TWI627507B - Photo sensitive resin composition, method for manufacturing cured film, cured film, organic el display device and liquid crystal display device - Google Patents

Photo sensitive resin composition, method for manufacturing cured film, cured film, organic el display device and liquid crystal display device Download PDF

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TWI627507B
TWI627507B TW102121647A TW102121647A TWI627507B TW I627507 B TWI627507 B TW I627507B TW 102121647 A TW102121647 A TW 102121647A TW 102121647 A TW102121647 A TW 102121647A TW I627507 B TWI627507 B TW I627507B
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resin composition
acid
photosensitive resin
compound
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TW201400986A (en
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山健太
疋田政憲
霜山達也
川島敬史
山田悟
米澤裕之
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富士軟片股份有限公司
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—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
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • 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
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
    • H10K71/233—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers by photolithographic etching
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/106—Binder containing

Abstract

本發明提供一種感光性樹脂組成物，其可達成顯影時以及用作硬化膜時的與基板的密接性。上述感光性樹脂組成物含有：(A)包含滿足下述(1)及(2)的至少一者的聚合物的聚合物成分：(1)包括(a1)具有酸基由酸分解性基保護的基團的構成單元、以及(a2)具有交聯性基的構成單元的聚合物，(2)包括(a1)具有酸基由酸分解性基保護的基團的構成單元的聚合物、以及包括(a2)具有交聯性基的構成單元的聚合物；(B)非離子性光酸產生劑；(C)下述通式(S)所表示的化合物；(D)溶劑；以及(E)烷氧基矽烷化合物。 The present invention provides a photosensitive resin composition which can achieve adhesion to a substrate at the time of development and when used as a cured film. The photosensitive resin composition contains: (A) a polymer component containing a polymer satisfying at least one of the following (1) and (2): (1) including (a1) having an acid group protected by an acid-decomposable group a constituent unit of the group, and (a2) a polymer having a structural unit having a crosslinkable group, and (2) a polymer comprising (a1) a constituent unit having a group in which an acid group is protected by an acid-decomposable group, and a polymer comprising (a2) a constituent unit having a crosslinkable group; (B) a nonionic photoacid generator; (C) a compound represented by the following formula (S); (D) a solvent; and (E) Alkoxydecane compound.

通式(S) General formula (S)

Description

感光性樹脂組成物、硬化膜的製造方法、硬化膜、有機EL顯示裝置及液晶顯示裝置 Photosensitive resin composition, method for producing cured film, cured film, organic EL display device, and liquid crystal display device

本發明是有關於一種感光性樹脂組成物(以下有時簡稱為「本發明的組成物」)。另外，本發明是有關於一種使用上述感光性樹脂組成物的硬化膜的製造方法、將感光性組成物硬化而成的硬化膜、使用上述硬化膜的各種影像顯示裝置。 The present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as "the composition of the present invention"). Further, the present invention relates to a method for producing a cured film using the photosensitive resin composition, a cured film obtained by curing a photosensitive composition, and various image display devices using the cured film.

更詳細而言，本發明是有關於一種適合於形成液晶顯示裝置、有機電激發光(electroluminescence，EL)顯示裝置、積體電路元件、固體攝影元件等電子零件的平坦化膜、保護膜或層間絕緣膜的感光性樹脂組成物以及使用該感光性樹脂組成物的硬化膜的製造方法。 More specifically, the present invention relates to a planarizing film, a protective film, or an interlayer layer suitable for forming electronic components such as a liquid crystal display device, an organic electroluminescence (EL) display device, an integrated circuit device, and a solid-state imaging device. A photosensitive resin composition of an insulating film and a method for producing a cured film using the photosensitive resin composition.

於有機EL顯示裝置、或液晶顯示裝置等中設置有形成有圖案的層間絕緣膜。就用以獲得必需的圖案形狀的步驟數少，而且可獲得充分的平坦性等而言，於該層間絕緣膜的形成中廣泛 使用感光性樹脂組成物。 An interlayer insulating film in which a pattern is formed is provided in an organic EL display device or a liquid crystal display device. In order to obtain a necessary pattern shape, the number of steps is small, and sufficient flatness can be obtained, etc., in the formation of the interlayer insulating film. A photosensitive resin composition is used.

對於上述顯示裝置中的層間絕緣膜，除了絕緣性、耐溶劑性、耐熱性、硬度、以及氧化銦錫(indium tin oxide，ITO)濺鍍適應性優異等硬化膜的物性以外，還期望高的透明性。因此，嘗試使用透明性優異的丙烯酸系樹脂作為膜形成成分，例如已知有日本專利特開2011-209681號公報中記載的樹脂。另外，感光性樹脂組成物亦已知日本專利特開2005-234449號公報中記載的組成物。 In addition to the physical properties of the cured film such as insulation, solvent resistance, heat resistance, hardness, and excellent indium tin oxide (ITO) sputtering compatibility, the interlayer insulating film in the display device is also desired to have high physical properties. Transparency. For this reason, an acrylic resin having excellent transparency is used as a film-forming component. For example, a resin described in JP-A-2011-209681 is known. Further, the composition described in Japanese Laid-Open Patent Publication No. 2005-234449 is also known as the photosensitive resin composition.

構成層間絕緣膜的感光性樹脂組成物的重要特性可列舉與基板的密接性。顯影步驟中有時產生自基板上的「膜剝落」，這成為問題之一。進而，近年來，隨著顯示裝置高性能化、高精細化，變得難以進行微細的圖案加工，亦要求硬化後的層間絕緣膜材料的密接性提高。 The important characteristics of the photosensitive resin composition constituting the interlayer insulating film are the adhesion to the substrate. In the developing step, "film peeling" on the substrate sometimes occurs, which is one of the problems. Further, in recent years, as display devices have become higher in performance and higher in definition, it has become difficult to perform fine pattern processing, and it is also required to improve adhesion of the interlayer insulating film material after curing.

如上所述，感光性樹脂組成物要求顯影時以及製成硬化膜的狀態下的與基底基板的密接性。尤其，配線基板中由於基板自身包含多種材料，故而形成於其表面的層間絕緣膜材料亦設置對多種基板的密接性。 As described above, the photosensitive resin composition is required to have adhesion to the base substrate at the time of development and in a state in which the cured film is formed. In particular, since the substrate itself contains a plurality of materials in the wiring substrate, the interlayer insulating film material formed on the surface thereof is also provided with adhesion to a plurality of substrates.

本發明的目的為解決上述課題，目的在於提供一種與基板的密接性良好的感光性樹脂組成物。尤其本發明的目的在於提供一種顯影時基板密接性以及對硬化後的各種基板的密接性高的 感光性樹脂組成物。 An object of the present invention is to solve the above problems, and an object of the invention is to provide a photosensitive resin composition which is excellent in adhesion to a substrate. In particular, it is an object of the present invention to provide a substrate adhesive property during development and a high adhesion to various substrates after curing. A photosensitive resin composition.

進而，本發明的目的在於提供一種使用此種感光性樹脂組成物的硬化膜的形成方法、硬化膜、有機EL顯示裝置、以及液晶顯示裝置。 Further, an object of the present invention is to provide a method for forming a cured film using such a photosensitive resin composition, a cured film, an organic EL display device, and a liquid crystal display device.

本發明者進行研究的結果發現，藉由感光性樹脂組成物中含有非離子性光酸產生劑、特定的通式所表示的化合物、及烷氧基矽烷，則顯影時、用作硬化膜時的與基板的密接性顯著提高。 As a result of the investigation, the present inventors have found that the photosensitive resin composition contains a nonionic photoacid generator, a compound represented by a specific formula, and an alkoxydecane, and is used as a cured film during development. The adhesion to the substrate is remarkably improved.

具體而言，藉由以下的解決手段<1>，較佳為藉由<2>~<12>，來解決上述課題。 Specifically, the above problem is solved by the following solution <1>, preferably by <2> to <12>.

<1>一種感光性樹脂組成物，其含有：(A)包含滿足下述(1)及(2)的至少一者的聚合物的聚合物成分：(1)包括(a1)具有酸基由酸分解性基保護的基團的構成單元、以及(a2)具有交聯性基的構成單元的聚合物，(2)包括(a1)具有酸基由酸分解性基保護的基團的構成單元的聚合物、以及包括(a2)具有交聯性基的構成單元的聚合物；(B)非離子性光酸產生劑；(C)下述通式(S)所表示的化合物：通式(S) <1> A photosensitive resin composition comprising: (A) a polymer component comprising a polymer satisfying at least one of the following (1) and (2): (1) comprising (a1) having an acid group a constituent unit of the acid-decomposable group-protected group, and (a2) a polymer having a structural unit having a crosslinkable group, and (2) a component comprising (a1) a group having an acid group protected by an acid-decomposable group. a polymer, and a polymer comprising (a2) a constituent unit having a crosslinkable group; (B) a nonionic photoacid generator; (C) a compound represented by the following formula (S): S)

(通式(S)中，R1表示包含至少1個以上氮原子的基團，A表示2價連結基，R2表示有機基)；(D)溶劑；以及(E)烷氧基矽烷化合物。 (In the general formula (S), R 1 represents a group containing at least one or more nitrogen atoms, A represents a divalent linking group, and R 2 represents an organic group;) (D) a solvent; and (E) an alkoxydecane compound .

<2>如<1>所述的感光性樹脂組成物，其中通式(S)中，R1為-NR3R4所表示的基團(其中，R3及R4分別為有機基，可相互鍵結而形成環)。 <2> The photosensitive resin composition according to <1>, wherein, in the formula (S), R 1 is a group represented by —NR 3 R 4 (wherein R 3 and R 4 are each an organic group, Can be bonded to each other to form a ring).

<3>如<1>或<2>所述的感光性樹脂組成物，其中通式(S)中，R1為5員環或者6員環的環狀基。 <3> The photosensitive resin composition according to <1>, wherein, in the formula (S), R 1 is a cyclic group of a 5-membered ring or a 6-membered ring.

<4>如<1>或<2>所述的感光性樹脂組成物，其中通式(S)中，R1為嗎啉基。 <4> The photosensitive resin composition according to <1>, wherein, in the formula (S), R 1 is a morpholinyl group.

<5>如<1>至<4>中任一項所述的感光性樹脂組成物，其中上述(B)的光酸產生劑為肟磺酸酯化合物。 The photosensitive resin composition of any one of the above-mentioned (B), wherein the photoacid generator of (B) is an oxime sulfonate compound.

<6>如<1>至<5>中任一項所述的感光性樹脂組成物，其中烷氧基矽烷化合物為二烷氧基矽烷化合物或者三烷氧基矽烷化合物。 The photosensitive resin composition according to any one of <1> to <5> wherein the alkoxydecane compound is a dialkoxy decane compound or a trialkoxy decane compound.

<7>如<1>至<6>中任一項所述的感光性樹脂組成 物，其包含(F)交聯劑。 <7> The photosensitive resin composition according to any one of <1> to <6> And comprising (F) a crosslinking agent.

<8>一種硬化膜的製造方法，其包括：(1)將如<1>至<7>中任一項所述的感光性樹脂組成物塗佈於基板上的步驟；(2)自所塗佈的感光性樹脂組成物中去除溶劑的步驟；(3)利用光化射線對去除了溶劑的感光性樹脂組成物進行曝光的步驟；(4)利用水性顯影液對經曝光的感光性樹脂組成物進行顯影的步驟；以及(5)對經顯影的感光性樹脂組成物進行熱硬化的後烘烤步驟。 <8> A method for producing a cured film, comprising: (1) a step of applying the photosensitive resin composition according to any one of <1> to <7> on a substrate; a step of removing a solvent in the applied photosensitive resin composition; (3) a step of exposing the solvent-removed photosensitive resin composition by actinic rays; (4) using an aqueous developing solution to expose the photosensitive resin a step of developing the composition; and (5) a post-baking step of thermally curing the developed photosensitive resin composition.

<9>如<8>所述的硬化膜的製造方法，其於上述顯影步驟後、上述後烘烤步驟前，包括對經顯影的感光性樹脂組成物進行全面曝光的步驟。 <9> The method for producing a cured film according to <8>, which comprises the step of performing total exposure of the developed photosensitive resin composition after the developing step and before the post-baking step.

<10>一種硬化膜，其是藉由如<8>或<9>所述的方法來形成。 <10> A cured film formed by the method as described in <8> or <9>.

<11>如<10>所述的硬化膜，其為層間絕緣膜。 <11> The cured film according to <10> which is an interlayer insulating film.

<12>一種有機EL顯示裝置或者液晶顯示裝置，其包括如<10>或<11>所述的硬化膜。 <12> An organic EL display device or a liquid crystal display device comprising the cured film according to <10> or <11>.

進而，亦藉由下述手段來解決上述課題。 Further, the above problems are also solved by the following means.

<13>如上述任一項所述的感光性樹脂組成物，其中相 對於總固體成分100質量份，包含(A)聚合物成分50質量份~99.9質量份、(B)非離子性光酸產生劑0.1質量份~10質量份、(C)通式(S)所表示的化合物0.001質量份~5質量份、烷氧基矽烷化合物0.1質量份~30質量份。 <13> The photosensitive resin composition according to any one of the above, wherein the phase 100 parts by mass of the total solid content, (A) polymer component 50 parts by mass to 99.9 parts by mass, (B) nonionic photoacid generator 0.1 parts by mass to 10 parts by mass, (C) formula (S) The compound shown is 0.001 parts by mass to 5 parts by mass, and the alkoxydecane compound is 0.1 parts by mass to 30 parts by mass.

<14>如上述任一項所述的感光性樹脂組成物，其中通式(S)所表示的化合物中，R1為-NR3R4所表示的基團，R3及R4分別為烷基、烯基、或者包含該些基團與-O-、-S-及-N-的至少1者的組合的基團，並且 R1為5員環或者6員環的環狀基。 <14> The photosensitive resin composition according to any one of the above-mentioned, wherein, in the compound represented by the formula (S), R 1 is a group represented by —NR 3 R 4 , and R 3 and R 4 are each An alkyl group, an alkenyl group, or a group comprising a combination of these groups and at least one of -O-, -S-, and -N-, and R 1 is a cyclic group of a 5-membered ring or a 6-membered ring.

依據本發明，能夠提供一種可達成顯影時以及用作硬化膜時的與基板的高密接性的感光性樹脂組成物。 According to the present invention, it is possible to provide a photosensitive resin composition which can achieve high adhesion to a substrate at the time of development and when used as a cured film.

1‧‧‧TFT(薄膜電晶體) 1‧‧‧TFT (thin film transistor)

2‧‧‧配線 2‧‧‧Wiring

3‧‧‧絕緣膜 3‧‧‧Insulation film

4‧‧‧平坦化膜 4‧‧‧Flat 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‧‧‧Insulation film

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

12‧‧‧背光單元 12‧‧‧Backlight unit

14、15‧‧‧玻璃基板 14, 15‧‧‧ glass substrate

16‧‧‧TFT 16‧‧‧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‧‧‧LCD

22‧‧‧彩色濾光片 22‧‧‧Color filters

圖1表示液晶顯示裝置的一例的構成概念圖。表示液晶顯示裝置中的主動矩陣基板的示意性剖面圖，包括作為層間絕緣膜的硬化膜17。 FIG. 1 is a conceptual diagram showing an example of a liquid crystal display device. A schematic cross-sectional view showing an active matrix substrate in a liquid crystal display device, including a cured film 17 as an interlayer insulating film.

圖2表示有機EL顯示裝置的一例的構成概念圖。表示底部發光型有機EL顯示裝置中的基板的示意性剖面圖，包括平坦化膜4。 FIG. 2 is a conceptual diagram showing an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, including a planarization film 4.

以下，對本發明的內容進行詳細說明。以下記載的構成 要件的說明是基於本發明的代表性實施方式來進行，但本發明並不限定於此種實施方式。此外，本申請案說明書中所謂「~」，是以包含其前後所記載的數值來作為下限值以及上限值的含義來使用。 Hereinafter, the contents of the present invention will be described in detail. The composition described below The description of the requirements is based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In addition, the "~" in the specification of the present application is used in the meaning of including the numerical values described before and after the lower limit value and the upper limit value.

此外，本說明書中的基團(原子團)的表述中，未記載經取代以及未經取代的表述不僅包含不具有取代基者，而且亦包含具有取代基者。例如所謂「烷基」，不僅包含不具有取代基的烷基(未經取代的烷基)，而且亦包含具有取代基的烷基(經取代的烷基)。 Further, in the expression of the group (atomic group) in the present specification, the description that the substituted or unsubstituted is not described includes not only a substituent but also a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

本發明的感光性樹脂組成物(以下有時稱為「本發明的組成物」)較佳為作為正型感光性樹脂組成物來使用。 The photosensitive resin composition of the present invention (hereinafter sometimes referred to as "the composition of the present invention") is preferably used as a positive photosensitive resin composition.

本發明的感光性樹脂組成物的特徵在於含有：(A)包含滿足下述(1)及(2)的至少一者的聚合物的聚合物成分：(1)包括(a1)具有酸基由酸分解性基保護的基團的構成單元、以及(a2)具有交聯性基的構成單元的聚合物，(2)包括(a1)具有酸基由酸分解性基保護的基團的構成單元的聚合物、以及包括(a2)具有交聯性基的構成單元的聚合物；(B)非離子性光酸產生劑；(C)上述通式(S)所表示的化合物； (D)溶劑；以及(E)烷氧基矽烷化合物。 The photosensitive resin composition of the present invention is characterized by comprising: (A) a polymer component comprising a polymer satisfying at least one of the following (1) and (2): (1) including (a1) having an acid group a constituent unit of the acid-decomposable group-protected group, and (a2) a polymer having a structural unit having a crosslinkable group, and (2) a component comprising (a1) a group having an acid group protected by an acid-decomposable group. a polymer, and a polymer comprising (a2) a constituent unit having a crosslinkable group; (B) a nonionic photoacid generator; (C) a compound represented by the above formula (S); (D) a solvent; and (E) an alkoxydecane compound.

藉由本發明，可提供一種顯影時、用作硬化膜時的與基板的密接性優異的感光性樹脂組成物。進而，耐化學品性亦可提高。 According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in adhesion to a substrate when used as a cured film during development. Further, chemical resistance can be improved.

以下，對本發明的組成物進行詳細說明。 Hereinafter, the composition of the present invention will be described in detail.

<(A)聚合物成分> <(A) Polymer component>

本發明的組成物包含以下聚合物的至少一者作為聚合物成分：(1)包括(a1)具有酸基由酸分解性基保護的基團的構成單元以及(a2)具有交聯性基的構成單元的聚合物；以及(2)包括(a1)具有酸基由酸分解性基保護的基團的構成單元的聚合物以及包括(a2)具有交聯性基的構成單元的聚合物。進而，亦可包含該些聚合物以外的聚合物。只要未特別說明，則本發明中的(A)聚合物成分(以下有時稱為「(A)成分」)是指除了包含上述(1)及/或(2)以外，還包含視需要添加的其他聚合物者。 The composition of the present invention contains at least one of the following polymers as a polymer component: (1) a constituent unit including (a1) a group having an acid group protected by an acid-decomposable group and (a2) having a crosslinkable group; a polymer constituting the unit; and (2) a polymer comprising (a1) a constituent unit having a group in which an acid group is protected by an acid-decomposable group, and a polymer comprising (a2) a constituent unit having a crosslinkable group. Further, a polymer other than the polymers may be contained. Unless otherwise specified, the (A) polymer component (hereinafter sometimes referred to as "(A) component)" in the present invention means that it is added as needed in addition to the above (1) and/or (2). Other polymerists.

<<構成單元(a1)>> <<constitution unit (a1)>>

成分A至少包括(a1)具有酸基由酸分解性基保護的基團的構成單元。藉由(A)成分包括構成單元(a1)，可製成感度極高的感光性樹脂組成物。 Component A includes at least (a1) a constituent unit having a group in which an acid group is protected by an acid-decomposable group. By including the constituent unit (a1) as the component (A), a photosensitive resin composition having an extremely high sensitivity can be obtained.

本發明中的「酸基由酸分解性基保護的基團」可使用作為酸基以及酸分解性基而公知的基團，並無特別限定。具體的酸 基較佳為可列舉羧基、以及酚性羥基。另外，酸分解性基可使用藉由酸而比較容易分解的基團(例如：後述基團的酯結構、四氫吡喃酯基、或者四氫呋喃酯基等縮醛系官能基)或藉由酸而比較難以分解的基團(例如：第三丁酯基等三級烷基、第三丁基碳酸酯基等三級烷基碳酸酯基)。 In the present invention, the "group in which the acid group is protected by the acid-decomposable group" is a group known as an acid group and an acid-decomposable group, and is not particularly limited. Specific acid The base is preferably a carboxyl group or a phenolic hydroxyl group. Further, as the acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, an ester structure of a group described later, an acetal functional group such as a tetrahydropyranyl ester group or a tetrahydrofuran ester group) or an acid can be used. It is a group which is relatively difficult to decompose (for example, a tertiary alkyl group such as a tert-butyl group such as a tert-butyl group or a tertiary alkyl carbonate group such as a third butyl carbonate group).

(a1)具有酸基由酸分解性基保護的基團的構成單元較佳為具有由酸分解性基保護的保護羧基的構成單元、或者具有由酸分解性基保護的保護酚性羥基的構成單元。 (a1) The constituent unit having a group having an acid group protected by an acid-decomposable group is preferably a constituent unit having a protective carboxyl group protected by an acid-decomposable group or a protective phenolic hydroxyl group having an acid-decomposable group. unit.

以下，依次對具有由酸分解性基保護的保護羧基的構成單元(a1-1)、及具有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)分別進行說明。 Hereinafter, the constituent unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group and the constituent unit (a1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group will be sequentially described.

<<<(a1-1)具有由酸分解性基保護的保護羧基的構成單元>>> <<<(a1-1) constituent unit having a protected carboxyl group protected by an acid-decomposable group>>>

上述具有由酸分解性基保護的保護羧基的構成單元(a1-1)是具有羧基的構成單元的羧基由以下所詳細說明的酸分解性基保護的具有保護羧基的構成單元。 The structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is a structural unit having a protective carboxyl group which is protected by an acid-decomposable group described below in detail.

上述具有由酸分解性基保護的保護羧基的構成單元(a1-1)中可使用的上述具有羧基的構成單元並無特別限制，可使用公知的構成單元。例如可列舉：來源於不飽和單羧酸、不飽和二羧酸、不飽和三羧酸等分子中具有至少1個羧基的不飽和羧酸等的構成單元(a1-1-1)；或同時具有乙烯性不飽和基及來源於酸 酐的結構的構成單元(a1-1-2)。 The constituent unit having a carboxyl group which can be used in the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is not particularly limited, and a known constituent unit can be used. For example, a constituent unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid; or Has ethylenically unsaturated groups and is derived from acid A constituent unit (a1-1-2) of the structure of the anhydride.

以下，依次對作為上述具有羧基的構成單元來使用的(a1-1-1)來源於分子中具有至少1個羧基的不飽和羧酸等的構成單元、以及(a1-1-2)同時具有乙烯性不飽和基及來源於酸酐的結構的構成單元分別進行說明。 In the following, (a1-1-1) which is used as the constituent unit having a carboxyl group, is derived from a constituent unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and (a1-1-2) The constituent units of the ethylenically unsaturated group and the structure derived from the acid anhydride will be separately described.

<<<<(a1-1-1)來源於分子中具有至少1個羧基的不飽和羧酸等的構成單元>>>> <<<<(a1-1-1) is derived from a constituent unit of an unsaturated carboxylic acid having at least one carboxyl group in a molecule>>>>

作為上述來源於分子中具有至少1個羧基的不飽和羧酸等的構成單元(a1-1-1)可使用如以下所列舉的不飽和羧酸作為本發明中使用的不飽和羧酸。即，不飽和單羧酸例如可列舉：丙烯酸、甲基丙烯酸、丁烯酸(crotonic acid)、α-氯丙烯酸、桂皮酸、2-(甲基)丙烯醯氧基乙基-丁二酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基-鄰苯二甲酸等。另外，不飽和二羧酸例如可列舉：順丁烯二酸、反丁烯二酸、衣康酸、檸康酸、中康酸等。另外，用於獲得具有羧基的構成單元的不飽和多元羧酸亦可為其酸酐。具體而言可列舉：順丁烯二酸酐、衣康酸酐、檸康酸酐等。另外，不飽和多元羧酸可為多元羧酸的單(2-甲基丙烯醯氧基烷基)酯，例如可列舉：丁二酸單(2-丙烯醯氧基乙基)酯、丁二酸單(2-甲基丙烯醯氧基乙基)酯、鄰苯二甲酸單(2-丙烯醯氧基乙基)酯、鄰苯二甲酸單(2-甲基丙烯醯氧基乙基)酯等。進而，不飽和多元羧酸可為其兩末端二羧基聚合物的單(甲基)丙烯酸 酯，例如可列舉ω-羧基聚己內酯單丙烯酸酯、ω-羧基聚己內酯單甲基丙烯酸酯等。另外，不飽和羧酸亦可使用：丙烯酸-2-羧基乙酯、甲基丙烯酸-2-羧基乙酯、順丁烯二酸單烷基酯、反丁烯二酸單烷基酯、4-羧基苯乙烯等。 As the constituent unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule, an unsaturated carboxylic acid as exemplified below can be used as the unsaturated carboxylic acid used in the present invention. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and 2-(methyl)acryloxyethyl succinic acid. 2-(Methyl)acryloxyethyl hexahydrophthalic acid, 2-(meth)acryloxyethyl-phthalic acid, and the like. Further, examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Further, the unsaturated polycarboxylic acid used to obtain a constituent unit 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 a mono(2-methylpropenyloxyalkyl)ester of a polyvalent carboxylic acid, and examples thereof include succinic acid mono(2-propenyloxyethyl) ester and dibutyl Acid mono(2-methylpropenyloxyethyl) ester, mono(2-propenyloxyethyl) phthalate, mono(2-methylpropenyloxyethyl) phthalate Ester and the like. Further, the unsaturated polycarboxylic acid may be a mono(meth)acrylic acid having a di-carboxyl polymer at both ends thereof. Examples of the ester include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. Further, as the unsaturated carboxylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, monoalkyl maleate, monoalkyl fumarate, 4- Carboxy styrene and the like.

