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TWI703405B - Photosensitive composition, method for forming pattern, cured product, and display device - Google Patents

Photosensitive composition, method for forming pattern, cured product, and display device Download PDF

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TWI703405B
TWI703405B TW105127562A TW105127562A TWI703405B TW I703405 B TWI703405 B TW I703405B TW 105127562 A TW105127562 A TW 105127562A TW 105127562 A TW105127562 A TW 105127562A TW I703405 B TWI703405 B TW I703405B
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meth
ring
substituent
acrylate
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TW201715307A (en
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大內康秀
染谷和也
引田二郎
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • 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
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133345—Insulating layers
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2012—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image using liquid photohardening compositions, e.g. for the production of reliefs such as flexographic plates or stamps
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
    • G03F7/203—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure comprising an imagewise exposure to electromagnetic radiation or corpuscular radiation

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Electromagnetism (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Polymerisation Methods In General (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

本發明提供一種對於曝光之感度充分，可藉由硬化而提供透過率充分之硬化物的感光性組合物、使用該感光性組合物之圖案形成方法、使用該感光性組合物所形成之硬化物、具備該硬化物之顯示裝置。 本發明之感光性組合物包含式(1)所表示之光聚合起始劑(A1)、及具有鍵結有硝基之芳香環骨架的光聚合起始劑(A2)。式(1)中，R1 為氫原子或1價有機基，R2 及R3 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，R2 與R3 亦可相互鍵結而形成環，R4 為具有特定環狀結構之有機基，R5 為氫原子、可具有取代基之碳原子數1～11之烷基、或可具有取代基之芳基，n為0～4之整數。其中，光聚合起始劑(A1)不具有硝基。

Figure 01_image002
The present invention provides a photosensitive composition that has sufficient sensitivity to exposure and can provide a cured product with sufficient transmittance by curing, a pattern forming method using the photosensitive composition, and a cured product formed using the photosensitive composition , A display device with the hardened object. The photosensitive composition of the present invention contains a photopolymerization initiator (A1) represented by formula (1) and a photopolymerization initiator (A2) having an aromatic ring skeleton to which a nitro group is bonded. In formula (1), R 1 is a hydrogen atom or a monovalent organic group, R 2 and R 3 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, and R 2 It can also be bonded to R 3 to form a ring, R 4 is an organic group with a specific cyclic structure, R 5 is a hydrogen atom, an optionally substituted alkyl group with 1 to 11 carbon atoms, or optionally substituted In the aryl group, n is an integer of 0-4. Among them, the photopolymerization initiator (A1) does not have a nitro group.
Figure 01_image002

Description

感光性組合物、圖案形成方法、硬化物、及顯示裝置Photosensitive composition, pattern forming method, cured product, and display device

本發明係關於一種感光性組合物、使用該感光性組合物之圖案形成方法、使用該感光性組合物所形成之硬化物、以及具備該硬化物之顯示裝置。The present invention relates to a photosensitive composition, a pattern forming method using the photosensitive composition, a cured product formed using the photosensitive composition, and a display device provided with the cured product.

於液晶顯示裝置之類的顯示裝置中，絕緣膜或間隔件之類的材料需要使自背光之類的光源所發出之光高效率地透過。因此，為了形成絕緣膜或間隔件之圖案，使用藉由曝光而提供透明之硬化膜的感光性組合物。藉由對此種感光性組合物選擇性地進行曝光，可形成透明硬化膜之圖案。 作為能夠形成透明之硬化膜之感光性組合物，例如提出有包含樹脂、聚合性化合物、特定結構之聚合起始劑、及溶劑之組合物(專利文獻1)。具體而言，於專利文獻1之實施例中揭示有包含如下者之感光性組合物：甲基丙烯酸與具有脂環式環氧基之丙烯酸酯之共聚物，二季戊四醇六丙烯酸酯，下述式之任意者所表示之聚合起始劑，以及包含3-甲氧基-1-丁醇、丙二醇單甲醚乙酸酯、3-乙氧基丙酸乙酯、及乙酸3-甲氧基丁酯之混合溶劑。 [化1]

Figure 02_image003
感光性組合物係藉由如下方式而硬化：作為其成分之一部分而含有之光聚合起始劑藉由曝光而產生自由基，該自由基使感光性組合物中所含之聚合性化合物進行聚合。因此，已知感光性組合物之感度根據其所含之光聚合起始劑之種類而受到影響。作為可使感光性組合物之感度良好之光聚合起始劑，於專利文獻2中提出有具有環烷基之肟酯化合物。於專利文獻2中所記載之實施例中，具體地揭示有下述化學式(a)及(b)所表示之化合物。 [化2]
Figure 02_image005
[先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2012-58728號公報 [專利文獻2]中華人民共和國公開專利公報 第101508744號In display devices such as liquid crystal display devices, materials such as insulating films or spacers need to efficiently transmit light emitted from light sources such as backlights. Therefore, in order to form an insulating film or a pattern of a spacer, a photosensitive composition which provides a transparent cured film by exposure is used. By selectively exposing this photosensitive composition, a pattern of a transparent cured film can be formed. As a photosensitive composition capable of forming a transparent cured film, for example, a composition containing a resin, a polymerizable compound, a polymerization initiator having a specific structure, and a solvent is proposed (Patent Document 1). Specifically, the examples of Patent Document 1 disclose a photosensitive composition comprising: a copolymer of methacrylic acid and an acrylate having an alicyclic epoxy group, dipentaerythritol hexaacrylate, and the following formula Any one of the polymerization initiator represented, and contains 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, and 3-methoxybutyl acetate Mixed solvent of ester. [化1]
Figure 02_image003
The photosensitive composition is hardened by the following method: the photopolymerization initiator contained as part of its components generates radicals by exposure, and the radicals polymerize the polymerizable compound contained in the photosensitive composition . Therefore, it is known that the sensitivity of a photosensitive composition is affected by the kind of photopolymerization initiator contained in it. As a photopolymerization initiator that can improve the sensitivity of the photosensitive composition, Patent Document 2 proposes an oxime ester compound having a cycloalkyl group. In the examples described in Patent Document 2, the compounds represented by the following chemical formulas (a) and (b) are specifically disclosed. [化2]
Figure 02_image005
[Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-open No. 2012-58728 [Patent Document 2] People’s Republic of China Patent Publication No. 101508744

[發明所欲解決之問題] 然而，專利文獻1或專利文獻2中所記載之感光性組合物對於曝光之感度並不充分，使用該感光性組合物所形成之硬化膜之透過率並不充分。 本發明係鑒於上述課題而成者，其目的在於提供對於曝光之感度充分，可藉由硬化而提供透過率充分之硬化物的感光性組合物、使用該感光性組合物之圖案形成方法、使用該感光性組合物所形成之硬化物、具備該硬化物之顯示裝置。 [解決問題之技術手段] 本發明者等人發現藉由於包含光聚合起始劑之感光性組合物中，使用具有特定結構之光聚合起始劑(A1)、具有鍵結有硝基之芳香環骨架的光聚合起始劑(A2)作為該光聚合起始劑，可解決上述課題，從而完成本發明。 本發明之第一態樣係一種感光性組合物，其包含下述式(1)所表示之光聚合起始劑(A1)、及具有鍵結有硝基之芳香環骨架的光聚合起始劑(A2)； [化3]

Figure 02_image007
(R1 為氫原子或1價有機基，R2 及R3 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，R2 與R3 亦可相互鍵結而形成環，R4 為下述式(R4-1)或(R4-2)所表示之基，R5 為氫原子、可具有取代基之碳原子數1～11之烷基、或可具有取代基之芳基，n為0～4之整數；其中，式(1)所表示之光聚合起始劑不具有硝基) [化4]
Figure 02_image009
(式(R4-1)及(R4-2)中，R7 及R8 分別為1價有機基，p為0～4之整數，於R7 及R8 存在於苯環上之鄰接之位置之情形時，R7 與R8 亦可相互鍵結而形成環，q為1～8之整數，r為1～5之整數，s為0～(r＋3)之整數，R9 為1價有機基)。 本發明之第二態樣係一種圖案形成方法，其係使用第一態樣之感光性組合物而形成塗膜或成形體，對該塗膜或成形體以特定圖案狀照射電磁波而進行顯影。 本發明之第三態樣係一種硬化物，其係使用第一態樣之感光性組合物而形成者。 本發明之第四態樣係一種顯示裝置，其具備第三態樣之硬化物。 [發明之效果] 藉由本發明可提供對於曝光之感度充分，可藉由硬化而提供透過率充分之硬化物的感光性組合物、使用該感光性組合物之圖案形成方法、使用該感光性組合物所形成之硬化物、具備該硬化物之顯示裝置。[Problems to be Solved by the Invention] However, the photosensitive composition described in Patent Document 1 or Patent Document 2 has insufficient sensitivity to exposure, and the transmittance of a cured film formed using the photosensitive composition is insufficient . The present invention was made in view of the above-mentioned problems, and its object is to provide a photosensitive composition that has sufficient sensitivity to exposure and can provide a cured product with sufficient transmittance by curing, a pattern formation method using the photosensitive composition, and use A cured product formed from the photosensitive composition, and a display device provided with the cured product. [Technical Means to Solve the Problem] The inventors found that the photosensitive composition containing a photopolymerization initiator uses a photopolymerization initiator (A1) having a specific structure and an aromatic compound with a nitro group bonded to it. The photopolymerization initiator (A2) of the ring skeleton can solve the above-mentioned problems as the photopolymerization initiator, thereby completing the present invention. The first aspect of the present invention is a photosensitive composition comprising a photopolymerization initiator (A1) represented by the following formula (1), and a photopolymerization initiator having an aromatic ring skeleton to which a nitro group is bonded剂(A2); [化3]
Figure 02_image007
(R 1 is a hydrogen atom or a monovalent organic group, R 2 and R 3 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R 2 and R 3 may also be They are bonded to each other to form a ring, R 4 is a group represented by the following formula (R4-1) or (R4-2), R 5 is a hydrogen atom, an optionally substituted alkyl group with 1 to 11 carbon atoms, Or an aryl group which may have a substituent, n is an integer from 0 to 4; wherein, the photopolymerization initiator represented by formula (1) does not have a nitro group) [formation 4]
Figure 02_image009
(In formulas (R4-1) and (R4-2), R 7 and R 8 are respectively a monovalent organic group, and p is an integer of 0-4, where R 7 and R 8 are present at adjacent positions on the benzene ring In this case, R 7 and R 8 may also be bonded to each other to form a ring, q is an integer of 1-8, r is an integer of 1 to 5, s is an integer of 0-(r+3), and R 9 is a monovalent organic base). The second aspect of the present invention is a pattern forming method that uses the photosensitive composition of the first aspect to form a coating film or molded body, and develops the coating film or molded body by irradiating electromagnetic waves in a specific pattern. The third aspect of the present invention is a cured product formed by using the photosensitive composition of the first aspect. The fourth aspect of the present invention is a display device provided with the hardened object of the third aspect. [Effects of the invention] The present invention can provide a photosensitive composition that has sufficient sensitivity to exposure and can provide a cured product with sufficient transmittance by curing, a pattern forming method using the photosensitive composition, and the use of the photosensitive composition The hardened object formed by the object, and the display device equipped with the hardened object.

≪感光性組合物≫ 本發明之感光性組合物包含上述式(1)所表示之光聚合起始劑(A1)、及具有鍵結有硝基之芳香環骨架的光聚合起始劑(A2)。以下，對感光性組合物中所含之各成分加以說明。 ＜光聚合起始劑(A)＞ 根據光聚合起始劑之種類，存在包含光聚合起始劑之感光性組合物之透過率、及使用該感光性組合物所形成之實施了後烘烤之圖案之透過率降低之情形。又，根據光聚合起始劑之種類，亦存在包含光聚合起始劑之感光性組合物之透過率降低之情形。然而，於使用包含上述式(1)所表示之光聚合起始劑(A1)(以下亦稱為「光聚合起始劑(A1)」或「(A1)成分」)之感光性組合物之情形時，難以產生因加熱所引起之圖案之透過率降低。同時，亦存在難以產生感光性組合物之透過率降低之情形。又，光聚合起始劑(A1)對於光為相對較高之感度。 另一方面，具有鍵結有硝基之芳香環骨架的光聚合起始劑(A2)(以下亦稱為「光聚合起始劑(A2)」或「(A2)成分」)對於光為高感度。 本發明之感光性組合物藉由光聚合起始劑(A1)與光聚合起始劑(A2)之組合而提供對於光之感度優異且維持較高之透過率之硬化物。因此，藉由使用本發明之感光性組合物，可以低曝光量而形成所需形狀之圖案，所形成之圖案具有較高之透過率。又，藉由使用感度優異之本發明之感光性組合物，可抑制形成圖案時之圖案剝落，且可抑制形成線圖案時於圖案之邊緣所產生之晃動之發生。 [式(1)所表示之光聚合起始劑(A1)] 本發明之感光性組合物含有上述式(1)所表示之光聚合起始劑(A1)。光聚合起始劑(A1)可單獨使用或將2種以上組合而使用。 式(1)中，R1 為氫原子或1價有機基。R1 係於式(1)中之茀環上，鍵結於與-CO-所表示之基所鍵結之6員芳香環不同之6員芳香環上。若滿足該條件，則於式(1)中，R1 相對於茀環之鍵結位置並無特別限定。於光聚合起始劑(A1)具有1個以上R1 之情形時，基於光聚合起始劑(A1)之合成容易等情況，較佳為1個以上R1 中之1個鍵結於茀環中之2位上。於R1 為複數個之情形時，複數個R1 可相同亦可不同。 於R1 為1價有機基之情形時，R1 只要為不阻礙本發明之目的之範圍，則無特別限定，可自各種1價有機基中適宜選擇。作為R1 為1價有機基之情形時之適宜例，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

