TWI502277B - 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 PDF

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TWI502277B
TWI502277B TW100101342A TW100101342A TWI502277B TW I502277 B TWI502277 B TW I502277B TW 100101342 A TW100101342 A TW 100101342A TW 100101342 A TW100101342 A TW 100101342A TW I502277 B TWI502277 B TW I502277B
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photosensitive resin
resin composition
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methyl
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TW201140232A (en
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Koichi Sugihara
Satoru Yamada
Kyouhei Sakita
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Fujifilm Corp
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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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—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
    • 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • 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
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/124—Insulating layers formed between TFT elements and OLED elements

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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  • Nanotechnology (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Crystal (AREA)

Description

感光性樹脂組成物、硬化膜之形成方法、硬化膜、有機EL顯示裝置及液晶顯示裝置Photosensitive resin composition, method for forming cured film, cured film, organic EL display device, and liquid crystal display device

本發明是關於一種感光性樹脂組成物、硬化膜之形成方法、硬化膜、有機EL(電激發光)顯示裝置及液晶顯示裝置。The present invention relates to a photosensitive resin composition, a method for forming a cured film, a cured film, an organic EL (electroluminescence) display device, and a liquid crystal display device.

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)。為形成該層間絕緣膜，感光性樹脂組成物是由於為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。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.

對於在上述顯示裝置之層間絕緣膜，除了如絕緣性、耐溶劑性、耐熱性、及氧化銦錫(ITO)濺鍍適性優異的硬化膜之物性以外，也期望高的透明性。因此，正在試圖以透明性優異的丙烯酸酯系樹脂作為膜形成成分而使用。In the interlayer insulating film of the display device described above, in addition to the physical properties of the cured film excellent in insulating properties, solvent resistance, heat resistance, and indium tin oxide (ITO) sputtering suitability, high transparency is also desired. Therefore, an acrylate resin having excellent transparency has been attempted as a film forming component.

在另一方面，已在使用將具有約3μm至100μm之透鏡徑的微透鏡、或將此等之微透鏡有規律地加以排列的微透鏡陣列作為傳真機、電子複印機、固態攝像元件等之晶載彩色濾光片(on-chip color filter)的成像光學系或光纖連結器之光學材料。On the other hand, a microlens having a lens diameter of about 3 μm to 100 μm or a microlens array in which the microlenses are regularly arranged has been used as a crystal of a facsimile machine, an electronic copying machine, a solid-state image pickup element, or the like. An optical material of an imaging optical system or an optical fiber connector that carries an on-chip color filter.

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，實施加熱處理以使其熔融流動而仍以其狀態直接利用作為透鏡之方法、或將經加以熔融流動的透鏡圖案作為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。關於形成前述透鏡圖案，已廣泛使用感放射線性樹脂組成物。In the formation of a microlens or a microlens array, it is known that after forming a photoresist pattern corresponding to a lens, heat treatment is performed to melt the flow, and the film is directly used as a lens in its state, or is melted and flowed. A method in which a lens pattern is dry-etched as a mask to transfer a lens shape to a substrate or the like. Regarding the formation of the aforementioned lens pattern, a radiation sensitive resin composition has been widely used.

如此之感光性樹脂組成物，例如在日本特開平5-165214號公報中，提案一種感光性樹脂組成物，其係具有：(A)作為(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)其他自由基聚合性化合物之共聚物之可溶於鹼水溶液的樹脂、以及(B)感放射線性酸形成化合物。In the photosensitive resin composition, for example, Japanese Laid-Open Patent Publication No. Hei 5-165214 proposes a photosensitive resin composition having (A) as (a) an unsaturated carboxylic acid or an unsaturated carboxylic anhydride; b) a radically polymerizable compound having an epoxy group, and (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.

此外，在日本特開2004-264623號公報中，提案一種感放射線性樹脂組成物，其係包含：(A)具有縮醛結構及/或縮酮結構、及環氧結構，以凝膠透層析法所測定之經聚苯乙烯換算得之重量平均分子量為2000以上之高分子量體、以及(B)由於照射放射線而產生pKa為4.0以下的酸之化合物。In addition, Japanese Laid-Open Patent Publication No. 2004-264623 proposes a radiation sensitive resin composition comprising: (A) having an acetal structure and/or a ketal structure, and an epoxy structure, and a gel permeation layer. A high molecular weight body having a weight average molecular weight of 2,000 or more obtained by polystyrene measurement, and (B) a compound having an acid having a pKa of 4.0 or less due to irradiation with radiation.

此外，在日本特開2009-98616號公報中，揭述一種正型感光性樹脂組成物，其係至少含有：(A)含有具有含酸解離性基(acid-dissociable group)的特定結構之結構單元，與具有可與羧基反應而形成共價鍵的官能基之結構單元，為鹼不溶性或鹼難溶性，且該酸解離性基解離時則成為鹼可溶性之樹脂、以及(B)由於照射活性光線(active light rays)或放射線而產生酸之化合物。In addition, Japanese Laid-Open Patent Publication No. 2009-98616 discloses a positive photosensitive resin composition containing at least: (A) a structure containing a specific structure having an acid-dissociable group. a unit having a functional group having a functional group capable of reacting with a carboxyl group to form a covalent bond, which is alkali-insoluble or alkali-insoluble, and which is an alkali-soluble resin when the acid-dissociable group dissociates, and (B) an irradiation activity A compound that produces acid by active light rays or radiation.

在前述日本特開平5-165214號公報所揭述之感光性樹脂組成物，感度及經時安定性是並不足夠，此外，由該感光性樹脂組成物所獲得之硬化膜是有由於烘烤而導致著色為大的問題。The photosensitive resin composition disclosed in Japanese Laid-Open Patent Publication No. H5-165214 is not sufficient in sensitivity and stability over time, and the cured film obtained from the photosensitive resin composition is baked. The problem that causes the coloring to be large.

此外，關於在前述日本特開2004-264623號公報及特開2009-98616號公報所揭述之感光性樹脂組成物也是並未獲得足夠的感度。In addition, a sufficient sensitivity is not obtained in the photosensitive resin composition disclosed in Japanese Laid-Open Patent Publication No. 2004-264623 and No. 2009-98616.

本發明之問題是提供一種感光性樹脂組成物，其係可獲得硬化後之透射率高，且即使加熱，透射率之降低也為小的硬化膜，且即使在曝光後未實施加熱(PEB：Post Exposure Baking)時，也具有非常高的感度。The problem of the present invention is to provide a photosensitive resin composition which is capable of obtaining a cured film having high transmittance after hardening and which is low in transmittance even if heated, and which is not heated even after exposure (PEB: Post Exposure Baking) also has a very high sensitivity.

此外，本發明之另一問題是提供一種使用本發明之感光性樹脂組成物之硬化膜及其製造方法、具備該硬化膜之有機EL顯示裝置及液晶顯示裝置。Further, another problem of the present invention is to provide a cured film using the photosensitive resin composition of the present invention, a method for producing the same, an organic EL display device including the cured film, and a liquid crystal display device.

本發明之模式如下所述。The mode of the present invention is as follows.

＜1＞一種感光性樹脂組成物，其係包含：(A)縮醛系樹脂、(B)光酸產生劑(photo-acid generator)、及(C)溶劑，該(A)縮醛系樹脂是含有具有由於酸而形成羧基的結構之結構單元(a1)、具有羧基或酚性羥基之結構單元(a2)、具有環氧基或氧雜環丁烷基(oxetanyl group)之結構單元(a3)、及具有羥基或伸烷氧基之結構單元(a4)，且具有縮醛結構或縮酮結構之聚合物，在該(A)縮醛系樹脂之結構單元(a1)至(a4)的含率，以莫耳換算計相對於(A)縮醛系樹脂為1時，則結構單元(a1)：結構單元(a2)：結構單元(a3)：結構單元(a4)=(0.2至0.65)：(0.02至0.2)：(0.2至0.6)：(0.005至0.3)，且在該(A)縮醛系樹脂之結構單元(a4)的含量，以質量基準計，則為在3至30質量%之範圍。<1> A photosensitive resin composition comprising: (A) an acetal resin, (B) a photo-acid generator, and (C) a solvent, (A) an acetal resin Is a structural unit (a1) having a structure in which a carboxyl group is formed by an acid, a structural unit (a2) having a carboxyl group or a phenolic hydroxyl group, or a structural unit having an epoxy group or an oxetanyl group (a3) And a polymer having a hydroxyl group or an alkoxy group (a4) and having an acetal structure or a ketal structure, and the structural units (a1) to (a4) of the (A) acetal resin When the content is 1 in terms of molar ratio with respect to (A) acetal resin, the structural unit (a1): structural unit (a2): structural unit (a3): structural unit (a4) = (0.2 to 0.65) : (0.02 to 0.2): (0.2 to 0.6): (0.005 to 0.3), and the content of the structural unit (a4) of the (A) acetal resin, on the mass basis, is from 3 to 30 The range of mass %.

＜2＞如第＜1＞項之感光性樹脂組成物，其中更進一步含有(M)顯影促進劑(development accelerator)，該(M)顯影促進劑是在分子內具有選自羧基、酚性羥基、及伸烷氧基中至少一種結構，且分子量為在100至2000之範圍的化合物。<2> The photosensitive resin composition of the item <1>, which further contains (M) a development accelerator which has a carboxyl group and a phenolic hydroxyl group in the molecule. And at least one structure having an alkoxy group and having a molecular weight in the range of from 100 to 2,000.

＜3＞如第＜1＞或＜2＞項之感光性樹脂組成物，其中更進一步含有(E)交聯劑。<3> The photosensitive resin composition of the item <1> or <2> which further contains (E) a crosslinking agent.

＜4＞如第＜1＞至＜3＞項中任一項之感光性樹脂組成物，其中該(B)光酸產生劑是肟磺酸酯化合物(oxime sulfonate compound)。The photosensitive resin composition according to any one of <1> to <3> wherein the (B) photoacid generator is an oxime sulfonate compound.

＜5＞如第＜1＞至＜4＞項中任一項之感光性樹脂組成物，其中該(B)光酸產生劑是選自以下述通式(OS-3)、通式(OS-4)、及通式(OS-5)所代表之化合物中至少一種之化合物：The photosensitive resin composition according to any one of <1> to <4> wherein the (B) photoacid generator is selected from the group consisting of the following general formula (OS-3), general formula (OS) -4), and a compound of at least one of the compounds represented by the formula (OS-5):

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、烷基氧基、磺酸基、胺基磺醯基、或烷氧基磺醯基，X是代表O或S，n是代表1或2，m是代表0至6之整數。In the formula (OS-3) to the formula (OS-5), R 1 represents an alkyl group, an aryl group or a heteroaryl group, and a plurality of R 2 may independently represent a hydrogen atom, an alkyl group, An aryl group or a halogen atom, which may be present in a plurality of R 6 each independently representing a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, X is Represents O or S, n represents 1 or 2, and m is an integer representing 0 to 6.

＜6＞如第＜1＞至＜5＞項中任一項之感光性樹脂組成物，其中更進一步含有(N)增感劑。The photosensitive resin composition of any one of <1> to <5> which further contains (N) sensitizer.

＜7＞如第＜1＞至＜6＞項中任一項之感光性樹脂組成物，其中在該(A)縮醛系樹脂之結構單元(a3)是源於丙烯酸(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)甲酯中任一者之結構單元。The photosensitive resin composition of any one of <1> to <6>, wherein the structural unit (a3) of the (A) acetal-based resin is derived from acrylic acid (3-ethyloxy) A structural unit of any one of a heterocyclic butane-3-yl)methyl ester and a (3-ethyloxetan-3-yl)methyl methacrylate.

＜8＞如第＜1＞至＜7＞項中任一項之感光性樹脂組成物，其中更進一步含有(F)密著改良劑。The photosensitive resin composition of any one of <1> to <7> which further contains (F) a adhesion improving agent.

＜9＞如第＜1＞至＜8＞項中任一項之感光性樹脂組成物，其中更進一步含有(G)鹼性化合物。The photosensitive resin composition of any one of <1> to <8> which further contains (G) a basic compound.

＜10＞如第＜1＞至＜9＞項中任一項之感光性樹脂組成物，其中更進一步含有氟系界面活性劑或矽系界面活性劑。The photosensitive resin composition of any one of <1> to <9> which further contains a fluorine-type surfactant or a quinone type surfactant.

另外，由於本發明之感光性樹脂組成物是製成為上述構成，硬化感度高、即使對曝光後之硬化膜未實施加熱處理也可形成良好形狀之圖案。更進一步使用此來形成微透鏡時，則也具有可形成具有高透射率之微透鏡的優點。In addition, the photosensitive resin composition of the present invention has the above-described configuration, and has a high degree of hardening sensitivity, and can form a pattern having a good shape even if the cured film after exposure is not subjected to heat treatment. Further, when this is used to form a microlens, there is an advantage that a microlens having high transmittance can be formed.

＜11＞一種硬化膜之形成方法，其包括下列步驟：<11> A method of forming a cured film, comprising the steps of:

(1)將如第＜1＞至＜10＞項中任一項之感光性樹脂組成物塗布於基板上；(1) The photosensitive resin composition according to any one of <1> to <10> is applied onto a substrate;

(2)從所塗布的感光性樹脂組成物移除溶劑；(2) removing the solvent from the applied photosensitive resin composition;

(3)將所塗布的感光性樹脂組成物以活性光線加以曝光；(3) exposing the applied photosensitive resin composition to active light;

(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(4) developing the exposed photosensitive resin composition with an aqueous developing solution;

(5)將經顯影的感光性樹脂組成物加以熱硬化。(5) The developed photosensitive resin composition is thermally cured.

＜12＞一種硬化膜，其係以如第＜11＞項之方法所形成。<12> A cured film formed by the method of the item <11>.

＜13＞如第＜12＞項之硬化膜，其係層間絕緣膜。<13> A cured film according to item <12>, which is an interlayer insulating film.

＜14＞一種有機EL顯示裝置，其係具備如第＜12＞或＜13＞項之硬化膜。<14> An organic EL display device comprising the cured film according to item <12> or <13>.

＜15＞一種液晶顯示裝置，其係具備如第＜12＞或＜13＞項之硬化膜。<15> A liquid crystal display device comprising the cured film according to item <12> or <13>.

如根據本發明之一模式，則可提供一種感光性樹脂組成物，其係可獲得硬化後之透射率高，且即使加熱，透射率之降低也為小的硬化膜，且即使在曝光後未實施加熱(PEB)時，也具有非常高的感度。According to one mode of the present invention, it is possible to provide a photosensitive resin composition which is capable of obtaining a high transmittance after hardening, and which has a small decrease in transmittance even if heated, and even after exposure When heating (PEB) is applied, it also has a very high sensitivity.

此外，如根據本發明之另一模式，則可提供一種使用上述感光性樹脂組成物之硬化膜及其製造方法、具備該硬化膜之有機EL顯示裝置及液晶顯示裝置。Further, according to another mode of the present invention, a cured film using the photosensitive resin composition, a method for producing the same, an organic EL display device including the cured film, and a liquid crystal display device can be provided.

[本發明之最佳實施方式][Best Embodiment of the Invention] [感光性樹脂組成物][Photosensitive Resin Composition]

在下文中，就本發明之感光性樹脂組成物詳細地加以說明。Hereinafter, the photosensitive resin composition of the present invention will be described in detail.

本發明之感光性樹脂組成物是包含：(A)縮醛系樹脂、(B)光酸產生劑、及(C)溶劑，且該(A)縮醛系樹脂是含有具有由於酸而形成羧基的結構之結構單元(a1)、具有羧基或酚性羥基之結構單元(a2)、具有環氧基或氧雜環丁烷基之結構單元(a3)、及具有羥基或伸烷氧基之結構單元(a4)，且具有縮醛結構或縮酮結構之聚合物，在該(A)縮醛系樹脂之結構單元(a1)至(a4)的含率，以莫耳換算計相對於(A)縮醛系樹脂為1時，則結構單元(a1)：結構單元(a2)：結構單元(a3)：結構單元(a4)=(0.2至0.65)：(0.02至0.2)：(0.2至0.6)：(0.005至0.3)，且在該(A)縮醛系樹脂之結構單元(a4)的含量，以質量基準計，則為在3至30質量%之範圍。The photosensitive resin composition of the present invention comprises: (A) an acetal resin, (B) a photoacid generator, and (C) a solvent, and the (A) acetal resin contains a carboxyl group formed by an acid. Structural unit (a1) having a structure, a structural unit having a carboxyl group or a phenolic hydroxyl group (a2), a structural unit having an epoxy group or an oxetanyl group (a3), and a structure having a hydroxyl group or an alkoxy group a unit (a4) having a polymer having an acetal structure or a ketal structure, and a content ratio of the structural units (a1) to (a4) of the (A) acetal resin in terms of moles relative to (A) When the acetal resin is 1, structural unit (a1): structural unit (a2): structural unit (a3): structural unit (a4) = (0.2 to 0.65): (0.02 to 0.2): (0.2 to 0.6) (0.005 to 0.3), and the content of the structural unit (a4) of the (A) acetal resin is in the range of 3 to 30% by mass based on the mass.

本發明之感光性樹脂組成物是正型感光性樹脂組成物。The photosensitive resin composition of the present invention is a positive photosensitive resin composition.

此外，本發明之感光性樹脂組成物較佳為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)。Further, the photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).

此外，在本說明書中，有時候將曝光後之加熱處理(Post Exposure Baking)稱為「PEB」。Further, in the present specification, the post-exposure heat treatment (Post Exposure Baking) is sometimes referred to as "PEB".

由於含有前述(A)至(C)成分，本發明之感光性樹脂組成物將成為具有非常高感度之感光性樹脂組成物。此外，可提供一種可獲得硬化後之透射率高，且即使加熱，透射率之降低也為小的硬化膜之感光性樹脂組成物。The photosensitive resin composition of the present invention contains a photosensitive resin composition having a very high sensitivity by containing the components (A) to (C). Further, it is possible to provide a photosensitive resin composition which can obtain a cured film having a high transmittance after hardening and which has a small decrease in transmittance even when heated.

在本發明中，則將硬化後之透射率高，且即使加熱，透射率之降低也為小的性質稱為「耐熱透明性」。In the present invention, the property that the transmittance after curing is high and the decrease in transmittance is small even when heated is referred to as "heat-resistant transparency".

在下文中，就構成感光性樹脂組成物之各成分加以說明。Hereinafter, each component constituting the photosensitive resin composition will be described.

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。Further, as for the label of the group (atomic group) in the present specification, it is not described that the substituted or unsubstituted label is also substituted with the substituent and the 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)縮醛系樹脂(A) acetal resin

本發明之感光性樹脂組成物是包含(A)縮醛系樹脂。The photosensitive resin composition of the present invention contains (A) an acetal resin.

本發明之感光性樹脂組成物所包含的(A)縮醛系樹脂是含有具有由於酸而形成羧基的結構之結構單元(a1)、具有羧基或酚性羥基之結構單元(a2)、具有環氧基或氧雜環丁烷基之結構單元(a3)、及具有羥基或伸烷氧基之結構單元(a4)，且具有縮醛結構或縮酮結構。The (A) acetal resin contained in the photosensitive resin composition of the present invention is a structural unit (a1) having a structure in which a carboxyl group is formed by an acid, a structural unit (a2) having a carboxyl group or a phenolic hydroxyl group, and a ring. a structural unit (a3) of an oxy or oxetane group, and a structural unit (a4) having a hydroxyl group or an alkoxy group, and having an acetal structure or a ketal structure.

此外，(A)縮醛系樹脂是可更進一步含有除了前述結構單元(a1)至(a4)以外的結構之結構單元(a5)。Further, the (A) acetal resin is a structural unit (a5) which can further contain a structure other than the above structural units (a1) to (a4).

(A)縮醛系樹脂較佳為鹼不溶性，且在具有由於酸而形成羧基的結構之結構單元(a1)中之酸分解性基(acid-decomposable group)分解時，則會成為鹼可溶性之樹脂。(A) The acetal-based resin is preferably alkali-insoluble, and when it is decomposed by an acid-decomposable group in the structural unit (a1) having a structure in which a carboxyl group is formed by an acid, it becomes alkali-soluble. Resin.

此外，在本發明所謂的「鹼可溶性」是意謂藉由將該化合物(樹脂)之溶液塗布於基板上，並在90℃加熱2分鐘所形成的該化合物(樹脂)之塗膜(厚度3μm)，對於在23℃之0.4質量%之氫氧化四甲基銨水溶液的溶解速度為0.01μm/秒鐘以上。此外，所謂的「鹼不溶性」是意謂藉由將該化合物(樹脂)之溶液塗布於基板上，並在90℃加熱2分鐘所形成的該化合物(樹脂)之塗膜(厚度3μm)，對於在23℃之0.4質量%之氫氧化四甲基銨水溶液的溶解速度為少於0.01μm/秒鐘，較佳為少於0.005μm/秒鐘。In addition, the term "alkali-soluble" in the present invention means a coating film of the compound (resin) formed by applying a solution of the compound (resin) to a substrate and heating at 90 ° C for 2 minutes (thickness: 3 μm) The dissolution rate of the tetramethylammonium hydroxide aqueous solution of 0.4% by mass at 23 ° C was 0.01 μm / sec. In addition, the term "alkali-insoluble" means a coating film (thickness: 3 μm) of the compound (resin) formed by applying a solution of the compound (resin) to a substrate and heating at 90 ° C for 2 minutes. The dissolution rate of the 0.4% by mass aqueous solution of tetramethylammonium hydroxide at 23 ° C is less than 0.01 μm / sec, preferably less than 0.005 μm / sec.

前述(A)縮醛系樹脂較佳為丙烯酸酯系聚合物。The acetal resin (A) is preferably an acrylate polymer.

在本發明之「丙烯酸酯系聚合物」是加成聚合型之樹脂，含有源於(甲基)丙烯酸或其酯之結構單元的聚合物，也可具有源於除了(甲基)丙烯酸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。此外，也可含有源於(甲基)丙烯酸及其酯之結構單元兩者。The "acrylate-based polymer" of the present invention is an addition polymerization type resin, and a polymer containing a structural unit derived from (meth)acrylic acid or an ester thereof may also have a source derived from (meth)acrylic acid or A structural unit other than the structural unit of the ester, for example, a structural unit derived from a styrene type, or a structural unit derived from a vinyl compound or the like. Further, both structural units derived from (meth)acrylic acid and its esters may also be contained.

前述(A)縮醛系樹脂相對於在(A)縮醛系樹脂之全部結構單元，較佳為含有50莫耳%以上之源於(甲基)丙烯酸或其酯之結構單元，更佳為含有80莫耳%以上，特佳為僅由源於(甲基)丙烯酸或其酯之結構單元所構成之聚合物。The acetal resin (A) is preferably a structural unit derived from (meth)acrylic acid or an ester thereof, more preferably 50 mol% or more, based on the entire structural unit of the (A) acetal resin. It is contained in an amount of 80 mol% or more, and particularly preferably a polymer composed only of structural units derived from (meth)acrylic acid or an ester thereof.

另外，在本說明書，也將「源於(甲基)丙烯酸或其酯之結構單元」稱為「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丙烯酸之總稱者。In addition, in the present specification, "a structural unit derived from (meth)acrylic acid or an ester thereof" is also referred to as an "acrylate structural unit". Further, (meth)acrylic acid means a general term for methacrylic acid and acrylic acid.

前述(A)縮醛系樹脂是具有縮醛結構或縮酮結構，也可具有縮醛結構及縮酮結構兩者。The (A) acetal resin may have an acetal structure or a ketal structure, and may have both an acetal structure and a ketal structure.

縮醛結構或縮酮結構較佳為以下述通式(I)所代表的結構。The acetal structure or the ketal structure is preferably a structure represented by the following general formula (I).

通式(I)中，R1 及R2 是各自獨立地代表氫原子、直鏈狀或分枝狀烷基或環烷基。但是，R1 及R2 之至少一者是代表烷基或環烷基。In the formula (I), R 1 and R 2 each independently represent a hydrogen atom, a linear or branched alkyl group or a cycloalkyl group. However, at least one of R 1 and R 2 represents an alkyl group or a cycloalkyl group.

R3 是代表直鏈狀或分枝狀烷基、環烷基、或芳烷基。R 3 represents a linear or branched alkyl group, a cycloalkyl group, or an aralkyl group.

R1 與R3 是可鍵結而形成環狀醚，R2 與R3 是可鍵結而形成環狀醚。R 1 and R 3 are bondable to form a cyclic ether, and R 2 and R 3 are bondable to form a cyclic ether.

通式(I)之作為R1 或R2 之烷基較佳為碳數為1至6之直鏈狀或分枝狀烷基。作為R1 或R2 之環烷基較佳為碳數為3至6之環烷基。The alkyl group as R 1 or R 2 of the formula (I) is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. The cycloalkyl group as R 1 or R 2 is preferably a cycloalkyl group having a carbon number of 3 to 6.

作為R3 之烷基較佳為碳數為1至10之直鏈狀或分枝狀烷基。作為R3 之環烷基較佳為碳數為3至10之環烷基。The alkyl group as R 3 is preferably a linear or branched alkyl group having a carbon number of 1 to 10. The cycloalkyl group as R 3 is preferably a cycloalkyl group having a carbon number of 3 to 10.

作為R3 之芳烷基較佳為碳數為7至10之芳烷基。The aralkyl group as R 3 is preferably an aralkyl group having a carbon number of 7 to 10.

在R1 與R3 、或R2 與R3 是鍵結而形成環狀醚時，則較佳為R1 與R3 、或R2 與R3 是鍵結而形成碳數為2至5之伸烷基鏈。When R 1 and R 3 or R 2 and R 3 are bonded to form a cyclic ether, it is preferred that R 1 and R 3 or R 2 and R 3 are bonded to form a carbon number of 2 to 5. The alkyl chain.

作為R3 之烷基、環烷基、芳烷基是可具有取代基，取代基是可列舉：例如，烷基、烷氧基、鹵素原子，取代基之碳數較佳為6以下。The alkyl group, the cycloalkyl group or the aralkyl group of R 3 may have a substituent. The substituent may, for example, be an alkyl group, an alkoxy group or a halogen atom, and the number of carbon atoms of the substituent is preferably 6 or less.

在上述通式(I)中，R1 及R2 之一者為氫原子時，在羧酸之縮醛酯結構(-COOR7 )之R7 是可列舉：例如，1-甲氧基乙基、1-乙氧基乙基、1-正丙氧基乙基、1-異丙氧基乙基、1-正丁氧基乙基、1-異丁氧基乙基、1-二級丁氧基乙基、1-三級丁氧基乙基、1-環戊氧基乙基、1-環己氧基乙基、1-降冰片氧基乙基、1-冰片氧基乙基、1-苯甲氧基乙基、1-苯乙氧基乙基、(環己基)(甲氧基)甲基、(環己基)(乙氧基)甲基、(環己基)(正丙氧基)甲基、(環己基)(異丙氧基)甲基、(環己基)(環己氧基)甲基、(環己基)(苯甲氧基)甲基、(苯基)(甲氧基)甲基、(苯基)(乙氧基)甲基、(苯基)(正丙氧基)甲基、(苯基)(異丙氧基)甲基、(苯基)(環己氧基)甲基、(苯基)(苯甲氧基)甲基、(苯甲基)(甲氧基)甲基、(苯甲基)(乙氧基)甲基、(苯甲基)(正丙氧基)甲基、(苯甲基)(異丙氧基)甲基、(苯甲基)(環己氧基)甲基、(苯甲基)(苯甲氧基)甲基、2-四氫呋喃基、2-四氫哌喃基等。In the above formula (I), when one of R 1 and R 2 is a hydrogen atom, R 7 of the acetal structure (-COOR 7 ) of the carboxylic acid is exemplified by, for example, 1-methoxyB. , 1-ethoxyethyl, 1-n-propoxyethyl, 1-isopropoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-second Butoxyethyl, 1-tert-butoxyethyl, 1-cyclopentyloxyethyl, 1-cyclohexyloxyethyl, 1-norbornyloxyethyl, 1-borneyloxyethyl , 1-benzyloxyethyl, 1-phenylethoxyethyl, (cyclohexyl)(methoxy)methyl, (cyclohexyl)(ethoxy)methyl, (cyclohexyl)(n-propyl) Oxy)methyl, (cyclohexyl)(isopropoxy)methyl, (cyclohexyl)(cyclohexyloxy)methyl, (cyclohexyl)(benzyloxy)methyl, (phenyl) ( Methoxy)methyl, (phenyl)(ethoxy)methyl, (phenyl)(n-propoxy)methyl, (phenyl)(isopropoxy)methyl, (phenyl)( Cyclohexyloxy)methyl, (phenyl)(benzyloxy)methyl, (benzyl)(methoxy)methyl, (benzyl)(ethoxy)methyl, (benzoyl) (n-propoxy)methyl, (benzyl)(isopropoxy)methyl, (benzyl)(cyclohexyloxy)methyl, (benzene Yl) (phenylmethoxy) methyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl group and the like.

在上述通式(I)中R1 及R2 之任一者皆非為氫原子時，在羧酸之縮酮酯結構(-COOR8 )中之R8 是可列舉：例如，1-甲基-1-甲氧基乙基、1-甲基-1-乙氧基乙基、1-甲基-1-正丙氧基乙基、1-甲基-1-異丙氧基乙基、1-甲基-1-正丁氧基乙基、1-甲基-1-異丁氧基乙基、1-甲基-1-二級丁氧基乙基、1-甲基-1-三級丁氧基乙基、1-甲基-1-環戊氧基乙基、1-甲基-1-環己氧基乙基、1-甲基-1-降冰片氧基乙基、1-甲基-1-冰片氧基乙基、1-甲基-1-苯甲氧基乙基、1-甲基-1-苯乙氧基乙基、1-環己基-1-甲氧基乙基、1-環己基-1-乙氧基乙基、1-環己基-1-正丙氧基乙基、1-環己基-1-異丙氧基乙基、1-環己基-1-環己氧基乙基、1-環己基-1-苯甲氧基乙基、1-苯基-1-甲氧基乙基、1-苯基-1-乙氧基乙基、1-苯基-1-正丙氧基乙基、1-苯基-1-異丙氧基乙基、1-苯基-1-環己氧基乙基、1-苯基-1-苯甲氧基乙基、1-苯甲基-1-甲氧基乙基、1-苯甲基-1-乙氧基乙基、1-苯甲基-1-正丙氧基乙基、1-苯甲基-1-異丙氧基乙基、1-苯甲基-1-環己氧基乙基、1-苯甲基-1-苯甲氧基乙基、2-甲基-2-四氫呋喃基、2-甲基-2-四氫哌喃基、1-甲氧基環戊基、1-甲氧基-環己基等。In the above formula (I), when either of R 1 and R 2 is not a hydrogen atom, R 8 in the ketal ester structure (-COOR 8 ) of the carboxylic acid is exemplified by, for example, 1-methyl. 1-methoxyethyl, 1-methyl-1-ethoxyethyl, 1-methyl-1-n-propoxyethyl, 1-methyl-1-isopropoxyethyl , 1-methyl-1-n-butoxyethyl, 1-methyl-1-isobutoxyethyl, 1-methyl-1-dimethoxybutoxyethyl, 1-methyl-1 - Tert-butoxyethyl, 1-methyl-1-cyclopentyloxyethyl, 1-methyl-1-cyclohexyloxyethyl, 1-methyl-1-norbornyloxyethyl , 1-methyl-1-borneoyloxyethyl, 1-methyl-1-benzyloxyethyl, 1-methyl-1-phenylethoxyethyl, 1-cyclohexyl-1-methyl Oxyethyl, 1-cyclohexyl-1-ethoxyethyl, 1-cyclohexyl-1-n-propoxyethyl, 1-cyclohexyl-1-isopropoxyethyl, 1-cyclohexyl 1-cyclohexyloxyethyl, 1-cyclohexyl-1-benzyloxyethyl, 1-phenyl-1-methoxyethyl, 1-phenyl-1-ethoxyethyl, 1-phenyl-1-n-propoxyethyl, 1-phenyl-1-isopropoxyethyl, 1-phenyl-1-cyclohexyloxyethyl, 1-phenyl-1-benzene Methoxyethyl, 1-benzyl-1-methoxy Ethyl, 1-benzyl-1-ethoxyethyl, 1-benzyl-1-n-propoxyethyl, 1-benzyl-1-isopropoxyethyl, 1-benzene Methyl-1-cyclohexyloxyethyl, 1-benzyl-1-phenylmethoxyethyl, 2-methyl-2-tetrahydrofuranyl, 2-methyl-2-tetrahydropyranyl, 1-methoxycyclopentyl, 1-methoxy-cyclohexyl and the like.