其中，就顯影性的觀點而言，為了形成上述來源於分子中具有至少1個羧基的不飽和羧酸等的構成單元(a1-1-1)，較佳為使用丙烯酸、甲基丙烯酸、2-(甲基)丙烯醯氧基乙基-丁二酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基-鄰苯二甲酸、或者不飽和多元羧酸的酸酐等，更佳為使用丙烯酸、甲基丙烯酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸。 In order to form the structural unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule, acrylic acid, methacrylic acid, and 2 are preferably used. -(Meth)propenyloxyethyl-succinic acid, 2-(methyl)propenyloxyethylhexahydrophthalic acid, 2-(methyl)propenyloxyethyl-o-benzene An acid anhydride such as dicarboxylic acid or an unsaturated polycarboxylic acid, or the like, more preferably acrylic acid, methacrylic acid or 2-(meth)acryloxyethyl hexahydrophthalic acid.

上述來源於分子中具有至少1個羧基的不飽和羧酸等的構成單元(a1-1-1)可單獨包含1種，亦可包含2種以上。 The constituent unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule may be contained alone or in combination of two or more.

<<<<(a1-1-2)同時具有乙烯性不飽和基及來源於酸酐的結構的構成單元>>>> <<<<(a1-1-2) A constituent unit having both an ethylenically unsaturated group and an acid anhydride-derived structure>>>>

同時具有乙烯性不飽和基及來源於酸酐的結構的構成單元(a1-1-2)較佳為來源於使具有乙烯性不飽和基的構成單元中所存在的羥基與酸酐進行反應而獲得的單體的單元。 The constituent unit (a1-1-2) having both an ethylenically unsaturated group and an acid anhydride-derived structure is preferably obtained by reacting a hydroxyl group present in a constituent unit having an ethylenically unsaturated group with an acid anhydride. Monomer unit.

上述酸酐可使用公知的酸酐，具體而言可列舉：順丁烯二酸酐、丁二酸酐、衣康酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、氯橋酸酐(chlorendic anhydride)等二元酸酐；偏苯三甲酸酐、均苯四甲酸酐、二苯基酮四羧酸酐、聯苯 四羧酸酐等酸酐。該些酸酐中，就顯影性的觀點而言，較佳為鄰苯二甲酸酐、四氫鄰苯二甲酸酐、或者丁二酸酐。 As the acid anhydride, a known 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 chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, diphenylketone tetracarboxylic anhydride, biphenyl An acid anhydride such as tetracarboxylic anhydride. Among these acid anhydrides, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferred from the viewpoint of developability.

就顯影性的觀點而言，上述酸酐對羥基的反應率較佳為10莫耳%~100莫耳%，更佳為30莫耳%~100莫耳%。 The reaction rate of the above acid anhydride to the hydroxyl group is preferably from 10 mol% to 100 mol%, more preferably from 30 mol% to 100 mol%, from the viewpoint of developability.

<<<<構成單元(a1-1)中可使用的酸分解性基>>>> <<<<Acidolytic Groups Usable in Building Unit (a1-1)>>>>

上述具有由酸分解性基保護的保護羧基的構成單元(a1-1)中可使用的上述酸分解性基可使用上述酸分解性基。 The acid-decomposable group which can be used in the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group can be used.

就感光性樹脂組成物的基本物性，特別是感度或圖案形狀、接觸孔的形成性、感光性樹脂組成物的保存穩定性的觀點而言，該些酸分解性基中，羧基較佳為由縮醛的形式來保護的保護羧基。進而就感度的觀點而言，酸分解性基中，羧基更佳為由下述通式(a1-10)所表示的縮醛的形式來保護的保護羧基。此外，於羧基為由下述通式(a1-10)所表示的縮醛的形式來保護的保護羧基的情況下，保護羧基的整體形成-(C=O)-O-CR101R102(OR103)的結構。 The carboxyl group is preferably composed of the basic physical properties of the photosensitive resin composition, particularly the sensitivity, the pattern shape, the contact hole formation property, and the storage stability of the photosensitive resin composition. The acetal form protects the carboxyl group. Further, in the acid-decomposable group, the carboxyl group is more preferably a protected carboxyl group protected by the form of an acetal represented by the following formula (a1-10). Further, in the case where the carboxyl group is a protected carboxyl group protected by the form of an acetal represented by the following general formula (a1-10), the entire protective carboxyl group is formed -(C=O)-O-CR 101 R 102 ( OR 103 ) structure.

(式(a1-10)中，R101及R102分別獨立地表示氫原子或者烷基，其中，R101與R102均為氫原子的情況除外；R103表示烷基；R101或R102、與R103可連結而形成環狀醚。) (In the formula (a1-10), R 101 and R 102 each independently represent a hydrogen atom or an alkyl group, wherein R 101 and R 102 are each a hydrogen atom; R 103 represents an alkyl group; R 101 or R 102 And R 103 can be linked to form a cyclic ether.)

上述通式(a1-10)中，R101~R103分別獨立地表示氫原子或者烷基，上述烷基可為直鏈狀、分支鏈狀、環狀的任一種。此處，不存在R101及R102的兩者均表示氫原子的情況，R101及R102的至少一者表示烷基。 In the above formula (a1-10), R 101 to R 103 each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be any of a linear chain, a branched chain, and a cyclic group. Here, there is no case where both of R 101 and R 102 represent a hydrogen atom, and at least one of R 101 and R 102 represents an alkyl group.

上述通式(a1-10)中，於R101、R102及R103表示烷基的情況下，上述烷基可為直鏈狀、分支鏈狀或者環狀的任一種。 In the above formula (a1-10), when R 101 , R 102 and R 103 represent an alkyl group, the alkyl group may be linear, branched or cyclic.

上述直鏈狀或者分支鏈狀的烷基較佳為碳數1~12，更佳為碳數1~6，尤佳為碳數1~4。具體而言可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、新戊基、正己基、2,3-二甲基-2-丁基(thexyl)、正庚基、正辛基、2-乙基己基、正壬基、正癸基等。 The linear or branched alkyl group is preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, and particularly preferably a carbon number of 1 to 4. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, 2 , 3-dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-decyl, and the like.

上述環狀烷基較佳為碳數3~12，更佳為碳數4~8，尤佳為碳數4~6。上述環狀烷基例如可列舉：環丙基、環丁基、環戊基、環己基、環庚基、環辛基、降冰片基、異冰片基等。 The above cyclic alkyl group preferably has a carbon number of 3 to 12, more preferably a carbon number of 4 to 8, and particularly preferably a carbon number of 4 to 6. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

上述烷基可具有取代基，取代基可例示鹵素原子、芳基、烷氧基。於具有鹵素原子作為取代基的情況下，R101、R102、R103成為鹵代烷基，於具有芳基作為取代基的情況下，R101、R102、R103成為芳烷基。 The above alkyl group may have a substituent, and the substituent may, for example, be a halogen atom, an aryl group or an alkoxy group. Having a halogen atom as the substituent, R 101, R 102, R 103 becomes a haloalkyl group, an aryl group having as the substituent, R 101, R 102, R 103 become aralkyl.

上述鹵素原子可例示：氟原子、氯原子、溴原子、碘原子，該些鹵素原子中較佳為氟原子或者氯原子。 The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and among these halogen atoms, a fluorine atom or a chlorine atom is preferred.

另外，上述芳基較佳為碳數6~20的芳基，更佳為碳數6~12，具體而言，可例示苯基、α-甲基苯基、萘基等，經芳基取代的烷基整體即芳烷基可例示苄基、α-甲基苄基、苯乙基、萘基甲基等。 Further, the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a carbon number of 6 to 12, and specifically, a phenyl group, an α-methylphenyl group, a naphthyl group or the like may be exemplified by an aryl group. The alkyl group as a whole, that is, an aralkyl group, may, for example, be a benzyl group, an α-methylbenzyl group, a phenethyl group or a naphthylmethyl group.

上述烷氧基較佳為碳數1~6的烷氧基，更佳為碳數1~4，進而更佳為甲氧基或者乙氧基。 The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably a methoxy group or an ethoxy group.

另外，於上述烷基為環烷基的情況下，上述環烷基可具有碳數1~10的直鏈狀或者分支鏈狀的烷基作為取代基，於烷基為直鏈狀或者分支鏈狀的烷基的情況下，可具有碳數3~12的環烷基作為取代基。 Further, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group may be a linear or branched chain. In the case of an alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.

該些取代基可進一步經上述取代基所取代。 These substituents may be further substituted with the above substituents.

上述通式(a1-10)中，於R101、R102及R103表示芳基的情況下，上述芳基較佳為碳數6~12，更佳為碳數6~10。上述芳基可具有取代基，上述取代基較佳為可例示碳數1~6的烷基。芳基例如可例示：苯基、甲苯基、矽烷基、枯烯基、1-萘基等。 In the above formula (a1-10), when R 101 , R 102 and R 103 represent an aryl group, the aryl group is preferably a carbon number of 6 to 12, more preferably a carbon number of 6 to 10. The aryl group may have a substituent, and the above substituent is preferably an alkyl group having 1 to 6 carbon atoms. The aryl group may, for example, be phenyl, tolyl, decyl, cumenyl, 1-naphthyl or the like.

另外，R101、R102及R103可相互鍵結而與它們所鍵結的碳原子一起形成環。R101與R102、R101與R103或者R102與R103鍵結的情況下的環結構例如可列舉：環丁基、環戊基、環己基、環庚基、四氫呋喃基、金剛烷基以及四氫吡喃基等。 Further, R 101 , R 102 and R 103 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. R 101 and R 102, the ring structure in the case of R 101 and R 103 or R 102 and R 103 bonded include, for example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, tetrahydrofuranyl, adamantyl And tetrahydropyranyl and the like.

此外，上述通式(a1-10)中，較佳為R101及R102的任一者為氫原子或者甲基。 Further, in the above formula (a1-10), it is preferred that any of R 101 and R 102 is a hydrogen atom or a methyl group.

用於形成具有上述通式(a1-10)所表示的保護羧基的構成單元的自由基聚合性單體可使用市售者，亦可使用以公知方法合成者。例如可利用日本專利特開2011-221494號公報的段落編號0037~段落編號0040中記載的合成方法等來合成。 The radical polymerizable monomer for forming a structural unit having a protective carboxyl group represented by the above formula (a1-10) can be used commercially, or can be synthesized by a known method. For example, it can be synthesized by the synthesis method described in Paragraph No. 0037 to Paragraph No. 0040 of JP-A-2011-221494.

上述具有由酸分解性基保護的保護羧基的構成單元(a1-1)的第一較佳態樣為下述通式所表示的構成單元。 The first preferred embodiment of the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is a constituent unit represented by the following formula.

(式中，R1及R2分別表示氫原子、烷基或者芳基，至少R1及R2的任一者為烷基或者芳基，R3表示烷基或者芳基，R1或R2、與R3可連結而形成環狀醚，R4表示氫原子或者甲基，X表示單鍵或者伸芳基。) (wherein R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R 1 and R 2 is an alkyl group or an aryl group, and R 3 represents an alkyl group or an aryl group, and R 1 or R 2 , R 3 can be linked to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or an extended aryl group.

於R1及R2為烷基的情況下，較佳為碳數為1~10的烷基。於R1及R2為芳基的情況下，較佳為苯基。R1及R2分別較佳為氫原子或者碳數1~4的烷基。 When R 1 and R 2 are an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. In the case where R 1 and R 2 are an aryl group, a phenyl group is preferred. R 1 and R 2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R3表示烷基或者芳基，較佳為碳數1~10的烷基，更佳 為碳數1~6的烷基。 R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

X表示單鍵或者伸芳基，較佳為單鍵。 X represents a single bond or an extended aryl group, preferably a single bond.

上述具有由酸分解性基保護的保護羧基的構成單元(a1-1)的第二較佳態樣為下述通式的結構單元。 A second preferred embodiment of the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is a structural unit of the following formula.

(式中，R121表示氫原子或者碳數1~4的烷基，L1表示羰基或者伸苯基，R122~R128分別獨立地表示氫原子或者碳數1~4的烷基。) (wherein R 121 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 122 to R 128 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

R121較佳為氫原子或者甲基。 R 121 is preferably a hydrogen atom or a methyl group.

L1較佳為羰基。 L 1 is preferably a carbonyl group.

R122~R128較佳為氫原子。 R 122 to R 128 are preferably a hydrogen atom.

上述具有由酸分解性基保護的保護羧基的構成單元(a1-1)的較佳具體例可例示下述構成單元。此外，R表示氫原子或者甲基。 A preferred specific example of the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is exemplified by the following constituent unit. Further, R represents a hydrogen atom or a methyl group.

<<<(a1-2)具有由酸分解性基保護的保護酚性羥基的構成單元>>> <<<(a1-2) constituent unit having a protective phenolic hydroxyl group protected by an acid-decomposable group>>>

上述具有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)為具有酚性羥基的構成單元由以下所詳細說明的酸分解性基所保護的具有保護酚性羥基的構成單元。 The structural unit (a1-2) having a phenolic hydroxyl group protected by an acid-decomposable group is a constituent unit having a phenolic hydroxyl group and a constituent unit having a phenolic hydroxyl group protected by an acid-decomposable group described below. .

<<<<(a1-2-1)具有酚性羥基的構成單元>>>> <<<<(a1-2-1) constitutive unit having a phenolic hydroxyl group>>>>

上述具有酚性羥基的構成單元可列舉羥基苯乙烯系構成單元或酚醛清漆系樹脂中的構成單元，該些構成單元中，就感度的觀點而言，較佳為來源於羥基苯乙烯、或者α-甲基羥基苯乙烯的構成單元。另外，就感度的觀點而言，具有酚性羥基的構成單元亦較佳為下述通式(a1-20)所表示的構成單元。 The constituent unit having a phenolic hydroxyl group may be a constituent unit in a hydroxystyrene-based constituent unit or a novolak-based resin, and among these constituent units, from the viewpoint of sensitivity, it is preferably derived from hydroxystyrene or α. a constituent unit of methyl hydroxystyrene. In addition, from the viewpoint of sensitivity, the constituent unit having a phenolic hydroxyl group is also preferably a constituent unit represented by the following formula (a1-20).

(通式(a1-20)中，R220表示氫原子或者甲基，R221表示單鍵或者二價連結基，R222表示鹵素原子或者碳數1~5的直鏈或者分支鏈狀的烷基，a表示1~5的整數，b表示0~4的整數，a+b為5以下；此外，於R222存在2個以上的情況下，該些R222可相互不同亦可相同。) (In the formula (a1-20), R 220 represents a hydrogen atom or a methyl group, R 221 represents a single bond or a divalent linking group, and R 222 represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. A, a represents an integer from 1 to 5, b represents an integer from 0 to 4, and a+b is 5 or less. Further, when two or more R 222 are present, the R 222 may be different from each other or the same.

上述通式(a1-20)中，R220表示氫原子或者甲基，較佳為甲基。 In the above formula (a1-20), R 220 represents a hydrogen atom or a methyl group, preferably a methyl group.

另外，R221表示單鍵或者二價連結基。於單鍵的情況下，可提高感度，進而可提高硬化膜的透明性，因此較佳。R221的二價連結基可例示伸烷基，R221為伸烷基的具體例可列舉：亞甲基、伸乙基、伸丙基、伸異丙基、伸正丁基、伸異丁基、伸第三丁基、伸戊基、伸異戊基、伸新戊基、伸己基等。其中，R221較佳為單鍵、亞甲基、伸乙基。另外，上述二價連結基可具有取代基，取代基可列舉鹵素原子、羥基、烷氧基等。另外，a表示1~5的整數，但就本發明的效果的觀點、或製造容易的方面而言，較佳為a為1或2，更佳為a為1。 Further, R 221 represents a single bond or a divalent linking group. In the case of a single bond, the sensitivity can be improved, and the transparency of the cured film can be improved, which is preferable. Specific examples of the divalent linking group of R 221 may be an alkylene group, and R 221 is an alkylene group: methylene, ethyl, propyl, isopropyl, n-butyl, and isobutylene. Stretching the third butyl group, stretching the pentyl group, stretching the isoamyl group, stretching the neopentyl group, and stretching the hexyl group. Among them, R 221 is preferably a single bond, a methylene group or an ethyl group. Further, the divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group and the like. Further, a represents an integer of 1 to 5. However, from the viewpoint of the effects of the present invention or the ease of production, a is preferably 1 or 2, and more preferably a is 1.

另外，當以與R221鍵結的碳原子為基準(1位)時，苯環中的羥基的鍵結位置較佳為鍵結於4位。 Further, when the carbon atom bonded to R 221 is used as a reference (1 position), the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4 position.

R222為鹵素原子或者碳數1~5的直鏈或者分支鏈狀的烷基。具體而言可列舉：氟原子、氯原子、溴原子、甲基、乙基、 丙基、異丙基、正丁基、異丁基、第三丁基、戊基、異戊基、新戊基等。其中就製造容易的方面而言，較佳為氯原子、溴原子、甲基或者乙基。 R 222 is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples thereof include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Base. Among them, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferred in terms of ease of production.

另外，b表示0或者1~4的整數。 In addition, b represents an integer of 0 or 1 to 4.

<<<<構成單元(a1-2)中可使用的酸分解性基>>>> <<<<Acidolytic Groups Usable in Building Unit (a1-2)>>>>

上述具有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)中可使用的上述酸分解性基可與上述具有由酸分解性基保護的保護羧基的構成單元(a1-1)中可使用的上述酸分解性基同樣地使用公知者，並無特別限定。就感光性樹脂組成物的基本物性，特別是感度或圖案形狀、感光性樹脂組成物的保存穩定性、接觸孔的形成性的觀點而言，酸分解性基中較佳為具有由縮醛保護的保護酚性羥基的構成單元。進而，就感度的觀點而言，酸分解性基中更佳為酚性羥基由上述通式(a1-10)所表示的縮醛的形式來保護的保護酚性羥基。此外，於酚性羥基為由上述通式(a1-10)所表示的縮醛的形式來保護的保護酚性羥基的情況下，保護酚性羥基的整體形成-Ar-O-C'R101R102(OR103)的結構。 The acid-decomposable group which can be used in the structural unit (a1-2) having a phenolic hydroxyl group which is protected by an acid-decomposable group, and the above-mentioned constituent unit having a protective carboxyl group protected by an acid-decomposable group (a1-1) The acid-decomposable group which can be used in the above is similarly used, and is not particularly limited. The acid-decomposable group preferably has acetal protection from the viewpoint of the basic physical properties of the photosensitive resin composition, particularly the sensitivity or the pattern shape, the storage stability of the photosensitive resin composition, and the formation of contact pores. A constituent unit that protects a phenolic hydroxyl group. Further, from the viewpoint of sensitivity, the acid-decomposable group is more preferably a phenolic hydroxyl group protected by a form of an acetal represented by the above formula (a1-10). Further, in the case where the phenolic hydroxyl group is a phenolic hydroxyl group protected by the form of the acetal represented by the above formula (a1-10), the overall formation of the phenolic hydroxyl group is protected - Ar-O-C'R 101 The structure of R 102 (OR 103 ).

此外，Ar表示伸芳基。 Further, Ar represents an aryl group.

酚性羥基的縮醛酯結構的較佳例可例示R101=R102=R103=甲基或R101=R102=甲基且R103=苄基的組合。 A preferred example of the acetal ester structure of the phenolic hydroxyl group is exemplified by a combination of R 101 = R 102 = R 103 = methyl or R 101 = R 102 = methyl and R 103 = benzyl.

另外，用於形成具有酚性羥基由縮醛的形式來保護的保 護酚性羥基的構成單元的自由基聚合性單體例如可列舉日本專利特開2011-215590號公報的段落編號0042中記載的自由基聚合性單體等。 In addition, it is used to form a phenolic hydroxyl group protected by an acetal form. The radically polymerizable monomer of the constituent unit of the phenolic hydroxyl group is, for example, a radical polymerizable monomer described in Paragraph No. 0044 of JP-A-2011-215590.

該些自由基聚合性單體中，就透明性的觀點而言，較佳為甲基丙烯酸4-羥基苯酯的1-烷氧基烷基保護體、甲基丙烯酸4-羥基苯酯的四氫吡喃基保護體。 Among these radically polymerizable monomers, from the viewpoint of transparency, a 1-alkoxyalkyl protecting agent of 4-hydroxyphenyl methacrylate or a 4-hydroxyphenyl methacrylate is preferred. Hydropyranyl protecting agent.

酚性羥基的縮醛保護基的具體例可列舉1-烷氧基烷基，例如可列舉：1-乙氧基乙基、1-甲氧基乙基、1-正丁氧基乙基、1-異丁氧基乙基、1-(2-氯乙氧基)乙基、1-(2-乙基己氧基)乙基、1-正丙氧基乙基、1-環己氧基乙基、1-(2-環己基乙氧基)乙基、1-苄氧基乙基等，該些基團可單獨使用或者將2種以上組合使用。 Specific examples of the acetal protecting group of the phenolic hydroxyl group include a 1-alkoxyalkyl group, and examples thereof include 1-ethoxyethyl, 1-methoxyethyl, and 1-n-butoxyethyl. 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1-n-propoxyethyl, 1-cyclohexyloxy Ethyl ethyl group, 1-(2-cyclohexylethoxy)ethyl group, 1-benzyloxyethyl group, etc., these groups may be used individually or in combination of 2 or more types.

用於形成上述具有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)的自由基聚合性單體可使用市售者，亦可使用以公知的方法合成者。例如，可藉由使具有酚性羥基的化合物於酸觸媒的存在下與乙烯基醚進行反應而合成。上述合成可使具有酚性羥基的單體與其他單體預先共聚合，然後於酸觸媒的存在下與乙烯基醚進行反應。 The radical polymerizable monomer for forming the structural unit (a1-2) having the above-mentioned protective phenolic hydroxyl group protected by an acid-decomposable group can be used commercially, or can be synthesized by a known method. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with a vinyl ether in the presence of an acid catalyst. The above synthesis allows a monomer having a phenolic hydroxyl group to be previously copolymerized with another monomer and then reacted with a vinyl ether in the presence of an acid catalyst.

上述具有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)的較佳具體例可例示下述構成單元，但本發明並不限定於該些構成單元。 A preferred specific example of the structural unit (a1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group is exemplified by the following constituent unit, but the present invention is not limited to the constituent units.

<<<構成單元(a1)的較佳態樣>>> <<<The preferred aspect of the constituent unit (a1)>>>

於含有上述構成單元(a1)的聚合物實質上不含構成單元(a2)的情況下，含有該構成單元(a1)的聚合物中，構成單元(a1)較佳為20莫耳%~100莫耳%，更佳為30莫耳%~90莫耳%。 In the case where the polymer containing the above-mentioned structural unit (a1) does not substantially contain the structural unit (a2), the constituent unit (a1) preferably contains 20 mol% to 100% of the polymer containing the structural unit (a1). Molar%, more preferably 30% by mole to 90% by mole.

於含有上述構成單元(a1)的聚合物含有下述構成單元 (a2)的情況下，含有該構成單元(a1)與構成單元(a2)的聚合物中，就感度的觀點而言，構成單元(a1)較佳為3莫耳%~70莫耳%，更佳為10莫耳%~60莫耳%。另外，尤其於上述構成單元(a1)中可使用的上述酸分解性基為具有羧基由縮醛的形式來保護的保護羧基的構成單元的情況下，較佳為20莫耳%~50莫耳%。 The polymer containing the above structural unit (a1) contains the following constituent units In the case of (a2), in the polymer containing the structural unit (a1) and the structural unit (a2), the structural unit (a1) is preferably from 3 mol% to 70 mol%, from the viewpoint of sensitivity. More preferably 10% by mole to 60% by mole. Further, in particular, in the case where the acid-decomposable group which can be used in the above-mentioned structural unit (a1) is a constituent unit having a protective carboxyl group in which a carboxyl group is protected by an acetal, it is preferably 20 mol% to 50 mol. %.