Figure 105127562-A0304-12-0001-4
-1-基等。 於R1 為烷基之情形時，烷基之碳原子數較佳為1～20，更佳為1～6。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-)。作為於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1～20，更佳為1～6。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3～10，更佳為3～6。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2～21，更佳為2～7。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、正十一醯基、正十二醯基、正十三醯基、正十四醯基、正十五醯基、及正十六醯基等。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、正十一醯氧基、正十二醯氧基、正十三醯氧基、正十四醯氧基、正十五醯氧基、及正十六醯氧基等。 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2～20，更佳為2～7。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7～20，更佳為7～10。又，於R1 為萘基烷基之情形時，萘基烷基之碳原子數較佳為11～20，更佳為11～14。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，雜環基為包含1個以上N、S、及/或O之5員或6員之單環，或該單環彼此、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，所縮合之環數為3以下。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，可列舉呋喃環、噻吩環、吡咯環、
Figure 105127562-A0304-12-0001-1
唑環、異
Figure 105127562-A0304-12-0001-1
唑環、噻唑環、噻二唑環、異噻唑環、咪唑環、吡唑環、三唑環、吡啶環、吡
Figure 105127562-A0304-12-0001-4
環、嘧啶環、嗒
Figure 105127562-A0304-12-0001-4
環、苯并呋喃環、苯并噻吩環、吲哚環、異吲哚環、吲哚
Figure 105127562-A0304-12-0001-4
環、苯并咪唑環、苯并三唑環、苯并
Figure 105127562-A0304-12-0001-1
唑環、苯并噻唑環、咔唑環、嘌呤環、喹啉環、異喹啉環、喹唑啉環、酞
Figure 105127562-A0304-12-0001-4
環、
Figure 105127562-A0304-12-0001-6
啉環、喹
Figure 105127562-A0304-12-0001-1
啉環、哌啶環、哌
Figure 105127562-A0304-12-0001-4
環、嗎啉環、哌啶環、四氫吡喃環、及四氫呋喃環等。於R1 為雜環基之情形時，雜環基亦可進而具有取代基。 於R1 為雜環基羰基之情形時，雜環基羰基中所含之雜環基與R1 為雜環基之情形相同。 於R1 為經1個或2個有機基取代之胺基之情形時，有機基之適宜例可列舉碳原子數1～20之烷基、碳原子數3～10之環烷基、碳原子數2～21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7～20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11～20之萘基烷基、及雜環基等。該等之適宜之有機基之具體例與R1 同樣。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、二乙基胺基、正丙基胺基、二正丙基胺基、異丙基胺基、正丁基胺基、二正丁基胺基、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 中所含之苯基、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1～6之烷基、碳原子數1～6之烷氧基、碳原子數2～7之飽和脂肪族醯基、碳原子數2～7之烷氧基羰基、碳原子數2～7之飽和脂肪族醯氧基、具有碳原子數1～6之烷基之單烷基胺基、具有碳原子數1～6之烷基之二烷基胺基、嗎啉-1-基、哌
Figure 105127562-A0304-12-0001-4
-1-基、鹵素原子、及氰基等。鹵素原子之具體例及適宜例如後所述。於R1 中所含之苯基、萘基、及雜環基進而具有取代基之情形時，其取代基之個數只要為不阻礙本發明之目的之範圍則無限定，較佳為1～4。於R1 中所含之苯基、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，於存在感度提高之傾向之方面而言，R1 較佳為R6 -CO-所表示之基。R6 只要為不阻礙本發明之目的之範圍則無特別限定，可自各種有機基中選擇。作為R6 而適宜之基之例，可列舉碳原子數1～20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 ，於該等基中尤佳為2-甲基苯基、噻吩-2-基、及α-萘基。 又，於存在透明性變良好之傾向之方面而言，作為R1 ，較佳為氫原子。再者，若R1 為氫原子且R4 為下述之式(R4-2)所表示之基，則存在透明性變得更良好之傾向。 式(1)中，R2 及R3 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。R2 與R3 亦可相互鍵結而形成環。該等基中，作為R2 及R3 ，較佳為可具有取代基之鏈狀烷基。於R2 及R3 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R2 及R3 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1～20，更佳為1～10，尤佳為1～6。作為R2 及R3 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R2 及R3 為烷基之情形時，烷基亦可於碳鏈中含有醚鍵(-O-)。作為於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R2 及R3 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1～20，更佳為1～10，尤佳為1～6。於該情形時，取代基之碳原子數並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。 烷基所亦可具有之取代基只要為不阻礙本發明之目的之範圍則無特別限定。作為取代基之適宜例，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R1 為環烷基之情形之適宜例同樣。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R1 為雜環基之情形之適宜例同樣。於R1 為烷氧基羰基之情形時，烷氧基羰基中所含之烷氧基可為直鏈狀亦可為支鏈狀，較佳為直鏈狀。烷氧基羰基中所含之烷氧基之碳原子數較佳為1～10，更佳為1～6。 於鏈狀烷基具有取代基之情形時，取代基數並無特別限定。較佳之取代基數與鏈狀烷基之碳原子數相應地改變。取代基數典型為1～20，較佳為1～10，更佳為1～6。 於R2 及R3 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R2 及R3 為環狀有機基之情形時，環狀有機基所亦可具有之取代基與R2 及R3 為鏈狀烷基之情形同樣。 於R2 及R3 為芳香族烴基之情形時，較佳為芳香族烴基為苯基，或為複數個苯環經由碳-碳鍵進行鍵結而形成之基，或為複數個苯環縮合而形成之基。於芳香族烴基為苯基，或為複數個苯環鍵結或縮合而形成之基之情形時，芳香族烴基中所含之苯環之環數並無特別限定，較佳為3個以下，更佳為2個以下，尤佳為1個。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R2 及R3 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3～20，更佳為3～10。作為單環式環狀烴基之例，可列舉環丙基、環丁基、環戊基、環己基、環庚基、環辛基、降
Figure 105127562-A0304-03-0013-01
基、異
Figure 105127562-A0304-03-0013-01
基、三環壬基、三環癸基、四環十二烷基、及金剛烷基等。 於R2 及R3 為雜環基之情形時，雜環基為包含1個以上N、S、及/或O之5員或6員之單環，或該單環彼此、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，所縮合之環數為3以下。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，可列舉呋喃環、噻吩環、吡咯環、
Figure 105127562-A0304-12-0001-1
唑環、異
Figure 105127562-A0304-12-0001-1
唑環、噻唑環、噻二唑環、異噻唑環、咪唑環、吡唑環、三唑環、吡啶環、吡
Figure 105127562-A0304-12-0001-4
環、嘧啶環、嗒
Figure 105127562-A0304-12-0001-4
環、苯并呋喃環、苯并噻吩環、吲哚環、異吲哚環、吲哚
Figure 105127562-A0304-12-0001-4
環、苯并咪唑環、苯并三唑環、苯并
Figure 105127562-A0304-12-0001-1
唑環、苯并噻唑環、咔唑環、嘌呤環、喹啉環、異喹啉環、喹唑啉環、酞
Figure 105127562-A0304-12-0001-4
環、
Figure 105127562-A0304-12-0001-6
啉環、喹
Figure 105127562-A0304-12-0001-1
啉環、哌啶環、哌
Figure 105127562-A0304-12-0001-4
環、嗎啉環、哌啶環、四氫吡喃環、及四氫呋喃環等。 R2 與R3 亦可相互鍵結而形成環。包含R2 與R3 所形成之環的基較佳為亞環烷基。於R2 與R3 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R2 與R3 鍵結而形成之基為亞環烷基之情形時，亞環烷基亦可與1個以上之其他環縮合。作為亦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
Figure 105127562-A0304-12-0001-4
環、及嘧啶環等。 作為以上所說明之R2 及R3 中適宜之基之例子，可列舉式-A1 -A2 所表示之基。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1～10，更佳為1～6。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1～10，更佳為1～6。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，鹵化烷基中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R2 及R3 所作為取代基而具有之環狀有機基同樣。於A2 為烷氧基羰基之情形時，烷氧基羰基之例與R2 及R3 所作為取代基而具有之烷氧基羰基同樣。 作為R2 及R3 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R2 及R3 ，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。 式(1)中，R4 は、下述式(R4-1)或(R4-2)所表示之基。 [化5]
Figure 02_image011
(式(R4-1)及(R4-2)中，R7 及R8 分別為1價有機基，p為0～4之整數，於R7 及R8 存在於苯環上之鄰接之位置上之情形時，R7 與R8 亦可相互鍵結而形成環，q為1～8之整數，r為1～5之整數，s為0～(r＋3)之整數，R9 為1價有機基) 關於式(R4-1)中之R7 及R8 之1價有機基之例與R1 同樣。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1～10，更佳為1～5，尤佳為1～3，最佳為1。即，最佳為R7 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(R4-1)所表示之基中的R7 與R8 形成環之基之適宜例，可列舉萘-1-基或1,2,3,4-四氫化萘-5-基等。上述式(R4-1)中，p為0～4之整數，較佳為0或1，更佳為0。 上述式(R4-2)中，R9 為1價有機基。作為1價有機基，可列舉與關於R1 而說明之1價有機基同樣之基。1價有機基中，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1～10，更佳為1～5，尤佳為1～3。作為R9 ，可較佳地例示甲基、乙基、丙基、異丙基、丁基等，該等中更佳為甲基。 上述式(R4-2)中，r為1～5之整數，較佳為1～3之整數，更佳為1或2。上述式(R4-2)中，s為0～(r＋3)，較佳為0～3之整數，更佳為0～2之整數，尤佳為0。上述式(R4-2)中，q為1～8之整數，較佳為1～5之整數，更佳為1～3之整數，尤佳為1或2。 式(1)中，R5 為氫原子、可具有取代基之碳原子數1～11之烷基、或可具有取代基之芳基。作為R5 為烷基之情形時所亦可具有之取代基，可較佳地例示苯基、萘基等。又，作為R1 為芳基之情形時所亦可具有之取代基，可較佳地例示碳原子數1～5之烷基、烷氧基、鹵素原子等。 式(1)中，作為R5 ，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(1)中，n為0～4之整數，較佳為0～2之整數，更佳為0或1，尤佳為0。 如上所述，光聚合起始劑(A1)不具有硝基。即，R1 ～R5 之任意者均不具有硝基。 光聚合起始劑(A1)之含量較佳為相對於感光性組合物之固形物成分而言為0.001～50質量%，更佳為0.01～30質量%，進而更佳為0.1～20質量%，尤佳為1～10質量%。光聚合起始劑(A1)之含量若為上述範圍內，則所獲得之組合物可維持對於曝光之良好之感度，由其組合物而獲得之硬化物之透過率容易變充分。 光聚合起始劑(A1)之含量例如若為相對於光聚合起始劑(A)全體而言為1～99.5質量%之範圍即可，較佳為50～99質量%，更佳為70～98質量%，進而更佳為80～97質量%。 光聚合起始劑(A1)之製造方法並無特別限定。光聚合起始劑(A1)較佳為藉由包含將下述式(2)所表示之化合物中所含之肟基(＝N-OH)轉換為＝N-O-COR5 所表示之肟酯基之步驟的方法而製造。R5 與式(1)中之R5 同樣。 [化6]
Figure 02_image013
(R1 、R2 、R3 、R4 、及n與式(1)同樣) 因此，上述式(2)所表示之化合物可用作光聚合起始劑(A1)之合成用中間物。 將肟基(＝N-OH)轉換為＝N-O-COR5 所表示之肟酯基之方法並無特別限定。典型為列舉使肟基中之羥基與提供-COR5 所表示之醯基之醯基化劑反應之方法。作為醯基化劑，可列舉(R5 CO)2 O所表示之酸酐或R5 COHal(Hal為鹵素原子)所表示之醯鹵。 光聚合起始劑(A1)例如可依照下述反應流程而合成。於下述反應流程中，使用下述式(1-1)所表示之茀衍生物作為原料。於R1 為1價有機基之情形時，式(1-1)所表示之茀衍生物可藉由眾所周知之方法，將取代基R1 導入至9位經R2 及R3 取代之茀衍生物而獲得。至於9位經R2 及R3 取代之茀衍生物，例如於R2 及R3 為烷基之情形時，如日本專利特開平06-234668號公報中所記載那樣，於鹼金屬氫氧化物之存在下，非質子性極性有機溶劑中，使茀與烷基化劑反應而獲得。又，於茀之有機溶劑溶液中，添加鹵化烷基之類的烷基化劑、鹼金屬氫氧化物之水溶液、四丁基碘化銨或第三丁醇鉀之類的相間轉移觸媒而進行烷基化反應，藉此可獲得9,9-烷基取代茀。 於式(1-1)所表示之茀衍生物中，藉由佛瑞德-克來福特醯基化反應而導入-CO-CH2 -R4 所表示之醯基，獲得式(2-1)所表示之茀衍生物。作為用以導入-CO-CH2 -R4 所表示之醯基之醯基化劑，較佳為式(1-8)所表示之羧醯鹵。式(1-8)中，Hal為鹵素原子。於茀環上導入醯基之位置可藉由適宜變更佛瑞德-克來福特反應之條件、於醯基化之位置之其他位置實施保護及去保護之方法而選擇。 其次，對式(2-1)所表示之化合物中之存在於R4 與羰基之間之亞甲基進行肟化，獲得下述式(2-3)所表示之酮肟化合物。對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(2-2)所表示之亞硝酸酯(RONO、R為碳數1～6之烷基)反應之方法。其次，可使下述式(2-3)所表示之酮肟化合物與下述式(2-4)所表示之酸酐((R5 CO)2 O)、或下述式(2-5)所表示之醯鹵(R5 COHal、Hal為鹵素原子)反應，從而獲得下述式(2-6)所表示之化合物。再者，於下述式(1-1)、(1-8)、(2-1)、(2-3)、(2-4)、(2-5)、及(2-6)中，R1 、R2 、R3 、R4 、及R5 與式(1)同樣。 又，於下述反應流程中，式(1-8)、式(2-1)、及式(2-3)所分別含有之R4 可相同亦可不同。即，式(1-8)、式(2-1)、及式(2-3)中之R4 亦可於作為下述反應流程而表示之合成過程中受到化學修飾。作為化學修飾之例，可列舉酯化、醚化、醯基化、醯胺化、鹵化、利用有機基取代胺基中之氫原子等。R4 亦可受到之化學修飾並不限定於該等。 ＜反應流程＞ [化7]
Figure 02_image015
作為光聚合起始劑(A1)之適宜之具體例，可列舉以下之化合物。 [化8]
Figure 02_image017
[化9]
Figure 02_image019
[具有鍵結有硝基之芳香環骨架的光聚合起始劑(A2)] 本發明之感光性組合物含有具有鍵結有硝基之芳香環骨架的光聚合起始劑(A2)。光聚合起始劑(A2)可單獨使用或將2種以上組合而使用。 作為光聚合起始劑(A2)，若為具有鍵結有硝基之芳香環骨架的光聚合起始劑，則無特別限定，例如可列舉具有如下芳香環骨架之化合物，上述芳香環骨架鍵結有硝基與具有肟酯鍵之基。 上述芳香環骨架較佳為茀或咔唑骨架之一部分，亦可為茀或咔唑骨架之一部分之芳香環。 又，光聚合起始劑(A2)亦可為下述之式(A2-1C)所表示之化合物、式(A2-1N)所表示之化合物之類的硝基鍵結於伸芳基、伸雜芳基上之化合物。 於光聚合起始劑(A2)中，硝基較佳為直接(即，並不經由伸烷基等連結基)或經由伸烷基等連結基而鍵結於芳香環骨架上，更佳為直接鍵結於芳香環骨架上。上述具有肟酯鍵之基較佳為直接或經由羰基而鍵結於芳香環骨架上。作為上述具有肟酯鍵之基，例如可列舉下述式(3)所表示之基。 -C(R14 )＝N-O-C(R15 )＝O   (3) (式中，R14 為1價有機基，R15 為氫原子、可具有取代基之碳原子數1～11之烷基、或可具有取代基之芳基) 作為光聚合起始劑(A2)之具體例，可列舉下述式(a-1)所表示之化合物： [化10]
Figure 02_image021
(R100 為下述式(a-2)： [化11]
Figure 02_image023
(R11 為氫原子、硝基、或1價有機基，R12 及R13 獨立為鏈狀烷基、環狀烴基、或雜芳基，R12 與R13 亦可相互鍵結而形成螺環，n1為1～4之整數。其中，R11 之至少1個為硝基) 所表示之基、下述式(a-3)： [化12]
Figure 02_image025
(R20 獨立為1價有機基、胺基、鹵素原子、硝基、或氰基，A為S或O，n2為1～4之整數。其中，R20 之至少1個為硝基) 所表示之基、或下述式(a-4)： [化13]
Figure 02_image027
(R21 為1價有機基，R22 為氫原子、硝基、或1價有機基，n3為1～4之整數。其中，R22 之至少1個為硝基) 所表示之基，R14 為1價有機基，R15 為氫原子、可具有取代基之碳原子數1～11之烷基、或可具有取代基之芳基，m為0或1)。 作為R14 之適宜之1價有機基之例，可與下述之R11 同樣地列舉烷基、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
Figure 105127562-A0304-12-0001-4
-1-基等。 於R14 為烷基之情形時，烷基之碳原子數較佳為1～20，更佳為1～6。又，於R14 為烷基之情形時，可為直鏈亦可為支鏈。作為R14 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R14 為烷基之情形時，烷基亦可於碳鏈中含有醚鍵(-O-)。作為於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R14 為烷氧基之情形時，烷氧基之碳原子數較佳為1～20，更佳為1～6。又，於R14 為烷氧基之情形時，可為直鏈亦可為支鏈。作為R14 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R14 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R14 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3～10，更佳為3～6。作為R14 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R14 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R14 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2～21，更佳為2～7。作為R14 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、正十一醯基、正十二醯基、正十三醯基、正十四醯基、正十五醯基、及正十六醯基等。作為R14 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、正十一醯氧基、正十二醯氧基、正十三醯氧基、正十四醯氧基、正十五醯氧基、及正十六醯氧基等。 於R14 為烷氧基羰基之情形時，烷氧基羰基之碳原子數較佳為2～20，更佳為2～7。作為R14 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R14 為苯基烷基之情形時，苯基烷基之碳原子數較佳為7～20，更佳為7～10。又，於R14 為萘基烷基之情形時，萘基烷基之碳原子數較佳為11～20，更佳為11～14。作為R14 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R14 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R14 為苯基烷基或萘基烷基之情形時，R14 亦可於苯基或萘基上進而具有取代基。 於R14 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，可將環數設至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、
Figure 105127562-A0304-12-0001-1
唑、異
Figure 105127562-A0304-12-0001-1
唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、三唑、吡啶、吡
Figure 105127562-A0304-12-0001-4
、嘧啶、嗒
Figure 105127562-A0304-12-0001-4
、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚
Figure 105127562-A0304-12-0001-4
、苯并咪唑、苯并三唑、苯并
Figure 105127562-A0304-12-0001-1
唑、苯并噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞
Figure 105127562-A0304-12-0001-4
、
Figure 105127562-A0304-12-0001-6
啉、及喹
Figure 105127562-A0304-12-0001-1
啉等。於R14 為雜環基之情形時，雜環基亦可進而具有取代基。 於R14 為雜環基羰基之情形時，雜環基羰基中所含之雜環基與R14 為雜環基之情形同樣。 於R14 為經1個或2個有機基取代之胺基之情形時，有機基之適宜例可列舉碳原子數1～20之烷基、碳原子數3～10之環烷基、碳原子數2～21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7～20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11～20之萘基烷基、及雜環基等。該等適宜之有機基之具體例與R14 同樣。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、二乙基胺基、正丙基胺基、二正丙基胺基、異丙基胺基、正丁基胺基、二正丁基胺基、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R14 中所含之苯基、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1～6之烷基、碳原子數1～6之烷氧基、碳原子數2～7之飽和脂肪族醯基、碳原子數2～7之烷氧基羰基、碳原子數2～7之飽和脂肪族醯氧基、具有碳原子數1～6之烷基之單烷基胺基、具有碳原子數1～6之烷基之二烷基胺基、嗎啉-1-基、哌
Figure 105127562-A0304-12-0001-4
-1-基、鹵素、硝基、及氰基等。於R14 中所含之苯基、萘基、及雜環基進而具有取代基之情形時，其取代基數於不阻礙本發明之目的之範圍內並無限定，較佳為1～4。於R14 中所含之苯基、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。 又，作為R14 ，亦較佳為環烷基烷基、亦可於芳香環上具有取代基之苯氧基烷基、亦可於芳香環上具有取代基之苯硫基烷基。苯氧基烷基、及苯硫基烷基所亦可具有之取代基與R14 中所含之苯基所亦可具有之取代基同樣。 於1價有機基中，作為R14 ，較佳為烷基、環烷基、可具有取代基之苯基、或環烷基烷基、亦可於芳香環上具有取代基之苯硫基烷基。作為烷基，較佳為碳原子數1～20之烷基，更佳為碳原子數1～8之烷基，尤佳為碳原子數1～4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。環烷基烷基中所含之環烷基之碳原子數較佳為5～10，更佳為5～8，尤佳為5或6。環烷基烷基中所含之伸烷基之碳原子數較佳為1～8，更佳為1～4，尤佳為2。於環烷基烷基中，較佳為環戊基乙基。亦可於芳香環上具有取代基之苯硫基烷基中所含之伸烷基之碳原子數較佳為1～8，更佳為1～4，尤佳為2。亦可於芳香環上具有取代基之苯硫基烷基中，較佳為2-(4-氯苯硫基)乙基。 以上，關於R14 而進行了說明，作為R14 ，較佳為下述式(R2-1)或(R2-2)所表示之基。 [化14]
Figure 02_image029
(式(R2-1)及(R2-2)中，R17 及R18 分別為1價有機基，p1為0～4之整數，於R17 及R18 存在於苯環上之鄰接之位置上之情形時，R17 與R18 亦可相互鍵結而形成環，q1為1～8之整數，r1為1～5之整數，s1為0～(r1＋3)之整數，R19 為烷基) 關於式(R2-1)中之R17 及R18 之有機基之例，與R14 同樣。作為R17 ，較佳為烷基或苯基。於R17 為烷基之情形時，其碳原子數較佳為1～10，更佳為1～5，尤佳為1～3，最佳為1。即，最佳為R17 為甲基。於R17 與R18 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(R2-1)所表示之基中之R17 與R18 形成環之基之適宜例，可列舉萘-1-基或1,2,3,4-四氫化萘-5-基等。上述式(R2-1)中，p1為0～4之整數，較佳為0或1，更佳為0。 上述式(R2-2)中，R19 為烷基。烷基之碳原子數較佳為1～10，更佳為1～5，尤佳為1～3。作為R19 ，可較佳地例示甲基、乙基、丙基、異丙基、丁基等，該等中更佳為甲基。 上述式(R2-2)中，r1為1～5之整數，較佳為1～3之整數，更佳為1或2。上述式(R2-2)中，s1為0～(r1＋3)，較佳為0～3之整數，更佳為0～2之整數，尤佳為0。上述式(R2-2)中，q1為1～8之整數，較佳為1～5之整數，更佳為1～3之整數，尤佳為1或2。 式(a-1)中，R15 為氫原子、可具有取代基之碳原子數1～11之烷基、或可具有取代基之芳基。作為R15 為烷基之情形時所亦可具有之取代基，可較佳地例示苯基、萘基等。又，作為R15 為芳基之情形時所亦可具有之取代基，可較佳地例示碳原子數1～5之烷基、烷氧基、鹵素原子等。 式(a-1)中，作為R15 ，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(a-2)中，R11 為氫原子、硝基或1價有機基。R11 鍵結於式(a-2)中之茀環上，與式(a-1)中之-(CO)m -所表示之基鍵結之6員芳香環不同之6員芳香環上。若滿足該條件，則於式(a-2)中，R11 相對於茀環之鍵結位置並無特別限定。至於R11 相對於茀環之鍵結位置，自容易合成R100 為式(a-2)所表示之基的式(a-1)所表示之化合物等考慮，較佳為茀環中之2位。 於R11 為1價有機基之情形時，R11 只要為不阻礙本發明之目的之範圍則無特別限定，可自各種有機基中適宜選擇。作為R11 為1價有機基之情形時之適宜例，可與R14 同樣地列舉烷基、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
Figure 105127562-A0304-12-0001-4
-1-基等。該等基之具體例與關於R14 而說明者同樣。 於以上所說明之基中，R11 若為硝基、或R11a -CO-所表示之基，則存在感度提高之傾向而較佳。其中，R11 之至少1個為硝基。R11a 只要為不阻礙本發明之目的之範圍則無特別限定，可自各種有機基中選擇。作為R11a 而適宜之基之例，可列舉碳原子數1～20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R11a ，於該等基中，尤佳為2-甲基苯基、噻吩-2-基、及α-萘基。 又，若R11 為氫原子，則存在透明性變良好之傾向而較佳。再者，若R11 為氫原子且R14 為上述之(R2-2)，則存在透明性變得更良好之傾向。 式(a-2)中，R12 及R13 分別為鏈狀烷基、環狀烴基、或雜芳基。該等基中，R12 及R13 較佳為鏈狀烷基。 於R12 及R13 為鏈狀烷基之情形時，鏈狀烷基可為直鏈烷基亦可為支鏈烷基。於R12 及R13 為鏈狀烷基之情形時，鏈狀烷基之碳原子數較佳為1～20，更佳為1～6。作為R12 及R13 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R12 及R13 為鏈狀烷基之情形時，鏈狀烷基亦可於碳鏈中含有醚鍵(-O-)。作為碳鏈中具有醚鍵之鏈狀烷基之例，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R12 及R13 為環狀烴基之情形時，環狀烴基可為脂肪族環狀烴基，亦可為芳香族環狀烴基。 於R12 及R13 為芳香族環狀烴基之情形時，較佳為芳香族環狀烴基為苯基、或複數個苯環經由碳-碳鍵鍵結而形成之基、或複數個苯環縮合而形成之基。於芳香族環狀烴基為苯基、或複數個苯環鍵結或縮合而形成之基之情形時，芳香族環狀烴基中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。作為芳香族環狀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R12 及R13 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3～20，更佳為3～10。作為單環式環狀烴基之例，可列舉環丙基、環丁基、環戊基、環己基、環庚基、環辛基、降
Figure 105127562-A0304-03-0013-01
基、異
Figure 105127562-A0304-03-0013-01
基、三環壬基、三環癸基、四環十二烷基、及金剛烷基等。 於R12 及R13 為雜芳基之情形時，雜芳基可為包含1個以上N、S、O之5員或6員之單環，或該單環彼此、或該單環與苯環縮合而成之雜芳基。於雜芳基為縮合環之情形時，可將環數設至3。作為構成該雜芳基之雜環，可列舉呋喃、噻吩、吡咯、
Figure 105127562-A0304-12-0001-1
唑、異
Figure 105127562-A0304-12-0001-1
唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、三唑、吡啶、吡
Figure 105127562-A0304-12-0001-4
、嘧啶、嗒
Figure 105127562-A0304-12-0001-4
、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚
Figure 105127562-A0304-12-0001-4
、苯并咪唑、苯并三唑、苯并
Figure 105127562-A0304-12-0001-1
唑、苯并噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞
Figure 105127562-A0304-12-0001-4
、
Figure 105127562-A0304-12-0001-6
啉、及喹
Figure 105127562-A0304-12-0001-1
啉等。 R12 與R13 亦可相互鍵結而形成螺環。包含R12 與R13 所形成之螺環之基較佳為亞環烷基。於R12 與R13 鍵結而形成亞環烷基之情形時，構成亞環烷基之螺環較佳為5員環～6員環，更佳為5員環。 於R12 與R13 鍵結而形成之基為亞環烷基之情形時，亞環烷基亦可與1個以上其他環縮合。作為亦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
Figure 105127562-A0304-12-0001-4
環、及嘧啶環等。 n1較佳為1～3之整數，更佳為1或2，尤佳為1。 式(a-3)中，R20 獨立為1價有機基、胺基、鹵素原子、硝基、或氰基。於R20 為1價有機基之情形時，可於不阻礙本發明之目的之範圍而選自各種有機基。作為R20 為1價有機基之情形時之適宜例，可列舉碳數1～6之烷基；碳數1～6之烷氧基；碳數2～7之飽和脂肪族醯基；碳數2～7之烷氧基羰基；碳數2～7之飽和脂肪族醯氧基；苯基；萘基；苯甲醯基；萘甲醯基；經選自由碳數1～6之烷基、嗎啉-1-基、哌
Figure 105127562-A0304-12-0001-4
-1-基、及苯基所組成之群中之基取代之苯甲醯基；具有碳數1～6之烷基之單烷基胺基；具有碳數1～6之烷基之二烷基胺基；嗎啉-1-基；哌
Figure 105127562-A0304-12-0001-4
-1-基。 R20 中，較佳為苯甲醯基；萘甲醯基；經選自由碳數1～6之烷基、嗎啉-1-基、哌
Figure 105127562-A0304-12-0001-4
-1-基、及苯基所組成之群中之基取代之苯甲醯基；硝基，更佳為苯甲醯基；萘甲醯基；2-甲基苯基羰基；4-(哌
Figure 105127562-A0304-12-0001-4
-1-基)苯基羰基；4-(苯基)苯基羰基；硝基。其中，R20 之至少1個為硝基。 又，n2較佳為1～3之整數，更佳為1或2，尤佳為1。於n2為1之情形時，R20 之鍵結位置較佳為相對於R20 所鍵結之苯基與原子A鍵結之鍵結鍵而言為對位。 A較佳為S。 式(a-4)中，R21 為1價有機基。R21 可於不阻礙本發明之目的之範圍內選自各種有機基。作為R21 之適宜例，碳數1～20之烷基、碳數3～10之環烷基、碳數2～20之飽和脂肪族醯基、碳數2～20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、可具有取代基之碳數7～20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、可具有取代基之碳數11～20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R21 中，較佳為碳數1～20之烷基，更佳為碳數1～6之烷基，尤佳為乙基。 作為R20 或R21 中所含之苯基、萘基、及雜環基進而具有取代基之情形時之取代基，可列舉碳數1～6之烷基、碳數1～6之烷氧基、碳數2～7之飽和脂肪族醯基、碳數2～7之烷氧基羰基、碳數2～7之飽和脂肪族醯氧基、具有碳數1～6之烷基之單烷基胺基、具有碳數1～6之烷基之二烷基胺基、嗎啉-1-基、哌
Figure 105127562-A0304-12-0001-4
-1-基、鹵素、硝基、及氰基等。於R20 或R21 中所含之苯基、萘基、及雜環基進而具有取代基之情形時，其取代基數只要為不阻礙本發明之目的之範圍則無限定，較佳為1～4。R20 或R21 中所含之苯基、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(a-4)中，R22 為氫原子、硝基、或1價有機基。R22 與R11 同樣，R22 之至少1個為硝基。 n3較佳為1～3之整數，更佳為1或2，尤佳為1。 式(a-1)所表示之化合物於m為0之情形時，例如可依照下述反應流程a1而合成。於反應流程a1中，使用下述式(a1-1)所表示之化合物作為原料。例如，於R100 為式(a-2)所表示之基之情形時，於反應流程a1中，使用下述式(a1-1-1)所表示之茀衍生物作為原料。於R11 為硝基或1價有機基之情形時，式(a1-1-1)所表示之茀衍生物可藉由周知之方法將取代基R11 導入至9位經R12 及R13 取代之茀衍生物而獲得。至於9位經R12 及R13 取代之茀衍生物，例如於R12 及R13 為烷基之情形時，可如日本專利特開平06-234668號公報中所記載般，於鹼金屬氫氧化物之存在下、非質子性極性有機溶劑中，使茀與烷基化劑反應而獲得。又，於茀之有機溶劑溶液中，添加鹵化烷基之類的烷基化劑、鹼金屬氫氧化物之水溶液、碘化四丁基銨或第三丁醇鉀之類的相間轉移觸媒而進行烷基化反應，藉此可獲得9,9-烷基取代茀。 使用式(a1-2)所表示之鹵羰基化合物，藉由佛瑞德-克來福特反應對式(a1-1)所表示之化合物進行醯基化而獲得式(a1-3)所表示之酮化合物。式(a1-2)中，Hal為鹵素原子。R100 中所含之芳香環上之藉由式(a1-2)所表示之化合物而醯基化之位置可藉由如下方法而選擇：適宜變更佛瑞德-克來福特反應之條件、對該芳香環上之藉由式(a1-2)所表示之化合物而醯基化之位置之其他位置實施保護及去保護。 其次，藉由羥胺對所獲得之式(a1-3)所表示之酮化合物進行肟化而獲得下述式(a1-4)所表示之肟化合物。可使式(a1-4)之肟化合物與下述式(a1-5)所表示之酸酐((R15 CO)2 O)、或下述式(a1-6)所表示之醯鹵(R15 COHal、Hal為鹵素原子)反應而獲得下述式(a1-7)所表示之化合物。 再者，於式(a1-1)、(a1-2)、(a1-3)、(a1-4)、(a1-5)、(a1-6)、(a1-7)、及(a1-1-1)中，R100 、R14 、R15 、R11 、R12 、及R13 與式(a-1)及式(a-2)同樣。 ＜反應流程a1＞ [化15]
Figure 02_image031
式(a-1)所表示之化合物於m為1之情形時，例如可依照下述反應流程a2而合成。於反應流程a2中，使用下述式(a2-1)所表示之化合物作為原料。式(a2-1)所表示之化合物係藉由與反應流程a1同樣之方法，藉由佛瑞德-克來福特反應對式(a1-1)所表示之化合物進行醯基化而獲得。於鹽酸之存在下，使式(a2-1)所表示之化合物與下述式(a2-2)所表示之亞硝酸酯(RONO、R為碳數1～6之烷基)反應而獲得下述式(a2-3)所表示之酮肟化合物。其次，使下述式(a2-3)所表示之酮肟化合物與下述式(a2-4)所表示之酸酐((R15 CO)2 O)、或下述式(a2-5)所表示之醯鹵(R15 COHal、Hal為鹵素原子)反應，可獲得下述式(a2-6)所表示之化合物。再者，於下述式(a2-1)、(a2-3)、(a2-4)、(a2-5)、及(a2-6)中，R100 、R14 、及R15 與式(a-1)同樣。 於m為1之情形時，存在可進而減低於使用含有式(a-1)所表示之化合物的感光性組合物所形成之硬化物中產生異物之傾向。 ＜反應流程a2＞ [化16]
Figure 02_image033
作為式(a-1)所表示之化合物之適宜之具體例，可列舉以下之化合物。 [化17]
Figure 02_image035
[化18]
Figure 02_image037
又，作為光聚合起始劑(A2)，亦可使用下述式(A2-1C)所表示之化合物。 [化19]
Figure 02_image039
(式(A2-1C)中，R1 表示硝基，R6 為伸芳基或伸雜芳基，該伸芳基或伸雜芳基亦可為含有1個以上選自碳-碳雙鍵及碳-碳三鍵之1個以上鍵之鏈狀脂肪族烴基組合而成之基。R2 及R3 分別獨立地表示亦可經取代之烷基或氫原子，R4 表示1價有機基、或氫原子，R5 表示1價有機基或氫原子，n表示0或1) 於式(A2-1C)中之R6 為伸芳基之情形時，該伸芳基若為自芳香族烴去除2個氫原子之基則無特別限定。伸芳基較佳為包含1個以上苯環之基。於伸芳基包含2個以上苯環之情形時，複數個苯環可藉由單鍵而相互鍵結，亦可相互縮合而形成萘環等縮合環。 伸芳基較佳為包含1～3個苯環，更佳為包含1或2個苯環。 作為伸芳基之適宜例，可列舉對伸苯基、間伸苯基、鄰伸苯基、萘-1,2-二基、萘-1,3-二基、萘1,4-二基、萘-1,5-二基、萘-1,7-二基、萘-1,8-二基、萘-2,3-二基、萘-2,6-二基、萘-2,7-二基、聯苯-4,4'-二基、聯苯-3,3'-二基、聯苯-2,2'-二基、聯苯-3,4'-二基、聯苯-3,2'-二基、及聯苯-2,4'-二基。 於式(A2-1C)中之R6 為伸雜芳基之情形時，該伸雜芳基若為自芳香族雜環去除2個氫原子而成之基，則無特別限定。伸雜芳基較佳為包含5員或6員之芳香環之基中的含有至少1個5員或6員之芳香族雜環之基。 於伸雜芳基為包含5員或6員之芳香環之基中的甘油至少1個5員或6員之芳香族雜環之基之情形時，複數個5員或6員之芳香環可藉由單鍵而相互鍵結，亦可相互縮合而形成縮合環。 伸雜芳基較佳為含有1～3個5員或6員之芳香環，更佳為含有1或2個5員或6員之芳香環。 作為伸雜芳基之適宜例，可列舉自呋喃、噻吩、吡咯、
Figure 105127562-A0304-12-0001-1
唑、異
Figure 105127562-A0304-12-0001-1
唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、三唑、吡啶、吡
Figure 105127562-A0304-12-0001-4
、嘧啶、嗒
Figure 105127562-A0304-12-0001-4
、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚
Figure 105127562-A0304-12-0001-4
、苯并咪唑、苯并三唑、苯并
Figure 105127562-A0304-12-0001-1
唑、苯并噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞
Figure 105127562-A0304-12-0001-4
、
Figure 105127562-A0304-12-0001-6
啉、及喹
Figure 105127562-A0304-12-0001-1
啉等芳香族雜環化合物去除與碳原子鍵結之2個氫原子而成之基。 關於含有1個以上選自碳-碳雙鍵及碳-碳三鍵之1個以上鍵之鏈狀脂肪族烴基，其碳原子數或碳-碳雙鍵及碳-碳三鍵數只要為不阻礙本發明之目的之範圍則無特別限定。 又，含有1個以上選自碳-碳雙鍵及碳-碳三鍵之1個以上鍵之鏈狀脂肪族烴基可為直鏈狀亦可為支鏈狀，較佳為直鏈狀。 含有1個以上選自碳-碳雙鍵及碳-碳三鍵之1個以上鍵之鏈狀脂肪族烴基之碳原子數較佳為2～10，更佳為2～6，尤佳為2～4。 鏈狀脂肪族烴基較佳為含有1個碳-碳雙鍵之伸烯基、或含有1個碳-碳三鍵之伸炔基。 作為含有1個以上選自碳-碳雙鍵及碳-碳三鍵之1個以上鍵之鏈狀脂肪族烴基之適宜例，可列舉乙烯-1,2-二基、乙炔-1,2-二基、丙-1-烯-1,2-二基、伸炔丙基、伸戊炔基。 例如，作為伸芳基與含有1個以上選自碳-碳雙鍵及碳-碳三鍵之1個以上鍵之鏈狀脂肪族烴基組合而成之基之較佳例，可列舉下述之2價基。 作為伸雜芳基與含有1個以上選自碳-碳雙鍵及碳-碳三鍵之1個以上鍵之鏈狀脂肪族烴基組合而成之基之較佳例，可列舉將下述之2價基中所含之伸芳基置換為各種伸雜芳基而成之基。 [化20]
Figure 02_image041
於式(A2-1C)中之R2 及R3 為不具有取代基之烷基之情形時，該烷基之碳原子數較佳為1～20，更佳為1～10，尤佳為1～6。作為R2 及R3 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。 於式(A2-1C)中之R2 及R3 為具有取代基之烷基之情形時，烷基之碳原子數較佳為1～20，更佳為1～10，尤佳為1～6。於該情形時，取代基之碳原子數並不包含於鏈狀烷基之碳原子數中。具有取代基之烷基可為直鏈狀亦可為支鏈狀，較佳為直鏈狀。 烷基所亦可具有之取代基只要為不阻礙本發明之目的之範圍則無特別限定。作為取代基之適宜例，可列舉氰基、鹵素原子、環狀有機基、烷氧基、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。 環烷基之碳原子數較佳為3～10，更佳為3～6。作為環烷基之具體例，可列舉環丙基、環丁基、環戊基、環己基、環庚基、及環辛基等。 作為芳香族烴基，可列舉苯基、萘基、聯苯基、蒽基、及菲基等。 雜環基係包含1個以上N、S、O之5員或6員之單環，或該單環彼此、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，縮合之環數為3以下。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、
Figure 105127562-A0304-12-0001-1
唑、異
Figure 105127562-A0304-12-0001-1
唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、三唑、吡啶、吡
Figure 105127562-A0304-12-0001-4
、嘧啶、嗒
Figure 105127562-A0304-12-0001-4
、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚
Figure 105127562-A0304-12-0001-4
、苯并咪唑、苯并三唑、苯并
Figure 105127562-A0304-12-0001-1
唑、苯并噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞
Figure 105127562-A0304-12-0001-4
、
Figure 105127562-A0304-12-0001-6
啉、喹
Figure 105127562-A0304-12-0001-1
啉、哌啶、哌
Figure 105127562-A0304-12-0001-4
、嗎啉、哌啶、四氫吡喃、及四氫呋喃等。於R2 及R3 為雜環基之情形時，雜環基亦可進而具有取代基。 作為烷氧基，較佳為碳原子數1～10之烷氧基，更佳為碳原子數1～6之烷氧基，尤佳為碳原子數1～4之烷氧基。作為具體例，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、及正己氧基。 烷氧基羰基中所含之烷氧基可為直鏈狀亦可為支鏈狀，較佳為直鏈狀。烷氧基羰基中所含之烷氧基之碳原子數較佳為1～10，更佳為1～6。作為具體例，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、及正己氧基羰基。 於烷基具有取代基之情形時，取代基數並無特別限定。較佳之取代基數與鏈狀烷基之碳原子數對應地變化。取代基數典型為1～20，較佳為1～10，更佳為1～6。 式(A2-1C)中之R2 與R3 亦可相互鍵結而形成環。包含R2 與R3 所形成之環之基較佳為亞環烷基。於R2 與R3 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R2 與R3 鍵結而形成之基為亞環烷基之情形時，亞環烷基亦可與1個以上其他環縮合。作為亦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
Figure 105127562-A0304-12-0001-4
環、及嘧啶環等。 作為以上所說明之R2 及R3 中適宜之基之例，可列舉式-A1 -A2 所表示之基。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1～10，更佳為1～6。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1～10，更佳為1～6，尤佳為1～4。 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，鹵化烷基中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R2 及R3 作為取代基而具有之環狀有機基同樣。於A2 為烷氧基羰基之情形時，烷氧基羰基之例與R2 及R3 作為取代基而具有之烷氧基羰基同樣。 作為R2 及R3 之適宜之具體例，可列舉乙基、正丙基、正丁基、正戊基、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R2 及R3 ，上述中適宜之基為乙基、正丙基、正丁基、正戊基、正己基、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。 式(A2-1C)中之R4 為1價有機基或氫原子。1價有機基只要為不阻礙本發明之目的之範圍則無特別限定。 作為R4 之適宜之有機基之例，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、可具有取代基之苯氧基烷基、可具有取代基之苯硫基烷基、N-取代胺基烷基、N,N-二取代胺基烷基、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、可具有取代基之萘氧基烷基、可具有取代基之萘硫基烷基、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
Figure 105127562-A0304-12-0001-4
-1-基等。 又，作為R4 ，亦較佳為環烷基烷基、亦可於芳香環上具有取代基之苯氧基烷基、亦可於芳香環上具有取代基之苯硫基烷基。 於R4 為烷基之情形時，烷基之碳原子數較佳為1～20，更佳為1～6。又，於R4 為烷基之情形時，可為直鏈亦可為支鏈。作為R4 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R4 為烷基之情形時，烷基亦可於碳鏈中含有醚鍵(-O-)。作為於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R4 為烷氧基之情形時，烷氧基之碳原子數較佳為1～20，更佳為1～6。又，於R4 為烷氧基之情形時，可為直鏈亦可為支鏈。作為R4 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R4 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R4 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3～10，更佳為3～6。作為R4 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R4 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R4 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2～21，更佳為2～7。作為R4 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、正十一醯基、正十二醯基、正十三醯基、正十四醯基、正十五醯基、及正十六醯基等。作為R4 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、正十一醯氧基、正十二醯氧基、正十三醯氧基、正十四醯氧基、正十五醯氧基、及正十六醯氧基等。 於R4 為烷氧基羰基之情形時，烷氧基羰基之碳原子數較佳為2～20，更佳為2～7。作為R4 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R4 為苯基烷基之情形時，苯基烷基之碳原子數較佳為7～20，更佳為7～10。又，於R4 為萘基烷基之情形時，萘基烷基之碳原子數較佳為11～20，更佳為11～14。 作為R4 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R4 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R4 為苯基烷基、或萘基烷基之情形時，R4 亦可於苯基、或萘基上進而具有取代基。 於R4 為苯氧基烷基、苯硫基烷基、萘氧基烷基、及萘硫基烷基之情形時，該等基中所含之伸烷基之碳原子數較佳為1～20，更佳為1～6。又，該伸烷基可為直鏈狀亦可為支鏈狀，較佳為直鏈狀。 作為苯氧基烷基之具體例，可列舉2-苯氧基乙基、3-苯氧基-正丙基、4-苯氧基-正丁基、5-苯氧基-正戊基、及6-苯氧基-正己基。 作為苯硫基烷基之具體例，可列舉2-苯硫基乙基、3-苯硫基-正丙基、4-苯硫基-正丁基、5-苯硫基-正戊基、及6-苯硫基-正己基。 作為萘氧基烷基之具體例，可列舉2-(α-萘氧基)乙基、3-(α-萘氧基)-正丙基、4-(α-萘氧基)-正丁基、5-(α-萘氧基)-正戊基、6-(α-萘氧基)-正己基、2-(β-萘氧基)乙基、3-(β-萘氧基)-正丙基、4-(β-萘氧基)-正丁基、5-(β-萘氧基)-正戊基、及6-(β-萘氧基)-正己基。 作為萘硫基烷基之具體例，可列舉2-(α-萘硫基)乙基、3-(α-萘硫基)-正丙基、4-(α-萘硫基)-正丁基、5-(α-萘硫基)-正戊基、6-(α-萘硫基)-正己基、2-(β-萘硫基)乙基、3-(β-萘硫基)-正丙基、4-(β-萘硫基)-正丁基、5-(β-萘硫基)-正戊基、及6-(β-萘硫基)-正己基。 於R4 為苯氧基烷基、苯硫基烷基、萘氧基烷基、或萘硫基烷基之情形時，R4 亦可於苯基、或萘基上進而具有取代基。 於R4 為雜環基之情形時，雜環基為包含1個以上N、S、O之5員或6員之單環，或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，縮合之環數為3以下。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、
Figure 105127562-A0304-12-0001-1
唑、異
Figure 105127562-A0304-12-0001-1
唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、三唑、吡啶、吡
Figure 105127562-A0304-12-0001-4
、嘧啶、嗒
Figure 105127562-A0304-12-0001-4
、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚
Figure 105127562-A0304-12-0001-4
、苯并咪唑、苯并三唑、苯并
Figure 105127562-A0304-12-0001-1
唑、苯并噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞
Figure 105127562-A0304-12-0001-4
、
Figure 105127562-A0304-12-0001-6
啉、喹
Figure 105127562-A0304-12-0001-1
啉、哌啶、哌
Figure 105127562-A0304-12-0001-4
、嗎啉、哌啶、四氫吡喃、及四氫呋喃等。於R4 為雜環基之情形時，雜環基亦可進而具有取代基。 於R4 為雜環基羰基之情形時，雜環基羰基中所含之雜環基與R4 為雜環基之情形同樣。 於R4 為N-取代胺基烷基、或N,N-二取代胺基烷基之情形時，作為與氮原子鍵結之取代基，較佳為有機基。 有機基之適宜例可列舉碳原子數1～20之烷基、碳原子數3～10之環烷基、碳原子數2～21之飽和脂肪族醯基、碳原子數2～21之飽和脂肪族醯氧基、可具有取代基之苯基、可具有取代基之苯甲醯基、可具有取代基之碳原子數7～20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11～20之萘基烷基、及雜環基等。 N-取代烷基、或N,N-二取代胺基烷基中所含之伸烷基之碳原子數較佳為1～20，更佳為1～6。又，該伸烷基可為直鏈狀亦可為支鏈狀。 作為N-取代烷基之具體例，可列舉2-(甲基胺基)乙基、2-(乙基胺基)乙基、2-(正丙基胺基)乙基、2-(正丁基胺基)乙基、3-(甲基胺基)正丙基、3-(乙基胺基)正丙基、3-(正丙基胺基)正丙基、3-(正丁基胺基)正丙基、2-(甲基胺基)正丙基、2-(乙基胺基)正丙基、2-(正丙基胺基)正丙基、2-(正丁基胺基)正丙基、2-(乙醯基胺基)乙基、2-(丙醯基胺基)乙基、2-(乙醯氧基胺基)乙基、2-(丙醯氧基胺基)乙基、3-(乙醯基胺基)正丙基、3-(丙醯基胺基)正丙基、3-(乙醯氧基胺基)正丙基、3-(丙醯氧基胺基)正丙基、2-(乙醯基胺基)正丙基、2-(丙醯基胺基)正丙基、2-(乙醯氧基胺基)正丙基、及2-(丙醯氧基胺基)正丙基。 作為N,N-二取代胺基烷基之具體例，可列舉2-(N,N-二甲基胺基)乙基、2-(N,N-二乙基胺基)乙基、2-(N,N-二正丙基胺基)乙基、2-(N,N-二正丁基胺基)乙基、3-(N,N-二甲基胺基)正丙基、3-(N,N-二乙基胺基)正丙基、3-(N,N-二正丙基胺基)正丙基、3-(N,N-二正丁基胺基)正丙基、2-(N,N-二甲基胺基)正丙基、2-(N,N-二乙基胺基)正丙基、2-(N,N-二正丙基胺基)正丙基、2-(N,N-二正丁基胺基)正丙基、2-(N,N-二乙醯基胺基)乙基、2-(N,N-二丙醯基胺基)乙基、2-(N,N-二乙醯氧基胺基)乙基、2-(N,N-二丙醯氧基胺基)乙基、3-(N,N-二乙醯基胺基)正丙基、3-(N,N-二丙醯基胺基)正丙基、3-(N,N-二乙醯氧基胺基)正丙基、3-(N,N-二丙醯氧基胺基)正丙基、2-(N,N-二乙醯基胺基)正丙基、2-(N,N-二丙醯基胺基)正丙基、2-(N,N-二乙醯氧基胺基)正丙基、2-(N,N-二丙醯氧基胺基)正丙基、2-(N-乙醯基-N-乙醯氧基胺基)乙基、2-(N-丙醯基-N-丙醯氧基胺基)乙基、3-(N-乙醯基-N-乙醯氧基胺基)正丙基、3-(N-丙醯基-N-丙醯氧基胺基)正丙基、2-(N-乙醯基-N-乙醯氧基胺基)正丙基、及2-(N-丙醯基-N-丙醯氧基胺基)正丙基。 作為R4 中所含之苯基、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1～6之烷基、碳原子數1～6之烷氧基、碳原子數2～7之飽和脂肪族醯基、碳原子數2～7之烷氧基羰基、碳原子數2～7之飽和脂肪族醯氧基、具有碳原子數1～6之烷基之單烷基胺基、具有碳原子數1～6之烷基之二烷基胺基、嗎啉-1-基、哌
Figure 105127562-A0304-12-0001-4
-1-基、鹵素、硝基、及氰基等。於R4 中所含之苯基、萘基、及雜環基進而具有取代基之情形時，該取代基數只要為不阻礙本發明之目的之範圍則無限定，較佳為1～4。於R4 中所含之苯基、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。 有機基中，R4 較佳為烷基、環烷基、可具有取代基之苯基、或環烷基烷基、亦可於芳香環上具有取代基之苯硫基烷基。作為烷基，較佳為碳原子數1～20之烷基，更佳為碳原子數1～8之烷基，尤佳為碳原子數1～4之烷基，最佳為甲基。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。環烷基烷基中所含之環烷基之碳原子數較佳為5～10，更佳為5～8，尤佳為5或6。環烷基烷基中所含之伸烷基之碳原子數較佳為1～8，更佳為1～4，尤佳為2。環烷基烷基中，較佳為環戊基乙基。亦可於芳香環上具有取代基之苯硫基烷基中所含之伸烷基之碳原子數較佳為1～8，更佳為1～4，尤佳為2。亦可於芳香環上具有取代基之苯硫基烷基中，較佳為2-(4-氯苯硫基)乙基。 又，作為R4 ，亦較佳為-A3 -CO-O-A4 所表示之基。A3 為2價有機基，較佳為2價之烴基，更佳為伸烷基。A4 為1價有機基，較佳為1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1～10，更佳為1～6，尤佳為1～4。 作為A4 之適宜例，可列舉碳原子數1～10之烷基、碳原子數7～20之芳烷基、及碳原子數6～20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。 式(A2-1C)中，R5 為1價有機基、或氫原子。作為1價有機基，例如為可具有取代基之碳原子數1～11之烷基、或可具有取代基之芳基。作為R5 為烷基之情形時所亦可具有之取代基，可較佳地例示苯基、萘基等。 式(A2-1C)中，作為R5 ，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。 又，式(A2-1C)所表示之化合物中，較佳為下述式(A2-1C-1)或式(A2-1C-2)所表示之化合物。 [化21]
Figure 02_image043
(式(A2-1C-1)及式(A2-1C-2)中，R2 、R3 、R4 、R5 、及n與式(A2-1C)所表示者同義) 又，作為光聚合起始劑(A2)，亦可使用下述式(A2-1N)所表示之化合物。 [化22]
Figure 02_image045
(式(A2-1N)中，R1 、R2 、R4 、R5 、R6 、及n與式(A2-1C)所表示者同義) 又，式(A2-1N)所表示之化合物中，較佳為下述式(A2-1N-1)或(A2-1N-2)所表示之化合物。 [化23]
Figure 02_image047
(式(A2-1N-1)及式(A2-1N-2)中，R2 、R4 、R5 、及n與式(A2-1C)所表示者同義) 作為式(A2-1C)所表示之化合物及式(A2-1N)所表示之化合物之適宜之具體例，可列舉以下之化合物1～化合物71。 [化24]
Figure 02_image049
[化25]
Figure 02_image051
[化26]
Figure 02_image053
[化27]
Figure 02_image055
[化28]
Figure 02_image057
光聚合起始劑(A2)之含量較佳為相對於感光性組合物之固形物成分而言為0.05～2質量%，更佳為0.07～1.9質量%，進而更佳為0.1～1.7質量%，尤佳為0.15～1.5質量%。光聚合起始劑(A2)之含量若為上述範圍內，則所獲得之硬化物維持良好之透過率，所獲得之組合物對於曝光之感度容易變充分。 光聚合起始劑(A2)之含量例如若相對於光聚合起始劑(A)全體而言為0.1～50質量%之範圍即可，較佳為0.5～30質量%，更佳為1～20質量%，進而更佳為1.5～18質量%。 [其他光聚合起始劑(A3)] 感光性組合物亦可於不阻礙本發明之目的之範圍內視需要含有(A1)成分及(A2)成分以外之其他光聚合起始劑(A3)。其他光聚合起始劑(A3)可單獨使用或將2種以上組合而使用。 作為其他光聚合起始劑(A3)之具體例，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(4-二甲基胺基苯基)酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁烷-1-酮、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基],1-(o-乙醯基肟)、2,4,6-三甲基苯甲醯基二苯基氧化膦、4-苯甲醯基-4'-甲基二甲硫醚、4-二甲基胺基苯甲酸、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸丁酯、4-二甲基胺基-2-乙基己基苯甲酸、4-二甲基胺基-2-異戊基苯甲酸、苯偶醯-β-甲氧基乙基縮醛、苯偶醯二甲基縮酮、1-苯基-1,2-丙二酮-2-(o-乙氧基羰基)肟、鄰苯甲醯苯甲酸甲酯、2,4-二乙基-9-氧硫
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
、2-氯-9-氧硫
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
、2,4-二甲基-9-氧硫
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
、1-氯-4-丙氧基-9-氧硫
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
、硫
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
、2-氯硫
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
、2,4-二乙基硫
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
、2-甲基硫
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
、2-異丙基硫
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
、2-乙基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-二苯基蒽醌、偶氮雙異丁腈、過氧化苯甲醯、過氧化異丙苯、2-巰基苯并咪唑、2-巰基苯并
Figure 105127562-A0304-12-0001-1
唑、2-巰基苯并噻唑、2-(鄰氯苯基)-4,5-二苯基咪唑二聚物、2-(鄰氯苯基)-4,5-二(甲氧基苯基)咪唑二聚物、2-(鄰氟苯基)-4,5-二苯基咪唑二聚物、2-(鄰甲氧基苯基)-4,5-二苯基咪唑二聚物、2-(對甲氧基苯基)-4,5-二苯基咪唑二聚物、2,4,5-三芳基咪唑二聚物、二苯甲酮、2-氯二苯甲酮、4,4'-雙(二甲基胺基)二苯甲酮(即，米其勒酮)、4,4'-雙(二乙基胺基)二苯甲酮(即，乙基米其勒酮)、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、安息香乙醚、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、對二甲基胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、對第三丁基苯乙酮、對二甲基胺基苯乙酮、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
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
、2-甲基-9-氧硫
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
、2-異丙基-9-氧硫
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
、二苯并環庚酮、4-二甲基胺基苯甲酸戊酯、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
Figure 105127562-A0304-12-0001-4
、2,4,6-三(三氯甲基)-均三
Figure 105127562-A0304-12-0001-4
、2-甲基-4,6-雙(三氯甲基)-均三
Figure 105127562-A0304-12-0001-4
、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-均三
Figure 105127562-A0304-12-0001-4
、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-均三
Figure 105127562-A0304-12-0001-4
、2-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-4,6-雙(三氯甲基)-均三
Figure 105127562-A0304-12-0001-4
、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-均三
Figure 105127562-A0304-12-0001-4
、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-均三
Figure 105127562-A0304-12-0001-4
、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)-均三
Figure 105127562-A0304-12-0001-4
、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)-均三
Figure 105127562-A0304-12-0001-4
、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯基-均三
Figure 105127562-A0304-12-0001-4
、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯基-均三
Figure 105127562-A0304-12-0001-4
、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯乙烯基苯基-均三
Figure 105127562-A0304-12-0001-4
、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯乙烯基苯基-均三
Figure 105127562-A0304-12-0001-4
等。該等中，就感度之方面而言，尤佳為使用肟系之光聚合起始劑。 於感光性組合物含有(A1)成分及(A2)成分以外之其他光聚合起始劑(A3)之情形時，其他光聚合起始劑(A3)之含量只要為不阻礙本發明之目的之範圍，則無特別限定。於該情形時，其他光聚合起始劑(A3)之含量典型而言相對於感光性組合物中所含之光聚合起始劑之總量而言，較佳為99質量%以下，更佳為50質量%以下，進而更佳為30質量%以下，尤佳為0～10質量%。 ＜聚合性基材成分(B)＞ 本發明之感光性組合物亦可進而含有聚合性基材成分(B)。聚合性基材成分(B)(以下，亦記為「(B)成分」)係對感光性組合物賦予光聚合性與膜形成能力之成分。聚合性基材成分(B)只要為含有可藉由光聚合起始劑(A1)及(A2)而進行聚合之成分且其係能夠製備可形成膜之感光性組合物之成分，則無特別限定。聚合性基材成分(B)可單獨使用或將2種以上組合而使用。 聚合性基材成分(B)典型為包含光聚合性化合物、或光聚合性化合物與樹脂。光聚合性化合物可為低分子化合物，亦可為樹脂之類的高分子化合物。光聚合性化合物及樹脂各自可單獨使用或將2種以上組合而使用。 至於聚合性基材成分(B)，就光聚合性之方面而言，較佳為包含並非聚合物之低分子量光聚合性化合物(以下，亦記為「光聚合性單體」)、及/或含有交聯性基之樹脂。 又，於聚合性基材成分(B)包含樹脂之情形時，就顯影性之觀點而言，較佳為包含鹼可溶性樹脂。鹼可溶性樹脂亦可包含交聯性基。就光聚合性與鹼顯影性之兩者之觀點而言，較佳為包含交聯性基(包含交聯性基作為結構單元中之取代基)之鹼可溶性樹脂。 以下，依序對作為(B)成分中所含之適宜成分的光聚合性單體、含有交聯性基之樹脂、及鹼可溶性樹脂加以說明。 [光聚合性單體] 作為感光性組合物中所含有之光聚合性單體，可較佳地使用具有乙烯性不飽和雙鍵之化合物。該具有乙烯性不飽和雙鍵之化合物中存在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、富馬酸、馬來酸、馬來酸酐、伊康酸、伊康酸酐、檸康酸、檸康酸酐、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、二甲基胺基(甲基)丙烯酸酯、(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或將2種以上組合而使用。 另一方面，作為多官能單體，可列舉1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、1,12-十二烷二醇二(甲基)丙烯酸酯、乙氧基化己二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、二季戊四醇二(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、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、乙氧基化新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚(伸乙基-伸丙基)二醇二(甲基)丙烯酸酯、聚丁二醇二(甲基)丙烯酸酯、乙氧基化雙酚A二(甲基)丙烯酸酯、丙氧基化雙酚A二(甲基)丙烯酸酯、丙氧基化乙氧基化雙酚A二(甲基)丙烯酸酯、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及六亞甲基二異氰酸酯等與 (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、三丙烯醯基縮甲醛、2,4,6-三側氧基六氫-1,3,5-三
Figure 105127562-A0304-12-0001-4
-1,3,5-三乙醇三丙烯酸酯、及2,4,6-三側氧基六氫-1,3,5-三
Figure 105127562-A0304-12-0001-4
-1,3,5-三乙醇二丙烯酸酯等。該等多官能單體可單獨使用或將2種以上組合而使用。 該等具有乙烯性不飽和雙鍵之化合物中，自獲得可提供強度、對基板之密接性優異之硬化物的感光性組合物之方面而言，較佳為3官能以上之多官能單體。 就控制玻璃轉移點(Tg)之觀點而言，可與3官能以上之多官能單體併用而使用單官能單體或2官能單體，該等中亦較佳為1,6-己二醇二(甲基)丙烯酸酯。 光聚合性單體之含量為相對於感光性組合物之固形物成分而言較佳為5～60質量%，更佳為10～50質量%。藉由將感光性組合物中之光聚合性單體之含量設為上述範圍，存在容易獲得感光性組合物之感度、顯影性、及解像性之平衡之傾向。 [含有交聯性基之樹脂] 本發明之感光性組合物若含有含有交聯性基之樹脂，則存在變得更容易使用該感光性組合物而形成硬化物之傾向。含有交聯性基之樹脂係具有交聯性基之樹脂，較佳為包含源自具有交聯性基之(甲基)丙烯酸酯之單元者。作為交聯性基，若為主要可藉由加熱而進行含有交聯性基之樹脂之交聯之官能基，則無特別限定，較佳為環氧基、乙烯性不飽和雙鍵。交聯性基例如可藉由包含由源自具有環氧基之(甲基)丙烯酸酯之單元及具有乙烯性不飽和雙鍵之單元所組成之群中的至少1種而導入至含有交聯性基之樹脂中。 作為含有交聯性基之樹脂，較佳為包含源自具有環氧基之(甲基)丙烯酸酯之單元的樹脂。藉由具有該單元，亦可提高使用感光性組合物所形成之絕緣膜對基材上之密接性或機械強度。 具有環氧基之(甲基)丙烯酸酯可為具有鏈狀脂肪族環氧基之(甲基)丙烯酸酯，亦可為如下述之具有脂環式環氧基之(甲基)丙烯酸酯。 具有環氧基之(甲基)丙烯酸酯亦可具有芳香族基。於本說明書中，芳香族基係具有芳香環之基。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、且具有環氧基之(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。 於使用感光性組合物所形成之膜要求透明性之情形時，具有環氧基之(甲基)丙烯酸較佳為不具有芳香族基者。 作為具有鏈狀脂肪族環氧基之(甲基)丙烯酸酯之例，可列舉(甲基)丙烯酸環氧基烷基酯、及(甲基)丙烯酸環氧基烷氧基烷基酯等之類的於酯基(-O-CO-)中之氧基(-O-)上鍵結有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亦可於鏈中含有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3～20，更佳為3～15，尤佳為3～10。 作為具有鏈狀脂肪族環氧基之(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-環氧基丁酯、(甲基)丙烯酸6,7-環氧基庚酯等(甲基)丙烯酸環氧基烷基酯；(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)丙烯酸環氧基烷氧基烷基酯。 作為具有脂環式環氧基之(甲基)丙烯酸酯之具體例，例如可列舉下述式(d2-1)～(d2-16)所表示之化合物。該等中，為了使感光性組合物之顯影性變適度，較佳為下述式(d2-1)～(d2-6)所表示之化合物，更佳為下述式(d2-1)～(d2-4)所表示之化合物。 又，關於該等各化合物，酯基之氧原子對於脂環之鍵結部位並不限於此處所示者，亦可包含部分位置異構物。 [化29]