在上述羧酸之縮醛結構或縮酮結構，從製程安定性的觀點，則更佳為縮醛結構。在羧酸之縮醛酯結構(-COOR7 )之較佳的R7 是較佳為1-乙氧基乙基、1-環己氧基乙基、2-四氫呋喃基、2-四氫哌喃基；從感度的觀點，則特佳為1-乙氧基乙基、1-環己氧基乙基。The acetal structure or the ketal structure of the above carboxylic acid is more preferably an acetal structure from the viewpoint of process stability. Preferred R 7 in the acetal structure of the carboxylic acid (-COOR 7 ) is preferably 1-ethoxyethyl, 1-cyclohexyloxyethyl, 2-tetrahydrofuranyl or 2-tetrahydroperoxide. From the viewpoint of sensitivity, it is particularly preferably 1-ethoxyethyl or 1-cyclohexyloxyethyl.

[具有由於酸而形成羧基的結構之結構單元(a1)][Structural unit (a1) having a structure in which a carboxyl group is formed by an acid]

在本發明之(A)縮醛系樹脂是含有具有由於酸而形成羧基的結構之結構單元(a1)(在下文中，則適當地稱為「結構單元(a1)」)。結構單元(a1)是含有羧基是受到保護之結構。The (A) acetal resin of the present invention is a structural unit (a1) having a structure in which a carboxyl group is formed by an acid (hereinafter, it is appropriately referred to as "structural unit (a1)"). The structural unit (a1) is a structure in which a carboxyl group is protected.

為形成結構單元(a1)而使用的化合物是由於羧基是受到保護，可成為為形成結構單元(a1)而使用的化合物者時，則可使用。「具有羧基之化合物」是可列舉：例如，丙烯酸、甲基丙烯酸、巴豆酸、α-甲基-對羧基苯乙烯等之一元羧酸；順丁烯二酸、反丁烯二酸、檸康酸、中康酸、伊康酸等之二羧酸，特佳為丙烯酸、甲基丙烯酸。此外，結構單元(a1)是可列舉源於此等羧基是受到保護的羧酸之結構單元為較佳者。The compound used for forming the structural unit (a1) can be used because the carboxyl group is protected and can be used as a compound for forming the structural unit (a1). The "compound having a carboxyl group" may, for example, be a monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid or α-methyl-p-carboxystyrene; maleic acid, fumaric acid, and citrine A dicarboxylic acid such as acid, mesaconic acid or itaconic acid, particularly preferably acrylic acid or methacrylic acid. Further, the structural unit (a1) is preferably a structural unit derived from a carboxylic acid whose carboxyl group is protected.

為形成結構單元(a1)而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1-乙氧基乙酯、丙烯酸1-乙氧基乙酯、甲基丙烯酸1-甲氧基乙酯、丙烯酸1-甲氧基乙酯、甲基丙烯酸1-正丁氧基乙酯、丙烯酸1-正丁氧基乙酯、甲基丙烯酸1-異丁氧基乙酯、丙烯酸1-異丁氧基乙酯、甲基丙烯酸1-(2-乙基己氧基)乙酯、丙烯酸1-(2-乙基己氧基)乙酯、甲基丙烯酸1-正丙氧基乙酯、丙烯酸1-正丙氧基乙酯、甲基丙烯酸1-環己氧基乙酯、丙烯酸1-環己氧基乙酯、甲基丙烯酸1-(2-環己基乙氧基)乙酯、丙烯酸1-(2-環己基乙氧基)乙酯、甲基丙烯酸1-苯甲氧基乙酯、丙烯酸1-苯甲氧基乙酯、甲基丙烯酸四氫-2H-哌喃-2-基酯、丙烯酸四氫-2H-哌喃-2-基酯、甲基丙烯酸四氫呋喃-2-基酯、丙烯酸四氫呋喃-2-基酯等；特佳為甲基丙烯酸1-乙氧基乙酯、丙烯酸1-乙氧基乙酯、甲基丙烯酸四氫呋喃-2-基酯、丙烯酸四氫呋喃-2-基酯、甲基丙烯酸1-環己氧基乙酯、及丙烯酸1-環己氧基乙酯。此等結構單元(a1)是可以一種單獨或兩種以上組合使用。Preferable specific examples of the radical polymerizable monomer used for forming the structural unit (a1) include, for example, 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, and methacrylic acid. 1-methoxyethyl ester, 1-methoxyethyl acrylate, 1-n-butoxyethyl methacrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl methacrylate , 1-isobutoxyethyl acrylate, 1-(2-ethylhexyloxy)ethyl methacrylate, 1-(2-ethylhexyloxy)ethyl acrylate, 1-n-propyl methacrylate Oxyethyl ester, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl methacrylate, 1-cyclohexyloxyethyl acrylate, 1-(2-cyclohexylethoxy) methacrylate Ethyl ester, 1-(2-cyclohexylethoxy)ethyl acrylate, 1-benzyloxyethyl methacrylate, 1-benzyloxyethyl acrylate, tetrahydro-2H-piperidyl methacrylate喃-2-yl ester, tetrahydro-2H-pentan-2-yl acrylate, tetrahydrofuran-2-yl methacrylate, tetrahydrofuran-2-yl acrylate, etc.; especially preferably 1-ethoxy methacrylate Ethyl ethyl ester, 1-ethoxyethyl acrylate, methacryl Tetrahydrofuran-2-yl acrylate, tetrahydrofuran-2-yl methacrylate, 1-cyclohexyloxy-ethyl acrylate, and 1-cyclohexyloxy-ethyl. These structural units (a1) may be used singly or in combination of two or more.

為形成結構單元(a1)而使用的自由基聚合性單體是可使用市售品，也可使用以習知的方法所合成者。例如，假如只要其為以下式(II)所代表之單體時，則如下所示可藉由將(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。The radical polymerizable monomer used for forming the structural unit (a1) may be a commercially available product, or may be synthesized by a conventional method. For example, if it is a monomer represented by the following formula (II), it can be synthesized by reacting (meth)acrylic acid with a vinyl ether compound in the presence of an acid catalyst as follows.

在式(II)中，R6 是代表氫原子或甲基，R5 是與在式(I)之R3 為同義。In the formula (II), R 6 represents a hydrogen atom or a methyl group, and R 5 is synonymous with R 3 in the formula (I).

此外，結構單元(a1)也可藉由將被保護的羧基與後述之結構單元(a2)至(a5)或其前驅物進行聚合後，將羧基與乙烯基醚化合物反應而形成。另外，藉此所形成的較佳結構單元的具體實例是與源於上述自由基聚合性單體之較佳具體實例之結構單元相同。Further, the structural unit (a1) can also be formed by polymerizing a protected carboxyl group with a structural unit (a2) to (a5) described later or a precursor thereof, and then reacting a carboxyl group with a vinyl ether compound. Further, a specific example of the preferred structural unit formed thereby is the same as the structural unit derived from the preferred embodiment of the above radical polymerizable monomer.

結構單元(a1)較佳為以下述通式(5)所代表的結構單元。The structural unit (a1) is preferably a structural unit represented by the following general formula (5).

通式(5)中，R1 是代表氫原子或碳數為1至4之烷基，L1 是代表羰基或伸苯基，R21 至R27 是各自獨立地代表氫原子或碳數為1至4之烷基。In the formula (5), R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 1 represents a carbonyl group or a phenyl group, and R 21 to R 27 each independently represent a hydrogen atom or have a carbon number of Alkyl groups of 1 to 4.

結構單元(a1)之較佳具體實例是可例示下列結構單元(a1-1)至(a1-8)。在此等之中，特佳為以(a1-1)至(a1-4)、(a1-7)及(a1-8)所代表的結構單元。Preferred specific examples of the structural unit (a1) are the following structural units (a1-1) to (a1-8). Among these, structural units represented by (a1-1) to (a1-4), (a1-7), and (a1-8) are particularly preferred.

在構成(A)縮醛系樹脂之全部結構單元中，結構單元(a1)的含率為20至60莫耳%，更佳為25至60莫耳%，特佳為25至55莫耳%。藉由使得以上述比例含有結構單元(a1)，則可獲得高感度之感光性樹脂組成物。In all the structural units constituting the (A) acetal resin, the content of the structural unit (a1) is 20 to 60 mol%, more preferably 25 to 60 mol%, particularly preferably 25 to 55 mol%. . By including the structural unit (a1) in the above ratio, a photosensitive resin composition having high sensitivity can be obtained.

[具有羧基或酚性羥基之結構單元(a2)][Structural unit (a2) having a carboxyl group or a phenolic hydroxyl group]

(A)縮醛系樹脂是含有具有羧基或酚性羥基之結構單元(a2)(在下文中，則適當地稱為「結構單元(a2)」)。(A) The acetal resin is a structural unit (a2) having a carboxyl group or a phenolic hydroxyl group (hereinafter, it is appropriately referred to as "structural unit (a2)").

具有羧基之結構單元(a2-1)是可列舉：例如，源於不飽和一元羧酸、不飽和二元羧酸、不飽和三元羧酸等之在分子中具有至少一個羧基之不飽和羧酸等之結構單元。The structural unit (a2-1) having a carboxyl group is, for example, an unsaturated carboxylic acid having at least one carboxyl group in the molecule derived from an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated tricarboxylic acid or the like. A structural unit such as an acid.

為獲得具有羧基之結構單元(a2-1)所使用的不飽和羧酸是可使用以下所例示者。The unsaturated carboxylic acid used for obtaining the structural unit (a2-1) having a carboxyl group can be exemplified below.

亦即，不飽和一元羧酸是可例示：丙烯酸、甲基丙烯酸、巴豆酸、α-氯丙烯酸、桂皮酸等。That is, the unsaturated monocarboxylic acid is exemplified by acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid or the like.

此外，不飽和二元羧酸是可例示：順丁烯二酸、反丁烯二酸、伊康酸、檸康酸、中康酸等。Further, the unsaturated dicarboxylic acid is exemplified by maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like.

此外，為獲得具有羧基之結構單元(a2-1)所使用的不飽和多元羧酸也可為其酸酐。具體而言，其可列舉：順丁烯二酸酐、伊康酸酐、檸康酸酐等。此外，不飽和多元羧酸是也可為多元羧酸之一(2-甲基丙烯醯氧基烷基)酯，其可列舉：例如，琥珀酸一(2-丙烯醯氧基乙基)酯、琥珀酸一(2-甲基丙烯醯氧基乙基)酯、鄰苯二甲酸一(2-丙烯醯氧基乙基)酯、鄰苯二甲酸一(2-甲基丙烯醯氧基乙基)酯等。Further, the unsaturated polycarboxylic acid used to obtain the structural unit (a2-1) having a carboxyl group may also be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. Further, the unsaturated polycarboxylic acid may be one (2-methacryloxyalkyl) ester of a polycarboxylic acid, and examples thereof include, for example, mono(2-propenyloxyethyl) succinate. , bis(2-methylpropenyloxyethyl) succinate, mono(2-propenyloxyethyl) phthalate, mono(2-methylpropenyloxy) phthalate Ester).

並且，不飽和多元羧酸是也可為其兩末端二羧基高分子之一(甲基)丙烯酸酯，其可列舉：例如，ω-羧基聚己內酯一丙烯酸酯、ω-羧基聚己內酯一甲基丙烯酸酯等。Further, the unsaturated polycarboxylic acid may be one (meth) acrylate of a di-carboxyl polymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxy polycap Ester monomethacrylate and the like.

此外，不飽和羧酸是也可使用：丙烯酸-2-羧基乙酯、甲基丙烯酸-2-羧基乙酯、順丁烯二酸一烷基酯、反丁烯二酸一烷基酯、4-羧基苯乙烯等。Further, an unsaturated carboxylic acid may also be used: 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, monoalkyl maleate, monoalkyl fumarate, 4 - Carboxystyrene and the like.

其中，從顯影性的觀點，若欲形成具有羧基之結構單元(a2-1)，則較佳為使用丙烯酸、甲基丙烯酸。Among them, from the viewpoint of developability, if a structural unit (a2-1) having a carboxyl group is to be formed, acrylic acid or methacrylic acid is preferably used.

此外，具有羧基之結構單元(a2-1)是也可藉由將具有羥基之結構單元與酸酐反應而獲得。Further, the structural unit (a2-1) having a carboxyl group can also be obtained by reacting a structural unit having a hydroxyl group with an acid anhydride.

酸酐是可使用習知者，具體而言，其可列舉：順丁烯二酸酐、琥珀酸酐、伊康酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、氯菌酸酐等之二元酸酐；偏苯三酸酐、焦蜜石酸酐、二苯甲酮四甲酸酐、聯苯基四甲酸酐等之酸酐。在此等之中，從顯影性的觀點，則較佳為鄰苯二甲酸酐、四氫鄰苯二甲酸酐、或琥珀酸酐。An acid anhydride can be used, and specific examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. A dibasic acid anhydride such as chloric acid anhydride; an acid anhydride such as trimellitic anhydride, pyrogallic anhydride, benzophenone tetracarboxylic anhydride or biphenyl tetracarboxylic anhydride. Among these, from the viewpoint of developability, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable.

為形成具有酚性羥基之結構單元(a2-2)所使用的自由基聚合性單體是可列舉：例如，對羥基苯乙烯、α-申基-對羥基苯乙烯等之羥基苯乙烯類、在日本特開2008-40183號公報中之段落[0011〕至[0016]所揭述之化合物、在發明專利第2888454號公報中之段落[0007〕至[0010]所揭述之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為較佳者。The radically polymerizable monomer used for forming the structural unit (a2-2) having a phenolic hydroxyl group may, for example, be a hydroxystyrene such as p-hydroxystyrene or α-sodium-p-hydroxystyrene. The compound disclosed in paragraphs [0011] to [0016] of JP-A-2008-40183, 4-hydroxybenzene disclosed in paragraphs [0007] to [0010] of the Patent No. 2888454 Preferred are formic acid derivatives, addition reactants of 4-hydroxybenzoic acid and glycidyl methacrylate, and addition reactants of 4-hydroxybenzoic acid and glycidyl acrylate.

在為形成結構單元(a2)所使用的自由基聚合性單體中，更佳為甲基丙烯酸、丙烯酸、在日本特開2008-40183號公報中之段落0011至0016所揭述之化合物、專利第2888454號公報中之段落0007至0010所揭述之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，但是從透明性的觀點，則特佳為甲基丙烯酸、丙烯酸。此等之結構單元是可以一種單獨或兩種以上組合使用。Among the radical polymerizable monomers used for forming the structural unit (a2), methacrylic acid, acrylic acid, and the compounds and patents disclosed in paragraphs 0011 to 0016 of JP-A-2008-40183 are more preferable. Addition of 4-hydroxybenzoic acid derivatives, 4-hydroxybenzoic acid to glycidyl methacrylate, 4-hydroxybenzoic acid and acrylic acid ring as disclosed in paragraphs 0007 to 0010 of Japanese Patent No. 2888454 The addition reaction product of oxypropyl ester is particularly preferably methacrylic acid or acrylic acid from the viewpoint of transparency. These structural units may be used alone or in combination of two or more.

結構單元(a2)較佳為在(A)縮醛系樹脂不致於變成鹼可溶性的範圍而導入。在構成前述(A)縮醛系樹脂之全部結構單元中，結構單元(a2)的含率為2至20莫耳%，更佳為2至15莫耳%，特佳為3至15莫耳%。藉由使得以上述比例含有結構單元(a2)，則可獲得高感度，此外，顯影性也會成為良好。特別是藉由併用後述之結構單元(a4)與結構單元(a2)，則可獲得非常高的感度。The structural unit (a2) is preferably introduced in a range in which the (A) acetal resin does not become alkali-soluble. In all the structural units constituting the aforementioned (A) acetal resin, the content of the structural unit (a2) is 2 to 20 mol%, more preferably 2 to 15 mol%, particularly preferably 3 to 15 mol%. %. By including the structural unit (a2) in the above ratio, high sensitivity can be obtained, and the developability is also good. In particular, by using the structural unit (a4) and the structural unit (a2) described later in combination, a very high sensitivity can be obtained.

[具有環氧基及/或氧雜環丁烷基之結構單元(a3)][Structural unit (a3) having an epoxy group and/or an oxetane group]

(A)縮醛系樹脂是含有具有環氧基或氧雜環丁烷基之結構單元(a3)(在下文中，則適當地稱為「結構單元(a3)」)。結構單元(a3)是可含有具有環氧基及氧雜環丁烷基之結構單元兩者。(A) The acetal resin is a structural unit (a3) having an epoxy group or an oxetanyl group (hereinafter, it is appropriately referred to as "structural unit (a3)"). The structural unit (a3) is a structural unit which may have an epoxy group and an oxetane group.

具有環氧基之基，若其為具有環氧基環時，則並無特殊限制，可例示較佳為環氧丙基(縮水甘油基：glycidyl group)、3,4-環氧基環己基甲基。The group having an epoxy group is not particularly limited as long as it has an epoxy group, and is preferably a glycidyl group or a 3,4-epoxycyclohexyl group. methyl.

具有氧雜環丁烷基之基，若其為具有氧雜環丁烷環時，則並無特殊限制，可例示較佳為(3-乙基氧雜環丁烷-3-基)甲基。The group having an oxetane group is not particularly limited as long as it has an oxetane ring, and preferably (3-ethyloxetan-3-yl)methyl group is exemplified. .

結構單元(a3)，若其為在一結構單元中具有至少一個環氧基或氧雜環丁烷基時即可，也可具有一個以上環氧基及一個以上氧雜環丁烷基、兩個以上環氧基、或兩個以上氧雜環丁烷基，並無特殊限制，較佳為具有合計1至3個之環氧基及/或氧雜環丁烷基，更佳為具有合計一或兩個之環氧基及/或氧雜環丁烷基，進一步更佳為具有一個環氧基或氧雜環丁烷基。The structural unit (a3) 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 oxetanyl groups, and two The above epoxy group or two or more oxetanyl groups are not particularly limited, and preferably have a total of 1 to 3 epoxy groups and/or oxetanyl groups, and more preferably have a total of One or two epoxy groups and/or oxetane groups further preferably have one epoxy group or oxetanyl group.

為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、甲基丙烯酸環氧丙酯、α-乙基丙烯酸環氧丙酯、α-正丙基丙烯酸環氧丙酯、α-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、在專利第4168443號公報中之段落[0031]至[0035]所揭述之含有脂環式環氧骨架之化合物等。Specific examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, and α-ethyl acrylate propyl acrylate. , α-n-propyl propylene glycol acrylate, α-n-butyl butyl acrylate, 3,4-epoxy butyl acrylate, 3,4-epoxybutyl methacrylate, acrylic acid -6,7-epoxyheptyl ester, -6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinyl benzyl epoxide An ether ring, m-vinylbenzyloxypropyl ether, p-vinylbenzyloxypropyl ether, and an alicyclic ring as disclosed in paragraphs [0031] to [0035] of Japanese Patent No. 4168843 a compound of the epoxy skeleton or the like.

為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2001-330953號公報中之段落[0011]至[0016〕所揭述之具有氧雜環丁烷基之(甲基)丙烯酸酯等。Examples of the radically polymerizable monomer used for forming the structural unit having an oxetane group are exemplified by, for example, paragraphs [0011] to [0016] in JP-A-2001-330953. The (meth) acrylate having an oxetane group and the like.

為形成(a3)結構單元而使用的自由基聚合性單體的實例較佳為含有甲基丙烯酸酯結構之單體、含有丙烯酸酯結構之單體。An example of the radical polymerizable monomer used for forming the (a3) structural unit is preferably a monomer having a methacrylate structure and a monomer having an acrylate structure.

在此等單體中，更佳為甲基丙烯酸環氧丙酯、丙烯酸環氧丙酯、在專利第4168443號公報中之段落[0034]至[0035]所揭述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[0011]至[0016]所揭述之具有氧雜環丁烷基之(甲基)丙烯酸酯。Among these monomers, more preferred are glycidyl methacrylate, glycidyl acrylate, and alicyclic epoxy as disclosed in paragraphs [416] to [0035] of Japanese Patent No. 4,184,443. The compound of the skeleton and the (meth) acrylate having an oxetane group as disclosed in paragraphs [0011] to [0016] of JP-A-2001-330953.

從耐熱透明性的觀點，則特佳為源於丙烯酸(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)甲酯中任一者之結構單元。From the viewpoint of heat-resistant transparency, it is particularly preferred from the group consisting of (3-ethyloxetan-3-yl)methyl acrylate and methacrylic acid (3-ethyloxetan-3-yl). a structural unit of any of the methyl esters.

此等結構單元(a3)是可以一種單獨或兩種以上組合使用。These structural units (a3) may be used singly or in combination of two or more.

結構單元(a3)之較佳具體實例是可例示下述之結構單元。A preferred specific example of the structural unit (a3) is a structural unit which can be exemplified below.

在構成前述(A)縮醛系樹脂之全部結構單元中，結構單元(a3)的含率為20至55莫耳%，更佳為25至55莫耳%，特佳為25至50莫耳%。藉由以上述比例含有結構單元(a3)，則硬化膜之物性將成為良好。In all the structural units constituting the aforementioned (A) acetal resin, the content of the structural unit (a3) is 20 to 55 mol%, more preferably 25 to 55 mol%, particularly preferably 25 to 50 mol%. %. When the structural unit (a3) is contained in the above ratio, the physical properties of the cured film become good.

[具有羥基或伸烷氧基之結構單元(a4)][Structural unit having a hydroxyl group or an alkoxy group (a4)]

前述(A)縮醛系樹脂是含有具有羥基或伸烷氧基之結構單元(a4)(在下文中，則適當地稱為「結構單元(a4)」)。也可含有具有羥基及伸烷氧基之結構單元兩者。The (A) acetal resin is a structural unit (a4) having a hydroxyl group or an alkylene group (hereinafter, appropriately referred to as "structural unit (a4)"). It is also possible to contain both structural units having a hydroxyl group and an alkoxy group.

在結構單元(a4)之羥基是指除了酚性羥基以外之羥基。此外，前述之結構單元(a1)至(a3)具有羥基時，則不作為結構單元(a4)來處理而作為各自之結構單元(a1)至(a3)來處理。The hydroxyl group in the structural unit (a4) means a hydroxyl group other than a phenolic hydroxyl group. Further, when the structural units (a1) to (a3) described above have a hydroxyl group, they are not treated as the structural unit (a4) and are treated as the respective structural units (a1) to (a3).

結構單元(a4)，若其為具有羥基及/或伸烷氧基之結構單元時，則可使用任意者，較佳者是可列舉：源於含有羥基之(甲基)丙烯酸酯、烷基末端聚伸烷基二醇之(甲基)丙烯酸酯及芳基末端聚伸烷基二醇之(甲基)丙烯酸酯等之結構單元。The structural unit (a4), if it is a structural unit having a hydroxyl group and/or an alkoxy group, any one may be used, and preferably, it is derived from a (meth) acrylate having a hydroxyl group, an alkyl group. The terminal unit is a structural unit such as a (meth) acrylate of an alkyl diol and a (meth) acrylate of an aryl terminal polyalkylene glycol.

「含有羥基之(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2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2,3-二羥基丙酯、(甲基)丙烯酸4-羥基丁酯等之(甲基)丙烯酸之羥基烷基酯；聚乙二醇一(甲基)丙烯酸酯、聚丙二醇一(甲基)丙烯酸酯、聚(乙二醇‧丙二醇)-一(甲基)丙烯酸酯、聚乙二醇‧聚丙二醇-一(甲基)丙烯酸酯、聚(乙二醇‧四亞甲基二醇)-一(甲基)丙烯酸酯、聚(丙二醇‧四亞甲基二醇)-一(甲基)丙烯酸酯、丙二醇‧聚丁二醇-一(甲基)丙烯酸酯作為較佳的實例。Examples of the "hydroxyl group-containing (meth) acrylate" include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. a hydroxyalkyl (meth)acrylate such as 2,3-dihydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate; polyethylene glycol mono(meth)acrylate, poly Propylene glycol mono(meth) acrylate, poly(ethylene glycol ‧ propylene glycol) - mono (meth) acrylate, polyethylene glycol ‧ polypropylene glycol - mono (meth) acrylate, poly (ethylene glycol ‧ four Methyl diol)-mono (meth) acrylate, poly(propylene glycol ‧ tetramethylene glycol) - mono (meth) acrylate, propylene glycol ‧ polybutylene glycol - mono (meth) acrylate as A good example.

烷基末端聚伸烷基二醇之(甲基)丙烯酸酯是可列舉：例如，甲氧基聚乙二醇-(甲基)丙烯酸酯、辛氧基聚乙二醇-聚丙二醇-(甲基)丙烯酸酯、月桂氧基聚乙二醇-(甲基)丙烯酸酯、硬脂氧基聚乙二醇-(甲基)丙烯酸酯作為較佳的實例。The (meth) acrylate of the alkyl terminal polyalkylene glycol is exemplified by, for example, methoxypolyethylene glycol-(meth) acrylate, octyloxy polyethylene glycol-polypropylene glycol-(A) Acrylate, lauryloxy polyethylene glycol-(meth) acrylate, stearyloxy polyethylene glycol-(meth) acrylate are preferred examples.

芳基末端聚伸烷基二醇之(甲基)丙烯酸酯是可列舉：例如，苯氧基聚乙二醇-(甲基)丙烯酸酯、苯氧基聚乙二醇-聚丙二醇-(甲基)丙烯酸酯、壬基苯氧基-聚乙二醇-(甲基)丙烯酸酯、壬基苯氧基-聚丙二醇-(甲基)丙烯酸酯、壬基苯氧基-聚(乙二醇-丙二醇)-(甲基)丙烯酸酯作為較佳的實例。The (meth) acrylate of the aryl terminal polyalkylene glycol is exemplified by, for example, phenoxy polyethylene glycol-(meth) acrylate, phenoxy polyethylene glycol-polypropylene glycol-(A) Acrylate, nonylphenoxy-polyethylene glycol-(meth)acrylate, nonylphenoxy-polypropylene glycol-(meth)acrylate, nonylphenoxy-poly(ethylene glycol) - Propylene glycol)-(meth) acrylate is a preferred example.

上述含有羥基之(甲基)丙烯酸酯、烷基末端聚伸烷基二醇之(甲基)丙烯酸酯及芳基末端聚伸烷基二醇之(甲基)丙烯酸酯是可使用市售品者。其代表性實例是可列舉：Blemmer E、Blemmer PE-90、Blemmer PE-200、Blemmer PE-350、Blemmer P、Blemmer PP-1000、Blemmer PP-500、Blemmer PP-800、Blemmer 50PEP-300、Blemmer 70PEP-350B、Blemmer 55PET-800、Blemmer PPT系列、Blemmer 10PPB-500B、Blemmer AE-90、Blemmer AE-200、Blemmer AE-400、Blemmer AP-150、Blemmer AP-400、Blemmer AP-550、Blemmer PME-100、Blemmer PME-200、Blemmer PME-400、Blemmer PME-1000、Blemmer 50POEP-800B、Blemmer PLE-200、Blemmer PSE-400、Blemmer PSE-1300、Blemmer PAE-50、Blemmer PAE-100、Blemmer 43PAPE-600B、Blemmer AME-400、Blemmer ALE系列、Blemmer ANP-300、Blemmer 75ANP-600、Blemmer AAE-50、Blemmer AAE-300(以上是商品名、日油股份有限公司製)等。The (meth) acrylate containing a hydroxyl group (meth) acrylate, an alkyl terminal polyalkylene glycol (meth) acrylate, and an aryl terminal polyalkylene glycol can be used as a commercial product. By. Representative examples thereof are: Blemmer E, Blemmer PE-90, Blemmer PE-200, Blemmer PE-350, Blemmer P, Blemmer PP-1000, Blemmer PP-500, Blemmer PP-800, Blemmer 50PEP-300, Blemmer 70PEP-350B, Blemmer 55PET-800, Blemmer PPT Series, Blemmer 10PPB-500B, Blemmer AE-90, Blemmer AE-200, Blemmer AE-400, Blemmer AP-150, Blemmer AP-400, Blemmer AP-550, Blemmer PME -100, Blemmer PME-200, Blemmer PME-400, Blemmer PME-1000, Blemmer 50POEP-800B, Blemmer PLE-200, Blemmer PSE-400, Blemmer PSE-1300, Blemmer PAE-50, Blemmer PAE-100, Blemmer 43PAPE -600B, Blemmer AME-400, Blemmer ALE series, Blemmer ANP-300, Blemmer 75ANP-600, Blemmer AAE-50, Blemmer AAE-300 (above, trade name, manufactured by Nippon Oil Co., Ltd.).

在結構單元(a4)之羥基數較佳為1至10個，更佳為1至5個，最佳為1至3個。此外，伸烷氧基之重複單元數較佳為1至25，更佳為1至15，最佳為1至10。The number of hydroxyl groups in the structural unit (a4) is preferably from 1 to 10, more preferably from 1 to 5, most preferably from 1 to 3. Further, the number of repeating units of the alkoxy group is preferably from 1 to 25, more preferably from 1 to 15, most preferably from 1 to 10.

結構單元(a4)之較佳的具體結構為(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2,3-二羥基丙酯、乙二醇重複單元為2至10個之甲氧基聚乙二醇-(甲基)丙烯酸酯、丙二醇重複單元為2至10個之甲氧基聚丙二醇-(甲基)丙烯酸酯、乙二醇重複單元與丙二醇重複單元之合計為2至10個之甲氧基聚乙二醇-聚丙二醇-(甲基)丙烯酸酯、乙二醇重複單元與丙二醇重複單元之合計為2至10個之辛氧基聚乙二醇-聚丙二醇-(甲基)丙烯酸酯、乙二醇重複單元為2至10個之聚乙二醇一(甲基)丙烯酸酯、丙二醇重複單元為2至10個之聚丙二醇一(甲基)丙烯酸酯、乙二醇重複單元與丙二醇重複單元之合計為3至10個之聚(乙二醇.丙二醇)-一(甲基)丙烯酸酯、乙二醇重複單元與丙二醇重複單元之合計為3至10個之聚乙二醇.聚丙二醇-一(甲基)丙烯酸酯等；更佳為(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2,3-二羥基丙酯、乙二醇重複單元為2至10個之甲氧基聚乙二醇-(甲基)丙烯酸酯、乙二醇重複單元與丙二醇重複單元之合計為2至10個之辛氧基聚乙二醇-聚丙二醇-(甲基)丙烯酸酯；最佳為乙二醇重複單元為2至10個之甲氧基聚乙二醇-(甲基)丙烯酸酯、及(甲基)丙烯酸2-羥基乙酯。Preferred specific structures of the structural unit (a4) are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylic acid. 2,3-dihydroxypropyl ester, ethylene glycol repeating unit is 2 to 10 methoxypolyethylene glycol-(meth) acrylate, propylene glycol repeating unit is 2 to 10 methoxypolypropylene glycol - The total amount of (meth) acrylate, ethylene glycol repeating unit and propylene glycol repeating unit is 2 to 10 methoxy polyethylene glycol-polypropylene glycol-(meth) acrylate, ethylene glycol repeating unit and propylene glycol repeat The total of the units is 2 to 10 octyloxy polyethylene glycol-polypropylene glycol-(meth) acrylate, and the ethylene glycol repeating unit is 2 to 10 polyethylene glycol mono(meth) acrylate, The propylene glycol repeating unit is 2 to 10 polypropylene glycol mono(meth) acrylate, ethylene glycol repeating unit and propylene glycol repeating unit in total of 3 to 10 poly(ethylene glycol. propylene glycol)-mono(methyl) A total of 3 to 10 polyethylene glycol, polypropylene glycol mono-(meth)acrylate, etc. 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, ethylene glycol The repeating unit is 2 to 10 methoxy polyethylene glycol-(meth) acrylate, ethylene glycol repeating unit and propylene glycol repeating unit in total of 2 to 10 octyloxy polyethylene glycol-polypropylene glycol - (Meth) acrylate; preferably methoxypolyethylene glycol-(meth) acrylate of 2 to 10 ethylene glycol repeating units, and 2-hydroxyethyl (meth) acrylate.