上述具有由酸分解性基保護的保護羧基的構成單元(a1-1)若與上述具有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)相比，則具有顯影快速的特徵。因此，於欲快速顯影的情況下，較佳為具有由酸分解性基保護的保護羧基的構成單元(a1-1)。相反，於欲減緩顯影的情況下，較佳為使用具有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)。 The constituent unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group has a rapid development ratio as compared with the constituent unit (a1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group. feature. Therefore, in the case of rapid development, it is preferably a constituent unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group. On the contrary, in the case where the development is to be slowed down, it is preferred to use a constituent unit (a1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group.

<<(a2)具有交聯性基的構成單元>> <<(a2) constituent unit having a crosslinkable group>>

(A)成分包括具有交聯性基的構成單元(a2)。上述交聯性基只要是可藉由加熱處理而產生硬化反應的基團，則無特別限定。較佳的具有交聯性基的構成單元的態樣可列舉包含選自由環氧基、氧雜環丁基、-NH-CH2-O-R(R為碳數1~20的烷基)所表示的基團以及乙烯性不飽和基所組成組群中的至少1個的構成單元，較佳為選自環氧基、氧雜環丁基、以及-NH-CH2-O-R(R為碳數1~20的烷基)所表示的基團中的至少1種。其中，本發明的感光性樹脂組成物較佳為上述(A)成分包括包含環氧基及氧雜 環丁基中的至少1個的構成單元。更詳細而言，可列舉以下的構成單元。 The component (A) includes a constituent unit (a2) having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group which can undergo a curing reaction by heat treatment. Preferred examples of the constituent unit having a crosslinkable group include those selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH 2 -OR (R is an alkyl group having 1 to 20 carbon atoms). The constituent group of at least one of the group consisting of the ethylenically unsaturated group and the ethylenically unsaturated group is preferably selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH 2 -OR (R is a carbon number) At least one of the groups represented by the alkyl group of 1 to 20). In the photosensitive resin composition of the present invention, the component (A) preferably contains at least one of an epoxy group and an oxetanyl group. More specifically, the following structural unit is mentioned.

<<<(a2-1)具有環氧基及/或氧雜環丁基的構成單元>>> <<<(a2-1) constituent unit having an epoxy group and/or an oxetanyl group>>>

上述(A)聚合物較佳為含有具有環氧基及/或氧雜環丁基的構成單元(構成單元(a2-1))。上述3員環的環狀醚基亦稱為環氧基，4員環的環狀醚基亦稱為氧雜環丁基。 The (A) polymer preferably contains a structural unit (constituting unit (a2-1)) having an epoxy group and/or an oxetanyl group. The cyclic ether group of the above 3-membered ring is also called an epoxy group, and the cyclic ether group of the 4-membered ring is also called an oxetanyl group.

上述具有環氧基及/或氧雜環丁基的構成單元(a2-1)只要於1個構成單元中具有至少1個環氧基或氧雜環丁基即可，可具有1個以上的環氧基以及1個以上的氧雜環丁基、2個以上的環氧基、或者2個以上的氧雜環丁基，並無特別限定，較佳為具有合計為1個~3個的環氧基及/或氧雜環丁基，更佳為具有合計為1個或2個的環氧基及/或氧雜環丁基，尤佳為具有1個環氧基或氧雜環丁基。 The constituent unit (a2-1) having an epoxy group and/or an oxetanyl group may have at least one epoxy group or oxetanyl group in one constituent unit, and may have one or more members. The epoxy group and one or more oxetanyl groups, two or more epoxy groups, or two or more oxetanyl groups are not particularly limited, and preferably have a total of one to three. The epoxy group and/or oxetanyl group is more preferably an epoxy group and/or an oxetanyl group having a total of 1 or 2, and particularly preferably having 1 epoxy group or oxirane. base.

用於形成具有環氧基的構成單元的自由基聚合性單體的具體例例如可列舉：丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、α-乙基丙烯酸縮水甘油酯、α-正丙基丙烯酸縮水甘油酯、α-正丁基丙烯酸縮水甘油酯、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-3,4-環氧環己基甲酯、甲基丙烯酸-3,4-環氧環己基甲酯、α-乙基丙烯酸-3,4-環氧環己基甲酯、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水 甘油醚、日本專利第4168443號公報的段落編號0031~段落編號0035中記載的含有脂環式環氧骨架的化合物等，該些內容併入本申請案說明書中。 Specific examples of the radical polymerizable monomer for forming a constituent unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, and α-n-propyl group. Glycidyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxy acrylate Hexylmethyl ester, 3,4-epoxycyclohexylmethyl methacrylate, α-ethyl acrylate-3,4-epoxycyclohexylmethyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl Glycidyl ether, p-vinylbenzyl shrinkage The glyceryl ether, the alicyclic epoxy skeleton-containing compound described in Paragraph No. 0031 to Paragraph No. 0035 of Japanese Patent No. 4,164,843, and the like are incorporated herein by reference.

用於形成具有氧雜環丁基的構成單元的自由基聚合性單體的具體例例如可列舉：日本專利特開2001-330953號公報的段落編號0011~段落編號0016中記載的具有氧雜環丁基的(甲基)丙烯酸酯等，該些內容併入本申請案說明書中。 Specific examples of the radically polymerizable monomer for forming a structural unit having an oxetanyl group include an oxygen heterocyclic ring described in Paragraph No. 0011 to Paragraph No. 0016 of JP-A-2001-330953. Butyl (meth) acrylates and the like, which are incorporated in the specification of the present application.

用於形成上述具有環氧基及/或氧雜環丁基的構成單元(a2-1)的自由基聚合性單體的具體例較佳為含有甲基丙烯酸酯結構的單體、含有丙烯酸酯結構的單體。 A specific example of the radical polymerizable monomer for forming the above-mentioned structural unit (a2-1) having an epoxy group and/or an oxetanyl group is preferably a monomer having a methacrylate structure and containing an acrylate. The monomer of the structure.

該些單體中較佳為甲基丙烯酸縮水甘油酯、丙烯酸3,4-環氧環己基甲酯、甲基丙烯酸3,4-環氧環己基甲酯、丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯、以及甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯。該些構成單元可單獨使用1種或者將2種以上組合使用。 Among these monomers, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and acrylic acid (3-ethyloxycyclohexane) are preferred. Butan-3-yl)methyl ester, and (3-ethyloxetan-3-yl)methyl methacrylate. These constituent units may be used alone or in combination of two or more.

上述具有環氧基及/或氧雜環丁基的構成單元(a2-1)的較佳具體例可例示下述構成單元。此外，R表示氫原子或者甲基。 A preferred specific example of the structural unit (a2-1) having an epoxy group and/or an oxetanyl group is exemplified by the following constituent unit. Further, R represents a hydrogen atom or a methyl group.

<<<(a2-2)具有乙烯性不飽和基的構成單元>>> <<<(a2-2) constituent unit having an ethylenically unsaturated group>>>

上述具有交聯性基的構成單元(a2)之一可列舉具有乙烯性不飽和基的構成單元(a2-2)(以下亦稱為「構成單元(a2-2)」)。上述具有乙烯性不飽和基的構成單元(a2-2)較佳為側鏈上具有乙烯性不飽和基的構成單元，更佳為末端具有乙烯性不飽和基且具有碳數3~16的側鏈的構成單元，尤佳為具有下述通式(a2-2-1)所表示的側鏈的構成單元。 One of the structural units (a2) having a crosslinkable group is a structural unit (a2-2) having an ethylenically unsaturated group (hereinafter also referred to as "constituting unit (a2-2)"). The structural unit (a2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in a side chain, more preferably an ethylenically unsaturated group at the terminal and having a side having 3 to 16 carbon atoms. The constituent unit of the chain is particularly preferably a constituent unit having a side chain represented by the following formula (a2-2-1).

(通式(a2-2-1)中，R301表示碳數1~13的二價連結基，R302表示氫原子或者甲基，*表示與具有交聯性基的構成單元(a2)的主鏈連結的部位。) (In the formula (a2-2-1), R 301 represents a divalent linking group having 1 to 13 carbon atoms, R 302 represents a hydrogen atom or a methyl group, and * represents a constituent unit (a2) having a crosslinkable group. The part where the main chain is connected.)

R301為碳數1~13的二價連結基，包含烯基、環烯基、伸芳基或者將該些基團組合而成的基團，亦可包含酯鍵、醚鍵、醯胺鍵、胺基甲酸酯鍵等鍵。另外，二價連結基可於任意的位置具有羥基、羧基等取代基。R301的具體例可列舉下述二價連結基。 R 301 is a divalent linking group having 1 to 13 carbon atoms, and includes an alkenyl group, a cycloalkenyl group, an extended aryl group or a group obtained by combining the groups, and may further contain an ester bond, an ether bond, or a guanamine bond. a bond such as a urethane bond. Further, the divalent linking group may have a substituent such as a hydroxyl group or a carboxyl group at any position. Specific examples of R 301 include the following divalent linking groups.

上述通式(a2-2-1)所表示的側鏈中，包含上述R301所表示的2價連結基，較佳為脂肪族的側鏈。 The side chain represented by the above formula (a2-2-1) includes the divalent linking group represented by the above R 301 , and is preferably an aliphatic side chain.

除此以外，(a2-2)具有乙烯性不飽和基的構成單元可參考日本專利特開2011-215580號公報的段落編號0072~段落編號0090的記載，該些內容併入本申請案說明書中。 In addition, the constituent unit having an ethylenically unsaturated group (a2-2) can be referred to the description of Paragraph No. 0072 to Paragraph No. 0090 of JP-A-2011-215580, which is incorporated in the specification of the present application. .

<<<(a2-3)具有-NH-CH2-O-R(R為碳數1~20的烷基)所表示的基團的構成單元>>> <<<(a2-3) A constituent unit of a group represented by -NH-CH 2 -OR (R is an alkyl group having 1 to 20 carbon atoms) >>>

本發明中使用的聚合物亦較佳為具有-NH-CH2-O-R(R為碳數1~20的烷基)所表示的基團的構成單元(a2-3)。藉由具有構成單元(a2-3)，可藉由緩和的加熱處理而產生硬化反應，可獲得諸特性優異的硬化膜。此處，R較佳為碳數1~9的烷基，更佳為碳數1~4的烷基。另外，烷基可為直鏈、分支或者環狀的烷基的任一者，較佳為直鏈或者分支的烷基。構成單元(a2)更佳 為具有下述通式(a2-30)所表示的基團的構成單元。 The polymer used in the present invention is also preferably a constituent unit (a2-3) having a group represented by -NH-CH 2 -OR (R is an alkyl group having 1 to 20 carbon atoms). By having the constituent unit (a2-3), a hardening reaction can be generated by a gentle heat treatment, and a cured film excellent in characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group. The constituent unit (a2) is more preferably a constituent unit having a group represented by the following formula (a2-30).

(通式(a2-30)中，R1表示氫原子或者甲基，R2表示碳數1~20的烷基。) (In the formula (a2-30), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 20 carbon atoms.)

R2較佳為碳數1~9的烷基，尤佳為碳數1~4的烷基。另外，烷基可為直鏈、分支或者環狀的烷基的任一者，較佳為直鏈或者分支的烷基。 R 2 is preferably an alkyl group having 1 to 9 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group.

R2的具體例可列舉甲基、乙基、正丁基、異丁基、環己基、以及正己基。其中較佳為異丁基、正丁基、甲基。 Specific examples of R 2 include a methyl group, an ethyl group, an n-butyl group, an isobutyl group, a cyclohexyl group, and a n-hexyl group. Among them, isobutyl, n-butyl and methyl groups are preferred.

<<<構成單元(a2)的較佳態樣>>> <<<The preferred aspect of the constituent unit (a2)>>>

於含有上述構成單元(a2)的聚合物實質上不含構成單元(a1)的情況下，含有該構成單元(a2)的聚合物中，構成單元(a2)較佳為5莫耳%~90莫耳%，更佳為20莫耳%~80莫耳%。 When the polymer containing the above-mentioned structural unit (a2) does not substantially contain the structural unit (a1), in the polymer containing the structural unit (a2), the structural unit (a2) is preferably 5 mol% to 90%. More than 20% of the moles, more preferably 20% by mole to 80% by mole.

於含有上述構成單元(a2)的聚合物含有上述構成單元(a1)的情況下，含有該構成單元(a1)及構成單元(a2)的聚 合物中，就耐化學品性的觀點而言，構成單元(a2)較佳為3莫耳%~70莫耳%，更佳為10莫耳%~60莫耳%。 When the polymer containing the above-mentioned structural unit (a2) contains the above-mentioned structural unit (a1), the polymerization of the structural unit (a1) and the constituent unit (a2) is included. In the compound, the structural unit (a2) is preferably from 3 mol% to 70 mol%, more preferably from 10 mol% to 60 mol%, from the viewpoint of chemical resistance.

本發明中，進而，不論哪一種態樣，(A)成分的總構成單元中，較佳為含有3莫耳%~70莫耳%的構成單元(a2)，更佳為含有10莫耳%~60莫耳%的構成單元(a2)。 In the present invention, in any aspect, the total structural unit of the component (A) preferably contains 3 mol% to 70 mol% of the constituent unit (a2), more preferably 10 mol%. ~60 mol% of the constituent unit (a2).

若為上述的數值範圍內，則由感光性樹脂組成物獲得的硬化膜的透明性以及耐化學品性變得良好。 When it is in the above numerical range, the cured film obtained from the photosensitive resin composition has good transparency and chemical resistance.

<<(a3)其他構成單元>> <<(a3) Other constituent units>>

本發明中，(A)成分除了包括上述構成單元(a1)及/或構成單元(a2)以外，亦可包括該些構成單元以外的其他構成單元(a3)。該些構成單元亦可包含上述聚合物成分(1)及/或聚合物成分(2)。另外，除上述聚合物成分(1)或聚合物成分(2)以外，亦可包括實質上不含構成單元(a1)及構成單元(a2)而包含其他構成單元(a3)的聚合物成分。在除上述聚合物成分(1)或聚合物成分(2)以外，包括實質上不含構成單元(a1)及構成單元(a2)而包含其他構成單元(a3)的聚合物成分的情況下，總聚合物成分中，該聚合物成分的調配量較佳為60質量%以下，更佳為40質量%以下，尤佳為20質量%以下。 In the present invention, the component (A) may include other constituent units (a3) other than the constituent units, in addition to the constituent unit (a1) and/or the constituent unit (a2). These constituent units may also contain the above polymer component (1) and/or polymer component (2). Further, in addition to the polymer component (1) or the polymer component (2), a polymer component containing substantially no constituent unit (a1) and a constituent unit (a2) and including another constituent unit (a3) may be included. In the case of including the polymer component (1) or the polymer component (2), the polymer component including the other structural unit (a3) and the constituent unit (a2) is substantially excluded, In the total polymer component, the amount of the polymer component is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less.

成為其他構成單元(a3)的單體並無特別限制，例如可列舉：苯乙烯類、(甲基)丙烯酸烷基酯、(甲基)丙烯酸環狀烷基酯、(甲基)丙烯酸芳基酯、不飽和二羧酸二酯、雙環不飽和化合物類、 順丁烯二醯亞胺化合物類、不飽和芳香族化合物、共軛二烯系化合物、不飽和單羧酸、不飽和二羧酸、不飽和二羧酸酐、其他不飽和化合物。另外，如後所述，亦可包括具有酸基的構成單元。成為其他構成單元(a3)的單體可單獨使用或者將2種以上組合使用。 The monomer to be another constituent unit (a3) is not particularly limited, and examples thereof include styrenes, alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, and aryl (meth)acrylates. Ester, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, A maleimide compound, an unsaturated aromatic compound, a conjugated diene compound, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic anhydride, or another unsaturated compound. Further, as will be described later, a constituent unit having an acid group may also be included. The monomers which are other constituent units (a3) may be used singly or in combination of two or more.

以下，列舉本發明的聚合物成分的較佳實施形態，但本發明並不限定於該些實施形態。 Hereinafter, preferred embodiments of the polymer component of the present invention are listed, but the present invention is not limited to the embodiments.

(第1實施形態) (First embodiment)

聚合物成分(1)更包括1種或者2種以上的其他構成單元(a3)的態樣。 The polymer component (1) further includes one or two or more kinds of other constituent units (a3).

(第2實施形態) (Second embodiment)

聚合物成分(2)的包括(a1)具有酸基由酸分解性基保護的基團的構成單元的聚合物更包括1種或者2種以上的其他構成單元(a3)的態樣。 The polymer of the polymer component (2) including (a1) a constituent unit having a group in which the acid group is protected by an acid-decomposable group further includes one or two or more kinds of other constituent units (a3).

(第3實施形態) (Third embodiment)

聚合物成分(2)的包括(a2)具有交聯性基的構成單元的聚合物更包括1種或者2種以上的其他構成單元(a3)的態樣。 The polymer of the polymer component (2) including (a2) a constituent unit having a crosslinkable group further includes one or two or more kinds of other constituent units (a3).

(第4實施形態) (Fourth embodiment)

上述第1實施形態~第3實施形態的任一者中，包括至少包含酸基的構成單元作為其他構成單元(a3)的態樣。 In any of the first to third embodiments, the constituent unit including at least an acid group is included as the other constituent unit (a3).

(第5實施形態) (Fifth Embodiment)

除上述聚合物成分(1)或聚合物成分(2)以外，更包含實質上不含構成單元(a1)及構成單元(a2)而包括其他構成單元(a3)的聚合物的態樣。 In addition to the polymer component (1) or the polymer component (2), a polymer containing substantially no constituent unit (a1) and a constituent unit (a2) but including another constituent unit (a3) is further included.

(第6實施形態) (Sixth embodiment)

包含上述第1實施形態~第5實施形態的2種以上的組合的形態。 The form of the combination of two or more types of the above-described first to fifth embodiments is included.

(第7實施形態) (Seventh embodiment)

至少包含聚合物成分(2)的態樣。尤其於上述第1實施形態~第6實施形態中，至少包含聚合物成分(2)的態樣。 At least the aspect of the polymer component (2) is included. In particular, in the first to sixth embodiments described above, at least the aspect of the polymer component (2) is contained.

具體而言，構成單元(a3)可列舉來源於以下化合物的構成單元：苯乙烯、第三丁氧基苯乙烯、甲基苯乙烯、羥基苯乙烯、α-甲基苯乙烯、乙醯氧基苯乙烯、甲氧基苯乙烯、乙氧基苯乙烯、氯苯乙烯、乙烯基苯甲酸甲酯、乙烯基苯甲酸乙酯、4-羥基苯甲酸(3-甲基丙烯醯氧基丙基)酯、(甲基)丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異冰片酯、丙烯腈、乙二醇單乙醯乙酸酯單(甲基)丙烯酸酯等。除此以外，可列舉日本專利特開2004-264623號公報的段落編號0021~段落編號0024中記載的化合物。 Specifically, the constituent unit (a3) may, for example, be a constituent unit derived from the following compounds: styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, ethoxylated. Styrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 4-hydroxybenzoic acid (3-methacryloxypropyl) Ester, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-hydroxyl (meth)acrylate Ethyl ester, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, acrylonitrile, ethylene glycol monoacetate mono(meth)acrylate Wait. In addition, the compound described in Paragraph No. 0021 to Paragraph No. 0024 of JP-A-2004-264623 is mentioned.

另外，就電特性的觀點，其他構成單元(a3)較佳為苯乙烯類、具有脂肪族環式骨架的基團。具體而言可列舉：苯乙烯、第三丁氧基苯乙烯、甲基苯乙烯、羥基苯乙烯、α-甲基苯乙烯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸苄酯等。 Further, from the viewpoint of electrical characteristics, the other constituent unit (a3) is preferably a styrene group or an aliphatic cyclic skeleton. Specific examples thereof include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, and cyclohexyl (meth)acrylate. Ester, isobornyl (meth)acrylate, benzyl (meth)acrylate, and the like.

另外，就密接性的觀點而言，其他構成單元(a3)較佳為(甲基)丙烯酸烷基酯。具體而言可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯等，更佳為(甲基)丙烯酸甲酯。構成聚合物(A)的構成單元中，上述構成單元(a3)的含有率較佳為60莫耳%以下，更佳為50莫耳%以下，尤佳為40莫耳%以下。下限值可為0莫耳%，但例如可設為1莫耳%以上，進而可設為5莫耳%以上。若為上述的數值範圍內，則由感光性樹脂組成物獲得的硬化膜的諸特性變得良好。 Further, from the viewpoint of adhesion, the other constituent unit (a3) is preferably an alkyl (meth)acrylate. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate, and more preferably methyl (meth)acrylate. . In the constituent unit constituting the polymer (A), the content of the constituent unit (a3) is preferably 60 mol% or less, more preferably 50 mol% or less, and particularly preferably 40 mol% or less. The lower limit value may be 0 mol%, but may be, for example, 1 mol% or more, and may be 5 mol% or more. When it is in the above numerical range, the characteristics of the cured film obtained from the photosensitive resin composition become good.

其他構成單元(a3)較佳為包含酸基。藉由包含酸基，而變得容易溶解於鹼性的顯影液中，更有效果地發揮本發明的效果。本發明中的所謂酸基，是指pKa小於7的質子解離性基。通常是使用可形成酸基的單體作為包含酸基的構成單元，而將酸基組入至聚合物中。藉由在聚合物中含有此種包含酸基的構成單元，而存在變得容易溶解於鹼性顯影液中的傾向。 The other constituent unit (a3) preferably contains an acid group. By containing an acid group, it is easy to be dissolved in an alkaline developing solution, and the effect of the present invention is more effectively exerted. The acid group in the present invention means a proton dissociative group having a pKa of less than 7. Usually, a monomer capable of forming an acid group is used as a constituent unit containing an acid group, and an acid group is incorporated into the polymer. When such a structural unit containing an acid group is contained in a polymer, it tends to be easily dissolved in an alkaline developing solution.

本發明中使用的酸基可例示：來源於羧酸基者、來源於磺醯胺基者、來源於膦酸基者、來源於磺酸基者、來源於酚性羥 基者、磺醯胺基、磺醯亞胺基(sulfonylimido)等，較佳為來源於羧酸基者及/或來源於酚性羥基者。 The acid group used in the present invention can be exemplified by those derived from a carboxylic acid group, those derived from a sulfonamide group, those derived from a phosphonic acid group, those derived from a sulfonic acid group, and derived from a phenolic hydroxyl group. The base, the sulfonylamino group, the sulfonylimido group, etc. are preferably those derived from a carboxylic acid group and/or derived from a phenolic hydroxyl group.

本發明中使用的包含酸基的構成單元更佳為來源於苯乙烯的構成單元、或來源於乙烯基化合物的構成單元、來源於(甲基)丙烯酸及/或其酯的構成單元。 The constituent unit containing an acid group used in the present invention is more preferably a constituent unit derived from styrene, a constituent unit derived from a vinyl compound, or a constituent unit derived from (meth)acrylic acid and/or an ester thereof.

本發明中，尤其就感度的觀點而言，特佳為含有具有羧基的構成單元、或者具有酚性羥基的構成單元。 In the present invention, in particular, from the viewpoint of sensitivity, a structural unit having a carboxyl group or a constituent unit having a phenolic hydroxyl group is particularly preferable.

包含酸基的構成單元較佳為總聚合物成分的構成單元的1莫耳%~80莫耳%，更佳為1莫耳%~50莫耳%，尤佳為5莫耳%~40莫耳%，特佳為5莫耳%~30莫耳%，最佳為5莫耳%~20莫耳%。 The constituent unit containing an acid group is preferably 1 mol% to 80 mol% of the constituent unit of the total polymer component, more preferably 1 mol% to 50 mol%, and particularly preferably 5 mol% to 40 mol. Ear %, particularly preferably 5 mole % to 30 mole %, optimally 5 mole % ~ 20 mole %.

本發明中，除上述聚合物成分(1)或聚合物成分(2)以外，亦可包含實質上不含構成單元(a1)及構成單元(a2)而包括其他構成單元(a3)的聚合物。 In the present invention, in addition to the polymer component (1) or the polymer component (2), a polymer including substantially no constituent unit (a1) and a constituent unit (a2) but including other constituent units (a3) may be contained. .

此種聚合物較佳為側鏈上具有羧基的樹脂。例如可列舉：如日本專利特開昭59-44615號、日本專利特公昭54-34327號、日本專利特公昭58-12577號、日本專利特公昭54-25957號、日本專利特開昭59-53836號、日本專利特開昭59-71048號的各公報中所記載的甲基丙烯酸共聚物、丙烯酸共聚物、衣康酸共聚物、丁烯酸共聚物、順丁烯二酸共聚物、部分酯化順丁烯二酸共聚物等，以及側鏈上具有羧基的酸性纖維素衍生物、於具有羥基的聚合物 中加成酸酐而成者等，進而亦可列舉側鏈上具有(甲基)丙烯醯基的高分子聚合物作為較佳者。 Such a polymer is preferably a resin having a carboxyl group in a side chain. For example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Publication No. Sho 54-34327, Japanese Patent Publication No. Sho 58-12577, Japanese Patent Publication No. Sho 54-25957, Japanese Patent Laid-Open No. 59-53836 The methacrylic acid copolymer, the acrylic copolymer, the itaconic acid copolymer, the butenoic acid copolymer, the maleic acid copolymer, and the partial ester described in each of the publications of Japanese Patent Laid-Open Publication No. SHO 59-71048 a maleic acid copolymer or the like, and an acidic cellulose derivative having a carboxyl group in a side chain, and a polymer having a hydroxyl group A compound obtained by adding an acid anhydride or the like may further be a polymer having a (meth) acrylonitrile group in a side chain.