Figure 02_image059
上述式中，Rd4 表示氫原子或甲基，Rd5 表示碳數1～6之2價之脂肪族飽和烴基，Rd6 表示碳數1～10之2價之烴基，n表示0～10之整數。作為Rd5 ，較佳為直鏈狀或支鏈狀之伸烷基，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。作為Rd6 ，例如較佳為亞甲基、伸乙基、伸丙基、四亞甲基、乙基伸乙基、五亞甲基、六亞甲基、伸苯基、伸環己基、-CH2 -Ph-CH2 -(Ph表示伸苯基)。 具有環氧基之(甲基)丙烯酸酯若為如上所述之具有脂環式環氧基之(甲基)丙烯酸酯，則與具有鏈狀脂肪族環氧基之(甲基)丙烯酸酯相比而言，含有源自該(甲基)丙烯酸酯之單元的含有交聯性基之樹脂、進而感光性組合物之保管穩定性優異，且於形成絕緣膜等時可預烘烤之溫度之範圍(預烘烤溫度餘裕)變廣，因此較佳。 含有交聯性基之樹脂而且亦可為包含具有乙烯性不飽和雙鍵作為交聯性基之單元的樹脂(於本說明書中，亦稱為「具有乙烯性不飽和雙鍵之樹脂」)。該乙烯性不飽和雙鍵較佳為構成(甲基)丙烯醯氧基之一部分。 作為具有乙烯性不飽和雙鍵之樹脂，例如可列舉具有(甲基)丙烯醯氧基之樹脂。 具有(甲基)丙烯醯氧基之樹脂例如可藉由如下方式而製備：使包含源自不飽和羧酸之單元的聚合物中所含之羧基之至少一部分，與上述具有脂環式環氧基之(甲基)丙烯酸酯及/或上述具有鏈狀脂肪族環氧基之(甲基)丙烯酸酯反應。 於含有交聯性基之樹脂為具有乙烯性不飽和雙鍵之樹脂之情形時，亦可為具有光聚合性者。由於含有交聯性基之樹脂含有該具有乙烯性不飽和雙鍵之光聚合性樹脂，因此可使感光性組合物之硬化性提高，使圖案形成變容易。 於含有交聯性基之樹脂中，相對於該樹脂之質量而言，源自具有交聯性基之(甲基)丙烯酸酯的單元之量較佳為20～80質量%，更佳為30～70質量%，進而更佳為33～65質量%；源自具有環氧基之(甲基)丙烯酸酯之單元之量較佳為10～80質量%，更佳為15～70質量%，進而更佳為20～65質量%；具有乙烯性不飽和雙鍵之單元之量較佳為15～40質量%，更佳為20～35質量%。作為含有交聯性基之樹脂，較佳為選自(甲基)丙烯酸及(甲基)丙烯酸酯之1種以上單體之聚合物，於該聚合物之情形時，該聚合物中之源自具有交聯性基之(甲基)丙烯酸酯之單元之含量亦相對於樹脂之質量而言與上述同樣。 含有交聯性基之樹脂亦可為包含源自具有環氧基之(甲基)丙烯酸酯之單元、具有乙烯性不飽和雙鍵之單元之兩者之樹脂，但亦可為包含源自具有環氧基之(甲基)丙烯酸酯之單元或具有乙烯性不飽和雙鍵之單元之任一者之樹脂，較佳為僅僅包含源自具有環氧基之(甲基)丙烯酸酯之單元作為交聯性基之樹脂。 含有交聯性基之樹脂較佳為具有交聯性基之樹脂，且其係鹼可溶性樹脂。感光性組合物藉由調配該鹼可溶性樹脂，可對感光性組合物賦予鹼顯影性。 於本說明書中，所謂鹼可溶性樹脂係指藉由樹脂濃度為20質量%之樹脂溶液(溶劑：丙二醇單甲醚乙酸酯)而於基板上形成膜厚為1 μm之樹脂膜，於濃度為0.05質量%之KOH水溶液中浸漬1分鐘時，膜厚溶解0.01 μm以上者。 於含有交聯性基之樹脂亦為鹼可溶性樹脂之情形時，通常具有鹼可溶性基。作為鹼可溶性基，若為對含有交聯性基之樹脂賦予對於上述鹼之溶解性之官能基，則無特別限定，較佳為羧基或去保護而產生羧基之基，例如可藉由含有下述之源自不飽和羧酸之單元，而且藉由使包含賦予鹼可溶性基之(甲基)丙烯酸酯之單體聚合，可將其導入至含有交聯性基之樹脂。於本說明書中，賦予鹼可溶性基之(甲基)丙烯酸酯可設為並不含有上述具有交聯性基之(甲基)丙烯酸酯者。 作為含有交聯性基之樹脂，於亦為鹼可溶性樹脂之情形時，亦可為不具有如下官能基之樹脂，上述官能基係抑制或抑止含有交聯性基之樹脂對於上述鹼之溶解性之官能基(以下，有時稱為「鹼溶解抑止基」或「溶解抑止基」)，但較佳為具有鹼可溶性基及溶解抑止基之樹脂。至於溶解抑止基，於具有使含有交聯性基之樹脂對於鹼之溶解性降低之功能之方面而言，亦可稱為鹼難溶解性基。含有交聯性基之樹脂具有鹼可溶性基及溶解抑止基，因此可調整對於鹼之溶解性，藉此可調整感光性組合物之鹼顯影性。作為溶解抑止基，例如可列舉下述之苯乙烯或苯乙烯衍生物；不飽和醯亞胺類；具有脂環式骨架之(甲基)丙烯酸酯(其中，具有環氧基者除外)；(甲基)丙烯酸苄酯等具有芳香族基之(甲基)丙烯酸酯等。於本說明書中，賦予溶解抑止基之(甲基)丙烯酸酯並不包含上述具有交聯性基之(甲基)丙烯酸酯。 含有交聯性基之樹脂中，自製膜性優異之方面，或容易藉由選擇單體而調整樹脂之特性等考慮，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；馬來酸、富馬酸、檸康酸、中康酸、伊康酸、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的烯丙基化合物；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、羥基乙基乙烯基醚、二乙二醇乙烯醚、二甲基胺基乙基乙烯基醚、二乙基胺基乙基乙烯基醚、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、及乙烯基蒽基醚之類的乙烯醚；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、乙酸乙烯基苯酯、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的乙烯酯；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的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1-二十烯之類的烯烴；馬來醯亞胺、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺等不飽和醯亞胺類。 於含有交聯性基之樹脂為具有乙烯性不飽和雙鍵之單體之聚合物之情形時，通常包含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；馬來酸、富馬酸、檸康酸、中康酸、伊康酸、該等二羧酸之酸酐。作為鹼可溶性樹脂而使用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，若使樹脂具有所需之鹼可溶性，則無特別限定。作為鹼可溶性樹脂而使用之樹脂中之源自不飽和羧酸之單元之量係相對於樹脂之質量而言較佳為5～25質量%，更佳為8～16質量%，於含有交聯性基之樹脂具有下述之溶解抑止基之情形時，該等量特佳。於含有交聯性基之樹脂不具有下述之溶解抑止基之情形時，該樹脂中之源自不飽和羧酸之單元之量係相對於樹脂之質量而言較佳為50～80質量%，更佳為60～70質量%。 於作為選自以上所例示之單體之1種以上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)丙烯酸酯之1種以上單體之聚合物。以下，關於選自(甲基)丙烯酸及(甲基)丙烯酸酯之1種以上單體之聚合物而加以說明。 選自(甲基)丙烯酸及(甲基)丙烯酸酯之1種以上單體之聚合物之製備中所使用的(甲基)丙烯酸酯只要為不阻礙本發明之目的之範圍則無特別限定，則可自公知之(甲基)丙烯酸酯中適宜選擇。 作為(甲基)丙烯酸酯之適宜例，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)丙烯酸糠酯；(甲基)丙烯酸苄酯等具有芳香族基之(甲基)丙烯酸酯；具有脂環式骨架之(甲基)丙烯酸酯。關於具有脂環式骨架之(甲基)丙烯酸酯之詳細如後所述。 又，於選自(甲基)丙烯酸及(甲基)丙烯酸酯之1種以上單體之聚合物中，自容易使用感光性組合物而形成透過率高之絕緣膜考慮，包含源自具有脂環式骨架之(甲基)丙烯酸酯之單元的樹脂亦較佳。於本說明書中，具有脂環式骨架之(甲基)丙烯酸酯並不包含上述具有交聯性基之(甲基)丙烯酸酯。 於具有脂環式骨架之(甲基)丙烯酸酯中，具有脂環式骨架之基較佳為具有脂環式烴基之基。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
Figure 105127562-A0304-03-0013-01
基、異
Figure 105127562-A0304-03-0013-01
基、三環壬基、三環癸基、四環十二烷基等。 作為具有脂環式骨架之(甲基)丙烯酸酯中的具有脂環式烴基之(甲基)丙烯酸酯，例如可列舉下述式(d1-1)～(d1-8)所表示之化合物。於該等中，較佳為下述式(d1-3)～(d1-8)所表示之化合物，更佳為下述式(d1-3)或(d1-4)所表示之化合物。 [化30]
Figure 02_image061
上述式中，Rd1 表示氫原子或甲基，Rd2 表示單鍵或碳原子數1～6之2價之脂肪族飽和烴基，Rd3 表示氫原子或碳原子數1～5之烷基。作為Rd2 ，較佳為單鍵、直鏈狀或支鏈狀之伸烷基，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。作為Rd3 ，較佳為甲基、乙基。 含有交聯性基之樹脂較佳為包含如下單元之樹脂：源自選自(甲基)丙烯酸及(甲基)丙烯酸酯之1種以上單體之單元、源自具有脂環式環氧基之(甲基)丙烯酸酯之單元。該樹脂亦可為進而包含源自具有脂環式骨架之(甲基)丙烯酸酯之單元之樹脂，於該情形時，樹脂中之源自具有脂環式骨架之(甲基)丙烯酸酯之單元之量可為10～35質量%，亦可為15～30質量%，亦可為20～25質量%。 又，包含源自具有脂環式骨架之(甲基)丙烯酸酯之單元的選自(甲基)丙烯酸及(甲基)丙烯酸酯之1種以上單體之聚合物中，較佳為包含源自(甲基)丙烯酸之單元、源自具有脂環式環氧基之 (甲基)丙烯酸酯之單元之樹脂。使用含有此種含有交聯性基之樹脂的感光性組合物所形成之膜對於基材之密接性優異。又，於使用此種樹脂之情形時，可能產生樹脂中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，則可藉由使用對膜進行加熱之方法等，產生羧基與脂環式環氧基之自反應，從而使所形成之膜之硬度之類的機械物性提高。 於含有源自(甲基)丙烯酸之單元(具有交聯性基者除外)、源自具有脂環式環氧基之(甲基)丙烯酸酯之單元的樹脂中，樹脂中之源自前者(甲基)丙烯酸之單元之量較佳為1～95質量%，更佳為10～70質量%。於含有該源自(甲基)丙烯酸之單元、源自具有脂環式環氧基之(甲基)丙烯酸酯之單元的樹脂中，樹脂中之源自具有脂環式環氧基之(甲基)丙烯酸酯之單元的量較佳為1～95質量%，更佳為10～50質量%。 於包含源自(甲基)丙烯酸之單元、源自具有脂環式環氧基之(甲基)丙烯酸酯之單元的選自(甲基)丙烯酸及(甲基)丙烯酸酯之1種以上單體之聚合物中，亦可為包含源自(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、源自具有脂環式環氧基之(甲基)丙烯酸酯之單元的樹脂。 於包含源自(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、源自具有脂環式環氧基之(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1～95質量%，更佳為10～50質量%。於包含源自(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、源自具有脂環式環氧基之(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)丙烯酸酯之單元之量較佳為1～95質量%，更佳為10～70質量%。於包含源自(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、源自具有脂環式環氧基之(甲基)丙烯酸酯之單元的樹脂中，樹脂中之源自具有脂環式環氧基之(甲基)丙烯酸酯之單元之量較佳為1～95質量%，更佳為30～80質量%。 含有交聯性基之樹脂之質量平均分子量(Mw：凝膠滲透層析法(GPC)之聚苯乙烯換算之測定值。於本說明書相同)較佳為2000～200000，更佳為2000～18000。藉由設為上述之範圍，存在容易獲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。 感光性組合物中的含有交聯性基之樹脂之含量為於感光性組合物之固形物成分中較佳為15～95質量%，更佳為35～85質量%，尤佳為50～70質量%。 [鹼可溶性樹脂] 鹼可溶性樹脂可自先前起便調配於各種感光性組合物中之樹脂中適宜選擇。再者，於本說明書中，於鹼可溶性樹脂中不含上述之含有交聯性基之樹脂。雖然存在可藉由於感光性組合物中調配鹼可溶性樹脂而提高感光性組合物之鹼顯影性之情形，但本發明之感光性組合物即使不含鹼可溶性樹脂，亦可藉由使用亦為鹼可溶性樹脂之上述含有交聯性基之樹脂而具有鹼顯影性。 作為適宜之鹼可溶性樹脂，可列舉含有於主鏈具有環結構之結構單元的聚合物。再者，於本說明書中，於含有於主鏈具有環結構之結構單元的聚合物中，並不包含具有不飽和鍵之單體之聚合物。 以下，關於含有於主鏈具有環結構之結構單元的聚合物而加以說明。 (含有於主鏈具有環結構之結構單元的聚合物) 含有於主鏈具有環結構之結構單元的聚合物若為具有特定之環結構且具有特定之鹼可溶性之樹脂，則無特別限定。作為含有於主鏈具有環結構之結構單元的聚合物之適宜例，可列舉含有源自馬來醯亞胺之結構單元(以下，亦稱為「結構單元(A2a)」)之聚合物(以下，亦稱為「聚合物(A2)」)及含有下述式(A-1)所表示之結構單元(以下，亦稱為「結構單元(A1a)」)之聚合物(以下，亦稱為「聚合物(A1)」)。 作為聚合物(A2)所具有之源自馬來醯亞胺之結構單元(A2a)，若為使具有馬來醯亞胺骨架之單體聚合而獲得者，則無特別限定。作為具有馬來醯亞胺骨架之單體，例如可列舉N-苄基馬來醯亞胺、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺等。 特別是包含聚合物(A1)之感光性組合物對於顯影液之溶解性良好，上述聚合物(A1)含有於主鏈具有環結構之結構單元(A1a)。 [化31]
Figure 02_image063
式(A-1)中，環A為具有1個氧原子作為環構成原子之碳數4～6之飽和脂肪族環式基。環A較佳為具有1個氧原子作為環構成原子之碳數4或5之飽和脂肪族環式基，更佳為四氫呋喃環或四氫吡喃環，進而更佳為下述式(A-3)所表示之結構單元(以下，亦稱為「結構單元(A1a1)」)中之四氫吡喃環或下述式(A-4)所表示之結構單元(以下，亦稱為「結構單元(A1a2)」)中之四氫呋喃環。 [化32]
Figure 02_image065
於主鏈含有上述式(A-1)所表示之結構單元的聚合物(聚合物(A1))通常於主鏈含有複數個上述式(A-1)所表示之結構單元(結構單元(A1a))。於複數個結構單元(A1a)中，各結構單元(A1a)中所含有之環A於構成聚合物(A1)之一個主鏈中可相互相同亦可不同。具體而言，構成聚合物(A1)之一個主鏈例如可僅僅具有上述式(A-3)所表示之結構單元作為該主鏈所含有之上述式(A-1)所表示之結構單元，亦可僅僅具有上述式(A-4)所表示之結構單元作為該主鏈所含有之上述式(A-1)所表示之結構單元，亦可並有上述式(A-3)所表示之結構單元與上述式(A-4)所表示之結構單元作為該主鏈所含有之上述式(A-1)所表示之結構單元。 上述式(A-1)、式(A-3)及式(A-4)中，Rb1 及Rb2 分別獨立為氫原子或-COORb3 ，Rb3 分別獨立為氫原子或可具有取代基之碳數1～25之烴基。Rb1 及Rb2 較佳為-COORb3 。於構成含有上述式(A-1)所表示之結構單元的聚合物(聚合物(A1))之一個主鏈含有複數個環A之情形時，與各環A鍵結之-COORb3 分別獨立，作為-COORb3 而相同或不同之基亦可鍵結於各環A上。 作為Rb1 及Rb2 所表示之可具有取代基之碳數1～25之烴基，並無特別限制。作為烴基之具體例，可列舉甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、第三戊基、硬脂基、月桂基、2-乙基己基等直鏈狀或分支狀之烷基；苯基等芳基；環己基、第三丁基環己基、二環戊二烯基、三環癸基、異
Figure 105127562-A0304-03-0013-01
基、金剛烷基、2-甲基-2-金剛烷基等脂環式基；1-甲氧基乙基、1-乙氧基乙基等經烷氧基取代之烷基；苄基等經芳基取代之烷基等。 於Rb1 及Rb2 為烴基之情形時，烴基之碳原子數較佳為8以下。作為碳原子數為8以下之烴基，自難以由於酸或熱而脫離考慮，較佳為烴基所具有之單末端自由之鍵結鍵與一級碳原子或二級碳原子鍵結之烴基。作為此種烴基，較佳為碳原子數為1～8之直鏈狀或支鏈狀之烷基，較佳為碳原子數為1～5之直鏈狀或支鏈狀之烷基。 作為此種烴基之具體例，可列舉甲基、乙基、環己基、苄基等，較佳為甲基。 於構成含有上述式(A-1)所表示之結構單元(結構單元(A1a))之聚合物(聚合物(A1))的一個主鏈含有複數個結構單元(A1a)之情形時，各結構單元(A1a)上所鍵結之Rb1 及Rb2 於各結構單元(A1a)間可相同亦可不同。 於含有該各結構單元(A1a)間相同或不同之環A之情形時，Rb1 及Rb2 並不依存於所鍵結之各環A之種類而相互獨立。 具體而言，於構成聚合物(A1)之一個主鏈含有複數個上述式(A-3)所表示之結構單元(結構單元(A1a1))之情形時，各結構單元(A1a1)中之Rb1 及Rb2 於各結構單元(A1a1)間可相同亦可不同。 於構成聚合物(A1)之一個主鏈含有複數個上述式(A-4)所表示之結構單元(結構單元(A1a2))之情形時，各結構單元(A1a2)中之Rb1 及Rb2 於各結構單元(A1a2)間可相同亦可不同。 進而，於構成聚合物(A1)之一個主鏈含有上述式(A-3)所表示之結構單元(結構單元(A1a1))與上述式(A-4)所表示之結構單元(結構單元(A1a2))之情形時，各結構單元(A1a1)中之Rb1 及Rb2 與各結構單元(A1a2)中之Rb1 及Rb2 可相同亦可不同。 上述式(A-3)所表示之結構單元(結構單元(A1a1))亦可為下述式(A-5)所表示之重複單元(以下亦稱為「重複單元(ar1)」)之一部分。上述式(A-4)所表示之結構單元(結構單元(A1a2))亦可為下述式(A-6)所表示之重複單元(以下亦稱為「重複單元(ar2)」)之一部分。 [化33]
Figure 02_image067
(式(A-5)及式(A-6)中，Rb1 及Rb2 分別獨立地與上述同樣) 作為提供上述式(A-5)及(A-6)所表示之各重複單元之單體，例如可列舉下述式所表示之1,6-二烯類。 [化34]
Figure 02_image069
(上述式中，Rb3 分別獨立地與上述同樣) 於提供於主鏈含有上述式(A-1)所表示之結構單元(結構單元(A1a))之聚合物(聚合物(A1))的單體組合物中，提供含有結構單元(A1a)之重複單元(可含有上述結構單元(A1a1)及結構單元(A1a2))的單體(A1ma)之含有比例係相對於單體組合物中之單體之總量而言較佳為1質量%～60質量%，更佳為5質量%～50質量%，尤佳為10質量%～40質量%。 聚合物(A1)較佳為於側鏈具有酸基之重複單元(A1b)。聚合物(A1)若具有於側鏈具有酸基之重複單元(A1b)，則可獲得鹼顯影性優異之感光性組合物。作為變得構成於側鏈具有酸基之重複單元(A1b)的單體(A1mb)，例如可列舉(甲基)丙烯酸、2-(甲基)丙烯醯氧基乙基丁二酸、伊康酸、ω-羧基-聚己內酯單丙烯酸酯等具有羧基之單體；馬來酸酐、伊康酸酐等具有羧酸酐基之單體等。其中較佳為(甲基)丙烯酸。 於提供聚合物(A1)之單體組合物中，變得構成於側鏈具有酸基之重複單元(A1b)的單體(A1mb)之含有比例係相對於單體組合物中之單體之總量而言較佳為1質量%～50質量%，更佳為5質量%～40質量%，進而更佳為10質量%～35質量%。 較佳為聚合物(A1)具有於側鏈具有碳雙鍵之重複單元(A1c)。於側鏈具有碳雙鍵之重複單元(A1c)可藉由如下方式而獲得：以於側鏈具有酸基之重複單元(A1b)之酸基之一部分或全部(較佳為一部分)為反應點，加成具有碳雙鍵之化合物。 於側鏈具有酸基之重複單元(A1b)之酸基為羧基之情形時，作為具有碳雙鍵之化合物，可使用具有環氧基與雙鍵之化合物、具有異氰酸酯基與雙鍵之化合物等。作為具有環氧基與雙鍵之化合物，例如可列舉(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧環己基甲酯、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、丙烯酸4-羥基丁酯縮水甘油醚等。作為具有異氰酸酯基與雙鍵之化合物，可列舉(甲基)丙烯酸2-異氰酸酯基乙酯等。於側鏈具有酸基之重複單元(A1b)之酸基為羧酸酐基之情形時，作為具有碳雙鍵之化合物，可使用具有羥基與雙鍵之化合物。作為具有羥基與雙鍵之化合物，例如可列舉(甲基)丙烯酸2-羥基乙酯等。 聚合物(A1)可進而具有其他重複單元(A1e)，上述其他重複單元(A1e)係源自可與上述單體(A1ma)、單體(A1mb)及/或單體(A1mc)共聚之其他單體(A1me)者。 作為其他單體(A1me)，例如亦可為進而具有於側鏈具有2個以上氧基伸烷基的重複單元者。作為於側鏈具有2個以上之氧基伸烷基的重複單元，例如可列舉下述式所表示之重複單元。 [化35]
Figure 02_image071
上述式中，Rb7 、Rb8 及Rb9 分別獨立為氫原子或甲基，較佳為氫原子。Rb10 為碳數為1～20之直鏈狀或分支狀之烷基、碳數為2～20之直鏈狀或分支狀之烯基或碳數為6～20之芳香族烴基，較佳為氫原子、碳數為1～20之直鏈狀之烷基、碳數為2～20之直鏈狀之烯基或碳數為6～20之芳香族烴基，更佳為碳數為1～10之直鏈狀之烷基或碳數為6～12之芳香族烴基，進而更佳為碳數為1～5之直鏈狀之烷基、苯基或聯苯基，尤佳為甲基、苯基或聯苯基。再者，烷基、烯基及芳香族烴基亦可具有取代基。AO表示氧基伸烷基。AO所表示之氧基伸烷基之碳數為2～20，較佳為2～10，更佳為2～5，進而更佳為2。於側鏈具有2個以上氧基伸烷基之重複單元可含有1種或2種以上氧基伸烷基。x表示0～2之整數。y表示0或1。z表示氧基伸烷基之平均加成莫耳數，為2以上，較佳為2～100，更佳為2～50，進而更佳為2～15。 於側鏈具有2個以上氧基伸烷基之重複單元係由於側鏈具有2個以上氧基伸烷基之單體而構成。作為該單體，例如可列舉下述式所表示之單體。 [化36]
Figure 02_image073
(上述式中，Rb7 、Rb8 、Rb9 、Rb10 、AO、x、y及z如上述說明那樣) 作為上述於側鏈具有2個以上氧基伸烷基之單體，例如可列舉乙氧基化鄰苯基苯酚(甲基)丙烯酸酯(EO為2莫耳)、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯(EO為4莫耳)、甲氧基聚乙二醇(甲基)丙烯酸酯(EO為9莫耳)、甲氧基聚乙二醇(甲基)丙烯酸酯(EO為13莫耳)、甲氧基三乙二醇(甲基)丙烯酸酯、乙氧基二乙二醇(甲基)丙烯酸酯、丁氧基二乙二醇(甲基)丙烯酸酯、2-乙基己基二乙二醇(甲基)丙烯酸酯、甲氧基二丙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯、壬基苯氧基聚乙二醇(甲基)丙烯酸酯(EO為4-17莫耳)、壬基苯氧基聚丙二醇(甲基)丙烯酸酯(PO為5莫耳)、EO改性甲酚(甲基)丙烯酸酯(EO為2莫耳)等。該等單體可單獨使用或將2種以上組合而使用。其中較佳為乙氧基化鄰苯基苯酚(甲基)丙烯酸酯(EO為2莫耳)、甲氧基聚乙二醇(甲基)丙烯酸酯(EO為9莫耳)、甲氧基聚乙二醇(甲基)丙烯酸酯(EO為13莫耳)。進而更佳為乙氧基化鄰苯基苯酚丙烯酸酯(EO為2莫耳)、甲氧基聚乙二醇丙烯酸酯(EO為9莫耳)、甲氧基聚乙二醇丙烯酸酯(EO為13莫耳)。再者，於本說明書中，例如「EO為2莫耳」、「PO為5莫耳」等記法係表示氧基伸烷基之平均加成莫耳數。 作為其他單體(A1me)，而且例如可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸苯酯、 (甲基)丙烯酸聯苯酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯、丁氧基乙二醇(甲基)丙烯酸酯、2-乙基己基乙二醇(甲基)丙烯酸酯、甲氧基丙二醇(甲基)丙烯酸酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸聯苯氧基乙酯、(甲基)丙烯酸二環戊基酯、(甲基)丙烯酸三環癸酯、(甲基)丙烯酸二環戊氧基乙酯、(甲基)丙烯酸三環癸氧基乙酯、壬基苯氧基乙二醇(甲基)丙烯酸酯、壬基苯氧基丙二醇、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-羥基乙酯、乙氧基化鄰苯基苯酚(甲基)丙烯酸酯等(甲基)丙烯酸酯類；(甲基)丙烯醯基嗎啉((甲基)丙烯酸嗎啉基酯)、(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-異丁基(甲基)丙烯醯胺、N-第三丁基(甲基)丙烯醯胺、N-第三辛基(甲基)丙烯醯胺、雙丙酮(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、N-羥基乙基(甲基)丙烯醯胺、N-環己基(甲基)丙烯醯胺、N-苯基(甲基)丙烯醯胺、N-苄基(甲基)丙烯醯胺、N-三苯基甲基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺等(甲基)丙烯醯胺類；苯乙烯、乙烯基甲苯、α-甲基苯乙烯等芳香族乙烯基化合物；丁二烯、異戊二烯等丁二烯或經取代之丁二烯化合物；乙烯、丙烯、氯乙烯、丙烯腈等乙烯或經取代之乙烯化合物；乙酸乙烯酯等乙烯酯類等。該等單體可單獨或將2種以上組合而使用。 於提供聚合物(A1)之單體組合物中，提供其他重複單元(A1e)之單體(A1me)之含有比例係相對於單體組合物中之單體之總量而言較佳為0質量%～55質量%，更佳為5質量%～50質量%，進而更佳為10質量%～45質量%。 聚合物(A1)可為無規共聚物，亦可為嵌段共聚物。作為聚合物(A1)，可單獨使用或將2種以上組合而使用。 聚合物(A1)之重量平均分子量較佳為藉由利用四氫呋喃(THF)溶劑之凝膠滲透層析法(GPC)所測得之值較佳為3,000～200,000，更佳為3,500～100,000，進而更佳為4,000～50,000。若為此種範圍，則可獲得確保耐熱性、且具有適合形成塗膜之黏度之感光性組合物。 聚合物(A1)可藉由任意適宜之方法使提供聚合物(A1)之單體組合物聚合而獲得。作為聚合方法，例如可列舉溶液聚合法。 提供聚合物(A1)之單體組合物可含有任意適宜之溶劑。作為溶劑，例如可列舉四氫呋喃、二
Figure 105127562-A0304-12-0001-1
烷、乙二醇二甲醚、二乙二醇二甲醚、丙二醇單甲醚等醚類；丙酮、甲基乙基酮等酮類；乙酸乙酯、乙酸丁酯、丙二醇單甲醚乙酸酯、乙酸3-甲氧基丁酯等酯類；甲醇、乙醇等醇類；甲苯、二甲苯、乙基苯等芳香族烴類；氯仿；二甲基亞碸等。該等溶劑可單獨使用或將2種以上組合而使用。上述單體組合物聚合時之聚合濃度較佳為5質量%～90質量%，更佳為5質量%～50質量%，進而更佳為10質量%～50質量%。 提供聚合物(A1)之單體組合物可含有任意適宜之聚合起始劑。作為聚合起始劑，例如可列舉氫過氧化異丙苯、氫過氧化二異丙基苯、過氧化二第三丁基、過氧化月桂醯、過氧化苯甲醯、過氧化異丙基碳酸第三丁酯、過氧-2-乙基己酸第三戊酯、過氧-2-乙基己酸第三丁酯等有機過氧化物；2,2'-偶氮雙(異丁腈)、1,1'-偶氮雙(環己甲腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(2-甲基丙酸)二甲酯等偶氮化合物等。聚合起始劑之含有比例係相對於單體組合物中之所有單體100質量份而言較佳為0.1質量份～15質量份，更佳為0.5質量份～10質量份。 藉由溶液聚合法使聚合物(A1)聚合時之聚合溫度較佳為40℃～150℃，更佳為60℃～130℃。 於獲得具有於側鏈具有碳雙鍵之重複單元(A1c)的聚合物(A1)之情形時，於上述聚合後，於所獲得之聚合物上加成上述具有碳雙鍵之化合物。作為加成具有碳雙鍵之化合物之方法，可採用任意適宜之方法。例如，於聚合抑制劑及觸媒之存在下，使具有碳雙鍵之化合物與於側鏈具有酸基之重複單元(A1b)之酸基之一部分或全部(較佳為一部分)反應而進行，藉此可形成於側鏈具有碳雙鍵之重複單元(A1c)。 上述具有碳雙鍵之化合物之加成量係相對於上述聚合後之聚合物(即，加成具有碳雙鍵之化合物之前之聚合物)100質量份而言較佳為5質量份以上，更佳為10質量份以上，進而更佳為15質量份以上，尤佳為20質量份以上。若為此種範圍，則可獲得曝光感度優異之感光性組合物。若使用此種感光性組合物，則存在容易形成緻密之硬化塗膜，獲得基板密接性亦優異之圖案之傾向。又，具有碳雙鍵之化合物之加成量若為上述範圍，則可藉由具有碳雙鍵之化合物之加成而充分地生成羥基，獲得對於鹼性顯影液之溶解性優異之感光性組合物。上述具有碳雙鍵之化合物之加成量之上限係相對於上述聚合後之聚合物(即，加成具有碳雙鍵之化合物之前之聚合物)100質量份而言較佳為170質量份以下，更佳為150質量份以下，進而更佳為140質量份以下。具有碳雙鍵之化合物之加成量若為上述範圍內，則可維持感光性組合物之保存穩定性及溶解性。 作為聚合抑制劑，例如可列舉6-第三丁基-2,4-二甲苯酚等烷基酚化合物。作為觸媒，例如可列舉二甲基苄基胺、三乙基胺等三級胺。 以上所說明之鹼可溶性樹脂亦可與含有於主鏈具有環結構之結構單元的聚合物一同含有該聚合物以外之樹脂。 感光性組合物中之鹼可溶性樹脂之含量為相對於感光性組合物之固形物成分之質量而言較佳為40質量%以下，更佳為30～10質量%，尤佳為25～15質量%。又，聚合性基材成分(B)中之鹼可溶性樹脂之含量較佳為80質量%以下，更佳為60～20質量%，尤佳為50～30質量%。 ＜其他成分＞ 於本發明之感光性組合物中可視需要含有各種添加劑。具體而言，可例示溶劑、表面調整劑、增感劑、硬化促進劑、光交聯劑、光敏劑、分散助劑、填充劑、密接促進劑、抗氧化劑、紫外線吸收劑、凝聚抑制劑、熱聚合抑制劑、消泡劑、界面活性劑、鏈轉移劑等。任意之添加劑均可使用先前公知之添加劑。作為界面活性劑，可列舉陰離子系化合物、陽離子系化合物、非離子系化合物等。作為密接性促進劑，可列舉先前公知之矽烷偶合劑。作為熱聚合抑制劑，可列舉對苯二酚、對苯二酚單乙醚等。作為消泡劑，可列舉聚矽氧系化合物、氟系化合物等。 作為鏈轉移劑，可列舉硫醇系化合物、鹵素系化合物、醌系化合物、α-甲基苯乙烯二聚物等。藉由含有鏈轉移劑，可良好地控制圖案形狀(特別是孔圖案之CD變化、曝光餘裕)。其中，2,4-二苯基-4-甲基-1-戊烯(α-甲基苯乙烯二聚物)除了上述效果以外，於可減低昇華物或著色、臭氣之方面而言較佳。 作為本發明之感光性組合物中所使用之溶劑，例如可列舉乙二醇單甲醚、乙二醇單乙醚、乙二醇正丙醚、乙二醇單正丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單正丙醚、二乙二醇單正丁醚、三乙二醇單甲醚、三乙二醇單乙醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單正丙醚、丙二醇單正丁醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單正丙醚、二丙二醇單正丁醚、三丙二醇單甲醚、三丙二醇單乙醚等(聚)烷二醇單烷基醚類；乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單乙醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯等(聚)烷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、二乙二醇二乙醚、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-甲基吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺類等。該等溶劑可單獨使用，亦可組合使用2種以上。 上述溶劑中，丙二醇單甲醚、乙二醇單甲醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、二乙二醇二甲醚、二乙二醇甲基乙基醚、環己酮、乙酸3-甲氧基丁酯對於上述(A1)成分及(A2)成分以及任意使用之(B)成分顯示出優異之溶解性，因此較佳；尤佳為使用丙二醇單甲醚乙酸酯、乙酸3-甲氧基丁酯。溶劑之含量可根據感光性組合物之用途而適宜決定，作為一例，可列舉相對於感光性組合物之固形物成分之合計100質量份而言為50～900質量份左右。 ＜感光性組合物之製備方法＞ 本發明之感光性組合物可使用磁力攪拌器對上述各成分進行攪拌、混合溶解，視需要藉由0.2 μm膜濾器等過濾器進行過濾而製備。 作為本發明之感光性組合物，自所獲得之硬化物之透過率容易變充分考慮，藉由光程長度為3 μm所測得之對於波長為400 nm之光之透過率較佳為95%以上，更佳為98%以上。 ≪圖案形成方法、硬化物、及顯示裝置≫ 本發明之圖案形成方法除了使用上述感光性組合物以外，與使用感光性組合物所形成之先前之圖案形成方法相同。 使用上述感光性組合物而形成圖案之方法並無特別限制，可自先前所採用之方法中適宜選擇。作為適宜之圖案形成方法，可列舉包含如下步驟之方法：塗膜或成形體形成步驟，使用上述感光性組合物而形成塗膜或成形體；曝光步驟，對上述塗膜或成形體以特定圖案狀照射電磁波；顯影步驟，對照射過電磁波之塗膜或成形體進行顯影而形成圖案。 首先，於塗膜或成形體形成步驟中，例如於欲形成圖案之基板上，使用輥式塗佈機、反向塗佈機、棒式塗佈機等接觸轉印型塗佈裝置或旋轉器(旋轉式塗佈裝置)、淋幕式平面塗佈機等非接觸型塗佈裝置而塗佈本發明之感光性組合物，視需要藉由乾燥(預烘烤)將溶劑除去、及/或藉由公知之成形法將上述感光性組合物成形，而形成塗膜或成形體。 其次，將所形成之塗膜或成形體供於曝光步驟。於曝光步驟中，經由負型遮罩對塗膜或成形體照射ArF準分子雷射、KrF準分子雷射、F2 準分子雷射、極紫外線(EUV)、真空紫外線(VUV)、電子束、X射線、軟X射線、g射線、i射線、h射線等放射線或電磁波，將塗膜或成形體部分地曝光為特定圖案狀。曝光量根據感光性組合物之組成而異，例如較佳為10 mJ/cm2 ～600 mJ/cm2 左右。 上述感光性組合物於曝光後不易過度地溶解於鹼性顯影液。因此，藉由使用上述感光性組合物，容易形成以曝光部為凸部、以未曝光部為凹部之良好形狀之圖案。 於顯影步驟中，藉由顯影液對照射過電磁波之塗膜或成形體進行顯影而形成特定圖案。顯影方法並無特別限定，可使用浸漬法、噴霧法等。作為顯影液之具體例，可列舉單乙醇胺、二乙醇胺、三乙醇胺等有機系之顯影液，或氫氧化鈉、氫氧化鉀、碳酸鈉、氨、四級銨鹽等之水溶液。 然後，視需要可對顯影後之圖案實施後烘烤而進行加熱硬化，藉此獲得硬化之圖案。後烘烤之溫度較佳為150～270℃。 本發明之硬化物係使用上述之感光性組合物而形成。上述硬化物較佳為絕緣膜、或積層於光阻膜上之保護膜。上述硬化物於製成厚度為3 μm(光程長度為3 μm)之試樣時對於波長為400 nm之光之透過率通常為95%以上、較佳為98%以上。如上所述，上述硬化物之透過率優異，因此可作為內嵌式觸控面板方式之液晶顯示裝置、UHA(Ultra High Aperture，超高孔徑)面板等之需要透明性優異之絕緣膜的顯示裝置用絕緣膜而適宜地使用。 [實施例] 以下，藉由實施例對本發明加以更詳細之說明，但本發明並不限定於該等實施例。 [感光性組合物之製備] 將含有交聯性基之樹脂65質量份、光聚合性單體35質量份、表1中所示之種類及量之光聚合起始劑、二乙二醇甲基乙基醚與丙二醇單甲醚乙酸酯之混合溶劑(質量比為55：45)加以混合而製成均一溶液，製備固形物成分濃度為24質量%之感光性組合物。再者，將含有交聯性基之樹脂及光聚合性單體之總量設為100質量份，於實施例11中光聚合起始劑之總量為4.5質量份，於實施例12中光聚合起始劑之總量為4質量份，於除此以外之實施例及所有比較例中光聚合起始劑之總量為5質量份。 又，於實施例1～12及比較例1～22中，使用以下所示之含有交聯性基之樹脂A，於實施例13及實施例14中，使用以下所示之含有交聯性基之樹脂B。 作為含有交聯性基之樹脂A，使用包含下述式所表示之結構單元之樹脂。結構單元彼此之質量比I-1：I-2：II-1：III-1為25：20：14：41。藉由凝膠滲透層析法(GPC)所求出之含有交聯性基之樹脂A之質量平均分子量(Mw)為7000。 [化37]
Figure 02_image075
作為含有交聯性基之樹脂B，使用包含下述式所表示之結構單元之樹脂。結構單元彼此之質量比I-3：II-1：III-2為71：12：17。藉由凝膠滲透層析法(GPC)所求出之含有交聯性基之樹脂B之質量平均分子量(Mw)為10200。 再者，作為結構單元I-3，使用包含以下所示之I-3之結構以及作為其部分位置異構物之I-3α之結構者。 [化38]
Figure 02_image077
[化39]
Figure 02_image079
作為光聚合性單體，使用二季戊四醇六丙烯酸酯。 作為光聚合起始劑，準備下述式所表示之起始劑1～11，將起始劑1及3～11用於感光性組合物之製備、以及感度及透過率之評價與測定中。 光聚合起始劑(A1) ・起始劑1：下述式(A1-1)所表示之化合物 ・起始劑2：下述式(A1-2)所表示之化合物 [化40]
Figure 02_image081
光聚合起始劑(A2) ・起始劑3：下述式(A2-1)所表示之化合物 ・起始劑4：下述式(A2-2)所表示之化合物 ・起始劑5：下述式(A2-3)所表示之化合物 ・起始劑7：下述式(A2-4)所表示之化合物 ・起始劑9：下述式(A2-5)所表示之化合物 ・起始劑12：下述式(A2-6)所表示之化合物 [化41]
Figure 02_image083
Figure 02_image085
其他光聚合起始劑(A3) ・起始劑6：下述式(A3-1)所表示之化合物 ・起始劑8：下述式(A3-2)所表示之化合物 ・起始劑10：下述式(A3-3)所表示之化合物 ・起始劑11：下述式(A3-4)所表示之化合物 [化42]
Figure 02_image087
關於各實施例及比較例中所獲得之感光性組合物，依照以下之方法而進行感度及透過率之評價與測定。將評價結果記於表1中。 (感度) 於玻璃基板上，藉由旋轉器(Mikasa旋轉器IH-360S、Mikasa股份有限公司製造)而旋轉塗佈上述各實施例及比較例中所製備之感光性組合物後，於100℃下對塗膜進行100秒之乾燥而形成感光性樹脂層。其次，藉由曝光裝置(MPA600FA、佳能股份有限公司製造)，於每個實驗中使曝光量變動而對感光性樹脂層進行曝光。其次，使用四甲基氫氧化銨之濃度為2.38質量%之水溶液作為顯影液，於23℃下進行100秒之浸置式顯影，形成具有孔徑為10 μm之範圍內之孔的孔圖案。於顯影後，以230℃對圖案進行20分鐘之後烘烤。後烘烤後之圖案之膜厚為3 μm。圖案之膜厚係使用觸針式表面形狀測定器(Dektak 3st、ULVAC股份有限公司製造)而測定。將後烘烤處理之孔之底部之孔徑成為8 μm之曝光量判定為精確感度。於上述曝光量為35 mJ/cm2 以下之情形時，評價為感度良好；於上述曝光量超過35 mJ/cm2 之情形時，評價為感度不良。上述曝光量較佳為30 mJ/cm2 以下。 (透過率) 將曝光量固定為上述精確感度而對感光性樹脂層進行曝光，代替於每個實驗中使曝光量變動而對感光性樹脂層進行曝光，除此以外與感度之評價方法同樣地進行，形成進行了後烘烤之感光性組合物之硬化膜。硬化膜之膜厚為3 μm。使用MCPD-3000(大塚電子股份有限公司製造)測定所形成之硬化膜之波長400 nm之透過率。於上述透過率為95%以上之情形時，評價為透過率良好；於上述透過率未達95%之情形時，評價為透過率不良。上述透過率較佳為98%以上。 [表1]
Figure 105127562-A0304-0001
 根據表1可知，確認包含式(1)所表示之光聚合起始劑(A1)、及具有鍵結有硝基之芳香環骨架的光聚合起始劑(A2)之本發明之感光性組合物對於曝光之感度充分，藉由硬化而提供透過率充分之硬化物。≪Photosensitive composition≫ The photosensitive composition of the present invention contains the photopolymerization initiator (A1) represented by the above formula (1) and the photopolymerization initiator (A2) having an aromatic ring skeleton to which a nitro group is bonded ). Hereinafter, each component contained in the photosensitive composition will be described. <Photopolymerization initiator (A)> Depending on the type of the photopolymerization initiator, there is the transmittance of the photosensitive composition containing the photopolymerization initiator and the post-baking formed using the photosensitive composition The transmittance of the pattern decreases. Moreover, depending on the type of the photopolymerization initiator, the transmittance of the photosensitive composition containing the photopolymerization initiator may decrease. However, when using a photosensitive composition containing the photopolymerization initiator (A1) represented by the above formula (1) (hereinafter also referred to as "photopolymerization initiator (A1)" or "(A1) component") In this case, it is difficult to reduce the transmittance of the pattern caused by heating. At the same time, it is difficult to cause a decrease in the transmittance of the photosensitive composition. In addition, the photopolymerization initiator (A1) has a relatively high sensitivity to light. On the other hand, the photopolymerization initiator (A2) (hereinafter also referred to as "photopolymerization initiator (A2)" or "(A2) component") having an aromatic ring skeleton to which a nitro group is bonded is high in light Sensitivity. The photosensitive composition of the present invention provides a cured product having excellent sensitivity to light and maintaining a high transmittance by the combination of the photopolymerization initiator (A1) and the photopolymerization initiator (A2). Therefore, by using the photosensitive composition of the present invention, a pattern of a desired shape can be formed with a low exposure amount, and the formed pattern has a higher transmittance. In addition, by using the photosensitive composition of the present invention with excellent sensitivity, the peeling of the pattern during pattern formation can be suppressed, and the occurrence of shaking at the edge of the pattern during the formation of a line pattern can be suppressed. [Photopolymerization initiator (A1) represented by formula (1)] The photosensitive composition of the present invention contains the photopolymerization initiator (A1) represented by the above formula (1). The photopolymerization initiator (A1) can be used alone or in combination of two or more kinds. In formula (1), R 1 It is a hydrogen atom or a monovalent organic group. R 1 It is attached to the fluorine ring in formula (1), and is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring to which the group represented by -CO- is bonded. If this condition is met, then in formula (1), R 1 There is no particular limitation on the position of the bond relative to the ring. In the photopolymerization initiator (A1), it has more than 1 R 1 In this case, based on the ease of synthesis of the photopolymerization initiator (A1), etc., preferably 1 or more R 1 One of the bonds is in the second position of the ring. To R 1 In the case of plural, plural R 1 Can be the same or different. To R 1 In the case of a monovalent organic group, R 1 As long as it is a range which does not hinder the objective of this invention, it will not specifically limit, It can select suitably from various monovalent organic groups. As R 1 Suitable examples in the case of monovalent organic groups include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyl groups, which may have Substituent phenyl group, optionally substituted phenoxy group, optionally substituted benzyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzyloxy group, optionally substituted group The phenylalkyl group, the naphthyl group which may have a substituent, the naphthyloxy group which may have a substituent group, the naphthyloxy group which may have a substituent group, the naphthoxycarbonyl group which may have a substituent group, the naphthyl group which may have a substituent group Anooxy, naphthylalkyl which may have substituents, heterocyclic groups which may have substituents, heterocyclic carbonyl groups which may have substituents, amino groups substituted with 1 or 2 organic groups, morpholine-1 -Base, and piperazine
Figure 105127562-A0304-12-0001-4
-1-base etc. To R 1 In the case of an alkyl group, the number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-6. Also, in R 1 In the case of an alkyl group, it may be linear or branched. As R 1 In the case of an alkyl group, specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, isoamyl Base, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-decyl, and Isodecyl etc. Also, in R 1 In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of alkyl groups having ether bonds in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl Oxyethyl, and methoxypropyl, etc. To R 1 In the case of an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1-20, more preferably 1-6. Also, in R 1 In the case of an alkoxy group, it may be a straight chain or a branched chain. As R 1 In the case of an alkoxy group, specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, and tertiary butoxy. Oxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second octyloxy, The third octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. Also, 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 alkoxy groups having ether bonds in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy. , Propoxyethoxyethoxy, and methoxypropoxy, etc. To R 1 In the case of a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or a cycloalkoxy group is preferably 3-10, more preferably 3-6. As R 1 In the case of a cycloalkyl group, specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As R 1 In the case of cycloalkoxy, specific examples include cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy. To R 1 In the case of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or saturated aliphatic acyl group is preferably 2-21, more preferably 2-7. As R 1 In the case of saturated aliphatic acyl groups, specific examples include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanyl, 2,2-dimethylpropionyl, N-hexyl, n-heptanyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-twelve, n-thirteen, n-fourteen, n-fifteen Base, and regular sixteen jiji. As R 1 In the case of saturated aliphatic oxy groups, specific examples include acetoxy, propoxy, n-butoxy, 2-methylpropoxy, n-pentoxy, 2,2 -Dimethylpropionyloxy, n-hexyloxy, n-heptanoyloxy, n-octyloxy, n-nonyloxy, n-decanoyloxy, n-undecanoyloxy, n-dodecanoyloxy Group, n-tridecanoyloxy, n-tetradecanoicoxy, n-pentadecanoicoxy, and n-hexadecanoicoxy, etc. To R 1 In the case of an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, more preferably 2-7. As R 1 In the case of an alkoxycarbonyl group, specific examples include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, second Butoxycarbonyl, tertiary butoxycarbonyl, n-pentoxycarbonyl, isopentoxycarbonyl, second pentoxycarbonyl, third pentoxycarbonyl, n-hexoxycarbonyl, n-heptoxycarbonyl, n Octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl, etc. . To R 1 In the case of a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7-20, more preferably 7-10. Also, in R 1 In the case of a naphthyl alkyl group, the number of carbon atoms of the naphthyl alkyl group is preferably 11-20, more preferably 11-14. As R 1 Specific examples in the case of phenylalkyl include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. As R 1 In the case of naphthylalkyl, specific examples include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl . To R 1 In the case of phenylalkyl or naphthylalkyl, R 1 It may further have a substituent on the phenyl group or the naphthyl group. To R 1 In the case of a heterocyclic group, the heterocyclic group is a monocyclic ring containing more than one N, S, and/or O with 5 or 6 members, or the monocyclic rings are condensed with each other, or the monocyclic ring and the benzene ring The heterocyclic group. When the heterocyclic group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. As the heterocyclic ring constituting the heterocyclic group, furan ring, thiophene ring, pyrrole ring,
Figure 105127562-A0304-12-0001-1
Azole ring, iso
Figure 105127562-A0304-12-0001-1
Azole ring, thiazole ring, thiadiazole ring, isothiazole ring, imidazole ring, pyrazole ring, triazole ring, pyridine ring, pyridine ring
Figure 105127562-A0304-12-0001-4
Ring, pyrimidine ring, ta
Figure 105127562-A0304-12-0001-4
Ring, benzofuran ring, benzothiophene ring, indole ring, isoindole ring, indole
Figure 105127562-A0304-12-0001-4
Ring, benzimidazole ring, benzotriazole ring, benzo
Figure 105127562-A0304-12-0001-1
Azole ring, benzothiazole ring, carbazole ring, purine ring, quinoline ring, isoquinoline ring, quinazoline ring, phthalein
Figure 105127562-A0304-12-0001-4
ring,
Figure 105127562-A0304-12-0001-6
Quinoline ring
Figure 105127562-A0304-12-0001-1
Morpholine ring, piperidine ring, piper
Figure 105127562-A0304-12-0001-4
Ring, morpholine ring, piperidine ring, tetrahydropyran ring, and tetrahydrofuran ring, etc. To R 1 In the case of a heterocyclic group, the heterocyclic group may further have a substituent. To R 1 In the case of a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group and R 1 The same applies to heterocyclic groups. To R 1 In the case of 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, a cycloalkyl group having 3 to 10 carbon atoms, and a carbon number of 2 to 21 saturated aliphatic aliphatic groups, optionally substituted phenyl groups, optionally substituted benzyl groups, optionally substituted C7-20 phenylalkyl groups, optionally substituted naphthyl groups , Optionally substituted naphthylmethyl group, optionally substituted naphthylalkyl group with 11 to 20 carbon atoms, heterocyclic group, etc. Specific examples of these suitable organic bases and R 1 same. Specific examples of amino groups substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropyl N-butylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamine Group, phenylamino group, naphthylamino group, acetylamino group, propionylamino group, n-butyrylamino group, n-pentanylamino group, n-hexylamino group, n-heptanylamino group, n Octanylamino group, n-decylamino group, benzylamino group, α-naphthylamino group, β-naphthylamino group, etc. As R 1 When the phenyl, naphthyl, and heterocyclic group contained in further have a substituent, the substituent includes an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, and carbon atoms Saturated aliphatic acyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated aliphatic acyloxy group with 2 to 7 carbon atoms, monoalkanes with an alkyl group of 1 to 6 carbon atoms Alkylamino group, dialkylamino group having an alkyl group of 1 to 6 carbon atoms, morpholin-1-yl, piper
Figure 105127562-A0304-12-0001-4
-1- group, halogen atom, cyano group, etc. Specific examples and suitable examples of the halogen atom will be described later. To R 1 When the phenyl group, the naphthyl group, and the heterocyclic group contained in further have a substituent, the number of the substituents is not limited as long as it does not hinder the purpose of the present invention, and it is preferably 1 to 4. To R 1 When the phenyl group, naphthyl group, and heterocyclic group contained in have a plurality of substituents, the plurality of substituents may be the same or different. In the above-explained basis, in terms of the tendency to increase sensitivity, R 1 Preferably R 6 The base represented by -CO-. R 6 There is no particular limitation as long as it does not hinder the purpose of the present invention, and it can be selected from various organic groups. As R 6 Examples of suitable groups include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclic group which may have a substituent. As R 6 Among these groups, 2-methylphenyl, thiophen-2-yl, and α-naphthyl are particularly preferred. Also, in terms of the tendency for transparency to become better, as R 1 , Preferably a hydrogen atom. Furthermore, if R 1 Is a hydrogen atom and R 4 The base represented by the following formula (R4-2) tends to have better transparency. In formula (1), R 2 And R 3 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 2 With R 3 They may also be bonded to each other to form a ring. Among these bases, as R 2 And R 3 , Preferably a chain alkyl group which may have a substituent. To R 2 And R 3 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. To R 2 And R 3 In the case of a chain alkyl group having no substituents, the number of carbon atoms of the chain alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. As R 2 And R 3 In the case of chain alkyl, specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, Isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-decyl , And isodecyl and so on. Also, in R 2 And R 3 In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of alkyl groups having ether bonds in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl Oxyethyl, and methoxypropyl, etc. To R 2 And R 3 In the case of a chain alkyl group having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear. The substituent that the alkyl group may have is not particularly limited as long as it is in a range that does not inhibit the purpose of the present invention. Suitable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. Examples of cyclic organic groups include cycloalkyl groups, aromatic hydrocarbon groups, and heterocyclic groups. As a specific example of cycloalkyl, and R 1 The same applies to the case of cycloalkyl. Specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl. As a specific example of a heterocyclic group, and R 1 The same applies to the case of a heterocyclic group. To R 1 In the case of an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1-10, more preferably 1-6. When the chain alkyl group has a substituent, the number of substituents is not particularly limited. The number of preferred substituents changes corresponding to the number of carbon atoms of the chain alkyl group. The number of substituents is typically 1-20, preferably 1-10, more preferably 1-6. To R 2 And R 3 In the case of a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include aliphatic cyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclic groups. To R 2 And R 3 In the case of a cyclic organic group, the substituents and R that the cyclic organic group may have 2 And R 3 The same applies to the chain alkyl group. To R 2 And R 3 In the case of an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a phenyl group, or a group formed by bonding a plurality of benzene rings via a carbon-carbon bond, 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 bonding or condensation of plural benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, and it is preferably 3 or less. More preferably, it is 2 or less, and particularly preferably is 1. Preferred specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl. To R 2 And R 3 In the case of an aliphatic cyclic hydrocarbon group, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but it is preferably 3-20, more preferably 3-10. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and
Figure 105127562-A0304-03-0013-01
Base, different
Figure 105127562-A0304-03-0013-01
Group, tricyclononyl, tricyclodecyl, tetracyclododecyl, adamantyl, etc. To R 2 And R 3 In the case of a heterocyclic group, the heterocyclic group is a monocyclic ring containing more than one N, S, and/or O with 5 or 6 members, or the monocyclic rings are condensed with each other, or the monocyclic ring and the benzene ring The heterocyclic group. When the heterocyclic group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. As the heterocyclic ring constituting the heterocyclic group, furan ring, thiophene ring, pyrrole ring,