結構單元(a4)是可以一種單獨或兩種以上組合使用。The structural unit (a4) may be used singly or in combination of two or more.

在構成(A)縮醛系樹脂之全部結構單元中，結構單元(a4)的含率為0.5至30莫耳%，更佳為0.5至25莫耳%，特佳為1至25莫耳%。In all the structural units constituting the (A) acetal resin, the content of the structural unit (a4) is from 0.5 to 30 mol%, more preferably from 0.5 to 25 mol%, particularly preferably from 1 to 25 mol%. .

此外，在構成(A)縮醛系樹脂之全部結構單元中，結構單元(a4)的含量為3至30質量%，更佳為3至25質量%，特佳為5至25質量%。藉由以上述比例含有結構單元(a4)，則顯影性為良好，可獲得高感度之感光性組成物。特別是藉由組合前述之結構單元(a2)與結構單元(a4)，則可獲得非常高感度之感光性樹脂組成物。Further, in all the structural units constituting the (A) acetal resin, the content of the structural unit (a4) is from 3 to 30% by mass, more preferably from 3 to 25% by mass, particularly preferably from 5 to 25% by mass. When the structural unit (a4) is contained in the above ratio, the developability is good, and a photosensitive composition having high sensitivity can be obtained. In particular, by combining the above-described structural unit (a2) and structural unit (a4), a highly sensitive photosensitive resin composition can be obtained.

[其他結構單元(a5)][Other structural units (a5)]

(A)縮醛系樹脂是可在不阻礙本發明之功效範圍，含有除了前述結構單元(a1)至(a4)以外之結構(在下文中，則適當地稱為「結構單元(a5)」)。(A) The acetal-based resin may contain a structure other than the above structural units (a1) to (a4) without hindering the effect of the present invention (hereinafter, appropriately referred to as "structural unit (a5)") .

為形成結構單元(a5)而使用的自由基聚合性單體是可列舉：例如，在日本特開2004-264623號公報中之段落[0021]至[0024]所揭述之化合物(但是，前述之結構單元(a1)至(a4)是除外)。The radically polymerizable monomer to be used for forming the structural unit (a5) is, for example, a compound disclosed in paragraphs [0021] to [0024] of JP-A-2004-264623 (although the foregoing The structural units (a1) to (a4) are excluded).

在此等之中，從提高電特性的觀點，則較佳為如(甲基)丙烯酸二環戊烷酯、(甲基)丙烯酸環己酯、丙烯酸環己酯之含有脂環結構之(甲基)丙烯酸酯類。此外，從透明性的觀點，則較佳為(甲基)丙烯酸甲酯。此外，從耐蝕刻性的觀點，則較佳為苯乙烯或α-甲基苯乙烯等之苯乙烯類。Among these, from the viewpoint of improving electrical properties, it is preferably an alicyclic structure such as dicyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate or cyclohexyl acrylate (A) Base) acrylates. Further, from the viewpoint of transparency, methyl (meth)acrylate is preferred. Further, from the viewpoint of etching resistance, styrene such as styrene or α-methylstyrene is preferable.

結構單元(a5)是可以一種單獨或兩種以上組合使用。The structural unit (a5) may be used alone or in combination of two or more.

在構成(A)縮醛系樹脂之全部結構單元中，結構單元(a5)的含率為0至40莫耳%。若(A)縮醛系樹脂是含有結構單元(a5)時，則在構成(A)縮醛系樹脂之全部結構單元中，結構單元(a5)的含率較佳為1至40莫耳%，更佳為5至30莫耳%，特佳為5至25莫耳%。In all the structural units constituting the (A) acetal resin, the content of the structural unit (a5) is from 0 to 40 mol%. When the (A) acetal resin contains the structural unit (a5), the content of the structural unit (a5) is preferably from 1 to 40 mol% in all the structural units constituting the (A) acetal resin. More preferably, it is 5 to 30 mol%, and particularly preferably 5 to 25 mol%.

在本發明之(A)縮醛系樹脂之重量平均分子量較佳為1,000至50,000，更佳為2,000至30,000，最佳為3,000至12,000。The weight average molecular weight of the (A) acetal resin of the present invention is preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 12,000.

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。Further, the weight average molecular weight in the present invention is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

此外，導入在本發明所使用的(A)縮醛系樹脂所含有的各結構單元之方法是可為聚合法或高分子反應法。Further, the method of introducing each structural unit contained in the (A) acetal resin used in the present invention may be a polymerization method or a polymer reaction method.

在聚合法，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，可藉由將含有結構單元(a1)、結構單元(a2)、結構單元(a3)、結構單元(a4)、及因應需要為形成結構單元(a5)而使用的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。In the polymerization method, monomers having a specific functional group are synthesized in advance, and these monomers are copolymerized. That is, the radical polymerizable single can be used by forming the structural unit (a1), the structural unit (a2), the structural unit (a3), the structural unit (a4), and the structural unit (a5) as needed. The radical polymerizable monomer mixture is synthesized by polymerization using a radical polymerization initiator in an organic solvent.

在高分子反應法，則在進行聚合反應後，利用在所獲得共聚物之結構單元所含有的反應性基來將必要的官能基導入於結構單元中。In the polymer reaction method, after the polymerization reaction is carried out, the necessary functional groups are introduced into the structural unit by using a reactive group contained in the structural unit of the obtained copolymer.

前述結構單元(a1)至(a5)對於前述(A)縮醛系樹脂之導入是可為聚合法或高分子反應法，也可該等兩種方法併用。The introduction of the structural units (a1) to (a5) to the (A) acetal resin may be a polymerization method or a polymer reaction method, or may be used in combination.

在下文中，例示較佳的在本發明所使用的(A)縮醛系樹脂，但是並不受限於此者。Hereinafter, the (A) acetal resin which is preferably used in the present invention is exemplified, but is not limited thereto.

另外，在下文所例示的(A)縮醛系樹脂之重量平均分子量是2,000至30,000。組成比，則以莫耳%表示於(　　)內。Further, the weight average molecular weight of the (A) acetal resin exemplified below is 2,000 to 30,000. The composition ratio is expressed in ( ) in % of moles.

甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸/甲基丙烯酸環氧丙酯/甲基丙烯酸2-羥基乙酯共聚物(45/8/35/12)、甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸/甲基丙烯酸環氧丙酯/甲基丙烯酸2-羥基乙酯/苯乙烯共聚物(40/8/35/12/5)、甲基丙烯酸1-環己氧基乙酯/甲基丙烯酸/甲基丙烯酸環氧丙酯/甲基丙烯酸2-羥基乙酯/苯乙烯共聚物(40/8/35/12/5)、甲基丙烯酸四氫呋喃-2-基酯/甲基丙烯酸/甲基丙烯酸環氧丙酯/甲基丙烯酸2-羥基乙酯共聚物(40/10/30/20)、甲基丙烯酸四氫呋喃-2-基酯/甲基丙烯酸/甲基丙烯酸環氧丙酯/甲基丙烯酸2-羥基乙酯/苯乙烯共聚物(35/10/30/15/10)、甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸/甲基丙烯酸環氧丙酯/甲基丙烯酸2-羥基乙酯/甲基丙烯酸二環戊烷酯共聚物(42/11/25/18/4)、甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸/甲基丙烯酸環氧丙酯/甲基丙烯酸2-羥基乙酯/甲基丙烯酸環己酯共聚物(35/10/30/20/5)、甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸/甲基丙烯酸環氧丙酯/聚(乙二醇‧丙二醇)-一甲基丙烯酸酯(Blemmer 50PEP-300、日油(股)製)/甲基丙烯酸二環戊烷酯共聚物(55/9/30/2/4)、甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸/甲基丙烯酸環氧丙酯/甲氧基聚乙二醇甲基丙烯酸酯(Blemmer PME-400、日油(股)製)共聚物(44/4.5/50/1.5)、甲基丙烯酸1-環己氧基乙酯/丙烯酸/甲基丙烯酸環氧丙酯/甲氧基聚乙二醇甲基丙烯酸酯(Blemmer PME-400、日油(股)製)共聚物(45/10/43/2)、甲基丙烯酸1-環己氧基乙酯/甲基丙烯酸/甲基丙烯酸環氧丙酯/甲氧基聚乙二醇甲基丙烯酸酯(Blemmer PME-400、日油(股)製)/甲基丙烯酸二環戊烷酯共聚物(43/15/30/2/10)、甲基丙烯酸四氫-2H-哌喃-2-基酯/甲基丙烯酸/甲基丙烯酸環氧丙酯/甲基丙烯酸2-羥基乙酯共聚物(40/12/28/20)、甲基丙烯酸四氫-2H-哌喃-2-基酯/甲基丙烯酸/甲基丙烯酸環氧丙酯/甲基丙烯酸2-羥基乙酯/苯乙烯共聚物(35/12/28/15/10)、甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸/甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯/甲基丙烯酸2-羥基乙酯共聚物(40/10/30/20)、甲基丙烯酸四氫呋喃-2-基酯/甲基丙烯酸/甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯/甲基丙烯酸2-羥基乙酯共聚物(40/10/30/20)、甲基丙烯酸四氫呋喃-2-基酯/甲基丙烯酸/甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯/甲基丙烯酸2-羥基乙酯共聚物(35/10/33/12/10)、甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸/甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯/甲氧基聚乙二醇甲基丙烯酸酯(Blemmer PME-400、日油(股)製)共聚物(40/10/46/4)、甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸/甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯/甲氧基聚乙二醇甲基丙烯酸酯(Blemmer PME-400、日油(股)製)/甲基丙烯酸2-羥基乙酯共聚物(45/10/30/1/14)、甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸/甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯/甲基丙烯酸2-羥基乙酯/甲基丙烯酸二環戊烷酯共聚物(40/10/25/20/5)、甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸/甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯/甲基丙烯酸2-羥基乙酯/甲基丙烯酸甲酯共聚物(38/7/35/15/5)、甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸/甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯/甲氧基聚乙二醇甲基丙烯酸酯(Blemmer PME-200、日油(股)製)共聚物(50/8/37/5)、甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸/甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯/甲基丙烯酸2,3-二羥基丙酯共聚物(40/7/30/23)、甲基丙烯酸1-環己氧基乙酯/甲基丙烯酸/甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯/甲氧基聚乙二醇甲基丙烯酸酯(Blemmer PME-400、日油(股)製)共聚物(41/14/41/4)、甲基丙烯酸1-環己氧基乙酯/甲基丙烯酸/甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯/甲基丙烯酸2-羥基乙酯共聚物(40/10/25/25)、甲基丙烯酸四氫-2H-哌喃-2-基酯/甲基丙烯酸/甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯/甲基丙烯酸2,3-二羥基丙酯共聚物(40/5/30/25)、甲基丙烯酸1-環己氧基乙酯/丙烯酸/丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯/甲氧基聚乙二醇甲基丙烯酸酯(Blemmer PME-200、日油(股)製)共聚物(40/12/44/4)、甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸/丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯/甲基丙烯酸2-羥基乙酯共聚物(40/10/32/18)、甲基丙烯酸1-乙氧基乙酯/甲基丙烯酸/甲基丙烯酸3,4-環氧基環己基甲酯/甲基丙烯酸2-羥基乙酯共聚物(40/5/35/20)、甲基丙烯酸1-乙氧基乙酯/丙烯酸/甲基丙烯酸3,4-環氧基環己基甲酯/甲氧基聚乙二醇甲基丙烯酸酯(Blemmer PME-200、日油(股)製)/甲基丙烯酸甲酯共聚物(40/15/35/5/5)、甲基丙烯酸1-乙氧基乙酯/4-羥基苯甲酸(3-甲基丙烯醯氧基-2-羥基丙基)酯/甲基丙烯酸環氧丙酯/甲基丙烯酸2-羥基乙酯共聚物(30/12/38/20)、甲基丙烯酸1-乙氧基乙酯/4-羥基苯甲酸(3-甲基丙烯醯氧基丙基)酯/甲基丙烯酸環氧丙酯/甲基丙烯酸2-羥基乙酯共聚物(40/7/35/18)。1-Ethoxyethyl methacrylate/methacrylic acid/glycidyl methacrylate/2-hydroxyethyl methacrylate copolymer (45/8/35/12), 1-ethoxy methacrylate Ethyl ethyl ester / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / styrene copolymer (40 / 8 / 35/12/5), 1-cyclohexyl methacrylate Ethyl/methacrylic acid/glycidyl methacrylate/2-hydroxyethyl methacrylate/styrene copolymer (40/8/35/12/5), tetrahydrofuran-2-yl methacrylate/ Methacrylic acid/glycidyl methacrylate/2-hydroxyethyl methacrylate copolymer (40/10/30/20), tetrahydrofuran-2-yl methacrylate/methacrylic acid/methacrylic acid ring Oxypropyl propyl ester / 2-hydroxyethyl methacrylate / styrene copolymer (35/10/30/15/10), 1-ethoxyethyl methacrylate / methacrylic acid / methacrylic acid propylene Ester/2-hydroxyethyl methacrylate/dicyclopentanyl methacrylate copolymer (42/11/25/18/4), 1-ethoxyethyl methacrylate/methacrylic acid/methyl Glycidyl acrylate / 2-hydroxyethyl methacrylate / cyclohexyl methacrylate (35/10/30/20/5), 1-ethoxyethyl methacrylate/methacrylic acid/glycidyl methacrylate/poly(ethylene glycol ‧ propylene glycol)-monomethacrylate (Blemmer 50PEP-300, manufactured by Nippon Oil Co., Ltd.) / Dicyclopentanyl methacrylate copolymer (55/9/30/2/4), 1-ethoxyethyl methacrylate / methacrylic acid /Glycidyl methacrylate / methoxy polyethylene glycol methacrylate (Blemmer PME-400, manufactured by Nippon Oil Co., Ltd.) copolymer (44/4.5/50/1.5), methacrylic acid 1- Cyclohexyloxyethyl ester / acrylic acid / glycidyl methacrylate / methoxy polyethylene glycol methacrylate (Blemmer PME-400, manufactured by Nippon Oil Co., Ltd.) copolymer (45/10/43/ 2) 1-cyclohexyloxyethyl methacrylate/methacrylic acid/glycidyl methacrylate/methoxy polyethylene glycol methacrylate (Blemmer PME-400, Nippon Oil Co., Ltd.) ) / Dicyclopentanyl methacrylate copolymer (43/15/30/2/10), tetrahydro-2H-pyran-2-yl methacrylate / methacrylic acid / methacrylic acid propylene Ester/2-hydroxyethyl methacrylate copolymer (40/12/28/20), tetrahydro-2H-pentan-2-yl methacrylate/methacrylic acid/methyl Glycidyl acrylate / 2-hydroxyethyl methacrylate / styrene copolymer (35/12/28/15/10), 1-ethoxyethyl methacrylate / methacrylic acid / methacrylic acid ( 3-Ethyloxetane-3-yl)methyl ester/2-hydroxyethyl methacrylate copolymer (40/10/30/20), tetrahydrofuran-2-yl methacrylate/methacrylic acid /(3-Ethyloxetane-3-yl)methyl methacrylate/2-hydroxyethyl methacrylate copolymer (40/10/30/20), tetrahydrofuran-2-yl methacrylate Ester/methacrylic acid/(3-ethyloxetan-3-yl)methyl methacrylate/2-hydroxyethyl methacrylate copolymer (35/10/33/12/10), A 1-Ethyl ethacrylate/methacrylic acid/(3-ethyloxetan-3-yl)methyl methacrylate/methoxy polyethylene glycol methacrylate (Blemmer PME- 400, Nippon Oil Co., Ltd. copolymer (40/10/46/4), 1-ethoxyethyl methacrylate/methacrylic acid/methacrylic acid (3-ethyloxetane- 3-yl)methyl ester/methoxy polyethylene glycol methacrylate (Blemmer PME-400, manufactured by Nippon Oil Co., Ltd.) / 2-hydroxyethyl methacrylate copolymer (45/10/30/1 /14), 1-Ethyl ethacrylate/methacrylic acid/(3-ethyloxetan-3-yl)methyl methacrylate/2-hydroxyethyl methacrylate/dicyclopentyl methacrylate Alkyl ester copolymer (40/10/25/20/5), 1-ethoxyethyl methacrylate/methacrylic acid/methacrylic acid (3-ethyloxetan-3-yl) A Ester/2-hydroxyethyl methacrylate/methyl methacrylate copolymer (38/7/35/15/5), 1-ethoxyethyl methacrylate/methacrylic acid/methacrylic acid (3 -Ethyloxetane-3-yl)methyl ester/methoxy polyethylene glycol methacrylate (Blemmer PME-200, manufactured by Nippon Oil Co., Ltd.) Copolymer (50/8/37/5 ), 1-ethoxyethyl methacrylate / methacrylic acid / (3-ethyloxetane-3-yl)methyl methacrylate / 2,3-dihydroxypropyl methacrylate copolymerization (40/7/30/23), 1-cyclohexyloxyethyl methacrylate/methacrylic acid/methacrylic acid (3-ethyloxetan-3-yl)methyl ester/methoxy Polyethylene glycol methacrylate (Blemmer PME-400, Nippon Oil Co., Ltd.) copolymer (41/14/41/4), 1-cyclohexyloxyethyl methacrylate / methacrylic acid / Methacrylic acid (3-B Base oxetane-3-yl)methyl ester/2-hydroxyethyl methacrylate copolymer (40/10/25/25), tetrahydro-2H-pentan-2-yl methacrylate/ Methacrylic acid/(3-ethyloxetan-3-yl)methyl methacrylate/2,3-dihydroxypropyl methacrylate copolymer (40/5/30/25), methyl 1-cyclohexyloxyethyl acrylate/acrylic acid/(3-ethyloxetan-3-yl)methyl acrylate/methoxy polyethylene glycol methacrylate (Blemmer PME-200, Nippon Oil) Copolymer (40/12/44/4), 1-ethoxyethyl methacrylate/methacrylic acid/(3-ethyloxetan-3-yl)methyl acrylate /2-Hydroxyethyl methacrylate copolymer (40/10/32/18), 1-ethoxyethyl methacrylate/methacrylic acid/3,4-epoxycyclohexylmethyl methacrylate / 2-hydroxyethyl methacrylate copolymer (40/5/35/20), 1-ethoxyethyl methacrylate / acrylic acid / methacrylic acid 3,4-epoxycyclohexyl methyl ester / A Oxypolyethylene glycol methacrylate (Blemmer PME-200, manufactured by Nippon Oil Co., Ltd.) / methyl methacrylate copolymer (40/15/35/5/5), 1-ethoxy methacrylate Ethyl ethyl ester / 4-hydroxybenzoic acid (3 -Methethyloxy-2-hydroxypropyl)methacrylate/glycidyl methacrylate/2-hydroxyethyl methacrylate copolymer (30/12/38/20), 1-b methacrylate Ethyloxyethyl/4-hydroxybenzoic acid (3-methacryloxypropyl)ester/glycidyl methacrylate/2-hydroxyethyl methacrylate copolymer (40/7/35/18) ).

(A)縮醛系樹脂是可在感光性樹脂組成物中以一種單獨或兩種以上組合使用。(A) The acetal-based resin can be used alone or in combination of two or more kinds in the photosensitive resin composition.

在(A)縮醛系樹脂之結構單元(a1)至(a5)之含率是以莫耳換算計相對於(A)縮醛系樹脂為1時，則結構單元(a1)：結構單元(a2)：結構單元(a3)：結構單元(a4)：結構單元(a5)=(0.2至0.65)：(0.02至0.2)：(0.2至0.60)：(0.005至0.3)：(0至0.4)，更佳為(0.25至0.6)：(0.02至0.15)：(0.25至0.55)：(0.005至0.25)：(0至0.3)，進一步更佳為(0.25至0.55)：(0.03至0.15)：(0.25至0.5)：(0.01至0.25)：(0至0.25)。When the content ratio of the structural units (a1) to (a5) of the (A) acetal resin is 1 in terms of moles relative to the (A) acetal resin, the structural unit (a1): structural unit ( A2): structural unit (a3): structural unit (a4): structural unit (a5) = (0.2 to 0.65): (0.02 to 0.2): (0.2 to 0.60): (0.005 to 0.3): (0 to 0.4) More preferably (0.25 to 0.6): (0.02 to 0.15): (0.25 to 0.55): (0.005 to 0.25): (0 to 0.3), further preferably (0.25 to 0.55): (0.03 to 0.15): (0.25 to 0.5): (0.01 to 0.25): (0 to 0.25).

此外，在構成(A)縮醛系樹脂之全部結構單元中，結構單元(a4)的含量為3至30質量%，更佳為3至25質量%，特佳為5至25質量%。Further, in all the structural units constituting the (A) acetal resin, the content of the structural unit (a4) is from 3 to 30% by mass, more preferably from 3 to 25% by mass, particularly preferably from 5 to 25% by mass.

在本發明之感光性樹脂組成物中之(A)縮醛系樹脂的含量，相對於感光性樹脂組成物之總固體成分，則較佳為20至99質量%，更佳為40至97質量%，進一步更佳為60至95質量%。若含量為在此範圍時，則經顯影時的圖案形成性為良好。另外，所謂的感光性樹脂組成物之固體成分含量是表示將溶劑等之揮發性成分除外之量。The content of the (A) acetal resin 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 preferably 60 to 95% by mass. When the content is in this range, the pattern formability at the time of development is good. In addition, the solid content of the photosensitive resin composition is an amount excluding a volatile component such as a solvent.

另外，在本發明之感光性樹脂組成物中，可在不阻礙本發明之功效範圍併用除了(A)縮醛系樹脂以外之樹脂。但是，除了(A)縮醛系樹脂以外之樹脂的含量，從顯影性的觀點，則較佳為少於(A)縮醛系樹脂的含量。Further, in the photosensitive resin composition of the present invention, a resin other than the (A) acetal resin can be used without impairing the efficacy of the present invention. However, the content of the resin other than the (A) acetal resin is preferably less than the content of the (A) acetal resin from the viewpoint of developability.

(B)光酸產生劑(B) Photoacid generator

本發明之感光性樹脂組成物是含有(B)光酸產生劑。在本發明使用之(B)光酸產生劑較佳為會感應波長300 nm以上，較佳為波長300至450 nm之活性光線而產生酸之化合物，但是其化學結構並無特殊限制者。此外，對於不會直接感應波長300 nm以上的活性光線之光酸產生劑，若其為藉由與增感劑併用即可感應波長300 nm以上的活性光線而產生酸之化合物時，則也可與增感劑組合使用。The photosensitive resin composition of the present invention contains (B) a photoacid generator. The (B) photoacid generator used in the present invention is preferably a compound which induces an acid having a wavelength of 300 nm or more, preferably 300 to 450 nm, to generate an acid, but the chemical structure thereof is not particularly limited. In addition, for a photoacid generator which does not directly induce active light having a wavelength of 300 nm or more, if it is a compound which generates an acid by using active light having a wavelength of 300 nm or more by using it together with a sensitizer, it is also Used in combination with a sensitizer.

在本發明使用之光酸產生劑較佳為會產生pKa為4以下之酸的光酸產生劑，更佳為會產生pKa為3以下之酸的光酸產生劑。「光酸產生劑」的實例是可列舉：三氯甲基-s-三氮類、鋶鹽或錪鹽、第四級銨鹽類、重氮甲烷化合物、醯亞胺基磺酸酯化合物、及肟磺酸酯化合物等。在此等之中，從高感度的觀點，較佳為使用肟磺酸酯化合物。此等光酸產生劑是可以一種單獨或兩種以上組合使用。The photoacid generator used in the present invention is preferably a photoacid generator which produces an acid having a pKa of 4 or less, more preferably a photoacid generator which produces an acid having a pKa of 3 or less. An example of the "photoacid generator" is exemplified by trichloromethyl-s-trinitrogen a class, a barium salt or a phosphonium salt, a fourth-order ammonium salt, a diazomethane compound, a guanidinium sulfonate compound, and an oxime sulfonate compound. Among these, from the viewpoint of high sensitivity, it is preferred to use an oxime sulfonate compound. These photoacid generators may be used alone or in combination of two or more.

此等「光酸產生劑」的具體實例是可例示如下：「三氯甲基-s-三氮類」是可例示：2-(3-氯苯基)-雙(4,6-三氯甲基)-s-三氮、2-(4-甲氧基苯基)-雙(4,6-三氯甲基)-s-三氮、2-(4-甲基苯硫基)-雙(4,6-三氯甲基)-s-三氮、2-(4-甲氧基-β-苯乙烯基)-雙(4,6-三氯甲基)-s-三氮、2-向日葵基-雙(4,6-三氯甲基)-s-三氮、2-[2-(呋喃-2-基)乙烯基]-雙(4,6-三氯甲基)-s-三氮、2-[2-(5-甲基呋喃-2-基)乙烯基]-雙(4,6-三氯甲基)-s-三氮、2-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-雙(4,6-三氯甲基)-s-三氮、或2-(4-甲氧基萘基)-雙(4,6-三氯甲基)-s-三氮等；「二芳基錪鹽類」是可例示：二苯基錪三氟醋酸鹽、二苯基錪三氟甲烷磺酸鹽、4-甲氧基苯基苯基錪三氟甲烷磺酸鹽、4-甲氧基苯基苯基錪三氟醋酸鹽、苯基-4-(2’-羥基-1’-十四氧基)苯基錪三氟甲烷磺酸鹽、4-(2’-羥基-1’-十四氧基)苯基錪六氟銻酸鹽、或苯基-4-(2’-羥基-1’-十四氧基)苯基錪對甲苯磺酸鹽等；「三芳基鋶鹽類」是可例示：三苯基鋶三氟甲烷磺酸鹽、三苯基鋶三氟醋酸鹽、4-甲氧基苯基二苯基鋶三氟甲烷磺酸鹽、4-甲氧基苯基二苯基鋶三氟醋酸鹽、4-苯基苯硫基二苯基鋶三氟甲烷磺酸鹽、或4-苯基苯硫基二苯基鋶三氟醋酸鹽等；「第四級銨鹽類」是可例示：四甲基銨丁基參(2,6-二氟苯基)硼酸鹽、四甲基銨己基參(對氯苯基)硼酸鹽、四甲基銨己基參(3-三氟甲基苯基)硼酸鹽、苯甲基二甲基苯基銨丁基參(2,6-二氟苯基)硼酸鹽、苯甲基二甲基苯基銨己基參(對氯苯基)硼酸鹽、苯甲基二甲基苯基銨己基參(3-三氟甲基苯基)硼酸鹽等；「重氮甲烷衍生物」是可例示：雙(環己基磺醯基)重氮甲烷、雙(三級丁基磺醯基)重氮甲烷、雙(對甲苯磺醯基)重氮甲烷等；「醯亞胺基磺酸酯衍生物」是可例示：三氟甲基磺醯氧基雙環[2.2.1]-庚-5-烯-二羧基醯亞胺、琥珀醯亞胺三氟甲基磺酸酯、鄰苯二甲醯亞胺三氟甲基磺酸酯、N-羥基萘二甲醯亞胺甲烷磺酸酯、N-羥基-5-降冰片烯-2,3-二羧基醯亞胺丙烷磺酸酯等。Specific examples of such "photoacid generators" can be exemplified as follows: "trichloromethyl-s-trinitrogen The class is exemplified: 2-(3-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazo 2-(4-methoxyphenyl)-bis(4,6-trichloromethyl)-s-triazole ,2-(4-methylphenylthio)-bis(4,6-trichloromethyl)-s-triazole , 2-(4-methoxy-β-styryl)-bis(4,6-trichloromethyl)-s-triazole , 2-mallowyl-bis(4,6-trichloromethyl)-s-triazole ,2-[2-(furan-2-yl)vinyl]-bis(4,6-trichloromethyl)-s-triazole ,2-[2-(5-methylfuran-2-yl)vinyl]-bis(4,6-trichloromethyl)-s-triazole ,2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-bis(4,6-trichloromethyl)-s-triazole Or 2-(4-methoxynaphthyl)-bis(4,6-trichloromethyl)-s-triazole Etc. "Diarylsulfonium salt" is exemplified: diphenylsulfonium trifluoroacetate, diphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenylphenylsulfonium trifluoromethanesulfonate 4-methoxyphenylphenylphosphonium trifluoroacetate, phenyl-4-(2'-hydroxy-1'-tetradecyloxy)phenylphosphonium trifluoromethanesulfonate, 4-(2'-hydroxy-1'-tetradecyloxy)phenylphosphonium hexafluoroantimonate, or phenyl-4-(2'-hydroxy-1'-tetradecyloxy)phenylindole p-toluenesulfonate; The "triarylsulfonium salt" is exemplified by triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylphosphonium trifluoromethanesulfonate, and 4 -Methoxyphenyldiphenylphosphonium trifluoroacetate, 4-phenylphenylthiodiphenylphosphonium trifluoromethanesulfonate, or 4-phenylphenylthiodiphenylphosphonium trifluoroacetate "Fourth-grade ammonium salt" is exemplified: tetramethylammonium butyl sulfonate (2,6-difluorophenyl) borate, tetramethylammonium hexyl ginseng (p-chlorophenyl) borate, tetramethyl Alkyl ammonium hexyl ginseng (3-trifluoromethylphenyl) borate, benzyl dimethyl phenyl ammonium butyl ginseng (2,6-difluorophenyl) borate, benzyl dimethyl phenyl Ammonium Base (p-chlorophenyl) borate, benzyldimethylphenyl ammonium hexyl ginseng (3-trifluoromethylphenyl) borate, etc.; "diazomethane derivative" is exemplified: double (ring Hexylsulfonyl)diazomethane, bis(tertiary butylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, etc.; "anthracene sulfonate derivative" is exemplified : Trifluoromethylsulfonyloxybicyclo[2.2.1]-hept-5-ene-dicarboxyarmine, amber quinone imine triflate, phthalimide trifluoromethyl A sulfonate, N-hydroxynaphthalene imine methane sulfonate, N-hydroxy-5-norbornene-2,3-dicarboxynonimine propane sulfonate, and the like.

本發明之感光性樹脂組成物較佳為(B)光酸產生劑是含有具有至少一個以下列結構(1)所代表之肟磺酸酯殘基之肟磺酸酯化合物。The photosensitive resin composition of the present invention is preferably (B) a photoacid generator which is an oxime sulfonate compound having at least one oxime sulfonate residue represented by the following structure (1).

具有至少一個以前述結構(1)所代表之肟磺酸酯殘基之化合物較佳為以下述通式(OS-3)、通式(OS-4)、或通式(OS-5)所代表之肟磺酸酯化合物。The compound having at least one oxime sulfonate residue represented by the above structure (1) is preferably represented by the following formula (OS-3), formula (OS-4), or formula (OS-5). Representative of sulfonate compounds.

通式(OS-3)至(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、烷基氧基、磺酸基、胺基磺醯基、或烷氧基磺醯基，X是代表O或S，n是代表1或2，m是代表0至6之整數。In the general formulae (OS-3) to (OS-5), R 1 represents an alkyl group, an aryl group or a heteroaryl group, and a plurality of R 2 may be independently represented by a hydrogen atom, an alkyl group or an aryl group. Or a halogen atom, a plurality of R 6 may each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, and X represents O. Or S, n represents 1 or 2, and m is an integer representing 0 to 6.

