TW201211681A - Negative photosensitive resin composition, photosensitive dry film, and light receiving device - Google Patents

Negative photosensitive resin composition, photosensitive dry film, and light receiving device Download PDF

Info

Publication number
TW201211681A
TW201211681A TW100112970A TW100112970A TW201211681A TW 201211681 A TW201211681 A TW 201211681A TW 100112970 A TW100112970 A TW 100112970A TW 100112970 A TW100112970 A TW 100112970A TW 201211681 A TW201211681 A TW 201211681A
Authority
TW
Taiwan
Prior art keywords
photosensitive resin
acid
meth
resin composition
negative photosensitive
Prior art date
Application number
TW100112970A
Other languages
Chinese (zh)
Other versions
TWI521301B (en
Inventor
Takahiro Senzaki
Tetsuya Kato
Original Assignee
Tokyo Ohka Kogyo Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tokyo Ohka Kogyo Co Ltd filed Critical Tokyo Ohka Kogyo Co Ltd
Publication of TW201211681A publication Critical patent/TW201211681A/en
Application granted granted Critical
Publication of TWI521301B publication Critical patent/TWI521301B/en

Links

Classifications

    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers

Abstract

To provide a negative photosensitive resin composition which can form a photosensitive resin layer having excellent developability, resolution and adhesiveness after patterning, a photosensitive dry film which has a photosensitive resin layer comprising the composition, and a light receiving device having a spacer that is obtained by curing the composition. A negative photosensitive resin composition according to the present invention suitable to forming a spacer 13 for a light receiving device 1 comprises an alkali-soluble resin (A); a compound (B) which generates an acid or a radical by irradiation of active rays; a compound (C) crosslinkable by the acid or radical; an epoxy resin (D) expressed by a general formula (D-1); and a solvent (S). (In the formula, R<SP POS="POST">d1</SP>and R<SP POS="POST">d2</SP>each independently presents a methyl group or the like; R<SP POS="POST">d3</SP>through R<SP POS="POST">d6</SP>each independently presents a hydrogen atom or the like; "A" represents a di(ethyleneoxy)ethyl group or the like; and "n" is a natural number and its average is 1.2-5.).

Description

201211681 六、發明說明 【發明所屬之技術領域】 本發明關於一種負型感光性樹脂組成物；一種感光性 乾薄膜，其係具有由該負型感光性樹脂組成物所構成之感 光性樹脂層；以及一種受光裝置，其係具備該負型感光性 樹脂組成物硬化而成之間隔物。 【先前技術】 近年來需要一種感光性乾薄膜，其係接著在半導體晶 圓等，在藉由曝光、顯像而形成圖型之後，可與玻璃等透 明基板壓接（參照專利文獻.1、2)。在使用這種感光性乾薄 膜的情況下，圖案化後的感光性乾薄膜，係具有半導體晶 圓與透明基板之間之間隔物的作用。 這種感光性乾薄膜之感光性樹脂層，需要能夠藉由光 蝕刻法而圖案化，以及能夠保持間隔物的形狀。另外，爲 了在曝光、顯像後與透明基板壓接，而需要有優異的顯像 性、解像性以及圖案化後的接著性。 [先前技術文獻] [專利文獻] [專利文獻1] 日本特開2006-323089號公報 [專利文獻2] 日本特開2008-297540號公報 【發明內容】 [發明所欲解決之課題] -5- 201211681 然而至目前爲止’現況中並沒有文獻提出一種感光性 樹脂組成物，能夠形成顯像性、解像性、圖案化後的接著 性任一者皆優異的感光性樹脂層。 本發明鑑於這些以往的實際狀況而完成，目的爲提供 —種負型感光性樹脂組成物，可形成顯像性、解像性、圖 案化後的接著性優異的感光性樹脂層；一種感光性乾薄 膜，係具有由該負型感光性樹脂組成物所構成之感光性樹 脂層；以及一種受光裝置，係具備該負型感光性樹脂組成 物硬化而成之間隔物。 [用於解決課題之方法] 本發明人等爲了解決上述課題潛心反覆硏究。其結果 發現，只要藉由一種含有特定構造之環氧樹脂之負型感光 性樹脂組成物，即可解決上述課題，而使本發明達到完 成。具體而言，本發明提供以下各項。 本發明之第一形態爲一種負型感光性樹脂組成物，其 係含有：鹼可溶性樹脂（A);藉由照射活性射線產生酸或 自由基之化合物（B);可藉由上述（B)成分所產生的酸或自 由基進行交聯的化合物（C);與下述一般式（D-1)所表示之 環氧樹脂（D);及溶劑（S)， 【化1】201211681 6. Technical Field [Technical Field] The present invention relates to a negative photosensitive resin composition, and a photosensitive dry film having a photosensitive resin layer composed of the negative photosensitive resin composition; And a light receiving device comprising a spacer formed by curing the negative photosensitive resin composition. [Prior Art] In recent years, there is a need for a photosensitive dry film which can be bonded to a transparent substrate such as glass after being formed into a pattern by exposure or development on a semiconductor wafer or the like (refer to Patent Document 1. 2). In the case of using such a photosensitive dry film, the patterned photosensitive dry film functions as a spacer between the semiconductor wafer and the transparent substrate. The photosensitive resin layer of such a photosensitive dry film needs to be patterned by photolithography and can maintain the shape of the spacer. Further, in order to be pressure-bonded to the transparent substrate after exposure and development, excellent developability, resolution, and adhesion after patterning are required. [Patent Document] [Patent Document 1] JP-A-2006-323089 [Patent Document 2] JP-A-2008-297540 SUMMARY OF INVENTION [Problems to be Solved by the Invention] -5- 201211681 However, there has been no documented photosensitive resin composition in the present state, and it is possible to form a photosensitive resin layer which is excellent in both developability, resolution, and adhesion after patterning. The present invention has been made in view of the above-described conventional circumstances, and it is an object of the invention to provide a negative photosensitive resin composition, which can form a photosensitive resin layer excellent in developability, resolution, and adhesion after patterning; The dry film is a photosensitive resin layer composed of the negative photosensitive resin composition, and a light receiving device comprising a spacer formed by curing the negative photosensitive resin composition. [Means for Solving the Problem] The present inventors have eagerly repeated research in order to solve the above problems. As a result, it has been found that the above problems can be solved by a negative photosensitive resin composition containing an epoxy resin having a specific structure, and the present invention can be completed. In particular, the present invention provides the following items. A first aspect of the present invention is a negative photosensitive resin composition comprising: an alkali-soluble resin (A); a compound (B) which generates an acid or a radical by irradiation with an active ray; and (B) a compound (C) which is crosslinked by an acid or a radical generated by a component; and an epoxy resin (D) represented by the following general formula (D-1); and a solvent (S), [Chem. 1]

(D-1) 201211681 [一般式（D-1)中，Rdl及Rd2各自獨立，表示氫原 基，Rd3〜Rd6各自獨立，表示氫原子、甲基、氯原 溴原子；A表示伸乙氧基乙基、二（伸乙氧基）乙基 乙氧基）乙基、伸丙氧基丙基、二（伸丙氧基）丙基、 丙氧基）丙基、或碳數2〜15之伸垸基；π爲自然 平均爲1.2〜5]。 本發明之第二形態爲一種感光性乾薄膜’其係 基材薄膜：與形成於該基材薄膜表面之感光性樹脂 上述感光性樹脂層係由本發明所關連之負型感光性 成物所構成。 本發明之第三形態爲一種受光裝置’其係具備 有半導體元件之支持基板；上述支持基板呈對向之 板；與設置於上述支持基板與上述透明基板之間 物，且上述間隔物係本發明所關連之負型感光性樹 物之硬化物。 [發明之效果] 依據本發明可提供：一種負型感光性樹脂組成 形成顯像性 '解像性、圖案化後的接著性優異的感 脂層；一種感光性乾薄膜’其係具有由該負型感光 組成物所構成之感光性樹脂層；及一種受光裝置’ 備該負型感光性樹脂組成物硬化而成之間隔物° 【實施方式】 子或甲 子、或 ‘三（伸 三（伸 數，其 具有： 層，而 樹脂組 :搭載 透明基 之間隔 脂組成 物，可 光性樹 性樹脂 其係具 201211681 &lt;負型感光性樹脂組成物）&gt; 本發明所關連之負型感光性樹脂組成物，係含有：鹼 可溶性樹脂（A);藉由照射活性射線產生酸或自由基之化 合物（B);可藉由上述（B)成分所產生的酸或自由基進行交 聯的化合物（C);特定構造之環氧樹脂（D);及溶劑（S)。 該負型感光性樹脂組成物，會有化學增幅型的情況與 自由基聚合型的情況，在各個情況中，上述（A)〜（C)成分 的種類相異。 以下針對本發明所關連之負型感光性樹脂組成物所含 有的各成分作詳細說明。 〈鹼可溶性樹脂（A)&gt; 鹼可溶性樹脂不受特別限制，而可採用以往化學增幅 型或自由基聚合型的負型感光性樹脂組成物所使用的物 質。具體而言，在化學增幅型的情況下，可採用具有酚性 羥基之鹼可溶性樹脂（A1)，在自由基聚合型的情況下，可 採用具有由不飽和羧酸所衍生的構成單位之鹼可溶性樹脂 (A2) ° (具有酚性羥基之鹼可溶性樹脂（A1)) 鹼可溶性樹脂（A 1 )並未受到特別限定，而可列舉聚羥 基苯乙烯系樹脂、酚醛樹脂、酚-茬二醇縮合樹脂、甲酚-茬二醇縮合樹脂、酚-二環戊二烯縮合樹脂等。在該等之 中，係以聚羥基苯乙烯系樹脂及酚醛樹脂爲佳，以聚羥基 苯乙烯系樹脂爲較佳。 -8 - 201211681 上述聚羥基苯乙烯系樹脂至少具有由羥基苯乙烯所衍 生的構成單位 此處「羥基苯乙烯」其槪念包括羥基苯乙烯及鍵結於 羥基苯乙烯的α位之氫原子被鹵素原子、烷基、鹵化烷基 等其他取代基取代之物質，以及該等衍生物之羥基苯乙烯 衍生物（單體）。 「羥基苯乙烯衍生物」包括至少維持著苯環與鍵結於 苯環之羥基，而例如鍵結於羥基苯乙烯的α位之氫原子被 鹵素原子、碳數1〜5之烷基、鹵化烷基等其他取代基取 代之物質，以及在羥基苯乙烯中鍵結有羥基之苯環，進一 步鍵結碳數1〜5之烷基之物質，或在該鍵結有羥基之苯 環，進一步鍵結1〜2個羥基之物質（此時羥基數目合計爲 2〜3)等。 鹵素原子可列舉氯原子、氟原子、溴原子等，而以氟 原子爲佳。 另外，「羥基苯乙烯的α位」，只要沒有特別註明， 是指鍵結有苯環之碳原子。 該羥基苯乙烯所衍生之構成單位，係例如下述一般式 (Α1-1)所表示。 【化2】 Ra1(D-1) 201211681 [In general formula (D-1), Rdl and Rd2 are each independently and represent a hydrogen primordium, and Rd3 to Rd6 are each independently represented by a hydrogen atom, a methyl group, or a chlorogenic bromine atom; and A represents an ethoxylate. Ethyl ethyl, bis(ethyleneoxy)ethylethoxy)ethyl, propoxypropyl, bis(propoxy)propyl, propoxy)propyl, or carbon number 2-15 The 垸 is based on π; the natural average is 1.2~5]. A second aspect of the present invention is a photosensitive dry film, wherein the base film is formed of a photosensitive resin formed on the surface of the base film, and the photosensitive resin layer is a negative photosensitive material associated with the present invention. . According to a third aspect of the present invention, a light receiving device includes: a support substrate having a semiconductor element; the support substrate is opposed to the support plate; and the spacer substrate is disposed between the support substrate and the transparent substrate, and the spacer is The cured product of the negative photosensitive tree associated with the invention. [Effects of the Invention] According to the present invention, a negative photosensitive resin composition can be used to form a developing layer having excellent developability and excellent adhesion after patterning; and a photosensitive dry film having a photosensitive resin layer composed of a negative photosensitive composition; and a light-receiving device for preparing a spacer formed by curing the negative photosensitive resin composition. [Embodiment] Sub- or K-, or 'three (extension) It has: a layer, and a resin group: a spacer resin having a transparent base, a photoreceptor resin, and a base resin 201211681 &lt; a negative photosensitive resin composition) &gt; a negative photosensitive property to which the present invention relates The resin composition contains: an alkali-soluble resin (A); a compound (B) which generates an acid or a radical by irradiation with an active ray; a compound which can be crosslinked by an acid or a radical generated by the above component (B) (C); epoxy resin (D) having a specific structure; and solvent (S). The negative photosensitive resin composition may have a chemical amplification type and a radical polymerization type, and in each case, (A)~ The components of the negative photosensitive resin composition to be used in the present invention are described in detail below. <Alkali-soluble resin (A)&gt; The alkali-soluble resin is not particularly limited, but may be A material used in a conventional chemically amplified or radically polymerized negative photosensitive resin composition. Specifically, in the case of a chemical amplification type, an alkali-soluble resin (A1) having a phenolic hydroxyl group can be used. In the case of a radical polymerization type, an alkali-soluble resin (A1) having a constituent unit derived from an unsaturated carboxylic acid (A2) ° (alkali-soluble resin having a phenolic hydroxyl group (A1)), an alkali-soluble resin (A 1 ), and The polyhydroxystyrene resin, the phenol resin, the phenol-nonanediol condensation resin, the cresol-nonanediol condensation resin, the phenol-dicyclopentadiene condensation resin, and the like are not particularly limited. Among them, a polyhydroxystyrene resin and a phenol resin are preferred, and a polyhydroxystyrene resin is preferred. -8 - 201211681 The above polyhydroxystyrene resin has at least a hydroxystyrene resin. Derived constituent unit Here, "hydroxystyrene" includes hydroxystyrene and a substance in which a hydrogen atom bonded to the alpha position of hydroxystyrene is substituted with another substituent such as a halogen atom, an alkyl group or a halogenated alkyl group, and a hydroxystyrene derivative (monomer) of such derivatives. "Hydroxystyrene derivative" includes a hydrogen which maintains at least a benzene ring and a hydroxyl group bonded to a benzene ring, for example, an alpha position bonded to a hydroxystyrene a substance in which an atom is substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkyl group such as a halogenated group, and a benzene ring having a hydroxyl group bonded to the hydroxystyrene, and further bonded to an alkyl group having 1 to 5 carbon atoms. The substance, or a benzene ring to which a hydroxyl group is bonded, a substance which further bonds 1 to 2 hydroxyl groups (in this case, the total number of hydroxyl groups is 2 to 3), and the like. The halogen atom may, for example, be a chlorine atom, a fluorine atom or a bromine atom, and a fluorine atom is preferred. Further, the "α-position of hydroxystyrene" means a carbon atom to which a benzene ring is bonded unless otherwise specified. The constituent unit derived from the hydroxystyrene is represented, for example, by the following general formula (Α1-1). [Chemical 2] Ra1

(A1-1) 上述一般式（A1-1)中，Ral表示氫原子、烷基、鹵素 -9- 201211681 原子、或鹵化烷基；Ra2表示碳數1〜5之烷基；p表示1 〜3之整數；q表示〇〜2之整數。(A1-1) In the above general formula (A1-1), Ral represents a hydrogen atom, an alkyl group, a halogen-9-201211681 atom, or a halogenated alkyl group; Ra2 represents an alkyl group having 1 to 5 carbon atoms; and p represents 1~ An integer of 3; q represents an integer of 〇~2.

Ral之烷基碳數宜爲1〜5。另外，直鏈狀或支鏈狀之 烷基爲佳，可列舉甲基 '乙基、丙基、異丙基、正丁基、 異丁基、第三丁基、戊基、異戊基、新戊基等。在該等之 中，工業上係以甲基爲佳。 鹵素原子可列舉氟原子、氯原子、溴原子、碘原子 等，而以氟原子爲佳。 鹵化烷基係上述碳數1〜5之烷基中一部分或全部的 氫原子被鹵素原子取代之基團。其中，以全部的氫原子被 氟原子取代爲佳。另外，以直鏈狀或支鏈狀之氟烷基爲 佳，三氟甲基、六氟乙基、七氟丙基、九氟丁基等爲較 佳，三氟甲基（-CF3)爲最佳。The alkyl carbon number of Ral is preferably from 1 to 5. Further, a linear or branched alkyl group is preferred, and examples thereof include methyl 'ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, New amyl and so on. Among these, the industry is preferably methyl. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is preferred. The halogenated alkyl group is a group in which a part or all of hydrogen atoms of the above-mentioned alkyl groups having 1 to 5 carbon atoms are substituted by a halogen atom. Among them, it is preferred that all of the hydrogen atoms are replaced by fluorine atoms. Further, a linear or branched fluoroalkyl group is preferred, and a trifluoromethyl group, a hexafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group or the like is preferred, and a trifluoromethyl group (-CF3) is preferred. optimal.