例如可列舉：(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸2-羥基乙酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、日本專利特開平7-140654號公報中記載的(甲基)丙烯酸2-羥基丙酯/聚苯乙烯巨單體(macromonomer)/甲基丙烯酸苄酯/甲基丙烯酸共聚物、丙烯酸2-羥基-3-苯氧基丙酯/聚甲基丙烯酸甲酯巨單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物、甲基丙烯酸2-羥基乙酯/聚苯乙烯巨單體/甲基丙烯酸甲酯/甲基丙烯酸共聚物、甲基丙烯酸2-羥基乙酯/聚苯乙烯巨單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物等。 For example, benzyl (meth)acrylate / (meth)acrylic acid copolymer, 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic copolymer, Japanese patent 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-benzene acrylate described in Kaiping No. 7-140654 Oxypropyl propyl ester / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / A Acrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, and the like.

除此以外，可使用：日本專利特開平7-207211號公報、日本專利特開平8-259876號公報、日本專利特開平10-300922號公報、日本專利特開平11-140144號公報、日本專利特開平11-174224號公報、日本專利特開2000-56118號公報、日本專利特開2003-233179號公報、日本專利特開2009-52020號公報等中記載的公知的高分子化合物，該些內容併入本申請案說明書中。 In addition, Japanese Patent Laid-Open No. Hei 7-207211, Japanese Patent Laid-Open No. Hei 8-259876, Japanese Patent Laid-Open No. Hei 10-300922, Japanese Patent Laid-Open No. Hei 11-140144, and Japanese Patent No. A known polymer compound described in, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Enter the application specification.

該些聚合物可僅包含1種，亦可包含2種以上。 These polymers may be contained alone or in combination of two or more.

該些聚合物亦可使用市售的：SMA 1000P、SMA 2000P、SMA 3000P、SMA 1440F、SMA 17352P、SMA 2625P、SMA 3840F、SMA EF-30、SMA EF-40、SMA EF-60、SMA EF-80(以上由美國 克雷威利有限責任公司(CRAY VALLEY USA,LLC)製造)，ARUFON UC-3000、ARUFON UC-3510、ARUFON UC-3900、ARUFON UC-3910、ARUFON UC-3920、ARUFON UC-3080(以上由東亞合成(股)製造)，Joncryl 690、Joncryl 678、Joncryl 67、Joncryl 586(以上由巴斯夫(BASF)製造)等。 These polymers are also commercially available: SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F, SMA EF-30, SMA EF-40, SMA EF-60, SMA EF- 80 (above by the United States) Made by CRAY VALLEY USA (LLC), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above by East Asia) Synthetic (manufactured), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above manufactured by BASF), and the like.

<<(A)聚合物的分子量>> <<(A) Molecular Weight of Polymer>>

(A)聚合物的分子量以聚苯乙烯換算重量平均分子量計，較佳為1,000~200,000，更佳為2,000~50,000的範圍。若為上述的數值範圍內，則諸特性良好。數量平均分子量與重量平均分子量的比(分散度)較佳為1.0~5.0，更佳為1.5~3.5。 The molecular weight of the (A) polymer is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000, in terms of polystyrene-equivalent weight average molecular weight. If it is within the above numerical range, the characteristics are good. The ratio (dispersion) of the number average molecular weight to the weight average molecular weight is preferably from 1.0 to 5.0, more preferably from 1.5 to 3.5.

<<(A)聚合物的製造方法>> <<(A) Method for producing polymer>>

另外，(A)成分的合成法亦已知多種方法，若列舉一例，則可藉由使用自由基聚合起始劑，將至少包含用於形成上述(a1)及上述(a3)所表示的構成單元的自由基聚合性單體的自由基聚合性單體混合物，於有機溶劑中進行聚合來合成。另外，亦可藉由所謂的高分子反應來合成。 Further, a plurality of methods are also known for the synthesis method of the component (A), and if an example is used, at least the composition represented by the above (a1) and the above (a3) may be contained by using a radical polymerization initiator. The radically polymerizable monomer mixture of the radical polymerizable monomer of the unit is synthesized by polymerization in an organic solvent. Further, it can also be synthesized by a so-called polymer reaction.

相對於總固體成分100質量份，本發明的感光性樹脂組成物較佳為以50質量份~99.9質量份的比例包含(A)成分，更佳為以70質量份~98質量份的比例包含(A)成分。 The photosensitive resin composition of the present invention preferably contains the component (A) in a proportion of 50 parts by mass to 99.9 parts by mass, more preferably 70 parts by mass to 98 parts by mass, based on 100 parts by mass of the total solid content. (A) ingredient.

<(B)非離子性光酸產生劑> <(B) Nonionic Photoacid Generator>

本發明的感光性樹脂組成物含有(B)非離子性光酸產 生劑。本發明中使用的非離子性光酸產生劑(亦稱為「(B)成分」)較佳為對波長為300nm以上、較佳為波長為300nm~450nm的光化射線進行感應而產生酸的化合物，但對其化學結構並無限制。另外，關於對波長為300nm以上的光化射線並不直接感應的光酸產生劑，亦只要是藉由與增感劑併用而對波長為300nm以上的光化射線進行感應來產生酸的化合物，則可與增感劑組合來較佳地使用。本發明中使用的光酸產生劑較佳為產生pKa為4以下的酸的光酸產生劑，更佳為產生pKa為3以下的酸的光酸產生劑，最佳為產生pKa為2以下的酸的光酸產生劑。 The photosensitive resin composition of the present invention contains (B) nonionic photoacid Health agent. The nonionic photoacid generator (also referred to as "(B) component") used in the present invention preferably generates an acid by inducing an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm. Compound, but there is no restriction on its chemical structure. In addition, the photoacid generator which does not directly induce the actinic ray having a wavelength of 300 nm or more is a compound which generates an acid by inducing an actinic ray having a wavelength of 300 nm or more by using it together with a sensitizer. It can then be used in combination with a sensitizer. 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, and preferably has a pKa of 2 or less. Acid photoacid generator.

非離子性光酸產生劑的例子可列舉三氯甲基-均三嗪類、重氮甲烷化合物、醯亞胺磺酸酯化合物、以及肟磺酸酯化合物等。該些化合物中，就絕緣性的觀點而言，較佳為使用肟磺酸酯化合物。該些光酸產生劑可單獨使用1種或者將2種以上組合使用。三氯甲基-均三嗪類、以及重氮甲烷衍生物的具體例可例示日本專利特開2011-221494號公報的段落編號0083~段落編號0088中記載的化合物。 Examples of the nonionic photoacid generator include a trichloromethyl-s-triazine, a diazomethane compound, a quinone sulfinate compound, and an oxime sulfonate compound. Among these compounds, an oxime sulfonate compound is preferably used from the viewpoint of insulating properties. These photoacid generators may be used alone or in combination of two or more. Specific examples of the trichloromethyl-s-triazines and the diazomethane derivatives include the compounds described in Paragraph No. 0083 to Paragraph No. 0088 of JP-A-2011-221494.

肟磺酸酯化合物即具有肟磺酸酯結構的化合物較佳為可例示含有下述通式(B1)所表示的肟磺酸酯結構的化合物，該些內容併入本申請案說明書中。 The oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, is preferably a compound containing an oxime sulfonate structure represented by the following formula (B1), which is incorporated in the specification of the present application.

通式(B1) General formula (B1)

(通式(B1)中，R21表示烷基或者芳基；波形線表示與其他基團的鍵。) (In the formula (B1), R 21 represents an alkyl group or an aryl group; a wavy line indicates a bond with another group.)

任一基團均可被取代，R21中的烷基可為直鏈狀，可為分支狀，亦可為環狀。以下對所容許的取代基進行說明。 Any group may be substituted, and the alkyl group in R 21 may be linear, may be branched, or may be cyclic. The permitted substituents will be described below.

R21的烷基較佳為碳數1~10的直鏈狀或者分支狀烷基。R21的烷基可經碳數6~11的芳基、碳數1~10的烷氧基、或者環烷基(包含7,7-二甲基-2-氧代降冰片基等橋環式脂環基，較佳為雙環烷基等)所取代。 The alkyl group of R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R 21 may be an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including a bridged ring such as 7,7-dimethyl-2-oxonorbornyl) The alicyclic group is preferably substituted with a bicycloalkyl group or the like.

R21的芳基較佳為碳數6~11的芳基，更佳為苯基或者萘基。R21的芳基可經低級烷基、烷氧基或者鹵素原子所取代。 The aryl group of R 21 is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group of R 21 may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

含有上述通式(B1)所表示的肟磺酸酯結構的上述化合物亦較佳為下述通式(B2)所表示的肟磺酸酯化合物。 The above compound containing the oxime sulfonate structure represented by the above formula (B1) is also preferably an oxime sulfonate compound represented by the following formula (B2).

(式(B2)中，R42表示烷基或者芳基，X表示烷基、烷氧基、或者鹵素原子，m4表示0~3的整數，當m4為2或3時，多個X可相同，亦可不同。) (In the formula (B2), R 42 represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, m4 represents an integer of 0 to 3, and when m4 is 2 or 3, a plurality of X may be the same , but also different.)

作為X的烷基較佳為碳數1~4的直鏈狀或者分支狀烷基。作為X的烷氧基較佳為碳數1~4的直鏈狀或者分支狀烷氧基。 The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.

作為X的鹵素原子較佳為氯原子或者氟原子。m4較佳為0或1。上述通式(B2)中，特佳為m4為1，X為甲基，X的取代位置為鄰位，R42為碳數1~10的直鏈狀烷基、7,7-二甲基-2-氧代降冰片基甲基、或者對甲苯甲醯基的化合物。 The halogen atom as X is preferably a chlorine atom or a fluorine atom. M4 is preferably 0 or 1. In the above formula (B2), it is particularly preferred that m4 is 1, X is a methyl group, the substitution position of X is an ortho position, and R 42 is a linear alkyl group having a carbon number of 1 to 10, and 7,7-dimethyl group. a compound of 2-oxo norbornylmethyl or p-tolylmethyl.

含有上述通式(B1)所表示的肟磺酸酯結構的化合物亦較佳為下述通式(B3)所表示的肟磺酸酯化合物。 The compound containing the oxime sulfonate structure represented by the above formula (B1) is also preferably an oxime sulfonate compound represented by the following formula (B3).

(式(B3)中，R43與式(B2)中的R42含義相同，X1表示鹵素原子、羥基、碳數1~4的烷基、碳數1~4的烷氧基、氰基或者硝基，n4表示0~5的整數。) (In the formula (B3), R 43 has the same meaning as R 42 in the formula (B2), and X 1 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 cyano group. Or nitro, n4 represents an integer from 0 to 5.)

上述通式(B3)中的R43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-氯苯基或者五氟苯基，特佳為正辛基。 R 43 in the above formula (B3) is preferably: methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, all Fluorine-n-butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, particularly preferably n-octyl.

X1較佳為碳數1~5的烷氧基，更佳為甲氧基。 X 1 is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group.

n4較佳為0~2，特佳為0~1。 N4 is preferably 0 to 2, and particularly preferably 0 to 1.

上述通式(B3)所表示的化合物的具體例可列舉：α-(甲基磺醯氧基亞胺基)苄甲腈(benzyl cyanide)、α-(乙基磺醯氧基亞胺基)苄甲腈、α-(正丙基磺醯氧基亞胺基)苄甲腈、α-(正丁基磺醯氧基亞胺基)苄甲腈、α-(4-甲苯磺醯氧基亞胺基)苄甲腈、α-[(甲基磺醯氧基亞胺基)-4-甲氧基苯基]乙腈、α-[(乙基磺醯氧基亞胺基)-4-甲氧基苯基]乙腈、α-[(正丙基磺醯氧基亞胺基)-4-甲氧基苯基]乙腈、α-[(正丁基磺醯氧基亞胺基)-4-甲氧基苯基]乙腈、α-[(4-甲苯磺醯氧基亞胺基)-4-甲氧基苯基]乙腈。 Specific examples of the compound represented by the above formula (B3) include α-(methylsulfonyloxyimido)benzyl benzyl nitrile and α-(ethylsulfonyloxyimino). Benzonitrile, α-(n-propylsulfonyloxyimino)benzylcarbonitrile, α-(n-butylsulfonyloxyimino)benzylcarbonitrile, α-(4-toluenesulfonyloxy) Imino)benzonitrile, α-[(methylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(ethylsulfonyloxyimino)-4- Methoxyphenyl]acetonitrile, α-[(n-propylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(n-butylsulfonyloxyimino)- 4-methoxyphenyl]acetonitrile, α-[(4-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile.

較佳的肟磺酸酯化合物的具體例可列舉下述化合物(i)~化合物(viii)等，可單獨使用1種或者將2種以上併用。化合物(i)~化合物(viii)可作為市售品來獲取。另外，亦可與其他種類的(B)光酸產生劑組合使用。 Specific examples of the preferred oxime sulfonate compound include the following compounds (i) to (viii), and the like, and may be used alone or in combination of two or more. The compound (i) to the compound (viii) can be obtained as a commercial product. Further, it can also be used in combination with other types of (B) photoacid generators.

含有上述通式(B1)所表示的肟磺酸酯結構的化合物亦較佳為下述通式(OS-1)所表示的化合物。 The compound containing the oxime sulfonate structure represented by the above formula (B1) is also preferably a compound represented by the following formula (OS-1).

上述通式(OS-1)中，R101表示氫原子、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、或者雜芳基。R102表示烷基、或者芳基。 In the above formula (OS-1), R 101 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a decyl group, an amine carbaryl group, an amine sulfonyl group, a sulfo group, a cyano group, or the like. Aryl or heteroaryl. R 102 represents an alkyl group or an aryl group.

X101表示-O-、-S-、-NH-、-NR105-、-CH2-、-CR106H-、或者-CR105R107-，R105~R107表示烷基、或者芳基。 X 101 represents -O-, -S-, -NH-, -NR 105 -, -CH 2 -, -CR 106 H-, or -CR 105 R 107 -, and R 105 to R 107 represent an alkyl group or an aromatic group. base.

R121~R124分別獨立地表示氫原子、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、或者芳基。R121~R124中的2個可分別相互鍵結而形成環。 R 121 to R 124 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 cyano group. Or aryl. R 121 ~ R 124 respectively in two mutually bonded to form a ring.

R121~R124較佳為氫原子、鹵素原子、以及烷基，另外，還可較佳地列舉R121~R124中的至少2個相互鍵結而形成芳基的態樣。其中，就感度的觀點而言，較佳為R121~R124均為氫原子的態樣。 R 121 to R 124 are preferably a hydrogen atom, a halogen atom, and an alkyl group. Further, it is preferable to exemplify a state in which at least two of R 121 to R 124 are bonded to each other to form an aryl group. Among them, from the viewpoint of sensitivity, it is preferred that all of R 121 to R 124 are hydrogen atoms.

已述的官能基均可進而具有取代基。 The functional groups described may each further have a substituent.

上述通式(OS-1)所表示的化合物更佳為下述通式(OS-2)所表示的化合物。 The compound represented by the above formula (OS-1) is more preferably a compound represented by the following formula (OS-2).

上述通式(OS-2)中，R101、R102、R121~R124分別與式(OS-1)中含義相同，並且較佳例亦相同。 In the above formula (OS-2), R 101 , R 102 and R 121 to R 124 have the same meanings as in the formula (OS-1), and preferred examples are also the same.

該些較佳例中，更佳為上述通式(OS-1)及上述通式 (OS-2)中的R101為氰基、或者芳基的態樣，最佳為上述通式(OS-2)所表示且R101為氰基、苯基或者萘基的態樣。 In these preferred embodiments, it is more preferred that R 101 in the above formula (OS-1) and the above formula (OS-2) is a cyano group or an aryl group, and the above formula (OS) is most preferred. -2) The aspect represented by R 101 being a cyano group, a phenyl group or a naphthyl group.

另外，上述肟磺酸酯化合物中肟或苯并噻唑環的立體結構(E,Z等)分別可為任一者，亦可為混合物。 Further, the steric structure (E, Z, etc.) of the hydrazine or benzothiazole ring in the above sulfonate compound may be either a mixture or a mixture.

本發明中可適宜使用的上述通式(OS-1)所表示的化合物的具體例可列舉日本專利特開2011-221494號公報的段落編號0128~段落編號0132中記載的化合物(例示化合物b-1~例示化合物b-34)，但本發明並不限定於此。 Specific examples of the compound represented by the above formula (OS-1) which can be suitably used in the present invention include the compounds described in Paragraph No. 0128 to Paragraph No. 0132 of JP-A-2011-221494 (exemplified compound b- 1 to the exemplified compound b-34), but the present invention is not limited thereto.

本發明中，含有上述通式(B1)所表示的肟磺酸酯結構的化合物較佳為下述通式(OS-3)、下述通式(OS-4)或者下述通式(OS-5)所表示的肟磺酸酯化合物。 In the present invention, the compound containing the oxime sulfonate structure represented by the above formula (B1) is preferably a compound of the following formula (OS-3), the following formula (OS-4) or the following formula (OS). -5) The oxime sulfonate compound represented.

(通式(OS-3)~通式(OS-5)中，R22、R25及R28分別獨立地表示烷基、芳基或者雜芳基，R23、R26及R29分別獨立地表示氫原子、烷基、芳基或者鹵素原子，R24、R27及R30分別獨立地表示鹵素原子、烷基、烷氧基、磺酸基、胺基磺醯基或者烷氧基磺醯基，X1~X3分別獨立地表示氧原子或者硫原子，n1~n3分別獨立地表示1或2，m1~m3分別獨立地表示0~6的整數。) (In the general formula (OS-3) to (OS-5), R 22 , R 25 and R 28 each independently represent an alkyl group, an aryl group or a heteroaryl group, and R 23 , R 26 and R 29 are each independently The ground represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonate. The thiol group, X 1 to X 3 each independently represents an oxygen atom or a sulfur atom, and n 1 to n 3 each independently represent 1 or 2, and m 1 to m 3 each independently represent an integer of 0 to 6.

上述通式(OS-3)~通式(OS-5)中，R22、R25及R28中的烷基、芳基或者雜芳基可具有取代基。 In the above formula (OS-3) to formula (OS-5), the alkyl group, the aryl group or the heteroaryl group in R 22 , R 25 and R 28 may have a substituent.

上述式(OS-3)~式(OS-5)中，R22、R25及R28中的烷基較佳為可具有取代基的總碳數1~30的烷基。 In the above formula (OS-3) to formula (OS-5), the alkyl group in R 22 , R 25 and R 28 is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.

另外，上述通式(OS-3)~通式(OS-5)中，R22、R25及R28中的芳基較佳為可具有取代基的總碳數6~30的芳基。 Further, in the above formula (OS-3) to formula (OS-5), the aryl group in R 22 , R 25 and R 28 is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent.

另外，上述通式(OS-3)~通式(OS-5)中，R1中的雜芳基較佳為可具有取代基的總碳數4~30的雜芳基。 Further, in the above formula (OS-3) to formula (OS-5), the heteroaryl group in R 1 is preferably a heteroaryl group having a total carbon number of 4 to 30 which may have a substituent.

上述通式(OS-3)~通式(OS-5)中，R22、R25及R28中的雜芳基只要至少1個環為雜芳香環即可，例如，雜芳香環與苯環亦可縮環。 In the above formula (OS-3) to formula (OS-5), the heteroaryl group in R 22 , R 25 and R 28 may be at least one ring which is a heteroaromatic ring, for example, a heteroaromatic ring and benzene. The ring can also be condensed.

上述通式(OS-3)~通式(OS-5)中，R23、R26及R29較佳為氫原子、烷基或者芳基，更佳為氫原子或者烷基。 In the above formula (OS-3) to formula (OS-5), R 23 , R 26 and R 29 are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

上述通式(OS~3)~通式(OS-5)中，較佳為化合物中存在2個以上的R23、R26及R29中的1個或者2個為烷基、芳基或者鹵素原子，更佳為1個為烷基、芳基或者鹵素原子，特佳為1個為烷基，且其餘為氫原子。 In the above formula (OS-3) to formula (OS-5), it is preferred that two or more of R 23 , R 26 and R 29 are present in the compound, or two or more are alkyl groups, aryl groups or More preferably, one halogen atom is an alkyl group, an aryl group or a halogen atom, and particularly preferably one is an alkyl group, and the balance is a hydrogen atom.

R23、R26及R29中的烷基較佳為可具有取代基的總碳數1~12的烷基，更佳為可具有取代基的總碳數1~6的烷基。 The alkyl group in R 23 , R 26 and R 29 is preferably an alkyl group having a total carbon number of 1 to 12 which may have a substituent, and more preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent.

R23、R26及R29中的芳基較佳為可具有取代基的總碳數6~30的芳基。 The aryl group in R 23 , R 26 and R 29 is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent.

上述通式(OS-3)~通式(OS-5)中，X1~X3分別獨立地表示O或S，較佳為O。 In the above formula (OS-3) to formula (OS-5), X 1 to X 3 each independently represent O or S, and is preferably O.

上述通式(OS-3)~通式(OS-5)中，包含X1~X3作為環員的環為5員環或者6員環。 In the above formula (OS-3) to formula (OS-5), the ring including X 1 to X 3 as a ring member is a 5-membered ring or a 6-membered ring.

上述通式(OS-3)~通式(OS-5)中，n1~n3分別獨立地表示1或2，於X1~X3為0的情況下，較佳為n1~n3分別獨立地為1，另外，於X1~X3為S的情況下，較佳為n1~n3分別獨立地為2。 In the above formula (OS-3) to formula (OS-5), n 1 to n 3 each independently represent 1 or 2, and when X 1 to X 3 are 0, it is preferably n 1 to n. 3 is independently 1 each, and when X 1 to X 3 are S, it is preferable that n 1 to n 3 are each independently 2.

上述通式(OS-3)~通式(OS-5)中，R24、R27及R30分別獨立地表示鹵素原子、烷基、烷氧基、磺酸基、胺基磺醯基或者烷氧基磺醯基。其中，較佳為R24、R27及R30分別獨立地為烷基或者烷氧基。 In the above formula (OS-3) to formula (OS-5), R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or Alkoxysulfonyl. Preferably, R 24 , R 27 and R 30 are each independently an alkyl group or an alkoxy group.

R24、R27及R30中的烷基、烷氧基、磺酸基、胺基磺醯基以及烷氧基磺醯基可具有取代基。 The alkyl group, alkoxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R 24 , R 27 and R 30 may have a substituent.

上述通式(OS-3)~通式(OS-5)中，R24、R27及R30中的烷基較佳為可具有取代基的總碳數1~30的烷基。 In the above formula (OS-3) to formula (OS-5), the alkyl group in R 24 , R 27 and R 30 is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.

上述通式(OS-3)~通式(OS-5)中，R24、R27及R30中的烷氧基較佳為可具有取代基的總碳數1~30的烷氧基。 In the above formula (OS-3) to formula (OS-5), the alkoxy group in R 24 , R 27 and R 30 is preferably an alkoxy group having a total carbon number of 1 to 30 which may have a substituent.

另外，上述通式(OS-3)~通式(OS-5)中，m1~m3分別獨立地表示0~6的整數，較佳為0~2的整數，更佳為0或1，特佳為0。 Further, in the above formula (OS-3) to formula (OS-5), m 1 to m 3 each independently represent an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1. , especially good is 0.

另外，關於上述(OS-3)~通式(OS-5)的各自的取代基，日本專利特開2011-221494號公報的段落編號0092~段落編號0109中記載的(OS-3)~(OS-5)的取代基的較佳範圍亦相同。 Further, regarding the respective substituents of the above (OS-3) to the general formula (OS-5), (OS-3) to (OS-3) to (paragraph No. 0092 to Paragraph No. 0109 of JP-A-2011-221494 The preferred range of the substituent of OS-5) is also the same.

另外，含有上述通式(B1)所表示的肟磺酸酯結構的化合物特佳為下述通式(OS-6)~通式(OS-11)的任一者所表示的肟磺酸酯化合物。 In addition, the compound containing the oxime sulfonate structure represented by the above formula (B1) is particularly preferably an oxime sulfonate represented by any one of the following formula (OS-6) to (OS-11). Compound.

(式(OS-6)~式(OS-11)中，R301~R306表示烷基、芳基或者雜芳基，R307表示氫原子或者溴原子，R308~R310、R313、R316及R318分別獨立地表示氫原子、碳數1~8的烷基、鹵素原子、氯甲基、溴甲基、溴乙基、甲氧基甲基、苯基或者氯苯基，R311及R314分別獨立地表示氫原子、鹵素原子、甲基或者甲氧基，R312、R315、R317及R319分別獨立地表示氫原子或者甲基。) (In the formula (OS-6)~(OS-11), R 301 to R 306 represent an alkyl group, an aryl group or a heteroaryl group, and R 307 represents a hydrogen atom or a bromine atom, and R 308 to R 310 and R 313 , R 316 and R 318 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R 311 and R314 each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R 312 , R 315 , R 317 and R 319 each independently represent a hydrogen atom or a methyl group.