在前述通式(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。在前述通式(OS-3)至(OS-5)中，以R1 所代表之烷基較佳為也可具有取代基之總碳數為1至30之烷基。以R1 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、胺基羰基。在前述通式(OS-3)至(OS-5)中，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、苯甲基等。In the above formulae (OS-3) to (OS-5), the alkyl group, the aryl group or the heteroaryl group represented by R 1 may have a substituent. In the above formulae (OS-3) to (OS-5), the alkyl group represented by R 1 is preferably an alkyl group having a total carbon number of 1 to 30 which may also have a substituent. The substituent which the alkyl group represented by R 1 may have is a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, Aminocarbonyl. In the above-mentioned general formulae (OS-3) to (OS-5), the alkyl group represented by R 1 may be exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, and dibutyl. Base, tertiary butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, benzyl and the like.

此外，在前述通式(OS-3)至(OS-5)中，以R1 所代表之芳基較佳為也可具有取代基之總碳數為6至30之芳基。Further, in the above formulae (OS-3) to (OS-5), the aryl group represented by R 1 is preferably an aryl group having a total carbon number of 6 to 30 which may also have a substituent.

以R1 所代表之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、烷氧基磺醯基。以R1 所代表之芳基較佳為苯基、對甲基苯基、對氯苯基、五氯苯基、五氟苯基、鄰甲氧基苯基、對苯氧基苯基。The substituent which the aryl group represented by R 1 may have may be exemplified by 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. The aryl group represented by R 1 is preferably a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group or a p-phenoxyphenyl group.

此外，在前述通式(OS-3)至(OS-5)中，以R1 所代表之雜芳基較佳為也可具有取代基之總碳數為4至30之雜芳基。Further, in the above formulae (OS-3) to (OS-5), the heteroaryl group represented by R 1 is preferably a heteroaryl group having a total carbon number of 4 to 30 which may also have a substituent.

以R1 所代表之雜芳基也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、烷氧基磺醯基。The substituent which the heteroaryl group represented by R 1 may have may be a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, An aryloxycarbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, an alkoxysulfonyl group.

在前述通式(OS-3)至(OS-5)中，以R1 所代表之雜芳基，若其為至少一個雜芳香族環時即可，例如雜芳香族環與苯環也可加以縮環。In the above formulae (OS-3) to (OS-5), the heteroaryl group represented by R 1 may be at least one heteroaromatic ring, for example, a heteroaromatic ring and a benzene ring may also be used. Reduce the loop.

以R1 所代表之雜芳基是可列舉：也可具有取代基之由選自由噻吩環、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移除一個氫原子之基。The heteroaryl group represented by R 1 may be exemplified by a substituent selected from a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzo compound. The ring in the group consisting of imidazole rings removes a group of hydrogen atoms.

在前述通式(OS-3)至(OS-5)中，R2 較佳為氫原子、烷基、或芳基，更佳為氫原子或烷基。In the above formulae (OS-3) to (OS-5), R 2 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

在該通式(OS-3)至(OS-5)中，在化合物中存在兩個以上之R2 中，較佳為一個或兩個為烷基、芳基或鹵素原子，更佳為一個為烷基、芳基或鹵素原子，特佳為一個為烷基，且其餘為氫原子。In the general formulae (OS-3) to (OS-5), in the compound, two or more of R 2 are present, preferably one or two are an alkyl group, an aryl group or a halogen atom, more preferably one. It is preferably an alkyl group, an aryl group or a halogen atom, and the other one is an alkyl group, and the remainder is a hydrogen atom.

在該通式(OS-3)至(OS-5)中，以R2 所代表之烷基或芳基是也可具有取代基。In the general formulae (OS-3) to (OS-5), the alkyl group or the aryl group represented by R 2 may have a substituent.

以R2 所代表之烷基或芳基也可具有之取代基是可例示與在前述R1 之烷基或芳基可具有的取代基相同之基。The alkyl group or the aryl group represented by R 2 may have a substituent which is the same as the substituent which the alkyl group or the aryl group of the above R 1 may have.

在前述通式(OS-3)至(OS-5)中，以R2 所代表之烷基較佳為也可具有取代基之總碳數為1至12之烷基，更佳為也可具有取代基之總碳數為1至6之烷基。In the above formulae (OS-3) to (OS-5), the alkyl group represented by R 2 is preferably an alkyl group having a total carbon number of 1 to 12 which may also have a substituent, more preferably also The alkyl group having a substituent having a total carbon number of 1 to 6 is used.

以R2 所代表之烷基較佳為甲基、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、苯甲基；更佳為甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、正己基；進一步更佳為甲基、乙基、正丙基、正丁基、正己基；特佳為甲基。The alkyl group represented by R 2 is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, n-hexyl, allyl, chloromethyl or bromine. Methyl, methoxymethyl, benzyl; more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, n-hexyl; further preferably Methyl, ethyl, n-propyl, n-butyl, n-hexyl; particularly preferred is methyl.

在前述通式(OS-3)至(OS-5)中，以R2 所代表之芳基較佳為也可具有取代基之總碳數為6至30之芳基。In the above formulae (OS-3) to (OS-5), the aryl group represented by R 2 is preferably an aryl group having a total carbon number of 6 to 30 which may also have a substituent.

以R2 所代表之芳基較佳為苯基、對甲基苯基、鄰氯苯基、對氯苯基、鄰甲氧基苯基、對苯氧基苯基。The aryl group represented by R 2 is preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group or a p-phenoxyphenyl group.

以R2 所代表之鹵素原子是可列舉氟原子、氯原子、溴原子、碘原子。在此等之中，較佳為氯原子、溴原子。The halogen atom represented by R 2 may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among these, a chlorine atom and a bromine atom are preferred.

在前述通式(OS-3)至(OS-5)中，X是代表O或S，較佳為O。In the above formulae (OS-3) to (OS-5), X represents O or S, preferably O.

通式(OS-3)至(OS-5)中，將X作為環員而含有之環為5員環或6員環。In the general formulae (OS-3) to (OS-5), the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.

在該通式(OS-3)至(OS-5)中，n是代表1或2，X為O時，則n較佳為1，此外，X為S時，則n較佳為2。In the general formulae (OS-3) to (OS-5), n represents 1 or 2, and when X is O, n is preferably 1, and when X is S, n is preferably 2.

在前述通式(OS-3)至(OS-5)中，以R6 所代表之烷基及烷基氧基是也可具有取代基。In the above formulae (OS-3) to (OS-5), the alkyl group and the alkyloxy group represented by R 6 may have a substituent.

在該通式(OS-3)至(OS-5)中，以R6 所代表之烷基較佳為也可具有取代基之總碳數為1至30之烷基。In the general formulae (OS-3) to (OS-5), the alkyl group represented by R 6 is preferably an alkyl group having a total carbon number of 1 to 30 which may also have a substituent.

以R6 所代表之烷基也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、胺基羰基。The substituent which the alkyl group represented by R 6 may have may be a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group or an aryloxycarbonyl group. , aminocarbonyl.

在前述通式(OS-3)至(OS-5)中，以R6 所代表之烷基較佳為甲基、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、苯甲基。In the above formulae (OS-3) to (OS-5), the alkyl group represented by R 6 is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group or a secondary butyl group. , tertiary butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, benzyl.

在前述通式(OS-3)至(OS-5)中，以R6 所代表之烷基氧基較佳為也可具有取代基之總碳數為1至30之烷基氧基。In the above formulae (OS-3) to (OS-5), the alkyloxy group represented by R 6 is preferably an alkyloxy group having a total carbon number of 1 to 30 which may also have a substituent.

以R6 所代表之烷基氧基也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、胺基羰基。The alkyloxy group represented by R 6 may have a substituent: halogen atom, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkoxycarbonyl group, aryloxy group Alkylcarbonyl, aminocarbonyl.

在前述通式(OS-3)至(OS-5)中，以R6 所代表之烷基氧基較佳為甲基氧基、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。In the above formulae (OS-3) to (OS-5), the alkyloxy group represented by R 6 is preferably a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group or a benzene group. Oxyethyloxy, trichloromethyloxy, or ethoxyethyloxy.

在R6 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、胺基磺醯基。The aminosulfonyl group at R 6 may, for example, be a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group or an amine group. Sulfonyl.

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、丁氧基磺醯基。The alkoxysulfonyl group represented by R 6 may, for example, be a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group or a butoxysulfonyl group.

此外，在前述通式(OS-3)至(OS-5)中，m是代表0至6之整數，較佳為0至2之整數，更佳為0或1，特佳為0。Further, in the above 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, and particularly preferably 0.

此外，以前述通式(OS-3)所代表之化合物特佳為以下述通式(OS-6)、(OS-10)或(OS-11)所代表之化合物；以前述通式(OS-4)所代表之化合物特佳為以下述通式(OS-7)所代表之化合物；以前述通式(OS-5)所代表之化合物特佳為以下述通式(OS-8)或(OS-9)所代表之化合物。Further, the compound represented by the above formula (OS-3) is particularly preferably a compound represented by the following formula (OS-6), (OS-10) or (OS-11); The compound represented by the above formula (4) is particularly preferably a compound represented by the following formula (OS-7); and the compound represented by the above formula (OS-5) is particularly preferably of the following formula (OS-8) or Compound represented by (OS-9).

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、碳數為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，R10 是代表氫原子或甲基。In the general formulae (OS-6) to (OS-11), R 1 represents an alkyl group, an aryl group or a heteroaryl group, R 7 represents a hydrogen atom or a bromine atom, and R 8 represents a hydrogen atom and has a carbon number of 1 To 8 alkyl, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl or chlorophenyl, R 9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group R 10 represents a hydrogen atom or a methyl group.

在前述通式(OS-6)至(OS-11)之R1 是與前述通式(OS-3)至(OS-5)之R1 為同義，較佳的模式也為相同。In the general formula (OS-6) to (OS-11) and R 1 is of the general formula (OS-3) to (OS-5) R 1 is the same meaning as the preferred mode is also the same.

在前述通式(OS-6)之R7 是代表氫原子或溴原子，較佳為氫原子。R 7 in the above formula (OS-6) represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

在該通式(OS-6)至(OS-11)之R8 是代表氫原子、碳數為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，較佳為碳數為1至8之烷基、鹵素原子或苯基，更佳為碳數為1至8之烷基，進一步更佳為碳數為1至6之烷基，特佳為甲基。R 8 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, or a methoxy group. a methyl group, a phenyl group or a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably a carbon number of An alkyl group of 1 to 6 is particularly preferably a methyl group.

在該通式(OS-8)及(OS-9)之R9 是代表氫原子、鹵素原子、甲基或甲氧基，較佳為氫原子。R 9 in the above formulae (OS-8) and (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, preferably a hydrogen atom.

在該通式(OS-8)至(OS-11)之R10 是代表氫原子或甲基，較佳為氫原子。R 10 in the general formulae (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

此外，在前述肟磺酸酯化合物中，關於肟之立體結構(E,Z)是任一者皆可，也可為混合物。Further, in the above oxime sulfonate compound, the three-dimensional structure (E, Z) of ruthenium may be either a mixture or a mixture.

以前述通式(OS-3)至通式(OS-5)所代表之肟磺酸酯化合物的具體實例是可列舉下列例示化合物，但是並不受限於此等者。Specific examples of the oxime sulfonate compound represented by the above formula (OS-3) to formula (OS-5) include the following exemplified compounds, but are not limited thereto.

具有至少一個以前述結構(1)所代表之肟磺酸酯基之肟磺酸酯化合物之適合的其他模式是可列舉以下述通式(OS-1)所代表之化合物。A further suitable mode of the oxime sulfonate compound having at least one oxime sulfonate group represented by the above structure (1) is a compound represented by the following formula (OS-1).

在前述通式(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。In the above formula (OS-1), R 1 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 or a cyanogen group. A aryl group, an aryl group, or a heteroaryl group. R 2 represents an alkyl group or an aryl group.

X是代表-O-、-S-、-NH-、-NR5 -、-CH2 -、-CR6 H-、或-CR6 R7 -，R5 至R7 是代表烷基、或芳基。X represent -O -, - S -, - NH -, - NR 5 -, - CH 2 -, - CR 6 H-, or -CR 6 R 7 -, R 5 to R 7 represent an alkyl group, or Aryl.

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。在R21 至R24 中之兩個是可各自相互鍵結而形成環。R 21 to R 24 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 or a cyanogen group. Base, or aryl. Two of R 21 to R 24 may be bonded to each other to form a ring.

R21 至R24 較佳為氫原子、鹵素原子、及烷基，此外，R21 至R24 中至少兩個相互鍵結而形成芳基之模式也可列舉。其中，從感度的觀點，則較佳為R21 至R24 任-者皆為氫原子之模式。R 21 to R 24 are preferably a hydrogen atom, a halogen atom, and an alkyl group, and a mode in which at least two of R 21 to R 24 are bonded to each other to form an aryl group is also exemplified. Among them, from the viewpoint of sensitivity, it is preferred that all of R 21 to R 24 are hydrogen atoms.

前述之取代基任一者皆可更進一步具有取代基。Any of the above substituents may further have a substituent.

以前述通式(OS-1)所代表之化合物更佳為以下述通式(OS-2)所代表之化合物。The compound represented by the above formula (OS-1) is more preferably a compound represented by the following formula (OS-2).

在前述通式(OS-2)中，R1 、R2 、R21 至R24 是各自與通式(OS-1)之R1 、R2 、R21 至R24 為同義，較佳的實例也為相同。在此等之中，通式(OS-1)、及通式(OS-2)之R1 為氰基、或芳基之模式為更佳，以通式(OS-2)所代表、R1 為氰基、苯基或萘基之模式為最佳。此外，在前述肟磺酸酯化合物，關於肟或苯并噻唑環之立體結構(E,Z等)是各自可為任一者或為混合物皆可。In the general formula (OS-2) of, R 1, R 2, R 21 to R 24 are each formula (OS-1) of R 1, R 2, R 21 to R 24 are synonymous, preferred The examples are also the same. Among these, the mode of the general formula (OS-1) and the general formula (OS-2) wherein R 1 is a cyano group or an aryl group is more preferably represented by the formula (OS-2), R The mode of 1 being a cyano group, a phenyl group or a naphthyl group is most preferred. Further, in the above oxime sulfonate compound, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.

在下文中，說明適合使用於本發明之以通式(OS-1)所代表之化合物的具體實例(例示化合物b-1至b-34)，但是本發明並不受限於此。另外，在具體實例中，Me是代表甲基，Et是代表乙基，Bn是代表苯甲基，Ph是代表苯基。Hereinafter, specific examples (exemplified compounds b-1 to b-34) which are suitable for use in the present invention, which are represented by the general formula (OS-1), are illustrated, but the invention is not limited thereto. Further, in a specific example, Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, and Ph represents a phenyl group.

在上述化合物中，從感度與安定性並存的觀點，則較佳為b-9、b-16、b-31、b-33。Among the above compounds, b-9, b-16, b-31, and b-33 are preferred from the viewpoint of coexistence of sensitivity and stability.

具有至少一個以上述結構(1)所代表之肟磺酸酯殘基之肟磺酸酯化合物較佳為以下述通式(2)所代表之化合物：The oxime sulfonate compound having at least one oxime sulfonate residue represented by the above structure (1) is preferably a compound represented by the following formula (2):

R1A －C(R2A )=N－O－SO2 －R3A 　(2)R 1A -C(R 2A )=N-O-SO 2 -R 3A (2)

。.

通式(2)中，R1A 是代表碳原子數為1至6之烷基、碳原子數為1至4之鹵化烷基、苯基、聯苯基、萘基、2-呋喃基、2-噻吩基、碳原子數為1至4之烷氧基或氰基；R1A 是苯基、聯苯基、萘基或蒽基時，此等基是可為經選自由鹵素原子、羥基、碳原子數為1至4之烷基、碳原子數為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 是代表碳原子數為1至10之烷基、碳原子數為1至10之烷氧基、碳原子數為1至5之鹵化烷基、碳原子數為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。R2A 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取代基之苯環鍵結。R3A 是代表碳原子數為1至10之烷基、碳原子數為1至10之烷氧基、碳原子數為1至5之鹵化烷基、碳原子數為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、碳原子數為1至10之烷基、碳原子數為1至10之烷氧基、碳原子數為1至5之鹵化烷基或碳原子數為1至5之鹵化烷氧基。In the formula (2), R 1A is an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, 2 a thienyl group, an alkoxy group having 1 to 4 carbon atoms or a cyano group; when R 1A is a phenyl group, a biphenyl group, a naphthyl group or a fluorenyl group, these groups may be selected from a halogen atom, a hydroxyl group, Substituents in the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a nitro group are substituted. R 2A 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, or 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. R 2A and R 1A are bondable to each other to form a 5-membered or 6-membered ring which is a benzene ring bond which may have one or two optional substituents. R 3A 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, or 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.

以R1A 所代表之碳原子數為1至6之烷基是可為直鏈或分枝鏈烷基，其可列舉：例如，甲基、乙基、丙基、異丙基、正丁基、二級丁基、三級丁基、正戊基、異戊基、正己基、或2-乙基丁基。The alkyl group having 1 to 6 carbon atoms represented by R 1A may be a linear or branched alkyl group, which may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group or a n-butyl group. , secondary butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, or 2-ethylbutyl.

以R1A 所代表之碳原子數為1至4之鹵化烷基是可列舉：例如，氯甲基、三氯甲基、三氟甲基、或2-溴丙基。The halogenated alkyl group having 1 to 4 carbon atoms represented by R 1A may, for example, be a chloromethyl group, a trichloromethyl group, a trifluoromethyl group or a 2-bromopropyl group.

以R1A 所代表之碳原子數為1至4之烷氧基是可列舉：甲氧基或乙氧基。The alkoxy group having 1 to 4 carbon atoms represented by R 1A may, for example, be a methoxy group or an ethoxy group.

R1A 是代表苯基、聯苯基、萘基或蒽基時，此等基可為經選自由鹵素原子(例如，氯原子、溴原子、碘原子等)、羥基、碳原子數為1至4之烷基(例如，甲基、乙基、丙基、異丙基、正丁基、二級丁基、三級丁基)、碳原子數為1至4之烷氧基(例如，甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基)及硝基所構成的群組中之取代基加以取代。When R 1A represents a phenyl group, a biphenyl group, a naphthyl group or a fluorenyl group, these groups may be selected from a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, and a carbon number of 1 to An alkyl group of 4 (for example, methyl, ethyl, propyl, isopropyl, n-butyl, dibutyl, tert-butyl), an alkoxy group having 1 to 4 carbon atoms (for example, A Substituents in the group consisting of an oxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, and a nitro group are substituted.

以R2A 所代表之碳原子數為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。Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R 2A include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and secondary butyl group. Tertiary butyl, n-pentyl, isopentyl, secondary pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl and the like.

以R2A 所代表之碳原子數為1至10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。Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R 2A include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and n-pentyloxy groups. Base, n-octyloxy, n-decyloxy and the like.

以R2A 所代表之碳原子數為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。Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R 2A include trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro-n-butyl, and perfluoro. - n-pentyl and the like.

以R2A 所代表之碳原子數為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。Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R 2A include trifluoromethoxy, pentafluoroethoxy, perfluoro-n-propoxy, and perfluoro-n-butyl Oxyl, perfluoro-n-pentyloxy and the like.

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。Specific examples of the phenyl group which may be substituted by W represented by R 2A include o-tolyl, 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-(tert-butyl)phenyl, p-(third Butyl)phenyl, p-(n-pentyl)phenyl, p-(isopentyl)phenyl, p-(tripentyl)phenyl, o-methoxyphenyl, m-methoxyphenyl, para Oxyphenyl, o-ethoxyphenyl, m-ethoxyphenyl, p-ethoxyphenyl, p-(n-propoxy)phenyl, p-(isopropoxy)phenyl, p-(n-butyl) Oxy)phenyl, p-(isobutoxy)phenyl, p-(di-butoxy)phenyl, p-(tertiary butoxy)phenyl, p-(n-pentyloxy)phenyl, p-( Isovaleryl)phenyl, p-(tripentyloxy)phenyl, p-chlorophenyl, p-bromophenyl, p-fluorophenyl, 2,4-dichlorophenyl, 2,4-dibromobenzene Base, 2,4-difluorophenyl, 2,4,6-trichlorophenyl, 2,4,6-tribromophenyl, 2,4,6-trifluorophenyl, pentachlorophenyl, five Bromophenyl, pentafluorophenyl, p-biphenyl, and the like.

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、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。Specific examples of the W-substituted naphthyl group represented by R 2A include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, and 4-methyl-1-naphthyl group. 5-methyl-1-naphthyl, 6-methyl-1-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.

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、10-甲基-2-蒽基等。Specific examples of the thiol group which may be substituted by W represented by R 2A include 2-methyl-1-indenyl group, 3-methyl-1-indenyl group, 4-methyl-1-indenyl group, 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-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. .

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。The dialkylamino group represented by R 2A may, for example, be a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group or a diphenylamino group.

以R3A 所代表之碳原子數為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。Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R 3A include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and secondary butyl group. Tertiary butyl, n-pentyl, isopentyl, secondary pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl and the like.

以R3A 所代表之碳原子數為1至10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。Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R 3A include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and n-pentyloxy groups. Base, n-octyloxy, n-decyloxy and the like.

以R3A 所代表之碳原子數為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。Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R 3A include trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro-n-butyl, and perfluoro- Orthopentyl and the like.

以R3A 所代表之碳原子數為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。Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R 3A include trifluoromethoxy, pentafluoroethoxy, perfluoro-n-propoxy, and perfluoro-n-butyl Oxyl, perfluoro-n-pentyloxy and the like.

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。Specific examples of the phenyl group which may be substituted by W represented by R 3A include o-tolyl, 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-(tert-butyl)phenyl, p-(third Butyl)phenyl, p-(n-pentyl)phenyl, p-(isopentyl)phenyl, p-(tripentyl)phenyl, o-methoxyphenyl, m-methoxyphenyl, para Oxyphenyl, o-ethoxyphenyl, m-ethoxyphenyl, p-ethoxyphenyl, p-(n-propoxy)phenyl, p-(isopropoxy)phenyl, p-(n-butyl) Oxy)phenyl, p-(isobutoxy)phenyl, p-(di-butoxy)phenyl, p-(tertiary butoxy)phenyl, p-(n-pentyloxy)phenyl, p-( Isovaleryl)phenyl, p-(tripentyloxy)phenyl, p-chlorophenyl, p-bromophenyl, p-fluorophenyl, 2,4-dichlorophenyl, 2,4-dibromobenzene Base, 2,4-difluorophenyl, 2,4,6-trichlorophenyl, 2,4,6-tribromophenyl, 2,4,6-trifluorophenyl, pentachlorophenyl, five Bromophenyl, pentafluorophenyl, p-biphenyl, and the like.

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-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、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。Specific examples of the W-substituted naphthyl group represented by R 3A include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, and 4-methyl-1-naphthyl group. 5-methyl-1-naphthyl, 6-methyl-1-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.

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-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、10-甲基-2-蒽基等。Specific examples of the thiol group which may be substituted by W represented by R 3A include 2-methyl-1-indenyl group, 3-methyl-1-indenyl group, and 4-methyl-1-indenyl group. 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-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. .

以W所代表之碳原子數為1至10之烷基、碳原子數為1至10之烷氧基、碳原子數為1至5之鹵化烷基、及碳原子數為1至5之鹵化烷氧基的具體實例是可列舉：與作為以R2A 或R3A 所代表之碳原子數為1至10之烷基、碳原子數為1至10之烷氧基、碳原子數為1至5之鹵化烷基、及碳原子數為1至5之鹵化烷氧基的具體實例所列舉者為相同者。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 group having 1 to 5 carbon atoms represented by W Specific examples of the alkoxy group include, for example, an alkyl group having 1 to 10 carbon atoms represented by R 2A or R 3A , 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 與R1A 是可相互鍵結而形成5員環或6員環。R 2A and R 1A are mutually bondable to form a 5-membered ring or a 6-membered ring.

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、噁唑、噻唑、哌喃、吡啶、吡、嗎啉、哌啶或哌環。該5員環或6員環是可與也可具有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、烷、茀、或硫環系。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。When R 2A and R 1A 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, cyclopentane. , cyclohexane, cycloheptane, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, piperazine, pyridine, pyridyl Morpholine, piperidine or piperazine ring. The 5-membered ring or the 6-membered ring may be bonded to a benzene ring which may have an arbitrary substituent, and examples thereof include tetrahydronaphthalene, indoline, and anthracene. Alkanes, hydrazine, Or sulfur Ring system. The 5-membered ring or the 6-membered ring may contain a carbonyl group, and examples thereof include a cyclohexadienone, a naphthone, and an anthrone ring system.

以通式(2)所代表之化合物之適合的模式之一為以下述通式(2-1)所代表之化合物。以該通式(2-1)所代表之化合物是通式(2)之R2A 與R1A 是鍵結而形成5員環之化合物。One of the suitable modes of the compound represented by the formula (2) is a compound represented by the following formula (2-1). The compound represented by the formula (2-1) is a compound in which R 2A and R 1A of the formula (2) are bonded to form a 5-membered ring.

通式(2-1)中，R3A 是與通式(2)之R3A 為同義，X是代表烷基、烷氧基、或鹵素原子，t是代表0至3之整數，t為2或3時，複數的X是可為相同或不同。R 3A general formula (2-1), R 3A is a general formula (2) of synonymous, X is represents an alkyl group, an alkoxy group, or a halogen atom, t is an integer from 0 to 3 of the representative, t is 2 Or 3, the plural X can be the same or different.

以X所代表之烷基較佳為碳原子數為1至4之直鏈狀或分枝狀烷基。The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

以X所代表之烷氧基較佳為碳原子數為1至4之直鏈狀或分枝狀烷氧基。The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.

以X所代表之鹵素原子較佳為氯原子或氟原子。The halogen atom represented by X is preferably a chlorine atom or a fluorine atom.

t較佳為0或1。t is preferably 0 or 1.

通式(2-1)中，特佳為t是1，X是甲基，X之取代位置是鄰位，R3A 是碳原子數為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。In the formula (2-1), particularly preferably t is 1, X is a methyl group, the substitution position of X is an ortho position, and R 3A is a linear alkyl group having 1 to 10 carbon atoms, 7,7- A compound of dimethyl-2-oxo-norbornylmethyl or p-tolylmethylhydrazine.

以通式(2-1)所代表之肟磺酸酯化合物的具體實例是可列舉：下列化合物(i)、化合物(ii)、化合物(iii)、化合物(iv)等，此等化合物是可單獨使用一種或兩種以上併用。化合物(i)至(iv)是可獲自市售品。Specific examples of the oxime sulfonate compound represented by the formula (2-1) include the following compounds (i), (ii), (iii), (iv), etc., which are One type or two or more types may be used alone. Compounds (i) to (iv) are commercially available.

此外，也可將此等化合物、與其他種類之特定光酸產生劑組合使用。Further, these compounds may be used in combination with other kinds of specific photoacid generators.

以通式(2)所代表之光酸產生劑之較佳模式之一是包括：R1A 是代表碳原子數為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 是代表碳原子數為1至10之烷基、碳原子數為1至10之烷氧基、碳原子數為1至5之鹵化烷基、碳原子數為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、碳原子數為1至10之烷基、碳原子數為1至10之烷氧基、碳原子數為1至5之鹵化烷基或碳原子數為1至5之鹵化烷氧基者。One of preferred modes of the photoacid generator represented by the formula (2) is that R 1A is an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group, or a second group. Chlorophenyl, methoxyphenyl, 4-biphenyl, naphthyl or anthracenyl; R 2A represents a cyano group; R 3A represents an alkyl group having 1 to 10 carbon atoms, and has 1 to 10 carbon atoms Alkoxy group of 10, 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 W The substituted 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. A group or a halogenated alkoxy group having 1 to 5 carbon atoms.

以通式(2)所代表之化合物較佳為以下述通式(2-2)所代表之化合物。The compound represented by the formula (2) is preferably a compound represented by the following formula (2-2).

通式(2-2)中，R4A 是代表鹵素原子、羥基、碳原子數為1至4之烷基、碳原子數為1至4之烷氧基、或硝基，1是代表0至5之整數。R3A 是代表碳原子數為1至10之烷基、碳原子數為1至10之烷氧基、碳原子數為1至5之鹵化烷基、碳原子數為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、碳原子數為1至10之烷基、碳原子數為1至10之烷氧基、碳原子數為1至5之鹵化烷基或碳原子數為1至5之鹵化烷氧基。In the formula (2-2), R 4A 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 0 to An integer of 5. R 3A 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, or 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, and W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, carbon An alkoxy group having 1 to 10 atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms.

通式(2-2)之R3A 較佳為甲基、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，特佳為甲基、乙基、正丙基、正丁基或對甲苯基。R 3A of the formula (2-2) is preferably methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro - n-Butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, particularly preferably methyl, ethyl, n-propyl, n-butyl or p-tolyl.

以R4A 所代表之鹵素原子較佳為氟原子、氯原子或溴原子。The halogen atom represented by R 4A is preferably a fluorine atom, a chlorine atom or a bromine atom.

以R4A 所代表之碳原子數為1至4之烷基較佳為甲基或乙基。The alkyl group having 1 to 4 carbon atoms represented by R 4A is preferably a methyl group or an ethyl group.

以R4A 所代表之碳原子數為1至4之烷氧基較佳為甲氧基或乙氧基。The alkoxy group having 1 to 4 carbon atoms represented by R 4A is preferably a methoxy group or an ethoxy group.

1較佳為0至2，特佳為0至r。1 is preferably 0 to 2, particularly preferably 0 to r.

在以通式(2)所代表之光酸產生劑中，包含於以通式(2-2)所代表之光酸產生劑的化合物之較佳模式是通式(2)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。In the photoacid generator represented by the formula (2), a preferred mode of the compound contained in the photoacid generator represented by the formula (2-2) is in the formula (2), and R 1A is Represents phenyl or 4-methoxyphenyl, R 2A represents a cyano group, and R 3A represents a mode of methyl, ethyl, n-propyl, n-butyl or 4-tolyl.

在下文中，將說明在以通式(2)所代表之光酸產生劑中，包含於以通式(2-2)所代表之光酸產生劑的化合物之特佳的實例，但是本發明並不受限於此等者。In the following, a particularly preferable example of the compound contained in the photoacid generator represented by the formula (2), which is contained in the photoacid generator represented by the formula (2-2), but the present invention is Not limited to these.

α-(甲基磺醯氧基亞胺基)苯甲基氰(R1A =苯基、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、R3A =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)、α-(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)、α-[(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)、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)、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)。Α-(methylsulfonyloxyimino)benzyl cyanide (R 1A = phenyl, R 2A =-CN, R 3A = methyl), α-(ethylsulfonyloxyimino) Benzyl cyanide (R 1A = phenyl, R 2A =-CN, R 3A = ethyl), α-(n-propylsulfonyloxyimino)benzyl cyanide (R 1A = phenyl) , R 2A =-CN group, R 3A = n-propyl), α-(n-butylsulfonyloxyimino)benzyl cyanide (R 1A =phenyl, R 2A =-CN, R 3A = n-butyl), α-(4-toluenesulfonyloxyimido)benzyl cyanide (R 1A = phenyl, R 2A =-CN, R 3A = 4-tolyl), α-[ (methylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile (R 1A = 4-methoxyphenyl, R 2A =-CN, R 3A = methyl), α-[ (ethylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile (R 1A = 4-methoxyphenyl, R 2A =-CN, R 3A = ethyl), α-[ (n-propylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile (R 1A = 4-methoxyphenyl, R 2A =-CN, R 3A = n-propyl), α -[(n-butylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile (R 1A = 4-methoxyphenyl, R 2A =-CN, R 3A = n-butyl) α-[(4-Toluenesulfonyloxyimino) 4-methoxyphenyl]acetonitrile (R 1A = 4-methoxyphenyl, R 2A =-CN, R 3A = 4-tolyl).