Ral係以氫原子或甲基爲佳，氫原子爲較佳。Ral is preferably a hydrogen atom or a methyl group, and a hydrogen atom is preferred.

Ra2之碳數1〜5之烷基可列舉與Ra 1的情況同樣的基 團。 q爲0〜2之整數。在該等之中，係以0或1爲佳， 工業上尤其以〇爲佳。The alkyl group having 1 to 5 carbon atoms of Ra2 may be the same as the case of Ra1. q is an integer of 0 to 2. Among these, 0 or 1 is preferred, and industrially, especially ruthenium is preferred.

Ra2之取代位置，在q爲1的情況下，爲鄰位、間 位、對位之任一者皆可，進一步而言，在q爲2的情況 下，可將任意的取代位置加以組合。 p爲1〜3之整數，宜爲1。 羥基之取代位置，在P爲1的情況下，爲鄰位、間 位、對位之任一者皆可，而從可輕易取得且低價的觀點看 -10- 201211681 來’係以對位爲佳。進一步而言，在P爲2或3的情況 下’可將任意的取代位置加以組合。 上述一般式（A 1-1)所表示之構成單位可單獨使用或組 合兩種以上使用。 上述聚羥基苯乙烯系樹脂中，由羥基苯乙烯所衍生的 構成單位之比例，係以相對於構成聚羥基苯乙烯系樹脂所 有的構成單位而言的60〜100莫耳％爲佳，以70〜100莫 耳％爲較佳’以80〜100莫耳％爲更佳。若在該範圍內， 則在製成負型感光性樹脂組成物時，可得到適度的鹼溶解 性。 上述聚羥基苯乙烯系樹脂，係以進一步具有苯乙烯所 衍生的構成單位爲佳。 此處「苯乙烯所衍生的構成單位」包括苯乙烯及苯乙 烯衍生物（但是不含羥基苯乙烯）之乙烯性雙鍵裂開而成之 構成單位。 「苯乙烯衍生物」包含鍵結於苯乙烯的α位的氫原子 被鹵素原子、烷基、鹵化烷基等其他取代基取代之物質， 以及苯乙烯之中苯基的氫原子被碳數1〜5之烷基等取代 基取代之物質等。 鹵素原子可列舉氯原子、氟原子、溴原子等，係以氟 原子爲佳。 另外，「苯乙烯的α位」只要沒有特別註明，是指鍵 結有苯環的碳原子。 此苯乙烯所衍生的構成單位，例如下述一般式（Α2- 1) -11 - 201211681 所表不。一般式（A2-1)中，Ral、Ra2、q與上述一般式 (A1-1)同義。 【化3 1The substitution position of Ra2 may be any of the ortho, meta and para positions when q is 1, and further, when q is 2, any substitution position may be combined. p is an integer of 1 to 3, preferably 1. The position of substitution of a hydroxyl group, in the case where P is 1, can be either ortho, meta or para, and from the viewpoint of being easily available and low-priced, -10-201211681 It is better. Further, in the case where P is 2 or 3, any substitution positions can be combined. The constituent units represented by the above general formula (A 1-1) may be used singly or in combination of two or more. In the polyhydroxystyrene resin, the ratio of the constituent units derived from the hydroxystyrene is preferably 60 to 100 mol% based on the constituent units of the polyhydroxystyrene resin. ~100% by mole is preferably '80% to 100% by mole. When it is in this range, when a negative photosensitive resin composition is produced, moderate alkali solubility can be obtained. The polyhydroxystyrene resin is preferably a constituent unit derived from styrene. Here, "the constituent unit derived from styrene" includes a constituent unit in which a vinyl double bond of styrene and a styrene derivative (but not containing hydroxystyrene) is cleaved. The "styrene derivative" includes a substance in which a hydrogen atom bonded to the α-position of styrene is substituted with another substituent such as a halogen atom, an alkyl group or a halogenated alkyl group, and a hydrogen atom of a phenyl group in styrene is carbon number 1 A substance substituted with a substituent such as an alkyl group of ～5. The halogen atom may, for example, be a chlorine atom, a fluorine atom or a bromine atom, and a fluorine atom is preferred. Further, the "α-position of styrene" means a carbon atom to which a benzene ring is bonded unless otherwise specified. The constituent unit derived from this styrene is represented by the following general formula (Α2- 1) -11 - 201211681. In the general formula (A2-1), Ral, Ra2, and q are synonymous with the above general formula (A1-1). [Chemical 3 1

Ra1Ra1

Ral及Ra2分別可列舉與上述—般式（A1_i)之Ral及 Ra2同樣的基團。 q爲〇〜2之整數。在該等之中，係以〇或1爲佳， 工業上尤其以0爲佳。Examples of Ral and Ra2 include the same groups as Ral and Ra2 of the above formula (A1_i). q is an integer of 〇~2. Among these, 〇 or 1 is preferred, and industrially, especially 0 is preferred.

Ra2之取代位置，在q爲1的情況下，爲鄰位、間 位、對位之任一者皆可，進一步而言，在q爲2的情況 下，可將任意的取代位置加以組合。 上述一般式（A2-1)所表示之構成單位可單獨使用或組 合兩種以上使用。 上述聚羥基苯乙烯系樹脂中，苯乙烯所衍生的構成單 位之比例，係以相對於構成聚羥基苯乙烯系樹脂所有的構 成單位而言的40莫耳％以下爲佳，以30莫耳％以下爲較 佳，以2 0莫耳％以下爲更佳。若在該範圍內，則在製成 負型感光性樹脂組成物時，可得到適度的鹼溶解性，而且 與其他構成單位的平衡性亦良好。 另外，上述聚羥基苯乙烯系樹脂，可具有羥基苯乙烯 所衍生的構成單位’或可具有苯乙烯所衍生的構成單位以 外之其他構成單位。較佳的情況爲上述聚羥基苯乙烯系樹 -12- 201211681 脂，係僅由羥基苯乙烯所衍生的構成單位所構成之聚合 物、或由羥基苯乙烯所衍生的構成單位與苯乙烯所衍生的 構成單位所構成之共聚物。 上述聚羥基苯乙烯系樹脂之質量平均分子量（藉由凝 膠滲透層析所得到的聚苯乙烯換算基準，以下在本說明書 之中亦相同）並未受到特別限定，而以1 500〜40000爲 佳，以2000〜8000爲較佳。 上述酚醛樹脂，可藉由在酸觸媒的存在下使酚類與醛 類加成縮合而得到。 上述酚類可列舉酚、鄰甲酚、間甲酚、對甲酚等甲酚 類；2,3-二甲酚、2,4-二甲酚、2,5-二甲酚、2,6-二甲酚、 3,4-二甲酚、3，5-二甲酚等二甲酚類；鄰乙酚、間乙酚、 對乙酚、2 -異丙酚、3 -異丙酚、4 -異丙酚、鄰丁酚、間丁 酚、對丁酚、對第三丁酚等烷基酚類；2,3，5-三甲酚、 3，4,5-三甲酚等三烷基酚類；間苯二酚、兒茶酚、氫醌、 氫醌單甲醚、五倍子酚、氟甘胺醇等多價酚類；烷基間苯 二酚、烷基兒茶酚、烷基氫醌等烷基多價酚類（任一烷基 之碳數爲1〜4); α-萘酚、/3-萘酚、羥基二苯、雙酚A 等。該等酚類可單獨使用或組合兩種以上使用。 在該等酚類之中，間甲酚、對甲酚爲佳，以倂用間甲 酚與對甲酚爲較佳。此情況下，藉由調整兩者的摻合比 例，可調整靈敏度等各項特性。 上述醛類可列舉甲醛、三聚甲醛、糠醛、苯甲醛、硝 基苯甲醛、乙醛等。該等醛類可單獨使用或組合兩種以上 -13- 201211681 使用。 上述酸觸媒可列舉鹽酸、硫酸、硝酸、磷酸、亞磷酸 等無機酸類；蟻酸、草酸、醋酸、二乙基硫酸、對甲苯磺 酸等有機酸類；醋酸鋅等金屬鹽類等。該等酸觸媒可單獨 使用或組合兩種以上使用。 以這種方式所得到的酚醛樹脂具體而言，可列舉酚/ 甲醛縮合酚醛樹脂、甲酚/甲醛縮合酚醛樹脂、酚-萘酚/甲 醛縮合酚醛樹脂等。 上述酚醛樹脂之質量平均分子量，係並未受到特別限 定，而1000〜30000爲佳，3000〜25000爲較佳。 (具有由不飽和羧酸所衍生的構成單位之鹼可溶性樹 脂（A2)) 鹼可溶性樹脂（A2)至少具有由不飽和羧酸所衍生的構 成單位。 不飽和羧酸可列舉（甲基）丙烯酸、巴豆酸等單羧酸； 馬來酸、富馬酸、伊康酸等二羧酸等。在該等之中，以 (甲基）丙烯酸爲佳。該等不飽和羧酸可單獨使用或組合兩 種以上使用。 另外，在本說明書之中，「（甲基）丙烯酸」是表示甲 基丙烯酸及丙烯酸這兩者》關於後述「（甲基）丙烯酸酯」 或「（甲基）丙烯醯胺」亦爲相同。 上述鹼可溶性樹脂（A2)中，由不飽和羧酸所衍生的構 成單位之比例’係以相對於構成鹼可溶性樹脂（A2)所有的 構成單位而言的2〜30莫耳％爲佳，以5〜20莫耳％爲較 -14- 201211681 佳。若在該範圍內，則在製成負型感光性樹脂組成物時， 可得到適度的鹼溶解性。 上述鹼可溶性樹脂（A2)，係以進一步具有上述不飽和 羧酸以外之其他聚合性單體所衍生的構成單位爲佳。 這種聚合性單體，可列舉（甲基）丙烯酸甲酯、（甲基） 丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸正丁酯、 (甲基）丙烯酸戊酯、（甲基）丙烯酸環己酯、二環戊基（甲基） 丙烯酸酯、（甲基）丙烯酸2-甲基環己酯、（甲基）丙烯酸異 冰片酯、（甲基）丙烯酸2，2-二甲基羥丙酯、（甲基）丙烯酸 2-羥乙酯、（甲基）丙烯酸5-羥戊酯、（甲基）丙烯酸2-甲氧 基乙酯、三羥甲基丙烷單（甲基）丙烯酸酯、季戊四醇單 (甲基）丙烯酸酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸甲氧 基苄酯、（甲基）丙烯酸呋喃甲酯、（甲基）丙烯酸四氫呋喃 甲酯、（甲基）丙烯酸苯酯等（甲基）丙烯酸酯類；（甲基）丙 烯醯胺、N-甲基（甲基）丙烯醯胺、N-乙基（甲基）丙烯醯 胺、N-丙基（甲基）丙烯醯胺、N-丁基（甲基）丙烯醯胺、N-苯基（甲基）丙烯醯胺、N-甲苯基（甲基）丙烯醯胺、N，N-二 甲基（甲基）丙烯醯胺、N，N-二乙基（甲基）丙烯醯胺、N，N-甲基乙基（甲基）丙烯醯胺、N，N-二苯（甲基）丙烯醯胺、N-甲基-N-苯基（甲基）丙烯醯胺、N-羥乙基-N-甲基（甲基）丙 烯醯胺、N-2-乙醯胺乙基-N-乙醯基（甲基）丙烯醯胺等（甲 基）丙烯醯胺類；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、羥乙基乙烯基醚、苄基乙烯基醚、乙烯 -15- 201211681 基苯醚 '乙烯基甲苯醚等乙烯基醚類；丁酸乙烯酯、異丁 酸乙烯酯、三甲基醋酸乙烯酯、甲氧基醋酸乙烯酯、苯基 醋酸乙烯酯、安息香酸乙烯酯、水楊酸乙烯酯、萘甲酸乙 烯酯等乙烯酯類；苯乙烯、N-乙烯基吡咯烷酮等其他乙烯 基化合物等。該等聚合性單體可單獨使用或組合兩種以上 使用。 上述鹼可溶性樹脂（A2)中，上述聚合性單體所衍生的 構成單位之比例，係以相對於構成鹼可溶性樹脂（A2)所有 的構成單位而言的70〜98莫耳％爲佳，80〜95莫耳％爲 較佳。若在該範圍內，則在製成負型感光性樹脂組成物 時，可得到適度的鹼溶解性，而且與其他構成單位的平衡 性亦良好。 〈藉由照射活性射線而產生酸或鹼之化合物（B) &gt; 藉由照射活性射線而產生酸或鹼之化合物並未受到特 別限定，只要是紫外線、遠紫外線、KrF、ArF等準分子 雷射、X射線、電子束等可藉由照射活性射線產生酸或自 由基之物質即可採用。具體而言，在化學增幅型的情況 下，可採用藉由照射活性射線產生酸之化合物（以下稱爲 「光酸產生劑」）（B1)，在自由基聚合型的情況下，可採 用自由基聚合起始劑（B2)。 (光酸產生劑（B1)) 光酸產生劑（B 1 )不受特別限制，而可採用以往周知的 化合物。可列舉例如鐄鑰鹽或鏑鹽等鎰鹽系酸產生劑、肟 -16- 201211681 磺酸鹽系酸產生劑、含鹵素的三嗪化合物、重氮甲烷系酸 產生劑、硝基苄磺酸鹽系酸產生劑（硝苄基衍生物）、亞胺 基磺酸鹽系酸產生劑、二颯系酸產生劑等。 在該等之中，從本發明之效果優異這點看來，係以鏑 鹽系酸產生劑、肟磺酸鹽系酸產生劑及含鹵素的三嗪化合 物爲佳。特別是從與後述交聯劑（C1)的交聯性良好，另一 方面與特定構造的環氧樹脂（D)的反應性遲鈍，並在圖案 化後可賦予更高的接著性這點看來，係以肟磺酸鹽系酸產 生劑及含鹵素的三嗪化合物爲佳。 適合的锍鹽系酸產生劑具體而言，可採用例如下述一 般式（B 1-1)所表示之化合物。The substitution position of Ra2 may be any of the ortho, meta and para positions when q is 1, and further, when q is 2, any substitution position may be combined. The constituent units represented by the above general formula (A2-1) may be used singly or in combination of two or more. In the polyhydroxystyrene resin, the ratio of the constituent units derived from styrene is preferably 40 mol% or less, and 30 mol%, based on the constituent units of the polyhydroxystyrene resin. The following is preferred, and more preferably 20% by mole or less. When it is in this range, when a negative photosensitive resin composition is produced, moderate alkali solubility can be obtained, and the balance with other constituent units is also good. Further, the polyhydroxystyrene resin may have a constituent unit derived from hydroxystyrene or may have other constituent units other than a constituent unit derived from styrene. Preferably, the polyhydroxystyrene tree-12-201211681 lipid is a polymer composed of a constituent unit derived only from hydroxystyrene or a constituent unit derived from hydroxystyrene and derived from styrene. a copolymer composed of constituent units. The mass average molecular weight of the polyhydroxystyrene resin (the polystyrene conversion standard obtained by gel permeation chromatography, which is also the same in the present specification) is not particularly limited, and is 1,500 to 40000. Good, 2000~8000 is preferred. The phenol resin can be obtained by condensing and condensing a phenol with an aldehyde in the presence of an acid catalyst. Examples of the phenols include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6 - xylenols such as xylenol, 3,4-xylenol, 3,5-xylenol; o-ethylphenol, m-ethylphenol, p-acetol, 2-propofol, 3-propofol, 4 - propofol, o-butylphenol, m-butylphenol, p-butylphenol, alkylphenols such as p-tert-butylphenol; trialkyl groups such as 2,3,5-trimethyl phenol, 3,4,5-trimethyl phenol Phenols; resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, gallicol, fluoroglycolol and other polyvalent phenols; alkyl resorcinol, alkyl catechol, alkyl hydrogen Alkyl polyvalent phenols such as hydrazine (the carbon number of any alkyl group is 1 to 4); α-naphthol, /3-naphthol, hydroxydiphenyl, bisphenol A, and the like. These phenols may be used singly or in combination of two or more. Among these phenols, m-cresol and p-cresol are preferred, and m-cresol and p-cresol are preferred. In this case, various characteristics such as sensitivity can be adjusted by adjusting the blending ratio of the two. Examples of the aldehydes include formaldehyde, trioxane, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like. These aldehydes may be used singly or in combination of two or more -13-201211681. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfonic acid, and p-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used singly or in combination of two or more. Specific examples of the phenol resin obtained in this manner include a phenol/formaldehyde condensed phenol resin, a cresol/formaldehyde condensed phenol resin, a phenol-naphthol/formaldehyde condensed phenol resin, and the like. The mass average molecular weight of the above phenol resin is not particularly limited, and is preferably from 1,000 to 30,000, and more preferably from 3,000 to 25,000. (Alkali-soluble resin (A2) having a constituent unit derived from an unsaturated carboxylic acid) The alkali-soluble resin (A2) has at least a constituent unit derived from an unsaturated carboxylic acid. Examples of the unsaturated carboxylic acid include monocarboxylic acids such as (meth)acrylic acid and crotonic acid; and dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid. Among these, (meth)acrylic acid is preferred. These unsaturated carboxylic acids may be used singly or in combination of two or more. In the present specification, "(meth)acrylic acid" means that both "methacrylic acid" and "acrylic acid" are the same as "(meth)acrylate" or "(meth)acrylamide" described later. In the alkali-soluble resin (A2), the ratio of the constituent units derived from the unsaturated carboxylic acid is preferably 2 to 30 mol% based on the constituent units constituting the alkali-soluble resin (A2). 5~20 mol% is better than -14-201211681. When it is in this range, when a negative photosensitive resin composition is produced, moderate alkali solubility can be obtained. The alkali-soluble resin (A2) is preferably a constituent unit derived from a polymerizable monomer other than the above unsaturated carboxylic acid. Examples of such a polymerizable monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and amyl (meth)acrylate. Cyclohexyl (meth)acrylate, dicyclopentyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylate 2, 2 - dimethylhydroxypropyl acrylate, 2-hydroxyethyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, trimethylolpropane mono ( Methyl) acrylate, pentaerythritol mono (meth) acrylate, benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, furan methyl (meth) acrylate, tetrahydrofuran (meth) acrylate (meth) acrylate such as ester or phenyl (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-tolyl (meth) acrylamide, N,N-dimethyl(meth) acrylamide, N,N-diethyl(meth) acrylamide, N,N-methylethyl (Meth) acrylamide, N,N-diphenyl(meth) acrylamide, N-methyl-N-phenyl(meth) acrylamide, N-hydroxyethyl-N-methyl ( Methyl) acrylamide, N-2-acetamidoethyl-N-ethinyl (meth) acrylamide, etc. (meth) acrylamide; hexyl vinyl ether, octyl vinyl ether, Mercapto vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, hydroxyethyl vinyl ether, benzyl vinyl ether, ethylene-15- 201211681 Vinyl ethers such as phenyl ether 'vinyl toluene ether; vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, methoxy vinyl acetate, phenyl vinyl acetate, vinyl benzoate, water Vinyl esters such as vinyl linate and vinyl naphthalate; other vinyl compounds such as styrene and N-vinylpyrrolidone. These polymerizable monomers may be used singly or in combination of two or more. In the alkali-soluble resin (A2), the ratio of the constituent units derived from the polymerizable monomer is preferably 70 to 98 mol% based on the constituent units constituting the alkali-soluble resin (A2). ~95 mole% is preferred. When it is in this range, when a negative photosensitive resin composition is produced, moderate alkali solubility can be obtained, and the balance with other constituent units is also good. <Compound (B) which generates an acid or a base by irradiation with an active ray&gt; The compound which generates an acid or a base by irradiation of an active ray is not specifically limited, as long as it is an excimer laser such as ultraviolet ray, far ultraviolet ray, KrF or ArF. A shot, an X-ray, an electron beam, or the like can be used by irradiating an active ray to generate an acid or a radical. Specifically, in the case of a chemical amplification type, a compound which generates an acid by irradiation with an active ray (hereinafter referred to as "photoacid generator") (B1) can be used, and in the case of a radical polymerization type, free Base polymerization initiator (B2). (Photoacid generator (B1)) The photoacid generator (B 1 ) is not particularly limited, and a conventionally known compound can be used. Examples thereof include a phosphonium salt generator such as a sulfonium salt or a phosphonium salt, a cesium-16-201211681 sulfonate acid generator, a halogen-containing triazine compound, a diazomethane acid generator, and a nitrobenzylsulfonic acid. A salt acid generator (nitrobenzyl derivative), an imidosulfonate acid generator, a diterpenoid generator, and the like. Among these, from the viewpoint of excellent effects of the present invention, an oxime salt-based acid generator, an oxime sulfonate-based acid generator, and a halogen-containing triazine compound are preferred. In particular, the crosslinkability with the crosslinking agent (C1) described later is good, and the reactivity with the epoxy resin (D) having a specific structure is inferior, and the adhesion can be imparted after patterning. The sulfonate-based acid generator and the halogen-containing triazine compound are preferred. As the suitable hydrazine salt-based acid generator, for example, a compound represented by the following general formula (B 1-1) can be used.

