烷氧基之情形時之具體例，可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第二丁氧基、第三丁氧基、正戊氧基、異戊氧基、第二戊氧基、第三戊氧基、正己氧基、正庚氧基、正辛氧基、異辛氧基、第二辛氧基、第三辛氧基、正壬氧基、異壬氧基、正癸氧基、及異癸氧基等。又，於R1 為烷氧基之情形時，烷氧基亦可於碳鏈中含有醚鍵(-O-)。作為於碳鏈中具有醚鍵之烷氧基之例，可列舉：甲氧基乙氧基、乙氧基乙氧基、甲氧基乙氧基乙氧基、乙氧基乙氧基乙氧基、丙氧基乙氧基乙氧基、及甲氧基丙氧基等。 於R1 為環烷基或環烷氧基之情形時，環烷基或環烷氧基之碳原子數較佳為3以上且10以下，更佳為3以上且6以下。作為R1 為環烷基之情形時之具體例，可列舉：環丙基、環丁基、環戊基、環己基、環庚基、及環辛基等。作為R1 為環烷氧基之情形時之具體例，可列舉：環丙氧基、環丁氧基、環戊氧基、環己氧基、環庚氧基、及環辛氧基等。 於R1 為飽和脂肪族醯基或飽和脂肪族醯氧基之情形時，飽和脂肪族醯基或飽和脂肪族醯氧基之碳原子數較佳為2以上且21以下，更佳為2以上且7以下。作為R1 為飽和脂肪族醯基之情形時之具體例，可列舉：乙醯基、丙醯基、正丁醯基、2-甲基丙醯基、正戊醯基、2,2-二甲基丙醯基、正己醯基、正庚醯基、正辛醯基、正壬醯基、正癸醯基、正十一碳醯基、正十二碳醯基、正十三碳醯基、正十四碳醯基、正十五碳醯基、及正十六碳醯基等。作為R1 為飽和脂肪族醯氧基之情形時之具體例，可列舉：乙醯氧基、丙醯氧基、正丁醯氧基、2-甲基丙醯氧基、正戊醯氧基、2,2-二甲基丙醯氧基、正己醯氧基、正庚醯氧基、正辛醯氧基、正壬醯氧基、正癸醯氧基、正十一碳醯氧基、正十二碳醯氧基、正十三碳醯氧基、正十四碳醯氧基、正十五碳醯氧基、及正十六碳醯氧基等。 於R1 為烷氧基羰基之情形時，烷氧基羰基之碳原子數較佳為2以上且20以下，更佳為2以上且7以下。作為R1 為烷氧基羰基之情形時之具體例，可列舉：甲氧基羰基、乙氧基羰基、正丙氧基羰基、異丙氧基羰基、正丁氧基羰基、異丁氧基羰基、第二丁氧基羰基、第三丁氧基羰基、正戊氧基羰基、異戊氧基羰基、第二戊氧基羰基、第三戊氧基羰基、正己氧基羰基、正庚氧基羰基、正辛氧基羰基、異辛氧基羰基、第二辛氧基羰基、第三辛氧基羰基、正壬氧基羰基、異壬氧基羰基、正癸氧基羰基、及異癸氧基羰基等。 於R1 為苯基烷基之情形時，苯基烷基之碳原子數較佳為7以上且20以下，更佳為7以上且10以下。又，於R1 為萘基烷基之情形時，萘基烷基之碳原子數較佳為11以上且20以下，更佳為11以上且14以下。作為R1 為苯基烷基之情形時之具體例，可列舉：苄基、2-苯基乙基、3-苯基丙基、及4-苯基丁基。作為R1 為萘基烷基之情形時之具體例，可列舉：α-萘基甲基、β-萘基甲基、2-(α-萘基)乙基、及2-(β-萘基)乙基。於R1 為苯基烷基、或萘基烷基之情形時，R1 亦可於苯基、或萘基上進而具有取代基。 於R1 為雜環基之情形時，雜環基為含有1個以上N、S、O之5員或6員之單環，或者為該單環彼此、或該單環與苯環縮合而成之雜環基。於雜環基為縮合環之情形時，環數至多為3。雜環基可為芳香族基(雜芳基)，亦可為非芳香族基。作為構成該雜環基之雜環，可列舉：呋喃、噻吩、吡咯、㗁唑、異㗁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、***、吡啶、吡𠯤、嘧啶、嗒𠯤、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚𠯤、苯并咪唑、苯并***、苯并㗁唑、苯并噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞𠯤、㖕啉、喹㗁啉、哌啶、哌𠯤、嗎啉、哌啶、四氫吡喃、及四氫呋喃等。於R1 為雜環基之情形時，雜環基可進而具有取代基。 於R1 為雜環基羰基之情形時，雜環基羰基所含之雜環基與R1 為雜環基之情形時相同。 於R1 為經1個或2個有機基取代之胺基之情形時，有機基之適宜之例可列舉：碳原子數1以上且20以下之烷基、碳原子數3以上且10以下之環烷基、碳原子數2以上且21以下之飽和脂肪族醯基、可具有取代基之苯基、可具有取代基之苯甲醯基、可具有取代基之碳原子數7以上且20以下之苯基烷基、可具有取代基之萘基、可具有取代基之萘甲醯基、可具有取代基之碳原子數11以上且20以下之萘基烷基、及雜環基等。該等適宜之有機基之具體例與R1 相同。作為經1個或2個有機基取代之胺基之具體例，可列舉：甲基胺基、乙基胺基、二乙胺基、正丙基胺基、二正丙胺基、異丙基胺基、正丁基胺基、二正丁胺基、正戊基胺基、正己基胺基、正庚基胺基、正辛基胺基、正壬基胺基、正癸基胺基、苯基胺基、萘基胺基、乙醯基胺基、丙醯基胺基、正丁醯基胺基、正戊醯基胺基、正己醯基胺基、正庚醯基胺基、正辛醯基胺基、正癸醯基胺基、苯甲醯基胺基、α-萘甲醯基胺基、及β-萘甲醯基胺基等。 作為R1 所含之苯基、萘基、及雜環基進而具有取代基之情形時之取代基，可列舉：烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、飽和脂肪族醯氧基、烷氧基羰基、可具有取代基之苯基、可具有取代基之苯氧基、可具有取代基之苯硫基、可具有取代基之苯甲醯基、可具有取代基之苯氧基羰基、可具有取代基之苯甲醯氧基、可具有取代基之苯基烷基、可具有取代基之萘基、可具有取代基之萘氧基、可具有取代基之萘甲醯基、可具有取代基之萘氧基羰基、可具有取代基之萘甲醯氧基、可具有取代基之萘基烷基、可具有取代基之雜環基、可具有取代基之雜環基羰基、胺基、經1個或2個有機基取代之胺基、嗎啉-1-基、哌𠯤-1-基、鹵素原子、硝基、及氰基等。 於R1 所含之苯基、萘基、及雜環基進而具有取代基之情形時，該取代基之個數於不阻礙本發明之目的之範圍內並無限定，較佳為1以上且4以下。於R1 所含之苯基、萘基、及雜環基具有複數個取代基之情形時，複數個取代基可相同亦可不同。 於取代基為烷基之情形時，較佳為碳原子數為1以上且20以下，更佳為碳原子數為1以上且6以下。於取代基為烷基之情形時，可為直鏈，亦可為支鏈。作為取代基為烷基之情形時之具體例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、異戊基、第二戊基、第三戊基、正己基、正庚基、正辛基、異辛基、第二辛基、第三辛基、正壬基、異壬基、正癸基、及異癸基等。又，於取代基為烷基之情形時，烷基亦可於碳鏈中含有醚鍵(-O-)。作為碳鏈中具有醚鍵之烷基之例，可列舉：甲氧基乙基、乙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙氧基乙氧基乙基、及甲氧基丙基等。 於取代基為烷氧基之情形時，較佳為碳原子數為1以上且20以下，更佳為碳原子數為1以上且6以下。又，於取代基為烷氧基之情形時，可為直鏈，亦可為支鏈。作為取代基為烷氧基之情形時之具體例，可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第二丁氧基、第三丁氧基、正戊氧基、異戊氧基、第二戊氧基、第三戊氧基、正己氧基、正庚氧基、正辛氧基、異辛氧基、第二辛氧基、第三辛氧基、正壬氧基、異壬氧基、正癸氧基、及異癸氧基等。又，於取代基為烷氧基之情形時，烷氧基亦可於碳鏈中含有醚鍵(-O-)。作為於碳鏈中具有醚鍵之烷氧基之例，可列舉：甲氧基乙氧基、乙氧基乙氧基、甲氧基乙氧基乙氧基、乙氧基乙氧基乙氧基、丙氧基乙氧基乙氧基、及甲氧基丙氧基等。 於取代基為環烷基或環烷氧基之情形時，較佳為碳原子數為3以上且10以下，更佳為碳原子數為3以上且6以下。作為取代基為環烷基之情形時之具體例，可列舉：環丙基、環丁基、環戊基、環己基、環庚基、及環辛基等。作為取代基為環烷氧基之情形時之具體例，可列舉：環丙氧基、環丁氧基、環戊氧基、環己氧基、環庚氧基、及環辛氧基等。 於取代基為飽和脂肪族醯基或飽和脂肪族醯氧基之情形時，較佳為碳原子數為2以上且20以下，更佳為碳原子數為2以上且7以下。作為取代基為飽和脂肪族醯基之情形時之具體例，可列舉：乙醯基、丙醯基、正丁醯基、2-甲基丙醯基、正戊醯基、2,2-二甲基丙醯基、正己醯基、正庚醯基、正辛醯基、正壬醯基、正癸醯基、正十一碳醯基、正十二碳醯基、正十三碳醯基、正十四碳醯基、正十五碳醯基、及正十六碳醯基等。作為取代基為飽和脂肪族醯氧基之情形時之具體例，可列舉：乙醯氧基、丙醯氧基、正丁醯氧基、2-甲基丙醯氧基、正戊醯氧基、2,2-二甲基丙醯氧基、正己醯氧基、正庚醯氧基、正辛醯氧基、正壬醯氧基、正癸醯氧基、正十一碳醯氧基、正十二碳醯氧基、正十三碳醯氧基、正十四碳醯氧基、正十五碳醯氧基、及正十六碳醯氧基等。 於取代基為烷氧基羰基之情形時，較佳為碳原子數為2以上且20以下，更佳為碳原子數為2以上且7以下。作為取代基為烷氧基羰基之情形時之具體例，可列舉：甲氧基羰基、乙氧基羰基、正丙氧基羰基、異丙氧基羰基、正丁氧基羰基、異丁氧基羰基、第二丁氧基羰基、第三丁氧基羰基、正戊氧基羰基、異戊氧基羰基、第二戊氧基羰基、第三戊氧基羰基、正己氧基羰基、正庚氧基羰基、正辛氧基羰基、異辛氧基羰基、第二辛氧基羰基、第三辛氧基羰基、正壬氧基羰基、異壬氧基羰基、正癸氧基羰基、及異癸氧基羰基等。 於取代基為可具有取代基之苯基烷基之情形時，較佳為碳原子數為7以上且20以下，更佳為碳原子數為7以上且10以下。又，於取代基為可具有取代基之萘基烷基之情形時，較佳為碳原子數為11以上且20以下，更佳為碳原子數為11以上且14以下。作為取代基為可具有取代基之苯基烷基之情形時之具體例，可列舉：苄基、2-苯基乙基、3-苯基丙基、及4-苯基丁基。作為取代基為可具有取代基之萘基烷基之情形時之具體例，可列舉：α-萘基甲基、β-萘基甲基、2-(α-萘基)乙基、及2-(β-萘基)乙基。 於取代基為可具有取代基之雜環基之情形時，上述雜環基為含有1個以上N、S、O之5員或6員之單環，或者為該單環彼此、或該單環與苯環縮合而成之雜環基。於上述雜環基為縮合環之情形時，環數最多為3。作為構成該雜環基之雜環，可列舉：呋喃、噻吩、吡咯、㗁唑、異㗁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、***、吡啶、吡𠯤、嘧啶、嗒𠯤、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚𠯤、苯并咪唑、苯并***、苯并㗁唑、苯并噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞𠯤、㖕啉、及喹㗁啉等。 於取代基為經1個或2個有機基取代之胺基之情形時，作為有機基之適宜之例，可列舉：碳原子數1以上且20以下之烷基、碳原子數3以上且10以下之環烷基、碳原子數2以上且20以下之飽和脂肪族醯基、可具有取代基之苯基、可具有取代基之苯甲醯基、可具有取代基之碳原子數7以上且20以下之苯基烷基、可具有取代基之萘基、可具有取代基之萘甲醯基、可具有取代基之碳原子數11以上且20以下之萘基烷基、及雜環基等。該等適宜之有機基之具體例與上述關於取代基所例示之基相同。作為經1個或2個有機基取代之胺基之具體例，可列舉：甲基胺基、乙基胺基、二乙胺基、正丙基胺基、二正丙胺基、異丙基胺基、正丁基胺基、二正丁胺基、正戊基胺基、正己基胺基、正庚基胺基、正辛基胺基、正壬基胺基、正癸基胺基、苯基胺基、萘基胺基、乙醯基胺基、丙醯基胺基、正丁醯基胺基、正戊醯基胺基、正己醯基胺基、正庚醯基胺基、正辛醯基胺基、正癸醯基胺基、苯甲醯基胺基、α-萘甲醯基胺基、及β-萘甲醯基胺基等。 於上述取代基中，作為苯基、萘基、及雜環基等進而具有取代基之情形時之取代基之例，可列舉：碳原子數1以上且6以下之烷基；碳原子數1以上且6以下之烷氧基；碳原子數2以上且7以下之飽和脂肪族醯基；碳原子數2以上且7以下之烷氧基羰基；碳原子數2以上且7以下之飽和脂肪族醯氧基；苯基；萘基；苯甲醯基；萘甲醯基；經選自由碳原子數1以上且6以下之烷基、嗎啉-1-基、哌𠯤-1-基、及苯基所組成之群中之基所取代之苯甲醯基；具有碳原子數1以上且6以下之烷基之單烷基胺基；具有碳原子數1以上且6以下之烷基之二烷基胺基；嗎啉-1-基；哌𠯤-1-基；鹵素原子；硝基；氰基。於上述取代基所含之苯基、萘基、及雜環基等進而具有取代基之情形時，該取代基之個數於不阻礙本發明之目的之範圍內並無限定，較佳為1以上且4以下。於苯基、萘基、及雜環基等具有複數個取代基之情形時，複數個取代基可相同亦可不同。 於有機基中，作為R1 ，較佳為烷基、環烷基、可具有取代基之苯基、或環烷基烷基、芳香環上可具有取代基之苯基硫基烷基。作為烷基，較佳為碳原子數1以上且20以下之烷基，更佳為碳原子數1以上且8以下之烷基，尤佳為碳原子數1以上且4以下之烷基，最佳為甲基。於可具有取代基之苯基中，較佳為甲基苯基，更佳為2-甲基苯基。環烷基烷基所含之環烷基之碳原子數較佳為5以上且10以下，更佳為5以上且8以下，尤佳為5或6。環烷基烷基所含之伸烷基之碳原子數較佳為1以上且8以下，更佳為1以上且4以下，尤佳為2。於環烷基烷基中，較佳為環戊基乙基。芳香環上可具有取代基之苯基硫基烷基所含之伸烷基之碳原子數較佳為1以上且8以下，更佳為1以上且4以下，尤佳為2。於芳香環上可具有取代基之苯基硫基烷基中，較佳為2-(4-氯苯基硫基)乙基。 又，作為R1 ，亦較佳為-Ab1 -CO-O-Ab2 所表示之基。Ab1 為二價有機基，較佳為二價烴基，較佳為伸烷基。Ab2 為一價有機基，較佳為一價之烴基。 於Ab1 為伸烷基之情形時，伸烷基可為直鏈狀，亦可為支鏈狀，較佳為直鏈狀。於Ab1 為伸烷基之情形時，伸烷基之碳原子數較佳為1以上且10以下，更佳為1以上且6以下，尤佳為1以上且4以下。 作為Ab2 之適宜之例，可列舉：碳原子數1以上且10以下之烷基、碳原子數7以上且20以下之芳烷基、及碳原子數6以上且20以下之芳香族烴基。作為Ab2 之適宜之具體例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、正己基、苯基、萘基、苄基、苯乙基、α-萘基甲基、及β-萘基甲基等。 作為-Ab1 -CO-O-Ab2 所表示之基之適宜之具體例，可列舉：2-甲氧基羰基乙基、2-乙氧基羰基乙基、2-正丙氧基羰基乙基、2-正丁氧基羰基乙基、2-正戊氧基羰基乙基、2-正己氧基羰基乙基、2-苄氧基羰基乙基、2-苯氧基羰基乙基、3-甲氧基羰基正丙基、3-乙氧基羰基正丙基、3-正丙氧基羰基正丙基、3-正丁氧基羰基正丙基、3-正戊氧基羰基正丙基、3-正己氧基羰基正丙基、3-苄氧基羰基正丙基、及3-苯氧基羰基正丙基等。 以上，已對R1 進行了說明，但作為R1 ，較佳為下述式(b1a)或(b1b)所表示之基。 [化9]
Figure 02_image017
(式(b1a)及(b1b)中，R7 及R8 分別為有機基，p為0以上且4以下之整數，於R7 及R8 存在於苯環上鄰接之位置之情形時，R7 與R8 可互相鍵結而形成環，q為1以上且8以下之整數，r為1以上且5以下之整數，s為0以上且(r＋3)以下之整數，R9 為有機基) 關於式(b1a)中之R7 及R8 之有機基之例與R1 相同。作為R7 ，較佳為烷基或苯基。於R7 為烷基之情形時，其碳原子數較佳為1以上且10以下，更佳為1以上且5以下，尤佳為1以上且3以下，最佳為1。即，R7 最佳為甲基。 於R7 與R8 鍵結而形成環之情形時，該環可為芳香族環，亦可為脂肪族環。作為式(b1a)所表示且R7 與R8 形成環之基之適宜之例，可列舉萘-1-基、或1,2,3,4-四氫萘-5-基等。上述式(b1a)中，p為0以上且4以下之整數，較佳為0或1，更佳為0。 上述式(b1b)中，R9 為有機基。作為有機基，可列舉與針對R1 所說明之有機基相同之基。 於作為R9 之有機基中，較佳為烷基。烷基可為直鏈狀，亦可為支鏈狀。烷基之碳原子數較佳為1以上且10以下，更佳為1以上且5以下，尤佳為1以上且3以下。作為R9 ，可較佳地例示甲基、乙基、丙基、異丙基、丁基等。該等基中，更佳為甲基。 上述式(b1b)中，r為1以上且5以下之整數，較佳為1以上且3以下之整數，更佳為1或2。上述式(b1b)中，s為0以上且(r＋3)以下，較佳為0以上且3以下之整數，更佳為0以上且2以下之整數，尤佳為0。上述式(b1b)中，q為1以上且8以下之整數，較佳為1以上且5以下之整數，更佳為1以上且3以下之整數，尤佳為1或2。 式(1)中，R2 為有機基。作為該有機基，較佳為可具有取代基之芳基、或可具有取代基之雜芳基。作為可具有取代基之芳基，例如可列舉可具有取代基之苯基。作為可具有取代基之雜芳基，例如可列舉可具有取代基之咔唑基。 於R2 中，芳基、雜芳基、苯基、或咔唑基可具有之取代基於不阻礙本發明之目的之範圍內並無特別限定。作為芳基、雜芳基、苯基、或咔唑基可於碳原子上具有之適宜之取代基之例，可列舉：烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、飽和脂肪族醯氧基、烷氧基羰基、可具有取代基之苯基、可具有取代基之苯氧基、可具有取代基之苯硫基、可具有取代基之苯甲醯基、可具有取代基之苯氧基羰基、可具有取代基之苯甲醯氧基、可具有取代基之苯基烷基、可具有取代基之萘基、可具有取代基之萘氧基、可具有取代基之萘甲醯基、可具有取代基之萘氧基羰基、可具有取代基之萘甲醯氧基、可具有取代基之萘基烷基、可具有取代基之雜環基、可具有取代基之雜環基羰基、胺基、經1個或2個有機基取代之胺基、嗎啉-1-基、哌𠯤-1-基、鹵素原子、硝基、及氰基等。 於R2 為雜芳基或咔唑基之情形時，作為雜芳基可於氮原子等雜原子上具有之適宜之取代基、及咔唑基可於氮原子上具有之適宜之取代基之例，可列舉：烷基、環烷基、飽和脂肪族醯基、烷氧基羰基、可具有取代基之苯基、可具有取代基之苯甲醯基、可具有取代基之苯氧基羰基、可具有取代基之苯基烷基、可具有取代基之萘基、可具有取代基之萘甲醯基、可具有取代基之萘氧基羰基、可具有取代基之萘基烷基、可具有取代基之雜環基、及可具有取代基之雜環基羰基等。該等取代基中，較佳為烷基，更佳為碳原子數1以上且20以下之烷基，進而更佳為碳原子數1以上且6以下之烷基，尤佳為乙基。 關於芳基、雜芳基、苯基、或咔唑基可具有之取代基之具體例，關於烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、飽和脂肪族醯氧基、烷氧基羰基、可具有取代基之苯基烷基、可具有取代基之萘基烷基、可具有取代基之雜環基、及經1個或2個有機基取代之胺基，與針對R1 所說明者相同。 於上述取代基中，關於苯基、萘基、及雜環基等進而具有取代基之情形時之取代基，與針對R1 所說明者相同。 於R2 中，就感光性組合物之感度優異之方面而言，較佳為下述式(1-1)或(1-2)所表示之基，更佳為下述式(1-1)所表示之基，尤佳為下述式(1-1)所表示且A為S之基。 [化10]
Figure 02_image019
(R4 為選自由一價有機基、胺基、鹵素原子、硝基、及氰基所組成之群中之基，A為S或O，n為0以上且4以下之整數) [化11]
Figure 02_image021
(R5 及R6 分別為一價有機基) 於使用感光性組合物形成圖案之情形時，因形成圖案時之後烘烤之步驟中之加熱，導致圖案容易產生著色。然而，於感光性組合物中，於使用R2 為上述式(1-1)所表示且A為S之基之式(1)所表示之肟酯化合物作為光聚合起始劑之情形時，容易抑制由加熱引起之圖案之著色。 於式(1-1)中之R4 為有機基之情形時，可於不阻礙本發明之目的之範圍內，從各種有機基中選擇。作為式(1-1)中R4 為有機基之情形時之適宜之例，可列舉：碳原子數1以上且6以下之烷基；碳原子數1以上且6以下之烷氧基；碳原子數2以上且7以下之飽和脂肪族醯基；碳原子數2以上且7以下之烷氧基羰基；碳原子數2以上且7以下之飽和脂肪族醯氧基；苯基；萘基；苯甲醯基；萘甲醯基；經選自由碳原子數1以上且6以下之烷基、嗎啉-1-基、哌𠯤-1-基、及苯基所組成之群中之基所取代之苯甲醯基；具有碳原子數1以上且6以下之烷基之單烷基胺基；具有碳原子數1以上且6以下之烷基之二烷基胺基；嗎啉-1-基；哌𠯤-1-基；鹵素；硝基；氰基。 於R4 中，較佳為：苯甲醯基；萘甲醯基；經選自由碳原子數1以上且6以下之烷基、嗎啉-1-基、哌𠯤-1-基、及苯基所組成之群中之基所取代之苯甲醯基；硝基，更佳為：苯甲醯基；萘甲醯基；2-甲基苯基羰基；4-(哌𠯤-1-基)苯基羰基；4-(苯基)苯基羰基。 又，於式(1-1)中，n較佳為0以上且3以下之整數，更佳為0以上且2以下之整數，尤佳為0或1。於n為1之情形時，較佳為R4 所鍵結之位置相對於R4 所鍵結之苯基與原子A鍵結之鍵結鍵而為對位。 式(1-2)中之R5 可於不阻礙本發明之目的之範圍內，從各種有機基中選擇。作為R5 之適宜之例，可列舉：碳原子數1以上且20以下之烷基、碳原子數3以上且10以下之環烷基、碳原子數2以上且20以下之飽和脂肪族醯基、碳原子數2以上且20以下之烷氧基烷基、碳原子數2以上且20以下之烷氧基羰基、可具有取代基之苯基、可具有取代基之苯甲醯基、可具有取代基之苯氧基羰基、可具有取代基之碳原子數7以上且20以下之苯基烷基、可具有取代基之萘基、可具有取代基之萘甲醯基、可具有取代基之萘氧基羰基、可具有取代基之碳原子數11以上且20以下之萘基烷基、可具有取代基之雜環基、及可具有取代基之雜環基羰基等。 於R5 中，較佳為碳原子數1以上且20以下之烷基或碳原子數2以上且20以下之烷氧基烷基，更佳為碳原子數1以上且6以下之烷基或碳原子數2以上且6以下之烷氧基烷基，尤佳為乙基或乙氧基乙基。 式(1-2)中之R6 於不阻礙本發明之目的之範圍內並無特別限定，可從各種有機基中選擇。作為適宜作為R6 之基之具體例，可列舉：碳原子數1以上且20以下之烷基、可具有取代基之苯基、可具有取代基之萘基、及可具有取代基之雜環基。作為R6 ，該等基中，更佳為可具有取代基之苯基或可具有取代基之噻吩基，尤佳為2-甲基苯基或噻吩基。 作為R4 、R5 、或R6 所含之苯基、萘基、及雜環基進而具有取代基之情形時之取代基，可列舉：碳原子數1以上且6以下之烷基、碳原子數1以上且6以下之烷氧基、碳原子數2以上且7以下之飽和脂肪族醯基、碳原子數2以上且7以下之烷氧基羰基、碳原子數2以上且7以下之飽和脂肪族醯氧基、具有碳原子數1以上且6以下之烷基之單烷基胺基、具有碳原子數1以上且6以下之烷基之二烷基胺基、嗎啉-1-基、哌𠯤-1-基、鹵素、硝基、及氰基等。於R4 、R5 、或R6 所含之苯基、萘基、及雜環基進而具有取代基之情形時，該取代基之個數於不阻礙本發明之目的之範圍內並無限定，較佳為1以上且4以下。於R4 、R5 、或R6 所含之苯基、萘基、及雜環基具有複數個取代基之情形時，複數個取代基可相同亦可不同。 式(1)中，R3 為有機基。作為有機基，並無特別限定，較佳為烷基、芳基。作為烷基，較佳為碳原子數1以上且11以下之烷基。作為芳基，為可具有取代基之苯基。可具有取代基之苯基中之取代基與針對R1 所說明之取代基相同。 作為R3 ，更佳為碳原子數1以上且6以下之烷基、及苯基，尤佳為甲基、乙基、及苯基，最佳為甲基、及乙基。 作為式(1)所表示之光聚合起始劑，亦較佳為使用下述式(b1)所表示之肟系化合物。 [化12]
Figure 02_image023
(Rb1 為選自由一價有機基、胺基、鹵素、硝基、及氰基所組成之群中之基， n1為0以上且4以下之整數， Rb2 為可具有取代基之苯基、或可具有取代基之咔唑基， Rb3 為氫原子、或碳原子數1以上且6以下之烷基) 於式(b1)中，Rb1 於不阻礙本發明之目的之範圍內並無特別限定，可從各種有機基中適當選擇。作為Rb1 為有機基之情形時之適宜之例，可列舉：烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、飽和脂肪族醯氧基、烷氧基羰基、可具有取代基之苯基、可具有取代基之苯氧基、可具有取代基之苯甲醯基、可具有取代基之苯氧基羰基、可具有取代基之苯甲醯氧基、可具有取代基之苯基烷基、可具有取代基之萘基、可具有取代基之萘氧基、可具有取代基之萘甲醯基、可具有取代基之萘氧基羰基、可具有取代基之萘甲醯氧基、可具有取代基之萘基烷基、可具有取代基之雜環基、胺基、經1個或2個有機基取代之胺基、嗎啉-1-基、及哌𠯤-1-基、鹵素、硝基、及氰基等。於n1為2以上且4以下之整數之情形時，Rb1 可相同亦可不同。又，取代基之碳原子數中不包括取代基所進而具有之取代基之碳原子數。 於Rb1 為烷基之情形時，較佳為碳原子數為1以上且20以下，更佳為碳原子數為1以上且6以下。又，於Rb1 為烷基之情形時，可為直鏈，亦可為支鏈。作為Rb1 為烷基之情形時之具體例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、異戊基、第二戊基、第三戊基、正己基、正庚基、正辛基、異辛基、第二辛基、第三辛基、正壬基、異壬基、正癸基、及異癸基等。又，於Rb1 為烷基之情形時，烷基亦可於碳鏈中含有醚鍵(-O-)。作為碳鏈中具有醚鍵之烷基之例，可列舉：甲氧基乙基、乙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙氧基乙氧基乙基、及甲氧基丙基等。 於Rb1 為烷氧基之情形時，較佳為碳原子數為1以上且20以下，更佳為碳原子數為1以上且6以下。又，於Rb1 為烷氧基之情形時，可為直鏈，亦可為支鏈。作為Rb1 為烷氧基之情形時之具體例，可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第二丁氧基、第三丁氧基、正戊氧基、異戊氧基、第二戊氧基、第三戊氧基、正己氧基、正庚氧基、正辛氧基、異辛氧基、第二辛氧基、第三辛氧基、正壬氧基、異壬氧基、正癸氧基、及異癸氧基等。又，於Rb1 為烷氧基之情形時，烷氧基亦可於碳鏈中含有醚鍵(-O-)。作為於碳鏈中具有醚鍵之烷氧基之例，可列舉：甲氧基乙氧基、乙氧基乙氧基、甲氧基乙氧基乙氧基、乙氧基乙氧基乙氧基、丙氧基乙氧基乙氧基、及甲氧基丙氧基等。 於Rb1 為環烷基、或環烷氧基之情形時，較佳為碳原子數為3以上且10以下，更佳為碳原子數為3以上且6以下。作為Rb1 為環烷基之情形時之具體例，可列舉：環丙基、環丁基、環戊基、環己基、環庚基、及環辛基等。作為Rb1 為環烷氧基之情形時之具體例，可列舉：環丙氧基、環丁氧基、環戊氧基、環己氧基、環庚氧基、及環辛氧基等。 於Rb1 為飽和脂肪族醯基、或飽和脂肪族醯氧基之情形時，較佳為碳原子數為2以上且20以下，更佳為碳原子數為2以上且7以下。作為Rb1 為飽和脂肪族醯基之情形時之具體例，可列舉：乙醯基、丙醯基、正丁醯基、2-甲基丙醯基、正戊醯基、2,2-二甲基丙醯基、正己醯基、正庚醯基、正辛醯基、正壬醯基、正癸醯基、正十一碳醯基、正十二碳醯基、正十三碳醯基、正十四碳醯基、正十五碳醯基、及正十六碳醯基等。作為Rb1 為飽和脂肪族醯氧基之情形時之具體例，可列舉：乙醯氧基、丙醯氧基、正丁醯氧基、2-甲基丙醯氧基、正戊醯氧基、2,2-二甲基丙醯氧基、正己醯氧基、正庚醯氧基、正辛醯氧基、正壬醯氧基、正癸醯氧基、正十一碳醯氧基、正十二碳醯氧基、正十三碳醯氧基、正十四碳醯氧基、正十五碳醯氧基、及正十六碳醯氧基等。 於Rb1 為烷氧基羰基之情形時，較佳為碳原子數為2以上且20以下，更佳為碳原子數為2以上且7以下。作為Rb1 為烷氧基羰基之情形時之具體例，可列舉：甲氧基羰基、乙氧基羰基、正丙氧基羰基、異丙氧基羰基、正丁氧基羰基、異丁氧基羰基、第二丁氧基羰基、第三丁氧基羰基、正戊氧基羰基、異戊氧基羰基、第二戊氧基羰基、第三戊氧基羰基、正己氧基羰基、正庚氧基羰基、正辛氧基羰基、異辛氧基羰基、第二辛氧基羰基、第三辛氧基羰基、正壬氧基羰基、異壬氧基羰基、正癸氧基羰基、及異癸氧基羰基等。 於Rb1 為苯基烷基之情形時，較佳為碳原子數為7以上且20以下，更佳為碳原子數為7以上且10以下。又，於Rb1 為萘基烷基之情形時，較佳為碳原子數為11以上且20以下，更佳為碳原子數為11以上且14以下。作為Rb1 為苯基烷基之情形時之具體例，可列舉：苄基、2-苯基乙基、3-苯基丙基、及4-苯基丁基。作為Rb1 為萘基烷基之情形時之具體例，可列舉：α-萘基甲基、β-萘基甲基、2-(α-萘基)乙基、及2-(β-萘基)乙基。於Rb1 為苯基烷基、或萘基烷基之情形時，Rb1 亦可於苯基、或萘基上進而具有取代基。 於Rb1 為雜環基之情形時，雜環基為含有1個以上N、S、O之5員或6員之單環，或者為該單環彼此、或該單環與苯環縮合而成之雜環基。於雜環基為縮合環之情形時，環數最多為3。作為構成該雜環基之雜環，可列舉：呋喃、噻吩、吡咯、㗁唑、異㗁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、***、吡啶、吡𠯤、嘧啶、嗒𠯤、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚𠯤、苯并咪唑、苯并***、苯并㗁唑、苯并噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞𠯤、㖕啉、及喹㗁啉等。於Rb1 為雜環基之情形時，雜環基可進而具有取代基。 於Rb1 為經1個或2個有機基取代之胺基之情形時，有機基之適宜之例可列舉：碳原子數1以上且20以下之烷基、碳原子數3以上且10以下之環烷基、碳原子數2以上且20以下之飽和脂肪族醯基、可具有取代基之苯基、可具有取代基之苯甲醯基、可具有取代基之碳原子數7以上且20以下之苯基烷基、可具有取代基之萘基、可具有取代基之萘甲醯基、可具有取代基之碳原子數11以上且20以下之萘基烷基、及雜環基等。該等適宜之有機基之具體例與Rb1 相同。作為經1個或2個有機基取代之胺基之具體例，可列舉：甲基胺基、乙基胺基、二乙胺基、正丙基胺基、二正丙胺基、異丙基胺基、正丁基胺基、二正丁胺基、正戊基胺基、正己基胺基、正庚基胺基、正辛基胺基、正壬基胺基、正癸基胺基、苯基胺基、萘基胺基、乙醯基胺基、丙醯基胺基、正丁醯基胺基、正戊醯基胺基、正己醯基胺基、正庚醯基胺基、正辛醯基胺基、正癸醯基胺基、苯甲醯基胺基、α-萘甲醯基胺基、及β-萘甲醯基胺基等。 作為Rb1 所含之苯基、萘基、及雜環基進而具有取代基之情形時之取代基，可列舉：碳原子數1以上且6以下之烷基、碳原子數1以上且6以下之烷氧基、碳原子數2以上且7以下之飽和脂肪族醯基、碳原子數2以上且7以下之烷氧基羰基、碳原子數2以上且7以下之飽和脂肪族醯氧基、具有碳原子數1以上且6以下之烷基之單烷基胺基、具有碳原子數1以上且6以下之烷基之二烷基胺基、嗎啉-1-基、哌𠯤-1-基、鹵素、硝基、及氰基等。於Rb1 所含之苯基、萘基、及雜環基進而具有取代基之情形時，該取代基之個數於不阻礙本發明之目的之範圍內並無限定，較佳為1以上且4以下。於Rb1 所含之苯基、萘基、及雜環基具有複數個取代基之情形時，複數個取代基可相同亦可不同。 於Rb1 中，就化學性穩定、或立體阻礙較少而容易合成肟酯化合物等方面而言，較佳為選自由碳原子數1以上且6以下之烷基、碳原子數1以上且6以下之烷氧基、及碳原子數2以上且7以下之飽和脂肪族醯基所組成之群中之基，更佳為碳原子數1以上且6以下之烷基，尤佳為甲基。 關於Rb1 於苯基上鍵結之位置，於將Rb1 所鍵結之苯基中苯基與肟酯化合物之主骨架之鍵結鍵之位置設為1位，將甲基之位置設為2位之情形時，較佳為4位、或5位，更佳為5位。又，n1較佳為0以上且3以下之整數，更佳為0以上且2以下之整數，尤佳為0、或1。 Rb2 為可具有取代基之苯基、或可具有取代基之咔唑基。又，於Rb2 為可具有取代基之咔唑基之情形時，咔唑基上之氮原子可被取代為碳原子數1以上且6以下之烷基。 於Rb2 中，苯基、或咔唑基所具有之取代基於不阻礙本發明之目的之範圍內並無特別限定。作為苯基、或咔唑基可於碳原子上具有之適宜之取代基之例，可列舉：碳原子數1以上且20以下之烷基、碳原子數1以上且20以下之烷氧基、碳原子數3以上且10以下之環烷基、碳原子數3以上且10以下之環烷氧基、碳原子數2以上且20以下之飽和脂肪族醯基、碳原子數2以上且20以下之烷氧基羰基、碳原子數2以上且20以下之飽和脂肪族醯氧基、可具有取代基之苯基、可具有取代基之苯氧基、可具有取代基之苯硫基、可具有取代基之苯甲醯基、可具有取代基之苯氧基羰基、可具有取代基之苯甲醯氧基、可具有取代基之碳原子數7以上且20以下之苯基烷基、可具有取代基之萘基、可具有取代基之萘氧基、可具有取代基之萘甲醯基、可具有取代基之萘氧基羰基、可具有取代基之萘甲醯氧基、可具有取代基之碳原子數11以上且20以下之萘基烷基、可具有取代基之雜環基、可具有取代基之雜環基羰基、胺基、經1個或2個有機基取代之胺基、嗎啉-1-基、及哌𠯤-1-基、鹵素、硝基、及氰基等。 於Rb2 為咔唑基之情形時，作為咔唑基可於氮原子上具有之適宜之取代基之例，可列舉：碳原子數1以上且20以下之烷基、碳原子數3以上且10以下之環烷基、碳原子數2以上且20以下之飽和脂肪族醯基、碳原子數2以上且20以下之烷氧基羰基、可具有取代基之苯基、可具有取代基之苯甲醯基、可具有取代基之苯氧基羰基、可具有取代基之碳原子數7以上且20以下之苯基烷基、可具有取代基之萘基、可具有取代基之萘甲醯基、可具有取代基之萘氧基羰基、可具有取代基之碳原子數11以上且20以下之萘基烷基、可具有取代基之雜環基、及可具有取代基之雜環基羰基等。該等取代基中，較佳為碳原子數1以上且20以下之烷基，更佳為碳原子數1以上且6以下之烷基，尤佳為乙基。 關於苯基、或咔唑基可具有之取代基之具體例，關於烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧基羰基、飽和脂肪族醯氧基、可具有取代基之苯基烷基、可具有取代基之萘基烷基、可具有取代基之雜環基、及經1個或2個有機基取代之胺基，與Rb1 相同。 於Rb2 中，作為苯基、或咔唑基所具有之取代基所含之苯基、萘基、及雜環基進而具有取代基之情形時之取代基之例，可列舉：碳原子數1以上且6以下之烷基；碳原子數1以上且6以下之烷氧基；碳原子數2以上且7以下之飽和脂肪族醯基；碳原子數2以上且7以下之烷氧基羰基；碳原子數2以上且7以下之飽和脂肪族醯氧基；苯基；萘基；苯甲醯基；萘甲醯基；經選自由碳原子數1以上且6以下之烷基、嗎啉-1-基、哌𠯤-1-基、及苯基所組成之群中之基所取代之苯甲醯基；具有碳原子數1以上且6以下之烷基之單烷基胺基；具有碳原子數1以上且6以下之烷基之二烷基胺基；嗎啉-1-基；哌𠯤-1-基；鹵素；硝基；氰基。於苯基、或咔唑基所具有之取代基所含之苯基、萘基、及雜環基進而具有取代基之情形時，該取代基之個數於不阻礙本發明之目的之範圍內並無限定，較佳為1以上且4以下。於苯基、萘基、及雜環基具有複數個取代基之情形時，複數個取代基可相同亦可不同。 於Rb2 中，就容易獲得感度優異之光聚合起始劑之方面而言，較佳為下述式(b2)、或(b3)所表示之基，更佳為下述式(b2)所表示之基，尤佳為下述式(b2)所表示且A為S之基。 [化13]
Figure 02_image025
(Rb4 為選自由一價有機基、胺基、鹵素、硝基、及氰基所組成之群中之基，A為S或O，n2為0以上且4以下之整數) [化14]
Figure 02_image027
(Rb5 及Rb6 分別為一價有機基) 於式(b2)中之Rb4 為有機基之情形時，可於不阻礙本發明之目的之範圍內，從各種有機基中選擇。作為式(b2)中Rb4 為有機基之情形時之適宜之例，可列舉：碳原子數1以上且6以下之烷基；碳原子數1以上且6以下之烷氧基；碳原子數2以上且7以下之飽和脂肪族醯基；碳原子數2以上且7以下之烷氧基羰基；碳原子數2以上且7以下之飽和脂肪族醯氧基；苯基；萘基；苯甲醯基；萘甲醯基；經選自由碳原子數1以上且6以下之烷基、嗎啉-1-基、哌𠯤-1-基、及苯基所組成之群中之基所取代之苯甲醯基；具有碳原子數1以上且6以下之烷基之單烷基胺基；具有碳原子數1以上且6以下之烷基之二烷基胺基；嗎啉-1-基；哌𠯤-1-基；鹵素；硝基；氰基。 於Rb4 中，較佳為：苯甲醯基；萘甲醯基；經選自由碳原子數1以上且6以下之烷基、嗎啉-1-基、哌𠯤-1-基、及苯基所組成之群中之基所取代之苯甲醯基；硝基，更佳為：苯甲醯基；萘甲醯基；2-甲基苯基羰基；4-(哌𠯤-1-基)苯基羰基；4-(苯基)苯基羰基。 又，於式(b2)中，n2較佳為0以上且3以下之整數，更佳為0以上且2以下之整數，尤佳為0或1。於n2為1之情形時，較佳為Rb4 所鍵結之位置相對於Rb4 所鍵結之苯基與氧原子或硫原子鍵結之鍵結鍵而為對位。 式(b3)中之Rb5 可於不阻礙本發明之目的之範圍內，從各種有機基中選擇。作為Rb5 之適宜之例，可列舉：碳原子數1以上且20以下之烷基、碳原子數3以上且10以下之環烷基、碳原子數2以上且20以下之飽和脂肪族醯基、碳原子數2以上且20以下之烷氧基烷基、碳原子數2以上且20以下之烷氧基羰基、可具有取代基之苯基、可具有取代基之苯甲醯基、可具有取代基之苯氧基羰基、可具有取代基之碳原子數7以上且20以下之苯基烷基、可具有取代基之萘基、可具有取代基之萘甲醯基、可具有取代基之萘氧基羰基、可具有取代基之碳原子數11以上且20以下之萘基烷基、可具有取代基之雜環基、及可具有取代基之雜環基羰基等。 於Rb5 中，較佳為碳原子數1以上且20以下之烷基、或碳原子數2以上且20以下之烷氧基烷基，更佳為碳原子數1以上且6以下之烷基、或碳原子數2以上且6以下之烷氧基烷基，尤佳為乙基、或乙氧基乙基。 式(b3)中之Rb6 於不阻礙本發明之目的之範圍內並無特別限定，可從各種有機基中選擇。作為適宜作為Rb6 之基之具體例，可列舉：碳原子數1以上且20以下之烷基、可具有取代基之苯基、可具有取代基之萘基、及可具有取代基之雜環基。作為Rb6 ，該等基中，更佳為可具有取代基之苯基、或可具有取代基之噻吩基，尤佳為2-甲基苯基、或噻吩基。 作為Rb4 、Rb5 、或Rb6 所含之苯基、萘基、及雜環基進而具有取代基之情形時之取代基，可列舉：碳原子數1以上且6以下之烷基、碳原子數1以上且6以下之烷氧基、碳原子數2以上且7以下之飽和脂肪族醯基、碳原子數2以上且7以下之烷氧基羰基、碳原子數2以上且7以下之飽和脂肪族醯氧基、具有碳原子數1以上且6以下之烷基之單烷基胺基、具有碳原子數1以上且6以下之烷基之二烷基胺基、嗎啉-1-基、哌𠯤-1-基、鹵素、硝基、及氰基等。於Rb4 、Rb5 、或Rb6 所含之苯基、萘基、及雜環基進而具有取代基之情形時，該取代基之個數於不阻礙本發明之目的之範圍內並無限定，較佳為1以上且4以下。於Rb4 、Rb5 、或Rb6 所含之苯基、萘基、及雜環基具有複數個取代基之情形時，複數個取代基可相同亦可不同。 式(b1)中之Rb3 為氫原子、或碳原子數1以上且6以下之烷基。作為Rb3 ，較佳為甲基、或乙基，更佳為甲基。 於式(b1)所表示之肟酯化合物中，作為尤其適宜之化合物，可列舉下述之PI-1～PI-42。 [化15]
Figure 02_image029
[化16]
Figure 02_image031
[化17]
Figure 02_image033
[化18]
Figure 02_image035
[化19]
Figure 02_image037
[化20]
Figure 02_image039
又，下述式(b4)所表示之肟酯化合物亦作為光聚合起始劑而較佳。 [化21]
Figure 02_image041
(Rb7 為氫原子、硝基或一價有機基，Rb8 及Rb9 分別為可具有取代基之鏈狀烷基、可具有取代基之環狀有機基、或氫原子，Rb8 與Rb9 可互相鍵結而形成環，Rb10 為一價有機基，Rb11 為氫原子、可具有取代基之碳原子數1以上且11以下之烷基、或可具有取代基之芳基，n3為0以上且4以下之整數) 此處，作為用以製造式(b4)之肟酯化合物之肟化合物，適宜為下式(b5)所表示之化合物。 [化22]
Figure 02_image043
(Rb7 、Rb8 、Rb9 、Rb10 、及n3與式(b4)相同) 於式(b4)及(b5)中，Rb7 為氫原子、硝基或一價有機基。Rb7 於式(b4)中之茀環上鍵結於與和羰基鍵結之6員芳香環不同之6員芳香環。於式(b4)中，Rb7 對茀環之鍵結位置並無特別限定。於式(b4)所表示之化合物具有1個以上Rb7 之情形時，就容易合成式(b4)所表示之化合物等方面而言，較佳為1個以上之Rb7 中之1個鍵結於茀環中之2位。於Rb7 為複數之情形時，複數個Rb7 可相同亦可不同。 於Rb7 為有機基之情形時，Rb7 於不阻礙本發明之目的之範圍內並無特別限定，可從各種有機基中適當選擇。作為Rb7 為有機基之情形時之適宜之例，可列舉：烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、飽和脂肪族醯氧基、烷氧基羰基、可具有取代基之苯基、可具有取代基之苯氧基、可具有取代基之苯甲醯基、可具有取代基之苯氧基羰基、可具有取代基之苯甲醯氧基、可具有取代基之苯基烷基、可具有取代基之萘基、可具有取代基之萘氧基、可具有取代基之萘甲醯基、可具有取代基之萘氧基羰基、可具有取代基之萘甲醯氧基、可具有取代基之萘基烷基、可具有取代基之雜環基、可具有取代基之雜環基羰基、經1個或2個有機基取代之胺基、嗎啉-1-基、及哌𠯤-1-基等。 於Rb7 為烷基之情形時，烷基之碳原子數較佳為1以上且20以下，更佳為1以上且6以下。又，於Rb7 為烷基之情形時，可為直鏈，亦可為支鏈。作為Rb7 為烷基之情形時之具體例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、異戊基、第二戊基、第三戊基、正己基、正庚基、正辛基、異辛基、第二辛基、第三辛基、正壬基、異壬基、正癸基、及異癸基等。又，於Rb7 為烷基之情形時，烷基亦可於碳鏈中含有醚鍵(-O-)。作為碳鏈中具有醚鍵之烷基之例，可列舉：甲氧基乙基、乙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙氧基乙氧基乙基、及甲氧基丙基等。 於Rb7 為烷氧基之情形時，烷氧基之碳原子數較佳為1以上且20以下，更佳為1以上且6以下。又，於Rb7 為烷氧基之情形時，可為直鏈，亦可為支鏈。作為Rb7 為烷氧基之情形時之具體例，可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第二丁氧基、第三丁氧基、正戊氧基、異戊氧基、第二戊氧基、第三戊氧基、正己氧基、正庚氧基、正辛氧基、異辛氧基、第二辛氧基、第三辛氧基、正壬氧基、異壬氧基、正癸氧基、及異癸氧基等。又，於Rb7 為烷氧基之情形時，烷氧基亦可於碳鏈中含有醚鍵(-O-)。作為於碳鏈中具有醚鍵之烷氧基之例，可列舉：甲氧基乙氧基、乙氧基乙氧基、甲氧基乙氧基乙氧基、乙氧基乙氧基乙氧基、丙氧基乙氧基乙氧基、及甲氧基丙氧基等。 於Rb7 為環烷基或環烷氧基之情形時，環烷基或環烷氧基之碳原子數較佳為3以上且10以下，更佳為3以上且6以下。作為Rb7 為環烷基之情形時之具體例，可列舉：環丙基、環丁基、環戊基、環己基、環庚基、及環辛基等。作為Rb7 為環烷氧基之情形時之具體例，可列舉：環丙氧基、環丁氧基、環戊氧基、環己氧基、環庚氧基、及環辛氧基等。 於Rb7 為飽和脂肪族醯基或飽和脂肪族醯氧基之情形時，飽和脂肪族醯基或飽和脂肪族醯氧基之碳原子數較佳為2以上且21以下，更佳為2以上且7以下。作為Rb7 為飽和脂肪族醯基之情形時之具體例，可列舉：乙醯基、丙醯基、正丁醯基、2-甲基丙醯基、正戊醯基、2,2-二甲基丙醯基、正己醯基、正庚醯基、正辛醯基、正壬醯基、正癸醯基、正十一碳醯基、正十二碳醯基、正十三碳醯基、正十四碳醯基、正十五碳醯基、及正十六碳醯基等。作為Rb7 為飽和脂肪族醯氧基之情形時之具體例，可列舉：乙醯氧基、丙醯氧基、正丁醯氧基、2-甲基丙醯氧基、正戊醯氧基、2,2-二甲基丙醯氧基、正己醯氧基、正庚醯氧基、正辛醯氧基、正壬醯氧基、正癸醯氧基、正十一碳醯氧基、正十二碳醯氧基、正十三碳醯氧基、正十四碳醯氧基、正十五碳醯氧基、及正十六碳醯氧基等。 於Rb7 為烷氧基羰基之情形時，烷氧基羰基之碳原子數較佳為2以上且20以下，更佳為2以上且7以下。作為Rb7 為烷氧基羰基之情形時之具體例，可列舉：甲氧基羰基、乙氧基羰基、正丙氧基羰基、異丙氧基羰基、正丁氧基羰基、異丁氧基羰基、第二丁氧基羰基、第三丁氧基羰基、正戊氧基羰基、異戊氧基羰基、第二戊氧基羰基、第三戊氧基羰基、正己氧基羰基、正庚氧基羰基、正辛氧基羰基、異辛氧基羰基、第二辛氧基羰基、第三辛氧基羰基、正壬氧基羰基、異壬氧基羰基、正癸氧基羰基、及異癸氧基羰基等。 於Rb7 為苯基烷基之情形時，苯基烷基之碳原子數較佳為7以上且20以下，更佳為7以上且10以下。又，於Rb7 為萘基烷基之情形時，萘基烷基之碳原子數較佳為11以上且20以下，更佳為11以上且14以下。作為Rb7 為苯基烷基之情形時之具體例，可列舉：苄基、2-苯基乙基、3-苯基丙基、及4-苯基丁基。作為Rb7 為萘基烷基之情形時之具體例，可列舉：α-萘基甲基、β-萘基甲基、2-(α-萘基)乙基、及2-(β-萘基)乙基。於Rb7 為苯基烷基、或萘基烷基之情形時，Rb7 亦可於苯基、或萘基上進而具有取代基。 於Rb7 為雜環基之情形時，雜環基為含有1個以上N、S、O之5員或6員之單環，或者為該單環彼此、或該單環與苯環縮合而成之雜環基。於雜環基為縮合環之情形時，環數最多為3。雜環基可為芳香族基(雜芳基)，亦可為非芳香族基。作為構成該雜環基之雜環，可列舉：呋喃、噻吩、吡咯、㗁唑、異㗁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、***、吡啶、吡𠯤、嘧啶、嗒𠯤、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚𠯤、苯并咪唑、苯并***、苯并㗁唑、苯并噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞𠯤、㖕啉、喹㗁啉、哌啶、哌𠯤、嗎啉、哌啶、四氫吡喃、及四氫呋喃等。於Rb7 為雜環基之情形時，雜環基可進而具有取代基。 於Rb7 為雜環基羰基之情形時，雜環基羰基所含之雜環基與Rb7 為雜環基之情形時相同。 於Rb7 為經1個或2個有機基取代之胺基之情形時，有機基之適宜之例可列舉：碳原子數1以上且20以下之烷基、碳原子數3以上且10以下之環烷基、碳原子數2以上且21以下之飽和脂肪族醯基、可具有取代基之苯基、可具有取代基之苯甲醯基、可具有取代基之碳原子數7以上且20以下之苯基烷基、可具有取代基之萘基、可具有取代基之萘甲醯基、可具有取代基之碳原子數11以上且20以下之萘基烷基、及雜環基等。該等適宜之有機基之具體例與Rb7 相同。作為經1個或2個有機基取代之胺基之具體例，可列舉：甲基胺基、乙基胺基、二乙胺基、正丙基胺基、二正丙胺基、異丙基胺基、正丁基胺基、二正丁胺基、正戊基胺基、正己基胺基、正庚基胺基、正辛基胺基、正壬基胺基、正癸基胺基、苯基胺基、萘基胺基、乙醯基胺基、丙醯基胺基、正丁醯基胺基、正戊醯基胺基、正己醯基胺基、正庚醯基胺基、正辛醯基胺基、正癸醯基胺基、苯甲醯基胺基、α-萘甲醯基胺基、及β-萘甲醯基胺基等。 作為Rb7 所含之苯基、萘基、及雜環基進而具有取代基之情形時之取代基，可列舉：碳原子數1以上且6以下之烷基、碳原子數1以上且6以下之烷氧基、碳原子數2以上且7以下之飽和脂肪族醯基、碳原子數2以上且7以下之烷氧基羰基、碳原子數2以上且7以下之飽和脂肪族醯氧基、具有碳原子數1以上且6以下之烷基之單烷基胺基、具有碳原子數1以上且6以下之烷基之二烷基胺基、嗎啉-1-基、哌𠯤-1-基、鹵素、硝基、及氰基等。於Rb7 所含之苯基、萘基、及雜環基進而具有取代基之情形時，該取代基之個數於不阻礙本發明之目的之範圍內並無限定，較佳為1以上且4以下。於Rb7 所含之苯基、萘基、及雜環基具有複數個取代基之情形時，複數個取代基可相同亦可不同。 於以上所說明之基中，若作為Rb7 而為硝基、或Rb12 -CO-所表示之基，則有感度提高之傾向而較佳。Rb12 於不阻礙本發明之目的之範圍內並無特別限定，可從各種有機基中選擇。作為適宜作為Rb12 之基之例，可列舉：碳原子數1以上且20以下之烷基、可具有取代基之苯基、可具有取代基之萘基、及可具有取代基之雜環基。作為Rb12 ，該等基中，尤佳為2-甲基苯基、噻吩-2-基、及α-萘基。 又，若Rb7 為氫原子，則有透明性變得良好之傾向而較佳。再者，若Rb7 為氫原子且Rb10 為下文所述之式(b4a)或(b4b)所表示之基，則有透明性變得更良好之傾向。 於式(b4)中，Rb8 及Rb9 分別為可具有取代基之鏈狀烷基、可具有取代基之環狀有機基、或氫原子。Rb8 與Rb9 可互相鍵結而形成環。該等基中，作為Rb8 及Rb9 ，較佳為可具有取代基之鏈狀烷基。於Rb8 及Rb9 為可具有取代基之鏈狀烷基之情形時，鏈狀烷基可為直鏈烷基，亦可為支鏈烷基。 於Rb8 及Rb9 為不具有取代基之鏈狀烷基之情形時，鏈狀烷基之碳原子數較佳為1以上且20以下，更佳為1以上且10以下，尤佳為1以上且6以下。作為Rb8 及Rb9 為鏈狀烷基之情形時之具體例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、異戊基、第二戊基、第三戊基、正己基、正庚基、正辛基、異辛基、第二辛基、第三辛基、正壬基、異壬基、正癸基、及異癸基等。又，於Rb8 及Rb9 為烷基之情形時，烷基亦可於碳鏈中含有醚鍵(-O-)。作為碳鏈中具有醚鍵之烷基之例，可列舉：甲氧基乙基、乙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙氧基乙氧基乙基、及甲氧基丙基等。 於Rb8 及Rb9 為具有取代基之鏈狀烷基之情形時，鏈狀烷基之碳原子數較佳為1以上且20以下，更佳為1以上且10以下，尤佳為1以上且6以下。於該情形時，取代基之碳原子數不包含於鏈狀烷基之碳原子數中。具有取代基之鏈狀烷基較佳為直鏈狀。 烷基可具有之取代基於不阻礙本發明之目的之範圍內並無特別限定。作為取代基之適宜之例，可列舉：氰基、鹵素原子、環狀有機基、及烷氧基羰基。作為鹵素原子，可列舉：氟原子、氯原子、溴原子、碘原子。該等中，較佳為氟原子、氯原子、溴原子。作為環狀有機基，可列舉：環烷基、芳香族烴基、雜環基。作為環烷基之具體例，與Rb7 為環烷基之情形時之適宜之例相同。作為芳香族烴基之具體例，可列舉：苯基、萘基、聯苯基、蒽基、及菲基等。作為雜環基之具體例，與Rb7 為雜環基之情形時之適宜之例相同。於Rb7 為烷氧基羰基之情形時，烷氧基羰基所含之烷氧基可為直鏈狀，亦可為支鏈狀，較佳為直鏈狀。烷氧基羰基所含之烷氧基之碳原子數較佳為1以上且10以下，更佳為1以上且6以下。 於鏈狀烷基具有取代基之情形時，取代基之個數並無特別限定。較佳之取代基之個數係根據鏈狀烷基之碳原子數而變化。取代基之個數典型而言為1以上且20以下，較佳為1以上且10以下，更佳為1以上且6以下。 於Rb8 及Rb9 為環狀有機基之情形時，環狀有機基可為脂環式基，亦可為芳香族基。作為環狀有機基，可列舉：脂肪族環狀烴基、芳香族烴基、雜環基。於Rb8 及Rb9 為環狀有機基之情形時，環狀有機基可具有之取代基與Rb8 及Rb9 為鏈狀烷基之情形時相同。 於Rb8 及Rb9 為芳香族烴基之情形時，芳香族烴基較佳為苯基、或複數個苯環經由碳-碳鍵鍵結所形成之基、或複數個苯環縮合所形成之基。於芳香族烴基為苯基、或者複數個苯環鍵結或縮合所形成之基之情形時，芳香族烴基所含之苯環之環數並無特別限定，較佳為3以下，更佳為2以下，尤佳為1。作為芳香族烴基之較佳之具體例，可列舉：苯基、萘基、聯苯基、蒽基、及菲基等。 於Rb8 及Rb9 為脂肪族環狀烴基之情形時，脂肪族環狀烴基可為單環式，亦可為多環式。脂肪族環狀烴基之碳原子數並無特別限定，較佳為3以上且20以下，更佳為3以上且10以下。作為單環式之環狀烴基之例，可列舉：環丙基、環丁基、環戊基、環己基、環庚基、環辛基、降𦯉基、異𦯉基、三環壬基、三環癸基、四環十二烷基、及金剛烷基等。 於Rb8 及Rb9 為雜環基之情形時，雜環基為含有1個以上N、S、O之5員或6員之單環，或者為該單環彼此、或該單環與苯環縮合而成之雜環基。於雜環基為縮合環之情形時，環數最多為3。雜環基可為芳香族基(雜芳基)，亦可為非芳香族基。作為構成該雜環基之雜環，可列舉：呋喃、噻吩、吡咯、㗁唑、異㗁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、***、吡啶、吡𠯤、嘧啶、嗒𠯤、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚𠯤、苯并咪唑、苯并***、苯并㗁唑、苯并噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞𠯤、㖕啉、喹㗁啉、哌啶、哌𠯤、嗎啉、哌啶、四氫吡喃、及四氫呋喃等。 Rb8 與Rb9 可互相鍵結而形成環。包含Rb8 與Rb9 所形成之環之基較佳為亞環烷基。於Rb8 與Rb9 鍵結而形成亞環烷基之情形時，構成亞環烷基之環較佳為5員環～6員環，更佳為5員環。 於Rb8 與Rb9 鍵結所形成之基為亞環烷基之情形時，亞環烷基可與1個以上其他環縮合。作為可與亞環烷基縮合之環之例，可列舉：苯環、萘環、環丁烷環、環戊烷環、環己烷環、環庚烷環、環辛烷環、呋喃環、噻吩環、吡咯環、吡啶環、吡𠯤環、及嘧啶環等。 以上所說明之Rb8 及Rb9 中，作為適宜之基之例，可列舉式-A1 -A2 所表示之基。可列舉式中，A1 為直鏈伸烷基，A2 為烷氧基、氰基、鹵素原子、鹵化烷基、環狀有機基、或烷氧基羰基。 A1 之直鏈伸烷基之碳原子數較佳為1以上且10以下，更佳為1以上且6以下。於A2 為烷氧基之情形時，烷氧基可為直鏈狀，亦可為支鏈狀，較佳為直鏈狀。烷氧基之碳原子數較佳為1以上且10以下，更佳為1以上且6以下。於A2 為鹵素原子之情形時，較佳為氟原子、氯原子、溴原子、碘原子，更佳為氟原子、氯原子、溴原子。於A2 為鹵化烷基之情形時，鹵化烷基所含之鹵素原子較佳為氟原子、氯原子、溴原子、碘原子，更佳為氟原子、氯原子、溴原子。鹵化烷基可為直鏈狀，亦可為支鏈狀，較佳為直鏈狀。於A2 為環狀有機基之情形時，環狀有機基之例與Rb8 及Rb9 作為取代基而具有之環狀有機基相同。於A2 為烷氧基羰基之情形時，烷氧基羰基之例與Rb8 及Rb9 作為取代基而具有之烷氧基羰基相同。 作為Rb8 及Rb9 之適宜之具體例，可列舉：乙基、正丙基、正丁基、正己基、正庚基、及正辛基等烷基；2-甲氧基乙基、3-甲氧基正丙基、4-甲氧基正丁基、5-甲氧基正戊基、6-甲氧基正己基、7-甲氧基正庚基、8-甲氧基正辛基、2-乙氧基乙基、3-乙氧基正丙基、4-乙氧基正丁基、5-乙氧基正戊基、6-乙氧基正己基、7-乙氧基正庚基、及8-乙氧基正辛基等烷氧基烷基；2-氰基乙基、3-氰基正丙基、4-氰基正丁基、5-氰基正戊基、6-氰基正己基、7-氰基正庚基、及8-氰基正辛基等氰基烷基；2-苯基乙基、3-苯基正丙基、4-苯基正丁基、5-苯基正戊基、6-苯基正己基、7-苯基正庚基、及8-苯基正辛基等苯基烷基；2-環己基乙基、3-環己基正丙基、4-環己基正丁基、5-環己基正戊基、6-環己基正己基、7-環己基正庚基、8-環己基正辛基、2-環戊基乙基、3-環戊基正丙基、4-環戊基正丁基、5-環戊基正戊基、6-環戊基正己基、7-環戊基正庚基、及8-環戊基正辛基等環烷基烷基；2-甲氧基羰基乙基、3-甲氧基羰基正丙基、4-甲氧基羰基正丁基、5-甲氧基羰基正戊基、6-甲氧基羰基正己基、7-甲氧基羰基正庚基、8-甲氧基羰基正辛基、2-乙氧基羰基乙基、3-乙氧基羰基正丙基、4-乙氧基羰基正丁基、5-乙氧基羰基正戊基、6-乙氧基羰基正己基、7-乙氧基羰基正庚基、及8-乙氧基羰基正辛基等烷氧基羰基烷基；2-氯乙基、3-氯正丙基、4-氯正丁基、5-氯正戊基、6-氯正己基、7-氯正庚基、8-氯正辛基、2-溴乙基、3-溴正丙基、4-溴正丁基、5-溴正戊基、6-溴正己基、7-溴正庚基、8-溴正辛基、3,3,3-三氟丙基、及3,3,4,4,5,5,5-七氟正戊基等鹵化烷基。 作為Rb8 及Rb9 ，上述中適宜之基為：乙基、正丙基、正丁基、正戊基、2-甲氧基乙基、2-氰基乙基、2-苯基乙基、2-環己基乙基、2-甲氧基羰基乙基、2-氯乙基、2-溴乙基、3,3,3-三氟丙基、及3,3,4,4,5,5,5-七氟正戊基。 作為Rb10 之適宜之有機基之例，與Rb7 同樣地，可列舉：烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧基羰基、飽和脂肪族醯氧基、可具有取代基之苯基、可具有取代基之苯氧基、可具有取代基之苯甲醯基、可具有取代基之苯氧基羰基、可具有取代基之苯甲醯氧基、可具有取代基之苯基烷基、可具有取代基之萘基、可具有取代基之萘氧基、可具有取代基之萘甲醯基、可具有取代基之萘氧基羰基、可具有取代基之萘甲醯氧基、可具有取代基之萘基烷基、可具有取代基之雜環基、可具有取代基之雜環基羰基、經1個或2個有機基取代之胺基、嗎啉-1-基、及哌𠯤-1-基等。該等基之具體例與針對Rb7 所說明之基相同。又，作為Rb10 ，亦較佳為環烷基烷基、芳香環上可具有取代基之苯氧基烷基、芳香環上可具有取代基之苯基硫基烷基。苯氧基烷基、及苯基硫基烷基可具有之取代基與Rb7 所含之苯基可具有之取代基相同。 於有機基中，作為Rb10 ，較佳為烷基、環烷基、可具有取代基之苯基、或環烷基烷基、芳香環上可具有取代基之苯基硫基烷基。作為烷基，較佳為碳原子數1以上且20以下之烷基，更佳為碳原子數1以上且8以下之烷基，尤佳為碳原子數1以上且4以下之烷基，最佳為甲基。於可具有取代基之苯基中，較佳為甲基苯基，更佳為2-甲基苯基。環烷基烷基所含之環烷基之碳原子數較佳為5以上且10以下，更佳為5以上且8以下，尤佳為5或6。環烷基烷基所含之伸烷基之碳原子數較佳為1以上且8以下，更佳為1以上且4以下，尤佳為2。於環烷基烷基中，較佳為環戊基乙基。芳香環上可具有取代基之苯基硫基烷基所含之伸烷基之碳原子數較佳為1以上且8以下，更佳為1以上且4以下，尤佳為2。於芳香環上可具有取代基之苯基硫基烷基中，較佳為2-(4-氯苯基硫基)乙基。 又，作為Rb10 ，亦較佳為-A3 -CO-O-A4 所表示之基。A3 為二價有機基，較佳為二價烴基，較佳為伸烷基。A4 為一價有機基，較佳為一價之烴基。 於A3 為伸烷基之情形時，伸烷基可為直鏈狀，亦可為支鏈狀，較佳為直鏈狀。於A3 為伸烷基之情形時，伸烷基之碳原子數較佳為1以上且10以下，更佳為1以上且6以下，尤佳為1以上且4以下。 作為A4 之適宜之例，可列舉：碳原子數1以上且10以下之烷基、碳原子數7以上且20以下之芳烷基、及碳原子數6以上且20以下之芳香族烴基。作為A4 之適宜之具體例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、正己基、苯基、萘基、苄基、苯乙基、α-萘基甲基、及β-萘基甲基等。 作為-A3 -CO-O-A4 所表示之基之適宜之具體例，可列舉：2-甲氧基羰基乙基、2-乙氧基羰基乙基、2-正丙氧基羰基乙基、2-正丁氧基羰基乙基、2-正戊氧基羰基乙基、2-正己氧基羰基乙基、2-苄氧基羰基乙基、2-苯氧基羰基乙基、3-甲氧基羰基正丙基、3-乙氧基羰基正丙基、3-正丙氧基羰基正丙基、3-正丁氧基羰基正丙基、3-正戊氧基羰基正丙基、3-正己氧基羰基正丙基、3-苄氧基羰基正丙基、及3-苯氧基羰基正丙基等。 以上，已對Rb10 進行了說明，但作為Rb10 ，較佳為下述式(b4a)或(b4b)所表示之基。 [化23]
