TW201140249A - Photosensitive resin composition, cured film and method of producing the same, organic EL display device, and liquid crystal display device - Google Patents
Photosensitive resin composition, cured film and method of producing the same, organic EL display device, and liquid crystal display device Download PDFInfo
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- TW201140249A TW201140249A TW100101571A TW100101571A TW201140249A TW 201140249 A TW201140249 A TW 201140249A TW 100101571 A TW100101571 A TW 100101571A TW 100101571 A TW100101571 A TW 100101571A TW 201140249 A TW201140249 A TW 201140249A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133345—Insulating layers
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- 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
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- 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
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/02—Materials and properties organic material
- G02F2202/022—Materials and properties organic material polymeric
- G02F2202/023—Materials and properties organic material polymeric curable
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Abstract
Description
201140249 六、發明說明: 【發明所屬之技術領域】 本發明是關於一種感光性樹脂組成物、硬化膜、硬化 膜之形成方法、有機EL (電激發光)顯示裝置及液晶顯 示裝置。 【先前技術】 在有機EL顯示裝置、或液晶顯示裝置等是設置有經 圖案形成之層間絕緣膜(interlayer insulating film)。爲形 成該層間絕緣膜,感光性樹脂組成物是由於爲獲得所必要 之圖案形狀所需之步驟數少,而且可獲得充分的平坦性而 被廣泛使用。 對於使用如上述感光性樹脂組成物所圖案形成之層間 絕緣膜或平坦化膜(planarization film),除了透明性外, 也要求必須爲耐溶劑性優異、可靠性高之硬化膜。 如此之感光性樹脂組成物,例如在日本特開平5 -1 652 1 4號公報中,提案一種感光性樹脂組成物,其係具 有:(A) (a)不飽和羧酸或不飽和羧酸酐、(b)具有 環氧基之自由基聚合性化合物、及(c)其他之自由基聚 合性化合物的共聚合物之可溶於鹼水溶液之樹脂、以及( B )感放射線性酸形成化合物。 此外,可確保保存安定性、感度、所形成的硬化膜之 高可靠性(透明性、耐溶劑性)之感光性樹脂組成物,例 如在日本特開2004-264623號公報中,揭示一種感放射線 性樹脂組成物,其係包含:具有縮醛結構或縮酮結構之( 201140249 甲基)丙烯酸酯化合物、具有環氧基之自由基聚合性化合 物、及其他自由基聚合性化合物之共聚物的樹脂、與可藉 由照射放射線而產生pKa爲4.0以下之酸的化合物。 此外,在日本特開2009-98616號公報中,揭述—種 正型感光性樹脂組成物,其係包含:具有特定的酸解離性 基(acid-dissociable group)之結構單元、可與殘基反應而 形成共價鍵之結構單元的共聚物之樹脂,及具有肟磺酸醋 基之光酸產生劑(photo-acid generator)。 在另一方面,在使用於傳真機、電子複印機、固態攝 像元件等之晶載彩色爐光片(〇n-chip color filter)的成像光 學系統或光纖連結器之光學材料方面,則已在使用將具有 約3//m至100/zm之透鏡徑的微透鏡、或將此等微透鏡 規律地排列之微透鏡陣列。 微透鏡或微透鏡陣列之形成,已知有經形成相當於透 鏡的光阻圖案後,以加熱處理使其熔融流動而仍以此狀態 直接利用作爲透鏡之方法、或將經加以熔融流動的透鏡圖 案作爲遮罩而進行乾式蝕刻以將透鏡形狀轉印於基底質之 方法等。關於如此的透鏡圖案之形成,已廣泛使用感放射 線性樹脂組成物(參閱例如日本特開平6- 1 8702號公報、 及特開平6- 1 3 6239號公報)。 【發明內容】 〔發明所欲解決之問題〕 對於用於形成層間絕緣膜之感光性樹脂組成物,則要 求必須爲高感度,且保存安定性爲良好,同時對於由該感 201140249 光性組成物所形成的硬化膜則要求高可靠性(透明性、耐 溶劑性等)。並且’對於層間絕緣膜,從形成接觸孔 (contact hole)等的觀點,則要求良好的圖案形狀之形成性 ,該圖案形狀較佳爲正向錐型。 然而,如在日本特開2004-264623號、及特開2〇〇9_ 986 1 6號公報中所揭示之正型感光性樹脂組成物,含有三 氮哄系、鑰鹽系、聘擴酸醋系等之光酸產生劑者是光酸產 生效率不佳’如就達成高感度化的觀點而言,則不一定是 可令人滿意者。 在另一方面’在使用感光性樹脂組成物來形成絕緣膜 等之圖案的情況,通常是在經感光性樹脂組成物之曝光後 實施加熱處理(後烘烤步驟),但是若爲先前的感光性樹 脂組成物,由於在後烘烤步驟後之圖案形狀是隨著高感度 化而接近於矩形,提高感度與良好的圖案形狀之形成性則 一向是成爲折衷選擇之關係。因此,目前的情況,雖然一 邊同時具有高感度與保存安定性,且一邊確保所形成的硬 化膜之高可靠性(透明性、耐溶劑性),但是並未獲得所 形成的圖案形狀爲良好的層間絕緣膜形成用之感光性樹脂 組成物。 本發明所欲解決之第一問題是提供一種感光性樹脂組 成物,其係可形成保存安定性及感度優異’且透明性、耐 溶劑性及圖案形狀優異的硬化膜者。 另外,本發明所欲解決之第二問題是提供一種以本發 明之正型感光性樹脂組成物所形成的透明性、耐溶劑性及 201140249 圖案形狀優異的硬化膜及形成該硬化膜之方法,具備該硬 化膜作爲層間絕緣膜的顯示特性優異且生產性高之有機 EL顯示裝置及液晶顯示裝置。 〔解決問題之方法〕 茲說明本發明之模式如下。 < 1 > 一種感光性樹脂組成物,其係包含:(A )含有具 有選自經酸分解性基保護之羧基及經酸分解性基保 護之酚性羥基中至少一者之結構單元(1 )與具有 選自環氧基及氧雜環丁垸基(oxetanyl group)中至少 一者之結構單元(2)之共聚物;(B)選自以下述 通式(I)、通式(OS-1)、通式(OS-3)、通式 (〇S-4 ) '及通式(OS-5)所代表之光酸產生劑中 至少一種光酸產生劑;(C )增感劑;及(D )溶 劑。 R1A— C(R2A) = N - O - S〇2- R3A (I) 通式(I)中,R1A是代表碳原子數爲1至6之烷基、 碳原子數爲1至4之鹵化烷基、苯基、聯苯基、萘基、2-呋喃基、2 -噻吩基、碳原子數爲1至4之烷氧基或氰基; RIA爲苯基、聯苯基、萘基或蒽基時,則此等之基可爲經 選自由鹵素原子、羥基 '碳原子數爲1至4之烷基、碳原 子數爲1至4之烷氧基及硝基所構成的群組中之取代基加 以取代。R2A是代表碳原子數爲1至10之烷基、碳原子數 爲1至10之院.氧基、碳原子數爲1至5之鹵化烷基、碳 原子數爲1至5之鹵化烷氧基、可經W取代之苯基、可 201140249 經W取代之萘基或可經w取代之蒽基、二烷基胺基、嗎 啉基或氰基。R2A與RlA是可相互鍵結而形成S員環或6 員環’該5員環或6員環是可與也可具有一個或兩個任意 之取代基的苯環鍵結。R3A是代表碳原子數爲丨至之烷 基、碳原子數爲1至10之烷氧基、碳原子數爲丨至5之 鹵化烷基、碳原子數爲1至5之鹵化烷氧基、可經W取 代之苯基、可經W取代之萘基或可經W取代之恵基。w 是代表鹵素原子、氰基、硝基、碳原子數爲1至10之烷 基、碳原子數爲1至10之烷氧基、碳原子數爲1至5之 鹵化烷基或碳原子數爲1至5之鹵化烷氧基。[Technical Field] The present invention relates to a photosensitive resin composition, a cured film, a method for forming a cured film, an organic EL (electroluminescence) display device, and a liquid crystal display device. [Prior Art] An organic EL display device, a liquid crystal display device or the like is provided with a patterned interlayer insulating film. In order to form the interlayer insulating film, the photosensitive resin composition is widely used because the number of steps required to obtain a necessary pattern shape is small and sufficient flatness can be obtained. In addition to the transparency, an interlayer insulating film or a planarization film patterned by using the photosensitive resin composition as described above is required to have a cured film which is excellent in solvent resistance and high in reliability. In the photosensitive resin composition, for example, Japanese Laid-Open Patent Publication No. Hei. No. 5-1 652-14 proposes a photosensitive resin composition having (A) (a) an unsaturated carboxylic acid or an unsaturated carboxylic anhydride. And (b) a radically polymerizable compound having an epoxy group; (c) a resin soluble in an aqueous alkali solution of a copolymer of another radical polymerizable compound; and (B) a radiation-sensitive acid forming compound. In addition, it is possible to ensure a photosensitive resin composition which has high stability (transparency and solvent resistance) of the cured film formed, and a radiation-sensitive line is disclosed in Japanese Laid-Open Patent Publication No. 2004-264623. A resin composition comprising: a resin having a acetal structure or a ketal structure (201140249 methyl) acrylate compound, a radical polymerizable compound having an epoxy group, and a copolymer of another radical polymerizable compound And a compound which can generate an acid having a pKa of 4.0 or less by irradiating radiation. Further, Japanese Laid-Open Patent Publication No. 2009-98616 discloses a positive photosensitive resin composition comprising a structural unit having a specific acid-dissociable group, and a residue capable of A resin which reacts to form a copolymer of a structural unit of a covalent bond, and a photo-acid generator having a sulfonic acid sulfonic acid group. On the other hand, in the optical materials of an imaging optical system or a fiber optic connector used for a RGB-chip color filter such as a facsimile machine, an electronic copying machine, or a solid-state image pickup device, it is already in use. A microlens having a lens diameter of about 3//m to 100/zm, or a microlens array in which the microlenses are regularly arranged. In the formation of a microlens or a microlens array, it is known that after forming a photoresist pattern corresponding to a lens, it is melted by heat treatment, and the lens is directly used as a lens in this state, or a lens that is melted and flowed. A method in which a pattern is dry-etched as a mask to transfer a lens shape to a substrate or the like. For the formation of such a lens pattern, a radiation-sensitive linear resin composition has been widely used (see, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The photosensitive resin composition for forming an interlayer insulating film is required to have high sensitivity, and the storage stability is good, and at the same time, for the photosensitive composition of the sense 201140249 The formed cured film requires high reliability (transparency, solvent resistance, etc.). Further, from the viewpoint of forming a contact hole or the like for the interlayer insulating film, a good pattern shape formation property is required, and the pattern shape is preferably a forward tapered shape. The positive photosensitive resin composition disclosed in Japanese Laid-Open Patent Publication No. 2004-264623, and Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei. In the case of a photoacid generator such as a photoacid generator, the photoacid generation efficiency is not good, and it is not necessarily satisfactory from the viewpoint of achieving high sensitivity. On the other hand, in the case where a photosensitive resin composition is used to form a pattern of an insulating film or the like, heat treatment (post-baking step) is usually performed after exposure of the photosensitive resin composition, but if it is a previous photosensitive film Since the pattern shape after the post-baking step is close to a rectangle with high sensitivity, the improvement of the sensitivity and the formation of a good pattern shape have always been a trade-off relationship. Therefore, in the current situation, although high sensitivity and storage stability are simultaneously ensured, and high reliability (transparency and solvent resistance) of the formed cured film is ensured, the formed pattern shape is not obtained as good. A photosensitive resin composition for forming an interlayer insulating film. The first problem to be solved by the present invention is to provide a photosensitive resin composition which can form a cured film excellent in transparency and solvent resistance and excellent in transparency and solvent resistance. Further, a second problem to be solved by the present invention is to provide a cured film excellent in transparency, solvent resistance, and 201140249 pattern shape formed by the positive photosensitive resin composition of the present invention, and a method of forming the cured film. An organic EL display device and a liquid crystal display device having excellent display characteristics and high productivity of the cured film as the interlayer insulating film. [Method for Solving the Problem] The mode of the present invention is explained as follows. < 1 > A photosensitive resin composition comprising: (A) a structural unit containing at least one selected from the group consisting of a carboxyl group protected by an acid-decomposable group and a phenolic hydroxyl group protected by an acid-decomposable group ( 1) a copolymer with a structural unit (2) having at least one selected from the group consisting of an epoxy group and an oxetanyl group; (B) is selected from the group consisting of the following general formula (I), general formula (OS- 1) at least one photoacid generator of the formula (OS-3), the formula (〇S-4)' and the photoacid generator represented by the formula (OS-5); (C) a sensitizer; And (D) solvent. R1A—C(R2A) = N - O - S〇2- R3A (I) In the formula (I), R1A is an alkyl group having 1 to 6 carbon atoms and a halogenated alkane having 1 to 4 carbon atoms a phenyl group, a biphenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, a 2-thienyl group, an alkoxy group having 1 to 4 carbon atoms or a cyano group; RIA is a phenyl group, a biphenyl group, a naphthyl group or an anthracene group; In the case of a base, the group may be selected from the group consisting of a halogen atom, an alkyl group having a hydroxyl group of 1 to 4, an alkoxy group having 1 to 4 carbon atoms, and a nitro group. Substituents are substituted. R2A is an alkyl group having 1 to 10 carbon atoms, a number of carbon atoms of 1 to 10, an alkyl group, a halogenated alkyl group having 1 to 5 carbon atoms, and a halogenated alkoxy group having 1 to 5 carbon atoms. A phenyl group which may be substituted by W, a naphthyl group which may be substituted by W in 201140249 or a fluorenyl group, a dialkylamino group, a morpholinyl group or a cyano group which may be substituted by w. R2A and RlA are mutually bondable to form an S-membered ring or a 6-membered ring. The 5-membered ring or 6-membered ring is a benzene ring bond which may have one or two optional substituents. R3A is an alkyl group having a carbon number of fluorene, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having a carbon number of 5 to 5, a halogenated alkoxy group having 1 to 5 carbon atoms, A phenyl group which may be substituted by W, a naphthyl group which may be substituted by W or a fluorenyl group which may be substituted by W. w is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a carbon number It is a halogenated alkoxy group of 1 to 5.
(OS- 1 ) 通式(OS-1)中’ R1是代表氫原子、烷基、烯基、 烷氧基、烷氧基羰基、醯基、胺甲醯基 '胺磺醯基、磺基 、氰基、芳基、或雜芳基。R2是代表烷基、或芳基。X是(OS-1) In the formula (OS-1), 'R1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a decyl group, an amine carbaryl 'amine sulfonyl group, a sulfo group , cyano, aryl, or heteroaryl. R2 represents an alkyl group or an aryl group. X is
CR6H —、或—CR6R7—,R5至R7是各自獨立地代表烷基 、或芳基。R21至R24是各自獨立地代表氫原子、鹵素原 子、烷基、烯基、烷氧基、胺基、烷氧基羰基、烷基羰基 、芳基羰基、醯胺基、磺基、氰基、或芳基。 201140249CR6H-, or -CR6R7-, R5 to R7 each independently represent an alkyl group or an aryl group. R21 to R24 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amine group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, a decylamino group, a sulfo group, a cyano group, Or aryl. 201140249
(r6\ 通式(OS-3)至通式(OS-5)中,R1是代表烷基、 芳基、或雜芳基,可存在數個的R2是各自獨立地代表氫 原子、烷基、芳基、或鹵素原子,可存在數個的 R6是各 自獨立地代表鹵素原子、烷基、烷氧基、磺酸基、胺基磺 醯基、或烷氧基磺醯基,X是代表〇或S,η是代表1或 2,m是代表0至6之整數。 < 2 > 如前述第< 1 >項之感光性樹脂組成物,其中前述 (C )增感劑是以下述通式(III )、通式(IV )、 通式(V )、或通式(VI )所代表之化合物。(r6\ In the formula (OS-3) to the formula (OS-5), R1 represents an alkyl group, an aryl group or a heteroaryl group, and a plurality of R2 may be independently represented by a hydrogen atom or an alkyl group. Or an aryl group or a halogen atom, and a plurality of R6 may independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, and X is a representative 〇 or S, η is a representative of 1 or 2, and m is an integer of 0 to 6. The photosensitive resin composition of the above item <1>, wherein the aforementioned (C) sensitizer is A compound represented by the following formula (III), formula (IV), formula (V), or formula (VI).
通式(III)中,R1及R2是代表碳原子數爲1至4之 烷基,且R1及R2是相同。R3及R4是各自獨立地代表一 價取代基。m及η是各自獨立地代表0至4之整數。 201140249 Ο (r7)f〇^X^(r6)〇 通式(IV )中,R5是代表碳原子數 或也可經取代之苯基。R6及R7是各自 代基。〇及P是各自獨立地代表0至In the formula (III), R1 and R2 represent an alkyl group having 1 to 4 carbon atoms, and R1 and R2 are the same. R3 and R4 each independently represent a monovalent substituent. m and η are integers each independently representing from 0 to 4. 201140249 Ο (r7)f〇^X^(r6) 〇 In the formula (IV), R5 is a phenyl group which represents a carbon number or may be substituted. R6 and R7 are the respective bases. 〇 and P are each independently representing 0 to
通式(V)中,R8、R9、及R1Q是 價取代基,q、1*及S是各自獨立地代表 、R9、及R 1 °是其兩個以上可相互鍵結 員環。 (IV) 爲1至6之烷基 獨立地代表一價取 :整數。 (V) 各自獨立地代表 0至2之整數。r8 而形成5員環或6In the formula (V), R8, R9 and R1Q are valent substituents, q, 1* and S are each independently represented, and R9 and R1 ° are two or more mutually bondable ring members. (IV) An alkyl group of 1 to 6 independently represents a monovalent: integer. (V) each independently represents an integer from 0 to 2. R8 and form a 5-member ring or 6
13 (VI) 通式(VI )中,R"及R12是各自獨立地代表經取代 或未經取代之碳原子數爲1至4之院基、或經取代或未經 取代之苯基。R13及RM是各自獨立地代表氫原子或碳原 201140249 子數爲1至20之脂肪族基、雜環基、或芳香族基。R13及 R 14是可相互鍵結而形成5員環或6員環。 < 3 > 如前述第< 1 >或< 2 >項之感光性樹脂組成物,其 中以前述通式(I )所代表之光酸產生劑是以下述 通式(II)所代表之光酸產生劑。13 (VI) In the formula (VI), R" and R12 each independently represent a substituted or unsubstituted phenyl group having 1 to 4 carbon atoms or a substituted or unsubstituted phenyl group. R13 and RM are an aliphatic group, a heterocyclic group or an aromatic group each independently representing a hydrogen atom or a carbon source of 201140249 having a number of 1 to 20. R13 and R14 are mutually bondable to form a 5-membered ring or a 6-membered ring. The photosensitive resin composition of the above-mentioned item <1> or <2>, wherein the photoacid generator represented by the above formula (I) is represented by the following formula (II) The photoacid generator represented.
0 N—0—S—R3A0 N—0—S—R3A
(II) 通式(II )中,R4A是代表鹵素原子、羥基、碳原子 數爲1至4之烷基、碳原子數爲1至4之烷氧基、或硝基 ,1是代表〇至5之整數。R3A是代表碳原子數爲1至1〇 之烷基、碳原子數爲1至1〇之烷氧基、碳原子數爲1至 5之鹵化院基、碳原子數爲1至5之鹵化院氧基、可經w 取代之苯基、可經W取代之萘基或可經W取代之蒽基。 W是代表鹵素原子、氰基、硝基、碳原子數爲1至1〇之 烷基、碳原子數爲1至1〇之烷氧基、碳原子數爲1至5 之鹵化烷基或碳原子數爲1至5之鹵化烷氧基》 < 4 > 如前述第< 1 >至< 3 >項中任一項之感光性樹脂組 成物,其中前述(A)共聚物所具有的結構單元(2 )是具有氧雜環丁烷基之結構單元。 < 5 > 如前述第< 1 >至< 4 >項中任一項之感光性樹脂組 成物,其中更進一步含有交聯劑。 < 6> 一種硬化膜,其係對前述第<1>至<5>項中任一 -10- 201140249 項之感光性樹脂組成物賦予光及熱中至少一者而形 成。 < 7 > 一種硬化膜之形成方法,其包括下列步驟: (1)將前述第<1>至<5>項中任一項之感光性樹 脂組成物塗布於基板上; (2 )從所塗布的感光性樹脂組成物移除溶劑; (3 )將所塗布的感光性樹脂組成物以活性光線 (active light rays)加以曝光; (4 )將經曝光的感光性樹脂組成物以水性顯影液加 以顯影;及 (5 )將經顯影的感光性樹脂組成物加以熱硬化。 < 8 > 一種硬化膜,其係以前述第<7>項之方法所形成 〇 < 9 > 如前述第< 6 >或< 8 >項之硬化膜,其係層間絕緣 膜。 <10> —種有機EL顯示裝置,其係具備如前述第<6> 、<8>或<9>項之硬化膜。 < 1 1 > 一種液晶.顯示裝置,其係具備如前述第< 6 >、< 8>或<9>項之硬化膜。 〔發明之功效〕 根據本發明之一模式,可提供一種感光性樹脂組成物 ’其係可形成保存安定性及感度優異,且透明性、耐溶劑 性及圖案形狀優異之硬化膜。 此外,根據本發明之另一模式,可提供一種以本發明 -11· 201140249 之正型感光性樹脂組成物所形成的透明性、耐溶劑性及圖 案形狀優異之硬化膜及形成該硬化膜之方法,將該硬化膜 作爲層間絕緣膜而具備之顯示特性優異且生產性高之有機 E L顯示裝置及液晶顯示裝置。 【實施方式】 〔本發明之最佳實施方式〕 (感光性樹脂組成物) 茲就本發明之感光性樹脂組成物詳加說明如下。 另外,在本發明中,所謂的感光性樹脂組成物之固體 成分含量是表示從包含在感光性樹脂組成物的全部成分之 總質量扣除溶劑等揮發性成分的質量後之質量。 在本說明書使用「至」所標記之數値範圍是表示將「 至」之前後所標記之數値分別作爲最小値及最大値而包含 之範圍。 本發明之感光性樹脂組成物係包含:(A)含有具有 選自經酸分解性基保護之羧基及經酸分解性基保護之酚性 羥基中至少一者之結構單元(1)與具有選自環氧基及氧 雜環丁烷基中至少一者之結構單元(2)之.共聚物;(B) 選自以下述通式(I)、通式(OS-1)、通式(OS-3)、 通式(OS-4 )、及通式(OS-5 )所代表之光酸產生劑中至 少一種光酸產生劑(在下文中,適當地總稱爲「光酸產生 劑(B )」);(C )增感劑;及(D )溶劑之感光性樹脂 組成物。 R1A— C(R2A) = N - O - S〇2- R3a (I) -12- 201140249 通式(I)中’ ria是代表碳原子數爲1至6之烷基' 碳原子數爲1至4之鹵化烷基、苯基、聯苯基、萘基、2_ 咲喃基' 2 -噻吩基、碳原子數爲1至4之烷氧基或氰基; R1A爲苯基 '聯苯基、萘基或蒽基時,則此等之基可爲經 選自由鹵素原子、羥基、碳原子數爲丨至4之烷基、碳原 子數爲1至4之烷氧基及硝基所構成的群組中之取代基加 以取代。R2A是代表碳原子數爲1至之烷基、碳原子數 爲1至丨〇之烷氧基、碳原子數爲1至5之鹵化烷基、碳 原子數爲1至5之鹵化烷氧基、可經w取代之苯基、可 經W取代之萘基或可經w取代之蒽基、二烷基胺基、嗎 咐基或氰基。R2A與RIA是可相互鍵結而形成5員環或6 員環’該5員環或6員環是可與也可具有一個或兩個任意 之取代基的苯環鍵結。R3A是代表碳原子數爲!至10之烷 基、碳原子數爲1至10之烷氧基、碳原子數爲1至5之 鹵化烷基、碳原子數爲1至5之鹵化烷氧基、可經W取 代之苯基、可經W取代之萘基或可經W取代之蒽基。W 是代表鹵素原子、氰基、硝基、碳原子數爲1至10之烷 基、碳原子數爲1至10之烷氧基、碳原子數爲1至5之 鹵化烷基或碳原子數爲1至5之鹵化烷氧基。 -13- 201140249(II) In the formula (II), R4A represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group, and 1 represents a hydrazine to An integer of 5. R3A is a halogenated compound having an alkyl group having 1 to 1 ring of carbon atoms, an alkoxy group having 1 to 1 carbon atom, a halogenated group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. An oxy group, a phenyl group which may be substituted by w, a naphthyl group which may be substituted by W or a fluorenyl group which may be substituted by W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 1 ring of carbon atoms, an alkoxy group having 1 to 1 carbon atom, a halogenated alkyl group having 1 to 5 carbon atoms or carbon. The photosensitive resin composition of any one of the above-mentioned (A), wherein the (A) copolymer is a photosensitive resin composition of any one of the above-mentioned items (1) The structural unit (2) which is contained is a structural unit having an oxetane group. The photosensitive resin composition of any one of the above-mentioned items, wherein the crosslinking agent further contains a crosslinking agent. <6> A cured film which is formed by imparting at least one of light and heat to the photosensitive resin composition of any one of the above-mentioned items <1> to <5>. < 7 > A method of forming a cured film, comprising the steps of: (1) applying the photosensitive resin composition according to any one of the above items <1> to <5> on a substrate; Removing the solvent from the applied photosensitive resin composition; (3) exposing the applied photosensitive resin composition to active light rays; (4) exposing the exposed photosensitive resin composition to The aqueous developing solution is developed; and (5) the developed photosensitive resin composition is thermally cured. < 8 > A cured film formed by the method of the above item <7>><9>, as described in the above <6> or <8> Interlayer insulating film. <10> An organic EL display device comprising the cured film of the above item <6>, <8> or <9>. < 1 1 > A liquid crystal display device comprising the cured film of the above item <6 >, <8> or <9>. [Effect of the Invention] According to one aspect of the present invention, it is possible to provide a photosensitive resin composition which is excellent in transparency and sensitivity, and which is excellent in transparency, solvent resistance and pattern shape. Further, according to another aspect of the present invention, it is possible to provide a cured film excellent in transparency, solvent resistance and pattern shape formed by the positive photosensitive resin composition of the invention -11 201140249, and a cured film formed thereon In this way, the cured film is used as an interlayer insulating film and has an organic EL display device and a liquid crystal display device which are excellent in display characteristics and high in productivity. [Embodiment] [Best Mode for Carrying Out the Invention] (Photosensitive Resin Composition) The photosensitive resin composition of the present invention will be described in detail below. In the present invention, the solid content of the photosensitive resin composition is a mass after deducting the mass of a volatile component such as a solvent from the total mass of all components contained in the photosensitive resin composition. The range of numbers marked with "to" in this specification means the range including the number 値 marked before and after "to" as the minimum 値 and maximum 値 respectively. The photosensitive resin composition of the present invention comprises: (A) a structural unit (1) comprising at least one selected from the group consisting of a carboxyl group protected by an acid-decomposable group and a phenolic hydroxyl group protected by an acid-decomposable group a copolymer of structural unit (2) of at least one of an epoxy group and an oxetanyl group; (B) is selected from the group consisting of the following general formula (I), general formula (OS-1), and general formula ( At least one photoacid generator of the photoacid generator represented by OS-3), the formula (OS-4), and the formula (OS-5) (hereinafter, appropriately referred to as "photoacid generator" (B) (C) a sensitizer; and (D) a photosensitive resin composition of a solvent. R1A—C(R2A) = N - O - S〇2- R3a (I) -12- 201140249 In the formula (I), 'ria is an alkyl group having 1 to 6 carbon atoms' and the number of carbon atoms is 1 to a halogenated alkyl group, a phenyl group, a biphenyl group, a naphthyl group, a 2 - fluorenyl ' 2 -thienyl group, an alkoxy group having 1 to 4 carbon atoms or a cyano group; R 1 A is a phenyl 'biphenyl group, In the case of a naphthyl group or a fluorenyl group, the group may be one selected from the group consisting of a halogen atom, a hydroxyl group, an alkyl group having a carbon number of 丨 to 4, an alkoxy group having 1 to 4 carbon atoms, and a nitro group. Substituents in the group are replaced. R2A is a halogenated alkoxy group having 1 to alkyl group, 1 to 10 alkoxy group, 1 to 5 halogenated alkyl group, and 1 to 5 carbon atoms. a phenyl group which may be substituted by w, a naphthyl group which may be substituted by W or a fluorenyl group which may be substituted by w, a dialkylamino group, a decyl group or a cyano group. R2A and RIA are mutually bondable to form a 5-membered ring or a 6-membered ring. The 5-membered ring or 6-membered ring is a benzene ring bond which may have one or two optional substituents. R3A is the number of carbon atoms! An alkyl group of 10, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted by W a naphthyl group which may be substituted by W or a fluorenyl group which may be substituted by W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a carbon number It is a halogenated alkoxy group of 1 to 5. -13- 201140249
通式(OS-1)中,R1是代表氫原子、烷基、烯基、 烷氧基、烷氧基羰基、醯基、胺甲醯基、胺磺醯基、磺基 、氰基、芳基、或雜芳基。R2是代表烷基、或芳基。X是 代表一〇_、一 S— 、— NH-、— NR5-、_CH2-、- CR6H -、或—CR6R7—,R5至R7是各自獨立地代表烷基 、或芳基。R21至R24是各自獨立地代表氫原子、鹵素原 子、烷基、烯基、烷氧基、胺基、烷氧基羰基、烷基羰基 、芳基羰基、醯胺基、磺基、氰基、或芳基。In the formula (OS-1), R1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a decyl group, an amine carbaryl group, an amine sulfonyl group, a sulfo group, a cyano group, an aromatic group. Base, or heteroaryl. R2 represents an alkyl group or an aryl group. X represents a 〇, a S-, -NH-, -NR5-, _CH2-, -CR6H-, or -CR6R7-, and R5 to R7 each independently represent an alkyl group or an aryl group. R21 to R24 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amine group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, a decylamino group, a sulfo group, a cyano group, Or aryl.
通式(OS-3)至通式(OS-5)中,R1是代表烷基、 芳基、或雜芳基,可存在數個的R2是各自獨立地代表氫 原子、烷基、芳基、或鹵素原子,可存在數個的R6是各 自獨立地代表鹵素原子、烷基、烷氧基、磺酸基、胺基磺 醯基、或烷氧基磺醯基,X是代表〇或S,η是代表1或 2,m是代表0至6之整數。 -14- 201140249 本發明之感光性樹脂組成物是正型感光性樹脂組成物 〇 此外,本發明之感光性樹脂組成物較佳爲化學增幅型 之正型感光性樹脂組成物(化學增幅正型感光性樹脂組成 物)。 本發明之感光性樹脂組成物由於含有前述(a )至( D)之各成分,將成爲保存安定性及感度優異者。 此外,本發明之感光樹脂組成物是可形成透明性及耐 溶劑性、及圖案形狀優異的硬化膜。 在此,在本發明所謂「圖案形狀」優異是意謂經形成 的圖案之形狀爲正向錐型》 因此,本發明之感光性樹脂組成物在層間絕緣膜形成 用方面是特別有用,在此情況時,則可進行適合於形成接 觸孔等的正向錐型形狀之圖案形成。 此外,在本發明所謂「透明性」是意謂在使用本發明 之感光性樹脂·組成物至少實施曝光後、加熱處理(烘烤處 理)所獲得之硬化膜,著色是受到抑制之性質。另外,在 下文中,有時候則將經以本發明之感光樹脂組成物所形成 的硬化膜所顯現的透明性,稱此爲「耐熱透明性」。 並且,本發明之感光性樹脂組成物是也可用作爲微透 鏡形成用。 其係對於微透鏡形成用之感光性樹脂組成物,除了感 度及保存安定性必須爲優異、由該感光性樹脂組成物所形 成的微透鏡(硬化膜)是必須爲透明性及耐溶劑性優異之 -15- 201140249 外,也對需要顯現良好的熔融形狀(吾所欲曲率半徑)有 所要求的時候,由於本發明之感光性樹脂組成物是具有感 度及保存安定性優異,由此所形成的硬化膜是透明性及耐 溶劑性優異’同時也可顯現良好的熔融形狀之優點。 在下文中’就在感光性樹脂組成物中所含有的各成分 加以說明。 此外’關於在本說明書中的基(原子團)之標記,未 記載經取代及未經取代之標記是與未具有取代基者同時也 包含具有取代基者。例如「烷基」不僅是未具有取代基之 烷基(未經取代之烷基),也包含具有取代基之烷基(經 取代之烷基)者。 〔(A )含有具有選自經酸分解性基保護之羧基及經酸分 解性基保護之酚性羥基中至少一者之結構單元(1 )與具 有選自環氧基及氧雜環丁烷基中至少一者之結構單元(2 )之共聚物〕 本發明之感光性樹脂組成物是包含(A)含有具有選 自經酸分解性基保護之羧基及經酸分解性基保護之酚性羥 基中至少一者之結構單元(1)與具有選自環氧基及氧雜 環丁烷基中至少一者之結構單元(2)之共聚物(在下文 中,則適當地稱爲「共聚物(A )」)。 共聚物(A )較佳爲鹼不溶性,且當分子內所具有的 酸分解性基分解時,則會變成鹼可溶性之樹脂。 在此,在本發明所謂的 「酸分解性基(acid-decomposable group)」 是 意謂由 於在酸 的存在 下分解 ,而 -16- 201140249 可形成該經酸分解性基保護之羧基或酚性羥基之官能基。 在本發明中,所謂的共聚物(A )爲「鹼可溶性」是 意謂:藉由將含有酸分解性基被分解後的共聚物(A)之 溶液塗布於基板上,並在9 (TC加熱2分鐘所形成的塗膜 (厚度所顯現對於在231之0.4%氫氧化四甲基銨 水溶液之溶解速度爲〇. 〇 1 μ m/秒鐘以上。該鹼可溶性更佳 爲0.005/zm/秒鐘以上》 此外,在本發明中,所謂的共聚物(A)爲「鹼不溶 性」是意謂:藉由將含有共聚物(A)之溶液塗布於基板 上,並在90°C加熱2分鐘所形成的塗膜(厚度3#m)所 顯現對於在23°C之0.4%氫氧化四甲基銨水溶液之溶解速 度爲少於〇 · 〇 1 # m /秒鐘。該鹼不溶性更佳爲少於〇 . 〇 〇 5 μ m/秒鐘。 共聚物(A)是只要保持其全體爲鹼不溶性時,則不 排除導入酸性基者。在共聚物(A)導入酸性基時,其實 例是可列舉:例如具有後述之結構單元(3 a )等的情況。 共聚物(A)較佳爲丙烯酸酯系聚合物。 在本發明之「丙烯酸酯系聚合物」是加成聚合型之樹 脂’其係含有源於(甲基)丙烯酸及/或其酯之結構單元 之聚合物’該丙烯酸酯系聚合物是可具有源於(甲基)丙 烯酸及/或其酯之結構單元以外之結構單元,例如源於苯 乙烯類之結構單元或源於乙烯基化合物之結構單元等。 共聚物(A )相對於在聚合物中的全部結構單元,較 佳爲含有50莫耳%以上之源於(甲基)丙烯酸及/或其酯 -17- 201140249 之結構單元’更佳爲含有8 0莫耳%以上,特佳爲僅由源 於(甲基)丙烯酸及/或其酯之結構單元所構成之聚合物 〇 另外’也將「源於(甲基)丙烯酸及/或其酯之結構 單元」稱爲「丙烯酸酯系結構單元」。此外,(甲基)丙 烯酸是意謂甲基丙烯酸及/或丙烯酸。 在下文中,就構成共聚物(A )之結構單元詳細地加 以說明。 <結構單元(1 ) > 共聚物(A)是含有具有選自經酸分解性基保護之羧 基及經酸分解性基保護之酚性羥基中至少一者之結構單元 (1 )(在下文中’適當地簡稱爲「結構單元(1 )」)。 結構單元(1)之較佳模式之一是具有選自以下式( I a )所代表的部分結構及以下式(lb )所代表的部分結構 中至少一者之結構單元。 以下式(la )所代表的部分結構是羧基爲經酸分解性 基保護之結構,可藉由酸脫保護而形成羧基。此外,以下 式(lb )所代表的部分結構是酚性羥基爲經酸分解性基保 護之部分結構,可藉由酸脫保護而形成酚性羥基。In the general formula (OS-3) to the general formula (OS-5), R1 represents an alkyl group, an aryl group or a heteroaryl group, and a plurality of R2 may be independently represented by a hydrogen atom, an alkyl group or an aryl group. Or a halogen atom, a plurality of R6 may be independently represented by a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, and X represents a hydrazine or S , η represents 1 or 2, and m is an integer representing 0 to 6. -14- 201140249 The photosensitive resin composition of the present invention is a positive photosensitive resin composition. Further, the photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive) Resin composition). The photosensitive resin composition of the present invention contains the components (a) to (D), and is excellent in storage stability and sensitivity. Further, the photosensitive resin composition of the present invention is a cured film which is excellent in transparency and solvent resistance and has a pattern shape. Here, the term "pattern shape" as used in the present invention means that the shape of the formed pattern is a forward tapered shape. Therefore, the photosensitive resin composition of the present invention is particularly useful for forming an interlayer insulating film. In the case, a pattern formation suitable for forming a forward tapered shape such as a contact hole or the like can be performed. In addition, the term "transparency" in the present invention means a cured film obtained by performing at least exposure and heat treatment (baking treatment) using the photosensitive resin composition of the present invention, and coloring is suppressed. Further, in the following, the transparency which is exhibited by the cured film formed of the photosensitive resin composition of the present invention is sometimes referred to as "heat-resistant transparency". Further, the photosensitive resin composition of the present invention can also be used as a microlens. The photosensitive resin composition for forming a microlens must be excellent in sensitivity and storage stability, and the microlens (cured film) formed of the photosensitive resin composition must be excellent in transparency and solvent resistance. -15-201140249 In addition, when it is required to exhibit a favorable melt shape (the radius of curvature of the desired one), the photosensitive resin composition of the present invention is excellent in sensitivity and storage stability, thereby forming The cured film is excellent in transparency and solvent resistance, and also exhibits a good melt shape. Hereinafter, each component contained in the photosensitive resin composition will be described. Further, as regards the labeling of the group (atomic group) in the present specification, it is not described that the substituted or unsubstituted label is a member having a substituent as well as a substituent having no substituent. For example, "alkyl" is not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). [(A) a structural unit (1) containing at least one of a phenolic hydroxyl group selected from a carboxyl group protected by an acid-decomposable group and protected by an acid-decomposable group, and having a selected from the group consisting of an epoxy group and an oxetane The copolymer of the structural unit (2) of at least one of the groups] The photosensitive resin composition of the present invention comprises (A) a phenolic group having a carboxyl group selected from the group consisting of acid-decomposable groups and protected by an acid-decomposable group. a copolymer of at least one of the structural units (1) of at least one of the hydroxyl groups and a structural unit (2) having at least one selected from the group consisting of an epoxy group and an oxetane group (hereinafter, suitably referred to as "copolymer" (A)"). The copolymer (A) is preferably alkali-insoluble, and when the acid-decomposable group in the molecule is decomposed, it becomes an alkali-soluble resin. Here, the term "acid-decomposable group" in the present invention means that the acid group is decomposed in the presence of an acid, and -16-201140249 can form the carboxyl group or phenolic group protected by the acid-decomposable group. a functional group of a hydroxyl group. In the present invention, the term "alkali soluble" in the copolymer (A) means that a solution of the copolymer (A) having an acid-decomposable group decomposed is applied onto a substrate, and at 9 (TC). The coating film formed by heating for 2 minutes (the thickness is expressed as a dissolution rate of 0.4% of a tetramethylammonium hydroxide aqueous solution of 231. 〇1 μ m/sec or more. The alkali solubility is more preferably 0.005/zm/ Further, in the present invention, the term "base-insoluble" in the copolymer (A) means that the solution containing the copolymer (A) is applied onto a substrate and heated at 90 ° C. The coating film formed by the minute (thickness 3#m) appears to have a dissolution rate of 0.4% 氢氧化1 # m / sec in a 0.4% aqueous solution of tetramethylammonium hydroxide at 23 ° C. The alkali is insoluble. It is less than 〇. 〇〇 5 μ m / sec. The copolymer (A) is not limited to the introduction of an acidic group as long as it is kept alkali-insoluble. When the copolymer (A) is introduced into an acidic group, an example thereof For example, it may include a structural unit (3 a ) or the like which will be described later. The copolymer (A) is preferably an acrylate system. The "acrylate-based polymer" of the present invention is an addition polymerization type resin which contains a polymer derived from a structural unit of (meth)acrylic acid and/or an ester thereof. The acrylate-based polymer It may be a structural unit other than a structural unit derived from (meth)acrylic acid and/or an ester thereof, for example, a structural unit derived from a styrene type or a structural unit derived from a vinyl compound, etc. The copolymer (A) is relative to Preferably, all structural units in the polymer contain 50 mol% or more of structural units derived from (meth)acrylic acid and/or its ester-17-201140249, more preferably 80% by mole or more. It is particularly preferable that the polymer constituting only the structural unit derived from (meth)acrylic acid and/or its ester is also referred to as "a structural unit derived from (meth)acrylic acid and/or its ester". Further, (meth)acrylic acid means methacrylic acid and/or acrylic acid. Hereinafter, the structural unit constituting the copolymer (A) will be described in detail. <Structural unit (1) > Copolymer (A) And a structural unit (1) containing at least one selected from the group consisting of a carboxyl group protected by an acid-decomposable group and a phenolic hydroxyl group protected by an acid-decomposable group (hereinafter, 'appropriately referred to as "structural unit (1)") One of the preferred modes of the structural unit (1) is a structural unit having at least one selected from the partial structure represented by the following formula (Ia) and the partial structure represented by the following formula (lb). The partial structure represented by the carboxyl group is a structure protected by an acid-decomposable group, and can be deprotected by acid to form a carboxyl group. Further, a partial structure represented by the following formula (lb) is a phenolic hydroxyl group which is an acid-decomposable group. Part of the structure of the protection, the phenolic hydroxyl group can be formed by acid deprotection.
