TW202138396A - Photosensitive composition, method of producing patterned cured film, and patterned cured film capable of forming a cured product having low dielectric constant and excellently patterned - Google Patents

Photosensitive composition, method of producing patterned cured film, and patterned cured film capable of forming a cured product having low dielectric constant and excellently patterned Download PDF

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TW202138396A
TW202138396A TW110105657A TW110105657A TW202138396A TW 202138396 A TW202138396 A TW 202138396A TW 110105657 A TW110105657 A TW 110105657A TW 110105657 A TW110105657 A TW 110105657A TW 202138396 A TW202138396 A TW 202138396A
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加藤広樹
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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

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Abstract

The present invention relates to a photosensitive composition, a method of producing a patterned cured film, and a patterned cured film. The present invention provides a photosensitive composition capable of forming a cured product having a low dielectric constant and excellently patterned, a cured product of the photosensitive composition, and a method of producing a cured product using the photosensitive composition. In the photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable compound (B), and a photopolymerization initiator (C), a polyfunctional compound having 3 or 4 (meth)acrylic groups as the photopolymerizable compound (B), and an oxime ester compound having a specific structure as the photopolymerization initiator (C) are used.

Description

感光性組合物、經圖案化的固化膜的製造方法及經圖案化的固化膜Photosensitive composition, method for producing patterned cured film, and patterned cured film

本發明有關感光性組合物、該感光性組合物的固化物、及使用該感光性組合物的固化物的製造方法。The present invention relates to a photosensitive composition, a cured product of the photosensitive composition, and a method for producing a cured product using the photosensitive composition.

在液晶顯示裝置這樣的顯示裝置中，絕緣膜這樣的材料需要使從背光源這樣的光源發出的光高效地透過。因此，為了形成絕緣膜，要求能夠形成透明性優異的膜的材料。 這樣的透明絕緣膜通常在基板上被圖案化。作為形成經圖案化的透明絕緣膜的方法，例如，使用包含具有氧雜環丁烷環的鹼溶性樹脂、聚合性多官能化合物、和α-氨基烷基苯酮系光聚合引發劑的負型感光性組合物的方法(參見專利文獻1)是已知的。 另一方面，近年來，隨著液晶顯示器的生產台數增加，濾色器的生產量也增大，從更進一步提高生產率的觀點考慮，期望能夠以低曝光量形成圖案的高敏感度的感光性組合物。 但是，在濾色器中包含的各種功能性膜中含有著色劑，而在感光性組合物含有著色劑的情況下，若使用專利文獻1中記載的α-氨基烷基苯酮系光聚合引發劑，則存在難以獲得足夠高的敏感度的問題。 在這樣的狀況下，作為高敏感度的感光性組合物，本申請的發明人提出了包含特定結構的肟酯化合物作為光聚合引發劑的高敏感度的感光性組合物(參見專利文獻2及3。)。 現有技術文獻 專利文獻 專利文獻1：日本特開2012-173678號公報 專利文獻2：日本特開2012-189996號公報 專利文獻3：日本特開2012-189997號公報In a display device such as a liquid crystal display device, a material such as an insulating film needs to efficiently transmit light emitted from a light source such as a backlight. Therefore, in order to form an insulating film, a material capable of forming a film with excellent transparency is required. Such a transparent insulating film is usually patterned on a substrate. As a method of forming a patterned transparent insulating film, for example, a negative type containing an alkali-soluble resin having an oxetane ring, a polymerizable polyfunctional compound, and an α-aminoalkylphenone-based photopolymerization initiator is used. The method of the photosensitive composition (see Patent Document 1) is known. On the other hand, in recent years, with the increase in the number of liquid crystal displays produced, the production volume of color filters has also increased. From the viewpoint of further improving productivity, a high-sensitivity photosensitive that can form patterns with a low exposure is desired. Sexual composition. However, various functional films contained in the color filter contain colorants, and when the photosensitive composition contains a colorant, if the α-aminoalkylphenone-based photopolymerization initiator described in Patent Document 1 is used There is a problem that it is difficult to obtain a sufficiently high sensitivity. Under such circumstances, as a highly sensitive photosensitive composition, the inventor of the present application proposes a highly sensitive photosensitive composition containing an oxime ester compound of a specific structure as a photopolymerization initiator (see Patent Document 2 and 3.). Prior art literature Patent literature Patent Document 1: JP 2012-173678 A Patent Document 2: JP 2012-189996 A Patent Document 3: JP 2012-189997 A

發明要解決的課題 但是，在包含肟酯化合物作為光聚合引發劑的感光性組合物中，雖然敏感度良好，但另一方面，存在難以形成相對介電常數低的固化物、或者難以形成被良好地圖案化的固化物的問題。 本發明是鑒於上述課題而作出的，目的在於提供能夠形成相對介電常數低且被良好地圖案化的固化物的感光性組合物、該感光性組合物的固化物、和使用該感光性組合物的固化物的製造方法。 用於解決課題的手段 本申請的發明人發現，通過在包含鹼溶性樹脂(A)、光聚合性化合物(B)及光聚合引發劑(C)的感光性組合物中，使用作為光聚合性化合物(B)的具有3或4個(甲基)丙烯醯基的多官能化合物、及作為光聚合引發劑(C)之特定結構的肟酯化合物，能夠解決上述的課題，從而完成了本發明。更具體而言，本發明提供以下的方案。 本發明的第1方式為感光性組合物，其包含鹼溶性樹脂(A)、光聚合性化合物(B)，及光聚合引發劑(C)， 光聚合性化合物(B)包含具有3或4個(甲基)丙烯醯基的多官能化合物， 光聚合引發劑(C)包含下述式(1)表示的化合物。

Figure 02_image001
(式(1)中，Rc1 為氫原子、硝基或一價有機基團，Rc2 及Rc3 各自為可具有取代基的鏈狀烷基、可具有取代基的環狀有機基團、或氫原子，Rc2 與Rc3 可以彼此鍵結而形成環，Rc4 為一價有機基團，Rc5 為氫原子、可具有取代基的碳原子數1以上且11以下的烷基、或者可具有取代基的芳基，n1為0以上且4以下的整數，n2為0或1。) 本發明的第2方式為第1方式有關的感光性組合物的固化物。 本發明的第3方式為固化物的製造方法，其包括下述步驟： 將第1方式有關的感光性組合物根據要形成的固化物的形狀來進行成型的步驟；和 對經成型的感光性組合物進行曝光的步驟。 發明的效果 根據本發明，可以提供能夠形成相對介電常數低且被良好地圖案化的固化物的感光性組合物、該感光性組合物的固化物、和使用該感光性組合物的固化物的製造方法。The problem to be solved by the invention However, in the photosensitive composition containing an oxime ester compound as a photopolymerization initiator, although the sensitivity is good, on the other hand, it is difficult to form a cured product with a low relative dielectric constant, or it is difficult to form a substrate. The problem of well-patterned cured products. The present invention was made in view of the above-mentioned problems, and its object is to provide a photosensitive composition capable of forming a cured product having a low relative permittivity and good patterning, a cured product of the photosensitive composition, and use of the photosensitive composition The manufacturing method of the cured product of the object. Means for Solving the Problem The inventors of the present application discovered that by using a photosensitive composition containing an alkali-soluble resin (A), a photopolymerizable compound (B), and a photopolymerization initiator (C) as a photopolymerizable Compound (B), a polyfunctional compound having 3 or 4 (meth)acryloyl groups and an oxime ester compound having a specific structure as a photopolymerization initiator (C), can solve the above-mentioned problems, thereby completing the present invention . More specifically, the present invention provides the following solutions. The first aspect of the present invention is a photosensitive composition containing an alkali-soluble resin (A), a photopolymerizable compound (B), and a photopolymerization initiator (C), and the photopolymerizable compound (B) contains 3 or 4 A (meth)acryloyl polyfunctional compound, and the photopolymerization initiator (C) includes a compound represented by the following formula (1).
Figure 02_image001
(In formula (1), R c1 is a hydrogen atom, a nitro group or a monovalent organic group, R c2 and R c3 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 c2 and R c3 may be bonded to each other to form a ring, R c4 is a monovalent organic group, R c5 is a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or For the optionally substituted aryl group, n1 is an integer of 0 or more and 4 or less, and n2 is 0 or 1.) The second aspect of the present invention is a cured product of the photosensitive composition according to the first aspect. The third aspect of the present invention is a method for producing a cured product, which includes the steps of: molding the photosensitive composition related to the first aspect according to the shape of the cured product to be formed; The composition is exposed to the step. Effects of the Invention According to the present invention, it is possible to provide a photosensitive composition capable of forming a cured product with a low relative permittivity and good patterning, a cured product of the photosensitive composition, and a cured product using the photosensitive composition的制造方法。 Manufacturing method.

≪感光性組合物≫ 感光性組合物包含鹼溶性樹脂(A)、光聚合性化合物(B)、和光聚合引發劑(C)。光聚合性化合物(B)包含具有3或4個(甲基)丙烯醯基的多官能化合物。另外，光聚合引發劑(C)包含下述式(1)表示的肟酯化合物。通過在感光性組合物中組合地含有上述的光聚合性化合物(B)、及光聚合引發劑(C)，能夠形成相對介電常數低且被良好地圖案化的固化物。

Figure 02_image003
(式(1)中，Rc1 各自獨立地為氫原子、硝基、或一價有機基團，Rc2 及Rc3 各自為可具有取代基的鏈狀烷基、可具有取代基的鏈狀烷氧基、可具有取代基的環狀有機基團、或氫原子，Rc2 與Rc3 可以彼此鍵結而形成環，Rc4 為一價有機基團，Rc5 為氫原子、可具有取代基的碳原子數1以上且20以下的脂肪族烴基、或者可具有取代基的芳基，n1為0以上且4以下的整數，n2為0或1。) 以下，針對感光性組合物所包含的必需或任選的成分、和感光性組合物的製造方法，依次進行說明。 ＜鹼溶性樹脂(A)＞ 感光性組合物包含鹼溶性樹脂(A)。作為鹼溶性樹脂(A)，沒有特別限定，可以從一直以來在各種感光性組合物中配合的鹼溶性樹脂中適當選擇。 此處，本說明書中，所謂鹼溶性樹脂(A)，是指在分子內具備具有鹼溶性的官能團(例如，酚式羥基、羧基、磺酸基等)的樹脂。 關於適合作為鹼溶性樹脂(A)的樹脂，可舉出具有Cardo結構的樹脂(a-I)(以下，也記載為“Cardo樹脂(a-I)”。)。 使用具有Cardo結構的樹脂(a-I)作為鹼溶性樹脂的情況下，容易得到分辨力優異的感光性組合物，容易使用感光性組合物來形成不易因加熱而過度流動的固化膜。因此，容易形成形狀良好的固化膜。 [具有Cardo結構的樹脂(a-I)] 作為具有Cardo骨架的樹脂(a-I)，可以使用在其結構中具有Cardo骨架、且具有規定的鹼溶性的樹脂。所謂Cardo骨架，是指在構成第1環狀結構的1個環碳原子上鍵結第2環狀結構和第3環狀結構而形成的骨架。需要說明的是，第2環狀結構與第3環狀結構可以為相同的結構，也可以為不同的結構。 作為Cardo骨架的代表例，可舉出在芴環的9位碳原子上鍵結兩個芳香環(例如苯環)而成的骨架。 作為Cardo樹脂(a-I)，沒有特別限定，可以使用以往已知的樹脂。其中，優選下述式(a-1)表示的樹脂。
Figure 02_image005
式(a-1)中，Xa 表示下述式(a-2)表示的基團。m1表示0以上且20以下的整數。
Figure 02_image007
上述式(a-2)中，Ra1 各自獨立地表示氫原子、碳原子數1以上且6以下的烴基、或鹵素原子，Ra2 各自獨立地表示氫原子或甲基，Ra3 各自獨立地表示直鏈或支鏈的亞烷基，m2表示0或1，Wa 表示下述式(a-3)表示的基團。
Figure 02_image009
式(a-2)中，作為Ra3 ，優選碳原子數1以上且20以下的亞烷基,更優選碳原子數1以上且10以下的亞烷基(alkylene)，特別優選碳原子數1以上且6以下的亞烷基，最優選乙烷-1,2-二基、丙烷-1,2-二基、及丙烷1,3-二基。 式(a-3)中的環A表示可以與芳香族環縮合的可具有取代基的脂肪族環。脂肪族環可以為脂肪族烴環，也可以為脂肪族雜環。 作為脂肪族環，可舉出單環烷烴、雙環烷烴、三環烷烴、四環烷烴等。 具體而言，可舉出環戊烷、環己烷、環庚烷、環辛烷等單環烷烴、金剛烷、降冰片烷、異冰片烷、三環癸烷、四環十二烷。 可與脂肪族環縮合的芳香族環可以為芳香族烴環，也可以為芳香族雜環，優選為芳香族烴環。具體而言，優選為苯環、及萘環。 作為式(a-3)表示的二價基團的優選例，可舉出下述的基團。
Figure 02_image011
式(a-1)中的二價基團Xa 可通過使提供殘基Za 的四羧酸二酐與下式(a-2a)表示的二醇化合物反應從而被導入至Cardo樹脂(a-I)中。
Figure 02_image013
式(a-2a)中，Ra1 、Ra2 、Ra3 、及m2如針對式(a-2)進行說明的那樣。關於式(a-2a)中的環A，如針對式(a-3)進行說明的那樣。 式(a-2a)表示的二醇化合物例如可利用以下的方法製造。 首先，根據需要，按照常規方法，將下述式(a-2b)表示的二醇化合物所具有的酚式羥基中的氫原子替換成-Ra3 -OH表示的基團，然後使用表氯醇等進行縮水甘油基化，得到下述式(a-2c)表示的環氧化合物。 接著，通過使式(a-2c)表示的環氧化合物與丙烯酸或甲基丙烯酸反應，從而得到式(a-2a)表示的二醇化合物。 式(a-2b)及式(a-2c)中，Ra1 、Ra3 、及m2如針對式(a-2)進行說明的那樣。關於式(a-2b)及式(a-2c)中的環A，如針對式(a-3)進行說明的那樣。 需要說明的是，式(a-2a)表示的二醇化合物的製造方法不限於上述的方法。
Figure 02_image015
作為式(a-2b)表示的二醇化合物的優選例，可舉出以下的二醇化合物。
Figure 02_image017
上述式(a-1)中，Ra0 為氫原子或-CO-Ya -COOH表示的基團。此處，Ya 表示從二羧酸酐中除去酸酐基(-CO-O-CO-)而得到的殘基。作為二羧酸酐的例子，可舉出馬來酸酐、琥珀酸酐、衣康酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基內亞甲基四氫鄰苯二甲酸酐、氯菌酸酐、甲基四氫鄰苯二甲酸酐、戊二酸酐等。 另外，上述式(a-1)中，Za 表示從四羧酸二酐中除去兩個酸酐基而得到的殘基。作為四羧酸二酐的例子，可舉出下述式(a-4)表示的四羧酸二酐、均苯四甲酸二酐、二苯甲酮四甲酸二酐、聯苯四甲酸二酐、二苯基醚四甲酸二酐等。 另外，上述式(a-1)中，m表示0以上且20以下的整數。
Figure 02_image019