上述通式(OS-6)~通式(OS-11)中的較佳範圍與日 本專利特開2011-221494號公報的段落編號0110~段落編號0112中記載的(OS-6)~(OS-11)的較佳範圍相同。 Preferred range and date in the above formula (OS-6) to formula (OS-11) The preferred ranges of (OS-6) to (OS-11) described in Paragraph No. 0110 to Paragraph No. 0112 of Japanese Laid-Open Patent Publication No. 2011-221494 are the same.

上述通式(OS-3)~上述通式(OS-5)所表示的肟磺酸酯化合物的具體例可列舉日本專利特開2011-221494號公報的段落編號0114~段落編號0120中記載的化合物，但本發明並不限定於該些化合物。 Specific examples of the oxime sulfonate compound represented by the above formula (OS-3) to the above formula (OS-5) include those described in paragraph No. 0114 to paragraph number 0120 of JP-A-2011-221494. A compound, but the invention is not limited to the compounds.

本發明的感光性樹脂組成物中，相對於感光性樹脂組成物中的總樹脂成分(較佳為總固體成分，更佳為聚合物的合計)100質量份，(B)非離子性光酸產生劑較佳為使用0.1質量份~10質量份，更佳為使用0.5質量份~10質量份。亦可將2種以上併用。 In the photosensitive resin composition of the present invention, the total resin component (preferably the total solid content, more preferably the total of the polymer) in the photosensitive resin composition is 100 parts by mass, and (B) the nonionic photoacid The generating agent is preferably used in an amount of from 0.1 part by mass to 10 parts by mass, more preferably from 0.5 part by mass to 10 parts by mass. Two or more types may be used in combination.

本發明中，亦可更包含(B')離子性光酸產生劑。(B')離子性光酸產生劑的例子可列舉鋶鹽或錪鹽、四級銨鹽類等。該些化合物中，就絕緣性的觀點而言，較佳為使用肟磺酸酯化合物。該些離子性光酸產生劑可單獨使用1種或者將2種以上組合使用。二芳基錪鹽類、三芳基鋶鹽類、四級銨鹽類的具體例可例示日本專利特開2011-221494號公報的段落編號0083~段落編號0088中記載的化合物。 In the present invention, the (B') ionic photoacid generator may be further included. Examples of the (B') ionic photoacid generator include a phosphonium salt, a phosphonium salt, a quaternary ammonium salt, and the like. Among these compounds, an oxime sulfonate compound is preferably used from the viewpoint of insulating properties. These ionic photoacid generators may be used alone or in combination of two or more. Specific examples of the diarylsulfonium salt, the triarylsulfonium salt, and the quaternary ammonium salt include the compounds described in Paragraph No. 0083 to Paragraph No. 0098 of JP-A-2011-221494.

本發明的感光性樹脂組成物中，於包含(B')離子性光酸產生劑的情況下，較佳為於不妨礙本發明效果的範圍內，相對於感光性樹脂組成物中的總樹脂成分(較佳為固體成分，更佳為 聚合物的合計)100質量份，使用0質量份~10質量份的(B')離子性光酸產生劑，更佳為使用0質量份~5質量份。另外，(B')離子性光酸產生劑的添加量尤佳為(B)非離子性光酸產生劑的添加量以下，較佳為10質量%以下。但本發明中，較佳為實質上不含(B')離子性光酸產生劑的態樣。 In the case where the (B') ionic photoacid generator is contained in the photosensitive resin composition of the present invention, it is preferably in a range which does not impair the effects of the present invention, relative to the total resin in the photosensitive resin composition. Ingredients (preferably solid ingredients, more preferably The total amount of the polymer is from 0 parts by mass to 10 parts by mass per 100 parts by mass of the (B') ionic photoacid generator, and more preferably from 0 parts by mass to 5 parts by mass. Further, the amount of the (B') ionic photoacid generator to be added is preferably at least the amount of the (B) nonionic photoacid generator added, preferably 10% by mass or less. However, in the present invention, it is preferred that the (B') ionic photoacid generator is substantially not contained.

<(C)下述通式(S)記載的化合物> <(C) A compound of the following formula (S)>

本發明的組成物包含(C)下述通式(S)所表示的化合物。 The composition of the present invention contains (C) a compound represented by the following formula (S).

(通式(S)中，R1表示包含至少1個以上氮原子的基團，A表示2價連結基，R2表示有機基。) (In the general formula (S), R 1 represents a group containing at least one or more nitrogen atoms, A represents a divalent linking group, and R 2 represents an organic group.)

R1表示包含至少1個以上氮原子的基團，較佳為包含1個~3個氮原子的基團，更佳為-NR3R4所表示的基團。 R 1 represents a group containing at least one or more nitrogen atoms, preferably a group containing 1 to 3 nitrogen atoms, more preferably a group represented by -NR 3 R 4 .

R1較佳為包含1個~10個碳原子與1個~3個包括氧原子、至少1個以上氮原子的雜原子的基團。該情況下的雜原子可列舉氧原子、硫原子，較佳為氧原子。R1較佳為環狀基，更佳為5員環或者6員環的環狀基。 R 1 is preferably a group containing one to ten carbon atoms and one to three hetero atoms including an oxygen atom and at least one nitrogen atom. The hetero atom in this case may, for example, be an oxygen atom or a sulfur atom, and is preferably an oxygen atom. R 1 is preferably a cyclic group, more preferably a cyclic group of a 5-membered ring or a 6-membered ring.

R3及R4分別表示有機基。有機基較佳為烷基、烯基， 或者包含該些基團與-O-、-S-及-N-的至少1個的組合的基團。R3及R4分別較佳為碳數1~3的基團。R3及R4可相互鍵結而形成環，較佳為形成環。 R 3 and R 4 each represent an organic group. The organic group is preferably an alkyl group, an alkenyl group, or a group containing a combination of these groups and at least one of -O-, -S-, and -N-. R 3 and R 4 are each preferably a group having 1 to 3 carbon atoms. R 3 and R 4 may be bonded to each other to form a ring, preferably a ring.

R1的較佳態樣可列舉以下態樣。 Preferred aspects of R 1 include the following aspects.

(1)R1為-NR3R4所表示的基團且R3與R4相互鍵結而形成環的態樣、或者R3與R4分別為脂肪族烴基的態樣。 (1) A state in which R 1 is a group represented by -NR 3 R 4 and R 3 and R 4 are bonded to each other to form a ring, or R 3 and R 4 are each an aliphatic hydrocarbon group.

(2)R1為-NR3R4所表示的基團且R3與R4相互鍵結而形成5員環或者6員環的態樣、或者R3與R4分別為碳數1~4的直鏈或者分支的脂肪族烴基的態樣。 (2) R 1 is a group represented by -NR 3 R 4 and R 3 and R 4 are bonded to each other to form a 5-membered ring or a 6-membered ring, or R 3 and R 4 are each a carbon number 1~ A linear or branched aliphatic hydrocarbon group of 4.

(3)R1為-NR3R4所表示的基團且R3與R4相互鍵結而形成包含2個以上雜原子(較佳為至少1個為氮原子，其餘為氧原子或者氮原子)的5員環或者6員環的態樣、或者R3與R4分別為碳數1~4的直鏈脂肪族烴基的態樣。 (3) R 1 is a group represented by -NR 3 R 4 and R 3 and R 4 are bonded to each other to form two or more hetero atoms (preferably at least one is a nitrogen atom, and the remainder is an oxygen atom or nitrogen) The aspect of the 5-membered ring or the 6-membered ring of the atom, or the state in which R 3 and R 4 are each a linear aliphatic hydrocarbon group having 1 to 4 carbon atoms.

R1的具體例例如可列舉：嗎啉基(morpholino)、肼基(hydrazino)、吡啶基(pyridyl)、咪唑基(imidazolyl)、喹啉基(quinolyl)、哌啶基(piperidyl)、吡咯啶基(pyrrolidinyl)、吡唑基(pyrazolyl)、噁唑基(oxazolyl)、噻唑基(thiazolyl)、苯并噁唑基(benzoxazolyl)、苯并咪唑基(benzimidazolyl)、苯并噻唑基(benzothiazolyl)、吡嗪基(pyrazinyl)、二乙胺基(diethylamino)等。其中，較佳為嗎啉基。 Specific examples of R 1 include morpholino, hydrazino, pyridyl, imidazolyl, quinolyl, piperidyl, and pyrrolidine. Pyrrolidinyl, pyrazolyl, oxazolyl, thiazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, Pyrazinyl, diethylamino, and the like. Among them, a morpholinyl group is preferred.

R2表示有機基。有機基較佳為烴基、或者包含烴基與-O- 及-C(=O)-的至少1個的組合的基團。R2的碳數較佳為1~20，更佳為1~10。 R 2 represents an organic group. The organic group is preferably a hydrocarbon group or a group containing a combination of a hydrocarbon group and at least one of -O- and -C(=O)-. The carbon number of R 2 is preferably from 1 to 20, more preferably from 1 to 10.

R2尤佳為碳數1~20的烷基或者碳數6~12的芳基、或者包含該些基團與-O-及-C(=O)-的至少1個的組合的基團。該些基團可具有取代基，取代基可例示鹵素原子。 R 2 is particularly preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, or a group containing a combination of at least one of these groups and -O- and -C(=O)-. . These groups may have a substituent, and the substituent may be a halogen atom.

於R2為烷基的情況下，較佳為碳數1~8的直鏈或者分支的烷基、或者環狀烷基。於R2為環狀烷基的情況下，較佳為5員環或者6員環的環狀烷基。 When R 2 is an alkyl group, a linear or branched alkyl group having 1 to 8 carbon atoms or a cyclic alkyl group is preferable. When R 2 is a cyclic alkyl group, a 5-membered ring or a 6-membered cyclic alkyl group is preferred.

於R2為芳基的情況下，可例示苯基及萘基，更佳為苯基。 In the case where R 2 is an aryl group, a phenyl group and a naphthyl group are exemplified, and a phenyl group is more preferable.

R2的較佳態樣可列舉以下態樣。 Preferred aspects of R 2 include the following aspects.

(1)碳數1~4(較佳為2或3)的直鏈伸烷基的態樣。 (1) A linear alkyl group having a carbon number of 1 to 4 (preferably 2 or 3).

A表示2價連結基，較佳為碳數1~20的烴基，更佳為碳數1~10的烴基，尤佳為碳數2~6的烴基。烴基可例示伸烷基以及伸芳基，較佳為伸烷基。 A represents a divalent linking group, preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably a hydrocarbon group having 2 to 6 carbon atoms. The hydrocarbon group may, for example, be an alkylene group and an extended aryl group, preferably an alkylene group.

伸烷基例如可例示：亞甲基、伸乙基、伸丙基、伸環己基、伸環戊基等。伸芳基例如可例示：1,2-伸苯基、1,3-伸苯基、1,4-伸苯基、伸萘基等。本發明中特佳為亞甲基、伸乙基、伸丙基，更佳為伸乙基或者伸丙基。 Examples of the alkylene group include a methylene group, an exoethyl group, a propyl group, a cyclohexylene group, a cyclopentyl group and the like. Examples of the extended aryl group include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, and naphthyl. Particularly preferred in the present invention are a methylene group, an ethyl group, a propyl group, and more preferably an ethyl group or a propyl group.

A的較佳態樣可列舉以下態樣。 The preferred aspect of A can be exemplified in the following aspects.

(1)碳數1~4的直鏈或者分支的烷基、5員環或者6 員環的環狀烷基、或者苯基的態樣。 (1) A linear or branched alkyl group having a carbon number of 1 to 4, a 5-membered ring or 6 A cyclic alkyl group of a member ring or a phenyl group.

通式(S)所表示的化合物可例示成為上述R1的較佳態樣、R2的較佳態樣、A的較佳態樣的組合的態樣作為特佳態樣。 The compound represented by the formula (S) can be exemplified as a preferred embodiment of the above R 1 , a preferred aspect of R 2 , and a combination of preferred aspects of A.

通式(S)所表示的化合物較佳為由通式(S1)所表示。 The compound represented by the formula (S) is preferably represented by the formula (S1).

(通式(S1)中，R2表示有機基，A表示2價連結基。) (In the formula (S1), R 2 represents an organic group, and A represents a divalent linking group.)

R2與上述式(S)中的R2含義相同，較佳範圍亦相同。 R 2 is (S) R 2 is the same meaning as the above formula, preferred ranges are also the same.

A與上述式(S)中的A含義相同，較佳範圍亦相同。 A has the same meaning as A in the above formula (S), and the preferred range is also the same.

通式(S1)中特佳為以下態樣。 Particularly preferred in the general formula (S1) is the following.

(1)A為碳數1~4的直鏈伸烷基且R2為直鏈、分支、或者環狀的烷基的態樣。 (1) A is a state in which a linear alkyl group having 1 to 4 carbon atoms and R 2 is a linear, branched or cyclic alkyl group.

(2)A為碳數2或3的伸烷基且R2為碳數2~6的直鏈、分支、或者環狀的烷基的態樣。 (2) A is a state in which an alkyl group having 2 or 3 carbon atoms and R 2 is a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms.

上述通式(S)的具體例可列舉如以下所述的化合物，但本發明中並不特別限定於此。此外，例示化合物中，Et表示乙基。 Specific examples of the above formula (S) include the following compounds, but the present invention is not particularly limited thereto. Further, in the exemplified compound, Et represents an ethyl group.

相對於總固體成分100質量份，本發明的感光性樹脂組成物較佳為以0.001質量份~5質量份的比例包含(C)成分，更佳為以0.003質量份~2質量份的比例包含(C)成分，尤佳為以0.005質量份~1質量份的比例包含(C)成分。(C)成分可僅為1種，亦可為2種以上。於2種以上的情況下，較佳為其合計為上述範圍。 The photosensitive resin composition of the present invention preferably contains the component (C) in a proportion of 0.001 parts by mass to 5 parts by mass, more preferably 0.003 parts by mass to 2 parts by mass, based on 100 parts by mass of the total solid content. The component (C) preferably contains the component (C) in a proportion of 0.005 part by mass to 1 part by mass. The component (C) may be one type or two or more types. In the case of two or more kinds, it is preferable to add up to the above range.

<(D)溶劑> <(D) Solvent>

本發明的感光性樹脂組成物含有(D)溶劑。本發明的感光性樹脂組成物較佳為製備成將本發明的必需成分、進而與後述任意的成分溶解於(D)溶劑中而成的溶液。 The photosensitive resin composition of the present invention contains (D) a solvent. The photosensitive resin composition of the present invention is preferably prepared by dissolving an essential component of the present invention and further a component described below in (D) a solvent.

本發明的感光性樹脂組成物中使用的(D)溶劑可使用公知的溶劑，可例示：乙二醇單烷基醚類、乙二醇二烷基醚類、 乙二醇單烷基醚乙酸酯類、丙二醇單烷基醚類、丙二醇二烷基醚類、丙二醇單烷基醚乙酸酯類、二乙二醇二烷基醚類、二乙二醇單烷基醚乙酸酯類、二丙二醇單烷基醚類、二丙二醇二烷基醚類、二丙二醇單烷基醚乙酸酯類、酯類、酮類、醯胺類、內酯類等。另外，本發明的感光性樹脂組成物中使用的(D)溶劑的具體例亦可列舉日本專利特開2011-221494號公報的段落編號0174~段落編號0178中記載的溶劑，該些內容併入本申請案說明書中。 The solvent (D) used in the photosensitive resin composition of the present invention may be a known solvent, and examples thereof include ethylene glycol monoalkyl ethers and ethylene glycol dialkyl ethers. Ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, propylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, diethylene glycol monoalkane Ethyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, guanamines, lactones, and the like. In addition, as a specific example of the solvent (D) used in the photosensitive resin composition of the present invention, the solvent described in Paragraph No. 0174 to Paragraph No. 0178 of JP-A-2011-221494 may be incorporated. In the specification of the present application.

另外，視需要亦可進而向該些溶劑中添加：苄基乙醚、二己醚、乙二醇單苯醚乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、異佛爾酮、己酸、辛酸、1-辛醇、1-壬醇、苄醇、苯甲醚(anisole)、乙酸苄酯、苯甲酸乙酯、乙二酸二乙酯、順丁烯二酸二乙酯、碳酸伸乙酯(ethylene carbonate)、碳酸伸丙酯等溶劑。該些溶劑可單獨使用1種或者將2種以上混合使用。本發明中可使用的溶劑較佳為單獨使用1種或者將2種併用，更佳為將2種併用，尤佳為將丙二醇單烷基醚乙酸酯類或者二烷基醚類、二乙酸酯類與二乙二醇二烷基醚類、或者酯類與丁二醇烷基醚乙酸酯類併用。 In addition, if necessary, it may be further added to the solvents: benzyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophor Ketone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate Solvents such as esters, ethylene carbonate, and propyl carbonate. These solvents may be used alone or in combination of two or more. The solvent which can be used in the present invention is preferably used singly or in combination of two or more, more preferably two kinds, and particularly preferably propylene glycol monoalkyl ether acetate or dialkyl ether or diacetate. It is used in combination with diethylene glycol dialkyl ethers or esters and butanediol alkyl ether acetate.

另外，成分D較佳為沸點為130℃以上且小於160℃的溶劑、沸點為160℃以上的溶劑、或者該些溶劑的混合物。 Further, the component D is preferably a solvent having a boiling point of 130 ° C or more and less than 160 ° C, a solvent having a boiling point of 160 ° C or higher, or a mixture of these solvents.

沸點為130℃以上且小於160℃的溶劑可例示：丙二醇單甲醚乙酸酯(沸點為146℃)、丙二醇單乙醚乙酸酯(沸點為158℃)、丙二醇甲基-正丁醚(沸點為155℃)、丙二醇甲基-正丙 醚(沸點為131℃)。 The solvent having a boiling point of 130 ° C or more and less than 160 ° C can be exemplified by propylene glycol monomethyl ether acetate (boiling point: 146 ° C), propylene glycol monoethyl ether acetate (boiling point: 158 ° C), propylene glycol methyl-n-butyl ether (boiling point) 155 ° C), propylene glycol methyl-positive C Ether (boiling point 131 ° C).

沸點為160℃以上的溶劑可例示：3-乙氧基丙酸乙酯(沸點為170℃)、二乙二醇甲基乙醚(沸點為176℃)、丙二醇單甲醚丙酸酯(沸點為160℃)、二丙二醇甲醚乙酸酯(沸點為213℃)、3-甲氧基丁醚乙酸酯(沸點為171℃)、二乙二醇二乙醚(沸點為189℃)、二乙二醇二甲醚(沸點為162℃)、丙二醇二乙酸酯(沸點為190℃)、二乙二醇單乙醚乙酸酯(沸點為220℃)、二丙二醇二甲醚(沸點為175℃)、1,3-丁二醇二乙酸酯(沸點為232℃)。 The solvent having a boiling point of 160 ° C or higher can be exemplified by ethyl 3-ethoxypropionate (boiling point: 170 ° C), diethylene glycol methyl ether (boiling point: 176 ° C), and propylene glycol monomethyl ether propionate (boiling point: 160 ° C), dipropylene glycol methyl ether acetate (boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), two Diol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C ), 1,3-butanediol diacetate (boiling point: 232 ° C).

相對於感光性樹脂組成物中的總樹脂成分100質量份，本發明的感光性樹脂組成物中的(D)溶劑的含量較佳為50質量份~95質量份，尤佳為60質量份~90質量份。 The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 50 parts by mass to 95 parts by mass, particularly preferably 60 parts by mass, based on 100 parts by mass of the total resin component in the photosensitive resin composition. 90 parts by mass.

(E)烷氧基矽烷化合物 (E) alkoxydecane compound

本發明的感光性樹脂組成物的特徵在於含有(E)烷氧基矽烷化合物(亦稱為「(E)成分」)。若使用烷氧基矽烷化合物，則可提高由本發明的感光性樹脂組成物形成的膜與基板的密接性，或者可調整由本發明的感光性樹脂組成物形成的膜的性質。烷氧基矽烷化合物較佳為二烷氧基矽烷化合物或者三烷氧基矽烷化合物，更佳為三烷氧基矽烷化合物。烷氧基矽烷化合物所具有的烷氧基的碳數較佳為1~5。 The photosensitive resin composition of the present invention is characterized by containing (E) an alkoxydecane compound (also referred to as "(E) component"). When an alkoxy decane compound is used, the adhesiveness of the film formed from the photosensitive resin composition of this invention and a board|substrate can be improved, or the film of the photosensitive resin composition of this invention can be adjusted. The alkoxydecane compound is preferably a dialkoxy decane compound or a trialkoxy decane compound, more preferably a trialkoxy decane compound. The alkoxy group of the alkoxydecane compound preferably has 1 to 5 carbon atoms.

本發明的感光性樹脂組成物中可使用的(E)烷氧基矽烷化合物較佳為提高成為基材的無機物(例如：矽、氧化矽、氮 化矽等矽化合物，金、銅、鉬、鈦、鋁等金屬)與絕緣膜的密接性的化合物。具體而言，公知的矽烷偶合劑等亦有效。 The (E) alkoxydecane compound which can be used in the photosensitive resin composition of the present invention preferably has an inorganic substance (for example, cerium, cerium oxide or nitrogen) which is used as a substrate. A compound in which an antimony compound such as ruthenium or the like is a metal such as gold, copper, molybdenum, titanium or aluminum) and an insulating film. Specifically, a known decane coupling agent or the like is also effective.

矽烷偶合劑例如可列舉：γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-縮水甘油氧基丙基三烷氧基矽烷、γ-縮水甘油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-巰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。該些化合物中，更佳為γ-縮水甘油氧基丙基三烷氧基矽烷或γ-甲基丙烯醯氧基丙基三烷氧基矽烷，尤佳為γ-縮水甘油氧基丙基三烷氧基矽烷，尤其更佳為3-縮水甘油氧基丙基三甲氧基矽烷。該些化合物可單獨使用1種或者將2種以上組合使用。 Examples of the decane coupling agent include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-glycidoxypropyltrialkoxydecane, and γ-glycidyloxy group. Propyl alkyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl alkyl dialkoxy decane, γ-chloropropyl three Alkoxydecane, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, vinyltrialkoxydecane. More preferably, these compounds are γ-glycidoxypropyltrialkoxydecane or γ-methacryloxypropyltrialkoxydecane, and particularly preferably γ-glycidoxypropyl III. The alkoxydecane is especially preferably 3-glycidoxypropyltrimethoxydecane. These compounds may be used alone or in combination of two or more.

另外，亦可較佳地採用下述化合物。 Further, the following compounds can also be preferably used.

上述中，Ph為苯基。 In the above, Ph is a phenyl group.

本發明的感光性樹脂組成物中的(E)烷氧基矽烷化合物並不特別限定於該些化合物，可使用公知的化合物。 The (E) alkoxydecane compound in the photosensitive resin composition of the present invention is not particularly limited to these compounds, and a known compound can be used.

相對於感光性組成物中的總固體成分100質量份，本發明的感光性樹脂組成物中的(E)烷氧基矽烷化合物的含量較佳為0.1質量份~30質量份，更佳為0.5質量份~20質量份。 The content of the (E) alkoxydecane compound in the photosensitive resin composition of the present invention is preferably from 0.1 part by mass to 30 parts by mass, more preferably 0.5, based on 100 parts by mass of the total solid content of the photosensitive composition. Parts by mass to 20 parts by mass.

<其他成分> <Other ingredients>

本發明的感光性樹脂組成物中除了上述成分以外，視需要可較佳地添加(F)交聯劑、(G)增感劑、(H)鹼性化合物、(I)界面活性劑、(J)抗氧化劑。進而本發明的感光性樹脂組成物中可添加酸增殖劑、顯影促進劑、塑化劑、熱自由基產生劑、熱酸產生劑、紫外線吸收劑、增黏劑、以及有機或無機的沈澱防止劑 等公知的添加劑。 In addition to the above components, the photosensitive resin composition of the present invention may preferably contain (F) a crosslinking agent, (G) a sensitizer, (H) a basic compound, (I) a surfactant, ( J) Antioxidants. Further, an acid proliferating agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a tackifier, and an organic or inorganic precipitation preventable agent can be added to the photosensitive resin composition of the present invention. Agent And other known additives.

(F)交聯劑 (F) crosslinker

本發明的感光性樹脂組成物較佳為視需要含有交聯劑。藉由添加交聯劑，可使由本發明的感光性樹脂組成物獲得的硬化膜形成更牢固的膜。 The photosensitive resin composition of the present invention preferably contains a crosslinking agent as needed. The cured film obtained from the photosensitive resin composition of the present invention can form a stronger film by adding a crosslinking agent.

交聯劑只要藉由熱而產生交聯反應，則無限制。(A成分除外)。例如可添加：以下所述的分子內具有2個以上環氧基或氧雜環丁基的化合物、含烷氧基甲基的交聯劑、或者具有至少1個乙烯性不飽和雙鍵的化合物、嵌段異氰酸酯化合物等。 The crosslinking agent is not limited as long as it generates a crosslinking reaction by heat. (except for component A). For example, a compound having two or more epoxy groups or oxetanyl groups, a crosslinking group containing an alkoxymethyl group, or a compound having at least one ethylenically unsaturated double bond in the molecule described below may be added. , block isocyanate compounds, and the like.