(lb) (la) -18 201140249 式(Ia )及式(lb )中,波線部分是代表與其他結構 之鍵結處。 式(Ia)及式(lb)中,R1是各自獨立地代表院基或 環烷基。 以R1所代表之烷基是可爲直鏈狀或分枝狀。 以R1所代表之烷基之碳原子數較佳爲1至20,更佳 爲1至10’進—步更佳爲1至7。 以R1所代表之環烷基之碳原子數較佳爲3至20 ,更 佳爲3至10,進一步更佳爲5至7。 另外’若R1是更進一步具有取代基時,則此等之碳 原子數也包含該取代基之碳原子數。 以R1所代表之烷基是可列舉··例如,甲基、乙基、 正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基 、正戊基、新戊基、正己基、正庚基、正辛基、2_乙基己 基、正壬基、正癸基等。 以R1所代表之環烷基是可列舉:例如,環丙基、環 丁基、環戊基、環己基、環庚基、環辛基、降冰片基、異 冰片基等。 此外’以R1所代表之烷基及環烷基是可具有取代基 。可導入於以R1所代表之烷基或環烷基之取代基是可例 示:碳原子數爲1至10之烷基(甲基、乙基、丙基、丁 基等)、碳原子數3至10之環烷基、碳原子數6至10之 芳基、鹵素原子(氟原子、氯原子、溴原子、碘原子)、 氰基、硝基、羥基、碳原子數爲1至10之烷氧基等,此 -19- 201140249 等之取代基是可更進一步經上述取代基加以取代。 此外,R1較佳爲碳原子數爲1至10之烷基、碳原子 數爲3至10之環烷基、或碳原子數爲7至11之芳烷基, 更佳爲碳原子數爲1至6之烷基、碳原子數爲3至6之環 烷基、或苯甲基,進一步更佳爲乙基或環己基,特佳爲乙 基。 式(la )及式(lb )中,R2是代表烷基。 以R2所代表之烷基是可爲直鏈狀或分枝狀。 以R2所代表之烷基之較佳的碳原子數是較佳爲1至 20’更佳爲1至10’進一步更佳爲1至7。 另外’若R2是更進一步具有取代基時,則此等之碳 原子數也包含該取代基之碳原子數。 以R2所代表之烷基較佳爲碳原子數爲1至6之烷基 ,特佳爲甲基。 式(lb)中’ Ar1是代表二價芳香族基,在芳香環上 具有—OCHiORiKR2)。 以Ar1所代表之二價芳香族基是並無特殊限制,可例 示:伸苯基、經取代之伸苯基、伸萘基、及經取代之伸萘 基等’較佳爲伸苯基、或經取代之伸苯基,更佳爲伸苯基 ’進一步更佳爲I,4 -伸苯基。 此外’以Ar1所代表之二價芳香族基是可在芳香環上 更進一步具有取代基’該取代基是可例示:碳原子數爲! 至10之烷基(甲基、乙基、丙基、丁基等)、碳原子數 3至10之環烷基、碳原子數6至1〇之芳基、鹵素原子( -20- 201140249 子 '碘原子) 之烷氧基等, 以取代。 氟原子、氯原子、漠原 、碳原子數爲1至1 〇 進一步經上述取代基加 、氰基、硝基、羥基 此等之取代基是可更 表的部分結構之結構單元是可使 竣基單體而導入於共聚物(A) 具有以式(U)所代 用可形成該結構單元的含 中。 可形成具有以式(Ia )所代表的部分結構之結構單元 之曰羧基單體,若爲由於該單體所具有的羧基是受到保護 而可成爲結構單元(i )者時,則可使用。其可列舉:例 如,丙烯酸、甲基丙烯酸、巴豆酸、甲基-對羧基苯乙 烯等之~元羧酸,順丁烯二酸 '反丁烯二酸、檸康酸、中 康酸、伊康酸等之二翔酸。 此外’結構單元(丨)是可列舉:較佳者爲源於此等 之含羧基單體之結構單元,且該單體所具有的羧基是受到 保護之結構單元。 具有以式(lb)所代表的部分結構之結構單元是可使 用可形成該結構單元的含酚性羥基單體而導入於共聚物( A )中。 具有可形成具有以式(lb )所代表的部分結構之結構 單元的含酚性羥基單體,若爲由於該單體所具有的酚性羥 基是受到保護而可成爲結構單元(1 )者時,則可使用。 此等含酚性羥基單體之較佳者是可列舉:例如,對羥基苯 乙烯、α-甲基-對羥基苯乙烯等之羥基苯乙烯類、在日本 特開2 00 8 -40 1 8 3號公報中之段落碼〔〇〇1 1〕至〔〇〇16〕 -21 - 201140249 所揭示之化合物、專利第 2 8 8 8 454號公報中之段落碼〔 0007〕至〔0010〕所揭示之4-羥基苯甲酸衍生物類、4-羥 基苯甲酸與甲基丙烯酸環氧丙酯之加成反應物、4-羥基苯 甲酸與丙烯酸環氧丙酯之加成反應物等。 在此等之中,含酚性羥基單體更佳爲α-甲基-對羥基 苯乙烯、在日本特開2008-40183號公報中之段落碼0011 至0016所揭示之化合物、專利第2888454號公報中之段 落碼0007至0010所揭示之4-羥基苯甲酸衍生物類、4 -羥 基苯甲酸與甲基丙烯酸環氧丙酯之加成反應物、4-羥基苯 甲酸與丙烯酸環氧丙酯之加成反應物。 在具有以上述式(la )所代表的部分結構或以式(lb )所代表的部分結構之結構單元中,作爲結構單元(1 ) 是特佳爲以下式(I c )所代表的結構單元。(lb) (la) -18 201140249 In the formulas (Ia) and (lb), the wave line portion represents the bond with other structures. In the formulae (Ia) and (lb), R1 each independently represents a noisy group or a cycloalkyl group. The alkyl group represented by R1 may be linear or branched. The number of carbon atoms of the alkyl group represented by R1 is preferably from 1 to 20, more preferably from 1 to 10', more preferably from 1 to 7. The number of carbon atoms of the cycloalkyl group represented by R1 is preferably from 3 to 20, more preferably from 3 to 10, still more preferably from 5 to 7. Further, when R1 is further substituted, the number of carbon atoms also includes the number of carbon atoms of the substituent. The alkyl group represented by R1 is exemplified by, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl, n-pentyl, Neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-decyl and the like. The cycloalkyl group represented by R1 may, for example, be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group or the like. Further, the alkyl group and the cycloalkyl group represented by R1 may have a substituent. The substituent which may be introduced into the alkyl group or the cycloalkyl group represented by R1 is exemplified by an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, butyl group, etc.), and 3 carbon atoms. a cycloalkyl group to 10, an aryl group having 6 to 10 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms. The oxy group or the like, the substituent of this -19-201140249 or the like can be further substituted by the above substituent. Further, R1 is preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms, more preferably 1 carbon atom. The alkyl group to 6 or a cycloalkyl group having 3 to 6 carbon atoms or a benzyl group is further more preferably an ethyl group or a cyclohexyl group, and particularly preferably an ethyl group. In the formula (la) and the formula (lb), R2 represents an alkyl group. The alkyl group represented by R2 may be linear or branched. The preferred number of carbon atoms of the alkyl group represented by R2 is preferably from 1 to 20', more preferably from 1 to 10', still more preferably from 1 to 7. Further, if R2 is further substituted, the number of carbon atoms also includes the number of carbon atoms of the substituent. The alkyl group represented by R2 is preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group. In the formula (lb), 'Ar1 represents a divalent aromatic group and has -OCHiORiKR2 on the aromatic ring. The divalent aromatic group represented by Ar1 is not particularly limited, and examples thereof include a phenyl group, a substituted phenyl group, a naphthyl group, and a substituted naphthyl group, which are preferably a phenyl group. Or a substituted phenyl group, more preferably a phenyl group, and further preferably an I, 4-phenylene group. Further, the divalent aromatic group represented by Ar1 may further have a substituent on the aromatic ring. The substituent is exemplified: the number of carbon atoms is! Alkyl groups (methyl, ethyl, propyl, butyl, etc.) to 10, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 1 carbon atoms, halogen atoms (-20-201140249 The 'alk atom' is substituted with an alkoxy group or the like. a fluorine atom, a chlorine atom, a desert atom, a carbon atom number of 1 to 1 〇 further added by the above substituent, a cyano group, a nitro group, a hydroxyl group or the like is a structural unit which can be more partially structurally The base monomer is introduced into the copolymer (A) having a compound which can be formed by substituting the formula (U) to form the structural unit. A fluorenylcarboxy group which can form a structural unit having a partial structure represented by the formula (Ia) can be used if it is a structural unit (i) because the carboxyl group of the monomer is protected. Examples thereof include, for example, acrylic acid, methacrylic acid, crotonic acid, methyl-p-carboxystyrene, etc., maleic acid 'fumaric acid, citraconic acid, mesaconic acid, and y. Diacidic acid such as soda. Further, the structural unit (丨) is preferably a structural unit derived from a carboxyl group-containing monomer derived therefrom, and the carboxyl group of the monomer is a protected structural unit. The structural unit having a partial structure represented by the formula (lb) can be introduced into the copolymer (A) by using a phenolic hydroxyl group-containing monomer capable of forming the structural unit. A phenolic hydroxy group-containing monomer having a structural unit having a partial structure represented by the formula (lb), if it is a structural unit (1) because the phenolic hydroxyl group of the monomer is protected , you can use it. Preferable examples of the phenolic hydroxy group-containing monomer include hydroxystyrenes such as p-hydroxystyrene and α-methyl-p-hydroxystyrene, and JP-A-200-8-40 1 8 Paragraphs in the No. 3 bulletin [〇〇1 1] to [〇〇16] -21 - 201140249 The disclosed compounds, paragraphs [0007] to [0010] in the patent No. 2 8 8 8454 a 4-hydroxybenzoic acid derivative, an addition reaction of 4-hydroxybenzoic acid with glycidyl methacrylate, an addition reaction of 4-hydroxybenzoic acid with glycidyl acrylate, and the like. Among these, the phenolic hydroxy group-containing monomer is more preferably α-methyl-p-hydroxystyrene, the compound disclosed in paragraphs 0011 to 0016 of JP-A-2008-40183, and the patent No. 2888454 Addition of 4-hydroxybenzoic acid derivatives, 4-hydroxybenzoic acid to glycidyl methacrylate, 4-hydroxybenzoic acid and glycidyl acrylate disclosed in paragraphs 0007 to 0010 Addition of the reactants. In the structural unit having a partial structure represented by the above formula (la) or a partial structure represented by the formula (lb), the structural unit (1) is particularly preferably a structural unit represented by the following formula (Ic) .
(Ic) 式(Ic )中’ R5是代表烷基或環烷基。r5之較佳模 式是與在式(la)及式(Ib)的Ri之較佳模式相同。 此外’式(Ic )中’ R6是代表氫原子或甲基。 S形成以式(I c )所代表的結構單元所使用的自由基 聚合性單體之較佳具體實例.是可列舉:例如,甲基丙烯酸 -22- 201140249 1-乙氧基乙醋、丙稀酸】每# 氧基乙酯、甲基丙烯酸1-甲氧 基乙酯、丙烯酸ι_甲氧基 基乙酷 '甲基丙烯酸1-正丁氧基 乙酯、丙烯酸1-正丁氧基7 基乙酯、甲基丙烯酸丨_異丁氧基 乙酯、丙烯酸1-異丁氧某 乙醋、甲基丙烯酸1-(2 -乙基己 氧基)乙酯、丙烯酸!·( 乙基己氧基)乙酯、甲基丙烯 酸1-正丙氧基乙醋 '丙嫌酿1 Μ柿酸1-正丙氧基乙酯、甲基丙烯 酸1-環己氧基乙酯、丙嫌 門佛酸1-環己氧基乙酯、甲基丙烯 酸1- ( 環己基乙氧基)乙 乙醋、丙烯酸1-(2-環己基乙氧 基)乙酯、甲基丙烯酸 本甲氧基乙酯、丙烯酸1-苯甲 氧基乙醋等;特佳择;田 "、、甲基丙烯酸1-乙氧基乙酯及丙烯酸 1-乙氧基乙醋。此等之白由甘 <目由基聚合性單體是可以一種單獨 或兩種以上組合使用。 爲形成3有以式(U)所代表的部分結構及以式( )所代表的部分結構之結構單元(丨)所使用的自由基聚 合注單體疋可使用巾售品者,或以習知的方法所合成者。 例如’若爲以下述結構式(A )所代表之單體時,則可以 如下列反應式所示將(甲基)丙烯酸在酸觸媒的存在下與 乙烯基醚化合物反應而合成。 ^VR CHS ο人。 VR5 VR6 5 酸 X +,CTR5 ——(Ic) In the formula (Ic), 'R5' represents an alkyl group or a cycloalkyl group. The preferred mode of r5 is the same as the preferred mode of Ri in equations (la) and (Ib). Further, 'R6' in the formula (Ic) represents a hydrogen atom or a methyl group. S is a preferred specific example of the radical polymerizable monomer used in the structural unit represented by the formula (Ic). For example, methacrylic acid-22-201140249 1-ethoxyethyl acetonate, C Dilute acid] #ethoxyethyl ester, 1-methoxyethyl methacrylate, ι_methoxy ethoxy methacrylate 1-n-butoxyethyl methacrylate, 1-n-butoxy acrylate 7 ethyl ester, 丨-isobutoxyethyl methacrylate, 1-isobutoxy acrylate, 1-(2-ethylhexyloxy)ethyl methacrylate, acrylic acid! ·(Ethylhexyloxy)ethyl ester, 1-n-propoxyethyl methacrylate propylene, 1 Μ11-, 1-n-propoxyethyl phthalate, 1-cyclohexyloxyethyl methacrylate , 1-cyclohexyloxyethyl acrylate, 1-(cyclohexylethoxy)ethyl methacrylate, 1-(2-cyclohexylethoxy)ethyl acrylate, methacrylic acid Methoxyethyl ester, 1-benzyloxyacetic acid acrylate, etc.; especially good choice; field ", 1-ethoxyethyl methacrylate and 1-ethoxyethyl acrylate. These whites can be used alone or in combination of two or more. To form a radical polymerizable monomer which has a partial structure represented by the formula (U) and a structural unit (丨) represented by the formula ( ), may be used as a towel seller, or The method of knowing the synthesis. For example, when it is a monomer represented by the following structural formula (A), (meth)acrylic acid can be synthesized by reacting with a vinyl ether compound in the presence of an acid catalyst as shown in the following reaction formula. ^VR CHS ο people. VR5 VR6 5 acid X +, CTR5 ——
Ο八OH (A) 上述反應式中’R5及R6是與在式(ic)之R5及Rl 爲同義 -23 201140249 此外’含有以式(I a )所代表的部分結構或以 ^ ( lb )所代表的部分結構之結構單元(1)是也可藉由將八 —'曰被 保護的羧基或酚性羥基單體與後述之結構單元(2)空 ^ ( 5 )或其前驅物進行聚合後’將羧基或酚性羥基與乙极 / 邮基_ 化合物反應而形成。另外’藉此所形成的較佳結檎單元之 具體實例是與上述源於自由基聚合性單體之具體實例 〜 < 結 構單元相同。 結構單元(1)之其他較佳模式是具有選自以下式( Ha )所代表的部分結構及以下式(nb )所代表的部分糸± 構中至少一者之結構單元。 人 /R3 Ar^ /R4 (Ha) (lib) 式(Ila )及式(lib )中,R3是代表第三級烷基、 四氫哌喃基或2-四氫呋喃基,R4是代表第三級烷基、三 級丁氧基羰基、2-四氫哌喃基或2-四氫呋喃基,Ar2是代 表二價芳香族基,波線部分是代表與其他結構之鍵結處。 在R3及R4之第三級烷基較佳爲碳數爲4至20者, 更佳爲碳數爲4至14者,進一步更佳爲碳數爲4至8者 〇 在 R3的第三級烷基、2 -四氫哌喃基或2 -四氫呋喃基 ,在R4的第三級烷基、三級丁氧基羰基、2-四氫哌喃基 -24- 201140249 或2 -四氫呋喃基,在Ar2的二價芳香族基是可具有取代基 。該取代基是可例示:碳數爲1至10之烷基(甲基、乙 基、丙基、丁基等)、碳數爲3至10之環烷基、碳數爲 6至10之芳基、鹵素原子(氟原子、氯原子、溴原子、 碘原子)、氰基、硝基、羥基、碳數爲1至10之院氧基 等。此等之取代基是可更進一步經上述取代基加以取代。 此外,在R3及R4之第三級烷基更佳爲選自由以如下 所示式(a )所代表之基所構成的群組中至少一種。 -C ( R9) ( R10) ( R11) ( a) 式(a)中,R9、R1()及R11是各自獨立地代表碳數爲 1至12之烷基、碳數爲3至12之環烷基、碳數爲6至12 之芳基或碳數爲7至12之芳烷基,此外,R9、R1。及 中任一者皆可兩個相互鍵結而與其等所鍵結的碳原子一起 形成環。 在式(a)以R9、R1»或R"所代表之碳數爲丨至12 之烷基是可爲直鏈狀或分枝鏈狀,可列舉:例如,甲基、 乙基、正丙基、異丙基、正丁基、異丁基、二級丁基 '三 級丁基、正戊基、新戊基、正己基、三級己基(2,3 -二甲 基_2· 丁基)、正庚基、正辛基、2-乙基己基、正壬基 '正 癸基等。 以R9、R1C)或R11所代表之碳數爲3至12之環烷基是 可列舉:例如,環丙基、環丁基'環戊基、環己基、環庚 基、環辛基、降冰片基、異冰片基等。 以R9、R1()或R11所代表之碳數爲6至12之芳基是可 •25- 201140249 列舉:例如,苯基、鄰甲苯基、茬基、異丙苯基 等。 以R9、R1C)或R11所代表之碳數爲7至12之 可列舉:例如,苯甲基、α-甲基苯甲基、苯乙基 基等。 此外,R9、RI()及R11是可相互鍵結而與其 之碳原子一起形成環。R9與R1Q、R9與R11、或 鍵結時的環結構是可列舉:例如,環丁基、環戊 基、環庚基、四氫呋喃基、金剛烷基、及四氫哌 此外,在式(Ila)之R3較佳爲碳數爲4至 級烷基、2 -四氫哌喃基或2 -四氫呋喃基,更佳爲 至8之第三級烷基、2 -四氫哌喃基或2 -四氫呋喃 步更佳爲三級丁基或2-四氫呋喃基,特佳爲2-基。 此外,在式(lib)之R4較佳爲碳數爲4至 三級烷基、三級丁氧基羰基、2-四氫哌喃基或2· 基,更佳爲碳數爲4至8之第三級烷基、2 -四氫 2 -四氫呋喃基,進一步更佳爲三級丁基或2 -四氫 特佳爲2 -四氫呋喃基。Ο8 OH (A) In the above reaction formula, 'R5 and R6 are synonymous with R5 and Rl in formula (ic)-23 201140249 In addition, 'containing part of the structure represented by formula (I a ) or ^ ( lb ) The structural unit (1) of the partial structure represented by the polymerization of the carboxy or phenolic hydroxy monomer which is protected by the octa-'曰 can be polymerized with the structural unit (2) described below or its precursor. It is formed by reacting a carboxyl group or a phenolic hydroxyl group with an ethyl group/postal group. Further, a specific example of a preferred crucible unit formed by this is the same as the above-described specific example of the radical polymerizable monomer to the <structural unit. Another preferred mode of the structural unit (1) is a structural unit having at least one selected from the partial structure represented by the following formula (Ha) and the partial 糸± structure represented by the following formula (nb). Human/R3 Ar^ /R4 (Ha) (lib) In the formula (Ila) and formula (lib), R3 represents a tertiary alkyl group, a tetrahydropyranyl group or a 2-tetrahydrofuranyl group, and R4 represents a third stage. An alkyl group, a tertiary butoxycarbonyl group, a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, Ar2 represents a divalent aromatic group, and a wavy portion represents a bond with another structure. The alkyl group of the third stage of R3 and R4 is preferably a carbon number of 4 to 20, more preferably a carbon number of 4 to 14, more preferably a carbon number of 4 to 8 and a third stage of R3. Alkyl, 2-tetrahydropentanyl or 2-tetrahydrofuranyl, a third alkyl group at R4, a tertiary butoxycarbonyl group, a 2-tetrahydropyranyl-24-201140249 or a 2-tetrahydrofuranyl group, The divalent aromatic group of Ar2 may have a substituent. The substituent is exemplified by an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, butyl group, etc.), a cycloalkyl group having 3 to 10 carbon atoms, and a carbon number of 6 to 10 a group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, a hydroxyl group, or a oxy group having a carbon number of 1 to 10. These substituents may be further substituted with the above substituents. Further, the alkyl group of the third stage of R3 and R4 is more preferably at least one selected from the group consisting of groups represented by the formula (a) shown below. -C ( R9) ( R10) ( R11 ) ( a) In the formula (a), R 9 , R 1 ( ) and R 11 are each independently represent an alkyl group having 1 to 12 carbon atoms and a carbon number of 3 to 12 An alkyl group, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, and further, R9 and R1. Either of the two may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. The alkyl group having a carbon number of from 丨 to 12 represented by R9, R1» or R" in the formula (a) may be a linear chain or a branched chain, and examples thereof include a methyl group, an ethyl group, and a n-propyl group. Base, isopropyl, n-butyl, isobutyl, secondary butyl 'tertiary butyl, n-pentyl, neopentyl, n-hexyl, tertiary hexyl (2,3-dimethyl-2-. Base), n-heptyl, n-octyl, 2-ethylhexyl, n-decyl 'n-decyl, and the like. The cycloalkyl group having a carbon number of 3 to 12 represented by R9, R1C) or R11 may, for example, be a cyclopropyl group, a cyclobutyl 'cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or a lower alkyl group. Borneol base, isobornyl base, etc. The aryl group having 6 to 12 carbon atoms represented by R9, R1() or R11 is pharmaceutically acceptable. 25-201140249 exemplified by phenyl, o-tolyl, fluorenyl, cumyl and the like. The carbon number represented by R9, R1C) or R11 is from 7 to 12, and examples thereof include a benzyl group, an α-methylbenzyl group, a phenethyl group and the like. Further, R9, RI() and R11 are bonded to each other to form a ring together with the carbon atoms thereof. R9 and R1Q, R9 and R11, or a ring structure at the time of bonding may, for example, be a cyclobutyl group, a cyclopentyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydroperpen further, in the formula (Ila) R3 is preferably a C 4 to alkyl group, a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, more preferably a tertiary alkyl group of 8 or 2 -tetrahydropyranyl or 2 - The tetrahydrofuran step is more preferably a tertiary butyl group or a 2-tetrahydrofuranyl group, particularly preferably a 2-based group. Further, R4 in the formula (lib) is preferably a carbon number of 4 to 3 alkyl, a tertiary butoxycarbonyl group, a 2-tetrahydropyranyl group or a 2 group group, more preferably a carbon number of 4 to 8 The third alkyl group, 2-tetrahydro-2-tetrahydrofuranyl group, further more preferably a tertiary butyl group or a 2-tetrahydrogen group is preferably a 2-tetrahydrofuranyl group.
I 式(lib )中,Ar2是代表二價芳香族基,在 具有 0(^(01^)(112)。 在式(lib )的 Ar2之較佳模式是與在前述 的A r 1之較佳模式相同。In the formula (lib), Ar2 represents a divalent aromatic group having 0 (^(01^)(112). The preferred mode of Ar2 in the formula (lib) is compared with the aforementioned A r 1 The best mode is the same.
由於羧基受到保護,可形成具有以式(IU 、1-萘基 芳烷基是 、萘基甲 等所鍵結 R10 與 R11 基、環己 喃基等。 12之第三 碳數爲4 基,進一 •四氫呋喃 i 12之第 -四氫呋喃 哌喃基或 呋喃基, 芳香環上 式(Ila ) )所代表 -26- 201140249 的結構之結構單元(1)之羧酸單體,若爲由於該單體所 具有的羧基受到保護而可形成以式(Ila )所代表的結構 者時,則可使用。該羧酸單體是可列舉:例如:丙烯酸、 甲基丙烯酸、巴豆酸、a-甲基-對羧基苯乙烯等之一元竣 酸;順丁烯二酸、反丁烯二酸、檸康酸、中康酸、伊康酸 等之二羧酸。此外,結構單元(1 )是可列舉源於此等殘 基是受到保護的羧酸之單體單元爲較佳者。 由於酚性羥基受到保護,可形成具有以前述式(lib )所代表的結構之結構單元(1)之具有酚性羥基之單體 ,若爲由於該單體所具有的酚性羥基受到保護而可形成以 式(Ila )所代表的結構者,則可使用。其較佳者是可列 舉:例~,對羥基苯乙烯、α-甲基·對羥基苯乙烯等之羥 基苯乙烯類、在日本特開200 8 -40 1 8 3號公報中之段落碼 001 1至0016所揭示之化合物、專利第2 8 8 8 4 54號公報中 之段落碼0007至0010所揭示之4-羥基苯甲酸衍生物類、 4-羥基苯甲酸與甲基丙烯酸環氧丙酯之加成反應物、4-羥 基苯甲酸與丙烯酸環氧丙酯之加成反應物等。 在此等之中,更佳爲α-甲基-對羥基苯乙烯、在日本 特開200 8 -40 1 8 3號公報中之段落碼〇〇11至〇〇16所揭示 之化合物、專利第2888454號公報中之段落碼〇〇〇7至 〇〇1〇所揭示之4-羥基苯甲酸衍生物類、4-羥基苯甲酸與 甲基丙烯酸環氧丙酯之加成反應物、4-羥基苯甲酸與丙烯 酸環氧丙酯之加成反應物。 在上述具有以式(Ila )所代表的部分結構或以式( -27- 201140249 lib )所代表的部分結構之結構單元中,作爲結構單元(1 )特佳爲以下式(Ilc)所代表的結構單元。Since the carboxyl group is protected, it can be formed by the formula (IU, 1-naphthylaralkyl, naphthyl, etc., R10 and R11 groups, cyclohexanyl, etc.. The third carbon number of 12 is 4 groups, The carboxylic acid monomer of the structural unit (1) of the structure of the structure of -26-201140249 represented by the formula -26-201140249 of the tetrahydrofuran i 12-tetrahydrofuranylpyranyl or furyl group, if it is due to the monomer When the carboxyl group is protected to form a structure represented by the formula (Ila), it can be used. The carboxylic acid monomer may, for example, be acrylic acid, methacrylic acid, crotonic acid, a-methyl-p-carboxystyrene or the like; maleic acid, fumaric acid, citraconic acid , dicarboxylic acid such as mesaconic acid and itaconic acid. Further, the structural unit (1) is preferably a monomer unit derived from a carboxylic acid whose residue is protected. Since the phenolic hydroxyl group is protected, a monomer having a phenolic hydroxyl group having the structural unit (1) of the structure represented by the above formula (lib) can be formed, if the phenolic hydroxyl group possessed by the monomer is protected It can be used if it can form a structure represented by the formula (Ila). Preferred examples thereof include hydroxystyrenes such as p-hydroxystyrene and α-methyl p-hydroxystyrene, and paragraph 001 in JP-A-200-8-40138. The compound disclosed in 1 to 0016, the 4-hydroxybenzoic acid derivative disclosed in paragraphs 0007 to 0010 of the Patent No. 2 8 8 8 54, 4-hydroxybenzoic acid and glycidyl methacrylate Addition reactant, addition reaction of 4-hydroxybenzoic acid and glycidyl acrylate, and the like. Among these, it is more preferably α-methyl-p-hydroxystyrene, a compound disclosed in paragraphs 11 to 16 of JP-A-200-8-40138, and Patent No. Addition of 4-hydroxybenzoic acid derivatives, 4-hydroxybenzoic acid to glycidyl methacrylate, 4-hydroxyl group disclosed in paragraphs 8887 to 〇〇1〇 of 2888454 An addition reaction of benzoic acid with glycidyl acrylate. In the above structural unit having a partial structure represented by the formula (Ila) or a partial structure represented by the formula (27-201140249 lib), the structural unit (1) is particularly preferably represented by the following formula (Ilc). Structural units.
(lie) 式(lie )中,R7是代表第三級烷基、2-四氫哌喃基 或2 -四氫呋喃基,R8是代表氫原子或甲基。 另外’式(lie)中’ R7之較佳模式是與在式(IU) 的R3之較佳模式相同。 爲形成以式(lie )所代表之單體單元所使用的自由 基聚合性單體之較佳具體實例是可列舉:例如,甲基丙烯 酸三級丁酯、丙烯酸三級丁酯、甲基丙烯酸四氫-2H-哌 喃-2-基酯、丙烯酸四氫-2H -哌喃-2 -基酯、甲基丙烯酸四 氫-2H -呋喃-2-基酯、丙烯酸四氫-2H -呋喃-2 -基酯、甲基 丙烯酸2-甲基-2-金剛烷酯、丙烯酸2_甲基-2-金剛烷酯、 甲基丙烯酸1-甲基環己酯、丙烯酸1-甲基環己酯等;特 佳爲甲基丙烯酸三級丁酯、丙烯酸三級丁酯、甲基丙烯酸 四氫-2H -呋喃-2 -基酯、丙烯酸四氫- 2H -呋喃-2-基酯。此 等之單體單元是可以一種單獨或兩種以上組合使用。 結構單元(1 )之較佳具體實例是可例示如下列(a 1 _ 1)至(al-4)及(a2-l)至(a2-6)所示之結構單元。 -28- 201140249(lie) In the formula (lie ), R7 represents a third-order alkyl group, 2-tetrahydropyranyl group or 2-tetrahydrofuranyl group, and R8 represents a hydrogen atom or a methyl group. Further, the preferred mode of 'R7' is the same as the preferred mode of R3 of the formula (IU). Preferred specific examples of the radical polymerizable monomer used for forming the monomer unit represented by the formula (lie) include, for example, tertiary butyl methacrylate, butyl acrylate, and methacrylic acid. Tetrahydro-2H-pentan-2-yl ester, tetrahydro-2H-pentan-2-yl acrylate, tetrahydro-2H-furan-2-yl methacrylate, tetrahydro-2H-furan acrylate- 2-based ester, 2-methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 1-methylcyclohexyl methacrylate, 1-methylcyclohexyl acrylate Etc.; particularly preferred is butyl methacrylate, butyl acrylate, tetrahydro-2H-furan-2-yl methacrylate, tetrahydro-2H-furan-2-yl acrylate. These monomer units may be used alone or in combination of two or more. Preferred specific examples of the structural unit (1) are structural units represented by the following (a 1 _ 1) to (al-4) and (a2-l) to (a2-6). -28- 201140249
-29- 201140249 ch3 CH3 ch3 0^0- oh3 -ch3 ch3 ch3 (a2-29- 201140249 ch3 CH3 ch3 0^0- oh3 -ch3 ch3 ch3 (a2
(32-2〉(32-2>
a2 - 3 )A2 - 3 )
(a2 - 4)(a2 - 4)
在此等之中’從感度、透明性並存的觀點’則最佳爲 以(a2-5)及(a2-6)所示結構單元。 在構成共聚物(A)之全部結構單元中’結構單元(1 )的含率較佳爲1 0至8 0莫耳% ’更佳爲1 5至7 0莫耳。/〇 ’特佳爲2 0至6 〇莫耳% ° <具有選自環氧基及氧雜環丁院基中至少一者之結構單元 (2 ) > 共聚物(A)是含有具有選自環氧基及氧雜環丁烷基 中至少一者之結構單元(2 )(在下文中’則適當地簡稱 -30- 201140249 爲「結構單元(2)」)。 結構單元(2)是只要在一個結構單元中具有至少一 個環氧基或氧雜環丁烷基即可,也可具有一個以上環氧基 及一個以上氧雜環丁院基、兩個以上環氧基、或兩個以上 氧雜環丁烷基,雖然並無特殊限制,但是較佳爲具有環氧 基及/或氧雜環丁烷基合計一至三個,更佳爲具有環氧基 及/或氧雜環丁烷基合計一或兩個,進一步更佳爲具有一 個環氧基或氧雜環丁烷基。 結構單元(2)較佳爲具有選自脂環環氧基及氧雜環 丁烷基中至少一者之結構單元,從感度、保存安定性的觀 點,則更佳爲具有氧雜環丁烷基之結構單元。 此外,在共聚物(A)之結構單元(1)與結構單元( 2)的組合較佳爲結構單元(1)爲具有經酸分解性基保護 之羧基之結構單元、結構單元(2)爲具有氧雜環丁烷基 之結構單元的組合。 脂環環氧基爲脂肪族環與環氧基環是形成縮合環之基 ,具體而言,其可列舉:例如,3,4-環氧環己基、2,3 -環 氧環己基、2,3-環氧環戊基等。 具有氧雜環丁烷基之基是只要具有氧雜環丁烷環時, 則並無特殊限制,其較佳可例示(3 _乙基氧雜環丁烷-3 -基 )甲基。 形成具有環氧基之結構單元所使用的自由基聚合性單 體的具體實例是可列舉:例如,丙烯酸環氧丙酯、甲基丙 稀酸環氧丙酯' α -乙基丙烯酸環氧丙酯、α-正丙基丙烯酸 -31 - 201140249 環氧丙酯、正丁基丙烯酸環氧丙酯、丙烯酸_3,4-環氧基 丁酯、甲基丙烯酸-3,4-環氧基丁酯、丙烯酸-6,7_環氧基 庚酯、甲基丙烯酸-6,7-環氧基庚酯、α_乙基丙烯酸-6,7-環 氧基庚酯、鄰乙烯基苯甲基環氧丙基醚、間乙烯基苯甲基 環氧丙基醚、對乙烯基苯甲基環氧丙基醚、專利第 4168443號公報中之段落碼〔 0031〕至〔〇〇35〕所揭示之 含有脂環式環氧骨架之化合物等。 形成具有氧雜環丁烷基之結構單元所使用的自由基聚 合性單體的實例是可列舉:例如,在日本特開200卜 330953號公報中之段落碼〔0011〕至〔〇〇16〕所揭示之 具有氧雜環丁烷基之(甲基)丙烯酸酯等。 形成具有環氧基及/或氧雜環丁烷基之結構單元所使 用的自由基聚合性單體的實例較佳爲含有甲基丙烯酸酯結 構之單體、含有丙烯酸酯結構之單體。 在此等單體中,更佳爲在專利第4168443號公報中之 段落碼00 3 4至003 5所揭示之含有脂環式環氧骨架之化合 物及在日本特開2001-330953號公報中之段落碼〇〇11至 00 16所揭示之具有氧雜環丁烷基之(甲基)丙烯酸酯, 特佳爲在特開200 1 - 3 3 095 3號公報中之段落碼 〇〇11至 〇〇16所揭示之具有氧雜環丁烷基之(甲基)丙烯酸酯。 此等之中,較佳爲丙烯酸3,4-環氧環己基甲酯、甲基丙烯 酸3,4-環氧基環己基甲酯、丙烯酸(3-乙基氧雜環丁烷- 3-基)甲酯' 及甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯 ;最佳爲丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯、及甲基 -32- 201140249 丙烯酸(3_乙基氧雜環丁烷_3-基)甲酯。此等之結構單元 是可以一種單獨或兩種以上組合使用° 結構單元(a3)之較隹具體實例是可例示以下列( a3-l )至(a3-6 )所代表的結構單兀。Among these, 'the viewpoint of sensitivity and transparency coexistence' is preferably a structural unit represented by (a2-5) and (a2-6). The content of the structural unit (1) in all the structural units constituting the copolymer (A) is preferably from 10 to 80 mol%, more preferably from 15 to 70 mol. /〇' particularly preferably from 20 to 6 mole % ° < structural unit having at least one selected from the group consisting of epoxy groups and oxetane groups (2) > copolymer (A) is contained A structural unit (2) selected from at least one of an epoxy group and an oxetane group (hereinafter, 'the appropriate name is -30-201140249 is "structural unit (2)"). The structural unit (2) may have at least one epoxy group or oxetanyl group in one structural unit, and may have one or more epoxy groups and one or more oxetane groups, and two or more rings. The oxy group or two or more oxetanyl groups, although not particularly limited, preferably have one to three in total of an epoxy group and/or an oxetane group, more preferably an epoxy group and The oxetane group has one or two in total, and more preferably has one epoxy group or oxetane group. The structural unit (2) preferably has a structural unit selected from at least one of an alicyclic epoxy group and an oxetane group, and more preferably has an oxetane viewpoint from the viewpoint of sensitivity and storage stability. The structural unit of the base. Further, in the combination of the structural unit (1) and the structural unit (2) of the copolymer (A), the structural unit (1) is preferably a structural unit having a carboxyl group protected by an acid-decomposable group, and the structural unit (2) is A combination of structural units having an oxetane group. The alicyclic epoxy group is a group in which an aliphatic ring and an epoxy ring form a condensed ring, and specific examples thereof include, for example, 3,4-epoxycyclohexyl, 2,3-epoxycyclohexyl, 2 , 3-epoxycyclopentyl and the like. The group having an oxetane group is not particularly limited as long as it has an oxetane ring, and preferably (3-ethyloxybutane-3-yl)methyl. Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate acrylate Ester, α-n-propylacrylic acid-31 - 201140249 propylene oxide, glycidyl n-butyl acrylate, _3,4-epoxybutyl acrylate, 3,4-epoxy butyl methacrylate Ester, acrylate-6,7-epoxyheptyl ester, -6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl Epoxypropyl ether, m-vinylbenzyloxypropyl ether, p-vinylbenzyloxypropyl ether, and paragraphs [0031] to [35] in Japanese Patent No. 4,184,443 A compound containing an alicyclic epoxy skeleton or the like. Examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include, for example, paragraphs [0011] to [〇〇16] in JP-A-200-330953. The disclosed (meth) acrylate having an oxetane group and the like. An example of the radical polymerizable monomer used to form the structural unit having an epoxy group and/or an oxetane group is preferably a monomer having a methacrylate structure or a monomer having an acrylate structure. Among these monomers, the alicyclic epoxy skeleton-containing compound disclosed in paragraphs 00 3 to 003 5 of the Japanese Patent No. 4,184,443, and the Japanese Patent Laid-Open Publication No. 2001-330953 The (meth) acrylate having an oxetane group disclosed in paragraphs 11 to 00 16 , particularly preferably in paragraphs 〇〇 11 to 〇 in JP-A-200 1 - 3 3 095 3 The (meth) acrylate having an oxetane group disclosed in 〇16. Among these, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and acrylic acid (3-ethyloxetane-3-yl) are preferred. Methyl ester' and (3-ethyloxetane-3-yl)methyl methacrylate; optimally (3-ethyloxetan-3-yl)methyl acrylate, and Base-32- 201140249 Acrylic acid (3-ethyloxetane-3-yl)methyl ester. Such structural units may be used singly or in combination of two or more. The structural example of the structural unit (a3) is exemplified by the structural unit represented by the following (a3-l) to (a3-6).