Figure 02_image045
(式(b4a)及(b4b)中，Rb13 及Rb14 分別為有機基，n4為0以上且4以下之整數，於Rb13 及R8 存在於苯環上鄰接之位置之情形時，Rb13 與Rb14 可互相鍵結而形成環，n5為1以上且8以下之整數，n6為1以上且5以下之整數，n7為0以上且(n6＋3)以下之整數，Rb15 為有機基) 關於式(b4a)中之Rb13 及Rb14 之有機基之例與Rb7 相同。作為Rb13 ，較佳為烷基或苯基。於Rb13 為烷基之情形時，其碳原子數較佳為1以上且10以下，更佳為1以上且5以下，尤佳為1以上且3以下，最佳為1。即，Rb13 最佳為甲基。於Rb13 與Rb14 鍵結而形成環之情形時，該環可為芳香族環，亦可為脂肪族環。作為式(b4a)所表示且Rb13 與Rb14 形成環之基之適宜之例，可列舉萘-1-基、或1,2,3,4-四氫萘-5-基等。上述式(b4a)中，n4為0以上且4以下之整數，較佳為0或1，更佳為0。 上述式(b4b)中，Rb15 為有機基。作為有機基，可列舉與針對Rb7 所說明之有機基相同之基。於有機基中，較佳為烷基。烷基可為直鏈狀，亦可為支鏈狀。烷基之碳原子數較佳為1以上且10以下，更佳為1以上且5以下，尤佳為1以上且3以下。作為Rb15 ，可較佳地例示甲基、乙基、丙基、異丙基、丁基等。該等基中，更佳為甲基。 上述式(b4b)中，n6為1以上且5以下之整數，較佳為1以上且3以下之整數，更佳為1或2。上述式(b4b)中，n7為0以上且(n6＋3)以下，較佳為0以上且3以下之整數，更佳為0以上且2以下之整數，尤佳為0。上述式(b4b)中，n5為1以上且8以下之整數，較佳為1以上且5以下之整數，更佳為1以上且3以下之整數，尤佳為1或2。 式(b4)中，Rb11 為氫原子、可具有取代基之碳原子數1以上且11以下之烷基、或可具有取代基之芳基。作為Rb11 為烷基之情形時可具有之取代基，可較佳地例示苯基、萘基等。又，作為Rb7 為芳基之情形時可具有之取代基，可較佳地例示碳原子數1以上且5以下之烷基、烷氧基、鹵素原子等。 式(b4)中，作為Rb11 ，可較佳地例示氫原子、甲基、乙基、正丙基、異丙基、正丁基、苯基、苄基、甲基苯基、萘基等，該等中，更佳為甲基或苯基。 式(b4)所表示之化合物係藉由包括將前述之式(b5)所表示之化合物所含之肟基(＞C=N-OH)轉換為＞C=N-O-CORb11 所表示之肟酯基之步驟之方法而製造。Rb11 與式(b4)中之Rb11 相同。 肟基(＞C=N-OH)向＞C=N-O-CORb11 所表示之肟酯基之轉換係藉由使前述之式(b5)所表示之化合物與醯化劑反應而進行。 作為提供-CORb11 所表示之醯基之醯化劑，可列舉(Rb11 CO)2 O所表示之酸酐、或Rb11 COHal(Hal為鹵素原子)所表示之醯鹵。 通式(b4)所表示之化合物例如可依照下述反應流程1而合成。於反應流程1中，使用下述式(b4-1)所表示之茀衍生物作為原料。於Rb7 為硝基或一價有機基之情形時，式(b4-1)所表示之茀衍生物可藉由周知之方法向9位被Rb8 及Rb9 取代之茀衍生物中導入取代基Rb7 而獲得。9位被Rb8 及Rb9 取代之茀衍生物於例如Rb8 及Rb9 為烷基之情形時，可如日本專利特開平06-234668號公報所記載般，於鹼金屬氫氧化物之存在下，於非質子性極性有機溶媒中使茀與烷基化劑反應而獲得。又，藉由在茀之有機溶媒溶液中添加如鹵化烷基之烷基化劑、鹼金屬氫氧化物之水溶液、及如碘化四丁基銨或第三丁醇鉀之相轉移觸媒而進行烷基化反應，可獲得9,9-烷基取代茀。 式(b4-2)所表示之茀衍生物係藉由佛瑞德-克來福特(Friedel-Crafts)反應向式(b4-1)所表示之化合物中導入-CO-CH2 -Rb10 所表示之醯基而獲得。用以導入醯基之醯化劑可為鹵羰基化合物，亦可為酸酐。作為醯化劑，較佳為式(b4-7)：Hal-CO-CH2 -Rb10 所表示之羧醯鹵。式(b4-7)中，Hal為鹵素原子。於茀環上導入醯基之位置可藉由適當改變Friedel-Crafts反應之條件、或對醯化位置以外之位置實施保護及去保護之方法而選擇。 繼而，將式(b4-2)所表示之化合物中存在於Rb10 與羰基之間之亞甲基進行肟化，而獲得下式(b4-4)所表示之酮肟化合物。將亞甲基進行肟化之方法並無特別限定，較佳為於鹽酸之存在下使下述式(b4-3)所表示之亞硝酸酯(RONO，R為碳原子數1以上且6以下之烷基)反應之方法。 繼而，使下述式(b4-4)所表示之酮肟化合物與下述式(b4-5)所表示之酸酐(Rb11 CO)2 O)、或下述式(b4-6)所表示之醯鹵(Rb11 COHal，Hal為鹵素原子)反應，而可獲得式(b4)所表示之化合物。 再者，於下述式(b4-1)、(b4-3)、(b4-4)、(b4-5)、及(b4-6)中，Rb7 、Rb8 、Rb9 、Rb10 、Rb11 、及n3與式(b4)相同。 又，於反應流程1中，式(b4-6)、式(b4-2)、及式(b4-4)各自所含之Rb10 可相同亦可不同。即，式(b4-6)、式(b4-2)、及式(b4-4)中之Rb10 於以反應流程1所表示之合成過程中可被化學修飾。作為化學修飾之例，可列舉酯化、醚化、醯化、醯胺化、鹵化、胺基中之氫原子被有機基取代等。Rb10 可受到之化學修飾並不限定於該等。 ＜反應流程1＞ [化24]
Figure 02_image047
作為式(b4)所表示之化合物之適宜之具體例，可列舉以下之PI-43～PI-76。 [化25]
Figure 02_image049
[化26]
Figure 02_image051
如上文所述，光聚合起始劑(B)亦可含有式(1)所表示之化合物以外之其他光聚合起始劑。 作為其他光聚合起始劑，具體而言，可列舉：1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、1-(4-十二烷基苯基)-2-羥基-2-甲基丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、雙(4-二甲胺基苯基)酮、2-甲基-1-[4-(甲基硫基)苯基]-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)-丁烷-1-酮、2-(苯甲醯氧基亞胺基)-1-[4-(苯基硫基)苯基]-1-辛酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、4-苯甲醯基-4'-甲基二甲基硫醚、4-二甲胺基苯甲酸、4-二甲胺基苯甲酸甲酯、4-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸丁酯、4-二甲胺基-2-乙基己基苯甲酸、4-二甲胺基-2-異戊基苯甲酸、苄基-β-甲氧基乙基縮醛、苯偶醯二甲基縮酮、鄰苯甲醯基苯甲酸甲酯、2,4-二乙基-9-氧硫𠮿
Figure 106136151-A0304-1
、2-氯-9-氧硫𠮿
Figure 106136151-A0304-1
、2,4-二甲基-9-氧硫𠮿
Figure 106136151-A0304-1
、1-氯-4-丙氧基-9-氧硫𠮿
Figure 106136151-A0304-1
、硫𠮿
Figure 106136151-A0304-1
、2-氯硫𠮿
Figure 106136151-A0304-1
、2,4-二乙基硫𠮿
Figure 106136151-A0304-1
、2-甲基硫𠮿
Figure 106136151-A0304-1
、2-異丙基硫𠮿
Figure 106136151-A0304-1
、2-乙基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-二苯基蒽醌、偶氮二異丁腈、過氧化苯甲醯、氫過氧化異丙苯、2-巰基苯并咪唑、2-巰基苯并㗁唑、2-巰基苯并噻唑、2-(鄰氯苯基)-4,5-二(間甲氧基苯基)-咪唑基二聚物、二苯甲酮、2-氯二苯甲酮、4,4'-雙二甲胺基二苯甲酮、4,4'-雙二乙胺基二苯甲酮、4,4'-二氯二苯甲酮、3,3-二甲基-4-甲氧基二苯甲酮、苯偶醯、安息香、安息香甲醚、安息香***、安息香異丙醚、安息香正丁醚、安息香異丁醚、安息香丁醚、苯乙酮、2,2-二乙氧基苯乙酮、對二甲基苯乙酮、對二甲胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、對第三丁基苯乙酮、對二甲胺基苯乙酮、對第三丁基三氯苯乙酮、對第三丁基二氯苯乙酮、α,α-二氯-4-苯氧基苯乙酮、9-氧硫𠮿
Figure 106136151-A0304-1
、2-甲基-9-氧硫𠮿
Figure 106136151-A0304-1
、2-異丙基-9-氧硫𠮿
Figure 106136151-A0304-1
、二苯并環庚酮、4-二甲胺基苯甲酸戊酯、9-苯基吖啶、1,7-雙-(9-吖啶基)庚烷、1,5-雙-(9-吖啶基)戊烷、1,3-雙-(9-吖啶基)丙烷、對甲氧基三𠯤、2,4,6-三(三氯甲基)-均三𠯤、2-甲基-4,6-雙(三氯甲基)-均三𠯤、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-均三𠯤、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-均三𠯤、2-[2-(4-二乙胺基-2-甲基苯基)乙烯基]-4,6-雙(三氯甲基)-均三𠯤、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-均三𠯤、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-均三𠯤、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)-均三𠯤、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)-均三𠯤、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯基-均三𠯤、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯基-均三𠯤、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯乙烯基苯基-均三𠯤、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯乙烯基苯基-均三𠯤等。該等其他光聚合起始劑可單獨使用或組合2種以上使用。 又，式(1-I)所表示之肟酯化合物亦作為式(1)所表示之化合物以外之其他光聚合起始劑而較佳。 [化27]
Figure 02_image053
(式(1-I)中，R1 、R2 、及R3 分別獨立為具有與碳原子鍵結之鍵結鍵之一價有機基) 於式(1-I)所表示之肟酯化合物中，較佳為下述式(b1-I)所表示之化合物、及式(b4-I)所表示之化合物。 [化28]
Figure 02_image055
(式(b1-I)中，Rb1 、Rb2 、Rb3 、及n1與上文所述之式(b1)相同) [化29]
Figure 02_image057
(式(b4-I)中，Rb7 、Rb8 、Rb9 、Rb10 、Rb11 、及n3與上文所述之式(b4)相同) 如上文所述，感光性組合物中之水分之量相對於感光性組合物整體為0.1質量%以下。因此，光聚合起始劑(B)所附帶之水分之量必須相對於光聚合起始劑(B)之質量與水分之質量之合計為1質量%以下。 此處，所謂光聚合起始劑(B)所附帶之水分意指附著於作為固體之光聚合起始劑(B)之表面之水分、或如水合般以分子級取入至光聚合起始劑(B)中之水分。 將光聚合起始劑(B)所附帶之水分之量減少為相對於光聚合起始劑(B)之質量與水分之質量之合計為1質量%以下之方法並無特別限定。作為該方法，較佳為於不會將光聚合起始劑(B)熱分解之溫度(例如為100℃以下，較佳為80℃以下)下在遮光下進行乾燥之方法。乾燥較佳為減壓條件下之乾燥方法。乾燥時間並無特別限定，例如為1小時以上且120小時以下，較佳為10小時以上且100小時以下。 又，從將光聚合起始劑(B)溶解於與水共沸之有機溶劑中而成之溶液中將溶媒蒸餾去除，並回收光聚合起始劑(B)，藉此亦可獲得水分之量得以減少之光聚合起始劑(B)。 又，光聚合起始劑(B)所附帶之式(2)所表示之羧酸之量必須相對於光聚合起始劑(B)之質量與式(2)所表示之羧酸之質量之合計為550質量ppb以下。 作為減少光聚合起始劑(B)所附帶之式(2)所表示之羧酸之量的方法，例如可列舉利用再結晶之精製、或利用有機溶劑之洗淨等。 光聚合起始劑(B)之含量相對於感光性組合物中之下文所述之溶劑(S)以外的成分之質量之合計，較佳為0.5質量%以上且30質量%以下，更佳為1質量%以上且20質量%以下。藉由將光聚合起始劑(B)之含量設為上述範圍，可獲得好感度且不易產生圖案形狀之不良之感光性組合物。 又，亦可於光聚合起始劑(B)中組合光起始助劑。作為光起始助劑，可列舉：三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲胺基苯甲酸甲酯、4-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸異戊酯、4-二甲胺基苯甲酸2-乙基己酯、苯甲酸2-二甲胺基乙酯、N,N-二甲基對甲苯胺、4,4'-雙(二甲胺基)二苯甲酮、9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10-二乙氧基蒽、2-巰基苯并噻唑、2-巰基苯并㗁唑、2-巰基苯并咪唑、2-巰基-5-甲氧基苯并噻唑、3-巰基丙酸、3-巰基丙酸甲酯、季戊四醇四巰基乙酸酯、3-巰基丙酸酯等硫醇化合物等。該等光起始助劑可單獨使用或組合2種以上使用。 ＜鹼溶性樹脂(C)＞ 感光性組合物亦可含有鹼溶性樹脂(C)作為用作光聚合性化合物(A)之樹脂以外之其他樹脂。藉由在感光性組合物中調配鹼溶性樹脂(C)，可對感光性組合物賦予良好之鹼性顯影性。 於本說明書中，所謂鹼溶性樹脂係指於藉由樹脂濃度20質量%之樹脂溶液(溶媒：丙二醇單甲醚乙酸酯)於基板上形成膜厚1 μm之樹脂膜，並且於濃度0.05質量%之KOH水溶液中浸漬1分鐘時，膜厚溶解0.01 μm以上之樹脂。 於鹼溶性樹脂(C)中，就製膜性優異之方面、或容易藉由單體之選擇而調整樹脂之特性等方面而言，較佳為具有乙烯性不飽和雙鍵之單體之聚合物。作為具有乙烯性不飽和雙鍵之單體，可列舉：(甲基)丙烯酸；(甲基)丙烯酸酯；(甲基)丙烯醯胺；丁烯酸；順丁烯二酸、反丁烯二酸、甲基順丁烯二酸、甲基反丁烯二酸、亞甲基丁二酸、該等二羧酸之酸酐；乙酸烯丙酯、己酸烯丙酯、辛酸烯丙酯、月桂酸烯丙酯、棕櫚酸烯丙酯、硬脂酸烯丙酯、苯甲酸烯丙酯、乙醯乙酸烯丙酯、乳酸烯丙酯、及烯丙氧基乙醇之類之烯丙基化合物；己基乙烯基醚、辛基乙烯基醚、癸基乙烯基醚、乙基己基乙烯基醚、甲氧基乙基乙烯基醚、乙氧基乙基乙烯基醚、氯乙基乙烯基醚、1-甲基-2,2-二甲基丙基乙烯基醚、2-乙基丁基乙烯基醚、羥乙基乙烯基醚、二乙二醇乙烯基醚、二甲胺基乙基乙烯基醚、二乙胺基乙基乙烯基醚、丁基胺基乙基乙烯基醚、苄基乙烯基醚、四氫糠基乙烯基醚、乙烯基苯基醚、乙烯基甲苯基醚、乙烯基氯苯基醚、乙烯基-2,4-二氯苯基醚、乙烯基萘基醚、及乙烯基鄰胺苯甲基醚之類之乙烯基醚；丁酸乙烯酯、異丁酸乙烯酯、三甲基乙酸乙烯酯、二乙基乙酸乙烯酯、特戊酸乙烯酯、己酸乙烯酯、氯乙酸乙烯酯、二氯乙酸乙烯酯、甲氧基乙酸乙烯酯、丁氧基乙酸乙烯酯、苯基乙酸乙烯酯、乙醯乙酸乙烯酯、乳酸乙烯酯、β-苯基丁酸乙烯酯、苯甲酸乙烯酯、水楊酸乙烯酯、氯苯甲酸乙烯酯、四氯苯甲酸乙烯酯、及萘甲酸乙烯酯之類之乙烯酯；苯乙烯、甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、二乙基苯乙烯、異丙基苯乙烯、丁基苯乙烯、己基苯乙烯、環己基苯乙烯、癸基苯乙烯、苄基苯乙烯、氯甲基苯乙烯、三氟甲基苯乙烯、乙氧基甲基苯乙烯、乙醯氧基甲基苯乙烯、甲氧基苯乙烯、4-甲氧基-3-甲基苯乙烯、二甲氧基苯乙烯、氯苯乙烯、二氯苯乙烯、三氯苯乙烯、四氯苯乙烯、五氯苯乙烯、溴苯乙烯、二溴苯乙烯、碘苯乙烯、氟苯乙烯、三氟苯乙烯、2-溴-4-三氟甲基苯乙烯、及4-氟-3-三氟甲基苯乙烯之類之苯乙烯或苯乙烯衍生物；乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、3-甲基-1-丁烯、3-甲基-1-戊烯、3-乙基-1-戊烯、4-甲基-1-戊烯、4-甲基-1-己烯、4,4-二甲基-1-己烯、4,4-二甲基-1-戊烯、4-乙基-1-己烯、3-乙基-1-己烯、1-辛烯、1-癸烯、1-十二烯、1-十四烯、1-十六烯、1-十八烯、及1-二十烯之類之烯烴。 作為具有乙烯性不飽和雙鍵之單體之聚合物的鹼溶性樹脂(C)通常含有源自不飽和羧酸之單元。作為不飽和羧酸之例，可列舉：(甲基)丙烯酸；(甲基)丙烯醯胺；丁烯酸；順丁烯二酸、反丁烯二酸、甲基順丁烯二酸、甲基反丁烯二酸、亞甲基丁二酸、該等二羧酸之酸酐。用作鹼溶性樹脂之具有乙烯性不飽和雙鍵之單體之聚合物中所含的源自不飽和羧酸之單元之量只要具有樹脂所需之鹼溶性，則無特別限定。用作鹼溶性樹脂之樹脂中的源自不飽和羧酸之單元之量相對於樹脂之質量，較佳為5質量%以上且25質量%以下，更佳為8質量%以上且16質量%以下。 於作為從以上所例示之單體中選擇之1種以上之單體之聚合物的具有乙烯性不飽和雙鍵之單體之聚合物中，較佳為選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物。以下，對選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物進行說明。 選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物的調製所使用之(甲基)丙烯酸酯於不阻礙本發明之目的之範圍內並無特別限定，可從公知之(甲基)丙烯酸酯中適當選擇。 作為(甲基)丙烯酸酯之適宜之例，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸第三辛酯等直鏈狀或支鏈狀之(甲基)丙烯酸烷基酯；(甲基)丙烯酸氯乙酯、(甲基)丙烯酸2,2-二甲基羥基丙酯、(甲基)丙烯酸2-羥基乙酯、三羥甲基丙烷單(甲基)丙烯酸酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸糠酯；含有具有環氧基之基之(甲基)丙烯酸酯；含有具有脂環式骨架之基之(甲基)丙烯酸酯。下文對含有具有環氧基之基之(甲基)丙烯酸酯、及含有具有脂環式骨架之基之(甲基)丙烯酸酯之詳細進行說明。 於選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物中，就使用感光性組合物所形成之透明絕緣膜對基材之密接性或機械強度優異之方面而言，較佳為含有源自含有具有環氧基之基之(甲基)丙烯酸酯之單元的樹脂。 含有具有環氧基之基之(甲基)丙烯酸酯可為含有具有鏈狀脂肪族環氧基之基之(甲基)丙烯酸酯，亦可為如下文所述之含有具有脂環式環氧基之基之(甲基)丙烯酸酯。 含有具有環氧基之基之(甲基)丙烯酸酯可含有芳香族基。作為構成芳香族基之芳香環之例，可列舉：苯環、萘環。作為具有芳香族基且含有具有環氧基之基之(甲基)丙烯酸酯之例，可列舉：(甲基)丙烯酸4-縮水甘油氧基苯酯、(甲基)丙烯酸3-縮水甘油氧基苯酯、(甲基)丙烯酸2-縮水甘油氧基苯酯、(甲基)丙烯酸4-縮水甘油氧基苯基甲酯、(甲基)丙烯酸3-縮水甘油氧基苯基甲酯、及(甲基)丙烯酸2-縮水甘油氧基苯基甲酯等。 於對使用感光性組合物所形成之膜要求透明性之情形時，較佳為含有具有環氧基之基之(甲基)丙烯酸不含芳香族基。 作為含有具有鏈狀脂肪族環氧基之基之(甲基)丙烯酸酯之例，可列舉：(甲基)丙烯酸環氧烷基酯、及(甲基)丙烯酸環氧烷基氧基烷基酯等之類之於酯基(-O-CO-)中之氧基(-O-)鍵結鏈狀脂肪族環氧基之(甲基)丙烯酸酯。此種(甲基)丙烯酸酯所具有之鏈狀脂肪族環氧基可於鏈中含有1個或複數個氧基(-O-)。鏈狀脂肪族環氧基之碳原子數並無特別限定，較佳為3以上且20以下，更佳為3以上且15以下，尤佳為3以上且10以下。 作為含有具有鏈狀脂肪族環氧基之基之(甲基)丙烯酸酯之具體例，可列舉：(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2-甲基縮水甘油酯、(甲基)丙烯酸3,4-環氧丁酯、(甲基)丙烯酸6,7-環氧庚酯等(甲基)丙烯酸環氧烷基酯；(甲基)丙烯酸2-縮水甘油氧基乙酯、(甲基)丙烯酸3-縮水甘油氧基正丙酯、(甲基)丙烯酸4-縮水甘油氧基正丁酯、(甲基)丙烯酸5-縮水甘油氧基正己酯、(甲基)丙烯酸6-縮水甘油氧基正己酯等(甲基)丙烯酸環氧烷基氧基烷基酯。 含有源自含有具有環氧基之基之(甲基)丙烯酸酯之單元的選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物中的源自含有具有環氧基之基之(甲基)丙烯酸酯之單元的含量相對於樹脂之重量，較佳為1質量%以上且95質量%以下，更佳為40質量%以上且80質量%以下。 又，於選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物中，就使用感光性組合物容易形成透明性優異之透明絕緣膜之方面而言，亦較佳為含有源自含有具有脂環式骨架之基之(甲基)丙烯酸酯之單元的樹脂。 於含有具有脂環式骨架之基之(甲基)丙烯酸酯中，具有脂環式骨架之基可為具有脂環式烴基之基，亦可為具有脂環式環氧基之基。構成脂環式骨架之脂環式基可為單環，亦可為多環。作為單環之脂環式基，可列舉：環戊基、環己基等。又，作為多環之脂環式基，可列舉：降𦯉基、異𦯉基、三環壬基、三環癸基、四環十二烷基等。 於含有具有脂環式骨架之基之(甲基)丙烯酸酯中，作為含有具有脂環式烴基之基之(甲基)丙烯酸酯，例如可列舉下述式(c1-1)～(c1-8)所表示之化合物。該等中，較佳為下述式(c1-3)～(c1-8)所表示之化合物，更佳為下述式(c1-3)或(c1-4)所表示之化合物。 [化30]
Figure 02_image059
上述式中，Rc1 表示氫原子或甲基，Rc2 表示單鍵或碳原子數1以上且6以下之二價之脂肪族飽和烴基，Rc3 表示氫原子或碳原子數1以上且5以下之烷基。作為Rc2 ，較佳為單鍵、直鏈狀或支鏈狀之伸烷基，例如為亞甲基、伸乙基、伸丙基、四亞甲基、乙基伸乙基、五亞甲基、六亞甲基。作為Rc3 ，較佳為甲基、乙基。 於含有具有脂環式骨架之基之(甲基)丙烯酸酯中，作為含有具有脂環式環氧基之基之(甲基)丙烯酸酯之具體例，例如可列舉下述式(c2-1)～(c2-16)所表示之化合物。該等中，為了使感光性組合物之顯影性成為適度之水準，較佳為下述式(c2-1)～(c2-6)所表示之化合物，更佳為下述式(c2-1)～(c2-4)所表示之化合物。 [化31]
Figure 02_image061
上述式中，Rc4 表示氫原子或甲基，Rc5 表示碳原子數1以上且6以下之二價之脂肪族飽和烴基，Rc6 表示碳原子數1以上且10以下之二價烴基，t表示0以上且10以下之整數。作為Rc5 ，較佳為直鏈狀或支鏈狀之伸烷基，例如為亞甲基、伸乙基、伸丙基、四亞甲基、乙基伸乙基、五亞甲基、六亞甲基。作為Rc6 ，較佳為例如亞甲基、伸乙基、伸丙基、四亞甲基、乙基伸乙基、五亞甲基、六亞甲基、伸苯基、伸環己基、-CH2 -Ph-CH2 -(Ph表示伸苯基)。 於選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物為含有源自含有具有脂環式骨架之基之(甲基)丙烯酸酯之單元的樹脂之情形時，樹脂中之源自含有具有脂環式骨架之基之(甲基)丙烯酸酯之單元的量較佳為5質量%以上且95質量%以下，更佳為10質量%以上且90質量%以下，進而較佳為30質量%以上且70質量%以下。 又，於含有源自含有具有脂環式骨架之基之(甲基)丙烯酸酯之單元的選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物中，較佳為含有源自(甲基)丙烯酸之單元與源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的樹脂。使用含有此種鹼溶性樹脂(C)之感光性組合物所形成之膜對基材之密接性優異。又，於使用此種樹脂之情形時，可發生樹脂所含之羧基與脂環式環氧基之自反應。因此，若使用含有此種樹脂之感光性組合物，則藉由使用加熱膜之方法等發生羧基與脂環式環氧基之自反應，而可提高所形成之膜之硬度之類的機械物性。 於含有源自(甲基)丙烯酸之單元與源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的樹脂中，樹脂中之源自(甲基)丙烯酸之單元之量較佳為1質量%以上且95質量%以下，更佳為10質量%以上且50質量%以下。於含有源自(甲基)丙烯酸之單元與源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的樹脂中，樹脂中之源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的量較佳為1質量%以上且95質量%以下，更佳為30質量%以上且70質量%以下。 於含有源自(甲基)丙烯酸之單元與源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物中，較佳為含有源自(甲基)丙烯酸之單元、源自具有脂環式烴基之(甲基)丙烯酸酯之單元、及源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的樹脂。 於含有源自(甲基)丙烯酸之單元、源自具有脂環式烴基之(甲基)丙烯酸酯之單元、及源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的樹脂中，樹脂中之源自(甲基)丙烯酸之單元之量較佳為1質量%以上且95質量%以下，更佳為10質量%以上且50質量%以下。於含有源自(甲基)丙烯酸之單元、源自具有脂環式烴基之(甲基)丙烯酸酯之單元、及源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的樹脂中，樹脂中之源自具有脂環式烴基之(甲基)丙烯酸酯之單元的量較佳為1質量%以上且95質量%以下，更佳為10質量%以上且70質量%以下。於含有源自(甲基)丙烯酸之單元、源自具有脂環式烴基之(甲基)丙烯酸酯之單元、及源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的樹脂中，樹脂中之源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的量較佳為1質量%以上且95質量%以下，更佳為30質量%以上且80質量%以下。 鹼溶性樹脂(C)之質量平均分子量(Mw：藉由凝膠滲透層析法(GPC)之聚苯乙烯換算獲得之測定值。於本說明書中相同)較佳為2000以上且200000以下，更佳為2000以上且18000以下。藉由設為上述範圍，有容易取得感光性組合物之膜形成能力、曝光後之顯影性之平衡之傾向。 於感光性組合物含有鹼溶性樹脂(C)之情形時，感光性組合物中之鹼溶性樹脂(C)之含量相對於感光性組合物中之下文所述之溶劑(S)以外的成分之質量之合計，較佳為15質量%以上且89.5質量%以下，更佳為35質量%以上且85質量%以下，尤佳為50質量%以上且70質量%以下。 以上所說明之鹼溶性樹脂(C)較佳為以感光性組合物中之水分之量與上文所述之式(2)所表示之羧酸之量分別成為特定之範圍內之方式，於調製感光性組合物前實施脫水等精製。 作為從鹼溶性樹脂(C)中去除水之方法，可列舉利用加熱進行之乾燥。又，作為從鹼溶性樹脂(C)中去除羧酸之方法，可列舉利用加熱之去除、或利用經脫水之有機溶劑之洗淨等方法。 ＜著色劑(D)＞ 感光性組合物亦可含有著色劑(D)。作為感光性組合物所含之著色劑(D)，並無特別限定，較佳為使用例如色指數(C.I.；The Society of Dyers and Colourists公司發行)中被分類為顏料(Pigment)之化合物，具體而言，較佳為使用附註有如下所述之色指數(C.I.)編號之化合物。 作為可適宜地使用之黃色顏料之例，可列舉：C.I.顏料黃1(以下，「C.I.顏料黃」相同而僅記載編號)、3、11、12、13、14、15、16、17、20、24、31、53、55、60、61、65、71、73，74、81、83、86、93、95、97、98、99、100、101、104、106、108、109、110、113、114、116、117、119、120、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、166、167、168、175、180、及185。 作為可適宜地使用之橙色顏料之例，可列舉：C.I.顏料橙1(以下，「C.I.顏料橙」相同而僅記載編號)、5、13、14、16、17、24、34、36、38、40、43、46、49、51、55、59、61、63、64、71、及73。 作為可適宜地使用之紫色顏料之例，可列舉：C.I.顏料紫1(以下，「C.I.顏料紫」相同而僅記載編號)、19、23、29、30、32、36、37、38、39、40、及50。 作為可適宜地使用之紅色顏料之例，可列舉：C.I.顏料紅1(以下，「C.I.顏料紅」相同而僅記載編號)2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、31、32、37、38、40、41、42、48：1、48：2、48：3、48：4、49：1、49：2、50：1、52：1、53：1、57、57：1、57：2、58：2、58：4、60：1、63：1、63：2、64：1、81：1、83、88、90：1、97、101、102、104、105、106、108、112、113、114、122、123、144、146、149、150、151、155、166、168、170、171、172、174、175、176、177、178、179、180、185、187、188、190、192、193、194、202、206、207、208、209、215、216、217、220、223、224、226、227、228、240、242、243、245、254、255、264、及265。 作為可適宜地使用之藍色顏料之例，可列舉：C.I.顏料藍1(以下，「C.I.顏料藍」相同而僅記載編號)、2、15、15：3、15：4、15：6、16、22、60、64、及66。 作為可適宜地使用之上述以外的色相之顏料之例，可列舉：C.I.顏料綠7、C.I.顏料綠36、C.I.顏料綠37等綠色顏料；C.I.顏料棕23、C.I.顏料棕25、C.I.顏料棕26、C.I.顏料棕28等棕色顏料；C.I.顏料黑1、C.I.顏料黑7等黑色顏料。 又，感光性組合物亦可含有遮光劑作為著色劑(D)。含有遮光劑之感光性組合物可適宜地用於液晶顯示面板中之黑矩陣或黑色管柱隔片(black column spacer)之形成、或有機EL(Electroluminescence，電致發光)元件中之發光層之劃分用之觸排的形成。 於以著色劑(D)作為遮光劑之情形時，較佳為使用黑色顏料或紫顏料作為遮光劑。作為黑色顏料或紫顏料之例，可不論有機物、無機物而列舉：碳黑、苝系顏料、內醯胺系顏料、鈦黑、銅、鐵、錳、鈷、鉻、鎳、鋅、鈣、銀等之金屬氧化物、複合氧化物、金屬硫化物、金屬硫酸鹽或金屬碳酸鹽等各種顏料。該等中，較佳為使用具有較高之遮光性之碳黑。 作為碳黑，可使用煙囪黑、爐黑、熱碳黑、燈黑等公知之碳黑，較佳為使用遮光性優異之煙囪黑。又，亦可使用樹脂被覆碳黑。 樹脂被覆碳黑由於與無樹脂被覆之碳黑相比導電性較低，因此於用作如液晶顯示器之液晶顯示元件之黑矩陣之情形時電流之洩漏較少，而能夠製造可靠性較高之低耗電之顯示器。 作為碳黑，亦較佳為已實施導入酸性基之處理之碳黑。導入至碳黑中之酸性基係表現出布忍斯特(Bronsted)之定義之酸性之官能基。作為酸性基之具體例，可列舉：羧基、磺酸基、磷酸基等。導入至碳黑中之酸性基亦可形成鹽。與酸性基形成鹽之陽離子於不阻礙本發明之目的之範圍內並無特別限定。作為陽離子之例，可列舉各種金屬離子、含氮化合物之陽離子、銨離子等，較佳為鈉離子、鉀離子、鋰離子等鹼金屬離子或銨離子。 於已實施以上所說明之導入酸性基之處理的碳黑中，就達成使用感光性組合物所形成之遮光性之硬化膜之高電阻的觀點而言，較佳為具有選自由羧酸基、羧酸鹽基、磺酸基、及磺酸鹽基所組成之群中之1種以上之官能基的碳黑。 對碳黑導入酸性基之方法並無特別限定。作為導入酸性基之方法，例如可列舉以下之方法。 1)藉由使用濃硫酸、發煙硫酸、氯磺酸等之直接取代法或使用亞硫酸鹽、亞硫酸氫鹽等之間接取代法對碳黑導入磺酸基之方法。 2)使具有胺基與酸性基之有機化合物與碳黑重氮偶合之方法。 3)藉由威廉森(Williamson)之醚化法使具有鹵素原子與酸性基之有機化合物與具有羥基之碳黑反應之方法。 4)使具有鹵羰基與由保護基保護之酸性基之有機化合物與具有羥基之碳黑反應之方法。 5)使用具有鹵羰基與由保護基保護之酸性基之有機化合物對碳黑進行Friedel-Crafts反應後進行去保護之方法。 於該等方法中，就酸性基之導入處理容易且安全之方面而言，較佳為方法2)。作為方法2)中所使用之具有胺基與酸性基之有機化合物，較佳為於芳香族基鍵結有胺基與酸性基之化合物。作為此種化合物之例，可列舉如磺胺酸之胺基苯磺酸、或如4-胺基苯甲酸之胺基苯甲酸。 導入至碳黑中之酸性基之莫耳數於不阻礙本發明之目的之範圍內並無特別限定。導入至碳黑中之酸性基之莫耳數相對於碳黑100 g，較佳為1 mmol以上且200 mmol以下，更佳為5 mmol以上且100 mmol以下。 導入有酸性基之碳黑亦可實施利用樹脂進行之被覆處理。於使用含有由樹脂被覆之碳黑之感光性組合物之情形時，容易形成遮光性及絕緣性優異、表面反射率較低之遮光性之硬化膜。再者，利用樹脂進行之被覆處理不會特別對使用感光性組合物所形成之遮光性之硬化膜的介電常數產生不良影響。作為可用於碳黑之被覆之樹脂之例，可列舉：酚系樹脂、三聚氰胺樹脂、二甲苯樹脂、鄰苯二甲酸二烯丙酯樹脂、甘酞樹脂、環氧樹脂、烷基苯樹脂等熱硬化性樹脂；或聚苯乙烯、聚碳酸酯、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、改性聚苯醚、聚碸、聚對伸苯基對苯二甲醯胺、聚醯胺醯亞胺、聚醯亞胺、聚胺基雙順丁烯二醯亞胺、聚醚碸聚苯碸、聚芳酯、聚醚醚酮等熱塑性樹脂。樹脂對碳黑之被覆量相對於碳黑之質量與樹脂之質量之合計，較佳為1質量%以上且30質量%以下。 又，作為遮光劑，亦較佳為苝系顏料。作為苝系顏料之具體例，可列舉下述式(d-1)所表示之苝系顏料、下述式(d-2)所表示之苝系顏料、及下述式(d-3)所表示之苝系顏料。於市售品中，可較佳地使用BASF公司製造之製品名K0084、及K0086或顏料黑21、30、31、32、33、及34等作為苝系顏料。 [化32]
Figure 02_image063
式(d-1)中，Rd1 及Rd2 分別獨立地表示碳原子數1以上且3以下之伸烷基，Rd3 及Rd4 分別獨立地表示氫原子、羥基、甲氧基、或乙醯基。 [化33]
Figure 02_image065
式(d-2)中，Rd5 及Rd6 分別獨立地表示碳原子數1以上且7以下之伸烷基。 [化34]
Figure 02_image067
式(d-3)中，Rd7 及Rd8 分別獨立為氫原子、碳原子數1以上且22以下之烷基，亦可含有N、O、S、或P之雜原子。於Rd7 及Rd8 為烷基之情形時，該烷基可為直鏈狀，亦可為支鏈狀。 上述式(d-1)所表示之化合物、式(d-2)所表示之化合物、及式(d-3)所表示之化合物例如可使用日本專利特開昭62-1753號公報、日本專利特公昭63-26784號公報所記載之方法而合成。即，以苝-3,5,9,10-四羧酸或其二酐與胺類作為原料，於水或有機溶媒中進行加熱反應。然後，使所獲得之粗產物於硫酸中再沈澱，或者於水、有機溶媒或該等之混合溶媒中再結晶，藉此可獲得目標物。 為了使苝系顏料於感光性組合物中良好地分散，苝系顏料之平均粒徑較佳為10 nm以上且1000 nm以下。 又，亦可含有內醯胺系顏料作為遮光劑。作為內醯胺系顏料，例如可列舉下述式(d-4)所表示之化合物。 [化35]
Figure 02_image069
式(d-4)中，Xd 表示雙鍵，作為幾何異構物而分別獨立為E體或Z體，Rd9 分別獨立地表示氫原子、甲基、硝基、甲氧基、溴原子、氯原子、氟原子、羧基、或磺基，Rd10 分別獨立地表示氫原子、甲基、或苯基，Rd11 各自獨立地表示氫原子、甲基、或氯原子。 式(d-4)所表示之化合物可單獨使用或組合2種以上而使用。 Rd9 就容易製造式(d-4)所表示之化合物之方面而言，較佳為鍵結於二氫吲哚酮環之6位，Rd11 較佳為鍵結於二氫吲哚酮環之4位。就同樣之觀點而言，Rd9 、Rd10 、及Rd11 較佳為氫原子。 式(d-4)所表示之化合物作為幾何異構物而具有EE體、ZZ體、EZ體，可為該等之任一種單一之化合物，亦可為該等幾何異構物之混合物。 式(d-4)所表示之化合物例如可藉由國際公開第2000/24736號，國際公開第2010/081624號所記載之方法而製造。 為了使內醯胺系顏料於組合物中良好地分散，內醯胺系顏料之平均粒徑較佳為10 nm以上且1000 nm以下。 進而，亦可較佳地使用以銀錫(AgSn)合金為主成分之微粒子(以下稱為「AgSn合金微粒子」)作為遮光劑。該AgSn合金微粒子只要AgSn合金為主成分即可，作為其他金屬成分，例如可含有Ni、Pd、Au等。 該AgSn合金微粒子之平均粒徑較佳為1 nm以上且300 nm以下。 AgSn合金於以化學式AgxSn表示之情形時，可獲得化學性穩定之AgSn合金之x之範圍為1≦x≦10，可同時獲得化學穩定性與黑色度之x之範圍為3≦x≦4。 此處，若於上述x之範圍內求出AgSn合金中之Ag之質量比，則 於x＝1之情形時，成為Ag/AgSn＝0.4762； 於x＝3之情形時，成為3・Ag/Ag3Sn＝0.7317； 於x＝4之情形時，成為4・Ag/Ag4Sn＝0.7843； 於x＝10之情形時，成為10・Ag/Ag10Sn＝0.9008。 因此，該AgSn合金於含有47.6質量%以上且90質量%以下之Ag之情形時變得化學性穩定，於含有73.17質量%以上且78.43質量%以上之Ag之情形時，相對於Ag量，可有效地獲得化學穩定性與黑色度。 該AgSn合金微粒子可使用通常之微粒子合成法而製作。作為微粒子合成法，可列舉：氣相反應法、噴霧熱分解法、霧化法、液相反應法、冷凍乾燥法、水熱合成法等。 AgSn合金微粒子之絕緣性較高，但為了根據感光性組合物之用途而進一步提高絕緣性，亦可以絕緣膜覆蓋表面。作為此種絕緣膜之材料，適宜為金屬氧化物或有機高分子化合物。 作為金屬氧化物，可適宜地使用具有絕緣性之金屬氧化物，例如可適宜地使用氧化矽(silica)、氧化鋁(alumina)、氧化鋯(zirconia)、氧化釔(yttria)、氧化鈦(titania)等。 又，作為有機高分子化合物，可適宜地使用具有絕緣性之樹脂，例如可適宜地使用聚醯亞胺、聚醚、聚丙烯酸酯、聚胺化合物等。 為了充分提高AgSn合金微粒子之表面之絕緣性，絕緣膜之膜厚較佳為1 nm以上且100 nm以下之厚度，更佳為5 nm以上且50 nm以下。 絕緣膜可藉由表面改質技術或表面之塗佈技術而容易地形成。尤其是若使用四乙氧基矽烷、三乙醇鋁等烷氧化物，則可於相對低溫下形成膜厚均勻之絕緣膜，故而較佳。 作為遮光劑，可單獨使用上述苝系顏料、內醯胺系顏料、AgSn合金微粒子，亦可組合該等而使用。 此外，遮光劑亦可以色調調整之目的等而於含有上述黑色顏料或紫顏料之同時含有紅、藍、綠、黃等色相之色素。黑色顏料或紫顏料以外之色相之色素可從公知之色素中適當選擇。例如作為黑色顏料或紫顏料以外之色相之色素，可使用上述各種顏料。黑色顏料或紫顏料以外之其他色相之色素之使用量相對於遮光劑之總質量，較佳為15質量%以下，更佳為10質量%以下。 為了使上述著色劑(D)於感光性組合物中均勻地分散，可進而使用分散劑。作為此種分散劑，較佳為使用聚伸乙基亞胺系、聚胺酯樹脂系、丙烯酸樹脂系之高分子分散劑。尤其是於使用碳黑作為著色劑之情形時，較佳為使用丙烯酸樹脂系之分散劑作為分散劑。 又，無機顏料與有機顏料可分別單獨使用，或可併用2種以上。於併用之情形時，較佳為相對於無機顏料與有機顏料之總量100質量份，而以10質量份以上且80質量份以下之範圍使用有機顏料，更佳為以20質量份以上且40質量份以下之範圍使用。 再者，感光性組合物中除了顏料以外，亦可使用染料作為著色劑(D)。該染料從公知之材料中適當選擇即可。 作為可用於本實施形態之感光性組合物之染料，例如可列舉：偶氮染料、金屬錯鹽偶氮染料、蒽醌染料、三苯基甲烷染料、𠮿
Figure 106136151-A0304-1
染料、花青染料、萘醌染料、醌亞胺染料、次甲基染料、酞菁染料等。 又，關於該等染料，可藉由進行色澱化(成鹽化)使之分散於有機溶劑等中，而將其用作著色劑(D)。 除了該等染料以外，例如亦可較佳地使用日本專利特開2013-225132號公報、日本專利特開2014-178477號公報、日本專利特開2013-137543號公報、日本專利特開2011-38085號公報、日本專利特開2014-197206號公報等所記載之染料等。 又，該等染料亦可與上文所述之顏料(例如苝系顏料、內醯胺系顏料、AgSn合金微粒子等)組合使用。 於感光性組合物含有著色劑(D)之情形時，感光性組合物中之著色劑(D)之使用量根據感光性組合物之用途而適當決定即可。作為一例，相對於感光性組合物中之下文所述之溶劑(S)以外的成分之質量之合計100質量份，較佳為5質量份以上且70質量份以下，更佳為25質量份以上且60質量份以下。藉由設為上述範圍，容易形成具有目標圖案形狀之黑矩陣或各著色層。 尤其是於使用含有遮光劑作為著色劑(D)之感光性組合物形成黑矩陣之情形時，較佳為以黑矩陣之每1 μm覆膜之OD(optical density，光密度)值成為4以上之方式調整感光性組合物中之遮光劑之量。若黑矩陣之每1 μm覆膜之OD值為4以上，則於用於液晶顯示器之黑矩陣之情形時，可獲得充分之顯示對比度。 著色劑(D)較佳為於製成使用分散劑使其以適當之濃度分散而成之分散液後添加至感光性組合物中。 以上所說明之著色劑(D)較佳為以感光性組合物中之水分之量與上文所述之式(2)所表示之羧酸之量分別成為特定之範圍內之方式，於調製感光性組合物前實施脫水等精製。 又，於使用著色劑(D)作為分散液之情形時，較佳為於分散液中之分散介質中，水分與式(2)所表示之羧酸之含量充分地少。 作為從著色劑(D)中去除水之方法，可列舉利用加熱進行之乾燥、或使用矽膠、分子篩等脫水劑之方法。作為從著色劑(D)中去除羧酸之方法，可列舉利用加熱之去除、或利用經脫水之有機溶劑之洗淨等方法。於從如分散介質之液狀成分中去除水或羧酸之情形時，可進行蒸餾等，亦可於液狀成分中添加矽膠、分子篩、活性碳等脫水劑或吸附劑。 ＜溶劑(S)＞ 感光性組合物含有溶劑(S)。關於溶劑(S)之種類，只要能夠調製水分之量與式(2)所表示之羧酸之量為特定範圍內之感光性組合物，則無特別限定。 作為溶劑(S)之適宜之具體例，例如可列舉：乙二醇單甲醚、乙二醇單***、乙二醇正丙醚、乙二醇單正丁醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇單正丙醚、二乙二醇單正丁醚、三乙二醇單甲醚、三乙二醇單***、丙二醇單甲醚、丙二醇單***、丙二醇單正丙醚、丙二醇單正丁醚、二丙二醇單甲醚、二丙二醇單***、二丙二醇單正丙醚、二丙二醇單正丁醚、三丙二醇單甲醚、三丙二醇單***等(聚)伸烷基二醇單烷基醚類；乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯等(聚)伸烷基二醇單烷基醚乙酸酯類；二乙二醇二甲醚、二乙二醇甲基乙基醚、二乙二醇二***、四氫呋喃等其他醚類；甲基乙基酮、環己酮、2-庚酮、3-庚酮等酮類；2-羥基丙酸甲酯、2-羥基丙酸乙酯等乳酸烷基酯類；2-羥基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、乙酸3-甲氧基丁酯、乙酸3-甲基-3-甲氧基丁酯、丙酸3-甲基-3-甲氧基丁酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-側氧丁酸乙酯等其他酯類；甲苯、二甲苯等芳香族烴類；N-甲基-2-吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N-二甲基異丁基醯胺、N,N-二乙基乙醯胺、N,N-二乙基甲醯胺、N-甲基己內醯胺、1,3-二甲基-2-咪唑啶酮、吡啶、及N,N,N',N'-四甲基脲等含氮極性有機溶劑等。該等溶劑(S)可單獨使用，亦可組合2種以上而使用。 該等中，較佳為伸烷基二醇單烷基醚類、伸烷基二醇單烷基醚乙酸酯類、上述其他醚類、乳酸烷基酯類、上述其他酯類，更佳為伸烷基二醇單烷基醚乙酸酯類、上述其他醚類、上述其他酯類。 又，就各成分之溶解性、或著色劑(D)之分散性等方面而言，亦較佳為溶劑(S)含有含氮極性有機溶劑。作為含氮極性有機溶劑，較佳為N,N,N',N'-四甲基脲。 該等溶劑可單獨使用或組合2種以上使用。 於上述溶劑中，較佳為丙二醇單甲醚、乙二醇單甲醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、二乙二醇二甲醚、二乙二醇甲基乙基醚、環己酮、乙酸3-甲氧基丁酯，尤佳為使用丙二醇單甲醚乙酸酯、乙酸3-甲氧基丁酯。 溶劑(S)之含量根據感光性組合物之用途而適當決定即可。作為一例，可列舉相對於感光性組合物之溶劑(S)以外之成分的質量之合計100質量份而為50質量份以上且1900質量份以下左右，較佳為80質量份以上且900質量份以下左右。 溶劑(S)較佳為以感光性組合物中之水分之量與上文所述之式(2)所表示之羧酸之量分別成為特定之範圍內之方式，於調製感光性組合物前實施脫水等精製。 作為從溶劑(S)中去除水之方法，可列舉蒸餾或使用矽膠、分子篩等脫水劑之方法等。 作為從溶劑(S)中去除羧酸之方法，可列舉蒸餾或者使用分子篩、活性碳等脫水劑或吸附劑之方法。 ＜其他成分＞ 感光性組合物除了含有上述成分以外，亦可視需要而含有各種添加劑。具體而言，可例示：硬化促進劑、光交聯劑、光增感劑、分散助劑、填充劑、密接促進劑、抗氧化劑、紫外線吸收劑、凝聚防止劑、熱聚合抑制劑、消泡劑、界面活性劑等。 作為熱聚合抑制劑，例如可列舉氫醌、氫醌單***等。又，作為消泡劑，可例示聚矽氧系、氟系等之化合物，作為界面活性劑，可例示陰離子系、陽離子系、非離子等之化合物。 ＜感光性組合物之製造方法＞ 感光性組合物之製造方法只要為能夠使上述所說明之特定之成分分別以所需之量均勻地分散或溶解於溶劑(S)中之方法，則無特別限定。 下文對適宜之製造方法進行說明。 ≪感光性組合物之製造方法≫ 感光性組合物之製造方法係包括將光聚合性化合物(A)與光聚合起始劑(B)溶解於溶劑(S)中之感光性組合物之製造方法。 於該製造方法中，使用含有上文所述之式(1)： [化36]
Figure 02_image071
(式(1)中，R1 、R2 、及R3 分別獨立為具有與碳原子鍵結之鍵結鍵之一價有機基) 所表示之化合物之光聚合起始劑(B)。 此外，溶解於溶劑(S)中之光聚合起始劑(B)所附帶之水分之量相對於光聚合起始劑之質量與水分之質量之合計為1質量%以下，較佳為0.5質量%以下，進而較佳為0.1質量%，尤佳為0.05質量%以下。藉由使用所附帶之水分之量為該範圍內之光聚合起始劑(B)製造感光性組合物，可獲得經時性之感度之降低受到抑制之感光性組合物。 為了使光聚合起始劑(B)所附帶之水分之量成為上述範圍內之值，較佳為感光性組合物之製造方法包括於不會將光聚合起始劑(B)熱分解之溫度下在遮光下進行乾燥。 又，關於溶解於溶劑(S)中之光聚合起始劑(B)，光聚合起始劑(B)所附帶之上文所述之式(2)所表示之羧酸的含量相對於光聚合起始劑(B)之質量與式(2)所表示之羧酸之質量之合計，較佳為550質量ppb以下，更佳為500質量ppb，尤佳為450質量ppb，最佳為420質量ppb以下。 於調製感光性組合物時，亦可使鹼溶性樹脂(C)與光聚合性化合物(A)及光聚合起始劑(B)一併溶解於溶劑(S)中。 進而，亦可於溶劑(S)中溶解上文所述之其他成分。 以上所說明之成分之使用量如上文關於感光性組合物所說明般。 使光聚合性化合物(A)、光聚合起始劑(B)、及鹼溶性樹脂(C)等溶解於溶劑(S)中之方法並無特別限定。 可將光聚合性化合物(A)、光聚合起始劑(B)、及鹼溶性樹脂(C)等同時添加至溶劑(S)中而使之溶解，亦可以任意之順序將光聚合性化合物(A)、光聚合起始劑(B)、及鹼溶性樹脂(C)等逐次添加至溶劑(S)中而溶解。 又，亦可將選自使光聚合性化合物(A)溶解於溶劑(S)中而成之溶液、使光聚合起始劑(B)溶解於溶劑中而成之溶液、使鹼溶性樹脂(C)溶解於溶劑(S)中而成之溶液、及使其他成分溶解於溶劑(S)中而成之溶液中之2種以上之溶液以任意之順序進行混合。 於在感光性組合物中含有上文所述之著色劑(D)之情形時，著色劑(D)之調配方法並無特別限定。 例如，可於獲得使著色劑(D)以外之成分均勻地溶解於溶劑(S)中而成之均勻之溶液後，將著色劑(D)或著色劑(D)之分散液添加至溶液中。 又，亦可於使著色劑(D)分散於特定量之溶劑(S)中後，使光聚合性化合物(A)、光聚合起始劑(B)、及鹼溶性樹脂(C)等溶解於含有溶劑(S)之分散液中。 根據以上所說明之方法，可調製即使含有式(1)所表示之化合物作為光聚合起始劑(B)亦不易發生經時性之感度降低之感光性組合物。 ≪光聚合起始劑≫ 光聚合起始劑含有式(1)： [化37]
Figure 02_image073
(式(1)中，R1 、R2 、及R3 分別獨立為具有與碳原子鍵結之鍵結鍵之一價有機基) 所表示之化合物。 光聚合起始劑所附帶之水分之量相對於光聚合起始劑之質量與光聚合起始劑所附帶之水之質量之合計為1質量%以下。 又，光聚合起始劑所附帶之下述式(2) R3 COOH・・・(2) (式(2)中，R3 所表示之羧酸之量相對於光聚合起始劑之質量與式(2)所表示之羧酸之質量之合計為550質量ppb以下。 藉由使用該光聚合起始劑(B)，容易調製高感度並且不易發生經時性之感度降低之感光性組合物。 關於光聚合起始劑(B)，式(1)所表示之化合物、式(1)所表示之化合物之含量、式(1)所表示之化合物以外可含有之其他光聚合起始劑、光聚合起始劑之調製方法等如上文關於感光性組合物、及感光性組合物之製造方法所說明般。 [實施例] 以下，示出實施例對本發明更具體地進行說明，但本發明之範圍並不限定於該等實施例。 [實施例1～4、及比較例1～6] 於實施例1、實施例2、及比較例1～3中，進行光聚合起始劑之保管試驗。 於實施例3、實施例4、及比較例4～6中，使用供於實施例1、實施例2、及比較例1～3中之試驗之光聚合起始劑，調製感光性組合物。 (感光性組合物之調製) 於實施例3、實施例4、及比較例4～6中，以固形物成分濃度成為24質量%之方式將下述結構(質量比I-1：I-2：II-1：III-1為25：20：14：41)之鹼溶性樹脂65質量份、二季戊四醇六丙烯酸酯(光聚合性單體)35質量份、以及表2所記載之種類及質量份之光聚合起始劑溶解於二乙二醇甲基乙基醚與丙二醇單甲醚乙酸酯之混合溶媒(質量比55：45)中，從而調製感光性組合物。 再者，依照下文所述之方法，於35℃下對光聚合起始劑進行48小時之保管試驗。關於各實施例及比較例，使用保管試驗前之光聚合起始劑與保管試驗後之光聚合起始劑，調製2種感光性組合物。 [化38]
Figure 02_image075
(光聚合起始劑(B)之保管試驗) 光聚合起始劑(B)之化學結構如以下所述。 [化39]
Figure 02_image077
再者，實施例所使用之光聚合起始劑(B)係於遮光下在分解溫度以下將使上述化合物再結晶而獲得之粉末加熱、減壓乾燥而獲得。實施例2中將減壓乾燥時間設為短於實施例1。 又，比較例所使用之光聚合起始劑(B)係以光聚合起始劑(B)所附帶之水分之量以相對於光聚合起始劑(B)之質量與水分之質量之合計的量(質量%)計而成為下述表1所記載之量之方式，對實施例所使用之光聚合起始劑添加水而調製。 再者，關於水分之量，係藉由卡氏(Karl Fischer)法所測定。 又，測定所獲得之光聚合起始劑(B)之剛製造後(初期)之乙酸含量(AC0 ，基於光聚合起始劑之質量與乙酸之質量之合計之質量ppb)、及於35℃下保管48小時後之乙酸含量(AC48 )。根據所獲得之AC0 之值與AC48 之值，基於上文所述之式而算出羧酸增加率。將AC0 、AC48 、及羧酸增加率記載於表1。 關於乙酸含量，藉由離子層析法進行測定。 [表1]
Figure 106136151-A0304-0001
 (感度評價) 使用實施例3、實施例4、及比較例4～6中獲得之感光性組合物，依照以下之方法進行感度評價。 ＜感度評價方法＞ 使用旋轉塗佈機，於10 cm×10 cm之玻璃旋轉塗佈感光性組合物而形成塗佈膜。將塗佈膜於100℃、120秒之條件下烘烤，而從塗佈膜中去除溶劑。繼而，藉由鏡面投影對準曝光器，以曝光量10、20、30、40、及50 mJ/cm2 對經烘烤之塗佈膜進行曝光。 曝光後，測定塗佈膜之膜厚。又，使用濃度0.05質量%之KOH水溶液將膜厚測定後之塗佈膜顯影處理60秒。繼而，測定顯影處理後之塗佈膜之膜厚。於各曝光量下算出顯影前後之膜厚差，確認膜厚差未達0.1 μm之最小曝光量，將最小曝光量設為感度。 下表2中之組合物中水分量係相對於組合物整體之質量之水分之量(質量%)，使用剛製造後之光聚合起始劑(B)之情形與使用經時後之光聚合起始劑(B)之情形下表現出同樣之數值。組合物中乙酸量係相對於光聚合起始劑(B)之質量與乙酸之質量之合計的乙酸之量(質量ppb)，與表1所記載之數值相同。 將含有保管前之起始劑之感光性組合物與含有保管後之起始劑之感光性組合物之感度無差異之情形評價為「良好」，將含有保管前之起始劑之感光性組合物與含有保管後之起始劑之感光性組合物之感度存在差異之情形評價為「不良」。 [表2]
Figure 106136151-A0304-0002
 根據實施例可知，於含有具有上文所述之式(1)所表示之結構的光聚合起始劑(B)之感光性組合物中，於使用乙酸之含量相對於光聚合起始劑(B)之質量與乙酸之質量之合計為550質量ppb以下且光聚合起始劑(B)所附帶之水分之量相對於上述光聚合起始劑(B)之質量與水分之質量之合計為1質量%以下之(B)調製感光性組合物之情形時，所調製之感光性組合物不會發生感度之降低。 另一方面，根據比較例可知，於感光性組合物中之乙酸之含量相對於光聚合起始劑(B)之質量與乙酸之質量之合計而超過550質量ppb，或水分之量相對於感光性組合物整體而超過0.1質量%之情形時，容易發生經時性之感度之降低。≪Photosensitive composition≫ The photosensitive composition contains a photopolymerizable compound (A), a photopolymerization initiator (B), and a solvent (S). The photopolymerization initiator (B) contains the following formula (1):
Figure 02_image007