本發明之感光性樹脂組成物較佳為會感應活性光線之(B)光酸產生劑是不含有1,2-醌二疊氮化合物。其理由是雖然1,2-醌二疊氮化合物會由於逐步型光化學反應(sequential photochemical reaction)而形成羧基，但是其量子收率(quantum yield)則為1以下，感度相較於肟磺酸酯化合物為低。The photosensitive resin composition of the present invention preferably has an active light ray (B) and the photoacid generator does not contain a 1,2-quinonediazide compound. The reason is that although the 1,2-quinonediazide compound forms a carboxyl group due to a sequential photochemical reaction, its quantum yield is 1 or less, and the sensitivity is compared to sulfonic acid. The ester compound is low.

與此相對，肟磺酸酯化合物是可推測為：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為觸媒而發生作用，以一個光量子之作用所形成的酸則有助於多數之脫保護反應，使得量子收率為超過1而成為例如10之數倍的大值之所謂的化學增幅之結果而獲得高感度。On the other hand, the oxime sulfonate compound is presumed to be that the acid formed by the inductively active light acts as a catalyst for the deprotection of the protected acidic group, and the acid formed by the action of one photon has A high sensitivity is obtained as a result of a so-called chemical increase of a large value of a quantum value of more than 1 and a quantum value of more than one.

在本發明之感光性樹脂組成物，(B)光酸產生劑相對於100質量份之(A)縮醛系樹脂較佳為使用0.1至10質量份，更佳為使用0.5至10質量份。In the photosensitive resin composition of the present invention, the photo-acid generator (B) is preferably used in an amount of 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the (A) acetal-based resin.

(C)溶劑本發明之感光性樹脂組成物是含有(C)溶劑。本發明之感光性樹脂組成物較佳為將作為必要成分的(A)縮醛系樹脂、及(B)光酸產生劑、以及作為較佳的成分之後述各種添加劑之任意成分，調製成經溶解於(C)溶劑之溶液。(C) Solvent The photosensitive resin composition of the present invention contains (C) a solvent. The photosensitive resin composition of the present invention is preferably prepared by using (A) an acetal-based resin as an essential component, (B) a photoacid generator, and an optional component of various additives described later as preferred components. A solution dissolved in (C) solvent.

在本發明之感光性樹脂組成物中所使用的(C)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、二伸丙二醇二烷基醚類、醋酸二伸丙二醇一烷基醚酯類、酯類、酮類、醯胺類、內酯類等。The solvent (C) used in the photosensitive resin composition of the present invention may be a conventional solvent, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, and ethyl acetate. Alcohol 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 And dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether esters, esters, ketones, guanamines, lactones and the like.

在本發明之感光性樹脂組成物中所使用的(C)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；(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；(17)γ-丁內酯等之內酯類等。The (C) solvent used in the photosensitive resin composition of the present invention may, for example, be (1) ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, Ethylene glycol monoalkyl ether such as ethylene glycol monobutyl ether; (2) ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, etc. Alkyl ethers; (3) acetic acid glycol monomethyl ether ester, ethylene glycol monoethyl ether ester, ethylene glycol monopropyl ether ester, acetic acid ethylene glycol monobutyl ether ester, etc. Ethylene glycol monoalkyl ether esters; (4) propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.; (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, digan Alcohol ethyl methyl Diethylene glycol dialkyl ethers; (8) diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol acetate Diethylene glycol monoalkyl ether acetates such as hydroxy ether esters; (9) dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether a propylene glycol monoalkyl ether; (10) dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether and the like dipropylene glycol dialkyl ether; 11) Acetic acid dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, etc. Ether esters; (12) lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate; (13) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, N-propyl acrylate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, An aliphatic carboxylic acid ester such as n-butyl butyrate or isobutyl butyrate; (14) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, 2-hydroxy-3-methylbutyl Ethyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, butyric acid 3- Other esters such as methyl-3-methoxybutyl ester, methyl acetoxyacetate, ethyl acetoxyacetate, methyl pyruvate, ethyl pyruvate; (15) methyl ethyl ketone, A Ketones such as propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, etc.; (16) N-methyl group Hydrazines such as decylamine, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone; (17) γ - lactones such as butyrolactone.

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、1-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。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, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate A solvent such as ethyl carbonate or propyl carbonate.

在上述溶劑中，特佳為二甘醇乙基甲基醚、醋酸丙二醇一甲基醚酯。Among the above solvents, particularly preferred are diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate.

可使用於本發明之溶劑較佳為單獨使用一種或兩種併用，更佳為兩種併用，進一步更佳為併用醋酸丙二醇一烷基醚酯類與二甘醇二烷基醚類。The solvent to be used in the present invention is preferably used singly or in combination of two or more, more preferably two, and further preferably a propylene glycol monoalkyl ether acetate and a diethylene glycol dialkyl ether.

在本發明之感光性樹脂組成物中之(C)溶劑的含量，相對於100質量份之(A)縮醛系樹脂，則較佳為50至3,000質量份，更佳為100至2,000質量份，進一步更佳為150至1,500質量份。The content of the solvent (C) in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by mass, more preferably 100 to 2,000 parts by mass, per 100 parts by mass of the (A) acetal resin. Further, it is more preferably from 150 to 1,500 parts by mass.

(其他成分)(other ingredients)

在本發明之感光性樹脂組成物較佳為含有其他成分。從感度的觀點，則其他成分較佳為含有(M)顯影促進劑，此外，從膜物性的觀點，則較佳為含有(E)交聯劑。此外，從感度的觀點，則較佳為添加(N)增感劑。並且，從基板密著性的觀點，則本發明之感光性樹脂組成物較佳為含有(F)密著改良劑；從液保存安定性的觀點，則較佳為含有(G)鹼性化合物；從塗布性的觀點，則較佳為含有(H)界面活性劑(氟系界面活性劑、矽系界面活性劑等)。The photosensitive resin composition of the present invention preferably contains other components. From the viewpoint of sensitivity, the other component preferably contains (M) a development accelerator, and from the viewpoint of film physical properties, it is preferred to contain (E) a crosslinking agent. Further, from the viewpoint of sensitivity, it is preferred to add a (N) sensitizer. Further, the photosensitive resin composition of the present invention preferably contains (F) a adhesion improving agent from the viewpoint of substrate adhesion, and preferably contains (G) a basic compound from the viewpoint of liquid storage stability. From the viewpoint of coatability, it is preferred to contain (H) a surfactant (a fluorine-based surfactant, a ruthenium-based surfactant, or the like).

並且，在本發明之感光性樹脂組成物因應需要而可加入(D)抗氧化劑、(I)塑化劑、及(J)熱自由基產生劑、(K)熱酸產生劑、(L)酸增殖劑(acid amplifier)、紫外線吸收劑、增黏劑、及有機或無機之抗沉降劑等之習知的添加劑。Further, in the photosensitive resin composition of the present invention, (D) an antioxidant, (I) a plasticizer, and (J) a thermal radical generator, (K) a thermal acid generator, (L) may be added as needed. A conventional additive such as an acid amplifier, an ultraviolet absorber, a tackifier, and an organic or inorganic anti-settling agent.

在下文中，說明在本發明之感光性樹脂組成物可包含的其他成分。Hereinafter, other components which may be contained in the photosensitive resin composition of the present invention will be described.

(N)增感劑(N) sensitizer

在本發明之感光性樹脂組成物，較佳為在前述之與(B)光酸產生劑的組合中添加(N)增感劑以促進其分解。增感劑將吸收活性光線或放射線而成為電子激發狀態。成為電子激發狀態之增感劑則與光酸產生劑接觸，產生電子移動、能量移動、放熱等作用。藉此光酸產生劑則發生化學變化、分解而形成酸。In the photosensitive resin composition of the present invention, it is preferred to add a (N) sensitizer to the combination of the above-mentioned (B) photoacid generator to promote decomposition thereof. The sensitizer will absorb active light or radiation and become an electronically excited state. The sensitizer that becomes an electronically excited state is in contact with the photoacid generator, and functions to move electrons, move energy, and release heat. Thereby, the photoacid generator chemically changes and decomposes to form an acid.

較佳的增感劑的實例是可列舉屬於下列之化合物類，且在由350 nm至450 nm域具有吸收波長之化合物。Examples of preferred sensitizers are those which are exemplified by the following compounds and having an absorption wavelength in the 350 nm to 450 nm domain.

「增感劑」的實例是可列舉：多核芳香族類(例如，芘、苝、聯三伸苯、蒽)；類(例如，螢光黃、曙紅、赤藻辛、玫瑰紅B、孟加拉玫瑰(Rose Bengal))；酮類(例如，酮、氧硫、二甲基氧硫、二乙基氧硫)；花青類(例如噻羰花青(噻喹啉藍：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)；角鯊鎓類(squaliums)(例如，角鯊鎓)；苯乙烯基類(styryls)；雙苯乙烯基類(bisstyryls)；香豆素類(例如，7-二乙基胺基-4-甲基香豆素)。在此等增感劑中，較佳為可吸收活性光線或放射線而成為電子激發狀態，且具有對光酸產生劑的電子移動作用之增感劑，特佳為多環芳香族類、吖啶酮類、香豆素類、雙苯乙烯基類。其中，最佳為蒽化合物。Examples of the "sensitizer" include polynuclear aromatics (for example, ruthenium, osmium, benzene, hydrazine); Classes (eg, fluorescent yellow, blush, red algae, rose red B, rose beng); Ketones (for example, Ketone, oxysulfide Dimethyl oxysulfide Diethyl oxysulfide ); cyanines (eg, thiocarbocyanine (thiacarbocyanine), oxacarbocyanine); merocyanoids (eg, procyanidins, carbonyl anthocyanins); Class (rhodacyanines); Oxonol class; thiazide Classes (eg, thiazide, methylene blue, toluidine blue); acridines (eg, acridine orange, chloroflavin, acriflavine); acridone (eg, acridone, 10-butyl-) 2-chloroacridone); anthraquinones (eg, anthraquinone); squaliums (eg, squalanes); styryls; bisstyryls; Coumarins (for example, 7-diethylamino-4-methylcoumarin). Among these sensitizers, a sensitizer capable of absorbing active light or radiation to be in an electronically excited state and having an electron-moving action on a photoacid generator is particularly preferred as a polycyclic aromatic compound or acridine. Ketones, coumarins, bisstyryl based. Among them, the best is a ruthenium compound.

增感劑是可使用市售品，也可藉由習知的合成方法而合成。The sensitizer may be a commercially available product or may be synthesized by a conventional synthesis method.

增感劑的添加量，從感度、透明性並存的觀點，相對於100質量份之(B)光酸產生劑，則較佳為20至300質量份，特佳為30至200質量份。The amount of the sensitizer to be added is preferably from 20 to 300 parts by mass, particularly preferably from 30 to 200 parts by mass, per 100 parts by mass of the (B) photoacid generator from the viewpoint of the sensitivity and the transparency.

(M)顯影促進劑(M) development accelerator

本發明之感光性樹脂組成物較佳為含有(M)顯影促進劑。The photosensitive resin composition of the present invention preferably contains (M) a development accelerator.

(M)顯影促進劑是可使用具有顯影促進功效之任意的化合物，較佳為具有選自羧基、酚性羥基、及伸烷氧基所構成的群組中之至少一種結構之化合物，更佳為具有羧基或酚性羥基之化合物，最佳為具有酚性羥基之化合物。(M) the development accelerator may be any compound having a development-promoting effect, preferably a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkoxy group, more preferably The compound having a carboxyl group or a phenolic hydroxyl group is preferably a compound having a phenolic hydroxyl group.

此外，(M)顯影促進劑之分子量較佳為100至2000，更佳為150至1500，最佳為150至1000。Further, the molecular weight of the (M) development accelerator is preferably from 100 to 2,000, more preferably from 150 to 1,500, most preferably from 150 to 1,000.

「顯影促進劑」的實例是包括：具有伸烷氧基者是可列舉：聚乙二醇、聚乙二醇之一甲基醚、聚乙二醇之二甲基醚、聚乙二醇甘油酯、聚丙二醇甘油酯、聚丙二醇二甘油酯、聚丁二醇、聚乙二醇-雙酚A醚、聚丙二醇-雙酚A醚、聚氧乙烯之烷基醚、聚氧乙烯之烷基酯、及在日本特開平9-222724號公報中所揭述之化合物等。Examples of the "development accelerator" include those having an alkoxy group: polyethylene glycol, one methyl ether of polyethylene glycol, dimethyl ether of polyethylene glycol, and polyethylene glycol glycerin. Ester, polypropylene glycol glyceride, polypropylene glycol diglyceride, polytetramethylene glycol, polyethylene glycol-bisphenol A ether, polypropylene glycol-bisphenol A ether, alkyl ether of polyoxyethylene, alkyl group of polyoxyethylene An ester or a compound as disclosed in Japanese Laid-Open Patent Publication No. Hei 9-222724.

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10-20501號公報、特開平11-338150號公報等中所揭述之化合物。The compound which is described in the above-mentioned Japanese Patent Publication No. 2000-66406, the Japanese Patent Publication No. Hei. No. Hei. No. Hei.

具有酚性羥基者是可列舉：在日本特開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2003-43679號公報等中所揭述之化合物。在此等之中，較適為苯環數為2至10個之酚系化合物，更適為苯環數為2至5個之酚系化合物。特佳為在日本特開平10-133366號公報中.作為溶解促進劑所揭示之酚性化合物。In the case of the phenolic hydroxyl group, JP-A-2005-346024, JP-A-H09-133366, JP-A-H09-194-415, JP-A-9-222724, JP-A-H09-172810 The compound disclosed in JP-A-2007-121766, JP-A-H09-297396, JP-A-2003-43679, and the like. Among these, a phenolic compound having 2 to 10 benzene rings is preferred, and a phenolic compound having 2 to 5 benzene rings is more preferred. The phenolic compound disclosed as a dissolution promoter is disclosed in Japanese Laid-Open Patent Publication No. Hei 10-133366.

(M)顯影促進劑是可單獨使用一種或兩種以上併用。(M) The development accelerators may be used alone or in combination of two or more.

在本發明之感光性樹脂組成物中，從感度與殘膜率的觀點，相對於100質量份之(A)縮醛系樹脂，則(M)顯影促進劑的添加量較佳為0.1至30質量份，更佳為0.2至20質量份，最佳為0.5至10質量份。In the photosensitive resin composition of the present invention, the amount of the development accelerator (M) is preferably from 0.1 to 30, based on 100 parts by mass of the (A) acetal resin, from the viewpoint of sensitivity and residual film ratio. The parts by mass are more preferably 0.2 to 20 parts by mass, most preferably 0.5 to 10 parts by mass.

(E)交聯劑本發明之感光性樹脂組成物較佳為因應需要，則含有(E)交聯劑。藉由添加(E)交聯劑，則可將硬化膜製成更強固的膜。(E) Crosslinking Agent The photosensitive resin composition of the present invention preferably contains (E) a crosslinking agent as needed. By adding (E) a crosslinking agent, the cured film can be made into a stronger film.

(E)交聯劑是可添加例如如下所述之在分子內具有兩個以上環氧基或氧雜環丁烷基之化合物、含有烷氧基甲基之交聯劑、或具有至少一個烯鍵性不飽和雙鍵之化合物。The (E) crosslinking agent is a compound which has two or more epoxy groups or oxetane groups in the molecule, a crosslinking agent containing an alkoxymethyl group, or at least one alkene, as described below. A compound of a bond-unsaturated double bond.

在此等交聯劑中，特佳為在分子內具有兩個以上環氧基或氧雜環丁烷基之化合物。Among these crosslinking agents, a compound having two or more epoxy groups or oxetane groups in the molecule is particularly preferred.

(在分子內具有兩個以上環氧基或氧雜環丁烷基之化合物)(a compound having two or more epoxy groups or oxetane groups in the molecule)

「在分子內具有兩個以上環氧基之化合物」的具體實例是可列舉：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、甲酚酚醛清漆型環氧樹脂、脂肪族環氧樹脂等。Specific 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, aliphatic epoxy resin, etc.

此等是可獲自市售品。其可列舉：例如，「雙酚A型環氧樹脂」是JER 827、JER 828、JER 834、JER 1001、JER 1002、JER 1003、JER 1055、JER 1007、JER 1009、JER 1010(以上是Japan Epoxy Resin(股)製)，EPICLON 860、EPICLON 1050、EPICLON 1051、EPICLON 1055(以上是DIC(股)製)等；「雙酚F型環氧樹脂」是JER 806、JER 807、JER 4004、JER 4005、JER 4007、JER 4010(以上是商品名、Japan Epoxy Resin(股)製)，EPICLON　830、EPICLON 835(以上是商品名、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 157S65(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-660、EPICLON N-665、EPICLON N-670、EPICLON N-673、EPICLON N-680、EPICLON N-690、EPICLON N-695(以上是商品名、DIC(股)製)，EOCN-1020(以上是商品名、日本化藥(股)製)等；「脂肪族環氧樹脂」是ADEKA RESIN EP-4080S、同EP-4085S、同EP-4088S(以上是商品名、(股)ADEKA製)，CELLOXIDE 2021P、CELLOXIDE 2081、CELLOXIDE 2083、CELLOXIDE 2085、EHPE 3150、EPOLEAD PB 3600、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-4000S、同EP-4003S、同EP-4010S、同EP-4011S(以上是商品名、(股)ADEKA製)，.NC-2000、NC-3000、NC-7300、XD-1000、EPPN-501、EPPN-502(以上是商品名、(股)ADEKA製)等。此等是可以一種單獨或兩種以上組合使用。These are available from commercial products. For example, "bisphenol A type epoxy resin" is JER 827, JER 828, JER 834, JER 1001, JER 1002, JER 1003, JER 1055, JER 1007, JER 1009, JER 1010 (above is Japan Epoxy Resin (share) system, EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (above DIC); "bisphenol F type epoxy resin" is JER 806, JER 807, JER 4004, JER 4005 , JER 4007, JER 4010 (above is the trade name, made by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (above is the trade name, DIC (share) system), LCE-21, RE-602S (above is the product) "Nippon Chemical Co., Ltd.", etc.; "phenol novolak type epoxy resin" is JER 152, JER 154, JER 157S70, JER 157S65 (above, trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N - 740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, trade name, DIC); "cresol novolac type epoxy resin" is EPICLON N-660, EPICLON N- 665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above is the trade name, DIC (share) system), EOCN-1020 (above Product name, Nippon Chemical Co., Ltd., etc.; "aliphatic epoxy resin" is ADEKA RESIN EP-4080S, with EP-4085S, with EP-4088S (above is the trade name, (share) made by ADEKA), CELLOXIDE 2021P CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, EHPE 3150, EPOLEAD PB 3600, and PB 4700 (the above are trade names, manufactured by DAICEL Chemical Industry Co., Ltd.). Others include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, and EP-4011S (the above are trade names, ADEKA), NC-2000, NC-3000, NC-7300. , XD-1000, EPPN-501, EPPN-502 (the above is the trade name, (share) made by ADEKA). These may be used alone or in combination of two or more.

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、及苯酚酚醛清漆型環氧樹脂；特佳為雙酚A型環氧樹脂。Among these, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a phenol novolak type epoxy resin are preferable, and a bisphenol A type epoxy resin is especially preferable.

「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)。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.) ).

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。Further, the compound containing an oxetane group may be used alone or in combination with a compound containing an epoxy group.

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100質量份之(A)縮醛系樹脂成分之總量，則較佳為1至50質量份，更佳為3至30質量份。The amount of the compound having two or more epoxy groups or oxetanyl groups in the molecule is preferably such that the amount of the photosensitive resin composition added is 100 parts by mass based on the total amount of the (A) acetal resin component. It is 1 to 50 parts by mass, more preferably 3 to 30 parts by mass.

(含有烷氧基甲基之交聯劑)(crosslinking agent containing alkoxymethyl group)

「含有烷氧基甲基之交聯劑」較佳為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，則特佳為甲氧基甲基。The "alkoxy group-containing crosslinking agent" is preferably an alkoxymethylated melamine, an alkoxymethylated benzoguanamine, an alkoxymethylated glycoluril, and an alkoxymethylated urea. Wait. These are obtained by converting a methylol group of methylolated melamine, methylolated 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.

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，則特佳為烷氧基甲基化甘脲。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.

此等「含有烷氧基甲基之交聯劑」是可獲自市售品，例如，較佳為使用CYMEL 300、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、(股)三和化學製)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，相對於100質量份之(A)縮醛系樹脂成分，則含有烷氧基甲基之交聯劑的添加量較佳為0.05至50質量份，更佳為0.5至10質量份。藉由以該範圍添加，則可獲得在顯影時之較佳的鹼溶解性、與硬化後之膜優異的耐溶劑性。Such "alkoxymethyl group-containing crosslinking agents" are commercially available, for example, preferably CYMEL 300, 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, 0382, -706, -708, -40, -31, -270, -280, -290, NIKALAC MS-11, NIKALAC MW-30HM, -100LM, -390 (the above are trade names, (shares) and chemical systems). When a crosslinking agent containing an alkoxymethyl group is used for the photosensitive resin composition of the present invention, the crosslinking agent containing an alkoxymethyl group is added to 100 parts by mass of the (A) acetal resin component. The amount is preferably from 0.05 to 50 parts by mass, more preferably from 0.5 to 10 parts by mass. By adding in this range, it is possible to obtain a preferable alkali solubility at the time of development and excellent solvent resistance to the film after curing.

(具有至少一個烯鍵性不飽和雙鍵之化合物)(a compound having at least one ethylenically unsaturated double bond)

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。A compound having at least one ethylenically unsaturated double bond is preferably a monofunctional (meth) acrylate, a difunctional (meth) acrylate, a trifunctional or higher (meth) acrylate, or the like (methyl). ) acrylate compound.

「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。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.

「二官能之(甲基)丙烯酸酯」是可列舉：例如，(甲基)丙烯酸乙二醇酯、二(甲基)丙烯酸1,6-己二醇酯、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茀酯、二丙烯酸雙苯氧基乙醇茀酯等。Examples of the "difunctional (meth) acrylate" include ethylene glycol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, and di(meth)acrylic acid 1. 9-decanediol ester, propylene glycol poly(meth)acrylate, tetraethylene glycol di(meth)acrylate, bisphenoxyethanol decyl diacrylate, bisphenoxyethanol decyl diacrylate, and the like.

「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。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.

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。These compounds having at least one ethylenically unsaturated double bond may be used alone or in combination of two or more.

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100質量份之(A)縮醛系樹脂成分，則較佳為50質量份以下，更佳為30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，則較佳為添加後述之(J)熱自由基產生劑。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 100 parts by mass of the (A) acetal resin component. More preferably, it is 30 parts by mass or less. By containing a compound having at least one ethylenically unsaturated double bond in an equal ratio, 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 (J) thermal radical generating agent described later.

(F)密著改良劑(F) adhesion improver

本發明之感光性樹脂組成物較佳為含有(F)密著改良劑。The photosensitive resin composition of the present invention preferably contains (F) a adhesion improving agent.

可使用於本發明之感光性樹脂組成物之(F)密著改良劑是用於提高作為基板之無機物例如矽、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。在本發明所使用的作為(F)密著改良劑之矽烷偶合劑是以界面之改質為目的者，可在並無特殊限制下使用習知者。The (F) adhesion improver which can be used for the photosensitive resin composition of the present invention is used for improving an inorganic substance such as ruthenium, iridium oxide or tantalum nitride as a substrate, and a metal such as gold, copper or aluminum and an insulating film. a close-knit compound. Specific examples thereof include a decane coupling agent, a thiol compound, and the like. The decane coupling agent used as the (F) adhesion improving agent used in the present invention is intended to be modified by the interface, and can be used without any particular limitation.

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、β-(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。Preferred examples of the "decane coupling agent" include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, and γ-glycidoxypropyltrialkoxy group.矽, γ-glycidoxypropyl alkyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl alkyl dialkoxide Baseline, γ-chloropropyltrialkoxydecane, γ-hydrothiopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, vinyl Trialkoxydecane.

在此等之中，更佳為γ-環氧丙氧基丙基三烷氧基矽烷、及γ-甲基丙烯醯氧基丙基三烷氧基矽烷，進一步更佳為γ-環氧丙氧基丙基三烷氧基矽烷。Among these, more preferred are γ-glycidoxypropyl trialkoxydecane, and γ-methacryloxypropyltrialkoxydecane, and further preferably γ-glycidyl Oxypropyl propyl alkoxy decane.

此等是可以一種單獨或兩種以上組合使用。此等是可有效地提高與基板之密著性，同時也可有效地調整與基板之錐角。These may be used alone or in combination of two or more. These can effectively improve the adhesion to the substrate, and can also effectively adjust the taper angle with the substrate.

在本發明之感光性樹脂組成物中，相對於100質量份之(A)縮醛系樹脂成分，(F)密著改良劑的含量較佳為0.1至20質量份，更佳為0.5至10質量份。In the photosensitive resin composition of the present invention, the content of the (F) adhesion improver is preferably from 0.1 to 20 parts by mass, more preferably from 0.5 to 10, per 100 parts by mass of the (A) acetal resin component. Parts by mass.

(G)鹼性化合物本發明之感光性樹脂組成物較佳為含有(G)鹼性化合物。(G) Basic compound The photosensitive resin composition of the present invention preferably contains (G) a basic compound.

(G)鹼性化合物是可從在化學增幅光阻所使用的化合物中任意選擇使用。其可列舉：例如，脂肪族胺、芳香族胺、雜環式胺、第四級氫氧化銨、及羧酸之第四級銨鹽等。(G) The basic compound can be arbitrarily selected from the compounds used in the chemically amplified photoresist. Examples thereof include an aliphatic amine, an aromatic amine, a heterocyclic amine, a fourth-order ammonium hydroxide, and a fourth-order ammonium salt of a carboxylic acid.

「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。Examples of the "aliphatic amine" include, for example, trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, and tri-n-pentane. Alkylamine, diethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

「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。Examples of the "aromatic amine" include aniline, benzylamine, N,N-dimethylaniline, and diphenylamine.

「雜環式胺」是可列舉：例如，吡啶、2-甲基吡啶、4-甲基吡啶、2-乙基吡啶、4-乙基吡啶、2-苯基吡啶、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、2,4,5-三苯基咪唑、菸鹼、菸鹼酸、菸鹼醯胺、喹啉、8-氧基喹啉、吡、吡唑、嗒、嘌呤、吡咯啶、哌啶、哌、嗎啉、4-甲基嗎啉、1,5-二吖雙環[4.3.0]-5-壬烯、1,8-二吖雙環[5.3.0]-7-十一烯等。The "heterocyclic amine" may, for example, be pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine or 4-phenylpyridine. N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole , nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyridinium , pyrazole, hydrazine , hydrazine, pyrrolidine, piperidine, piperidine , morpholine, 4-methylmorpholine, 1,5-dioxabicyclo[4.3.0]-5-pinene, 1,8-dioxabicyclo[5.3.0]-7-undecene, and the like.

「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。Examples of the "fourth-order ammonium hydroxide" include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.

「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-正丁基銨等。The "fourth ammonium salt of a carboxylic acid" may, for example, be tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate or tetra-n-butylammonium benzoate.

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併用，較佳為兩種以上併用，更佳為兩種併用，進一步更佳為將兩種雜環式胺併用。The basic compound to be used in the present invention may be used singly or in combination of two or more kinds, preferably two or more, more preferably two, and further preferably two heterocyclic amines are used in combination.

本發明之感光性樹脂組成物中，相對於100質量份之(A)縮醛系樹脂，(G)鹼性化合物的含量較佳為0.001至1質量份，更佳為0.002至0.2質量份。(H)界面活性劑(氟系界面活性劑、矽系界面活性劑等)本發明之感光性樹脂組成物較佳為含有(H)界面活性劑(氟系界面活性劑、或矽系界面活性劑等)。界面活性劑是可列舉：含有以如下所示之重複單元A與重複單元B之共聚物(3)作為較佳的實例。該共聚物之重量平均分子量(Mw)為1000以上且10000以下，較佳為1500以上且5000以下。重量平均分子量是以凝膠透層析法所測定之經聚苯乙烯換算得之值。In the photosensitive resin composition of the present invention, the content of the (G) basic compound is preferably 0.001 to 1 part by mass, more preferably 0.002 to 0.2 part by mass, per 100 parts by mass of the (A) acetal resin. (H) Surfactant (fluorine-based surfactant, fluorene-based surfactant, etc.) The photosensitive resin composition of the present invention preferably contains (H) a surfactant (fluorine-based surfactant, or lanthanide interface activity) Agent, etc.). The surfactant is a copolymer (3) containing a repeating unit A and a repeating unit B shown below as a preferred example. The weight average molecular weight (Mw) of the copolymer is 1,000 or more and 10,000 or less, preferably 1,500 or more and 5,000 or less. The weight average molecular weight is a value obtained by polystyrene conversion measured by gel permeation chromatography.

在共聚物(3)中，R21 及R23 是各自獨立地代表氫原子或甲基，R22 是代表碳數為1以上且4以下之直鏈伸烷基，R24 是代表氫原子或碳數為1以上且4以下之烷基，L是代表碳數為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10質量%以上且80質量%以下之數值，q是代表20質量%以上且90質量%以下之數值，r是代表1以上且18以下之整數，n是代表1以上且10以下之整數。In the copolymer (3), R 21 and R 23 each independently represent a hydrogen atom or a methyl group, R 22 represents a linear alkyl group having a carbon number of 1 or more and 4 or less, and R 24 represents a hydrogen atom or An alkyl group having a carbon number of 1 or more and 4 or less, L is an alkylene group having a carbon number of 3 or more and 6 or less, p and q are mass percentages representing a polymerization ratio, and p is 10% by mass or more and 80% by mass. In the following numerical values, q is a numerical value representing 20% by mass or more and 90% by mass or less, r is an integer representing 1 or more and 18 or less, and n is an integer representing 1 or more and 10 or less.

在重複單元B中，L較佳為以下式(4)所代表之伸烷基。In the repeating unit B, L is preferably an alkylene group represented by the following formula (4).

在式(4)中，R25 是代表碳數為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，則較佳為碳數為1以上且3以下之烷基，更佳為碳數為2或3之烷基。In the formula (4), R 25 is an alkyl group having a carbon number of 1 or more and 4 or less, and preferably has a carbon number of 1 or more and 3 or less from the viewpoint of compatibility and wettability to a surface to be coated. The alkyl group is more preferably an alkyl group having 2 or 3 carbon atoms.

此外，p與q之合計(p+q)較佳為p+q=100，亦即，為100質量%。Further, the total of p and q (p + q) is preferably p + q = 100, that is, 100% by mass.