(式(a-4)中，Ra4 、Ra5 、及Ra6 各自獨立地表示選自由氫原子、碳原子數1以上且10以下的烷基及氟原子組成的組中的1種，m3表示0以上且12以下的整數。) 可被選作式(a-4)中的Ra4 的烷基為碳原子數1以上且10以下的烷基。通過將烷基所具有的碳原子數設定在該範圍內，從而能夠進一步提高得到的羧酸酯的耐熱性。Ra4 為烷基時，從容易得到耐熱性優異的Cardo樹脂的方面考慮，其碳原子數優選為1以上且6以下,更優選為1以上且5以下，進一步優選為1以上且4以下，特別優選為1以上且3以下。 Ra4 為烷基時，該烷基可以為直鏈狀，也可以為支鏈狀。 作為式(a-4)中的Ra4 ，從容易得到耐熱性優異的Cardo樹脂的方面考慮，更優選各自獨立地為氫原子或碳原子數1以上且10以下的烷基。式(a-4)中的Ra4 更優選為氫原子、甲基、乙基、正丙基或異丙基，特別優選為氫原子或甲基。 從容易製備高純度的四羧酸二酐的方面考慮，式(a-4)中的多個Ra4 優選為相同的基團。 式(a-4)中的m3表示0以上且12以下的整數。通過使m3的值為12以下，能夠使四羧酸二酐的純化容易。 從四羧酸二酐的純化容易的方面考慮，m3的上限優選為5，更優選為3。 從四羧酸二酐的化學穩定性的方面考慮，m3的下限優選為1，更優選為2。 式(a-4)中的m3特別優選為2或3。 可被選作式(a-4)中的Ra5 及Ra6 的碳原子數1以上且10以下的烷基與可被選作Ra4 的碳原子數1以上且10以下的烷基同樣。 從四羧酸二酐的純化容易的方面考慮，Ra5 、及Ra6 優選為氫原子、或者碳原子數1以上且10以下(優選為1以上且6以下，更優選為1以上且5以下，進一步優選為1以上且4以下，特別優選為1以上且3以下)的烷基,特別優選為氫原子或甲基。 作為式(a-4)表示的四羧酸二酐，例如，可舉出降冰片烷-2-螺-α-環戊酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐(別名“降冰片烷-2-螺-2’-環戊酮-5’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐”)、甲基降冰片烷-2-螺-α-環戊酮-α’-螺-2”-(甲基降冰片烷)-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環己酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐(別名“降冰片烷-2-螺-2’-環己酮-6’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐”)、甲基降冰片烷-2-螺-α-環己酮-α’-螺-2”-(甲基降冰片烷)-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環丙酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環丁酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環庚酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環辛酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環壬酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環癸酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環十一烷酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環十二烷酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環十三烷酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環十四烷酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環十五烷酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-(甲基環戊酮)-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-(甲基環己酮)-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐等。 Cardo樹脂(a-I)的重量平均分子量優選為1000以上且40000以下,更優選為1500以上且30000以下，進一步優選為2000以上且10000以下。通過成為上述的範圍，從而能夠獲得良好的顯影性，並且對於使用感光性組合物形成的固化膜而言，能夠獲得充分的耐熱性和機械強度。 [Novolac樹脂(a-II)] 從容易形成不易因加熱而過度流動之固化物的方面考慮，還優選鹼溶性樹脂(A)包含Novolac樹脂(a-II)。 作為Novolac樹脂(a-II)，可以使用一直以來配合於感光性組合物中的各種Novolac樹脂。作為Novolac樹脂(a-II)，優選通過在酸催化下使具有酚式羥基的芳香族化合物(以下，簡稱為“酚類”。)與醛類進行加成縮合而得到。 (酚類) 作為製作Novolac樹脂(a-II)時可使用的酚類，例如，可舉出苯酚；鄰甲酚、間甲酚、對甲酚等甲酚類；2,3-二甲苯酚、2,4-二甲苯酚、2,5-二甲苯酚、2,6-二甲苯酚、3,4-二甲苯酚、3,5-二甲苯酚等二甲苯酚類；鄰乙基苯酚、間乙基苯酚、對乙基苯酚等乙基酚類；2-異丙基苯酚、3-異丙基苯酚、4-異丙基苯酚、鄰丁基苯酚、間丁基苯酚、對丁基苯酚、以及對叔丁基苯酚等烷基酚類；2,3,5-三甲基苯酚、及3,4,5-三甲基苯酚等三烷基酚類；間苯二酚、鄰苯二酚、對苯二酚、對苯二酚單甲基醚、連苯三酚、及間苯三酚等多元酚類；烷基間苯二酚、烷基鄰苯二酚、及烷基對苯二酚等烷基多元酚類(所有烷基的碳原子數均為1以上且4以下。)；α-萘酚；β-萘酚；羥基聯苯(hydroxydiphenyl)；以及雙酚A等。這些酚類可以單獨使用，也可組合使用兩種以上。 這些酚類中，優選間甲酚和對甲酚，更優選並用間甲酚和對甲酚。這種情況下，可通過調整兩者的配合比例，來調節使用感光性組合物形成的固化膜的耐熱性等各種特性。 間甲酚與對甲酚的配合比例沒有特別限定，以間甲酚/對甲酚的莫耳比計，優選為3/7以上且8/2以下。通過以上述範圍的比率使用間甲酚及對甲酚，從而容易得到能形成耐熱性優異的固化膜的感光性組合物。 另外，並用間甲酚和2,3,5-三甲基苯酚而製造的Novolac樹脂也是優選的。使用所述Novolac樹脂的情況下，特別容易得到能夠形成耐熱性優異的固化膜的感光性組合物。 間甲酚與2,3,5-三甲基苯酚的配合比例沒有特別限定，以間甲酚/2,3,5-三甲基苯酚的摩爾比計，優選為70/30以上且95/5以下。 (醛類) 作為製作Novolac樹脂(a-II)時可使用的醛類，例如，可舉出甲醛、多聚甲醛、糠醛、苯甲醛、硝基苯甲醛、及乙醛等。這些醛類可以單獨使用，也可以組合兩種以上而使用。 (酸催化劑) 作為製作Novolac樹脂(a-II)時可使用的酸催化劑，例如，可舉出鹽酸、硫酸、硝酸、磷酸、及亞磷酸等無機酸類；甲酸、草酸、乙酸、硫酸二乙酯、及對甲苯磺酸等有機酸類；以及乙酸鋅等金屬鹽類等。這些酸催化劑可以單獨使用，也可以組合兩種以上而使用。 (分子量) 就Novolac樹脂(a-II)的按照聚苯乙烯換算的重量平均分子量(Mw；以下，也簡稱為“重量平均分子量”。)而言，從使用感光性組合物形成的固化膜的耐熱性的觀點考慮，作為下限值，優選為2000,更優選為5000，特別優選為10000，進一步優選為15000，最優選為20000，作為上限值，優選為50000,更優選為45000，進一步優選為40000，最優選為35000。 作為Novolac樹脂(a-II)，可組合至少兩種按照聚苯乙烯換算的重量平均分子量不同的Novolac樹脂來使用。通過將重量平均分子量大小不同的Novolac樹脂進行組合來使用，從而能取得感光性組合物的顯影性、與使用感光性組合物形成的固化膜的耐熱性的均衡性。 [改性環氧樹脂(a-III)] 鹼溶性樹脂(A)可包含環氧化合物(a-3a)與含不飽和基團之羧酸(a-3b)之反應產物的多元酸酐(a-3c)加成物(a-3)。關於該加成物，也記載為“改性環氧樹脂(a-III)”。 本申請的說明書及申請專利範圍中，將符合上述定義的化合物，但不相當於上述具有Cardo結構之樹脂(a-I)的化合物作為改性環氧樹脂(a-III)。 以下，對於環氧化合物(a-3a)、含不飽和基團的羧酸(a-3b)、及多元酸酐(a-3c)進行說明。 ＜環氧化合物(a-3a)＞ 環氧化合物(a-3a)沒有特別限定，只要是具有環氧基的化合物即可，可為具有芳香族基團的芳香族環氧化合物，也可為不包含芳香族基團的脂肪族環氧化合物，優選為具有芳香族基團的芳香族環氧化合物。 環氧化合物(a-3a)可為單官能環氧化合物，也可為2官能以上的多官能環氧化合物，優選為多官能環氧化合物。 作為環氧化合物(a-3a)的具體例，可舉出雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚AD型環氧樹脂、萘型環氧樹脂、及聯苯型環氧樹脂等2官能環氧樹脂；二聚酸縮水甘油酯、及三縮水甘油酯等縮水甘油酯型環氧樹脂；四縮水甘油基氨基二苯基甲烷、三縮水甘油基對氨基苯酚、四縮水甘油基間苯二甲胺、及四縮水甘油基雙氨基甲基環己烷等縮水甘油胺型環氧樹脂；三縮水甘油基異氰脲酸酯等雜環式環氧樹脂；間苯三酚三縮水甘油基醚、三羥基聯苯三縮水甘油基醚、三羥基苯基甲烷三縮水甘油基醚、丙三醇三縮水甘油基醚、2-[4-(2,3-環氧丙氧基)苯基]-2-[4-[1,1-雙[4-(2,3-環氧丙氧基)苯基]乙基]苯基]丙烷、及1,3-雙[4-[1-[4-(2,3-環氧丙氧基)苯基]-1-[4-[1-[4-(2,3-環氧丙氧基)苯基]-1-甲基乙基]苯基]乙基]苯氧基]-2-丙醇等3官能型環氧樹脂；四羥基苯基乙烷四縮水甘油基醚、四縮水甘油基二苯甲酮、雙間苯二酚四縮水甘油基醚、及四環氧丙氧基聯苯等4官能型環氧樹脂。 另外，作為環氧化合物(a-3a)，優選具有聯苯骨架的環氧化合物。 具有聯苯骨架的環氧化合物優選在主鏈中具有至少一個以上的下述式(a-3a-1)表示的聯苯骨架。 具有聯苯骨架的環氧化合物優選為具有兩個以上環氧基的多官能環氧化合物。 通過使用具有聯苯骨架的環氧化合物，容易得到敏感度與顯影性的均衡性優異、且能形成與基板的密合性優異的固化膜的感光性組合物。
Figure 02_image021
(式(a-3a-1)中，Ra7 各自獨立地為氫原子、碳原子數1以上且12以下的烷基、鹵素原子、或者可具有取代基的苯基，j為1以上且4以下的整數。) Ra7 為碳原子數1以上且12以下的烷基時，作為烷基的具體例，可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基、正戊基、異戊基、仲戊基、叔戊基、正己基、正庚基、正辛基、異辛基、仲辛基、叔辛基、正壬基、異壬基、正癸基、異癸基、正十一烷基、及正十二烷基。 Ra7 為鹵素原子時，作為鹵素原子的具體例，可舉出氟原子、氯原子、溴原子、及碘原子。 Ra7 為可具有取代基的苯基時，苯基上的取代基數目沒有特別限定。苯基上的取代基數目為0以上且5以下，優選為0或1。 作為取代基的例子，可舉出碳原子數1以上且4以下的烷基、碳原子數1以上且4以下的烷氧基、碳原子數2以上且4以下的脂肪族醯基、鹵素原子、氰基、及硝基。 作為具有上述式(a-3a-1)表示的聯苯骨架的環氧化合物(a-3a)，没有特别限定，例如，可舉出下述式(a-3a-2)表示的環氧化合物。
Figure 02_image023
(式(a-3a-2)中，Ra7 及j與式(a-3a-1)同樣，k為括號內的結構結構單元的平均重複數，為0以上且10以下。) 式(a-3a-2)表示的環氧化合物中，從特别容易得到敏感度與顯影性的均衡性優異的感光性组合物的方面考慮，優選下述式(a-3a-3)表示的化合物。
Figure 02_image025
(式(a-3a-3)中，k與式(a-3a-2)同樣。) (含不飽和基團的羧酸(a-3b)) 在製備改性環氧化合物(a-3)時，使環氧化合物(a-3a)與含不飽和基團的羧酸(a-3b)反應。 作為含不飽和基團的羧酸(a-3b)，優選為在分子中含有丙烯酸系基團(acryl group)、甲基丙烯酸系基團(methacryl group)等反應性的不飽和雙鍵的一元羧酸。作為這樣的含不飽和基團的羧酸，例如，可舉出丙烯酸、甲基丙烯酸、β-苯乙烯基丙烯酸、β-糠基丙烯酸、α-氰基肉桂酸、肉桂酸等。另外，含不飽和基團的羧酸(a-3b)可以單獨使用或組合兩種以上而使用。 可以利用已知的方法使環氧化合物(a-3a)與含不飽和基團的羧酸(a-3b)反應。作為優選的反應方法，例如，可舉出下述方法：將三乙基胺、苄基乙基胺等叔胺、十二烷基三甲基氯化銨、四甲基氯化銨、四乙基氯化銨、苄基三乙基氯化銨等季銨鹽、吡啶、或三苯基膦等作為催化劑，在有機溶劑中，於50℃以上且150℃以下的反應溫度，使環氧化合物(a-3a)與含不飽和基團的羧酸(a-3b)反應數小時~數十小時的時間。 對於環氧化合物(a-3a)與含不飽和基團的羧酸(a-3b)的反應中的兩者的使用量的比率而言，以環氧化合物(a-3a)的環氧當量與含不飽和基團的羧酸(a-3b)的羧酸當量之比計，通常優選為1：0.5～1：2,更優選為1：0.8～1：1.25，特別優選為1：0.9～1：1.1。 環氧化合物(a-3a)的使用量與含不飽和基團的羧酸(a-3b)的使用量的比率以上述的當量比計為1：0.5～1：2時，有交聯效率提高的傾向，是優選的。 (多元酸酐(a-3c)) 多元酸酐(a-3c)為具有兩個以上羧基的羧酸的酐。 作為多元酸酐(a-3c)，沒有特別限定，例如，可舉出馬來酸酐、琥珀酸酐、衣康酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸酐、二苯甲酮四甲酸二酐、3-甲基六氫鄰苯二甲酸酐、4-甲基六氫鄰苯二甲酸酐、3-乙基六氫鄰苯二甲酸酐、4-乙基六氫鄰苯二甲酸酐、四氫鄰苯二甲酸酐、3-甲基四氫鄰苯二甲酸酐、4-甲基四氫鄰苯二甲酸酐、3-乙基四氫鄰苯二甲酸酐、4-乙基四氫鄰苯二甲酸酐、下述式(a-3c-1)表示的化合物、及下述式(a-3c-2)表示的化合物。另外，多元酸酐(a-3c)可以單獨使用或組合兩種以上而使用。
Figure 02_image027
(式(a-3c-2)中，Ra8 表示碳原子數1以上且10以下的可具有取代基的亞烷基。) 作為多元酸酐(a-3c)，從容易得到敏感度與顯影性的均衡性優異的感光性組合物的方面考慮，優選具有兩個以上的苯環的化合物。另外，多元酸酐(a-3c)更優選包含上述式(a-3c-1)表示的化合物、及上述式(a-3c-2)表示的化合物中的至少一者。 在使環氧化合物(a-3a)與含不飽和基團的羧酸(a-3b)反應後，與多元酸酐(a-3c)反應的方法可以從已知的方法中適當選擇。 另外，對於使用量之比而言，以環氧化合物(a-3a)與含不飽和基團的羧酸(a-3b)的反應後的成分中的OH基的摩爾數、與多元酸酐(a-3c)的酸酐基的當量比計，通常為1:1～1:0.1，優選為1:0.8～1:0.2。通過成為上述範圍，從而容易得到顯影性良好的感光性組合物。 另外，改性環氧樹脂(a-III)的酸值以樹脂固態成分計優選為10mgKOH/g以上且150mgKOH/g以下,更優選為70mgKOH/g以上且110mgKOH/g以下。通過使樹脂的酸值為10mgKOH/g以上，從而能得到在顯影液中的充分的溶解性，另外，通過使酸值為150mgKOH/g以下，從而能得到充分的固化性，能使表面性良好。 另外，改性環氧樹脂(a-III)的重量平均分子量優選為1000以上且40000以下，更優選為2000以上且30000以下。通過使重量平均分子量為1000以上，從而容易形成耐熱性和強度優異的固化膜。另外，通過使重量平均分子量為40000以下，從而容易得到呈現在顯影液中的充分的溶解性的感光性組合物。 [丙烯酸系樹脂(a-IV)] 丙烯酸系樹脂(a-IV)也優選作為構成鹼溶性樹脂(A)的成分。從容易同時實現低介電常數的固化物的形成、和良好的圖案化特性的方面考慮，鹼溶性樹脂(A)優選包含丙烯酸系樹脂(a-IV)。 丙烯酸系樹脂(a-IV)的質量相對於鹼溶性樹脂(A)的總質量而言的比率典型地優選為70質量%以上,更優選為80質量%以上，進一步優選為90質量%以上，更進一步優選為95質量%以上，特別優選為100質量%。 作為丙烯酸系樹脂(a-IV)，可以使用包含來自(甲基)丙烯酸的結構單元、及/或來自(甲基)丙烯酸酯等其他單體的結構單元的樹脂。(甲基)丙烯酸為丙烯酸或甲基丙烯酸。作為其他單體，典型地，優選使用下述式(a-4-1)表示的化合物。
Figure 02_image029
上述式(a-4-1)中，Ra9 為氫原子或甲基。Ra10 為一價有機基團。就該有機基團而言，可以在該有機基團中包含雜原子等除烴基以外的鍵、取代基。另外，該有機基團可以為直鏈狀、支鏈狀、環狀中的任意。Ra11 為-O-、或-NRa12 -表示的基團。Ra12 為氫原子、或者碳原子數1以上且6以下的烷基。 作為Ra10 的有機基團中的烴基以外的取代基，只要不損害本發明的效果，就沒有特別限定，可舉出鹵素原子、羥基、巰基、硫醚基、氰基、異氰基、氰酸酯基、異氰酸酯基、硫氰酸酯基、異硫氰酸酯基、甲矽烷基、矽烷醇基、烷氧基、烷氧基羰基、氨基甲醯基、硫代氨基甲醯基、硝基、亞硝基、羧基、羧酸鹽/酯基、醯基、醯基氧基、亞磺基、磺基、磺酸鹽/酯基、膦基、氧膦基、膦醯基、膦酸鹽/酯基、羥基亞氨基、烷基醚基、烷基硫醚基、芳基醚基、芳基硫醚基、氨基(-NH2 、-NHR、-NRR’：R及R’各自獨立地表示烴基)等。上述取代基中包含的氫原子可以被烴基取代。另外，上述取代基中包含的烴基可以為直鏈狀、支鏈狀、及環狀中的任意。 另外，作為Ra10 的有機基團可具有丙烯醯基氧基、甲基丙烯醯基氧基、環氧基、氧雜環丁基等反應性的官能團。 丙烯醯基氧基、甲基丙烯醯基氧基等具有不飽和雙鍵等的醯基例如可以通過下述方式製造：使丙烯酸、甲基丙烯酸等不飽和羧酸與包含具有環氧基的結構單元的丙烯酸系樹脂(a-IV)中的至少一部分環氧基反應。 也可以在使不飽和羧酸與至少一部分環氧基反應後，使多元酸酐與通過反應生成的基團反應。 作為多元酸酐的具體例，可舉出馬來酸酐、琥珀酸酐、衣康酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸酐、二苯甲酮四甲酸二酐、3-甲基六氫鄰苯二甲酸酐、4-甲基六氫鄰苯二甲酸酐、3-乙基六氫鄰苯二甲酸酐、4-乙基六氫鄰苯二甲酸酐、四氫鄰苯二甲酸酐、3-甲基四氫鄰苯二甲酸酐、4-甲基四氫鄰苯二甲酸酐、3-乙基四氫鄰苯二甲酸酐、及4-乙基四氫鄰苯二甲酸酐等。 作為具體例，使丙烯酸與來自甲基丙烯酸縮水甘油酯的結構單元反應時，生成下述反應式中示出的、具有羥基的結構單元。通過使四氫鄰苯二甲酸等多元酸酐與上述具有羥基的結構單元反應，從而生成具有羧基和不飽和雙鍵的、對樹脂賦予鹼溶性的結構單元。
Figure 02_image031
另外，通過使具有環氧基和不飽和雙鍵的化合物與丙烯酸系樹脂(a-IV)所具有的來自丙烯酸、甲基丙烯酸等不飽和羧酸的結構單元反應，從而能夠向丙烯酸系樹脂(a-IV)中導入不飽和雙鍵。作為具有環氧基和不飽和雙鍵的化合物，例如，可以使用(甲基)丙烯酸縮水甘油酯、後述的式(a-4-1a)～(a-4-1o)表示的化合物。 作為Ra10 ，優選烷基、芳基、環烷基、多環烷基(polycycloalkyl)、環烷基烷基、多環烷基烷基、芳烷基、或雜環基,這些基團可以被鹵素原子、羥基、烷基、或雜環基取代，也可以在這些基團上鍵結氧原子而形成環氧基。另外，這些基團含有亞烷基部分的情況下，亞烷基部分可以被醚鍵、硫醚鍵、酯鍵中斷。 烷基為直鏈狀或支鏈狀的情況下，其碳原子數優選為1以上且20以下,更優選為1以上且15以下，特別優選為1以上且10以下。作為合適的烷基的例子，可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基、正戊基、異戊基、仲戊基、叔戊基、正己基、正庚基、正辛基、異辛基、仲辛基、叔辛基、正壬基、異壬基、正癸基、異癸基等。 環烷基、多環烷基、環烷基烷基、多環烷基烷基、及這些基團以外的含脂環式基團的基團中，作為這些基團中包含的脂環式基團的優選例，可舉出環戊基、及環己基等單環的脂環式基團、金剛烷基、降冰片基、異冰片基、三環壬基、三環癸基、四環十二烷基、雙環-[2.1.1]-己基、雙環-[2.2.1]-庚基、雙環-[2.2.2]-辛基、雙環-[3.3.0]-辛基、雙環-[4.3.0]-壬基、及雙環-[4.4.0]-癸基等多環烷基。 作為由式(a4-1)表示、且具有環烷基、多環烷基、環烷基烷基、多環烷基烷基、及這些基團以外的含脂環式基團的基團作為Ra10 的化合物的優選例，可舉出下述式(a-4-1a)～(a-4-1h)表示的化合物。這些之中，為了使顯影性適度，優選為下述式(a-4-1c)～(a-4-1h)表示的化合物,更優選為下述式(a-4-1c)、或下述式(a-4-1d)表示的化合物。
Figure 02_image033
上述式中，Ra20 表示氫原子或甲基，Ra21 表示單鍵或碳原子數1～6的二價脂肪族飽和烴基，Ra22 表示氫原子或碳原子數1～5的烷基。作為Ra21 ，優選單鍵、直鏈狀或支鏈狀的亞烷基、例如亞甲基、亞乙基、亞丙基、1,4-亞丁基、乙基亞乙基、1,5-亞戊基、1,6-亞己基。作為Ra22 ，例如優選甲基、乙基。 從容易形成低介電常數的固化物的方面考慮，鹼溶性樹脂(A)優選含有包含來自(甲基)丙烯酸多環烷基酯(polycycloalkyl (meth)acrylate)的結構單元(A-1)的丙烯酸系樹脂。 即，丙烯酸系樹脂優選包含來自下述化合物的結構單元，所述化合物由上述式(a4-1c)～(a4-1h)中的任一者表示、且具有單鍵作為Ra21 。從特別容易形成低介電常數的固化物的方面考慮，丙烯酸系樹脂更優選包含來自下述化合物的結構單元作為結構單元(A-1)，所述化合物由式(a4-1c)、式(a4-1d)、或式(a4-1g)表示、且具有單鍵作為Ra21 。 丙烯酸系樹脂中的上述結構單元(A-1)的量在不損害本發明目的的範圍內沒有特別限定。丙烯酸系樹脂中的上述結構單元(A-1)的量相對於全部結構單元的量而言，優選為10質量%以上且50質量%以上,更優選為20質量%以上且40質量%以下，進一步優選為22質量%以上且35質量%以下。 關於式(a-4-1)表示的化合物具備具有環氧基的鏈狀基團作為Ra10 時的、式(a-4-1)表示的化合物的具體例，可舉出(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類。 另外，式(a-4-1)表示的化合物可以為含脂環式環氧基的(甲基)丙烯酸酯。構成脂環式環氧基的脂環式基團可以為單環也可以為多環。作為單環的脂環式基團，可舉出環戊基、環己基等環烷基。另外，作為多環的脂環式基團，可舉出降冰片基、異冰片基、三環壬基、三環癸基、四環十二烷基等多環烷基。 從容易形成低介電常數的固化物的方面考慮，鹼溶性樹脂(A)優選包含來自含有脂環式環氧基的(甲基)丙烯酸酯的結構單元(A-2)。 作為式(a-4-1)表示的化合物為含有脂環式環氧基的(甲基)丙烯酸酯時的具體例，例如可舉出下述式(a-4-1i)～(a-4-1w)表示的化合物。這些之中，為了使顯影性適度，優選下述式(a-4-1i)～(a-4-1m)表示的化合物,更優選下述式(a-4-1i)～(a-4-1k)表示的化合物。
Figure 02_image035
Figure 02_image037
Figure 02_image039
上述式中，Ra23 表示氫原子或甲基，Ra24 表示碳原子數1以上且6以下的二價的脂肪族飽和烴基，Ra25 表示碳原子數1以上且10以下的二價烴基，t表示0以上且10以下的整數。作為Ra24 ，優選直鏈狀或支鏈狀的亞烷基，例如亞甲基、亞乙基、亞丙基、1,4-亞丁基、乙基亞乙基、1,5-亞戊基、1,6-亞己基。作為Ra25 ，例如優選為亞甲基、亞乙基、亞丙基、1,4-亞丁基、乙基亞乙基、1,5-亞戊基、1,6-亞己基、亞苯基、亞環己基、-CH2 -Ph-CH2 -(Ph表示亞苯基)。 丙烯酸系樹脂(a-IV)中的、來自含有脂環式環氧基的(甲基)丙烯酸酯的結構單元(A-2)的量在不損害本發明目的的範圍內沒有特別限定，優選為30質量%以上且75質量%以下,更優選為50質量%以上且73質量%以下。使用這樣的樹脂的情況下，可能發生樹脂中包含的羧基、與脂環式環氧基的自身反應。因此，使用包含這樣的樹脂的感光性組合物時，可利用將膜加熱的方法等，使得發生羧基與脂環式環氧基的自身反應，由此提高形成的膜的硬度這樣的機械物性。 另外，丙烯酸系樹脂(a-IV)也可以是聚合有(甲基)丙烯酸酯以外的單體而得到的樹脂。作為這樣的單體，可舉出(甲基)丙烯醯胺類、不飽和羧酸類、烯丙基化合物、乙烯基醚類、乙烯基酯類、苯乙烯類等。這些單體可以單獨使用或組合兩種以上而使用。 作為(甲基)丙烯醯胺類，可舉出(甲基)丙烯醯胺、N-烷基(甲基)丙烯醯胺、N-芳基(甲基)丙烯醯胺、N,N-二烷基(甲基)丙烯醯胺、N,N-芳基(甲基)丙烯醯胺、N-甲基-N-苯基(甲基)丙烯醯胺、N-羥基乙基-N-甲基(甲基)丙烯醯胺等。 作為不飽和羧酸類，可舉出巴豆酸等一元羧酸；馬來酸、富馬酸、檸康酸、中康酸、衣康酸等二羧酸；這些二羧酸的酐；等等。 作為烯丙基化合物，可舉出：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、乳酸烯丙酯等烯丙基酯類；烯丙基氧基乙醇；等等。 作為乙烯基醚類，可舉出：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、二乙二醇乙烯基醚、二甲基氨基乙基乙烯基醚、二乙基氨基乙基乙烯基醚、丁基氨基乙基乙烯基醚、苄基乙烯基醚、四氫糠基乙烯基醚等烷基乙烯基醚；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、乙烯基蒽基醚等乙烯基芳基醚；等等。 作為乙烯基酯類，可舉出丁酸乙烯酯、異丁酸乙烯酯、三甲基乙酸乙烯酯、二乙基乙酸乙烯酯、戊酸乙烯酯、己酸乙烯酯、氯乙酸乙烯酯、二氯乙酸乙烯酯、甲氧基乙酸乙烯酯、丁氧基乙酸乙烯酯、苯基乙酸乙烯酯、乙醯乙酸乙烯酯、乳酸乙烯酯、β-苯基丁酸乙烯酯、苯甲酸乙烯酯、水楊酸乙烯酯、氯苯甲酸乙烯酯、四氯苯甲酸乙烯酯、萘甲酸乙烯酯等。 作為苯乙烯類，可舉出：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等烷基苯乙烯；甲氧基苯乙烯、4-甲氧基-3-甲基苯乙烯、二甲氧基苯乙烯等烷氧基苯乙烯；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、4-氟-3-三氟甲基苯乙烯等鹵代苯乙烯；等等。 丙烯酸系樹脂(a-IV)中的、來自(甲基)丙烯酸的結構單元的量、和來自其他單體的結構單元的量在不損害本發明目的的範圍內沒有特別限定。相對於丙烯酸系樹脂(a-IV)的全部結構單元的摩爾數而言，丙烯酸系樹脂(a-IV)中的來自(甲基)丙烯酸的結構單元的量優選為5質量%以上且50質量%以下,更優選為10質量%以上且30質量%以下。 丙烯酸系樹脂(a-IV)具備具有不飽和雙鍵的結構單元的情況下，相對於丙烯酸系樹脂(a-IV)的全部結構單元的摩爾數而言，丙烯酸系樹脂(a-IV)中的具有不飽和雙鍵的結構單元的量優選為1質量%以上且50質量%以下,更優選為1質量%以上且30質量%以下，特別優選為1質量%以上且20質量%以下。 通過使丙烯酸系樹脂(a-IV)包含上述範圍內的量的具有不飽和雙鍵的結構單元，從而能夠將丙烯酸系樹脂引入抗蝕劑膜內的交聯反應，從而實現均勻化，因此，對於固化膜的耐熱性、機械特性的提高是有效的。 丙烯酸系樹脂(a-IV)的重量平均分子量在不損害本發明目的的範圍內沒有特別限定。丙烯酸系樹脂(a-IV)的重量平均分子量優選為9000以上,更優選為9000以上且50000以下，進一步優選為9100以上且30000以下，更進一步優選為9200以上且20000以下，特別優選為9500以上且15000以下。通過成為上述的範圍，有容易獲得感光性組合物的膜形成能力、曝光後的顯影性的均衡性的傾向。 相對於除了後述的有機溶劑(S)的質量以外的感光性組合物的質量(固態成分整體)而言，鹼溶性樹脂(A)的含量優選為20質量%以上且85質量%以下,更優選為25質量%以上且75質量%以下。通過成為上述的範圍，容易得到顯影性優異的感光性組合物。 ＜光聚合性化合物(B)＞ 作為光聚合性化合物(B)，可優選使用具有烯鍵式不飽和基團的單體。光聚合性化合物包含具有3或4個(甲基)丙烯醯基的多官能化合物作為該具有烯鍵式不飽和基團的單體。通過使該多官能化合物進行基於後述的特定光聚合引發劑(C)的固化，容易形成介電常數低且被良好地圖案化的固化物。 在不損害本發明目的的範圍內，光聚合性化合物(B)可以包含除了具有3或4個(甲基)丙烯醯基的多官能化合物以外的其他光聚合性化合物。其他光聚合性化合物可以為單官能化合物或2官能化合物，也可以為5官能以上的多官能化合物。具有3或4個(甲基)丙烯醯基的多官能化合物的質量相對於光聚合性化合物(B)的質量而言的比率優選為80質量%以上,更優選為90質量%以上，進一步優選為95質量%以上，特別優選為100質量%。 作為具有3或4個(甲基)丙烯醯基的多官能化合物的具體例，可舉出三羥甲基丙烷三(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、及丙三醇三(甲基)丙烯酸酯等。這些多官能單體可以單獨使用或組合兩種以上而使用。 從容易形成低介電常數的固化物的方面考慮，具有3或4個(甲基)丙烯醯基的多官能化合物優選包含具有下述式(B1)表示的部分骨架的化合物。典型地，式(B1)表示的部分骨架來自三羥甲基丙烷。
Figure 02_image041
光聚合性化合物(B)優選包含下述式(B2)表示的化合物作為具有式(B1)表示的部分骨架的多官能化合物。
Figure 02_image043