上述一般式（B1-1)中，Rbl及Rb2各自獨立，表示氫 原子、鹵素原子、氧原子或可具有鹵素原子之烴基、或可 具有取代基之烷氧基；Rb3表示可具有鹵素原子或烷基之 對位伸苯基；Rb4表示氫原子、氧原子或可具有鹵素原子 之烴基、可具有取代基之苯甲醯基、或可具有取代基之多 苯基；X胃表示鑰離子之相對離子。 在上述一般式（B1-1)之中，X·具體而言可列舉SbF6· 、PF6-、AsF6-、BF4-、SbCl6-、C104·、CF3S〇r、CH3S03· 、FSOT、F2P〇T、對甲苯磺酸根、九氟丁烷磺酸根、金 •17- 201211681 剛烷羧酸根、四芳香基硼酸根，下述一般式（B 1-2)所表示 之氟化烷基氟磷酸陰離子等。 【化5】 [(ROmPFentJ* (B1-2) 上述一般式（B1-2)中，Rf表示80%以上的氫原子被氟 原子取代之烷基。m表示其個數，而爲1〜5之整數。„! 個Rf可彼此相同或相異。 上述一般式（B1-1)所表示之光酸產生劑，可列舉4-(2-氯-4-苯甲醯基苯基硫代）苯基二苯鏑六氟銻酸鹽、4-(2-氯-4-苯甲醯基苯基硫代）苯基雙（4-氟苯基）鏑六氟銻酸 鹽、4-(2-氯-4-苯甲醯基苯基硫代）苯基雙（4-氯苯基）毓六 氟銻酸鹽、4-(2-氯-4-苯甲醯基苯基硫代）苯基雙（4-甲基苯 基）鏑六氟銻酸鹽、4-(2-氯-4-苯甲醯基苯基硫代）苯基雙 (4-(々-羥基乙氧基）苯基）鏑六氟銻酸鹽、4-(2-甲基-4-苯 甲醯基苯基硫代）苯基雙（4-氟苯基）锍六氟銻酸鹽、4-(3-甲基-4-苯甲醯基苯基硫代）苯基雙（4-氟苯基）鏑六氟銻酸 鹽、4-(2-氟4_苯甲醯基苯基硫代）苯基雙（4-氟苯基）鏑六 氟銻酸鹽、4-(2-甲基-4-苯甲醯基苯基硫代）苯基雙（4_氟苯 基）鏑六氟銻酸鹽、4-(2,3,5,6 -四甲基-4 -苯甲醯基苯基硫 代）苯基雙（4 -氟苯基）鏑六氟錄酸鹽、4-(2,6 -二氯-4 -苯甲 醯基苯基硫代）苯基雙（4-氟苯基）锍六氟銻酸鹽、4-(2,6-二 甲基-4-苯甲醯基苯基硫代）苯基雙（4-氟苯基）锍六氟銻酸 鹽、4-(2,3-二甲基-4-苯甲醯基苯基硫代）苯基雙（4-氟苯基） 锍六氟銻酸鹽、4-(2-甲基-4-苯甲醯基苯基硫代）苯基雙（4- -18- 201211681 氯苯基）鏑六氟銻酸鹽、4_(3_甲基-4_苯甲醯基苯基硫代） 本基雙（4-氯苯基）锍六氟銻酸鹽、4_(2氟t苯甲醯基苯基 硫代）苯基雙（4-氯苯基）鏑六氟銻酸鹽、4-(2_甲基-4_苯甲 酿基苯基硫代）苯基雙（4_氯苯基）锍六氟銻酸鹽、4_ (2,3,5,6-四甲基_4_苯甲醯基苯基硫代）苯基雙（4_氯苯基）鏑 /、氟銻酸鹽、4-(2,6-二氯_4_苯甲醯基苯基硫代）苯基雙（4_ 氯苯基）鏑六氟銻酸鹽' 4_(2,6_二甲基-4_苯甲醯基苯基硫 代）本基雙（4_氯苯基）毓六氟銻酸鹽、4_(2,3_二甲基_4_苯 甲酿基苯基硫代）苯基雙（4_氯苯基）锍六氟銻酸鹽、4_(2_ 氯-4-乙醯基苯基硫代）苯基二苯鏑六氟銻酸鹽、4_(2_氯-4_ (4-甲基苯甲醯基）苯基硫代）苯基二苯锍六氟銻酸鹽、4_ (2·氯-4-(4-氟苯甲醯基）苯基硫代）苯基二苯锍六氟銻酸 鹽、4-(2-氯-4-(4-甲氧基苯甲醯基）苯基硫代）苯基二苯鏑 六氟銻酸鹽、4-(2-氯-4-十二醯基苯基硫代）苯基二苯毓六 氟銻酸鹽、4-(2 -氯-4 -乙醯基苯基硫代）苯基雙（4 -氟苯基） 鏑六氟銻酸鹽、4-(2-氯-4-(4-甲基苯甲醯基）苯基硫代）苯 基雙（4-氟苯基）锍六氟銻酸鹽、4-(2-氯-4-(4-氟苯甲醯基） 苯基硫代）苯基雙（4-氟苯基）毓六氟銻酸鹽、4-(2-氯-4-(4-甲氧基苯甲醯基）苯基硫代）苯基雙（4-氟苯基）锍六氟銻酸 鹽、4-(2-氯-4-十二醯基苯基硫代）苯基雙（4-氟苯基）毓六 氟銻酸鹽、4-(2-氯-4-乙醯基苯基硫代）苯基雙（4-氯苯基） 鏑六氟銻酸鹽、4-(2-氯-4-(4-甲基苯甲醯基）苯基硫代）苯 基雙（4 -氯苯基）鏡六氟鍊酸鹽、4-(2 -氯-4-(4 -氣本甲釀基） 苯基硫代）苯基雙（4-氯苯基）锍六氟銻酸鹽、4-(2-氯-4-(4- -19- 201211681 甲氧基苯甲醯基）苯基硫代）苯基雙（4-氯苯基）毓六氟銻酸 鹽、4-(2-氯-4-十二醯基苯基硫代）苯基雙（4-氯苯基）鏑六 氟銻酸鹽、4-(2-氯_4_苯甲醯基苯基硫代）苯基二苯锍六氟 磷酸酯、4-(2-氯-4-苯甲醯基苯基硫代）苯基二苯鏑四氟硼 酸鹽、4-(2·氯-4_苯甲醯基苯基硫代）苯基二苯鏑高氯酸 鹽、4-(2-氯-4-苯甲醯基苯基硫代）苯基二苯鏑三氟甲烷磺 酸鹽、4-(2-氯-4-苯甲醯基苯基硫代）苯基雙（4-氟苯基）銃 六氟磷酸酯、4-(2-氯-4-苯甲醯基苯基硫代）苯基雙（4-氟苯 基）鏑四氟硼酸鹽、4-(2-氯-4-苯甲醯基苯基硫代）苯基雙 (4-氟苯基）鏑高氯酸鹽、4-(2-氯-4-苯甲醯基苯基硫代）苯 基雙（4-氟苯基）鏑三氟甲烷磺酸鹽、4-(2-氯-4-苯甲醯基苯 基硫代）苯基雙（4-氟苯基）鏑對甲苯磺酸鹽、4-(2-氯-4-苯 甲醯基苯基硫代）苯基雙（4-氟苯基）鏑樟腦磺酸鹽、4-(2-氯-4-苯甲醯基苯基硫代）苯基雙（4-氟苯基）锍九氟丁烷磺 酸鹽、4-(2-氯-4-苯甲醯基苯基硫代）苯基雙（4-氯苯基）锍 六氟磷酸酯、4-(2-氯-4-苯甲醯基苯基硫代）苯基雙（4-氯苯 基）鏑四氟硼酸鹽、4-(2-氯-4-苯甲醯基苯基硫代）苯基雙 (4-氯苯基）鏑高氯酸鹽、4-(2-氯-4-苯甲醯基苯基硫代）苯 基雙（4-氯苯基）毓三氟甲烷磺酸鹽、二苯[4-(苯基硫代）苯 基]鏑三氟參五氟乙基磷酸鹽、二苯[4-(對聯三苯基硫代） 苯基]毓六氟銻酸鹽、二苯[4-(對聯三苯基硫代）苯基]锍三 氟參五氟乙基磷酸鹽等。 其他鑰鹽系酸產生劑，可列舉將上述一般式（B1-1)的 陽離子部分以例如三苯鏑、（4·第三丁氧基苯基）二苯鏑、 -20- 201211681 雙（4-第三丁氧基苯基）苯基毓、參（4-第三丁氧基苯基） 毓、（3-第三丁氧基苯基）二苯鏑、雙（3-第三丁氧基苯基） 苯基锍、參（3-第三丁氧基苯基）鏑、（3,4-二第三丁氧基苯 基）二苯錡、雙（3,4-二第三丁氧基苯基）苯基毓、參（3,4-二 第三丁氧基苯基）锍、二苯（4-硫代苯氧基苯基）锍、（4-第 三丁氧基羰基甲氧基苯基）二苯锍、參（4-第三丁氧基羰基 甲氧基苯基）鏑、（4-第三丁氧基苯基）雙（4-二甲基胺基苯 基）锍、參（4-二甲基胺基苯基）锍、2-萘二苯锍、二甲基-2-萘锍、4-羥苯基二甲基锍、4-甲氧基苯基二甲基鏑、三 甲基锍、2-氧環己基環己基甲基毓、三萘基鏑、三苄基銃 等锍陽離子、或二苯鎭鑰、雙（4-第三丁基苯基）碘鑰、（4-第三丁氧基苯基）苯基鎮鑰、（4-甲氧基苯基）苯基鎮鑰等芳 香基碘鑰陽離子等鋏鏺陽離子取代之物質。 肟磺酸鹽系酸產生劑，可列舉[2-(丙基磺醯氧基醯亞 胺基）-2,3-二氫噻吩-3-亞基](鄰甲苯基）乙腈、α-(對甲苯 磺醯氧基醯亞胺基）-苯基乙腈、α-(苯磺醯氧基醯亞胺 基）-2,4-二氯苯基乙腈、α-(苯磺醯氧基醯亞胺基）-2,6-二 氯苯基乙腈、α -(2-氯苯磺醯氧基醯亞胺基）-4-甲氧基苯 基乙腈、α-(乙基磺醯氧基醯亞胺基）-1-環戊烯基乙腈 等。 除了上述之外，還可列舉下述一般式（B 1-3)所表示之 化合物， 【化6】In the above general formula (B1-1), Rb1 and Rb2 are each independently and represent a hydrogen atom, a halogen atom, an oxygen atom or a hydrocarbon group which may have a halogen atom, or an alkoxy group which may have a substituent; and Rb3 represents a halogen atom or a para-phenyl group of the alkyl group; Rb4 represents a hydrogen atom, an oxygen atom or a hydrocarbon group which may have a halogen atom, a benzamyl group which may have a substituent, or a polyphenyl group which may have a substituent; the X stomach represents a key ion Relative ions. In the above general formula (B1-1), X·specifically, SbF6·, PF6-, AsF6-, BF4-, SbCl6-, C104·, CF3S〇r, CH3S03·, FSOT, F2P〇T, P-toluenesulfonate, nonafluorobutanesulfonate, gold 17-201211681 adamantanecarboxylate, tetraarylborate, a fluorinated alkylfluorophosphate anion represented by the following general formula (B1-2), and the like. [(5) In the above general formula (B1-2), Rf represents an alkyl group in which 80% or more of hydrogen atoms are replaced by a fluorine atom. m represents the number thereof, and is 1 to 5 An integer of „! Rf may be the same or different from each other. The photoacid generator represented by the above general formula (B1-1) may, for example, be 4-(2-chloro-4-benzomethylphenylthio). Phenyldiphenylphosphonium hexafluoroantimonate, 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2) -Chloro-4-benzylidylphenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-benzylidenephenylthio)benzene Bis(4-methylphenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-(anthracene-hydroxyethoxy)benzene Hexafluoroantimonate, 4-(2-methyl-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(3- Methyl-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-fluoro-4-benzoylphenylthio)phenyl Bis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-methyl-4-benzylidenephenylthio) Phenyl bis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2,3,5,6-tetramethyl-4-benzylidenephenylthio)phenyl bis(4-fluoro Phenyl) hexafluoroantimonate, 4-(2,6-dichloro-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4- (2,6-Dimethyl-4-benzoylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2,3-dimethyl-4- Benzopyridylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-methyl-4-benzylidenephenylthio)phenyl bis (4 - -18- 201211681 chlorophenyl) hydrazine hexafluoroantimonate, 4_(3_methyl-4_benzylidenephenylthio) benzyl bis(4-chlorophenyl)phosphonium hexafluoroantimonate , 4-(2-fluorot-benzylidenephenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-methyl-4-phenylphenylthiophenyl) Phenyl bis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4_(2,3,5,6-tetramethyl-4-phenylidenephenylthio)phenyl bis(4-chloro Phenyl) fluorene, fluoroantimonate, 4-(2,6-dichloro-4-phenyl benzhydrylphenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate' 4_( 2,6_two 4-(benzylidenephenylthio)benyl bis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4_(2,3-dimethyl-7-benzylphenylthio Phenyl bis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4_(2_chloro-4-ethenylphenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4_(2_chloro- 4-(4-Methylbenzylidene)phenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4_(2·chloro-4-(4-fluorobenzylidene)phenylthio)benzene Dibenzoquinone hexafluoroantimonate, 4-(2-chloro-4-(4-methoxybenzylidene)phenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4-(2 -chloro-4-dodecylphenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4-(2-chloro-4-ethylcyanophenylthio)phenylbis(4-fluorobenzene Hexafluoroantimonate, 4-(2-chloro-4-(4-methylbenzylidene)phenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-(4-fluorobenzylidene)phenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-() 4-methoxybenzylidene)phenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-dodecylphenylthio) Phenyl double 4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-ethenylphenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-( 2-Chloro-4-(4-methylbenzylidene)phenylthio)phenylbis(4-chlorophenyl) hexafluoroallate, 4-(2-chloro-4-(4- Phenyl thio)phenyl bis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-(4- -19- 2012-11681 methoxybenzamide) Phenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-dodecylphenylthio)phenyl bis(4-chlorobenzene Hexafluoroantimonate, 4-(2-chloro-4-phenylbenzhydrylphenylthio)phenyldiphenylphosphonium hexafluorophosphate, 4-(2-chloro-4-benzhydryl) Phenylthio)phenyldiphenylhydrazine tetrafluoroborate, 4-(2·chloro-4-benzoylphenylthio)phenyldiphenylhydrazine perchlorate, 4-(2-chloro- 4-Benzylmercaptophenylthio)phenyldiphenylfluorene trifluoromethanesulfonate, 4-(2-chloro-4-benzylidenephenylthio)phenyl bis(4-fluorophenyl)铳 hexafluorophosphate, 4-(2-chloro-4-benzylidenephenylthio)phenyl bis(4-fluorophenyl)phosphonium tetrafluoroborate, 4-(2-chloro-4- Benzyl Nonylphenylthio)phenylbis(4-fluorophenyl)phosphonium perchlorate, 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)镝Trifluoromethanesulfonate, 4-(2-chloro-4-benzylidenephenylthio)phenyl bis(4-fluorophenyl)phosphonium p-toluenesulfonate, 4-(2-chloro 4-Benzylmercaptophenylthio)phenylbis(4-fluorophenyl)camphorsulfonate, 4-(2-chloro-4-benzylidenephenylthio)phenyl bis ( 4-fluorophenyl)nonafluorobutanesulfonate, 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluorophosphate, 4 -(2-chloro-4-benzylidenephenylthio)phenylbis(4-chlorophenyl)phosphonium tetrafluoroborate, 4-(2-chloro-4-benzylidenephenylthio Phenyl bis(4-chlorophenyl)phosphonium perchlorate, 4-(2-chloro-4-benzylidenephenylthio)phenyl bis(4-chlorophenyl)phosphonium trifluoromethanesulfonate Acid salt, diphenyl [4-(phenylthio)phenyl] fluorene trifluoropentafluoroethyl phosphate, diphenyl [4-(paratriphenylthio) phenyl] quinone hexafluoroantimonate Diphenyl [4-(paratriphenylthio)phenyl] fluorene trifluoropentafluoroethyl phosphate. Other key salt acid generators include the cationic moiety of the above general formula (B1-1), for example, triphenylsulfonium, (4·t-butoxyphenyl)diphenyl hydrazine, -20-201211681 bis (4) -Tertibutoxyphenyl)phenyl hydrazine, ginseng (4-tert-butoxyphenyl) fluorene, (3-tert-butoxyphenyl)diphenyl hydrazine, bis(3-tert-butoxy Phenyl hydrazine, phenylindole (3-tert-butoxyphenyl) fluorene, (3,4-di-t-butoxyphenyl)diphenyl hydrazine, bis(3,4-di-third butyl Oxyphenyl)phenylhydrazine, ginseng (3,4-di-t-butoxyphenyl)anthracene, diphenyl(4-thiophenoxyphenyl)anthracene, (4-tert-butoxycarbonyl) Methoxyphenyl)diphenyl hydrazine, ginseng (4-tert-butoxycarbonylmethoxyphenyl)anthracene, (4-tert-butoxyphenyl)bis(4-dimethylaminophenyl)锍, ginseng (4-dimethylaminophenyl) fluorene, 2-naphthalene diphenyl hydrazine, dimethyl-2-naphthoquinone, 4-hydroxyphenyl dimethyl hydrazine, 4-methoxyphenyl a ruthenium cation such as dimethyl hydrazine, trimethyl hydrazine, 2-oxocyclohexylcyclohexylmethyl hydrazine, trinaphthyl fluorene or tribenzyl hydrazine, or a diphenyl sulfonium key or a bis (4-tert-butyl group) The substituent group) iodide key, (4-tert-butoxy phenyl) phenyl key town, (4-methoxyphenyl) phenyl key town like an aromatic iodide key cation clip Po cationic species. The sulfonate-based acid generator may, for example, be [2-(propylsulfonyloxyindolido)-2,3-dihydrothiophene-3-ylidene] (o-tolyl)acetonitrile, α-( p-Toluenesulfonyloxyindenido)-phenylacetonitrile, α-(phenylsulfonyloxyindenido)-2,4-dichlorophenylacetonitrile, α-(phenylsulfonyloxyphthalazide Amino)-2,6-dichlorophenylacetonitrile, α-(2-chlorophenylsulfonyloxyindenido)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyhydrazine Imino)-1-cyclopentenylacetonitrile and the like. In addition to the above, a compound represented by the following general formula (B 1-3) may also be mentioned, [Chemical 6]