(a3 -1 ) (a3 · 2)(a3 -1 ) (a3 · 2)
在構成共聚物(A)的全部結構單元中,結構單元(2 )的含率較佳爲1〇至8〇莫耳%,更佳爲15至70莫耳% ,特佳爲20至65莫耳%。藉由具有上述比例之結構單元 (2 ),則本發明之感光性樹脂組成物所獲得硬化膜之物 性爲良好。 -33- 201140249 在共聚物(A)之結構單元(1)與結構單元 含率,以莫耳比計,則較佳爲結構單元(1 ):結 (2)=100: (10 至 200),更佳爲 1〇〇: (10 至 ,進一步更佳爲100: (50至150)。 <其他結構單元(3 ) > 共聚物(A)是可在不阻礙本發明之功效範圍 其他結構單元(3 ),該結構單元(3 )是可列舉: 基、羧酸酐殘基及/或酚性羥基之結構單元(3 a ) 結構單元(1 )至(2 ) 、( 3 a )以外之結構單元( <具有羧基、羧酸酐殘基及/或酚性羥基之結構單 )> 共聚物(A)較佳爲在該共聚物(A)不成爲 性之範圍’含有具有羧基、羧酸酐殘基及/或酚性 結構單元(3 a )(在下文中,則適當地簡稱爲「結 (3a )」),更佳爲含有具有羧基及/或酚性羥基 單元。 爲形成具有羧基之結構單元所使用的自由基聚 體是可列舉:例如,較佳爲丙烯酸、甲基丙烯酸、 等之一元羧酸;順丁烯二酸、反丁烯二酸、檸康酸 酸、伊康酸等之二羧酸。 此外’爲形成具有羧酸酐殘基之結構單元所使 由基聚合性單體是可列舉:例如,較佳爲順丁烧二 伊康酸酐等。爲形成具有酚性羥基之結構單元所使 由基聚合性單體是可列舉:例如,較佳爲對羥基苯 (2 )之 構單元 ί 150) ,具有 具有羧 、前述 3b ) ° 元(3a 鹼可溶 羥基之 構單元 之結構 合性單 巴豆酸 、中康 用的自 酸酐、 用的自 乙烯、 -34- 201140249 α -甲基-對羥基苯乙烯等之羥基苯乙烯類、在日本特開 2 0 0 8 - 4 0 1 8 3號公報中之段落碼0 〇 1 1至0 0 1 6所揭示之化合 物、在專利第 2 8 8 8 454號公報中之段落碼〔〇〇〇7〕至〔 〇〇1〇〕所揭示之4-羥基苯甲酸衍生物類' 4-羥基苯甲酸與 甲基丙烯酸環氧丙酯之加成反應物、4 -羥基苯甲酸與丙烯 酸環氧丙酯之加成反應物等。 在此等之中,用於將結構單元(3a)導入於共聚物( A)之自由基聚合性單體更佳爲甲基丙烯酸、丙烯酸、在 曰本特開2008-40183號公報中之段落碼0011至0016所 揭示之化合物、專利第2 8 8 8 454號公報中之段落碼〔〇〇〇7 〕至〔0010〕所揭示之4-羥基苯甲酸衍生物類、4-羥基苯 甲酸與甲基丙烯酸環氧丙酯之加成反應物、4-羥基苯甲酸 與丙烯酸環氧丙酯之加成反應物;特佳爲在日本特開 2008-40183號公報中之段落碼〔0011〕至〔0016〕所揭示 之化合物、專利第2888454號公報中之段落碼〔 0007〕至 〔〇〇1〇〕所揭示之4·羥基苯甲酸衍生物類、4-羥基苯甲酸 與甲基丙烯酸環氧丙酯之加成反應物、4-羥基苯甲酸與丙 烯酸環氧丙酯之加成反應物。此等之結構單元是可以一種 單獨或兩種以上組合使用。 結構單元(3 a )之較佳具體實例是可例示以下列( a 4 -1 )至(a 4 -1 1 )所代表的結構單元。 -35- 201140249In all the structural units constituting the copolymer (A), the content of the structural unit (2) is preferably from 1 to 8 mol%, more preferably from 15 to 70 mol%, particularly preferably from 20 to 65 mol. ear%. By the structural unit (2) having the above ratio, the physical properties of the cured film obtained by the photosensitive resin composition of the present invention are good. -33- 201140249 In the copolymer (A) structural unit (1) and structural unit content, in terms of molar ratio, it is preferably structural unit (1): knot (2) = 100: (10 to 200) More preferably, it is 1 : (10 to, further preferably 100: (50 to 150). <Other structural unit (3) > Copolymer (A) is a range which does not inhibit the efficacy of the present invention. The structural unit (3), which is exemplified by: a structural unit of a carboxylic anhydride residue and/or a phenolic hydroxyl group (3 a ) other than structural units (1) to (2) and (3 a ) (Structure unit having a carboxyl group, a carboxylic acid anhydride residue, and/or a phenolic hydroxyl group) > The copolymer (A) preferably has a carboxyl group in the range in which the copolymer (A) is not inferior The carboxylic acid anhydride residue and/or the phenolic structural unit (3 a ) (hereinafter, abbreviated as "junction (3a )"), more preferably contains a carboxyl group and/or a phenolic hydroxyl group. The radical polymer used in the structural unit may, for example, be preferably a monocarboxylic acid such as acrylic acid, methacrylic acid or the like; maleic acid or the opposite a dicarboxylic acid such as butenedioic acid, citraconic acid or itaconic acid. Further, the radical polymerizable monomer which is a structural unit having a carboxylic anhydride residue is exemplified by, for example, preferably The diaconic anhydride or the like is produced. The base polymerizable monomer which is a structural unit having a phenolic hydroxyl group is, for example, preferably a structural unit of p-hydroxybenzene (2) ί 150) having a carboxyl group. The above 3b) ° (3a structurally compatible mono-crotonic acid of the alkali-soluble hydroxyl group, self-anhydride for Zhongkang, used from ethylene, -34- 201140249 α-methyl-p-hydroxystyrene and other hydroxyl groups Styrene, a compound disclosed in paragraphs 0 〇1 1 to 0 0 1 6 of Japanese Patent Laid-Open Publication No. 2000-401, No. 2 8 8 454 Addition reaction of 4-hydroxybenzoic acid derivative 4-hydroxybenzoic acid to glycidyl methacrylate disclosed in paragraphs [〇〇〇7] to [〇〇1〇], 4-hydroxybenzene An addition reaction product of formic acid and glycidyl acrylate, etc. Among these, the structural unit (3a) is used for introduction. The radical polymerizable monomer of the material (A) is more preferably a methacrylic acid or an acrylic acid, a compound disclosed in paragraphs 0011 to 0016 of JP-A-2008-40183, and a patent No. 2 8 8 8 454. 4-hydroxybenzoic acid derivatives, 4-hydroxybenzoic acid and glycidyl methacrylate addition reactants, 4-hydroxybenzene disclosed in paragraphs [〇〇〇7] to [0010] The addition reaction of formic acid and glycidyl acrylate; the compound disclosed in paragraphs [0011] to [0016] of JP-A-2008-40183, and the paragraph number in Patent No. 2888454 Addition of 4-hydroxybenzoic acid derivatives, 4-hydroxybenzoic acid to glycidyl methacrylate, 4-hydroxybenzoic acid and acrylic acid epoxy, as disclosed in [0007] to [〇〇1〇] The addition reaction of propyl ester. These structural units may be used singly or in combination of two or more. Preferred specific examples of the structural unit (3a) are structural units represented by the following (a 4 -1 ) to (a 4 -1 1 ). -35- 201140249
共聚物(A)是具有結構單元(3a)時,在構成共聚 物(A )的全部結構單元中,則結構單元(3 a )的含率較 佳爲1至25莫耳%,更佳爲2至25莫耳%,特佳爲3至 2 0莫耳%。藉由具有上述比例之結構單元(3 a ),則可獲 得高感度,且顯影性也爲良好。 〈除了( 1 )至(2 ) 、 ( 3a )以外之結構單元(3b ) > 共聚物(A)是可在不阻礙本發明之功效範圍,含有 除了前述(1 )至(2 ) 、 ( 3 a )以外之結構單元(3 b )( 在下文中,則適當地簡稱爲「結構單元(3 b )」)。 爲形成結構單元(3b )所使用的自由基聚合性單體是 -36- 201140249 可列舉:例如,在日本特開2004-264623號公報中之段落 碼〔 0021〕至〔 0024〕所揭示之化合物(但是,形成前述 結構單元(1 )至(2 ) 、( 3 a )之單體則除外)。 在此等之中,爲獲得結構單元(3b )之自由基聚合性 單體,從提高電特性的觀點,則較佳爲如(甲基)丙烁酸 二環戊烷酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸環 己酯之含有脂環結構之(甲基)丙烯酸酯類、及苯乙烯類 。從透明性的觀點,則較佳爲(甲基)丙烯酸甲酯。從感 度的觀點,則較佳爲(甲基)丙烯酸2 -羥基乙酯。在此等 之中,更佳爲(甲基)丙烯酸2 -羥基乙酯。 結構單元(3b)是可爲一種單獨或組合兩種以上。 共聚物(A )是具有結構車元(3 a )時’則在構成共 聚物(A )的全部結構單元中,結構單元(3 a )的含率較 佳爲1至5 0莫耳%,更佳爲5至4 0莫耳%,特佳爲5至 3 0莫耳%。 共聚物(A)之重量平均分子量較佳爲 1,〇〇〇至 100,000,更佳爲2,000至50,000。另外,在本發明之重 量平均分子量是以凝膠透層析法(GPC )所測定之經聚苯 乙烯換算得之重量平均分子量。 將共聚物(A )所具有的各結構單元導入於共聚物( A)中之方法是可爲聚合法或高分子反應法,也可此等之 兩方法倂用。 若使用聚合法時,則預先合成含有特定官能基之單體 後’將此等單體加以共聚合。亦即,共聚物(A)是可藉 -37- 201140249 由將結構單元(1)、結構單元(2)、及因應需要爲形成 結構單元(3a) 、(3b)而使用的含有自由基聚合性單體 之自由基聚合性單體混合物,在有機溶劑中,使用自由基 聚合引發劑進行聚合而合成。 例如,可將具有以式(1 a )或式(1 b )所代表的部分 結構之烯鍵性不飽和化合物、及具有環氧基或氧雜環丁烷 基之烯鍵性不飽和化合物加以混合、加成聚合而獲得作爲 目的之共聚物(A )。 若使用高分子反應法時,則使用特定的種類之單體進 行聚合反應後,利用在所獲得共聚物之結構單元所含有的 反應性基,將必要的官能基導入於結構單元中。在此,可 導入之官能基是可例示:用於保護酚性羥基或羧基同時用 於在強酸的存在下分解而使此等游離之保護基、環氧基或 氧雜環丁烷基等之交聯性基、如酚性羥基或羧基之鹼可溶 性基(酸性基)等。 例如,可例示將經共聚合甲基丙烯酸2-羥基乙酯的共 聚物與表氯醇反應而導入環氧基。如上所述,經進行共聚 合具有反應性基之烯鍵性不飽和化合物後,有效利用殘留 於側鏈的反應性基,藉由高分子反應則可將如以式(la ) 及/或式(lb )所代表的部分結構或交聯性基之官能基導 入於共聚物(A )之側鏈。 在下文中,例示較佳的在本發明使用之共聚物(A) ,但是本發明並不受限於此等者。 另外,於下述所例示的共聚物(A)之重量平均分子 -38- 201140249 量爲2,000至50,000。組成比是以在(.)內之莫耳°/。來 表示。 甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸環氧丙酯共聚 物(5 0/5 0 )、 甲基丙烯酸1·乙氧基乙酯/甲基丙烯酸環氧丙酯/甲基 丙烯酸共聚物(50/40/1 0 )、 甲基丙條酸1-乙氧基乙酯/甲基丙嫌酸環氧丙醋/甲基 丙烯酸/甲基丙烯酸2-羥基乙酯共聚物( 40/30/1 0/20) ' 甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸四氫- 2H-哌喃-2-基酯/甲基丙烯酸環氧丙酯/甲基丙烯酸/甲基丙烯酸2-羥 基乙酯共聚物( 2 0/2 0/3 0/ 1 0/2 0 )、 甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸四氫- 2H-呋喃-2-基酯/甲基丙烯酸環氧丙酯/甲基丙烯酸/甲基丙烯酸2-羥 基乙酯共聚物( 20/20/3 0/ 1 0/20 )、 甲基丙烯酸四氫-2H -呋喃-2 -基酯/甲基丙烯酸環氧丙 酯/甲基丙烯酸/甲基丙烯酸 2_羥基乙酯共聚物( 40/30/10/20)、 甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸3,4-環氧基環 己基甲酯/甲基丙烯酸共聚物( 45/40/ 1 5 )、 甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸3,4-環氧基環 己基甲酯/甲基丙烯酸/甲基丙烯酸2-羥基乙酯共聚物( 40/30/10/20)、 甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸3,4-環氧基環 己基甲酯V4-羥基苯甲酸(3-甲基丙烯醯氧基-2-羥基丙基 •39- 201140249 )酯/甲基丙烯酸2-羥基乙酯共聚物( 40/3 0/ 1 0/2 0 )、 甲基丙烯酸1-乙氧基乙醋/甲基丙烯酸(3-乙基氧雜 環丁烷-3-基)甲酯共聚物(50/50)、 甲基丙烯酸卜乙氧基乙醋/甲基丙烯酸(3-乙基氧雜 環丁烷-3-基)甲酯/甲基两稀酸共聚物(50/40/1 0 )、 甲基丙烯酸1-乙氧基乙醋/甲基丙烯酸(3-乙基氧雜 環丁烷-3-基)甲酯/甲基丙嫌酸/甲基丙烯酸2-羥基乙酯共 聚物(40/3 0/ 1 0/20 ) ' 甲基丙烯酸四氫- 2H -哌喃-2-基酯/甲基丙烯酸(3 -乙 基氧雜環丁烷-3-基)甲酯/甲基丙烯酸/甲基丙烯酸2-羥基 乙酯共聚物(40/3 0/ 1 0/20 )、 甲基丙烯酸四氫- 2H -呋喃-2-基酯/甲基丙烯酸(3 -乙 基氧雜環丁烷-3-基)甲酯/甲錾丙烯酸/甲基丙烯酸2 -羥基 乙酯共聚物(4 0/3 0/ 1 0/20 )、 甲基丙烯酸四氫-2H-呋喃-2-基酯/甲基丙烯酸(3-乙 基氧雜環丁烷-3-基.)甲酯/甲基丙烯酸/甲基丙烯酸2-羥基 乙酯/苯乙烯共聚物( 40/30/1 0/ 1 0/1 0 )、 甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸(3-乙基氧雜 環丁烷-3-基)甲酯/4-羥基苯甲酸(3-甲基丙烯醯氧基丙 基)酯/甲基丙烯酸2-羥基乙酯共聚物(40/30/1 0/2〇)、 甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸1-甲基-卜環己 酯/甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯/甲基丙烯 酸/甲基丙烯酸2-羥基乙酯共聚物( 20/20/30/10/20)、 甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸四氫- 2H-哌喃- -40- 201140249 2-基酯/甲基丙烯酸(3_乙基氧雜環丁垸-3·基)甲醋/4_羥 基苯甲酸(3·甲基丙烯醯氧基丙基)醋/甲基丙稀酸2·羥 基乙酯共聚物(20/2 0/3 0/ 1 0/2 0 )、 甲基丙烯酸1-(環己氧基)乙酯/甲基丙烯酸環氧丙 酯/甲基丙烯酸共聚物(5〇/35/15)、 甲基丙烯酸1-(環己氧基)乙酯/甲基丙烯酸環氧丙 酯/甲基丙烯酸/甲基丙烯酸 2-羥基乙酯共聚物( 3 5/3 0/ 1 0/2 5 ) ' 甲基丙烯酸1-(環己氧基)乙酯/甲基丙烯酸3,4-環 氧基環己基甲酯/甲基丙烯酸共聚物( 5 0/40/ 1 0 )、 甲基丙烯酸1-(環己氧基)乙酯/甲基丙烯酸3,4-環 氧基環己基甲酯/甲基丙烯酸/甲基丙烯酸2 -羥基乙酯共聚 物(40/3 0/ 1 0/20 )、 甲基丙烯酸1-(環己氧基)乙酯/甲基丙烯酸(3-乙 基氧雜環丁烷-3-基)甲酯/甲基丙烯酸共聚物(5 0/40/ 1 0 )' 甲基丙烯酸1-(環己氧基)乙酯/甲基丙烯酸(3 -乙 基氧雜環丁烷-3-基)甲酯/甲基丙烯酸/甲基丙烯酸2 -羥基 乙酯共聚物(40/30/1 0/20 )、 甲基丙嫌酸1-(環己氧基)乙酯/甲基丙嫌酸(3 -乙 基氧雜環丁烷-3-基)甲酯α-甲基-對羥基苯乙烯/甲基丙烯 酸2 -羥基乙酯共聚物( 30/30/20/20)、 甲基丙烯酸1·(環己氧基)乙酯/甲基丙烯酸四氫― 2Η-哌喃-2-基酯/甲基丙烯酸(3_乙基氧雜環丁院·3_基) -41 - 201140249 甲酯/4-羥基苯甲酸(3-甲基丙烯醯氧基丙基)酯/甲基丙 烯酸2-羥基乙酯共聚物( 40/30/15/15)、 4-羥基苯甲酸(3-甲基丙烯醯氧基丙基)酯之1-乙氧 基乙基醚/甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯/甲 基丙烯酸/甲基丙烯酸2-羥基乙酯共聚物( 40/3 0/ 1 0/2 0 ) 〇 本發明之感光性樹脂組成物是可含有單獨一種或組合 兩種以上之共聚物(A)。 本發明之感光性樹脂組成物中之共聚物(A)的含量 ,相對於感光性樹脂組成物之總固體成分,則較佳爲20 至99質量%,更佳爲40至97質量%,進一步更佳爲60 至95質量%。若共聚物(A )的含量爲在該範圍時,則經 顯影時之圖案形成性將成爲良好。 另外,本發明之感光性樹脂組成物是可在不阻礙本發 明之功效範圍,倂用除了共聚物(A )以外之樹脂。但是 ,從顯影性的觀點,則除了共聚物(A )以外之樹脂的含 量較佳爲少於共聚物(A )的含量。 〔(B )光酸產生劑〕 本發明之感光性樹脂組成物是含有在下文中所詳細說 明的選自以通式(I)、通式(OS-1)、通式(OS-3)、 通式(OS-4 )、及通式(OS-5 )所代表的光酸產生劑中至 少一種光酸產生劑(光酸產生劑(B))。 在光酸產生劑(B)所包含的各光酸產生劑中,最佳 爲以通式(I)、通式(OS-3)、通式(OS-4)、或通式 -42- 201140249 (◦ S - 5 )所代表之光酸產生劑。 . 在下文中,就在光酸產生劑(B)所包含的各光酸產 生劑詳細地加以說明。 在光酸產生劑(B)所包含的光酸產生劑之一模式是 以下述通式(I )所代表之光酸產生劑。 r1a—c(r2A) = n-o-so2- r3A (I) 通式(I)中,R1A是代表碳原子數爲1至6之烷基、 碳原子數爲1至4之鹵化烷基、苯基、聯苯基、萘基、2-呋喃基、2 -噻吩基、碳原子數爲1至4之烷氧基或氰基; 若R1A爲苯基、聯苯基、萘基或蒽基時,則此等之基是也 可爲經選自由鹵素原子、羥基、碳原子數爲1至4之烷基 、碳原子數爲1至4之烷氧基及硝基所構成的群組中之取 代基加以取代。R2A是代表碳原子數爲1至1 0之烷基、碳 原子數爲1至10之烷氧基、碳原子數爲1至5之鹵化烷 基、碳原子數爲1至5之鹵化烷氧基、可經W取代之苯 基、可經W取代之萘基或可經W取代之蒽基、二烷基胺 基、嗎啉基或氰基。尺^與R1A是可相互鍵結而形成5員 環或6員環,該5員環或6員環是可與也可具有一個或兩 個任意之取代基的苯環鍵結。R3A是代表碳原子數爲丨至 10之烷基、碳原子數爲1至10之烷氧基、碳原子數爲1 至5之鹵化烷基、碳原子數爲丨至5之鹵化烷氧基、可經 W取代之苯基、可經W取代之萘基或可經W取代之蒽基 。评是代表鹵素原子、氰基、硝基、碳原子數爲1至1〇 之烷基、碳原子數爲1至10之烷氧基、碳原子數爲1至 -43- 201140249 5之鹵化烷基率碳原子數爲1至5之鹵化烷$ 以R1A所代表之碳原子數爲1至6之烷 或分枝鏈烷基,其可列舉:例如,甲基、乙 丙基、正丁基、二級丁基、三級丁基、正戊 正己基、或2-乙基丁基。 以RIA所代表之碳原子數爲1至4之幽 舉:例如,氯甲基、三氯甲基、三氟甲基、 以RIA所代表之碳原子數爲1至4之烷 甲氧基或乙氧基。 R1A是代表苯基、聯苯基、萘基或蒽基 基是也可爲經選自由鹵素原子(例如,氯原 碘原子等)、羥基、碳原子數爲1至4之烷 基、乙基、丙基、異丙基、正丁基、二級丁 )、碳原子數爲1至4之烷氧基(例如,甲 、正丙氧基、異丙氧基、正丁氧基)及硝基 中之取代基加以取代。 以R2A所代表之碳原子數爲1至10之 例是可列舉:甲基、乙基、正丙基、異丙基 丁基、二級丁基、三級丁基、正戊基、異戊 、正己基、正庚基、正辛基、正壬基、正癸 以R2A所代表之碳原子數爲1至10之 實例是可列舉:甲氧基、乙氧基、正丙氧基 正丁氧基、正戊氧基、正辛氧基、正癸氧基 以R2A所代表之碳原子數爲1至5之鹵 萬基。 基是可爲直鏈 基、丙基、異 基、異戊基、 化烷基是可列 或2 -溴丙基。 氧基是可列舉 時,則此等之 子、溴原子、 基(例如,甲 基、三級丁基 氧基、乙氧基 所構成的群組 烷基的具體實 、正丁基、異 基、二級戊基 基等。 烷氧基的具體 、異丙氧基、 等。 化烷基的具體 -44- 201140249 實例是可列舉:三氟甲基、五氟乙基、全氟-正丙基、全 氟-正丁基、全氟-正戊基等。 以R2A所代表之碳原子數爲1至5之鹵化烷氧基的具 體實例是可列舉:三氟甲氧基、五氟乙氧基、全氟-正丙 氧基、全氟-正丁氧基、全氟-正戊氧基等。 以R2A所代表之可經 w取代之苯基的具體實例是可 列舉:鄰甲苯基、間甲苯基、對甲苯基、鄰乙基苯基、間 乙基苯基、對乙基苯基、對(正丙基)苯基、對(異丙基 )苯基、對(正丁基)苯基、對(異丁基)苯基、對(二 級丁基)苯基、對(三級丁基)苯基、對(正戊基)苯基 、對(異戊基)苯基、對(三級戊基)苯基、鄰甲氧基苯 基、間甲氧基苯基、對甲氧基苯基、鄰乙氧基苯基、間乙 氧基苯基、對乙氧基苯基、對(正丙氧基)苯基、對(異 丙氧基)苯基、對(正丁氧基)苯基、對(異丁氧基)苯 基、對(二級丁氧基)苯基、對(三級丁氧基)苯基、對 (正戊氧基)苯基、對(異戊氧基)苯基、對(三級戊氧 基)苯基、對氯苯基、對溴苯基、對氟苯基、2,4-二氯苯 基、2,4-二溴苯基、2,4-二氟苯基、2,4,6-三氯苯基、 2,4,6-三溴苯基、2,4,6-三氟苯基、五氯苯基、五溴苯基、 五氟苯基、對聯苯基等。 以R2A所代表之可經W取代之萘基的具體實例是可 列舉:2 -甲基-1-萘基、3 -甲基-1-萘基、4 -甲基-1-萘基、 5-甲基-1-萘基、6-甲基-1-萘基、7-甲基-1-萘基、8-甲基-1-萘基、1-甲基-2-萘基、3-甲基-2-萘基、4-甲基-2-萘基 -45- 201140249 、5-甲基-2-萘基、6-甲基-2-萘基、7-甲基-2-萘基、8-甲 基-2-萘基等。 以R2A所代表之可經w取代之蒽基的具體實例是可 列舉:2 -甲基-1-蒽基、3·甲基-1-蒽基、4 -甲基-1-蒽基、 5-甲基-1-蒽基、6-甲基-1-蒽基、7-甲基-1-蒽基、8-甲基-1-蒽基、9_甲基-1-蒽基、10-甲基-1-蒽基、1-甲基-2-蒽基 、3-甲基-2-蒽基、4-甲基-2-蒽基、5-甲基-2-蒽基、6-甲 基-2-蒽基、7-甲基-2-蒽基、8-甲基-2-蒽基、9-甲基-2-蒽 基、1 〇-甲基-2-蒽基等。 以R2A所代表之二烷基胺基是可列舉:二甲基胺基、 二乙基胺基、二丙基胺基、二丁基胺基、二苯基胺基等。 以R3A所代表之碳原子數爲1至10之烷基的具體實 例是可列舉:甲基、乙基、正丙基、異丙基、正丁基、異 丁基、二級丁基、三級丁基、正戊基、異戊基、二級戊基 、正己基、正庚基、正辛基、正壬基、正癸基等。 以R3A所代表之碳原子數爲1至1 0之烷氧基的具體 實例是可列舉:甲氧基、乙氧基、正丙氧基、異丙氧基、 正丁氧基、正戊氧基、正辛氧基、正癸氧基等。 以R3A所代表之碳原子數爲1至5之鹵化烷基的具體 實例是可列舉:三氟甲基、五氟乙基、全氟-正丙基、全 氟-正丁基、全氟·正戊基等。 以R3A所代表之碳原子數爲1至5之鹵化烷氧基的具 體實例是可列舉:三氟甲氧基、五氟乙氧基、全氟-正丙 氧基、全氟-正丁氧基、全氟-正戊氧基等。 -46 - 201140249 以R3A所代表之可經 W取代之苯基的具體實例是可 列舉:鄰甲苯基、間甲苯基、對甲苯基、鄰乙基苯基、間 乙基苯基、對乙基苯基、對(正丙基)苯基、對(異丙基 )苯基、對(正丁基)苯基、對(異丁基)苯基、對(二 級丁基)苯基、對(三級丁基)苯基、對(正戊基)苯基 、對(異戊基)苯基、對(三級戊基)苯基、鄰甲氧基苯 基、間甲氧基苯基、對甲氧基苯基、鄰乙氧基苯基、間乙 氧基苯基、對乙氧基苯基、對(正丙氧基)苯基、對(異 丙氧基)苯基、對(正丁氧基)苯基、對(異丁氧基)苯 基、對(二級丁氧基)苯基、對(三級丁氧基)苯基、對 (正戊氧基)苯基、對(異戊氧基)苯基、對(三級戊氧 基)苯基、對氯苯基、對溴苯基、對氟苯基、2,4-二氯苯 基、2,4-二溴苯基、2,4-二氟苯基、2,4,6-三氯苯基、 2,4,6-三溴苯基、2,4,6-三氟苯基、五氯苯基、五溴苯基、 五氟苯基、對聯苯基等。 以R3A所代表之可經W取代之萘基的具體實例是可 列舉:2-甲基-1-萘基、3-甲基-1-萘基、4-甲基-1-萘基、 5 -甲基-1-萘基、6 -甲基-卜萘基、7 -甲基-1-萘基、8 -甲基-1-萘基、1-甲基-2-萘基、3-甲基-2-萘基、4-甲基-2-萘基 、5-甲基-2-萘基、6-甲基-2-萘基、7-甲基-2-萘基、8-甲 基-2-萘基等。 以R3A所代表之可經W取代之蒽基的具體實例是可 列舉:2 -甲基-1-蒽基、3 -甲基-1-蒽基、4 -甲基-1-蒽基、 5 -甲基-1-蒽基、6 -甲基-卜蒽基、7 -甲基-1-蒽基、8 -甲基· • 47- 201140249 1-蒽基、9-甲基-1-蒽基、10-甲基-1-蒽基、i-甲基_2·蒽基 、3-甲基-2-蒽基、4-甲基-2-蒽基、5·甲基-2-蒽基、6-甲 基-2-蒽基、7-甲基-2-蒽基、8-甲基-2-蒽基、9-甲基-2-蒽 基、10-甲基-2-蒽基等。 以W所代表之碳原子數爲1至1〇之烷基、碳原子數 爲1至10之烷氧基、碳原子數爲1至5之鹵化烷基、及 碳原子數爲1至5之鹵化烷氧基的具體實例是可列舉:與 作爲以R2A或R3A所代表之碳原子數爲1至1〇之烷基、 碳原子數爲1至10之烷氧基、碳原子數爲1至5之鹵化 烷基、及碳原子數爲1至5之鹵化烷氧基的具體實例所列 舉者爲相同者。 R2A與R1A是可相互鍵結而形成5員環或6員環。 若R2A與R1A是相互鍵結而形成5員環或6員環時’ 則該5員環或6員環是可列舉:碳環式基及雜環式環基, 例如,環戊烷、環己烷、環庚烷、吡咯、呋喃、噻吩、咪 唑、噚唑、噻唑、哌喃、吡啶、吡畊、嗎啉、哌啶或哌阱 環。該5員環或6員環是可爲與也可具有一個或兩個任意 的取代基之苯環鍵結,其實例是可列舉:四氫萘、二氫蒽 、茚、暁烷、莽、灿哩或硫卩III唱環系。該5員環或6員環是 可含有羰基,其實例是可列舉:環己二烯酮、萘酮及蒽酮 環系。 光酸產生劑(B )之較佳模式之一.是以下述通式(1-1 )所代表之目g擴酸醋化合物(oxime sulfonate compound)。 該肟磺酸酯化合物是通式(I)的11^與R>A是鍵結而形 -48- 201140249 成5員環之化合物。When the copolymer (A) has the structural unit (3a), the content of the structural unit (3 a ) is preferably from 1 to 25 mol%, more preferably in all the structural units constituting the copolymer (A). 2 to 25 mol%, particularly preferably 3 to 20 mol%. By having the structural unit (3 a ) in the above ratio, high sensitivity can be obtained, and developability is also good. <Structural unit (3b) other than (1) to (2), (3a) > Copolymer (A) can be contained in addition to the above (1) to (2), without impeding the scope of the present invention. A structural unit other than 3 a ) ( 3 b ) (hereinafter, simply referred to as "structural unit (3 b )"). The radically polymerizable monomer to be used for the formation of the structural unit (3b) is -36-201140249. For example, the compound disclosed in paragraphs [0021] to [0024] in JP-A-2004-264623 (However, the monomers forming the aforementioned structural units (1) to (2) and (3 a) are excluded). Among these, in order to obtain a radically polymerizable monomer of the structural unit (3b), from the viewpoint of improving electrical properties, it is preferably, for example, (cyclo)methyl phenyl thioglycolate (methyl) Cyclohexyl acrylate, (meth) acrylate containing alicyclic structure of cyclohexyl (meth) acrylate, and styrene. From the viewpoint of transparency, methyl (meth)acrylate is preferred. From the viewpoint of sensitivity, 2-hydroxyethyl (meth)acrylate is preferred. Among these, 2-hydroxyethyl (meth)acrylate is more preferred. The structural unit (3b) may be one type or a combination of two or more types. When the copolymer (A) is a structural vehicle element (3a), the content of the structural unit (3a) is preferably from 1 to 50% by mole in all the structural units constituting the copolymer (A). More preferably, it is 5 to 40% by mole, and particularly preferably 5 to 30% by mole. The weight average molecular weight of the copolymer (A) is preferably from 〇〇〇 to 100,000, more preferably from 2,000 to 50,000. Further, the weight average molecular weight of the present invention is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). The method of introducing each structural unit of the copolymer (A) into the copolymer (A) may be a polymerization method or a polymer reaction method, or may be used in two methods. When a polymerization method is used, a monomer having a specific functional group is synthesized in advance, and these monomers are copolymerized. That is, the copolymer (A) is a radical-containing polymerization which can be used by forming the structural unit (1), the structural unit (2), and the structural unit (3a) and (3b) as needed, by -37-201140249. The radical polymerizable monomer mixture of the monomer is synthesized by polymerization using a radical polymerization initiator in an organic solvent. For example, an ethylenically unsaturated compound having a partial structure represented by the formula (1 a ) or the formula (1 b ), and an ethylenically unsaturated compound having an epoxy group or an oxetanyl group may be added. The copolymer (A) is obtained by mixing and addition polymerization. When a polymer reaction method is used, a specific type of monomer is used for the polymerization reaction, and then a necessary functional group is introduced into the structural unit by using a reactive group contained in the structural unit of the obtained copolymer. Here, the functional group which can be introduced is exemplified by a protecting group, an epoxy group or an oxetane group which is used for protecting a phenolic hydroxyl group or a carboxyl group and decomposing in the presence of a strong acid. A crosslinkable group such as an alkali-soluble group (acid group) of a phenolic hydroxyl group or a carboxyl group. For example, a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate with epichlorohydrin can be exemplified to introduce an epoxy group. As described above, after the copolymerization of the ethylenically unsaturated compound having a reactive group, the reactive group remaining in the side chain is effectively utilized, and by the polymer reaction, the formula (la) and/or the formula can be used. The functional group of the partial structure or the crosslinkable group represented by (lb) is introduced into the side chain of the copolymer (A). Hereinafter, the copolymer (A) which is preferably used in the present invention is exemplified, but the present invention is not limited thereto. Further, the amount of the weight average molecular weight -38 to 201140249 of the copolymer (A) exemplified below is 2,000 to 50,000. The composition ratio is in the range of (.). To represent. 1-Ethoxyethyl methacrylate/glycidyl methacrylate copolymer (5 0/5 0 ), ethoxyethyl methacrylate/glycidyl methacrylate/methacrylic acid Copolymer (50/40/1 0 ), 1-ethoxyethyl methacrylate / methyl propylene acid propylene acrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (40 /30/1 0/20) '1-Ethyloxyethyl methacrylate/tetrahydro-2H-pyran-2-yl methacrylate/glycidyl methacrylate/methacrylic acid/methyl 2-hydroxyethyl acrylate copolymer (2 0/2 0/3 0/ 1 0/2 0 ), 1-ethoxyethyl methacrylate / tetrahydro-2H-furan-2-yl methacrylate /Glycidyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer ( 20/20/3 0/ 1 0/20 ), tetrahydro-2H-furan-2-yl methacrylate Ester/glycidyl methacrylate/methacrylic acid/2-hydroxyethyl methacrylate copolymer (40/30/10/20), 1-ethoxyethyl methacrylate/methacrylic acid 3, 4-epoxycyclohexylmethyl methacrylate/methacrylic acid copolymer (45/40/15), 1-ethoxy methacrylate /3,4-Epoxycyclohexylmethyl methacrylate/methacrylic acid/2-hydroxyethyl methacrylate copolymer (40/30/10/20), 1-ethoxyethyl methacrylate /3,4-Epoxycyclohexylmethyl methacrylate V4-hydroxybenzoic acid (3-methacryloxy-2-hydroxypropyl • 39- 201140249 ) ester / 2-hydroxyethyl methacrylate Copolymer (40/3 0/ 1 0/2 0 ), 1-ethoxyethyl methacrylate / (3-ethyloxetan-3-yl)methyl methacrylate copolymer (50 /50), Ethyl ethoxide methacrylate / (3-ethyloxetan-3-yl)methyl methacrylate / methyl diacid copolymer (50/40/1 0 ) , 1-ethoxyethyl methacrylate / (3-ethyloxetan-3-yl)methyl methacrylate / methyl propyl amide / 2-hydroxyethyl methacrylate copolymer ( 40/3 0/ 1 0/20 ) 'tetrahydro-2H-pentan-2-yl methacrylate/(3-ethyloxetan-3-yl)methyl methacrylate/methyl Acrylic acid/2-hydroxyethyl methacrylate copolymer (40/30/1 0/20), tetrahydro-2H-furan-2-yl methacrylate/methacrylic acid (3 -ethyloxetane-3-yl)methyl ester / formazan acrylic acid / 2-hydroxyethyl methacrylate copolymer (4 0/3 0/ 1 0/20 ), tetrahydro-2H methacrylate -furan-2-yl ester/methyl methacrylate (3-ethyloxetan-3-yl.) methyl ester/methacrylic acid/2-hydroxyethyl methacrylate/styrene copolymer (40/ 30/1 0/ 1 0/1 0 ), 1-ethoxyethyl methacrylate/(3-ethyloxetan-3-yl)methyl methacrylate/4-hydroxybenzoic acid ( 3-Methyl propylene methoxypropyl) ester / 2-hydroxyethyl methacrylate copolymer (40/30/1 0/2 〇), 1-ethoxyethyl methacrylate / methacrylic acid 1 -Methyl-bucyclohexyl ester/(3-ethyloxetan-3-yl)methyl methacrylate/methacrylic acid/2-hydroxyethyl methacrylate copolymer (20/20/30) /10/20), 1-ethoxyethyl methacrylate/tetrahydro-2H-pyranyl--40- 201140249 2-Base ester/methacrylic acid (3_ethyloxetanium) -3·yl)methacetic acid/4-hydroxybenzoic acid (3·methacryloxypropyl) vinegar/methyl acrylate 2·hydroxyethyl ester copolymer (20/2 0/3 0/ 1 0 /2 0 ), 1-(Cyclohexyloxy)ethyl methacrylate/glycidyl methacrylate/methacrylic acid copolymer (5〇/35/15), 1-(cyclohexyloxy)ethyl methacrylate/ Glycidyl methacrylate/methacrylic acid/2-hydroxyethyl methacrylate copolymer (3 5/3 0/ 1 0/2 5 ) '1-(cyclohexyloxy)ethyl methacrylate/ 3,4-Epoxycyclohexylmethyl methacrylate/methacrylic acid copolymer (50/40/10), 1-(cyclohexyloxy)ethyl methacrylate/methacrylic acid 3,4 -Epoxycyclohexylmethylester/methacrylic acid/2-hydroxyethyl methacrylate copolymer (40/30/1 0/20), 1-(cyclohexyloxy)ethyl methacrylate/A (3-Ethyloxetan-3-yl)methyl methacrylate/methacrylic acid copolymer (5 0/40/ 1 0 )' 1-(cyclohexyloxy)ethyl methacrylate/A (3-Ethyloxetane-3-yl)methyl methacrylate/methacrylic acid/2-hydroxyethyl methacrylate copolymer (40/30/1 0/20), methyl propylene acid 1-(cyclohexyloxy)ethyl ester/methylpropionic acid (3-ethyloxetan-3-yl)methyl ester α-methyl-p-hydroxystyrene/A 2-Hydroxyethyl acrylate copolymer (30/30/20/20), 1·(cyclohexyloxy)ethyl methacrylate/tetrahydro-2Η-pentan-2-yl methacrylate/methyl Acrylic acid (3_ethyloxetane·3_yl) -41 - 201140249 Methyl ester/4-hydroxybenzoic acid (3-methylpropenyloxypropyl) ester/2-hydroxyethyl methacrylate Copolymer (40/30/15/15), 3-ethoxypropoxypropyl) 4-ethoxyethyl ether/methacrylic acid (3-ethyloxa) Cyclobutane-3-yl)methyl ester/methacrylic acid/2-hydroxyethyl methacrylate copolymer (40/3 0/1 0/2 0 ) The photosensitive resin composition of the present invention may contain a single One or a combination of two or more kinds of copolymers (A). The content of the copolymer (A) in the photosensitive resin composition of the present invention is preferably from 20 to 99% by mass, more preferably from 40 to 97% by mass, based on the total solid content of the photosensitive resin composition, further. More preferably, it is 60 to 95% by mass. When the content of the copolymer (A) is in this range, the pattern formation property at the time of development becomes good. Further, the photosensitive resin composition of the present invention can be used in addition to the copolymer (A) without hindering the effect of the present invention. However, from the viewpoint of developability, the content of the resin other than the copolymer (A) is preferably less than the content of the copolymer (A). [(B) Photoacid generator] The photosensitive resin composition of the present invention contains a compound selected from the group consisting of Formula (I), Formula (OS-1), and Formula (OS-3), which will be described in detail below. At least one photoacid generator (photoacid generator (B)) of the photoacid generator represented by the formula (OS-4) and the formula (OS-5). Among the photoacid generators contained in the photoacid generator (B), it is preferred to use the formula (I), the formula (OS-3), the formula (OS-4), or the formula -42- Photoacid generator represented by 201140249 (◦ S - 5 ). Hereinafter, each photoacid generator contained in the photoacid generator (B) will be described in detail. One mode of the photoacid generator contained in the photoacid generator (B) is a photoacid generator represented by the following formula (I). R1a—c(r2A) = no-so2- r3A (I) In the formula (I), R1A is an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or a phenyl group. a biphenyl group, a naphthyl group, a 2-furyl group, a 2-thienyl group, an alkoxy group having 1 to 4 carbon atoms or a cyano group; if R1A is a phenyl group, a biphenyl group, a naphthyl group or a fluorenyl group, Then, the basis of these may be a group selected from the group consisting of a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a nitro group. Replace the base. R2A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a halogenated alkoxy group having 1 to 5 carbon atoms. A phenyl group which may be substituted by W, a naphthyl group which may be substituted by W or a fluorenyl group which may be substituted by W, a dialkylamino group, a morpholinyl group or a cyano group. The ruler and R1A are mutually bondable to form a 5-membered ring or a 6-membered ring which is bondable to a benzene ring which may have one or two optional substituents. R3A is an alkoxy group having a carbon number of from 10 to 10, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a halogenated alkoxy group having 5 to 5 carbon atoms. a phenyl group which may be substituted by W, a naphthyl group which may be substituted by W or a fluorenyl group which may be substituted by W. The evaluation is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 1 ring of carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogenated alkane having 1 to -43 to 201140249 5 A halogenated alkane having a carbon number of from 1 to 5, and an alkyl or branched alkyl group having 1 to 6 carbon atoms represented by R1A, which may, for example, be a methyl group, a propyl group or a n-butyl group. , secondary butyl, tert-butyl, n-pentyl hexyl, or 2-ethyl butyl. a spectreous of 1 to 4 carbon atoms represented by RIA: for example, chloromethyl, trichloromethyl, trifluoromethyl, an alkoxy group having 1 to 4 carbon atoms represented by RIA or Ethoxy. R1A is a phenyl group, a biphenyl group, a naphthyl group or an anthracenyl group which may be selected from a halogen atom (for example, a chlorogenic iodine atom or the like), a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an ethyl group. , propyl, isopropyl, n-butyl, dibutyl), alkoxy groups having 1 to 4 carbon atoms (for example, methyl, n-propoxy, isopropoxy, n-butoxy) and nitrate Substituents in the group are substituted. Examples of the number of carbon atoms represented by R2A from 1 to 10 include methyl, ethyl, n-propyl, isopropylbutyl, secondary butyl, tert-butyl, n-pentyl, and isuf. Examples of n-hexyl, n-heptyl, n-octyl, n-decyl, and n-decene represented by R2A having from 1 to 10 carbon atoms are methoxy, ethoxy, n-propoxy-n-butyl The oxy group, the n-pentyloxy group, the n-octyloxy group, and the n-decyloxy group have a halo group having 1 to 5 carbon atoms represented by R2A. The group may be a linear group, a propyl group, an iso-yl group, an isopentyl group, or an alkyl group which may be a column or a 2-bromopropyl group. When the oxy group is exemplified, the specific alkyl group, the bromine atom, the group (for example, a methyl group, a tertiary butyloxy group, or an ethoxy group) may be a specific alkyl group, an n-butyl group or an iso group. Alkyl pentyl group, etc. Specific alkoxy group, isopropoxy group, etc. Specific alkyl-44-201140249 Examples are: trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl And perfluoro-n-butyl group, perfluoro-n-pentyl group, etc. Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R2A include trifluoromethoxy group and pentafluoroethoxy group. a base, perfluoro-n-propoxy group, perfluoro-n-butoxy group, perfluoro-n-pentyloxy group, etc. Specific examples of the phenyl group which may be substituted by w represented by R2A are exemplified by o-tolyl group, M-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, p-(n-propyl)phenyl, p-(isopropyl)phenyl, p-(n-butyl) Phenyl, p-(isobutyl)phenyl, p-(di-butyl)phenyl, p-(tert-butyl)phenyl, p-(n-pentyl)phenyl, p-(isopentyl)phenyl, Pair III Phenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-ethoxyphenyl, m-ethoxyphenyl, p-ethoxyphenyl, p-(n-propoxy) Phenyl, p-(isopropoxy)phenyl, p-(n-butoxy)phenyl, p-(isobutoxy)phenyl, p-(t-butoxy)phenyl, p-(tertiary Butoxy)phenyl, p-(n-pentyloxy)phenyl, p-(isopentyloxy)phenyl, p-(tripentyloxy)phenyl, p-chlorophenyl, p-bromophenyl, p-fluoro Phenyl, 2,4-dichlorophenyl, 2,4-dibromophenyl, 2,4-difluorophenyl, 2,4,6-trichlorophenyl, 2,4,6-tribromobenzene Base, 2,4,6-trifluorophenyl, pentachlorophenyl, pentabromophenyl, pentafluorophenyl, p-biphenyl, etc. A specific example of a W-substituted naphthyl group represented by R2A is Listed: 2-methyl-1-naphthyl, 3-methyl-1-naphthyl, 4-methyl-1-naphthyl, 5-methyl-1-naphthyl, 6-methyl-1-naphthalene , 7-methyl-1-naphthyl, 8-methyl-1-naphthyl, 1-methyl-2-naphthyl, 3-methyl-2-naphthyl, 4-methyl-2-naphthalene -45- 201140249, 5-methyl-2-naphthyl, 6-methyl-2-naphthyl, 7-methyl-2-naphthyl And 8-methyl-2-naphthyl and the like. Specific examples of the fluorenyl group which may be substituted by w represented by R2A are exemplified by 2-methyl-1-indenyl group and 3-methyl-1-indenyl group. , 4-methyl-1-indenyl, 5-methyl-1-indenyl, 6-methyl-1-indenyl, 7-methyl-1-indenyl, 8-methyl-1-indenyl , 9-methyl-1-indenyl, 10-methyl-1-indenyl, 1-methyl-2-indolyl, 3-methyl-2-indenyl, 4-methyl-2-indenyl , 5-methyl-2-indolyl, 6-methyl-2-indolyl, 7-methyl-2-indolyl, 8-methyl-2-indenyl, 9-methyl-2-indenyl , 1 〇-methyl-2-indenyl and the like. The dialkylamino group represented by R2A may, for example, be a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group or a diphenylamino group. Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R3A include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group and the like. Butyl, n-pentyl, isopentyl, secondary pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl and the like. Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R3A include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and n-pentyloxy groups. Base, n-octyloxy, n-decyloxy and the like. Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R3A include trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro-n-butyl, and perfluoro- Orthopentyl and the like. Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R3A include trifluoromethoxy, pentafluoroethoxy, perfluoro-n-propoxy, and perfluoro-n-butoxy Base, perfluoro-n-pentyloxy and the like. -46 - 201140249 Specific examples of the phenyl group which may be substituted by W represented by R3A are: o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethyl Phenyl, p-(n-propyl)phenyl, p-(isopropyl)phenyl, p-(n-butyl)phenyl, p-(isobutyl)phenyl, p-(tert-butyl)phenyl, p- (tertiary butyl)phenyl, p-(n-pentyl)phenyl, p-(isopentyl)phenyl, p-(tripentyl)phenyl, o-methoxyphenyl, m-methoxyphenyl , p-methoxyphenyl, o-ethoxyphenyl, m-ethoxyphenyl, p-ethoxyphenyl, p-(n-propoxy)phenyl, p-(isopropoxy)phenyl, (n-butoxy)phenyl, p-(isobutoxy)phenyl, p-(t-butoxy)phenyl, p-(tertiary butoxy)phenyl, p-(n-pentyloxy)phenyl , p-(isopentyloxy)phenyl, p-(tripentyloxy)phenyl, p-chlorophenyl, p-bromophenyl, p-fluorophenyl, 2,4-dichlorophenyl, 2,4- Dibromophenyl, 2,4-difluorophenyl, 2,4,6-trichlorophenyl, 2,4,6-tribromophenyl, 2, 4,6-trifluorophenyl, pentachlorophenyl, pentabromophenyl, pentafluorophenyl, p-biphenyl, and the like. Specific examples of the W-substituted naphthyl group represented by R3A include 2-methyl-1-naphthyl, 3-methyl-1-naphthyl, 4-methyl-1-naphthyl, and 5 -methyl-1-naphthyl, 6-methyl-p-naphthyl, 7-methyl-1-naphthyl, 8-methyl-1-naphthyl, 1-methyl-2-naphthyl, 3-methyl -2-Naphthyl, 4-methyl-2-naphthyl, 5-methyl-2-naphthyl, 6-methyl-2-naphthyl, 7-methyl-2-naphthyl, 8-methyl -2-Naphthyl and the like. Specific examples of the thiol group which may be substituted by W represented by R3A include 2-methyl-1-indenyl group, 3-methyl-1-indenyl group, 4-methyl-1-indenyl group, and 5 -methyl-1-indenyl, 6-methyl-didecyl, 7-methyl-1-indenyl, 8-methyl- • 47- 201140249 1-decyl, 9-methyl-1-indenyl, 10-methyl-1-indenyl, i-methyl-2-indenyl, 3-methyl-2-indenyl, 4-methyl-2-indenyl, 5-methyl-2-indenyl, 6-methyl-2-indenyl, 7-methyl-2-indenyl, 8-methyl-2-indenyl, 9-methyl-2-indenyl, 10-methyl-2-indenyl, etc. . An alkyl group having 1 to 1 ring of carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms represented by W Specific examples of the halogenated alkoxy group include an alkyl group having 1 to 1 ring of carbon atoms represented by R2A or R3A, an alkoxy group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. Specific examples of the halogenated alkyl group of 5 and the halogenated alkoxy group having 1 to 5 carbon atoms are the same. R2A and R1A are mutually bondable to form a 5-membered ring or a 6-membered ring. When R2A and R1A are bonded to each other to form a 5-membered ring or a 6-membered ring, the 5-membered ring or the 6-membered ring may be exemplified by a carbocyclic group and a heterocyclic ring group, for example, a cyclopentane or a ring. Hexane, cycloheptane, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, piperazine, pyridine, pyridin, morpholine, piperidine or piperazine ring. The 5-membered ring or the 6-membered ring may be a benzene ring bond which may have one or two optional substituents, and examples thereof include tetrahydronaphthalene, indoline, hydrazine, decane, and hydrazine. Chansu or sulphur III sing ring system. The 5-membered or 6-membered ring may contain a carbonyl group, and examples thereof include a cyclohexadienone, a naphthone, and an anthrone ring system. One of the preferred modes of the photoacid generator (B) is an oxime sulfonate compound represented by the following formula (1-1). The oxime sulfonate compound is a compound of the formula (I) wherein 11 and R>A are bonded and form -48-201140249 into a 5-membered ring.