(式(B2)中，Rb1 各自獨立地為氫原子或甲基，Rb2 為二價連接基團，a1為0或1，a2為0或1。) 式(B2)中，a1為0時，式(B2)表示的化合物為3官能化合物。a1為1時，式(B2)表示的化合物為4官能化合物。 式(B2)中的Rb2 為二價連接基團。該連接基團可以為烴基，也可以為含有雜原子的有機基團。作為連接基團可含有的雜原子，例如，可舉出O、N、S、Se、P、Si、B、及鹵素原子。 作為二價連結基團的優選例，可舉出-CO-、-Rb3 -、-CO-Rb3 -CO-、-Rb3 -CO-、-Rb4 -O-Rb4 -、-Rb4 -S-Rb4 -、及 -Rb4 -CO-Rb4 -表示的基團。Rb3 為碳原子數1以上且10以下的二價烴基。Rb4 為碳原子數1以上且6以下的二價烴基。 以上說明的基團中，從容易合成、獲得式(B2)表示的化合物等方面考慮，優選-CO-、-Rb3 -、及-CO-Rb3 -CO-。 作為連結基團的優選具體例，可舉出-CO-、-CH2 -、 -CH2 CH2 -、-CH=CH-、-CH2 CH2 CH2 -、-CH2 C(CH3 )H-、 -CO-CH2 -CO-、--CO-CH2 CH2 -CO-、-CO-CH=CH-CO-、 -CO-CH2 CH2 CH2 -CO-、-CO-CH2 CH2 -及下述結構的基團。
Figure 02_image045
作為具有3或4個(甲基)丙烯醯基的多官能化合物的特別優選的具體例，可舉出下述的化合物。下述式中，Rb1 各自獨立地為氫原子或甲基。
Figure 02_image047
光聚合性化合物(B)包含除了具有3或4個(甲基)丙烯醯基的多官能化合物以外的其他光聚合性化合物的情況下，該其他光聚合性化合物在不損害本發明目的的範圍內沒有特別限定。其他光聚合性化合物可以為單官能化合物，也可以為2官能或5官能以上的多官能化合物。 作為單官能化合物，可舉出(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、衣康酸、衣康酸酐、檸康酸、檸康酸酐、巴豆酸、2-丙烯醯胺基-2-甲基丙磺酸、叔丁基丙烯醯胺磺酸、(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)丙烯醯基氧基-2-羥基丙酯、甘油單(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠基酯、(甲基)丙烯酸二甲基氨基乙酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、鄰苯二甲酸衍生物的(甲基)丙烯酸半酯等。這些單官能化合物可以單獨使用或組合兩種以上而使用。 作為二元或五元以上的多官能化合物，可舉出乙二醇二(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、丙三醇二(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、季戊四醇二(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)丙烯醯氧基多乙氧基苯基)丙烷、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯基氧基丙酯、乙二醇二縮水甘油基醚二(甲基)丙烯酸酯、二乙二醇二縮水甘油基醚二(甲基)丙烯酸酯、鄰苯二甲酸二縮水甘油酯二(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯(即，甲苯二異氰酸酯、三甲基-1,6-己二異氰酸酯、或1,6-己二異氰酸酯等與(甲基)丙烯酸2-羥基乙酯的反應產物)、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)丙烯醯胺的縮合物等多官能化合物、1,3,5-三丙烯醯基六氫-1,3,5-三嗪(triacrylformal)等。這些多官能化合物可以單獨使用或組合兩種以上而使用。 這些具有烯鍵式不飽和基團的其他光聚合性化合物中，從存在提高感光性組合物與基板的密合性、感光性組合物在固化後的強度的傾向的方面考慮，進一步優選5官能以上的多官能單體。 相對於除了後述的有機溶劑(S)的質量以外的感光性組合物的質量(固態成分整體)而言，光聚合性化合物(B)在感光性組合物中的含量優選為1質量%以上且50質量%以下,更優選為5質量%以上且40質量%以下。通過成為上述的範圍，有容易獲得敏感度、顯影性、分辨力的均衡性的傾向。 ＜光聚合引發劑(C)＞ 感光性組合物包含下述式(1)表示的化合物作為光聚合引發劑(C)。 通過利用曝光而使上述的光聚合性化合物(B)在包含式(1)表示的化合物的光聚合引發劑(C)的存在下進行固化，從而能夠將低介電常數的固化物良好地圖案化。
Figure 02_image049
(式(1)中，Rc1 為氫原子、硝基或一價有機基團，Rc2 及Rc3 各自為可具有取代基的鏈狀烷基、可具有取代基的環狀有機基團、或氫原子，Rc2 與Rc3 可以彼此鍵結而形成環，Rc4 為一價有機基團，Rc5 為氫原子、可具有取代基的碳原子數1以上且11以下的烷基、或者可具有取代基的芳基，n1為0以上且4以下的整數，n2為0或1。) 式(1)中，Rc1 為氫原子、硝基或一價有機基團。Rc1 在式(1)中的芴環上鍵結於與-(CO)n2 -表示的基團所鍵結的六元芳香環不同的六元芳香環上。式(1)中，Rc1 相對於芴環的鍵結位置沒有特別限定。式(1)表示的化合物具有1個以上的Rc1 的情況下，從容易合成式(1)表示的化合物等方面考慮，優選1個以上的Rc1 中的1個與芴環中的2位鍵結。Rc1 為多個的情況下，多個Rc1 可以相同，也可以不同。 Rc1 為有機基團時，Rc1 在不損害本發明的目的的範圍內沒有特別限定，可從各種有機基團中適當選擇。作為Rc1 為有機基團時的優選例，可舉出烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、飽和脂肪族醯基氧基、烷氧基羰基、可具有取代基的苯基、可具有取代基的苯氧基、可具有取代基的苯甲醯基、可具有取代基的苯氧基羰基、可具有取代基的苯甲醯基氧基、可具有取代基的苯基烷基、可具有取代基的萘基、可具有取代基的萘氧基、可具有取代基的萘甲醯基、可具有取代基的萘氧基羰基、可具有取代基的萘甲醯基氧基、可具有取代基的萘基烷基、可具有取代基的雜環基、可具有取代基的雜環基羰基、被1個或2個有機基團取代的氨基、嗎啉-1-基、及哌嗪(Piperazine)-1-基等。 Rc1 為烷基時，烷基的碳原子數優選為1以上且20以下,更優選為1以上且6以下。另外，Rc1 為烷基時，可以為直鏈，也可以為支鏈。作為Rc1 為烷基時的具體例，可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基、正戊基、異戊基、仲戊基、叔戊基、正己基、正庚基、正辛基、異辛基、仲辛基、叔辛基、正壬基、異壬基、正癸基、及異癸基等。另外，Rc1 為烷基時，烷基可在碳鏈中包含醚鍵(-O-)。作為在碳鏈中具有醚鍵的烷基的例子，可舉出甲氧基乙基、乙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙基氧基乙氧基乙基、及甲氧基丙基等。 Rc1 為烷氧基時，烷氧基的碳原子數優選為1以上且20以下，更優選為1以上且6以下。另外，Rc1 為烷氧基時，可以為直鏈，也可以為支鏈。作為Rc1 為烷氧基時的具體例，可舉出甲氧基、乙氧基、正丙基氧基、異丙基氧基、正丁基氧基、異丁基氧基、仲丁基氧基、叔丁基氧基、正戊基氧基、異戊基氧基、仲戊基氧基、叔戊基氧基、正己基氧基、正庚基氧基、正辛基氧基、異辛基氧基、仲辛基氧基、叔辛基氧基、正壬基氧基、異壬基氧基、正癸基氧基、及異癸基氧基等。另外，Rc1 為烷氧基時，烷氧基可在碳鏈中包含醚鍵(-O-)。作為在碳鏈中具有醚鍵的烷氧基的例子，可舉出甲氧基乙氧基、乙氧基乙氧基、甲氧基乙氧基乙氧基、乙氧基乙氧基乙氧基、丙基氧基乙氧基乙氧基、及甲氧基丙基氧基等。 Rc1 為環烷基或環烷氧基時，環烷基或環烷氧基的碳原子數優選為3以上且10以下,更優選為3以上且6以下。作為Rc1 為環烷基時的具體例，可舉出環丙基、環丁基、環戊基、環己基、環庚基、及環辛基等。作為Rc1 為環烷氧基時的具體例，可舉出環丙基氧基、環丁基氧基、環戊基氧基、環己基氧基、環庚基氧基、及環辛基氧基等。 Rc1 為飽和脂肪族醯基或飽和脂肪族醯基氧基時，飽和脂肪族醯基或飽和脂肪族醯基氧基的碳原子數優選為2以上且21以下,更優選為2以上且7以下。作為Rc1 為飽和脂肪族醯基時的具體例，可舉出乙醯基、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、正十一烷醯基、正十二烷醯基、正十三烷醯基、正十四烷醯基、正十五烷醯基、及正十六烷醯基等。作為Rc1為飽和脂肪族醯基氧基時的具體例，可舉出乙醯基氧基、丙醯基氧基、正丁醯基氧基、2-甲基丙醯基氧基、正戊醯基氧基、2,2-二甲基丙醯基氧基、正己醯基氧基、正庚醯基氧基、正辛醯基氧基、正壬醯基氧基、正癸醯基氧基、正十一烷醯基氧基、正十二烷醯基氧基、正十三烷醯基氧基、正十四烷醯基氧基、正十五烷醯基氧基、及正十六烷醯基氧基等。 Rc1 為烷氧基羰基時，烷氧基羰基的碳原子數優選為2以上且20以下,更優選為2以上且7以下。作為Rc1 為烷氧基羰基時的具體例，可舉出甲氧基羰基、乙氧基羰基、正丙基氧基羰基、異丙基氧基羰基、正丁基氧基羰基、異丁基氧基羰基、仲丁基氧基羰基、叔丁基氧基羰基、正戊基氧基羰基、異戊基氧基羰基、仲戊基氧基羰基、叔戊基氧基羰基、正己基氧基羰基、正庚基氧基羰基、正辛基氧基羰基、異辛基氧基羰基、仲辛基氧基羰基、叔辛基氧基羰基、正壬基氧基羰基、異壬基氧基羰基、正癸基氧基羰基、及異癸基氧基羰基等。 Rc1 為苯基烷基時，苯基烷基的碳原子數優選為7以上且20以下,更優選為7以上且10以下。另外，Rc1 為萘基烷基時，萘基烷基的碳原子數優選為11以上且20以下,更優選為11以上且14以下。作為Rc1 為苯基烷基時的具體例，可舉出苄基、2-苯基乙基、3-苯基丙基、及4-苯基丁基。作為Rc1 為萘基烷基時的具體例，可舉出α-萘基甲基、β-萘基甲基、2-(α-萘基)乙基、及2-(β-萘基)乙基。Rc1 為苯基烷基或萘基烷基時，Rc1 可在苯基或萘基上進一步具有取代基。 Rc1 為雜環基時，雜環基為包含1個以上的N、S、O的五元或六元的單環，或者為所述單環彼此縮合、或所述單環與苯環縮合而成的雜環基。雜環基為稠環時，構成稠環的單環的環數為3以下。雜環基可以為芳香族基團(雜芳基)，也可以為非芳香族基團。作為構成該雜環基的雜環，可舉出呋喃、噻吩、吡咯、噁唑、異噁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、三唑、吡啶、吡嗪、嘧啶、噠嗪、苯並呋喃、苯並噻吩、吲哚、異吲哚、吲哚嗪、苯並咪唑、苯並三唑、苯並噁唑、苯並噻唑、哢唑、嘌呤、喹啉、異喹啉、喹唑啉、酞嗪、噌啉、喹喔啉、哌啶、哌嗪、嗎啉、哌啶、四氫吡喃、及四氫呋喃等。Rc1 為雜環基時，雜環基可以進一步具有取代基。 Rc1 為雜環基羰基時，雜環基羰基中包含的雜環基與Rc1 為雜環基時同樣。 Rc1 為被1個或2個有機基團取代的氨基時，關於有機基團的優選例，可舉出碳原子數1以上且20以下的烷基、碳原子數3以上且10以下的環烷基、碳原子數2以上且21以下的飽和脂肪族醯基、可具有取代基的苯基、可具有取代基的苯甲醯基、可具有取代基的碳原子數7以上且20以下的苯基烷基、可具有取代基的萘基、可具有取代基的萘甲醯基、可具有取代基的碳原子數11以上且20以下的萘基烷基、及雜環基等。這些優選的有機基團的具體例與Rc1 同樣。作為被1個或2個有機基團取代的氨基的具體例，可舉出甲基氨基、乙基氨基、二乙基氨基、正丙基氨基、二正丙基氨基、異丙基氨基、正丁基氨基、二正丁基氨基、正戊基氨基、正己基氨基、正庚基氨基、正辛基氨基、正壬基氨基、正癸基氨基、苯基氨基、萘基氨基、乙醯基氨基、丙醯基氨基、正丁醯基氨基、正戊醯基氨基、正己醯基氨基、正庚醯基氨基、正辛醯基氨基、正癸醯基氨基、苯甲醯基氨基、α-萘甲醯基氨基、及β-萘甲醯基氨基等。 作為Rc1 中包含的苯基、萘基、及雜環基進一步具有取代基時的取代基，可舉出碳原子數1以上且6以下的烷基、碳原子數1以上且6以下的烷氧基、碳原子數2以上且7以下的飽和脂肪族醯基、碳原子數2以上且7以下的烷氧基羰基、碳原子數2以上且7以下的飽和脂肪族醯基氧基、具有碳原子數1以上且6以下的烷基的單烷基氨基、具有碳原子數1以上且6以下的烷基的二烷基氨基、嗎啉-1-基、哌嗪-1-基、鹵素、硝基、及氰基等。Rc1 中包含的苯基、萘基、及雜環基進一步具有取代基時，該取代基的個數在不妨礙本發明的目的的範圍內沒有限制，優選為1以上且4以下。Rc1 中包含的苯基、萘基、及雜環基具有多個取代基時，多個取代基可以相同也可以不同。 上文中說明的基團中，作為Rc1 ，為硝基或Rc10 -CO-表示的基團時，存在敏感度提高的傾向，是優選的。Rc10 在不妨礙本發明的目的的範圍內沒有特別限制，可以從各種有機基團中選擇。關於優選作為Rc10 的基團的例子，可舉出碳原子數1以上且20以下的烷基、可具有取代基的苯基、可具有取代基的萘基、及可具有取代基的雜環基。這些基團中，作為Rc10 ，特別優選2-甲基苯基、噻吩-2-基、及α-萘基。 另外，Rc1 為氫原子時，存在透明性變得良好的傾向，是優選的。需要說明的是，Rc1 為氫原子且Rc4 為後述的式(1a)或(1b)表示的基團時，存在透明性變得更良好的傾向。 式(1)中，Rc2 和Rc3 各自為可具有取代基的鏈狀烷基、可具有取代基的環狀有機基團、或氫原子。Rc2 與Rc3 可以相互鍵結而形成環。這些基團中，作為Rc2 和Rc3 ，優選可具有取代基的鏈狀烷基。Rc2 和Rc3 為可具有取代基的鏈狀烷基時，鏈狀烷基可以是直鏈烷基，也可以是支鏈烷基。 Rc2 及Rc3 為不具有取代基的鏈狀烷基時，鏈狀烷基的碳原子數優選為1以上且20以下，更優選為1以上且10以下，特別優選為1以上且6以下。作為Rc2 和Rc3 為鏈狀烷基時的具體例，可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基、正戊基、異戊基、仲戊基、叔戊基、正己基、正庚基、正辛基、異辛基、仲辛基、叔辛基、正壬基、異壬基、正癸基、及異癸基等。另外，Rc2 和Rc3 為烷基時，烷基可在碳鏈中包含醚鍵(-O-)。作為在碳鏈中具有醚鍵的烷基的例子，可舉出甲氧基乙基、乙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙基氧基乙氧基乙基、及甲氧基丙基等。 Rc2 及Rc3 為具有取代基的鏈狀烷基時，鏈狀烷基的碳原子數優選為1以上且20以下，更優選為1以上且10以下，特別優選為1以上且6以下。這種情況下，鏈狀烷基的碳原子數不包括取代基的碳原子數。具有取代基的鏈狀烷基優選為直鏈狀。 烷基可以具有的取代基在不妨礙本發明的目的的範圍內沒有特別限制。作為取代基的優選例，可舉出氰基、鹵素原子、環狀有機基團、及烷氧基羰基。作為鹵素原子，可舉出氟原子、氯原子、溴原子、碘原子。這些中，優選氟原子、氯原子、溴原子。作為環狀有機基團，可舉出環烷基、芳香族烴基、雜環基。作為環烷基的具體例，與Rc1 為環烷基時的優選例同樣。作為芳香族烴基的具體例，可舉出苯基、萘基、聯苯基、蒽基、及菲基等。作為雜環基的具體例，與Rc1 為雜環基時的優選例同樣。Rc1 為烷氧基羰基時，烷氧基羰基中包含的烷氧基可以為直鏈狀，也可以為支鏈狀，優選為直鏈狀。烷氧基羰基中包含的烷氧基的碳原子數優選為1以上且10以下，更優選為1以上且6以下。 鏈狀烷基具有取代基時，取代基的個數沒有特別限制。優選的取代基的個數根據鏈狀烷基的碳原子數而發生變化。取代基的個數典型地為1以上且20以下，優選為1以上且10以下，更優選為1以上且6以下。 Rc2 和Rc3 為環狀有機基團時，環狀有機基團可以是脂環式基團，也可以是芳香族基團。作為環狀有機基團，可舉出脂肪族環狀烴基、芳香族烴基、雜環基。Rc2 和Rc3 為環狀有機基團時，環狀有機基團可以具有的取代基與Rc2 和Rc3 為鏈狀烷基時同樣。 Rc2 及Rc3 為芳香族烴基時，芳香族烴基優選為：苯基、或多個苯環介由碳-碳鍵鍵結而形成的基團、或多個苯環縮合而形成的基團。芳香族烴基為苯基、或多個苯環鍵結或縮合而形成的基團時，芳香族烴基中包含的苯環的環數沒有特別限制，優選為3以下，更優選為2以下，特別優選為1。作為芳香族烴基的優選具體例，可舉出苯基、萘基、聯苯基、蒽基、及菲基等。 Rc2 及Rc3 為脂肪族環狀烴基時，脂肪族環狀烴基可以為單環式也可以為多環式。脂肪族環狀烴基的碳原子數沒有特別限制，優選為3以上且20以下，更優選為3以上且10以下。作為單環式的環狀烴基的例子，可舉出環丙基、環丁基、環戊基、環己基、環庚基、環辛基、降冰片基、異冰片基、三環壬基、三環癸基、四環十二烷基、及金剛烷基等。 Rc2 及Rc3 為雜環基時，雜環基為包含1個以上的N、S、O的五元或六元的單環，或者為所述單環彼此縮合、或所述單環與苯環縮合而成的雜環基。雜環基為稠環時，構成稠環的單環的環數為3以下。雜環基可以為芳香族基團(雜芳基)，也可以為非芳香族基團。作為構成該雜環基的雜環，可舉出呋喃、噻吩、吡咯、噁唑、異噁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、三唑、吡啶、吡嗪、嘧啶、噠嗪、苯並呋喃、苯並噻吩、吲哚、異吲哚、吲哚嗪、苯並咪唑、苯並三唑、苯並噁唑、苯並噻唑、哢唑、嘌呤、喹啉、異喹啉、喹唑啉、酞嗪、噌啉、喹喔啉、哌啶、哌嗪、嗎啉、哌啶、四氫吡喃、及四氫呋喃等。 Rc2 與Rc3 可以相互鍵結而形成環。包含Rc2 與Rc3 形成的環的基團優選為環烷叉基(cycloalkylidene group)。Rc2 與Rc3 鍵結而形成環烷叉基時，構成環烷叉基的環優選為五元環或六元環，更優選為五元環。 Rc2 與Rc3 鍵結而形成的基團為環烷叉基時，環烷叉基可與1個以上的其他環縮合。作為可與環烷叉基縮合的環的例子，可舉出苯環、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、吡嗪環、及嘧啶環等。 上文中說明的Rc2 和Rc3 中，作為優選的基團的例子，可舉出式-A1 -A2 表示的基團。式中，A1 為直鏈亞烷基，A2 為烷氧基、氰基、鹵素原子、鹵代烷基、環狀有機基團、或烷氧基羰基。 A1 的直鏈亞烷基的碳原子數優選為1以上且10以下，更優選為1以上且6以下。A2 為烷氧基時，烷氧基可以為直鏈狀，也可以為支鏈狀，優選為直鏈狀。烷氧基的碳原子數優選為1以上且10以下，更優選為1以上且6以下。A2 為鹵素原子時，優選為氟原子、氯原子、溴原子、碘原子，更優選為氟原子、氯原子、溴原子。A2 為鹵代烷基時，鹵代烷基中包含的鹵素原子優選為氟原子、氯原子、溴原子、碘原子，更優選為氟原子、氯原子、溴原子。鹵代烷基可以為直鏈狀，也可以為支鏈狀，優選為直鏈狀。A2 為環狀有機基團時，環狀有機基團的例子與Rc2 和Rc3 作為取代基而具有的環狀有機基團同樣。A2 為烷氧基羰基時，烷氧基羰基的例子與Rc2 和Rc3 作為取代基而具有的烷氧基羰基同樣。 作為Rc2 及Rc3 的優選具體例，可舉出乙基、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代烷基。 作為Rc2 和Rc3 ，上述中優選的基團為乙基、正丙基、正丁基、正戊基、2-甲氧基乙基、2-氰基乙基、2-苯基乙基、2-環己基乙基、2-甲氧基羰基乙基、2-氯乙基、2-溴乙基、3,3,3-三氟丙基、及3,3,4,4,5,5,5-七氟正戊基。 作為Rc4 的優選的有機基團的例子，與Rc1 同樣，可舉出烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧基羰基、飽和脂肪族醯基氧基、可具有取代基的苯基、可具有取代基的苯氧基、可具有取代基的苯甲醯基、可具有取代基的苯氧基羰基、可具有取代基的苯甲醯基氧基、可具有取代基的苯基烷基、可具有取代基的萘基、可具有取代基的萘氧基、可具有取代基的萘甲醯基、可具有取代基的萘氧基羰基、可具有取代基的萘甲醯基氧基、可具有取代基的萘基烷基、可具有取代基的雜環基、可具有取代基的雜環基羰基、被1個或2個有機基團取代的氨基、嗎啉-1-基、及哌嗪-1-基等。這些基團的具體例與針對Rc1 的說明同樣。另外，作為Rc4 ，還優選環烷基烷基、可在芳香環上具有取代基的苯氧基烷基、可在芳香環上具有取代基的苯基硫基烷基。苯氧基烷基、及苯基硫基烷基可以具有的取代基與Rc1 中包含的苯基可以具有的取代基同樣。 有機基團中，作為Rc4 ，優選烷基、環烷基、可具有取代基的苯基或環烷基烷基、可在芳香環上具有取代基的苯基硫基烷基。作為烷基，優選為碳原子數1以上且20以下的烷基，更優選為碳原子數1以上且8以下的烷基，特別優選為碳原子數1以上且4以下的烷基，最優選為甲基。可具有取代基的苯基中，優選甲基苯基，更優選2-甲基苯基。環烷基烷基中包含的環烷基的碳原子數優選為5以上且10以下，更優選為5以上且8以下，特別優選為5或6。環烷基烷基中包含的亞烷基的碳原子數優選為1以上且8以下，更優選為1以上且4以下，特別優選為2。環烷基烷基中，優選環戊基乙基。可在芳香環上具有取代基的苯基硫基烷基中包含的亞烷基的碳原子數優選為1以上且8以下，更優選為1以上且4以下，特別優選為2。可在芳香環上具有取代基的苯基硫基烷基中，優選2-(4-氯苯基硫基)乙基。 另外，作為Rc4 ，還優選-A3 -CO-O-A4 表示的基團。A3 為二價有機基團，優選為二價烴基，優選為亞烷基。A4 為一價有機基團，優選為一價烴基。 A3 為亞烷基時，亞烷基可以為直鏈狀，也可以為支鏈狀，優選為直鏈狀。A3 為亞烷基時，亞烷基的碳原子數優選為1以上且10以下，更優選為1以上且6以下，特別優選為1以上且4以下。 作為A4 的優選例，可舉出碳原子數1以上且10以下的烷基、碳原子數7以上且20以下的芳烷基、以及碳原子數6以上且20以下的芳香族烴基。作為A4 的優選具體例，可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基、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 表示的基團的優選具體例，可舉出2-甲氧基羰基乙基、2-乙氧基羰基乙基、2-正丙基氧基羰基乙基、2-正丁基氧基羰基乙基、2-正戊基氧基羰基乙基、2-正己基氧基羰基乙基、2-苄基氧基羰基乙基、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-正丙基氧基羰基正丙基、3-正丁基氧基羰基正丙基、3-正戊基氧基羰基正丙基、3-正己基氧基羰基正丙基、3-苄基氧基羰基正丙基、及3-苯氧基羰基正丙基等。 以上，對Rc4 進行了說明，作為Rc4 ，優選下述式(1a)或下述式(1b)表示的基團。
Figure 02_image051
(式(1a)及式(1b)中，Rc7 及Rc8 各自為有機基團，n3為0以上且4以下的整數，Rc7 及Rc8 存在於苯環上的相鄰位置時，Rc7 與Rc8 可以彼此鍵結而形成環，n4為1以上且8以下的整數，n5為1以上且5以下的整數，n6為0以上且(n5+3)以下的整數，Rc9 為有機基團。) 式(1a)中的Rc7 及Rc8 有關的有機基團的例子與Rc1 同樣。作為Rc7 ，優選烷基或苯基。Rc7 為烷基時，其碳原子數優選為1以上且10以下,更優選為1以上且5以下，特別優選為1以上且3以下，最優選為1。即，Rc7 最優選為甲基。Rc7 與Rc8 鍵結而形成環時，該環可以為芳香族環，也可以為脂肪族環。作為Rc7 與Rc8 形成了環的由式(1a)表示的基團的優選例，可舉出萘-1-基、1,2,3,4-四氫萘-5-基等。上述式(1a)中，n3為0以上且4以下的整數，優選為0或1,更優選為0。 上述式(1b)中，Rc9 為有機基團。作為有機基團，可舉出與針對Rc1 而說明的有機基團同樣的基團。有機基團中，優選烷基。烷基可以為直鏈狀，也可以為支鏈狀。烷基的碳原子數優選為1以上且10以下，更優選為1以上且5以下，特別優選為1以上且3以下。作為Rc9 ，可優選示例甲基、乙基、丙基、異丙基、丁基等，這些之中，更優選甲基。 上述式(1b)中，n5為1以上且5以下的整數，優選為1以上且3以下的整數,更優選為1或2。上述式(1b)中，n6為0以上且(n5+3)以下，優選為0以上且3以下的整數,更優選為0以上且2以下的整數，特別優選為0。上述式(1b)中，n4為1以上且8以下的整數，優選為1以上且5以下的整數,更優選為1以上且3以下的整數，特別優選為1或2。 式(1)中，Rc5 為氫原子、可具有取代基的碳原子數1以上且11以下的烷基、或者可具有取代基的芳基。作為Rc5 為烷基時可具有的取代基，可優選示例苯基、萘基等。另外，作為Rc1 為芳基時可具有的取代基，可優選示例碳原子數1以上且5以下的烷基、烷氧基、鹵素原子等。 式(1)中，作為Rc5 ，可優選示例氫原子、甲基、乙基、正丙基、異丙基、正丁基、苯基、苄基、甲基苯基、萘基等，這些之中，更優選甲基或苯基。 作為式(1)表示的化合物的優選具體例，可舉出以下的PI-1～PI-41。
Figure 02_image053
Figure 02_image055
感光性組合物可以在包含上述的式(1)表示的化合物的同時還包含其他光聚合引發劑作為光聚合引發劑(C)。作為其他光聚合引發劑，只要是不屬於上述的式(1)表示的化合物的光聚合引發劑即可，沒有特別限定。 作為其他光聚合引發劑的優選例，可示例：2-(苯甲醯基氧基亞氨基)-1-[4-(苯硫基)苯基]-1-辛酮(例如，作為OXE-01(BASF公司製)被市售。)、及O-乙醯基-1-[6-(2-甲基苯甲醯基)-9-乙基-9H-哢唑-3-基]乙酮肟(例如，作為OXE-02(BASF公司製)被市售。)等具有不屬於上述式(C1)的結構的肟酯化合物；2-苄基-2-二甲基氨基-1-(4-嗎啉代苯基)丁烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代丙烷-1-酮、2-苄基-2-二甲基氨基-1-(4-二甲基氨基苯基)丁烷-1-酮、2-(4-甲基苄基)-2-二乙基氨基-1-(4-嗎啉代苯基)丁烷-1-酮、2-甲基-1-苯基-2-嗎啉代丙烷-1-酮、2-甲基-1-[4-(己基)苯基]-2-嗎啉代丙烷-1-酮、2-乙基-2-二甲基氨基-1-(4-嗎啉代苯基)丁烷-1-酮等α-氨基酮系化合物；1-苯基-2-羥基-2-甲基丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、4-(2-羥基乙氧基)苯基-(2-羥基-2-丙基)酮、1-羥基環己基苯基酮等α-羥基酮系光聚合引發劑；苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻丙基醚、苄基甲基縮酮等苯偶姻系光聚合引發劑；二苯甲酮、苯甲醯基苯甲酸、苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、羥基二苯甲酮、丙烯酸化二苯甲酮、4-苯甲醯、4’-甲基二苯基硫醚、4,4’-雙二乙基氨基二苯甲酮等二苯甲酮系光聚合引發劑；噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、異丙基噻噸酮、2,4-二異丙基噻噸酮等噻噸酮系光聚合引發劑；2,4,6-三氯均三嗪、2-苯基-4,6-雙(三氯甲基)均三嗪、2-(對甲氧基苯基)-4,6-雙(三氯甲基)均三嗪、2-(對甲苯基)-4,6-雙(三氯甲基)均三嗪、2-胡椒基(pipenyl)-4,6-雙(三氯甲基)均三嗪、2,4-雙(三氯甲基)-6-苯乙烯基均三嗪、2-(萘-1-基)-4,6-雙(三氯甲基)均三嗪、2-(4-甲氧基-萘-1-基)-4,6-雙(三氯甲基)均三嗪、2,4-三氯甲基-(胡椒基)-6-三嗪、2,4-三氯甲基-(4’-甲氧基苯乙烯基)-6-三嗪、2-[4-(4-甲氧基苯乙烯基)苯基]-4,6-雙(三氯甲基)-1,3,5-三嗪等三嗪系光聚合引發劑；哢唑系光聚合引發劑；2,2’-雙(2-氯苯基)-4,4’,5,5’-四(4-乙氧基羰基苯基)-1,2’-聯咪唑、2,2’-雙(2-溴苯基)-4,4’,5,5’-四(4-乙氧基羰基苯基)-1,2’-聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2,4,6-三氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2-溴苯基)-4,4,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2,4-二溴苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2,4,6-三溴苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑等聯咪唑系光聚合引發劑；下述式表示的這樣的苯並咪唑啉系光聚合引發劑；等等。