5-Ac=n- \CN5-Ac=n- \CN

Rb5-f-C=N-0-S02Rb6 -21 - 201211681 上述一般式（B 1-3)中，Rb5表示1價、2價或3價之有 機基、Rb6表示取代或未取代之飽和烴基、不飽和烴基或 芳香族化合物基，r表示1〜6之整數》Rb5-fC=N-0-S02Rb6 -21 - 201211681 In the above general formula (B 1-3), Rb5 represents a monovalent, divalent or trivalent organic group, Rb6 represents a substituted or unsubstituted saturated hydrocarbon group, and is unsaturated. a hydrocarbon group or an aromatic compound group, and r represents an integer of 1 to 6

Rb5係以芳香族化合物之基爲特佳，這種芳香族化合 物基可列舉苯基、萘基等芳香族烴基、或呋喃基、噻吩基 等雜環基等。該等在環上可具有1個以上適當的取代基， 例如鹵素原子、烷基、烷氧基、硝基等。另外，Rb6係以 碳數1〜6之烷基爲特佳，可列舉甲基、乙基、丙基、丁 基。另外’ r係以1〜3之整數爲佳，以1或2爲較佳。 上述一般式（B1-3)所表示之光酸產生劑，可列舉在r =1時，Rb5爲苯基、甲基苯基及甲氧基苯基中之任一 者’且Rb6爲甲基之化合物。更詳細而言，上述一般式 (B1-3)所表示之光酸產生劑，可列舉^_(甲基磺醯氧基醯 亞胺基）-1-苯乙腈、α-(甲基磺醯氧基醯亞胺基）-1-(對甲 基苯基）乙腈及α -(甲基磺醯氧基醯亞胺基）-1-(對甲氧基 苯基）乙腈。 上述一般式（B1-3)所表示之光酸產生劑，可列舉在r =2時，下述式〜（B1_3_8)所表示之光酸產生劑。 -22- 201211681 【化7】 H3C—S〇2 一Ο—N=Rb5 is particularly preferably a group of an aromatic compound, and examples of the aromatic compound group include an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, or a heterocyclic group such as a furyl group or a thienyl group. These may have one or more suitable substituents on the ring, such as a halogen atom, an alkyl group, an alkoxy group, a nitro group or the like. Further, Rb6 is particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. Further, 'r is preferably an integer of 1 to 3, preferably 1 or 2. The photoacid generator represented by the above general formula (B1-3) may, when r = 1, Rb5 be any of a phenyl group, a methylphenyl group and a methoxyphenyl group, and Rb6 is a methyl group. Compound. More specifically, the photoacid generator represented by the above general formula (B1-3) may, for example, be exemplified by methyl sulfonate oxime iminoacetonitrile or α-(methyl sulfonamide). Oxyquinone imido)-1-(p-methylphenyl)acetonitrile and α-(methylsulfonyloxyindolylene)-1-(p-methoxyphenyl)acetonitrile. The photoacid generator represented by the above formula (B1-3) may, for example, be a photoacid generator represented by the following formula (B1_3_8) when r = 2. -22- 201211681 【化7】 H3C—S〇2 一Ο—N=

Ν—Ο—S〇2—CH3Ν—Ο—S〇2—CH3

H3C-SO2—ο—N=(p一—(p=N—〇-S02—CH3 CN CN C2H5—S02—〇—N=H3C-SO2—ο—N=(p_—(p=N—〇-S02—CH3 CN CN C2H5—S02—〇—N=

C4H9—SOC4H9-SO

F3C-SOF3C-SO

1=〒一|j^Y~〒=N-0-S02-C2H5 CN CN 〇-N=〒一〒=N-〇-S02-C4H9 CN CN 2—0—N=C——?=N—〇 CN CN )-so2-cf3 (B1-3-1) (B1-3-2) (B1-3-3) (B1-3-4) (B1-3-5) (B1-3-6) (B1-3-7) (B1-3-8) 含鹵素的三嗪化合物，可列舉2,4-雙（三氯甲基）-6-胡 椒基-1,3,5-三嗪、2,4-雙（三氯甲基）-6-[2-(2-呋喃基）乙烯 基]-s-三嗦、2,4-雙（三氯甲基）·6-[2-(5 -甲基-2-呋喃基）乙 烯基]-s-三嗪、2,4-雙（三氯甲基）_6-[2-(5-乙基-2-呋喃基） 乙烯基]-s -三嗪、2,4-雙（三氯甲基）_6-[2-(5-丙基-2-呋喃 基）乙烯基]-s-三嗪、2,4-雙（三氯甲基）-6-[2-(3,5-二甲氧基 苯基）乙烯基]-s-三嗪、2,4-雙（三氯甲基）-6-[2-(3,5-二乙氧 基苯基）乙烯基]-s-三嗪、2,4-雙（三氯甲基）-6-[2-(3,5-二丙 氧基苯基）乙烯基]-s-三嗪、2,4-雙（三氯甲基）-6-[2-(3-甲 氧基-5-乙氧基苯基）乙烯基]-s-三嗪、2,4-雙（三氯甲基）-6-[2-(3-甲氧基-5-丙氧基苯基）乙烯基]-s-三嗪、2,4-雙（三氯 -23- 201211681 甲基）-6-[2-(3,4-亞甲基二氧苯基）乙烯基]-s-三嗪、2,4-雙 (三氯甲基）-6-(3,4-亞甲基二氧苯基）-s-三嗪、2,4-雙-三氯 甲基-6-(3-溴-4-甲氧基）苯基-s-三嗪、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基）苯基-s-三嗪、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基）苯乙烯基苯基-s-三嗪、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基）苯乙烯基苯基-s-三嗪、2-(4-甲氧基苯基）-4,6-雙 (三氯甲基）-1，3,5-三嗪、2-(4-甲氧基萘基）-4,6-雙（三氯甲 基）-1，3,5-三嗪、2-[2-(2-呋喃基）乙烯基]-4,6-雙（三氯甲 基）-1,3,5-三嗪、2-[2-(5-甲基-2-呋喃基）乙烯基]-4,6-雙 (三氯甲基）-1，3,5-三嗪、2-[2-(3,5-二甲氧基苯基）乙烯基]_ 4,6-雙（三氯甲基）_1，3,5_三嗪、2-[2-(3,4-二甲氧基苯基）乙 烯基]_4,6-雙（三氯甲基）-1，3,5-三嗪、2-(3,4-亞甲基二氧 苯基）-4,6-雙（三氯甲基）-1,3,5-三嗪、參（i，3-二溴丙基）_ 1，3,5-三嗪、參（2,3-二溴丙基）-1，3,5-三嗪等含鹵素的三曝 化合物以及參（2,3 -二溴丙基）異氰尿酸酯等下述—般式 (B 1-4)所表示之含鹵素的三嗪化合物。 【化8】1=〒一|j^Y~〒=N-0-S02-C2H5 CN CN 〇-N=〒一〒=N-〇-S02-C4H9 CN CN 2-0-N=C——?=N- 〇CN CN )-so2-cf3 (B1-3-1) (B1-3-2) (B1-3-3) (B1-3-4) (B1-3-5) (B1-3-6) (B1-3-7) (B1-3-8) The halogen-containing triazine compound may, for example, be 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine, 2 ,4-bis(trichloromethyl)-6-[2-(2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)·6-[2-(5 -methyl-2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)_6-[2-(5-ethyl-2-furanyl)vinyl]-s -Triazine, 2,4-bis(trichloromethyl)_6-[2-(5-propyl-2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl) -6-[2-(3,5-Dimethoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5- Diethoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)vinyl]-s -Triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-ethoxyphenyl)vinyl]-s-triazine, 2,4-double (trichloromethyl)-6-[2-(3-methoxy-5-propoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloro-23- 201211681 methyl)-6-[2-(3,4-methylenedioxyphenyl)vinyl]-s-triazine, 2,4-bis (three Chloromethyl)-6-(3,4-methylenedioxyphenyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy) Phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl -6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)benzene Vinyl phenyl-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxy Naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2-furyl)vinyl]-4,6-bis(trichloromethane) -1,3,5-triazine, 2-[2-(5-methyl-2-furyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5- Triazine, 2-[2-(3,5-dimethoxyphenyl)vinyl]_ 4,6-bis(trichloromethyl)_1,3,5-triazine, 2-[2-( 3,4-dimethoxyphenyl)vinyl]_4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxyphenyl) -4,6-bis(trichloromethyl)-1,3,5-triazine, ginseng (i,3-dibromopropyl) Halogen-containing three-exposure compound such as 1,3,5-triazine, ginseng (2,3-dibromopropyl)-1,3,5-triazine, and ginseng (2,3-dibromopropyl) A halogen-containing triazine compound represented by the following formula (B1-4) such as cyanurate. 【化8】