通式(1-1)中’ r3A是與通式(〇的113八爲同義,X 是代表院基、院氧基、或鹵素原子’t是代表0至3之整 數,t爲2或3時,複數之X是可爲相同或不同。 以X所代表之烷基較佳爲碳原子數爲1至4之直鏈狀 或分枝狀烷基。 以X所代表之烷氧基較佳爲碳原子數爲1至4之直鏈 狀或分枝狀烷氧基。 以X所代.表之鹵素原子較佳爲氯原子或氟原子。 t較佳爲〇或1。 通式(1-1)中,特佳爲〖是^乂是甲基,X之取代 位置是鄰位’R3A是碳原子數爲1至10之直鏈狀烷基' 7,7_二甲基·2-側氧基降冰片基甲基、或對甲苯甲醯基之化 合物。 以通式(I-1 )所代表之肟磺酸酯化合物的具體實例 是可列舉:下述化合物(i )、化合物(i i )、化合物(i i i )、化合物(iv )等,此等化合物是可以一種單獨使用、 或兩種類以上倂用。化合物(i )至(iv )是可獲自市售 • 49 - 201140249 品。 此外,以通式(I-1 )所代表之肟磺酸酯化合物是可 與其他種類之光酸產生劑(B )組合使用。In the general formula (1-1), 'r3A is synonymous with the formula (113 of the oxime, X is a representative group, a oxy group, or a halogen atom 't is an integer representing 0 to 3, and t is 2 or 3) The plural X may be the same or different. The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably. It is a linear or branched alkoxy group having 1 to 4 carbon atoms. It is represented by X. The halogen atom in the table is preferably a chlorine atom or a fluorine atom. t is preferably ruthenium or 1. In -1), it is particularly preferred that 〖is ^ is a methyl group, the substitution position of X is an ortho position 'R3A is a linear alkyl group having a carbon number of 1 to 10' 7,7-dimethyl-2 Specific examples of the oxime sulfonate compound represented by the formula (I-1) include the following compounds (i) and compounds ( Ii), compound (iii), compound (iv), etc., which may be used alone or in combination of two or more types. Compounds (i) to (iv) are commercially available from 49 to 201140249. In addition, by the general formula (I The sulfonate compound represented by -1 ) can be used in combination with other kinds of photoacid generator (B).
(i)(i)
〇〇
II N-〇—S-Π-〇3Η7 όII N-〇—S-Π-〇3Η7 ό
'3 CN 〇 N-〇_S—n-CgHi7 0'3 CN 〇 N-〇_S-n-CgHi7 0
-50- 201140249 以通式(I)所代表之光酸產生劑之較佳模式之一是 R1A是代表碳原子數爲1至4之烷基、三氟甲基、苯 基、氯苯基、二氯苯基、甲氧基苯基、4 -聯苯基、萘基或 蒽基; R2A是代表氰基: R3A是代表碳原子數爲1至10之烷基、碳原子數爲1 至10之烷氧基、碳原子數爲1至5之鹵化烷基、碳原子 數爲1至5之鹵化烷氧基、可經W取代之苯基、可經W 取代之萘基或可經w取代之蒽基;W是代表鹵素原子、 氰基、硝基、碳原子數爲1至10之烷基、碳原子數爲1 至10之烷氧基、碳原子數爲1至5之鹵化烷基或碳原子 數爲1至5之鹵化烷氧基者。 以通式(I)所代表之光酸產生劑較佳爲以通式(II ) 所代表之光酸產生劑。 0 3A (II)-50- 201140249 One of the preferred modes of the photoacid generator represented by the formula (I) is that R1A represents an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group, Dichlorophenyl, methoxyphenyl, 4-biphenylyl, naphthyl or anthracenyl; R2A represents a cyano group: R3A represents an alkyl group having 1 to 10 carbon atoms and a carbon number of 1 to 10 Alkoxy group, halogenated alkyl group having 1 to 5 carbon atoms, halogenated alkoxy group having 1 to 5 carbon atoms, phenyl group which may be substituted by W, naphthalene group which may be substituted by W or may be substituted by w A fluorenyl group; W is a halogen atom representing a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and 1 to 5 carbon atoms; Or a halogenated alkoxy group having 1 to 5 carbon atoms. The photoacid generator represented by the formula (I) is preferably a photoacid generator represented by the formula (II). 0 3A (II)
N—0—S—R (όN—0—S—R (ό
CN 通式(II )中’ R4A是代表鹵素原子、羥基、碳原子 數爲1至4之烷基、碳原子數爲1至4之烷氧基、或硝基 ,1是代表〇至5之整數。R3A是代表碳原子數爲1至10 之烷基、碳原子數爲1至1〇之烷氧基、碳原子數爲I至 -51 - 201140249 5之鹵化烷基、碳原子數爲1至5之鹵化烷氧基、可經W 取代之苯基、可經W取代之萘基或可經W取代之蒽基; W是代表鹵素原子、氰基、硝基、碳原子數爲1至10之 烷基、碳原子數爲1至1〇之烷氧基、碳原子數爲1至5 之鹵化烷基或碳原子數爲1至5之鹵化烷氧基者。 通式(II)中,R3A較佳爲甲基、乙基、正丙基、正 丁基、正辛基、三氟甲基、五氟乙基、全氟-正丙基、全 氟-正丁基、對甲苯基、4-氯苯基或五氟苯基;特佳爲甲 基、乙基、正丙基、正丁基或對甲苯基。 以R4A所代表之鹵素原子較佳爲氟、氯或溴。 以R4A所代表之碳原子數爲1至4之烷基較佳爲甲基 或乙基。 以R4A所代表之碳原子數爲1至4之烷氧基較佳爲甲 氧基或乙氧基。 1較佳爲0至2,特佳爲0至1。 在以通式(I )所代表之光酸產生劑中,包含在以通 式(Π )所代表之光酸產生劑的化合物之較佳模式爲:通 式(I)中,R1A是代表苯基或4-甲氧基苯基,R2A是代表 氰基’ R3A是代表甲基、乙基、正丙基、正丁基或4 -甲苯 基之模式。 在下文中,例示特佳的在以通式(I )所代表之光酸 產生劑中之包含在以通式(II )所代表之光酸產生劑的化 合物,但是本發明並不受限於此等者: α-(甲基礎醯氧基亞胺基)苯甲基氰(r1a =苯基、 -52- 201140249 R2A= - CN 基、R3A=甲基); α-(乙基磺醯氧基亞胺基)苯甲基氰(R1A =苯基、 R2A = - CN 基、R3 A =乙基); α -(正丙基磺醯氧基亞胺基)苯甲基氰(R1A =苯基 、R2A=-CN 基、R3A =正丙基); α -(正丁基磺醯氧基亞胺基)苯甲基氰(R1A =苯基 、R2A=— CN 基、R3A =正丁基); 〇:-(4-甲苯磺醯氧基亞胺基)苯甲基氰(R1A =苯基 、R2A=-CN 基、R3A=4 -甲苯基); 〇:-〔(甲基磺醯氧基亞胺基)-4-甲氧基苯基〕乙腈 (r1a=4 -甲氧基苯基、R2A = - CN基、R3A =甲基); α-〔(乙基磺醯氧基亞胺基)-4-甲氧基苯基〕乙腈 (r1a=4-甲氧基苯基、R2A = - CN基、R3A =乙基); α -〔(正丙基磺醯氧基亞胺基)-4-甲氧基苯基〕乙 腈(R1A=4-甲氧基苯基、R2A=— CN基、R3A =正丙基) t α -〔(正丁基磺醯氧基亞胺基)_4·甲氧基苯基〕乙 腈(R1A=4 -甲氧基苯基、R2A=-CN基、R3A =正丁基)In the formula (II), 'R4A represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group, and 1 represents a ruthenium to 5 Integer. R3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 1 carbon atom, a halogenated alkyl group having 1 to -51 - 201140249 5 carbon atoms, and 1 to 5 carbon atoms. a halogenated alkoxy group, a W-substituted phenyl group, a W-substituted naphthyl group or a W-substituted fluorenyl group; W is a halogen atom, a cyano group, a nitro group, and has 1 to 10 carbon atoms. An alkyl group, an alkoxy group having 1 to 1 carbon atom, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms. In the formula (II), R3A is preferably methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro-positive Butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl; particularly preferably methyl, ethyl, n-propyl, n-butyl or p-tolyl. The halogen atom represented by R4A is preferably fluorine, chlorine or bromine. The alkyl group having 1 to 4 carbon atoms represented by R4A is preferably a methyl group or an ethyl group. The alkoxy group having 1 to 4 carbon atoms represented by R4A is preferably a methoxy group or an ethoxy group. 1 is preferably 0 to 2, particularly preferably 0 to 1. In the photoacid generator represented by the formula (I), a preferred mode of the compound contained in the photoacid generator represented by the formula (Π) is: in the formula (I), R1A represents benzene Or a 4-methoxyphenyl group, R2A is a pattern representing a cyano group 'R3A' is a methyl, ethyl, n-propyl, n-butyl or 4-tolyl group. In the following, a compound which is contained in the photoacid generator represented by the general formula (I) and which is contained in the photoacid generator represented by the general formula (II) is exemplified, but the present invention is not limited thereto. Etc.: α-(methyl-based methoxyl imido)benzyl cyanide (r1a = phenyl, -52- 201140249 R2A= - CN group, R3A=methyl); α-(ethylsulfonyloxy Imino)benzylidene cyanide (R1A = phenyl, R2A = -CN group, R3 A = ethyl); α -(n-propylsulfonyloxyimino)benzyl cyanide (R1A = phenyl , R2A=-CN group, R3A = n-propyl); α-(n-butylsulfonyloxyimino)benzyl cyanide (R1A = phenyl, R2A=-CN group, R3A = n-butyl) 〇:-(4-toluenesulfonyloxyimino)benzyl cyanide (R1A = phenyl, R2A=-CN, R3A=4-tolyl); 〇:-[(methylsulfonate) Iminoamino)-4-methoxyphenyl]acetonitrile (r1a=4-methoxyphenyl, R2A=-CN based, R3A=methyl); α-[(ethylsulfonyloxyimine) 4-methoxyphenyl]acetonitrile (r1a=4-methoxyphenyl, R2A=-CN based, R3A=ethyl); α-[(n-propyl sulfonate)醯oxyimino)-4-methoxyphenyl]acetonitrile (R1A=4-methoxyphenyl, R2A=—CN group, R3A=n-propyl) t α -[(n-butylsulfonate) Oxyimido) 4 methoxyphenyl] acetonitrile (R1A = 4-methoxyphenyl, R2A = -CN, R3A = n-butyl)
I α-〔 (4-甲苯磺醯氧基亞胺基)-4-甲氧基苯基〕乙 腈(R1A=4 -甲氧基苯基、R2A=-CN基、R3A=4 -甲苯基 )° 在光酸產生劑(B)所包含的光酸產生劑之其他模式 是以下述通式(OS-3)、通式(OS-4)、或通式(OS-5 -53- 201140249 )所代表之光酸產生劑。I α-[(4-Toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile (R1A=4-methoxyphenyl, R2A=-CN, R3A=4-tolyl) ° Other modes of the photoacid generator contained in the photoacid generator (B) are the following general formula (OS-3), general formula (OS-4), or general formula (OS-5-53-201140249) The photoacid generator represented.
(os·3) (OS-4) 0 (〇S-5) 通式(OS-3)至通式(〇S_5)中,是代表烷基、 芳基或雜芳基’可存在數個的R2是各自獨立地代表氫原 子、烷基、芳基或鹵素原子’可存在數個的R6是各自獨 立地代表鹵素原子、烷基、烷氧基、磺酸基、胺基磺醯基 或院氧基擴醯基’X是代表Ο或S,η是代表1或2,m 是代表〇至6之整數。 通式(OS-3)至(OS-5)中,以R1所代表之烷基、 芳基、或雜芳基是也可具有取代基。 通式(OS-3)至(OS-5)中,以R1所代表之烷基較 佳爲也可具有取代基之總碳數爲1至30之烷基。 以R1所代表之院基可具有之取代基是可列舉:鹵素 原子、烷基氧基、芳基氧基、烷基硫基、芳基硫基、烷氧 基羰基、芳氧基羰基、及胺基羰基等。 以R1所代表之烷基是可列舉:甲基、乙基、正丙基 、異丙基、正丁基、二級丁基、三級丁基、正戊基、正己 基、正辛基、正癸基、正十二烷基、三氟甲基、全氟丙基 、全氟己基、及本甲基等。 此外,逋式(0 s -3)至(〇s -5)中’以R1所代表之 芳基較佳爲也可具有取代基之總碳數爲6至30之芳基。 -54- 201140249 β Rl所代表之芳基可具有之取代基是可列舉:齒素 原子院基、院基氧基、方基氧基、院基硫基、芳基硫基 、院氧基羰基、芳氧基羰基、胺基羰基、磺酸基、胺基磺 醯基、及烷氧基磺醯基等》 以R1所代表之芳基是可列舉:苯基、對甲基苯基、 對氯苯基、五氯苯基、五氟苯基、鄰甲氧基苯基、及對苯 氧基苯基%。 此外’通式(0 S - 3 )至(〇 s - 5 )中,以 R1所代表之 雜芳基較佳爲也可具有取代基之總碳數爲4至30之雜芳 基。 以R1所代表之雜芳基可具有之取代基是可列舉:鹵 素原子、烷基、烷基氧基、芳基氧基、烷基硫基、芳基硫 基、烷氧基羰基、芳氧基羰基、胺基羰基、磺酸基、胺基 磺醯基、及烷氧基磺醯基等。 通式(OS-3)至(OS-5)中,以R1所代表之雜芳基 是只要其爲含有至少一個雜芳香族環者時即可,例如,雜 芳香族環與苯環是也可加以縮環。 以R1所代表之雜芳基是可列舉:也可具有取代基之 選自由噻吩環、吡咯環、噻唑環、咪唑環、呋喃環、苯并 噻吩環、苯并噻唑環、及苯并咪唑環所構成的群組中之環 中移除一個氫原子之基等。 通式(OS-3)至(OS-5)中,R2較佳爲氫原子、烷 基、或芳基,更佳爲氫原子或烷基。 通式(OS-3)至(OS-5)中,在化合物中存在兩個以 -55- 201140249 上之R時’較佳爲一個或兩個是院基、芳基或_素原子 ,更佳爲一個爲烷基、芳基或鹵素原子,特佳爲一個爲烷 基,且其餘爲氫原子。 通式(OS-3)至(〇s_5)中,以R2所代表之烷基或 芳基是可具有取代基。 以R所代表之院基或芳基可具有之取代基是可例示 與則述以R1所代表之烷基或芳基可具有之取代基爲相同 之基。 以R2所代表之烷基較佳爲可具有取代基之總碳數爲 1至12之烷基,更佳爲可具有取代基之總碳數爲1至6 之烷基。 以r2所代表之烷基是可列舉:甲基、乙基、正丙基 、異丙基、正丁基、異丁基、二級丁基、正己基、烯丙基 、氯甲基、溴甲基、甲氧基甲基、及苯甲基等;較佳爲甲 基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基 、或正己基;更佳爲甲基、乙基、正丙基、正丁基、或正 己基;特佳爲甲基。 以R2所代表之芳基較佳爲可具有取代基之總碳數爲 6至30之芳基。 以 R2所代表之芳基是可列舉:苯基、對甲基苯基、 鄰氯苯基、對氯苯基、鄰甲氧基苯基、或對苯氧基苯基等 〇 & R2所代表之鹵素原子是可列舉:氟原子、氯原子 、溴原子、及碘原子等。 -56- 201140249 在此等之中,較佳爲氯原子、或溴原子。 通式(OS-3)至(OS-5)中,X是代表〇或s,較佳 爲0 〇 通式(OS-3)至(OS-5)中,含有X作爲環員之環 是5員環或6員環。 通式(OS-3)至(OS-5)中’ η是代表1或2,X爲 〇時,則較佳爲η是1 ’此外,X爲s時,則較佳爲η是 2 ° 通式(OS-3)至(OS-5)中,以R6所代表之烷基及 烷基氧基是可具有取代基。 通式(Ο S - 3 )至(Ο S - 5 )中’以R6所代表之烷基較 佳爲可具有取代基之總碳數爲1至3 0之烷基。 以R6所代表之烷基可具有之取代基是可列舉:鹵素 原子、烷基氧基、芳基氧基、烷基硫基、芳基硫基、烷氧 基羰基、芳氧基羰基、及胺基羰基等。 以R6所代表之烷基是可列舉:甲基、乙基、正丙基 、異丙基、正丁基、二級丁基、三級丁基、正戊基、正己 基、正辛基、正癸基、正十二烷基、三氟甲基、全氟丙基 、全氟己基、及苯甲基等。 通式(OS-3 )至(OS-5 )中,以R6所代表之烷基氧 基較佳爲可具有取代基之總碳數爲1至30之烷基氧基。 以R6所代表之烷基氧基可具有之取代基是可列舉: 鹵素原子、烷基氧基、芳基氧基、烷基硫基、芳基硫基、 烷氧基羰基、芳氧基羰基、及胺基羰基等。 -57- 201140249 以R6所代表之烷基氧基是可列舉:甲基氧基、乙基 氧基、丁基氧基、己基氧基、苯氧基乙基氧基、三氯甲基 氧基、乙氧基乙基氧基、甲硫基乙基氧基、苯硫基乙基氧 基、乙氧基羰基乙基氧基、苯氧基羰基乙基氧基、及二甲 基胺基羰基乙基氧基等。 在此等之中,較佳爲甲基氧基、乙基氧基、丁基氧基 、己基氧基、苯氧基乙基氧基、三氯甲基氧基、或乙氧基 乙基氧基。 通式(OS-3 )至(OS-5 )中,以R6所代表之胺基磺 醯基是可列舉:甲基胺基磺醯基、二甲基胺基磺醯基、苯 基胺基磺醯基、甲基苯基胺基磺醯基、及胺基磺醯基等。 通式(OS-3)至(OS-5)中,以R6所代表之烷氧基 磺醯基是可列舉:甲氧基磺醯基、乙氧基磺醯基、丙氧基 磺醯基、及丁氧基磺醯基等。 此外,通式(OS-3)至(OS-5)中,m是代表0至6 之整數,較佳爲0至2之整數,更佳爲0或1,特佳爲0 此外,以前述通式(OS-3 )所代表之光酸產生劑特佳 爲以下述通式(OS-6) 、 (OS-10)或(OS-11)所代表 之光酸產生劑;以前述通式(OS-4 )所代表之光酸產生劑 特佳爲以下述通式(Ο S - 7 )所代表之光酸產生劑;以前述 通式(OS-5)所代表之光酸產生劑特佳爲以下述通式( OS-8)或(OS-9)所代表之光酸產生劑。 -58- 201140249(os·3) (OS-4) 0 (〇S-5) In the formula (OS-3) to the formula (〇S_5), it is represented by an alkyl group, an aryl group or a heteroaryl group. R 2 is each independently a hydrogen atom, an alkyl group, an aryl group or a halogen atom. A plurality of R 6 may be independently represented by a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an amine sulfonyl group or a hospital. The oxyalkyl group 'X' represents Ο or S, η represents 1 or 2, and m is an integer representing 〇 to 6. In the general formulae (OS-3) to (OS-5), the alkyl group, the aryl group or the heteroaryl group represented by R1 may have a substituent. In the general formulae (OS-3) to (OS-5), the alkyl group represented by R1 is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent. The substituent which the substituent represented by R1 may have is a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, and Aminocarbonyl and the like. The alkyl group represented by R1 may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, N-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, and methyl. Further, the aryl group represented by R1 in the formula (0 s -3) to (〇s -5) is preferably an aryl group having a total carbon number of 6 to 30 which may also have a substituent. -54- 201140249 The substituents which the aryl group represented by β Rl may have are exemplified by a dentate atom, a phenyloxy group, a aryloxy group, a thiol group, an arylthio group, an oxycarbonyl group. , an aryloxycarbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, an alkoxysulfonyl group, etc. The aryl group represented by R1 is exemplified by a phenyl group, a p-methylphenyl group, a pair. Chlorophenyl, pentachlorophenyl, pentafluorophenyl, o-methoxyphenyl, and p-phenoxyphenyl%. Further, in the general formula (0 S - 3 ) to (〇 s - 5 ), the heteroaryl group represented by R1 is preferably a heteroaryl group having a total carbon number of 4 to 30 which may also have a substituent. The substituent which the heteroaryl group represented by R1 may have is a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, or an aryloxy group. A carbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, an alkoxysulfonyl group or the like. In the general formulae (OS-3) to (OS-5), the heteroaryl group represented by R1 may be as long as it contains at least one heteroaromatic ring, for example, a heteroaromatic ring and a benzene ring are also Can be condensed. The heteroaryl group represented by R1 is exemplified by a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring. A ring of a hydrogen atom or the like is removed from the ring in the group formed. In the general formulae (OS-3) to (OS-5), R2 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group. In the general formulae (OS-3) to (OS-5), when two R are present in the compound at -55 to 201140249, it is preferred that one or two are a group, an aryl group or a _ atom, and Preferably, one is an alkyl group, an aryl group or a halogen atom, particularly preferably one is an alkyl group, and the remainder is a hydrogen atom. In the general formulae (OS-3) to (〇s_5), the alkyl group or the aryl group represented by R2 may have a substituent. The substituent which the or the aryl group represented by R may have is the same as the substituent which the alkyl group or the aryl group represented by R1 may have. The alkyl group represented by R2 is preferably an alkyl group having a total carbon number of from 1 to 12 which may have a substituent, more preferably an alkyl group having a total carbon number of from 1 to 6 which may have a substituent. The alkyl group represented by r2 is exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, n-hexyl, allyl, chloromethyl, bromine Methyl, methoxymethyl, and benzyl, etc.; preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl or n-hexyl; Preferably, it is methyl, ethyl, n-propyl, n-butyl or n-hexyl; particularly preferred is methyl. The aryl group represented by R2 is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent. The aryl group represented by R2 may, for example, be a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group or a p-phenoxyphenyl group; Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. -56- 201140249 Among these, a chlorine atom or a bromine atom is preferred. In the general formulae (OS-3) to (OS-5), X represents 〇 or s, preferably 0 〇 in the formula (OS-3) to (OS-5), and the ring containing X as a ring member is 5-member ring or 6-member ring. In the general formulae (OS-3) to (OS-5), 'η represents 1 or 2, and when X is 〇, η is preferably 1'. Further, when X is s, η is preferably 2 °. In the general formulae (OS-3) to (OS-5), the alkyl group and the alkyloxy group represented by R6 may have a substituent. The alkyl group represented by R6 in the formula (Ο S - 3 ) to (Ο S - 5 ) is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent. The alkyl group represented by R6 may have a substituent: a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, and Aminocarbonyl and the like. The alkyl group represented by R6 may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, N-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, and benzyl. In the general formulae (OS-3) to (OS-5), the alkyloxy group represented by R6 is preferably an alkyloxy group having a total carbon number of 1 to 30 which may have a substituent. The alkyloxy group represented by R6 may have a substituent: halogen atom, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group And an aminocarbonyl group and the like. -57- 201140249 The alkyloxy group represented by R6 may, for example, be a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group or a trichloromethyloxy group. , ethoxyethyloxy, methylthioethyloxy, phenylthioethyloxy, ethoxycarbonylethyloxy, phenoxycarbonylethyloxy, and dimethylaminocarbonyl Ethyloxy and the like. Among these, a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group is preferred. base. In the general formulae (OS-3) to (OS-5), the aminosulfonyl group represented by R6 may, for example, be a methylaminosulfonyl group, a dimethylaminosulfonyl group or a phenylamino group. A sulfonyl group, a methylphenylaminosulfonyl group, an aminosulfonyl group, and the like. In the general formulae (OS-3) to (OS-5), the alkoxysulfonyl group represented by R6 may, for example, be a methoxysulfonyl group, an ethoxysulfonyl group or a propoxysulfonyl group. And butoxysulfonyl and the like. Further, in the general formulae (OS-3) to (OS-5), m is an integer representing 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, particularly preferably 0. The photoacid generator represented by the formula (OS-3) is particularly preferably a photoacid generator represented by the following formula (OS-6), (OS-10) or (OS-11); The photoacid generator represented by (OS-4) is particularly preferably a photoacid generator represented by the following formula (Ο S - 7 ); the photoacid generator represented by the above formula (OS-5) It is preferably a photoacid generator represented by the following formula (OS-8) or (OS-9). -58- 201140249
Ο Ό-S-R1 (OS - 6) {OS - 7) R10 (OS - 8) S,、R8Ο Ό-S-R1 (OS - 6) {OS - 7) R10 (OS - 8) S, R8
R10 (OS-10) (OS-11) O-S-R1 通式(OS-6)至(OS-11)中’ R1是代表烷基、芳基 或雜芳基,R7是代表氫原子或溴原子’ r8是代表氫原子 、碳數爲1至8之烷基、鹵素原子、氯甲基、溴甲基、溴 乙基、甲氧基甲基、苯基或氯苯基’ R9是代表氫原子、 鹵素原子、甲基或甲氧基,R1Q是代表氫原子或甲基。 通式(OS-6)至(OS-11)中之R1是與在前述通式( OS-3)至(OS-5)中的R1爲同義,且較佳模式也是相同 〇 通式(OS-6 )中之R7是代表氫原子或溴原子,較佳 爲氫原子。 通式(OS-6)至(OS-11)中之R8是代表氫原子、碳 數爲1至8之烷基、鹵素原子、氯甲基、溴甲基' 溴乙基 、甲氧基甲基、苯基、或氯苯基’較佳爲碳數爲1至8之 烷基、鹵素原子、或苯基,更佳爲碳數爲〗至8之烷基, 進一步更佳爲碳數爲1至6之烷基,特佳爲甲基。 通式(OS-8)及式(〇s_9)中之R9是代表氫原子、 鹵素原子、甲基、或甲氧基,較佳爲氫原子。 -59- 201140249 通式(OS-8)至(OS-11)中之R10是代表氣原子或 甲基,較佳爲氫原子。 此外,在前述肟磺酸酯化合物中,關於西之立體'結構 (E,Z)是可爲任一者、或爲混合物》 在以前述通式(〇S_6 )至(OS-1 1 )所代表之化合物 中,從液保存性、感度及透明性的觀點’則更佳爲(0S-6 )° 以前述通式(OS·3)至通式(OS-5)所代表之光酸產 生劑的具體實例是可列舉下述例示化合物,但是本發明並 不受限於此等者。R10 (OS-10) (OS-11) OS-R1 In the formula (OS-6) to (OS-11), 'R1 represents an alkyl group, an aryl group or a heteroaryl group, and R7 represents a hydrogen atom or a bromine atom. 'r8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group. R9 is a hydrogen atom. A halogen atom, a methyl group or a methoxy group, and R1Q represents a hydrogen atom or a methyl group. R1 in the general formulae (OS-6) to (OS-11) is synonymous with R1 in the above general formulae (OS-3) to (OS-5), and the preferred mode is also the same oxime (OS) R7 in -6) represents a hydrogen atom or a bromine atom, preferably a hydrogen atom. R8 in the general formulae (OS-6) to (OS-11) is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, and a methoxy group. The group, phenyl group or chlorophenyl group is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having a carbon number of from 8 to 8, still more preferably a carbon number of An alkyl group of 1 to 6 is particularly preferably a methyl group. R9 in the formula (OS-8) and formula (〇s_9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, preferably a hydrogen atom. -59- 201140249 R10 in the formula (OS-8) to (OS-11) represents a gas atom or a methyl group, preferably a hydrogen atom. Further, in the aforementioned oxime sulfonate compound, the stereoscopic 'structure (E, Z) may be either or a mixture with respect to the west, in the above formula (〇S_6) to (OS-1 1 ) The representative compound is more preferably (0S-6)° from the viewpoint of liquid preservability, sensitivity, and transparency. Photoacid generation represented by the above general formula (OS·3) to (OS-5) Specific examples of the agent include the following exemplified compounds, but the present invention is not limited thereto.
0 ‘0-异一 0C3H7 0 0 /0-S-CH30 ‘0- 异一 0C3H7 0 0 /0-S-CH3
-60- 201140249-60- 201140249
-61 - 201140249-61 - 201140249
是以下述通式(os-1)所代表之光酸產生劑。 -62- 201140249It is a photoacid generator represented by the following general formula (os-1). -62- 201140249
通式(OS-1)中,R1是代表氫原子、烷基 烷氧基、烷氧基羰基、醯基、胺甲醯基、胺磺醯 '氰基、芳基、或雜芳基。R2是代表烷基、或芳 通式(OS-1)中,X是代表一〇_、一 S — 、-NR5 -、- CH2 -、- CR6H -、或-CR6r7-R7是各自獨立地代表烷基、或芳基。 通式(OS-1)中,R21至R24是各自獨立地 子、鹵素原子、烷基、烯基、烷氧基、胺基、烷 、烷基羰基、芳基羰基、醯胺基、磺基、氰基、 R2 1至R24中之兩個是可各自相互鍵結而形成環。 R21至R24是各自獨立地代表較佳爲氫原子 子、及烷基,此’外,R21至R24中之至少兩個是 而形成芳基之模式也可列舉。其中,從感度的觀 佳爲R21至R24是任一者皆爲氫原子之模式。 前文所述之官能基是任一者皆可更進一步具 〇 以通式(0 S -1 )所代表之光酸產生劑更佳爲 式(OS-2 )所代表之光酸產生劑。 、烯基、 基、磺基 基。 、-NH --,R5 至 代表氫原 氧基羰基 或芳基。 、鹵素原 相互鍵結 點,則較 有取代基 以下述通 -63- 201140249In the formula (OS-1), R1 represents a hydrogen atom, an alkyl alkoxy group, an alkoxycarbonyl group, a fluorenyl group, an amine carbaryl group, an amine sulfonium 'cyano group, an aryl group or a heteroaryl group. R2 represents an alkyl group, or an aromatic formula (OS-1), wherein X represents a 〇, a S — , —NR 5 —, — CH 2 —, — CR 6 H —, or —CR 6 r 7 — R 7 are independently represented Alkyl, or aryl. In the formula (OS-1), R21 to R24 are each independently a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amine group, an alkane group, an alkylcarbonyl group, an arylcarbonyl group, a decylamino group or a sulfo group. Two of cyano, R2 1 to R24 may be bonded to each other to form a ring. R21 to R24 each independently represent a hydrogen atom and an alkyl group, and a mode in which at least two of R21 to R24 are formed to form an aryl group is also exemplified. Among them, the sensitivity is preferably a mode in which R21 to R24 are each a hydrogen atom. Any of the above-mentioned functional groups may further have a photoacid generator represented by the formula (0 S -1 ), more preferably a photoacid generator represented by the formula (OS-2). , alkenyl, benzyl, sulfo group. , -NH --, R5 to represent a hydrogen orthooxycarbonyl group or an aryl group. , halogen original mutual bond point, then more substituents with the following pass -63- 201140249
通式 與在前述 且較佳的 在此 是氰基、 代表且R 此外 環之立體 在下 所代表之 ),但是 Me是代 是代表苯 (OS-2 )中,R1、R2、R21至 R24是各自獨立地 通式(OS-1)中之R1、R2、R21至R24爲同義, 實例也是相同。 等之中,通式(OS-1)及通式(OS-2)中之 R1 或芳基之模式爲更佳,最佳爲以通式(OS-2 )所 1是氰基、苯基或萘基之模式。 ,在前述肟磺酸酯化合物中,關於肟或苯并噻唑 結構(E, Z )是各自可爲任一者、或爲混合物。 文中,說明適合使用於本發明之以通式(OS-1) 光酸產生劑的具體實例(例示化合物b-Ι至b-34 本發明並不受限於此等。另外,在具體實例中, 良甲基,Et是代表乙基,Bn是代表苯甲基,Ph 基。 -64- 201140249 SO^Me SQ2MeThe formula is represented by the above and preferred herein is a cyano group, and R is a ring of the ring, but Me is a representative of benzene (OS-2), and R1, R2, R21 to R24 are R1, R2, R21 to R24 in the respective formula (OS-1) are synonymous, and the examples are the same. Among them, the mode of R1 or aryl in the general formula (OS-1) and the general formula (OS-2) is more preferred, and most preferably, the general formula (OS-2) is a cyano group or a phenyl group. Or naphthyl mode. In the above oxime sulfonate compound, the oxime or benzothiazole structure (E, Z) may be either or both. Herein, specific examples of the photoacid generator of the general formula (OS-1) which are suitable for use in the present invention are illustrated (exemplified compounds b-Ι to b-34) The present invention is not limited thereto. Further, in a specific example , good methyl, Et represents ethyl, Bn represents benzyl, Ph. -64- 201140249 SO^Me SQ2Me
SQ2Me Me Me b-1 b-2 b-3SQ2Me Me Me b-1 b-2 b-3
MeMe
N S〇2MeN S〇2Me
N—O S C02Et b -6 b - 4 b-5N-O S C02Et b -6 b - 4 b-5
65 20114024965 201140249
b - 24 b - 25 b - 26b - 24 b - 25 b - 26
在上述化合物中,從感度與安定性並存的觀點,則較 佳爲 b-9、 b-16、 b-31、 b-33。 -66 - 201140249 光酸產生劑(B)是可以一種單獨或兩種以上組合使 用。 在本發明之感光性樹脂組成物中,相對於1 00質量份 之共聚物(A),光酸產生劑(B)較佳爲含有0.1至10 質量份,更佳爲含有〇.5至1〇質量份。 本發明之感光性樹脂組成物,因應需要也可含有除了 光酸產生劑(B )以外之光酸產生劑作爲會感應活性光線 之光酸產生劑,但是較佳爲不含有1,2_醌二疊氮化合物。 其理由是1,2 -醌二疊氮化合物雖然會由於逐步型光化學反 應(sequential photochemical reaction)而形成竣基,但是 其量子產率(quantum yield)是一定爲1以下、感度爲低。 與此相對,光酸產生劑(B )是可推測爲:由於感應活性 光線所形成的酸是對受到保護的酸性基之脫保護作爲觸媒 而發生作用,以一個光量子之作用所形成的酸則有助於多 數的脫保護反應,使得量子產率爲超過1而成爲例如 之數倍的大値之所謂的「化學增幅」之結果而獲得高感度 〇 〔(C )增感劑〕 本發明之感光性樹脂組成物’在與光酸產生劑(B ) 之組合中,爲促進其分解而含有增感劑。 增感劑將吸收活性光線或放射線而成爲電子激發狀態 。成爲電子激發狀態之增感劑與光酸產生劑接觸而產生電 子移動、能量移動、放熱等作用。藉此’光酸產生劑會發 生化學變化、分解而形成酸。 -67- 201140249 較佳的增感劑的實例是可列舉屬於下列之化合物類, 且在350 nm至450 nm域具有吸收波長之化合物。 多核芳香族類(例如,芘、茈、聯三伸苯、蒽、 9,10-二丁氧基蒽' 9,10-二丁氧基-3,7-二甲氧基蒽、9,10-二丙氧基蒽);卩ill哩類(例如,螢光黃、曙紅、赤藻辛、 玫瑰紅B、孟加拉玫瑰(R 〇 s e B e n g a 1));她酮類(例如, 卩山酮、氧硫卩ill卩星、二甲基氧硫卩ill喝、二乙基氧硫卩ill唱); 花青類(例如,噻羯花青(噻唾咐藍:thiacarbocyanine )、氧雜羰花青):部花青素類(例如,部花青素、羰部 花青素);若丹花青類(rhodacyanines) ; Oxonol類;噻哄 類(例如,噻嚀 '亞甲基藍、甲苯胺藍);吖啶類(例如 ’吖啶橙、氯黃素、吖啶黃素):吖啶酮類(例如,吖啶 酮' 10-丁基-2-氯吖啶酮);蒽醌類(例如,蒽醌):角 鯊鑰類(squaliums)(例如,角鯊鑰)·,苯乙烯基類 (styryls);雙苯乙嫌基類(bisstyryls)(例如,2-〔 2-〔 4-(二甲基胺基)苯基〕乙烯基〕苯并噚唑):香豆素類( 例如,7 -二乙基胺基-4 -甲基香豆素、7 -羥基-4 -甲基香豆 素、2,3,6,7 -四氫-9-甲基-1H,5H,11H-[1]苯并哌喃基[6,7,8-U]喹畊-1 1-酮))。 在此等增感劑中,較佳爲會收吸活性光線或放射線而 成爲電子激發狀態,具有對光酸產生劑的電子移動作用之 增感劑,特佳爲多環芳香族類、吖啶酮類、苯乙烯基類、 雙苯乙烯基類、香豆素類。 在上述增感劑中,更進一步適合的增感劑是可列舉: -68- 201140249 在以下述通式(III)、通式(IV)、通式(V)、或通式 (VI )所代表之化合物所包含的增感劑。Among the above compounds, b-9, b-16, b-31, and b-33 are preferable from the viewpoint of coexistence of sensitivity and stability. -66 - 201140249 The photoacid generator (B) can be used singly or in combination of two or more. In the photosensitive resin composition of the present invention, the photoacid generator (B) is preferably contained in an amount of 0.1 to 10 parts by mass, more preferably 〇.5 to 1 based on 100 parts by mass of the copolymer (A). 〇 mass parts. The photosensitive resin composition of the present invention may contain a photoacid generator other than the photoacid generator (B) as a photoacid generator which induces active light, if necessary, but preferably does not contain 1,2_醌Azide compound. The reason for this is that the 1,2-quinonediazide compound forms a sulfhydryl group due to a sequential photochemical reaction, but its quantum yield is always 1 or less and the sensitivity is low. On the other hand, the photoacid generator (B) is presumed to be an acid formed by the action of a photon quantum because the acid formed by the inductively active light acts as a catalyst for the deprotection of the protected acidic group. The invention is advantageous in that a majority of the deprotection reaction is obtained, and the quantum yield is a result of so-called "chemical amplification" which is, for example, several times greater than that of a large number of times, and a high sensitivity ( [(C) sensitizer] is obtained. The photosensitive resin composition 'in combination with the photoacid generator (B) contains a sensitizer to promote decomposition thereof. The sensitizer will absorb active light or radiation and become an electronically excited state. The sensitizer which is in an electronically excited state is brought into contact with the photoacid generator to cause electron movement, energy movement, heat release and the like. Thereby, the photoacid generator undergoes chemical changes and decomposition to form an acid. -67- 201140249 Examples of preferred sensitizers are compounds which are exemplified by the following compounds and having an absorption wavelength in the 350 nm to 450 nm domain. Polynuclear aromatics (for example, ruthenium, osmium, triphenylene, anthracene, 9,10-dibutoxyanthracene 9,10-dibutoxy-3,7-dimethoxyanthracene, 9,10 - dipropoxy fluorene); 卩ill 哩 (for example, fluorescent yellow, blush, red algae, rose red B, rose radish (R 〇se B enga 1)); her ketones (for example, Lushan Ketone, oxysulfonium ill comet, dimethyl oxysulfonate ill, diethyl oxysulfonate ill sing; cyanine (for example, thiocyanine: thiacarbocyanine) Cyanine): anthocyanins (eg, anthocyanins, carbonyl anthocyanins); rhodacyanines; Oxonols; thiazides (eg, thiazide 'methylene blue, toluidine blue) Acridines (eg 'acridine orange, chloroflavin, acridine flavin): acridone (eg acridone ' 10-butyl-2-chloroacridone); anthraquinones (eg , 蒽醌): squaliums (eg, squalanes), styryls; bisstyryls (eg, 2-[2-[4-( Dimethylamino)phenyl]vinyl]benzoxazole : Coumarins (for example, 7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2,3,6,7-tetrahydro-9- Base-1H,5H,11H-[1]benzopyrano[6,7,8-U]quino-1-1-one)). Among these sensitizers, it is preferred to absorb active light or radiation to become an electron-excited state, and to have a sensitizer for the electron-moving action of the photo-acid generator, particularly preferably a polycyclic aromatic compound or acridine. Ketones, styrenes, bisstyryls, coumarins. Among the above sensitizers, further suitable sensitizers are: -68- 201140249 in the following general formula (III), general formula (IV), general formula (V), or general formula (VI) A sensitizer comprised by a representative compound.
通式(III)中,R1及R2是代表碳原子數爲1至4之 烷基,且R1及R2是相同。R3及R4是各自獨立地代表— 價取代基。m及η是各自獨立地代表0至4之整數。 以R1或R2所代表之碳原子數爲1至4之烷基較佳爲 甲基、乙基、正丙基、或正丁基。 以R3或R4所代表之一價取代基是可列舉:鹵素原子 、羥基、碳原子數爲1至4之烷基、碳原子數爲1至4之 燒氧基、或硝基,較佳爲甲基、乙基、正丙基、甲氧基、 乙氧基、或正丙基氧基。 m較佳爲〇至2,更佳爲0至1。 η較佳爲0至2,更佳爲0至1。In the formula (III), R1 and R2 represent an alkyl group having 1 to 4 carbon atoms, and R1 and R2 are the same. R3 and R4 are each independently represented as a valence substituent. m and η are integers each independently representing from 0 to 4. The alkyl group having 1 to 4 carbon atoms represented by R1 or R2 is preferably a methyl group, an ethyl group, a n-propyl group or an n-butyl group. The valent substituent represented by R3 or R4 may, for example, be a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group, preferably Methyl, ethyl, n-propyl, methoxy, ethoxy, or n-propyloxy. m is preferably from 〇 to 2, more preferably from 0 to 1. η is preferably from 0 to 2, more preferably from 0 to 1.
通式(IV)中,R5是代表碳原子數爲1至6之烷基 -69- 201140249 或也可經取代之苯基。R6及R7是各自獨立地代表一價取 代基》〇及p是各自獨立地代表〇至4之整數^ 以R5所代表之碳原子數爲1至6之烷基較佳爲甲基 、乙基、正丙基、或正丁基。可經取代之苯基是以未經取 代者爲較佳。 以R6或R7所代表之一價取代基是可列舉:鹵素原子 、羥基、碳原子數爲1至4之烷基、碳原子數爲1至*之 烷氧基、或硝基;較佳爲氟原子、氣原子、溴原子、甲基 、乙基、正丙基、甲氧基、乙氧基、或正丙基氧基。 〇較佳爲〇至2,更佳爲0至1。 P較佳爲〇至2,更佳爲〇至1。In the formula (IV), R5 represents an alkyl group having from 1 to 6 carbon atoms -69 to 201140249 or a phenyl group which may also be substituted. R6 and R7 each independently represent a monovalent substituent. 〇 and p are each an integer independently representing 〇 to 4. The alkyl group having 1 to 6 carbon atoms represented by R5 is preferably a methyl group or an ethyl group. , n-propyl, or n-butyl. The phenyl group which may be substituted is preferably one which is not substituted. The valent substituent represented by R6 or R7 may, for example, be a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to * carbon atoms, or a nitro group; A fluorine atom, a gas atom, a bromine atom, a methyl group, an ethyl group, a n-propyl group, a methoxy group, an ethoxy group, or a n-propyloxy group. Preferably, 〇 is 〇 to 2, more preferably 0 to 1. P is preferably from 〇 to 2, more preferably from 〇 to 1.