Figure 02_image057
作為上述的式(1)表示的化合物的上述以外的優選具體例，可舉出以下的化合物。
Figure 02_image059
Figure 02_image061
Figure 02_image063
Figure 02_image065
Figure 02_image067
Figure 02_image069
Figure 02_image071
Figure 02_image073
Figure 02_image075
Figure 02_image077
Figure 02_image079
Figure 02_image081
Figure 02_image083
上述式(1)表示的化合物的質量相對於光聚合引發劑(C)的質量而言的比率在不損害本發明目的的範圍內沒有特別限定。相對於光聚合引發劑(C)的質量而言的、上述式(1)表示的化合物的比率優選為50質量%以上,更優選為70質量%以上，進一步優選為80質量%以上，更進一步優選為90質量%以上，特別優選為100質量%。 相對於感光性組合物的固態成分整體的質量而言，光聚合引發劑(C)的含量優選為0.1質量%以上且30質量%以下,更優選為0.5質量%以上且20質量%以下。通過使光聚合引發劑(C)的含量成為上述的範圍，能夠得到固化性良好、不易產生圖案形狀不良的感光性組合物。 ＜有機溶劑(S)＞ 典型地，感光性組合物可以出於調節塗布性的目的等而包含有機溶劑(S)。作為有機溶劑(S)，例如可舉出乙二醇單甲基醚、乙二醇單乙基醚、乙二醇正丙基醚、乙二醇單正丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單正丙基醚、二乙二醇單正丁基醚、三乙二醇單甲基醚、三乙二醇單乙基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單正丙基醚、丙二醇單正丁基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單正丙基醚、二丙二醇單正丁基醚、三丙二醇單甲基醚、三丙二醇單乙基醚等(聚)亞烷基二醇單烷基醚類；乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯等(聚)亞烷基二醇單烷基醚乙酸酯類；二乙二醇二甲基醚、二乙二醇甲基乙基醚、二乙二醇二乙基醚、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-甲氧基丁酯、乙酸3-甲基-3-甲氧基丁酯、丙酸3-甲基-3-甲氧基丁酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸乙酯等其他酯類；甲苯、二甲苯等芳香族烴類；N-甲基吡咯烷酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺類等。這些溶劑可以單獨使用，也可以組合兩種以上而使用。 有機溶劑(S)的使用量可根據感光性組合物的用途而適當確定。作為有機溶劑(S)的使用量，作為一例，可舉出感光性組合物的固態成分濃度為1質量%以上且50質量%以下的範圍的量。 ＜其他成分＞ 感光性組合物中，可根據需要包含除上述以外的其他各種添加劑。具體而言，可示例分散助劑、填充劑、填料、密合促進劑、抗氧化劑、紫外線吸收劑、抗凝集劑、熱阻聚劑、消泡劑、表面活性劑等。 作為感光性組合物中使用的熱阻聚劑，例如，可舉出對苯二酚、對苯二酚單乙基醚等。另外，分別地，作為消泡劑，可示例有機矽系、氟系等的化合物，作為表面活性劑，可示例陰離子系、陽離子系、非離子等的化合物。 ＜感光性組合物的製備方法＞ 感光性組合物可通過將各自所期望量的上述各成分均勻地混合而製備。需要說明的是，製備的感光性組合物不含顏料等不溶性的成分的情況下，可以使用過濾器進行過濾以使感光性組合物變均勻。 ≪固化物的製造方法≫ 典型地，以上說明的感光性組合物通過包括下述步驟的方法而製成固化物： 將感光性組合物根據固化物的形狀來進行成型的步驟；和 對經成型的感光性組合物進行曝光的步驟。 由上述的方法製造的固化物顯示出優選2.86以下、更優選2.84以下、進一步優選2.80以下、特別優選2.77以下的相對介電常數。因此，製造的固化物可以用於要求低介電常數的用途，例如絕緣膜等。另外，製造的固化物的透明性高，因此在OLED、有機EL或液晶等顯示裝置的用途中有用，可合適地用於平坦化膜、層間絕緣膜、濾色器用保護膜、用於使液晶顯示裝置中的液晶層的厚度保持恆定的間隔件、或固體攝像元件中的微透鏡等。 將感光性組合物成型的方法沒有特別限定，可根據固化物的形狀進行適當選擇。作為固化物的形狀，可舉出膜形狀、透鏡形狀、線形狀、棱鏡形狀等，但不限於這些。這些形狀中，優選膜形狀。 作為將感光性組合物成型的方法，沒有特別限定。在固化物的形狀為透鏡形狀、棱鏡形狀等的情況下，可以使用刮板等，將感光性組合物填充於與固化物的形狀相符合的鑄模中。 固化物的形狀為線形狀等的情況下，可以根據固化物的形狀將感光性組合物塗布於基材上。作為塗布方法，例如，可舉出噴墨法等印刷法。 作為將感光性組合物塗布為膜形狀的方法，可舉出使用輥塗機、逆向塗布機、棒塗機等接觸轉印型塗布裝置、旋轉器(旋轉式塗布裝置)、幕流式塗布機等非接觸型塗布裝置的方法。另外，也可以利用噴墨法等印刷法將感光性組合物塗布為膜形狀。 作為塗布膜的厚度，沒有特別限定。作為塗布膜的厚度，優選為0.05μm以上,更優選為1μm以上。塗布膜的厚度例如可以為7μm以上，可以為10μm以上。塗布膜的厚度的上限沒有特別限定，例如可以為50μm以下，可以為20μm以下。塗布膜的厚度優選為10μm以下,更優選為5μm以下，進一步優選為2μm以下。 塗布膜的厚度的範圍優選為0.05μm以上且10μm以下,更優選為1μm以上且5μm以下，進一步優選為1μm以上且2μm以下。 接著，根據需要使塗布膜乾燥。乾燥方法沒有特別限定。作為乾燥方法，例如，可舉出：(1)利用加熱板，於80℃以上且120℃以下、優選90℃以上且100℃以下的溫度，乾燥60秒以上且120秒以下的時間的方法；(2)於室溫放置數小時至數天的方法；(3)放入溫風加熱器、紅外線加熱器中數十分鐘至數小時而除去溶劑的方法；等等。 通過對該塗布膜進行曝光，從而可形成固化膜。 曝光中，光源沒有特別限定，例如，可舉出高壓汞燈、超高壓汞燈、氙燈、碳弧燈、LED等。可以使用這樣的光源對塗布膜照射ArF準分子鐳射、KrF準分子鐳射、F2 準分子鐳射、遠紫外線(EUV)、真空紫外線(VUV)、電子束、X射線、軟X射線、g線、i線、h線、j線、k線等放射線、或電磁波，從而對塗布膜進行曝光。 曝光量根據感光性組合物的組成的不同而不同，例如優選為10mJ/cm2 以上且2000mJ/cm2 以下,更優選為100 mJ/cm2 以上且1500mJ/cm2 以下，進一步優選為200mJ/cm2 以上且1200mJ/cm2 以下。曝光照度也根據感光性組合物的組成的不同而不同，優選在1mW/cm2 以上且50mW/cm2 以下的範圍內。 可以對通過曝光而固化的固化膜進行加熱。進行加熱時的溫度沒有特別限定，優選為180℃以上且280℃以下,更優選為200℃以上且260℃以下，特別優選為220℃以上且250℃以下。加熱時間典型地優選為1分鐘以上且60分鐘以下,更優選為10分鐘以上且50分鐘以下，特別優選為20分鐘以上且40分鐘以下。 另一方面，可以位置選擇性地對塗布膜進行曝光。該情況下，針對塗布膜，隔著具有與固化膜的圖案形狀相對應的形狀的透光部的負型掩模，位置選擇性地進行曝光。 除了使用負型掩模以外，曝光方法與上述的曝光方法同樣。 接著，利用顯影液將經曝光的塗布膜顯影，由此形成經圖案化的固化膜。顯影方法沒有特別限定，例如，可以使用浸漬法、噴霧法等。作為顯影液，可舉出單乙醇胺、二乙醇胺、三乙醇胺等有機系的顯影液、氫氧化鈉、氫氧化鉀、碳酸鈉、氨、季銨鹽等的水溶液。 針對顯影後得到的經圖案化的固化膜，可以與對上述的經圖案化的塗布膜實施曝光方法的方法同樣地進行加熱。 通過使用上述的感光性組合物，即使在形成微細的圖案的情況下，也能夠良好地形成所期望形狀的圖案。 實施例 以下，利用實施例更詳細地說明本發明，但本發明並不限於這些實施例。 [實施例1～4、比較例1～5] 實施例及比較例中，作為鹼溶性樹脂(A)，使用下述結構的丙烯酸系樹脂P1、及下述結構的丙烯酸系樹脂P2。樹脂P1、及樹脂P2的按照聚苯乙烯換算的重量平均分子量均為10000。
Figure 02_image085
實施例及比較例中，作為光聚合性化合物(B)，使用以下的B-1～B-4。 B-1：三羥甲基丙烷三丙烯酸酯 B-2：雙三羥甲基丙烷四丙烯酸酯 B-3：二季戊四醇六丙烯酸酯 B-4：ε-己內酯改性二季戊四醇六丙烯酸酯(KAYARAD DPCA-120，日本化藥公司製) 實施例及比較例中，作為光聚合引發劑(C)，使用以下的C-1、及C-2。
Figure 02_image087
將表1中記載之種類的鹼溶性樹脂(A)((A)成分)13.73質量份、表1中記載之種類的光聚合性化合物(B)((B)成分)6.8質量份、表1中記載之種類的光聚合性化合物(C)((C)成分)1.22質量份、二乙二醇甲基乙基醚31.2質量份、丙二醇單甲基醚乙酸酯46.7質量份、3-環氧丙氧基丙基三甲氧基矽烷0.2質量份、表面活性劑(BYK-310，BYK-Chemie公司製)0.05質量份，及抗氧化劑(IR1010，BASF Japan公司製)0.1質量份進行混合，得到各實施例及各比較例的感光性組合物。 使用所得到的感光性組合物，按照以下的方法，對相對介電常數及圖案形成性進行評價。將此等評價結果記載於表1。 ＜相對介電常數測定＞ 作為相對介電常數的測定方法，利用汞探針法。能夠利用汞探針法進行相對介電常數測定的裝置，使用SSM-495(日本Semilab公司製)。藉由以下的步驟1)～4)，使用各實施例及比較例的組合物，形成膜厚為1μm的膜狀固化物。然後，針對形成的固化物，測定相對介電常數。 1)在矽晶片上塗布固化組合物，形成塗布膜。 2)將形成的塗布膜以100℃加熱120秒。 3)將塗布膜以1J/cm2 的曝光量進行曝光。 4)將經曝光後的塗布膜以230℃加熱20分鐘。 ＜圖案形成性評價＞ 使用旋塗機，將各實施例及比較例的固化性組合物塗布於玻璃基板上，以100℃加熱120秒，形成塗布膜。接著，使用接近式曝光機(製品名：TME-150RTO，股份公司TOPCON製)，隔著20μm×20μm之孔圖案形成用負型掩模，將紫外線(i線)以50mJ/cm2 的曝光量照射至塗布膜。使用25℃之2.38質量%TMAH水溶液中，將曝光後的塗布膜顯影50秒後，於230℃下進行30分鐘後烘烤，由此形成孔圖案。使用光學顯微鏡對得到的圖案進行觀察，按以下的基準對孔形狀進行評價。 〇：掩模之遮光部分的正方形形狀通過孔圖案中的孔而得以再現，掩模轉印性良好。 ×：掩模之遮光部分的正方形形狀通過孔圖案中的孔無法再現，掩模轉印性不佳
Figure 02_image089
根據表1可知，為組合地包含具有3或4個丙烯醯基之多官能化合物及相當於於式(1)表示之化合物之C-1的實施例的感光性組合物時，能夠同時實現形成相對介電常數低的固化物及良好的圖案形成性。 另一方面，對於未包含組合具有3或4個丙烯醯基之多官能化合物及式(1)表示之化合物之比較例的感光性組合物，無法同時實現形成介電常數低的固化物及良好的圖案形成性。≪Photosensitive composition≫ The photosensitive composition contains an alkali-soluble resin (A), a photopolymerizable compound (B), and a photopolymerization initiator (C). The photopolymerizable compound (B) contains a polyfunctional compound having 3 or 4 (meth)acrylic groups. In addition, the photopolymerization initiator (C) contains an oxime ester compound represented by the following formula (1). By containing the above-mentioned photopolymerizable compound (B) and the photopolymerization initiator (C) in combination in the photosensitive composition, it is possible to form a cured product having a low relative dielectric constant and being well patterned.
Figure 02_image003
(In formula (1), R c1 is each independently a hydrogen atom, a nitro group, or a monovalent organic group, and R c2 and R c3 are each a chain alkyl group that may have a substituent, and a chain shape that may have a substituent. An alkoxy group, a cyclic organic group that may have a substituent, or a hydrogen atom, R c2 and R c3 may be bonded to each other to form a ring, R c4 is a monovalent organic group, R c5 is a hydrogen atom, which may be substituted The group has an aliphatic hydrocarbon group with 1 or more and 20 or less carbon atoms, or an aryl group that may have a substituent, n1 is an integer of 0 or more and 4 or less, and n2 is 0 or 1.) Below, for the photosensitive composition included The necessary or optional components of and the method for producing the photosensitive composition will be described in order. <Alkali-soluble resin (A)> The photosensitive composition contains alkali-soluble resin (A). The alkali-soluble resin (A) is not particularly limited, and it can be appropriately selected from alkali-soluble resins conventionally blended in various photosensitive compositions. Here, in this specification, the alkali-soluble resin (A) refers to a resin having an alkali-soluble functional group (for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, etc.) in the molecule. Regarding the resin suitable as the alkali-soluble resin (A), a resin (aI) having a Cardo structure (hereinafter, also described as "Cardo resin (aI)") is mentioned. When the resin (aI) having a Cardo structure is used as the alkali-soluble resin, it is easy to obtain a photosensitive composition having excellent resolution, and it is easy to use the photosensitive composition to form a cured film that is less likely to flow excessively due to heating. Therefore, it is easy to form a cured film with a good shape. [Resin (aI) having a Cardo structure] As the resin (aI) having a Cardo skeleton, a resin having a Cardo skeleton in its structure and having predetermined alkali solubility can be used. The cardo skeleton refers to a skeleton formed by bonding a second cyclic structure and a third cyclic structure to one ring carbon atom constituting the first cyclic structure. It should be noted that the second cyclic structure and the third cyclic structure may be the same structure or different structures. A representative example of the Cardo skeleton includes a skeleton in which two aromatic rings (for example, a benzene ring) are bonded to the 9-position carbon atom of the fluorene ring. The Cardo resin (aI) is not particularly limited, and conventionally known resins can be used. Among them, the resin represented by the following formula (a-1) is preferred.
Figure 02_image005
In the formula (a-1), X a represents a group represented by the following formula (a-2). m1 represents an integer of 0 or more and 20 or less.
Figure 02_image007
In the above formula (a-2), each of R a1 independently represents a hydrogen atom, a hydrocarbon group having from 1 to 6 carbon atoms, or a halogen atom, each of R a2 independently represents a hydrogen atom or a methyl group, and each of R a3 independently represents It represents a linear or branched alkylene group, m2 represents 0 or 1, and Wa represents a group represented by the following formula (a-3).
Figure 02_image009
In the formula (a-2), as Ra3 , an alkylene group having 1 or more and 20 or less carbon atoms is preferred, an alkylene having 1 or more and 10 or less carbon atoms is more preferred, and an alkylene having 1 or more and 10 carbon atoms is particularly preferred. The alkylene groups above and below 6 are most preferably ethane-1,2-diyl, propane-1,2-diyl, and propane 1,3-diyl. The ring A in the formula (a-3) represents an aliphatic ring which may be condensed with an aromatic ring and may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring. Examples of the aliphatic ring include monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specific examples include monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The aromatic ring that can be condensed with the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring. Specifically, a benzene ring and a naphthalene ring are preferable. As a preferable example of the divalent group represented by formula (a-3), the following groups can be mentioned.
Figure 02_image011
Of formula (a-1) a divalent group X a Z a residue available by reacting tetracarboxylic dianhydride with a diol compound represented by the following formula (a-2a) so as to be introduced into Cardo resin (aI )middle.
Figure 02_image013
In the formula (a-2a), Ra1 , Ra2 , Ra3 , and m2 are as described for the formula (a-2). Regarding the ring A in the formula (a-2a), as described for the formula (a-3). The diol compound represented by formula (a-2a) can be produced by the following method, for example. First, if necessary, according to a conventional method, replace the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) with a group represented by -R a3 -OH, and then use epichlorohydrin The etc. are glycidylated to obtain an epoxy compound represented by the following formula (a-2c). Next, by reacting the epoxy compound represented by the formula (a-2c) with acrylic acid or methacrylic acid, the diol compound represented by the formula (a-2a) is obtained. In formula (a-2b) and formula (a-2c), Ra1 , Ra3 , and m2 are as described with respect to formula (a-2). Regarding the ring A in the formula (a-2b) and the formula (a-2c), as described for the formula (a-3). In addition, the manufacturing method of the diol compound represented by Formula (a-2a) is not limited to the above-mentioned method.
Figure 02_image015
As a preferable example of the diol compound represented by Formula (a-2b), the following diol compounds are mentioned.
Figure 02_image017