上述一般式（B1-4)中，Rb7、Rb8、Rb9各自獨立，表 示碳數1〜6之鹵化烷基。 另外，其他光酸產生劑，可列舉雙（對甲苯磺醯基）重 氮甲烷、甲基磺醯基對甲苯磺醯基重氮甲烷、丨_環己基擴 -24- 201211681 醯基-1-(1,1-二甲基乙基磺醯基）重氮甲烷、雙（1，1-二甲基 乙基磺醯基）重氮甲烷 '雙（1-甲基乙基磺醯基）重氮甲烷、 雙（環己基磺醯基）重氮甲烷、雙（2,4-二甲基苯磺醯基）重 氮甲烷、雙（4-乙苯磺醯基）重氮甲烷、雙（3-甲基苯磺醯基） 重氮甲烷、雙（4-甲氧基苯磺醯基）重氮甲烷、雙（4_氟苯磺 醯基）重氮甲烷、雙（4-氯苯磺醯基）重氮甲烷、雙（4-第三 丁基苯磺醯基）重氮甲烷等雙磺醯基重氮甲烷類；2-甲基-2-(對甲苯磺醯基）丙醯苯、2-(環己基羰基）-2-(對甲苯磺醯 基）丙烷、2 -甲烷磺醯基-2 -甲基-(對甲基硫代）丙醯苯、 2.4- 二甲基-2-(對甲苯磺醯基）戊-3-酮等磺醯基羰基烷類； 1-對甲苯磺醯基-1-環己基羰基重氮甲烷、1-重氮-1-甲基 磺醯基-4-苯基-2-丁酮、1-環己基磺醯基-1-環己基羰基重 氮甲烷、1-重氮-1-環己基磺醯基-3,3-二甲基-2-丁酮、1-重氮-1-(1，1-二甲基乙基磺醯基）-3,3-二甲基-2-丁酮、1-乙 醯基-1-(1-甲基乙基磺醯基）重氮甲烷、1-重氮-1-(對甲苯 磺醯基）-3,3-二甲基-2-丁酮、1-重氮-1-苯磺醯基-3,3-二甲 基-2-丁酮、1-重氮-1-(對甲苯磺醯基）-3-甲基-2-丁酮、2-重氮-2-(對甲苯磺醯基）醋酸環己酯、2-重氮-2-苯磺醯基 醋酸-第三丁基、2-重氮-2-甲烷磺醯基醋酸異丙酯、2-重 氮-2-苯磺醯基醋酸環己酯、2-重氮-2-(對甲苯磺醯基）醋 酸-第三丁基等磺醯基羰基重氮甲烷類；對甲苯磺酸-2-硝 苄基、對甲苯磺酸-2,6-二硝苄基、對三氟甲基苯磺酸- 2.4- 二硝苄基等硝苄基衍生物；五倍子酚之甲磺酸酯、五 倍子酚之苯磺酸酯、五倍子酚之對甲苯磺酸酯、五倍子酚 -25- 201211681 之對甲氧基苯磺酸酯、五倍子酚之均三甲苯磺酸酯、五倍 子酚之苄磺酸酯、沒食子酸烷酯之甲磺酸酯、沒食子酸烷 酯之苯磺酸酯、沒食子酸烷酯之對甲苯磺酸酯、沒食子酸 烷酯（烷基之碳數爲1〜15)之對甲氧基苯磺酸酯、沒食子 酸烷酯之均三甲苯磺酸酯、沒食子酸烷酯之苄磺酸酯等多 羥基化合物與脂肪族或芳香族磺酸之酯類等。 該等光酸產生劑可單獨使用或組合兩種以上使用》 光酸產生劑（B 1 )的含量，係以相對於鹼可溶性樹脂 (A 1)100質量份而言的0.05〜30質量份爲佳，〇.1〜1〇質 量份爲較佳。若在該範圍內，則負型感光性樹脂組成物的 硬化性良好。 (自由基聚合起始劑（B2)) 自由基聚合起始劑（B 2)不受特別限制，而可採用以往 周知的化合物。 具體而言，可列舉2,4 -二乙基噻噸酮、異丙基噻噸 酮、2-氣噻噸酮、2,4-二甲基噻噸酮等噻噸酮衍生物；二 苯酮、N，N'-四甲基-4,4'-二胺基二苯酮、n，N，-四乙基· 4,4'-二胺基二苯酮、4-甲氧基-4'-二甲基胺基二苯酮、2_ 苄基-2-二甲基胺基-1_(4-嗎咐基苯基）-丁酮- L2 —甲基-^ [4-(甲基硫代）苯基]-2 -嗎琳基-丙酮-1等芳香族酮；2 -乙基 恵醒、菲酿、2 -第三丁基恵醌、八甲基恵·、ι,2_苯并恵 醌、2,3-苯并蒽醌、2-苯基恵酿、2,3-二苯恵醌、氯恵 醌、2 -甲基惠醒、1,4 -萘醒、9,10 -菲醒、2 -甲基l，4 -萘 醌、2,3-二甲基蒽醌等醌類；安息香甲醚、安息香乙酸、 -26- 201211681 安息香苯醚等安息香醚化合物；安息香、甲基安息香、乙 基安息香等安息香化合物；苄基二甲基縮酮等苄基衍生 物；2-(鄰氯苯基）·4,5-二苯咪唑二聚物、2-(鄰氯苯基）· 4,5-二（甲氧基苯基）咪唑二聚物、2-(鄰氟苯基）-4,5-二苯 咪唑二聚物、2-(鄰甲氧基苯基）-4,5 -二苯咪唑二聚物、2_ (對甲氧基苯基）-4,5-二苯咪唑二聚物、2，4,5-三芳香基咪 唑二聚物等2,4，5-三芳香基咪唑二聚物：9-苯基吖啶、 1，7_雙（9,9|-吖啶基）庚烷等吖啶衍生物；1-[9-乙基-6-(2-甲基苯甲醯基）-9H-咔唑-3-基]-乙酮1-(0-乙醯肟）等肟酯 類；N-苯基甘胺酸；香豆素系化合物等。 該等自由基聚合起始劑可單獨使用或組合兩種以上使 用。 自由基聚合起始劑（B2)的含量，係以相對於鹼可溶性 樹脂（A2) 100質量份而言的0.05〜30質量份爲佳，0.5〜 1 0質量份爲較佳。若在該範圍內，則負型感光性樹脂組 成物之硬化性良好。 &lt;可藉由酸或自由基進行交聯的化合物（c)&gt; 可藉由酸或自由基進行交聯的化合物，只要是可藉由 上述（B)成分所產生的酸或自由基，使其他化合物之間或 使該化合物彼此交聯的物質，則可不受特別限定地使用。 具體而言，在化學增幅型的情況下，可採用交聯劑（C 1 ), 在自由基聚合型的情況下，可採用聚合性單體（C2) ^ (交聯劑（C1)) -27- 201211681 交聯劑（Cl)係藉由上述光酸產生劑（B1)所產生的酸之 作用，而與鹼可溶性樹脂（A1)進行交聯。 這種交聯劑並未受到特別限定，而可採用例如在分子 中具有至少兩個經烷醚化之胺基之化合物。此化合物可列 舉（多）羥甲基化三聚氰胺、（多）羥甲基化甘脲、（多）羥甲 基化苯并胍胺、（多）羥甲基化尿素等一部分或全部的活性 羥甲基發生烷醚化之含氮化合物》烷基可列舉甲基、乙 基、丁基、或該等的混合物，亦可含有一部分自行縮合而 成的寡聚物成分。具體而言，可列舉六甲氧基甲基化三聚 氰胺、六丁氧基甲基化三聚氰胺、四甲氧基甲基化甘脲、 四丁氧基甲基化甘脲等。 該等交聯劑可單獨使用或組合兩種以上使用。 交聯劑（C 1)的含量，係以相對於鹼可溶性樹脂 (Al)100質量份而言的5〜50質量份爲佳，10〜30質量份 爲較佳。若在該範圍內，則負型感光性樹脂組成物之硬化 性、圖案化特性良好。 (聚合性單體（C2)) 聚合性單體（C2)，係藉由上述自由基聚合起始劑（B2) 所產生的自由基的作用，互相交聯而高分子化。 這種聚合性單體，已知有單官能單體與多官能單體。 單官能單體可列舉（甲基）丙烯醯胺、羥甲基（甲基）丙 烯醯胺、甲氧基甲基（甲基）丙烯醯胺、乙氧基甲基（甲基） 丙烯醯胺、丙氧基甲基（甲基）丙烯醯胺、丁氧基甲氧基甲 基（甲基）丙烯醯胺、N-羥甲基（甲基）丙烯醯胺、N-羥甲基 -28- 201211681 (甲基）丙烯醯胺、（甲基）丙烯酸、富馬酸、馬來酸、馬來 酸酐、伊康酸、伊康酸酐、檸康酸、檸康酸酐、巴豆酸、 2 -丙烯醯胺-2-甲基丙磺酸、第三丁基丙烯醯胺磺酸、（甲 基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丁酯、 (甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸環己酯、（甲基） 丙烯酸2-羥乙酯、（甲基）丙烯酸2-羥丙酯、（甲基）丙烯酸 2-羥丁酯、（甲基）丙烯酸2-苯氧基-2-羥丙酯、2-(甲基）丙 烯醯氧基_2_羥丙基酞酸酯、甘油單（甲基）丙烯酸酯、（甲 基）丙烯酸四氫呋喃甲酯、（甲基）丙烯酸二甲胺基酯、（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、苯二甲酸衍生物之半（甲 基）丙烯酸酯等。該等單官能單體可單獨使用或組合兩種 以上使用。 另一方面，多官能單體可列舉乙二醇二（甲基）丙烯酸 酯、二乙二醇二（甲基）丙烯酸酯、四乙二醇二（甲基）丙烯 酸酯、聚乙二醇二（甲基）丙烯酸酯、丙二醇二（甲基）丙烯 酸酯、聚丙二醇二（甲基）丙烯酸酯、丁二醇二（甲基）丙烯 酸酯、新戊二醇二（甲基）丙烯酸酯、1，6-己二醇二（甲基） 丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸酯、甘油二（甲 基）丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸 酯、二季戊四醇四（甲基）丙烯酸酯、二季戊四醇五丙烯酸 酯 '二季戊四醇六丙烯酸酯、季戊四醇二（甲基）丙烯酸 酯、季戊四醇三（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯 酸酯、二季戊四醇五（甲基）丙烯酸酯、二季戊四醇六（甲 -29 - 201211681 基）丙烯酸酯' 2,2-雙（4-(甲基）丙烯醯氧基二乙氧基苯基） 丙烷、2,2-雙（4-(甲基）丙烯醯氧基聚乙氧基苯基）丙烷、 (甲基）丙烯酸2-羥基-3-(甲基）丙烯醯氧基丙酯、乙二醇二 縮水甘油醚二（甲基）丙烯酸酯、二乙二醇二縮水甘油醚二 (甲基）丙烯酸酯、苯二甲酸二縮水甘油酯二（甲基）丙烯酸 酯、甘油三丙烯酸酯、甘油多縮水甘油醚多（甲基）丙烯酸 酯、胺甲酸乙酯（甲基）丙烯酸酯（亦即甲伸苯基二異氰酸 酯）、三甲基六亞甲基二異氰酸酯與六亞甲基二異氰酸酯 與（甲基）丙烯酸2-羥乙酯之反應產物、亞甲基雙（甲基）丙 烯醯胺、（甲基）丙烯醯胺亞甲基醚、多價醇與N-羥甲基 (甲基）丙烯醯胺之縮合物等多官能單體、或三丙烯醯基六 氫三嗪（Triacrylformal)等。該等多官能單體可單獨使用或 組合兩種以上使用。 聚合性單體（C2)的含量，係以相對於鹼可溶性樹脂 (A2)100質量份而言的10〜100質量份爲佳，30〜80質量 份爲較佳。若在該範圍內，則負型感光性樹脂組成物之硬 化性、圖案化特性良好。 〈特定構造之環氧樹脂（D)&gt; 特定構造之環氧樹脂，如下述一般式（D-1)所表示。 藉著將這種環氧樹脂添加至負型感光性樹脂組成物’在製 成負型感光性樹脂組成物時，可形成顯像性' 解像性、圖 案化後的接著性優異的感光性樹脂層。 -30- 201211681 I化9】In the above general formula (B1-4), Rb7, Rb8 and Rb9 are each independently and represent a halogenated alkyl group having 1 to 6 carbon atoms. In addition, as other photoacid generators, bis(p-toluenesulfonyl)diazomethane, methylsulfonyl p-toluenesulfonyldiazomethane, 丨_cyclohexyl extended-24-201211681 thiol-1- (1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane'bis(1-methylethylsulfonyl) Nitrogen methane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, bis(4-ethylbenzenesulfonyl)diazomethane, double (3) -Methylbenzenesulfonyl) Diazomethane, bis(4-methoxyphenylsulfonyl)diazomethane, bis(4-fluorophenylsulfonyl)diazomethane, bis(4-chlorophenylsulfonate) Diazomethane diazomethane such as diazomethane, bis(4-t-butylphenylsulfonyl)diazomethane, 2-methyl-2-(p-toluenesulfonyl)propene benzene, 2-(cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane, 2-methanesulfonyl-2-methyl-(p-methylthio)propanylbenzene, 2.4-dimethyl-2- a sulfonylcarbonylalkane such as (p-toluenesulfonyl)pentan-3-one; 1-p-toluenesulfonyl-1-cyclohexylcarbonyldiazomethane , 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-cyclohexyl Sulfomethyl-3,3-dimethyl-2-butanone, 1-diazo-1-(1,1-dimethylethylsulfonyl)-3,3-dimethyl-2-butene Ketone, 1-ethenyl-1-(1-methylethylsulfonyl)diazomethane, 1-diazo-1-(p-toluenesulfonyl)-3,3-dimethyl-2- Butanone, 1-diazo-1-phenylsulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1-(p-toluenesulfonyl)-3-methyl-2- Butanone, 2-diazo-2-(p-toluenesulfonyl)acetic acid cyclohexyl ester, 2-diazo-2-benzenesulfonyl acetic acid-t-butyl, 2-diazo-2-methanesulfonate Isopropyl acetate, cyclohexyl 2-diazo-2-benzenesulfonyl acetate, sulfonylcarbonyl diazomethane such as 2-diazo-2-(p-toluenesulfonyl)acetate-t-butyl a nitrobenzyl derivative such as p-toluenesulfonic acid-2-nitrobenzyl, p-toluenesulfonic acid-2,6-dinitrobenzyl, p-trifluoromethylbenzenesulfonic acid-2.4-dinitrobenzyl; gallnut Phenolic mesylate, gallic acid benzenesulfonate, galliclophenol p-toluenesulfonate, gallicol-25-201211681 p-methoxybenzene Sulfonate, mesitylene sulfonate of gallic phenol, benzyl sulfonate of gallic phenol, mesylate of alkyl gallate, benzenesulfonate of alkyl gallate, gallic acid a p-toluenesulfonate of an alkyl ester, an alkyl ester of gallic acid (a carbon number of the alkyl group of 1 to 15), a p-methoxybenzenesulfonate, a mesitylene ester of an alkyl gallate, An ester of a polyhydroxy compound such as a benzilsulfonate of a gallic acid ester and an aliphatic or aromatic sulfonic acid. The photoacid generator may be used alone or in combination of two or more kinds of photoacid generators (B 1 ) in an amount of 0.05 to 30 parts by mass based on 100 parts by mass of the alkali-soluble resin (A 1 ). Preferably, 〇.1~1〇 parts by mass is preferred. When it is within this range, the negative photosensitive resin composition has good curability. (Radical Polymerization Initiator (B2)) The radical polymerization initiator (B 2) is not particularly limited, and a conventionally known compound can be used. Specific examples thereof include thioxanthone derivatives such as 2,4-diethylthioxanthone, isopropylthioxanthone, 2-oxythioxanthone, and 2,4-dimethylthioxanthone; and diphenylbenzene; Ketone, N,N'-tetramethyl-4,4'-diaminobenzophenone, n,N,-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy- 4'-Dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1_(4-ythylphenyl)-butanone-L2-methyl-^ [4-(methyl Aromatic ketones such as thio)phenyl]-2-carbinyl-acetone-1; 2-ethyl oxime, phenanthrene, 2-tert-butyl fluorene, octamethyl hydrazine, ι, 2 benzo Bismuth, 2,3-benzopyrene, 2-phenyl oxime, 2,3-diphenyl hydrazine, chloranil, 2-methyl awake, 1,4 -naphthalene, 9,10-phenanthrene Awake, 2-methyl-1,4-naphthoquinone, 2,3-dimethylhydrazine and the like; benzoin methyl ether, benzoin acetic acid, -26-201211681 benzoin phenyl ether and other benzoin ether compounds; benzoin, methyl benzoin a benzoin compound such as ethyl benzoin; a benzyl derivative such as benzyl dimethyl ketal; 2-(o-chlorophenyl)·4,5-dibenzimidazole dimer, 2-(o-chlorophenyl)· 4,5-bis(methoxyphenyl)imidazole dimerization , 2-(o-fluorophenyl)-4,5-dibenzimidazole dimer, 2-(o-methoxyphenyl)-4,5-dibenzimidazole dimer, 2_(p-methoxybenzene) 2,4,5-triarylimidazole dimer such as 4,5-dibenzimidazole dimer, 2,4,5-triaryl imidazole dimer: 9-phenyl acridine, 1 , acridine derivative such as 7-bis(9,9|-acridinyl)heptane; 1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazole-3- Anthracene esters such as ethyl]-ethanone 1-(0-acetamidine); N-phenylglycine; coumarin compounds. These radical polymerization initiators may be used singly or in combination of two or more. The content of the radical polymerization initiator (B2) is preferably 0.05 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the alkali-soluble resin (A2). When it is within this range, the negative photosensitive resin composition is excellent in curability. &lt;Compound (c) which can be crosslinked by an acid or a radical&gt; A compound which can be crosslinked by an acid or a radical, as long as it is an acid or a radical which can be produced by the above (B) component, A substance which crosslinks other compounds or crosslinks the compounds with each other can be used without particular limitation. Specifically, in the case of a chemical amplification type, a crosslinking agent (C 1 ) can be used, and in the case of a radical polymerization type, a polymerizable monomer (C2) ^ (crosslinking agent (C1)) can be used - 27-201211681 The crosslinking agent (Cl) is crosslinked with the alkali-soluble resin (A1) by the action of an acid generated by the above photoacid generator (B1). The crosslinking agent is not particularly limited, and for example, a compound having at least two alkyl etherified amine groups in the molecule can be used. Examples of the compound include (poly)hydroxymethylated melamine, (poly)methylolated glycoluril, (poly)methylolated benzoguanamine, (poly)methylolated urea, etc., some or all of the active hydroxyl groups. The nitrogen-containing compound in which the methyl group is etherified can be exemplified by a methyl group, an ethyl group, a butyl group, or a mixture thereof, or a part of an oligomer component obtained by self-condensation. Specific examples thereof include hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, and the like. These crosslinking agents may be used singly or in combination of two or more. The content of the crosslinking agent (C1) is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the alkali-soluble resin (Al). When it is in this range, the negative photosensitive resin composition has good curability and patterning properties. (Polymerizable monomer (C2)) The polymerizable monomer (C2) is crosslinked and polymerized by the action of a radical generated by the radical polymerization initiator (B2). As such a polymerizable monomer, a monofunctional monomer and a polyfunctional monomer are known. Examples of the monofunctional monomer include (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide. , propoxymethyl (meth) acrylamide, butoxy methoxymethyl (meth) acrylamide, N- hydroxymethyl (meth) acrylamide, N-hydroxymethyl -28 - 201211681 (Methyl) acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-propene Hydrazine-2-methylpropanesulfonic acid, t-butyl acrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate 2-ethylhexyl ester, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( 2-phenoxy-2-hydroxypropyl methacrylate, 2-(meth) propylene methoxy-2-hydroxypropyl phthalate, glycerol mono(meth) acrylate, (meth) acrylate Tetrahydrofuran methyl ester , dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2, 2, 3, 3- (meth) acrylate A semi-(meth) acrylate such as tetrafluoropropyl ester or a phthalic acid derivative. These monofunctional monomers may be used singly or in combination of two or more. On the other hand, examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and polyethylene glycol II. (Meth) acrylate, propylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, butane diol di(meth) acrylate, neopentyl glycol di(meth) acrylate, 1 , 6-hexanediol di(meth) acrylate, trimethylolpropane tri(meth) acrylate, glycerol di(meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetra ( Methyl) acrylate, dipentaerythritol pentaacrylate 'dipentaerythritol hexaacrylate, pentaerythritol di(meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol five (a) Acrylate, dipentaerythritol hexa(methyl-29 - 201211681 acrylate) acrylate 2,2-bis(4-(methyl)propenyloxydiethoxyphenyl)propane, 2,2-dual ( 4-(methyl)-propyl Eneoxypolyethoxyphenyl)propane, 2-hydroxy-3-(methyl)propenyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, Diethylene glycol diglycidyl ether di(meth) acrylate, diglycidyl phthalate di(meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth) acrylate, amine Reaction product of ethyl formate (meth) acrylate (also known as methyl phenyl diisocyanate), trimethyl hexamethylene diisocyanate and hexamethylene diisocyanate with 2-hydroxyethyl (meth) acrylate a polyfunctional monomer such as methylene bis(meth) acrylamide, (meth) acrylamide dimethyl ether, a condensate of a polyvalent alcohol and N-methylol (meth) acrylamide, Or triacrylformal or the like. These polyfunctional monomers may be used singly or in combination of two or more. The content of the polymerizable monomer (C2) is preferably 10 to 100 parts by mass based on 100 parts by mass of the alkali-soluble resin (A2), and preferably 30 to 80 parts by mass. When it is in this range, the negative photosensitive resin composition has good hardenability and patterning properties. <Epoxy resin (D) of a specific structure> The epoxy resin of a specific structure is represented by the following general formula (D-1). By adding such an epoxy resin to the negative photosensitive resin composition', when the negative photosensitive resin composition is formed, it is possible to form developability, resolution, and excellent adhesion after patterning. Resin layer. -30- 201211681 I 9]