(V) 通式(V )中,R8、R9、及R1Q是各自獨立地代表一 價取代基,q、r及s是各自獨立地代表〇至2之整數。R8 、R9、及RIG是其兩個以上可互相鍵結而形成5員環或6 員環。 以R8、R9、或R 1 Q所代表之一價取代基是可列舉:鹵 素原子、氰基、羥基、碳原子數爲丨至4之烷基、碳原子 數爲1至4之烷氧基、碳原子數爲1至4之醯基、碳原子 數爲1至4之羧酸酯基、碳原子數爲1至4之烷基胺基、 -70- 201140249(V) In the formula (V), R8, R9, and R1Q each independently represent a monovalent substituent, and q, r, and s are each an integer independently representing 〇 to 2. R8, R9, and RIG are two or more of them that can be bonded to each other to form a 5-member ring or a 6-member ring. The valent substituent represented by R8, R9 or R 1 Q may, for example, be a halogen atom, a cyano group, a hydroxyl group, an alkyl group having a carbon number of 4 to 4, or an alkoxy group having 1 to 4 carbon atoms. a mercapto group having 1 to 4 carbon atoms, a carboxylate group having 1 to 4 carbon atoms, an alkylamino group having 1 to 4 carbon atoms, -70- 201140249
2-苯并噻唑基2-benzothiazolyl
此外,由R8、R 胃壤或6員環是 '及所形成的 可列舉:可具有任意的取代基之苯環、 ,’6,7-四氫喹阱 環、環戊烷環、環己烷環。 q較佳爲0至3’更佳爲〇至2。 r較佳爲0至2’更佳爲〇至1。 s較佳爲0至3,更佳爲〇至2。In addition, R8, R gastric soil or 6-membered ring is 'and can be exemplified: benzene ring which may have any substituent, '6,7-tetrahydroquinoline ring, cyclopentane ring, cyclohexene Alkane ring. q is preferably from 0 to 3', more preferably from 2 to 2. r is preferably from 0 to 2', more preferably from 〇 to 1. s is preferably from 0 to 3, more preferably from 2 to 2.
通式(VI)中’ R11及R12是各自獨立地代表經取代 或未經取代之碳原子數爲1至4之垸基、或經取代或未經 取代之苯基。R13及R14是各自獨立地代表氫原子或碳原 子數爲1至20之脂肪族基、雜環基、芳香族基、或芳香 脂肪族基。R13及R14是可互相鍵結而形成5員環或6員 環。 以R11或R12所代表之碳原子數爲1至4之垸基較佳 爲甲基、乙基、正丙基。 -71 - 201140249 此外,可導入於以R11或R12所代表之烷基或苯基之 取代基是可列舉:鹵素原子、氰基、或羥基。 以R13或R14所代表之碳原子數爲1至20之脂肪族基 較佳爲:甲基、乙基、正丙基、異丙基、正丁基、異丁基 '二級丁基、三級丁基、正戊基、異戊基、二級戊基、正 己基、正庚基、正辛基、正壬基、正癸基、甲氧基、乙氧 基、正丙氧基、異丙氧基、正丁氧基、正戊氧基、正辛氧 基、正癸氧基等。 以R13或R14所代表之雜環基較佳爲可具有任意的取 代基之2 -喹啉基、2-咪唑基、2-噻唑基、2 -Df唑基。 以R13或R14所代表之芳香族基較佳爲可具有任意的 取代基之苯基、萘基、蒽基。 以R 1 3或R 1 4所代表之芳香脂肪族基較佳爲:可具有 任意的取代基之苯乙烯基' 2-乙烯基呋喃基、2-乙烯基四 氫呋喃基、2 -乙烯基哌喃基、2 -乙烯基四氫哌喃基。 R13及R14相互鍵結而形成之5員環或6員環較佳爲 :可具有任意的取代基之 2 -喹啉基、2 -咪唑基、2-噻唑基 、2-噚唑基。 在以通式(III)、通式(IV)、通式(V)、或通式 (VI )所代表之化合物所包含的增感劑中,從感度、透明 性的觀點,則較佳爲9, 10 -二丁氧基蒽、9, 10 -二丙氧基蒽 、10-丁基-2-氯吖啶酮、2-〔 2-〔 4-(二甲基胺基)苯基 〕乙烯基〕苯并噚唑;2 3 6,7_四氫-9·甲基·1H,5H,11H-[1] 苯并脈喃基[6,7,8-ij]喹阱-1卜酮);更佳爲9,10-二丁氧基 -72- 201140249 蒽、9,10-二丙氧基蒽、10-丁基-2-氯吖啶酮。 增感劑是可使用市售品、或以習知的合成方法合成。 此外,增感劑是可以一種單獨或兩種以上組合使用。 從感度、透明性並存的觀點,相對於1 0 0質量份之光 酸產生劑(B ),則增感劑較佳爲2 0至3 0 0質量份,更佳 爲30至200質量份。 〔(D )溶劑〕 本發明之感光性樹脂組成物是含有溶劑。 本發明之感光性樹脂組成物較佳爲將必須成分的共聚 物(A )及光酸產生劑(B )、以及後述之各種添加劑等 的任意成分調製成爲經溶解於溶劑之溶液。 使用於本發明之感光性樹脂組成物之溶劑是可使用習 知的溶劑,其可例示:乙二醇一烷基醚類、乙二醇二烷基 醚類、醋酸乙二醇一烷基醚酯類、丙二醇一烷基醚類、丙 二醇二烷基醚類、醋酸丙二醇一烷基醚酯類、二甘醇二烷 基醚類、醋酸二甘醇一烷基醚酯類、二伸丙二醇一烷基醚 類、二伸丙二醇二烷基醱類、醋酸二伸丙二醇一烷基醚酯 類、酯類、酮類、醯胺類、內酯類等。 可使用於本發明之感光性樹脂組成物之溶劑是可列舉 :例如, (1) 乙二醇一甲基醚、乙二醇一乙基醚、乙二醇一丙基 醚、乙二醇一丁基醚等之乙二醇一烷基醚類; (2) 乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丙基 醚等之乙二醇二烷基醚類; -73- 201140249 (3) 醋酸乙二醇一甲基醚酯、醋酸乙二醇一乙基醚酯、 醋酸乙二醇一丙基醚酯、醋酸乙二醇一丁基醚酯等 之醋酸乙二醇一烷基醚酯類; (4) 丙二醇一甲基醚、丙二醇一乙基醚、丙二醇一丙基 醚、丙二醇一丁基醚等之丙二醇一烷基醚類; (5) 丙二醇二甲基醚、丙二醇二乙基醚、二甘醇一甲基 醚、二甘醇一乙基醚等之丙二醇二烷基醚類; (6) 醋酸丙二醇一甲基醚酯、醋酸丙二醇一乙基醚酯、 醋酸丙二醇一丙基醚酯、醋酸丙二醇一丁基醚酯等 之醋酸丙二醇一烷基醚酯類; (7) 二甘醇二甲基醚、二甘醇二乙基醚、二甘醇乙基甲 基醚等之二甘醇二烷基醚類; (8) 醋酸二甘醇一甲基醚酯、醋酸二甘醇一乙基醚酯、 醋酸二甘醇一丙基醚酯、醋酸二甘醇一丁基醚酯等 之醋酸二甘醇一烷基醚酯類; (9) 二伸丙二醇一甲基醚、二伸丙二醇一乙基醚、二伸 丙二醇一丙基醚、二伸丙二醇一丁基醚等之二伸丙 二醇一烷基醚類; (10) 二伸丙二醇二甲基醚、二伸丙二醇二乙基醚 '二 伸丙二醇乙基甲基醚等之二伸丙二醇二烷基醚類 » (11) 醋酸二伸丙二醇一甲基醚酯、醋酸二伸丙二醇一 乙基醚酯、醋酸二伸丙二醇一丙基醚酯、醋酸二 伸丙二醇一丁基醚酯等之醋酸二伸丙二醇一烷基 -74- 201140249 醚酯類; (12) 乳酸甲酯、乳酸乙酯、乳酸正丙酯、乳酸異丙酯 、乳酸正丁酯、乳酸異丁酯、乳酸正戊酯、乳酸 異戊酯等之乳酸酯類; (13) 醋酸正丁酯、醋酸異丁酯、醋酸正戊酯、醋酸異 戊酯、醋酸正己酯、醋酸2-乙基己酯、丙酸乙酯 、丙酸正丙酯、丙酸異丙酯、丙酸正丁酯、丙酸 異丁酯、丁酸甲酯、丁酸乙酯、丁酸乙酯、丁酸 正丙酯、丁酸異丙酯、丁酸正丁酯、丁酸正丁酯 、丁酸異丁酯等之脂肪族羧酸酯類; (14) 羥基醋酸乙酯、2-羥基-2-甲基丙酸乙酯、2-羥基-3 -甲基丁酸乙酯、甲氧基醋酸乙酯、乙氧基醋酸 乙酯、3 -甲氧基丙酸甲酯、3 -甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3 -乙氧基丙酸乙酯、醋酸3 -甲 氧基丁酯、醋酸3-甲基-3-甲氧基丁酯、丙酸3-甲 基-3 -甲氧基丁酯、丁酸3 -甲基-3-甲氧基丁酯、乙 醯基醋酸甲酯、乙醯基醋酸乙酯、丙酮酸甲酯、 丙酮酸乙酯等之其他酯類; (15) 甲基乙基酮、甲基丙基酮、甲基正丁基酮、甲基 異丁基酮、2-庚酮、3-庚酮、4-庚酮、環己酮等之 酮類; (16) N-甲基甲醯胺、N,N-二甲基甲醯胺、N-甲基乙醯 胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等之醯 胺類; -75- 201140249 (17) r-丁內酯等之內酯類等。 此外,因應需要可更進一步對此等溶劑添加苯甲基乙 基醚、二己基醚、醋酸乙二醇一苯基醚酯、二甘醇一甲基 醚、二甘醇一乙基醚、異佛酮、己酸、辛酸、1-辛醇、i-壬醇、苯甲基醇、大茴香醚 '醋酸苯甲酯、苯甲酸乙酯、 草酸二乙酯、順丁烯二酸二乙酯、碳酸伸乙酯、碳酸伸丙 酯等之溶劑。 在上述溶劑中,特佳爲二甘醇乙基甲基醚、醋酸丙二 醇一甲基醚酯。 溶劑是可以一種單獨或兩種以上混合使用。 可使用於本發明之溶劑較佳爲一種單獨或兩種併用, 較佳爲兩種併用,更佳爲醋酸丙二醇~烷基醚酯類與二甘 醇二烷基醚類倂用。 在本發明之感光性樹脂組成物中之的溶劑的含量,相 對於每100質量份之共聚物(A),則較佳爲50至3,000 質量份,更佳爲100至2,000質量份,進—步更佳爲15〇 至1,5 0 0質量份。 〔其他成分〕 在本發明之感光性樹脂組成物,除了前述(A)成分 至(D)成分以外’因應需要可作爲任意成分而加入以下 所述之(E )抗氧化劑、(F )交聯劑、、(G )密著改良劑 、(Η )鹼性化合物、(I )界面活性劑、(J )塑化劑、 及(Κ)熱自由基產生劑、(L)熱酸產生劑、(Μ)酸增 殖劑(acid amplifier)、及(Ν )顯影促進劑(development -76- 201140249 accelerator)等之習知的添加劑。 < (E )抗氧化劑> 本發明之感光性樹脂組成物較佳爲含有抗氧化劑 抗氧化劑是可含有習知的抗氧化劑。 由於添加抗氧化劑,則具有可防止硬化膜之著色 減少由於分解所引起之膜厚減少,且耐熱透明性優異 點。 如此之抗氧化劑是可列舉:例如,磷系抗氧化劑 基肼類、’位阻型胺系抗氧化劑、硫系抗氧化劑、酚系 化劑、抗壞血酸類、硫酸鋅、糖類、亞硝酸鹽、亞硫 、硫代硫酸鹽、羥基胺衍生物等。在此等之中,從硬 之著色、膜厚減少的觀點,則特佳爲酚系抗氧化劑。 是可以一種單獨使用或兩種以上混合使用。 「酚系抗氧化劑」之市售品是可列舉:例如, STAB AO-60 (商品名、ADEKA(股)製);ADK STAB 8〇 (商品名、ADEKA(股)製)、IRGANOX 1 098 ( Japan(股)製)。 抗氧化劑的含量,相對於感光性樹脂組成物之總 成分,則較佳爲0.1至6質量%,更佳爲0.2至5質量 特佳爲0.5至4質量%。若爲在此範圍時,則所形成 可獲得充分的透明性,且在圖案形成時之感度也爲良 此外,除了抗氧化劑以外之添加劑是可將在「 子添加劑之新發展(日刊工業新聞(股))」中所揭述 種紫外線吸收劑、或金屬去活化劑等添加至本發明之 、或 之優 acaic 、醒 抗氧 酸鹽 化膜 此等 ADK AO-C i b a 固體 :%, 的膜 好。 高分 之各 感光 -77- 201140249 性樹脂組成物中。 〔(F )交聯劑〕 從感度、保存安定性的觀點,因應需要本發明之 性樹脂組成物是可含有交聯劑。 交聯劑是可添加例如如下所述之在分子內具有兩 上環氧基或氧雜環丁烷基之化合物、含有烷氧基甲基 聯劑、具有至少一個烯鍵性不飽和雙鍵之化合物。 藉由添加交聯劑,則可使得從本發明之感光性樹 成物所獲得之硬化膜成爲更強固的膜》 (在分子內具有兩個以上環氧基或氧雜環丁烷基之化 ) 「在分子內具有兩個以上環氧基之化合物」的具 例是可列舉:雙酚A型環氧樹脂、雙酚F型環氧樹脂 酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、 族環氧樹脂等。 此等之交聯劑是可獲自市售品。可獲自市售品之 劑的實例(皆爲商品名)是可列舉:例如,「雙酚A 氧樹月旨」是 JER 827 ' JER 828、JER 834' JER 100 1、 1 002、JER 1 003、JER 1 05 5、JER 1 007、JER 1 009、 1010 (以上是商品名、Japan Epoxy Resin(股)製 EPICLON 860 、 EPICLON 1 05 0 、 EPICLON 1 〇ί EPICLON 1055 (以上是商品名、DIC(股)製)等;「 F型環氧樹月旨」是 JER 806、JER 807、JER 4004、 4005、JER 4007、JER 4010 (以上是商品名' : 感光 個以 之交 脂組 合物 體實 '苯 脂肪 交聯 型環 JER JER ), 1 ' 雙酚 JER ap an -78- 201140249In the formula (VI), R11 and R12 each independently represent a substituted or unsubstituted fluorenyl group having 1 to 4 carbon atoms or a substituted or unsubstituted phenyl group. R13 and R14 are each an aliphatic group, a heterocyclic group, an aromatic group or an aromatic aliphatic group each independently representing a hydrogen atom or a carbon atom number of 1 to 20. R13 and R14 are mutually bondable to form a 5-member ring or a 6-member ring. The fluorenyl group having 1 to 4 carbon atoms represented by R11 or R12 is preferably a methyl group, an ethyl group or a n-propyl group. Further, the substituent which may be introduced into the alkyl group or the phenyl group represented by R11 or R12 may, for example, be a halogen atom, a cyano group or a hydroxyl group. The aliphatic group represented by R13 or R14 having 1 to 20 carbon atoms is preferably: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl 'secondary butyl, three Butyl, n-pentyl, isopentyl, secondary pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, methoxy, ethoxy, n-propoxy, iso Propyloxy, n-butoxy, n-pentyloxy, n-octyloxy, n-decyloxy and the like. The heterocyclic group represented by R13 or R14 is preferably a 2-quinolyl group, a 2-imidazolyl group, a 2-thiazolyl group or a 2-Dfazolyl group which may have an arbitrary substituent. The aromatic group represented by R13 or R14 is preferably a phenyl group, a naphthyl group or an anthracenyl group which may have an arbitrary substituent. The aromatic aliphatic group represented by R 1 3 or R 1 4 is preferably a styryl '2-vinylfuranyl group, a 2-vinyltetrahydrofuranyl group, a 2-vinylpyranyl group which may have an arbitrary substituent. Base, 2-vinyltetrahydropyranyl. The 5-membered or 6-membered ring formed by bonding R13 and R14 to each other is preferably a 2-quinolyl group, a 2-imidazolyl group, a 2-thiazolyl group or a 2-carbazolyl group which may have an arbitrary substituent. In the sensitizer contained in the compound represented by the general formula (III), the general formula (IV), the general formula (V), or the general formula (VI), it is preferably from the viewpoint of sensitivity and transparency. 9, 10-dibutoxyanthracene, 9,10-dipropoxy fluorene, 10-butyl-2-chloroacridone, 2-[2-[4-(dimethylamino)phenyl] Vinyl]benzoxazole; 2 3 6,7_tetrahydro-9·methyl·1H,5H,11H-[1] Benzo-indolyl[6,7,8-ij]quinoline-1 More preferred is 9,10-dibutoxy-72- 201140249 蒽, 9,10-dipropoxy fluorene, 10-butyl-2-chloroacridone. The sensitizer can be synthesized using a commercially available product or by a conventional synthesis method. Further, the sensitizer may be used alone or in combination of two or more. The sensitizer is preferably from 20 to 300 parts by mass, more preferably from 30 to 200 parts by mass, per 100 parts by mass of the photoacid generator (B) from the viewpoint of sensitivity and transparency. [(D) Solvent] The photosensitive resin composition of the present invention contains a solvent. The photosensitive resin composition of the present invention is preferably prepared by dissolving an optional component such as a copolymer (A), a photoacid generator (B), and various additives described later into a solution dissolved in a solvent. The solvent used in the photosensitive resin composition of the present invention can be a conventional solvent, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, and ethylene glycol monoalkyl ether. Esters, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether esters, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether esters, dipropylene glycol Alkyl ethers, dipropylene glycol dialkyl hydrazines, dipropylene glycol monoalkyl ether esters, esters, ketones, guanamines, lactones, and the like. The solvent which can be used for the photosensitive resin composition of the present invention is, for example, (1) ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol one. Ethylene glycol monoalkyl ethers such as butyl ether; (2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether ; -73- 201140249 (3) Acetic acid glycol monomethyl ether ester, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether ester, acetic acid ethylene glycol monobutyl ether ester and other acetic acid Ethylene glycol monoalkyl ether esters; (4) propylene glycol monomethyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; (5) propylene glycol II a propylene glycol dialkyl ether such as methyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether; (6) propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate a propylene glycol monoalkyl ether acetate such as an ether ester, propylene glycol monopropyl ether acetate or propylene glycol monobutyl ether acetate; (7) diethylene glycol dimethyl ether, diethylene glycol diethyl ether Diethylene glycol dialkyl ethers such as ether and diethylene glycol ethyl methyl ether; (8) diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoacetate Diethylene glycol monoalkyl ether acetates such as hydroxy ether esters and diethylene glycol monobutyl ether acetate; (9) dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropylene a dipropylene glycol monoalkyl ether such as a diether or a dipropylene glycol monobutyl ether; (10) dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, etc. Dipropylene glycol dialkyl ethers» (11) Dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate Ethyl acetate di-propylene glycol monoalkyl-74- 201140249 ether esters; (12) methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, lactic acid a lactic acid ester such as n-amyl ester or isoamyl lactate; (13) n-butyl acetate, isobutyl acetate, n-amyl acetate, and acetic acid Amyl ester, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate, butyl An aliphatic carboxylic acid ester such as ethyl acetate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, n-butyl butyrate or isobutyl butyrate; (14) Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-3-methylbutanoate, ethyl methoxyacetate, ethyl ethoxyacetate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl acetate 3-methoxybutyl ester, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoxyacetate, ethyl acetoxyacetate Other esters such as ester, methyl pyruvate, ethyl pyruvate; (15) methyl ethyl ketone, methyl propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, 2-heptanone a ketone such as 3-heptanone, 4-heptanone or cyclohexanone; (16) N-methylformamide, N,N-dimethylformamide, N-methylethyl Amine, N, N- dimethylacetamide, N- methylpyrrolidinone, etc. Amides; -75- 201140249 (17) r- butyrolactone within esters. In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether ester, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and the like may be further added to the solvent as needed. Carbaryl, caproic acid, caprylic acid, 1-octanol, i-nonanol, benzyl alcohol, anisole' benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate A solvent such as ethyl carbonate or propyl carbonate. Among the above solvents, particularly preferred are diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate. The solvent may be used singly or in combination of two or more. The solvent to be used in the present invention is preferably used singly or in combination of two or more, preferably two, and more preferably propylene glycol-alkyl ether acetate and diethylene glycol dialkyl ether. The content of the solvent in the photosensitive resin composition of the present invention is preferably from 50 to 3,000 parts by mass, more preferably from 100 to 2,000 parts by mass, per 100 parts by mass of the copolymer (A). The further step is preferably 15 〇 to 1,500 parts by mass. [Other components] In addition to the above-mentioned components (A) to (D), the photosensitive resin composition of the present invention may be added as an optional component to (E) an antioxidant and (F) cross-linking as described below. Agent, (G) adhesion improver, (Η) basic compound, (I) surfactant, (J) plasticizer, (Κ) thermal radical generator, (L) thermal acid generator, A conventional additive such as an acid amplifier or a development accelerator (development - 76-201140249 accelerator). <(E) Antioxidant> The photosensitive resin composition of the present invention preferably contains an antioxidant. The antioxidant may contain a conventional antioxidant. By adding an antioxidant, it is possible to prevent the coloring of the cured film from being reduced, and the film thickness due to decomposition is reduced, and the heat-resistant transparency is excellent. Examples of such an antioxidant include phosphorus-based antioxidant oximes, 'hindered amine-based antioxidants, sulfur-based antioxidants, phenol-based agents, ascorbic acid, zinc sulfate, saccharides, nitrites, and sub- Sulfur, thiosulfate, hydroxylamine derivatives, and the like. Among these, phenolic antioxidants are particularly preferred from the viewpoint of hard coloring and film thickness reduction. They may be used alone or in combination of two or more. The commercially available product of the "phenolic antioxidant" is, for example, STAB AO-60 (trade name, manufactured by ADEKA Co., Ltd.); ADK STAB 8 (trade name, manufactured by ADEKA Co., Ltd.), and IRGANOX 1 098 ( Japan (share) system). The content of the antioxidant is preferably from 0.1 to 6% by mass, more preferably from 0.2 to 5% by mass, particularly preferably from 0.5 to 4% by mass, based on the total of the photosensitive resin composition. If it is in this range, sufficient transparency can be obtained, and the sensitivity at the time of pattern formation is also good. In addition to additives other than antioxidants, the new development of "sub-additives" (Japanese Journal of Industry News) A film of the AKB AO-C iba solid: %, added to the present invention, or an acaic or awake oxidative acidified film, as disclosed in the above)) it is good. Each of the high-sensitivity photosensitive materials -77- 201140249 resin composition. [(F) Crosslinking Agent] From the viewpoint of sensitivity and storage stability, the resin composition of the present invention may contain a crosslinking agent as needed. The crosslinking agent may be, for example, a compound having two epoxy groups or oxetanyl groups in the molecule, an alkoxymethyl linking agent, and at least one ethylenically unsaturated double bond, as described below. Compound. By adding a crosslinking agent, the cured film obtained from the photosensitive dendrimer of the present invention can be made into a stronger film (having two or more epoxy groups or oxetane groups in the molecule) Examples of the "compound having two or more epoxy groups in the molecule" include bisphenol A type epoxy resin, bisphenol F type epoxy resin phenol novolak type epoxy resin, and cresol novolak type. Epoxy resin, family epoxy resin, etc. These crosslinkers are commercially available. Examples of the agent which can be obtained from a commercial product (all are trade names) include, for example, "bisphenol A oxygen tree" is JER 827 'JER 828, JER 834' JER 100 1, 1 002, JER 1 003, JER 1 05 5, JER 1 007, JER 1 009, 1010 (The above are the trade name, Japan Epoxy Resin Co., Ltd. EPICLON 860, EPICLON 1 05 0, EPICLON 1 〇ί EPICLON 1055 (above is the trade name, DIC (share) system, etc.; "F-type epoxy tree month" is JER 806, JER 807, JER 4004, 4005, JER 4007, JER 4010 (above is the trade name ': sensitized one with a cross-fat combination object' Benzene fat cross-linked ring JER JER ), 1 'bisphenol JER ap an -78- 201140249
Epoxy(股)製),EPICLON 830、EPICLON 835 (以上、 DIC(股)製),LCE-21、RE-602S (以上是商品名、日本化 藥(股)製)等;「苯酚酚醛清漆型環氧樹脂」是JER 152 、JER 154、JER 157S70、JER 157S65C 以上是商品名、 Japan Epoxy Resin(股)製),EPICLON N-740 ' EPICLON N-740 ' EPICLON N-770、EPICLON N-775 (以上是商品 名、DIC(股)製)等;「甲酚酚醛清漆型環氧樹脂」是 EPICLON N- 66 0、EPICLON N-6 6 5、EPICLON N- 67 0、 EPICLON N-67 3、EPICLON N-6 8 0、EPICLON N-690、 EPICLON N-695 (以上是商品名、DIC(股)製),EOCN-1 020 (以上是商品名、日本化藥(股)製)等;「脂肪族環 氧樹月旨」是 ADEKA RESIN EP-4080S、同 EP-4085 S、同 EP-40 8 8 S (以上是商品名、ADEKA(股)製), CELLOXIDE 202 1 P 、 CELLOXIDE 2 0 8 1 、 CELLOXIDE 2083 、 CELLOXIDE 2085 、 EHPE 3150 、 EPOLEAD PB 3 600、同 PB 4700 (以上是商品名、DAICEL化學工業( 股)製)等。其他,也可列舉 ADEKA RESIN EP-40 00 S、 同 EP-4003S、同 EP-4010S、同 EP-4011S (以上是商品 名、ADEKA(股)製)’ NC-2000、NC-3000、NC-7300、 XD-1000、EPPN-501 、 EPPN-5 02 (以上是商品名、 ADEKA(股)製)等。此等是可以一種單獨或兩種以上組合 使用。 在此等之中較佳者是可列舉:雙酚A型環氧樹脂、雙 酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂。特佳爲雙酚 -79- 201140249 A型環氧樹脂、苯酚酚醛清漆型環氧樹脂。 「在分子內具有兩個以上氧雜環丁烷基之化合物」的 具體實例是可使用 ARON OXETANE OXT-121、OXT-221 、OX-SQ、PNOX (以上是商品名、東亞合成(股)製)。 此外,含有氧雜環丁烷基之化合物是可以單獨或與含 有環氧基之化合物混合使用。 在分子內具有兩個以上環氧基或氧雜環丁烷基之化合 物對於感光性樹脂組成物的添加量,相對於1 0 0質量份之 共聚物(A )之總量,則較佳爲1至5 0質量份,更佳爲3 至3 0質量份。 (含有烷氧基甲基之交聯劑) 「含有烷氧基甲基之交聯劑」較佳爲烷氧基甲基化三 聚氰胺、烷氧基甲基化苯并胍胺、烷氧基甲基化甘脲及烷 氧基甲基化脲等。此等是可分別將羥甲基化三聚氰胺、羥 甲基化苯并胍胺、羥甲基化甘脲、或羥甲基化脲之羥甲基 加以轉換成烷氧基甲基而獲得。關於該烷氧基甲基之種類 是並無特殊限制者,其可列舉:例如,甲氧基甲基、乙氧 基甲基、丙氧基甲基、丁氧基甲基等;從脫氣之產生量的 觀點,則特佳爲甲氧基甲基。 在此等交聯性化合物中,較佳的交聯性化合物是可列 舉:烷氧基甲基化三聚氰胺、烷氧基甲基化苯并胍胺、烷 氧基甲基化甘脲;從透明性的觀點,則特佳爲烷氧基甲基 化甘脲。 此等「含有烷氧基甲基之交聯劑」是可獲自市售品, -80- 201140249 任一者皆爲商品名’可使用:例如,CYMEL 3 00、301、 303、 370、 325、 327、 701、 266、 267、 238、 1141、 272 、202、 1156、 1158、 1123、 1170、 1174、 UFR 65' 300 ( 以上是商品名、三井Cyanamide(股)製);NIKALAC MX-750 、 -032 、 -706 、 -708 、 -40 、 -31 、 -270 、 -280 、 -290 、 NIKALAC MS-11、NIKALAC MW-30HM、-100LM、-390 ( 以上是商品名、三和化學(股)製)等。 在本發明之感光性樹脂組成物使用含有烷氧基甲基之 交聯劑時,含有烷氧基甲基之交聯劑的添加量,相對於 100質量份之共聚物(A),則較佳爲0.05至50質量份 ,更佳爲〇_5至10質量份。藉由以該範圍添加含有烷氧 基甲基之交聯劑,則可獲得顯影時之較佳鹼溶解性、與硬 化後之膜之優異的耐溶劑性。 (具有至少一個烯鍵性不飽和雙鍵之化合物) 具有至少一個烯鍵性不飽和雙鍵之化合物是適合使用 單官能之(甲基)丙烯酸酯、二官能之(甲基)丙烯酸酯 、三官能以上之(甲基)丙烯酸酯等之(甲基)丙烯酸酯 化合物。 「單官能之(甲基)丙烯酸酯」是可列舉:例如,( 甲基)丙烯酸2 -羥基乙酯、(甲基)丙烯酸卡必醇酯、( 甲基)丙烯酸異冰片酯、(甲基)丙烯酸3 -甲氧基丁酯、 鄰苯二甲酸2-(甲基)丙烯醯氧基乙基-2_羥基丙酯等。 「二官能之(甲基)丙烯酸酯」是可列舉:例如,( 甲基)丙嫌酸乙二醇酯、二(甲基)丙烯酸1,6-己二醇酯 -81 - 201140249 、二(甲基)丙烯酸1,9·壬二醇酯、聚二(甲基)丙烯酸 丙二醇酯、二(甲基)丙烯酸四甘醇酯、二丙烯酸雙苯氧 基乙醇苐酯、二丙烯酸雙苯氧基乙醇莽酯等。 「三官能以上之(甲基)丙烯酸酯」是可列舉:例如 ,三(甲基)丙烯酸三羥甲基丙烷酯、三(甲基)丙烯酸 新戊四醇酯、磷酸三((甲基)丙烯醯氧基乙基)酯、四 (甲基)丙烯酸新戊四醇酯、五(甲基)丙烯酸二新戊四 醇酯、六(甲基)丙烯酸二新戊四醇酯等。 此等具有至少一個烯鍵性不飽和雙鍵之化合物是可以 一種單獨或兩種以上組合使用。 在本發明之感光性樹脂組成物中,具有至少一個烯鍵 性不飽和雙鍵之化合物的使用比例,相對於1 〇 〇質量份之 (A )成分’則較佳爲5 0質量份以下,更佳爲3 0質量份 以下。藉由以此等比例含有具有至少一個烯鍵性不飽和雙 鍵之化合物’則可提高從本發明之感光性樹脂組成物所獲 得硬化膜之耐熱性及表面硬度等。在加入具有至少一個烯 鍵性不飽和雙鍵之化合物時,較佳爲添加後述之(K )熱 自由基產生劑。 < (G )密著改良劑> 本發明之感光性樹脂組成物是也可具有密著改良劑。 可使用於本發明之感光性樹脂組成物之密著改良劑是 用於提高作爲基材之無機物例如矽、氧化矽、氮化矽等矽 化合物’金、銅、鋁等金屬與絕緣膜之密著性的化合物。 具體而言,其可列舉矽烷偶合劑、硫醇系化合物等。 -82- 201140249 在本發明所使用的作爲密著改良劑之矽烷偶合劑是以 界面之改質爲目的者,可在並無特殊限制下使用習知者。 較佳的「矽烷偶合劑」是可列舉:例如,γ-胺基丙基 三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-環氧丙氧基 丙基三烷氧基矽烷' γ-環氧丙氧基丙基烷基二烷氧基矽烷 、γ-甲基丙烯醯氧基丙基三烷氧基矽烷、γ-甲基丙烯醯氧 基丙基烷基二烷氧基矽烷、γ-氯丙基三烷氧基矽烷、γ-氫 硫基丙基三烷氧基矽烷、Ρ-(3,4-環氧基環己基)乙基三 烷氧基矽烷、乙烯基三烷氧基矽烷。 在此等之中,更佳爲γ-環氧丙氧基丙基三烷氧基矽烷 或γ-甲基丙烯醯氧基丙基三烷氧基矽烷,進一步更佳爲 γ-環氧丙氧基丙基三烷氧基矽烷。 此等之密著改良劑是可以一種單獨或兩種以上組合使 用。密著改良劑之添加是在基板上以本發明之感光性樹脂 組成物來形成硬化膜時,可有效地提高基板與硬化膜之密 著性,同時在將硬化膜形成爲圖案狀時,也可有效地調整 基板與圖案狀之硬化膜的錐角。 在本發明之感光性樹脂組成物中,相對於1 00質量份 之共聚物(Α),密著改良劑的含量較佳爲0.1至20質量 份,更佳爲0.5至1 0質量份。 < (Η )鹼性化合物> 本發明之感光性樹脂組成物是可含有鹼性化合物。 鹼性化合物是可從在化學增幅光阻所使用者中任意選 擇使用。其可列舉:例如,脂肪族胺、芳香族胺、雜環式 -83- 201140249 胺、第四級氫氧化銨、及羧酸之第四級銨鹽等。 「脂肪族胺」是可列舉:例如,三甲基胺、二乙基胺 、三乙基胺、二正丙基胺、三-正丙基胺、二-正戊基胺、 三-正戊基胺、二乙醇胺、三乙醇胺、二環己基胺、二環 己基甲基胺等。 「芳香族胺」是可列舉:例如,苯胺、苯甲基胺、 N,N-二甲基苯胺、二苯基胺等。 「雜環式胺」是可列舉:例如,吡啶、2 -甲基吡啶、 4 -甲基啦Π定、2 -乙基卩比D定、4 -乙基卩比陡、2 -苯基卩比陡、4 -苯基吡啶、N -甲基-4 -苯基吡啶、4 -二甲基胺基吡啶、咪 唑、苯并咪唑、4-甲基咪唑、2-苯基苯并咪唑、2,4,5_三 苯基咪哩、薛鹼、薛鹼酸、薛鹼酿胺、喹琳、8 -氧基喹啉 、吡阱、吡哩、嗒阱、嚷D令、吡咯卩定、脈D定、哌阱、嗎啉 、4-甲基嗎啉、1,5 -二吖雙環[4·3·0]-5 -壬烯、丨,8-二卩丫雙 環[5·3·0]-7-十一烯。 「第四級氫氧化銨」是可列舉:例如,氫氧化四甲基 銨、氫氧化四乙基銨、氫氧化四-正丁基銨、氫氧化四-正 己基銨等。 「羧酸之第四級銨鹽」是可列舉:例如,醋酸四甲基 銨、苯甲酸四甲基銨、醋酸四-正丁基銨、苯甲酸四-正丁 基錢等。 可使用於本發明之鹼性化合物是可以一種單獨使用或 兩種以上倂用,較佳爲兩種以上倂用,更佳爲兩種併用, 進一步更佳爲將兩種雜環式胺倂用。 -84- 201140249 在本發明之感光性樹脂組成物中, 之共聚物(A ),鹼性化合物的含量較ί 量份,更佳爲0.005至0.2質量份。 < (I )界面活性劑> 本發明之感光性樹脂組成物是可含 界面活性劑是陰離子系、陽離子系 性中任一者皆可使用,較佳的界面活性 活性劑。 「非離子系界面活性劑」的實例是 高級烷基醚類、聚氧乙烯高級烷基苯基 醇之高級脂肪酸二酯類、聚矽氧系、氟 此外,可列舉下列商品名:KP ( f| )、POLYFL0W (共榮社化學(股)製) 公司製)、MEGAFACE ( DIC(股)製) 3M(股)製)、Asahi Guard、Surflon ( PolyFox(OMNOVA公司製)等之各系; 界面活性劑是可列舉:含有以如下 與重複單元B之共聚物(1)作爲較佳 之重量平均分子量(Mw)爲1〇〇〇以上 佳爲1500以上且5000以下。重量平玲 層析法所測定之經聚苯乙烯換算得之値 相對於100質量份 爸爲0.001至1質 有界面活性劑。 、非離子系、或兩 劑是非離子系界面 可列舉:聚氧乙烯 醚類、聚氧乙烯二 系界面活性劑。 (越化學工業(股)製 ' EFTOP ( JEMCO 、FLUORAD (住友 旭硝子(股)製)、 ί\\ 〇 所示之重複單元 A 的實例。該共聚物 且1 0000以下,較 分子量是以凝膠透 -85- (1) 201140249Epoxy (stock) system, EPICLON 830, EPICLON 835 (above, DIC (share) system), LCE-21, RE-602S (above is the trade name, Nippon Chemical Co., Ltd.); "phenol novolak type Epoxy resin is JER 152, JER 154, JER 157S70, JER 157S65C or higher, trade name, Japan Epoxy Resin Co., Ltd., EPICLON N-740 ' EPICLON N-740 ' EPICLON N-770, EPICLON N-775 ( The above is the trade name, DIC (share) system, etc.; "cresol novolac type epoxy resin" is EPICLON N-660, EPICLON N-6 6 5, EPICLON N-67 0, EPICLON N-67 3, EPICLON N-6 8 0, EPICLON N-690, EPICLON N-695 (above is the trade name, DIC (share) system), EOCN-1 020 (above is the trade name, Nippon Chemical Co., Ltd.); "Ethylene Ethylene Tree" is ADEKA RESIN EP-4080S, with EP-4085 S, with EP-40 8 8 S (above is the trade name, ADEKA (share) system), CELLOXIDE 202 1 P, CELLOXIDE 2 0 8 1 , CELLOXIDE 2083, CELLOXIDE 2085, EHPE 3150, EPOLEAD PB 3 600, and PB 4700 (above is the trade name, DAICEL Chemical Industry Co., Ltd.). Others include ADEKA RESIN EP-40 00 S, EP-4003S, EP-4010S, and EP-4011S (the above are trade names, ADEKA). NC-2000, NC-3000, NC- 7300, XD-1000, EPPN-501, and EPPN-5 02 (the above are trade names, ADEKA (share) system). These may be used alone or in combination of two or more. Among these, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol novolak type epoxy resin. Particularly preferred is bisphenol -79- 201140249 A type epoxy resin, phenol novolak type epoxy resin. A specific example of the "compound having two or more oxetanyl groups in the molecule" is ARON OXETANE OXT-121, OXT-221, OX-SQ, PNOX (above, trade name, East Asia Synthetic Co., Ltd.) ). Further, the compound containing an oxetane group may be used singly or in combination with a compound containing an epoxy group. The amount of the compound having two or more epoxy groups or oxetanyl groups in the molecule to be added to the photosensitive resin composition is preferably the total amount of the copolymer (A) per 100 parts by mass. 1 to 50 parts by mass, more preferably 3 to 30 parts by mass. (Alkoxymethyl group-containing crosslinking agent) "Alkoxymethyl group-containing crosslinking agent" is preferably alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxy group Alkalized glycoluril and alkoxymethylated urea, and the like. These are obtained by converting a methylol group of methylolated melamine, hydroxymethylated benzoguanamine, methylolated glycoluril or methylolated urea to an alkoxymethyl group, respectively. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, and the like; The viewpoint of the amount of production is particularly preferably a methoxymethyl group. Among the crosslinkable compounds, preferred crosslinkable compounds include alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril; From a sexual point of view, alkoxymethylated glycoluril is particularly preferred. These "alkoxymethyl group-containing cross-linking agents" are commercially available, and -80-201140249 is a trade name 'may be used: for example, CYMEL 3 00, 301, 303, 370, 325 , 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR 65' 300 (above is the trade name, manufactured by Mitsui Cyanamide Co., Ltd.); NIKALAC MX-750, -032, -706, -708, -40, -31, -270, -280, -290, NIKALAC MS-11, NIKALAC MW-30HM, -100LM, -390 (above is the trade name, Sanhe Chemical) ))). When a crosslinking agent containing an alkoxymethyl group is used as the photosensitive resin composition of the present invention, the amount of the crosslinking agent containing an alkoxymethyl group is more than 100 parts by mass of the copolymer (A). It is preferably from 0.05 to 50 parts by mass, more preferably from 〇5 to 10 parts by mass. By adding a crosslinking agent containing an alkoxymethyl group in this range, it is possible to obtain a preferable alkali solubility at the time of development and excellent solvent resistance of the film after hardening. (Compound having at least one ethylenically unsaturated double bond) A compound having at least one ethylenically unsaturated double bond is suitable for use of a monofunctional (meth) acrylate, a difunctional (meth) acrylate, and three A (meth) acrylate compound having a functional or higher (meth) acrylate or the like. Examples of the "monofunctional (meth) acrylate" include 2-hydroxyethyl (meth)acrylate, carbitol (meth)acrylate, isobornyl (meth)acrylate, and (methyl). 3 - methoxybutyl acrylate, 2-(methyl) propylene methoxyethyl 2- hydroxypropyl phthalate, and the like. The "difunctional (meth) acrylate" is exemplified by, for example, (meth)acrylic acid decanoic acid glycol ester, di(meth)acrylic acid 1,6-hexanediol ester-81 - 201140249, 1,9·nonanediol ester of methyl)acrylic acid, propylene glycol poly(meth)acrylate, tetraethylene glycol di(meth)acrylate, bisphenoxyethanol decyl diacrylate, bisphenoxy diacrylate Ethyl ethoxide and the like. The "trifunctional or higher (meth) acrylate" is exemplified by, for example, trimethylolpropane tris(meth)acrylate, neopentyl glycol tri(meth)acrylate, and tris((methyl) phosphate). Propylene methoxyethyl ester, neopentyl tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like. These compounds having at least one ethylenically unsaturated double bond may be used alone or in combination of two or more. In the photosensitive resin composition of the present invention, the use ratio of the compound having at least one ethylenically unsaturated double bond is preferably 50 parts by mass or less based on 1 part by mass of the component (A). More preferably, it is 30 mass parts or less. By containing the compound having at least one ethylenically unsaturated double bond in the same ratio, the heat resistance, surface hardness and the like of the cured film obtained from the photosensitive resin composition of the present invention can be improved. When a compound having at least one ethylenically unsaturated double bond is added, it is preferred to add a (K) thermal radical generating agent described later. < (G) adhesion improving agent> The photosensitive resin composition of the present invention may have a adhesion improving agent. The adhesion improving agent to be used in the photosensitive resin composition of the present invention is used for improving the density of a metal such as ruthenium, osmium oxide or tantalum nitride as a base material, such as ruthenium, ruthenium or ruthenium nitride. Sexual compounds. Specific examples thereof include a decane coupling agent, a thiol compound, and the like. -82- 201140249 The decane coupling agent used as the adhesion improving agent used in the present invention is intended to be modified by the interface, and can be used without any particular limitation. Preferred examples of the "decane coupling agent" include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, and γ-glycidoxypropyltrialkoxy group.矽 ' γ-glycidoxypropyl alkyl dialkoxy decane, γ-methacryloxypropyl trialkoxy decane, γ-methyl propylene methoxy propyl alkyl dialkoxide Base decane, γ-chloropropyl trialkoxy decane, γ-hydrothiopropyltrialkoxy decane, Ρ-(3,4-epoxycyclohexyl)ethyltrialkoxy decane, vinyl Trialkoxydecane. Among these, more preferred is γ-glycidoxypropyltrialkoxydecane or γ-methylpropenyloxypropyltrialkoxydecane, and further more preferably γ-glycidoxypropane Propyltrialkoxydecane. These adhesion improvers may be used alone or in combination of two or more. When the adhesion improving agent is added to form a cured film on the substrate with the photosensitive resin composition of the present invention, the adhesion between the substrate and the cured film can be effectively improved, and when the cured film is formed into a pattern, The taper angle of the substrate and the patterned cured film can be effectively adjusted. In the photosensitive resin composition of the present invention, the content of the adhesion improving agent is preferably from 0.1 to 20 parts by mass, more preferably from 0.5 to 10 parts by mass, per 100 parts by mass of the copolymer. < (Η) Basic compound> The photosensitive resin composition of the present invention may contain a basic compound. The basic compound can be arbitrarily selected from the users of the chemically amplified photoresist. Examples thereof include an aliphatic amine, an aromatic amine, a heterocyclic compound of -83 to 201140249, a fourth-order ammonium hydroxide, and a fourth-order ammonium salt of a carboxylic acid. Examples of the "aliphatic amine" include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, and tri-n-pentane. Alkylamine, diethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like. Examples of the "aromatic amine" include aniline, benzylamine, N,N-dimethylaniline, and diphenylamine. The "heterocyclic amine" is exemplified by, for example, pyridine, 2-methylpyridine, 4-methylglycolidine, 2-ethylanthracene D, 4-ethylpyrene ratio, 2-phenylhydrazine. Ratio steep, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2 , 4,5_ triphenylimidazoline, Xue base, sylvestreic acid, Xue base, amine, quinoline, 8-oxoquinoline, pyrimide, pyridinium, sputum trap, 嚷D, pyrrole, Pulse D, pipe trap, morpholine, 4-methylmorpholine, 1,5-dioxabicyclo[4·3·0]-5-decene, anthracene, 8-diindole bicyclo[5·3· 0]-7-undecene. The "fourth-order ammonium hydroxide" may, for example, be tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide or tetra-n-hexylammonium hydroxide. The "fourth ammonium salt of a carboxylic acid" may, for example, be tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate or tetra-n-butyl benzoate. The basic compound which can be used in the present invention can be used singly or in combination of two or more kinds, preferably two or more kinds, more preferably two kinds, and more preferably two kinds of heterocyclic amines. . In the photosensitive resin composition of the present invention, the copolymer (A) and the basic compound are contained in an amount of from 0.005 to 0.2 parts by mass, more preferably from 0.005 to 0.2 parts by mass. < (I) Surfactant> The photosensitive resin composition of the present invention is preferably an interface active agent which can be used in any of an anionic or cationic surfactant. Examples of the "nonionic surfactant" are higher alkyl ethers, higher fatty acid diesters of polyoxyethylene higher alkyl phenyl alcohols, polyfluorene oxides, and fluorine. Further, the following trade names are available: KP (f |), POLYFL0W (Kyoeisha Chemical Co., Ltd.) company, MEGAFACE (DIC system) 3M (share) system, Asahi Guard, Surflon (PolyFox (OMNOVA company), etc.; interface The active agent is preferably a copolymer (1) having a weight average molecular weight (Mw) of 1 or more and preferably 1,500 or more and 5,000 or less, as determined by weight chromatography. The polystyrene conversion is 0.001 to 1 with respect to 100 masses of dad. There are surfactants. Nonionic, or two agents are nonionic interfaces: polyoxyethylene ethers, polyoxyethylenes It is an example of a repeating unit A shown by EFTOP (JEMCO, FLUORAD) and ί\\ 。. The copolymer is less than 10,000. Molecular weight is gel-permeability-85- (1) 2011 40249