相對於感光性樹脂組成物的總固體成分100質量份，本發明的感光性樹脂組成物中的交聯劑的添加量較佳為0.01質量份~50質量份，更佳為0.1質量份~30質量份，尤佳為0.5質量份~20質量份。藉由以該範圍添加，而獲得機械強度以及耐溶劑性優異的硬化膜。交聯劑亦可併用多種，該情況下將交聯劑全部合計來計算含量。 The amount of the crosslinking agent added to the photosensitive resin composition of the present invention is preferably from 0.01 part by mass to 50 parts by mass, more preferably from 0.1 part by mass to 30 parts by mass per 100 parts by mass of the total solid content of the photosensitive resin composition. The mass part is preferably from 0.5 part by mass to 20 parts by mass. By adding in this range, a cured film excellent in mechanical strength and solvent resistance is obtained. A plurality of crosslinking agents may be used in combination, and in this case, the total amount of the crosslinking agents is totaled to calculate the content.

<分子內具有2個以上環氧基或氧雜環丁基的化合物> <Compound having two or more epoxy groups or oxetanyl groups in the molecule>

分子內具有2個以上環氧基的化合物的具體例可列舉：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 a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, and a cresol novolak type epoxy resin. Aliphatic epoxy resin, etc.

該些化合物可作為市售品而獲取。例如可列舉：JER157S70、JER157S65(三菱化學控股(Mitsubishi Chemical Holdings)(股)製造)等日本專利特開2011-221494號公報的段落編號0189中記載的市售品等。 These compounds are available as commercial products. For example, JER157S70 and JER157S65 (Mitsubishi Chemical Holdings) A commercially available product such as the one described in paragraph No. 0189 of JP-A-2011-221494.

除此以外，可列舉：ADEKA RESIN EP-4000S、ADEKA RESIN EP-4003S、ADEKA RESIN EP-4010S、ADEKA RESIN EP-4011S(以上由艾迪科(ADEKA)(股)製造)、NC-2000、NC-3000、NC-7300、XD-1000、EPPN-501、EPPN-502(以上由艾迪科(股)製造)、Denacol EX-611、Denacol EX-612、Denacol EX-614、Denacol EX-614B、Denacol EX-622、Denacol EX-512、Denacol EX-521、Denacol EX-411、Denacol EX-421、Denacol EX-313、Denacol EX-314、Denacol EX-321、Denacol EX-211、Denacol EX-212、Denacol EX-810、Denacol EX-811、Denacol EX-850、Denacol EX-851、Denacol EX-821、Denacol EX-830、Denacol EX-832、Denacol EX-841、Denacol EX-911、Denacol EX-941、Denacol EX-920、Denacol EX-931、Denacol EX-212L、Denacol EX-214L、Denacol EX-216L、Denacol EX-321L、Denacol EX-850L、DLC-201、Denacol DLC-203、Denacol DLC-204、Denacol DLC-205、Denacol DLC-206、Denacol DLC-301、Denacol DLC-402(以上由長瀨化成(Nagase ChemteX)製造)、YH-300、YH-301、YH-302、YH-315、YH-324、YH-325(以上由新日鐵化學製造)、Celloxide 2021P、Celloxide 2081、Celloxide 3000、EHPE 3150、Epolead GT400、Celvenus B0134、Celvenus B0177(大賽璐(Daicel) (股))、EPICLON EXA-4850-150(迪愛生(DIC)(股)製造)、EPICLON EXA-4850-1000(迪愛生(股)製造)等。 Other than this, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (above manufactured by ADEKA), NC-2000, NC -3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above manufactured by Eddy Co.), Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-614B, Denacol EX-622, Denacol EX-512, Denacol EX-521, Denacol EX-411, Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-211, Denacol EX-212, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931, Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L, Denacol EX-850L, DLC-201, Denacol DLC-203, Denacol DLC-204, Denacol DLC-205, Denacol DLC-206, Denacol DLC-301, Denacol DLC-402 (above manufactured by Nagase ChemteX), YH-300, YH-301, YH-302, YH-315, YH-324 , YH-325 ( Manufactured by the Nippon Steel Chemical Co.), Celloxide 2021P, Celloxide 2081, Celloxide 3000, EHPE 3150, Epolead GT400, Celvenus B0134, Celvenus B0177 (Daicel (of Daicel) (share)), EPICLON EXA-4850-150 (made by Di Aisheng (DIC) Co., Ltd.), EPICLON EXA-4850-1000 (made by Di Aisheng (share)).

該些化合物可單獨使用1種或者將2種以上組合使用。 These compounds may be used alone or in combination of two or more.

該些化合物中，更佳為可列舉：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以及脂肪族環氧樹脂，特佳為可列舉雙酚A型環氧樹脂。 Among these compounds, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, and an aliphatic epoxy resin are more preferable, and a bisphenol A type is especially preferable. Epoxy resin.

分子內具有2個以上氧雜環丁基的化合物的具體例可使用：Aron Oxetane OXT-121、Aron Oxetane OXT-221、Aron Oxetane OX-SQ、Aron Oxetane PNOX(以上由東亞合成(股)製造)。 Specific examples of the compound having two or more oxetanyl groups in the molecule can be used: Aron Oxetane OXT-121, Aron Oxetane OXT-221, Aron Oxetane OX-SQ, Aron Oxetane PNOX (above manufactured by East Asia Synthetic Co., Ltd.) .

另外，包含氧雜環丁基的化合物較佳為單獨使用或者與包含環氧基的化合物混合使用。 Further, the compound containing an oxetanyl group is preferably used singly or in combination with a compound containing an epoxy group.

另外，其他交聯劑亦可較佳地使用日本專利特開2012-8223號公報的段落編號0107~段落編號0108中記載的含烷氧基甲基的交聯劑、以及具有至少1個乙烯性不飽和雙鍵的化合物等，該些內容併入本申請案說明書中。含烷氧基甲基的交聯劑較佳為烷氧基甲基化甘脲。 Further, the other crosslinking agent may preferably be an alkoxymethyl group-containing crosslinking agent described in Paragraph No. 0107 to Paragraph No. 0108 of JP-A-2012-8223, and having at least one ethylenic property. Compounds of unsaturated double bonds, etc., are incorporated herein by reference. The alkoxymethyl group-containing crosslinking agent is preferably an alkoxymethylated glycoluril.

<嵌段異氰酸酯化合物> <Block isocyanate compound>

本發明的感光性樹脂組成物中，亦可較佳地採用嵌段異氰酸酯系化合物作為交聯劑。嵌段異氰酸酯化合物只要是具有嵌段異氰酸基(isocyanato)的化合物，則無特別限制，就硬化性的觀點而言，較佳為1分子內具有2個以上嵌段異氰酸基的化合物。 In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also be preferably used as the crosslinking agent. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanato group, and is preferably a compound having two or more blocked isocyanato groups in one molecule from the viewpoint of curability. .

此外，本發明中的所謂嵌段異氰酸基，是指可藉由熱而生成異氰酸基的基團，例如，較佳為可例示使嵌段劑與異氰酸基反應來保護異氰酸基的基團。另外，上述嵌段異氰酸基較佳為可藉由90℃~250℃的熱而生成異氰酸基的基團。 Further, the term "block isocyanate group" in the present invention means a group which can form an isocyanate group by heat. For example, it is preferred to exemplify a reaction between a block agent and an isocyanate group to protect the difference. a group of cyanate groups. Further, the block isocyanate group is preferably a group which can form an isocyanate group by heat of from 90 ° C to 250 ° C.

另外，嵌段異氰酸酯化合物對其骨架並無特別限定，只要是1分子中具有2個異氰酸基者，則可為任意者，宜為脂肪族、脂環族或者芳香族的聚異氰酸酯，例如適宜使用：2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、異佛爾酮二異氰酸酯、1,6-六亞甲基二異氰酸酯、1,3-三亞甲基二異氰酸酯、1,4-四亞甲基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯、1,9-九亞甲基二異氰酸酯、1,10-十亞甲基二異氰酸酯、1,4-環己烷二異氰酸酯、2,2'-二乙醚二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯、鄰二甲苯二異氰酸酯、間二甲苯二異氰酸酯、對二甲苯二異氰酸酯、亞甲基雙(環己基異氰酸酯)、環己烷-1,3-二亞甲基二異氰酸酯、環己烷-1,4-二亞甲基二異氰酸酯、1,5-萘二異氰酸酯、對苯二異氰酸酯(p-phenylene diisocyanate)、3,3'-亞甲基二甲苯-4,4'-二異氰酸酯、4,4'-二苯醚二異氰酸酯、四氯伸苯基二異氰酸酯、降冰片烷二異氰酸酯、氫化1,3-苯二甲基二異氰酸酯、氫化1,4-苯二甲基二異氰酸酯等異氰酸酯化合物以及由該些化合物衍生的預聚物型骨架的化合物。該些化合物中，特佳為甲苯二異氰酸酯(tolylene diisocyanate，TDI)或二苯基甲烷二異氰酸酯 (diphenylmethane diisocyanate，MDI)、六亞甲基二異氰酸酯(hexamethylene diisocyanate，HDI)、異佛爾酮二異氰酸酯(isophorone diisocyanate，IPDI)。 Further, the blocked isocyanate compound is not particularly limited as long as it has two isocyanato groups in one molecule, and is preferably an aliphatic, alicyclic or aromatic polyisocyanate, for example. Suitable for use: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4 -tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate 1,10-Teethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate , m-xylene diisocyanate, p-xylene diisocyanate, methylene bis(cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene Diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene xylene-4,4'-diisocyanate Ester, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, hydrogenated 1,3-benzyldimethylisocyanate, hydrogenated 1,4-benzyldimethylisocyanate Isocyanate compounds and compounds of the prepolymer type backbone derived from such compounds. Among these compounds, particularly preferred is tolylene diisocyanate (TDI) or diphenylmethane diisocyanate. (diphenylmethane diisocyanate, MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI).

本發明的感光性樹脂組成物中的嵌段異氰酸酯化合物的母結構可列舉：縮二脲(biuret)型、異三聚氰酸酯(isocyanurate)型、加合物(adduct)型、2官能預聚物型等。 The parent structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention may be a biuret type, an isocyanurate type, an adduct type or a bifunctional type. Polymer type, etc.

形成上述嵌段異氰酸酯化合物的嵌段結構的嵌段劑可列舉：肟化合物、內醯胺化合物、酚化合物、醇化合物、胺化合物、活性亞甲基化合物、吡唑化合物、硫醇化合物、咪唑系化合物、醯亞胺系化合物等。該些化合物中，特佳為選自肟化合物、內醯胺化合物、酚化合物、醇化合物、胺化合物、活性亞甲基化合物、吡唑化合物中的嵌段劑。 Examples of the block forming the block structure of the above-mentioned blocked isocyanate compound include an anthracene compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a thiol compound, and an imidazole system. a compound, a quinone imine compound, or the like. Among these compounds, a block agent selected from the group consisting of an anthracene compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferred.

上述肟化合物可列舉肟、以及酮肟，具體而言可例示：丙酮肟(acetoxime)、甲醛肟(formaldoxime)、環己烷肟、甲基乙基酮肟、環己酮肟、二苯甲酮肟等。 Examples of the above hydrazine compound include hydrazine and ketoxime, and specific examples thereof include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketoxime, cyclohexanone oxime, and benzophenone. Hey.

上述內醯胺化合物可例示：ε-己內醯胺、γ-丁內醯胺等。 The above-mentioned indoleamine compound can be exemplified by ε-caprolactam, γ-butylide or the like.

上述酚化合物可例示：苯酚、萘酚、甲酚、二甲酚、經鹵素取代的苯酚等。 The phenol compound may, for example, be phenol, naphthol, cresol, xylenol or halogen-substituted phenol.

上述醇化合物可例示：甲醇、乙醇、丙醇、丁醇、環己醇、乙二醇單烷基醚、丙二醇單烷基醚、乳酸烷基酯等。 The alcohol compound may, for example, be methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether or alkyl lactate.

作為上述胺化合物，可列舉1級胺以及2級胺，可為芳 香族胺、脂肪族胺、脂環族胺的任一種，可例示：苯胺、二苯基胺、伸乙基亞胺、聚伸乙基亞胺(polyethyleneimine)等。 Examples of the above amine compound include a primary amine and a secondary amine, which may be aromatic. Any of an aromatic amine, an aliphatic amine, and an alicyclic amine may, for example, be aniline, diphenylamine, ethylenimine or polyethyleneimine.

上述活性亞甲基化合物可例示：丙二酸二乙酯、丙二酸二甲酯、乙醯乙酸乙酯、乙醯乙酸甲酯等。 The active methylene compound may, for example, be diethyl malonate, dimethyl malonate, ethyl acetate or ethyl acetate.

上述吡唑化合物可例示：吡唑、甲基吡唑、二甲基吡唑等。 The above pyrazole compound can be exemplified by pyrazole, methylpyrazole, dimethylpyrazole and the like.

上述硫醇化合物可例示：烷基硫醇、芳基硫醇等。 The above thiol compound can be exemplified by an alkylthiol, an arylthiol or the like.

本發明的感光性樹脂組成物中可使用的嵌段異氰酸酯化合物可作為市售品而獲取，例如較佳為可使用：Coronate AP Stable M、Coronate 2503、Coronate 2515、Coronate 2507、Coronate 2513、Coronate 2555、Millionate MS-50(以上由日本聚胺基甲酸酯工業(Nippon Polyurethane Industry)(股)製造)、Takenate B-830、Takenate B-815N、Takenate B-820NSU、Takenate B-842N、Takenate B-846N、Takenate B-870N、Takenate B-874N、Takenate B-882N(以上由三井化學(股)製造)、Duranate 17B-60PX、Duranate 17B-60P、Duranate TPA-B80X、Duranate TPA-B80E、Duranate MF-B60X、Duranate MF-B60B、Duranate MF-K60X、Duranate MF-K60B、Duranate E402-B80B、Duranate SBN-70D、Duranate SBB-70P、Duranate K6000(以上由旭化成化學(股)製造)、Desmodur BL1100、Desmodur BL1265 MPA/X、Desmodur BL3575/1、Desmodur BL3272MPA、Desmodur BL3370MPA、 Desmodur BL3475BA/SN、Desmodur BL5375MPA、Desmodur VPLS2078/2、Desmodur BL4265SN、Desmodur PL340、Desmodur PL350、Sumidur BL3175(以上由住化拜耳胺基甲酸酯(Sumika Bayer Urethane)(股)製造)等。 The blocked isocyanate compound which can be used in the photosensitive resin composition of the present invention can be obtained as a commercial product, and for example, Coronate AP Stable M, Coronate 2503, Coronate 2515, Coronate 2507, Coronate 2513, Coronate 2555 can be preferably used. , Millionate MS-50 (above made by Nippon Polyurethane Industry), Takenate B-830, Takenate B-815N, Takenate B-820NSU, Takenate B-842N, Takenate B- 846N, Takenate B-870N, Takenate B-874N, Takenate B-882N (above manufactured by Mitsui Chemicals Co., Ltd.), Duranate 17B-60PX, Duranate 17B-60P, Duranate TPA-B80X, Duranate TPA-B80E, Duranate MF- B60X, Duranate MF-B60B, Duranate MF-K60X, Duranate MF-K60B, Duranate E402-B80B, Duranate SBN-70D, Duranate SBB-70P, Duranate K6000 (above manufactured by Asahi Kasei Chemicals Co., Ltd.), Desmodur BL1100, Desmodur BL1265 MPA/X, Desmodur BL3575/1, Desmodur BL3272MPA, Desmodur BL3370MPA, Desmodur BL3475BA/SN, Desmodur BL5375MPA, Desmodur VPLS2078/2, Desmodur BL4265SN, Desmodur PL340, Desmodur PL350, Sumidur BL3175 (above manufactured by Sumika Bayer Urethane).

(G)增感劑 (G) sensitizer

本發明的感光性樹脂組成物在與(B)光酸產生劑的組合中，為了促進其分解，較佳為含有增感劑。增感劑吸收光化射線或者放射線而成為電子激發狀態。成為電子激發狀態的增感劑與光酸產生劑接觸而產生電子轉移、能量轉移、發熱等作用。藉此，光酸產生劑產生化學變化而分解，生成酸。較佳的增感劑的例子可列舉屬於以下化合物類，且於350nm至450nm的波長區域的任一波長下具有吸收波長的化合物。 In combination with the (B) photoacid generator, the photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote decomposition thereof. The sensitizer absorbs actinic rays or radiation and becomes an electronically excited state. The sensitizer that is in an electronically excited state is brought into contact with the photoacid generator to cause electron transfer, energy transfer, heat generation, and the like. Thereby, the photoacid generator generates a chemical change to decompose and generate an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength at any wavelength in the wavelength region of 350 nm to 450 nm.

多核芳香族類(例如：芘(pyrene)、苝(perylene)、聯伸三苯、蒽、9,10-二丁氧基蒽、9,10-二乙氧基蒽、3,7-二甲氧基蒽、9,10-二丙氧基蒽)、二苯并哌喃(xanthene)類(例如：螢光素(fluorescein)、曙紅(eosin)、赤蘚紅(erythrosine)、玫瑰紅B(rhodamine B)、孟加拉玫瑰紅(rose bengal))、氧雜蒽酮(xanthone)類(例如：氧雜蒽酮、硫雜蒽酮(thioxanthone)、二甲硫雜蒽酮、二乙硫雜蒽酮)、花青(cyanine)類(例如：硫雜羰花青(thiacarbocyanine)、氧雜羰花青(oxacarbocyanine))、部花青(merocyanine)類(例如：部花青、羰部花青 (carbomerocyanine))、若丹菁(rhodacyanine)類、氧雜菁(oxonol)類、噻嗪(thiazine)類(例如：噻嚀(thionine)、亞甲藍(methylene blue)、甲苯胺藍(toluidine blue))、吖啶(acridine)類(例如：吖啶橙(acridine orange)、氯黃素(chloroflavin)、吖啶黃素(acriflavine))、吖啶酮(acridone)類(例如：吖啶酮、10-丁基-2-氯吖啶酮)、蒽醌(anthraquinone)類(例如：蒽醌)、酸化合物(squarylium)類(例如：方酸化合物)、苯乙烯基類、鹼性苯乙烯基類(例如：2-[2-[4-(二甲基胺基)苯基]乙烯基]苯并噁唑)、香豆素(coumarin)類(例如：7-二乙胺基-4-甲基香豆素、7-羥基-4-甲基香豆素、2,3,6,7-四氫-9-甲基-1H,5H,11H[1]苯并吡喃並[6,7,8-ij]喹嗪-11-酮)。 Polynuclear aromatics (eg, pyrene, perylene, extended triphenyl, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxy Base, 9,10-dipropoxypurine, xanthene (eg fluorescein, eosin, erythrosine, rose B) Rhodamine B), rose bengal, xanthone (eg xanthonesone, thioxanthone, dimethylthiazolone, dithionone) ), cyanine (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (eg, merocyanine, carbonyl cyclamate) (carbomerocyanine)), rhodacyanine, oxonol, thiazine (eg, thionine, methylene blue, toluidine blue) )), acridine (for example: acridine orange, chloroflavin, acriflavine), acridonone (eg acridone, 10-butyl-2-chloroacridone), anthraquinone (eg, hydrazine), squarylium (eg, squaraine), styryl, basic styryl Classes (eg, 2-[2-[4-(dimethylamino)phenyl]vinyl]benzoxazole), coumarin (eg, 7-diethylamino-4- Methyl coumarin, 7-hydroxy-4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H[1]benzopyrano[6, 7,8-ij] quinolizin-11-one).

該些增感劑中，較佳為多核芳香族類、吖啶酮類、苯乙烯基類、鹼性苯乙烯基類、香豆素類，更佳為多核芳香族類。多核芳香族類中最佳為蒽衍生物。 Among these sensitizers, polynuclear aromatics, acridones, styrenes, basic styrenes, and coumarins are preferred, and polynuclear aromatics are more preferred. Among the polynuclear aromatics, the most preferred is an anthracene derivative.

相對於感光性樹脂組成物的光酸產生劑100質量份，本發明的感光性樹脂組成物中的增感劑的添加量較佳為0質量份~1000質量份，更佳為10質量份~500質量份，尤佳為50質量份~200質量份。 The amount of the sensitizer added to the photosensitive resin composition of the present invention is preferably from 0 part by mass to 1000 parts by mass, more preferably 10 parts by mass, based on 100 parts by mass of the photoacid generator of the photosensitive resin composition. 500 parts by mass, particularly preferably 50 parts by mass to 200 parts by mass.

亦可併用2種以上。 Two or more types may be used in combination.

(H)其他鹼性化合物 (H) other basic compounds

本發明的感光性樹脂組成物除了含有上述通式(S)所 表示的化合物以外，可更含有(H)鹼性化合物。(H)鹼性化合物可自化學增幅抗蝕劑所使用者中任意選擇來使用。例如可列舉：脂肪族胺、芳香族胺、雜環式胺、氫氧化四級銨、羧酸的四級銨鹽等。該些化合物的具體例可列舉日本專利特開2011-221494號公報的段落編號0204~段落編號0207中記載的化合物，該些內容併入本申請案說明書中。 The photosensitive resin composition of the present invention contains the above formula (S) In addition to the compound shown, (H) a basic compound may be further contained. (H) The basic compound can be arbitrarily selected from the users of the chemical amplification resist. For example, an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, a quaternary ammonium salt of a carboxylic acid, etc. are mentioned. Specific examples of such a compound include the compounds described in Paragraph No. 0204 to Paragraph No. 0207 of JP-A-2011-221494, the contents of which are incorporated herein by reference.

本發明中可使用的鹼性化合物可單獨使用1種，亦可併用2種以上。 The basic compound which can be used in the present invention may be used alone or in combination of two or more.

於包含其他鹼性化合物的情況下，相對於感光性樹脂組成物中的總固體成分100質量份，本發明的感光性樹脂組成物中的(H)其他鹼性化合物的含量較佳為0.001質量份~3質量份，更佳為0.005質量份~1質量份。然而，本發明的感光性樹脂組成物由於包含通式(S)所表示的化合物，故而亦可設為實質上不含其他鹼性化合物的態樣。 In the case where the other basic compound is contained, the content of the (H) other basic compound in the photosensitive resin composition of the present invention is preferably 0.001 by mass based on 100 parts by mass of the total solid content in the photosensitive resin composition. It is preferably 3 parts by mass, more preferably 0.005 parts by mass to 1 part by mass. However, since the photosensitive resin composition of the present invention contains a compound represented by the general formula (S), it may be substantially free from other basic compounds.

(I)界面活性劑 (I) surfactant

本發明的感光性樹脂組成物亦可含有(I)界面活性劑。(I)界面活性劑可使用陰離子系、陽離子系、非離子系、或者兩性中的任一種，較佳的界面活性劑為非離子界面活性劑。 The photosensitive resin composition of the present invention may further contain (I) a surfactant. (I) The surfactant may be any of an anionic, cationic, nonionic or amphoteric surfactant, and a preferred surfactant is a nonionic surfactant.

非離子系界面活性劑的例子可列舉：聚氧乙烯高級烷基醚類、聚氧乙烯高級烷基苯基醚類、聚氧乙二醇的高級脂肪酸二酯類、矽酮系、氟系界面活性劑。另外，可列舉以下商品名：KP (信越化學工業(股)製造)、Polyflow(共榮社化學(股)製造)、Eftop(三菱材料電子化成(JEMCO)公司製造)、Megafac(迪愛生(股)製造)、Fluorad(住友3M(股)製造)、Asahi Guard、Surflon(旭硝子(股)製造)、PolyFox(歐諾法(OMNOVA)公司製造)、SH-8400(東麗道康寧矽酮(Toray Dow Corning Silicone))等各系列。 Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, anthrone series, and fluorine interface. Active agent. In addition, the following product names are listed: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), Eftop (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Megafac (Di Aisheng) ) Manufacturing), Fluorad (manufactured by Sumitomo 3M), Asahi Guard, Surflon (made by Asahi Glass), PolyFo x (made by OMNOVA), SH-8400 (Toray Dow Corning (Toray) Dow Corning Silicone)) and other series.

另外，界面活性劑可列舉如下共聚物作為較佳例，該共聚物包含下述通式(I-1)所表示的構成單元A以及構成單元B，且利用將四氫呋喃(tetrahydrofuran，THF)作為溶劑的情況下的凝膠滲透層析法進行測定而得的聚苯乙烯換算的重量平均分子量(Mw)為1,000以上、10,000以下。 Further, the surfactant is preferably a copolymer comprising the constituent unit A represented by the following formula (I-1) and the constituent unit B, and using tetrahydrofuran (THF) as a solvent. The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography in the case of the measurement is 1,000 or more and 10,000 or less.

(式(I-1)中，R401及R403分別獨立地表示氫原子或者甲基，R402表示碳數1以上、4以下的直鏈伸烷基，R404表示氫原子或者碳數1以上、4以下的烷基，L表示碳數3以上、6以下的伸烷基， p及q是表示聚合比的質量百分率，p表示10質量%以上、80質量%以下的數值，q表示20質量%以上90質量%以下的數值，r表示1以上、18以下的整數，s表示1以上、10以下的整數。) (In the formula (I-1), R 401 and R 403 each independently represent a hydrogen atom or a methyl group, R 402 represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R 404 represents a hydrogen atom or a carbon number of 1; In the above alkyl group, 4 or less, L represents an alkylene group having 3 or more and 6 or less carbon atoms, p and q are mass percentages indicating a polymerization ratio, and p is a numerical value of 10% by mass or more and 80% by mass or less, and q is 20. A numerical value of 90% by mass or more, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less.)