Figure 105127562-A0304-12-0001-1
Azole ring, iso
Figure 105127562-A0304-12-0001-1
Azole ring, thiazole ring, thiadiazole ring, isothiazole ring, imidazole ring, pyrazole ring, triazole ring, pyridine ring, pyridine ring
Figure 105127562-A0304-12-0001-4
Ring, pyrimidine ring, ta
Figure 105127562-A0304-12-0001-4
Ring, benzofuran ring, benzothiophene ring, indole ring, isoindole ring, indole
Figure 105127562-A0304-12-0001-4
Ring, benzimidazole ring, benzotriazole ring, benzo
Figure 105127562-A0304-12-0001-1
Azole ring, benzothiazole ring, carbazole ring, purine ring, quinoline ring, isoquinoline ring, quinazoline ring, phthalein
Figure 105127562-A0304-12-0001-4
ring,
Figure 105127562-A0304-12-0001-6
Quinoline ring
Figure 105127562-A0304-12-0001-1
Morpholine ring, piperidine ring, piper
Figure 105127562-A0304-12-0001-4
Ring, morpholine ring, piperidine ring, tetrahydropyran ring, and tetrahydrofuran ring, etc. R 2 With R 3 They may also be bonded to each other to form a ring. Contains R 2 With R 3 The group of the formed ring is preferably a cycloalkylene group. To R 2 With R 3 In the case of bonding to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring. To R 2 With R 3 When the group formed by bonding is a cycloalkylene group, the cycloalkylene group may be condensed with one or more other rings. Examples of the ring that may be condensed with the cycloalkylene ring include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, Thiophene ring, pyrrole ring, pyridine ring, pyridine ring
Figure 105127562-A0304-12-0001-4
Ring, and pyrimidine ring, etc. As the R described above 2 And R 3 Examples of suitable bases in the formula -A 1 -A 2 The base expressed. In the formula, A 1 Is a straight chain alkylene, A 2 It 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 straight-chain alkylene is preferably 1-10, more preferably 1-6. At A 2 In the case of an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group is preferably 1-10, more preferably 1-6. At A 2 In the case of 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. At 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, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated alkyl group may be linear or branched, and is preferably linear. At A 2 In the case of a cyclic organic group, the example of a cyclic organic group is the same as R 2 And R 3 The cyclic organic group possessed as a substituent is the same. At A 2 In the case of alkoxycarbonyl, the example of alkoxycarbonyl is the same as R 2 And R 3 The alkoxycarbonyl group possessed as a substituent is the same. As R 2 And R 3 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 Group, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8-methoxy-n-octyl , 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy-n-pentyl, 6-ethoxy-n-hexyl, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl and 8-ethoxy-n-octyl; 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl, 6-cyano-n-hexyl, 7-cyano-n-heptyl, and 8-cyano-n-octyl and other cyanoalkyl groups; 2-phenylethyl, 3- Phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl Group and other phenylalkyl groups; 2-cyclohexylethyl, 3-cyclohexyl-n-propyl, 4-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 and other cycloalkylalkyl groups; 2-methoxycarbonylethyl, 3-Methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl, 6-methoxycarbonyl-n-hexyl, 7-methoxycarbonyl- N-heptyl, 8-methoxycarbonyl-n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n-propyl, 4-ethoxycarbonyl-n-butyl, 5-ethoxy Alkoxycarbonylalkyl groups such as carbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl, and 8-ethoxycarbonyl-n-octyl; 2-chloro Ethyl, 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-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n Halogenated alkyl groups such as octyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5,5,5-heptafluoro-n-pentyl. As R 2 And R 3 , The suitable groups mentioned above are ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl, 2-cyclohexylethyl , 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5,5,5-heptafluoro -N-pentyl. In formula (1), R 4 は, a group represented by the following formula (R4-1) or (R4-2). [化5]
Figure 02_image011
(In formulas (R4-1) and (R4-2), R 7 And R 8 Each is a monovalent organic group, p is an integer of 0-4, in R 7 And R 8 In the case of adjacent positions on the benzene ring, R 7 With R 8 It may also be bonded to each other to form a ring, q is an integer of 1-8, r is an integer of 1-5, s is an integer of 0-(r+3), R 9 Is a monovalent organic group) Regarding R in formula (R4-1) 7 And R 8 The example of monovalent organic base and R 1 same. As R 7 , Preferably alkyl or phenyl. To R 7 In the case of an alkyl group, the number of carbon atoms is preferably 1-10, more preferably 1-5, particularly preferably 1-3, most preferably 1. That is, the best is R 7 For methyl. To R 7 With R 8 In the case of bonding to form a ring, the ring may be an aromatic ring or an aliphatic ring. As R in the base represented by formula (R4-1) 7 With R 8 Suitable examples of the ring-forming group include naphth-1-yl or 1,2,3,4-tetralin-5-yl. In the above formula (R4-1), p is an integer of 0-4, preferably 0 or 1, more preferably 0. In the above formula (R4-2), R 9 It is a monovalent organic group. As a monovalent organic group, those related to R 1 The monovalent organic group described is the same base. Among the monovalent 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 1-10, more preferably 1-5, and particularly preferably 1-3. As R 9 , A methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. can be preferably exemplified, and among these, a methyl group is more preferable. In the above formula (R4-2), r is an integer of 1-5, preferably an integer of 1-3, more preferably 1 or 2. In the above formula (R4-2), s is 0 to (r+3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0. In the above formula (R4-2), q is an integer of 1-8, preferably an integer of 1-5, more preferably an integer of 1-3, and particularly preferably 1 or 2. In formula (1), R 5 It is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As R 5 In the case of an alkyl group, the substituent which may be possessed is preferably exemplified by a phenyl group and a naphthyl group. Also, as R 1 In the case of an aryl group, the substituent which may be possessed is preferably exemplified by an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom. In formula (1), as R 5 , Hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group, etc. can be preferably exemplified, among which methyl group is more preferable Or phenyl. In formula (1), n is an integer of 0-4, preferably an integer of 0-2, more preferably 0 or 1, and particularly preferably 0. As described above, the photopolymerization initiator (A1) does not have a nitro group. That is, R 1 ~R 5 None of them has a nitro group. The content of the photopolymerization initiator (A1) is preferably 0.001 to 50% by mass, more preferably 0.01 to 30% by mass, and still more preferably 0.1 to 20% by mass relative to the solid content of the photosensitive composition , Particularly preferably 1-10% by mass. If the content of the photopolymerization initiator (A1) is within the above range, the obtained composition can maintain good sensitivity to exposure, and the transmittance of the cured product obtained from the composition is likely to become sufficient. The content of the photopolymerization initiator (A1) may be, for example, in the range of 1-99.5 mass% relative to the photopolymerization initiator (A) as a whole, preferably 50-99 mass%, more preferably 70 -98% by mass, more preferably 80-97% by mass. The manufacturing method of the photopolymerization initiator (A1) is not particularly limited. It is preferable that the photopolymerization initiator (A1) converts the oxime group (=N-OH) contained in the compound represented by the following formula (2) into =NO-COR by containing 5 It is produced by the method of the step of the oxime ester group shown. R 5 And R in formula (1) 5 same. [化6]
Figure 02_image013
(R 1 , R 2 , R 3 , R 4 , And n are the same as the formula (1)) Therefore, the compound represented by the above formula (2) can be used as an intermediate for the synthesis of the photopolymerization initiator (A1). Convert the oxime group (=N-OH) to=NO-COR 5 The method of the oxime ester group shown is not specifically limited. Typical is to enumerate the hydroxyl in the oxime group and provide -COR 5 The method of the reaction of the acylation agent of the acyl group. As the acylating agent, (R 5 CO) 2 Anhydride represented by O or R 5 A halogen represented by COHal (Hal is a halogen atom). The photopolymerization initiator (A1) can be synthesized in accordance with the following reaction scheme, for example. In the following reaction scheme, the stilbene derivative represented by the following formula (1-1) is used as a raw material. To R 1 In the case of a monovalent organic group, the fluorine derivative represented by formula (1-1) can be substituted with the substituent R 1 Import to 9 digits by R 2 And R 3 Obtained by substitution of Fu derivatives. As for the 9th by R 2 And R 3 Substituted 茀 derivatives, for example in R 2 And R 3 In the case of an alkyl group, as described in Japanese Patent Laid-Open No. 06-234668, in the presence of an alkali metal hydroxide in an aprotic polar organic solvent, it is obtained by reacting stilbene with an alkylating agent . In addition, in the organic solvent solution of 茀, an alkylating agent such as alkyl halide, an aqueous solution of alkali metal hydroxide, an interphase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide is added. The alkylation reaction is carried out to obtain 9,9-alkyl substituted sulphur. In the tea derivative represented by the formula (1-1), -CO-CH is introduced through the Friedel-Crafts acylation reaction 2 -R 4 The expressed acyl group obtains the 茀 derivative represented by formula (2-1). As used to import-CO-CH 2 -R 4 The acylating agent of the acyl group represented is preferably the carboxylic halide represented by formula (1-8). In formula (1-8), Hal is a halogen atom. The position of introducing the base on the ring can be selected by appropriately changing the conditions of the Friedel-Crafts reaction, and implementing protection and deprotection methods at other positions of the base. Secondly, for the compound represented by formula (2-1) that exists in R 4 The methylene group between the carbonyl group is oximated to obtain the ketoxime compound represented by the following formula (2-3). The method for oximating the methylene group is not particularly limited, but it is preferable to make the nitrite represented by the following formula (2-2) (RONO, R is an alkyl group with 1 to 6 carbons) in the presence of hydrochloric acid. ) The method of reaction. Next, the ketoxime compound represented by the following formula (2-3) and the acid anhydride represented by the following formula (2-4) ((R 5 CO) 2 O), or the halogen represented by the following formula (2-5) (R 5 COHal and Hal are halogen atoms) react to obtain a compound represented by the following formula (2-6). Furthermore, in the following formulas (1-1), (1-8), (2-1), (2-3), (2-4), (2-5), and (2-6) , R 1 , R 2 , R 3 , R 4 , And R 5 Same as formula (1). In addition, in the following reaction schemes, R contained in formula (1-8), formula (2-1) and formula (2-3), respectively 4 Can be the same or different. That is, R in formula (1-8), formula (2-1), and formula (2-3) 4 It can also be chemically modified during the synthesis process shown as the following reaction scheme. Examples of chemical modification include esterification, etherification, acylation, amination, halogenation, and substitution of hydrogen atoms in an amino group with an organic group. R 4 The chemical modification that can be received is not limited to these. ＜Reaction Process＞ [化7]
Figure 02_image015
As suitable specific examples of the photopolymerization initiator (A1), the following compounds can be cited. [化8]
Figure 02_image017
[化9]
Figure 02_image019
[Photopolymerization initiator (A2) having an aromatic ring skeleton to which a nitro group is bonded] The photosensitive composition of the present invention contains a photopolymerization initiator (A2) having an aromatic ring skeleton to which a nitro group is bonded. The photopolymerization initiator (A2) can be used alone or in combination of two or more kinds. As the photopolymerization initiator (A2), if it is a photopolymerization initiator having an aromatic ring skeleton to which a nitro group is bonded, it is not particularly limited. For example, compounds having the following aromatic ring skeletons are mentioned. It has a nitro group and a group with an oxime ester bond. The above-mentioned aromatic ring skeleton is preferably a part of the tungsten or carbazole skeleton, and may also be an aromatic ring of a part of the tungsten or carbazole skeleton. In addition, the photopolymerization initiator (A2) may be a compound represented by the following formula (A2-1C), or a compound represented by the formula (A2-1N). Compounds on heteroaryl groups. In the photopolymerization initiator (A2), the nitro group is preferably bonded to the aromatic ring skeleton directly (that is, not via a linking group such as an alkylene group) or via a linking group such as an alkylene group, and more preferably It is directly bonded to the aromatic ring skeleton. The above-mentioned group having an oxime ester bond is preferably bonded to the aromatic ring skeleton directly or via a carbonyl group. As said group which has an oxime ester bond, the group represented by following formula (3) is mentioned, for example. -C(R 14 )=NOC(R 15 )=O (3) (where R 14 It is a monovalent organic group, R 15 Is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent) As a specific example of the photopolymerization initiator (A2), the following formula (a-1) ) The compound represented by: [化 10]
Figure 02_image021
(R 100 It is the following formula (a-2): [化11]
Figure 02_image023
(R 11 Is a hydrogen atom, a nitro group, or a monovalent organic group, R 12 And R 13 Independently chain alkyl, cyclic hydrocarbon, or heteroaryl, R 12 With R 13 They may be bonded to each other to form a spiro ring, and n1 is an integer of 1-4. Where R 11 At least one of which is a nitro group) represented by the following formula (a-3): [化12]
Figure 02_image025
(R 20 It is independently a monovalent organic group, an amino group, a halogen atom, a nitro group, or a cyano group, A is S or O, and n2 is an integer of 1 to 4. Where R 20 At least one of which is a nitro group) or the following formula (a-4): [化 13]
Figure 02_image027
(R twenty one It is a monovalent organic group, R twenty two It is a hydrogen atom, a nitro group, or a monovalent organic group, and n3 is an integer of 1 to 4. Where R twenty two At least one of them is a nitro group), R 14 It is a monovalent organic group, R 15 It is a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group, and m is 0 or 1). As R 14 Examples of suitable monovalent organic groups can be combined with the following R 11 Similarly, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, and those which may have a substituent Phenoxy group, optionally substituted benzyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzyloxy group, optionally substituted phenylalkyl group, optionally substituted group Naphthyl, naphthyloxy which may have substituents, naphthyloxy which may have substituents, naphthoxycarbonyl which may have substituents, naphthyloxy which may have substituents, naphthyl which may have substituents Alkyl groups, heterocyclic groups which may have substituents, heterocyclic carbonyl groups which may have substituents, amine groups substituted by one or two organic groups, morpholin-1-yl, and piperidine
Figure 105127562-A0304-12-0001-4
-1-base etc. To R 14 In the case of an alkyl group, the number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-6. Also, in R 14 In the case of an alkyl group, it may be linear or branched. As R 14 In the case of an alkyl group, specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, isoamyl Base, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-decyl, and Isodecyl etc. Also, in R 14 In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of alkyl groups having ether bonds in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl Oxyethyl, and methoxypropyl, etc. To R 14 In the case of an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1-20, more preferably 1-6. Also, in R 14 In the case of an alkoxy group, it may be a straight chain or a branched chain. As R 14 In the case of an alkoxy group, specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, and tertiary butoxy. Oxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second octyloxy, The third octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. Also, in R 14 In the case of an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having ether bonds in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy. , Propoxyethoxyethoxy, and methoxypropoxy, etc. To R 14 In the case of a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or a cycloalkoxy group is preferably 3-10, more preferably 3-6. As R 14 In the case of a cycloalkyl group, specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As R 14 In the case of cycloalkoxy, specific examples include cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy. To R 14 In the case of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or saturated aliphatic acyl group is preferably 2-21, more preferably 2-7. As R 14 In the case of saturated aliphatic acyl groups, specific examples include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanyl, 2,2-dimethylpropionyl, N-hexyl, n-heptanyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-twelve, n-thirteen, n-fourteen, n-fifteen Base, and regular sixteen jiji. As R 14 In the case of saturated aliphatic oxy groups, specific examples include acetoxy, propoxy, n-butoxy, 2-methylpropoxy, n-pentoxy, 2,2 -Dimethylpropionyloxy, n-hexyloxy, n-heptanoyloxy, n-octyloxy, n-nonyloxy, n-decanoyloxy, n-undecanoyloxy, n-dodecanoyloxy Group, n-tridecanoyloxy, n-tetradecanoicoxy, n-pentadecanoicoxy, and n-hexadecanoicoxy, etc. To R 14 In the case of an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, more preferably 2-7. As R 14 In the case of an alkoxycarbonyl group, specific examples include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, second Butoxycarbonyl, tertiary butoxycarbonyl, n-pentoxycarbonyl, isopentoxycarbonyl, second pentoxycarbonyl, third pentoxycarbonyl, n-hexoxycarbonyl, n-heptoxycarbonyl, n Octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl, etc. . To R 14 In the case of a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7-20, more preferably 7-10. Also, in R 14 In the case of a naphthyl alkyl group, the number of carbon atoms of the naphthyl alkyl group is preferably 11-20, more preferably 11-14. As R 14 Specific examples in the case of phenylalkyl include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. As R 14 In the case of naphthylalkyl, specific examples include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl . To R 14 In the case of phenylalkyl or naphthylalkyl, R 14 It may further have a substituent on the phenyl group or the naphthyl group. To R 14 In the case of a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing more than one N, S, O, or a heterocyclic ring formed by condensing the monocyclic rings with each other or the monocyclic ring and a benzene ring base. When the heterocyclic group is a condensed ring, the number of rings can be set to 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. As the heterocyclic ring constituting the heterocyclic group, furan, thiophene, pyrrole,
Figure 105127562-A0304-12-0001-1
Azole, iso
Figure 105127562-A0304-12-0001-1
Azole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridine
Figure 105127562-A0304-12-0001-4
, Pyrimidine, da
Figure 105127562-A0304-12-0001-4
, Benzofuran, benzothiophene, indole, isoindole, indole
Figure 105127562-A0304-12-0001-4
, Benzimidazole, benzotriazole, benzo
Figure 105127562-A0304-12-0001-1
Azole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalein
Figure 105127562-A0304-12-0001-4
,
Figure 105127562-A0304-12-0001-6
Quinoline and quinoline
Figure 105127562-A0304-12-0001-1
Morpho etc. To R 14 In the case of a heterocyclic group, the heterocyclic group may further have a substituent. To R 14 In the case of a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group and R 14 The same applies to heterocyclic groups. To R 14 In the case of 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, a cycloalkyl group having 3 to 10 carbon atoms, and a carbon number of 2 to 21 saturated aliphatic aliphatic groups, optionally substituted phenyl groups, optionally substituted benzyl groups, optionally substituted C7-20 phenylalkyl groups, optionally substituted naphthyl groups , Optionally substituted naphthylmethyl group, optionally substituted naphthylalkyl group with 11 to 20 carbon atoms, heterocyclic group, etc. Specific examples of these suitable organic bases and R 14 same. Specific examples of amino groups substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropyl N-butylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamine Group, phenylamino group, naphthylamino group, acetylamino group, propionylamino group, n-butyrylamino group, n-pentanylamino group, n-hexylamino group, n-heptanylamino group, n Octanylamino group, n-decylamino group, benzylamino group, α-naphthylamino group, β-naphthylamino group, etc. As R 14 When the phenyl, naphthyl, and heterocyclic group contained in further have a substituent, the substituent includes an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, and carbon atoms Saturated aliphatic acyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated aliphatic acyloxy group with 2 to 7 carbon atoms, monoalkanes with an alkyl group of 1 to 6 carbon atoms Alkylamino group, dialkylamino group having an alkyl group of 1 to 6 carbon atoms, morpholin-1-yl, piper
Figure 105127562-A0304-12-0001-4
-1-yl, halogen, nitro, and cyano, etc. To R 14 When the phenyl group, the naphthyl group, and the heterocyclic group contained in further have a substituent, the number of the substituents is not limited within a range that does not hinder the purpose of the present invention, and is preferably 1 to 4. To R 14 When the phenyl group, naphthyl group, and heterocyclic group contained in have a plurality of substituents, the plurality of substituents may be the same or different. Also, as R 14 It is also preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a thiophenylalkyl group which may have a substituent on the aromatic ring. Phenoxyalkyl and phenylthioalkyl may also have substituents and R 14 The substituents that the phenyl group contained in may have are the same. In the monovalent organic group, as R 14 Preferably, it is an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, or a thiophenylalkyl group which may have a substituent group on the aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferred, and a 2-methylphenyl group is more preferred. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5-10, more preferably 5-8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1-8, more preferably 1-4, and particularly preferably 2. Among cycloalkylalkyls, cyclopentylethyl is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may also have a substituent on the aromatic ring is preferably 1-8, more preferably 1-4, and particularly preferably 2. Among the phenylthioalkyl groups that may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl is preferred. Above, about R 14 And it was explained, as R 14 It is preferably a group represented by the following formula (R2-1) or (R2-2). [化14]
Figure 02_image029
(In formulas (R2-1) and (R2-2), R 17 And R 18 Each is a monovalent organic group, p1 is an integer of 0-4, in R 17 And R 18 In the case of adjacent positions on the benzene ring, R 17 With R 18 It can also be bonded to each other to form a ring, q1 is an integer of 1-8, r1 is an integer of 1-5, s1 is an integer of 0-(r1+3), R 19 Is alkyl) Regarding R in formula (R2-1) 17 And R 18 The organic base example, and R 14 same. As R 17 , Preferably alkyl or phenyl. To R 17 In the case of an alkyl group, the number of carbon atoms is preferably 1-10, more preferably 1-5, particularly preferably 1-3, most preferably 1. That is, the best is R 17 For methyl. To R 17 With R 18 In the case of bonding to form a ring, the ring may be an aromatic ring or an aliphatic ring. As R in the base represented by formula (R2-1) 17 With R 18 Suitable examples of the ring-forming group include naphth-1-yl or 1,2,3,4-tetralin-5-yl. In the above formula (R2-1), p1 is an integer of 0-4, preferably 0 or 1, more preferably 0. In the above formula (R2-2), R 19 Is an alkyl group. The number of carbon atoms of the alkyl group is preferably 1-10, more preferably 1-5, and particularly preferably 1-3. As R 19 , A methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. can be preferably exemplified, and among these, a methyl group is more preferable. In the above formula (R2-2), r1 is an integer of 1-5, preferably an integer of 1-3, more preferably 1 or 2. In the above formula (R2-2), s1 is 0 to (r1+3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0. In the above formula (R2-2), q1 is an integer of 1-8, preferably an integer of 1-5, more preferably an integer of 1-3, and particularly preferably 1 or 2. In formula (a-1), R 15 It is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As R 15 In the case of an alkyl group, the substituent which may be possessed is preferably exemplified by a phenyl group and a naphthyl group. Also, as R 15 In the case of an aryl group, the substituent which may be possessed is preferably exemplified by an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom. In formula (a-1), as R 15 , Hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group, etc. can be preferably exemplified, among which methyl group is more preferable Or phenyl. In formula (a-2), R 11 It is a hydrogen atom, a nitro group or a monovalent organic group. R 11 Bonded to the ring in formula (a-2), and -(CO) in formula (a-1) m -The 6-membered aromatic ring to which the indicated group is bonded is different from the 6-membered aromatic ring. If this condition is met, then in formula (a-2), R 11 There is no particular limitation on the position of the bond relative to the ring. As for R 11 Relative to the bonding position of the ring, it is easy to synthesize R 100 Considering the compound represented by formula (a-1) which is a group represented by formula (a-2), etc., the 2-position in the sulphur ring is preferred. To R 11 In the case of a monovalent organic group, R 11 It is not particularly limited as long as it does not hinder the purpose of the present invention, and it can be appropriately selected from various organic groups. As R 11 A suitable example when it is a monovalent organic group, it can be combined with R 14 Similarly, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, and those which may have a substituent Phenoxy group, optionally substituted benzyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzyloxy group, optionally substituted phenylalkyl group, optionally substituted group Naphthyl, naphthyloxy which may have substituents, naphthyloxy which may have substituents, naphthoxycarbonyl which may have substituents, naphthyloxy which may have substituents, naphthyl which may have substituents Alkyl groups, heterocyclic groups which may have substituents, heterocyclic carbonyl groups which may have substituents, amine groups substituted by one or two organic groups, morpholin-1-yl, and piperidine
Figure 105127562-A0304-12-0001-4
-1-base etc. Specific examples of these bases and related R 14 And the explainer is the same. In the base explained above, R 11 If it is nitro, or R 11a The base represented by -CO- has a tendency to increase sensitivity and is preferable. Where R 11 At least one of them is a nitro group. R 11a There is no particular limitation as long as it does not hinder the purpose of the present invention, and it can be selected from various organic groups. As R 11a Examples of suitable groups include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclic group which may have a substituent. As R 11a Among these groups, 2-methylphenyl, thiophen-2-yl, and α-naphthyl are particularly preferred. Also, if R 11 A hydrogen atom tends to improve transparency, which is preferable. Furthermore, if R 11 Is a hydrogen atom and R 14 The above (R2-2) tends to have better transparency. In formula (a-2), R 12 And R 13 Each is a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group. Among these bases, R 12 And R 13 It is preferably a chain alkyl group. To R 12 And R 13 In the case of a chain alkyl group, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group. To R 12 And R 13 In the case of a chain alkyl group, the number of carbon atoms of the chain alkyl group is preferably 1-20, more preferably 1-6. As R 12 And R 13 In the case of chain alkyl, specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, Isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-decyl , And isodecyl and so on. Also, in R 12 And R 13 In the case of a chain alkyl group, the chain alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of chain alkyl groups having ether bonds in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxy Ethoxyethyl, and methoxypropyl, etc. To R 12 And R 13 In the case of a cyclic hydrocarbon group, the cyclic hydrocarbon group may be an aliphatic cyclic hydrocarbon group or an aromatic cyclic hydrocarbon group. To R 12 And R 13 In the case of an aromatic cyclic hydrocarbon group, it is preferable that the aromatic cyclic hydrocarbon group is a phenyl group, or 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 cyclic hydrocarbon group is a phenyl group or a group formed by bonding or condensation of plural benzene rings, the number of benzene rings contained in the aromatic cyclic hydrocarbon group is not particularly limited, and is preferably 3 Below, it is more preferably 2 or less, and particularly preferably 1. Preferred specific examples of the aromatic cyclic hydrocarbon group include phenyl, naphthyl, biphenyl, anthryl, and phenanthryl. To R 12 And R 13 In the case of an aliphatic cyclic hydrocarbon group, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but it is preferably 3-20, more preferably 3-10. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and
Figure 105127562-A0304-03-0013-01
Base, different
Figure 105127562-A0304-03-0013-01
Group, tricyclononyl, tricyclodecyl, tetracyclododecyl, adamantyl, etc. To R 12 And R 13 In the case of a heteroaryl group, the heteroaryl group may be a monocyclic ring containing more than one of 5 or 6 members of N, S, O, or a heterocyclic ring formed by condensing the monocyclic ring and the benzene ring. Aryl. When the heteroaryl group is a condensed ring, the number of rings can be set to 3. As the heterocyclic ring constituting the heteroaryl group, furan, thiophene, pyrrole,
Figure 105127562-A0304-12-0001-1
Azole, iso
Figure 105127562-A0304-12-0001-1
Azole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridine
Figure 105127562-A0304-12-0001-4
, Pyrimidine, da
Figure 105127562-A0304-12-0001-4
, Benzofuran, benzothiophene, indole, isoindole, indole
Figure 105127562-A0304-12-0001-4
, Benzimidazole, benzotriazole, benzo
Figure 105127562-A0304-12-0001-1
Azole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalein
Figure 105127562-A0304-12-0001-4
,
Figure 105127562-A0304-12-0001-6
Quinoline and quinoline
Figure 105127562-A0304-12-0001-1
Morpho etc. R 12 With R 13 They can also be bonded to each other to form a spiro ring. Contains R 12 With R 13 The group of the spiro ring formed is preferably a cycloalkylene group. To R 12 With R 13 In the case of bonding to form a cycloalkylene group, the spiro ring constituting the cycloalkylene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring. To R 12 With R 13 When the group formed by bonding is a cycloalkylene group, the cycloalkylene group may be condensed with one or more other rings. Examples of the ring that may be condensed with the cycloalkylene ring include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, Thiophene ring, pyrrole ring, pyridine ring, pyridine ring
Figure 105127562-A0304-12-0001-4
Ring, and pyrimidine ring, etc. n1 is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1. In formula (a-3), R 20 It is independently a monovalent organic group, an amino group, a halogen atom, a nitro group, or a cyano group. To R 20 In the case of a monovalent organic group, various organic groups can be selected from a range that does not hinder the purpose of the present invention. As R 20 Suitable examples in the case of a monovalent organic group include alkyl groups with 1 to 6 carbons; alkoxy groups with 1 to 6 carbons; saturated aliphatic acyl groups with 2 to 7 carbons; and 2 to 7 carbons. Alkoxycarbonyl; saturated aliphatic oxy with 2 to 7 carbons; phenyl; naphthyl; benzyl; naphthyl; selected from alkyls with 1 to 6 carbons, morpholine- 1-base, piperazine
Figure 105127562-A0304-12-0001-4
Benzoyl substituted with a group consisting of -1-yl and phenyl; monoalkylamino group having an alkyl group having 1 to 6 carbons; dialkyl having an alkyl group having 1 to 6 carbons Amino; Morpholin-1-yl; Piper
Figure 105127562-A0304-12-0001-4
-1-base. R 20 Among them, benzyl; naphthyl; selected from alkyl groups with 1 to 6 carbons, morpholin-1-yl, piperidine
Figure 105127562-A0304-12-0001-4