(In formula (1), R 1 , R 2 , and R 3 Each independently is a compound represented by a valent organic group having a bond with a carbon atom. The following formula (2) in the photosensitive composition: R 3 COOH・・・(2) (In formula (2), R 3 The same as above) The content of the carboxylic acid represented by the total of the mass of the photopolymerization initiator (B) and the mass of the carboxylic acid represented by the formula (2) is 550 mass ppb or less, preferably 500 The mass ppb is more preferably 450 mass ppb, particularly preferably 420 mass ppb or less. The quantity of the water|moisture content in the photosensitive composition is 0.1 mass % or less with respect to the said whole photosensitive composition, Preferably it is 0.08 mass % or less, More preferably, it is 0.05 mass % or less. The reason for the decrease in sensitivity over time of the photosensitive composition containing the compound represented by the formula (1) as the photopolymerization initiator (B) was investigated. As a result, it was found that the water content in the photosensitive composition is the same as that of the above formula (2). The carboxylic acid represented by ) adversely affects the decrease in sensitivity over time. That is, by making the photosensitive composition satisfy the above requirements, the decrease in the sensitivity of the photosensitive composition over time is suppressed. In the photosensitive composition, in order to keep the amount of water and the amount of the carboxylic acid represented by the formula (2) within the above-mentioned specific ranges, it is preferable to store the photosensitive composition at a low temperature in an airtight and light-shielding container middle. Specifically, the temperature during storage is preferably 35°C or lower, more preferably 25°C or lower, particularly preferably 15°C or lower, and most preferably 5°C or lower. The lower limit of the storage temperature is not particularly limited, but it is preferably a temperature at which curing of the photosensitive composition or compositional analysis of the photosensitive composition does not occur. By keeping the photosensitive composition under such conditions, the amount of water in the photosensitive composition and the amount of the carboxylic acid represented by the formula (2) can be prevented from increasing, especially the increase in the amount of carboxylic acid can be prevented . Moreover, it is preferable that the photosensitive composition contains the following CA according to the following formula 0 (quality ppb) with CA 48 (mass ppb) The photosensitive composition of the photopolymerization initiator (B) whose calculated carboxylic acid increase rate (%) is 10 mass % or less, more preferably 5 mass % or less. The photosensitive composition containing the above-mentioned photopolymerization initiator (B) with a small increase rate (%) of carboxylic acid has a tendency that the amount of carboxylic acid is not easily increased with time, and accordingly, it is easy to suppress the time-lapse of the photosensitive composition. Sexual sensitivity decreased. (Calculation formula of carboxylic acid increase rate) Carboxylic acid increase rate (%)=(CA 48 /CA 0 -1.00)×100 (CA 0 and CA 48 definition) CA 0 : The amount of the carboxylic acid represented by the formula (2) (mass ppb) CA relative to the sum of the mass of the photopolymerization initiator (B) immediately after production and the mass of the carboxylic acid represented by the formula (2) 48 : The amount of the carboxylic acid represented by the formula (2) (mass ppb) Again, the above CA 48 It is preferably 450 mass ppb or less, more preferably 430 mass ppb or less, particularly preferably 410 mass ppb or less, and most preferably 400 mass ppm or less. Contains CA 48 The amount of carboxylic acid in the photosensitive composition of the photopolymerization initiator (B) having a value within the above range is less likely to increase over time, and it is easy to suppress the decrease in sensitivity over time. The amount of the carboxylic acid represented by the formula (2) in the photosensitive composition can be measured by ion chromatography. Hereinafter, essential or optional components contained in the photosensitive composition will be described. <Photopolymerizable compound (A)> The photosensitive composition contains a photopolymerizable compound (A). It does not specifically limit as a photopolymerizable compound (A), A conventionally well-known photopolymerizable compound can be used. Among them, a resin having an ethylenically unsaturated group or a monomer having an ethylenically unsaturated group is preferable. A resin having an ethylenically unsaturated group and a monomer having an ethylenically unsaturated group may be used in combination. When the resin which has an ethylenically unsaturated group and the monomer which has an ethylenically unsaturated group are combined, the curability of the photosensitive composition improves, and it becomes easy to form a pattern. [Resin having an ethylenically unsaturated group] Examples of the resin having an ethylenically unsaturated group include (meth)acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, Monoethyl fumarate, 2-hydroxyethyl (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, glycerin (methyl) Acrylate, (meth)acrylamide, acrylonitrile, methacrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylic acid 2 -Ethylhexyl, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol Ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolpropane tetra (Meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexane Oligomers obtained by polymerization of glycol di(meth)acrylate, phenolphthalein-based epoxy diacrylate, etc.; polyester prepolymer obtained by condensing polyols with monobasic or polybasic acids Polyester (meth)acrylate obtained by reacting with acrylic acid; poly(meth)acrylate urethane obtained by reacting polyol with a compound having 2 isocyanate groups and then reacting with (meth)acrylic acid ; Make bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, trisphenol methane type epoxy resin Epoxy resin and (meth)acrylic acid such as oxygen resin, polycarboxylate polyglycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxybenzene type epoxy resin, etc. Epoxy (meth)acrylate resin and the like obtained by the reaction. Furthermore, what made epoxy (meth)acrylate resin and polybasic acid anhydride react can be used suitably. In addition, in this specification, "(meth)acryl group" means "acryl group or methacryl group". When the photopolymerizable compound (A) is a polymer having an ethylenically unsaturated group, the polymer is preferably a polymer (A') having an ethylenically unsaturated group and having a Cardo structure. When the polymer (A') containing the Cardo structure described above is used as the photopolymerizable compound (A), it is easy to obtain a photosensitive composition excellent in the balance of curability and developability under exposure. When a coloring agent (D) is contained, it becomes easy to disperse|distribute a coloring agent (D) favorably. Moreover, as resin which has an ethylenically unsaturated group, the resin obtained by making the reaction product of an epoxy compound and an unsaturated group-containing carboxylic acid compound further react with a polybasic acid anhydride can be used suitably. Among them, a compound represented by the following formula (a-1) is preferred. The compound represented by the following formula (a-1) is suitable as the polymer (A') containing the Cardo structure described above. The compound represented by this formula (a-1) is preferable in that the photocurability itself is high. [hua 5]
Figure 02_image009
In the above formula (a-1), X a represents a group represented by the following formula (a-2). [hua 6]
Figure 02_image011
In the above formula (a-2), R a1 Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R a2 Represent independently a hydrogen atom or a methyl group, W a represents a single bond or a group represented by the following formula (a-3). [hua 7]
Figure 02_image013
Furthermore, in the above formula (a-1), Y a Indicates the residue obtained by removing the acid anhydride group (-CO-O-CO-) from the dicarboxylic acid anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, methylenesuccinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl Base methylene tetrahydrophthalic anhydride, chloro bridge anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc. Furthermore, in the above formula (a-1), Z a Indicates the residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. As an example of a tetracarboxylic dianhydride, a pyromellitic dianhydride, a benzophenone tetracarboxylic dianhydride, a biphenyl tetracarboxylic dianhydride, a biphenyl ether tetracarboxylic dianhydride, etc. are mentioned. Moreover, in said Formula (a-1), m represents the integer of 0 or more and 20 or less. The acid value of the resin having an ethylenically unsaturated group is preferably 10 mgKOH/g or more and 150 mgKOH/g or less, more preferably 70 mgKOH/g or more and 110 mgKOH/g or less, in terms of resin solid content. By setting the acid value to be 10 mgKOH/g or more, sufficient solubility with respect to the developer can be obtained, which is preferable. Moreover, since sufficient hardenability can be obtained by making an acid value into 150 mgKOH/g or less, and surface property can be made favorable, it is preferable. Moreover, the mass average molecular weight of the resin which has an ethylenically unsaturated group becomes like this. Preferably it is 1000 or more and 40000 or less, More preferably, it is 2000 or more and 30000 or less. Since favorable heat resistance and film strength can be obtained by making a mass average molecular weight into 1000 or more, it is preferable. Moreover, since favorable developability can be obtained by making a mass average molecular weight into 40000 or less, it is preferable. [Monomer having an ethylenically unsaturated group] The monomer having an ethylenically unsaturated group includes a monofunctional monomer and a polyfunctional monomer. As a monofunctional monomer, (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, methylenesuccinic acid, methylenesuccinic anhydride, methylcis Butenedioic acid, methyl maleic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, methyl (meth)acrylate, ( Ethyl meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylate ) 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy phthalate -2-hydroxypropyl, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, (methyl) ) 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, half (meth)acrylate of phthalic acid derivatives, etc. These monofunctional monomers may be used alone or in combination of two or more. On the other hand, as a polyfunctional monomer, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, (Meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate base) acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol Di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2- Bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, (methyl) 2-Hydroxy-3-(meth)acryloyloxypropyl acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, ortho Diglycidyl phthalate di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (ie, toluene diisocyanate, Trimethylhexamethylene diisocyanate, or the reaction product of hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate), methylenebis(meth)acrylamide, (meth)propylene Polyfunctional monomers such as amide methylene ether, polyol and N-methylol (meth)acrylamide condensate, triacrylate formal, etc. These polyfunctional monomers may be used alone or in combination of two or more. The content of the photopolymerizable compound (A) in the photosensitive composition is preferably 10% by mass or more and 70% by mass relative to the total mass of the components other than the solvent (S) described below in the photosensitive composition Below, it is more preferable that it is 20 mass % or more and 65 mass % or less, and it is especially preferable that it is 30 mass % or more and 60 mass % or less. The photopolymerizable compound (A) described above is preferably such that the amount of water in the photosensitive composition and the content of the carboxylic acid represented by the above-mentioned formula (2) are within specific ranges, respectively, Purification such as dehydration is performed before preparing the photosensitive composition. As a method of removing water from a photopolymerizable compound (A), drying by heating is mentioned. Moreover, after dissolving the photopolymerizable compound (A) in an organic solvent azeotroped with water, the organic solvent may be distilled off from the obtained solution to reduce the water content in the photopolymerizable compound (A). As a method of removing the carboxylic acid from the photopolymerizable compound (A), methods such as removal by heating and washing by a dehydrated organic solvent can be exemplified. <Photopolymerization initiator (B)> The photosensitive composition contains a photopolymerization initiator (B). The photopolymerization initiator (B) contains the following formula (1):
Figure 02_image015
(In formula (1), R 1 , R 2 , and R 3 Each independently is a compound represented by a valent organic group having a bond with a carbon atom. Therefore, the sensitivity of the photosensitive composition is excellent. However, the sensitivity of the previously known photosensitive composition containing the compound represented by the formula (1) as a photopolymerization initiator tends to decrease with time. However, in the photosensitive composition containing the compound represented by the formula (1) as a photopolymerization initiator, the amount of water and the amount of the carboxylic acid represented by the above-mentioned formula (2) are respectively within specific ranges. In a small amount, the decrease in the sensitivity of the photosensitive composition over time can be suppressed. The photopolymerization initiator (B) may contain two or more compounds represented by the formula (1) in combination. The photopolymerization initiator (B) may contain photopolymerization initiators other than the compound represented by the formula (1) within a range that does not inhibit the purpose of the present invention. The content of the compound represented by the formula (1) in the photopolymerization initiator (B) is preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass . In formula (1), R is preferably used as 1 Examples of the organic group include: alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic alkoxy, alkoxycarbonyl, saturated aliphatic alkoxy, optionally substituted phenyl , phenoxy which may have substituent, benzyl which may have substituent, phenoxycarbonyl which may have substituent, benzyloxy which may have substituent, phenylalkyl which may have substituent , Naphthyl which may have substituent, naphthyloxy which may have substituent, naphthyloxy which may have substituent, naphthoxycarbonyl which may have substituent, naphthyloxy which may have substituent, Substituted naphthylalkyl, optionally substituted heterocyclyl, optionally substituted heterocyclylcarbonyl, 1 or 2 organic substituted amino, morpholin-1-yl, and piper 𠯤-1-base etc. Again, as R 1 , and also preferably cycloalkylalkyl, phenoxyalkyl which may have substituents on the aromatic ring, and phenylsulfanylalkyl which may have substituents on the aromatic ring. Substituents that phenoxyalkyl and phenylthioalkyl may have and R 1 The phenyl groups contained may have the same substituents. in R 1 In the case of an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Again, in R 1 In the case of an alkyl group, it may be a straight chain or a branched chain. as R 1 Specific examples in the case of an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopropyl Pentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-decyl, and isodecyl, etc. Again, in R 1 In the case of an alkyl group, the alkyl group may also contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl oxyethyl, and methoxypropyl, etc. in R 1 In the case of an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Again, in R 1 In the case of an alkoxy group, it may be a straight chain or a branched chain. as R 1 Specific examples in the case of alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, third Butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second octyloxy , the third octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy, etc. Again, in R 1 In the case of an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy group, propoxyethoxyethoxy, and methoxypropoxy, etc. in R 1 In the case of a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. as R 1 Specific examples in the case of a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. as R 1 Specific examples in the case of a cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group. in R 1 In the case of a saturated aliphatic alkoxy group or a saturated aliphatic alkoxy group, the carbon number of the saturated aliphatic alkoxy group or saturated aliphatic alkoxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less . as R 1 Specific examples in the case of a saturated aliphatic acid group include acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentyl group, and 2,2-dimethylpropionyl group. , n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group , n-pentadecyl, and n-hexadecanoyl, etc. as R 1 Specific examples in the case of a saturated aliphatic alkoxy group include acetyloxy, propanoyloxy, n-butanoyloxy, 2-methylpropanoyloxy, n-pentanoyloxy, 2, 2-Dimethylpropionyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecanyloxy, n-dodecyloxy Carboalkoxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecyloxy, n-hexadecanoyloxy, and the like. in R 1 In the case of an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. as R 1 Specific examples in the case of alkoxycarbonyl include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, Dibutoxycarbonyl, third butoxycarbonyl, n-pentoxycarbonyl, isopentyloxycarbonyl, second pentoxycarbonyl, third pentoxycarbonyl, n-hexyloxycarbonyl, n-heptoxycarbonyl, n-Octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxycarbonyl Wait. in R 1 In the case of a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. Again, in R 1 In the case of a naphthylalkyl group, the number of carbon atoms in the naphthylalkyl group is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. as R 1 Specific examples in the case of a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. as R 1 Specific examples in the case of naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl base. in R 1 In the case of phenylalkyl or naphthylalkyl, R 1 A phenyl group or a naphthyl group may further have a substituent. in R 1 In the case of a heterocyclic group, the heterocyclic group is a 5- or 6-membered monocyclic ring containing at least one N, S, O, or a heterocyclic condensed monocyclic ring or a benzene ring. ring base. When the heterocyclic group is a condensed ring, the number of rings is at most 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine, Beta, benzofuran, benzothiophene, indole, isoindole, indole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline Linen, quinazoline, phthaloline, quinoline, quinoline, piperidine, piperidine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran, etc. in R 1 In the case of a heterocyclic group, the heterocyclic group may further have a substituent. in R 1 In the case of a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group and R 1 The same is true in the case of a heterocyclic group. in R 1 In the case of an amine group substituted with one or two organic groups, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. , Saturated aliphatic aryl group with 2 or more and 21 or less carbon atoms, phenyl group which may have substituents, benzyl group which may have substituents, phenyl group which may have substituted groups with 7 or more and 20 or less carbon atoms An alkyl group, an optionally substituted naphthyl group, an optionally substituted naphthylcarboxyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, and a heterocyclic group, etc. Specific examples of such suitable organic groups and R 1 same. Specific examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamine N-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, benzene amino, naphthyl amino, acetyl amino, propionyl amino, n-butyl amino, n-pentyl amino, n-hexyl amino, n-heptyl amino, n-octyl amino , n-decylamino, benzylamino, α-naphthylamino, and β-naphthylamino, etc. as R 1 When the contained phenyl group, naphthyl group, and heterocyclic group further have a substituent, the substituent may include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acid group, a saturated Aliphatic alkoxy, alkoxycarbonyl, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylthio, optionally substituted benzyl, optionally substituted phenoxycarbonyl, optionally substituted benzyloxy, optionally substituted phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyloxy, optionally substituted naphthyl, optionally substituted naphthyloxycarbonyl, optionally substituted naphthyloxy, optionally substituted naphthylalkyl, optionally substituted heterocyclic, optionally substituted Heterocyclic carbonyl group, amino group, amino group substituted with one or two organic groups, morpholin-1-yl, piperazine-1-yl, halogen atom, nitro group, cyano group and the like. in R 1 When the contained phenyl group, naphthyl group, and heterocyclic group further have substituents, the number of the substituents is not limited as long as the object of the present invention is not inhibited, but preferably 1 or more and 4 or less. in R 1 When the contained phenyl group, naphthyl group, and heterocyclic group have plural substituents, the plural substituents may be the same or different. When the substituent is an alkyl group, it is preferably 1 or more and 20 or less carbon atoms, and more preferably 1 or more and 6 or less carbon atoms. When the substituent is an alkyl group, it may be a straight chain or a branched chain. Specific examples when the substituent is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl base, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-octyl Decyl, and isodecyl, etc. Moreover, when a substituent is an alkyl group, an ether bond (-O-) may be contained in an alkyl group in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl oxyethyl, and methoxypropyl, etc. When the substituent is an alkoxy group, the number of carbon atoms is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Moreover, when a substituent is an alkoxy group, a straight chain may be sufficient as it, and a branched chain may be sufficient. Specific examples when the substituent is an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a second butoxy group. , third butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second Octyloxy, tertiary octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, isodecyloxy and the like. Moreover, when a substituent is an alkoxy group, an alkoxy group may contain an ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy group, propoxyethoxyethoxy, and methoxypropoxy, etc. When the substituent is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 or more and 10 or less, and more preferably the number of carbon atoms is 3 or more and 6 or less. As a specific example when a substituent is a cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. are mentioned. Specific examples when the substituent is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group. When the substituent is a saturated aliphatic alkoxy group or a saturated aliphatic alkoxy group, the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably the number of carbon atoms is 2 or more and 7 or less. Specific examples in the case where the substituent is a saturated aliphatic group include acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentyl group, and 2,2-dimethyl group. Propyl radical, n-hexyl radical, n-heptyl radical, n-octyl radical, n-nonyl radical, n-decyl radical, n-decyl radical, n-dodecyl radical, n-tdecyl radical, n-tetradecyl radical Carbonyl, n-pentadecyl, and n-hexadecyl, etc. Specific examples in the case where the substituent is a saturated aliphatic alkoxyl group include acetyloxyl, propionyloxy, n-butyryloxy, 2-methylpropionyloxy, n-pentyloxyl , 2,2-dimethylpropionyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecanyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecyloxy, n-hexadecanoyloxy, and the like. When the substituent is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably the number of carbon atoms is 2 or more and 7 or less. Specific examples when the substituent is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxy Carbonyl, second-butoxycarbonyl, third-butoxycarbonyl, n-pentoxycarbonyl, isopentyloxycarbonyl, second-pentoxycarbonyl, third-pentoxycarbonyl, n-hexyloxycarbonyl, n-heptyloxy ylcarbonyl, n-octoxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyl Oxycarbonyl, etc. When the substituent is an optionally substituted phenylalkyl group, it is preferably 7 or more and 20 or less carbon atoms, more preferably 7 or more and 10 or less carbon atoms. Moreover, when a substituent is the naphthyl alkyl group which may have a substituent, it is preferable that carbon number is 11 or more and 20 or less, and it is more preferable that carbon number is 11 or more and 14 or less. Specific examples when the substituent is an optionally substituted phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples when the substituent is an optionally substituted naphthylalkyl group include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-naphthylmethyl. -(β-naphthyl)ethyl. When the substituent is a heterocyclic group which may have a substituent, the above-mentioned heterocyclic group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, O, or the monocyclic ring or the monocyclic ring. A heterocyclic group formed by the condensation of a ring with a benzene ring. When the above-mentioned heterocyclic group is a condensed ring, the number of rings is at most 3. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine, Beta, benzofuran, benzothiophene, indole, isoindole, indole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline Line, quinazoline, phthaloline, quinoline, and quinoline, etc. When the substituent is an amino group substituted with one or two organic groups, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, an alkyl group having 3 to 10 carbon atoms The following cycloalkyl groups, saturated aliphatic aryl groups having 2 or more and 20 or less carbon atoms, phenyl groups which may have substituents, benzyl groups which may have substituents, and carbon atoms which may have 7 or more and which may have substituents Phenyl alkyl groups with 20 or less, naphthyl groups which may have substituents, naphthyl groups which may have substituents, naphthyl alkyl groups which may have 11 to 20 carbon atoms, and heterocyclic groups which may have substituents . Specific examples of these suitable organic groups are the same as those exemplified above for the substituents. Specific examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamine N-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, benzene amino, naphthyl amino, acetyl amino, propionyl amino, n-butyl amino, n-pentyl amino, n-hexyl amino, n-heptyl amino, n-octyl amino , n-decylamino, benzylamino, α-naphthylamino, and β-naphthylamino, etc. Among the above-mentioned substituents, examples of the substituent in the case where a phenyl group, a naphthyl group, a heterocyclic group, etc. further have a substituent group include: an alkyl group having 1 to 6 carbon atoms; an alkyl group having 1 or more carbon atoms; Alkoxy groups of at least 6 and less than 6 carbon atoms; saturated aliphatic aryl groups with 2 or more and 7 or less carbon atoms; alkoxycarbonyl groups with 2 or more and 7 or less carbon atoms; saturated aliphatic groups with 2 or more and 7 or less carbon atoms Benzyloxy; phenyl; naphthyl; benzyl; naphthyl; A benzyl group substituted by a group in the group consisting of phenyl; a monoalkylamine group having an alkyl group with 1 to 6 carbon atoms; two of an alkyl group with 1 to 6 carbon atoms or less Alkylamino; Morpholin-1-yl; Pipi-1-yl; Halogen atom; Nitro; Cyano. When the phenyl group, naphthyl group, heterocyclic group, etc. contained in the above-mentioned substituent group further has a substituent group, the number of the substituent group is not limited to the extent that it does not hinder the purpose of the present invention, and is preferably 1 more than 4 and less than 4. When a phenyl group, a naphthyl group, a heterocyclic group, etc. have a plurality of substituents, the plurality of substituents may be the same or different. In organic groups, as R 1 , preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, a phenylthioalkyl group which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group having 1 or more and 20 or less carbon atoms, more preferably an alkyl group having 1 or more and 8 or less carbon atoms, particularly preferably an alkyl group having 1 or more and 4 or less carbon atoms, most preferably Preferably methyl. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, particularly preferably 5 or 6. The number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms in the alkylene group contained in the optionally substituted phenylsulfanylalkyl group on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, particularly preferably 2. Among the phenylsulfanylalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylsulfanyl)ethyl is preferred. Again, as R 1 , also preferably -A b1 -CO-OA b2 the base indicated. A b1 is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. A b2 It is a monovalent organic group, preferably a monovalent hydrocarbon group. in A b1 In the case of an alkylene group, the alkylene group may be linear or branched, but preferably linear. in A b1 In the case of an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, particularly preferably 1 or more and 4 or less. as A b2 Suitable examples include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. as A b2 Suitable specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl , naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl, etc. AS-A b1 -CO-OA b2 Suitable specific examples of the group represented include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl, and 2-n-butoxycarbonylethyl , 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 3- Ethoxycarbonyl-n-propyl, 3-n-propoxycarbonyl-n-propyl, 3-n-butoxycarbonyl-n-propyl, 3-n-pentoxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl , 3-benzyloxycarbonyl-n-propyl, and 3-phenoxycarbonyl-n-propyl, etc. Above, has been applied to R 1 is illustrated, but as R 1 , preferably a group represented by the following formula (b1a) or (b1b). [Chemical 9]
Figure 02_image017
(In formulas (b1a) and (b1b), R 7 and R 8 Each is an organic group, p is an integer of 0 or more and 4 or less, in R 7 and R 8 When present in the adjacent position on the benzene ring, R 7 with R 8 can be bonded to each other to form a ring, q is an integer of 1 or more and 8 or less, r is an integer of 1 or more and 5 or less, s is an integer of 0 or more and (r+3) or less, R 9 is an organic group) about R in formula (b1a) 7 and R 8 Examples of organic groups and R 1 same. as R 7 , preferably alkyl or phenyl. in R 7 In the case of an alkyl group, the number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and most preferably 1. That is, R 7 The best is methyl. in R 7 with R 8 When a ring is formed by bonding, the ring may be an aromatic ring or an aliphatic ring. as represented by formula (b1a) and R 7 with R 8 Suitable examples of the group forming the ring include naphthalene-1-yl, 1,2,3,4-tetrahydronaphthalene-5-yl and the like. In the above formula (b1a), p is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0. In the above formula (b1b), R 9 is an organic base. As the organic group, there can be listed 1 The organic groups described are the same groups. as R 9 Among the organic groups, alkyl groups are preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. as R 9 , methyl, ethyl, propyl, isopropyl, butyl and the like can be preferably exemplified. Among these groups, a methyl group is more preferred. In the above formula (b1b), r is an integer of 1 or more and 5 or less, preferably 1 or more and 3 or less, and more preferably 1 or 2. In the above formula (b1b), s is 0 or more and (r+3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, particularly preferably 0. In the above formula (b1b), q is an integer of 1 or more and 8 or less, preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, and particularly preferably 1 or 2. In formula (1), R 2 is an organic base. As the organic group, an aryl group which may have a substituent or a heteroaryl group which may have a substituent is preferable. As an aryl group which may have a substituent, the phenyl group which may have a substituent is mentioned, for example. As a heteroaryl group which may have a substituent, the carbazolyl group which may have a substituent is mentioned, for example. in R 2 Among them, the substitution which the aryl group, the heteroaryl group, the phenyl group, or the carbazolyl group may have is not particularly limited in the range that does not hinder the purpose of the present invention. Examples of suitable substituents that an aryl group, a heteroaryl group, a phenyl group, or a carbazolyl group may have on a carbon atom include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, and a saturated aliphatic group. aliphatic alkoxy, saturated aliphatic alkoxy, alkoxycarbonyl, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylthio, optionally substituted benzyl group, optionally substituted phenoxycarbonyl, optionally substituted benzyloxy, optionally substituted phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyloxy, optionally substituted naphthyl, optionally substituted naphthyloxycarbonyl, optionally substituted naphthyloxy, optionally substituted naphthylalkyl, optionally substituted heterocyclic group, Optionally substituted heterocyclic carbonyl group, amino group, amino group substituted with one or two organic groups, morpholin-1-yl, piperazine-1-yl, halogen atom, nitro group, and cyano group, etc. . in R 2 In the case of a heteroaryl group or a carbazolyl group, examples of a suitable substituent which the heteroaryl group may have on a heteroatom such as a nitrogen atom and a suitable substituent which the carbazolyl group may have on the nitrogen atom are: Examples include: alkyl, cycloalkyl, saturated aliphatic, alkoxycarbonyl, optionally substituted phenyl, optionally substituted benzyl, optionally substituted phenoxycarbonyl, optionally substituted Substituted phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyl, optionally substituted naphthoxycarbonyl, optionally substituted naphthylalkyl, optionally substituted The heterocyclic group, and the heterocyclic carbonyl group which may have a substituent, etc. Among these substituents, an alkyl group is preferred, an alkyl group having 1 to 20 carbon atoms is more preferred, an alkyl group having 1 to 6 carbon atoms is still more preferred, and an ethyl group is particularly preferred. Specific examples of the substituent which the aryl group, the heteroaryl group, the phenyl group, or the carbazolyl group may have are the alkyl group, the alkoxy group, the cycloalkyl group, the cycloalkoxy group, the saturated aliphatic aryl group, the saturated aliphatic group Alkyloxy, alkoxycarbonyl, optionally substituted phenylalkyl, optionally substituted naphthylalkyl, optionally substituted heterocyclyl, and amine substituted with one or two organic groups base, with R for R 1 The description is the same. Among the above-mentioned substituents, the substituents in the case of phenyl, naphthyl, and heterocyclic groups having further substituents are the same as those for R 1 The description is the same. in R 2 Among them, the group represented by the following formula (1-1) or (1-2) is preferable, and the group represented by the following formula (1-1) is more preferable in that the sensitivity of the photosensitive composition is excellent. The base is particularly preferably a base represented by the following formula (1-1) in which A is S. [Chemical 10]
Figure 02_image019
(R 4 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen atom, a nitro group, and a cyano group, A is S or O, and n is an integer of 0 or more and 4 or less) [Chemical 11]
Figure 02_image021
(R 5 and R 6 (respectively, monovalent organic groups) When a photosensitive composition is used to form a pattern, the pattern is likely to be colored due to the heating in the baking step after the pattern is formed. However, in the photosensitive composition, when using R 2 When the oxime ester compound represented by the formula (1) in which A is a group of S and which is represented by the above formula (1-1) is used as a photopolymerization initiator, it is easy to suppress the coloring of the pattern by heating. R in formula (1-1) 4 In the case of an organic group, it can be selected from various organic groups within a range that does not inhibit the purpose of the present invention. as R in formula (1-1) 4 In the case of an organic group, suitable examples include: an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; and a saturated fat having 2 to 7 carbon atoms. alkoxycarbonyl group with 2 to 7 carbon atoms; saturated aliphatic alkoxyl group with 2 to 7 carbon atoms; phenyl group; naphthyl group; benzyl group; naphthoyl group; A benzalyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, and a phenyl group; having carbon atoms Monoalkylamine group having an alkyl group of 1 or more and 6 or less; dialkylamine group having an alkyl group of 1 or more and 6 or less carbon atoms; morpholin-1-yl; piperazine-1-yl; halogen ; nitro; cyano. in R 4 Among them, preferably: benzyl group; naphthyl group; selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperidine-1-yl, and phenyl Benzyl substituted by the group in the group; nitro, more preferably: benzyl; naphthyl; 2-methylphenylcarbonyl; 4-(piperidin-1-yl)phenyl Carbonyl; 4-(phenyl)phenylcarbonyl. Moreover, in Formula (1-1), n is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1. When n is 1, preferably R 4 The position of the bond is relative to R 4 The bonding bond between the phenyl group and atom A is the para position. R in formula (1-2) 5 It can be selected from various organic groups within the range which does not inhibit the objective of this invention. as R 5 Suitable examples include: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic aliphatic group having 2 to 20 carbon atoms, and a carbon atom Alkoxyalkyl having 2 or more and 20 or less, alkoxycarbonyl having 2 or more and 20 or less carbon atoms, optionally substituted phenyl, optionally substituted benzyl, optionally substituted Phenoxycarbonyl group, optionally substituted phenylalkyl group having 7 to 20 carbon atoms, optionally substituted naphthyl, optionally substituted naphthylcarboxyl, optionally substituted naphthyloxy A carbonyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, an optionally substituted heterocyclic group, and an optionally substituted heterocyclic carbonyl group, and the like. in R 5 Among them, an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms or an alkyl group having 6 or less carbon atoms is more preferable. The alkoxyalkyl group of 2 or more and 6 or less is particularly preferably an ethyl group or an ethoxyethyl group. R in formula (1-2) 6 It does not specifically limit in the range which does not inhibit the objective of this invention, It can select from various organic groups. as appropriate as R 6 Specific examples of the group include an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted heterocyclic group. as R 6 , among these groups, a phenyl group which may have a substituent or a thienyl group which may have a substituent is more preferable, and a 2-methylphenyl group or a thienyl group is particularly preferable. as R 4 , R 5 , or R 6 When the contained phenyl group, naphthyl group, and heterocyclic group further have a substituent, the substituent may include an alkyl group having 1 or more and 6 or less carbon atoms, and an alkoxy group having 1 or more and 6 or less carbon atoms. group, saturated aliphatic alkoxy group with 2 or more and 7 or less carbon atoms, alkoxycarbonyl group with 2 or more and 7 or less carbon atoms, saturated aliphatic alkoxy group with 2 or more and 7 or less carbon atoms, having carbon atoms Monoalkylamine group having an alkyl group having 1 or more and 6 or less, dialkylamine group having an alkyl group having 1 or more and 6 or less carbon atoms, morpholin-1-yl, piperazine-1-yl, halogen , nitro, and cyano, etc. in R 4 , R 5 , or R 6 When the contained phenyl group, naphthyl group, and heterocyclic group further have substituents, the number of the substituents is not limited as long as the object of the present invention is not inhibited, but preferably 1 or more and 4 or less. in R 4 , R 5 , or R 6 When the contained phenyl group, naphthyl group, and heterocyclic group have plural substituents, the plural substituents may be the same or different. In formula (1), R 3 is an organic base. Although it does not specifically limit as an organic group, Preferably it is an alkyl group and an aryl group. The alkyl group is preferably an alkyl group having 1 or more and 11 or less carbon atoms. The aryl group is a phenyl group which may have a substituent. Substituents in the optionally substituted phenyl group and for R 1 The substituents described are the same. as R 3 , more preferably an alkyl group having 1 or more and 6 or less carbon atoms, and a phenyl group, particularly preferably a methyl group, an ethyl group, and a phenyl group, and most preferably a methyl group and an ethyl group. It is also preferable to use an oxime-based compound represented by the following formula (b1) as the photopolymerization initiator represented by the formula (1). [Chemical 12]
Figure 02_image023
(R b1 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, n1 is an integer of 0 or more and 4 or less, R b2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent, R b3 is a hydrogen atom, or an alkyl group having 1 or more and 6 or less carbon atoms) In formula (b1), R b1 It does not specifically limit in the range which does not inhibit the objective of this invention, It can select from various organic groups suitably. as R b1 In the case of an organic group, suitable examples include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic alkoxy group, a saturated aliphatic alkoxy group, an alkoxycarbonyl group, which may have Substituted phenyl, optionally substituted phenoxy, optionally substituted benzyl, optionally substituted phenoxycarbonyl, optionally substituted benzyloxy, optionally substituted phenylalkyl, optionally substituted naphthyl, optionally substituted naphthoxy, optionally substituted naphthyl, optionally substituted naphthoxycarbonyl, optionally substituted naphthyl Ethyloxy, optionally substituted naphthylalkyl, optionally substituted heterocyclic group, amine group, amine group substituted with 1 or 2 organic groups, morpholin-1-yl, and piperazine- 1-yl, halogen, nitro, and cyano, etc. When n1 is an integer of 2 or more and 4 or less, R b1 Can be the same or different. In addition, the carbon number of the substituent which the substituent further has is not included in the carbon number of a substituent. in R b1 In the case of an alkyl group, the number of carbon atoms is preferably 1 or more and 20 or less, and more preferably the number of carbon atoms is 1 or more and 6 or less. Again, in R b1 In the case of an alkyl group, it may be a straight chain or a branched chain. as R b1 Specific examples in the case of an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopropyl Pentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-decyl, and isodecyl, etc. Again, in R b1 In the case of an alkyl group, the alkyl group may also contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl oxyethyl, and methoxypropyl, etc. in R b1 In the case of an alkoxy group, the number of carbon atoms is preferably 1 or more and 20 or less, and more preferably the number of carbon atoms is 1 or more and 6 or less. Again, in R b1 In the case of an alkoxy group, it may be a straight chain or a branched chain. as R b1 Specific examples in the case of alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, third Butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second octyloxy , the third octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy, etc. Again, in R b1 In the case of an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy group, propoxyethoxyethoxy, and methoxypropoxy, etc. in R b1 In the case of a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 or more and 10 or less, and more preferably the number of carbon atoms is 3 or more and 6 or less. as R b1 Specific examples in the case of a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. as R b1 Specific examples in the case of a cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group. in R b1 In the case of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably the number of carbon atoms is 2 or more and 7 or less. as R b1 Specific examples in the case of a saturated aliphatic acid group include acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentyl group, and 2,2-dimethylpropionyl group. , n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group , n-pentadecyl, and n-hexadecanoyl, etc. as R b1 Specific examples in the case of a saturated aliphatic alkoxy group include acetyloxy, propanoyloxy, n-butanoyloxy, 2-methylpropanoyloxy, n-pentanoyloxy, 2, 2-Dimethylpropionyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecanyloxy, n-dodecyloxy Carboalkoxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecyloxy, n-hexadecanoyloxy, and the like. in R b1 In the case of an alkoxycarbonyl group, the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably the number of carbon atoms is 2 or more and 7 or less. as R b1 Specific examples in the case of alkoxycarbonyl include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, Dibutoxycarbonyl, third butoxycarbonyl, n-pentoxycarbonyl, isopentyloxycarbonyl, second pentoxycarbonyl, third pentoxycarbonyl, n-hexyloxycarbonyl, n-heptoxycarbonyl, n-Octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxycarbonyl Wait. in R b1 In the case of a phenylalkyl group, the number of carbon atoms is preferably 7 or more and 20 or less, and more preferably the number of carbon atoms is 7 or more and 10 or less. Again, in R b1 In the case of a naphthyl alkyl group, the number of carbon atoms is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. as R b1 Specific examples in the case of a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. as R b1 Specific examples in the case of naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl base. in R b1 In the case of phenylalkyl or naphthylalkyl, R b1 A phenyl group or a naphthyl group may further have a substituent. in R b1 In the case of a heterocyclic group, the heterocyclic group is a 5- or 6-membered monocyclic ring containing at least one N, S, O, or a heterocyclic condensed monocyclic ring or a benzene ring. ring base. When the heterocyclic group is a condensed ring, the number of rings is at most 3. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine, Beta, benzofuran, benzothiophene, indole, isoindole, indole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline Line, quinazoline, phthaloline, quinoline, and quinoline, etc. in R b1 In the case of a heterocyclic group, the heterocyclic group may further have a substituent. in R b1 In the case of an amine group substituted with one or two organic groups, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. , Saturated aliphatic aliphatic group with 2 to 20 carbon atoms, phenyl group which may have substituents, benzyl group which may have substituents, phenyl group with 7 to 20 carbon atoms which may have substituents An alkyl group, an optionally substituted naphthyl group, an optionally substituted naphthylcarboxyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, and a heterocyclic group, etc. Specific examples of such suitable organic groups and R b1 same. Specific examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamine N-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, benzene amino, naphthyl amino, acetyl amino, propionyl amino, n-butyl amino, n-pentyl amino, n-hexyl amino, n-heptyl amino, n-octyl amino , n-decylamino, benzylamino, α-naphthylamino, and β-naphthylamino, etc. as R b1 When the contained phenyl group, naphthyl group, and heterocyclic group further have a substituent, the substituent may include an alkyl group having 1 or more and 6 or less carbon atoms, and an alkoxy group having 1 or more and 6 or less carbon atoms. group, saturated aliphatic alkoxy group with 2 or more and 7 or less carbon atoms, alkoxycarbonyl group with 2 or more and 7 or less carbon atoms, saturated aliphatic alkoxy group with 2 or more and 7 or less carbon atoms, having carbon atoms Monoalkylamine group having an alkyl group having 1 or more and 6 or less, dialkylamine group having an alkyl group having 1 or more and 6 or less carbon atoms, morpholin-1-yl, piperazine-1-yl, halogen , nitro, and cyano, etc. in R b1 When the contained phenyl group, naphthyl group, and heterocyclic group further have substituents, the number of the substituents is not limited as long as the object of the present invention is not inhibited, but preferably 1 or more and 4 or less. in R b1 When the contained phenyl group, naphthyl group, and heterocyclic group have plural substituents, the plural substituents may be the same or different. in R b1 Among them, it is preferably selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and an alkane having 1 to 6 carbon atoms and an alkane having 6 or less carbon atoms in terms of chemical stability, less steric hindrance and easy synthesis of an oxime ester compound, etc. The group in the group consisting of an oxy group and a saturated aliphatic acyl group having 2 or more and 7 or less carbon atoms is more preferably an alkyl group having 1 or more and 6 or less carbon atoms, particularly preferably a methyl group. About R b1 At the position of the bond on the phenyl group, the R b1 In the bonded phenyl group, the position of the bond between the phenyl group and the main skeleton of the oxime ester compound is set to the 1st position, and when the position of the methyl group is set to the 2nd position, it is preferably the 4th position or the 5th position, More preferably, it is 5 digits. Moreover, n1 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1. R b2 It is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. Again, in R b2 In the case of an optionally substituted carbazolyl group, the nitrogen atom in the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms. in R b2 Among them, the substitution of the phenyl group or the carbazolyl group is not particularly limited in the range that does not inhibit the purpose of the present invention. Examples of suitable substituents that the phenyl group or the carbazolyl group may have on carbon atoms include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, Cycloalkyl having 3 or more and 10 or less carbon atoms, cycloalkoxy having 3 or more and 10 or less carbon atoms, saturated aliphatic acyl group having 2 or more and 20 or less carbon atoms, 2 or more and 20 or less carbon atoms alkoxycarbonyl group, saturated aliphatic alkoxyl group having 2 to 20 carbon atoms, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted phenylthio group, optionally substituted Substitutable benzyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzyloxy group, optionally substituted phenylalkyl group with 7 to 20 carbon atoms, optionally substituted Substituent naphthyl, optionally substituted naphthyloxy, optionally substituted naphthyl, optionally substituted naphthoxycarbonyl, optionally substituted naphthyloxy, optionally substituted naphthyl alkyl groups with 11 or more and 20 carbon atoms, optionally substituted heterocyclic groups, optionally substituted heterocyclic carbonyl groups, amine groups, amine groups substituted with one or two organic groups, Morpholin-1-yl, piperidine-1-yl, halogen, nitro, and cyano, etc. in R b2 In the case of a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on a nitrogen atom include an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 3 to 10 carbon atoms. Cycloalkyl, saturated aliphatic aryl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, optionally substituted phenyl, optionally substituted benzyl , A phenoxycarbonyl group which may have a substituent, a phenylalkyl group which may have a carbon number of 7 or more and 20 or less, a naphthyl group which may have a substituent, a naphthylcarboxyl group which may have a substituent, Substituent naphthyloxycarbonyl, optionally substituted naphthylalkyl having 11 to 20 carbon atoms, optionally substituted heterocyclic group, optionally substituted heterocyclic carbonyl, and the like. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred. Specific examples of the substituent that the phenyl group or the carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acid group, an alkoxycarbonyl group, and a saturated aliphatic acid group. R b1 same. in R b2 Among them, examples of the substituent in the case where the phenyl group or the phenyl group, naphthyl group, and heterocyclic group contained in the substituent group of the carbazolyl group further have a substituent group include those having 1 or more carbon atoms and Alkyl group with 6 or less carbon atoms; alkoxy group with 1 or more and 6 or less carbon atoms; saturated aliphatic acyl group with 2 or more and 7 or less carbon atoms; alkoxycarbonyl group with 2 or more and 7 or less carbon atoms; carbon atoms Saturated aliphatic alkoxyl group having 2 or more and 7 or less; phenyl group; naphthyl group; benzalyl group; naphthoyl group; benzyl group substituted by a group in the group consisting of phenyl, piperidine-1-yl, and phenyl; monoalkylamine group having an alkyl group with 1 to 6 carbon atoms; having a carbon number of 6 Dialkylamino group of an alkyl group of 1 or more and 6 or less; morpholin-1-yl; piperazine-1-yl; halogen; nitro; cyano. When the phenyl group, or the phenyl group, naphthyl group, and heterocyclic group contained in the substituent group of the carbazolyl group have further substituent groups, the number of the substituent groups is within the range that does not hinder the purpose of the present invention. Although not limited, 1 or more and 4 or less are preferable. When a phenyl group, a naphthyl group, and a heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different. in R b2 Among them, the group represented by the following formula (b2) or (b3) is preferable, and the group represented by the following formula (b2) is more preferable in that it is easy to obtain a photopolymerization initiator excellent in sensitivity. , and A is preferably a group represented by the following formula (b2), wherein A is S. [Chemical 13]
Figure 02_image025
(R b4 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, A is S or O, and n2 is an integer of 0 or more and 4 or less) [Chemical 14]
Figure 02_image027
(R b5 and R b6 respectively a monovalent organic group) R in formula (b2) b4 In the case of an organic group, it can be selected from various organic groups within a range that does not inhibit the purpose of the present invention. as R in formula (b2) b4 In the case of an organic group, suitable examples include: an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; and a saturated fat having 2 to 7 carbon atoms. alkoxycarbonyl group with 2 or more and 7 or less carbon atoms; saturated aliphatic alkoxyl group with 2 or more and 7 or less carbon atoms; phenyl group; naphthyl group; benzalyl group; naphthylcarboxyl group; A benzalyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, and a phenyl group; having carbon atoms Monoalkylamine group having an alkyl group of 1 or more and 6 or less; dialkylamine group having an alkyl group of 1 or more and 6 or less carbon atoms; morpholin-1-yl; piperazine-1-yl; halogen ; nitro; cyano. in R b4 Among them, preferably: benzyl group; naphthyl group; selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperidine-1-yl, and phenyl Benzyl substituted by the group in the group; nitro, more preferably: benzyl; naphthyl; 2-methylphenylcarbonyl; 4-(piperidin-1-yl)phenyl Carbonyl; 4-(phenyl)phenylcarbonyl. Moreover, in formula (b2), n2 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1. When n2 is 1, preferably R b4 The position of the bond is relative to R b4 The bonding bond between the phenyl group and the oxygen atom or the sulfur atom is the para position. R in formula (b3) b5 It can be selected from various organic groups within the range which does not inhibit the objective of this invention. as R b5 Suitable examples include: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic aliphatic group having 2 to 20 carbon atoms, and a carbon atom Alkoxyalkyl having 2 or more and 20 or less, alkoxycarbonyl having 2 or more and 20 or less carbon atoms, optionally substituted phenyl, optionally substituted benzyl, optionally substituted Phenoxycarbonyl group, optionally substituted phenylalkyl group having 7 to 20 carbon atoms, optionally substituted naphthyl, optionally substituted naphthylcarboxyl, optionally substituted naphthyloxy A carbonyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, an optionally substituted heterocyclic group, and an optionally substituted heterocyclic carbonyl group, and the like. in R b5 Among them, preferably an alkyl group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, or a carbon The alkoxyalkyl group having 2 or more and 6 or less atoms is particularly preferably an ethyl group or an ethoxyethyl group. R in formula (b3) b6 It does not specifically limit in the range which does not inhibit the objective of this invention, It can select from various organic groups. as appropriate as R b6 Specific examples of the group include an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted heterocyclic group. as R b6 , among these groups, a phenyl group which may have a substituent or a thienyl group which may have a substituent is more preferable, and a 2-methylphenyl group or a thienyl group is particularly preferable. as R b4 , R b5 , or R b6 When the contained phenyl group, naphthyl group, and heterocyclic group further have a substituent, the substituent may include an alkyl group having 1 or more and 6 or less carbon atoms, and an alkoxy group having 1 or more and 6 or less carbon atoms. group, saturated aliphatic alkoxy group with 2 or more and 7 or less carbon atoms, alkoxycarbonyl group with 2 or more and 7 or less carbon atoms, saturated aliphatic alkoxy group with 2 or more and 7 or less carbon atoms, having carbon atoms Monoalkylamine group having an alkyl group of 1 or more and 6 or less, dialkylamine group having an alkyl group having 1 or more and 6 or less carbon atoms, morpholin-1-yl, piperazine-1-yl, halogen , nitro, and cyano, etc. in R b4 , R b5 , or R b6 When the contained phenyl group, naphthyl group, and heterocyclic group further have substituents, the number of the substituents is not limited as long as the object of the present invention is not inhibited, but preferably 1 or more and 4 or less. in R b4 , R b5 , or R b6 When the contained phenyl group, naphthyl group, and heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different. R in formula (b1) b3 is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms. as R b3 , preferably methyl or ethyl, more preferably methyl. Among the oxime ester compounds represented by the formula (b1), particularly suitable compounds include the following PI-1 to PI-42. [Chemical 15]
Figure 02_image029
[Chemical 16]
Figure 02_image031
[Chemical 17]
Figure 02_image033
[Chemical 18]
Figure 02_image035
[Chemical 19]
Figure 02_image037
[hua 20]
Figure 02_image039
Moreover, the oxime ester compound represented by following formula (b4) is also preferable as a photoinitiator. [Chemical 21]
Figure 02_image041
(R b7 is a hydrogen atom, a nitro group or a monovalent organic group, R b8 and R b9 are respectively a chain alkyl group which may have a substituent group, a cyclic organic group which may have a substituent group, or a hydrogen atom, R b8 with R b9 can be bonded to each other to form a ring, R b10 is a monovalent organic group, R b11 is a hydrogen atom, an optionally substituted alkyl group having 1 or more and 11 or less carbon atoms, or an optionally substituted aryl group, and n3 is an integer of 0 or more and 4 or less) Here, as the formula (b4) ), the oxime compound of the oxime ester compound is preferably a compound represented by the following formula (b5). [Chemical 22]
Figure 02_image043
(R b7 , R b8 , R b9 , R b10 , and n3 are the same as formula (b4)) In formulas (b4) and (b5), R b7 It is a hydrogen atom, a nitro group or a monovalent organic group. R b7 The perylene ring in the formula (b4) is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the carbonyl group. In formula (b4), R b7 The bonding position of the perylene ring is not particularly limited. The compound represented by the formula (b4) has one or more R b7 In this case, from the viewpoint of easy synthesis of the compound represented by the formula (b4), etc., one or more R is preferably b7 One of them is bonded to the 2-position in the ring. in R b7 In the case of complex numbers, the number of R b7 Can be the same or different. in R b7 In the case of an organic group, R b7 It does not specifically limit in the range which does not inhibit the objective of this invention, It can select from various organic groups suitably. as R b7 In the case of an organic group, suitable examples include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic alkoxy group, a saturated aliphatic alkoxy group, an alkoxycarbonyl group, which may have Substituted phenyl, optionally substituted phenoxy, optionally substituted benzyl, optionally substituted phenoxycarbonyl, optionally substituted benzyloxy, optionally substituted phenylalkyl, optionally substituted naphthyl, optionally substituted naphthoxy, optionally substituted naphthyl, optionally substituted naphthoxycarbonyl, optionally substituted naphthyl Ethyloxy, optionally substituted naphthylalkyl, optionally substituted heterocyclic group, optionally substituted heterocyclic carbonyl, optionally substituted amine group, morpholine-1 - base, and piper 𠯤-1-base, etc. in R b7 In the case of an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Again, in R b7 In the case of an alkyl group, it may be a straight chain or a branched chain. as R b7 Specific examples in the case of an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopropyl Pentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-decyl, and isodecyl, etc. Again, in R b7 In the case of an alkyl group, the alkyl group may also contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl oxyethyl, and methoxypropyl, etc. in R b7 In the case of an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Again, in R b7 In the case of an alkoxy group, it may be a straight chain or a branched chain. as R b7 Specific examples in the case of alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, third Butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second octyloxy , the third octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy, etc. Again, in R b7 In the case of an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy group, propoxyethoxyethoxy, and methoxypropoxy, etc. in R b7 In the case of a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. as R b7 Specific examples in the case of a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. as R b7 Specific examples in the case of a cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group. in R b7 In the case of a saturated aliphatic alkoxy group or a saturated aliphatic alkoxy group, the carbon number of the saturated aliphatic alkoxy group or saturated aliphatic alkoxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less . as R b7 Specific examples in the case of a saturated aliphatic acid group include acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentyl group, and 2,2-dimethylpropionyl group. , n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group , n-pentadecyl, and n-hexadecanoyl, etc. as R b7 Specific examples in the case of a saturated aliphatic alkoxy group include acetyloxy, propanoyloxy, n-butanoyloxy, 2-methylpropanoyloxy, n-pentanoyloxy, 2, 2-Dimethylpropionyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecanyloxy, n-dodecyloxy Carboalkoxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecyloxy, n-hexadecanoyloxy, and the like. in R b7 In the case of an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. as R b7 Specific examples in the case of alkoxycarbonyl include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, Dibutoxycarbonyl, third butoxycarbonyl, n-pentoxycarbonyl, isopentyloxycarbonyl, second pentoxycarbonyl, third pentoxycarbonyl, n-hexyloxycarbonyl, n-heptoxycarbonyl, n-Octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxycarbonyl Wait. in R b7 In the case of a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. Again, in R b7 In the case of a naphthylalkyl group, the number of carbon atoms in the naphthylalkyl group is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. as R b7 Specific examples in the case of a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. as R b7 Specific examples in the case of naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl base. in R b7 In the case of phenylalkyl or naphthylalkyl, R b7 A phenyl group or a naphthyl group may further have a substituent. in R b7 In the case of a heterocyclic group, the heterocyclic group is a 5- or 6-membered monocyclic ring containing at least one N, S, O, or a heterocyclic condensed monocyclic ring or a benzene ring. ring base. When the heterocyclic group is a condensed ring, the number of rings is at most 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine, Beta, benzofuran, benzothiophene, indole, isoindole, indole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline Linen, quinazoline, phthaloline, quinoline, quinoline, piperidine, piperidine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran, etc. in R b7 In the case of a heterocyclic group, the heterocyclic group may further have a substituent. in R b7 In the case of a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group and R b7 The same is true in the case of a heterocyclic group. in R b7 In the case of an amine group substituted with one or two organic groups, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. , Saturated aliphatic aryl group with 2 or more and 21 or less carbon atoms, phenyl group which may have substituents, benzyl group which may have substituents, phenyl group which may have substituted groups with 7 or more and 20 or less carbon atoms An alkyl group, an optionally substituted naphthyl group, an optionally substituted naphthylcarboxyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, and a heterocyclic group, etc. Specific examples of such suitable organic groups and R b7 same. Specific examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamine N-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, benzene amino, naphthyl amino, acetyl amino, propionyl amino, n-butyl amino, n-pentyl amino, n-hexyl amino, n-heptyl amino, n-octyl amino , n-decylamino, benzylamino, α-naphthylamino, and β-naphthylamino, etc. as R b7 When the contained phenyl group, naphthyl group, and heterocyclic group further have a substituent, the substituent may include an alkyl group having 1 or more and 6 or less carbon atoms, and an alkoxy group having 1 or more and 6 or less carbon atoms. group, saturated aliphatic alkoxy group with 2 or more and 7 or less carbon atoms, alkoxycarbonyl group with 2 or more and 7 or less carbon atoms, saturated aliphatic alkoxy group with 2 or more and 7 or less carbon atoms, having carbon atoms Monoalkylamine group having an alkyl group having 1 or more and 6 or less, dialkylamine group having an alkyl group having 1 or more and 6 or less carbon atoms, morpholin-1-yl, piperazine-1-yl, halogen , nitro, and cyano, etc. in R b7 When the contained phenyl group, naphthyl group, and heterocyclic group further have substituents, the number of the substituents is not limited as long as the object of the present invention is not inhibited, but preferably 1 or more and 4 or less. in R b7 When the contained phenyl group, naphthyl group, and heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different. In the basis described above, if as R b7 instead of nitro, or R b12 The base represented by -CO- has a tendency to increase the sensitivity and is preferable. R b12 It does not specifically limit in the range which does not inhibit the objective of this invention, It can select from various organic groups. as appropriate as R b12 Examples of the group include an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted heterocyclic group. as R b12 , among these groups, 2-methylphenyl, thiophen-2-yl, and α-naphthyl are particularly preferred. Again, if R b7 If it is a hydrogen atom, transparency tends to be good, and it is preferable. Furthermore, if R b7 is a hydrogen atom and R b10 When it is a group represented by the formula (b4a) or (b4b) mentioned later, there exists a tendency for transparency to become more favorable. In formula (b4), R b8 and R b9 Each is a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R b8 with R b9 can be bonded to each other to form a ring. In these bases, as R b8 and R b9 , preferably a chain alkyl group which may have a substituent. in R b8 and R b9 In the case of a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group. in R b8 and R b9 In the case of an unsubstituted chain alkyl group, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, particularly preferably 1 or more and 6 or less. as R b8 and R b9 Specific examples in the case of a chain alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl , isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-decyl base, and isodecyl, etc. Again, in R b8 and R b9 In the case of an alkyl group, the alkyl group may also contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl oxyethyl, and methoxypropyl, etc. in R b8 and R b9 In the case of a chain alkyl group having a substituent, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, particularly preferably 1 or more and 6 or less. In this case, the carbon number of the substituent is not included in the carbon number of the chain alkyl group. The chain alkyl group having a substituent is preferably a straight chain. The substitution which an alkyl group may have is not specifically limited in the range which does not inhibit the objective of this invention. Suitable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. As a cyclic organic group, a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group are mentioned. As a specific example of a cycloalkyl group, with R b7 In the case of a cycloalkyl group, a suitable example is the same. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and a phenanthryl group. As a specific example of the heterocyclic group, with R b7 In the case of a heterocyclic group, suitable examples are the same. in R b7 In the case of an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When the chain alkyl group has a substituent, the number of the substituent is not particularly limited. The number of preferable substituents varies depending on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. in R b8 and R b9 In the case of a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. As a cyclic organic group, an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group are mentioned. in R b8 and R b9 In the case of a cyclic organic group, the substituent that the cyclic organic group may have is the same as that of R. b8 and R b9 The same applies to the case of a chain alkyl group. in R b8 and R b9 In the case of an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by bonding a plurality of benzene rings via carbon-carbon bonds, or a group formed by condensation of a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by the bonding or condensation of a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, and is preferably 3 or less, more preferably 2 or less, preferably 1. Preferable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and a phenanthryl group. in R b8 and R b9 In the case of an aliphatic cyclic hydrocarbon group, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 or more and 20 or less, more preferably 3 or more and 10 or less. Examples of the monocyclic cyclic hydrocarbon group include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norxyl, isoxyl, tricyclononyl, Tricyclodecyl, tetracyclododecyl, and adamantyl, etc. in R b8 and R b9 In the case of a heterocyclic group, the heterocyclic group is a 5- or 6-membered monocyclic ring containing at least one N, S, O, or a heterocyclic condensed monocyclic ring or a benzene ring. ring base. When the heterocyclic group is a condensed ring, the number of rings is at most 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine, Beta, benzofuran, benzothiophene, indole, isoindole, indole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline Linen, quinazoline, phthaloline, quinoline, quinoline, piperidine, piperidine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran, etc. R b8 with R b9 can be bonded to each other to form a ring. contains R b8 with R b9 The group of the formed ring is preferably a cycloalkylene group. in R b8 with R b9 When a cycloalkylene group is formed by bonding, the ring constituting the cycloalkylene group is preferably a 5- to 6-membered ring, more preferably a 5-membered ring. in R b8 with R b9 When the group formed by the bond is a cycloalkylene group, the cycloalkylene group may be condensed with one or more other rings. Examples of rings that can be condensed with a cycloalkylene ring include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, Thiophene ring, pyrrole ring, pyridine ring, pyridine ring, and pyrimidine ring, etc. R described above b8 and R b9 Among them, as an example of a suitable base, the formula-A can be exemplified 1 -A 2 the base indicated. In the enumeration formula, A 1 is a straight-chain alkyl group, A 2 is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group. A 1 The number of carbon atoms of the linear alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. in A 2 In the case of an alkoxy group, the alkoxy group may be linear or branched, but preferably linear. The number of carbon atoms in the alkoxy group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. in A 2 When it is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a fluorine atom, a chlorine atom, and a bromine atom are more preferable. in A 2 In the case of a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated alkyl group may be straight-chain or branched, but straight-chain is preferred. in A 2 In the case of a cyclic organic group, examples of the cyclic organic group are the same as R b8 and R b9 The same cyclic organic group as a substituent is present. in A 2 In the case of alkoxycarbonyl, the example of alkoxycarbonyl is the same as that of R b8 and R b9 The same alkoxycarbonyl group as a substituent. as R b8 and R b9 Suitable specific examples include: alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; 2-methoxyethyl, 3-methoxy-n-propyl , 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8-methoxy-n-octyl, 2-ethoxy ethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy-n-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy-n-heptyl, and 8 -Ethoxy-n-octyl and other alkoxyalkyl groups; 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl, 6-cyano-n-hexyl cyanoalkyl, 7-cyano-n-heptyl, and 8-cyano-n-octyl; 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-benzene phenylalkyl groups such as n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl; 2-cyclohexylethyl, 3-cyclohexyl-n-propyl, 4-cyclohexyl -Cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl n-propyl, 4-cyclopentyl-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl, etc. Cycloalkylalkyl; 2-methoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl, 6-methoxycarbonyl Carbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, 8-methoxycarbonyl-n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n-propyl, 4-ethoxycarbonyl-n-propyl Butyl, 5-ethoxycarbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl, and 8-ethoxycarbonyl-n-octyl alkoxycarbonylalkyl groups; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-octyl, 2-bromo Ethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl, 3,3,3- Halogenated alkyl groups such as trifluoropropyl and 3,3,4,4,5,5,5-heptafluoro-n-pentyl. as R b8 and R b9 , the suitable bases in the above are: ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl, 2-cyclohexylethyl yl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5,5,5-hepta Fluoro-n-pentyl. as R b10 An example of a suitable organic group, with R b7 Similarly, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic alkoxy group, an alkoxycarbonyl group, a saturated aliphatic alkoxy group, a phenyl group which may have a substituent, a phenyl group which may have a Substituent phenoxy, optionally substituted benzyl, optionally substituted phenoxycarbonyl, optionally substituted benzyloxy, optionally substituted phenylalkyl, optionally substituted Substituent naphthyl, optionally substituted naphthyloxy, optionally substituted naphthyl, optionally substituted naphthoxycarbonyl, optionally substituted naphthyloxy, optionally substituted naphthylalkyl, optionally substituted heterocyclyl, optionally substituted heterocyclylcarbonyl, amine substituted with one or two organic groups, morpholin-1-yl, and piperazine-1 - Ki et al. Specific examples of these bases and for R b7 The bases described are the same. Again, as R b10 , and also preferably cycloalkylalkyl, phenoxyalkyl which may have substituents on the aromatic ring, and phenylsulfanylalkyl which may have substituents on the aromatic ring. Substituents that phenoxyalkyl and phenylthioalkyl may have and R b7 The phenyl groups contained may have the same substituents. In organic groups, as R b10 , preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, a phenylthioalkyl group which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group having 1 or more and 20 or less carbon atoms, more preferably an alkyl group having 1 or more and 8 or less carbon atoms, particularly preferably an alkyl group having 1 or more and 4 or less carbon atoms, and most preferably Preferably methyl. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, particularly preferably 5 or 6. The number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms in the alkylene group contained in the optionally substituted phenylsulfanylalkyl group on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, particularly preferably 2. Among the phenylsulfanylalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylsulfanyl)ethyl is preferred. Again, as R b10 , also preferably -A 3 -CO-OA 4 the base indicated. A 3 is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. A 4 It is a monovalent organic group, preferably a monovalent hydrocarbon group. in A 3 In the case of an alkylene group, the alkylene group may be linear or branched, but preferably linear. in A 3 In the case of an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, particularly preferably 1 or more and 4 or less. as A 4 Suitable examples include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. as A 4 Suitable specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl , naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl, etc. AS-A 3 -CO-OA 4 Suitable specific examples of the group represented include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl, and 2-n-butoxycarbonylethyl , 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 3- Ethoxycarbonyl-n-propyl, 3-n-propoxycarbonyl-n-propyl, 3-n-butoxycarbonyl-n-propyl, 3-n-pentoxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl , 3-benzyloxycarbonyl-n-propyl, and 3-phenoxycarbonyl-n-propyl, etc. Above, has been applied to R b10 is illustrated, but as R b10 , preferably a group represented by the following formula (b4a) or (b4b). [Chemical 23]
Figure 02_image045
(In formulas (b4a) and (b4b), R b13 and R b14 are organic groups, respectively, n4 is an integer of 0 or more and 4 or less, in R b13 and R 8 When present in the adjacent position on the benzene ring, R b13 with R b14 can be bonded to each other to form a ring, n5 is an integer of 1 or more and 8 or less, n6 is an integer of 1 or more and 5 or less, n7 is an integer of 0 or more and (n6+3) or less, R b15 is an organic group) about R in formula (b4a) b13 and R b14 Examples of organic groups and R b7 same. as R b13 , preferably alkyl or phenyl. in R b13 In the case of an alkyl group, the number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and most preferably 1. That is, R b13 The best is methyl. in R b13 with R b14 When a ring is formed by bonding, the ring may be an aromatic ring or an aliphatic ring. As represented by formula (b4a) and R b13 with R b14 Suitable examples of the group forming the ring include naphthalene-1-yl, 1,2,3,4-tetrahydronaphthalene-5-yl and the like. In the above formula (b4a), n4 is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0. In the above formula (b4b), R b15 is an organic base. As the organic group, there can be listed b7 The organic groups described are the same groups. Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. as R b15 , methyl, ethyl, propyl, isopropyl, butyl and the like can be preferably exemplified. Among these groups, a methyl group is more preferred. In the said formula (b4b), n6 is an integer of 1 or more and 5 or less, Preferably it is an integer of 1 or more and 3 or less, More preferably, it is 1 or 2. In the above formula (b4b), n7 is 0 or more and (n6+3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, particularly preferably 0. In the above formula (b4b), n5 is an integer of 1 or more and 8 or less, preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, and particularly preferably 1 or 2. In formula (b4), R b11 It is a hydrogen atom, an optionally substituted alkyl group having 1 or more and 11 or less carbon atoms, or an optionally substituted aryl group. as R b11 As the substituent which may be possessed in the case of an alkyl group, a phenyl group, a naphthyl group and the like can be preferably exemplified. Again, as R b7 The substituent which may be possessed in the case of an aryl group preferably includes an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group, a halogen atom, and the like. In formula (b4), as R b11 , can preferably exemplify a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, benzyl, methylphenyl, naphthyl, etc. Among them, methyl is more preferred base or phenyl. The compound represented by the formula (b4) is formed by converting the oxime group (>C=N-OH) contained in the compound represented by the aforementioned formula (b5) to >C=NO-COR b11 Manufactured by the method of the step of the oxime ester group shown. R b11 and R in formula (b4) b11 same. Oxime group (>C=N-OH) to >C=NO-COR b11 Conversion of the represented oxime ester group is performed by reacting the compound represented by the aforementioned formula (b5) with an acylating agent. Provided as-COR b11 The acyl-based acylation agent represented can be exemplified by (R b11 CO) 2 Anhydride represented by O, or R b11 The halide represented by COHal (Hal is a halogen atom). The compound represented by the general formula (b4) can be synthesized according to the following reaction scheme 1, for example. In Reaction Scheme 1, a fortium derivative represented by the following formula (b4-1) was used as a raw material. in R b7 In the case of a nitro group or a monovalent organic group, the fluoride derivative represented by the formula (b4-1) can be converted to R at the 9-position by a known method. b8 and R b9 Introduce the substituent R into the substituted perylene derivatives b7 and obtained. 9 bits are R b8 and R b9 Substituted pyrene derivatives in e.g. R b8 and R b9 In the case of an alkyl group, as described in Japanese Patent Laid-Open No. Hei 06-234668, in the presence of an alkali metal hydroxide, it can be obtained by reacting fluoride with an alkylating agent in an aprotic polar organic solvent. . Also, by adding an alkylating agent such as a halogenated alkyl group, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tertiary butoxide to an organic solvent solution of fenugreek Alkylation reaction can be carried out to obtain 9,9-alkyl-substituted perylene. The perylene derivative represented by the formula (b4-2) is introduced into the compound represented by the formula (b4-1) by introducing -CO-CH into the compound represented by the formula (b4-1) by the Friedel-Crafts reaction. 2 -R b10 obtained by the indicated acyl group. The acylation agent for introducing the acyl group may be a halocarbonyl compound or an acid anhydride. As the acylation agent, it is preferably the formula (b4-7): Hal-CO-CH 2 -R b10 The carboxylate halide indicated. In formula (b4-7), Hal is a halogen atom. The position at which the acyl group is introduced into the perylene ring can be selected by appropriately changing the conditions of the Friedel-Crafts reaction, or the method of protecting and deprotecting the position other than the acyl group. Then, in the compound represented by the formula (b4-2), R b10 The ketoxime compound represented by the following formula (b4-4) is obtained by oximation with the methylene group between the carbonyl groups. The method for oximation of a methylene group is not particularly limited, but preferably a nitrite (RONO, R is 1 to 6 carbon atoms) represented by the following formula (b4-3) in the presence of hydrochloric acid. The method of the alkyl) reaction. Next, the ketoxime compound represented by the following formula (b4-4) and the acid anhydride (R b11 CO) 2 O), or halide (R) represented by the following formula (b4-6) b11 COHal, Hal is a halogen atom) reaction, and the compound represented by formula (b4) can be obtained. Furthermore, in the following formulae (b4-1), (b4-3), (b4-4), (b4-5), and (b4-6), R b7 , R b8 , R b9 , R b10 , R b11 , and n3 are the same as formula (b4). Moreover, in Reaction Scheme 1, R contained in each of formula (b4-6), formula (b4-2), and formula (b4-4) b10 Can be the same or different. That is, R in formula (b4-6), formula (b4-2), and formula (b4-4) b10 Can be chemically modified during the synthesis represented by Reaction Scheme 1. Examples of chemical modification include esterification, etherification, amidation, amidation, halogenation, substitution of a hydrogen atom in an amine group with an organic group, and the like. R b10 The chemical modifications that can be received are not limited to these. <Reaction Scheme 1> [Chemical 24]
Figure 02_image047
Suitable specific examples of the compound represented by the formula (b4) include the following PI-43 to PI-76. [Chemical 25]
Figure 02_image049
[Chemical 26]
Figure 02_image051
As described above, the photopolymerization initiator (B) may contain other photopolymerization initiators other than the compound represented by the formula (1). Specific examples of other photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2 -Hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1 -ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1 - ketone, bis(4-dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl Alkyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(benzyloxyimino)-1-[4-(phenylthio base)phenyl]-1-octanone, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 4-benzyl-4'-methyldimethyl sulfide, 4- Dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethyl Benzylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzalkonium dimethyl ketal, methyl o-benzyl benzoate Ester, 2,4-diethyl-9-oxothiol
Figure 106136151-A0304-1
, 2-chloro-9-oxysulfur
Figure 106136151-A0304-1
, 2,4-dimethyl-9-oxothio
Figure 106136151-A0304-1
, 1-chloro-4-propoxy-9-oxothio
Figure 106136151-A0304-1
, sulfur
Figure 106136151-A0304-1
, 2-chlorosulfur
Figure 106136151-A0304-1
, 2,4-diethylsulfide
Figure 106136151-A0304-1
, 2-methyl sulfide
Figure 106136151-A0304-1
, 2-isopropyl sulfide
Figure 106136151-A0304-1
, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzyl peroxide, isohydroperoxide Propylbenzene, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)-imidazolyl Dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bis-dimethylaminobenzophenone, 4,4'-bis-diethylaminobenzophenone, 4,4 '-Dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzoin, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, Benzoin isobutyl ether, butyl benzoin, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichlorobenzene Ethyl ketone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro- 4-phenoxyacetophenone, 9-oxysulfur 𠮿
Figure 106136151-A0304-1
, 2-methyl-9-oxothio
Figure 106136151-A0304-1
, 2-isopropyl-9-oxothio
Figure 106136151-A0304-1
, Dibenzocycloheptanone, Amyl 4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9 - Acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytris', 2,4,6-tris(trichloromethyl)-mesestris, 2- Methyl-4,6-bis(trichloromethyl)-mesotriazole, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl) -Mestris, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-mesestris, 2-[2-(4-diethylamino- 2-Methylphenyl)vinyl]-4,6-bis(trichloromethyl)-mesesial, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4, 6-Bis(trichloromethyl)-mestris, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-meses, 2-(4-ethoxy styryl)-4,6-bis(trichloromethyl)-mestris, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-meses, 2,4-Bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-mestris, 2,4-bis-trichloromethyl-6-(2-bromo-4 -Methoxy)phenyl-mestris, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-mesestris, 2,4- Bis-trichloromethyl-6-(2-bromo-4-methoxy) styryl phenyl-mesesial, etc. These other photopolymerization initiators may be used alone or in combination of two or more. Moreover, the oxime ester compound represented by formula (1-I) is also preferable as another photopolymerization initiator other than the compound represented by formula (1). [Chemical 27]
Figure 02_image053
(In formula (1-I), R 1 , R 2 , and R 3 each independently a valent organic group having a bond with a carbon atom) Among the oxime ester compounds represented by the formula (1-I), preferably a compound represented by the following formula (b1-I), And the compound represented by formula (b4-I). [Chemical 28]
Figure 02_image055
(In formula (b1-I), R b1 , R b2 , R b3 , and n1 is the same as the formula (b1) described above) [Chem. 29]
Figure 02_image057
(In formula (b4-I), R b7 , R b8 , R b9 , R b10 , R b11 , and n3 are the same as above-mentioned formula (b4)) As above-mentioned, the quantity of the water|moisture content in a photosensitive composition is 0.1 mass % or less with respect to the whole photosensitive composition. Therefore, the amount of water attached to the photopolymerization initiator (B) must be 1 mass % or less based on the total of the mass of the photopolymerization initiator (B) and the mass of the water. Here, the moisture attached to the photopolymerization initiator (B) means the moisture adhered to the surface of the solid photopolymerization initiator (B), or the moisture that is taken into the photopolymerization initiator at the molecular level like hydration. Moisture in agent (B). The method of reducing the quantity of water|moisture content attached to the photopolymerization initiator (B) to 1 mass % or less with respect to the sum total of the mass of the photopolymerization initiator (B) and the mass of water|moisture content is not specifically limited. This method is preferably a method of drying under light shielding at a temperature (eg, 100° C. or lower, preferably 80° C. or lower) at which the photopolymerization initiator (B) is not thermally decomposed. Drying is preferably a drying method under reduced pressure. The drying time is not particularly limited, but is, for example, 1 hour or more and 120 hours or less, preferably 10 hours or more and 100 hours or less. In addition, the photopolymerization initiator (B) can also be obtained by distilling off the solvent from a solution obtained by dissolving the photopolymerization initiator (B) in an organic solvent that azeotropes with water, and recovering the photopolymerization initiator (B). The amount of the photopolymerization initiator (B) is reduced. In addition, the amount of the carboxylic acid represented by the formula (2) attached to the photopolymerization initiator (B) must be equal to the mass of the photopolymerization initiator (B) and the mass of the carboxylic acid represented by the formula (2). The total is 550 mass ppb or less. As a method of reducing the amount of the carboxylic acid represented by the formula (2) attached to the photopolymerization initiator (B), for example, purification by recrystallization, washing by an organic solvent, etc. are mentioned. The content of the photopolymerization initiator (B) is preferably 0.5 mass % or more and 30 mass % or less, and more preferably 1 mass % or more and 20 mass % or less. By making content of a photopolymerization initiator (B) into the said range, the photosensitive composition which is good in sensitivity and is hard to produce the defect of a pattern shape can be obtained. Moreover, you may combine a photoinitiator auxiliary agent with a photoinitiator (B). Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoate. Isoamyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4,4'- Bis(dimethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl 9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 3-mercaptobenzimidazole Thiol compounds such as propionic acid, methyl 3-mercaptopropionate, pentaerythritol tetramercaptoacetate, 3-mercaptopropionate, and the like. These photoinitiating aids may be used alone or in combination of two or more. <Alkali-soluble resin (C)> The photosensitive composition may contain alkali-soluble resin (C) as resin other than the resin used as a photopolymerizable compound (A). By blending the alkali-soluble resin (C) in the photosensitive composition, favorable alkali developability can be imparted to the photosensitive composition. In this specification, the so-called alkali-soluble resin means that a resin film having a thickness of 1 μm is formed on a substrate with a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), and the concentration is 0.05 mass %. When immersed in KOH aqueous solution of % for 1 minute, the film thickness of 0.01 μm or more dissolves the resin. Among the alkali-soluble resins (C), polymerization of a monomer having an ethylenically unsaturated double bond is preferable in terms of excellent film-forming properties, or in terms of being easy to adjust the properties of the resin by selection of monomers, etc. thing. As a monomer having an ethylenically unsaturated double bond, (meth)acrylic acid; (meth)acrylate; (meth)acrylamide; crotonic acid; maleic acid, fumaric acid acid, methyl maleic acid, methyl fumaric acid, methylene succinic acid, anhydrides of these dicarboxylic acids; allyl acetate, allyl hexanoate, allyl octoate, lauryl Allyl compounds such as allyl acid, allyl palmitate, allyl stearate, allyl benzoate, allyl acetyl acetate, allyl lactate, and allyloxyethanol; Hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1 -Methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether Ether, Diethylaminoethyl Vinyl Ether, Butylaminoethyl Vinyl Ether, Benzyl Vinyl Ether, Tetrahydrofurfuryl Vinyl Ether, Vinyl Phenyl Ether, Vinyl Tolyl Ether, Vinyl Vinyl ethers such as chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl o-anisyl ether; vinyl butyrate, vinyl isobutyrate , Trimethyl vinyl acetate, diethyl vinyl acetate, vinyl pivalate, vinyl hexanoate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy vinyl acetate , phenyl vinyl acetate, acetyl vinyl acetate, vinyl lactate, vinyl β-phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl esters such as vinyl naphthoate; styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butyl Styrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene Ethylene, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorobenzene Ethylene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene styrene or styrene derivatives such as; ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl -1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- Olefins such as hexadecene, 1-octadecene, and 1-eicosene. The alkali-soluble resin (C) which is a polymer of a monomer having an ethylenically unsaturated double bond usually contains a unit derived from an unsaturated carboxylic acid. Examples of unsaturated carboxylic acids include: (meth)acrylic acid; (meth)acrylamide; crotonic acid; maleic acid, fumaric acid, methylmaleic acid, methyl methacrylate fumaric acid, methylenesuccinic acid, anhydrides of these dicarboxylic acids. The amount of the unit derived from the unsaturated carboxylic acid contained in the polymer of the monomer having an ethylenically unsaturated double bond used as the alkali-soluble resin is not particularly limited as long as it has the alkali solubility required for the resin. The amount of the unit derived from the unsaturated carboxylic acid in the resin used as the alkali-soluble resin is preferably 5% by mass or more and 25% by mass or less, more preferably 8% by mass or more and 16% by mass or less with respect to the mass of the resin. . Among the polymers of monomers having an ethylenically unsaturated double bond, which are polymers of one or more monomers selected from the above-exemplified monomers, those selected from (meth)acrylic acid and (meth)acrylic acid are preferred. A polymer of one or more monomers in acrylic acid ester. Hereinafter, a polymer of one or more monomers selected from the group consisting of (meth)acrylic acid and (meth)acrylate will be described. Preparation of a polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid ester The (meth)acrylic acid ester used is not particularly limited in the range that does not inhibit the purpose of the present invention can be appropriately selected from known (meth)acrylates. Suitable examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate ) Linear or branched alkyl (meth)acrylates such as tert-octyl acrylate; chloroethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, ( 2-hydroxyethyl meth)acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, furfuryl (meth)acrylate; (methyl) containing epoxy group ) acrylate; (meth)acrylate containing a group having an alicyclic skeleton. The details of the (meth)acrylate containing a group having an epoxy group and the (meth)acrylate containing a group having an alicyclic skeleton are described below. In a polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid ester, the transparent insulating film formed using the photosensitive composition is excellent in adhesion to a substrate or mechanical strength On the other hand, the resin containing the unit derived from the (meth)acrylate containing the group which has an epoxy group is preferable. The (meth)acrylate containing a group having an epoxy group may be a (meth)acrylate containing a group having a chain aliphatic epoxy group, or may be a (meth)acrylate containing a group having an alicyclic epoxy group as described below. The (meth)acrylate of the base. The (meth)acrylate containing the group which has an epoxy group may contain an aromatic group. As an example of the aromatic ring which comprises an aromatic group, a benzene ring and a naphthalene ring are mentioned. Examples of (meth)acrylates having an aromatic group and a group having an epoxy group include 4-glycidyloxyphenyl (meth)acrylate and 3-glycidyloxy (meth)acrylate. phenyl phenyl ester, 2-glycidyloxyphenyl (meth)acrylate, 4-glycidyloxyphenylmethyl (meth)acrylate, 3-glycidyloxyphenylmethyl (meth)acrylate, And (meth)acrylic acid 2-glycidyloxyphenyl methyl ester and so on. When transparency is required to the film formed using the photosensitive composition, it is preferable that the (meth)acrylic acid containing the group which has an epoxy group does not contain an aromatic group. Examples of the (meth)acrylate containing a group having a chain aliphatic epoxy group include epoxyalkyl (meth)acrylate and epoxyalkyloxyalkyl (meth)acrylate. A (meth)acrylate in which an oxy group (-O-) in an ester group (-O-CO-) is bonded to a chain-like aliphatic epoxy group, such as an ester. The chain-like aliphatic epoxy group which such a (meth)acrylate has may contain one or a plurality of oxy groups (-O-) in a chain. The number of carbon atoms in the chain aliphatic epoxy group is not particularly limited, but is preferably 3 or more and 20 or less, more preferably 3 or more and 15 or less, and particularly preferably 3 or more and 10 or less. Specific examples of the (meth)acrylate containing a group having a chain-like aliphatic epoxy group include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, (meth)acrylate base) 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl (meth)acrylate and other epoxyalkyl (meth)acrylates; 2-glycidyloxyethyl (meth)acrylate , 3-glycidyloxy-n-propyl (meth)acrylate, 4-glycidyloxy-n-butyl (meth)acrylate, 5-glycidyloxy-n-hexyl (meth)acrylate, (meth)acrylic acid Epoxyalkyloxyalkyl (meth)acrylates such as 6-glycidyloxyn-hexyl ester. In a polymer derived from a unit derived from a (meth)acrylate containing a group having an epoxy group, one or more monomers selected from the group consisting of (meth)acrylic acid and (meth)acrylate 1 mass % or more and 95 mass % or less are preferable with respect to the resin weight, and, as for content of the unit of the (meth)acrylate which has a group which has an epoxy group, 40 mass % or more and 80 mass % or less are more preferable. Furthermore, in the polymer of one or more monomers selected from the group consisting of (meth)acrylic acid and (meth)acrylate, it is easy to form a transparent insulating film with excellent transparency using the photosensitive composition, The resin containing the unit derived from the (meth)acrylate containing the group which has an alicyclic skeleton is also preferable. In the (meth)acrylate containing a group having an alicyclic skeleton, the group having an alicyclic skeleton may be a group having an alicyclic hydrocarbon group or a group having an alicyclic epoxy group. The alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. As a monocyclic alicyclic group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. Moreover, as a polycyclic alicyclic group, a nordicyl group, an isosacyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group, etc. are mentioned. Among the (meth)acrylates containing a group having an alicyclic skeleton, examples of the (meth)acrylates containing a group having an alicyclic hydrocarbon group include the following formulae (c1-1) to (c1- 8) The compound represented. Among these, compounds represented by the following formulae (c1-3) to (c1-8) are preferable, and compounds represented by the following formula (c1-3) or (c1-4) are more preferable. [Chemical 30]