R21' [R23] •CH2—C— — 一 -CH〇-C- L 1」 P 重複單元A 、。一作中 人Hl-oVR: 24R21' [R23] • CH2—C— — a —CH〇-C- L 1” P repeat unit A , . In a work Hl-oVR: 24
重複單元B 在共聚物(1)中,R21及R23是各自獨立地代表氫原 子或甲基,R22是代表碳數爲1以上且4以下之直鏈伸烷 基,R24是代表氫原子或碳數爲1以上且4以下之烷基’ L 是代表碳數爲3以上且6以下之伸烷基,p及q是代表聚 合比之質量百分率,p是代表1 〇質量%以上且8 0質量%以 下之數値,q是代表2 0質量%以上且9 0質量%以下之數値 ’ r是代表1以上且is以下之整數,η是代表1以上且 以下之整數。 在重複單元Β中,L較佳爲以下式(2 )所代表之仲 烷基。 25Repeating Unit B In the copolymer (1), R21 and R23 each independently represent a hydrogen atom or a methyl group, R22 represents a linear alkyl group having a carbon number of 1 or more and 4 or less, and R24 represents a hydrogen atom or carbon. The alkyl group 'L having a number of 1 or more and 4 or less is an alkylene group having a carbon number of 3 or more and 6 or less, p and q are the mass percentages representing the polymerization ratio, and p is 1% by mass or more and 80% by mass. % below the number 値, q is a number representing 20% by mass or more and 90% by mass or less ′′ r is an integer representing 1 or more and is equal to or less, and η is an integer representing 1 or more and below. In the repeating unit Β, L is preferably a secondary alkyl group represented by the following formula (2). 25
RCH2CHRCH2CH
) 式(2)中’ R25是代表碳數爲1以上且4以下之烷基 ’從相溶性與對被塗布面之可濕潤性的觀點,則較佳爲碳 數爲1以上且3以下之烷基,更佳爲碳數爲2或3之烷基 此外’P與q之合計(p + q)較佳爲p + q=1〇〇,亦 即,爲100質量%。 -86- 201140249 此等界面活性劑是可以一種單獨或兩種以上混合 〇 在本發明之感光性樹脂組成物中,相對於1 0 〇質 之共聚物(A),界面活性劑的添加量較佳爲10質量 下,更佳爲0.01至10質量份,進一步更佳爲0.01至 量份。 < (J)塑化劑> 本發明之感光性樹脂組成物是可含有塑化劑。 「塑化劑」是可列舉:例如,鄰苯二甲酸二丁酯 苯二甲酸二辛酯、鄰苯二甲酸二-十二烷酯、聚乙二 甘油、鄰苯二甲酸二甲基甘油酯、酒石酸二丁酯、己 二辛酯、三乙醯基甘油等。 在本發明之感光性樹脂組成物中,相對於1 0 0質 之共聚物(A ),塑化劑的添加量較佳爲0. 1至3 0質 ,更佳爲1至1 〇質量份。 < (K)熱自由基產生劑> 本發明之感光性樹脂組成物是可含有熱自由基產 。在含有如前述之具有至少一個烯鍵性不飽和雙鍵之 物的烯鍵性不飽和化合物的情浣,則較佳爲含有熱自 產生劑。 在本發明之熱自由基產生劑是可使用習知的熱自 產生劑。 熱自由基產生劑是會由於熱之能量而產生自由基 發或促進聚合性化合物之聚合反應的化合物。藉由添 使用 量份 份以 1質 、鄰 醇、 二酸 量份 量份 生劑 化合 由基 由基 來引 加熱 -87- 201140249 自由基產生劑,則所獲得硬化膜將變得更強韌而可提高耐 熱性、耐溶劑性。 較佳的「熱自由基產生劑」是可列舉:芳香族酮類、 鑰鹽化合物、有機過氧化物、硫基化合物、六芳基聯二咪 唑化合物、酮肟酯化合物、硼酸鹽化合物、鉼化合物 (azinium compound)、二茂金屣化合物、活性醋化合物、 具有碳-鹵素鍵之化合物、偶氮系化合物、聯苯甲基化合 物等。 熱自由基產生劑是可以一種單獨使用或兩種以上倂用 〇 在本發明之感光性樹脂組成物中,從提高膜物性的觀 點,相對於100質S份之共聚物(A) \則熱自由基產生 劑的添加量較佳爲0.01至50質量份,更佳爲0.1至20質 量份,最佳爲0.5至10質量份。 < (L )熱酸產生劑> 在本發明中,也可爲改良在低溫硬化之膜物性等而使 用熱酸產生劑。 本發明之熱酸產生劑是可藉由熱而產生酸的化合物, 通常是熱分解溫度爲在130 °C至250 °C,較佳爲在150 °C 至2 2 0 °C之範圍的化合物,例如其係可藉由加熱而產生磺 酸、羧酸 '二磺醯基醯亞胺等低親核性之酸的化合物。 所產生的酸較佳爲pKa爲如2以下之強的經磺酸或電 子吸引基取代之烷基羧酸或芳基羧酸、及經電子吸引基取 代之二磺醯基醯亞胺等。電子吸引基是可列舉:氟原子等 -88- 201140249 鹵素原子、三氟甲基等鹵化烷基、硝基、氰基。 此外,在本發明也可使用不藉由照射曝光光而實質地 產生酸,而可藉由熱而產生酸之磺酸酯。 所謂的「不藉由照射曝光光而實質地產生酸」是藉由 在化合物的曝光前後之IR光譜、NMR光譜測定而在光譜 上並無變化來加以判定。 磺酸酯之分子量通常爲230至1000,較佳爲230至 8 00 = 在本發明可使用之磺酸酯是可使用市售品、或使用以 習知的方法所合成者。磺酸酯是例如可在鹼性條件下,將 磺醯基氯或磺酸酐與對應的多元醇反應而合成。 磺酸酯對於感光性樹脂組成物的添加量,相對於100 質量份之(A)成分,則較佳爲0.5至20質量份,特佳爲 1至1 5質量份。 < (Μ )酸增殖劑> 本發明之感光性樹脂組成物是可以提高感度爲目的而 使用酸增殖劑。在本發明使用之酸增殖劑是由於酸觸媒反 應而可更進一步產生酸使得反應系統內之酸濃度上升的化 合物,在酸不存在之狀態是安定地存在的化合物。如此之 化合物,由於以一次反應則增加一個以上之酸,反應則將 隨著反應進行而加速地進行,但是由於所產生的酸本身是 會誘導自分解,在此所產生的酸之強度是酸解離常數(acid dissociation constant) pKa較佳爲3以下,特佳爲2以下 -89- 201140249 酸增殖劑的具體實例是可列舉:在曰 1508號公報〔0203〕至〔0223〕、特開平1 報〔0016〕至〔005 5〕及特表平9- 5 1 249 8號 第1 2行至第47頁第2行中所揭述之化合物 在本發明可使用之酸增殖劑是可列舉: 劑所產生之酸而分解以產生二氯醋酸、三氯 酸、苯磺酸、三氟甲烷磺酸、苯基膦酸等之 之酸的化合物。 從曝光部與未曝光部之溶解對比的觀點 於感光性樹脂組成物的添加量,相對於1 〇〇 產生劑(B ),則較佳爲1 0至1 000質量份, 5 〇 〇質量份。 < (N )顯影促進劑> 本發明之感光性樹脂組成物是可含有顯】 顯影促進劑是可使用具有顯影促進功效 物,較佳爲具有選自羧基、酚性羥基、及伸 少一種結構之化合物,更佳爲具有選自羧基 至少一種結構之化合物,最佳爲具有酚性羥; 此外,顯影促進劑之分子量較佳爲1 00 佳爲100至2000,最佳爲150至1000。 顯影促進劑的實例,具有伸烷氧基者是 二醇、聚乙二醇之—甲基醚、聚乙二醇之二 二醇甘油酯、聚丙二醇甘油酯、聚丙二醇二 二醇、聚乙二醇-雙酚A醚、聚丙二醇·雙酚 本特開平10-0-282642 號公 [公報第3 9頁 〇 可藉由酸產生 醋酸、甲烷磺 pKa爲3以下 ,酸增殖劑對 質量份之光酸 更佳爲2 0至 衫促進劑。 之任意的化合 院氧基中之至 或酚性羥基之 基之化合物》 至 3000,更 可列舉:聚乙 甲基醚、聚乙 甘油酯、聚丁 A醚、聚氧乙 -90- 201140249 烯之烷基醚、聚氧乙烯之烷基酯、在日本特開平9_222724 號公報中所揭述之化合物等。 顯影促進劑的實例’具有羧基者是可列舉:在日本特 開2000-66406號公報、特開平9_6001號公報、特開平 10-2〇501號公報、特開平丨50號公報等中所揭述之 化合物。 顯影促進劑的實例,具有酚性羥基者是可列舉:在曰 本特開2005-346024號公報、特開平10-133366號公報、 特開平9-194415號公報、特開平9-222724號公報、特開 平11-171810號公報、特開2007-121766號公報、特開平 9-:297396號公報、特開20〇3-43079號公報等中所揭述之 化合物。在此等之中’較佳爲苯環數爲2至10個之酚系 化合物’更佳爲苯環數爲2至5個之酚系化合物。特佳者 可列舉在日本特開平1 0- 1 3 3 3 66號公報中作爲溶解促進劑 所揭述之酚性化合物。 顯影促進劑是可以一種單獨使用或兩種以上倂用。 在本發明之感光性樹脂組成物的顯影促進劑的添加量 ,從感度與殘膜率'的觀點,相對於1 00質量份之共聚物( A ) ’則較佳爲0.1至30質量份,更佳爲0.2至20質量 份,最佳爲0 _ 5至1 0質量份。 〔硬化膜之形成方法〕 其次,說明本發明之硬化膜之形成方法。 本發明之硬化膜之形成方法,包括下列第(1 )至(5 )項各步驟: -91- 201140249 (1 )將本發明之感光性樹脂組成物塗布於基板上( 塗布步驟); (2)由所塗布的感光性樹脂組成物移除溶劑(溶劑 移除步驟); (3 )將所塗布的感光性樹脂組成物以活性光線加以 曝光(曝光步驟); (4 )將經曝光的感光性樹脂組成物以水性顯影液加 以顯影(顯影步驟);及 (5 )將經顯影的感光性樹脂組成物加以熱硬化(後 烘烤步驟)。 在下文中,依序說明各步驟。 在塗布步驟,將本發明之感光性樹脂組成物塗布於基 板上而形成含有溶劑之濕潤膜。 在溶劑移除步驟,從所塗布的濕潤膜以減壓(眞空) 及/或加熱移除溶劑而在基板上形成乾燥塗膜。 在曝光步驟,對所獲得乾燥塗膜照射波長爲3 00 nm 以上4 5 0 nm以下之活性光線。在此步驟,光酸產生劑(B )分解而產生酸。由於所產生的酸之觸媒作用,在共聚物 (A )中所含有的結構單元(1 )中之酸分解性基水解而形 成羧基及/或酚性羥基。 在酸觸媒之形成區域,爲使上述水解反應加速進行, 因應需要可施加曝光後加熱處理(Post Exposure Bake: 在下文中也稱爲「PEB」)。藉由PEB,可促進源自酸分 解性基的羧基及/或酚性羥基之形成。 -92- 201140249 共聚物(A)所具有結構單元(1)中之酸分解性基 由於酸分解之活性化能低,且因來自曝光所引起的酸產 劑之酸容易分解而產生羧基及/或酚性羥基,因此不一 需要施加PEB也可以顯影而形成正型影像。 另外,藉由在較低溫下進行PEB,也可在不致於發 交聯反應下促進酸分解性基之水解。 在進行PEB時之溫度較佳爲30°C以上且13(TC以 ,更佳爲40°C以上且1 10°C以下,特佳爲50°C以上且 °C以下。 在顯影步驟,將具有經游離的羧基及/或酚性羥基 聚合物使用鹼性顯影液進行顯影。藉由移除含有具有易 解於鹼性顯影液的羧基及/或酚性羥基之樹脂組成物的 光部區域而形成正型影像。 在後烘烤步驟,可藉由將所獲得正型影像加熱,使 結構單元(1 )中之酸分解性基熱分解而形成羧基及/或 雜環丁烷基,而與環氧基及/或氧雜環丁烷基交聯以形 硬化膜。該加熱較佳爲加熱至1 5 (TC以上之高溫,更佳 加熱至180至25(TC,特佳爲加熱至200至2 5 0 °C。加 時間是可因應加熱溫度等而適當地設定,較佳爲在10 90分鐘之範圍內。 若在後烘烤步驟前,追加以活性光線(較佳爲紫外 )全面照射正型影像之步驟時,則可藉由活性光線照射 產生的酸而促進交聯反應。 其次,具體說明使用本發明之感光性樹脂組成物的 生 定 生 下 90 之 溶 曝 得 氧 成 爲 熱 至 線 所 硬 -93- 201140249 化膜之形成方法。 < <感光性樹脂組成物之調製> > 將共聚物(A)、光酸產生劑(B)、增感劑(C)、 及溶劑(D )之必須成分以特定比例且以任意方法進行混 合,並加以攪拌溶解以調製感光性樹脂組成物。也可例如 將共聚物(A )、光酸產生劑(B )或增感劑(C )分別預 先溶解於溶劑(D )而製成溶液後,以特定比例混合此等 以調製樹脂組成物。經如上述所調製得組成物溶液是可使 用孔徑爲0.2 // m之濾網等加以過濾後使用。 <塗布步驟及溶劑移除步驟> 將感光性樹樹脂組成物塗布於特定的基板,並藉由減 壓及/或加熱(預烘烤)來移除溶媒而形成吾所欲之乾燥 塗膜。 例如,在液晶顯示元件之製造方面,基板是可例示: 設置有偏光板、更進一步因應需要而設置黑色矩陣層、彩 色濾光片層,並且設置有透明導電電路層之玻璃板等。 感光性樹樹脂組成物對基板之塗布方法是並無特殊限 制,例如可使用狹縫塗布法、噴霧法、輥式塗布法、旋轉 塗布法等方法。其中,從適用於大型基板的觀點,較佳爲 狹縫塗布法。在此,所謂的大型基板是意謂各邊爲1 m以 上之大小的基板。 此外,溶劑移除步驟之加熱條件爲不會導致在未曝光 部的共聚物(A)中之結構單元(1)所具有的酸分解性基 分解,且使共聚物(A)變成對鹼顯影液爲可溶性之範圍 • 94- 201140249 ,雖然也因各成分之種類或混合比而不同,但是較 80至130 °C爲約30至120秒鐘。 <曝光步驟> 在曝光步驟,對經設置乾燥塗膜之基板照射特 案之活性光線。曝光是可通過遮罩而進行,也可直 。活性光線是較佳爲使用具有k長爲300 ηιη以上 nm以下之活性光線。 在曝光步驟之後,因應需要可施加加熱處理 〇 在藉由活性光線的曝光是可使用低壓水銀燈、 銀燈、超高壓水銀燈、化學燈、LED (發光二極體 、雷射產生裝置等。 使用水銀燈時,較佳爲使用具有g-射線(436 i-射線( 365 nm) 、h-射線( 405 nm)等之波長的 線。與雷射相比較,水銀燈是由於適合大面積之曝 較佳。 使用雷射時,若爲固體(YAG )雷射則使用 、3 5 5 nm,若爲準分子雷射則使用351 nm ( XeF) ,若爲半導體雷射則使用3 7 5 nm、405 nm。在此 ,從安定性、成本等的觀點,則更佳爲3 5 5 nra、 。雷射是可分成一次或數次來照射塗膜。 雷射每1脈衝之能量密度較佳爲0.1 nU/cm2 1 0 0 0 0 m J / c m2以下。爲使塗膜充分地硬化,則更fi mJ/cm2以上,最佳爲0.5 mJ/cm2以上,爲使得不 佳爲在 定的圖 接描繪 且 450 PEB ) 商壓水 )光源 nm ).、 活性光 光而爲 3 4 3 n m ,並且 等之中 4 0 5 n m 以上且 € 爲 0.3 致於因 -95- 1000 201140249 剝蝕(a b 1 a t i ο η )現象而導致塗膜分解時,則更佳爲 mJ/cm2以下’最佳爲1〇〇 mJ/cm2以下。 此外’脈衝寬度(pulse width)較佳爲0.1 nsec以 3 0 0 0 0 n s e c以下。爲使得不致於因剝蝕現象而導致色 分解時’則更佳爲0.5 nsec以上,最佳爲1 nsec以 若欲提高在掃描曝光時之對'準精確度時,則更佳爲 nsec以下,最佳爲50 nsec以下》 並且’雷射之頻率較佳爲1 Hz以上且50000 Hz ,更佳爲10 Hz以上且1000 Hz以下。 並且,雷射之頻率,若欲縮短曝光處理時間時, 佳爲10 Hz以上,最佳爲1〇〇 Hz以上,欲提高掃描 時之對準精確度時,則更佳爲1 0000 Hz以下,最 1000 Hz 以下。 與水銀燈相比較,雷射是由於容易縮小焦點,不 在曝光步驟之圖案形成之遮罩而可降低成本的觀點而 佳。 可使用於本發明之曝光裝置是並無特殊限制,可 Callisto (商品名、V Technology股份有限公司製) AEGIS (商品名、V Technology股份有限公司製) DF2200G (商品名、大日本Screen股份有限公司製) 市售者。另外,除了上述以外之裝置也適合使用。 此外,因應需要也可通過例如長波長截止濾 (long wavelength cut filter)、短波長截止滅波器、帶 波器(band-pass filter)之光譜濾波器而調整照射光。 上且 塗膜 上, 1000 以下 則更 曝光 佳爲 需要 爲較 使用 、或 、或 等已 波器 通濾 -96- 201140249 <顯影步驟> 在顯影步驟,使用鹼性顯影液來移除曝光部區域以形 成影像圖案。 在鹼性顯影液可含有的鹼性化合物是可列舉:例如, 氫氧化鋰、氫氧化鈉、氫氧化鉀等之鹼金屬氫氧化物類; 碳酸鈉、碳酸鉀等之鹼金屬碳酸鹽類;碳酸氫鈉、碳酸氫 鉀等之鹼金屬碳酸氫鹽類;氫氧化四甲基銨、氫氧化四乙 基銨、氫氧化膽鹼等之氫氧化銨類;矽酸鈉、偏矽酸鈉等 之水溶液。 此外,也可在上述含有鹼性化合物之水溶液中添加適 量的甲醇或乙醇等之水溶性有機溶劑或界面活性劑之水溶 液作爲顯.影液而使用。 顯影液之pH較佳爲10.0至14.0。 顯影時間是通常爲30至180秒鐘,此外,顯影方法 是在槳翼式法(paddling method)、浸漬法等中之任一者皆 可。顯影後實施流水洗淨3 0至9 0秒鐘,以形成吾所欲之 圖案。 <後烘烤步驟(交聯步驟)> 關於經顯影所獲得之對應於未曝光區域的圖案,藉由 使用熱板或烘箱等之加熱裝置,在特定的溫度例如在1 8 0 至2 5 0 °C歷時特定的時間,例如若在熱板上則爲5至6 0 分鐘,若爲烘箱則爲3 0至90分鐘進行加熱處理,使得在 共聚物(A)之酸分解性基分解,產生羧基及/或酚性羥基 ,將此等與共聚物(A)中之環氧基及/或氧雜環丁烷基之 -97- 201140249 交聯性基反應而使其交聯,藉此可形成耐熱性、硬度等優 異的保護膜或層間絕緣膜等之硬化膜。 此外,在進行加熱處理時,藉由在氮氣大氣下進行, 也可提高硬化膜之透明性。 另外,在加熱處理前,較佳爲對硬化膜是已形成圖案 狀的基板以活性光線加以再曝光後,進行後烘烤(再曝光 /後烘烤)使得存在於未曝光部分之光酸產生劑(B)產生 酸,以作爲促進交聯步驟之觸媒而發生作用。 亦即,本發明之硬化膜之形成方法,較佳爲在顯影步 驟與後烘烤步驟之間包括以活性光線加以再曝光之再曝光 步驟。 在再曝光步驟之曝光是可以與前述曝光步驟相同的方 法進行,但是在前述再曝光步驟,則較佳爲對基板的具有 以本發明之感光性樹脂組成物所形成的膜之側進行全面曝 光。再曝光步驟之較佳曝光量爲100至l,〇〇〇mJ/cm2。 由於本發明之感光性樹脂組成物,可獲得絕緣性優異 ,即使在高溫下烘烤時也可獲得具有高透·明性之硬化膜, 該硬化膜是可用作爲層間絕緣膜。使用本發明之感光性樹 脂組成物所構成之層間絕緣膜是具有高透明性、優異的硬 化膜物性,因此,可使用於有機EL顯示裝置或液晶顯示 裝置之用途。 此外,本發明之感光性樹脂組成物及本發明之硬化膜 是不受限定於前述用途,可使用於各式各樣的用途。例如 ,除了平坦化膜、保護層、層間絕緣膜以外,也適合使用 -98- 201140249 於使得在液晶顯示裝置的液晶層之厚度保持於一定的間隙 控制材或在固態攝像元件設置於彩色濾光片上之微透鏡等 〇 本發明之有機EL顯示裝置及液晶顯示裝置是除了具 有使用本發明之感光性樹脂組成物所形成的硬化膜作爲平 坦化膜或層間絕緣膜以外,其他則並無特殊限制,其可列 舉採取各式各樣結構之習知的各種有機EL顯示裝置或液 晶顯示裝置。 第1圖是展示在可作爲本發明之有機EL顯示裝置而 適用之底部發光型(bottom-emission type)有機EL顯示裝 置的基板之示意性截面圖。 第 1圖中,在玻璃基板 6上形成下閘極型(bottom gate type)之TFT 1,且以覆蓋該TFT 1之狀態而形成由 Si3N4所構成之絕緣膜3。在絕緣膜3形成接觸孔(省略 圖示)後,透過該接觸孔所連接於TFT 1之配線2 (高度 1·0#ηι)是形成於絕緣膜3上。配線2是用於連接TFT 1 之間、或在後續步驟所形成的有機EL元件與TFT 1者。 並且,爲將由於形成配線2所造成的凹凸加以平坦化 ,以塡埋由於配線2造成的凹凸之狀態在絕緣膜3上形成 平坦化膜4。 在平坦化膜4上,形成底部發光型之有機EL元件。 亦即,在平坦化膜4上形成透過接觸孔7而連接於配線2 之由IT Ο所構成之第一電極5。第一電極5是相當於有機 E L元件之陽極。 -99- 201140249 形成覆蓋第一電極5的周緣之形狀的絕緣膜g 設置該絕緣膜8,可防止第一電極5與在隨後的步 成的第二電極間的短路。 並且,在第1圖雖然未圖示,透過吾所欲圖案 序蒸鍵而設置電洞傳輸層(hole transport layer)、 光層、電子傳輸層,接著,在基板上方全面形成E 鋁)所構成之第二電極,使用封止用玻璃板與紫外 型環氧樹脂來貼合而加以封止,藉此可獲得經在 EL元件連接用於驅動其TFT 1而成之主動矩陣型 matrix type)有機EL顯示裝置。 第2圖是展示可作爲本發明之液晶顯示裝置而 主動矩陣方式之液晶顯示裝置之一實例示意性截面 第2圖中,液晶顯示裝置10是在背面具有背光單j 液晶面板,液晶面板是配置有對應於配置於經貼附 的兩片玻璃基板1 4、1 5之間的所有畫素的TFT 1 6 。在形成於玻璃基板上之各元件,則配線有通過形 化膜17中的接觸孔18而形成畫素電極之IT0透 1 9。在IT0透明電極1 9之上則設置經配置液晶20 黑色矩陣的RGB彩色濾光片22。 《實施例》 其次,以實施例更具體地說明本發明。但是本 並不受限於此等實施例者。另外,除非另有特別指 「份」、「%」是以質量爲基準。 在下列合成例中,下列簡稱符號是分別代表下 ,由於 驟所形 遮罩依 有機發 3 A1 ( 線硬化 各有機 (active 適用之 圖。在 Ϊ; 12 之 偏光膜 之元件 成於硬 明電極 之層與 發明是 定外, 列化合 -100- 201140249 物: V - 6 5 : 2,2,-偶氮雙(2,4 -二甲基戊腈) GMA : 甲基丙烯酸環氧丙酯 M A A : 甲基丙烯酸 HEMA: 甲基丙烯酸2-羥基乙酯 EDM : 二甘醇乙基甲基醚 <聚合物A-1之合成> 作爲共,聚物(A )的聚合物A -1是以如下所述.而合成 〇 在144.2份(2莫耳當量)之乙基乙烯基醚添加0.5 份之啡噻哄(phenothiazine),一邊將反應系統中冷卻至10 °C以下,一邊逐滴加入86.1份(1莫耳當量)之甲基丙烯 酸後,在室溫(2 5 °C )攪拌4小時。添加5.0份之對甲苯 磺酸吡啶鎩後,在室溫攪拌2小時,在室溫放置一夜。對 反應液添加5份之碳酸氫鈉及5份之硫酸鈉,在室溫攪拌 _ 1小時,將不溶物加以過濾後,在40 °C以下進行減壓濃縮 ,將殘渣之黃色油狀物加以減壓蒸餾,以獲得134.0份之 沸點(bp.)爲43至45°C/7mmHg餾分之甲基丙烯酸1_乙 氧基乙酯(MAEVE )之無色油狀物。 將所獲得之甲基丙烯酸1-乙氧基乙酯(63_28份(〇.4 莫耳當量))、GMA(42_65份(0.3莫耳當量))、 ΜΑΑ(8·61 份(0.1 莫耳當量))、ΗΕΜΑ(26.〇3 份( 0.2莫耳當量))及EDM ( 1 10.8份)之混合溶液在氮氣 氣流下加熱至7〇 °C。一邊攪拌該混合溶液,一邊逐滴加 -101 - 201140249 入自由基聚合引發劑V-65(和光純藥工業(股)製、4份) 與EDM ( 100.0份)之混合溶液歷時2.5小時。在逐滴加 入結束後’使其在7 0 °C進行反應4小時,以獲得聚合物 A-1之EDM溶液(固體成份濃度:40%)。 所獲得聚合物A- 1以凝膠透層析法(GPC )所測定之 重量平均分子量爲1 5,000。 <聚合物A-2至A-9之合成> 除了將所使用的各單體及其使用量變更爲如下表1所 示者以外,其餘則以與聚合物A -1之合成相同的方式分別 合成聚合物A-2至A-10作爲共聚物(A)。 表1 聚合物 結構單元(1) 結構單元⑵ 結構單兀(3) Mw 種類 莫耳 當量 種類 莫耳 當量 種類 莫耳 當量 種類 莫耳 當量 種類 "•tl.— 莫耳 -當量 A-1 MAEVE 0.4 GMA 0.3 MAA 0.1 HEMA 0.2 15000 A-2 MAEVE 0.4 M100 0.3 MAA 0.1 HEMA 0.2 16000 A-3 MAEVE 0.4 OXE-30 0.3 MAA 0.1 HEMA 0.2 17000 Α·4 CHOEMA 0.4 OXE-30 0.3 MAA 0.1 HEMA 0.2 14000 Α-5 MATHF 0.4 GMA 0.3 MAA 0.1 HEMA 0.2 12000 Α-6 MATHF 0.4 OXE-30 0.3 MAA 0.1 HEMA 0.2 17000 Α-7 P-Ph-1 0.4 OXE-30 0.3 MAA 0.1 HEMA 0.2 16000 Α-8 P-Ph-1 0.4 GMA 0.3 MAA 0.1 HEMA 0.2 13000 Α·9 P-Ph-1 0.4 OXE-30 0.3 Ph-1 0.1 HEMA 0.2 15000 A-10 MATHF 0.4 OXE-30 0.3 MAA 0.1 HEMA 0.1 St 15000 此外,表1中之簡稱符號是如下所示: MAEVE: 甲基丙烯酸1-乙氧基乙酯 GMA: 甲基丙烯酸環氧丙酯 OXE-30: 甲基丙烯酸(3 -乙基氧雜環丁烷-3-基) 甲酯(大阪有機化學工業(股)製) HEM A : 甲基丙烯酸2 -羥基乙酯 M100: 甲基丙烯酸3,4-環氧基環己基甲酯( DAICEL化學工業(股)製) -102- 201140249 MAA: 甲基丙烯酸 CHOEMA: 甲基丙烯酸1-(環己氧基)乙酯 MATHF: 甲基丙烯酸四氫- 2H-呋喃-2-基酯In the formula (2), R25 is an alkyl group having a carbon number of 1 or more and 4 or less. From the viewpoint of compatibility and wettability to a surface to be coated, the carbon number is preferably 1 or more and 3 or less. The alkyl group is more preferably an alkyl group having 2 or 3 carbon atoms. Further, the total of 'P and q (p + q) is preferably p + q = 1 Å, that is, 100% by mass. -86- 201140249 These surfactants may be used alone or in combination of two or more kinds in the photosensitive resin composition of the present invention, and the amount of the surfactant added is compared with the copolymer (A) of 10 enamel. More preferably, it is 0.01 to 10 parts by mass, more preferably 0.01 to part by mass, based on 10 parts by mass. <(J) Plasticizer> The photosensitive resin composition of the present invention may contain a plasticizer. The "plasticizer" is exemplified by, for example, dioctyl phthalate dioctyl phthalate, di-dodecyl phthalate, polyethylene diglyceride, dimethyl phthalate. , dibutyl tartrate, hexodioctyl ester, triethylene glyceryl and the like. In the photosensitive resin composition of the present invention, the amount of the plasticizer is preferably from 0.1 to 30, more preferably from 1 to 1 part by mass, based on the copolymer (A) of the polymer of the present invention. . <(K) Thermal radical generating agent> The photosensitive resin composition of the present invention may contain a thermal radical. In the case of the ethylenically unsaturated compound having at least one ethylenically unsaturated double bond as described above, it is preferred to contain a heat generating agent. In the thermal radical generating agent of the present invention, a conventional thermal self-generating agent can be used. The thermal radical generating agent is a compound which generates radicals due to the energy of heat or promotes polymerization of a polymerizable compound. The cured film obtained by the use of a mass fraction of a mass, an o-alcohol, a diacid, and a radical-derived radical-derived-87-201140249 radical generator will become stronger. Heat resistance and solvent resistance can be improved. Preferred examples of the "thermal radical generator" include aromatic ketones, key salt compounds, organic peroxides, sulfur compounds, hexaarylbiimidazole compounds, ketoxime compounds, borate compounds, and cesium. An azinium compound, a ferrocene compound, an active vinegar compound, a compound having a carbon-halogen bond, an azo compound, a biphenylmethyl compound, or the like. The thermal radical generating agent may be used alone or in combination of two or more kinds in the photosensitive resin composition of the present invention, and the copolymer (A) with respect to 100 masses of S is heated from the viewpoint of improving the physical properties of the film. The amount of the radical generator added is preferably from 0.01 to 50 parts by mass, more preferably from 0.1 to 20 parts by mass, most preferably from 0.5 to 10 parts by mass. <(L) Thermal acid generator> In the present invention, a thermal acid generator may be used to improve the physical properties of the film which is cured at a low temperature. The thermal acid generator of the present invention is a compound which can generate an acid by heat, and is usually a compound having a thermal decomposition temperature in the range of 130 ° C to 250 ° C, preferably 150 ° C to 2 20 ° C. For example, it is a compound which can generate a low nucleophilic acid such as a sulfonic acid or a carboxylic acid 'disulfonyl quinone imine by heating. The acid to be produced is preferably an alkyl carboxylic acid or an aryl carboxylic acid having a pKa of 2 or less, substituted with a sulfonic acid or an electron attracting group, and a disulfonyl ruthenium imine substituted by an electron attracting group. The electron attracting group may, for example, be a fluorine atom or the like -88- 201140249 A halogenated alkyl group such as a halogen atom or a trifluoromethyl group, a nitro group or a cyano group. Further, in the present invention, it is also possible to use a sulfonate which generates an acid by heat without irradiating the exposure light, and which generates an acid by heat. The phrase "the acid is not generated by irradiation of the exposure light" is determined by the IR spectrum and the NMR spectrum before and after the exposure of the compound, and there is no change in the spectrum. The molecular weight of the sulfonate is usually from 230 to 1,000, preferably from 230 to 800. The sulfonate which can be used in the present invention can be synthesized using a commercially available product or by a conventional method. The sulfonate is synthesized, for example, by reacting a sulfonyl chloride or a sulfonic acid anhydride with a corresponding polyol under basic conditions. The amount of the sulfonic acid ester to be added to the photosensitive resin composition is preferably from 0.5 to 20 parts by mass, particularly preferably from 1 to 15 parts by mass, per 100 parts by mass of the component (A). <(Μ) Acid Proliferating Agent> The photosensitive resin composition of the present invention is an acid proliferating agent for the purpose of improving sensitivity. The acid proliferator used in the present invention is a compound which can further generate an acid due to an acid catalyst reaction to increase the acid concentration in the reaction system, and is a compound which is stably present in the absence of acid. In such a compound, since more than one acid is added in one reaction, the reaction proceeds with the progress of the reaction, but since the generated acid itself induces self-decomposition, the strength of the acid produced here is acid. The dissociation constant (pKa) is preferably 3 or less, particularly preferably 2 or less. -89 - 201140249 Specific examples of the acid proliferator are exemplified by: 曰1508 (0203) to [0223], and the special report 1 [0016] to [005 5] and the specific compounds disclosed in the first aspect of the present invention, which are disclosed in the first aspect of the present invention, the acid-proliferating agent which can be used in the present invention is exemplified by the agent: The acid produced is decomposed to produce a compound of an acid such as dichloroacetic acid, trichloro acid, benzenesulfonic acid, trifluoromethanesulfonic acid or phenylphosphonic acid. The amount of addition of the photosensitive resin composition from the viewpoint of the dissolution of the exposed portion and the unexposed portion is preferably 10 to 1,000 parts by mass, and 5 parts by mass, based on the amount of the first generation agent (B). . < (N) Development Accelerator> The photosensitive resin composition of the present invention may contain a development accelerator, and may have a development-promoting effect, preferably having a carboxyl group, a phenolic hydroxyl group, and a stretching agent. A compound of a structure, more preferably a compound having at least one structure selected from the group consisting of carboxyl groups, preferably having a phenolic hydroxyl group; further, the molecular weight of the development accelerator is preferably from 100 to 2,000, preferably from 150 to 1,000. . Examples of the development accelerator, those having an alkoxy group are a diol, a polyethylene glycol-methyl ether, a polyethylene glycol didiol glyceride, a polypropylene glycol glyceride, a polypropylene glycol didiol, and a polyethylene Glycol-bisphenol A ether, polypropylene glycol, bisphenol, and the like. [Publication of acetic acid, methanesulfonic acid pKa of 3 or less, acid proliferator to mass fraction The photoacid is preferably a 20 to a shirt enhancer. Any compound of the compound of the compound oxy group or the phenolic hydroxyl group to 3000, more specifically: polyethyl methyl ether, polyethylene glycol ester, polybutylene ether, polyoxyethylene-90-201140249 The alkyl ether, the alkyl ester of polyoxyethylene, the compound disclosed in Japanese Laid-Open Patent Publication No. Hei 9-222724, and the like. The example of the development accelerator is described in Japanese Laid-Open Patent Publication No. 2000-66406, JP-A-H09-6001, JP-A-10-20-501, JP-A No. 50, and the like. Compound. Examples of the development accelerators include a phenolic hydroxyl group, and a phenolic hydroxyl group, which is disclosed in JP-A-2005-346024, JP-A-10-133366, JP-A-9-194415, JP-A-9-222724, A compound disclosed in JP-A-H07-171810, JP-A-2007-121766, JP-A-H09-A No. 297396, and JP-A No. Hei. Among these, 'preferably a phenolic compound having 2 to 10 benzene rings' is more preferably a phenolic compound having 2 to 5 benzene rings. The phenolic compound disclosed as a dissolution promoter in Japanese Patent Publication No. Hei 10-1353366 can be cited. The development accelerator may be used alone or in combination of two or more. The amount of the development accelerator to be added to the photosensitive resin composition of the present invention is preferably from 0.1 to 30 parts by mass per 100 parts by mass of the copolymer (A)' from the viewpoint of sensitivity and residual film ratio. More preferably, it is 0.2 to 20 parts by mass, and most preferably 0 to 5 to 10 parts by mass. [Method of Forming Cured Film] Next, a method of forming the cured film of the present invention will be described. The method for forming a cured film of the present invention comprises the following steps (1) to (5): -91- 201140249 (1) applying the photosensitive resin composition of the present invention to a substrate (coating step); Removing the solvent from the applied photosensitive resin composition (solvent removal step); (3) exposing the applied photosensitive resin composition to active light (exposure step); (4) exposing the exposed light The resin composition is developed with an aqueous developing solution (developing step); and (5) the developed photosensitive resin composition is thermally hardened (post-baking step). In the following, the steps are explained in order. In the coating step, the photosensitive resin composition of the present invention is applied onto a substrate to form a wet film containing a solvent. In the solvent removal step, a dry coating film is formed on the substrate by removing the solvent from the applied wet film under reduced pressure (hollowing) and/or heating. In the exposure step, the obtained dried coating film is irradiated with active light having a wavelength of 300 nm or more and 450 nm or less. At this step, the photoacid generator (B) is decomposed to generate an acid. The acid-decomposable group in the structural unit (1) contained in the copolymer (A) is hydrolyzed to form a carboxyl group and/or a phenolic hydroxyl group by the catalytic action of the acid generated. In the formation region of the acid catalyst, in order to accelerate the hydrolysis reaction, post-exposure heat treatment (Post Exposure Bake: hereinafter also referred to as "PEB") may be applied as needed. The formation of a carboxyl group and/or a phenolic hydroxyl group derived from an acid-decomposable group can be promoted by PEB. -92- 201140249 The acid-decomposable group in the structural unit (1) of the copolymer (A) has low activation energy due to acid decomposition, and the acid of the acid generator due to exposure is easily decomposed to generate a carboxyl group and/or Or a phenolic hydroxyl group, so it is not necessary to apply PEB to develop a positive image. Further, by carrying out PEB at a lower temperature, hydrolysis of the acid-decomposable group can be promoted without causing crosslinking reaction. The temperature at the time of PEB is preferably 30 ° C or more and 13 (TC, more preferably 40 ° C or more and 10 10 ° C or less, particularly preferably 50 ° C or more and ° C or less. In the development step, Developing with a free carboxyl group and/or a phenolic hydroxyl polymer using an alkaline developing solution by removing a light portion containing a resin composition having a carboxyl group and/or a phenolic hydroxyl group which is easily solvable in an alkaline developing solution Forming a positive image. In the post-baking step, the acid-decomposable group in the structural unit (1) is thermally decomposed to form a carboxyl group and/or a heterocyclobutane group by heating the obtained positive image. The film is cured by crosslinking with an epoxy group and/or an oxetane group. The heating is preferably carried out to a temperature of 15 (above TC), more preferably to 180 to 25 (TC, particularly preferably heated to 200 to 250 ° C. The addition time is appropriately set depending on the heating temperature, etc., preferably in the range of 10 90 minutes. If the active light is added (preferably ultraviolet) before the post-baking step When the step of fully illuminating the positive image is carried out, the crosslinking reaction can be promoted by the acid generated by the irradiation of the active light. Specifically, a method of forming a film formed by using a photosensitive resin composition of the present invention and producing a film of a heat-to-line hard-93-201140249 can be specifically described. <<> Modulation of a photosensitive resin composition>> The essential components of the copolymer (A), the photoacid generator (B), the sensitizer (C), and the solvent (D) are mixed in a specific ratio and by any method, and stirred and dissolved to prepare a photosensitive film. a resin composition. For example, the copolymer (A), the photoacid generator (B) or the sensitizer (C) may be previously dissolved in the solvent (D) to prepare a solution, and then mixed in a specific ratio. The composition of the composition is prepared by filtering the composition solution prepared as described above using a sieve having a pore diameter of 0.2 // m, etc. <Coating step and solvent removing step> Photosensitive resin composition It is applied to a specific substrate, and the solvent is removed by decompression and/or heating (prebaking) to form a desired dry coating film. For example, in the manufacture of a liquid crystal display element, the substrate is exemplified: Polarized plate, more one A black matrix layer, a color filter layer, a glass plate provided with a transparent conductive circuit layer, and the like are provided as needed. The method of applying the photosensitive resin composition to the substrate is not particularly limited, and for example, slit coating may be used. A method such as a method, a spray method, a roll coating method, or a spin coating method. Among them, a slit coating method is preferred from the viewpoint of being applied to a large substrate. Here, the so-called large substrate means that each side is 1 m or more. In addition, the heating condition of the solvent removal step is such that the acid-decomposable group of the structural unit (1) in the copolymer (A) in the unexposed portion is not decomposed, and the copolymer (A) is obtained. It becomes a range which is soluble in the alkali developer. • 94- 201140249. Although it varies depending on the type or mixing ratio of each component, it is about 30 to 120 seconds from 80 to 130 °C. <Exposure step> In the exposure step, the substrate on which the dried coating film is provided is irradiated with the specific active light. Exposure can be done through a mask or straight. The active light is preferably an active light having a k length of 300 ηιη or more and nm or less. After the exposure step, heat treatment may be applied as needed. Under exposure by active light, a low pressure mercury lamp, a silver lamp, an ultra high pressure mercury lamp, a chemical lamp, an LED (light emitting diode, a laser generating device, etc. may be used. Using a mercury lamp) Preferably, a line having a wavelength of g-ray (436 i-ray (365 nm), h-ray (405 nm), etc. is used. Compared with laser, the mercury lamp is preferred for large-area exposure. When using a laser, use 355 nm (XeF) for solid (YAG) lasers, 375 nm (XeF) for excimer lasers, and 375 nm, 405 nm for semiconductor lasers. Here, from the viewpoints of stability, cost, etc., it is more preferably 3 5 5 nra. The laser can be irradiated with the coating film once or several times. The energy density per 1 pulse of the laser is preferably 0.1 nU/ Cm2 1 0 0 0 0 m J / c m2 or less. In order to sufficiently harden the coating film, it is more than fiMJ/cm2 or more, and preferably 0.5 mJ/cm2 or more, so that it is not suitable for drawing in a predetermined pattern. 