In the above formula (a-1), Ra0 is a hydrogen atom or a group represented by -CO-Y a -COOH. Here, Y a represents a residue obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic anhydride. As examples of dicarboxylic anhydrides, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylene tetrahydro Phthalic anhydride, chlorobacteric acid anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc. Further, in the above formula (a-1), Z a represents a residue formed by removing two acid anhydride groups in the tetracarboxylic dianhydride obtained. Examples of tetracarboxylic dianhydride include tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and biphenyl tetracarboxylic dianhydride represented by the following formula (a-4) , Diphenyl ether tetracarboxylic dianhydride, etc. In addition, in the above formula (a-1), m represents an integer of 0 or more and 20 or less.
Figure 02_image019
(In formula (a-4), R a4 , R a5 , and R a6 each independently represent one kind selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, m3 It represents an integer of 0 or more and 12 or less.) The alkyl group that can be selected as R a4 in the formula (a-4) is an alkyl group having 1 or more and 10 or less carbon atoms. By setting the number of carbon atoms of the alkyl group within this range, the heat resistance of the obtained carboxylic acid ester can be further improved. When R a4 is an alkyl group, the number of carbon atoms is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, and still more preferably 1 or more and 4 or less from the viewpoint of easily obtaining a Cardo resin having excellent heat resistance. Especially preferably, it is 1 or more and 3 or less. When R a4 is an alkyl group, the alkyl group may be linear or branched. Formula (a4) in R a4, easily obtained is excellent in heat resistance resin Cardo consideration, are each independently a hydrogen atom or more carbon atoms, an alkyl group, and more preferably 10 or less. R a4 in the formula (a-4) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group. From the viewpoint of easy production of high-purity tetracarboxylic dianhydride, it is preferable that a plurality of Ra4 in the formula (a-4) are the same group. M3 in formula (a-4) represents an integer of 0 or more and 12 or less. By making the value of m3 12 or less, the purification of tetracarboxylic dianhydride can be made easy. From the viewpoint of easy purification of tetracarboxylic dianhydride, the upper limit of m3 is preferably 5, and more preferably 3. From the viewpoint of the chemical stability of tetracarboxylic dianhydride, the lower limit of m3 is preferably 1, and more preferably 2. In formula (a-4), m3 is particularly preferably 2 or 3. The alkyl group having 1 or more and 10 or less carbon atoms that can be selected as Ra5 and Ra6 in the formula (a-4) is the same as the alkyl group having 1 or more and 10 or less carbon atoms that can be selected as R a4. From the viewpoint of easy purification of tetracarboxylic dianhydride, R a5 and R a6 are preferably hydrogen atoms, or carbon atoms of 1 or more and 10 or less (preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less) , More preferably 1 or more and 4 or less, particularly preferably 1 or more and 3 or less) alkyl group, particularly preferably a hydrogen atom or a methyl group. Examples of the tetracarboxylic dianhydride represented by the formula (a-4) include norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride (alias "norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2"-norbornane-5,5",6,6"- Tetracarboxylic dianhydride”), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-(methylnorbornane)-5,5”,6,6”-tetra Formic acid dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride (alias "norbornane -2-spiro-2'-cyclohexanone-6'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride”), methylnorbornane-2-spiro -α-Cyclohexanone-α'-spiro-2”-(methylnorbornane)-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloacetone -α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclobutanone-α'-spiro-2”- Norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloheptanone-α'-spiro-2”-norbornane-5,5”, 6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclooctanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride , Norbornane-2-spiro-α-cyclononanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro- α-Cyclodecanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanone-α '-Spiro-2”-Norbornane-5,5”,6,6”-tetracarboxylic dianhydride, Norbornane-2-spiro-α-cyclododecanone-α'-spiro-2”- Norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotridecanone-α'-spiro-2”-norbornane-5,5 ”,6,6”-Tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotetradecylone-α'-spiro-2”-norbornane-5,5”,6,6”- Tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane Alkyl-2-spiro-α-(methylcyclopentanone)-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro -α-(methylcyclohexanone)-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, etc. The weight average molecular weight of Cardo resin (aI) is preferably 1000 or more and 40000 or less, more preferably 1500 or more and 30000 or less, still more preferably 2000 or more and 10000 or less. By being in the above range, a good display can be obtained In addition, it is possible to obtain sufficient heat resistance and mechanical strength for a cured film formed using the photosensitive composition. [Novolac resin (a-II)] It is also preferable that the alkali-soluble resin (A) contains the Novolac resin (a-II) from the viewpoint that it is easy to form a cured product that does not flow excessively due to heating. As the Novolac resin (a-II), various Novolac resins conventionally compounded in photosensitive compositions can be used. The Novolac resin (a-II) is preferably obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenols") and aldehydes under acid catalysis. (Phenols) Examples of phenols that can be used when producing Novolac resin (a-II) include phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol , 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol and other xylenols; o-ethylphenol , M-ethylphenol, p-ethylphenol and other ethyl phenols; 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butyl Alkylphenols such as phenol and p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; resorcinol, o-benzene Polyphenols such as diphenols, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglucinol; alkyl resorcinol, alkyl catechol, and alkyl pair Alkyl polyphenols such as hydroquinone (the number of carbon atoms of all alkyl groups is 1 or more and 4 or less); α-naphthol; β-naphthol; hydroxydiphenyl; and bisphenol A, etc. These phenols may be used alone or in combination of two or more kinds. Among these phenols, m-cresol and p-cresol are preferred, and the combined use of m-cresol and p-cresol is more preferred. In this case, by adjusting the mixing ratio of the two, various properties such as heat resistance of the cured film formed using the photosensitive composition can be adjusted. The mixing ratio of m-cresol and p-cresol is not particularly limited, but it is preferably 3/7 or more and 8/2 or less in terms of the molar ratio of m-cresol/p-cresol. By using m-cresol and p-cresol in the ratio in the above-mentioned range, a photosensitive composition capable of forming a cured film excellent in heat resistance can be easily obtained. In addition, Novolac resin produced by using m-cresol and 2,3,5-trimethylphenol in combination is also preferable. When the Novolac resin is used, it is particularly easy to obtain a photosensitive composition capable of forming a cured film having excellent heat resistance. The blending ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited, but it is preferably 70/30 or more and 95/m in terms of the molar ratio of m-cresol/2,3,5-trimethylphenol. 5 or less. (Aldehydes) Examples of aldehydes that can be used when producing Novolac resin (a-II) include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more kinds. (Acid catalyst) As an acid catalyst that can be used in the production of Novolac resin (a-II), for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; formic acid, oxalic acid, acetic acid, and diethyl sulfate , And organic acids such as p-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more kinds. (Molecular weight) The weight average molecular weight (Mw; hereafter, also referred to simply as "weight average molecular weight") of Novolac resin (a-II) in terms of polystyrene is derived from a cured film formed using a photosensitive composition From the viewpoint of heat resistance, the lower limit is preferably 2,000, more preferably 5,000, particularly preferably 10,000, still more preferably 15,000, most preferably 20,000, and the upper limit is preferably 50,000, more preferably 45,000, and further Preferably it is 40,000, most preferably 35,000. As the Novolac resin (a-II), at least two Novolac resins having different weight average molecular weights in terms of polystyrene can be used in combination. By combining and using Novolac resins with different weight average molecular weights, the developability of the photosensitive composition and the heat resistance of the cured film formed using the photosensitive composition can be balanced. [Modified epoxy resin (a-III)] Alkali-soluble resin (A) may contain polybasic acid anhydride (a -3c) Adduct (a-3). This adduct is also described as "modified epoxy resin (a-III)". In the specification of this application and the scope of the patent application, compounds meeting the above definition but not equivalent to the above resin (aI) with the Cardo structure are regarded as modified epoxy resins (a-III). Hereinafter, the epoxy compound (a-3a), the unsaturated group-containing carboxylic acid (a-3b), and the polybasic acid anhydride (a-3c) will be described. <Epoxy compound (a-3a)> The epoxy compound (a-3a) is not particularly limited, as long as it is a compound having an epoxy group, it may be an aromatic epoxy compound having an aromatic group, or it may be The aliphatic epoxy compound not containing an aromatic group is preferably an aromatic epoxy compound having an aromatic group. The epoxy compound (a-3a) may be a monofunctional epoxy compound or a polyfunctional epoxy compound having two or more functions, and is preferably a polyfunctional epoxy compound. Specific examples of the epoxy compound (a-3a) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, and naphthalene type epoxy resin. Epoxy resins, biphenyl type epoxy resins and other bifunctional epoxy resins; dimer acid glycidyl esters and triglycidyl esters and other glycidyl ester type epoxy resins; tetraglycidylaminodiphenylmethane, triglycidyl Glycidyl amine type epoxy resins such as glycidyl p-aminophenol, tetraglycidyl metaxylylenediamine, and tetraglycidyl bisaminomethyl cyclohexane; heterocyclic rings such as triglycidyl isocyanurate Formula epoxy resin; Phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerol triglycidyl ether, 2-[4- (2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane , And 1,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropane (Oxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol and other trifunctional epoxy resins; tetrahydroxyphenylethane tetraglycidyl ether, tetra Four-functional epoxy resins such as glycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxy biphenyl. Moreover, as an epoxy compound (a-3a), the epoxy compound which has a biphenyl skeleton is preferable. The epoxy compound having a biphenyl skeleton preferably has at least one biphenyl skeleton represented by the following formula (a-3a-1) in the main chain. The epoxy compound having a biphenyl skeleton is preferably a polyfunctional epoxy compound having two or more epoxy groups. By using an epoxy compound having a biphenyl skeleton, it is easy to obtain a photosensitive composition that is excellent in the balance between sensitivity and developability and can form a cured film having excellent adhesion to the substrate.