Figure 02_image059
In the above formula, R c1 Represents a hydrogen atom or a methyl group, R c2 Represents a single bond or a divalent aliphatic saturated hydrocarbon group with 1 to 6 carbon atoms, R c3 Represents a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms. as R c2 , preferably a single bond, linear or branched alkylene, such as methylene, ethylidene, propylidene, tetramethylene, ethylethylene, pentamethylene, hexamethylene methyl. as R c3 , preferably methyl and ethyl. Among the (meth)acrylates containing a group having an alicyclic skeleton, as a specific example of the (meth)acrylate containing a group having an alicyclic epoxy group, the following formula (c2-1) can be mentioned, for example. ) ~ (c2-16) represented by the compound. Among these, in order to bring the developability of the photosensitive composition to an appropriate level, compounds represented by the following formulae (c2-1) to (c2-6) are preferred, and the following formula (c2-1) is more preferred ) ~ (c2-4) represented by the compound. [Chemical 31]
Figure 02_image061
In the above formula, R c4 Represents a hydrogen atom or a methyl group, R c5 Represents a divalent aliphatic saturated hydrocarbon group with 1 to 6 carbon atoms, R c6 represents a divalent hydrocarbon group having 1 or more and 10 or less carbon atoms, and t represents an integer of 0 or more and 10 or less. as R c5 , preferably linear or branched alkylene, such as methylene, ethylidene, propylidene, tetramethylene, ethylethylene, pentamethylene, hexamethylene. as R c6 , preferably such as methylene, ethylidene, propylidene, tetramethylene, ethylethylidene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH 2 -Ph-CH 2 -(Ph represents a phenylene group). The polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylate is a resin containing a unit derived from a (meth)acrylate having a group having an alicyclic skeleton. In this case, the amount of the unit derived from the (meth)acrylate containing a group having an alicyclic skeleton in the resin is preferably 5 mass % or more and 95 mass % or less, more preferably 10 mass % or more and 90 mass % % or less, more preferably 30 mass % or more and 70 mass % or less. Furthermore, in a polymer containing at least one monomer selected from the group consisting of (meth)acrylic acid and (meth)acrylic acid ester containing a unit derived from a (meth)acrylate having a group having an alicyclic skeleton , It is preferably a resin containing a unit derived from (meth)acrylic acid and a unit derived from a (meth)acrylate containing a group having an alicyclic epoxy group. The film formed using the photosensitive composition containing such an alkali-soluble resin (C) is excellent in adhesiveness to a base material. Moreover, in the case of using such a resin, a self-reaction between a carboxyl group and an alicyclic epoxy group contained in the resin may occur. Therefore, when a photosensitive composition containing such a resin is used, the self-reaction between the carboxyl group and the alicyclic epoxy group occurs by the method of using a heating film, etc., and the mechanical properties such as the hardness of the formed film can be improved. . In a resin containing a unit derived from (meth)acrylic acid and a unit derived from a (meth)acrylate containing a group having an alicyclic epoxy group, the proportion of the unit derived from (meth)acrylic acid in the resin is The amount is preferably 1% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 50% by mass or less. Among resins containing units derived from (meth)acrylic acid and units derived from (meth)acrylates containing a group having an alicyclic epoxy group, the 1 mass % or more and 95 mass % or less are preferable, and, as for the quantity of the unit of the (meth)acrylate of the base, 30 mass % or more and 70 mass % or less are more preferable. In the group consisting of (meth)acrylic acid and (meth)acrylate containing a unit derived from (meth)acrylic acid and a unit derived from a (meth)acrylate containing a group having an alicyclic epoxy group Among the polymers of one or more monomers, those derived from units derived from (meth)acrylic acid, units derived from (meth)acrylates having an alicyclic hydrocarbon group, and those derived from units having an alicyclic hydrocarbon group are preferred. Resin of epoxy group-based (meth)acrylate unit. In those containing units derived from (meth)acrylic acid, units derived from (meth)acrylates having an alicyclic hydrocarbon group, and units derived from (meth)acrylates having groups having an alicyclic epoxy group In the resin of the unit, the amount of the unit derived from (meth)acrylic acid in the resin is preferably 1% by mass or more and 95% by mass or less, and more preferably 10% by mass or more and 50% by mass or less. In those containing units derived from (meth)acrylic acid, units derived from (meth)acrylates having an alicyclic hydrocarbon group, and units derived from (meth)acrylates having groups having an alicyclic epoxy group In the resin of the unit, the amount of the unit derived from the (meth)acrylate having an alicyclic hydrocarbon group in the resin is preferably 1% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 70% by mass the following. In those containing units derived from (meth)acrylic acid, units derived from (meth)acrylates having an alicyclic hydrocarbon group, and units derived from (meth)acrylates having groups having an alicyclic epoxy group In the resin of the unit, the amount of the unit derived from the (meth)acrylate containing a group having an alicyclic epoxy group in the resin is preferably 1 mass % or more and 95 mass % or less, more preferably 30 mass % More than 80 mass % or less. The mass-average molecular weight (Mw: a measured value obtained in terms of polystyrene by gel permeation chromatography (GPC). The same applies in this specification) of the alkali-soluble resin (C) is preferably 2,000 or more and 200,000 or less, and more Preferably it is 2000 or more and 18000 or less. By setting it as the said range, there exists a tendency for the balance of the film forming ability of the photosensitive composition and the developability after exposure to be easily acquired. When the photosensitive composition contains the alkali-soluble resin (C), the content of the alkali-soluble resin (C) in the photosensitive composition relative to the components other than the solvent (S) described below in the photosensitive composition The total mass is preferably 15 mass % or more and 89.5 mass % or less, more preferably 35 mass % or more and 85 mass % or less, and particularly preferably 50 mass % or more and 70 mass % or less. The alkali-soluble resin (C) described above is preferably in such a manner that the amount of water in the photosensitive composition and the amount of the carboxylic acid represented by the above-mentioned formula (2) fall within specific ranges, respectively. Before preparing the photosensitive composition, purification such as dehydration is performed. As a method of removing water from an alkali-soluble resin (C), drying by heating is mentioned. Moreover, as a method of removing a carboxylic acid from an alkali-soluble resin (C), the removal by heating, the method of washing|cleaning by a dehydrated organic solvent, etc. are mentioned. <Colorant (D)> The photosensitive composition may contain a colorant (D). The coloring agent (D) contained in the photosensitive composition is not particularly limited, but it is preferable to use, for example, a compound classified as a pigment (Pigment) in the color index (CI; issued by The Society of Dyers and Colourists). In particular, it is preferable to use a compound with a color index (CI) number as described below. Examples of yellow pigments that can be suitably used include CI Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and only the number is described), 3, 11, 12, 13, 14, 15, 16, 17, 20 , 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110 , 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167 , 168, 175, 180, and 185. Examples of orange pigments that can be suitably used include CI Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same and only the number is described), 5, 13, 14, 16, 17, 24, 34, 36, 38 , 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, and 73. Examples of violet pigments that can be suitably used include CI Pigment Violet 1 (hereinafter, "CI Pigment Violet" is the same and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39 , 40, and 50. Examples of red pigments that can be suitably used include CI Pigment Red 1 (hereinafter, "CI Pigment Red" is the same and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265. Examples of blue pigments that can be suitably used include CI Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same and only the number is described), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, and 66. Examples of pigments with hues other than the above that can be suitably used include green pigments such as CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 37; CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Brown 26 , CI Pigment Brown 28 and other brown pigments; CI Pigment Black 1, CI Pigment Black 7 and other black pigments. Moreover, the photosensitive composition may contain a light-shielding agent as a coloring agent (D). The photosensitive composition containing a light-shielding agent can be suitably used for the formation of a black matrix or a black column spacer in a liquid crystal display panel, or a light-emitting layer in an organic EL (Electroluminescence) element. The division is used to touch the formation of the row. In the case of using the colorant (D) as the opacifying agent, it is preferable to use a black pigment or a violet pigment as the opacifying agent. Examples of black pigments and violet pigments include carbon black, perylene-based pigments, lactamide-based pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, regardless of organic or inorganic substances. Various pigments such as metal oxides, composite oxides, metal sulfides, metal sulfates or metal carbonates. Among these, it is preferable to use carbon black which has a high light-shielding property. As the carbon black, well-known carbon blacks such as chimney black, furnace black, thermal black, and lamp black can be used, and chimney black having excellent light-shielding properties is preferably used. In addition, resin-coated carbon black may also be used. Resin-coated carbon black has lower electrical conductivity than non-resin-coated carbon black, so when it is used as a black matrix of a liquid crystal display element such as a liquid crystal display, the leakage of current is less, and it is possible to manufacture high reliability. Displays with low power consumption. As carbon black, the carbon black which performed the process to introduce|transduce an acidic group is also preferable. The acidic group introduced into the carbon black is a functional group which exhibits the acidity of Bronsted's definition. As a specific example of an acidic group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned. Acid groups introduced into carbon black can also form salts. The cation that forms a salt with an acidic group is not particularly limited as long as the object of the present invention is not inhibited. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions, and the like, and preferred are alkali metal ions such as sodium ions, potassium ions, and lithium ions, or ammonium ions. In the carbon black which has performed the process of introducing an acidic group as demonstrated above, it is preferable to have the thing selected from the carboxylic acid group, Carbon black with one or more functional groups in the group consisting of a carboxylate group, a sulfonic acid group, and a sulfonate group. The method of introducing an acidic group to carbon black is not particularly limited. As a method of introducing an acidic group, the following method is mentioned, for example. 1) A method of introducing a sulfonic acid group to carbon black by a direct substitution method using concentrated sulfuric acid, oleum, chlorosulfonic acid, etc., or an indirect substitution method using sulfite, hydrogen sulfite, or the like. 2) A method of coupling an organic compound having an amine group and an acidic group with carbon black diazo. 3) A method of reacting an organic compound having a halogen atom and an acidic group with carbon black having a hydroxyl group by the etherification method of Williamson. 4) A method of reacting an organic compound having a halocarbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group. 5) A method of deprotecting carbon black after Friedel-Crafts reaction using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group. Among these methods, the method 2) is preferable in terms of easy and safe introduction and treatment of the acidic group. The organic compound having an amine group and an acidic group used in the method 2) is preferably a compound having an amine group and an acidic group bonded to an aromatic group. Examples of such compounds include aminobenzenesulfonic acid such as sulfanilic acid, and aminobenzoic acid such as 4-aminobenzoic acid. The molar number of the acidic group introduced into carbon black is not particularly limited within a range that does not inhibit the purpose of the present invention. The molar number of the acidic group introduced into carbon black is preferably 1 mmol or more and 200 mmol or less, more preferably 5 mmol or more and 100 mmol or less, with respect to 100 g of carbon black. Carbon black into which an acid group is introduced can also be subjected to coating treatment with resin. When a photosensitive composition containing carbon black coated with a resin is used, it is easy to form a light-shielding cured film having excellent light-shielding properties and insulating properties and low surface reflectance. In addition, the coating process by resin does not adversely affect the dielectric constant of the light-shielding cured film formed using the photosensitive composition in particular. Examples of resins that can be used for the coating of carbon black include phenol-based resins, melamine resins, xylene resins, diallyl phthalate resins, glycerol resins, epoxy resins, and alkylbenzene resins. Curable resin; or polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polystilbene, polyparaphenylene terephthalate Amine, polyamide imide, polyimide, polyamine bismaleimide, polyether polyphenylene, polyarylate, polyether ether ketone and other thermoplastic resins. The coating amount of the carbon black with the resin is preferably 1 mass % or more and 30 mass % or less with respect to the total of the mass of the carbon black and the mass of the resin. Moreover, as a light-shielding agent, a perylene type pigment is also preferable. Specific examples of the perylene-based pigment include a perylene-based pigment represented by the following formula (d-1), a perylene-based pigment represented by the following formula (d-2), and a perylene-based pigment represented by the following formula (d-3). Said perylene pigment. Among the commercially available products, the product names K0084 and K0086 manufactured by BASF, or Pigment Black 21, 30, 31, 32, 33, and 34, etc., can be preferably used as the perylene-based pigments. [Chemical 32]
Figure 02_image063
In formula (d-1), R d1 and R d2 Each independently represents an alkylene group having 1 or more and 3 or less carbon atoms, and R d3 and R d4 Each independently represents a hydrogen atom, a hydroxyl group, a methoxy group, or an acetyl group. [Chemical 33]
Figure 02_image065
In formula (d-2), R d5 and R d6 Each independently represents an alkylene group having 1 or more and 7 or less carbon atoms. [Chemical 34]
Figure 02_image067
In formula (d-3), R d7 and R d8 Each independently is a hydrogen atom, an alkyl group having 1 or more and 22 or less carbon atoms, and may contain a hetero atom of N, O, S, or P. in R d7 and R d8 In the case of an alkyl group, the alkyl group may be linear or branched. The compound represented by the above formula (d-1), the compound represented by the formula (d-2), and the compound represented by the formula (d-3) can be used, for example, Japanese Patent Laid-Open No. 62-1753, Japanese Patent Application Laid-Open No. 62-1753 It was synthesized by the method described in Japanese Patent Publication No. 63-26784. That is, perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines are used as raw materials, and a heating reaction is performed in water or an organic solvent. Then, the obtained crude product is reprecipitated in sulfuric acid, or recrystallized in water, an organic solvent, or a mixed solvent thereof, whereby the target product can be obtained. In order to disperse the perylene-based pigment well in the photosensitive composition, the average particle diameter of the perylene-based pigment is preferably 10 nm or more and 1000 nm or less. Moreover, a lactamide type pigment may be contained as a light-shielding agent. As a lactamide type pigment, the compound represented by following formula (d-4) is mentioned, for example. [Chemical 35]
Figure 02_image069
In formula (d-4), X d Represents a double bond, and is independently E or Z as geometric isomers, R d9 Each independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, a chlorine atom, a fluorine atom, a carboxyl group, or a sulfo group, and R d10 Each independently represents a hydrogen atom, a methyl group, or a phenyl group, and R d11 Each independently represents a hydrogen atom, a methyl group, or a chlorine atom. The compound represented by formula (d-4) may be used alone or in combination of two or more. R d9 In terms of easy production of the compound represented by the formula (d-4), it is preferably bonded to the 6-position of the indoline ring, and R d11 It is preferably bonded to the 4-position of the indolinone ring. From the same point of view, R d9 , R d10 , and R d11 Preferably it is a hydrogen atom. The compound represented by the formula (d-4) has an EE body, a ZZ body, and an EZ body as geometric isomers, and may be any of these single compounds or a mixture of these geometric isomers. The compound represented by the formula (d-4) can be produced, for example, by the method described in International Publication No. 2000/24736 and International Publication No. 2010/081624. In order to disperse the lactamide-based pigment well in the composition, the average particle diameter of the lactamide-based pigment is preferably 10 nm or more and 1000 nm or less. Furthermore, fine particles mainly composed of a silver-tin (AgSn) alloy (hereinafter referred to as "AgSn alloy fine particles") can also be preferably used as a light-shielding agent. The AgSn alloy fine particles only need to have an AgSn alloy as the main component, and as other metal components, for example, Ni, Pd, Au and the like may be contained. The average particle diameter of the AgSn alloy fine particles is preferably 1 nm or more and 300 nm or less. When the AgSn alloy is represented by the chemical formula AgxSn, the range of x that can obtain chemically stable AgSn alloy is 1≦x≦10, and the range of x that can simultaneously obtain chemical stability and blackness is 3≦x≦4. Here, if the mass ratio of Ag in the AgSn alloy is obtained within the above range of x, in the case of x=1, Ag/AgSn=0.4762; in the case of x=3, it becomes 3·Ag/ Ag3Sn=0.7317; In the case of x=4, it becomes 4·Ag/Ag4Sn=0.7843; In the case of x=10, it becomes 10·Ag/Ag10Sn=0.9008. Therefore, the AgSn alloy becomes chemically stable when it contains 47.6 mass % or more and 90 mass % or less of Ag, and when it contains 73.17 mass % or more and 78.43 mass % or more of Ag, it can be Effectively obtain chemical stability and blackness. The AgSn alloy fine particles can be produced by a general fine particle synthesis method. Examples of the fine particle synthesis method include a gas phase reaction method, a spray thermal decomposition method, an atomization method, a liquid phase reaction method, a freeze drying method, a hydrothermal synthesis method, and the like. AgSn alloy fine particles have high insulating properties, but in order to further improve the insulating properties according to the application of the photosensitive composition, the surface may be covered with an insulating film. As a material of such an insulating film, a metal oxide or an organic polymer compound is suitable. As the metal oxide, an insulating metal oxide can be suitably used, for example, silicon oxide (silica), aluminum oxide (alumina), zirconia (zirconia), yttria (yttria), and titanium oxide (titania) can be suitably used )Wait. Moreover, as an organic polymer compound, the resin which has insulating property can be used suitably, for example, a polyimide, a polyether, a polyacrylate, a polyamine compound, etc. can be used suitably. In order to sufficiently improve the insulating properties of the surface of the AgSn alloy fine particles, the thickness of the insulating film is preferably 1 nm or more and 100 nm or less, more preferably 5 nm or more and 50 nm or less. The insulating film can be easily formed by a surface modification technique or a surface coating technique. In particular, if an alkoxide such as tetraethoxysilane and aluminum triethoxide is used, an insulating film with a uniform thickness can be formed at a relatively low temperature, which is preferable. As the light-shielding agent, the above-mentioned perylene-based pigments, lactamide-based pigments, and AgSn alloy fine particles may be used alone, or may be used in combination. In addition, the light-shielding agent may contain pigments of hues such as red, blue, green, and yellow in addition to the above-mentioned black pigment or violet pigment for the purpose of adjusting the color tone. Pigments of hues other than black pigments and violet pigments can be appropriately selected from known pigments. For example, the above-mentioned various pigments can be used as pigments for hues other than black pigments and violet pigments. The usage-amount of the pigment of other hues other than the black pigment or the violet pigment is preferably 15 mass % or less, more preferably 10 mass % or less, with respect to the total mass of the light-shielding agent. In order to disperse the said coloring agent (D) uniformly in a photosensitive composition, a dispersing agent can be used further. As such a dispersant, a polyethylenimine-based, polyurethane resin-based, and acrylic resin-based polymer dispersant is preferably used. In particular, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant. Moreover, an inorganic pigment and an organic pigment can be used individually, respectively, or 2 or more types can be used together. In the case of combined use, the organic pigment is preferably used in the range of 10 parts by mass or more and 80 parts by mass or less, more preferably 20 parts by mass or more and 40 parts by mass, relative to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. Use within the range of parts by mass or less. In addition to the pigment, a dye may be used as a colorant (D) in the photosensitive composition. The dye may be appropriately selected from known materials. Examples of dyes that can be used in the photosensitive composition of the present embodiment include azo dyes, metal zirconium salt azo dyes, anthraquinone dyes, triphenylmethane dyes,