氟系界面活性劑、矽系界面活性劑的實例，具體而言，其可列舉在日本特開昭62-36663號、特開昭61-226746號、特開昭61-226745號、特開昭62-170950號、特開昭63-34540號、特開平7-230165號、特開平8-62834號、特開平9-54432號、特開平9-5988號、特開2001-330953號等之各公報中所揭述之界面活性劑，也可使用市售之界面活性劑。可使用的「市售之界面活性劑」是可列舉：例如，EFTOP EF301、EF303(以上是商品名、新秋田化成(股)製)；FLUORAD FC430、431(以上是商品名、住友3M(股)製)；MEGAFACE F171、F173、F176、F189、R08(以上是商品名、DIC(股)製)；SURFLON S-382、SC101、102、103、104、105、106(以上是商品名、旭硝子(股)製)；PolyFox系列(商品名、OMNOVA公司製)等之氟系界面活性劑或矽系界面活性劑。此外，聚矽氧烷高分子KP-341(商品名、信越化學工業(股)製)也可用作為矽系界面活性劑。Specific examples of the fluorine-based surfactant and the lanthanoid surfactant are specifically disclosed in JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and JP-A-2013. No. 62-170950, special opening 63-34540, special Kaiping 7-230165, special Kaiping 8-62834, special Kaiping 9-54432, special Kaiping 9-5988, special opening 2001-330953, etc. Commercially available surfactants can also be used as the surfactants disclosed in the publication. For example, EFTOP EF301 and EF303 (the above are the trade name, the new Akita Chemicals Co., Ltd.); FLUORAD FC430, 431 (the above is the trade name, Sumitomo 3M (shares) )); MEGAFACE F171, F173, F176, F189, R08 (above is the trade name, DIC (share) system); SURFLON S-382, SC101, 102, 103, 104, 105, 106 (above is the trade name, Asahi Glass) (Shares) system; a fluorine-based surfactant or a quinone-based surfactant such as a PolyFox series (trade name, manufactured by OMNOVA Co., Ltd.). Further, a polyoxyalkylene polymer KP-341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a lanthanoid surfactant.

此等界面活性劑是可以一種單獨或兩種以上混合使用。此外，也可將氟系界面活性劑與矽系界面活性劑併用。在本發明之感光性樹脂組成物中，相對於100質量份之(A)縮醛系樹脂，(H)界面活性劑(包含氟系界面活性劑及/或矽系界面活性劑)的添加量較佳為10質量份以下，更佳為0.01至10質量份，進一步更佳為0.01至1質量份。These surfactants may be used alone or in combination of two or more. Further, a fluorine-based surfactant may be used in combination with a lanthanoid surfactant. In the photosensitive resin composition of the present invention, the amount of (H) surfactant (including a fluorine-based surfactant and/or a lanthanoid surfactant) is added to 100 parts by mass of the (A) acetal resin. It is preferably 10 parts by mass or less, more preferably 0.01 to 10 parts by mass, still more preferably 0.01 to 1 part by mass.

(D)抗氧化劑本發明之感光性樹脂組成物是可含有(D)抗氧化劑。(D)抗氧化劑是可含有習知的抗氧化劑。由於添加(D)抗氧化劑，可防止硬化膜之著色，或減少由於分解引起之膜厚減少，又有耐熱透明性優異之優點。(D) Antioxidant The photosensitive resin composition of the present invention may contain (D) an antioxidant. (D) The antioxidant may contain a conventional antioxidant. By adding (D) an antioxidant, it is possible to prevent the coloration of the cured film, or to reduce the film thickness due to decomposition, and to have excellent heat-resistant transparency.

此等抗氧化劑是可列舉：例如，磷系抗氧化劑、醯基肼類、位阻型胺系抗氧化劑、硫系抗氧化劑、酚系抗氧化劑、抗壞血酸類、硫酸鋅、糖類、亞硝酸鹽、亞硫酸鹽、硫代硫酸鹽、羥基胺衍生物等。在此等之中，從硬化膜之著色、膜厚減少的觀點，則特佳為酚系抗氧化劑。此等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，ADK STAB AO-60、ADK STAB AO-80(以上是商品名、(股)ADEKA製)；IRGANOX 1098(商品名、Ciba Japan(股)製)。Examples of such antioxidants include phosphorus-based antioxidants, mercaptosteroids, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, ascorbic acid, zinc sulfate, sugars, and nitrites. Sulfite, thiosulfate, hydroxylamine derivative, and the like. Among these, from the viewpoint of coloring and film thickness reduction of the cured film, a phenolic antioxidant is particularly preferred. These may be used alone or in combination of two or more. The commercially available product of the "phenolic antioxidant" is, for example, ADK STAB AO-60, ADK STAB AO-80 (the above is a trade name, manufactured by Adeka); IRGANOX 1098 (trade name, Ciba Japan) )system).

(D)抗氧化劑的含量，相對於感光性樹脂組成物之總固體成分，則較佳為0.1至6質量%，更佳為0.2至5質量%，特佳為0.5至4質量%。設定為在此範圍時，則所形成的膜可獲得充分的透明性，且在圖案形成時之感度也為良好。The content of the antioxidant (D) is preferably from 0.1 to 6% by mass, more preferably from 0.2 to 5% by mass, even more preferably from 0.5 to 4% by mass, based on the total solid content of the photosensitive resin composition. When it is set in this range, the formed film can obtain sufficient transparency, and the sensitivity at the time of pattern formation is also favorable.

此外，除了抗氧化劑以外之添加劑是可將在「高分子添加劑之新發展((股)日刊工業新聞公司)」中所揭述之各種紫外線吸收劑、或金屬去活化劑等添加至本發明之感光性樹脂組成物中。In addition, various additives other than the antioxidants may be added to the present invention by various ultraviolet absorbers, metal deactivators, and the like disclosed in "New Development of Polymer Additives" (Industry News) In the photosensitive resin composition.

(I)塑化劑本發明之感光性樹脂組成物是可含有(I)塑化劑。(I)塑化劑是可列舉：例如，鄰苯二甲酸二丁酯、鄰苯二甲酸二辛酯、鄰苯二甲酸二-十二烷酯、聚乙二醇、甘油、鄰苯二甲酸二甲基甘油酯、酒石酸二丁酯、己二酸二辛酯、三乙醯基甘油等。(I) Plasticizer The photosensitive resin composition of the present invention may contain (I) a plasticizer. (I) Plasticizers include, for example, dibutyl phthalate, dioctyl phthalate, di-dodecyl phthalate, polyethylene glycol, glycerin, phthalic acid Dimethyl glyceride, dibutyl tartrate, dioctyl adipate, triethylene glycerol, and the like.

在本發明之感光性樹脂組成物中，相對於100質量份之(A)縮醛系樹脂，(I)塑化劑的含量較佳為0.1至30質量份，更佳為1至10質量份。In the photosensitive resin composition of the present invention, the content of the (I) plasticizer is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 10 parts by mass, per 100 parts by mass of the (A) acetal resin. .

(J)熱自由基產生劑本發明之感光性樹脂組成物是可含有(J)熱自由基產生劑，在含有如前述之具有至少一個烯鍵性不飽和雙鍵之化合物的烯鍵性不飽和化合物的情況，則較佳為更進一步含有(J)熱自由基產生劑。(J) Thermal radical generating agent The photosensitive resin composition of the present invention may contain (J) a thermal radical generating agent, and the ethylenic bond containing a compound having at least one ethylenically unsaturated double bond as described above In the case of a saturated compound, it is preferred to further contain (J) a thermal radical generating agent.

在本發明之熱自由基產生劑是可使用習知的熱自由基產生劑。In the thermal radical generator of the present invention, a conventional thermal radical generator can be used.

熱自由基產生劑是會由於熱之能量而產生自由基來引發或促進聚合性化合物之聚合反應的化合物。藉由添加熱自由基產生劑時，則所獲得硬化膜將變得更強韌而可提高耐熱性、耐溶劑性。The thermal radical generating agent is a compound which generates a radical due to the energy of heat to initiate or promote polymerization of a polymerizable compound. When a thermal radical generator is added, the obtained cured film becomes stronger and heat resistance and solvent resistance can be improved.

較佳的「熱自由基產生劑」是可列舉：芳香族酮類、鎓鹽化合物、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、(金)化合物(azinium compound)、二茂金屬化合物、活性酯化合物、具有碳-鹵素鍵之化合物、偶氮系化合物、聯苯甲基化合物等。Preferred examples of the "thermal radical generating agent" include aromatic ketones, phosphonium salt compounds, organic peroxides, sulfur compounds, hexaarylbiimidazole compounds, ketoxime compounds, and borate compounds, gold An azinium compound, a metallocene compound, an active ester compound, a compound having a carbon-halogen bond, an azo compound, a biphenylmethyl compound or the like.

(J)熱自由基產生劑是可以一種單獨使用或兩種以上併用。(J) The thermal radical generating agent may be used alone or in combination of two or more.

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質量份之(A)縮醛系樹脂，則(J)熱自由基產生劑的含量較佳為0.01至50質量份，更佳為0.1至20質量份，最佳為0.5至10質量份。In the photosensitive resin composition of the present invention, the content of the (J) thermal radical generating agent is preferably from 0.01 to 50 by mass based on 100 parts by mass of the (A) acetal resin from the viewpoint of improving the physical properties of the film. It is more preferably 0.1 to 20 parts by mass, most preferably 0.5 to 10 parts by mass.

(K)熱酸產生劑在本發明中，也可為改良在低溫硬化時之膜物性等而使用(K)熱酸產生劑。(K) Thermal acid generator In the present invention, a (K) thermal acid generator may be used to improve the film properties and the like at the time of low-temperature curing.

本發明之熱酸產生劑是可藉由熱而產生酸的化合物，通常是熱分解溫度為在130℃至250℃，較佳為在150℃至220℃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。所產生的酸較佳為pKa為如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。一般而言，磺酸酯之分子量為230至1000，較佳為230至800。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 220 ° C, for example, it can be borrowed A compound of a low nucleophilic acid such as a sulfonic acid, a carboxylic acid or a disulfonyl sulfenimide is produced 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 with an electron attracting group. Examples of the electron attracting group include a halogen atom such as a fluorine atom, a halogenated alkyl group such as a trifluoromethyl group, a nitro group, and a cyano group. Further, in the present invention, a sulfonic acid ester which can generate an acid by heat without irradiating the exposure light can be used. The phrase "the acid is not substantially generated by irradiation of the exposure light" is determined by the IR spectrum and the NMR spectrum measurement before and after the exposure of the compound, and there is no change in the spectrum. In general, the sulfonate has a molecular weight of from 230 to 1,000, preferably from 230 to 800.

在本發明可使用之磺酸酯是可使用市售品或以習知的方法所合成者。磺酸酯是例如可藉由在鹼性條件下，將磺醯基氯或磺酸酐與對應的多元醇反應而合成。磺酸酯在感光性樹脂組成物中的含量，相對於100質量份之(A)縮醛系樹脂成分，則較佳為0.5至20質量份，特佳為1至15質量份。The sulfonate which can be used in the present invention can be synthesized using a commercially available product or by a known method. The sulfonate can be synthesized, for example, by reacting a sulfonyl chloride or a sulfonic acid anhydride with a corresponding polyol under basic conditions. The content of the sulfonate in 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 (A) acetal resin component.

(L)酸增殖劑(L) acid proliferator

本發明之感光性樹脂組成物是可以提高感度為目的而使用(L)酸增殖劑。在本發明使用之酸增殖劑是可藉由酸觸媒反應而更進一步產生酸使得反應系統內之酸濃度上升的化合物，在酸不存在的狀態下是可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會誘發自分解，在此所產生的酸之強度較佳為酸解離常數(acid dissociation constant) pKa為3以下，特佳為2以下。The photosensitive resin composition of the present invention is a (L) acid multiplying agent for the purpose of improving sensitivity. The acid multiplying agent used in the present invention is a compound which can further generate an acid by an acid catalyst reaction to increase the acid concentration in the reaction system, and is a compound which can be stably present in the absence of an acid. In such a compound, since one or more acids are 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 generated here is preferably The acid dissociation constant pKa is 3 or less, and particularly preferably 2 or less.

酸增殖劑的具體實例是可列舉：在日本特開平10-1508號公報第[0203]至[0223]段落、特開平10-282642號公報第[0016]至[0055]段落、及特表平9-512498號公報第39頁第12行至第47頁第2行所揭述之化合物。在本發明可使用之酸增殖劑是可列舉：會因由酸產生劑所產生之酸而分解以產生二氯醋酸、三氯醋酸、甲烷磺酸、苯磺酸、三氟甲烷磺酸、苯基膦酸等之pKa為3以下的酸之化合物。Specific examples of the acid-proliferating agent include paragraphs [0203] to [0223] of JP-A-10-1508, paragraphs [0016] to [0055] of JP-A-10-282642, and special paragraphs. Compounds recited on page 39, line 12 to page 47, line 2, No. 9-512498. The acid multiplying agent which can be used in the present invention is exemplified by decomposition of an acid generated by an acid generator to produce dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenyl. A compound of an acid such as phosphonic acid having a pKa of 3 or less.

從曝光部與未曝光部之溶解對比的觀點，酸增殖劑在感光性樹脂組成物中的含量，相對於100質量份之(B)光酸產生劑，較佳為10至1000質量份，更佳為20至500質量份。The content of the acid-proliferating agent in the photosensitive resin composition is preferably from 10 to 1,000 parts by mass, based on 100 parts by mass of the (B) photoacid generator, from the viewpoint of the dissolution of the exposed portion and the unexposed portion. It is preferably 20 to 500 parts by mass.

(硬化膜之形成方法)(Method of forming a cured film)

其次，說明在本發明之硬化膜之形成方法。在本發明之硬化膜之形成方法是包括下列第(1)至(5)項之步驟：(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)從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)；(5)將經顯影的感光性樹脂組成物加以熱硬化(後烘烤步驟)。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 steps of the following items (1) to (5): (1) applying the photosensitive resin composition of the present invention to a substrate (coating step); (2) The coated photosensitive resin composition removes the solvent (solvent removal step); (3) exposes the applied photosensitive resin composition with active light (exposure step); (4) combines the exposed photosensitive resin The material is developed with an aqueous developing solution (developing step); (5) the developed photosensitive resin composition is thermally hardened (post-baking step).

在下文中，依序說明各步驟。In the following, the steps are explained in order.

在第(1)項之塗布步驟，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。In the coating step of the item (1), the photosensitive resin composition of the present invention is applied onto a substrate to form a wet film containing a solvent.

在第(2)項之溶劑移除步驟，從所塗布的上述膜以減壓(真空)及/或加熱移除溶劑而在基板上形成乾燥塗膜。In the solvent removal step of the item (2), a dry coating film is formed on the substrate by removing the solvent from the applied film under reduced pressure (vacuum) and/or heat.

在第(3)項之曝光步驟，對所獲得塗膜照射波長300 nm以上且450 nm以下之活性光線。在此步驟，(B)光酸產生劑分解而產生酸。由於所產生的酸之觸媒作用，在(A)縮醛系樹脂中所含有的結構單元(a1)中之酸分解性基分解而形成羧基。In the exposure step of the item (3), the obtained coating film is irradiated with active light having a wavelength of 300 nm or more and 450 nm or less. At this step, (B) the photoacid generator is decomposed to generate an acid. The acid-decomposable group in the structural unit (a1) contained in the (A) acetal-based resin is decomposed to form a carboxyl group by the catalytic action of the acid generated.

在酸觸媒之形成區域，為使上述分解反應加速進行，因應需要可施加PEB(曝光後加熱處理)。藉由PEB，可促進源自酸分解性基的羧基之形成。In the formation region of the acid catalyst, in order to accelerate the above decomposition reaction, PEB (heat treatment after exposure) can be applied as needed. The formation of a carboxyl group derived from an acid-decomposable group can be promoted by PEB.

在本發明之結構單元(a1)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生劑之酸容易分解而形成羧基，因此不一定需要施加PEB也可以顯影而形成正型影像。The acid-decomposable group in the structural unit (a1) of the present invention has a low activation energy due to acid decomposition, and since the acid derived from the acid generator from the exposure is easily decomposed to form a carboxyl group, it is not necessary to apply PEB. It can be developed to form a positive image.

另外，藉由在較低溫下進行PEB，也可在不致於發生交聯反應下促進酸分解性基之水解。在進行PEB時之溫度較佳為30℃以上且130℃以下，更佳為40℃以上且110℃以下，特佳為50℃以上且90℃以下。Further, by carrying out PEB at a lower temperature, hydrolysis of the acid-decomposable group can be promoted without causing a crosslinking reaction. The temperature at the time of PEB is preferably 30° C. or higher and 130° C. or lower, more preferably 40° C. or higher and 110° C. or lower, and particularly preferably 50° C. or higher and 90° C. or lower.

在第(4)項之顯影步驟，將具有經游離的羧基之(A)縮醛系樹脂使用鹼性顯影液進行顯影。藉由移除含有具有易溶解於鹼性顯影液的羧基之樹脂組成物的曝光部區域而形成正型影像。In the developing step of the item (4), the (A) acetal resin having a free carboxyl group is developed using an alkaline developing solution. A positive image is formed by removing an exposed portion region containing a resin composition having a carboxyl group which is easily dissolved in an alkaline developing solution.

在第(5)項之後烘烤步驟，可藉由將所獲得正型影像加熱，使得結構單元(a1)中之酸分解性基熱分解而形成羧基，而與環氧基及/或氧雜環丁烷基交聯以形成硬化膜。該加熱較佳為加熱至150℃以上之高溫，更佳為加熱至180至250℃，特佳為加熱至200至250℃。加熱時間是可因應加熱溫度等而適當地設定，較佳為在10至90分鐘之範圍內。In the baking step after the item (5), the acid-decomposable group in the structural unit (a1) is thermally decomposed to form a carboxyl group by heating the obtained positive image, and is combined with an epoxy group and/or an oxygen group. The cyclobutane is crosslinked to form a cured film. The heating is preferably carried out to a high temperature of 150 ° C or higher, more preferably to 180 to 250 ° C, and particularly preferably to 200 to 250 ° C. The heating time can be appropriately set depending on the heating temperature and the like, and is preferably in the range of 10 to 90 minutes.

若在後烘烤步驟前，追加以活性光線(較佳為紫外線)全面照射顯影圖案之步驟時，則可藉由活性光線照射所產生的酸而促進交聯反應。If the step of fully irradiating the developing pattern with active light (preferably ultraviolet light) is added before the post-baking step, the crosslinking reaction can be promoted by the acid generated by the irradiation of the active light.

其次，具體說明使用本發明之感光性樹脂組成物的硬化膜之形成方法。Next, a method of forming a cured film using the photosensitive resin composition of the present invention will be specifically described.

＜＜感光性樹脂組成物之調製方法＞＞<<Modulation method of photosensitive resin composition>>

將(A)縮醛系樹脂、(B)光酸產生劑、及(C)溶劑之必要成分以特定比例且以任意之方法進行混合，並加以攪拌溶解以調製感光性樹脂組成物。也可例如將(A)縮醛系樹脂或(B)光酸產生劑分別預先溶解於(C)溶劑而製成溶液後，以特定比例混合此等以調製感光性樹脂組成物。經上述所調製得感光性樹脂組成物之溶液是可使用孔徑為0.1μm之濾網等加以過濾後使用。The necessary components of the (A) acetal resin, (B) photoacid generator, and (C) solvent are mixed at a specific ratio and arbitrarily mixed, and stirred and dissolved to prepare a photosensitive resin composition. For example, (A) an acetal resin or (B) photoacid generator may be previously dissolved in a solvent (C) to prepare a solution, and then mixed in a specific ratio to prepare a photosensitive resin composition. The solution of the photosensitive resin composition prepared as described above can be used by filtering using a sieve having a pore diameter of 0.1 μm or the like.

＜塗布步驟及溶劑移除步驟＞<Coating step and solvent removal step>

將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。例如在液晶顯示裝置之製造方面，該基板是可例示：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。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，較佳為狹縫塗布法。在此，所謂的大型基板是意謂各邊為1 m以上之大小的基板。The resin composition is applied to a specific substrate, and the solvent is removed by depressurization and/or heating (prebaking) to form a desired dried coating film. For example, in the manufacture of a liquid crystal display device, the substrate is exemplified by a polarizing plate, a black matrix layer, a color filter layer, and a glass plate provided with a transparent conductive circuit layer. The method of applying the substrate is not particularly limited, and for example, a method such as a slit coating method, a spray method, a roll coating method, or a spin coating method can be used. Among them, from the viewpoint of being applied to a large substrate, a slit coating method is preferred. Here, the large-sized substrate means a substrate having a size of 1 m or more on each side.

此外，(2)溶劑移除步驟之加熱條件為不會導致在未曝光部的(A)縮醛系樹脂中之(a1)結構單元酸分解性基分解，且使(A)縮醛系樹脂變成對鹼顯影液為可溶性之範圍，雖然也因各成分之種類或混合比而不同，但是較佳為在70至120℃為約30至300秒鐘。Further, (2) the heating condition of the solvent removal step is such that the (a1) structural unit acid-decomposable group is decomposed in the (A) acetal-based resin in the unexposed portion, and the (A) acetal resin is caused. The range which becomes soluble to the alkali developing solution differs depending on the kind or mixing ratio of each component, but is preferably about 30 to 300 seconds at 70 to 120 °C.

＜曝光步驟＞<Exposure step>

在(3)曝光步驟，對經設置乾燥塗膜之基板照射特定的圖案之活性光線。曝光是可通過遮罩而進行，也可直接描繪特定的圖案。較佳為使用具有波長為300 nm以上且450 nm以下之活性光線。在曝光步驟後，因應需要可施加PEB。In the (3) exposure step, the substrate on which the dried coating film is disposed is irradiated with a specific pattern of active light rays. Exposure can be done by masking or by drawing a specific pattern directly. It is preferred to use active light having a wavelength of 300 nm or more and 450 nm or less. After the exposure step, PEB can be applied as needed.

在藉由活性光線的曝光是可使用低壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、雷射產生裝置、LED(發光二極體)光源等。A low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a laser generating device, an LED (light emitting diode) light source, or the like can be used for exposure by active light.

使用水銀燈時，較佳為使用具有g-射線(436 nm)、i-射線(365 nm)、h-射線(405 nm)等之波長的活性光線。與雷射相比較，水銀燈是由於適合大面積之曝光而為較佳。When a mercury lamp is used, it is preferred to use active light having a wavelength of g-ray (436 nm), i-ray (365 nm), h-ray (405 nm) or the like. Mercury lamps are preferred for exposure to large areas compared to lasers.

使用雷射時，若為固體(YAG)雷射則使用343 nm、355 nm，若為準分子雷射則使用351 nm(XeF)，並且，若為半導體雷射則使用375 nm、405 nm。在此等之中，從安定性、成本等的觀點，則更佳為355 nm、405 nm。雷射是可分成一次或數次來照射塗膜。For lasers, 343 nm and 355 nm are used for solid (YAG) lasers, 351 nm (XeF) for excimer lasers, and 375 nm and 405 nm for semiconductor lasers. Among these, from the viewpoints of stability, cost, etc., it is more preferably 355 nm or 405 nm. The laser can be irradiated with the coating film once or several times.

雷射每1脈衝之能量密度較佳為0.1 mJ/cm2 以上且10000 mJ/cm2 以下。為使塗膜充分地硬化，則更佳為0.3 mJ/cm2 以上，最佳為0.5 mJ/cm2 以上，為使得不致於因剝蝕(ablation)現象而導致塗膜分解時，則更佳為1000 mJ/cm2 以下，最佳為100 mJ/cm2 以下。The energy density per 1 pulse of the laser is preferably 0.1 mJ/cm 2 or more and 10000 mJ/cm 2 or less. In order to sufficiently harden the coating film, it is more preferably 0.3 mJ/cm 2 or more, and most preferably 0.5 mJ/cm 2 or more, and it is more preferable that the coating film is not decomposed by the ablation phenomenon. It is 1000 mJ/cm 2 or less, preferably 100 mJ/cm 2 or less.

此外，脈衝寬度(pulse width)較佳為0.1 nsec以上且30000 nsec以下。為使得不致於因剝蝕現象而導致色塗膜分解時，則更佳為0.5 nsec以上，最佳為1 nsec以上，若欲提高在掃描曝光時之對準精確度時，則更佳為1000 nsec以下，最佳為50 nsec以下。Further, the pulse width is preferably 0.1 nsec or more and 30,000 nsec or less. It is more preferably 0.5 nsec or more, and most preferably 1 nsec or more in order to prevent the color coating film from being decomposed by the ablation phenomenon, and more preferably 1000 nsec if it is desired to improve the alignment accuracy at the time of scanning exposure. Hereinafter, the optimum is 50 nsec or less.

並且，雷射之頻率較佳為1至50000 Hz，更佳為10至1000 Hz。若雷射之頻率為低於1 Hz時，則曝光處理時間變長，若超過50000 Hz時，則在掃描曝光時之對準精確度降低。Also, the frequency of the laser is preferably from 1 to 50,000 Hz, more preferably from 10 to 1,000 Hz. If the frequency of the laser is less than 1 Hz, the exposure processing time becomes longer, and if it exceeds 50,000 Hz, the alignment accuracy during scanning exposure is lowered.

並且，雷射之頻率較佳為1 Hz以上且50000 Hz以下。若欲縮短曝光處理時間，則更佳為10 Hz以上，最佳為100 Hz以上，若欲提高在掃描曝光時之對準精確度時，則更佳為10000 Hz以下，最佳為1000 Hz以下。Further, the frequency of the laser is preferably 1 Hz or more and 50,000 Hz or less. If the exposure processing time is to be shortened, it is preferably 10 Hz or more, and preferably 100 Hz or more. If the alignment accuracy during scanning exposure is to be improved, it is preferably 10000 Hz or less, and most preferably 1000 Hz or less. .

與水銀燈相比較，雷射是由於容易縮小焦點，不需要在曝光步驟之圖案形成之遮罩而可降低成本的觀點而為較佳。Compared with a mercury lamp, a laser is preferred because it is easy to reduce the focus and does not require a mask formed by the pattern of the exposure step to reduce the cost.

可使用於本發明之曝光裝置是並無特殊限制，可使用Callisto(商品名、V Technology股份有限公司製)、或AEGIS(商品名、V Technology股份有限公司製)、或DF-2200G(商品名、大日本Screen股份有限公司製)等已市售者。此外，除了上述以外之裝置也適合使用。The exposure apparatus to be used in the present invention is not particularly limited, and any use of Callisto (trade name, manufactured by V Technology Co., Ltd.), or AEGIS (trade name, manufactured by V Technology Co., Ltd.), or DF-2200G (trade name) can be used. It has been marketed, such as Dainippon Screen Co., Ltd.). Further, devices other than the above are also suitable for use.

此外，因應需要也可通過例如長波長截止濾波器(long wavelength cut filter)、短波長截止濾波器、帶通濾波器(band-pass filter)之光譜濾波器而調整照射光。Further, the illumination light may be adjusted by a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band-pass filter, if necessary.

＜顯影步驟＞<Development step>

在(4)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。鹼性化合物是可使用：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，也可在上述鹼類之水溶液中添加適量的甲醇或乙醇等水溶性有機溶劑或界面活性劑之水溶液作為顯影液而使用。In the (4) development step, an alkali developer is used to remove the exposed portion region to form an image pattern. As the basic compound, for example, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide; an alkali metal carbonate such as sodium carbonate or potassium carbonate; sodium hydrogencarbonate or potassium hydrogencarbonate; Alkali metal hydrogencarbonate; ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline hydroxide; aqueous solution of sodium citrate or sodium metasilicate. 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 of the above-mentioned base as a developing solution.

顯影液之pH較佳為10.0至14.0。The pH of the developer is preferably from 10.0 to 14.0.

顯影時間通常為30至180秒鐘，此外，顯影方法是槳翼式法(paddling method)、浸漬法、噴淋法等中之任一者皆可。顯影後實施流水洗淨10至90秒鐘，以形成吾所欲之圖案。The development time is usually 30 to 180 seconds, and the development method may be any of a paddling method, a dipping method, a shower method, and the like. After development, the water is washed for 10 to 90 seconds to form a desired pattern.

＜後烘烤步驟(交聯步驟)＞<Post-baking step (cross-linking step)>

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180至250℃歷時特定的時間，例如若在熱板上則為5至60分鐘，若為烘箱則為30至90分鐘進行加熱處理，使得(A)縮醛系樹脂中之酸分解性基分解、產生羧基、並與(A)縮醛系樹脂中之環氧基及/或氧雜環丁烷基的交聯性基反應而交聯，藉此可形成耐熱性、硬度等優異的保護膜或層間絕緣膜。此外，在進行加熱處理時，藉由在氮氣大氣下進行，也可提高透明性。Regarding the pattern obtained by development corresponding to the unexposed area, by using a heating means such as a hot plate or an oven, for a specific time, for example, at 180 to 250 ° C for a specific time, for example, 5 on a hot plate. In the case of an oven, the heat treatment is carried out for 30 to 90 minutes in an oven to decompose the acid-decomposable group in the (A) acetal resin, to generate a carboxyl group, and to form an epoxy group in the (A) acetal resin. And/or the crosslinkable group of the oxetanyl group reacts and crosslinks, whereby a protective film or an interlayer insulating film excellent in heat resistance, hardness, and the like can be formed. Further, when the heat treatment is performed, the transparency can be improved by performing the reaction under a nitrogen atmosphere.

另外，在加熱處理前，較佳為對經形成圖案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(B)光酸產生劑產生酸，以作為促進交聯之觸媒而發生作用。Further, before the heat treatment, it is preferred to perform post-baking (re-exposure/post-baking) on the patterned substrate by re-exposure of the active light to cause the (B) photoacid generator present in the unexposed portion. Acid is produced to act as a catalyst for promoting crosslinking.

亦即，在本發明之硬化膜之形成方法，較佳為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。That is, in the method of forming the cured film of the present invention, it is preferred to include a re-exposure step of re-exposure with active light between the developing step and the post-baking step.

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，則較佳為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為100至1,000 mJ/cm2 。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. . A preferred exposure amount for the re-exposure step is 100 to 1,000 mJ/cm 2 .

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，因此可用作為層間絕緣膜。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。According to the photosensitive resin composition of the present invention, excellent insulating properties can be obtained, and a cured film having high transparency can be obtained even when baked at a high temperature, and thus it 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 cured film physical properties, and therefore can be used for an organic EL display device or a liquid crystal display device.

本發明之有機EL顯示裝置或液晶顯示裝置是除了具有使用前述本發明之感光性樹脂組成物所形成的硬化膜作為平坦化膜(planarization film)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。The organic EL display device or the liquid crystal display device of the present invention is not particularly limited as long as it has a cured film formed using the photosensitive resin composition of the present invention as a planarization film or an interlayer insulating film. Examples thereof include various organic EL display devices or liquid crystal display devices which are conventionally used in various configurations.

第1圖是展示有機EL顯示裝置之一實例構成概念圖。其係展示在底部發光型(bottom-emission type)有機EL顯示裝置的基板之模式截面圖，且具有平坦化膜4。Fig. 1 is a conceptual diagram showing an example of an organic EL display device. This is a schematic cross-sectional view of a substrate which is shown in a bottom-emission type organic EL display device, and has a planarization film 4.

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Si3 N4 所構成之絕緣膜3。在絕緣膜3形成接觸孔(contact hole)(在此，省略圖示)後，通過該接觸孔所連接於TFT 1之配線2(高度1.0μm)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。A TFT 1 of a bottom gate type is formed on the glass substrate 6, and an insulating film 3 made of Si 3 N 4 is formed in a state of covering the TFT 1 . After the contact hole (not shown) is formed in the insulating film 3, the wiring 2 (having a height of 1.0 μm) 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 formed in a subsequent step.

並且，為將由於形成配線2所造成的凹凸加以平坦化，以填埋由於配線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ITO所構成之第一電極5。第一電極5是相當於有機EL元件之陽極。In addition, 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 filled. On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO 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.

形成覆蓋第一電極5周緣之形狀的絕緣膜8，由於設置該絕緣膜8，則可防止第一電極5與在隨後的步驟所形成的第二電極間之短路。The insulating film 8 covering the shape of the periphery of the first electrode 5 is formed, and since the insulating film 8 is provided, the short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

並且，在第1圖雖然未圖示，透過吾所欲圖案遮罩依序蒸鍍而設置電洞傳輸層(hole transport layer)、有機發光層、電子傳輸層，接著，在基板上方全面形成由Al(鋁)所構成之第二電極，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，藉此可獲得經在各有機EL元件連接用於驅動其TFT 1而成之主動矩陣型(active matrix type)有機EL顯示裝置。Further, although not shown in the first drawing, a hole transport layer, an organic light-emitting layer, and an electron transport layer are provided by sequential vapor deposition in a pattern mask, and then the entire substrate is formed over the substrate. The second electrode made of Al (aluminum) is bonded and sealed with an ultraviolet curable epoxy resin using a sealing glass plate, whereby it is possible to connect the respective organic EL elements for driving the TFT 1 thereof. An active matrix type organic EL display device.