Figure 02_image021
(In the formula (a-3a-1), R a7 is each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a substituted phenyl group, and j is 1 or more and 4 The following integers.) When Ra7 is an alkyl group having 1 to 12 carbon atoms, specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, iso Butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, N-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, and n-dodecyl. When R a7 is a halogen atom, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. When R a7 is an optionally substituted phenyl group, the number of substituents on the phenyl group is not particularly limited. The number of substituents on the phenyl group is 0 or more and 5 or less, preferably 0 or 1. Examples of substituents include alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, aliphatic acyl groups having 2 to 4 carbon atoms, and halogen atoms. , Cyano, and nitro. The epoxy compound (a-3a) having a biphenyl skeleton represented by the above formula (a-3a-1) is not particularly limited. For example, an epoxy compound represented by the following formula (a-3a-2) can be mentioned .
Figure 02_image023
(In the formula (a-3a-2), Ra7 and j are the same as in the formula (a-3a-1), and k is the average repeating number of the structural unit in the parentheses, and is 0 or more and 10 or less.) Formula (a Among the epoxy compounds represented by -3a-2), a compound represented by the following formula (a-3a-3) is preferred from the viewpoint that it is particularly easy to obtain a photosensitive composition having an excellent balance of sensitivity and developability.
Figure 02_image025
(In formula (a-3a-3), k is the same as formula (a-3a-2).) (Unsaturated group-containing carboxylic acid (a-3b)) In the preparation of modified epoxy compound (a-3) ), the epoxy compound (a-3a) is reacted with the unsaturated group-containing carboxylic acid (a-3b). The unsaturated group-containing carboxylic acid (a-3b) is preferably a monobasic unit containing reactive unsaturated double bonds such as an acryl group and a methacryl group in the molecule. carboxylic acid. Examples of such unsaturated group-containing carboxylic acids include acrylic acid, methacrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, α-cyanocinnamic acid, and cinnamic acid. In addition, the unsaturated group-containing carboxylic acid (a-3b) can be used alone or in combination of two or more kinds. The epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) can be reacted by a known method. As a preferable reaction method, for example, the following method can be mentioned: tertiary amines such as triethylamine and benzylethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylamine, etc. Quaternary ammonium chloride, benzyl triethyl ammonium chloride and other quaternary ammonium salts, pyridine, or triphenyl phosphine, etc. as a catalyst, in an organic solvent, the epoxy compound (a-3a) React with unsaturated group-containing carboxylic acid (a-3b) for several hours to several tens of hours. Regarding the ratio of the two amounts used in the reaction of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b), the epoxy equivalent of the epoxy compound (a-3a) The ratio to the carboxylic acid equivalent of the unsaturated group-containing carboxylic acid (a-3b) is usually preferably 1:0.5 to 1:2, more preferably 1:0.8 to 1:1.25, and particularly preferably 1:0.9 ~ 1: 1.1. When the ratio of the amount of epoxy compound (a-3a) to the amount of unsaturated group-containing carboxylic acid (a-3b) is 1:0.5 to 1:2, the crosslinking efficiency is achieved. The tendency to increase is preferred. (Polybasic acid anhydride (a-3c)) The polybasic acid anhydride (a-3c) is an anhydride of a carboxylic acid having two or more carboxyl groups. The polybasic acid anhydride (a-3c) is not particularly limited. For example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride Acid anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyl Tetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, the following formula (a- The compound represented by 3c-1) and the compound represented by the following formula (a-3c-2). Moreover, polybasic acid anhydride (a-3c) can be used individually or in combination of 2 or more types.
Figure 02_image027
(In formula (a-3c-2), Ra8 represents an alkylene group having 1 to 10 carbon atoms and optionally having substituents.) As the polybasic acid anhydride (a-3c), sensitivity and developability can be easily obtained from From the viewpoint of a photosensitive composition having excellent balance of, a compound having two or more benzene rings is preferable. In addition, the polybasic acid anhydride (a-3c) more preferably contains at least one of the compound represented by the above formula (a-3c-1) and the compound represented by the above formula (a-3c-2). The method of reacting the epoxy compound (a-3a) with the unsaturated group-containing carboxylic acid (a-3b) and the polybasic acid anhydride (a-3c) can be appropriately selected from known methods. In addition, the ratio of the amount used is based on the number of moles of OH groups in the component after the reaction of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) and the polybasic acid anhydride ( The equivalent ratio of the acid anhydride group of a-3c) is usually 1:1 to 1:0.1, preferably 1:0.8 to 1:0.2. By setting it as the said range, it becomes easy to obtain the photosensitive composition with good developability. In addition, the acid value of the modified epoxy resin (a-III) is preferably 10 mgKOH/g or more and 150 mgKOH/g or less, and more preferably 70 mgKOH/g or more and 110 mgKOH/g or less in terms of resin solid content. By setting the acid value of the resin to 10 mgKOH/g or more, sufficient solubility in the developer can be obtained. In addition, by setting the acid value to 150 mgKOH/g or less, sufficient curability can be obtained and the surface properties can be improved. . In addition, the weight average molecular weight of the modified epoxy resin (a-III) is preferably 1,000 or more and 40,000 or less, and more preferably 2,000 or more and 30,000 or less. By setting the weight average molecular weight to 1000 or more, it is easy to form a cured film excellent in heat resistance and strength. In addition, by setting the weight average molecular weight to 40,000 or less, it is easy to obtain a photosensitive composition exhibiting sufficient solubility in the developer. [Acrylic resin (a-IV)] The acrylic resin (a-IV) is also preferable as a component constituting the alkali-soluble resin (A). The alkali-soluble resin (A) preferably contains acrylic resin (a-IV) from the viewpoint of facilitating the formation of a cured product with a low dielectric constant and good patterning characteristics at the same time. The ratio of the mass of the acrylic resin (a-IV) to the total mass of the alkali-soluble resin (A) is typically preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more, More preferably, it is 95% by mass or more, and particularly preferably 100% by mass. As the acrylic resin (a-IV), a resin containing a structural unit derived from (meth)acrylic acid and/or a structural unit derived from other monomers such as (meth)acrylate can be used. (Meth)acrylic acid is acrylic acid or methacrylic acid. As other monomers, typically, a compound represented by the following formula (a-4-1) is preferably used.
Figure 02_image029
In the above formula (a-4-1), Ra9 is a hydrogen atom or a methyl group. R a10 is a monovalent organic group. The organic group may include a bond and substituent other than a hydrocarbon group, such as a hetero atom, in the organic group. In addition, the organic group may be any of linear, branched, and cyclic. R a11 is a group represented by -O- or -NR a12 -. R a12 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The substituents other than the hydrocarbon group in the organic group of Ra10 are not particularly limited as long as they do not impair the effects of the present invention. Examples include halogen atoms, hydroxyl groups, mercapto groups, thioether groups, cyano groups, isocyano groups, and cyano groups. Ester group, isocyanate group, thiocyanate group, isothiocyanate group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamethan group, nitro Group, nitroso group, carboxyl group, carboxylate/ester group, acyl group, acyloxy group, sulfinyl group, sulfo group, sulfonate/ester group, phosphino group, phosphinyl group, phosphinyl group, phosphonic acid Salt/ester group, hydroxyimino group, alkyl ether group, alkyl sulfide group, aryl ether group, aryl sulfide group, amino group (-NH 2 , -NHR, -NRR': R and R'are independent地 means a hydrocarbyl group) and so on. The hydrogen atom contained in the above-mentioned substituent may be substituted by a hydrocarbon group. In addition, the hydrocarbon group contained in the above-mentioned substituent may be any of linear, branched, and cyclic. In addition, the organic group as R a10 may have a reactive functional group such as an acryloxy group, a methacryloxy group, an epoxy group, and an oxetanyl group. Acrylic groups such as acryloxy and methacryloxy groups having unsaturated double bonds can be produced, for example, by combining an unsaturated carboxylic acid such as acrylic acid and methacrylic acid with a structure containing an epoxy group. At least a part of epoxy groups in the acrylic resin (a-IV) of the unit react. After reacting an unsaturated carboxylic acid with at least a part of epoxy groups, the polybasic acid anhydride may be reacted with the groups generated by the reaction. Specific examples of polybasic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Acid anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydro Phthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, etc. As a specific example, when acrylic acid and a structural unit derived from glycidyl methacrylate are reacted, a structural unit having a hydroxyl group shown in the following reaction formula is produced. By reacting a polybasic acid anhydride such as tetrahydrophthalic acid with the above-mentioned structural unit having a hydroxyl group, a structural unit having a carboxyl group and an unsaturated double bond and imparting alkali solubility to the resin is produced.
Figure 02_image031
In addition, by reacting a compound having an epoxy group and an unsaturated double bond with a structural unit derived from an unsaturated carboxylic acid such as acrylic acid and methacrylic acid that the acrylic resin (a-IV) has, it can be converted to the acrylic resin ( In a-IV), an unsaturated double bond is introduced. As the compound having an epoxy group and an unsaturated double bond, for example, glycidyl (meth)acrylate and compounds represented by the following formulas (a-4-1a) to (a-4-1o) can be used. As R a10 , preferably alkyl, aryl, cycloalkyl, polycycloalkyl, cycloalkylalkyl, polycycloalkylalkyl, aralkyl, or heterocyclic group, these groups can be It is substituted with a halogen atom, a hydroxyl group, an alkyl group, or a heterocyclic group, and an oxygen atom may be bonded to these groups to form an epoxy group. In addition, when these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond. When the alkyl group is linear or branched, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 1 or more and 15 or less, and particularly preferably 1 or more and 10 or less. Examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec Pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, isodecyl, etc. Among cycloalkyl, polycycloalkyl, cycloalkylalkyl, polycycloalkylalkyl, and alicyclic group-containing groups other than these groups, as the alicyclic group contained in these groups Preferred examples of the group include monocyclic alicyclic groups such as cyclopentyl and cyclohexyl, adamantyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclodecyl, etc. Dialkyl, bicyclo-[2.1.1]-hexyl, bicyclo-[2.2.1]-heptyl, bicyclo-[2.2.2]-octyl, bicyclo-[3.3.0]-octyl, bicyclo-[ Polycyclic alkyl groups such as 4.3.0]-nonyl and bicyclo-[4.4.0]-decyl. As a group represented by formula (a4-1) and having cycloalkyl, polycycloalkyl, cycloalkylalkyl, polycycloalkylalkyl, and alicyclic group-containing groups other than these groups, as Preferred examples of the compound of R a10 include compounds represented by the following formulas (a-4-1a) to (a-4-1h). Among these, in order to make developability moderate, compounds represented by the following formulas (a-4-1c) to (a-4-1h) are preferable, and the following formula (a-4-1c) or the following are more preferable The compound represented by the formula (a-4-1d).
Figure 02_image033
In the above formula, R a20 represents a hydrogen atom or a methyl group, R a21 represents a single bond or a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R a22 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R a21 is preferably a single bond, linear or branched alkylene group, such as methylene, ethylene, propylene, 1,4-butylene, ethylethylene, 1,5- Pentylene, 1,6-hexylene. As R a22 , for example, a methyl group and an ethyl group are preferable. From the viewpoint of easy formation of a cured product with a low dielectric constant, the alkali-soluble resin (A) preferably contains a structural unit (A-1) derived from polycycloalkyl (meth)acrylate. Acrylic resin. That is, the acrylic resin preferably contains a structural unit derived from a compound represented by any one of the above-mentioned formulas (a4-1c) to (a4-1h) and having a single bond as R a21 . From the viewpoint that it is particularly easy to form a cured product with a low dielectric constant, the acrylic resin more preferably contains a structural unit derived from the following compound as the structural unit (A-1), and the compound is represented by formula (a4-1c) and formula ( a4-1d) or formula (a4-1g), and has a single bond as R a21 . The amount of the aforementioned structural unit (A-1) in the acrylic resin is not particularly limited as long as it does not impair the purpose of the present invention. The amount of the above-mentioned structural unit (A-1) in the acrylic resin is preferably 10% by mass or more and 50% by mass or more, and more preferably 20% by mass or more and 40% by mass or less with respect to the amount of all the structural units, More preferably, it is 22 mass% or more and 35 mass% or less. When the compound represented by the formula (a-4-1) has a chain group having an epoxy group as R a10 , specific examples of the compound represented by the formula (a-4-1) include (methyl) Glycidyl acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, etc. Base) Epoxyalkyl acrylates. In addition, the compound represented by the formula (a-4-1) may be an alicyclic epoxy group-containing (meth)acrylate. The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cycloalkyl groups such as cyclopentyl and cyclohexyl. In addition, examples of polycyclic alicyclic groups include polycyclic alkyl groups such as norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl. From the viewpoint of easy formation of a cured product with a low dielectric constant, the alkali-soluble resin (A) preferably contains a structural unit (A-2) derived from an alicyclic epoxy group-containing (meth)acrylate. As a specific example when the compound represented by the formula (a-4-1) is an alicyclic epoxy group-containing (meth)acrylate, for example, the following formulas (a-4-1i) to (a- The compound represented by 4-1w). Among these, in order to make developability moderate, compounds represented by the following formulas (a-4-1i) to (a-4-1m) are preferred, and the following formulas (a-4-1i) to (a-4) are more preferred. -1k) The compound represented.
Figure 02_image035
Figure 02_image037
Figure 02_image039
In the above formula, R a23 represents a hydrogen atom or a methyl group, R a24 represents a divalent saturated aliphatic hydrocarbon group with 1 to 6 carbon atoms, Ra25 represents a divalent hydrocarbon group with 1 to 10 carbon atoms, t It represents an integer of 0 or more and 10 or less. R a24 is preferably a linear or branched alkylene group, such as methylene, ethylene, propylene, 1,4-butylene, ethylethylene, and 1,5-pentylene , 1,6-hexylene. As R a25 , for example, methylene, ethylene, propylene, 1,4-butylene, ethylethylene, 1,5-pentylene, 1,6-hexylene, and phenylene are preferred. , Cyclohexylene, -CH 2 -Ph-CH 2- (Ph represents phenylene). The amount of the structural unit (A-2) derived from an alicyclic epoxy group-containing (meth)acrylate in the acrylic resin (a-IV) is not particularly limited within a range that does not impair the purpose of the present invention, but is preferably It is 30% by mass or more and 75% by mass or less, and more preferably 50% by mass or more and 73% by mass or less. In the case of using such a resin, self-reaction of the carboxyl group contained in the resin and the alicyclic epoxy group may occur. Therefore, when a photosensitive composition containing such a resin is used, the method of heating the film or the like can cause self-reaction of the carboxyl group and the alicyclic epoxy group to increase the mechanical properties such as the hardness of the formed film. In addition, the acrylic resin (a-IV) may be a resin obtained by polymerizing a monomer other than (meth)acrylate. Examples of such monomers include (meth)acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These monomers can be used individually or in combination of 2 or more types. Examples of (meth)acrylamides include (meth)acrylamide, N-alkyl (meth)acrylamide, N-aryl(meth)acrylamide, N,N-di Alkyl(meth)acrylamide, N,N-aryl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, N-hydroxyethyl-N-methyl Base (meth)acrylamide and the like. Examples of unsaturated carboxylic acids include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; anhydrides of these dicarboxylic acids; and the like. Examples of allyl compounds include: allyl acetate, allyl hexanoate, allyl octoate, allyl laurate, allyl palmitate, allyl stearate, and allyl benzoate , Allyl esters such as allyl acetate and allyl lactate; allyloxyethanol; etc. Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, and ethoxyethyl vinyl ether. Ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether Ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether and other alkyl vinyl ethers ; Vinyl phenyl ether, vinyl cresyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthracenyl ether and other vinyl aryl ethers ;and many more. Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, and diethyl vinyl acetate. Vinyl chloroacetate, methoxy vinyl acetate, butoxy vinyl acetate, phenyl vinyl acetate, vinyl acetyl acetate, vinyl lactate, vinyl β-phenyl butyrate, vinyl benzoate, water Vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc. Examples of styrenes include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, and butyl styrene , Hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy methyl styrene, acetoxy methyl styrene, etc. Alkylstyrene; Alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.; Chlorostyrene, dichlorostyrene, trichlorostyrene , Tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro- Halogenated styrenes such as 3-trifluoromethylstyrene; etc. The amount of structural units derived from (meth)acrylic acid and the amount of structural units derived from other monomers in the acrylic resin (a-IV) are not particularly limited as long as they do not impair the purpose of the present invention. The amount of (meth)acrylic acid-derived structural units in the acrylic resin (a-IV) is preferably 5% by mass or more and 50% by mass relative to the number of moles of all structural units of the acrylic resin (a-IV) % Or less, more preferably 10% by mass or more and 30% by mass or less. When the acrylic resin (a-IV) has structural units with unsaturated double bonds, relative to the number of moles of all the structural units of the acrylic resin (a-IV), in the acrylic resin (a-IV) The amount of the structural unit having an unsaturated double bond is preferably 1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 30% by mass or less, and particularly preferably 1% by mass or more and 20% by mass or less. By allowing the acrylic resin (a-IV) to contain the structural unit having an unsaturated double bond in an amount within the above-mentioned range, the acrylic resin can be introduced into the crosslinking reaction in the resist film to achieve homogenization. Therefore, It is effective for improving the heat resistance and mechanical properties of the cured film. The weight average molecular weight of the acrylic resin (a-IV) is not particularly limited as long as it does not impair the purpose of the present invention. The weight average molecular weight of the acrylic resin (a-IV) is preferably 9000 or more, more preferably 9000 or more and 50,000 or less, still more preferably 9100 or more and 30,000 or less, still more preferably 9200 or more and 20,000 or less, particularly preferably 9500 or more And below 15,000. By being in 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 obtained easily. The content of the alkali-soluble resin (A) is preferably 20% by mass or more and 85% by mass or less with respect to the mass of the photosensitive composition (whole solid content) other than the mass of the organic solvent (S) described later, more preferably It is 25% by mass or more and 75% by mass or less. By being in the above-mentioned range, it is easy to obtain a photosensitive composition having excellent developability. <Photopolymerizable compound (B)> As the photopolymerizable compound (B), a monomer having an ethylenically unsaturated group can be preferably used. The photopolymerizable compound contains a polyfunctional compound having 3 or 4 (meth)acrylic groups as the monomer having an ethylenically unsaturated group. By curing the polyfunctional compound with the specific photopolymerization initiator (C) described later, it is easy to form a cured product having a low dielectric constant and being well patterned. In a range that does not impair the purpose of the present invention, the photopolymerizable compound (B) may contain other photopolymerizable compounds other than the polyfunctional compound having 3 or 4 (meth)acryloyl groups. The other photopolymerizable compound may be a monofunctional compound or a bifunctional compound, or may be a polyfunctional compound having pentafunctional or higher functions. The ratio of the mass of the polyfunctional compound having 3 or 4 (meth)acryloyl groups to the mass of the photopolymerizable compound (B) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably It is 95% by mass or more, particularly preferably 100% by mass. As specific examples of the polyfunctional compound having 3 or 4 (meth)acryloyl groups, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate can be mentioned. Base) acrylate, glycerol tri(meth)acrylate, etc. These polyfunctional monomers can be used individually or in combination of 2 or more types. From the viewpoint of easy formation of a cured product with a low dielectric constant, the polyfunctional compound having 3 or 4 (meth)acrylic groups preferably includes a compound having a partial skeleton represented by the following formula (B1). Typically, the partial skeleton represented by the formula (B1) is derived from trimethylolpropane.