上述L較佳為下述通式(I-2)所表示的分支伸烷基。通式(I-2)中的R405表示碳數1以上、4以下的烷基，就相容性及對被塗佈面的潤濕性的方面而言，較佳為碳數1以上、3以下的烷基，更佳為碳數2或3的烷基。p與q之和(p+q)較佳為p+q=100，即100質量%。 The above L is preferably a branched alkyl group represented by the following formula (I-2). R 405 in the formula (I-2) represents an alkyl group having 1 or more and 4 or less carbon atoms, and preferably has a carbon number of 1 or more in terms of compatibility and wettability to a surface to be coated. An alkyl group of 3 or less is more preferably an alkyl group having 2 or 3 carbon atoms. The sum of p and q (p+q) is preferably p+q=100, that is, 100% by mass.

上述共聚物的重量平均分子量(Mw)更佳為1,500以上、5,000以下。 The weight average molecular weight (Mw) of the above copolymer is more preferably 1,500 or more and 5,000 or less.

該些界面活性劑可單獨使用1種或者將2種以上混合使用。 These surfactants may be used alone or in combination of two or more.

相對於感光性樹脂組成物中的總固體成分100質量份，本發明的感光性樹脂組成物中的(I)界面活性劑的添加量較佳為10質量份以下，更佳為0.001質量份~10質量份，尤佳為0.01質量份~3質量份。 The amount of the (I) surfactant added to the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, more preferably 0.001 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition. 10 parts by mass, particularly preferably 0.01 parts by mass to 3 parts by mass.

(J)抗氧化劑 (J) Antioxidants

本發明的感光性樹脂組成物可含有抗氧化劑。作為抗氧化劑，可含有公知的抗氧化劑。藉由添加抗氧化劑而具有以下優點：可防止硬化膜的著色，或者可降低由分解引起的膜厚減少，另外，耐熱透明性優異。 The photosensitive resin composition of the present invention may contain an antioxidant. As the antioxidant, a known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or reduction in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.

此種抗氧化劑例如可列舉：磷系抗氧化劑、醯胺類、醯肼類、受阻胺系抗氧化劑、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。該些化合物中，就硬化膜的著色、膜厚減少的觀點而言，特佳為酚系抗氧化劑、醯胺系抗氧化劑、醯肼系抗氧化劑、硫系抗氧化劑。該些化合物可單獨使用1種，或將2種以上混合。 Examples of such an antioxidant include phosphorus-based antioxidants, guanamines, guanidines, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, ascorbic acid, zinc sulfate, saccharides, nitrites, and sub- Sulfate, thiosulfate, hydroxylamine derivative, and the like. Among these compounds, a phenolic antioxidant, a guanamine antioxidant, a lanthanoid antioxidant, and a sulfur-based antioxidant are particularly preferable from the viewpoint of coloring and film thickness reduction of the cured film. These compounds may be used alone or in combination of two or more.

酚系抗氧化劑的市售品例如可列舉：Adekastab AO-15、Adekastab AO-18、Adekastab AO-20、Adekastab AO-23、Adekastab AO-30、Adekastab AO-37、Adekastab AO-40、Adekastab AO-50、Adekastab AO-51、Adekastab AO-60、Adekastab AO-70、Adekastab AO-80、Adekastab AO-330、Adekastab AO-412S、Adekastab AO-503、Adekastab A-611、Adekastab A-612、Adekastab A-613、Adekastab PEP-4C、Adekastab PEP-8、Adekastab PEP-8W、Adekastab PEP-24G、Adekastab PEP-36、Adekastab PEP-36Z、Adekastab HP-10、Adekastab 2112、Adekastab 260、Adekastab 522A、Adekastab 1178、Adekastab 1500、Adekastab C、Adekastab 135A、Adekastab 3010、Adekastab TPP、Adekastab CDA-1、Adekastab CDA-6、Adekastab ZS-27、Adekastab ZS-90、Adekastab ZS-91(以上由艾迪科(股)製造)、Irganox 245FF、Irganox 1010FF、Irganox 1010、Irganox MD1024、Irganox 1035FF、Irganox 1035、Irganox 1098、Irganox 1330、Irganox 1520L、Irganox 3114、Irganox 1726、Irgafos 168、Irgamod 295(巴斯夫(股)製造)等。其中，可適宜使用Adekastab AO-60、Adekastab AO-80、Irganox 1726、Irganox 1035、Irganox 1098。 Commercial products of phenolic antioxidants include, for example, Adekastab AO-15, Adekastab AO-18, Adekastab AO-20, Adekastab AO-23, Adekastab AO-30, Adekastab AO-37, Adekastab AO-40, Adekastab AO- 50. Adekastab AO-51, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-330, Adekastab AO-412S, Adekastab AO-503, Adekastab A-611, Adekastab A-612, Adekastab A- 613, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-8W, Adekastab PEP-24G, Adekastab PEP-36, Adekastab PEP-36Z, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP, Adekastab CDA-1, Adekastab CDA-6, Adekastab ZS-27, Adekastab ZS-90, Adekastab ZS-91 (above manufactured by Eddy Co., Ltd.), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (manufactured by BASF), and the like. Among them, Adekastab AO-60, Adekastab AO-80, Irganox 1726, Irganox 1035, Irganox 1098 can be suitably used.

相對於感光性樹脂組成物的總固體成分，抗氧化劑的含量較佳為0.1質量%~10質量%，更佳為0.2質量%~5質量%，特佳為0.5質量%~4質量%。藉由設為該範圍，而獲得所形成的膜的充分透明性，且圖案形成時的感度亦變得良好。 The content of the antioxidant is preferably from 0.1% by mass to 10% by mass, more preferably from 0.2% by mass to 5% by mass, even more preferably from 0.5% by mass to 4% by mass based on the total solid content of the photosensitive resin composition. By setting it as this range, the transparency of the formed film is acquired, and the sensitivity at the time of pattern formation also becomes favorable.

另外，作為抗氧化劑以外的添加劑，亦可將「高分子添加劑的新展開(日刊工業新聞社(股))」中記載的各種紫外線吸收劑、或金屬鈍化劑等添加於本發明的感光性樹脂組成物中。 In addition, as the additive other than the antioxidant, various ultraviolet absorbers, metal passivators, and the like described in "New Development of Polymer Additives" (Nikkei Kogyo Co., Ltd.) may be added to the photosensitive resin of the present invention. In the composition.

[酸增殖劑] [acid proliferator]

本發明的感光性樹脂組成物可出於提高感度的目的而使用酸增殖劑。 The photosensitive resin composition of the present invention can use an acid multiplier for the purpose of improving sensitivity.

本發明中可使用的酸增殖劑是可藉由酸觸媒反應而進一步產生酸，使反應系統內的酸濃度上升的化合物，是於不存在酸的狀態下穩定存在的化合物。此種化合物由於藉由1次反應而 增加1個以上的酸，故而隨著反應的進行而加速進行反應，但由於所產生的酸自身引起自我分解，故而此處所產生的酸的強度以酸解離常數、pKa計，較佳為3以下，特佳為2以下。 The acid multiplying agent which can be used in the present invention is a compound which can further generate an acid by an acid catalyst reaction and raise the acid concentration in the reaction system, and is a compound which is stably present in the absence of an acid. This compound is due to one reaction When one or more acids are added, the reaction proceeds as the reaction progresses. However, since the generated acid itself causes self-decomposition, the strength of the acid generated here is preferably 3 or less in terms of acid dissociation constant and pKa. , especially good for 2 or less.

酸增殖劑的具體例可列舉：日本專利特開平10-1508號公報的段落編號0203~段落編號0223、日本專利特開平10-282642號公報的段落編號0016~段落編號0055、以及日本專利特表平9-512498號公報第39頁第12行~第47頁第2行中記載的化合物，該些內容併入本申請案說明書中。 Specific examples of the acid-proliferating agent include paragraph number 0203 to paragraph number 0223 of JP-A-10-1508, paragraph number 0016 to paragraph number 0055 of Japanese Patent Laid-Open No. Hei 10-282642, and Japanese Patent Special Table. The compounds described in Japanese Patent Publication No. Hei 9-512498, page 39, line 12 to page 47, line 2, are incorporated herein by reference.

本發明中可使用的酸增殖劑可列舉利用由酸產生劑產生的酸而分解，產生二氯乙酸、三氯乙酸、甲磺酸、苯磺酸、三氟甲磺酸、苯基膦酸等pKa為3以下的酸的化合物。 The acid multiplying agent which can be used in the present invention is decomposed by using an acid generated by an acid generator to produce dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, phenylphosphonic acid, or the like. A compound having an acid having a pKa of 3 or less.

具體而言可列舉： Specifically, it can be enumerated:

等。 Wait.

就曝光部與未曝光部的溶解對比度的觀點而言，相對於光酸產生劑100質量份，酸增殖劑於感光性組成物中的含量較佳為設為10質量份~1,000質量份，尤佳為設為20質量份~500質量份。 The content of the acid-proliferating agent in the photosensitive composition is preferably from 10 parts by mass to 1,000 parts by mass, based on 100 parts by mass of the photo-acid generator, from the viewpoint of the dissolution ratio of the exposed portion and the unexposed portion. The optimum is set to 20 parts by mass to 500 parts by mass.

[顯影促進劑] [development accelerator]

本發明的感光性樹脂組成物可含有顯影促進劑。 The photosensitive resin composition of the present invention may contain a development accelerator.

顯影促進劑可參考日本專利特開2012-042837號公報的段落編號0171~段落編號0172的記載，該內容併入本申請案說明書中。 The development accelerator can be referred to the description of Paragraph No. 0171 to Paragraph No. 0172 of Japanese Patent Laid-Open No. 2012-042837, which is incorporated herein by reference.

顯影促進劑可單獨使用1種，亦可將2種以上併用。 One type of the development accelerator may be used alone or two or more types may be used in combination.

就感度與殘膜率的觀點而言，相對於感光性組成物的總固體成分100質量份，本發明的感光性樹脂組成物中的顯影促進劑的添加量較佳為0質量份~30質量份，更佳為0.1質量份~20質量份，最佳為0.5質量份~10質量份。 From the viewpoint of the sensitivity and the residual film ratio, the amount of the development accelerator added to the photosensitive resin composition of the present invention is preferably from 0 to 30 mass% per 100 parts by mass of the total solid content of the photosensitive composition. The portion is more preferably 0.1 part by mass to 20 parts by mass, most preferably 0.5 part by mass to 10 parts by mass.

另外，其他添加劑亦可使用日本專利特開2012-8223號公報的段落編號0120~段落編號0121中記載的熱自由基產生劑、WO2011/136074A1中記載的含氮化合物以及熱酸產生劑，該些內容併入本申請案說明書中。 In addition, as the other additive, the thermal radical generating agent described in Paragraph No. 0120 to Paragraph No. 0121 of JP-A-2012-8223, the nitrogen-containing compound described in WO2011/136074A1, and a thermal acid generator may be used. The content is incorporated into the specification of the present application.

<感光性樹脂組成物的製備方法> <Method for Preparing Photosensitive Resin Composition>

以規定的比例且利用任意方法將各成分混合，攪拌溶解而製備感光性樹脂組成物。例如亦可將成分分別預先溶解於溶劑中而製成溶液後，將該些溶液以規定的比例混合而製備樹脂組成物。以上述方式製備的組成物溶液亦可使用孔徑為0.2μm的過濾器等進行過濾後，供於使用。 The components are mixed at a predetermined ratio and by any method, and stirred and dissolved to prepare a photosensitive resin composition. For example, after the components are each dissolved in a solvent to prepare a solution, the solutions are mixed at a predetermined ratio to prepare a resin composition. The composition solution prepared in the above manner can also be used after being filtered using a filter having a pore size of 0.2 μm or the like.

[硬化膜的製造方法] [Method for producing cured film]

繼而，對本發明的硬化膜的製造方法進行說明。 Next, a method of producing the cured film of the present invention will be described.

本發明的硬化膜的製造方法較佳為包括以下的(1)~(5)的步驟。 The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).

(1)將本發明的感光性樹脂組成物塗佈於基板上的步驟；(2)自所塗佈的感光性樹脂組成物中去除溶劑的步驟；(3)利用光化射線對去除了溶劑的感光性樹脂組成物進行曝光的步驟；(4)利用水性顯影液對經曝光的感光性樹脂組成物進行顯影的步驟；(5)對經顯影的感光性樹脂組成物進行熱硬化的後烘烤步驟。 (1) a step of applying the photosensitive resin composition of the present invention onto a substrate; (2) a step of removing a solvent from the applied photosensitive resin composition; and (3) removing a solvent by an actinic ray pair a step of exposing the photosensitive resin composition; (4) a step of developing the exposed photosensitive resin composition with an aqueous developing solution; (5) post-baking for thermally curing the developed photosensitive resin composition Baking steps.

以下對各步驟依次進行說明。 Each step will be described in order below.

(1)的塗佈步驟中，較佳為將本發明的感光性樹脂組成物塗佈於基板上而製成包含溶劑的濕潤膜。較佳為於將感光性樹脂組成物塗佈於基板上之前進行鹼清洗或電漿清洗等基板的清洗，更佳為於基板清洗後進而以六甲基二矽氮烷對基板表面進行處理。藉由進行該處理，存在感光性樹脂組成物對基板的密接性提高的傾向。以六甲基二矽氮烷對基板表面進行處理的方法並無特別限定，例如可列舉事先將基板曝露於六甲基二矽氮烷蒸氣中的方法等。 In the coating step of (1), it is preferred to apply the photosensitive resin composition of the present invention onto a substrate to form a wet film containing a solvent. It is preferred to perform cleaning of the substrate such as alkali cleaning or plasma cleaning before applying the photosensitive resin composition onto the substrate, and it is more preferable to treat the surface of the substrate with hexamethyldiaziridine after the substrate is cleaned. By performing this treatment, the adhesion of the photosensitive resin composition to the substrate tends to be improved. The method of treating the surface of the substrate with hexamethyldioxane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldioxane vapor in advance.

上述基板可列舉無機基板、樹脂、樹脂複合材料等。 Examples of the substrate include an inorganic substrate, a resin, a resin composite material, and the like.

無機基板例如可列舉：玻璃、石英、矽酮、氮化矽，以及於如上所述的基板上蒸鍍有鉬、鈦、鋁、銅等的複合基板。 Examples of the inorganic substrate include glass, quartz, anthrone, and tantalum nitride, and a composite substrate obtained by depositing molybdenum, titanium, aluminum, copper, or the like on the substrate as described above.

作為樹脂，可列舉包含：聚對苯二甲酸丁二酯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二酯、聚苯乙烯、聚碳酸酯、聚碸、聚醚碸、聚芳酯、烯丙基二醇碳酸酯、聚醯胺、聚醯亞胺、聚醯胺醯亞胺、聚醚醯亞胺、聚苯并唑(polybenzazole)、聚苯硫醚、聚環烯烴、降冰片烯樹脂、聚氯三氟乙烯等氟樹脂、液晶聚合物、丙烯酸樹脂、環氧樹脂、矽酮樹脂、離子聚合物樹脂、氰酸酯樹脂、交聯反丁烯二酸二酯、環狀聚烯烴、芳香族醚、順丁烯二醯亞胺-烯烴、纖維素、環硫化物(episulfide)化合物等合成樹脂的基板。 Examples of the resin include: polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, and poly Bismuth, polyether oxime, polyarylate, allyl diol carbonate, polyamine, polyimide, polyamidimide, polyether phthalimide, polybenzazole, polyphenylene Fluoroether, polycycloolefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, fluorenone resin, ionic polymer resin, cyanate resin, cross-linked anti-butyl A substrate of a synthetic resin such as an enedic acid diester, a cyclic polyolefin, an aromatic ether, a maleimide-olefin, a cellulose, or an episulfide compound.

該些基板以上述形態直接使用的情況少，通常藉由最終製品的形態而形成例如薄膜電晶體(Thin Film Transistor，TFT)元件之類的多層積層結構。 These substrates are rarely used as they are in the above-described form, and a multilayer laminated structure such as a thin film transistor (TFT) element is usually formed by the form of the final product.

對基板的塗佈方法並無特別限定，例如可使用：狹縫塗佈法、噴射法、輥塗佈法、旋轉塗佈法、流延塗佈法、狹縫及旋轉法(slit-and-spin method)等方法。進而，亦可應用如日本專利特開2009-145395號公報中記載的所謂預濕法(pre-wet method)。 The method of applying the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a cast coating method, a slit, and a spin method (slit-and- Spin method) and other methods. Further, a so-called pre-wet method described in Japanese Laid-Open Patent Publication No. 2009-145395 can also be applied.

應用時的濕式膜厚並無特別限定，能夠以根據用途的膜厚來塗佈，通常以0.5μm~10μm的範圍使用。 The wet film thickness at the time of application is not particularly limited, and it can be applied in accordance with the film thickness of the application, and is usually used in the range of 0.5 μm to 10 μm.

(2)的溶劑去除步驟中，藉由減壓(真空)及/或加熱， 自所應用的上述膜上去除溶劑而於基板上形成乾燥塗膜。溶劑去除步驟的加熱條件較佳為70℃~130℃且30秒~300秒左右。於溫度及時間為上述範圍的情況下，存在圖案的密接性更良好，且殘渣亦可進一步減少的傾向。 In the solvent removal step of (2), by depressurization (vacuum) and/or heating, A dry coating film is formed on the substrate by removing the solvent from the above applied film. The heating condition in the solvent removal step is preferably from 70 ° C to 130 ° C and from about 30 seconds to about 300 seconds. When the temperature and time are in the above range, the adhesion of the pattern is further improved, and the residue tends to be further reduced.

(3)的曝光步驟中，對設置有塗膜的基板，隔著具有規定圖案的遮罩來照射光化射線。該步驟中，光酸產生劑分解而產生酸。利用所產生的酸的觸媒作用，塗膜成分中所含的酸分解性基被水解而生成羧基或者酚性羥基。 In the exposure step of (3), the substrate on which the coating film is provided is irradiated with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. The acid-decomposable group contained in the coating film component is hydrolyzed by the catalytic action of the generated acid to form a carboxyl group or a phenolic hydroxyl group.

藉由光化射線的曝光光源可使用：低壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、發光二極體(light emitting diode，LED)光源、準分子雷射產生裝置等，可較佳地使用g射線(436nm)，i射線(365nm)、h射線(405nm)等具有波長300nm以上、450nm以下的波長的光化射線。另外，視需要亦可通過長波長截止濾波器、短波長截止濾波器、帶通濾波器(band pass filter)之類的分光濾波器來調整照射光。 The exposure light source by actinic ray can be used: a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generating device, etc., which can be preferably used. An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as g-ray (436 nm), i-ray (365 nm), and h-ray (405 nm). Further, the illumination light may be adjusted by a long-wavelength cut filter, a short-wavelength cut filter, or a band pass filter such as a band pass filter as needed.

曝光裝置可使用：鏡面投影對準曝光器(mirror projection aligner)、步進器(stepper)、掃描器(scanner)，近接式(proximity)、接觸式(contact)、微透鏡陣列(microlens array)、雷射曝光等各種方式的曝光機。 The exposure device can be used: a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, Various types of exposure machines such as laser exposure.

於生成有酸觸媒的區域，為了加快上述水解反應，可進行曝光後加熱處理：曝光後烘烤(Post Exposure Bake)(以下亦稱 為「PEB」)。藉由PEB，可促進由酸分解性基生成羧基或者酚性羥基。進行PEB的情況下的溫度較佳為30℃以上、130℃以下，更佳為40℃以上、110℃以下，特佳為50℃以上、100℃以下。 In the area where the acid catalyst is formed, in order to accelerate the above hydrolysis reaction, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as It is "PEB"). By PEB, it is possible to promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature in the case of performing 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 100° C. or lower.

其中，本發明中的酸分解性基由於酸分解的活化能量低，容易因由曝光所產生的源自酸產生劑的酸而分解，產生羧基或者酚性羥基，故而亦可不必進行PEB，而藉由顯影來形成正影像。 In particular, the acid-decomposable group in the present invention has a low activation energy due to acid decomposition, and is easily decomposed by an acid derived from an acid generator generated by exposure to produce a carboxyl group or a phenolic hydroxyl group, so that it is not necessary to carry out PEB. A positive image is formed by development.

(4)的顯影步驟中，使用鹼性顯影液將具有游離的羧基或酚性羥基的聚合物進行顯影。藉由將包含具有容易溶解於鹼性顯影液中的羧基或者酚性羥基的樹脂組成物的曝光部區域去除，而形成正影像。 In the developing step of (4), a polymer having a free carboxyl group or a phenolic hydroxyl 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 or a phenolic hydroxyl group which is easily dissolved in an alkaline developing solution.

顯影步驟中使用的顯影液中較佳為包含鹼性化合物。鹼性化合物例如可使用：氫氧化鋰、氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物類；碳酸鈉、碳酸鉀等鹼金屬碳酸鹽類；碳酸氫鈉、碳酸氫鉀等鹼金屬碳酸氫鹽類；四甲基氫氧化銨、四乙基氫氧化銨、氫氧化膽鹼(choline hydroxide)等氫氧化銨類；矽酸鈉、偏矽酸鈉等的水溶液。另外，亦可將於上述鹼類的水溶液中添加有適量的甲醇或乙醇等水溶性有機溶劑或界面活性劑的水溶液用作顯影液。 The developer used in the developing step preferably contains a basic compound. 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; or an alkali metal hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate; Salt; ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline hydroxide; aqueous solution of sodium citrate or sodium metasilicate. Further, an aqueous solution of an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous solution of the above-mentioned alkali as a developing solution.

較佳的顯影液可列舉：四乙基氫氧化銨的0.4%水溶液、0.5%水溶液、0.7%水溶液、2.38%水溶液。 A preferred developing solution is a 0.4% aqueous solution of tetraethylammonium hydroxide, a 0.5% aqueous solution, a 0.7% aqueous solution, and a 2.38% aqueous solution.

顯影液的pH值較佳為10.0~14.0。 The pH of the developer is preferably from 10.0 to 14.0.

顯影時間較佳為30秒~500秒，另外，顯影的手法可為覆液法(puddle method)、浸漬法(dipping method)等的任一種。顯影後，通常可進行30秒~300秒的流水清洗，形成所需的圖案。顯影後，亦可進行淋洗步驟。淋洗步驟中，藉由以純水等對顯影後的基板進行清洗，而進行所附著的顯影液去除、顯影殘渣去除。淋洗方法可使用公知的方法。例如可列舉噴淋淋洗或浸漬淋洗等。 The development time is preferably from 30 seconds to 500 seconds, and the development method may be any one of a puddle method and a dipping method. After development, it is usually carried out by running water for 30 seconds to 300 seconds to form a desired pattern. After development, a rinsing step can also be performed. In the rinsing step, the developed substrate is cleaned by pure water or the like, and the adhered developer is removed and the development residue is removed. A known method can be used for the rinsing method. For example, spray rinsing, immersion rinsing, etc. are mentioned.

(5)的後烘烤步驟中，藉由對所得的正影像進行加熱，而將酸分解性基進行熱分解，生成羧基或者酚性羥基，與交聯性基、交聯劑等進行交聯，藉此可形成硬化膜。該加熱較佳為使用加熱板或烘箱等加熱裝置，於規定的溫度，例如180℃~250℃下，進行規定時間的加熱處理，例如若為加熱板上則進行5分鐘~90分鐘，若為烘箱則進行30分鐘~120分鐘。藉由進行此種交聯反應，可形成耐熱性、硬度等更優異的保護膜或層間絕緣膜。另外，進行加熱處理時藉由在氮氣環境下進行，亦可進一步提高透明性。 In the post-baking step of (5), the acid-decomposable group is thermally decomposed by heating the obtained positive image to form a carboxyl group or a phenolic hydroxyl group, and cross-linking with a crosslinkable group, a crosslinking agent, or the like. Thereby, a cured film can be formed. Preferably, the heating is performed by a heating means such as a hot plate or an oven at a predetermined temperature, for example, 180 ° C to 250 ° C, for a predetermined period of time, for example, 5 minutes to 90 minutes on a hot plate, if The oven is carried out for 30 minutes to 120 minutes. By performing such a crosslinking reaction, a protective film or an interlayer insulating film which is more excellent in heat resistance and hardness can be formed. Further, the transparency can be further improved by performing the heat treatment in a nitrogen atmosphere.