第2圖是展示主動矩陣方式之液晶顯示裝置10之一實例示意性截面圖。該彩色液晶顯示裝置10是在背面具有背光單元12之液晶面板，液晶面板是配置有對應於配置於經貼附偏光膜的兩片玻璃基板14、15之間的所有畫素的TFT 16之元件。在形成於玻璃基板上之各元件，則配線有通過形成於硬化膜17中的接觸孔18而形成畫素電極之ITO透明電極19。在ITO透明電極19之上則設置經配置液晶20之層與黑色矩陣的RGB彩色濾光片22。Fig. 2 is a schematic cross-sectional view showing an example of an active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel is a member in which a TFT 16 corresponding to all the pixels disposed between the two glass substrates 14 and 15 to which the polarizing film is attached is disposed. . On each element formed on the glass substrate, the ITO transparent electrode 19 which forms a pixel electrode through the contact hole 18 formed in the cured film 17 is wired. On the ITO transparent electrode 19, an RGB color filter 22 in which a layer of the liquid crystal 20 and a black matrix are disposed is provided.

《實施例》"Embodiment"

其次，以實施例更具體地說明本發明。但是本發明是並不受限於此等實施例者。另外，除非另有特別指定外，「份」、「%」是以質量為基準。Next, the present invention will be more specifically described by way of examples. However, the invention is not limited to the embodiments. In addition, "parts" and "%" are based on quality unless otherwise specified.

在下列合成例.中，下列簡稱符號是分別代表下列化合物：In the following synthesis examples, the following abbreviations are respectively representative of the following compounds:

V-65：2,2’-偶氮雙(2,4-二甲基戊腈)V-65: 2,2'-azobis(2,4-dimethylvaleronitrile)

GMA：甲基丙烯酸環氧丙酯GMA: glycidyl methacrylate

PGMEA：醋酸丙二醇一甲基醚酯PGMEA: propylene glycol monomethyl ether acetate

[聚合物A-1之合成][Synthesis of Polymer A-1]

在144.2份(2莫耳當量)之乙基乙烯基醚添加0.5份之啡噻(phenothiazine)，一邊將反應系統中冷卻至10℃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(25℃)攪拌4小時。添加5.0份之對甲苯磺酸吡啶鎓後，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℃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.)為43至45℃/7 mmHg餾分之甲基丙烯酸1-乙氧基乙酯之無色油狀物。Adding 0.5 parts of morphine to 144.2 parts (2 moles equivalent) of ethyl vinyl ether (phenothiazine), while cooling the reaction system to 10 ° C or lower, 86.1 parts (1 mole equivalent) of methacrylic acid was added dropwise, followed by stirring at room temperature (25 ° C) for 4 hours. After 5.0 parts of pyridinium p-toluenesulfonate was added, the mixture was stirred at room temperature for 2 hours, and allowed to stand at room temperature overnight. To the reaction mixture, 5 parts of sodium hydrogencarbonate and 5 parts of sodium sulfate were added, and the mixture was stirred at room temperature for 1 hour, and the insoluble matter was filtered, and then concentrated under reduced pressure at 40 ° C or less to decompress the yellow oil of the residue. Distillation to obtain 134.0 parts of a colorless oil of 1-ethoxyethyl methacrylate having a boiling point (bp.) of 43 to 45 ° C / 7 mmHg.

將66.41份(0.4莫耳當量)之所獲得甲基丙烯酸1-乙氧基乙酯、6.89份(0.08莫耳當量)之甲基丙烯酸、49.75份(0.35莫耳當量)之GMA、19.52份(0.15莫耳等量)之甲基丙烯酸2-羥基乙酯、及132.5份之PGMEA之混合溶液在氮氣氣流下加熱至70℃。一邊攪拌該混合溶液，一邊逐滴加入自由基聚合引發劑V-65(和光純藥工業(股)製、12.4份)與100.0份之PGMEA之混合溶液歷時2.5小時。在逐滴加入結束後，使其在70℃進行反應4小時，以獲得聚合物A-1之PGMEA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為8,000。66.41 parts (0.4 mole equivalent) of 1-ethoxyethyl methacrylate, 6.89 parts (0.08 mole equivalent) of methacrylic acid, 49.75 parts (0.35 mole equivalent) of GMA, 19.52 parts ( A mixed solution of 0.15 mole equivalent of 2-hydroxyethyl methacrylate and 132.5 parts of PGMEA was heated to 70 ° C under a nitrogen stream. While stirring the mixed solution, a mixed solution of a radical polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd., 12.4 parts) and 100.0 parts of PGMEA was added dropwise over 2.5 hours. After completion of the dropwise addition, the reaction was carried out at 70 ° C for 4 hours to obtain a PGMEA solution of polymer A-1 (solid content concentration: 40%). The obtained polymer A-1 had a weight average molecular weight of 8,000 as measured by gel permeation chromatography (GPC).

[聚合物A-2至A-19、A-30、A-31、A-34至A-36、及A’-20至29之合成][Synthesis of Polymers A-2 to A-19, A-30, A-31, A-34 to A-36, and A'-20 to 29]

除了將在聚合物A-1之合成所使用的各單體變更為如表1所示之各結構單元(a1)至(a5)，使各結構單元之使用量變更為如表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19、A-30、A-31、A-34至A-36、及A’-20至29。另外，自由基聚合引發劑V-65的添加量是分別加以調整成能獲得如表1所示之分子量。The respective units used in the synthesis of the polymer A-1 were changed to the respective structural units (a1) to (a5) shown in Table 1, and the amounts of the respective structural units were changed to those shown in Table 1. The rest were synthesized as the polymers A-2 to 19, A-30, A-31, A-34 to A-36, and A'-20 to 29, respectively, in the same manner as the synthesis of the polymer A-1. Further, the amount of the radical polymerization initiator V-65 added was adjusted to obtain the molecular weights shown in Table 1, respectively.

另外，如表1所示之莫耳比是各結構單元之共聚合比，(a4)結構單元之質量%是在聚合物中的(a-4)結構單元之質量%。表1中「-」是代表並未使用該結構單元，而在聚合物A-8是代表使用10莫耳%之HEMA與1莫耳%之PME-400作為(a4)結構單元，在聚合物A’-26是代表使用10莫耳%之HEMA與5莫耳%之PME-400作為(a4)結構單元。Further, the molar ratio shown in Table 1 is the copolymerization ratio of each structural unit, and (a4) the mass % of the structural unit is the mass % of the (a-4) structural unit in the polymer. "-" in Table 1 means that the structural unit is not used, and in the polymer A-8, it is represented by using 10 mol% of HEMA and 1 mol% of PME-400 as (a4) structural unit in the polymer. A'-26 is represented by using 10 mol% of HEMA and 5 mol% of PME-400 as (a4) structural unit.

此外，表1中之簡稱符號是如下所示。In addition, the abbreviation symbols in Table 1 are as follows.

MAEVE：甲基丙烯酸1-乙氧基乙酯MAEVE: 1-ethoxyethyl methacrylate

CHOEMA：甲基丙烯酸1-(環己氧基)乙酯CHOEMA: 1-(cyclohexyloxy)ethyl methacrylate

MATHF：甲基丙烯酸四氫呋喃-2-基酯MATHF: tetrahydrofuran-2-yl methacrylate

GMA：甲基丙烯酸環氧丙酯GMA: glycidyl methacrylate

OXE-30：甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯(商品名、大阪有機化學工業(股)製)OXE-30: (3-ethyloxetan-3-yl)methyl methacrylate (trade name, Osaka Organic Chemical Industry Co., Ltd.)

OXE-10：丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯(商品名、大阪有機化學工業(股)製)OXE-10: (3-ethyloxetan-3-yl)methyl acrylate (trade name, Osaka Organic Chemical Industry Co., Ltd.)

M100：甲基丙烯酸3,4-環氧基環己基甲酯(商品名、DAICEL化學工業(股)製)M100: 3,4-epoxycyclohexylmethyl methacrylate (trade name, manufactured by DAICEL Chemical Industry Co., Ltd.)

MAA：甲基丙烯酸MAA: Methacrylic acid

AA：丙烯酸AA: Acrylic

Ph-2：4-羥基苯甲酸(2-甲基丙烯醯氧基乙基)酯Ph-2: 4-hydroxypropenyloxyethyl ester

HEMA：甲基丙烯酸2-羥基乙酯HEMA: 2-hydroxyethyl methacrylate

PME-400：甲基末端聚甲基丙烯酸乙二醇酯(Blemmer PME-400、商品名、日油(股)製)PME-400: methyl terminated polyethylene glycol methacrylate (Blemmer PME-400, trade name, Nippon Oil Co., Ltd.)

MMA：甲基丙烯酸甲酯MMA: Methyl methacrylate

DCPM：甲基丙烯酸二環戊烷酯DCPM: Dicyclopentanyl methacrylate

CHMA：甲基丙烯酸環己酯CHMA: cyclohexyl methacrylate

BzMA：甲基丙烯酸苯甲酯BzMA: benzyl methacrylate

St：苯乙烯St: Styrene

C1：醋酸丙二醇一甲基醚酯C1: propylene glycol monomethyl ether acetate

C2：二甘醇乙基甲基醚C2: diethylene glycol ethyl methyl ether

另外，CHOEMA、及MATHF是以與上述甲基丙烯酸1-乙氧基乙酯相同的方法所合成。Further, CHOEMA and MATHF were synthesized in the same manner as the above 1-ethoxyethyl methacrylate.

此外，Ph-2是以如下所述之方法合成。Further, Ph-2 was synthesized in the following manner.

在21克之4-羥基苯甲酸(2-羥基乙基)酯之100毫升乙腈溶液，在攪拌下加入20毫升之N,N-二甲基乙醯胺，並且加入20克之甲基丙烯醯氯。在35℃歷時8小時，一邊攪拌一邊進行反應後，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/正己烷加以再結晶，以獲得4-羥基苯甲酸(2-羥基乙基)酯。In a solution of 21 g of (2-hydroxyethyl) 4-hydroxybenzoate in 100 ml of acetonitrile, 20 ml of N,N-dimethylacetamide was added with stirring, and 20 g of methacrylic acid chloride was added. After reacting at 35 ° C for 8 hours while stirring, 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 (2). -Hydroxyethyl)ester.

[聚合物A’-32之合成][Synthesis of Polymer A'-32]

在三頸燒瓶中，飼入二甘醇乙基甲基醚(25克)，在氮氣大氣下升溫至70℃。將MAA(3.44克)、MAEVE(14.23克)、甲基丙烯酸苯甲酯(12.33克)、V-65(3.477克、相對於單體為7莫耳%)溶解於二甘醇乙基甲基醚(25克)後逐滴加入此溶液中，歷時2小時。逐滴加入結束後攪拌4小時，使反應結束，以獲得聚合物A’-32之二甘醇乙基甲基醚溶液(固體成份濃度：40%)。所獲得聚合物A’-32以凝膠透層析法(GPC)所測定之重量平均分子量為7,200。In a three-necked flask, diethylene glycol ethyl methyl ether (25 g) was added, and the temperature was raised to 70 ° C under a nitrogen atmosphere. MAA (3.44 g), MAEVE (14.23 g), benzyl methacrylate (12.33 g), V-65 (3.477 g, 7 mol% relative to the monomer) were dissolved in diethylene glycol ethyl methyl Ether (25 g) was added dropwise to this solution over 2 hours. After completion of the dropwise addition, the mixture was stirred for 4 hours to complete the reaction to obtain a solution of the polymer A'-32 diethylene glycol ethyl methyl ether (solid content concentration: 40%). The weight average molecular weight of the obtained polymer A'-32 as measured by gel permeation chromatography (GPC) was 7,200.

[聚合物A-33之合成][Synthesis of Polymer A-33]

在三頸燒瓶中，飼入二甘醇乙基甲基醚(24.5克)，在氮氣大氣下升溫至70℃。將MAEVE(12.65克)、GMA(10.23克)、HEMA(6.24克)、V-65(3.477克、相對於單體為7莫耳%)溶解於二甘醇乙基甲基醚(24.5克)後逐滴加入此溶液中歷時2小時。逐滴加入結束後攪拌4小時。其後，將溫度升溫至90℃以進行可使得少量的MAEVE進行熱分解之熟成步驟，攪拌3小時，使反應結束，以獲得聚合物A-33之二甘醇乙基甲基醚溶液(固體成份濃度：40%)。藉由NMR及實測之酸價測定，聚合物A-33之組成比(莫耳比)是MAA/MAVEV/GMA/HEMA=4.5/35.5/36/24，以凝膠透層析法(GPC)所測定之重量平均分子量為7,500。此外，(a4)結構單元之質量%為22%。In a three-necked flask, diethylene glycol ethyl methyl ether (24.5 g) was added, and the temperature was raised to 70 ° C under a nitrogen atmosphere. MAEVE (12.65 g), GMA (10.23 g), HEMA (6.24 g), V-65 (3.477 g, 7 mol% relative to the monomer) were dissolved in diethylene glycol ethyl methyl ether (24.5 g) This solution was added dropwise to the solution for 2 hours. After the end of the dropwise addition, the mixture was stirred for 4 hours. Thereafter, the temperature was raised to 90 ° C to carry out a ripening step in which a small amount of MAEVE was thermally decomposed, and the mixture was stirred for 3 hours to complete the reaction to obtain a solution of the polymer A-33 diethylene glycol ethyl methyl ether (solid Ingredient concentration: 40%). The composition ratio (molar ratio) of polymer A-33 was MAA/MAVEV/GMA/HEMA=4.5/35.5/36/24 by gel spectroscopy (GPC) as determined by NMR and measured acid value. The weight average molecular weight measured was 7,500. Further, the mass % of the (a4) structural unit was 22%.

[實施例1至119、比較例1至11、比較例14][Examples 1 to 119, Comparative Examples 1 to 11, and Comparative Example 14] (1)感光性樹脂組成物之調製(1) Modulation of photosensitive resin composition

將如下表2所示各成分加以混合以形成均勻溶液後，使用具有0.1μm孔徑之聚四氟乙烯製濾網進行過濾，且分別調製實施例1至119、比較例1至11、比較例14之感光性樹脂組成物之溶液。The components shown in the following Table 2 were mixed to form a homogeneous solution, and then filtered using a sieve made of polytetrafluoroethylene having a pore diameter of 0.1 μm, and Examples 1 to 119, Comparative Examples 1 to 11, and Comparative Example 14 were separately prepared. A solution of the photosensitive resin composition.

在表2至5中，在實施例30、實施例70及實施例107，聚合物是使用A’-32與A-33兩種。此外，在表中揭述種類有兩種者是表示使用兩種，其數量是例如在實施例37之交聯劑是表示使用8份之E2與1.5份之E3。In Tables 2 to 5, in Example 30, Example 70 and Example 107, the polymer was used in two types of A'-32 and A-33. Further, two types of species are disclosed in the table to indicate that two types are used, and the amount thereof is, for example, that the crosslinking agent in Example 37 means that 8 parts of E2 and 1.5 parts of E3 are used.

另外，在表2至5中之簡稱符號是如下所示。In addition, the abbreviations in Tables 2 to 5 are as follows.

B1：CGI1397(商品名、下述之結構、Ciba Japan(股)製)B1: CGI1397 (trade name, structure below, Ciba Japan)

B2：CGI1325(商品名、下述之結構、Ciba Japan(股)製)B2: CGI1325 (trade name, structure below, Ciba Japan)

B3：PAI-1001(商品名、下述之結構、Midori化學(股)製)B3: PAI-1001 (trade name, structure described below, Midori Chemical Co., Ltd.)

B4：PAI-101(商品名、下述之結構、Midori化學(股)製)B4: PAI-101 (trade name, structure described below, Midori Chemical Co., Ltd.)

B5：α-(對甲苯磺醯氧基亞胺基)苯基乙腈(合成方法是如下所述)B5: α-(p-toluenesulfonyloxyimino)phenylacetonitrile (synthesis method is as follows)

B6：下述之化合物B6: The following compounds

B7：下述之化合物B7: The following compounds

B8：下述之化合物B8: The following compounds

B9：下述之化合物B9: The following compounds

N1：NBCA(商品名、下述之結構、黑金化成(股)製)N1: NBCA (trade name, structure below, black gold chemical (share) system)

N2：DBA(商品名、9,10-二丁氧基蒽、下述之結構、川崎化成工業)N2: DBA (trade name, 9,10-dibutoxy oxime, structure described below, Kawasaki Chemical Industry Co., Ltd.)

C1：醋酸丙二醇一甲基醚酯C1: propylene glycol monomethyl ether acetate

C2：二甘醇乙基甲基醚C2: diethylene glycol ethyl methyl ether

E1：JER 157S70(商品名、多官能酚醛清漆型環氧樹脂(環氧當量為200至220 g/eq)、Japan Epoxy Resin(股)製)E1: JER 157S70 (trade name, polyfunctional novolac type epoxy resin (epoxy equivalent: 200 to 220 g/eq), manufactured by Japan Epoxy Resin Co., Ltd.)

E2：JER 157S65(商品名、多官能酚醛清漆型環氧樹脂(環氧當量為200至220 g/eq)、Japan Epoxy Resin(股)製)E2: JER 157S65 (trade name, polyfunctional novolac type epoxy resin (epoxy equivalent: 200 to 220 g/eq), made by Japan Epoxy Resin Co., Ltd.)

E3：NIKALAC MW-100LM(商品名、(股)三和化學製)E3: NIKALAC MW-100LM (trade name, (share) three and chemical system)

E4：NIKALAC MX-270(商品名、(股)三和化學製)E4: NIKALAC MX-270 (trade name, (share) three and chemical system)

E5：KAYARAD DPHA(商品名、日本化藥(股)製)E5: KAYARAD DPHA (trade name, Nippon Kayaku Co., Ltd.)

H1：PolyFox PF-6320(商品名、氟系界面活性劑、OMNOVA公司製)H1: PolyFox PF-6320 (trade name, fluorine-based surfactant, manufactured by OMNOVA)

H2：下述結構之化合物W-3H2: Compound W-3 of the following structure

G1：4-二甲基胺基吡啶G1: 4-dimethylaminopyridine

G2：1,5-二吖雙環[4.3.0]-5-壬烯G2: 1,5-di-bicyclobicyclo[4.3.0]-5-decene

G3：三苯基咪唑G3: triphenylimidazole

G4：二吖雙環十一烯G4: Diterpene bicycloundecene

G5：1,4-二吖雙環[2.2.2]辛烷G5: 1,4-dioxabicyclo[2.2.2]octane

F1：3-環氧丙氧基丙基三甲氧基矽烷(KBM-403(商品名、信越化學工業(股)製))F1: 3-glycidoxypropyltrimethoxydecane (KBM-403 (trade name, Shin-Etsu Chemical Co., Ltd.))

M1：下述之化合物M1: the following compounds

M2：下述之化合物M2: the following compounds

J1：(2,3-二甲基-2,3-二苯基丁烷)(NOFMER BC-90(商品名、日油(股)製))J1: (2,3-dimethyl-2,3-diphenylbutane) (NOFMER BC-90 (trade name, Nippon Oil Co., Ltd.))

K1：下述結構之化合物K-1K1: Compound K-1 of the following structure

L1：下述結構之化合物L-1L1: Compound L-1 of the following structure

[B5之合成][Synthesis of B5]

根據在日本特表2002-528451號公報中之段落碼[0108]所揭述之方法合成α-(對甲苯磺醯氧基亞胺基)苯基乙腈。The α-(p-toluenesulfonyloxyimino)phenylacetonitrile was synthesized according to the method described in paragraph code [0108] of JP-A-2002-528451.

[B6之合成][Synthesis of B6] 1-1.合成中間體B-6A之合成1-1. Synthesis of synthetic intermediate B-6A

將2-胺基苯硫醇：31.3克(東京化成工業(股)製)在室溫(25℃)下溶解於甲苯：100毫升(和光純藥工業(股)製)中。其次，將苯基乙醯基氯：40.6克(東京化成工業股份有限公司製造)逐滴加入，在室溫下歷時1小時、接著在100℃下加以攪拌以進行反應歷時2小時。在所獲得反應液中飼入500毫升水使得所析出之鹽溶解，萃取甲苯油分，並以旋轉式蒸發器濃縮萃取液，以獲得合成中間體B-6A。2-Aminobenzenethiol: 31.3 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in toluene: 100 ml (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature (25 ° C). Next, phenylacetonitrile chloride: 40.6 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was stirred at room temperature for 1 hour, followed by stirring at 100 ° C for 2 hours. 500 ml of water was added to the obtained reaction solution to dissolve the precipitated salt, toluene oil was extracted, and the extract was concentrated by a rotary evaporator to obtain a synthetic intermediate B-6A.

1-2.B-6之合成1-2. Synthesis of B-6

將2.25克之前述所獲得合成中間體B-6A與四氫呋喃：10毫升(和光純藥工業(股)製)混合後，浸入冰浴中以將反應液冷卻至5℃以下。其次，將氫氧化四甲基銨：4.37克(25重量%甲醇溶液、Alfa Acer公司製)逐滴加入，在冰浴下攪拌0.5小時而使其反應。並且，將亞硝酸異戊酯：7.03克一邊保持於內溫20℃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，攪拌1小時。2.25 g of the above-obtained synthetic intermediate B-6A and tetrahydrofuran: 10 ml (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, and then immersed in an ice bath to cool the reaction liquid to 5 ° C or lower. Next, tetramethylammonium hydroxide: 4.37 g (25 wt% methanol solution, manufactured by Alfa Acer Co., Ltd.) was added dropwise, and the mixture was stirred for 0.5 hour in an ice bath to cause a reaction. Further, isoamyl nitrite: 7.03 g was added dropwise while maintaining the internal temperature at 20 ° C or lower, and after the dropwise addition was completed, the reaction liquid was allowed to warm to room temperature, and then stirred for 1 hour.

接著，將反應液冷卻至5℃以下後，飼入對甲苯磺醯基氯(1.9克)(東京化成工業(股)製)，一邊保持於10℃以下一邊攪拌1小時。其後飼入80毫升水，在0℃攪拌1小時。將所獲得析出物過濾後，飼入60毫升之異丙醇(IPA)，加熱至50℃而攪拌1小時，並經熱時過濾、乾燥而獲得1.8克之(B6：前述結構)。Then, the reaction liquid 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 being kept at 10 ° C or lower. Thereafter, 80 ml of water was fed and stirred at 0 ° C for 1 hour. After the obtained precipitate was filtered, it was fed with 60 ml of isopropyl alcohol (IPA), heated to 50 ° C and stirred for 1 hour, and filtered while being heated, and dried to obtain 1.8 g (B6: the above structure).

所獲得B6之1 H-NMR光譜(300 MHz、氘化DMSO((D3 C)2 S=O))：δ=8.2至8.17(m,1H)、8.03至8.00(m,1H)、7.95至7.9(m,2H)、7.6至7.45(m,9H)、2.45(s,3H)。 1 H-NMR spectrum of B6 obtained (300 MHz, deuterated DMSO ((D 3 C) 2 S=O)): δ = 8.2 to 8.17 (m, 1H), 8.03 to 8.00 (m, 1H), 7.95 To 7.9 (m, 2H), 7.6 to 7.45 (m, 9H), 2.45 (s, 3H).

由上述1 H-NMR測定結果，可推定所獲得B6是一種單獨之順式或反式異構物。From the results of the above 1 H-NMR measurement, it was presumed that the obtained B6 was a single cis or trans isomer.

[B7之合成][Synthesis of B7]

在2-萘酚(10克)、氯苯(30毫升)之懸浮溶液添加氯化鋁(10.6克)、2-氯丙醯基氯(10.1克)，將混合液加熱至40℃而使其反應2小時。在冰冷下，將4N HCl水溶液(60毫升)逐滴加入反應液中，添加醋酸乙酯(50毫升)而加以分液。對有機層加入碳酸鉀(19.2克)，在40℃反應1小時後，添加2N HCl水溶液(60毫升)而加以分液，將有機層進行濃縮後，將結晶以二異丙基醚(10毫升)加以再漿體化，並加以過濾、乾燥而獲得酮化合物(6.5克)。In a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 ml), aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added, and the mixture was heated to 40 ° C to make it Reaction for 2 hours. 4N HCl aqueous solution (60 ml) was added dropwise to the reaction mixture under ice-cooling, and ethyl acetate (50 ml) was added and partitioned. Potassium carbonate (19.2 g) was added to the organic layer, and after reacting at 40 ° C for 1 hour, 2N aqueous HCl solution (60 ml) was added and the mixture was separated, and the organic layer was concentrated to give crystals of diisopropyl ether (10 ml). It was repulped, filtered, and dried to obtain a ketone compound (6.5 g).

在所獲得酮化合物(3.0克)、甲醇(30毫升)之懸浮溶液中，添加醋酸(7.3克)、50質量%之羥基胺水溶液(8.0克)，並進行加熱回流。放冷後，加入水(50毫升)，將所析出之結晶加以過濾，以冷甲醇洗淨後，並加以乾燥而獲得肟化合物(2.4克)。Into a suspension solution of the obtained ketone compound (3.0 g) and methanol (30 ml), acetic acid (7.3 g) and a 50% by mass aqueous solution of hydroxylamine (8.0 g) were added, and the mixture was heated under 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).

將所獲得肟化合物(1.8克)溶解於丙酮(20毫升)，在冰冷下添加三乙基胺(1.5克)、對甲苯磺醯基氯(2.4克)、升溫至室溫而使其反應1小時。對反應液添加水(50毫升)、將所析出之結晶加以過濾後，以甲醇(20毫升)加以再漿體化，並加以過濾、乾燥而獲得B7(2.3克)。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 thereto under ice cooling, and the mixture was heated to room temperature to react. hour. Water (50 ml) was added to the reaction mixture, and the precipitated crystals were filtered, and then resluded with methanol (20 ml), filtered and dried to give B7 (2.3 g).

另外，B7之1 H-NMR光譜(300 MHz、CDCl3 )：δ=8.3(d,1H)、8.0(d,2H)、7.9(d,1H)、7.8(d,1H)、7.6(dd,1H)、7.4(dd,1H)、7.3(d,2H)、7.1(d,1H)、5.6(q,1H)、2.4(s,3H)、1.7(d,3H)。In addition, 1 H-NMR spectrum of B7 (300 MHz, CDCl 3 ): δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd , 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H).

[B8之合成][Synthesis of B8]

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℃使其反應2小時。水(300毫升)、醋酸乙酯(200毫升)添加至反應液中而加以分液，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(50毫升)、水(50毫升)並使其反應2小時。將反應液浸入1N HCl水溶液(500毫升)中，將所析出之結晶加以過濾、水洗而獲得羧酸粗體後，添加30克之聚磷酸並在170℃進行反應30分鐘。將反應液浸入水(300毫升)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而獲得酮化合物(10克)。2-Naphthol (20 g) was dissolved in N,N-dimethylacetamide (150 ml), potassium carbonate (28.7 g) and ethyl 2-bromooctanoate (52.2 g) were added and allowed to stand at 100 °C. Reaction for 2 hours. Water (300 ml) and ethyl acetate (200 ml) were added to the reaction solution to separate the layers, and the organic layer was concentrated. Then, a 48% by weight aqueous sodium hydroxide solution (23 g), ethanol (50 ml), and water were added. (50 ml) and 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 thereto, and the reaction was carried out at 170 ° C for 30 minutes. The reaction solution was immersed in water (300 ml), and ethyl acetate (300 ml) was added and the mixture was separated, and the organic layer was concentrated, and then purified by hydrazine gel column chromatography to obtain a ketone compound (10 g). ).

在所獲得酮化合物(10.0克)、甲醇(100毫升)之懸浮溶液添加醋酸鈉(30.6克)、鹽酸羥胺(hydroxylamine hydrochloride)(25.9克)、硫酸鎂(4.5克)，並進行24小時之加熱回流。放冷後，添加水(150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而獲得肟化合物(5.8克)。Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g), magnesium sulfate (4.5 g) were added to the suspension of the obtained ketone compound (10.0 g) and methanol (100 ml), and heated for 24 hours. Reflux. After cooling, water (150 ml) and ethyl acetate (150 ml) were added and the mixture was separated, and the organic layer was partitioned 4 times with 80 ml of water. After concentration, the column was subjected to column chromatography. Purification was carried out to obtain a hydrazine compound (5.8 g).

就所獲得肟(3.1克)，以與B7相同的方式進行磺酸酯化而獲得B8(3.2克)。With respect to the obtained hydrazine (3.1 g), sulfonation was carried out in the same manner as B7 to obtain B8 (3.2 g).

另外，B8之1 H-NMR光譜(300 MHz、CDCl3 )：δ=8.3(d,1H)、8.0(d,2H)、7.9(d,1H)、7.8(d,1H)、7.6(dd,1H)、7.5(dd,1H)、7.3(d,2H)、7.1(d,1H)、5.6(dd,1H)、2.4(s,3H)、2.2(ddt,1H)、1.9(ddt,1H)、1.4至1.2(m,8H)、0.8(t,3H)。In addition, 1 H-NMR spectrum of B8 (300 MHz, CDCl 3 ): δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd , 1H), 7.5 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (dd, 1H), 2.4 (s, 3H), 2.2 (ddt, 1H), 1.9 (ddt, 1H), 1.4 to 1.2 (m, 8H), 0.8 (t, 3H).

[B9之合成][Synthesis of B9]

除了取代在B7之合成的對甲苯磺醯基氯而使用苯磺醯基氯以外，其餘則以與B7之合成相同的方式合成B9。Except that phenylsulfonyl chloride was used instead of p-toluenesulfonyl chloride synthesized in B7, B9 was synthesized in the same manner as in the synthesis of B7.

另外，B9之1 H-NMR光譜(300 MHz、CDCl3 )：δ=8.3(d,1H)、8.1(d,2H)、7.9(d,1H)、7.8(d,1H)、7.7-7.5(m,4H)、7.4(dd,1H)、7.1(d,1H)、5.6(q,1H)、1.7(d,3H)。In addition, 1 H-NMR spectrum of B9 (300 MHz, CDCl 3 ): δ = 8.3 (d, 1H), 8.1 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.7-7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d, 1H), 5.6 (q, 1H), 1.7 (d, 3H).

另外，在比較例12所使用的組成物是在日本特開2004-264623號公報中所揭述之實施例1的組成物。在比較例13所使用的組成物是在特開2009-98616號公報中所揭述之實施例7的組成物。在比較例14所使用的組成物是在特開平10-26829號公報中所揭述之實施例1的組成物。Further, the composition used in Comparative Example 12 is the composition of Example 1 disclosed in Japanese Laid-Open Patent Publication No. 2004-264623. The composition used in Comparative Example 13 is the composition of Example 7 disclosed in Japanese Laid-Open Patent Publication No. 2009-98616. The composition used in Comparative Example 14 is the composition of Example 1 described in JP-A-10-26829.

(2)感光性樹脂組成物之評估(2) Evaluation of photosensitive resin composition (2-1)感度之評估(無PEB)(2-1) Evaluation of sensitivity (without PEB)

在具有矽氧化膜之矽晶圓上，將實施例1至119、比較例1至14之感光性樹脂組成物之溶液分別加以旋轉塗布後，在90℃之熱板上預烘烤120秒鐘以形成膜厚為3μm之塗膜。The solutions of the photosensitive resin compositions of Examples 1 to 119 and Comparative Examples 1 to 14 were spin-coated on a tantalum wafer having a tantalum oxide film, and then prebaked on a hot plate at 90 ° C for 120 seconds. A coating film having a film thickness of 3 μm was formed.