-1-yl, and benzyl substituted with a group in the group consisting of phenyl; nitro, more preferably benzyl; naphthyl; 2-methylphenylcarbonyl; 4-(piper
Figure 105127562-A0304-12-0001-4
-1-yl)phenylcarbonyl; 4-(phenyl)phenylcarbonyl; nitro. Where R 20 At least one of them is a nitro group. Moreover, n2 is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1. When n2 is 1, R 20 The bonding position is preferably relative to R 20 The bonding bond between the bonded phenyl group and atom A is in the para position. A is preferably S. In formula (a-4), R twenty one It is a monovalent organic group. R twenty one Various organic groups can be selected from within the range that does not hinder the purpose of the present invention. As R twenty one Suitable examples include alkyl groups with 1 to 20 carbons, cycloalkyl groups with 3 to 10 carbons, saturated aliphatic acyl groups with 2 to 20 carbons, alkoxycarbonyl groups with 2 to 20 carbons, which may have substituents Phenyl group, optionally substituted benzyl group, optionally substituted phenoxycarbonyl group, optionally substituted phenylalkyl group with 7 to 20 carbon atoms, optionally substituted naphthyl group, may have Substituent naphthoyl group, optionally substituted naphthyloxycarbonyl, optionally substituted naphthylalkyl having 11 to 20 carbons, optionally substituted heterocyclic group, and optionally substituted hetero Cyclic carbonyl, etc. To R twenty one Among them, 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. As R 20 Or R twenty one When the phenyl group, naphthyl group, and heterocyclic group contained therein further have a substituent, the substituent includes an alkyl group having 1 to 6 carbons, an alkoxy group having 1 to 6 carbons, and a carbon number of 2 to 7 saturated aliphatic acyl groups, alkoxycarbonyl groups having 2 to 7 carbons, saturated aliphatic acyloxy groups having 2 to 7 carbons, monoalkylamino groups having an alkyl group of 1 to 6 carbons, Dialkylamino group, morpholin-1-yl, piperidine of alkyl group of number 1 to 6
Figure 105127562-A0304-12-0001-4
-1-yl, halogen, nitro, and cyano, etc. To R 20 Or R twenty one When the phenyl group, the naphthyl group, and the heterocyclic group contained in further have a substituent, the number of substituents is not limited as long as it does not hinder the purpose of the present invention, and it is preferably 1 to 4. R 20 Or R twenty one When the phenyl group, naphthyl group, and heterocyclic group contained in have a plurality of substituents, the plurality of substituents may be the same or different. In formula (a-4), R twenty two It is a hydrogen atom, a nitro group, or a monovalent organic group. R twenty two With R 11 Similarly, R twenty two At least one of them is a nitro group. n3 is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1. When m is 0, the compound represented by formula (a-1) can be synthesized, for example, according to the following reaction scheme a1. In reaction scheme a1, a compound represented by the following formula (a1-1) is used as a raw material. For example, in R 100 In the case of the group represented by the formula (a-2), in the reaction scheme a1, the stilbene derivative represented by the following formula (a1-1-1) is used as a raw material. To R 11 In the case of a nitro group or a monovalent organic group, the fluorine derivative represented by formula (a1-1-1) can be substituted with the substituent R by a known method 11 Import to 9 digits by R 12 And R 13 Obtained by substitution of Fu derivatives. As for the 9th by R 12 And R 13 Substituted 茀 derivatives, for example in R 12 And R 13 In the case of an alkyl group, as described in Japanese Patent Laid-Open No. 06-234668, in the presence of an alkali metal hydroxide in an aprotic polar organic solvent, the stilbene can be reacted with an alkylating agent. obtain. In addition, in the organic solvent solution of 茀, add an alkylating agent such as alkyl halide, an aqueous solution of alkali metal hydroxide, tetrabutylammonium iodide or potassium tert-butoxide and other phase transfer catalysts. The alkylation reaction is carried out to obtain 9,9-alkyl substituted sulphur. Using the halocarbonyl compound represented by the formula (a1-2), the compound represented by the formula (a1-1) is acylated by Friedel-Crafts reaction to obtain the compound represented by the formula (a1-3) Ketone compounds. In formula (a1-2), Hal is a halogen atom. R 100 The position of the compound represented by the formula (a1-2) on the aromatic ring contained in the aromatic ring can be selected by the following method: appropriately changing the conditions of the Friedel-Crafts reaction, the aromatic The other positions on the ring that are acylated by the compound represented by formula (a1-2) are protected and deprotected. Next, the ketone compound represented by the obtained formula (a1-3) is oximated with hydroxylamine to obtain the oxime compound represented by the following formula (a1-4). The oxime compound of formula (a1-4) can be combined with the acid anhydride represented by the following formula (a1-5) ((R 15 CO) 2 O), or the halogen represented by the following formula (a1-6) (R 15 COHal and Hal are halogen atoms) react to obtain a compound represented by the following formula (a1-7). Furthermore, in formulas (a1-1), (a1-2), (a1-3), (a1-4), (a1-5), (a1-6), (a1-7), and (a1 -1-1), R 100 , R 14 , R 15 , R 11 , R 12 , And R 13 It is the same as formula (a-1) and formula (a-2). ＜Reaction Scheme a1＞ [化15]
Figure 02_image031
When m is 1, the compound represented by formula (a-1) can be synthesized according to the following reaction scheme a2, for example. In reaction scheme a2, a compound represented by the following formula (a2-1) is used as a raw material. The compound represented by the formula (a2-1) is obtained by acylating the compound represented by the formula (a1-1) by the Friedel-Crafts reaction in the same manner as in the reaction scheme a1. In the presence of hydrochloric acid, the compound represented by formula (a2-1) is reacted with the nitrite (RONO, R is an alkyl group with 1 to 6 carbons) represented by the following formula (a2-2) to obtain the following The ketoxime compound represented by the formula (a2-3). Next, the ketoxime compound represented by the following formula (a2-3) and the acid anhydride represented by the following formula (a2-4) ((R 15 CO) 2 O), or the halogen represented by the following formula (a2-5) (R 15 COHal and Hal are halogen atoms) react to obtain a compound represented by the following formula (a2-6). Furthermore, in the following formulas (a2-1), (a2-3), (a2-4), (a2-5), and (a2-6), R 100 , R 14 , And R 15 Same as formula (a-1). When m is 1, there is a tendency to further reduce the occurrence of foreign matter in the cured product formed using the photosensitive composition containing the compound represented by formula (a-1). ＜Reaction Scheme a2＞ [化16]
Figure 02_image033
Suitable specific examples of the compound represented by the formula (a-1) include the following compounds. [化17]
Figure 02_image035
[化18]
Figure 02_image037
In addition, as the photopolymerization initiator (A2), a compound represented by the following formula (A2-1C) can also be used. [化19]
Figure 02_image039
(In formula (A2-1C), R 1 Represents nitro, R 6 It is an aryl group or a heteroaryl group, which can also be a chain aliphatic hydrocarbon group containing more than one bond selected from carbon-carbon double bonds and carbon-carbon triple bonds The base of combination. R 2 And R 3 Each independently represents an alkyl group or a hydrogen atom that may be substituted, R 4 Represents a monovalent organic group or hydrogen atom, R 5 Represents a monovalent organic group or a hydrogen atom, n represents 0 or 1) R in formula (A2-1C) 6 In the case of an arylene group, the arylene group is not particularly limited as long as it is a group in which two hydrogen atoms are removed from an aromatic hydrocarbon. The arylene group is preferably a group containing one or more benzene rings. When the aryl extension group contains two or more benzene rings, a plurality of benzene rings may be bonded to each other by a single bond, or may be condensed with each other to form a condensed ring such as a naphthalene ring. The arylene group preferably contains 1 to 3 benzene rings, and more preferably contains 1 or 2 benzene rings. Suitable examples of arylene groups include para-phenylene, meta-phenylene, o-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, and naphthalene 1,4-diyl , Naphthalene-1,5-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2, 7-diyl, biphenyl-4,4'-diyl, biphenyl-3,3'-diyl, biphenyl-2,2'-diyl, biphenyl-3,4'-diyl, biphenyl Benzene-3,2'-diyl and biphenyl-2,4'-diyl. R in formula (A2-1C) 6 In the case of a heteroaryl extension, if the heteroaryl extension is a group obtained by removing two hydrogen atoms from an aromatic heterocyclic ring, it is not particularly limited. The heteroaryl group is preferably a group containing at least one 5-membered or 6-membered aromatic heterocyclic ring among groups containing 5-membered or 6-membered aromatic rings. When the heteroaryl group contains at least one 5-membered or 6-membered aromatic heterocyclic ring in the group containing a 5-membered or 6-membered aromatic ring, a plurality of 5-membered or 6-membered aromatic rings may be They may be bonded to each other by a single bond, or may be condensed with each other to form a condensed ring. The heteroaryl group preferably contains 1 to 3 5-membered or 6-membered aromatic rings, and more preferably contains 1 or 2 5-membered or 6-membered aromatic rings. Suitable examples of heteroaryl groups include furan, thiophene, pyrrole,
Figure 105127562-A0304-12-0001-1
Azole, iso
Figure 105127562-A0304-12-0001-1
Azole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridine
Figure 105127562-A0304-12-0001-4
, Pyrimidine, da
Figure 105127562-A0304-12-0001-4
, Benzofuran, benzothiophene, indole, isoindole, indole
Figure 105127562-A0304-12-0001-4
, Benzimidazole, benzotriazole, benzo
Figure 105127562-A0304-12-0001-1
Azole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalein
Figure 105127562-A0304-12-0001-4
,
Figure 105127562-A0304-12-0001-6
Quinoline and quinoline
Figure 105127562-A0304-12-0001-1
Aromatic heterocyclic compound such as a phylloline is a group formed by removing two hydrogen atoms bonded to a carbon atom. For chain aliphatic hydrocarbon groups containing one or more bonds selected from carbon-carbon double bonds and carbon-carbon triple bonds, the number of carbon atoms or the number of carbon-carbon double bonds and carbon-carbon triple bonds is not The scope that hinders the purpose of the present invention is not particularly limited. In addition, the chain aliphatic hydrocarbon group containing one or more bonds selected from carbon-carbon double bonds and carbon-carbon triple bonds may be linear or branched, and is preferably linear. The number of carbon atoms of the chain aliphatic hydrocarbon group containing one or more bonds selected from carbon-carbon double bonds and carbon-carbon triple bonds is preferably 2-10, more preferably 2-6, and particularly preferably 2 ~4. The chain aliphatic hydrocarbon group is preferably an alkenylene group containing one carbon-carbon double bond or an alkynylene group containing one carbon-carbon triple bond. Suitable examples of chain aliphatic hydrocarbon groups containing one or more bonds selected from carbon-carbon double bonds and carbon-carbon triple bonds include ethylene-1,2-diyl and acetylene-1,2- Diyl, prop-1-ene-1,2-diyl, propargylene, pentynylene. For example, as a preferred example of a combination of an aryl extension group and a chain aliphatic hydrocarbon group containing one or more bonds selected from carbon-carbon double bonds and carbon-carbon triple bonds, the following can be cited 2-valent base. As a preferred example of a combination of a heteroaryl group and a chain aliphatic hydrocarbon group containing one or more bonds selected from carbon-carbon double bonds and carbon-carbon triple bonds, the following can be cited The aryl extension contained in the divalent group is substituted with various heteroaryl extensions. [化20]
Figure 02_image041
R in formula (A2-1C) 2 And R 3 In the case of an alkyl group having no substituent, the number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. As R 2 And R 3 In the case of an alkyl group, specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, isoamyl Base, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-decyl, and Isodecyl etc. R in formula (A2-1C) 2 And R 3 In the case of an alkyl group having a substituent, the number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The alkyl group having a substituent may be linear or branched, and is preferably linear. The substituent that the alkyl group may have is not particularly limited as long as it is in a range that does not inhibit the purpose of the present invention. Suitable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, an alkoxy group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. Examples of cyclic organic groups include cycloalkyl groups, aromatic hydrocarbon groups, and heterocyclic groups. The number of carbon atoms of the cycloalkyl group is preferably 3-10, more preferably 3-6. Specific examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As an aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, etc. are mentioned. The heterocyclic group includes at least one 5-membered or 6-membered monocyclic ring of N, S, O, or a heterocyclic group formed by condensing the monocyclic rings with each other, or the monocyclic ring and a benzene ring. When the heterocyclic group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. As the heterocyclic ring constituting the heterocyclic group, furan, thiophene, pyrrole,
Figure 105127562-A0304-12-0001-1
Azole, iso
Figure 105127562-A0304-12-0001-1
Azole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridine
Figure 105127562-A0304-12-0001-4
, Pyrimidine, da
Figure 105127562-A0304-12-0001-4
, Benzofuran, benzothiophene, indole, isoindole, indole
Figure 105127562-A0304-12-0001-4
, Benzimidazole, benzotriazole, benzo
Figure 105127562-A0304-12-0001-1
Azole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalein
Figure 105127562-A0304-12-0001-4
,
Figure 105127562-A0304-12-0001-6
Quinoline
Figure 105127562-A0304-12-0001-1
Morpholine, piperidine, piper
Figure 105127562-A0304-12-0001-4
, Morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. To R 2 And R 3 In the case of a heterocyclic group, the heterocyclic group may further have a substituent. The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and particularly preferably an alkoxy group having 1 to 4 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, tertiary butoxy, and n-pentoxy. , Isopentyloxy, second pentyloxy, third pentyloxy, and n-hexyloxy. The alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1-10, more preferably 1-6. Specific examples include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, second butoxycarbonyl, and tertiary butoxycarbonyl. Oxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, second pentyloxycarbonyl, third pentyloxycarbonyl, and n-hexyloxycarbonyl. When the alkyl group has a substituent, the number of substituents is not particularly limited. The number of preferred substituents varies correspondingly to the number of carbon atoms of the chain alkyl group. The number of substituents is typically 1-20, preferably 1-10, more preferably 1-6. R in formula (A2-1C) 2 With R 3 They may also be bonded to each other to form a ring. Contains R 2 With R 3 The group of the formed ring is preferably a cycloalkylene group. To R 2 With R 3 In the case of bonding to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring. To R 2 With R 3 When the group formed by bonding is a cycloalkylene group, the cycloalkylene group may be condensed with one or more other rings. Examples of the ring that may be condensed with the cycloalkylene ring include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, Thiophene ring, pyrrole ring, pyridine ring, pyridine ring
Figure 105127562-A0304-12-0001-4
Ring, and pyrimidine ring, etc. As the R described above 2 And R 3 An example of a suitable base in the formula-A 1 -A 2 The base expressed. In the formula, A 1 Is a straight chain alkylene, A 2 It 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 straight-chain alkylene is preferably 1-10, more preferably 1-6. At A 2 In the case of an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group is preferably from 1 to 10, more preferably from 1 to 6, and particularly preferably from 1 to 4. At A 2 In the case of 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. At 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, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated alkyl group may be linear or branched, and is preferably linear. At A 2 In the case of a cyclic organic group, the example of a cyclic organic group is the same as R 2 And R 3 The cyclic organic group possessed as a substituent is the same. At A 2 In the case of alkoxycarbonyl, the example of alkoxycarbonyl is the same as R 2 And R 3 The alkoxycarbonyl group possessed as a substituent is the same. As R 2 And R 3 Suitable specific examples include alkyl groups such as ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl; 2-methoxyethyl, 3-methoxy Base-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8-methoxy -N-octyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy-n-pentyl, 6-ethoxy-n-hexyl Group, 7-ethoxy-n-heptyl, and 8-ethoxy-n-octyl and other alkoxyalkyl groups; 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano- Cyanoalkyl groups such as n-butyl, 5-cyano-n-pentyl, 6-cyano-n-hexyl, 7-cyano-n-heptyl, and 8-cyano-n-octyl; 2-phenylethyl Group, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-benzene Phenyl alkyl groups such as hexyl-n-octyl; 2-cyclohexylethyl, 3-cyclohexyl-n-propyl, 4-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 and other cycloalkylalkyl groups; 2-methoxy Carbonylethyl, 3-methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl, 6-methoxycarbonyl-n-hexyl, 7-methyl Oxycarbonyl-n-heptyl, 8-methoxycarbonyl-n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n-propyl, 4-ethoxycarbonyl-n-butyl, Alkoxycarbonyl alkyl groups such as 5-ethoxycarbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl, and 8-ethoxycarbonyl-n-octyl ; 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-bromoethyl, 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-trifluoropropyl, and 3,3,4,4,5,5,5-heptafluoro-n-pentyl and other halogenated alkyl groups. As R 2 And R 3 The suitable groups mentioned above are ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl, 2-ring Hexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5,5,5 -Heptafluoro-n-pentyl. R in formula (A2-1C) 4 It is a monovalent organic group or a hydrogen atom. The monovalent organic group is not particularly limited as long as it is in a range that does not inhibit the purpose of the present invention. As R 4 Examples of suitable organic groups include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, and optionally substituted benzene Group, phenoxy group which may have substituents, benzyl group which may have substituents, phenoxycarbonyl group which may have substituents, benzyloxy group which may have substituents, phenylalkane which may have substituents Group, optionally substituted phenoxyalkyl group, optionally substituted phenylthioalkyl group, N-substituted aminoalkyl group, N,N-disubstituted aminoalkyl group, optionally substituted naphthyl group , Naphthyloxy group which may have substituents, naphthyloxy group which may have substituents, naphthyloxycarbonyl group which may have substituents, naphthyloxy group which may have substituents, naphthylalkyl which may have substituents , Naphthyloxyalkyl which may have substituents, naphthylthioalkyl which may have substituents, heterocyclic groups which may have substituents, heterocyclic carbonyl groups which may have substituents, through 1 or 2 organic groups Substituted amino, morpholin-1-yl, and piperidine
Figure 105127562-A0304-12-0001-4
-1-base etc. Also, as R 4 It is also preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a thiophenylalkyl group which may have a substituent on the aromatic ring. To R 4 In the case of an alkyl group, the number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-6. Also, in R 4 In the case of an alkyl group, it may be linear or branched. As R 4 In the case of an alkyl group, specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, isoamyl Base, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-decyl, and Isodecyl etc. Also, in R 4 In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of alkyl groups having ether bonds in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl Oxyethyl, and methoxypropyl, etc. To R 4 In the case of an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1-20, more preferably 1-6. Also, in R 4 In the case of an alkoxy group, it may be a straight chain or a branched chain. As R 4 In the case of an alkoxy group, specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, and tertiary butoxy. Oxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second octyloxy, The third octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. Also, in R 4 In the case of an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having ether bonds in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy. , Propoxyethoxyethoxy, and methoxypropoxy, etc. To R 4 In the case of a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or a cycloalkoxy group is preferably 3-10, more preferably 3-6. As R 4 In the case of a cycloalkyl group, specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As R 4 In the case of cycloalkoxy, specific examples include cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy. To R 4 In the case of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or saturated aliphatic acyl group is preferably 2-21, more preferably 2-7. As R 4 In the case of saturated aliphatic acyl groups, specific examples include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanyl, 2,2-dimethylpropionyl, N-hexyl, n-heptanyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-twelve, n-thirteen, n-fourteen, n-fifteen Base, and regular sixteen jiji. As R 4 In the case of saturated aliphatic oxy groups, specific examples include acetoxy, propoxy, n-butoxy, 2-methylpropoxy, n-pentoxy, 2,2 -Dimethylpropionyloxy, n-hexyloxy, n-heptanoyloxy, n-octyloxy, n-nonyloxy, n-decanoyloxy, n-undecanoyloxy, n-dodecanoyloxy Group, n-tridecanoyloxy, n-tetradecanoicoxy, n-pentadecanoicoxy, and n-hexadecanoicoxy, etc. To R 4 In the case of an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, more preferably 2-7. As R 4 In the case of an alkoxycarbonyl group, specific examples include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, second Butoxycarbonyl, tertiary butoxycarbonyl, n-pentoxycarbonyl, isopentoxycarbonyl, second pentoxycarbonyl, third pentoxycarbonyl, n-hexoxycarbonyl, n-heptoxycarbonyl, n Octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl, etc. . To R 4 In the case of a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7-20, more preferably 7-10. Also, in R 4 In the case of a naphthyl alkyl group, the number of carbon atoms of the naphthyl alkyl group is preferably 11-20, more preferably 11-14. As R 4 Specific examples in the case of phenylalkyl include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. As R 4 In the case of naphthylalkyl, specific examples include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl . To R 4 In the case of phenylalkyl or naphthylalkyl, R 4 It may further have a substituent on the phenyl group or the naphthyl group. To R 4 In the case of phenoxyalkyl, phenylthioalkyl, naphthoxyalkyl, and naphthylthioalkyl, the number of carbon atoms of the alkylene group contained in these groups is preferably 1-20. More preferably, it is 1-6. In addition, the alkylene group may be linear or branched, and is preferably linear. Specific examples of phenoxyalkyl include 2-phenoxyethyl, 3-phenoxy-n-propyl, 4-phenoxy-n-butyl, 5-phenoxy-n-pentyl, And 6-phenoxy-n-hexyl. Specific examples of phenylthioalkyl include 2-phenylthioethyl, 3-phenylthio-n-propyl, 4-phenylthio-n-butyl, 5-phenylthio-n-pentyl, And 6-phenylthio-n-hexyl. Specific examples of naphthyloxyalkyl groups include 2-(α-naphthyloxy)ethyl, 3-(α-naphthyloxy)-n-propyl, 4-(α-naphthyloxy)-n-butyl Group, 5-(α-naphthyloxy)-n-pentyl, 6-(α-naphthyloxy)-n-hexyl, 2-(β-naphthyloxy) ethyl, 3-(β-naphthyloxy) -N-propyl, 4-(β-naphthyloxy)-n-butyl, 5-(β-naphthyloxy)-n-pentyl, and 6-(β-naphthyloxy)-n-hexyl. Specific examples of naphthylthioalkyl include 2-(α-naphthylthio)ethyl, 3-(α-naphthylthio)-n-propyl, 4-(α-naphthylthio)-n-butyl Group, 5-(α-naphthylthio)-n-pentyl, 6-(α-naphthylthio)-n-hexyl, 2-(β-naphthylthio) ethyl, 3-(β-naphthylthio) -N-propyl, 4-(β-naphthylthio)-n-butyl, 5-(β-naphthylthio)-n-pentyl, and 6-(β-naphthylthio)-n-hexyl. To R 4 In the case of phenoxyalkyl, phenylthioalkyl, naphthoxyalkyl, or naphthylthioalkyl, R 4 It may further have a substituent on the phenyl group or the naphthyl group. To R 4 In the case of a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing more than one N, S, O, or a heterocyclic group formed by condensing the monocyclic rings or the monocyclic ring with a benzene ring . When the heterocyclic group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. As the heterocyclic ring constituting the heterocyclic group, furan, thiophene, pyrrole,
Figure 105127562-A0304-12-0001-1
Azole, iso
Figure 105127562-A0304-12-0001-1
Azole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridine
Figure 105127562-A0304-12-0001-4
, Pyrimidine, da
Figure 105127562-A0304-12-0001-4
, Benzofuran, benzothiophene, indole, isoindole, indole
Figure 105127562-A0304-12-0001-4
, Benzimidazole, benzotriazole, benzo
Figure 105127562-A0304-12-0001-1
Azole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalein
Figure 105127562-A0304-12-0001-4
,
Figure 105127562-A0304-12-0001-6
Quinoline
Figure 105127562-A0304-12-0001-1
Morpholine, piperidine, piper
Figure 105127562-A0304-12-0001-4
, Morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. To R 4 In the case of a heterocyclic group, the heterocyclic group may further have a substituent. To R 4 In the case of a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group and R 4 The same applies to heterocyclic groups. To R 4 In the case of an N-substituted aminoalkyl group or an N,N-disubstituted aminoalkyl group, the substituent bonded to the nitrogen atom is preferably an organic group. Suitable examples of the organic group include alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, saturated aliphatic aliphatic groups with 2 to 21 carbon atoms, and saturated fats with 2 to 21 carbon atoms. Group anoyloxy group, optionally substituted phenyl group, optionally substituted benzyl group, optionally substituted C7-20 phenylalkyl group, optionally substituted naphthyl group, may have Substituent naphthyl group, optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, heterocyclic group, etc. The number of carbon atoms of the alkylene group contained in the N-substituted alkyl group or the N,N-disubstituted aminoalkyl group is preferably 1-20, more preferably 1-6. In addition, the alkylene group may be linear or branched. Specific examples of N-substituted alkyl groups include 2-(methylamino)ethyl, 2-(ethylamino)ethyl, 2-(n-propylamino)ethyl, 2-(normal Butylamino) ethyl, 3-(methylamino) n-propyl, 3-(ethylamino) n-propyl, 3-(n-propylamino) n-propyl, 3-(n-butyl Amino) n-propyl, 2-(methylamino) n-propyl, 2-(ethylamino) n-propyl, 2-(n-propylamino) n-propyl, 2-(n-butyl Amino) n-propyl, 2-(acetamido) ethyl, 2-(propanoamino) ethyl, 2-(acetoxyamino) ethyl, 2-(propanoyl (Oxyamino) ethyl, 3-(acetamido) n-propyl, 3-(propanoamino) n-propyl, 3-(acetoxyamino) n-propyl, 3- (Propyloxyamino) n-propyl, 2-(acetylamino) n-propyl, 2-(propionylamino) n-propyl, 2-(acetoxyamino) n-propyl Group, and 2-(propanoxyamino) n-propyl group. As specific examples of N,N-disubstituted aminoalkyl groups, 2-(N,N-dimethylamino)ethyl, 2-(N,N-diethylamino)ethyl, 2 -(N,N-di-n-propylamino)ethyl, 2-(N,N-di-n-butylamino)ethyl, 3-(N,N-dimethylamino)n-propyl, 3-(N,N-diethylamino)n-propyl, 3-(N,N-di-n-propylamino)n-propyl, 3-(N,N-di-n-butylamino)n-propyl Propyl, 2-(N,N-dimethylamino)n-propyl, 2-(N,N-diethylamino)n-propyl, 2-(N,N-di-n-propylamino) ) N-propyl, 2-(N,N-di-n-butylamino) n-propyl, 2-(N,N-diethylamino)ethyl, 2-(N,N-dipropylamino) Amino) ethyl, 2-(N,N-diethoxyamino)ethyl, 2-(N,N-dipropionoxyamino)ethyl, 3-(N,N- Diacetylamino) n-propyl, 3-(N,N-dipropionylamino) n-propyl, 3-(N,N-diacetyloxyamino) n-propyl, 3- (N,N-dipropionyloxyamino) n-propyl, 2-(N,N-diethylamino) n-propyl, 2-(N,N-dipropionylamino) n Propyl, 2-(N,N-diethoxyamino) n-propyl, 2-(N,N-dipropoxyamino) n-propyl, 2-(N-acetoxy- N-acetoxyamino) ethyl, 2-(N-propionyl-N-propionyloxyamino) ethyl, 3-(N-acetoxy-N-acetoxyamino) ) N-propyl, 3-(N-propanyl-N-propanyloxyamino) n-propyl, 2-(N-acetyl-N-acetoxyamino) n-propyl, and 2-(N-Propyloxy-N-Propyloxyamino) n-propyl group. As R 4 When the phenyl, naphthyl, and heterocyclic group contained in further have a substituent, the substituent includes an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, and carbon atoms Saturated aliphatic acyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated aliphatic acyloxy group with 2 to 7 carbon atoms, monoalkanes with an alkyl group of 1 to 6 carbon atoms Alkylamino group, dialkylamino group having an alkyl group of 1 to 6 carbon atoms, morpholin-1-yl, piper
Figure 105127562-A0304-12-0001-4
-1-yl, halogen, nitro, and cyano, etc. To R 4 When the phenyl group, the naphthyl group, and the heterocyclic group contained in further have a substituent, the number of the substituent is not limited as long as it does not hinder the purpose of the present invention, and it is preferably 1 to 4. To R 4 When the phenyl group, naphthyl group, and heterocyclic group contained in have a plurality of substituents, the plurality of substituents may be the same or different. In organic base, R 4 Preferably, it is an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, and a thiophenylalkyl group which may have a substituent group on the aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups that may have a substituent, methylphenyl is preferred, and 2-methylphenyl is more preferred. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5-10, more preferably 5-8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1-8, more preferably 1-4, and particularly preferably 2. Among cycloalkylalkyls, cyclopentylethyl is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may also have a substituent on the aromatic ring is preferably 1-8, more preferably 1-4, and particularly preferably 2. Among the phenylthioalkyl groups that may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl is preferred. Also, as R 4 , Also preferably -A 3 -CO-OA 4 The base expressed. A 3 It is a divalent organic group, preferably a divalent hydrocarbon group, and more preferably an alkylene group. A 4 It is a monovalent organic group, preferably a monovalent hydrocarbon group. At A 3 In the case of an alkylene group, the alkylene group may be linear or branched, and is preferably linear. At A 3 In the case of an alkylene group, the number of carbon atoms of the alkylene group is preferably 1-10, more preferably 1-6, and particularly preferably 1-4. 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, second butyl, tertiary butyl, n-pentyl, n-hexyl, phenyl, Naphthyl, benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, etc. As-A 3 -CO-OA 4 Suitable specific examples of the represented group include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl, 2-n-butoxycarbonylethyl, 2-n-pentoxycarbonylethyl, 2-n-hexoxycarbonylethyl, 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-hexyloxy Carbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl, and 3-phenoxycarbonyl-n-propyl, etc. In formula (A2-1C), R 5 It is a monovalent organic group or a hydrogen atom. As a monovalent organic group, it is a C1-C11 alkyl group which may have a substituent, or an aryl group which may have a substituent, for example. As R 5 In the case of an alkyl group, the substituent which may be possessed is preferably exemplified by a phenyl group and a naphthyl group. In formula (A2-1C), as R 5 , Hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group, etc. can be preferably exemplified, among which methyl group is more preferable Or phenyl. Moreover, among the compounds represented by the formula (A2-1C), the compound represented by the following formula (A2-1C-1) or formula (A2-1C-2) is preferred. [化21]
Figure 02_image043
(In formula (A2-1C-1) and formula (A2-1C-2), R 2 , R 3 , R 4 , R 5 , And n have the same meaning as those represented by formula (A2-1C)) In addition, as the photopolymerization initiator (A2), a compound represented by the following formula (A2-1N) can also be used. [化22]
Figure 02_image045
(In formula (A2-1N), R 1 , R 2 , R 4 , R 5 , R 6 , And n are synonymous with those represented by formula (A2-1C)) In addition, among the compounds represented by formula (A2-1N), the following formula (A2-1N-1) or (A2-1N-2) is preferred The compound represented. [化23]
Figure 02_image047
(In formula (A2-1N-1) and formula (A2-1N-2), R 2 , R 4 , R 5 , And n are synonymous with those represented by formula (A2-1C)) Suitable specific examples of the compound represented by formula (A2-1C) and the compound represented by formula (A2-1N) include the following compounds 1 to Compound 71. [化24]
Figure 02_image049
[化25]
Figure 02_image051
[化26]
Figure 02_image053
[化27]
Figure 02_image055
[化28]
Figure 02_image057