450 PEB) commercial pressure water) source nm)., active light is 3 4 3 nm, and etc. 4 0 5 n m or more and € is 0.3. Therefore, when the coating film is decomposed due to the phenomenon of ab 1 a t i ο η (a b 1 a t i ο η ), it is more preferably mJ/cm 2 or less, and most preferably 1 〇〇 mJ/cm 2 or less. Further, the pulse width is preferably 0.1 nsec or less to 3 0 0 0 n s e c or less. In order to prevent the color decomposition from being caused by the ablation phenomenon, it is more preferably 0.5 nsec or more, and most preferably 1 nsec. If it is desired to improve the accuracy of the scanning exposure, it is preferably nsec or less. Preferably, the frequency is below 50 nsec and the frequency of the laser is preferably 1 Hz or more and 50000 Hz, more preferably 10 Hz or more and 1000 Hz or less. Further, if the frequency of the laser is to be shortened, the exposure time is preferably 10 Hz or more, preferably 1 Hz or more, and when the alignment accuracy during scanning is to be improved, it is preferably 1 0000 Hz or less. Below 1000 Hz. Compared with mercury lamps, lasers are preferred because they tend to reduce the focus and prevent the cost from being formed by masking the pattern of the exposure step. There is no particular limitation on the exposure apparatus to be used in the present invention. Callisto (trade name, manufactured by V Technology Co., Ltd.) AEGIS (trade name, manufactured by V Technology Co., Ltd.) DF2200G (trade name, Dainippon Screen Co., Ltd.) System). In addition, devices other than the above are also suitable for use. Further, the illumination light may be adjusted by a spectral filter such as a long wavelength cut filter, a short wavelength cutoff filter, or a band-pass filter, as needed. On the coated film, if it is below 1000, it is more suitable. It needs to be filtered for use, or, or the like. -96- 201140249 <Development step> In the development step, the alkaline developer is used to remove the exposure. The area is formed to form an image pattern. Examples of the basic compound which may be contained in the alkaline developing solution include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; and alkali metal carbonates such as sodium carbonate and potassium carbonate; An alkali metal hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate; ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline hydroxide; sodium citrate or sodium metasilicate; An aqueous solution. Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or an aqueous solution of a surfactant may be added to the aqueous solution containing the basic compound as a visible liquid. The pH of the developer is preferably from 10.0 to 14.0. The development time is usually 30 to 180 seconds, and the development method is either a paddling method, a dipping method, or the like. After development, the water is washed for 30 to 90 seconds to form a pattern desired. <Post-baking step (cross-linking step)> Regarding the pattern obtained by development corresponding to the unexposed area, by using a heating device such as a hot plate or an oven, at a specific temperature, for example, 180 to 2 50 ° C for a specific time, for example, 5 to 60 minutes on a hot plate, 30 to 90 minutes for an oven, heat treatment, so that the acid decomposition of the copolymer (A) decomposition To produce a carboxyl group and/or a phenolic hydroxyl group, which are reacted with the epoxy group of the copolymer (A) and/or the oxetane-crosslinking group of -97-201140249 to be crosslinked. This can form a cured film such as a protective film or an interlayer insulating film which is excellent in heat resistance and hardness. Further, when the heat treatment is performed, the transparency of the cured film can be improved by performing in a nitrogen atmosphere. Further, before the heat treatment, it is preferred that the cured film is formed into a patterned substrate by re-exposure with active light, and then post-baking (re-exposure/post-baking) causes photoacid generation in the unexposed portion. The agent (B) generates an acid to function as a catalyst for promoting the crosslinking step. That is, the method of forming the cured film of the present invention preferably comprises a re-exposure step of re-exposure with active light between the developing step and the post-baking step. The exposure in the re-exposure step can be carried out in the same manner as the above-described exposure step, but in the above-described re-exposure step, it is preferred to perform full exposure on the side of the substrate having the film formed of the photosensitive resin composition of the present invention. . The preferred exposure amount for the re-exposure step is 100 to 1, 〇〇〇mJ/cm2. According to the photosensitive resin composition of the present invention, excellent insulating properties can be obtained, and a cured film having high transparency and clarity can be obtained even when baked at a high temperature, and the cured film can be used as an interlayer insulating film. The interlayer insulating film comprising the photosensitive resin composition of the present invention has high transparency and excellent hard film properties, and therefore can be used for an organic EL display device or a liquid crystal display device. Further, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above applications, and can be used for various purposes. For example, in addition to the planarizing film, the protective layer, and the interlayer insulating film, it is also suitable to use -98-201140249 to maintain the thickness of the liquid crystal layer of the liquid crystal display device at a certain gap control material or to set the color filter in the solid-state image sensor element. The on-chip microlens, etc. The organic EL display device and the liquid crystal display device of the present invention are not particularly limited as long as they have a cured film formed using the photosensitive resin composition of the present invention as a planarizing film or an interlayer insulating film. As a limitation, various organic EL display devices or liquid crystal display devices which are conventionally used in various structures can be cited. Fig. 1 is a schematic cross-sectional view showing a substrate of a bottom-emission type organic EL display device which can be used as the organic EL display device of the present invention. In the first embodiment, a TFT 1 of a bottom gate type is formed on a glass substrate 6, and an insulating film 3 made of Si3N4 is formed in a state of covering the TFT 1. After the insulating film 3 is formed with a contact hole (not shown), the wiring 2 (height 1·0#ηι) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is an organic EL element and a TFT 1 for connecting between the TFTs 1 or in a subsequent step. Further, in order to planarize the unevenness due to the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness due to the wiring 2 is buried. On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 composed of IT 透过 connected to the wiring 2 through the contact hole 7 is formed on the planarizing film 4. The first electrode 5 is an anode corresponding to the organic EL element. -99- 201140249 An insulating film g which covers the shape of the periphery of the first electrode 5 is formed. This insulating film 8 is provided to prevent short-circuiting between the first electrode 5 and the second electrode which is subsequently formed. Further, although not shown in the first drawing, a hole transport layer, an optical layer, and an electron transport layer are provided through a steaming key of a desired pattern, and then an aluminum layer is formed over the substrate. The second electrode is sealed by bonding with a glass plate for sealing and a UV-type epoxy resin, whereby an active matrix type obtained by connecting the EL element to the TFT 1 can be obtained. EL display device. 2 is a schematic cross-sectional view showing an example of a liquid crystal display device which can be used as an active matrix device of the liquid crystal display device of the present invention. In the second embodiment, the liquid crystal display device 10 has a backlight single j liquid crystal panel on the back side, and the liquid crystal panel is disposed. There is a TFT 16 corresponding to all the pixels disposed between the attached two glass substrates 14 and 15. In each of the elements formed on the glass substrate, the wiring has an IT0 transparent through which the contact holes 18 in the film 17 are formed to form a pixel electrode. An RGB color filter 22 in which a black matrix of the liquid crystal 20 is disposed is disposed above the IT0 transparent electrode 19. <<Embodiment>> Next, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the embodiments. In addition, unless otherwise specified, "parts" and "%" are based on quality. In the following synthesis examples, the following abbreviations are respectively represented, since the masks are shaped according to the organic hair 3 A1 (the line hardens each organic (actively applied figure. In the Ϊ; 12 of the polarizing film components are formed into the hard electrode) The layer and the invention are fixed, column-in-100- 201140249 substance: V - 6 5 : 2,2,-azobis(2,4-dimethylvaleronitrile) GMA: glycidyl methacrylate MAA : Methacrylic acid HEMA: 2-hydroxyethyl methacrylate EDM : Diethylene glycol ethyl methyl ether <Synthesis of polymer A-1> Polymer A-1 as a co-polymer (A) is Synthetic hydrazine was added to 144.2 parts (2 mole equivalents) of ethyl vinyl ether by adding 0.5 parts of phenothiazine as described below, and was added dropwise while cooling the reaction system to below 10 °C. After 86.1 parts (1 mole equivalent) of methacrylic acid, it was stirred at room temperature (25 ° C) for 4 hours. After adding 5.0 parts of pyridinium p-toluenesulfonate, it was stirred at room temperature for 2 hours and allowed to stand at room temperature. One night. Add 5 parts of sodium bicarbonate and 5 parts of sodium sulfate to the reaction solution, stir at room temperature for _ 1 hour, will not After the solution was filtered, it was concentrated under reduced pressure at 40 ° C or less, and the residuey yellow oil was distilled under reduced pressure to obtain 134.0 parts of a methyl group having a boiling point (bp.) of 43 to 45 ° C / 7 mmHg. a colorless oil of 1-ethoxyethyl acrylate (MAEVE). 1-Ethyl methacrylate obtained (63_28 parts (〇.4 mole equivalent)), GMA (42_65 parts (0.3) a mixture of molar equivalents)), ΜΑΑ (8·61 parts (0.1 mole equivalent)), ΗΕΜΑ (26. 〇 3 parts (0.2 mole equivalent)) and EDM (1 10.8 parts) was heated under a nitrogen stream to 7 〇 ° C. While stirring the mixed solution, a mixed solution of a radical polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd., 4 parts) and EDM (100.0 parts) was added dropwise -101 - 201140249 After 2.5 hours, the reaction was carried out at 70 ° C for 4 hours to obtain an EDM solution of polymer A-1 (solid content concentration: 40%). The obtained polymer A-1 was obtained. The weight average molecular weight measured by gel permeation chromatography (GPC) was 15,000. <Synthesis of Polymers A-2 to A-9> Each of the monomers and the amount thereof used were changed to those shown in the following Table 1, and the other polymers A-2 to A-10 were synthesized as the copolymer (A) in the same manner as in the synthesis of the polymer A-1. Table 1 Polymer structural unit (1) Structural unit (2) Structure monoterpene (3) Mw Species Molar equivalent species Moh-equivalent species Mohr equivalent species Moh-equivalent species "•tl.- Moer-equivalent A-1 MAEVE 0.4 GMA 0.3 MAA 0.1 HEMA 0.2 15000 A-2 MAEVE 0.4 M100 0.3 MAA 0.1 HEMA 0.2 16000 A-3 MAEVE 0.4 OXE-30 0.3 MAA 0.1 HEMA 0.2 17000 Α·4 CHOEMA 0.4 OXE-30 0.3 MAA 0.1 HEMA 0.2 14000 Α- 5 MATHF 0.4 GMA 0.3 MAA 0.1 HEMA 0.2 12000 Α-6 MATHF 0.4 OXE-30 0.3 MAA 0.1 HEMA 0.2 17000 Α-7 P-Ph-1 0.4 OXE-30 0.3 MAA 0.1 HEMA 0.2 16000 Α-8 P-Ph-1 0.4 GMA 0.3 MAA 0.1 HEMA 0.2 13000 Α·9 P-Ph-1 0.4 OXE-30 0.3 Ph-1 0.1 HEMA 0.2 15000 A-10 MATHF 0.4 OXE-30 0.3 MAA 0.1 HEMA 0.1 St 15000 In addition, the abbreviation in Table 1 The symbols are as follows: MAEVE: 1-Ethyl Ethyl Acetate GMA: Ethylene Oxide Epoxy Propyl ester OXE-30: (3-ethyloxetane-3-yl)methyl methacrylate (made by Osaka Organic Chemical Industry Co., Ltd.) HEM A : 2-hydroxyethyl methacrylate M100: A 3,4-Epoxycyclohexylmethyl acrylate (DAICEL Chemical Industry Co., Ltd.) -102- 201140249 MAA: methacrylic acid CHOEMA: 1-(cyclohexyloxy)ethyl methacrylate MATHF: methyl Tetrahydro- 2H-furan-2-yl acrylate
Ph-Ι: 4·羥基苯甲酸(3-甲基丙烯醯氧基丙基 )酯 P-Ph-Ι : 4-羥基苯甲酸(3-甲基丙烯醯氧基丙基 )酯之1-乙氧基乙基醚 St: 苯乙烯 PGMEA: 醋酸丙二醇一甲基醚酯 < CHOEMA之合成> 以與在前述聚合物A-1之合成的MAEVE之合成法相 同的方法進行CHOEMA之合成。 < MATHF之合成> 將甲基丙烯酸(86克、1莫耳)預先冷卻至15°C後 添加樟腦磺酸(4.6克、0.02莫耳)。對該溶液逐滴加入 2-二氫呋喃(71克、1莫耳、1.〇當量)。攪拌1小時後 ’加入飽和碳酸氫鈉(500毫升),以醋酸乙酯(500毫 升)萃取’以硫酸鎂乾燥後,將不溶物過濾後在40 °C以 下進行減壓濃縮,將殘渣之黃色油狀物加以減壓蒸餾,以 獲得125克之沸點(bp.) 54至56 °C /3.5 mmHg餾分之甲 基丙烯酸四氫-2H-呋喃-2-基酯(MATHF)之無色油狀物 (產率8 0 % )。 此外’ Ph-l (4-羥基苯甲酸(3 -甲基丙烯醯氧基丙基 )酯)是以如下所述之方法進行合成。 -103- 201140249 < Ph-1之合成> 在23克之4-羥基苯甲酸(3-羥基丙基)酯之100毫 升乙腈溶液,在攪拌下加入20毫升之N-甲基吡略啶酮, 並且加入16克之甲基丙烯醯氯。在35。C 一邊攪拌一邊進 行反應歷時8小時後,將反應混合物浸入冰水中,將所析 出之結晶加以濾取,以醋酸乙酯/正己烷進行再結晶,以 獲得4·羥基苯甲酸(3 -甲基丙烯醯氧基丙基)酯。 P-Ph-Ι是藉由將Ph-Ι以1-乙氧基乙基醚加以保護而 獲得。Ph-Ι之1-乙氧基乙基醚保護是以與在前述合成例i 所揭示之方法相同的方法實施。 〔實施例1〕 將各成分加以溶解混合成如下述組成 A,並以孔徑 0.2 // m之聚四氟乙烯製濾網加以過濾,以獲得實施例1 之感光性樹脂組成物。 <組成A > • 共聚物(A):聚合物A-1之聚醋酸乙 100.0份 二醇甲基醚酯〔在下文中,簡稱爲「 PGMEA」。(D)成分〕以溶液固體 成分計爲: • 光酸產生劑(B ):如下所示之B -1 2 · 0份 • 增感劑(C ):如下所示之C-1 2.0份 • 密著改良劑(G ):如下所示之G-l 0·5份 • 界面活性劑(I):如下所示之1-1 〇.〇2份 〔實施例2至49、比較例1〕 -104- 201140249 除了將在實施例1所使用的各化合物變更爲如.表2或 表3所示之化合物以外,其餘則以與實施例1相同的添加 量進行溶解混合,以調製實施例2至49及比較例1之感 光性樹脂組成物。 另外,在使用交聯劑(F)之實施例4至14、21至 24及26至49,則以下述添加量添加下述之交聯劑。 此外,在使用鹼性化合物(Η )之實施例24至49, 貝IJ以下述添加量添加下述之鹼性化合物。 • 交聯劑(F ):如下所示之F-1 2.0份 • 鹼性化合物(Η ):如下所示之Η-1 0.1份 • 鹼性化合物(Η ):如下所示之Η-2 〇_〇1份 代表使用於實施例1至49、比較例1的各化合物之 胃稱符號的詳細細節是如下所示: Β-1 : ΡΑΙ-1001 (商品名、如下所示之結構、Ph-Ι: 4-hydroxypropionic acid (3-methacryloxypropyl) ester P-Ph-Ι : 4-hydroxybenzoic acid (3-methacryloxypropyl) ester 1-B Oxyethyl ether St: styrene PGMEA: propylene glycol monomethyl ether acetate <Synthesis of CHOEMA> The synthesis of CHOEMA was carried out in the same manner as the synthesis of MAEVE synthesized in the above polymer A-1. <Synthesis of MATHF> After methacrylic acid (86 g, 1 mol) was previously cooled to 15 ° C, camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1. 〇 equivalent) was added dropwise. After stirring for 1 hour, 'saturated sodium hydrogencarbonate (500 ml) was added and the mixture was extracted with ethyl acetate (500 ml). After drying over magnesium sulfate, the insolubles were filtered and concentrated under reduced pressure at 40 ° C. The oil was distilled under reduced pressure to give a colorless oil (yield: 125 g, bp.), 54 to 56 ° C / 3.5 mmHg of tetrahydro-2H-furan-2-yl methacrylate (MATHF). Yield 80%). Further, ' Ph-l (3-methylpropenyloxypropyl) 4-hydroxybenzoate) was synthesized in the following manner. -103- 201140249 <Synthesis of Ph-1> In 23 g of 3-hydroxybenzoic acid (3-hydroxypropyl) ester in 100 ml of acetonitrile, 20 ml of N-methylpyrrolidone was added with stirring. And added 16 grams of methacrylic acid ruthenium chloride. At 35. C The reaction was carried out while stirring for 8 hours, and then the reaction mixture was immersed in ice water, and the precipitated crystals were filtered, and recrystallized from ethyl acetate / n-hexane to obtain 4-hydroxybenzoic acid (3-methyl group). Propylene methoxypropyl) ester. P-Ph-oxime was obtained by protecting Ph-oxime with 1-ethoxyethyl ether. Ph-indole 1-ethoxyethyl ether protection was carried out in the same manner as disclosed in the above Synthesis Example i. [Example 1] Each component was dissolved and mixed into a composition A as described below, and filtered through a sieve made of polytetrafluoroethylene having a pore diameter of 0.2 / m to obtain a photosensitive resin composition of Example 1. <Composition A > • Copolymer (A): Polyacetate B of Polymer A-1 100.0 parts of diol methyl ether ester (hereinafter, simply referred to as "PGMEA"). (D) component] is based on the solid content of the solution: • Photoacid generator (B): B -1 2 · 0 parts as shown below • Sensitizer (C): C-1 2.0 parts as shown below • Adhesion improver (G): Gl 0·5 parts as shown below • Surfactant (I): 1-1 〇.〇2 parts as shown below [Examples 2 to 49, Comparative Example 1] -104 - 201140249 In addition to changing each compound used in Example 1 to a compound as shown in Table 2 or Table 3, the other addition amounts were the same as in Example 1, to prepare Examples 2 to 49. And the photosensitive resin composition of the comparative example 1. Further, in Examples 4 to 14, 21 to 24 and 26 to 49 in which the crosslinking agent (F) was used, the following crosslinking agent was added in the following amounts. Further, in Examples 24 to 49 in which a basic compound (Η) was used, the following basic compound was added in the following addition amount. • Crosslinking agent (F): F-1 2.0 parts as shown below • Basic compound (Η): Η-1 0.1 parts as shown below • Basic compound (Η): Η-2 如下 as shown below _〇1 parts The detailed details of the gastric symbols of the respective compounds used in Examples 1 to 49 and Comparative Example 1 are as follows: Β-1 : ΡΑΙ-1001 (trade name, structure shown below,
Midori化學(股)製) B-2 PAI-1003 (商品名、如下所示之結構、Midori Chemical Co., Ltd.) B-2 PAI-1003 (trade name, structure shown below,
Midori化學(股)製) B - 3 : C G I - 1 3 9 7 (商品名、如下所示之結構、c ib aMidori Chemical Co., Ltd.) B - 3 : C G I - 1 3 9 7 (trade name, structure shown below, c ib a
Specialty Chemicals 公司製) Β - 4 : P AI -1 0 1 (商品名、如下所示之結構、Specialty Chemicals Co., Ltd. Β - 4 : P AI -1 0 1 (trade name, structure shown below,
CibaSpecialty Chemicals 公司製) Β - 5 : 如下所示之結構(在後述之合成例) B - 6 : 如下所示之結構(在後述之合成例) B-7 : 如下所示之結構(在後述之合成例) -105- 201140249 B-8 : B-9 : B-1 0 : N-1 : N-2 : N-3 : N-4 : N-5 : N-6 : F- 1 : G - 1 : H· 1 : 如下所示之結構(在後述之合成例) 如下所示之結構(在後述之合成例) 如下所示之結構(在後述之合成例) N B C A (商品名、1 0 - 丁基-2 -氯吖啶酮、如下 所示之結構、黑金化成C股)製) DBA (商品名、9,10-二丁氧基蒽、如下所示 之結構、川崎化成工業(股)製) NKX-1768 (商品名、2,3,6,7-四氫-9.-甲基· 1?1,511,11^[丨]苯并哌喃基[6,7,8-丨〗]喹畊-11-酮)、如下所示之結構、林原生物化學硏究 所(股)製) NK-1342 (商品名、2-〔 2-〔 4-(二甲基胺基 )苯基〕乙烯基〕苯并噚唑、如下所示之結 構、林原生物化學硏究所(股)製) DPA (商品名、9, 10 -二丙氧基蒽、如下所示 之結構、川崎化成工業(股)製) DEA (商品名、9,10 -二乙氧基蒽、如下所示 之結構、川崎化成工業(股)製) JER 157S70(商品名、苯酚酚醛清漆型環氧 樹脂、Japan Ep0Xy Resin(股)製) KBM-403 (商品名、3_環氧丙氧基丙基三甲 氧基矽烷、如下所示之結構、信越化學工業( 股)製) 1,5-二吖雙環[4.3·〇]-5-壬烯 -106- 201140249 H-2 : 三苯基咪唑 1-1 : PolyFox PF-6 3 2 0 (商品名、氟系界面活性劑 ' OMNOVA公司製). 1-2: 以下述結構式(W-3 )所代表之含有全氟烷 基之非離子性界面活性劑 0CibaSpecialty Chemicals Co., Ltd. Β - 5 : Structure shown below (synthesis example described later) B - 6 : Structure shown below (combination example described later) B-7 : Structure shown below (described later) Synthesis Example) -105- 201140249 B-8 : B-9 : B-1 0 : N-1 : N-2 : N-3 : N-4 : N-5 : N-6 : F- 1 : G - 1 : H· 1 : Structure shown below (synthesis example described later) The structure shown below (combination example described later) The structure shown below (combination example described later) NBCA (trade name, 1 0 - Butyl-2-chloroacridone, the structure shown below, black gold into a C-share)) DBA (trade name, 9,10-dibutoxy fluorene, structure shown below, Kawasaki Chemical Industry Co., Ltd.) NKX-1768 (trade name, 2,3,6,7-tetrahydro-9.-methyl·1?1,511,11^[丨]benzopyranyl [6,7,8-丨〗 〖Quineng-11-ketone), the structure shown below, Linyuan Biochemical Research Institute (share) NK-1342 (trade name, 2-[2-[4-(dimethylamino)benzene) Vinyl]benzoxazole, the structure shown below, Linyuan Biochemical Research Institute DPA (trade name, 9,10-dipropoxy fluorene, structure shown below, manufactured by Kawasaki Chemicals Co., Ltd.) DEA (trade name, 9,10-diethoxy oxime, structure shown below, Kawasaki Chemicals Co., Ltd.) JER 157S70 (trade name, phenol novolak type epoxy resin, manufactured by Japan Ep0Xy Resin Co., Ltd.) KBM-403 (trade name, 3_glycidoxypropyltrimethoxydecane) Structure shown below, Shin-Etsu Chemical Co., Ltd.) 1,5-Di-bicyclobicyclo[4.3·〇]-5-decene-106- 201140249 H-2 : Triphenylimidazole 1-1 : PolyFox PF -6 3 2 0 (trade name, fluorine-based surfactant - manufactured by OMNOVA). 1-2: Perfluoroalkyl-containing nonionic surfactant represented by the following structural formula (W-3)
h3coH3co
9 CH3 CN N-O-S—n-C3H7 CGI-1397 h3co-{ γλ,ν-°-|-〇-°Η3 」CN 0 a—^ N—〇一S—CH3 〇< δ CN PAI-101 B-59 CH3 CN N-O-S-n-C3H7 CGI-1397 h3co-{ γλ,ν-°-|-〇-°Η3 ”CN 0 a—^ N—〇一S—CH3 〇< δ CN PAI-101 B-5
-107- 201140249-107- 201140249
CH 3CH 3
CH3CH3
ΟΟ
OBuOBu
OBu DBA CH,OBu DBA CH,
NK-1342 -108- 201140249 〇Pr OEtNK-1342 -108- 201140249 〇Pr OEt
OPrOPr
DPA DEA KBM-403 W-3 CH3 -ch2-c-)-o人〇〆 c»3 -fCH2-C- 20SS% CH2CH3 、0— -CH2CH——〇-80¾¾% •11DPA DEA KBM-403 W-3 CH3 -ch2-c-)-o〇〆 c»3 -fCH2-C- 20SS% CH2CH3 , 0— -CH2CH——〇-803⁄43⁄4% •11
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Mw: 1500 < B-5之合成> 如B-5所示之化合物(a-(甲基磺醯氧基亞胺基)-2-苯碁乙腈)是以如下所述之方式進行合·成。 a-(羥基亞胺基)-2-苯基乙腈之合成 將5 · 8 5克之苯基乙腈(東京化成工業(股)製)混合於 四氫呋喃:5 0毫升(和光純藥工業(股)製),浸入冰浴中 -109- 201140249 使反應液冷卻至5°C以下。其次,逐滴加入11.6克之SM-28 (甲氧鈉28%甲醇溶液、和光純藥工業(股)製),在冰 浴下攪拌30分鐘使其進行反應。其次,將7.03克之亞硝 酸異戊酯(東京化成工業(股)製)一邊保持在內溫2 (TC以 下一邊逐滴加入,在逐滴加入結束後,使反應液室溫化並 進行反應歷時1小時。將所獲得反應液飼入於經溶解1克 之氫氧化鈉之1 5 0毫升水,使其完全溶解,其次添加1 〇 〇 毫升之醋酸乙酯而加以分液,以獲得具有目的物之約1 8 0 毫升之水層。並且,再度添加100毫升之醋酸乙酯,以濃 鹽酸使水層成爲pH 3以下之酸性,萃取產物並加以濃縮 。將粗結晶以己烷洗淨,可獲得4.6克之α-(羥基亞胺基 )-2-苯基乙腈(產率爲63% )。 (2 ) α-(甲基磺醯氧基亞胺基)-2-苯基乙腈(化合物 Β-5 )之合成 將1〗.5克之ot-(羥基亞胺基)-2-苯基乙腈溶解於 四氫呋喃:1 〇 〇毫升(和光純藥工業(股)製)後,浸入冰 浴中使反應液冷卻至5°C以下。其次,逐滴加入9.9克之 甲烷磺醯基氯(和光純藥工業(股)製),其次將9.55克 之三乙基胺(和光純藥工業(股)製)一邊保持在內溫20 t以下一邊逐滴加入,在冰浴下攪拌1小時使其進行反 Bffi 〇 /ό、 將所獲得反應液逐滴加入於500毫升之水,在室溫下 攪拌1小時。將所獲得粉末狀之析出物加以過濾、乾燥, 可獲得16克之α-(甲基磺醯氧基亞胺基)-2-苯基乙腈( -110- 201140249 化合物Β·5)(產率爲90%)。該化合物之1H-NMR光譜 是顯現產物爲肟結構異構物(·順式/反式)之混合物,且 其存在比爲順式··反式=2 5 / 7 5。 < B-6之合成> 根據在日本特表 2002-528451號公報中之段落碼〔 〇1〇8〕所揭述之方法,進行合成α_(對甲苯磺醯氧基亞胺 基)苯基乙腈(化合物Β-6 )。 < Β-7之合成> 1-1.合成中間體Β-7Α之合成 將2-胺基苯硫醇·· 31.3克(東京化成工業(股·)製)在 室溫(25 °C )下溶解於甲苯·· 100毫升(和光純藥工業(股 )製)。其次,對所獲得溶液在室溫下逐滴加入40.6克之 苯基乙醯基氯(東京化成工業(股)製)歷時1小時,其次 在1 〇〇°C攪拌2小時使其進行反應。在所獲得反應液飼入 5 00毫升水使所析出的鹽溶解,萃取甲苯油分,將萃取液 以旋轉式蒸發器加以濃縮,以獲得合成中間體Β-7A。 1-2. B-7之合成 將2.25克之藉由如前述所獲得合成中間體B-7A混合 於四氫呋喃:10毫升(和光純藥工業(股)製)後,浸入冰 浴中使反應液冷卻至5 °C以下。其次,對反應液逐滴加入 4.37克之氫氧化四甲基銨(25重量%甲醇溶液、Alfa Acer公司製),在冰浴下攪拌0.5小時使其進行反應。並 且,將7.03克之亞硝酸異戊酯一邊保持在內溫2 0°C以下 一邊逐滴加入,在逐滴加入結束後使反應液升溫至室溫後 -111- 201140249 ,攪拌一小時。 接著’將反暉液冷卻至5 °C以下後,飼入對甲苯磺醯 基氯(1.9克)(東京化成工業(股)製),一邊保持在10 °C以下一邊攪拌1小時。其後’飼入8 0毫升水,在0 °C 攪拌1小時。將所獲得析出物加以過濾後,飼入6 0毫升 之異丙醇(IPA ),在50°C加熱攪拌1小時,加以熱過濾 、乾燥,以獲得1.8克之B-7(前述之結構)。 所獲得B-7之1H-NMR光譜(300 MHz、気化DMSO ((D3C)2S=0) ) : δ=8·2 至 8.17 ( m, 1Η) ' 8.03 至 8.00 ( m, 1Η ) 、7.95 至 7.9 ( m,2Η ) 、7.6 至 7.45 ( m, 9H) ' 2.45 ( s, 3 Η )。 由上述之1H-NMR測定結果,可推定所獲得之Β-7是 —種單獨之幾何異構物。 < Β-8之合成> 在2-萘酚(10克)、氯苯(30毫升)之懸浮溶液中 ,添加氯化鋁(10.6克)'2 -氯丙醯基氯(10.1克),將 混合液加熱至4 0 °C使其反應2小時。在冰冷下,對反應 液逐滴加入4N HC1水溶液(60毫升),添加醋酸乙酯( 5〇毫升)而加以分液。在有機層中,加入碳酸鉀(19.2 克),在40°C使其反應1小時後,添加2N HC1水溶液( 60毫升)而加以分液,將有機層加以濃縮後,將結晶以 二異丙基醚(1 〇毫升)加以再漿體化,並加以過濾、乾 燥,以獲得酮化合物(6·5克)。 在所獲得酮化合物(3 · 0克)、甲醇(3 0毫升)之懸 -112- 201140249 浮溶液中,添加醋酸(7.3克)、5 0重量%之羥基胺水溶 液(8.0克),並進行加熱回流。放冷後’加入水(5 0毫 升),將所析出的結晶加以過濾、以冷甲醇洗淨後’加以 乾燥,以獲得肟化合物(2.4克)。 將所獲得肟化合物(1 .8克)溶解於丙酮(20毫升) 中,在冰冷下,添加三乙基胺(1.5克)、對甲苯磺醯基 氯(2.4克),升溫至室溫使其反應1小時。在反應液添 加水(5 0毫升),將所析出的結晶加以過濾後,以甲醇 (2 0毫升)加以再漿體化,並加以過濾、乾燥’以獲得 2.3克之B-8(前述之結構)。_ 另外,B-8 之 iH-NMR 光譜(300 MHz、CDC13) : δ =8.3 ( d, 1 Η ) 、8.0 ( d,2H) 、7.9 ( d,1H) 、7.8 ( d, 1 H ) ' 7.6 ( dd, 1H ) ' 7.4 ( dd, 1H ) 7.3 ( d, 2H ) 、7.1 (d,lH) ' 5.6 ( q, 1H ) 、2.4(s, 3H) 、1.7(d,3H)。 < B-9之合成> 將2-萘酚(20克)溶解於N,N-二甲基乙醯胺(150 毫升),添加碳酸鉀(28.7克)、2-溴辛酸乙酯(52.2克 ),並在100 °C使其反應2小時。在反應液添加水(300 毫升)、醋酸乙酯(200毫升)而加以分液’將有機層加 以濃縮後,添加48重量%氫氧化鈉水溶液(23克)、乙 醇(5 0毫升)、水(5 0毫升),使其反應2小時。將反 應液浸入1N HC1水溶液(5 00毫升),將所析出的結晶 加以過濾、水洗以獲得羧酸粗體後’添加3 0克之聚磷酸 使其在170 °C反應30分鐘。將反應液浸入水(300毫升) -113- 201140249 中,添加醋酸乙酯(300毫升)而加以分液,將有機層加 以濃縮後,以矽凝膠管柱式層析法進行精製,以獲得酮化 合物(10克)。 在所獲得酮化合物(10.0克)、甲醇(100毫升)之 懸浮溶液中,添加醋酸鈉(30.6克)、鹽酸羥胺 (hydroxylamine hydrochloride) ( 25.9 克)、硫酸鎂(4.5 克),並加熱回流2 4小時。放冷後,添加水(1 5 0毫升 )、醋酸乙酯(150毫升)而加以分液,將有機層以80 毫升水加以分液4次,經濃縮後,以矽凝膠管柱式層析法 進行精製,以獲得肟化合物(5 . 8克)。 對所獲得肟(3 · 1克),以與B - 8相同的方式進行磺 酸酯化,以獲得3.2克之B-9 (前述之結構)。 另外,B-9 之1H-NMR 光譜( 300 MHz、CDC13) : δ =8.3 ( d, 1 Η ) 、8.0(d,2H) ' 7.9 ( d, 1 Η ) 、7.8(d, 1 Η ) ' 7.6 ( dd, 1 Η ) ' 7.5 ( dd, 1 Η ) 7.3 ( d, 2H ) ' 7.1Mw: 1500 <Synthesis of B-5> The compound (a-(methylsulfonyloxyimino)-2-phenylindoleacetonitrile) as shown in B-5 was synthesized in the following manner. ·to make. Synthesis of a-(hydroxyimino)-2-phenylacetonitrile 5·85 g of phenylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with tetrahydrofuran: 50 ml (manufactured by Wako Pure Chemical Industries, Ltd.) ), immersed in an ice bath -109- 201140249 The reaction solution was cooled to below 5 °C. Next, 11.6 g of SM-28 (sodium methoxide 28% methanol solution, Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was stirred for 30 minutes in an ice bath to carry out a reaction. Next, 7.03 g of isoamyl nitrite (manufactured by Tokyo Chemical Industry Co., Ltd.) was kept at an internal temperature of 2 (the amount was added dropwise below TC, and after the dropwise addition was completed, the reaction solution was allowed to stand at room temperature and reacted for a duration of time. 1 hour. The obtained reaction solution was fed into 150 ml of water dissolved in 1 g of sodium hydroxide to completely dissolve it, and then 1 ml of ethyl acetate was added thereto to separate the liquid to obtain the desired product. The aqueous layer is about 180 ml, and 100 ml of ethyl acetate is added again, and the aqueous layer is made acidic with a concentration of hydrochloric acid below pH 3. The product is extracted and concentrated. The crude crystal is washed with hexane. 4.6 g of α-(hydroxyimino)-2-phenylacetonitrile was obtained (yield was 63%). (2) α-(Methylsulfonyloxyimino)-2-phenylacetonitrile (Compound Β -5) Synthesis: 1 gram of ot-(hydroxyimino)-2-phenylacetonitrile was dissolved in tetrahydrofuran: 1 〇〇 ml (manufactured by Wako Pure Chemical Industries, Ltd.), and immersed in an ice bath. The reaction solution was cooled to below 5 ° C. Next, 9.9 g of methanesulfonyl chloride was added dropwise (Wako Pure Chemical Industries, Ltd.) ())), and 9.55 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise while maintaining the internal temperature of 20 t or less, and stirred for 1 hour in an ice bath to carry out anti-Bffi 〇/ ό, the obtained reaction liquid was added dropwise to 500 ml of water, and stirred at room temperature for 1 hour. The obtained powdery precipitate was filtered and dried to obtain 16 g of α-(methylsulfonyloxy group). Imino)-2-phenylacetonitrile (-110-201140249 compound Β·5) (yield 90%). The 1H-NMR spectrum of the compound is the apparent product of the oxime structural isomer (·cis/anti a mixture of the formula), and its existence ratio is cis··trans = 2 5 / 7 5 . <Synthesis of B-6> According to the paragraph code in Japanese Patent Laid-Open Publication No. 2002-528451 [ 〇 1〇 8] The method described is carried out to synthesize α_(p-toluenesulfonyloxyimino)phenylacetonitrile (compound Β-6). <Synthesis of Β-7> 1-1. Synthesis of intermediate Β- Synthesis of 7Α 2-aminophenylthiol··31.3 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in toluene·100 ml at room temperature (25 °C) (Wako Pure Chemicals) (Stock)). Next, 40.6 g of phenylethenyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the obtained solution at room temperature for 1 hour, followed by stirring at 1 °C for 2 hours. The reaction was carried out by feeding 500 ml of water to the obtained reaction solution to dissolve the precipitated salt, extracting toluene oil, and concentrating the extract in a rotary evaporator to obtain a synthetic intermediate Β-7A. Synthesis of B-7 2.25 g of the synthetic intermediate B-7A obtained as described above was mixed with tetrahydrofuran: 10 ml (manufactured by Wako Pure Chemical Industries, Ltd.), and immersed in an ice bath to cool the reaction solution to 5 °. Below C. Next, 4.37 g of tetramethylammonium hydroxide (25 wt% methanol solution, manufactured by Alfa Acer Co., Ltd.) was added dropwise to the reaction liquid, and the mixture was stirred for 0.5 hour in an ice bath to carry out a reaction. Further, 7.03 g of isoamyl nitrite was added dropwise while maintaining the internal temperature at 20 ° C or lower, and after the dropwise addition was completed, the reaction solution was allowed to warm to room temperature -111 - 201140249, and stirred for one hour. Then, the reaction mixture was cooled to 5 ° C or lower, and then p-toluenesulfonyl chloride (1.9 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred for 1 hour while maintaining the temperature below 10 °C. Thereafter, 80 ml of water was fed and stirred at 0 ° C for 1 hour. The obtained precipitate was filtered, and then 60 ml of isopropyl alcohol (IPA) was added thereto, and the mixture was heated and stirred at 50 ° C for 1 hour, and then hot-filtered and dried to obtain 1.8 g of B-7 (structure described above). 1H-NMR spectrum of B-7 obtained (300 MHz, deuterated DMSO ((D3C)2S=0)): δ=8·2 to 8.17 (m, 1Η) ' 8.03 to 8.00 (m, 1Η), 7.95 to 7.9 ( m, 2 Η ) , 7.6 to 7.45 ( m, 9H) ' 2.45 ( s, 3 Η ). From the results of the above 1H-NMR measurement, it was presumed that the obtained Β-7 was a single geometric isomer. <Synthesis of Β-8> In a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 ml), aluminum chloride (10.6 g) of '2-chloropropenyl chloride (10.1 g) was added. The mixture was heated to 40 ° C for 2 hours. Under ice cooling, a 4N aqueous HCl solution (60 ml) was added dropwise, and ethyl acetate (5 ml) was added and the mixture was separated. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 ° C for 1 hour, and then a 2N aqueous solution of HCl (60 ml) was added thereto to carry out liquid separation, and the organic layer was concentrated to crystallize diisopropyl. The ether (1 ml) was repulped and filtered and dried to obtain a ketone compound (6.5 g). To the suspension of the obtained ketone compound (3.0 g) and methanol (30 ml) - 112-201140249, acetic acid (7.3 g), 50% by weight aqueous hydroxylamine solution (8.0 g) was added and carried out. Heat to reflux. After cooling, 'water (50 ml) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain a hydrazine compound (2.4 g). The obtained hydrazine compound (1.8 g) was dissolved in acetone (20 ml), and triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the mixture was allowed to warm to room temperature. It reacted for 1 hour. Water (50 ml) was added to the reaction mixture, and the precipitated crystals were filtered, and then re-slurryed with methanol (20 ml), filtered and dried to obtain 2.3 g of B-8 (the above structure) ). _ In addition, the iH-NMR spectrum of B-8 (300 MHz, CDC13): δ = 8.3 (d, 1 Η), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1 H ) ' 7.6 ( dd, 1H ) ' 7.4 ( dd, 1H ) 7.3 ( d, 2H ) , 7.1 (d,lH) ' 5.6 ( q, 1H ) , 2.4 (s, 3H) , 1.7 (d, 3H). <Synthesis of B-9> 2-Naphthol (20 g) was dissolved in N,N-dimethylacetamide (150 ml), and potassium carbonate (28.7 g) and ethyl 2-bromooctanoate were added ( 52.2 g) and allowed to react at 100 ° C for 2 hours. Water (300 ml) and ethyl acetate (200 ml) were added to the reaction mixture for liquid separation. After the organic layer was concentrated, 48% by weight aqueous sodium hydroxide solution (23 g), ethanol (50 ml), and water were added. (50 ml), allowed to react for 2 hours. The reaction solution was immersed in a 1 N aqueous HCl solution (500 ml), and the precipitated crystals were filtered and washed with water to obtain crude carboxylic acid, and then 30 g of polyphosphoric acid was added and allowed to react at 170 ° C for 30 minutes. The reaction solution was immersed in water (300 ml) -113-201140249, and ethyl acetate (300 ml) was added to separate the layers, and the organic layer was concentrated, and then purified by a gel column chromatography to obtain Ketone compound (10 g). Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g), magnesium sulfate (4.5 g), and heated under reflux were added to a suspension of the obtained ketone compound (10.0 g) in methanol (100 ml). 4 hours. After allowing to cool, water (150 ml) and ethyl acetate (150 ml) were added and liquid-separated, and the organic layer was partitioned 4 times with 80 ml of water. After concentration, the column was layered with a gel. The purification was carried out by an analytical method to obtain a hydrazine compound (5.8 g). The obtained hydrazine (3.1 g) was sulfonated in the same manner as B-8 to obtain 3.2 g of B-9 (the foregoing structure). In addition, 1H-NMR spectrum of B-9 (300 MHz, CDC13): δ = 8.3 (d, 1 Η), 8.0 (d, 2H) '7.9 (d, 1 Η), 7.8 (d, 1 Η ) ' 7.6 ( dd, 1 Η ) ' 7.5 ( dd, 1 Η ) 7.3 ( d, 2H ) ' 7.1