Figure 106136151-A0304-1
Dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, etc. Moreover, these dyes can be used as a colorant (D) by being laked (salified) and dispersed in an organic solvent or the like. In addition to these dyes, for example, Japanese Patent Laid-Open No. 2013-225132, Japanese Patent Laid-Open No. 2014-178477, Japanese Patent Laid-Open No. 2013-137543, and Japanese Patent Laid-Open No. 2011-38085 can also be preferably used. Dyes and the like described in Gazette No. 2014-197206 and the like. In addition, these dyes can also be used in combination with the above-mentioned pigments (eg, perylene-based pigments, lactamide-based pigments, AgSn alloy fine particles, etc.). When the photosensitive composition contains a coloring agent (D), the usage-amount of the coloring agent (D) in the photosensitive composition may be appropriately determined according to the application of the photosensitive composition. As an example, it is preferably 5 parts by mass or more and 70 parts by mass or less, more preferably 25 parts by mass or more, based on 100 parts by mass in total of the mass of the components other than the solvent (S) described below in the photosensitive composition and 60 parts by mass or less. By setting it as the said range, it becomes easy to form the black matrix and each coloring layer which have a target pattern shape. In particular, in the case of forming a black matrix using a photosensitive composition containing a light-shielding agent as a colorant (D), the OD (optical density, optical density) value per 1 μm of the black matrix film is preferably 4 or more. The amount of the sunscreen agent in the photosensitive composition is adjusted in this way. If the OD value per 1 μm of the black matrix film is 4 or more, sufficient display contrast can be obtained when it is used in the black matrix of a liquid crystal display. The coloring agent (D) is preferably added to the photosensitive composition after preparing a dispersion liquid prepared by dispersing at an appropriate concentration using a dispersing agent. The coloring agent (D) described above is preferably prepared in such a way that the amount of water in the photosensitive composition and the amount of the carboxylic acid represented by the above-mentioned formula (2) fall within specific ranges, respectively. Before the photosensitive composition, purification such as dehydration is performed. Moreover, when using a coloring agent (D) as a dispersion liquid, it is preferable that the content of the carboxylic acid represented by a water|moisture content and Formula (2) in a dispersion medium in a dispersion liquid is sufficiently small. As a method of removing water from the colorant (D), drying by heating, or a method of using a dehydrating agent such as silica gel and molecular sieves, can be mentioned. As a method of removing the carboxylic acid from the colorant (D), methods such as removal by heating and washing by a dehydrated organic solvent can be exemplified. When removing water or carboxylic acid from a liquid component such as a dispersion medium, distillation or the like may be performed, and a dehydrating agent or adsorbent such as silica gel, molecular sieve, and activated carbon may be added to the liquid component. <Solvent (S)> The photosensitive composition contains a solvent (S). The kind of the solvent (S) is not particularly limited as long as it can prepare a photosensitive composition in which the amount of water and the amount of the carboxylic acid represented by the formula (2) are within a specific range. Suitable specific examples of the solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (poly) Alkylene glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate , propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other (poly) alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, Diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate Lactic acid alkyl esters such as esters; ethyl 2-hydroxy-2-methyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methyl butyrate, 3-methoxybutyl acetate, 3-methyl acetate -3-Methoxybutyl ester, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-formic acid Amyl, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-pyruvate Propyl ester, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxybutyrate and other esters; aromatic hydrocarbons such as toluene and xylene; N-methyl-2-pyrrolidone, N ,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylacetamide, N,N-diethylacetamide, N,N-diethylacetamide Ethylformamide, N-methylcaprolactamide, 1,3-dimethyl-2-imidazolidinone, pyridine, and N,N,N',N'-tetramethylurea and other nitrogen-containing polar organic solvents, etc. These solvents (S) may be used alone or in combination of two or more. Among them, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, the above-mentioned other ethers, lactic acid alkyl esters, and the above-mentioned other esters are preferable, and the above-mentioned other esters are more preferable. Alkylene glycol monoalkyl ether acetates, other ethers mentioned above, and other esters mentioned above. Moreover, it is also preferable that the solvent (S) contains a nitrogen-containing polar organic solvent from the viewpoints of the solubility of each component, the dispersibility of the colorant (D), and the like. The nitrogen-containing polar organic solvent is preferably N,N,N',N'-tetramethylurea. These solvents may be used alone or in combination of two or more. Among the above-mentioned solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol are preferred. Methyl ethyl ether, cyclohexanone, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are particularly preferably used. The content of the solvent (S) may be appropriately determined according to the application of the photosensitive composition. As an example, it is about 50 mass parts or more and 1900 mass parts or less, preferably 80 mass parts or more and 900 mass parts with respect to 100 mass parts in total of the mass of the components other than the solvent (S) of the photosensitive composition. The following or so. The solvent (S) is preferably used before preparing the photosensitive composition so that the amount of water in the photosensitive composition and the amount of the carboxylic acid represented by the above-mentioned formula (2) are within specific ranges, respectively. Purification such as dehydration is carried out. As a method of removing water from a solvent (S), distillation, the method of using a dehydrating agent, such as a silica gel and a molecular sieve, etc. are mentioned. As a method of removing the carboxylic acid from the solvent (S), distillation or a method of using a dehydrating agent or an adsorbent such as molecular sieve and activated carbon can be mentioned. <Other components> In addition to the above-mentioned components, the photosensitive composition may contain various additives as necessary. Specifically, hardening accelerators, photocrosslinking agents, photosensitizers, dispersing aids, fillers, adhesion accelerators, antioxidants, ultraviolet absorbers, aggregation inhibitors, thermal polymerization inhibitors, antifoaming agents can be exemplified. agents, surfactants, etc. As a thermal polymerization inhibitor, hydroquinone, hydroquinone monoethyl ether, etc. are mentioned, for example. Moreover, as a defoaming agent, the compound, such as a polysiloxane type and a fluorine type, can be illustrated, and as a surfactant, the compound, such as an anionic type, a cation type, and a nonion, can be illustrated. <The production method of the photosensitive composition> The production method of the photosensitive composition is not particularly limited as long as the specific components described above can be uniformly dispersed or dissolved in the solvent (S) in a desired amount, respectively. limited. A suitable production method will be described below. ≪Manufacturing method of photosensitive composition≫ The manufacturing method of the photosensitive composition is the manufacturing method of the photosensitive composition including dissolving the photopolymerizable compound (A) and the photopolymerization initiator (B) in the solvent (S) . In this production method, the formula (1) containing the above-mentioned: [Chem. 36] is used.
Figure 02_image071
(In formula (1), R 1 , R 2 , and R 3 The photopolymerization initiators (B) are each independently a compound represented by a valent organic group having a bond with a carbon atom. In addition, the amount of water attached to the photopolymerization initiator (B) dissolved in the solvent (S) is 1 mass % or less, preferably 0.5 mass, based on the total of the mass of the photopolymerization initiator and the mass of the water. % or less, more preferably 0.1 mass %, particularly preferably 0.05 mass % or less. By producing a photosensitive composition using the photopolymerization initiator (B) in which the amount of the attached water is within this range, a photosensitive composition in which the decrease in the sensitivity over time is suppressed can be obtained. In order to make the amount of water attached to the photopolymerization initiator (B) within the above-mentioned range, it is preferable that the production method of the photosensitive composition includes a temperature at which the photopolymerization initiator (B) is not thermally decomposed Dry under shading. In addition, regarding the photopolymerization initiator (B) dissolved in the solvent (S), the content of the carboxylic acid represented by the above-mentioned formula (2) attached to the photopolymerization initiator (B) is relative to the photopolymerization initiator (B). The total of the mass of the polymerization initiator (B) and the mass of the carboxylic acid represented by the formula (2) is preferably 550 mass ppb or less, more preferably 500 mass ppb, particularly preferably 450 mass ppb, and most preferably 420 mass ppb Quality below ppb. When preparing the photosensitive composition, the alkali-soluble resin (C) may be dissolved in the solvent (S) together with the photopolymerizable compound (A) and the photopolymerization initiator (B). Furthermore, the other components mentioned above can also be melt|dissolved in a solvent (S). The usage-amounts of the ingredients described above are as described above with respect to the photosensitive composition. The method of dissolving a photopolymerizable compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), etc. in a solvent (S) is not specifically limited. The photopolymerizable compound (A), the photopolymerization initiator (B), the alkali-soluble resin (C), etc. may be added to the solvent (S) at the same time and dissolved, or the photopolymerizable compound may be added in any order. (A), the photopolymerization initiator (B), the alkali-soluble resin (C), and the like are sequentially added to the solvent (S) and dissolved. Moreover, a solution obtained by dissolving a photopolymerizable compound (A) in a solvent (S), a solution obtained by dissolving a photopolymerization initiator (B) in a solvent, and an alkali-soluble resin ( C) The solution which melt|dissolved in solvent (S), and the solution which melt|dissolved other components in solvent (S) 2 or more types of solutions are mixed in arbitrary order. When the above-mentioned coloring agent (D) is contained in the photosensitive composition, the preparation method of the coloring agent (D) is not particularly limited. For example, after obtaining a uniform solution in which components other than the colorant (D) are uniformly dissolved in the solvent (S), the colorant (D) or the dispersion liquid of the colorant (D) may be added to the solution . Moreover, after dispersing the colorant (D) in the solvent (S) of a specific amount, the photopolymerizable compound (A), the photopolymerization initiator (B), the alkali-soluble resin (C), etc. may be dissolved. in a dispersion containing solvent (S). According to the method demonstrated above, even if it contains the compound represented by Formula (1) as a photopolymerization initiator (B), the photosensitive composition which does not easily reduce the sensitivity with time can be prepared. ≪Photopolymerization initiator≫ The photopolymerization initiator contains the formula (1): [Chemical 37]
Figure 02_image073
(In formula (1), R 1 , R 2 , and R 3 Each independently is a compound represented by a valent organic group having a bond with a carbon atom. The amount of water attached to the photopolymerization initiator is 1 mass % or less relative to the total of the mass of the photopolymerization initiator and the mass of the water attached to the photopolymerization initiator. In addition, the following formula (2) R attached to the photopolymerization initiator 3 COOH・・・(2) (In formula (2), R 3 The amount of the carboxylic acid represented with respect to the total of the mass of the photopolymerization initiator and the mass of the carboxylic acid represented by the formula (2) is 550 mass ppb or less. By using this photopolymerization initiator (B), it becomes easy to prepare a photosensitive composition which has high sensitivity and which does not easily reduce the sensitivity over time. Regarding the photopolymerization initiator (B), the compound represented by the formula (1), the content of the compound represented by the formula (1), other photopolymerization initiators that may be contained in addition to the compound represented by the formula (1), light The preparation method of a polymerization initiator, etc. are as demonstrated above about the photosensitive composition, and the manufacturing method of the photosensitive composition. [Examples] Hereinafter, the present invention will be described more specifically with reference to examples, but the scope of the present invention is not limited to these examples. [Examples 1 to 4 and Comparative Examples 1 to 6] In Example 1, Example 2, and Comparative Examples 1 to 3, a storage test of the photopolymerization initiator was performed. In Example 3, Example 4, and Comparative Examples 4 to 6, photosensitive compositions were prepared using the photopolymerization initiators used in the tests of Example 1, Example 2, and Comparative Examples 1 to 3. (Preparation of Photosensitive Composition) In Example 3, Example 4, and Comparative Examples 4 to 6, the following structures (mass ratio I-1:I-2) were mixed so that the solid content concentration was 24% by mass : II-1: III-1 is 25:20:14:41) alkali-soluble resin 65 mass parts, dipentaerythritol hexaacrylate (photopolymerizable monomer) 35 mass parts, and the kind and mass described in Table 2 Part of the photopolymerization initiator was dissolved in a mixed solvent (mass ratio 55:45) of diethylene glycol methyl ethyl ether and propylene glycol monomethyl ether acetate to prepare a photosensitive composition. Furthermore, according to the method described below, the storage test of the photopolymerization initiator was carried out at 35° C. for 48 hours. About each Example and a comparative example, two types of photosensitive compositions were prepared using the photopolymerization initiator before the storage test and the photopolymerization initiator after the storage test. [Chemical 38]
Figure 02_image075
(Storage test of photopolymerization initiator (B)) The chemical structure of the photopolymerization initiator (B) is as follows. [Chemical 39]
Figure 02_image077
In addition, the photopolymerization initiator (B) used in an Example was obtained by heating the powder obtained by recrystallizing the above-mentioned compound below the decomposition temperature under light shielding, and drying under reduced pressure. In Example 2, the drying time under reduced pressure was made shorter than that in Example 1. In addition, the photopolymerization initiator (B) used in the comparative example is based on the amount of water attached to the photopolymerization initiator (B) relative to the total of the mass of the photopolymerization initiator (B) and the mass of the water. Water was added to the photopolymerization initiator used in the examples so that the amount (mass %) would be the amount described in the following Table 1, and it was prepared. In addition, the quantity of water was measured by Karl Fischer method. Furthermore, the acetic acid content (AC) immediately after production (initial stage) of the obtained photopolymerization initiator (B) was measured. 0 , based on the total mass ppb of the mass of the photopolymerization initiator and the mass of acetic acid), and the acetic acid content (AC 48 ). According to the AC obtained 0 value and AC 48 The carboxylic acid increase rate was calculated based on the above-mentioned formula. will AC 0 , AC 48 , and the carboxylic acid increase rate are described in Table 1. The acetic acid content was measured by ion chromatography. [Table 1]
Figure 106136151-A0304-0001
(Sensitivity evaluation) Using the photosensitive compositions obtained in Example 3, Example 4, and Comparative Examples 4 to 6, sensitivity evaluation was performed according to the following method. <Sensitivity Evaluation Method> Using a spin coater, the photosensitive composition was spin-coated on a glass of 10 cm×10 cm to form a coating film. The coating film was baked at 100° C. for 120 seconds to remove the solvent from the coating film. Then, the exposure device was aligned by mirror projection, and the exposure amount was 10, 20, 30, 40, and 50 mJ/cm 2 The baked coated film is exposed to light. After exposure, the film thickness of the coating film was measured. In addition, the coating film after film thickness measurement was developed and processed for 60 seconds using a KOH aqueous solution having a concentration of 0.05 mass %. Next, the film thickness of the coating film after the development process was measured. The film thickness difference before and after image development was calculated at each exposure amount, and it was confirmed that the film thickness difference did not reach the minimum exposure amount of 0.1 μm, and the minimum exposure amount was set as the sensitivity. The amount of moisture in the composition in Table 2 below is the amount of moisture (mass %) relative to the mass of the entire composition, the case of using the photopolymerization initiator (B) immediately after production and the photopolymerization after use The same values are shown in the case of the starter (B). The amount of acetic acid in the composition is the amount of acetic acid (mass ppb) relative to the sum of the mass of the photopolymerization initiator (B) and the mass of acetic acid, and is the same as the value described in Table 1. The case where there is no difference in the sensitivity of the photosensitive composition containing the initiator before storage and the photosensitive composition containing the initiator after storage was evaluated as "good", and the photosensitive composition containing the initiator before storage was combined When there was a difference in sensitivity between the product and the photosensitive composition containing the initiator after storage, it was evaluated as "defective". [Table 2]
Figure 106136151-A0304-0002
According to the examples, in the photosensitive composition containing the photopolymerization initiator (B) having the structure represented by the above-mentioned formula (1), the content of the acetic acid used is relative to the photopolymerization initiator ( The sum of the mass of B) and the mass of acetic acid is 550 mass ppb or less, and the amount of water attached to the photopolymerization initiator (B) relative to the sum of the mass of the photopolymerization initiator (B) and the mass of the water is When the photosensitive composition is prepared in 1 mass % or less of (B), the prepared photosensitive composition does not decrease in sensitivity. On the other hand, according to the comparative example, the content of acetic acid in the photosensitive composition exceeds 550 ppb by mass relative to the sum of the mass of the photopolymerization initiator (B) and the mass of acetic acid, or the amount of water relative to the photosensitive When it exceeds 0.1 mass % as a whole composition, the fall of the sensitivity of time-dependent property is easy to generate|occur|produce.

Claims (7)

一種感光性組合物，其係含有光聚合性化合物(A)、光聚合起始劑(B)、及溶劑(S)者，且上述光聚合起始劑(B)含有下述式(1)：
Figure 106136151-A0305-02-0097-1
 (式(1)中，R1、R2、及R3分別獨立為具有與碳原子鍵結之鍵結鍵之一價有機基)所表示之化合物，上述感光性組合物中，下述式(2)：R3COOH‧‧‧(2)(式(2)中，R3與上述式(1)中之R3相同)所表示之羧酸之含量相對於上述光聚合起始劑(B)之質量與上述式(2)所表示之羧酸之質量之合計為550質量ppb以下，上述感光性組合物中，水分之量相對於上述感光性組合物整體為0.1質量%以下。 A photosensitive composition containing a photopolymerizable compound (A), a photopolymerization initiator (B), and a solvent (S), wherein the photopolymerization initiator (B) contains the following formula (1) :
Figure 106136151-A0305-02-0097-1
 (In formula (1), R 1 , R 2 , and R 3 are each independently a valent organic group having a bonding bond to a carbon atom.) The compound represented by the above photosensitive composition has the following formula (2): R 3 COOH‧‧‧ ( 2) ( in the formula (2), R 3 the same as (1) in the above formula R 3) represents the content of carboxylic acids with respect to the photopolymerization initiator ( The sum of the mass of B) and the mass of the carboxylic acid represented by the above formula (2) is 550 mass ppb or less, and the amount of water in the photosensitive composition is 0.1 mass % or less with respect to the entire photosensitive composition. 如請求項1之感光性組合物，其進而含有鹼溶性樹脂(C)。 The photosensitive composition according to claim 1, which further contains an alkali-soluble resin (C). 一種感光性組合物之製造方法，其包括將光聚合性化合物(A)與光聚合起始劑(B)溶解於溶劑(S)中，且上述光聚合起始劑(B)含有下述式(1)：
Figure 106136151-A0305-02-0098-2
 (式(1)中，R1、R2、及R3分別獨立為具有與碳原子鍵結之鍵結鍵之一價有機基)所表示之化合物，溶解於上述溶劑(S)中之上述光聚合起始劑(B)所附帶之水分之量相對於上述光聚合起始劑(B)之質量與水分之質量之合計為1質量%以下，溶解於上述溶劑(S)中之上述光聚合起始劑(B)所附帶之下述式(2)：R3COOH‧‧‧(2)(式(2)中，R3與上述式(1)中之R3相同)所表示之羧酸之含量相對於上述光聚合起始劑(B)之質量與上述式(2)所表示之羧酸之質量之合計為550質量ppb以下。 A method for producing a photosensitive composition, comprising dissolving a photopolymerizable compound (A) and a photopolymerization initiator (B) in a solvent (S), wherein the photopolymerization initiator (B) contains the following formula (1):
Figure 106136151-A0305-02-0098-2
 The compound represented by (in the formula (1), R 1 , R 2 , and R 3 are each independently a valent organic group having a bonding bond to a carbon atom) is dissolved in the above-mentioned solvent (S) The amount of water attached to the photopolymerization initiator (B) is 1 mass % or less relative to the total of the mass of the photopolymerization initiator (B) and the mass of the water, and the above-mentioned photopolymer dissolved in the above-mentioned solvent (S) polymerization initiator (B) is included with the following formula (2): represented by the R 3 COOH‧‧‧ (2) (in the formula (2), the same as R 3 (1) in the above formula R 3) The content of the carboxylic acid is 550 mass ppb or less with respect to the sum of the mass of the photopolymerization initiator (B) and the mass of the carboxylic acid represented by the above formula (2). 如請求項3之方法，其進而將鹼溶性樹脂(C)溶解於溶劑(S)中。 The method of claim 3, which further dissolves the alkali-soluble resin (C) in the solvent (S). 如請求項3或4之方法，其包括於不會將上述光聚合起始劑(B)熱分解之溫度下在遮光下進行乾燥。 The method of claim 3 or 4, which comprises drying under shading at a temperature at which the above-mentioned photopolymerization initiator (B) is not thermally decomposed. 一種光聚合起始劑，其係含有下述式(1)：
Figure 106136151-A0305-02-0099-3
 (式(1)中，R1、R2、及R3分別獨立為具有與碳原子鍵結之鍵結鍵之一價有機基)所表示之化合物者，且上述光聚合起始劑所附帶之水分之量相對於上述光聚合起始劑之質量與上述水分之質量之合計為1質量%以下，上述光聚合起始劑所附帶之下述式(2)：R3COOH‧‧‧(2)(式(2)中，R3與上述式(1)中之R3相同)所表示之羧酸之含量相對於上述光聚合起始劑之質量與上述式(2)所表示之羧酸之質量之合計為550質量ppb以下。 A photopolymerization initiator, which contains the following formula (1):
Figure 106136151-A0305-02-0099-3
 (In formula (1), R 1 , R 2 , and R 3 are each independently a compound represented by a valent organic group having a bond to a carbon atom), and the above-mentioned photopolymerization initiator is attached The amount of water in the above-mentioned photopolymerization initiator is 1 mass % or less in total with respect to the mass of the above-mentioned photopolymerization initiator and the above-mentioned water. The following formula (2) attached to the above-mentioned photopolymerization initiator: R 3 COOH···( 2, R identical) (formula 2 () to 3 (1) in the above formula R 3) represents the content of carboxylic acids with respect to the mass of a photopolymerization initiator and (2) represented by the above formula of carboxamide The total mass of the acid is 550 mass ppb or less. 一種光聚合起始劑之調製方法，其係如請求項6之光聚合起始劑之調製方法，且其包括於不會將上述光聚合起始劑(B)熱分解之溫度下在遮光下進行乾燥。 A preparation method of a photopolymerization initiator, which is the preparation method of a photopolymerization initiator as claimed in claim 6, and which comprises shading at a temperature that does not thermally decompose the photopolymerization initiator (B) Dry.
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