(D-1) 上述一般式（D-l)中，RdI及Rd2各自獨立，表示氫原 子或甲基。Rd3〜Rd6各自獨立，表示氫原子、甲基、氯原 子、或溴原子，其中係以氫原子爲佳。A表示伸乙氧基乙 基、二（伸乙氧基）乙基、三（伸乙氧基）乙基、伸丙氧基丙 基、二（伸丙氧基）丙基、三（伸丙氧基）丙基、或碳數2〜 15之伸烷基。η爲自然數，其平均爲1.2〜5。 上述一般式（D-1)所表示之環氧樹脂的具體例子，可 列舉下述式（D-1-1)〜（D-1-14)所表示之樹脂》 該等化合物可單獨使用或組合兩種以上使用。 ί化1 〇 S7&quot;0 ,0、 ο(D-1) In the above general formula (D-1), RdI and Rd2 are each independently represented by a hydrogen atom or a methyl group. Rd3 to Rd6 are each independently a hydrogen atom, a methyl group, a chlorine atom or a bromine atom, and a hydrogen atom is preferred. A represents ethoxyethyl, di(exetyloxy)ethyl, tris(ethyloxy)ethyl, propoxypropyl, bis(propoxy)propyl, tris (extended) An oxy) propyl group or an alkylene group having a carbon number of 2 to 15. η is a natural number and has an average of 1.2 to 5. Specific examples of the epoxy resin represented by the above general formula (D-1) include resins represented by the following formulas (D-1-1) to (D-1-14). These compounds may be used singly or Use two or more combinations.化化1 〇 S7&quot;0,0, ο

'〇 丫 〇O-fO^· I 〇 人。〜〇v^〇〜0 丫 (D-1-2) 0 0 0 人 ^4^J〇^〇^v〇^°Y°^f〇4〇-V7 Jn 〇 -31 - 201211681 0*^X7 (D-1-6) ο 、〇九0广〇 九0 丫 (D-1-7) 【化11 )Ό4&quot;0~( ρ^0&quot;〇/^Ο~&lt; ^Ο-Ό-*c Λ.'〇 丫 〇O-fO^· I 〇 person. ~〇v^〇~0 丫(D-1-2) 0 0 0人^4^J〇^〇^v〇^°Y°^f〇4〇-V7 Jn 〇-31 - 201211681 0*^X7 (D-1-6) ο, 〇九0广〇九0 丫(D-1-7) 【化11】Ό4&quot;0~( ρ^0&quot;〇/^Ο~&lt; ^Ο-Ό-* c Λ.

S^O 'Ογο-Ο^Ό^' 〇^^ς7 ,0γ°-〇^〇^ Ό-^7 ，。丫〇~Ό〇^. 〇^Χ7 Ο (D-1-8) (D-1-9) (D-1-10) (D-M1) &gt;γ〇-〇^〇4( &gt;ΧΝ^ (D-M2)S^O 'Ογο-Ο^Ό^' 〇^^ς7 ,0γ°-〇^〇^ Ό-^7 ,.丫〇~Ό〇^. 〇^Χ7 Ο (D-1-8) (D-1-9) (D-1-10) (D-M1) &gt;γ〇-〇^〇4( &gt;ΧΝ ^ (D-M2)