The content of the photopolymerization initiator (A2) is preferably 0.05 to 2% by mass relative to the solid content of the photosensitive composition, more preferably 0.07 to 1.9% by mass, and still more preferably 0.1 to 1.7% by mass , Particularly preferably 0.15 to 1.5 mass%. If the content of the photopolymerization initiator (A2) is within the above range, the obtained cured product maintains a good transmittance, and the obtained composition tends to have sufficient sensitivity to exposure. The content of the photopolymerization initiator (A2) may be, for example, in the range of 0.1 to 50% by mass relative to the entire photopolymerization initiator (A), preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, more preferably 1.5-18% by mass. [Other photopolymerization initiators (A3)] The photosensitive composition may optionally contain other photopolymerization initiators (A3) other than the components (A1) and (A2) within the range that does not hinder the object of the present invention . Other photopolymerization initiators (A3) can be used alone or in combination of two or more kinds. Specific examples of other photopolymerization initiators (A3) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-( 2-hydroxyethoxy)phenyl)-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane- 1-ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-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-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1-one, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl) (Acetyl)-9H-carbazol-3-yl), 1-(o-Acetyl oxime), 2,4,6-trimethylbenzyl diphenylphosphine oxide, 4-benzyl oxime -4'-Methyl dimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl Butyl amino benzoate, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isopentyl benzoic acid, benzil-β-methoxyethyl Acetal, benzil dimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, methyl phthalate benzoate, 2,4- Diethyl-9-oxysulfur
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
, 2-chloro-9-oxysulfur
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
, 2,4-Dimethyl-9-oxysulfur
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
, 1-Chloro-4-propoxy-9-oxysulfur
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
,sulfur
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
, 2-Chlorosulfur
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
, 2,4-Diethylsulfide
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
, 2-Methylsulfide
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
, 2-isopropyl sulfide
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzyl peroxide, isopropyl peroxide Benzene, 2-mercaptobenzimidazole, 2-mercaptobenzo
Figure 105127562-A0304-12-0001-1
Azole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl) ) Imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4 ,4'-bis(dimethylamino) benzophenone (ie, Michele ketone), 4,4'-bis(diethylamino) benzophenone (ie, ethyl Michele Ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzidine, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether , Benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloro Acetophenone, trichloroacetophenone, p-tertiary butyl acetophenone, p-dimethylamino acetophenone, p-tertiary butyl trichloroacetophenone, p-tertiary butyl dichloroacetophenone , Α,α-Dichloro-4-phenoxyacetophenone, 9-oxysulfur
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
, 2-Methyl-9-oxysulfur
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
, 2-isopropyl-9-oxysulfur
Figure 105127562-A0304-12-0019-1
Figure 105127562-A0304-12-0019-3
, Dibenzocycloheptanone, pentyl 4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9- Acridinyl)pentane, 1,3-bis(9-acridinyl)propane, p-methoxytri
Figure 105127562-A0304-12-0001-4
, 2,4,6-tris(trichloromethyl)-tris
Figure 105127562-A0304-12-0001-4
, 2-Methyl-4,6-bis(trichloromethyl)-tris
Figure 105127562-A0304-12-0001-4
, 2-[2-(5-Methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-tris
Figure 105127562-A0304-12-0001-4
, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-tris
Figure 105127562-A0304-12-0001-4
, 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-tris
Figure 105127562-A0304-12-0001-4
, 2-[2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-tris
Figure 105127562-A0304-12-0001-4
, 2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-tris
Figure 105127562-A0304-12-0001-4
, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-tris
Figure 105127562-A0304-12-0001-4
, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-tris
Figure 105127562-A0304-12-0001-4
, 2,4-Bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-tris
Figure 105127562-A0304-12-0001-4
, 2,4-Bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-tris
Figure 105127562-A0304-12-0001-4
, 2,4-Bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-tris
Figure 105127562-A0304-12-0001-4
, 2,4-Bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-tris
Figure 105127562-A0304-12-0001-4
Wait. Among these, it is particularly preferable to use an oxime-based photopolymerization initiator in terms of sensitivity. When the photosensitive composition contains other photopolymerization initiators (A3) than the components (A1) and (A2), the content of the other photopolymerization initiators (A3) is such that it does not hinder the purpose of the present invention The range is not particularly limited. In this case, the content of the other photopolymerization initiator (A3) is typically preferably 99% by mass or less with respect to the total amount of the photopolymerization initiator contained in the photosensitive composition, and more preferably It is 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 0-10% by mass. <Polymerizable substrate component (B)> The photosensitive composition of the present invention may further contain a polymerizable substrate component (B). The polymerizable substrate component (B) (hereinafter, also referred to as "(B) component") is a component that imparts photopolymerization and film-forming ability to the photosensitive composition. The polymerizable substrate component (B) is not particularly limited as long as it contains a component that can be polymerized by the photopolymerization initiators (A1) and (A2) and is a component capable of preparing a photosensitive composition capable of forming a film. limited. The polymerizable substrate component (B) can be used alone or in combination of two or more kinds. The polymerizable base component (B) typically contains a photopolymerizable compound or a photopolymerizable compound and resin. The photopolymerizable compound may be a low-molecular compound or a high-molecular compound such as a resin. The photopolymerizable compound and the resin can be used alone or in combination of two or more kinds. As for the polymerizable base material component (B), in terms of photopolymerization properties, it is preferable to include a low molecular weight photopolymerizable compound (hereinafter, also referred to as "photopolymerizable monomer") that is not a polymer, and/ Or a resin containing a crosslinkable group. Moreover, when the polymerizable base material component (B) contains a resin, it is preferable to contain an alkali-soluble resin from the viewpoint of developability. The alkali-soluble resin may also contain a crosslinkable group. From the viewpoint of both photopolymerization properties and alkali developability, an alkali-soluble resin containing a crosslinkable group (including a crosslinkable group as a substituent in a structural unit) is preferred. Hereinafter, the photopolymerizable monomer, the crosslinkable group-containing resin, and the alkali-soluble resin as suitable components contained in the component (B) will be described in order. [Photopolymerizable monomer] As the photopolymerizable monomer contained in the photosensitive composition, a compound having an ethylenically unsaturated double bond can be preferably used. There are monofunctional monomers and polyfunctional monomers in the compound having ethylenically unsaturated double bonds. Examples of monofunctional monomers include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, and ethoxymethyl (meth)acrylic acid. Amide, propoxymethyl(meth)acrylamide, butoxymethoxymethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxymethyl (Meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylic acid Amine-2-methyl propane sulfonic acid, tertiary butyl acrylamide sulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid 2 -Ethylhexyl, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylate Base) 2-phenoxy-2-hydroxypropyl acrylate, 2-(meth)acryloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, (meth)acrylic acid Tetrahydrofurfuryl ester, dimethylamino (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2 (meth)acrylate ,3,3-Tetrafluoropropyl ester, half (meth)acrylate of phthalic acid derivatives, etc. These monofunctional monomers can be used individually or in combination of 2 or more types. On the other hand, as multifunctional monomers, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, (Meth) acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol bis(meth) ) Acrylate, ethoxylated hexanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, (meth)acrylate 2-hydroxy-3-(meth)acrylic acid Oxypropyl ester, dipentaerythritol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, three Propylene glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, poly(ethylene-propylene glycol) two (Meth) acrylate, polybutylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, acrylic Oxylated ethoxylated bisphenol A di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth) Acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane Glycol di(meth)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 , (Meth) acrylic acid 2-hydroxy-3-(meth) propylene oxypropyl ester, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether two (methyl) ) Acrylate, diglycidyl phthalate di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, (meth)acrylate urethane (i.e. , Toluene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc. and the reactants of 2-hydroxyethyl (meth)acrylate, methylene bis(meth)acrylamide, (Meth)acrylamide methylene ether, polyol and N-methylol (meth)acrylamide condensate, triacrylamide formal, 2,4,6-trilateral hexahydro -1,3,5-three
Figure 105127562-A0304-12-0001-4
-1,3,5-triethanol triacrylate, and 2,4,6-trilateral hexahydro-1,3,5-tri
Figure 105127562-A0304-12-0001-4
-1,3,5-triethanol diacrylate, etc. These polyfunctional monomers can be used individually or in combination of 2 or more types. Among these compounds having ethylenically unsaturated double bonds, in terms of obtaining a photosensitive composition that can provide a hardened product with excellent strength and excellent adhesion to a substrate, a trifunctional or higher polyfunctional monomer is preferred. From the viewpoint of controlling the glass transition point (Tg), a monofunctional monomer or a bifunctional monomer can be used in combination with a polyfunctional monomer with more than trifunctionality. Among these, 1,6-hexanediol is preferred. Di(meth)acrylate. The content of the photopolymerizable monomer is preferably from 5 to 60% by mass, and more preferably from 10 to 50% by mass with respect to the solid content of the photosensitive composition. By setting the content of the photopolymerizable monomer in the photosensitive composition within the above range, there is a tendency to easily obtain a balance of sensitivity, developability, and resolution of the photosensitive composition. [Crosslinkable group-containing resin] If the photosensitive composition of the present invention contains a crosslinkable group-containing resin, it tends to be easier to use the photosensitive composition to form a cured product. The crosslinkable group-containing resin is a crosslinkable group-containing resin, and preferably contains a unit derived from a (meth)acrylate having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a functional group that can crosslink the crosslinkable group-containing resin mainly by heating, but an epoxy group and an ethylenically unsaturated double bond are preferred. The crosslinkable group can be introduced into a crosslinkable group by including at least one of the group consisting of a unit derived from a (meth)acrylate having an epoxy group and a unit having an ethylenically unsaturated double bond. In the base resin. As a resin containing a crosslinkable group, the resin containing the unit derived from the (meth)acrylate which has an epoxy group is preferable. By having this unit, the adhesion or mechanical strength of the insulating film formed using the photosensitive composition to the substrate can also be improved. The (meth)acrylate having an epoxy group may be a (meth)acrylate having a chain aliphatic epoxy group, or the (meth)acrylate having an alicyclic epoxy group as described below. The (meth)acrylate having an epoxy group may also have an aromatic group. In this specification, the aromatic group is a group having an aromatic ring. Examples of the aromatic ring constituting the aromatic group include a benzene ring and a naphthalene ring. Examples of (meth)acrylates having an aromatic group and epoxy groups include 4-glycidoxyphenyl (meth)acrylate and 3-glycidoxyphenyl (meth)acrylate , 2-glycidoxyphenyl (meth)acrylate, 4-glycidoxyphenylmethyl (meth)acrylate, 3-glycidoxyphenylmethyl (meth)acrylate, and (meth)acrylate Base) 2-glycidoxyphenyl methyl acrylate and the like. When transparency is required for the film formed using a photosensitive composition, (meth)acrylic acid which has an epoxy group is preferable to have no aromatic group. Examples of (meth)acrylates having a chain aliphatic epoxy group include epoxy alkyl (meth)acrylate, epoxy alkoxyalkyl (meth)acrylate, etc. It is a kind of (meth)acrylate with chain aliphatic epoxy group bonded to the oxy group (-O-) in the ester group (-O-CO-). The chain aliphatic epoxy group possessed by such (meth)acrylate may contain one or more oxy groups (-O-) in the chain. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, but is preferably 3-20, more preferably 3-15, and particularly preferably 3-10. Specific examples of (meth)acrylates having a chain aliphatic epoxy group include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 3 (meth)acrylate ,4-epoxybutyl ester, 6,7-epoxyheptyl (meth)acrylate and other (meth)acrylate epoxy alkyl esters; (meth)acrylate 2-glycidoxyethyl, 3-glycidoxy-n-propyl (meth)acrylate, 4-glycidoxy-n-butyl (meth)acrylate, 5-glycidoxy-n-hexyl (meth)acrylate, (methyl) ) 6-glycidoxy-n-hexyl acrylate and other (meth)acrylate epoxy alkoxyalkyl esters. As a specific example of the (meth)acrylate which has an alicyclic epoxy group, the compound represented by following formula (d2-1)-(d2-16) is mentioned, for example. Among these, in order to moderate the developability of the photosensitive composition, the compounds represented by the following formulas (d2-1) to (d2-6) are preferred, and the following formulas (d2-1) to are more preferred. (d2-4) The compound represented by. In addition, regarding each of these compounds, the bonding site of the oxygen atom of the ester group to the alicyclic ring is not limited to those shown here, and may include partial positional isomers. [化29]
Figure 02_image059
In the above formula, R d4 Represents a hydrogen atom or a methyl group, R d5 Represents a divalent aliphatic saturated hydrocarbon group with 1 to 6 carbons, R d6 It represents a divalent hydrocarbon group with 1-10 carbon atoms, and n represents an integer of 0-10. As R d5 , Preferably a linear or branched alkylene group, such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene. As R d6 , For example, preferably methylene, ethylene, propylene, tetramethylene, ethyl ethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH 2 -Ph-CH 2 -(Ph represents phenylene). If the (meth)acrylate having an epoxy group is the (meth)acrylate having an alicyclic epoxy group as described above, it is the same as the (meth)acrylate having a chain aliphatic epoxy group In comparison, the crosslinkable group-containing resin containing the unit derived from the (meth)acrylate ester and the photosensitive composition are excellent in storage stability and can be pre-baked when forming an insulating film, etc. The range (pre-baking temperature margin) becomes wider, so it is preferable. The resin containing a crosslinkable group may also be a resin containing a unit having an ethylenically unsaturated double bond as a crosslinkable group (in this specification, it is also referred to as a "resin having an ethylenically unsaturated double bond"). The ethylenically unsaturated double bond preferably constitutes a part of the (meth)propylene oxy group. Examples of resins having ethylenically unsaturated double bonds include resins having (meth)acryloxy groups. The resin having a (meth)acryloyloxy group can be prepared by, for example, making at least a part of the carboxyl group contained in a polymer containing a unit derived from an unsaturated carboxylic acid and the aforementioned alicyclic epoxy resin (Meth)acrylate and/or the above-mentioned (meth)acrylate having a chain aliphatic epoxy group is reacted. When the resin containing a crosslinkable group is a resin having an ethylenically unsaturated double bond, it may be a resin having photopolymerization properties. Since the resin containing the crosslinkable group contains the photopolymerizable resin having the ethylenically unsaturated double bond, the curability of the photosensitive composition can be improved and the pattern formation can be facilitated. In the resin containing a crosslinkable group, the amount of the unit derived from the (meth)acrylate having a crosslinkable group is preferably 20 to 80% by mass, more preferably 30 relative to the mass of the resin ~70% by mass, and more preferably 33-65% by mass; the amount of units derived from (meth)acrylate having epoxy groups is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, More preferably, it is 20 to 65% by mass; the amount of the unit having an ethylenically unsaturated double bond is preferably 15 to 40% by mass, and more preferably 20 to 35% by mass. The resin containing a crosslinkable group is preferably a polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylate. In the case of the polymer, the source of the polymer is The content of the unit from the (meth)acrylate having a crosslinkable group is also the same as above with respect to the mass of the resin. The resin containing a crosslinkable group may also be a resin containing both units derived from epoxy-containing (meth)acrylate and units with ethylenically unsaturated double bonds, but may also contain The resin of either one of epoxy-based (meth)acrylate units or units with ethylenically unsaturated double bonds, preferably contains only units derived from epoxy-based (meth)acrylates as Cross-linkable resin. The resin containing a crosslinkable group is preferably a resin having a crosslinkable group, and it is an alkali-soluble resin. The photosensitive composition can impart alkali developability to the photosensitive composition by blending the alkali-soluble resin. In this specification, the so-called alkali-soluble resin means that a resin film with a thickness of 1 μm is formed on a substrate by a resin solution (solvent: propylene glycol monomethyl ether acetate) with a resin concentration of 20% by mass. When immersed in a 0.05 mass% KOH aqueous solution for 1 minute, the film thickness will dissolve at least 0.01 μm. When the resin containing a crosslinkable group is also an alkali-soluble resin, it usually has an alkali-soluble group. The alkali-soluble group is not particularly limited as long as it is a functional group that imparts solubility to the above-mentioned alkali to the resin containing a crosslinkable group. It is preferably a carboxyl group or a group that generates a carboxyl group by deprotection, for example, by containing the following The above-mentioned unit derived from unsaturated carboxylic acid can be introduced into a resin containing a crosslinkable group by polymerizing a monomer containing an alkali-soluble group-imparting (meth)acrylate. In this specification, the (meth)acrylate which imparts an alkali-soluble group can be what does not contain the (meth)acrylate which has the said crosslinkable group. As a resin containing a crosslinkable group, when it is also an alkali-soluble resin, it may also be a resin that does not have the following functional groups. The above-mentioned functional group inhibits or inhibits the solubility of the resin containing the crosslinkable group with respect to the alkali The functional group (hereinafter, sometimes referred to as "alkali dissolution inhibitor" or "dissolution inhibitor"), but preferably a resin having an alkali soluble group and a dissolution inhibitor. As for the dissolution inhibitor group, it can also be referred to as an alkali-hardly soluble group in terms of its function of reducing the solubility of the crosslinkable group-containing resin to alkali. The crosslinkable group-containing resin has an alkali-soluble group and a dissolution inhibitor group, so that the solubility to alkali can be adjusted, thereby allowing the alkali developability of the photosensitive composition to be adjusted. Examples of the dissolution inhibitor include the following styrene or styrene derivatives; unsaturated imines; (meth)acrylates having an alicyclic skeleton (except those having epoxy groups); (Meth)acrylates having aromatic groups such as benzyl methacrylate. In this specification, the (meth)acrylate to which the dissolution inhibiting group is imparted does not include the (meth)acrylate having the above-mentioned crosslinkable group. Among the resins containing crosslinkable groups, in terms of self-made film properties, or easy adjustment of resin characteristics by selecting monomers, polymers of monomers having ethylenically unsaturated double bonds are preferred. Examples of monomers having ethylenically unsaturated double bonds include (meth)acrylic acid; (meth)acrylate; (meth)acrylamide; crotonic acid; maleic acid, fumaric acid, citraconic acid , Meconic acid, itaconic acid, anhydrides of these dicarboxylic acids; allyl acetate, allyl hexanoate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate Allyl compounds such as esters, allyl benzoate, allyl acetate, allyl lactate, and allyloxyethanol; hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether , Ethylhexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethyl propyl vinyl ether , 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylamine Ethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorobenzene Vinyl ether, vinyl naphthyl ether, and vinyl anthracenyl ether; vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl pivalate Ester, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, methoxy vinyl acetate, butoxy vinyl acetate, vinyl phenyl acetate, vinyl acetyl acetate, vinyl lactate, β- Vinyl phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate; styrene, methyl styrene, Dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl Styrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, 4-methoxy-3-methylbenzene Ethylene, dimethoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, Styrene or styrene derivatives such as trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; 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-hexadecene, 1-octadecene, and 1-eicosene Alkenes; unsaturated imines such as maleimines, N-phenylmaleimines, N-cyclohexylmaleimines. When the resin containing a crosslinkable group is a polymer of a monomer having an ethylenically unsaturated double bond, it 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, citraconic acid, mesaconic acid, itaconic acid, etc. Anhydride of dicarboxylic acid. The amount of the unsaturated carboxylic acid-derived unit contained in the polymer of the monomer having the ethylenically unsaturated double bond used as the alkali-soluble resin is not particularly limited as long as the resin has the required alkali solubility. The amount of unsaturated carboxylic acid-derived units in the resin used as an alkali-soluble resin is preferably 5-25% by mass, more preferably 8-16% by mass relative to the mass of the resin. The same amount is particularly preferred when the resin of the resin has the following dissolution inhibitor. When the crosslinkable group-containing resin does not have the following dissolution inhibiting group, the amount of the unsaturated carboxylic acid-derived unit in the resin is preferably 50 to 80% by mass relative to the mass of the resin , More preferably 60 to 70% by mass. Among the polymers of monomers having ethylenically unsaturated double bonds, which are polymers of one or more monomers selected from the monomers exemplified above, preferably selected from (meth)acrylic acid and (meth) A polymer of more than one monomer of acrylate. Hereinafter, the polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid ester will be described. The (meth)acrylate used in the preparation of the polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylate is not particularly limited as long as it is in a range that does not hinder the purpose of the present invention. It can be appropriately selected from known (meth)acrylates. Suitable examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, pentyl (meth)acrylate, and (meth)acrylic acid. The third octyl ester and other linear or branched (meth) acrylate alkyl esters; (meth) chloroethyl acrylate, (meth) acrylate 2,2-dimethyl hydroxypropyl ester, (methyl) ) 2-hydroxyethyl acrylate, trimethylolpropane mono(meth)acrylate, furfuryl (meth)acrylate; benzyl (meth)acrylate and other (meth)acrylates with aromatic groups; with (Meth)acrylate with alicyclic skeleton. The details of the (meth)acrylate having an alicyclic skeleton will be described later. In addition, in the polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid esters, the photosensitive composition can be easily used to form an insulating film with high transmittance. The resin of the unit of (meth)acrylate of cyclic skeleton is also preferable. In this specification, the (meth)acrylate having an alicyclic skeleton does not include the above-mentioned (meth)acrylate having a crosslinkable group. In the (meth)acrylate having an alicyclic skeleton, the group having an alicyclic skeleton is preferably a group having an alicyclic hydrocarbon group. The alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl and cyclohexyl. Moreover, as the polycyclic alicyclic group, there can be mentioned
Figure 105127562-A0304-03-0013-01
Base, different
Figure 105127562-A0304-03-0013-01
Group, tricyclononyl, tricyclodecyl, tetracyclododecyl, etc. As the (meth)acrylate having an alicyclic hydrocarbon group in the (meth)acrylate having an alicyclic skeleton, for example, compounds represented by the following formulas (d1-1) to (d1-8) can be cited. Among these, the compounds represented by the following formulas (d1-3) to (d1-8) are preferred, and the compounds represented by the following formulas (d1-3) or (d1-4) are more preferred. [化30]
Figure 02_image061
In the above formula, R d1 Represents a hydrogen atom or a methyl group, R d2 Represents a single bond or a divalent aliphatic saturated hydrocarbon group with 1 to 6 carbon atoms, R d3 It represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As R d2 , Preferably a single bond, linear or branched alkylene, such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene base. As R d3 , Preferably methyl and ethyl. The resin containing a crosslinkable group is preferably a resin containing the following units: units derived from one or more monomers selected from (meth)acrylic acid and (meth)acrylate, derived from alicyclic epoxy groups The (meth)acrylate unit. The resin may also be a resin that further contains units derived from (meth)acrylate having an alicyclic skeleton. In this case, the resin in the resin is derived from units derived from (meth)acrylate having an alicyclic skeleton The amount can be 10 to 35% by mass, 15 to 30% by mass, or 20 to 25% by mass. In addition, in a polymer containing one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid esters, which are derived from units derived from (meth)acrylic acid esters having an alicyclic skeleton, it is preferable to include a source A resin derived from a unit of (meth)acrylic acid and a unit of (meth)acrylate having an alicyclic epoxy group. A film formed using a photosensitive composition containing such a crosslinkable group-containing resin has excellent adhesion to the substrate. In addition, in the case of using such a resin, a self-reaction between the carboxyl group and the alicyclic epoxy group contained in the resin may occur. Therefore, if a photosensitive composition containing such a resin is used, it is possible to generate self-reaction between carboxyl groups and alicyclic epoxy groups by heating the film, etc., thereby increasing the hardness of the formed film. Improved mechanical properties. In resins containing units derived from (meth)acrylic acid (except those with crosslinkable groups) and units derived from (meth)acrylates with alicyclic epoxy groups, the resins are derived from the former ( The amount of meth)acrylic acid units is preferably 1 to 95% by mass, more preferably 10 to 70% by mass. In the resin containing the unit derived from (meth)acrylic acid and the unit derived from (meth)acrylate having alicyclic epoxy group, the resin in the resin is derived from the (meth)acrylate having alicyclic epoxy group The amount of the acrylate unit is preferably 1 to 95% by mass, more preferably 10 to 50% by mass. At least one monomer selected from (meth)acrylic acid and (meth)acrylate containing units derived from (meth)acrylic acid and units derived from (meth)acrylate having alicyclic epoxy groups In the polymer of the body, it is also possible to include units derived from (meth)acrylic acid, units derived from (meth)acrylates with alicyclic hydrocarbon groups, and units derived from (meth)acrylates with alicyclic epoxy groups. ) Resins of acrylate units. In resins containing units derived from (meth)acrylic acid, units derived from (meth)acrylates with alicyclic hydrocarbon groups, and units derived from (meth)acrylates with alicyclic epoxy groups The amount of (meth)acrylic acid-derived units in the resin is preferably 1 to 95% by mass, more preferably 10 to 50% by mass. In resins containing units derived from (meth)acrylic acid, units derived from (meth)acrylates with alicyclic hydrocarbon groups, and units derived from (meth)acrylates with alicyclic epoxy groups The amount of the unit derived from the (meth)acrylate having an alicyclic hydrocarbon group in the resin is preferably 1 to 95% by mass, more preferably 10 to 70% by mass. In resins containing units derived from (meth)acrylic acid, units derived from (meth)acrylates with alicyclic hydrocarbon groups, and units derived from (meth)acrylates with alicyclic epoxy groups The amount of the unit derived from the (meth)acrylate having an alicyclic epoxy group in the resin is preferably 1-95% by mass, more preferably 30-80% by mass. The mass average molecular weight (Mw: measured value of gel permeation chromatography (GPC) conversion of polystyrene. The same as in this specification) of the resin containing crosslinkable groups is preferably 2000 to 200000, more preferably 2000 to 18000 . By setting it as the above-mentioned range, there exists a tendency for the balance of the film-forming ability of a photosensitive composition and the developability after exposure to be easily obtained. The content of the crosslinkable group-containing resin in the photosensitive composition is preferably 15-95% by mass, more preferably 35-85% by mass, and particularly preferably 50-70 in the solid content of the photosensitive composition quality%. [Alkali-soluble resin] The alkali-soluble resin can be appropriately selected from resins that have been blended in various photosensitive compositions from before. Furthermore, in this specification, the above-mentioned crosslinkable group-containing resin is not included in the alkali-soluble resin. Although there are cases in which the alkali developability of the photosensitive composition can be improved by blending an alkali-soluble resin in the photosensitive composition, the photosensitive composition of the present invention can also be alkali-soluble even if it does not contain alkali-soluble resin. The above-mentioned crosslinkable group-containing resin of the soluble resin has alkali developability. As a suitable alkali-soluble resin, the polymer containing the structural unit which has a ring structure in a main chain is mentioned. Furthermore, in this specification, a polymer containing a structural unit having a ring structure in the main chain does not include a polymer of a monomer having an unsaturated bond. Hereinafter, the polymer containing a structural unit having a ring structure in the main chain will be described. (Polymer containing a structural unit having a ring structure in the main chain) The polymer containing a structural unit having a ring structure in the main chain is not particularly limited if it is a resin having a specific ring structure and having specific alkali solubility. A suitable example of a polymer containing a structural unit having a ring structure in the main chain includes a polymer containing a structural unit derived from maleimine (hereinafter, also referred to as "structural unit (A2a)") (hereinafter , Also referred to as "polymer (A2)") and a polymer containing the structural unit represented by the following formula (A-1) (hereinafter also referred to as "structural unit (A1a)") (hereinafter also referred to as "Polymer (A1)"). The maleimine-derived structural unit (A2a) possessed by the polymer (A2) is not particularly limited as long as it is obtained by polymerizing a monomer having a maleimine skeleton. As a monomer having a maleimide skeleton, for example, N-benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like can be cited. In particular, the photosensitive composition containing the polymer (A1) has good solubility in the developer, and the polymer (A1) contains a structural unit (A1a) having a ring structure in the main chain. [化31]