Figure 02_image041
The photopolymerizable compound (B) preferably contains a compound represented by the following formula (B2) as a polyfunctional compound having a partial skeleton represented by the formula (B1).
Figure 02_image043
(In formula (B2), R b1 is each independently a hydrogen atom or a methyl group, R b2 is a divalent linking group, a1 is 0 or 1, and a2 is 0 or 1.) In formula (B2), a1 is 0 In this case, the compound represented by the formula (B2) is a trifunctional compound. When a1 is 1, the compound represented by formula (B2) is a tetrafunctional compound. R b2 in formula (B2) is a divalent linking group. The linking group may be a hydrocarbon group or an organic group containing a heteroatom. Examples of heteroatoms that the linking group may contain include O, N, S, Se, P, Si, B, and halogen atoms. Preferred examples of the divalent linking group include -CO-, -R b3 -, -CO-R b3 -CO-, -R b3 -CO-, -R b4 -OR b4 -, -R b4- A group represented by SR b4 -and -R b4 -CO-R b4 -. R b3 is a divalent hydrocarbon group having 1 or more and 10 or less carbon atoms. R b4 is a divalent hydrocarbon group having 1 or more and 6 or less carbon atoms. Among the groups described above, -CO-, -R b3 -, and -CO-R b3 -CO- are preferred from the viewpoints of easy synthesis and obtaining the compound represented by formula (B2). Preferred specific examples of the linking group include -CO-, -CH 2 -, -CH 2 CH 2 -, -CH=CH-, -CH 2 CH 2 CH 2 -, -CH 2 C(CH 3 )H-, -CO-CH 2 -CO-, --CO-CH 2 CH 2 -CO-, -CO-CH=CH-CO-, -CO-CH 2 CH 2 CH 2 -CO-, -CO -CH 2 CH 2 -and groups of the following structures.
Figure 02_image045
As a particularly preferable specific example of the polyfunctional compound having 3 or 4 (meth)acryloyl groups, the following compounds can be given. In the following formula, R b1 is each independently a hydrogen atom or a methyl group.
Figure 02_image047
When the photopolymerizable compound (B) contains other photopolymerizable compounds other than the polyfunctional compound having 3 or 4 (meth)acrylic acid groups, the other photopolymerizable compound is within a range that does not impair the purpose of the present invention. There is no particular limitation inside. The other photopolymerizable compound may be a monofunctional compound, or may be a bifunctional or pentafunctional or more polyfunctional compound. Examples of monofunctional compounds 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-acrylamide 2-methyl propane sulfonic acid, tert-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, (methyl) ) 2-phenoxy-2-hydroxypropyl acrylate, 2-(meth)acryloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, (meth)acrylic acid Tetrahydrofurfuryl ester, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, (meth)acrylate 2, 2,3,3-Tetrafluoropropyl ester, phthalic acid derivative (meth)acrylate half ester, etc. These monofunctional compounds can be used alone or in combination of two or more kinds. Examples of polyfunctional compounds having two or more valences include 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-hexanediol di(meth)acrylate (Meth) acrylate, glycerol di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol di(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)acryloyloxypropyl ester, ethylene glycol diglycidyl ether two( Meth) acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate, urethane (meth)acrylate ( That is, the reaction product of toluene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, or 1,6-hexamethylene diisocyanate with 2-hydroxyethyl (meth)acrylate), methylene bis(methyl) ) Multifunctional compounds such as acrylamide, (meth)acrylamide methylene ether, polyol and N-methylol (meth)acrylamide condensation products, 1,3,5-triacrylamide Hexahydro-1,3,5-triazine (triacrylformal) and so on. These polyfunctional compounds can be used alone or in combination of two or more kinds. Among these other photopolymerizable compounds having an ethylenically unsaturated group, pentafunctional is more preferable in terms of the tendency to improve the adhesion between the photosensitive composition and the substrate and the strength of the photosensitive composition after curing. The above multifunctional monomer. The content of the photopolymerizable compound (B) in the photosensitive composition is preferably 1% by mass or more relative to the mass of the photosensitive composition (whole solid content) other than the mass of the organic solvent (S) described later 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less. By being in the above range, there is a tendency to easily obtain a balance of sensitivity, developability, and resolution. <Photoinitiator (C)> The photosensitive composition contains a compound represented by the following formula (1) as a photoinitiator (C). By exposing the above-mentioned photopolymerizable compound (B) to curing in the presence of a photopolymerization initiator (C) containing the compound represented by formula (1), a cured product with a low dielectric constant can be patterned satisfactorily change.
Figure 02_image049
(In formula (1), R c1 is a hydrogen atom, a nitro group or a monovalent organic group, R c2 and R c3 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 c2 and R c3 may be bonded to each other to form a ring, R c4 is a monovalent organic group, R c5 is a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or For the aryl group which may have a substituent, n1 is an integer of 0 or more and 4 or less, and n2 is 0 or 1.) In the formula (1), R c1 is a hydrogen atom, a nitro group, or a monovalent organic group. R c1 is bonded to the fluorene ring in the formula (1) to a six-membered aromatic ring different from the six-membered aromatic ring to which the group represented by -(CO) n2-is bonded. In formula (1), the bonding position of R c1 with respect to the fluorene ring is not particularly limited. When the compound represented by the formula (1) has one or more R c1 , from the viewpoints of easy synthesis of the compound represented by the formula (1), etc., it is preferable that one of the more than one R c1 and the 2-position in the fluorene ring Bond. R c1 is plural, a plurality of R c1 may be the same or different. When R c1 is an organic group, R c1 is not particularly limited as long as it does not impair the purpose of the present invention, and can be appropriately selected from various organic groups. Preferable examples when R c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, The optionally substituted phenyl group, the optionally substituted phenoxy group, the optionally substituted benzyl group, the optionally substituted phenoxycarbonyl group, the optionally substituted benzyloxy group, the A substituted phenylalkyl group, a substituted naphthyl group, a substituted naphthyloxy group, a substituted naphthyloxy group, a substituted naphthyloxycarbonyl group, a substituted naphthyl group The naphthyloxy group, optionally substituted naphthylalkyl, optionally substituted heterocyclic group, optionally substituted heterocyclic carbonyl group, amino substituted by one or two organic groups, Morpholin-1-yl, Piperazine-1-yl, etc. When R c1 is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. In addition, when R c1 is an alkyl group, it may be linear or branched. Specific examples when R c1 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isoamyl Base, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl, etc. . In addition, when R c1 is an alkyl group, the alkyl group may include an ether bond (-O-) in the carbon chain. Examples of alkyl groups having ether bonds in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxy Ethoxyethyl, methoxypropyl, etc. When R c1 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. In addition, when R c1 is an alkoxy group, it may be linear or branched. Specific examples when R c1 is an alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, and sec-butyloxy. Oxy, tert-butyloxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, Isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, isodecyloxy, etc. In addition, when R c1 is an alkoxy group, the alkoxy group may include 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. Group, propyloxyethoxyethoxy, and methoxypropyloxy, etc. When R c1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. Specific examples when R c1 is a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Specific examples when R c1 is a cycloalkoxy group include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy Base and so on. When R c1 is 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 acyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 the following. Specific examples when R c1 is a saturated aliphatic group include acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentyl group, and 2,2-dimethylpropionyl group. N-hexyl, n-hexyl, n-heptanyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl Group, n-pentadecyl group, and n-hexadecyl group, etc. Specific examples when Rc1 is a saturated aliphatic oxy group include acetyloxy group, propoxy group, n-butoxy group, 2-methylpropoxy group, and n-pentoxy group. Group, 2,2-dimethylpropanyloxy, n-hexyloxy, n-heptanyloxy, n-octanyloxy, n-nonyloxy, n-decanoyloxy, n-undecyloxy Alkyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, and n-hexadecyloxy Base and so on. When R c1 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less. Specific examples when R c1 is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyl Oxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxy Carbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl , N-decyloxycarbonyl, and isodecyloxycarbonyl, etc. When R c1 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. In addition, when R c1 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. Specific examples when R c1 is a phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples when R c1 is naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl) Ethyl. When R c1 is a phenylalkyl group or a naphthylalkyl group, R c1 may further have a substituent on the phenyl group or the naphthyl group. When R c1 is a heterocyclic group, the heterocyclic group is a five-membered or six-membered monocyclic ring containing at least one N, S, and O, or the monocyclic rings are condensed with each other, or the monocyclic ring is condensed with a benzene ring From the heterocyclic group. When the heterocyclic group is a condensed ring, the number of monocyclic rings constituting the condensed ring is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, Pyridazine, benzofuran, benzothiophene, indole, isoindole, indoleazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, oxazole, purine, quinoline, isoquine Morpholine, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran, etc. When R c1 is a heterocyclic group, the heterocyclic group may further have a substituent. When R c1 is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group is the same as when R c1 is a heterocyclic group. When R c1 is an amino group substituted with one or two organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, and a ring having 3 to 10 carbon atoms. Alkyl groups, saturated aliphatic acyl groups having 2 or more and 21 carbon atoms, optionally substituted phenyl groups, optionally substituted benzyl groups, optionally substituted carbon atoms of 7 or more and 20 or less A phenylalkyl group, an optionally substituted naphthyl group, an optionally substituted naphthylmethyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclic group, and the like. The specific examples of these preferable organic groups are the same as R c1. Specific examples of amino groups substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, and n-propylamino. Butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetyl Amino, propylamino, n-butyrylamino, n-pentylamino, n-hexylamino, n-heptanylamino, n-octylamino, n-decylamino, benzylamino, α-naphthylamino Amino, and β-naphthocarboxylamino, etc. Examples of substituents when the phenyl group, naphthyl group, and heterocyclic group contained in R c1 further have a substituent include an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Oxy, saturated aliphatic aliphatic oxy groups having 2 or more and 7 or less carbon atoms, alkoxycarbonyl groups having 2 or more and 7 or less carbon atoms, saturated aliphatic oxycarbonyl groups having 2 or more and 7 or less carbon atoms, A monoalkylamino group of an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group of 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, halogen , Nitro, and cyano, etc. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R c1 further have a substituent, the number of the substituent is not limited as long as it does not interfere with the purpose of the present invention, and it is preferably 1 or more and 4 or less. When the phenyl group, naphthyl group, and heterocyclic group contained in R c1 have multiple substituents, the multiple substituents may be the same or different. Among the groups described above, when R c1 is a nitro group or a group represented by R c10 -CO-, the sensitivity tends to increase, which is preferable. R c10 is not particularly limited as long as it does not interfere with the purpose of the present invention, and it can be selected from various organic groups. Examples of groups preferably used as R c10 include alkyl groups having 1 or more and 20 carbon atoms, optionally substituted phenyl groups, optionally substituted naphthyl groups, and optionally substituted heterocycles. base. Among these groups, as R c10 , 2-methylphenyl, thiophen-2-yl, and α-naphthyl are particularly preferred. In addition, when R c1 is a hydrogen atom, transparency tends to become good, which is preferable. In addition, when R c1 is a hydrogen atom and R c4 is a group represented by the formula (1a) or (1b) described later, transparency tends to become better. In the formula (1), R c2 and R c3 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 c2 and R c3 may be bonded to each other to form a ring. Among these groups, as R c2 and R c3 , a chain alkyl group which may have a substituent is preferable. When R c2 and R c3 are 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. When R c2 and R c3 are unsubstituted chain alkyl groups, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less . Specific examples when R c2 and R c3 are chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-propyl Pentyl, isopentyl, sec-pentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, t-octyl, n-nonyl, isononyl, n-decyl, And isodecyl and so on. In addition, when R c2 and R c3 are an alkyl group, the alkyl group may include an ether bond (-O-) in the carbon chain. Examples of alkyl groups having ether bonds in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxy Ethoxyethyl, methoxypropyl, etc. When R c2 and R c3 are a chain alkyl group having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. In this case, the carbon number of the chain alkyl does not include the carbon number of the substituent. 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 does not interfere with the purpose of the present invention. Preferable 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 the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group. The specific examples of the cycloalkyl group are the same as the preferred examples when R c1 is a cycloalkyl group. As a specific example of an aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, etc. are mentioned. Specific examples of the heterocyclic group are the same as the preferred examples when R c1 is a heterocyclic group. When R c1 is 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 or more and 10 or less, and more preferably 1 or more and 6 or less. When the chain alkyl group has a substituent, the number of substituents is not particularly limited. The number of preferred substituents varies according to the number of carbon atoms of the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When R c2 and R c3 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of cyclic organic groups include aliphatic cyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclic groups. When R c2 and R c3 are cyclic organic groups, the substituents that the cyclic organic group may have are the same as when R c2 and R c3 are chain alkyl groups. When R c2 and R c3 are aromatic hydrocarbon groups, 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 condensing multiple benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, and is preferably 3 or less, more preferably 2 or less, especially Preferably it is 1. Preferable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group. When R c2 and R c3 are 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 is preferably 3 or more and 20 or less, and more preferably 3 or more and 10 or less. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, Tricyclodecyl, tetracyclododecyl, adamantyl, etc. When R c2 and R c3 are heterocyclic groups, the heterocyclic group is a five-membered or six-membered monocyclic ring containing at least one N, S, O, or the monocyclic rings are condensed with each other, or the monocyclic ring and A heterocyclic group formed by the condensation of a benzene ring. When the heterocyclic group is a condensed ring, the number of monocyclic rings constituting the condensed ring is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, Pyridazine, benzofuran, benzothiophene, indole, isoindole, indoleazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, oxazole, purine, quinoline, isoquine Morpholine, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran, etc. R c2 and R c3 may be bonded to each other to form a ring. The group containing the ring formed by R c2 and R c3 is preferably a cycloalkylidene group. When R c2 and R c3 are bonded to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a five-membered ring or a six-membered ring, and more preferably a five-membered ring. When the group formed by bonding R c2 and R c3 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of rings that can be condensed with cycloalkylidene groups include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, Thiophene ring, pyrrole ring, pyridine ring, pyrazine ring, and pyrimidine ring, etc. Among R c2 and R c3 explained above, examples of preferred groups include groups represented by the formula -A 1 -A 2. In the formula, A 1 is a linear alkylene group, and A 2 is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group. The number of carbon atoms of the linear alkylene group of A 1 is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A 2 is 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 or more and 10 or less, and more preferably 1 or more and 6 or less. When A 2 is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a fluorine atom, a chlorine atom, and a bromine atom are more preferable. When A 2 is 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. When A 2 is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group that R c2 and R c3 have as substituents. When A 2 is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group that R c2 and R c3 have as substituents. Preferred specific examples of R c2 and R c3 include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; 2-methoxyethyl, 3- Methoxy n-propyl, 4-methoxy n-butyl, 5-methoxy n-pentyl, 6-methoxy n-hexyl, 7-methoxy n-heptyl, 8-methoxy n-octyl , 2-ethoxyethyl, 3-ethoxy n-propyl, 4-ethoxy n-butyl, 5-ethoxy n-pentyl, 6-ethoxy n-hexyl, 7-ethoxy n Heptyl, and 8-ethoxy n-octyl and other alkoxyalkyl groups; 2-cyanoethyl, 3-cyano n-propyl, 4-cyano n-butyl, 5-cyano n-pentyl, Cyanoalkyl groups such as 6-cyano n-hexyl, 7-cyano n-heptyl, and 8-cyano n-octyl; 2-phenylethyl, 3-phenyl n-propyl, 4-phenyl n-butyl Phenylalkyl groups such as 5-phenyl n-pentyl, 6-phenyl n-hexyl, 7-phenyl n-heptyl, and 8-phenyl n-octyl; 2-cyclohexyl ethyl, 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-cyclopentyl ethyl , 3-cyclopentyl n-propyl, 4-cyclopentyl n-butyl, 5-cyclopentyl n-pentyl, 6-cyclopentyl n-hexyl, 7-cyclopentyl n-heptyl, and 8-cyclopentyl Cycloalkylalkyl groups such as n-octyl; 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- Alkoxy groups such as ethoxycarbonyl n-butyl, 5-ethoxycarbonyl n-pentyl, 6-ethoxycarbonyl n-hexyl, 7-ethoxycarbonyl n-heptyl, and 8-ethoxycarbonyl n-octyl Carbonyl carbonyl alkyl; 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 Base, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-pentyl, 6-bromo-hexyl, 7-bromo-heptyl, 8-bromo-octyl, 3 ,3,3-trifluoropropyl, and 3,3,4,4,5,5,5-heptafluoro-n-pentyl and other halogenated alkyl groups. As R c2 and R c3 , the preferred 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. Examples of preferable organic groups for R c4 include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, and saturated aliphatic groups in the same manner as R c1. Phenyloxy group, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted benzyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzyl group Group oxy, optionally substituted phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyloxy, optionally substituted naphthyloxy, optionally substituted naphthyloxycarbonyl , Optionally substituted naphthyloxy, optionally substituted naphthylalkyl, optionally substituted heterocyclic group, optionally substituted heterocyclic carbonyl group, substituted by 1 or 2 organic groups Group substituted amino, morpholin-1-yl, and piperazin-1-yl, etc. The specific examples of these groups are the same as those explained for R c1. In addition, as R c4 , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferable. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group included in R c1 may have. Among the organic groups, R c4 is preferably an alkyl group, a cycloalkyl group, a phenyl group or a cycloalkylalkyl group which may have a substituent, and a phenylthioalkyl group which may have a substituent 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 For methyl. 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 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among cycloalkylalkyls, cyclopentylethyl is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl is preferred. In addition, as R c4 , a group represented by -A 3 -CO-OA 4 is also preferable. A 3 is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A 4 is a monovalent organic group, preferably a monovalent hydrocarbon group. When A 3 is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. When A 3 is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less. Preferred examples of A 4 include an alkyl group having 1 or more and 10 or less carbon atoms, an aralkyl group having 7 or more and 20 or less carbon atoms, and an aromatic hydrocarbon group having 6 or more and 20 or less carbon atoms. Preferred specific examples of A 4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, and phenyl. , Naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl. Preferred specific examples of the group represented by -A 3 -CO-OA 4 include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propyloxycarbonylethyl, 2-n-butyloxycarbonylethyl, 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl , 3-methoxycarbonyl n-propyl, 3-ethoxycarbonyl n-propyl, 3-n-propyloxycarbonyl n-propyl, 3-n-butyloxycarbonyl n-propyl, 3-n-pentyl Oxycarbonyl n-propyl, 3-n-hexyloxycarbonyl n-propyl, 3-benzyloxycarbonyl n-propyl, 3-phenoxycarbonyl n-propyl and the like. As mentioned above, R c4 has been described. As R c4 , a group represented by the following formula (1a) or the following formula (1b) is preferable.