Ό-Ό-

-OHhO^t0^3 (D-1-13) (CM-14) (D)成分的含量，係以相對於（Α)成分1〇〇質量份而言 的1〜40質量份爲佳’ 5〜35質量份爲較佳。若在該範圍 內，則在製成負型感光性樹脂組成物時，可形成顯像性、 解像性、圖案化後的接著性優異的感光性樹脂層。 &lt;溶劑（S)&gt; 溶劑（S)不受特別限制，而可採用以往負型感光性樹 脂組成物之溶劑所周知之物質。 -32- 201211681 具體而言，可列舉乙二醇單甲醚醋酸酯、乙二醇 醚醋酸酯等乙二醇單烷醚醋酸酯類；丙二醇單甲醚、 醇單乙醚、丙二醇單丙醚、丙二醇單丁醚等丙二醇單 類；丙二醇二甲醚、丙二醇二乙醚、丙二醇二丙醚、 醇二丁醚等丙二醇二烷醚類；丙二醇單甲醚醋酸酯、 醇單乙醚醋酸酯、丙二醇單丙醚醋酸酯、丙二醇單丁 酸酯等丙二醇單烷醚醋酸酯類；乙基溶纖劑、丁基溶 等溶纖劑類；丁基卡必醇等卡必醇類；乳酸甲酯、乳 酯、乳酸正丙酯、乳酸異丙酯等乳酸酯類；醋酸乙酯 酸正丙酯、醋酸異丙酯、醋酸正丁酯、醋酸異丁酯、 正戊酯、醋酸異戊酯、丙酸異丙酯、丙酸正丁酯、丙 丁酯等脂肪族羧酸酯類；3-甲氧基丙酸甲酯、3-甲氧 酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、丙 甲酯、丙酮酸乙酯等其他酯類；甲苯、二甲苯等芳香 類；2-庚酮、3_庚酮、4-庚酮、環己酮等酮類；N-二 甲醯胺、N-甲基乙醯胺、N，N-二甲基乙醯胺、N-甲基 烷酮等醯胺類；r-丁內酯等內酯類等。 該等溶劑可單獨使用或組合兩種以上使用。 (S)成分的含量並未受到特別限定，而一般而言 型感光性樹脂組成物的固體成分濃度成爲10〜60質 之量爲佳，成爲20〜50質量％之量爲較佳。 &lt;其他成分&gt; 本發明所關連之負型感光性樹脂組成物，亦可依 單乙 丙二 烷醚 丙二 丙二 醚醋 纖劑 酸乙 '醋 醋酸 酸異 基丙 酮酸 族烴 甲基 吡咯 ，負 量％ 照需 -33- 201211681 要而含有附帶添加的樹脂、安定劑、著色劑、界面活性劑 等。 &lt;感光性乾薄膜&gt; 本發明所關連之感光性乾薄膜，係具有基材薄膜、與 形成於該基材薄膜表面之感光性樹脂層，此感光性樹脂 層，係由本發明所關連之負型感光性樹脂組成物所構成。 基材薄膜係以具有光透過性爲佳。具體而言，可列舉 聚對苯二甲酸乙二酯（PET)薄膜、聚丙烯（PP)薄膜、聚乙 烯（PE)薄膜等，而從光透過性及破裂強度的平衡性優異這 點來考量，係以聚對苯二甲酸乙二酯（PET)薄膜爲佳。 在基材薄膜上形成感光性樹脂層時，係使用塗佈器、 棒式塗佈機、線棒式塗佈機、輥式塗佈機、淋幕式塗佈機 等，以使乾燥膜厚爲5〜ΙΟΟμπι的方式，將本發明所關連 之負型感光性樹脂組成物塗佈在基材薄膜上，並使其乾 燥。 本發明所關連之感光性乾薄膜亦可在感光性樹脂層上 進一步具有保護薄膜。此保護薄膜可列舉聚對苯二甲酸乙 二酯（PET)薄膜、聚丙烯（ΡΡ)薄膜、聚乙烯（ΡΕ)薄膜等。 &lt;受光裝置&gt; 本發明所關連之受光裝置，係具備：搭載有半導體元 件之支持基板；支持基板呈對向之透明基板；與設置於支 持基板與透明基板之間之間隔物，且上述間隔物係本發明 -34- 201211681 所關連之負型感光性樹脂組成物之硬化物。 將受光裝置的剖面模式圖表示於圖1。如圖1所示 般，受光裝置1係具備：支持基板10;由搭載於支持基 板10上之半導體元件所構成之受光部11;與支持基板10 呈對向之透明基板12:與設置於支持基板10與透明基板 1 2之間之間隔物1 3。 該受光裝置1可採用例如以下的方式製造。 首先將感光性乾薄膜貼附在支持基板10上，以使受 光部11與感光性樹脂層相接。接下來，對於感光性樹脂 層之中成爲間隔物的部分照射紫外線等活性射線，因應必 要以40〜200°c將感光性樹脂層加熱。接下來，藉由將感 光性乾薄膜之基材薄膜剝離，並藉由四甲基氫氧化銨 (TMAH)水溶液等顯像液使未硬化部分溶解除去，而形成 間隔物1 3。然後，在間隔物1 3上載置透明基板1 2，藉由 熱壓接，可得到受光裝置1。熱壓接的條件係例如1 〇〇〜 2 00°C、0.05 〜100MPa° 另外，在上述例子中，藉由貼附感光性乾薄膜而使感 光性樹脂層形成於受光部11上’然而並不受此限定。例 如亦可藉由在受光部1 1上塗佈上述負型感光性樹脂組成 物，並使其乾燥，以使感光性樹脂層形成於受光部11 上。從膜厚均勻性變高這點看來’塗佈方法係以旋轉塗佈 爲佳。由於膜厚均勻性變高，在圖案化後’各間隔物13 與透明基板1 2的接著面整齊’接著性變得良好。 -35- 201211681 [實施例] 以下，對於本發明之實施例作說明，而本發明之範圍不 受到該等實施例所限定。 &lt;實施例1〜1 1、比較例1〜4 &gt; 依照表1所記載之配方（單位爲質量份），將鹼可溶性 樹脂、光酸產生劑、交聯劑、環氧樹脂及溶劑加以混合， 調製出實施例1〜7、比較例1、2的負型感光性樹脂組成 物》 另外，依照表2所記載之配方（單位爲質量份），將鹼 可溶性樹脂、自由基聚合起始劑、聚合性單體、環氧樹脂 及溶劑加以混合，調製出實施例8〜1 1、比較例3、4的 負型感光性樹脂組成物。 表1、2中各成分的詳細如以下所述。 鹼可溶性樹脂 A:聚羥基苯乙烯（質量平均分子量 2500) 鹼可溶性樹脂B:羥基苯乙烯/苯乙烯= 80/20(莫耳比） 之共聚物（質量平均分子量2500) 鹼可溶性樹脂C :以間甲酚/對甲酚：60/40(質量比） 將間甲酚與對甲酚加以混合，並加入福馬林，依照常法進 行加成縮合所得到的甲酚酚醛樹脂（質量平均分子量 20000) 鹼可溶性樹脂D:丙烯酸2-甲氧基乙酯/丙烯酸正丁 酯/二環戊基甲基丙烯酸酯/甲基丙烯酸/甲基丙烯酸2-羥 -36- 201211681 乙酯=4/4/65/20/7(莫耳比）之共聚物（質量平均分子量 20000) 鹼可溶性樹脂E:丙烯酸2_甲氧基乙酯/丙烯酸正丁 酯/二環戊基甲基丙烯酸酯/甲基丙烯酸/甲基丙烯酸2-羥 乙酯/N-乙烯基吡咯烷酮=4/4/66/1 6/9/1(莫耳比）之共聚物 (質量平均分子量20000) 光酸產生劑A: [2-(丙基磺醯氧基醯亞胺基）-2,3-二氫 噻吩-3-亞基] (鄰甲苯基）乙腈（Ciba Specialty Chemicals股份有限 公司製，IRGACURE PAG103) 光酸產生劑B:二苯[4-(苯基硫代）苯基]鏑三氟參五 氟乙基磷酸鹽（San-Apro股份有限公司製，CPI-210S) 光酸產生劑C: 4-(2-氯-4-苯甲醯基苯基硫代）苯基雙 (4-氟苯基）毓六氟銻酸鹽（ADEKA股份有限公司製， Optomer SP-172) 光酸產生劑D: α,α-雙（丁磺醯氧基醯亞胺基）間苯 二乙腈（上述式（Β 1-3-3)所表示之化合物。以日本特開平 9-2〇8 5 54號公報之記載爲基準進行合成。） 光酸產生劑Ε: 〇：-(甲磺醯氧基醯亞胺基）-1-(對甲氧 基苯基）乙腈（以日本特開平9-95479號公報之記載爲基準 進行合成。） 自由基聚合起始劑 A : 1-[9 -乙基-6-(2 -甲基苯甲醯 基）-9H -咔唑-3-基]乙酮-1-(0-乙醯肟）（Ciba Specialty Chemicals股份有限公司製，CGI242) -37- 201211681 交聯劑A: 2,4,6-參[雙（甲氧基甲基）胺基]-1，3,5-三嗪 (三和化學股份有限公司製，Mw-IOOLM) 交聯劑B: 1，3,4,6-肆（甲氧基甲基）甘脲（三和化學股 份有限公司製，Mw-270) 聚合性單體A:二季戊四醇四丙烯酸酯（DP Η A) 聚合性單體B:三羥甲基丙烷三（甲基）丙烯酸酯（東亞 合成股份有限公司製，ARON IX M3 09) 聚合性單體C:聚乙二醇二丙烯酸酯（東亞合成股份 有限公司製，ARONIX M240) 環氧樹脂A:在上述式（D-1-1)之中，n= 1.6 (平均値） 之樹脂（DIC股份有限公司製，EXA48 5 0- 1 5 0) 環氧樹脂B:在上述式（D-1-1)之中，η=1·2(平均値） 之樹脂（DIC股份有限公司製，ΕΧΑ4850- 1 000) 環氧樹脂C: 2官能雙酚Α型環氧樹脂（Japan Epoxy Resin股份有限公司製，jER828) 溶劑A:丙二醇單甲醚醋酸酯 &lt;顯像性的評估&gt; 以旋轉塗佈機將實施例1〜1 1、比較例1〜4的負型 感光性樹脂組成物塗佈在8英吋矽晶圓上，並在1 20 °C乾 燥5分鐘，得到膜厚50μιη的感光性樹脂層。接下來，隔 著光罩以250mJ/cm2的照射量對此感光性樹脂層照射ghi 射線。接下來，在Π 5 °C熱板上加熱5分鐘之後，藉由採 用2.38質量％四甲基氫氧化銨水溶液的覆液顯像（60秒鐘 -38- 201211681 χ 2)，使未硬化部分溶解除去，而所形成具有線與間隙的 圖型，係包含了線寬4 0 μ m之間隙圖型。然後，將在間隙 部分沒有殘渣存在的情況評爲〇，有殘渣存在的情況評爲 X，評估感光性樹脂層的顯像性。將結果揭示於表1、2。 &lt;接著性的評估&gt; 以旋轉塗佈機將實施例1〜11、比較例1〜4的負型 感光性樹脂組成物塗佈在8英吋矽晶圓上，並在1 20°C乾 燥5分鐘，得到膜厚50μπι的感光性樹脂層。接下來，以 250mJ/cm2的照射量對此感光性樹脂層照射ghi射線，並 在115 °C熱板上加熱5分鐘。接下來，以1〇〇 °C、0.1 MPa 的條件將厚度0.7mm的玻璃基板熱壓接在加熱後的感光 性樹脂層之上。然後，將玻璃基板貼附住的情況評爲〇， 將沒有貼附的情況評爲X，評估感光性樹脂層的接著性。 將結果揭示於表1、2。 &lt;解像性的評估&gt; 以旋轉塗佈機將實施例1〜1 1、比較例1〜4的負型 感光性樹脂組成物塗佈8英吋矽晶圓上，並在1 20°C乾燥 5分鐘，得到膜厚50μιη的感光性樹脂層。接下來，隔著 光罩以2 50mJ/cm2的照射量對此感光性樹脂層照射ghi射 線》接下來，在1 1 5 °C熱板上加熱5分鐘之後，藉由採用 2.38質量％四甲基氫氧化銨水溶液的覆液顯像（60秒鐘 x2)，使未硬化部分溶解除去，而形成具有線與間隙的圖 39 - 201211681 型。然後，藉由改變光罩尺寸’求得極限解像度。將結果 揭示於表1、2。 &lt;殘膜率之評估&gt; 以旋轉塗佈機將實施例1〜11、比較例1〜4的負型 感光性樹脂組成物塗佈在8英吋矽晶圓上’並在1 20°c乾 燥5分鐘，得到膜厚50μιη的感光性樹脂層。接下來，以 2 5 0mJ/cm2的照射量對此感光性樹脂層照射ghi射線，並 在115 °C熱板上加熱5分鐘。進一步使用無塵烘箱，在 1 80°C加熱2小時。然後，求得加熱後的膜厚相對於原本 的膜厚之比例（％)，而評估殘膜率。將結果揭示於表1、 2 ° [表1] 實施例 比較例 1 2 3 4 5 6 7 1 2 鹼可溶性樹脂A 100 100 50 100 100 100 100 鹼可溶性樹脂B 100 50 鹸可溶忡樹脂C 100 光酸產生劑A 1 1 1 1 1 光酸產生劑B 3 光酸產牛劑C 3 光酸產牛劑D 2 光酸產生劑E 2 交聯劑A 11 11 11 11 11 11 11 11 交聯劑B 11 環氧樹脂A 30 30 30 30 30 環氧樹脂B 30 30 , 環氧樹脂C 30 溶劑A 100 100 100 100 100 100 100 100 100 顯像性 〇 〇 〇 〇 〇 〇 〇 X 〇 接著性 〇 〇 〇 〇 〇 〇 〇 〇 X 解像性_ 10 10 10 10 10 10 10 10 10 殘膜率(％) 90 88 90 88 80 90 90 90 90 -40 - 201211681 [表2] 實施例 比較例 8 9 10 11 3 4 鹼可溶性樹脂D 100 100 100 100 鹼可溶性樹脂E 100 100 自由基聚合起始劑A 6 6 6 6 6 6 衆饪単歡 6 6 6 6 聚合性單體B 20 20 25 30 20 20 聚合性車體C 20 20 20 20 20 環氧樹脂A 30 30 環氧樹脂B 30 30 環氯樹脂C 30 30 溶劑A 100 100 100 100 100 100 顯像性 〇 〇 〇 X X 接著性 〇 〇 〇 〇 〇 解像性(卿） 40 40 40 60 80 80 殘腠率(%) 85 85 85 88 86 85 由表1可知，在化學增幅型的負型感光性樹脂組成物 的情況中，實施例1〜7採用了含有上述一般式（D- 1 )所表 示之環氧樹脂之負型感光性樹脂組成物，其感光性樹脂層 之顯像性、解像性、圖案化後的接著性、殘膜率之任一者 皆優異。另一方面，比較例1採用了含有與上述一般式 (D-1)所表示之環氧樹脂相異的環氧樹脂之負型感光性樹 脂組成物，其顯像性較差，採用不含環氧樹脂的負型感光 性樹脂組成物之比較例2，其接著性較差。 將上述 &lt; 顯像性的評估 &gt; 之中，實施例1所得到具有 線與間隙的圖型表示於圖2，比較例1所得到具有線與間 隙的圖型表示於圖3。在圖中，所觀察到最白的部分爲間 隙部分。由此圖2、3可知，在實施例1中，在間隙部分 沒有殘渣存在，相對於此，在比較例1中，存在很多殘 渣。 像這樣顯像性出現差異，推測是因爲在將感光性樹脂 -41 - 201211681 層加熱時、比較例1所使用通常的環氧樹脂會與交聯劑發 生反應，殘渣容易殘留，相對於此，實施例1〜7所使用 的上述一般式（D-1)所表示之環氧樹脂與交聯劑反應性遲 鈍，殘渣不易殘留。 另外由表2可知，在自由基聚合型的負型感光性樹脂 組成物的情況中，實施例8〜11採用了含有上述一般式 (D-1)所表示之環氧樹脂之負型感光性樹脂組成物，其感 光性樹脂層之顯像性、解像性、圖案化後的接著性、殘膜 率之任一者皆優異。另一方面，比較例3、4採用了含有 與上述一般式（D-1)所表示之環氧樹脂相異的環氧樹脂之 負型感光性樹脂組成物，其顯像性、解像性較差。 其中顯像性出現差異，推測是因爲在將感光性樹脂層 加熱時’比較例3、4所使用通常的環氧樹脂會與鹼可溶 性樹脂之羧基發生反應，殘渣容易殘留，相對於此，實施 例8〜11所使用的上述一般式所表示之環氧樹脂與 羧基的反應性遲鈍，殘渣不易殘留。 【圖式簡單說明】 圖1表示受光裝置的剖面模式圖。 圖2表示實施例1所得到具有線與間隙的圖型。 圖3表示比較例1所得到具有線與間隙的圖型。 【主要元件符號說明】 1 :受光裝置 -42- 201211681 1 〇:支持基板 1 1 :受光部 1 2 :透明基板 1 3 :間隔物 -43-OHhO^t0^3 (D-1-13) (CM-14) The content of the component (D) is preferably 1 to 40 parts by mass based on 1 part by mass of the (Α) component. ～35 parts by mass is preferred. When the negative photosensitive resin composition is formed in this range, a photosensitive resin layer excellent in developability, resolution, and adhesion after patterning can be formed. &lt;Solvent (S)&gt; The solvent (S) is not particularly limited, and a material known from the solvent of the conventional negative photosensitive resin composition can be used. -32- 201211681 Specifically, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and glycol ether acetate; propylene glycol monomethyl ether, alcohol monoethyl ether, propylene glycol monopropyl ether, Propylene glycol monobutyl ether and other propylene glycol mono-type; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, alcohol dibutyl ether and other propylene glycol dialkyl ethers; propylene glycol monomethyl ether acetate, alcohol monoethyl ether acetate, propylene glycol monopropyl Propylene glycol monoalkyl ether acetates such as ether acetate, propylene glycol monobutyrate; ethyl cellosolve, cellosolve such as butyl solution; carbitol such as butyl carbitol; methyl lactate, lactate, lactic acid Lactate esters such as n-propyl ester and isopropyl lactate; n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl ester, isoamyl acetate, isopropyl propionate , aliphatic carboxylic acid esters such as n-butyl propionate and butyl butyrate; methyl 3-methoxypropionate, ethyl 3-methoxyate, methyl 3-ethoxypropionate, 3-ethoxyl Other esters such as ethyl propionate, propyl methyl ester and ethyl pyruvate; aromatics such as toluene and xylene; 2-heptanone a ketone such as heptanone, 4-heptanone or cyclohexanone; N-dimethylamine, N-methylacetamide, N,N-dimethylacetamide, N-methylalkanone, etc. Indoleamines; lactones such as r-butyrolactone. These solvents may be used singly or in combination of two or more. The content of the component (S) is not particularly limited, and the solid content of the photosensitive resin composition is preferably 10 to 60% by mass, and preferably 20 to 50% by mass. &lt;Other components&gt; The negative photosensitive resin composition to which the present invention is related may also be a methyl ethyl propylene ether propylene dipropylene ether vinegar acid ethyl acetyl acetonate acetic acid Pyrrole, % by weight -33-201211681 Contains added resin, stabilizer, colorant, surfactant, etc. &lt;Photosensitive dry film&gt; The photosensitive dry film to which the present invention relates is a base film and a photosensitive resin layer formed on the surface of the base film, and the photosensitive resin layer is related to the present invention. A negative photosensitive resin composition is used. The base film is preferably light transmissive. Specifically, a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film, or the like is used, and the balance between light transmittance and breaking strength is considered. Preferably, a polyethylene terephthalate (PET) film is preferred. When a photosensitive resin layer is formed on a base film, an applicator, a bar coater, a bar coater, a roll coater, a curtain coater, or the like is used to make a dry film thickness. The negative photosensitive resin composition to which the present invention is applied is applied onto a substrate film in a manner of 5 to ΙΟΟμπι, and dried. The photosensitive dry film to which the present invention is applied may further have a protective film on the photosensitive resin layer. Examples of the protective film include a polyethylene terephthalate (PET) film, a polypropylene film, a polyethylene film, and the like. &lt;Light-receiving device&gt; The light-receiving device to which the present invention relates includes a support substrate on which a semiconductor element is mounted, a transparent substrate on which the support substrate is opposed, and a spacer provided between the support substrate and the transparent substrate, and the above The spacer is a cured product of the negative photosensitive resin composition associated with the present invention -34-201211681. A cross-sectional schematic view of the light receiving device is shown in Fig. 1. As shown in FIG. 1, the light-receiving device 1 includes a support substrate 10, a light-receiving portion 11 composed of a semiconductor element mounted on the support substrate 10, and a transparent substrate 12 opposed to the support substrate 10: A spacer 13 between the substrate 10 and the transparent substrate 12. The light receiving device 1 can be manufactured, for example, in the following manner. First, a photosensitive dry film is attached to the support substrate 10 so that the light receiving portion 11 is in contact with the photosensitive resin layer. Then, the portion to be a spacer in the photosensitive resin layer is irradiated with an active ray such as ultraviolet ray, and the photosensitive resin layer is heated at 40 to 200 ° C. Next, the substrate 13 of the photosensitive dry film is peeled off, and the unhardened portion is dissolved and removed by a developing solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution to form a spacer 13. Then, the transparent substrate 1 is placed on the spacer 13 and the light receiving device 1 is obtained by thermocompression bonding. The condition of the thermocompression bonding is, for example, 1 〇〇 to 200 ° C, 0.05 to 100 MPa °. In the above example, the photosensitive resin film is formed on the light receiving portion 11 by attaching a photosensitive dry film. Not limited to this. For example, the negative photosensitive resin composition may be applied to the light-receiving portion 1 1 and dried to form a photosensitive resin layer on the light-receiving portion 11. From the viewpoint that the uniformity of the film thickness becomes high, the coating method is preferably spin coating. Since the uniformity of the film thickness is high, the adhesion between the spacers 13 and the subsequent surface of the transparent substrate 12 after patterning is improved. [35] [Embodiment] Hereinafter, the embodiments of the present invention will be described, and the scope of the present invention is not limited by the embodiments. &lt;Examples 1 to 1 1 and Comparative Examples 1 to 4 &gt; According to the formulation (unit: parts by mass) described in Table 1, an alkali-soluble resin, a photoacid generator, a crosslinking agent, an epoxy resin, and a solvent were added. The negative photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2 were prepared by mixing, and the alkali-soluble resin and radical polymerization initiation were carried out according to the formulation (unit: parts by mass) described in Table 2. The negative photosensitive resin composition of Examples 8 to 1 and Comparative Examples 3 and 4 was prepared by mixing a solvent, a polymerizable monomer, an epoxy resin, and a solvent. The details of the components in Tables 1 and 2 are as follows. Alkali-soluble resin A: polyhydroxystyrene (mass average molecular weight 2500) Alkali-soluble resin B: hydroxystyrene/styrene = 80/20 (mole ratio) copolymer (mass average molecular weight 2500) Alkali-soluble resin C: M-cresol/p-cresol: 60/40 (mass ratio) A mixture of m-cresol and p-cresol, and added to formalin, and the cresol novolac resin obtained by addition condensation according to the usual method (mass average molecular weight 20000) Alkali-soluble resin D: 2-methoxyethyl acrylate/n-butyl acrylate/dicyclopentyl methacrylate/methacrylic acid/methacrylic acid 2-hydroxy-36- 201211681 Ethyl ester=4/4/ 65/20/7 (Morby) copolymer (mass average molecular weight 20000) Alkali soluble resin E: 2-methoxyethyl acrylate / n-butyl acrylate / dicyclopentyl methacrylate / methacrylic acid /Copolymer of 2-hydroxyethyl methacrylate/N-vinylpyrrolidone=4/4/66/1 6/9/1 (mole ratio) (mass average molecular weight 20000) Photoacid generator A: [2 -(propylsulfonyloxyindenido)-2,3-dihydrothiophene-3-ylidene] (o-tolyl)acetonitrile (Ciba Specialty Chemicals has Company, IRGACURE PAG103) Photoacid generator B: Diphenyl [4-(phenylthio)phenyl] fluorene trifluoropentafluoroethyl phosphate (CPI-210S, manufactured by San-Apro Co., Ltd.) Acid generator C: 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate (made by ADEKA Co., Ltd., Optomer SP-172 Photoacid generator D: α,α-bis(butylsulfonyloxyindolide)-isophthalonitrile (a compound represented by the above formula (Β 1-3-3). Synthesis is based on the description in 〇8 5 54.) Photoacid generator Ε: 〇:-(methylsulfonyloxyindolylene)-1-(p-methoxyphenyl)acetonitrile (in Japanese The synthesis is carried out on the basis of the description in Kaikai No. 9-95479.) Radical polymerization initiator A: 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole-3- Ethyl ketone-1-(0-acetamidine) (CGI 242, manufactured by Ciba Specialty Chemicals Co., Ltd.) -37- 201211681 Crosslinking agent A: 2,4,6-gin[bis(methoxymethyl) Amino]-1,3,5-triazine (Mw-IOOLM, manufactured by Sanwa Chemical Co., Ltd.) Crosslinking agent B: 1,3,4,6-肆Methoxymethyl) glycoluril (Mw-270, manufactured by Sanwa Chemical Co., Ltd.) Polymerizable monomer A: dipentaerythritol tetraacrylate (DP Η A) Polymerizable monomer B: trimethylolpropane tri Methyl) acrylate (ARON IX M3 09, manufactured by Toagosei Co., Ltd.) Polymerizable monomer C: polyethylene glycol diacrylate (ARONIX M240, manufactured by Toagosei Co., Ltd.) Epoxy resin A: in the above formula (D-1-1), n = 1.6 (average 値) resin (EXA48 5 0- 1 0 0, manufactured by DIC Corporation) Epoxy resin B: in the above formula (D-1-1) Medium, η = 1 · 2 (average 値) resin (manufactured by DIC Co., Ltd., ΕΧΑ 4850 - 1 000) Epoxy resin C: 2-functional bisphenol oxime type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., jER828) Solvent A: propylene glycol monomethyl ether acetate &lt;Evaluation of development property&gt; The negative photosensitive resin compositions of Examples 1 to 1 1 and Comparative Examples 1 to 4 were applied to 8 inches in a spin coater. The wafer was dried at 1 20 ° C for 5 minutes to obtain a photosensitive resin layer having a film thickness of 50 μm. Next, the photosensitive resin layer was irradiated with ghi rays at an irradiation dose of 250 mJ/cm 2 through a photomask. Next, after heating on a hot plate at 5 ° C for 5 minutes, the unhardened portion was made by liquid-covering using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (60 seconds - 38 - 201211681 χ 2). The pattern with lines and gaps formed by dissolution and removal includes a gap pattern with a line width of 40 μm. Then, the case where no residue was present in the gap portion was evaluated as 〇, and the case where the residue was present was evaluated as X, and the developability of the photosensitive resin layer was evaluated. The results are disclosed in Tables 1 and 2. &lt;Evaluation of Adhesiveness&gt; The negative photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 4 were applied onto an 8-inch wafer by a spin coater at 1 20 ° C. After drying for 5 minutes, a photosensitive resin layer having a film thickness of 50 μm was obtained. Next, the photosensitive resin layer was irradiated with ghi rays at an irradiation dose of 250 mJ/cm 2 and heated on a hot plate at 115 ° C for 5 minutes. Next, a glass substrate having a thickness of 0.7 mm was thermocompression bonded to the heated photosensitive resin layer under conditions of 1 ° C and 0.1 MPa. Then, the case where the glass substrate was attached was evaluated as 〇, and the case where no glass was attached was evaluated as X, and the adhesion of the photosensitive resin layer was evaluated. The results are disclosed in Tables 1 and 2. &lt;Evaluation of Resolving Property&gt; The negative photosensitive resin compositions of Examples 1 to 1 1 and Comparative Examples 1 to 4 were applied onto a 8-inch wafer by a spin coater at 1 20 °. C was dried for 5 minutes to obtain a photosensitive resin layer having a film thickness of 50 μm. Next, the photosensitive resin layer was irradiated with ghi rays at an irradiation dose of 2 50 mJ/cm 2 through a photomask. Next, after heating on a hot plate at 1 15 ° C for 5 minutes, by using 2.38 mass% of the four A liquid-covering image of the aqueous solution of ammonium hydroxide (60 seconds x 2) was used to dissolve and remove the uncured portion to form a type having a line and a gap as shown in Fig. 39 - 201211681. Then, the limit resolution is obtained by changing the mask size'. The results are disclosed in Tables 1 and 2. &lt;Evaluation of Residual Film Rate&gt; The negative photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 4 were coated on an 8-inch wafer by a spin coater' at 1 20 ° c was dried for 5 minutes to obtain a photosensitive resin layer having a film thickness of 50 μm. Next, the photosensitive resin layer was irradiated with ghi rays at an irradiation dose of 250 mJ/cm 2 and heated on a hot plate at 115 ° C for 5 minutes. Further use a clean oven and heat at 1 80 ° C for 2 hours. Then, the ratio (%) of the film thickness after heating to the original film thickness was determined, and the residual film ratio was evaluated. The results are disclosed in Table 1, 2 ° [Table 1] Examples Comparative Example 1 2 3 4 5 6 7 1 2 Alkali-soluble resin A 100 100 50 100 100 100 100 Alkali-soluble resin B 100 50 鹸 Soluble oxime resin C 100 Photoacid generator A 1 1 1 1 1 Photoacid generator B 3 Photoacid bovine C 3 Photoacid bovine D 2 Photoacid generator E 2 Crosslinker A 11 11 11 11 11 11 11 11 Crosslinking Agent B 11 Epoxy Resin A 30 30 30 30 30 Epoxy Resin B 30 30 , Epoxy Resin C 30 Solvent A 100 100 100 100 100 100 100 100 100 Imaging 〇〇〇〇〇〇〇X 〇Adhesive 〇 〇〇〇〇〇〇〇X resolution _ 10 10 10 10 10 10 10 10 10 Residual film rate (%) 90 88 90 88 80 90 90 90 90 -40 - 201211681 [Table 2] Example Comparative Example 8 9 10 11 3 4 Alkali-soluble resin D 100 100 100 100 Alkali-soluble resin E 100 100 Radical polymerization initiator A 6 6 6 6 6 6 众単単 6 6 6 6 Polymerizable monomer B 20 20 25 30 20 20 Polymeric body C 20 20 20 20 20 Epoxy resin A 30 30 Oxygen Resin B 30 30 Cyclo Resin C 30 30 Solvent A 100 100 100 100 100 100 Imaging 〇〇〇 XX Subsequent 〇〇〇〇〇 Resolution (Qing) 40 40 40 60 80 80 Residual Rate (% 85 85 85 88 86 85 It can be seen from Table 1 that in the case of the chemically amplified negative photosensitive resin composition, Examples 1 to 7 employ the epoxy resin represented by the above general formula (D-1). The negative photosensitive resin composition is excellent in any of the photosensitive resin layer in terms of developability, resolution, adhesion after patterning, and residual film ratio. On the other hand, in Comparative Example 1, a negative photosensitive resin composition containing an epoxy resin different from the epoxy resin represented by the above general formula (D-1) was used, and the developing property was inferior, and the ring was used. In Comparative Example 2 of the negative photosensitive resin composition of the oxygen resin, the adhesion was inferior. Among the above-mentioned <Evaluation of developing property>, the pattern having the line and the gap obtained in Example 1 is shown in Fig. 2, and the pattern having the line and the gap obtained in Comparative Example 1 is shown in Fig. 3. In the figure, the whitest portion observed is the gap portion. As is apparent from Figs. 2 and 3, in the first embodiment, no residue remained in the gap portion, whereas in Comparative Example 1, a large amount of residue was present. When the photosensitive resin-41 - 201211681 layer is heated, the normal epoxy resin used in Comparative Example 1 reacts with the crosslinking agent, and the residue tends to remain. The epoxy resin and the crosslinking agent represented by the above general formula (D-1) used in Examples 1 to 7 were slow in reactivity, and the residue was not easily left. Further, as is clear from Table 2, in the case of the radically polymerizable negative photosensitive resin composition, Examples 8 to 11 employed a negative photosensitive property containing the epoxy resin represented by the above general formula (D-1). The resin composition is excellent in any of the photosensitive resin layer in terms of developability, resolution, adhesion after patterning, and residual film ratio. On the other hand, in Comparative Examples 3 and 4, a negative photosensitive resin composition containing an epoxy resin different from the epoxy resin represented by the above general formula (D-1) was used, and its developing property and resolution were used. Poor. In the case where the photosensitive resin layer is heated, it is presumed that the usual epoxy resin used in Comparative Examples 3 and 4 reacts with the carboxyl group of the alkali-soluble resin, and the residue is likely to remain. The epoxy resin represented by the above general formula used in Examples 8 to 11 was insensitive to reactivity with a carboxyl group, and the residue was not easily left. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a light receiving device. Fig. 2 is a view showing a pattern having a line and a gap obtained in the first embodiment. Fig. 3 is a view showing a pattern having a line and a gap obtained in Comparative Example 1. [Explanation of main component symbols] 1 : Light-receiving device -42- 201211681 1 〇: Support substrate 1 1 : Light-receiving part 1 2 : Transparent substrate 1 3 : Spacer -43