其次，使用i-射線步進機(Canon(股)製造、商品名：FPA-3000i5+)，透過特定的遮罩而進行曝光。曝光後將基板在室溫放置10分鐘後，以0.4%之氫氧化四甲基銨水溶液在23℃以槳翼式法進行顯影60秒鐘，並且，以超純水洗滌歷時45秒鐘。經這些操作而將10μm之線寬與間距以1：1加以解析時之最適曝光量(Eopt)作為感度。感度是在比70 mJ/cm2 為低曝光量的情況時，則可稱為高感度。評估結果展示於表6、7。Next, exposure was performed through a specific mask using an i-ray stepper (manufactured by Canon, trade name: FPA-3000i5+). After the exposure, the substrate was allowed to stand at room temperature for 10 minutes, and developed with a 0.4% aqueous solution of tetramethylammonium hydroxide at 23 ° C for 60 seconds in a paddle method, and washed with ultrapure water for 45 seconds. The optimum exposure amount (Eopt) when the line width of 10 μm and the pitch were analyzed by 1:1 was used as the sensitivity by these operations. When the sensitivity is a case where the exposure amount is lower than 70 mJ/cm 2 , it can be called high sensitivity. The results of the assessment are shown in Tables 6 and 7.

另外，在表6、7之感度(無PEB)之欄中標記為「**」是代表在顯影時發生剝離而無法進行圖案化，另外，標記為「*」是代表無法以200 mJ/cm2 形成圖案。In addition, the mark "**" in the column of the sensitivity (without PEB) of Tables 6 and 7 indicates that peeling occurs during development and cannot be patterned, and the mark "*" means that it cannot be 200 mJ/cm. 2 form a pattern.

(2-2)耐熱透明性之評估(2-2) Evaluation of heat resistance transparency

在玻璃基板(商品名：EAGLE 2000、Corning公司製)將實施例1至119、及比較例1至14(以200 mJ/cm2 無法形成圖案者除外)之感光性樹脂組成物的溶液加以旋轉塗布後，在90℃之熱板上預烘烤120秒鐘而形成膜厚為3μm之塗膜。將所獲得塗膜以0.4%之氫氧化四甲基銨水溶液在23℃以槳翼式法進行顯影60秒鐘，並且，以超純水洗滌45秒鐘後，以佳能公司製造之PLA-501F曝光機(商品名、超高壓水銀燈)進行曝光使得積算照射量成為300 mJ/cm2 (照度：20 mW/cm2 )，其後，將該基板在230℃之烘箱中加熱1小時而獲得硬化膜。將所獲得硬化膜在230℃之烘箱再加熱2小時後，使用分光光度計(spectrophotometer)「150-20型Double Beam(商品名、日立製作所製)」以在400至800 nm之範圍的波長進行測定光線透射率。此時之最低光線透射率之評估(耐熱透明性之評估)是如表6、7所示。A solution of the photosensitive resin composition of Examples 1 to 119 and Comparative Examples 1 to 14 (excluding those in which no pattern was formed at 200 mJ/cm 2 ) was rotated on a glass substrate (trade name: EAGLE 2000, manufactured by Corning). After coating, it was prebaked on a hot plate at 90 ° C for 120 seconds to form a coating film having a film thickness of 3 μm. The obtained coating film was developed by a paddle method with a 0.4% aqueous solution of tetramethylammonium hydroxide at 23 ° C for 60 seconds, and after washing with ultrapure water for 45 seconds, PLA-501F manufactured by Canon Inc. The exposure machine (trade name, ultrahigh pressure mercury lamp) was exposed so that the integrated irradiation amount was 300 mJ/cm 2 (illuminance: 20 mW/cm 2 ), and thereafter, the substrate was heated in an oven at 230 ° C for 1 hour to obtain hardening. membrane. After the obtained cured film was further heated in an oven at 230 ° C for 2 hours, a spectrophotometer "150-20 type Double Beam (trade name, manufactured by Hitachi, Ltd.)" was used to carry out wavelengths in the range of 400 to 800 nm. The light transmittance was measured. The evaluation of the lowest light transmittance at this time (evaluation of heat resistance transparency) is shown in Tables 6 and 7.

評估基準是如下所示。另外，最低光線透射率之值是經換算成在230℃加熱2小時後之每2μm膜厚之值。The evaluation criteria are as follows. Further, the value of the minimum light transmittance is a value per 2 μm film thickness after being converted into heating at 230 ° C for 2 hours.

0：92%以上、0: 92% or more,

1：87%以上且低於92%、1:87% or more and less than 92%,

2：85%以上且低於87%、2: 85% or more and less than 87%,

3：82%以上且低於85%、3: 82% or more and less than 85%,

4：低於82%。4: Less than 82%.

(2-3)耐ITO濺鍍性之評估(2-3) Evaluation of ITO Sputter Resistance

在玻璃基板「EAGLE 2000(商品名、Corning公司製)」上將實施例1至119、比較例1至14(以200 mJ/cm2 無法形成圖案者除外)之感光性樹脂組成物加以旋轉塗布後，在90℃之熱板上進行預烘烤120秒鐘而形成膜厚為3μm之塗膜。對所獲得塗膜以佳能公司製造之PLA-501F曝光機(商品名、超高壓水銀燈)進行曝光使得積算照射量成為300 mJ/cm2 (照度：20 mW/cm2 )，其後，將該基板在230℃之烘箱加熱1小時而獲得硬化膜。將所獲得各自之硬化膜，以ULVAC公司製之SIH-3030(商品名)在基板溫度210℃進行ITO濺鍍，以在硬化膜上製造0.14μm之ITO膜。以光學顯微鏡觀察濺鍍後之表面，並進行評估有無表面皺裂(chaps)。評估結果是如表6、7所示。另外，評估基準是如下所示：The photosensitive resin compositions of Examples 1 to 119 and Comparative Examples 1 to 14 (excluding those in which no pattern was formed at 200 mJ/cm 2 ) were spin-coated on a glass substrate "EAGLE 2000 (trade name, manufactured by Corning)". Thereafter, prebaking was performed on a hot plate at 90 ° C for 120 seconds to form a coating film having a film thickness of 3 μm. The obtained coating film was exposed to a PLA-501F exposure machine (trade name, ultrahigh pressure mercury lamp) manufactured by Canon Inc. so that the integrated irradiation amount was 300 mJ/cm 2 (illuminance: 20 mW/cm 2 ), and thereafter, The substrate was heated in an oven at 230 ° C for 1 hour to obtain a cured film. Each of the obtained cured films was subjected to ITO sputtering at a substrate temperature of 210 ° C under the SIH-3030 (trade name) manufactured by ULVAC Co., Ltd. to produce a 0.14 μm ITO film on the cured film. The surface after sputtering was observed with an optical microscope and evaluated for presence or absence of surface cracks (chaps). The evaluation results are shown in Tables 6 and 7. In addition, the evaluation benchmark is as follows:

1：觀察不到表面皺裂、1: No surface cracking is observed,

2：稍可觀察到表面皺裂，但是為實務應用上並無問題之水準、2: The surface is slightly cracked, but there is no problem in practical application.

3：觀察到表面皺裂，是在實務應用上不容許之水準、3: Observing surface cracking is a level that is not allowed in practical applications.

4：表面皺裂激烈。4: The surface is cracked fiercely.

(2-4)實施PEB(曝光後加熱)時之感度(2-4) Sensitivity when performing PEB (heating after exposure)

除了就實施例9至實施例12、實施例50至實施例52、實施例87至實施例89及比較例13之感光性樹脂組成物，在曝光後1分鐘後以熱板實施80℃ 60秒鐘之PEB以外，其餘則以與上述(2-1)感度之評估(無PEB)相同的方式評估實施PEB時之感度。結果是展示於表6、表7。The photosensitive resin compositions of Examples 9 to 12, Examples 50 to 52, and Examples 87 to 89 and Comparative Example 13 were subjected to a hot plate at 80 ° C for 60 seconds 1 minute after the exposure. Other than the PEB of the bell, the sensitivity of the PEB was evaluated in the same manner as the evaluation of the sensitivity of the above (2-1) (without PEB). The results are shown in Tables 6 and 7.

從表6、表7可得知本發明之感光性樹脂組成物是任一者即使未實施PEB時，皆具有為非常高的感度，耐熱透明性良好，且耐ITO濺鍍性優異。此外，也可得知本發明之感光性樹脂組成物是即使未實施PEB而感度是非常高，但是經實施PEB時，則感度為更高。From Tables 6 and 7, it is understood that any of the photosensitive resin compositions of the present invention has a very high sensitivity even when PEB is not applied, and has excellent heat-resistant transparency and excellent ITO sputtering resistance. Further, it was also found that the photosensitive resin composition of the present invention has a very high sensitivity even if PEB is not applied, but when PEB is applied, the sensitivity is higher.

與此相對，未使用本發明之比較例是在未實施PEB時，感度為低，即使實施PEB，與本發明之實施例相比較，感度為低。On the other hand, in the comparative example which did not use this invention, when the PEB was not implemented, the sensitivity was low, and even if PEB was implemented, the sensitivity was low compared with the Example of this invention.

(2-5)玻璃基板上之密著性(2-5) Adhesion on the glass substrate

並且，關於實施例1至實施例119之感光性樹脂組成物，在上述(2-1)感度之評估(無PEB)中，除了取代矽晶圓而使用玻璃基板「EAGLE 2000(商品名、Corning公司製)」以外，其餘則以與上述(2-1)相同的方式形成塗膜，並使用近接式曝光裝置(USHIO電機公司製、商品名：UX-1000SM)，使特定的遮罩密著而使用在365 nm之光強度為16 mW/cm2 之紫外線進行曝光。玻璃基板是將經施加一般的洗淨者、與洗淨後再在乾燥器中曝晒於六甲基二矽氮烷蒸氣歷時3分鐘者之兩種分別對各自之感光性樹脂組成物而使用。Further, in the photosensitive resin compositions of Examples 1 to 119, in the evaluation of (2-1) sensitivity (PEB-free), a glass substrate "EAGLE 2000 (trade name, Corning) was used instead of the silicon wafer. A coating film is formed in the same manner as in the above (2-1), and a close-contact exposure apparatus (manufactured by USHIO Electric Co., Ltd., trade name: UX-1000SM) is used to make a specific mask close. Exposure was carried out using ultraviolet light having a light intensity of 16 mW/cm 2 at 365 nm. The glass substrate was used for each of the photosensitive resin compositions which were subjected to a general rinsing, and after being washed and then exposed to a hexamethyldiazepine vapor in a desiccator for 3 minutes.

曝光是以可將10μm之線寬與間距以1：1加以解析之曝光量進行。其次，以與上述(2-1)相同的方式曝光後，將基板在室溫放置10分鐘後，使用0.4%之氫氧化四甲基銨水溶液在23℃以槳翼式法顯影60秒鐘，並且以超純水洗滌45秒鐘。此時，在實施例1至實施例119之感光性樹脂組成物之任一者皆未發生圖案之缺口及剝落。The exposure was carried out with an exposure amount which can be resolved by a line width of 10 μm and a pitch of 1:1. Next, after exposure in the same manner as in the above (2-1), the substrate was allowed to stand at room temperature for 10 minutes, and then developed by a paddle method at 0.4 ° C for 60 seconds using a 0.4% aqueous solution of tetramethylammonium hydroxide. And washed with ultrapure water for 45 seconds. At this time, no pattern peeling or peeling occurred in any of the photosensitive resin compositions of Examples 1 to 119.

(2-6)355 nm雷射曝光(2-6) 355 nm laser exposure

並且，關於實施例1至實施例119之感光性樹脂組成物，在上述(2-1)感度之評估(無PEB)中，除了變更曝光為如下所示以外，其餘則以與上述(2-1)相同的方式形成圖案。亦即，從塗膜隔著150μm之間隔而架設特定的光罩，且以10至100 mJ/cm2 之曝光量照射波長為355 nm之雷射。另外，雷射裝置是使用V Technology公司製之「AEGIS」(商品名)(波長355 nm、脈衝寬度6 nsec)，曝光量是使用OPHIR公司製之「PE10B-V2」(商品名)來進行測定。Further, in the photosensitive resin compositions of Examples 1 to 119, in the evaluation of (2-1) sensitivity (PEB-free), the exposure was changed as follows, and the other was 1) Form the pattern in the same way. That is, a specific photomask was placed from the coating film at intervals of 150 μm, and a laser having a wavelength of 355 nm was irradiated with an exposure amount of 10 to 100 mJ/cm 2 . In addition, the "AEGIS" (trade name) (wavelength 355 nm, pulse width 6 nsec) manufactured by V Technology Co., Ltd. was used, and the exposure amount was measured using "PE10B-V2" (trade name) manufactured by OPHIR Co., Ltd. .

結果得知在實施例1至實施例119之感光性樹脂組成物中任一者皆可在355 nm雷射曝光而形成圖案。As a result, it was found that any of the photosensitive resin compositions of Examples 1 to 119 can be exposed by laser exposure at 355 nm to form a pattern.

(2-7)UV-LED曝光(2-7) UV-LED exposure

並且，關於實施例1至實施例119之感光性樹脂組成物，除了曝光由i-射線步進機變更為UV-LED光源曝光機以外，其餘則以與上述(2-1)感度之評估(無PEB)相同的方式實施評估結果，得知任一者皆可形成圖案。Further, the photosensitive resin compositions of Examples 1 to 119 were evaluated in addition to the above-mentioned (2-1) sensitivity, except that the exposure was changed from an i-ray stepper to a UV-LED source exposure machine. The results of the evaluation were carried out in the same manner without PEB, and it was found that either of them could be patterned.

[實施例120][Example 120]

以如下所述之方法進行製造使用薄膜電晶體(TFT：Thin Film Transistor)之有機EL顯示裝置(參閱第1圖)。An organic EL display device using a thin film transistor (TFT: Thin Film Transistor) was produced by the method described below (see Fig. 1).

在玻璃基板6上形成下閘極型之TFT 1，並以覆蓋該TFT 1之狀態而形成由Si3 N4 所構成之絕緣膜3。其次，在該絕緣膜3形成接觸孔後，將透過該接觸孔而連接至TFT 1的配線2(高度1.0μm)形成於絕緣膜3上。A lower gate type TFT 1 is formed on the glass substrate 6, and an insulating film 3 made of Si 3 N 4 is formed in a state of covering the TFT 1. Next, after the contact hole is formed in the insulating film 3, the wiring 2 (having a height of 1.0 μm) which is connected to the TFT 1 through the contact hole is formed on the insulating film 3.

並且，為將由於形成配線2所引起之凹凸加以平坦化，則以填埋由於配線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11之感光性樹脂組成物旋轉塗布於基板上，在熱板上預烘烤(90℃×2分鐘)後，由遮罩上使用高壓水銀燈將i-射線(365 nm)照射25 mJ/cm2 (照度20 mW/cm2 )後，以鹼水溶液進行顯影而形成圖案，並在230℃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。並且，配線2之平均高度差異為500 nm、所製造之平坦化膜4之膜厚為2000 nm。In addition, 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 filled. The formation process of the planarizing film 4 on the insulating film 3 was as follows: the photosensitive resin composition of Example 11 was spin-coated on a substrate, and pre-baked on a hot plate (90 ° C × 2 minutes), and then masked. After i-ray (365 nm) was irradiated with 25 mJ/cm 2 (illuminance: 20 mW/cm 2 ) using a high-pressure mercury lamp, development was carried out with an aqueous alkali solution to form a pattern, and heat treatment was performed at 230 ° C for 60 minutes. The coating property when the photosensitive resin composition was applied was good, and no crease or crack was observed in the cured film obtained after exposure, development, and firing. Further, the average height difference of the wiring 2 was 500 nm, and the film thickness of the produced planarizing film 4 was 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ITO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曝光，加以顯影。將此光阻圖案作為遮罩而以使用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(REMOVER 100、AZ Electronics Materials公司製)在50℃剝離該光阻圖案。經上述所獲得第一電極5是相當於有機EL元件之陽極。Next, on the obtained planarizing film 4, a bottom emission type organic EL element was formed. First, the first electrode 5 made of ITO connected to the wiring 2 through the contact hole 7 is formed on the planarization film 4. Thereafter, the photoresist is applied, pre-baked, exposed by a mask of a desired pattern, and developed. This photoresist pattern was used as a mask to perform pattern processing by wet etching using an ITO etchant. Thereafter, the photoresist pattern was peeled off at 50 ° C using a photoresist stripper (REMOVER 100, manufactured by AZ Electronics Materials Co., Ltd.). The first electrode 5 obtained as described above is an anode corresponding to the organic EL element.

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12之感光性樹脂組成物，且以與前述相同的方法形成。Next, an insulating film 8 covering the shape of the periphery of the first electrode 5 is formed. The insulating film 8 was formed using the photosensitive resin composition of Example 12 in the same manner as described above.

並且，在真空蒸鍍裝置內通過吾所欲圖案遮罩，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Al(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。Further, a hole transport layer, an organic light-emitting layer, and an electron transport layer were provided in a vacuum vapor deposition apparatus by a desired pattern mask and sequentially vapor deposition. Next, a second electrode made of Al (aluminum) is formed over the entire substrate. The obtained substrate was taken out by a vapor deposition machine, and sealed with a glass plate for sealing and an ultraviolet curable epoxy resin, and sealed.

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，且為可靠性高之有機EL顯示裝置。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 the display characteristics are good, and the organic EL display device has high reliability.

[實施例121][Example 121]

在實施例120，除了將形成平坦化膜4的實施例11之感光性樹脂組成物、及形成絕緣膜8的實施例12之感光性樹脂組成物之任一者皆變更為實施例43之感光性樹脂組成物以外，其餘則以與實施例120相同的方式製造有機EL顯示裝置。結果得知所獲得有機EL顯示裝置是可顯現良好的顯示特性，且為可靠性高之有機EL顯示裝置。In Example 120, the photosensitive resin composition of Example 11 in which the planarizing film 4 was formed and the photosensitive resin composition of Example 12 in which the insulating film 8 was formed were changed to the photosensitive light of Example 43. An organic EL display device was produced in the same manner as in Example 120 except for the resin composition. As a result, it was found that the obtained organic EL display device is an organic EL display device which can exhibit good display characteristics and is highly reliable.

[實施例122][Example 122]

在實施例120，除了將形成平坦化膜4的實施例11之感光性樹脂組成物、及形成絕緣膜8的實施例12之感光性樹脂組成物之任一者皆變更為實施例80之感光性樹脂組成物以外，其餘則以與實施例120相同的方式製造有機EL顯示裝置。結果得知所獲得有機EL顯示裝置是可顯現良好的顯示特性，且為可靠性高之有機EL顯示裝置。In Example 120, the photosensitive resin composition of Example 11 in which the planarizing film 4 was formed and the photosensitive resin composition of Example 12 in which the insulating film 8 was formed were changed to the photosensitive light of Example 80. An organic EL display device was produced in the same manner as in Example 120 except for the resin composition. As a result, it was found that the obtained organic EL display device is an organic EL display device which can exhibit good display characteristics and is highly reliable.

[實施例123][Example 123]

在實施例120，除了將形成平坦化膜4的實施例11之感光性樹脂組成物、及形成絕緣膜8的實施例12之感光性樹脂組成物之任一者皆變更為實施例119之感光性樹脂組成物以外，其餘則以與實施例120相同的方式製造有機EL顯示裝置。結果得知所獲得有機EL顯示裝置是可顯現良好的顯示特性，且為可靠性高之有機EL顯示裝置。In Example 120, the photosensitive resin composition of Example 11 in which the planarizing film 4 was formed and the photosensitive resin composition of Example 12 in which the insulating film 8 was formed were changed to the photosensitive light of Example 119. An organic EL display device was produced in the same manner as in Example 120 except for the resin composition. As a result, it was found that the obtained organic EL display device is an organic EL display device which can exhibit good display characteristics and is highly reliable.

[實施例124][Example 124]

在專利第3321003號公報中之第1圖及第2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17作為層間絕緣膜而獲得實施例124之液晶顯示裝置。In the active matrix type liquid crystal display device disclosed in Figs. 1 and 2 of the Japanese Patent No. 3321003, the cured film 17 is formed as an interlayer insulating film by the following method to obtain the liquid crystal display device of the embodiment 124.

亦即，使用實施例11之感光性樹脂組成物，以與在上述實施例120中之有機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17作為層間絕緣膜。In the same manner as the method of forming the planarizing film 4 of the organic EL display device of the above-described Example 120, the cured film 17 was used as the interlayer insulating film.

對所獲得液晶顯示裝置，外加驅動電壓結果，得知其係可顯現良好的顯示特性，且為可靠性高之液晶顯示裝置。As a result of applying a driving voltage to the obtained liquid crystal display device, it was found that the liquid crystal display device was excellent in display characteristics and exhibited high reliability.

[實施例125][Example 125]

除了將實施例11之感光性樹脂組成物變更為實施例43之感光性樹脂組成物以外，其餘則以與實施例124相同的方式製造液晶顯示裝置。結果得知所獲得液晶顯示裝置是可顯現良好的顯示特性，且為可靠性高之液晶顯示裝置。A liquid crystal display device was produced in the same manner as in Example 124 except that the photosensitive resin composition of Example 11 was changed to the photosensitive resin composition of Example 43. As a result, it was found that the obtained liquid crystal display device is a liquid crystal display device which can exhibit good display characteristics and is highly reliable.

[實施例126][Example 126]

除了將實施例11之感光性樹脂組成物變更為實施例80之感光性樹脂組成物以外，其餘則以與實施例124相同的方式製造液晶顯示裝置。結果得知所獲得液晶顯示裝置是可顯現良好的顯示特性，且為可靠性高之液晶顯示裝置。A liquid crystal display device was produced in the same manner as in Example 124 except that the photosensitive resin composition of Example 11 was changed to the photosensitive resin composition of Example 80. As a result, it was found that the obtained liquid crystal display device is a liquid crystal display device which can exhibit good display characteristics and is highly reliable.

[實施例127][Example 127]

除了將實施例11之感光性樹脂組成物變更為實施例119之感光性樹脂組成物以外，其餘則以與實施例124相同的方式製造液晶顯示裝置。結果得知所獲得液晶顯示裝置是可顯現良好的顯示特性，且為可靠性高之液晶顯示裝置。A liquid crystal display device was produced in the same manner as in Example 124 except that the photosensitive resin composition of Example 11 was changed to the photosensitive resin composition of Example 119. As a result, it was found that the obtained liquid crystal display device is a liquid crystal display device which can exhibit good display characteristics and is highly reliable.

[實施例128][Example 128]

在日本特開2008-146004號公報中之第2圖所揭述之液晶顯示裝置中，使用實施例119之感光性樹脂組成物來形成保護膜141而獲得實施例128之液晶顯示裝置。In the liquid crystal display device disclosed in FIG. 2 of the Japanese Patent Publication No. 2008-146004, the protective film 141 is formed using the photosensitive resin composition of Example 119, and the liquid crystal display device of Example 128 is obtained.

對所獲得液晶顯示裝置，外加驅動電壓結果，得知其係可顯現良好的顯示特性，且為可靠性高之液晶顯示裝置。As a result of applying a driving voltage to the obtained liquid crystal display device, it was found that the liquid crystal display device was excellent in display characteristics and exhibited high reliability.

[實施例129][Example 129]

在日本特開2000-267073號公報中之第1圖所揭述之液晶顯示裝置中，使用實施例119之感光性樹脂組成物來形成外護膜15而獲得實施例129之液晶顯示裝置。In the liquid crystal display device disclosed in Fig. 1 of the Japanese Patent Publication No. 2000-267073, the liquid crystal display device of Example 129 was obtained by forming the outer film 15 using the photosensitive resin composition of Example 119.

對所獲得液晶顯示裝置，外加驅動電壓結果，得知其係可顯現良好的顯示特性，且為可靠性高之液晶顯示裝置。As a result of applying a driving voltage to the obtained liquid crystal display device, it was found that the liquid crystal display device was excellent in display characteristics and exhibited high reliability.

1．．．TFT1. . . TFT

2．．．配線2. . . Wiring

3．．．絕緣膜3. . . Insulating film

4．．．平坦化膜4. . . Planar film

5．．．第一電極5. . . First electrode

6．．．玻璃基板6. . . glass substrate

7．．．接觸孔7. . . Contact hole

8．．．絕緣膜8. . . Insulating film

10．．．液晶顯示裝置10. . . Liquid crystal display device

12．．．背光單元12. . . Backlight unit

14．．．玻璃基板14. . . glass substrate

15．．．玻璃基板15. . . glass substrate

16．．．TFT16. . . TFT

17．．．硬化膜17. . . Hardened film

18．．．接觸孔18. . . Contact hole

19．．．ITO透明電極19. . . ITO transparent electrode

20．．．液晶20. . . liquid crystal

22．．．RGB彩色濾光片twenty two. . . RGB color filter

第1圖是展示將使用本發明之感光性樹脂組成物的硬化膜作為絕緣膜、平坦化膜而適用的有機EL顯示裝置之一實例構成概念圖。Fig. 1 is a conceptual view showing an example of an organic EL display device to which a cured film of the photosensitive resin composition of the present invention is used as an insulating film or a planarizing film.

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概念圖。Fig. 2 is a conceptual 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.

10．．．液晶顯示裝置10. . . Liquid crystal display device

12．．．背光單元12. . . Backlight unit

14．．．玻璃基板14. . . glass substrate

15．．．玻璃基板15. . . glass substrate

16．．．TFT16. . . TFT

17．．．硬化膜17. . . Hardened film

18．．．接觸孔18. . . Contact hole

19．．．ITO透明電極19. . . ITO transparent electrode

20．．．液晶20. . . liquid crystal

22．．．RGB彩色濾光片twenty two. . . RGB color filter

Claims (15)

一種感光性樹脂組成物，其係包含：(A)縮醛系樹脂、(B)光酸產生劑、及(C)溶劑，且該(A)縮醛系樹脂是含有具有由於酸而形成羧基的結構之結構單元(a1)、具有羧基或酚性羥基之結構單元(a2)、具有環氧基或氧雜環丁烷基之結構單元(a3)、及具有羥基或伸烷氧基之結構單元(a4)，且具有縮醛結構或縮酮結構之聚合物，且就該結構單元(a4)，具有伸烷氧基之結構單元為源於烷基末端聚伸烷基二醇之(甲基)丙烯酸酯之結構單元、或源於芳基末端聚伸烷基二醇之(甲基)丙烯酸酯之結構單元，在該(A)縮醛系樹脂之結構單元(a1)至(a4)的含率，以莫耳換算計相對於(A)縮醛系樹脂為1時，則結構單元(a1)：結構單元(a2)：結構單元(a3)：結構單元(a4)=(0.2至0.65)：(0.02至0.2)：(0.2至0.6)：(0.005至0.3)，且在該(A)縮醛系樹脂之結構單元(a4)的含量，以質量基準計，則為在3至30質量%之範圍。 A photosensitive resin composition comprising: (A) an acetal resin, (B) a photoacid generator, and (C) a solvent, wherein the (A) acetal resin contains a carboxyl group formed by an acid Structural unit (a1) having a structure, a structural unit having a carboxyl group or a phenolic hydroxyl group (a2), a structural unit having an epoxy group or an oxetanyl group (a3), and a structure having a hydroxyl group or an alkoxy group a unit (a4) having a polymer of an acetal structure or a ketal structure, and with respect to the structural unit (a4), the structural unit having an alkoxy group is derived from an alkyl terminal-terminated alkyl diol (A) a structural unit of an acrylate, or a structural unit derived from a (meth) acrylate of an aryl terminal-terminated alkyl diol, in the structural units (a1) to (a4) of the (A) acetal resin When the content is in a molar ratio of 1 to (A) acetal resin, the structural unit (a1): structural unit (a2): structural unit (a3): structural unit (a4) = (0.2 to 0.65): (0.02 to 0.2): (0.2 to 0.6): (0.005 to 0.3), and the content of the structural unit (a4) of the (A) acetal resin, based on the mass basis, is 3 to 30% by mass range. 如申請專利範圍第1項之感光性樹脂組成物，其中更進一步含有(M)顯影促進劑，該(M)顯影促進劑是在分子內具有選自羧基、酚性羥基、及伸烷氧基中至少一種結構，且分子量為在100至2000之範圍的化合物。 The photosensitive resin composition of claim 1, further comprising (M) a development accelerator having a carboxyl group, a phenolic hydroxyl group, and an alkoxy group in the molecule. At least one structure and a molecular weight in the range of from 100 to 2,000. 如申請專利範圍第1項之感光性樹脂組成物，其中更進一步含有(E)交聯劑。 The photosensitive resin composition of claim 1, further comprising (E) a crosslinking agent. 如申請專利範圍第1項之感光性樹脂組成物，其中該(B)光酸產生劑是肟磺酸酯化合物。 The photosensitive resin composition of claim 1, wherein the (B) photoacid generator is an oxime sulfonate compound. 如申請專利範圍第1項之感光性樹脂組成物，其中該(B)光酸產生劑是選自以下述通式(OS-3)、通式(OS-4)、及通式(OS-5)所代表之化合物中至少一種之化合物： 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、烷基氧基、磺酸基、胺基磺醯基、或烷氧基磺醯基，X是代表O或S，n是代表1或2，m是代表0至6之整數。The photosensitive resin composition of claim 1, wherein the (B) photoacid generator is selected from the group consisting of the following general formula (OS-3), general formula (OS-4), and general formula (OS-) 5) at least one of the compounds represented by: In the formula (OS-3) to the formula (OS-5), R 1 represents an alkyl group, an aryl group or a heteroaryl group, and a plurality of R 2 may independently represent a hydrogen atom, an alkyl group, An aryl group or a halogen atom, which may be present in a plurality of R 6 each independently representing a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, X is Represents O or S, n represents 1 or 2, and m is an integer representing 0 to 6. 如申請專利範圍第1項之感光性樹脂組成物，其中更進一步含有(N)增感劑。 The photosensitive resin composition of claim 1, further comprising (N) a sensitizer. 如申請專利範圍第1項之感光性樹脂組成物，其中在該(A)縮醛系樹脂之結構單元(a3)是源於丙烯酸(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)甲酯中任一者之結構單元。 The photosensitive resin composition of claim 1, wherein the structural unit (a3) of the (A) acetal resin is derived from (3-ethyloxet-3-yl)acrylic acid A structural unit of any of esters and (3-ethyloxetan-3-yl)methyl methacrylate. 如申請專利範圍第1項之感光性樹脂組成物，其中更進一步含有(F)密著改良劑。 The photosensitive resin composition of claim 1, further comprising (F) a adhesion improving agent. 如申請專利範圍第1項之感光性樹脂組成物，其中更進一步含有(G)鹼性化合物。 The photosensitive resin composition of claim 1, further comprising (G) a basic compound. 如申請專利範圍第1項之感光性樹脂組成物，其中更進一步含有氟系界面活性劑或矽系界面活性劑。 The photosensitive resin composition of claim 1, further comprising a fluorine-based surfactant or a lanthanoid surfactant. 一種硬化膜之形成方法，其包括下列步驟：(1)將如申請專利範圍第1至10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。 A method of forming a cured film, comprising the steps of: (1) applying a photosensitive resin composition according to any one of claims 1 to 10 to a substrate; and (2) applying a photosensitive resin from the coating a composition removing solvent; (3) exposing the applied photosensitive resin composition to active light; (4) developing the exposed photosensitive resin composition as an aqueous developing solution; and (5) developing the composition The photosensitive resin composition is thermally hardened. 一種硬化膜，其係以如申請專利範圍第11項之方法所形成。 A cured film formed by the method of claim 11 of the patent application. 如申請專利範圍第12項之硬化膜，其係層間絕緣膜。 For example, the cured film of claim 12 is an interlayer insulating film. 一種有機EL顯示裝置，其係具備如申請專利範圍第12項之硬化膜。 An organic EL display device comprising the cured film of claim 12 of the patent application. 一種液晶顯示裝置，其係具備如申請專利範圍第12項之硬化膜。A liquid crystal display device comprising the cured film of claim 12 of the patent application.
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