Figure 02_image051
(In formula (1a) and formula (1b), R c7 and R c8 are each an organic group, n3 is an integer from 0 to 4, and R c7 and R c8 are present at adjacent positions on the benzene ring, R c7 and R c8 can be bonded to each other to form a ring, n4 is an integer of 1 or more and 8 or less, n5 is an integer of 1 or more and 5 or less, n6 is an integer of 0 or more and (n5+3) or less, and R c9 is an organic Group.) Examples of organic groups related to R c7 and R c8 in the formula (1a) are the same as R c1. As R c7 , an alkyl group or a phenyl group is preferable. When R c7 is an alkyl group, the number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and most preferably 1. That is, R c7 is most preferably a methyl group. When R c7 and R c8 are bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferable examples of the group represented by formula (1a) in which R c7 and R c8 form a ring include naphth-1-yl, 1,2,3,4-tetrahydronaphthalen-5-yl, and the like. In the above formula (1a), n3 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0. In the above formula (1b), R c9 is an organic group. As an organic group, the same group as the organic group demonstrated with respect to R c1 can be mentioned. Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. As R c9 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. are preferably exemplified. Among these, a methyl group is more preferable. In the above formula (1b), n5 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2. In the above formula (1b), n6 is 0 or more and (n5+3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0. In the above formula (1b), n4 is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2. In the formula (1), R c5 is a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. As the substituent which may be possessed when R c5 is an alkyl group, a phenyl group, a naphthyl group and the like are preferably exemplified. In addition, as substituents that may be possessed when R c1 is an aryl group, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group, a halogen atom, etc. can be preferably exemplified. In the formula (1), as R c5 , hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, benzyl, methylphenyl, naphthyl, etc. can be preferably exemplified. Among them, a methyl group or a phenyl group is more preferable. Preferable specific examples of the compound represented by formula (1) include the following PI-1 to PI-41.
Figure 02_image053
Figure 02_image055
The photosensitive composition may contain the compound represented by the above-mentioned formula (1) as well as another photopolymerization initiator as the photopolymerization initiator (C). The other photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator that does not belong to the compound represented by the above-mentioned formula (1). As a preferable example of other photopolymerization initiators, 2-(benzyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone (for example, as OXE- 01 (manufactured by BASF Corporation) is commercially available.), and O-acetyl-1-[6-(2-methylbenzyl)-9-ethyl-9H-azol-3-yl]ethyl Ketone oxime (for example, commercially available as OXE-02 (manufactured by BASF Corporation).) and other oxime ester compounds having a structure not belonging to the above formula (C1); 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)butane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl- 2-Dimethylamino-1-(4-dimethylaminophenyl)butan-1-one, 2-(4-methylbenzyl)-2-diethylamino-1-(4-meth) (Pholinophenyl)butane-1-one, 2-methyl-1-phenyl-2-morpholinopropane-1-one, 2-methyl-1-[4-(hexyl)phenyl]- Α-amino ketone compounds such as 2-morpholinopropane-1-one and 2-ethyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one; 1- Phenyl-2-hydroxy-2-methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethyl) (Oxy) phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone and other α-hydroxy ketone-based photopolymerization initiators; benzoin, benzoin methyl ether, benzidine Benzoin-based photopolymerization initiators such as benzoin ethyl ether, benzoin propyl ether, and benzyl methyl ketal; benzophenone, benzoic acid, methyl benzoic acid, 4 -Phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzophenone, 4'-methyldiphenyl sulfide, 4,4'-bisdiethylaminodiphenyl Benzophenone-based photopolymerization initiators such as ketone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Thioxanthone-based photopolymerization initiators; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxybenzene) Yl)-4,6-bis(trichloromethyl)s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)s-triazine, 2-piperonyl (pipenyl)-4 ,6-bis(trichloromethyl)s-triazine, 2,4-bis(trichloromethyl)-6-styryls-triazine, 2-(naphthalene-1-yl)-4,6-bis (Trichloromethyl)s-triazine, 2-(4-methoxy-naphthalene-1-yl)-4,6-bis(trichloromethyl)s-triazine, 2,4-trichloromethyl- (Piperonyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine, 2-[4-(4-methoxystyryl) )Phenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine and other triazine-based photopolymerization initiators; oxazole-based photopolymerization initiators; 2,2'-bis(2 -Chlorophenyl)-4,4',5,5'- Tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetra(4-ethoxy Carbonyl phenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4, 6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4,5, 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2' -Biimidazole, 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and other biimidazole photopolymerization Initiator; such a benzimidazoline-based photopolymerization initiator represented by the following formula; etc.
Figure 02_image057
As preferred specific examples other than the above of the compound represented by the above formula (1), the following compounds can be given.
Figure 02_image059
Figure 02_image061
Figure 02_image063
Figure 02_image065
Figure 02_image067
Figure 02_image069
Figure 02_image071
Figure 02_image073
Figure 02_image075
Figure 02_image077
Figure 02_image079
Figure 02_image081
Figure 02_image083
The ratio of the mass of the compound represented by the above formula (1) to the mass of the photopolymerization initiator (C) is not particularly limited within a range that does not impair the purpose of the present invention. The ratio of the compound represented by the above formula (1) relative to the mass of the photopolymerization initiator (C) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and still further It is preferably 90% by mass or more, and particularly preferably 100% by mass. The content of the photopolymerization initiator (C) is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 0.5% by mass or more and 20% by mass or less with respect to the mass of the entire solid content of the photosensitive composition. By setting the content of the photopolymerization initiator (C) in the above-mentioned range, a photosensitive composition having good curability and less likely to cause pattern shape defects can be obtained. <Organic solvent (S)> Typically, the photosensitive composition may contain an organic solvent (S) for the purpose of adjusting coatability. Examples of the organic solvent (S) 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 (Poly)alkylene glycol monoalkyl ethers such as n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc.; 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, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl Ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and other alkyl lactates; 2-hydroxy-2-methyl Ethyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate Ester, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl propionate 3-methoxybutyl, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, butyric acid Ethyl acetate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, 2 -Other esters such as ethyl oxobutyrate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. Amides and so on. These solvents may be used alone or in combination of two or more kinds. The use amount of the organic solvent (S) can be appropriately determined according to the use of the photosensitive composition. As an example of the usage amount of the organic solvent (S), the solid content concentration of the photosensitive composition is an amount in the range of 1% by mass to 50% by mass. <Other components> In the photosensitive composition, various additives other than the above can be contained as needed. Specifically, dispersion aids, fillers, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents, thermal polymerization inhibitors, defoamers, surfactants, etc. can be exemplified. Examples of the thermal polymerization inhibitor used in the photosensitive composition include hydroquinone, hydroquinone monoethyl ether, and the like. In addition, as the defoaming agent, compounds such as organosilicon, fluorine, etc. can be exemplified, and as the surfactant, compounds such as anionic, cationic, and nonionic can be exemplified. <The preparation method of the photosensitive composition> The photosensitive composition can be prepared by uniformly mixing the said each component of each desired amount. In addition, when the prepared photosensitive composition does not contain insoluble components, such as a pigment, you can filter with a filter so that the photosensitive composition may become uniform. ≪Method for manufacturing cured product≫ Typically, the photosensitive composition described above is made into a cured product by a method including the following steps: a step of molding the photosensitive composition according to the shape of the cured product; and The photosensitive composition is exposed to the step. The cured product produced by the above method has a relative dielectric constant of preferably 2.86 or less, more preferably 2.84 or less, still more preferably 2.80 or less, and particularly preferably 2.77 or less. Therefore, the produced cured product can be used for applications requiring a low dielectric constant, such as insulating films. In addition, the cured product produced has high transparency, so it is useful for display devices such as OLED, organic EL, or liquid crystal. It can be suitably used for flattening films, interlayer insulating films, protective films for color filters, and A spacer in which the thickness of the liquid crystal layer in a display device is kept constant, or a microlens in a solid-state image sensor, or the like. The method of molding the photosensitive composition is not particularly limited, and can be appropriately selected according to the shape of the cured product. Examples of the shape of the cured product include a film shape, a lens shape, a linear shape, a prism shape, etc., but it is not limited to these. Among these shapes, a film shape is preferable. The method of molding the photosensitive composition is not particularly limited. When the shape of the cured product is a lens shape, a prism shape, etc., a squeegee or the like can be used to fill the photosensitive composition in a mold that matches the shape of the cured product. When the shape of the cured product is a linear shape or the like, the photosensitive composition can be applied to the substrate according to the shape of the cured product. As the coating method, for example, a printing method such as an inkjet method can be cited. As a method of applying the photosensitive composition into a film shape, there can be mentioned the use of a roller coater, a reverse coater, a bar coater, or the like, a contact transfer type coating device, a spinner (rotary coating device), and a curtain flow coater. And other non-contact coating device methods. In addition, the photosensitive composition may be applied to a film shape by a printing method such as an inkjet method. The thickness of the coating film is not particularly limited. The thickness of the coating film is preferably 0.05 μm or more, and more preferably 1 μm or more. The thickness of the coating film may be, for example, 7 μm or more, and may be 10 μm or more. The upper limit of the thickness of the coating film is not particularly limited. For example, it may be 50 μm or less, and may be 20 μm or less. The thickness of the coating film is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 2 μm or less. The range of the thickness of the coating film is preferably 0.05 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less, and still more preferably 1 μm or more and 2 μm or less. Next, the coating film is dried as needed. The drying method is not particularly limited. Examples of the drying method include: (1) using a hot plate to dry at a temperature of 80°C or more and 120°C or less, preferably 90°C or more and 100°C or less, for a time of 60 seconds or more and 120 seconds or less; (2) Put it at room temperature for several hours to several days; (3) Put it in a warm air heater or infrared heater for tens of minutes to several hours to remove the solvent; etc. By exposing this coating film, a cured film can be formed. In the exposure, the light source is not particularly limited. For example, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and an LED can be mentioned. Such a light source can be used to irradiate the coating film with ArF excimer laser, KrF excimer laser, F 2 excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beam, X-ray, soft X-ray, g-ray, Radiation rays such as i-line, h-line, j-line, and k-line, or electromagnetic waves, expose the coating film. The amount of exposure varies depending on the composition of the photosensitive composition. For example, it is preferably 10 mJ/cm 2 or more and 2000 mJ/cm 2 or less, more preferably 100 mJ/cm 2 or more and 1500 mJ/cm 2 or less, and even more preferably 200 mJ/cm 2 cm 2 or more and 1200 mJ/cm 2 or less. The exposure illuminance also differs depending on the composition of the photosensitive composition, but it is preferably in the range of 1 mW/cm 2 or more and 50 mW/cm 2 or less. The cured film cured by exposure may be heated. The temperature during heating is not particularly limited, but is preferably 180°C or higher and 280°C or lower, more preferably 200°C or higher and 260°C or lower, and particularly preferably 220°C or higher and 250°C or lower. The heating time is typically preferably 1 minute or more and 60 minutes or less, more preferably 10 minutes or more and 50 minutes or less, and particularly preferably 20 minutes or more and 40 minutes or less. On the other hand, the coated film can be exposed to position selectively. In this case, the coated film is exposed to position selectively via a negative mask having a light-transmitting portion having a shape corresponding to the pattern shape of the cured film. Except for using a negative mask, the exposure method is the same as the above-mentioned exposure method. Next, the exposed coating film is developed with a developing solution, thereby forming a patterned cured film. The development method is not particularly limited, and for example, a dipping method, a spray method, etc. can be used. Examples of the developer include organic developers such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. The patterned cured film obtained after development can be heated in the same manner as the method of applying the exposure method to the patterned coating film described above. By using the above-mentioned photosensitive composition, even when a fine pattern is formed, a pattern of a desired shape can be formed satisfactorily. Examples Hereinafter, the present invention will be explained in more detail using examples, but the present invention is not limited to these examples. [Examples 1 to 4, Comparative Examples 1 to 5] In the examples and comparative examples, the acrylic resin P1 of the following structure and the acrylic resin P2 of the following structure were used as the alkali-soluble resin (A). The weight average molecular weights in terms of polystyrene of the resin P1 and the resin P2 are both 10,000.
Figure 02_image085
In the Examples and Comparative Examples, the following B-1 to B-4 were used as the photopolymerizable compound (B). B-1: Trimethylolpropane triacrylate B-2: Ditrimethylolpropane tetraacrylate B-3: Dipentaerythritol hexaacrylate B-4: ε-caprolactone modified dipentaerythritol hexaacrylate (KAYARAD DPCA-120, manufactured by Nippon Kayaku Co., Ltd.) In the examples and comparative examples, the following C-1 and C-2 were used as the photopolymerization initiator (C).
Figure 02_image087
13.73 parts by mass of the alkali-soluble resin (A) (component (A)) of the type described in Table 1, and 6.8 parts by mass of the photopolymerizable compound (B) (component (B)) of the type described in Table 1, Table 1 Photopolymerizable compound (C) (component (C)) 1.22 parts by mass, 31.2 parts by mass of diethylene glycol methyl ethyl ether, 46.7 parts by mass of propylene glycol monomethyl ether acetate, 3-ring 0.2 parts by mass of oxypropoxypropyltrimethoxysilane, 0.05 parts by mass of surfactant (BYK-310, manufactured by BYK-Chemie), and 0.1 parts by mass of antioxidant (IR1010, manufactured by BASF Japan) were mixed to obtain The photosensitive composition of each example and each comparative example. Using the obtained photosensitive composition, the relative dielectric constant and pattern formation properties were evaluated in accordance with the following methods. The results of these evaluations are shown in Table 1. <Measurement of relative permittivity> As a method of measuring relative permittivity, a mercury probe method was used. As an apparatus capable of measuring relative permittivity by the mercury probe method, SSM-495 (manufactured by Semilab, Japan) was used. According to the following steps 1) to 4), the compositions of the respective examples and comparative examples were used to form a film-like cured product having a film thickness of 1 μm. Then, the relative dielectric constant of the formed cured product was measured. 1) Coating the cured composition on the silicon wafer to form a coating film. 2) The formed coating film is heated at 100°C for 120 seconds. 3) Expose the coated film with an exposure amount of 1 J/cm 2. 4) The exposed coating film is heated at 230°C for 20 minutes. <Evaluation of pattern formation> Using a spin coater, the curable composition of each Example and Comparative Example was coated on a glass substrate and heated at 100°C for 120 seconds to form a coating film. Next, using a proximity exposure machine (product name: TME-150RTO, manufactured by TOPCON Co., Ltd.), a negative mask for forming a hole pattern of 20 μm×20 μm was used to expose ultraviolet rays (i-line) to an exposure amount of 50 mJ/cm 2 Irradiate to the coating film. Using a 2.38% by mass TMAH aqueous solution at 25°C, the exposed coating film was developed for 50 seconds and then post-baked at 230°C for 30 minutes, thereby forming a hole pattern. The obtained pattern was observed using an optical microscope, and the hole shape was evaluated based on the following criteria. ○: The square shape of the light-shielding portion of the mask is reproduced by the holes in the hole pattern, and the transferability of the mask is good. ×: The square shape of the light-shielding part of the mask cannot be reproduced through the holes in the hole pattern, and the transferability of the mask is not good
Figure 02_image089
It can be seen from Table 1 that when the photosensitive composition of the example containing a multifunctional compound having 3 or 4 acryloyl groups and C-1 of the compound represented by formula (1) in combination, it can be formed at the same time. Cured product with low relative dielectric constant and good pattern formation. On the other hand, for the photosensitive composition that does not include a comparative example of a combination of a polyfunctional compound having 3 or 4 acryl groups and a compound represented by formula (1), it is impossible to achieve both the formation of a cured product with a low dielectric constant and a good The pattern formation.

Claims (8)

一種感光性組合物，其包含鹼溶性樹脂(A)、光聚合性化合物(B)，及光聚合引發劑(C)， 前述光聚合性化合物(B)包含具有3或4個(甲基)丙烯醯基的多官能化合物， 前述光聚合引發劑(C)包含下述式(1)表示的化合物，
Figure 03_image001
式(1)中，Rc1 為氫原子、硝基或一價有機基團，Rc2 及Rc3 各自為可具有取代基的鏈狀烷基、可具有取代基的環狀有機基團、或氫原子，Rc2 與Rc3 可彼此鍵結而形成環，Rc4 為一價有機基團，Rc5 為氫原子、可具有取代基之碳原子數1以上且11以下的烷基、或可具有取代基的芳基，n1為0以上且4以下的整數，n2為0或1。A photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable compound (B), and a photopolymerization initiator (C). The aforementioned photopolymerizable compound (B) contains 3 or 4 (methyl) groups. The polyfunctional compound of acryloyl group, the photopolymerization initiator (C) includes a compound represented by the following formula (1),
Figure 03_image001
In the formula (1), R c1 is a hydrogen atom, a nitro group or a monovalent organic group, and R c2 and R c3 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 c2 and R c3 can be bonded to each other to form a ring, R c4 is a monovalent organic group, R c5 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms that may have a substituent, or In the substituted aryl group, n1 is an integer of 0 or more and 4 or less, and n2 is 0 or 1. 如請求項1的感光性組合物，其中具有3或4個(甲基)丙烯醯基之前述多官能化合物包含具有下述式(B1)表示的部分骨架的化合物，
Figure 03_image003
。The photosensitive composition according to claim 1, wherein the aforementioned polyfunctional compound having 3 or 4 (meth)acryloyl groups includes a compound having a partial skeleton represented by the following formula (B1),
Figure 03_image003
. 如請求項2的感光性組合物，其中具有3或4個(甲基)丙烯醯基的前述多官能化合物包含下述式(B2)表示的化合物，
Figure 03_image005
式(B2)中，Rb1 各自獨立地為氫原子或甲基，Rb2 為二價連接基團，a1為0或1，a2為0或1。The photosensitive composition according to claim 2, wherein the aforementioned polyfunctional compound having 3 or 4 (meth)acryloyl groups includes a compound represented by the following formula (B2),
Figure 03_image005
In formula (B2), R b1 is each independently a hydrogen atom or a methyl group, R b2 is a divalent linking group, a1 is 0 or 1, and a2 is 0 or 1. 如請求項1～3中任一項的感光性組合物，其中前述鹼溶性樹脂(A)包含丙烯酸系樹脂。The photosensitive composition according to any one of claims 1 to 3, wherein the alkali-soluble resin (A) contains an acrylic resin. 如請求項4的感光性組合物，其中前述丙烯酸系樹脂包含來自(甲基)丙烯酸多環烷基酯的結構單元(A-1)。The photosensitive composition according to claim 4, wherein the acrylic resin contains a structural unit (A-1) derived from a polycyclic alkyl (meth)acrylate. 如請求項5所述的感光性組合物，其中前述丙烯酸系樹脂包含結構單元(A-2)，前述結構單元(A-2)來自含有脂環式環氧基的(甲基)丙烯酸酯。The photosensitive composition according to claim 5, wherein the acrylic resin contains a structural unit (A-2), and the structural unit (A-2) is derived from an alicyclic epoxy group-containing (meth)acrylate. 一種固化物，其為請求項1～6中任一項之感光性組合物的固化物。A cured product which is a cured product of the photosensitive composition according to any one of claims 1 to 6. 一種固化物的製造方法，其包括下述步驟： 將請求項1～6中任一項的感光性組合物依據形成之固化物的形狀來進行成型的步驟；及 對經成型的感光性組合物進行曝光的步驟。A method for manufacturing a cured product, which includes the following steps: The step of molding the photosensitive composition of any one of claims 1 to 6 according to the shape of the formed cured product; and The step of exposing the molded photosensitive composition.
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