Figure 02_image063
In the formula (A-1), the ring A is a saturated aliphatic cyclic group with 4 to 6 carbons having one oxygen atom as a ring constituent atom. Ring A is preferably a saturated aliphatic cyclic group with 4 or 5 carbon atoms having one oxygen atom as the ring constituent atom, more preferably a tetrahydrofuran ring or a tetrahydropyran ring, and still more preferably the following formula (A- 3) The tetrahydropyran ring in the structural unit represented (hereinafter, also referred to as "structural unit (A1a1)") or the structural unit represented by the following formula (A-4) (hereinafter, also referred to as "structural unit (A1a1)") The tetrahydrofuran ring in unit (A1a2)”). [化32]
Figure 02_image065
The polymer (polymer (A1)) containing the structural unit represented by the above formula (A-1) in the main chain usually contains a plurality of structural units represented by the above formula (A-1) in the main chain (structural unit (A1a) )). Among the plural structural units (A1a), the ring A contained in each structural unit (A1a) may be the same as or different from each other in one main chain constituting the polymer (A1). Specifically, one main chain constituting the polymer (A1) may have only the structural unit represented by the above formula (A-3) as the structural unit represented by the above formula (A-1) contained in the main chain, for example, It may have only the structural unit represented by the above formula (A-4) as the structural unit represented by the above formula (A-1) contained in the main chain, or may be combined with the structural unit represented by the above formula (A-3) The structural unit and the structural unit represented by the above formula (A-4) are the structural unit represented by the above formula (A-1) contained in the main chain. In the above formula (A-1), formula (A-3) and formula (A-4), R b1 And R b2 Each independently is a hydrogen atom or -COOR b3 , R b3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. R b1 And R b2 Preferably -COOR b3 . When one main chain of the polymer (polymer (A1)) containing the structural unit represented by the above formula (A-1) contains a plurality of rings A, -COOR bonded to each ring A b3 Separately, as -COOR b3 The same or different groups can also be bonded to each ring A. As R b1 And R b2 The represented hydrocarbon group having 1 to 25 carbon atoms which may have a substituent is not particularly limited. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, tertiary pentyl, stearyl, lauryl, 2-ethyl Linear or branched alkyl groups such as hexyl; aryl groups such as phenyl; cyclohexyl, tertiary butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, iso
Figure 105127562-A0304-03-0013-01
Alkyl group, adamantyl group, 2-methyl-2-adamantyl group, etc.; 1-methoxyethyl group, 1-ethoxyethyl group, etc. substituted by alkoxy; benzyl group, etc. Alkyl substituted by aryl, etc. To R b1 And R b2 In the case of a hydrocarbon group, the number of carbon atoms of the hydrocarbon group is preferably 8 or less. The hydrocarbon group having 8 or less carbon atoms is unlikely to be removed by acid or heat, and it is preferably a hydrocarbon group having a single-terminal free bonding bond with a primary carbon atom or a secondary carbon atom. As such a hydrocarbon group, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms is preferable. As a specific example of such a hydrocarbon group, a methyl group, an ethyl group, a cyclohexyl group, a benzyl group, etc. are mentioned, Preferably it is a methyl group. When a main chain of a polymer (polymer (A1)) containing the structural unit represented by the above formula (A-1) (structural unit (A1a)) contains a plurality of structural units (A1a), each structure R bonded on unit (A1a) b1 And R b2 It may be the same or different among each structural unit (A1a). When it contains the same or different ring A among the structural units (A1a), R b1 And R b2 It does not depend on the type of each ring A to be bonded but is independent of each other. Specifically, when one main chain constituting the polymer (A1) contains a plurality of structural units (structural unit (A1a1)) represented by the above formula (A-3), R in each structural unit (A1a1) b1 And R b2 It may be the same or different among each structural unit (A1a1). When one main chain constituting the polymer (A1) contains a plurality of structural units (structural unit (A1a2)) represented by the above formula (A-4), R in each structural unit (A1a2) b1 And R b2 It may be the same or different among each structural unit (A1a2). Furthermore, one main chain constituting the polymer (A1) contains the structural unit represented by the above formula (A-3) (structural unit (A1a1)) and the structural unit represented by the above formula (A-4) (structural unit ( In the case of A1a2)), the R in each structural unit (A1a1) b1 And R b2 And R in each structural unit (A1a2) b1 And R b2 Can be the same or different. The structural unit represented by the above formula (A-3) (structural unit (A1a1)) may also be a part of the repeating unit represented by the following formula (A-5) (hereinafter also referred to as "repeating unit (ar1)") . The structural unit (structural unit (A1a2)) represented by the above formula (A-4) may also be a part of the repeating unit represented by the following formula (A-6) (hereinafter also referred to as "repeating unit (ar2)") . [化33]
Figure 02_image067
(In formula (A-5) and formula (A-6), R b1 And R b2 Each independently is the same as above) As a monomer that provides each repeating unit represented by the above formulas (A-5) and (A-6), for example, 1,6-dienes represented by the following formulas can be cited. [化34]
Figure 02_image069
(In the above formula, R b3 Each independently is the same as above) is provided in the monomer composition of the polymer (polymer (A1)) containing the structural unit (structural unit (A1a)) represented by the above formula (A-1) in the main chain, The content ratio of the monomer (A1ma) containing the repeating unit of the structural unit (A1a) (which may contain the above structural unit (A1a1) and the structural unit (A1a2)) is relative to the total amount of monomers in the monomer composition It is preferably 1% by mass to 60% by mass, more preferably 5% by mass to 50% by mass, and particularly preferably 10% by mass to 40% by mass. The polymer (A1) is preferably a repeating unit (A1b) having an acid group in the side chain. If the polymer (A1) has a repeating unit (A1b) having an acid group in the side chain, a photosensitive composition having excellent alkali developability can be obtained. As the monomer (A1mb) which becomes the repeating unit (A1b) having an acid group in the side chain, for example, (meth)acrylic acid, 2-(meth)acryloxyethyl succinic acid, Ikon Acids, ω-carboxy-polycaprolactone monoacrylate and other monomers with carboxyl groups; monomers with carboxylic anhydride groups such as maleic anhydride and itaconic anhydride. Among them, (meth)acrylic acid is preferred. In the monomer composition providing the polymer (A1), the content ratio of the monomer (A1mb) that becomes the repeating unit (A1b) having an acid group in the side chain is relative to the monomer composition in the monomer composition The total amount is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and still more preferably 10% by mass to 35% by mass. It is preferable that the polymer (A1) has a repeating unit (A1c) having a carbon double bond in the side chain. The repeating unit (A1c) having a carbon double bond in the side chain can be obtained by the following method: taking part or all (preferably a part) of the acid group of the repeating unit (A1b) having an acid group in the side chain as the reaction point , Add compounds with carbon double bonds. When the acid group of the repeating unit (A1b) having an acid group in the side chain is a carboxyl group, as the compound having a carbon double bond, a compound having an epoxy group and a double bond, a compound having an isocyanate group and a double bond, etc. can be used . As the compound having an epoxy group and a double bond, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, o-vinylbenzyl glycidyl ether, methylene Benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, etc. As a compound which has an isocyanate group and a double bond, 2-isocyanatoethyl (meth)acrylate etc. are mentioned. When the acid group of the repeating unit (A1b) having an acid group in the side chain is a carboxylic anhydride group, as the compound having a carbon double bond, a compound having a hydroxyl group and a double bond can be used. As a compound which has a hydroxyl group and a double bond, 2-hydroxyethyl (meth)acrylate etc. are mentioned, for example. The polymer (A1) may further have other repeating units (A1e), and the above-mentioned other repeating units (A1e) are derived from others that can be copolymerized with the above monomers (A1ma), monomers (A1mb) and/or monomers (A1mc) Monomer (A1me). As the other monomer (A1me), for example, it may further have a repeating unit having two or more oxyalkylene groups in the side chain. Examples of the repeating unit having two or more oxyalkylene groups in the side chain include repeating units represented by the following formulas. [化35]
Figure 02_image071
In the above formula, R b7 , R b8 And R b9 Each is independently a hydrogen atom or a methyl group, preferably a hydrogen atom. R b10 It is a linear or branched alkyl group with 1 to 20 carbons, a linear or branched alkenyl group with 2 to 20 carbons, or an aromatic hydrocarbon group with 6 to 20 carbons, preferably hydrogen Atoms, straight-chain alkyl with 1-20 carbons, straight-chain alkenyl with 2-20 carbons, or aromatic hydrocarbon group with 6-20 carbons, more preferably 1-10 carbons A straight-chain alkyl group or an aromatic hydrocarbon group with 6-12 carbons, more preferably a straight-chain alkyl group with 1 to 5 carbons, a phenyl group or a biphenyl group, and a methyl group, Phenyl or biphenyl. Furthermore, an alkyl group, an alkenyl group, and an aromatic hydrocarbon group may have a substituent. AO represents an oxyalkylene group. The carbon number of the oxyalkylene group represented by AO is 2-20, preferably 2-10, more preferably 2-5, and still more preferably 2. The repeating unit having two or more oxyalkylene groups in the side chain may contain one or more oxyalkylene groups. x represents an integer of 0-2. y represents 0 or 1. z represents the average added mole number of the oxyalkylene group, and is 2 or more, preferably 2-100, more preferably 2-50, and still more preferably 2-15. The repeating unit having two or more oxyalkylene groups in the side chain is constituted by a monomer having two or more oxyalkylene groups in the side chain. Examples of the monomer include monomers represented by the following formula. [化36]
Figure 02_image073
(In the above formula, R b7 , R b8 , R b9 , R b10 , AO, x, y, and z are as described above) As the monomer having two or more oxyalkylene groups in the side chain, for example, ethoxylated o-phenylphenol (meth)acrylate (EO is 2 mol), phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate (EO is 4 mol), methoxy polyethylene glycol (methyl) ) Acrylate (EO is 9 mol), methoxy polyethylene glycol (meth) acrylate (EO is 13 mol), methoxy triethylene glycol (meth) acrylate, ethoxy two Ethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, 2-ethylhexyldiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylic acid Ester, methoxy polypropylene glycol (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate (EO is 4-17 mol), nonyl phenoxy polypropylene glycol (meth) Acrylate (PO is 5 mol), EO modified cresol (meth)acrylate (EO is 2 mol), etc. These monomers can be used individually or in combination of 2 or more types. Among them, ethoxylated ortho-phenylphenol (meth)acrylate (EO is 2 mol), methoxy polyethylene glycol (meth)acrylate (EO is 9 mol), methoxy Polyethylene glycol (meth)acrylate (13 mol EO). More preferably, ethoxylated ortho-phenylphenol acrylate (EO is 2 mol), methoxy polyethylene glycol acrylate (EO is 9 mol), methoxy polyethylene glycol acrylate (EO Is 13 moles). In addition, in this specification, notation systems such as "EO is 2 mol" and "PO is 5 mol" represent the average number of added mol of oxyalkylene. Examples of other monomers (A1me) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylate. N-Butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid Lauryl ester, stearyl (meth)acrylate, phenyl (meth)acrylate, biphenyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate , Butoxyethylene glycol (meth)acrylate, 2-Ethylhexyl glycol (meth)acrylate, Methoxypropylene glycol (meth)acrylate, Phenoxyethyl (meth)acrylate , Biphenoxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, tricyclodecyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, (methyl) )Tricyclodecyloxyethyl acrylate, nonylphenoxyethylene glycol (meth)acrylate, nonylphenoxypropylene glycol, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate , Ethoxylated o-phenylphenol (meth)acrylate and other (meth)acrylates; (meth)acryloylmorpholine ((meth)acrylate morpholinyl ester), (meth)propylene Amide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) propylene Amide, N-tertiary butyl (meth) acrylamide, N-tertiary octyl (meth) acrylamide, diacetone (meth) acrylamide, N-hydroxymethyl (meth) Acrylic amide, N-hydroxyethyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) propylene (Meth)acrylamides such as amide, N-triphenylmethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, etc.; styrene, vinyl toluene, α -Aromatic vinyl compounds such as methyl styrene; butadiene or substituted butadiene compounds such as butadiene and isoprene; ethylene or substituted vinyl compounds such as ethylene, propylene, vinyl chloride, and acrylonitrile ; Vinyl esters such as vinyl acetate. These monomers can be used individually or in combination of 2 or more types. In the monomer composition providing the polymer (A1), the content ratio of the monomer (A1me) providing other repeating units (A1e) is preferably 0 relative to the total amount of monomers in the monomer composition Mass%-55% by mass, more preferably 5% by mass to 50% by mass, and still more preferably 10% by mass to 45% by mass. The polymer (A1) may be a random copolymer or a block copolymer. As a polymer (A1), it can use individually or in combination of 2 or more types. The weight average molecular weight of the polymer (A1) is preferably a value measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, preferably 3,000 to 200,000, more preferably 3,500 to 100,000, and further More preferably, it is 4,000 to 50,000. If it is such a range, it is possible to obtain a photosensitive composition having a viscosity suitable for forming a coating film while ensuring heat resistance. The polymer (A1) can be obtained by polymerizing the monomer composition that provides the polymer (A1) by any suitable method. As the polymerization method, for example, a solution polymerization method can be cited. The monomer composition for providing the polymer (A1) may contain any suitable solvent. As the solvent, for example, tetrahydrofuran, two
Figure 105127562-A0304-12-0001-1
Ethers such as alkane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetic acid Ester, 3-methoxybutyl acetate and other esters; alcohols such as methanol and ethanol; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, etc.; chloroform; dimethyl sulfide, etc. These solvents can be used individually or in combination of 2 or more types. The polymerization concentration during the polymerization of the monomer composition is preferably 5 mass% to 90 mass%, more preferably 5 mass% to 50 mass%, and still more preferably 10 mass% to 50 mass%. The monomer composition providing the polymer (A1) may contain any suitable polymerization initiator. Examples of the polymerization initiator include cumene hydroperoxide, dicumyl benzene hydroperoxide, di-tert-butyl peroxide, lauryl peroxide, benzyl peroxide, and isopropyl peroxide. Tertiary butyl ester, tertiary pentyl peroxy-2-ethylhexanoate, tertiary butyl peroxy-2-ethylhexanoate and other organic peroxides; 2,2'-azobis(isobutyronitrile ), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methyl Azo compounds such as propionic acid) dimethyl ester. The content ratio of the polymerization initiator is preferably 0.1 parts by mass to 15 parts by mass, and more preferably 0.5 parts by mass to 10 parts by mass relative to 100 parts by mass of all monomers in the monomer composition. The polymerization temperature when polymerizing the polymer (A1) by the solution polymerization method is preferably 40°C to 150°C, more preferably 60°C to 130°C. When obtaining a polymer (A1) having a repeating unit (A1c) having a carbon double bond in a side chain, after the above polymerization, the compound having a carbon double bond is added to the obtained polymer. As a method of adding a compound having a carbon double bond, any appropriate method can be adopted. For example, in the presence of a polymerization inhibitor and a catalyst, a compound having a carbon double bond is reacted with part or all (preferably a part) of the acid group of the repeating unit (A1b) having an acid group in the side chain. This can form a repeating unit (A1c) having a carbon double bond in the side chain. The addition amount of the compound having a carbon double bond is preferably 5 parts by mass or more relative to 100 parts by mass of the polymer after the polymerization (ie, the polymer before adding the compound having the carbon double bond), and more It is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more. If it is this range, the photosensitive composition excellent in exposure sensitivity can be obtained. If such a photosensitive composition is used, there is a tendency that a dense hardened coating film is easily formed, and a pattern with excellent substrate adhesion also tends to be obtained. In addition, if the addition amount of the compound having a carbon double bond is in the above range, the hydroxyl group can be sufficiently generated by the addition of the compound having a carbon double bond, and a photosensitive composition having excellent solubility in alkaline developers can be obtained. Things. The upper limit of the addition amount of the compound having a carbon double bond is preferably 170 parts by mass or less relative to 100 parts by mass of the polymer after the above polymerization (ie, the polymer before addition of the compound having a carbon double bond) , More preferably 150 parts by mass or less, and still more preferably 140 parts by mass or less. If the addition amount of the compound having a carbon double bond is within the above range, the storage stability and solubility of the photosensitive composition can be maintained. Examples of the polymerization inhibitor include alkylphenol compounds such as 6-tert-butyl-2,4-xylenol. Examples of the catalyst include tertiary amines such as dimethylbenzylamine and triethylamine. The alkali-soluble resin described above may also contain a resin other than the polymer together with a polymer containing a structural unit having a ring structure in the main chain. The content of the alkali-soluble resin in the photosensitive composition is preferably 40% by mass or less, more preferably 30-10% by mass, and particularly preferably 25-15% by mass relative to the mass of the solid component of the photosensitive composition %. Furthermore, the content of the alkali-soluble resin in the polymerizable substrate component (B) is preferably 80% by mass or less, more preferably 60 to 20% by mass, and particularly preferably 50 to 30% by mass. <Other components> The photosensitive composition of the present invention may optionally contain various additives. Specifically, solvents, surface modifiers, sensitizers, hardening accelerators, photocrosslinkers, photosensitizers, dispersing aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, Thermal polymerization inhibitors, defoamers, surfactants, chain transfer agents, etc. Any additives can use previously known additives. Examples of the surfactant include anionic compounds, cationic compounds, nonionic compounds, and the like. As the adhesion promoter, a conventionally known silane coupling agent can be cited. As a thermal polymerization inhibitor, hydroquinone, hydroquinone monoethyl ether, etc. are mentioned. Examples of the defoaming agent include silicone compounds and fluorine compounds. Examples of chain transfer agents include thiol-based compounds, halogen-based compounds, quinone-based compounds, α-methylstyrene dimer, and the like. By containing a chain transfer agent, the pattern shape (especially the CD change of the hole pattern and the exposure margin) can be well controlled. Among them, 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer), in addition to the above effects, is more effective in terms of reducing sublimation, coloring, and odor. good. Examples of the solvent used in the photosensitive composition of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol monomethyl ether. 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, etc. (poly)alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethyl Glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Alkyl lactate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethoxy ethyl propionate, ethoxy ethyl acetate, hydroxy ethyl acetate, 2-hydroxy-3-methylbutyrate methyl ester, 3-methyl-3-methoxybutyl acetate, propionic acid 3-Methyl-3-methoxybutyl ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-propionate Butyl ester, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, acetone Other esters such as ethyl acetate and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethylformamide, N,N- Dimethyl acetamide and other amides. These solvents may be used alone or in combination of two or more kinds. Among the above 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 methyl ethyl Ether, cyclohexanone, and 3-methoxybutyl acetate show excellent solubility for the above-mentioned (A1) component and (A2) component and optional (B) component, so it is preferred; particularly preferably, propylene glycol mono Methyl ether acetate, 3-methoxybutyl acetate. The content of the solvent can be appropriately determined according to the use of the photosensitive composition, and as an example, it may be about 50 to 900 parts by mass relative to 100 parts by mass of the total solid components of the photosensitive composition. <The preparation method of the photosensitive composition> The photosensitive composition of the present invention can be prepared by stirring, mixing and dissolving the above-mentioned components using a magnetic stirrer, and filtering with a filter such as a 0.2 μm membrane filter if necessary. As the photosensitive composition of the present invention, since the transmittance of the cured product obtained is easy to change, the transmittance measured by the optical path length of 3 μm for light with a wavelength of 400 nm is preferably 95% Above, more preferably 98% or more. ≪Pattern forming method, cured product, and display device≫ The pattern forming method of the present invention is the same as the previous pattern forming method formed by using the photosensitive composition except that the above-mentioned photosensitive composition is used. The method of forming a pattern using the said photosensitive composition is not specifically limited, It can select suitably from the method used previously. As a suitable pattern formation method, a method including the following steps: forming a coating film or a molded body, forming a coating film or a molded body using the above-mentioned photosensitive composition; an exposure step, forming a specific pattern on the coating film or molded body Shape irradiating electromagnetic waves; the developing step is to develop the coating film or molded body irradiated with electromagnetic waves to form a pattern. First, in the coating film or molded body forming step, for example, on the substrate to be patterned, use a roll coater, a reverse coater, a bar coater, etc. to contact a transfer coating device or spinner Coating the photosensitive composition of the present invention with a non-contact coating device such as a (rotary coating device), a curtain-type flat coater, and drying (pre-baking) to remove the solvent, and/or The above-mentioned photosensitive composition is molded by a known molding method to form a coating film or a molded body. Next, the formed coating film or molded body is subjected to an exposure step. In the exposure step, ArF excimer laser, KrF excimer laser, F 2 Excimer lasers, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beams, X-rays, soft X-rays, g-rays, i-rays, h-rays and other radiation or electromagnetic waves to partially expose the coating film or molded body to Specific pattern shape. The amount of exposure varies according to the composition of the photosensitive composition, for example, 10 mJ/cm is preferred 2 ～600 mJ/cm 2 about. The above-mentioned photosensitive composition is unlikely to be excessively dissolved in an alkaline developer after exposure. Therefore, by using the above-mentioned photosensitive composition, it is easy to form a pattern with a good shape in which the exposed part is a convex part and the unexposed part is a concave part. In the development step, a specific pattern is formed by developing a coating film or a molded body irradiated with electromagnetic waves by a developer. The development method is not particularly limited, and a dipping method, spray method, etc. can be used. Specific examples of the developer include organic developers such as monoethanolamine, diethanolamine, and triethanolamine, or aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. Then, if necessary, post-baking may be performed on the developed pattern to heat and harden, thereby obtaining a hardened pattern. The post-baking temperature is preferably 150 to 270°C. The cured product of the present invention is formed using the above-mentioned photosensitive composition. The cured product is preferably an insulating film or a protective film laminated on a photoresist film. When the above-mentioned cured product is prepared into a sample with a thickness of 3 μm (optical path length is 3 μm), the transmittance of light with a wavelength of 400 nm is usually 95% or more, preferably 98% or more. As mentioned above, the cured material has excellent transmittance, so it can be used as an in-cell touch panel type liquid crystal display device, UHA (Ultra High Aperture, ultra-high aperture) panel and other display devices that require an insulating film with excellent transparency Use an insulating film appropriately. [Examples] Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples. [Preparation of photosensitive composition] 65 parts by mass of resin containing crosslinkable groups, 35 parts by mass of photopolymerizable monomers, type and amount of photopolymerization initiator as shown in Table 1, diethylene glycol methyl A mixed solvent (mass ratio of 55:45) of methyl ethyl ether and propylene glycol monomethyl ether acetate was mixed to prepare a uniform solution, and a photosensitive composition with a solid content concentration of 24% by mass was prepared. Furthermore, the total amount of the resin containing the crosslinkable group and the photopolymerizable monomer was set to 100 parts by mass. In Example 11, the total amount of the photopolymerization initiator was 4.5 parts by mass. The total amount of the polymerization initiator is 4 parts by mass, and the total amount of the photopolymerization initiator is 5 parts by mass in the examples and all comparative examples other than this. In addition, in Examples 1-12 and Comparative Examples 1-22, the crosslinkable group-containing resin A shown below was used, and in Example 13 and Example 14, the crosslinkable group-containing resin A shown below was used的resin B. As the resin A containing a crosslinkable group, a resin containing a structural unit represented by the following formula is used. The mass ratio of the structural units I-1:I-2:II-1:III-1 is 25:20:14:41. The mass average molecular weight (Mw) of the crosslinkable group-containing resin A determined by gel permeation chromatography (GPC) was 7000. [化37]
Figure 02_image075
As the resin B containing a crosslinkable group, a resin containing a structural unit represented by the following formula is used. The mass ratio of the structural units I-3:II-1:III-2 is 71:12:17. The mass average molecular weight (Mw) of the crosslinkable group-containing resin B determined by gel permeation chromatography (GPC) was 10,200. Furthermore, as the structural unit I-3, a structure including the structure of I-3 shown below and the structure of I-3α as a partial positional isomer thereof is used. [化38]
Figure 02_image077
[化39]
Figure 02_image079
As the photopolymerizable monomer, dipentaerythritol hexaacrylate was used. As the photopolymerization initiator, initiators 1 to 11 represented by the following formulae were prepared, and initiators 1 and 3 to 11 were used in the preparation of the photosensitive composition, and the evaluation and measurement of sensitivity and transmittance. Photopolymerization initiator (A1) ・Initiator 1: The compound represented by the following formula (A1-1) ・Initiator 2: The compound represented by the following formula (A1-2) [Chemical 40]
Figure 02_image081
Photopolymerization initiator (A2) ・Initiator 3: A compound represented by the following formula (A2-1) ・Initiator 4: A compound represented by the following formula (A2-2) ・Initiator 5: The compound represented by the following formula (A2-3)・Starter 7: The compound represented by the following formula (A2-4)・Starter 9: The compound represented by the following formula (A2-5)・Starter Starting agent 12: The compound represented by the following formula (A2-6) [Chemical Compound 41]
Figure 02_image083
Figure 02_image085
Other photopolymerization initiator (A3) ・Initiator 6: The compound represented by the following formula (A3-1) ・Initiator 8: The compound represented by the following formula (A3-2) ・Initiator 10 : The compound represented by the following formula (A3-3)·Starter 11: The compound represented by the following formula (A3-4) [Chemical 42]
Figure 02_image087
With regard to the photosensitive compositions obtained in the respective examples and comparative examples, the sensitivity and transmittance were evaluated and measured according to the following methods. The evaluation results are shown in Table 1. (Sensitivity) After spin-coating the photosensitive composition prepared in each of the above examples and comparative examples with a spinner (Mikasa spinner IH-360S, manufactured by Mikasa Co., Ltd.) on a glass substrate, the temperature was set at 100°C Next, the coating film was dried for 100 seconds to form a photosensitive resin layer. Next, with an exposure device (MPA600FA, manufactured by Canon Co., Ltd.), the exposure amount was varied in each experiment to expose the photosensitive resin layer. Secondly, using an aqueous solution of tetramethylammonium hydroxide with a concentration of 2.38% by mass as the developer, immersion development was performed at 23° C. for 100 seconds to form a hole pattern with holes in the range of 10 μm. After development, the pattern was post-baked at 230°C for 20 minutes. The film thickness of the pattern after post-baking is 3 μm. The film thickness of the pattern was measured using a stylus type surface profile measuring device (Dektak 3st, manufactured by ULVAC Co., Ltd.). The exposure at the bottom of the post-baking hole at 8 μm was judged as the accuracy sensitivity. The above exposure is 35 mJ/cm 2 In the following cases, the sensitivity is evaluated as good; when the above exposure exceeds 35 mJ/cm 2 In this case, it was evaluated as poor sensitivity. The above exposure is preferably 30 mJ/cm 2 the following. (Transmittance) The photosensitive resin layer is exposed by fixing the exposure amount to the above-mentioned precise sensitivity. Instead of exposing the photosensitive resin layer by changing the exposure amount in each experiment, it is the same as the sensitivity evaluation method except that Proceed to form a cured film of the post-baked photosensitive composition. The thickness of the cured film is 3 μm. Using MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.), the transmittance of the formed cured film at a wavelength of 400 nm was measured. When the above-mentioned transmittance is 95% or more, the transmittance is evaluated as good; when the above-mentioned transmittance is less than 95%, the transmittance is evaluated as poor. The above-mentioned transmittance is preferably 98% or more. [Table 1]
Figure 105127562-A0304-0001
 According to Table 1, it is confirmed that the photosensitive combination of the present invention comprising the photopolymerization initiator (A1) represented by the formula (1) and the photopolymerization initiator (A2) having an aromatic ring skeleton bonded with a nitro group The object has sufficient sensitivity to exposure, and by curing, it provides a cured object with sufficient transmittance.