Claims (1)

201211681 七、申請專利範園 1. 一種負型感光性樹脂組成物’其含有：鹼可溶性樹 脂（A)、藉由照射活性射線產生酸或自由基之化合物（B)、 可藉由前述（B)成分所產生的酸或自由基進行交聯的化合 物（C)、下述一般式（D-1)所表示之環氧樹脂（D)及溶劑 (S)， 【化1】201211681 VII. Application for Patent Park 1. A negative photosensitive resin composition which contains: an alkali-soluble resin (A), a compound (B) which generates an acid or a radical by irradiation with an active ray, and can be used by the above (B) a compound (C) in which an acid or a radical generated by a component is crosslinked, an epoxy resin (D) represented by the following general formula (D-1), and a solvent (S), [Chemical Formula 1] 人，、人 J Π (D-1) [―般式（D-1)中，Rdl及Rd2各自獨立表示氫原子或甲基、 Rd3〜Rd6各自獨立表示氫原子、甲基、氯原子、或溴原 子’ A表示伸乙氧基乙基、二（伸乙氧基）乙基、三（伸乙氧 基）乙基、伸丙氧基丙基、二（伸丙氧基）丙基、三（伸丙氧 基）丙基、或碳數2〜15之伸烷基，η爲自然數，其平均 爲1.2〜5]。 2 .如申請專利範圍第1項之負型感光性樹脂組成物， 其中前述（D)成分的含量相對於前述（Α)成分100質量份而 言爲5〜40質量份。 3 .如申請專利範圍第〗項之負型感光性樹脂組成物， 其中前述（Α)成分係具有酚性羥基之鹼可溶性樹脂（Α1)或 具有由不飽和羧酸所衍生之構成單位之鹼可溶性樹脂 (Α2) 〇 4‘一種感光性乾薄膜，其具有：基材薄膜、與形成於 -44- 201211681 該基材薄膜表面之感光性樹脂層，而前述感光性樹脂層係 由如申請專利範圍第1〜3之項中任一項之負型感光性樹 脂組成物所構成。 5.—種受光裝置，其具備： 搭載有半導體元件之支持基板； 與前述支持基板呈對向之透明基板； 設置於前述支持基板與前述透明基板之間之間隔物， 且 前述間隔物係如申請專利範圍第1〜3之項中任一項 之負型感光性樹脂組成物之硬化物。 -45-Person, human J Π (D-1) [In the general formula (D-1), Rdl and Rd2 each independently represent a hydrogen atom or a methyl group, and Rd3 to Rd6 each independently represent a hydrogen atom, a methyl group, a chlorine atom, or The bromine atom 'A' represents ethoxyethyl, di(ethyleneoxy)ethyl, tris(ethyloxy)ethyl, propoxypropyl, bis(propoxy)propyl, three (propenyloxy) propyl, or alkylene with 2 to 15 carbon atoms, η is a natural number, and the average is 1.2 to 5]. (2) The negative photosensitive resin composition of the first aspect of the invention, wherein the content of the component (D) is 5 to 40 parts by mass based on 100 parts by mass of the (Α) component. 3. The negative photosensitive resin composition according to the invention of claim 1, wherein the (Α) component is an alkali-soluble resin having a phenolic hydroxyl group (Α1) or a base having a constituent unit derived from an unsaturated carboxylic acid Soluble resin (Α2) 感光4' is a photosensitive dry film having a base film and a photosensitive resin layer formed on the surface of the base film of -44-201211681, and the photosensitive resin layer is as claimed in the patent application The negative photosensitive resin composition according to any one of the items 1 to 3 of the invention. 5. A light receiving device comprising: a support substrate on which a semiconductor element is mounted; a transparent substrate facing the support substrate; a spacer disposed between the support substrate and the transparent substrate, wherein the spacer is A cured product of a negative photosensitive resin composition according to any one of the items 1 to 3 of the invention. -45-
TW100112970A 2010-04-19 2011-04-14 A negative photosensitive resin composition, a photosensitive dry film, and a light receiving device TWI521301B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2010095913A JP5624794B2 (en) 2010-04-19 2010-04-19 Negative photosensitive resin composition, photosensitive dry film, and light receiving device

Publications (2)

Publication Number Publication Date
TW201211681A true TW201211681A (en) 2012-03-16
TWI521301B TWI521301B (en) 2016-02-11

Family

ID=45031183

Family Applications (1)

Application Number Title Priority Date Filing Date
TW100112970A TWI521301B (en) 2010-04-19 2011-04-14 A negative photosensitive resin composition, a photosensitive dry film, and a light receiving device

Country Status (3)

Country Link
JP (1) JP5624794B2 (en)
KR (1) KR101666231B1 (en)
TW (1) TWI521301B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3249469A4 (en) 2015-03-26 2018-04-04 Tokyo Ohka Kogyo Co., Ltd. Negative photosensitive composition and pattern formation method
EP3360933A1 (en) * 2017-02-08 2018-08-15 Evonik Degussa GmbH Formulations based on metal oxide precursors which can be directly structured for the production of oxide coatings
JP7419255B2 (en) * 2018-10-31 2024-01-22 東京応化工業株式会社 Surface treatment liquid, surface treatment method, and method for manufacturing surface-treated rolled sheet

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4632077B2 (en) * 2002-10-15 2011-02-16 Ｄｉｃ株式会社 Epoxy resin composition, method for producing epoxy resin, novel epoxy resin, and novel phenol resin
JP2006156024A (en) * 2004-11-26 2006-06-15 Sanyo Electric Co Ltd Battery system unit
JP2006235371A (en) * 2005-02-25 2006-09-07 Nitto Denko Corp Photosensitive resin composition and wiring circuit board having solder resist obtained using the same
JP4633500B2 (en) * 2005-03-01 2011-02-16 ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． Negative photosensitive resin composition containing epoxy-containing substance
JP2006323089A (en) 2005-05-18 2006-11-30 Hitachi Chem Co Ltd Photosensitive resin composition and photosensitive film using same
TWI432897B (en) * 2006-11-02 2014-04-01 Toyo Ink Mfg Co Photosensitive resin and cured resin thereof, and process for manufacturing photosensitive resin
JP4959627B2 (en) * 2007-05-25 2012-06-27 住友ベークライト株式会社 Resin composition, resin spacer film and semiconductor device
JP2008297540A (en) 2008-04-14 2008-12-11 Sumitomo Bakelite Co Ltd Photosensitive adhesive resin composition, adhesive film and light-receiving device

Also Published As

Publication number Publication date
KR101666231B1 (en) 2016-10-13
JP2011227246A (en) 2011-11-10
TWI521301B (en) 2016-02-11
JP5624794B2 (en) 2014-11-12
KR20110116988A (en) 2011-10-26

Similar Documents

Publication Publication Date Title
JP6711104B2 (en) Resist underlayer film forming method and pattern forming method
CN111217946B (en) Composition comprising a compound containing a vinyl group
US9012126B2 (en) Positive photosensitive material
TW201302894A (en) Resin composition, polymer, curable film, electronic component
WO2007122929A1 (en) Radiation-sensitive insulating resin composition
WO2011102064A1 (en) METHOD FOR FORMATION OF ELECTRODE ON n-TYPE SEMICONDUCTOR LAYER
JP2016167047A (en) Composition for forming resist underlay film, resist underlay film, and method for manufacturing patterned substrate
TW200905383A (en) Photosensitive insulating resin composition
WO2017208796A1 (en) Composition for forming film, film, method for forming resist underlayer film, method for manufacturing patterned substrate, and compound
JP5792548B2 (en) Glass processing method
JP6370093B2 (en) Photosensitive composition containing vinyl group-containing compound
TW201211681A (en) Negative photosensitive resin composition, photosensitive dry film, and light receiving device
JP2019086559A (en) Resin composition for negative photoresist and cured film
TW201202856A (en) Composition for forming resist underlayer film and pattern forming method
TWI582138B (en) Modified phenolic novolak type phenol resin and its manufacturing method and resistance material
KR20100097007A (en) Photosensitive resin composition, dry film, and method for forming pattern
JP5125825B2 (en) Underlayer film forming composition for multilayer resist process
TWI505026B (en) Photosensitive composition, resin composition, cured film and producing method thereof, method for producing patterning cured film and electronic component
TWI803587B (en) Radiation sensitive composition, cured film and display element
JP6342648B2 (en) Processing method of chemically strengthened glass substrate
US11667620B2 (en) Composition, film, film-forming method and patterned substrate-producing method
JP2015057633A (en) Method for forming resist pattern
KR20220157954A (en) Composition, method for forming resist underlayer film, and method for forming resist pattern
TW201219982A (en) exhibiting excellent resolution and showing excellent electrical insulating property and strength in a cured product thereof
TWI830827B (en) Resist primer film forming composition, resist primer film, and resist pattern forming method