(d, 1H ) > 5.6 ( dd, 1H ) 、2.4(s, 3H) 、2.2(ddt,1 H )、1.9(ddt, 1H) 、1.4 至 l_2(m,8H) 、〇.8(t,3H) o < B-1 〇之合成> 除了取代在B-8之對甲苯磺醯基氯而使用苯磺醯基氯 以外,其餘則以與B - 8相同的方式合成B -1 0 (前述之結 構)。 另外,B-10 之1H-NMR 光譜( 3 00 MHz、CDC13) : δ =8.3 ( d, 1 Η ) ' 8.1 ( d, 2Η ) > 7.9 ( d, 1 Η ) 、7.8(d, -114- 201140249 1 Η ) 、7.7-7_5(m,4H) 、7.4(dd,1Η) 、7.1(d,1H) ' 5.6 ( q, 1 H ) 、1 .7 ( d,3H )。 〔比較例2 :使用1,2-醌二疊氮化合物之例〕 比較例2之感光性樹脂組成物是調製在日本特開平5-1 6 5 2 1 4號公報中之實施例1所揭述之組成物。 〔比較例3 :使用鎗鹽系光酸產生劑之例〕 比較例3之感光性樹脂組成物是以如下所述之方式進 行調製在日本特開2004-264623號公報中之實施例1所揭 述之組成物。 . -比較例3之感光性樹脂組成物之調製_ 在配備冷卻管、攪拌機之燒瓶中,裝入7份之2,2’-偶氮雙(2,4-二甲基戊腈)、200份之二甘醇乙基甲基醚 。接著,裝入40份之甲基丙烯酸1-(環己氧基)乙酯、5 份之苯乙烯、45份之甲基丙烯酸環氧丙酯、10份之甲基 丙烯酸2-羥基乙酯及3份之α-甲基苯乙烯二聚物經氮氣 取代後,緩慢地開始攪拌。使溶液溫度上升至70°C ’在 該溫度保持5小時,以獲得含有共聚物之聚合物溶 '液°所 獲得共聚物之經聚苯乙烯換算得之重量平均分子量(Mw )爲1 1,000。此外.,在此所獲得聚合物溶液之固體成分濃 .度爲 3 1 . 6 %。 將含有藉由上述所合成之共聚物之溶液,以相當於 1〇〇份(固體成分)之共聚物的量,及5份之三氟甲院碌 酸4,7-二-正丁氧基-1-萘基四氫噻吩鏺,溶解妗二甘醇甲 基乙基醚使得固體成分濃度成爲30%後,以孔徑爲02 ^ -115- 201140249 m之薄膜過濾器加以過濾,以獲得比較例3之感光性樹脂 組成物。 〔比較例4:使用肟磺酸酯系光酸產生劑之例〕 比較例 4之感光性樹脂組成物是調製在日本特開 2009-98616號公報中之實施例8所揭述之組成物。· 就藉由上述所獲得實施例1至49、及比較例1至4 之感光性樹脂組成物進行如下所述之各種評估。 <液經時安定性(液保存性)之評估> , 以E型黏度計(東機產業(股)製)測定剛調製後之感 光性樹脂組成物的黏度(初期黏度)、與經在30°C儲存1 週後及2週後之感光性樹脂組成物的黏度(經時黏度)。 評估基準是經時黏度相對於初期黏度(1 〇〇% )的相對性 評估是變化1 〇 %以上者爲「3」、黏度之變化爲少於1 〇 % 且5 %以上時爲「2」、黏度之變化爲少於5 %時則爲「1」 。「1」及「2」爲在實務應用上無問題之水準。結果展示 於表2。 <感度之評估> 在玻璃基板(商品名:Corning 1737、厚度爲〇.7 mm 、Corning公司製)上,將各感光性樹脂組成物加以狹縫 塗布後,在熱板上進行90 °C /120秒鐘之預烘烤使溶劑揮 發,以形成膜厚爲3 · 0 # m之感光性樹脂組成物層。 其次,將所獲得感光性.樹脂組成物層使用C an ο η (股) 製之PLA-501F曝光機(商品名、超高壓水銀燈)’通過 特定的遮罩加以曝光。並且’將曝光後之感光性組成物層 -116- 201140249 以鹼顯影液(0.4質量%之氫氧化四甲基銨水溶液)加以 2 3 °C / 6 0秒鐘之顯影後,以超純水洗滌2 0秒鐘。 由於此等之操作可將1 0 /Z m之線寬與間距以1 : 1加 以解析時的最適i-射線曝光量(Eopt)作爲感度。另外, 評估基準是如下所示。「1」及「2」爲在實務應用上並無 問題之水準。結果展示於表2及表3。 1: 少於 40mJ/cm2、 2: 40mJ/cm2 以上且少於 60mJ/cm2、 3: 60mJ/cm2 以上且少於 80mJ/cm2、 4: 80mJ/cm2 以上。 <透明性之評估> 在玻璃基板(商品名:Corning 1 7 3 7、厚度爲0.7 mm 、Corning公司製)上,將各感光性樹脂組成物加以狹縫 塗布後,在熱板上以90 °C /120秒鐘之加熱來移除溶劑, 以形成膜厚爲3.0 // m之感光性樹脂組成物層。 將所獲得感光性樹脂組成物層以Canon(股)製造之 P L A - 5 0 1 F曝光機(商品名、超高壓水銀燈)加以曝光使 得積算照射量成爲 3 00 mJ/cm2 (照度:20 mW/cm2、i-射 線),其後,將此基板在2 3 0 °C之烘箱中加熱1小時以獲 得硬化膜。 具有該硬化膜的玻璃基板之光線透射率是使用分光光 度計(spectrophotometer)「150-20 型 Double Beam (商品 名、日立製作所(股)製)」以400至8〇〇 nm範圍之波長 進行測定。將此時之最低光線透射率作爲透明性之評估而 -117- 201140249 展示於表2及表3。 另外,評估基準是如下所述β 「1」及「2」爲在實務 應用上並無問題之水準。 1 : 9 2 %以上、 2 : 9 0 %以上且少於9 2 % ' 3 : 8 8 %以上且少於9 0 %、 4 : 少於8 8 % » <耐溶劑性之評估> 以與透明性之評估相同的方式,在玻璃基板(商品名 :Corning 1737、厚度爲 0.7 mm、Corning 公司製)上形 成硬化膜。 將所獲得硬化膜之膜厚(T 1 )加以測定。並且,將經 形成該硬化膜之基板浸漬於溫度控制在7〇°C之二甲基亞 楓中歷時20分鐘後,測定浸漬後之硬化膜之膜厚(t1 ) ,計算出由於浸漬所引起之膜厚變化率{ | t^T1 | /T1} X 100(%)。結果展示於表2及表3。 膜厚變化率之値爲少於3 % (亦即,獲得基準1至3 之結果時)時’則可視爲硬化膜之耐溶劑性爲良好。 1 : 少於1 %、 2 : 1 %以上且少於2 %、 3 : 2 %以上且少於3 %、 4 : 3 %以上。 <圖案形狀之評估〉 在玻璃基板(商品名:Corning 1737、厚度爲〇.7 mm -118- 201140249 、Corning公司製)上,將各感光性樹脂組成物加以狹縫 塗布後,在熱板上以901/120秒鐘移除溶劑而形成膜厚 爲3.0 jtz m之感光性樹脂組成物層。 接著,將所獲得感光性樹脂組成物層’以〇 . 4 %氣氧 化四甲基銨水溶液作爲顯影液’在2 3 °C加以顯影6 0秒鐘 後,以能獲得1 〇 ^ m見方之接觸孔圖案之曝光量(照度: 20 mW/cm2、i-射線),通過具有l〇ym見方之圖案開口 部的遮罩進行曝光。 將曝光後之基板以〇.4 %氫氧化四甲基銨水溶液作爲 顯影液,在 23 °C進行 60秒鐘之槳翼式顯影(paddle development) ° 將經圖案化之感光性樹脂組成物層以佳能公司製造之 P L A - 5 0 1 F曝光機(商品名、超高壓水銀燈)加以曝光使 得積算照射量成爲 300 mJ/cm2 (照度:20 mW/cm2、i-射 線),其後,將此基板在2 3 0 °C之烘箱中加熱1小時以獲 得硬化膜。 切削所獲得附有硬化膜之玻璃基板,將經圖案化的接 觸孔之截面形狀以場發射掃描式電子顯微鏡(Field Emission Scanning Electron Microscope) S - 4 8 0 0 (商品名 、Η IT A C Η I公司製)加以觀察,並進行評估。 評估基準是如下所述。結果展示於表2及表3。 所獲得接觸孔之錐形角度爲小於5 0度時(亦即,獲 得基準1之結果時),則圖案形狀是可稱得上是良好。 1: 錐形角度爲在10以上且小於50度之範圍(正 •119- 201140249 向錐型)、 2 : 錐形角度爲在50以上且少於90度之範圍(矩 形)、 3 : 錐形角度爲在90度以上之範圍(倒向錐型)。 -120- 201140249 (N« 評估 圖案形狀 — — *•4 - ν·»^ ^―· ,丨— — 一 一 一 — 耐溶劑性 ΓΛ fN ΓΛ (Ν (Ν CN 透明性 (N rs r-H F·^ <N (Ν r-H m 蹈 (N CN (Ν (N fN (N (N <Ν CN (N CN CN (Ν CN ••Η r*"H 液保存性 fN r-H <N (Ν ψ-^ 其他成分 1 HH 二 二 r-H 二 1 一 Λ CN 二 二 Λ 二 —Η 2 鹼性 化合物 (H) 密著 改良劑 (G) 〇 〇 6 ό ώ ό a *—H a ό o ^•Η ό ό ό ό a 6 ό 6 ό ό 6 ό 6 交聯劑 (F) 摧 摧 揉 ρί uL Pu Uh U, Ui 璀 摧 捶 摧 璀 uL *·Μ uL 溶劑 (D) PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA j PGMEA 1 PGMEA ! PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA 增感劑 (C) Z έ z 1 Z cs z (N Z (N z (N (Ν ζ ΓΟ z CN Z Z Ζ ζ Z Z (N % 光酸 產生劑 (B) ώ PQ ώ ώ CQ ΓΛ ώ ώ CN PQ rn CQ Tj- ώ »η ώ 1 PQ r«H PQ m CQ ώ CQ ώ f"H CQ ώ ώ ώ CQ v〇 ώ 共聚物 (A) 聚合物Α-1 聚合物A-2 聚合物Α-3 聚合物Α-3 聚合物A-3 聚合物A-3 聚合物A-3 ! 聚合物A-3 聚合物A-3 聚合物A-3 聚合物Α-3 聚合物A-3 聚合物A-3 聚合物A-3 聚合物A-4 聚合物A-5 聚合物Α-6 聚合物A-7 聚合物Α-8 聚合物A-9 聚合物A-3 聚合物A-3 聚合物A-3 實施例1 實施例2 實施例3 實施例4 實施例5 L實施例6 實施例7 實施例8 實施例9 實施例10 1實施例11 實施例12 實施例13 1實施例14 實施例15 實施例16 實施例17 實施例18 實施例19 實施例20 實施例21 實施例22 1實施例23 201140249 担 & 圖案形狀 *—Η •-H *—H *·< CN m 耐溶劑性 <Ν (Ν (N (N CN CN (N CN F-4 (N 寸 fO m 透明性 ψ fS CS (N CN (N CN CN 寸 m m m m — m (Ν 液保存性 (N fN CN fN fN fN (N m (N φ Κ 界面 活性劑 (I) (N 二 CN <N (N fN HH CjJ (Ν (N (N <N (N (N fN 二 (N (Ν (N (N (N (N <N (N (N 二 (N CN <N HH 二 •N m •-H m 握 n η ΰ- 滕 寸 CM v〇 *Λ •H- ππ W Ν 留 ϋ- 賺 <4 盤 VO S (Ν S 〇 CN S i: 恃 ΠΠ 坩 链 Ν 職 00 闺 伽( •Ν ϋ- r>w JMJ v〇 Ό 〇〇 CTN § 1 SM t: 柃 m 鹼性 化雜 (H) H-l/H-2 H-l/H-2 1 H-l/H-2 I | H-l/H-2 | H-l/H-2 I H-l/H-2 | | H-l/H-2 | 1 H-l/H-2 1 | H-l/H-2 | | H-l/H-2 | I H-l/H-2 | I H-l/H-2 | ! H-l/H-2 | | H-l/H-2 I H-l/H-2 1 H-l/H-2 1 I H-l/H-2 | I H-l/H-2 | I H-l/H-2 | H-l/H-2 | H-l/H-2 | ! H-l/H-2 | H-l/H-2 H-l/H-2 | H-l/H-2 | H-l/H-2 改良劑 (G) 0 1 α 6 1 o 1 6 〇 6 L_ G-l 1 »«·< 〇 〇 a 6 0 〇 ♦•H ό ϋ ό 0 ό 1 a 6 〇 ό ό 1 G-l | G-l | 6 交聯劑 (F) 璀 Uh ti uL »-Η Uh Pu ρί r—H Uh Uh ϋπ Mh (Jh m 溶劑 (D) PGMEA PGMEA \ PGMEA | | PGMEA | PGMEA I PGMEA | | PGMEA | 1 PGMEA 1 1 PGMEA | I PGMEA | | PGMEA | I PGMEA | 1 PGMEA | I PGMEA | PGMEA 1 PGMEA | | PGMEA | I PGMEA | 1 PGMEA | PGMEA PGMEA 1 PGMEA | PGMEA | PGMEA | i PGMEA | PGMEA PGMEA 增感劑 (C) N-2 N-l 1 N-2 I 1 N-2 I 1 N-2 I 1 N-2 j 1 N-2 j 1 N-2 1 1 N-2 1 1 N-2 I 1 N-2 j 1 N-2 I 1 N-2 I 1 N-2 1 1 N-2 I 1 N-2 I 1 N-2 1 1 N-2 I 1 N-2 j 1 N-2 I 1 N-2 I 1 N-2 I 1 N-2 I ί N-2 I 1 N-2 1 1 n-2 i 摧 光酸 產生劑 (Β) 1 B-6 1 Β-1 1 B-7 1 B-7 1 B-7 1 B-7 I 1 B-7 I 1 B-7 I 1 B-7 I 1 B-7 I 1 B-7 I 1 b-7 1 1 B-8 I 1 B-8 1 1 B-8 I 1 B-8 I 1 B-8 1 1 b-8 I 1 B-8 I I B-8 I B-8 | B-8 1 B-9 1 B-9 1 ! B-10 | :B-10 | V-H 1 ffl 共聚物 ㈧ < m <n 嵌 聚合物Α-10 1聚合物A-l 1聚合物A-2 | 聚合物A-3 寸 < m <n m 丨聚合物A-5 | < 1 齡 r- < 1 嵌 1聚合物A-8 | 1聚合物A-9 | I聚合物A-10 | 1聚合物A-l | 丨聚合物A-2 | ΓΟ < 1 跋 丨聚合物A_4 | 1聚合物A-5 | < 1 嵌 1聚合物A-7 | 聚合物A-8 聚合物A-9 I聚合物A-10 | 聚合物A-3 1聚合物A-6 I 1聚合物A-3 | 1聚合物A-6 聚合物A-l 留 in (Ν 習 W 1實施例26 | 1實施例27 | 1實施例28 〇\ cs 辑 fc 1實施例30 1 1實施例31 1 1實施例32 1 1實施例33 | 丨實施例34 | 1實施例35 | 1實施例36 | 1實施例37] 丨實施例38 1實施例39 1 1實施例40 | 1實施例41 1 1實施例42 | 1實施例43 丨實施例44 1實施例45 | 1實施例46 Ϊ 握 1實施例48] Os i 闺 in 1比較例2 1 1比較例3 | 1比較例4 •0. 201140249 如表2及表3所示,可知各實施例之感光性樹脂組成 物是在與各比較例之相對比較方面,關於液保存性、透明 性、耐溶劑性、圖案形狀中任一項之評估皆可獲得優異的 結果。 〔實施例5 0〕 在實施例5 0,除了使用實施例1之感光性樹脂組成 物、將基板由玻璃基板(商品名:Corning 1737、厚度爲 0.7 mm、Corning公司製)變更爲6英寸砂晶圓以外,其 餘則以與實施例1之對感光性樹脂組成物所實施的感度及 圖案形狀之評估相同的方式進行評估感度及圖案形狀。 結果展示於表4。 〔實施例5 1〕 在實施例5 1,除了使用實施例1之感光性樹脂組成 物、將曝光機由〇&11〇11(股)製之?1^-5〇1?曝光機(商品 名)變更爲Nikon(股)製之FX- 8 03 M (商品名、gh-Line步 進機)以外,其餘則以與實施例1之對感光性樹脂組成物 所實施的感度及圖案形狀之評估相同的方式進行評估感度 及圖案形狀。 結果展示於表4。 〔實施例52〕 在實施例2 6,除了使用實施例1之感光性樹脂組成 物、將曝光機由匚311〇11(股)製之?1^-501?曝光機(商品 名)變更爲355 nm雷射曝光機而進行355 nm雷射曝光以 外,其餘則以與實施例1之對感光性樹脂組成物所實施的 -123- 201140249 感度及圖案形狀之評估相同的方式進行評估感度及圖案形 狀。 另外,355 nm雷射曝光機是使用V Technology公司 製之「AEGIS」(波長3 5 5 nm、脈衝寬度6 nsec),曝光 量是使用OPHIR公司製造之「PE10B-V2」進行測定》 結果展示於表4。 〔實施例5 3〕 在實施例5 3,除了使用實施例1之感光性樹脂組成 物、將曝光機由Canon公司製造之PLA-501F曝光機(商 品名)變更爲UV-LED光源曝光機以外’其餘則以與實施 例1之對感光性樹脂組成物所實施的感度及圖案形狀之評 估相同的方式進行評估感度及圖案形狀。 結果展示於表4 » 表4 感度 圖案形狀 實施例50 2 1 實施例51 2 1 實施例52 2 1 實施例53 2 1 如表4所示,可知實施例之感光性樹脂組成物是不論 基板、曝光機如何’皆可顯現優異的感度’且所形成的圖 案之形狀也是優異。 〔實施例54〕 以如下所述之方法進行製造使用薄膜電晶體(TFT :(d, 1H ) > 5.6 ( dd, 1H ), 2.4 (s, 3H), 2.2 (ddt, 1 H ), 1.9 (ddt, 1H), 1.4 to l_2 (m, 8H), 〇.8 (t , 3H) o < Synthesis of B-1 〇> In addition to the use of phenylsulfonyl chloride in place of p-8 toluenesulfonyl chloride, the other is synthesized in the same manner as B-8 0 (the aforementioned structure). In addition, 1H-NMR spectrum of B-10 (300 MHz, CDC13): δ = 8.3 ( d, 1 Η ) ' 8.1 ( d, 2 Η ) > 7.9 ( d, 1 Η ), 7.8 (d, -114 - 201140249 1 Η ) , 7.7-7_5 (m, 4H), 7.4 (dd, 1Η), 7.1 (d, 1H) ' 5.6 ( q, 1 H ) , 1. 7 ( d, 3H ). [Comparative Example 2: Example using a 1,2-quinonediazide compound] The photosensitive resin composition of Comparative Example 2 is disclosed in Example 1 of JP-A-5-1 6 5 2 1 4 The composition described. [Comparative Example 3: Example of using a gun salt-based photoacid generator] The photosensitive resin composition of Comparative Example 3 was prepared as described below in Example 1 of JP-A-2004-264623. The composition described. - Preparation of photosensitive resin composition of Comparative Example 3 - In a flask equipped with a cooling tube and a stirrer, 7 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), 200 were charged. Diethylene glycol ethyl methyl ether. Next, 40 parts of 1-(cyclohexyloxy)ethyl methacrylate, 5 parts of styrene, 45 parts of glycidyl methacrylate, and 10 parts of 2-hydroxyethyl methacrylate were charged. After 3 parts of the α-methylstyrene dimer was replaced with nitrogen, stirring was slowly started. The polystyrene-converted weight average molecular weight (Mw) of the copolymer obtained by heating the solution to a temperature of 5 ° C for 5 hours to obtain a polymer-soluble solution containing the copolymer was 11. 000. Further, the solid content of the polymer solution obtained herein was 31.6%. A solution containing the copolymer synthesized as described above, in an amount equivalent to 1 part by weight (solid content) of the copolymer, and 5 parts of 4,7-di-n-butoxy group of trifluoromethane 1-naphthyltetrahydrothiophene oxime, after dissolving 妗glycol methyl ethyl ether so that the solid content concentration is 30%, it is filtered through a membrane filter having a pore diameter of 02 ^ -115 - 201140249 m to obtain a comparative example. A photosensitive resin composition of 3. [Comparative Example 4: Example of using an oxime sulfonate-based photoacid generator] The photosensitive resin composition of Comparative Example 4 is a composition disclosed in Example 8 of JP-A-2009-98616. The various evaluations as described below were carried out on the photosensitive resin compositions of Examples 1 to 49 and Comparative Examples 1 to 4 obtained as described above. <Evaluation of Stability (Liquid Preservation) of Liquid and Liquid; The viscosity (initial viscosity) of the photosensitive resin composition immediately after preparation was measured by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) The viscosity (time-dependent viscosity) of the photosensitive resin composition after storage for one week and two weeks at 30 °C. The evaluation criteria are the relative evaluation of the time-dependent viscosity with respect to the initial viscosity (1%). The change is 1% or more, the change is "3", the viscosity change is less than 1%, and the 5% or more is "2". When the change in viscosity is less than 5%, it is "1". "1" and "2" are the level of no problem in practical applications. The results are shown in Table 2. <Evaluation of Sensitivity> Each of the photosensitive resin compositions was subjected to slit coating on a glass substrate (trade name: Corning 1737, thickness: 7.7 mm, manufactured by Corning), and then subjected to 90 ° on a hot plate. Pre-baking at C / 120 seconds evaporates the solvent to form a photosensitive resin composition layer having a film thickness of 3 · 0 # m. Next, the obtained photosensitive resin composition layer was exposed to a specific mask using a PLA-501F exposure machine (trade name, ultrahigh pressure mercury lamp) manufactured by Can. And 'the photosensitive composition layer after exposure-116-201140249 was developed with an alkali developer (0.4% by mass aqueous solution of tetramethylammonium hydroxide) at 23 ° C / 60 seconds, and then ultrapure water. Wash for 20 seconds. Since these operations can be used, the optimum i-ray exposure (Eopt) of the line width and pitch of 1 0 /Z m is analyzed by 1:1 as the sensitivity. In addition, the evaluation criteria are as follows. "1" and "2" are the standard of no problem in practical applications. The results are shown in Tables 2 and 3. 1: less than 40 mJ/cm2, 2: 40 mJ/cm2 or more and less than 60 mJ/cm2, 3: 60 mJ/cm2 or more and less than 80 mJ/cm2, 4: 80 mJ/cm2 or more. <Evaluation of Transparency> Each of the photosensitive resin compositions was subjected to slit coating on a glass substrate (trade name: Corning No. 7 7 3, thickness: 0.7 mm, manufactured by Corning), and then placed on a hot plate. The solvent was removed by heating at 90 ° C / 120 seconds to form a photosensitive resin composition layer having a film thickness of 3.0 / m. The obtained photosensitive resin composition layer was exposed to a PLA - 5 0 1 F exposure machine (trade name, ultrahigh pressure mercury lamp) manufactured by Canon to make the integrated irradiation amount to 300 mJ/cm 2 (illuminance: 20 mW/ Cm 2 , i-ray), after which the substrate was heated in an oven at 230 ° C for 1 hour to obtain a cured film. The light transmittance of the glass substrate having the cured film is measured by a spectrophotometer "150-20 type Double Beam (trade name, manufactured by Hitachi, Ltd.)" at a wavelength in the range of 400 to 8 〇〇 nm. . The lowest light transmittance at this time was evaluated as transparency -117-201140249 is shown in Tables 2 and 3. In addition, the evaluation criteria are as follows: β “1” and “2” are levels that are not problematic in practical applications. 1 : 9 2 % or more, 2 : 9 0 % or more and less than 9 2 % ' 3 : 8 8 % or more and less than 90 %, 4 : less than 8 8 % » <Evaluation of solvent resistance> A cured film was formed on a glass substrate (trade name: Corning 1737, thickness: 0.7 mm, manufactured by Corning) in the same manner as in the evaluation of transparency. The film thickness (T 1 ) of the obtained cured film was measured. Further, after the substrate on which the cured film was formed was immersed in dimethyl sulfoxide at a temperature of 7 ° C for 20 minutes, the film thickness (t1 ) of the cured film after immersion was measured, and it was calculated that the immersion was caused. The film thickness change rate { | t^T1 | /T1} X 100 (%). The results are shown in Tables 2 and 3. When the film thickness change rate is less than 3% (i.e., when the results of the reference 1 to 3 are obtained), it can be considered that the solvent resistance of the cured film is good. 1 : less than 1%, 2: 1% or more and less than 2%, 3: 2% or more, less than 3%, and 4: 3% or more. <Evaluation of Pattern Shape> On a glass substrate (trade name: Corning 1737, thickness: 7.7 mm -118-201140249, manufactured by Corning), each photosensitive resin composition was subjected to slit coating, and then on a hot plate. The solvent was removed at 901/120 seconds to form a photosensitive resin composition layer having a film thickness of 3.0 jtz m. Next, the obtained photosensitive resin composition layer 'developed with 4% of a gas oxidized tetramethylammonium aqueous solution as a developing solution' at 23 ° C for 60 seconds, to obtain 1 〇 ^ m square The exposure amount of the contact hole pattern (illuminance: 20 mW/cm2, i-ray) was exposed by a mask having a pattern opening of a l〇ym square. The exposed substrate was subjected to paddle development at 23 ° C for 60 seconds using a 4% aqueous solution of tetramethylammonium hydroxide as a developing solution. The patterned photosensitive resin composition layer was used. Exposure was performed with a PLA-500F exposure machine (trade name, ultra-high pressure mercury lamp) manufactured by Canon Inc., so that the integrated irradiation amount was 300 mJ/cm2 (illuminance: 20 mW/cm2, i-ray), and thereafter, The substrate was heated in an oven at 230 ° C for 1 hour to obtain a cured film. A glass substrate with a cured film obtained by cutting, and a cross-sectional shape of the patterned contact hole is a Field Emission Scanning Electron Microscope S - 4 800 (trade name, Η IT AC Η I) Company system) to observe and evaluate. The evaluation criteria are as follows. The results are shown in Tables 2 and 3. When the taper angle of the contact hole obtained is less than 50 degrees (i.e., when the result of the reference 1 is obtained), the pattern shape is judged to be good. 1: The taper angle is in the range of 10 or more and less than 50 degrees (positive • 119-201140249 to the taper type), 2: the taper angle is in the range of 50 or more and less than 90 degrees (rectangular), 3: taper The angle is in the range of 90 degrees or more (reverse cone type). -120- 201140249 (N« Evaluation pattern shape - *•4 - ν·»^ ^―· , 丨 - 十一 - Solvent resistance ΓΛ fN ΓΛ (Ν (Ν CN Transparency (N rs rH F· ^ <N (Ν rH m舞(N CN(Ν(N fN (N (N <N CN(N CN CN(Ν CN ••Η r*"H liquid preservation fN rH <N (Ν Ψ-^ Other Ingredients 1 HH Di 2rH 2 1 Λ CN 2 Λ 2 Η 2 Basic Compound (H) Adhesion Improver (G) 〇〇6 ό ώ ό a *—H a ό o ^• GM ό ό ό ό a 6 ό 6 ό ό 6 ό 6 Crosslinking agent (F) Destroy 揉ρί uL Pu Uh U, Ui 璀 捶 捶 璀 uL *·Μ uL Solvent (D) PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA j PGMEA 1 PGMEA ! PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA Sensitizer (C) Z έ z 1 Z cs z (NZ (N ( (N ζ ΓΟ z CN ZZ Ζ ζ ZZ (N % photoacid generator (B) ώ PQ ώ ώ CQ ΓΛ ώ ώ CN PQ rn CQ Tj- ώ »η ώ 1 PQ r«H PQ m CQ ώ CQ ώ f"H CQ ώ ώ ώ CQ v〇ώ Copolymer (A) Polymer Α-1 Polymer A-2 Polymer Α-3 Polymer Α-3 Polymer A-3 Polymer A-3 Polymer A-3 ! Polymer A-3 Polymer A-3 Polymer A-3 Polymer Α-3 Polymer A-3 Polymer A-3 Polymer A-3 Polymer A-4 Polymer A- 5 Polymer Α-6 Polymer A-7 Polymer Α-8 Polymer A-9 Polymer A-3 Polymer A-3 Polymer A-3 Example 1 Example 2 Example 3 Example 4 Example 5 L Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 1 Embodiment 11 Embodiment 12 Embodiment 13 1 Embodiment 14 Example 15 Example 16 Example 17 Example 18 Example 19 Implementation Example 21 Example 22 1 Example 23 201140249 Load & pattern shape * - Η • -H * - H * · < CN m Solvent resistance < Ν (Ν (N (N CN CN (N CN F-4) (N inch fO m transparency ψ fS CS (N CN (N CN CN inchmmmm — m (Ν f liquid preservation (N fN CN fN fN fN (N m (N φ Κ surfactant (I) ( N 二CN <N (N fN HH CjJ (Ν (N (N &N; N (N (N (N (N (N (N (N (N (N (N (N (N (N (N (N (N (N (N (N (N ;N HH 二•N m •-H m grip n η ΰ- Teng inch CM v〇*Λ •H- ππ W Ν ϋ ϋ - earn <4 VO S (Ν S 〇CN S i: 恃ΠΠ 坩Chain Ν 00 闺 ( ( •Ν r- r>w JMJ v〇Ό 〇〇CTN § 1 SM t: 柃m Alkaline (H) Hl/H-2 Hl/H-2 1 Hl/H- 2 I | Hl/H-2 | Hl/H-2 I Hl/H-2 | | Hl/H-2 | 1 Hl/H-2 1 | Hl/H-2 | | Hl/H-2 | Hl/H-2 | I Hl/H-2 | ! Hl/H-2 | | Hl/H-2 I Hl/H-2 1 Hl/H-2 1 I Hl/H-2 | I Hl/H -2 | I Hl/H-2 | Hl/H-2 | Hl/H-2 | ! Hl/H-2 | Hl/H-2 Hl/H-2 | Hl/H-2 | Hl/H- 2 Modifier (G) 0 1 α 6 1 o 1 6 〇6 L_ Gl 1 »«·< 〇〇a 6 0 〇♦•H ό ϋ ό 0 ό 1 a 6 〇ό ό 1 Gl | Gl | 6 Crosslinking agent (F) 璀Uh ti uL »-Η Uh Pu ρί r—H Uh Uh ϋπ Mh (Jh m solvent (D) PGMEA PGMEA \ PGMEA | | PGMEA | PGMEA I PGMEA | | PGMEA | 1 PGMEA 1 1 PGMEA I PGMEA | | PGMEA | I PGMEA | 1 PGMEA | I PGMEA | PGMEA 1 PGMEA | | PGMEA | IP GMEA | 1 PGMEA | PGMEA PGMEA 1 PGMEA | PGMEA | PGMEA | i PGMEA | PGMEA PGMEA Sensitizer (C) N-2 Nl 1 N-2 I 1 N-2 I 1 N-2 I 1 N-2 j 1 N-2 j 1 N-2 1 1 N-2 1 1 N-2 I 1 N-2 j 1 N-2 I 1 N-2 I 1 N-2 1 1 N-2 I 1 N-2 I 1 N-2 1 1 N-2 I 1 N-2 j 1 N-2 I 1 N-2 I 1 N-2 I 1 N-2 I ί N-2 I 1 N-2 1 1 n-2 i Destroy Photoacid generator (Β) 1 B-6 1 Β-1 1 B-7 1 B-7 1 B-7 1 B-7 I 1 B-7 I 1 B-7 I 1 B-7 I 1 B- 7 I 1 B-7 I 1 b-7 1 1 B-8 I 1 B-8 1 1 B-8 I 1 B-8 I 1 B-8 1 1 b-8 I 1 B-8 II B-8 I B-8 | B-8 1 B-9 1 B-9 1 ! B-10 | :B-10 | VH 1 ffl Copolymer (8) < m <n Inlay Polymer Α-10 1 Polymer Al 1 Polymer A-2 | Polymer A-3 inch < m < nm 丨 Polymer A-5 | < 1 Age r- < 1 Inlay 1 Polymer A-8 | 1 Polymer A-9 | I Polymer A-10 | 1 polymer Al | 丨 polymer A-2 | ΓΟ < 1 跋丨 polymer A_4 | 1 polymer A-5 | < 1 embedded 1 polymer A-7 | 8 Polymer A-9 I Polymer A-10 | Polymer A-3 1 Polymer A-6 I 1 Polymer A-3 | 1 Polymer A-6 Polymer Al Retained in (Ν W 1 Example 26 | 1 Example 27 | 1 Example 28 〇\cs series fc 1 embodiment 30 1 1 embodiment 31 1 1 embodiment 32 1 1 embodiment 33 | 丨 embodiment 34 | 1 embodiment 35 | 1 embodiment 36 | 1 embodiment 37] Example 38 1 Example 39 1 1 Example 40 | 1 Example 41 1 1 Example 42 | 1 Example 43 丨 Example 44 1 Example 45 | 1 Example 46 Ϊ Grip 1 Example 48] Os i 闺in 1 Comparative Example 2 1 1 Comparative Example 3 | 1 Comparative Example 4 • 0. 201140249 As shown in Table 2 and Table 3, it is understood that the photosensitive resin composition of each example is in comparison with each comparative example, Excellent results were obtained in any of the evaluations of storage stability, transparency, solvent resistance, and pattern shape. [Example 50] In Example 50, except that the photosensitive resin composition of Example 1 was used, the substrate was changed from a glass substrate (trade name: Corning 1737, thickness: 0.7 mm, manufactured by Corning) to 6 inch sand. Other than the wafer, the sensitivity and the pattern shape were evaluated in the same manner as the evaluation of the sensitivity and the pattern shape of the photosensitive resin composition of Example 1. The results are shown in Table 4. [Example 5 1] In Example 5, except that the photosensitive resin composition of Example 1 was used, and the exposure machine was made of 〇&11〇11 (share)? 1^-5〇1? The exposure machine (trade name) was changed to FX- 8 03 M (trade name, gh-Line stepper) manufactured by Nikon Co., Ltd., and the other was compared with the photosensitive property of Example 1. The sensitivity and pattern shape were evaluated in the same manner as the evaluation of the sensitivity and pattern shape performed by the resin composition. The results are shown in Table 4. [Example 52] In Example 2 6, except that the photosensitive resin composition of Example 1 was used, and the exposure machine was made of 匚311〇11 (share)? The 1^-501? exposure machine (trade name) was changed to a 355 nm laser exposure machine for 355 nm laser exposure, and the rest was performed with the -123-201140249 sensitivity of the photosensitive resin composition of Example 1. The sensitivity and pattern shape are evaluated in the same manner as the evaluation of the pattern shape. In addition, the 355 nm laser exposure machine uses "AEGIS" (wavelength 355 nm, pulse width 6 nsec) manufactured by V Technology, and the exposure is measured using "PE10B-V2" manufactured by OPHIR. Table 4. [Example 5 3] In Example 5, except that the photosensitive resin composition of Example 1 was used, and the exposure machine was changed from a PLA-501F exposure machine (trade name) manufactured by Canon Inc. to a UV-LED light source exposure machine. The rest were evaluated for sensitivity and pattern shape in the same manner as the evaluation of the sensitivity and pattern shape of the photosensitive resin composition of Example 1. The results are shown in Table 4 » Table 4 Sensitivity pattern shape Example 50 2 1 Example 51 2 1 Example 52 2 1 Example 53 2 1 As shown in Table 4, it is understood that the photosensitive resin composition of the example is a substrate, The exposure machine can 'appear excellent sensitivity' and the shape of the formed pattern is also excellent. [Example 54] Fabrication was carried out by the method described below using a thin film transistor (TFT:
Thin Film Transistor)之有機EL顯不裝置(參閱第1圖 -124- 201140249 在玻璃基板6上形成下閘極型之TFT 1,並以覆蓋該 T F T 1之狀態而形成由S i 3 N 4所構成之絕緣膜3。其次’ 在該絕緣膜3形成接觸孔(在此,省略圖示)後,將通過 該接觸孔而連接至TFT 1的配線2(高度1.0/zm)形成於 絕緣膜3上。配線2是用於連接TFT 1之間、或在後續步 驟所形成的有機EL元件與TFT 1者。 並且,爲將由於形成配線2所引起之凹凸加以平坦化 ,則以塡埋由於配線2所引起之凹凸的狀態在絕緣膜3上 形成平坦化膜4。對於絕緣膜3上之平坦化膜4之形成過 程如下:將實施例4之感光性樹脂組成物旋轉塗布於基板 上,在熱板上加以預烘烤(90 °C x2分鐘)後’由遮罩上 使用高壓水銀燈將i -射線(3 6 5 n m )照射4 5 m J / c m 2 (照 度2 0 m W / c m2 )後,以鹼水溶液進行顯影而形成圖案,並 在230 °C實施60分鐘之加熱處理。 塗布該感光性樹脂組成物時之塗布性是良好’在經曝 光、顯影、燒成後所獲得硬化膜並未觀察到摺痕(crease) 或龜裂(crack)的發生。另外,配線2之平均高度差異爲 5 00 nm、所製造之平坦化膜4之膜厚爲2000 nm。 其次,在所獲得平坦化膜4上,形成底部發光型之有 機EL元件。首先,在平坦化膜4上形成通過接觸孔7而 連接於配線2之由IT Ο所構成之第一電極5。其後,塗布 光阻,加以預烘烤,通過吾所欲圖案之遮罩而加以曝光’ 並加以顯影。將此光阻圖案作爲遮罩而以使用ITO蝕刻劑 之濕式蝕刻來實施圖案加工。其後,使用光阻剝離液( -125- 201140249 REMOVER 1〇〇、AZ Electronics Materials 公司製)在 50 °C剝離該光阻圖案。經如上述所獲得第一電極5是相當於 有機EL元件之陽極。 其次,形成覆蓋第一電極5的周緣之形狀的絕緣膜8 。絕緣膜8是使用實施例7之感光性樹脂組成物,且以與 前述相同的方法形成。 並且,在真空蒸鍍裝置內通過吾所欲的圖案遮罩,依 序蒸鍍而設置電洞傳輸層、有機發光層、電子傳輸層。接 著,在基板上方全面形成由 A1 (鋁)所構成之第二電極 。由蒸鍍機取出所獲得上述基板,使用封止用玻璃板與紫 外線硬化型環氧樹脂來貼合而加以封止。 經如上所述而獲得經在各有機EL元件連接用於驅動 其TFT 1所成的主動矩陣型之有機EL顯示裝置。經通過 驅動電路而外加電壓結果,得知其係可顯現良好的顯示特 性,且爲可靠性高之有機EL顯示裝置。 〔實施例5 5〕 在專利第3 3 2 1 0 0 3號公報中之第1圖所揭述之主動 矩陣型液晶顯示裝置中,以如下所述方法形成硬化膜 1 7作爲層間絕緣膜,以獲得實施例5 5之液晶顯示裝置 〇 亦即’使用實施例7之感光性樹脂組成物,以與在上 述實施例54之有機EL顯示裝置之平坦化膜4之形成方法 相同的方法,形成硬化膜1 7作爲層間絕緣膜。 對所獲得液晶顯示裝置,外加驅動電壓結果,得知其 -126- 201140249 係可顯現良好的顯示特性’且爲可靠性高之液晶顯示裝置 〇 【圖式簡單說明】 第1圖是展不將使用本發明之感光性樹脂組成物的硬 化膜作爲絕緣膜、平坦化膜而適用的有機EL顯示裝置之 一實例構成槪念圖。 第2圖是展示經適用使用本發明之感光性樹脂組成物 的硬化膜之液晶顯示裝置之一實例構成槪念圖。 【主要元件符號說明】 1 TFT 2 配線 3 絕緣膜 4 平坦化膜 5 第一電極 6 玻璃基板 7 接觸孔 _ 8 絕緣膜 10 液晶顯示裝置 12 背光單元 14 玻璃基板 15 玻璃基板 16 TFT 17 硬化膜 18 接觸孔 -127- 201140249 19 I Τ Ο透明電極 2 0 液晶 22 RGB彩色濾光片 -128Organic EL display device of Thin Film Transistor (refer to FIG. 1 - 124 - 201140249, a lower gate type TFT 1 is formed on the glass substrate 6, and is formed by S i 3 N 4 in a state of covering the TFT 1 The insulating film 3 is formed. Next, after the contact hole (here, not shown) is formed in the insulating film 3, the wiring 2 (height 1.0/zm) connected to the TFT 1 through the contact hole is formed in the insulating film 3. The wiring 2 is used to connect the organic EL element and the TFT 1 formed between the TFTs 1 or in the subsequent step. Further, in order to planarize the unevenness due to the formation of the wiring 2, the wiring is buried. The flattening film 4 is formed on the insulating film 3 in the state of the unevenness caused by 2. The formation process of the planarizing film 4 on the insulating film 3 is as follows: the photosensitive resin composition of Example 4 is spin-coated on the substrate, After pre-baking on the hot plate (90 °C x 2 minutes), the i-ray (3 6 5 nm ) is irradiated with 4 5 m J / cm 2 by a high-pressure mercury lamp on the mask (illuminance 2 0 m W / c m2) After that, development is carried out with an aqueous alkali solution to form a pattern, and heating is performed at 230 ° C for 60 minutes. The coating property when the photosensitive resin composition was applied was good. 'The crease or crack was not observed in the cured film obtained after exposure, development, and firing. The average height difference of 2 is 500 nm, and the film thickness of the produced planarizing film 4 is 2000 nm. Next, on the obtained planarizing film 4, a bottom emission type organic EL element is formed. First, in a planarizing film 4, a first electrode 5 made of IT 连接 connected to the wiring 2 through the contact hole 7 is formed. Thereafter, a photoresist is applied, pre-baked, exposed by a mask of a desired pattern, and exposed The patterning was carried out by wet etching using an ITO etchant using this photoresist pattern as a mask. Thereafter, a photoresist stripping solution (-125-201140249 REMOVER 1®, manufactured by AZ Electronics Materials Co., Ltd.) was used. The photoresist pattern is peeled off at 50 ° C. The first electrode 5 obtained as described above is an anode corresponding to the organic EL element. Next, an insulating film 8 covering the periphery of the first electrode 5 is formed. The insulating film 8 is used. Example 7 The resin composition is formed in the same manner as described above. Further, a hole transport layer, an organic light-emitting layer, and an electron transport layer are provided in a vacuum vapor deposition apparatus by a desired pattern mask, followed by vapor deposition. A second electrode made of A1 (aluminum) was formed on the entire surface of the substrate. The substrate obtained by taking out the substrate by a vapor deposition machine was bonded and sealed with an ultraviolet curable epoxy resin using a sealing glass plate. An active matrix type organic EL display device in which the organic EL elements are connected to drive the TFTs 1 is obtained as described above. When a voltage is applied through the driving circuit, it is found that it exhibits good display characteristics and is an organic EL display device with high reliability. [Embodiment 5 5] In the active matrix type liquid crystal display device disclosed in Fig. 1 of the Japanese Patent Publication No. 3 3 203, the cured film 17 is formed as an interlayer insulating film by the following method. The liquid crystal display device of Example 5 was obtained, that is, the photosensitive resin composition of Example 7 was used in the same manner as the method of forming the planarizing film 4 of the organic EL display device of Example 54 described above. The cured film 17 is used as an interlayer insulating film. As a result of the application of the driving voltage to the obtained liquid crystal display device, it is known that the -126-201140249 system can exhibit good display characteristics' and is a highly reliable liquid crystal display device. [Simple description of the drawing] Fig. 1 is an exhibition An example of an organic EL display device to which the cured film of the photosensitive resin composition of the present invention is applied as an insulating film or a planarizing film is a schematic view. Fig. 2 is a view showing an example of a liquid crystal display device to which a cured film of the photosensitive resin composition of the present invention is applied. [Main component symbol description] 1 TFT 2 wiring 3 Insulating film 4 Planing film 5 First electrode 6 Glass substrate 7 Contact hole _ 8 Insulating film 10 Liquid crystal display device 12 Backlight unit 14 Glass substrate 15 Glass substrate 16 TFT 17 Cured film 18 Contact hole-127- 201140249 19 I Τ Ο transparent electrode 2 0 liquid crystal 22 RGB color filter -128
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TWI588601B (en) * | 2012-07-30 | 2017-06-21 | 富士軟片股份有限公司 | Photosensitive resin composition, method for manufacturing cured film, cured film, organic el display device and liquid crystal display device |
CN104508554B (en) * | 2012-07-30 | 2018-08-24 | 富士胶片株式会社 | Photosensitive polymer combination, cured film and its manufacturing method, organic EL display device, liquid crystal display device and compound |
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