Claims (8)

一種感光性組合物，其包含下述式(1)所表示之光聚合起始劑(A1)、及具有鍵結有硝基之芳香環骨架的光聚合起始劑(A2)，上述光聚合起始劑(A1)之含量為上述感光性組合物之固形物成分之0.001~50質量%，上述光聚合起始劑(A2)之含量為上述感光性組合物之固形物成分之0.05~2質量%，
Figure 105127562-A0305-02-0097-1
 R1為氫原子、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、或哌
Figure 105127562-A0305-02-0097-3
-1-基，R2及R3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，R2與R3亦可相互鍵結而形成環，R4為下述式(R4-1)或(R4-2)所表示之基，R5為氫原子、可具有取代基之碳原子數1~11之烷基、或可具有 取代基之芳基，n為0~4之整數；其中，式(1)所表示之光聚合起始劑不具有硝基；
Figure 105127562-A0305-02-0098-2
 式(R4-1)及(R4-2)中，R7及R8分別為烷基、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、或哌
Figure 105127562-A0305-02-0098-4
-1-基，p為0~4之整數，於R7及R8存在於苯環上之鄰接之位置之情形時，R7與R8亦可相互鍵結而形成環，q為1~8之整數，r為1~5之整數，s為0~(r+3)之整數，R9為1價有機基。 A photosensitive composition comprising a photopolymerization initiator (A1) represented by the following formula (1), and a photopolymerization initiator (A2) having an aromatic ring skeleton to which a nitro group is bonded, the photopolymerization The content of the initiator (A1) is 0.001-50% by mass of the solid component of the photosensitive composition, and the content of the photopolymerization initiator (A2) is 0.05-2 of the solid component of the photosensitive composition quality%,
Figure 105127562-A0305-02-0097-1
 R 1 is a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, and may have Substituent phenoxy group, optionally substituted phenoxycarbonyl group, optionally substituted benzyloxy group, optionally substituted phenylalkyl group, optionally substituted naphthyl group, optionally substituted group The naphthyloxy group, the naphthyloxy group which may have a substituent, the naphthyloxycarbonyl group which may have a substituent, the naphthyloxycarbonyl group which may have a substituent, the naphthylalkyl group which may have a substituent, the naphthylalkyl group which may have a substituent The heterocyclic group, the heterocyclic carbonyl group which may have substituents, the amino group substituted by 1 or 2 organic groups, morpholin-1-yl, or piperyl
Figure 105127562-A0305-02-0097-3
-1-yl, R 2 and R 3 are each a linear alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R 2 and R 3 may be bonded to each other to form a ring, R 4 is a group represented by the following formula (R4-1) or (R4-2), R 5 is a hydrogen atom, an optionally substituted alkyl group with 1 to 11 carbon atoms, or an optionally substituted aromatic group Group, n is an integer of 0-4; wherein, the photopolymerization initiator represented by formula (1) does not have a nitro group;
Figure 105127562-A0305-02-0098-2
 In formulas (R4-1) and (R4-2), R 7 and R 8 are alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated fat, respectively Group oxy group, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted benzyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzyl group An oxy group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, The naphthyloxy group which may have substituents, the naphthylalkyl group which may have substituents, the heterocyclic group which may have substituents, the heterocyclic carbonyl group which may have substituents, the substituted by 1 or 2 organic groups Amino, morpholin-1-yl, or piperidine
Figure 105127562-A0305-02-0098-4
-1-yl, p is an integer from 0 to 4, when R 7 and R 8 are present at adjacent positions on the benzene ring, R 7 and R 8 can also be bonded to each other to form a ring, and q is 1~ An integer of 8, r is an integer of 1 to 5, s is an integer of 0 to (r+3), and R 9 is a monovalent organic group. 如請求項1之感光性組合物，其中上述芳香環骨架為茀或咔唑骨架之一部分或伸芳基或伸雜芳基。 The photosensitive composition according to claim 1, wherein the above-mentioned aromatic ring skeleton is a part of the fluorine or carbazole skeleton or an aryl group or a heteroaryl group. 如請求項1或2之感光性組合物，其進而含有聚合性基材成分(B)，上 述聚合性基材成分(B)含有光聚合性化合物、或光聚合性化合物與樹脂。 The photosensitive composition of claim 1 or 2, which further contains a polymerizable substrate component (B), above The polymerizable substrate component (B) contains a photopolymerizable compound or a photopolymerizable compound and resin. 如請求項1或2之感光性組合物，其中以光程長度3μm所測得之對於波長為400nm之光的透過率為95%以上。 The photosensitive composition of claim 1 or 2, wherein the transmittance of light with a wavelength of 400 nm measured with an optical path length of 3 μm is 95% or more. 一種圖案形成方法，其係使用如請求項1至4中任一項之感光性組合物而形成塗膜或成形體，對該塗膜或成形體以特定圖案狀照射電磁波而進行顯影。 A pattern forming method which uses the photosensitive composition as claimed in any one of claims 1 to 4 to form a coating film or a molded body, and develops the coating film or molded body by irradiating electromagnetic waves in a specific pattern. 一種硬化物，其係使用如請求項1至4中任一項之感光性組合物而形成者。 A cured product formed using the photosensitive composition according to any one of claims 1 to 4. 如請求項6之硬化物，其係絕緣膜、或積層於光阻膜上之保護膜。 Such as the cured product of claim 6, which is an insulating film or a protective film laminated on a photoresist film. 一種顯示裝置，其具備如請求項7之硬化物。 A display device provided with a hardened object as in Claim 7.
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