於後烘烤之前，亦可於比較低的溫度下進行烘烤後進行後烘烤(中間烘烤步驟的追加)。於進行中間烘烤的情況下，較佳為於90℃~150℃下加熱1分鐘~60分鐘後，於200℃以上的高溫下進行後烘烤。另外，亦可將中間烘烤、後烘烤分成3階段以上的多階段來進行加熱。藉由如上所述的中間烘烤、後烘烤的操作，可調整圖案的錐角。該些加熱可使用加熱板、烘箱、紅外線加熱 器等公知的加熱方法。 Before baking, it is also possible to perform post-baking after baking at a relatively low temperature (addition of the intermediate baking step). In the case of performing intermediate baking, it is preferred to perform post-baking at a high temperature of 200 ° C or higher after heating at 90 ° C to 150 ° C for 1 minute to 60 minutes. Further, the intermediate baking and the post-baking may be divided into three or more stages to perform heating. The taper angle of the pattern can be adjusted by the intermediate baking and post-baking operations as described above. The heating can be done using a heating plate, an oven, or infrared heating. A known heating method such as a device.

此外，於後烘烤之前，利用光化射線對形成有圖案的基板進行全面再曝光(後曝光)後，進行後烘烤，藉此可由存在於未曝光部分的光酸產生劑來產生酸，而作為促進交聯步驟的觸媒而發揮功能，可促進膜的硬化反應。包括後曝光步驟的情況下的較佳曝光量較佳為100mJ/cm2~3,000mJ/cm2，特佳為100mJ/cm2~500mJ/cm2。 Further, after the post-baking, the substrate on which the pattern is formed is subjected to total re-exposure (post-exposure) by actinic rays, and post-baking is performed, whereby the acid can be generated from the photo-acid generator present in the unexposed portion. Further, it functions as a catalyst for promoting the crosslinking step, and promotes the hardening reaction of the film. Preferably, the amount of exposure in the case of post-exposure step comprising preferably 100mJ / cm 2 ~ 3,000mJ / cm 2, particularly preferably 100mJ / cm 2 ~ 500mJ / cm 2.

進而，由本發明的感光性樹脂組成物獲得的硬化膜亦可用作抗乾式蝕刻劑。於將藉由後烘烤步驟而熱硬化所得的硬化膜用作抗乾式蝕刻劑的情況下，蝕刻處理可進行灰化、電漿蝕刻、臭氧蝕刻等乾式蝕刻處理。 Further, the cured film obtained from the photosensitive resin composition of the present invention can also be used as an anti-dry etchant. In the case where the cured film obtained by heat-hardening by the post-baking step is used as an anti-dry etchant, the etching treatment may be subjected to dry etching treatment such as ashing, plasma etching, or ozone etching.

[硬化膜] [hardened film]

本發明的硬化膜是將本發明的感光性樹脂組成物硬化而獲得的硬化膜。 The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.

本發明的硬化膜可適宜用作層間絕緣膜。另外，本發明的硬化膜較佳為利用本發明的硬化膜的形成方法而獲得的硬化膜。 The cured film of the present invention can be suitably used as an interlayer insulating film. Further, the cured film of the present invention is preferably a cured film obtained by the method for forming a cured film of the present invention.

利用本發明的感光性樹脂組成物，獲得絕緣性優異、且於在高溫下被烘烤的情況下亦具有高透明性的層間絕緣膜。使用本發明的感光性樹脂組成物而成的層間絕緣膜具有高透明性，且硬化膜物性優異，因此可用於有機EL顯示裝置或液晶顯示裝置的 用途。 According to the photosensitive resin composition of the present invention, an interlayer insulating film which is excellent in insulating properties and has high transparency even when baked at a high temperature is obtained. The interlayer insulating film which is obtained by using the photosensitive resin composition of the present invention has high transparency and is excellent in physical properties of a cured film, and therefore can be used for an organic EL display device or a liquid crystal display device. use.

[液晶顯示裝置] [Liquid Crystal Display Device]

本發明的液晶顯示裝置的特徵在於包括本發明的硬化膜。 The liquid crystal display device of the present invention is characterized by comprising the cured film of the present invention.

本發明的液晶顯示裝置除了具有使用上述本發明的感光性樹脂組成物而形成的平坦化膜或層間絕緣膜以外，並無特別限制，可列舉採取多種結構的公知液晶顯示裝置。 The liquid crystal display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and a known liquid crystal display device having various structures can be cited.

例如，本發明的液晶顯示裝置所包括的薄膜電晶體(Thin-Film Transistor，TFT)的具體例可列舉：非晶矽-TFT、低溫多晶矽-TFT、氧化物半導體TFT等。本發明的硬化膜由於電特性優異，故而可組合於該些TFT中而較佳地使用。 Specific examples of the thin film transistor (TFT) included in the liquid crystal display device of the present invention include amorphous germanium-TFT, low-temperature polycrystalline germanium-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

另外，本發明的液晶顯示裝置可採取的液晶驅動方式可列舉：扭轉向列(Twisted Nematic，TN)方式、垂直配向(Vertical Alignment，VA)方式、共面切換(In-Plane-Switching，IPS)方式、邊緣場切換(Fringe Field Switching，FFS)方式、光學補償彎曲(Optical Compensated Bend，OCB)方式等。 Further, examples of the liquid crystal driving method that can be employed in the liquid crystal display device of the present invention include a twisted nematic (TN) method, a vertical alignment (VA) method, and an in-plane switching (In-Plane-Switching, IPS). Mode, Fringe Field Switching (FFS) mode, Optical Compensated Bend (OCB) mode, etc.

面板構成中，彩色濾光片陣列(Color Filter on Array，COA)方式的液晶顯示裝置中亦可使用本發明的硬化膜，例如可用作日本專利特開2005-284291號公報的有機絕緣膜(115)、或日本專利特開2005-346054號公報的有機絕緣膜(212)。 In the panel structure, the cured film of the present invention can also be used in a liquid crystal display device of a color filter on Array (COA) type, and can be used, for example, as an organic insulating film of Japanese Laid-Open Patent Publication No. 2005-284291 ( 115) or an organic insulating film (212) of JP-A-2005-346054.

另外，本發明的液晶顯示裝置可採取的液晶配向膜的具 體配向方式可列舉摩擦配向法、光配向法等。另外，亦可利用日本專利特開2003-149647號公報或日本專利特開2011-257734號公報中記載的聚合物穩定配向(Polymer Sustained Alignment，PSA)技術而經聚合物配向支持。 In addition, the liquid crystal alignment film of the present invention can be used as a liquid crystal alignment film. Examples of the body alignment method include a rubbing alignment method and a photo alignment method. In addition, the polymer alignment support can be carried out by the Polymer Sustained Alignment (PSA) technique described in JP-A-2003-149647 or JP-A-2011-257734.

另外，本發明的感光性樹脂組成物以及本發明的硬化膜並不限定於上述用途，可用於多種用途。例如，除了平坦化膜或層間絕緣膜以外，亦可適宜用於彩色濾光片的保護膜、或用以使液晶顯示裝置中的液晶層的厚度保持固定的間隔片或於固體攝影元件中設置於彩色濾光片上的微透鏡等。 Further, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above applications, and can be used for various purposes. For example, in addition to the planarization film or the interlayer insulating film, a protective film suitable for a color filter or a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device fixed may be provided in the solid-state imaging element. Microlenses and the like on a color filter.

圖1是表示主動矩陣方式的液晶顯示裝置10的一例的概念性剖面圖。該彩色液晶顯示裝置10是於背面具有背光單元12的液晶面板，液晶面板配置有TFT 16的元件，該TFT 16的元件與配置於貼附有偏光膜的2塊玻璃基板14、玻璃基板15之間的所有畫素對應。形成於玻璃基板上的各元件上，通過形成於硬化膜17中的接觸孔18，配線有形成畫素電極的ITO透明電極19。於ITO透明電極19上設置有液晶20的層與配置有黑色矩陣的紅綠藍(red green blue，RGB)彩色濾光片22。 FIG. 1 is a conceptual 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 provided with an element of the TFT 16, and the elements of the TFT 16 are disposed on two glass substrates 14 and a glass substrate 15 to which a polarizing film is attached. All pixels in between correspond. On each element formed on the glass substrate, an ITO transparent electrode 19 on which a pixel electrode is formed is wired through a contact hole 18 formed in the cured film 17. A layer of the liquid crystal 20 and a red green blue (RGB) color filter 22 in which a black matrix is disposed are disposed on the ITO transparent electrode 19.

背光的光源並無特別限定，可使用公知的光源。例如可列舉：白色LED、藍色．紅色．綠色等多色LED、螢光燈(冷陰極管)、有機EL等。 The light source of the backlight is not particularly limited, and a known light source can be used. For example, white LED, blue. red. Multicolor LEDs such as green, fluorescent lamps (cold cathode tubes), organic EL, etc.

另外，液晶顯示裝置亦可製成三維(three dimensional， 3D)(立體視野)型裝置，或者製成觸控面板型裝置。進而亦可製成可撓型，並可用作日本專利特開2011-145686號公報的第2層間絕緣膜(48)、或日本專利特開2009-258758號公報的層間絕緣膜(520)。 In addition, the liquid crystal display device can also be made into three dimensions (three dimensional, 3D) (stereoscopic) type device, or made into a touch panel type device. Further, it can be made into a flexible type, and can be used as the second interlayer insulating film (48) of JP-A-2011-145686 or the interlayer insulating film (520) of JP-A-2009-258758.

[有機EL顯示裝置] [Organic EL display device]

本發明的有機EL顯示裝置的特徵在於包括本發明的硬化膜。 The organic EL display device of the present invention is characterized by comprising the cured film of the present invention.

本發明的有機EL顯示裝置除了具有使用上述本發明的感光性樹脂組成物而形成的平坦化膜或層間絕緣膜以外，並無特別限制，可列舉採取多種結構的公知的各種有機EL顯示裝置或液晶顯示裝置。 The organic EL display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and various known organic EL display devices having various structures or Liquid crystal display device.

例如，本發明的有機EL顯示裝置所包括的薄膜電晶體(Thin-Film Transistor，TFT)的具體例可列舉：非晶矽-TFT、低溫多晶矽-TFT、氧化物半導體TFT等。本發明的硬化膜由於電特性優異，故而可組合於該些TFT中而較佳地使用。 Specific examples of the thin film transistor (TFT) included in the organic EL display device of the present invention include amorphous germanium-TFT, low-temperature polycrystalline germanium-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

圖2是有機EL顯示裝置的一例的構成概念圖。表示底部發光型的有機EL顯示裝置中的基板的示意性剖面圖，包括平坦化膜4。 FIG. 2 is a conceptual diagram showing an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, including a planarization film 4.

於玻璃基板6上形成底閘極(bottom gate)型TFT 1，以覆蓋該TFT 1的狀態形成包含Si3N4的絕緣膜3。於絕緣膜3上形成此處省略圖示的接觸孔後，經由該接觸孔而在絕緣膜3上形 成連接於TFT 1的配線2(高度為1.0μm)。配線2是用以將TFT 1間或者後述步驟中形成的有機EL元件與TFT 1連接。 A bottom gate type TFT 1 is formed on the glass substrate 6 to cover the TFT 1 to form an insulating film 3 containing Si 3 N 4 . After the contact hole (not shown) is formed on the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 is formed on the insulating film 3 via the contact hole. The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or in the step described later to the TFT 1.

進而，為了使由配線2的形成引起的凹凸平坦化，而以埋入由配線2引起的凹凸的狀態於絕緣膜3上形成平坦化膜4。 Further, in order to planarize the unevenness due to the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness caused by the wiring 2 is buried.

於平坦化膜4上形成底部發光型的有機EL元件。即，於平坦化膜4上，包含ITO的第一電極5是經由接觸孔7而連接於配線2來形成。另外，第一電極5相當於有機EL元件的陽極。 A bottom emission type organic EL element is formed on the planarization film 4. That is, on the planarizing film 4, the first electrode 5 including ITO is formed by being connected to the wiring 2 via the contact hole 7. Further, the first electrode 5 corresponds to the anode of the organic EL element.

形成覆蓋第一電極5的周緣的形狀的絕緣膜8，藉由設置該絕緣膜8，可防止第一電極5與其後步驟中形成的第二電極之間的短路。 The insulating film 8 having a shape covering the periphery of the first electrode 5 is formed, and by providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

進而，圖2中未圖示，隔著所需的圖案遮罩，依次蒸鍍設置電洞傳輸層、有機發光層、電子傳輸層，繼而，於基板上方的整個面形成包含Al的第二電極，藉由使用紫外線硬化型環氧樹脂而與密封用玻璃板貼合來密封，獲得於各有機EL元件上連接用以將其驅動的TFT 1而成的主動矩陣型有機EL顯示裝置。 Further, in FIG. 2, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially deposited by vapor deposition through a desired pattern mask, and then a second electrode including Al is formed on the entire upper surface of the substrate. An ultraviolet-curable epoxy resin is bonded to the glass plate for sealing and sealed, and an active matrix organic EL display device in which the TFTs 1 for driving the organic EL elements are connected to each other is obtained.

本發明的感光性樹脂組成物由於硬化性以及硬化膜特性優異，故而作為微機電系統(microelectromechanical system，MEMS)裝置的結構構件，將使用本發明的感光性樹脂組成物而形成的抗蝕劑圖案製成隔壁，或者作為機械驅動零件的一部分而加以組裝來使用。此種MEMS用裝置例如可列舉：表面聲波(surface acoustic wave，SAW)濾波器、體聲波(bulk acoustic wave，BAW) 濾波器、陀螺儀感測器(gyro sensor)、顯示器用微快門(microshutter)、影像感測器(image sensor)、電子紙、噴墨頭(inkjet head)、生物晶片(biochip)、密封劑等零件。更具體的例子例示於日本專利特表2007-522531號公報、日本專利特開2008-250200號公報、日本專利特開2009-263544號公報等中。 Since the photosensitive resin composition of the present invention is excellent in curability and cured film properties, a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a microelectromechanical system (MEMS) device is used. It is made into a partition or assembled as part of a mechanically driven part. Examples of such a MEMS device include a surface acoustic wave (SAW) filter and a bulk acoustic wave (BAW). Filters, gyro sensors, microshutters for displays, image sensors, electronic paper, inkjet heads, biochips, sealants, etc. Components. More specific examples are exemplified in JP-A-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

本發明的感光性樹脂組成物由於平坦性或透明性優異，故而例如亦可用於形成：日本專利特開2011-107476號公報的圖2中記載的堆積層(bank layer)(16)以及平坦化膜(57)、日本專利特開2010-9793號公報的圖4(a)中記載的隔壁(12)以及平坦化膜(102)、日本專利特開2010-27591號公報的圖10中記載的堆積層(221)以及第3層間絕緣膜(216b)、日本專利特開2009-128577號公報的圖4(a)中記載的第2層間絕緣膜(125)以及第3層間絕緣膜(126)、日本專利特開2010-182638號公報的圖3中記載的平坦化膜(12)以及畫素分離絕緣膜(14)等。 The photosensitive resin composition of the present invention is excellent in flatness and transparency, and can be used, for example, in forming a bank layer (16) and planarization described in Fig. 2 of JP-A-2011-107476. The partition (12) and the flattening film (102) described in Fig. 4 (a) of the Japanese Patent Publication No. 2010-9793, and the description of Fig. 10 of Japanese Patent Laid-Open Publication No. 2010-27591 The deposition layer (221) and the third interlayer insulating film (216b), the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4(a) of JP-A-2009-128577 The flattening film (12) and the pixel separation insulating film (14) described in Fig. 3 of Japanese Laid-Open Patent Publication No. 2010-182638.

[實施例] [Examples]

以下列舉實施例，對本發明進一步進行具體說明。以下實施例中所示的材料、使用量、比例、處理內容、處理程序等只要不脫離本發明的主旨，則可適當變更。因此，本發明的範圍並不限定於以下所示的具體例。此外，只要無特別說明，則「份」、「%」為質量基準。 The present invention will be further specifically described below by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "parts" and "%" are quality standards unless otherwise specified.

以下合成例中，以下符號分別表示以下化合物。 In the following synthesis examples, the following symbols represent the following compounds, respectively.

MATHF：甲基丙烯酸2-四氫呋喃酯(合成品) MATHF: 2-tetrahydrofuran methacrylate (synthetic)

MAEVE：甲基丙烯酸1-乙氧基乙酯(和光純藥工業公司製造) MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

OXE-30：甲基丙烯酸3-乙基-3-氧雜環丁基甲酯(大阪有機化學工業公司製造) OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

GMA：甲基丙烯酸縮水甘油酯(和光純藥工業公司製造) GMA: glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

NBMA：正丁氧基甲基丙烯醯胺(東京化成製造) NBMA: n-Butoxymethyl propylene decylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

HEMA：甲基丙烯酸羥基乙酯(和光純藥公司製造) HEMA: Hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

MAA：甲基丙烯酸(和光純藥工業公司製造) MAA: Methacrylic Acid (manufactured by Wako Pure Chemical Industries, Ltd.)

MMA：甲基丙烯酸甲酯(和光純藥工業公司製造) MMA: Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

St：苯乙烯(和光純藥工業公司製造) St: Styrene (manufactured by Wako Pure Chemical Industries, Ltd.)

DCPM：甲基丙烯酸二環戊酯 DCPM: Dicyclopentyl Methacrylate

V-601：二甲基-2,2'-偶氮雙(2-甲基丙酸酯)(和光純藥工業公司製造) V-601: dimethyl-2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

V-65：2,2'-偶氮雙(2,4-二甲基戊腈)(和光純藥工業公司製造) V-65: 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)

MEDG：甲基乙基二甘醇(日本乳化劑(股)製造) MEDG: methyl ethyl diglycol (manufactured by Japan Emulsifier)

PGMEA：乙酸甲氧基丙酯(昭和電工公司製造) PGMEA: methoxypropyl acetate (manufactured by Showa Denko)

<MATHF的合成> <Synthesis of MATHF>

預先將甲基丙烯酸(86g，1mol)冷卻至15℃，添加樟腦磺酸(4.6g，0.02mol)。於該溶液中，滴加2-二氫呋喃(71g，1mol，1.0當量)。攪拌1小時後，添加飽和碳酸氫鈉(500mL)，以乙酸乙酯(500mL)進行萃取，以硫酸鎂乾燥後，將不溶物過 濾，然後於40℃以下進行減壓濃縮，將殘渣的黃色油狀物減壓蒸餾而獲得沸點(bp.)為54~56℃/3.5mmHg餾分的甲基丙烯酸四氫-2H-呋喃-2-基酯(MATHF)125g作為無色油狀物(產率為80%)。 Methacrylic acid (86 g, 1 mol) was previously cooled to 15 ° C, and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 eq.) was added dropwise. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, and ethyl acetate (500 mL) was evaporated. Filtration, and then concentrating under reduced pressure at 40 ° C or less, and the residue was subjected to distillation under reduced pressure to give a THF (tetrahydro-2H-furan-2) hexanes. 125 g of the base ester (MATHF) was used as a colorless oil (yield 80%).

<聚合物P-1的合成例> <Synthesis Example of Polymer P-1>

於三口燒瓶中加入PGMEA(89g)，於氮氣環境下升溫至90℃。於該溶液中溶解MAA(成為總單體成分中的9.5mol%的量)、MATHF(成為總單體成分中的43mol%的量)、GMA(相當於總單體成分中的47.5mol%)、V-65(相對於總單體成分的合計100mol%，相當於4mol%)，花2小時來滴加。滴加結束後攪拌2小時，使反應結束。藉此獲得聚合物P-1。此外，將PGMEA與其他成分的合計量的比設為60：40。即，製備固體成分濃度為40%的聚合物溶液。 PGMEA (89 g) was added to a three-necked flask and the temperature was raised to 90 ° C under a nitrogen atmosphere. MAA (in an amount of 9.5 mol% in the total monomer component), MATHF (in an amount of 43 mol% in the total monomer component), and GMA (corresponding to 47.5 mol% in the total monomer component) were dissolved in the solution. V-65 (corresponding to 100 mol% of total monomer components, equivalent to 4 mol%) was added dropwise over 2 hours. After the completion of the dropwise addition, the mixture was stirred for 2 hours to complete the reaction. Thereby, the polymer P-1 was obtained. Further, the ratio of the total amount of PGMEA to other components was set to 60:40. Namely, a polymer solution having a solid concentration of 40% was prepared.

將單體種類等變更為如下述表所示，來合成其他聚合物。 The other types of polymers were synthesized by changing the monomer type and the like to the following table.

上述表中，表中的未特別標註單位的數值是以mol%作為單位。聚合起始劑以及添加劑的數值是將單體成分設為100mol%的情況下的mol%。固體成分濃度是表示為單體質量/(單體質量+溶劑質量)×100(單位質量%)。於使用V-601作為聚合起始劑的情況下，反應溫度設為90℃，於使用V-65的情況下將70℃作為反應溫度。 In the above table, the values of the units not specifically labeled in the table are in mol%. The numerical value of the polymerization initiator and the additive is mol% in the case where the monomer component is 100 mol%. The solid content concentration is expressed as monomer mass / (monomer mass + solvent mass) × 100 (unit mass %). In the case of using V-601 as a polymerization initiator, the reaction temperature was set to 90 ° C, and in the case of using V-65, 70 ° C was taken as the reaction temperature.

<感光性樹脂組成物的製備> <Preparation of photosensitive resin composition>

以成為下述表所述的固體成分比的方式，將聚合物成分、非離子性光酸產生劑、增感劑、通式(S)所表示的化合物、烷氧基矽烷化合物、界面活性劑、通式(S)所表示的化合物以外的鹼性化合物、以及其他成分溶解混合於溶劑(MEDG)中，直至固體成分濃度成為32%為止，利用口徑為0.2μm的聚四氟乙烯製過濾器進行過濾，獲得各種實施例以及比較例的感光性樹脂組成物。此外，表中的添加量為質量%。 A polymer component, a nonionic photoacid generator, a sensitizer, a compound represented by the formula (S), an alkoxydecane compound, and a surfactant are used so as to have a solid content ratio as described in the following table. The basic compound other than the compound represented by the formula (S) and other components are dissolved and mixed in a solvent (MEDG) until the solid content concentration is 32%, and a filter made of polytetrafluoroethylene having a diameter of 0.2 μm is used. Filtration was carried out to obtain photosensitive resin compositions of the respective examples and comparative examples. Further, the amount added in the table is % by mass.

實施例以及比較例中使用的表示各化合物的略號的詳情如下。 The details of the abbreviations indicating the respective compounds used in the examples and the comparative examples are as follows.

(表1記載以外的(A)成分) (Component (A) other than those described in Table 1)

P-21：Joncryl 67(巴斯夫製造) P-21: Joncryl 67 (manufactured by BASF)

P-22：ARUFON UC-3910(東亞合成(股)製造) P-22: ARUFON UC-3910 (made by East Asia Synthetic Co., Ltd.)

P-23：SMA 1000P(美國克雷威利有限責任公司製造) P-23: SMA 1000P (manufactured by American Craywell Co., Ltd.)

P-24：SMA 2000P(美國克雷威利有限責任公司製造) P-24: SMA 2000P (manufactured by American Craywell Co., Ltd.)

P-25：SMA 3000P(美國克雷威利有限責任公司製造) P-25: SMA 3000P (manufactured by American Craywell Co., Ltd.)

P-26：SMA EF-30(美國克雷威利有限責任公司製造) P-26: SMA EF-30 (manufactured by American Craywell Co., Ltd.)

P-27：SMA EF-40(美國克雷威利有限責任公司製造) P-27: SMA EF-40 (made by American Crayville Co., Ltd.)

P-28：SMA EF-60(美國克雷威利有限責任公司製造) P-28: SMA EF-60 (manufactured by American Craywell Co., Ltd.)

P-29：SMA EF-80(美國克雷威利有限責任公司製造) P-29: SMA EF-80 (manufactured by American Craywell Co., Ltd.)

P-30：SMA 2625P(美國克雷威利有限責任公司製造) P-30: SMA 2625P (manufactured by Crayville, LLC)

P-31：SMA 3840F(美國克雷威利有限責任公司製造) P-31: SMA 3840F (manufactured by Crayville, LLC)

(非離子性光酸產生劑) (nonionic photoacid generator)

B-1：下述所示的結構(下文對合成例進行說明) B-1: Structure shown below (the synthesis example will be described below)

B-2：PAG-103(商品名，下述所示的結構，巴斯夫公司製造) B-2: PAG-103 (trade name, structure shown below, manufactured by BASF Corporation)

B-3：α-(羥基亞胺基)-2-苯基乙腈(下文對合成例進行說明) B-3: α-(hydroxyimino)-2-phenylacetonitrile (described below for synthesis)

<B-1的合成> <Synthesis of B-1>

於2-萘酚(10g)、氯苯(30mL)的懸浮溶液中添加氯化鋁(10.6g)、2-氯丙醯氯(10.1g)，將混合液加熱至40℃，反應2小時。於冰浴冷卻下，向反應液中滴加4N HCl水溶液(60mL)，添加乙酸乙酯(50mL)進行分液。於有機層中添加碳酸鉀(19.2g)，於40℃下反應1小時後，添加2N HCl水溶液(60mL) 進行分液，將有機層濃縮後，利用二異丙醚(10mL)將結晶進行再漿料化，過濾、乾燥而獲得酮化合物(6.5g)。 Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C 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. 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. After liquid separation, the organic layer was concentrated, and the crystal was reslurryed with diisopropyl ether (10 mL), filtered, and dried to obtain a ketone compound (6.5 g).

於所得的酮化合物(3.0g)、甲醇(30mL)的懸浮溶液中添加乙酸(7.3g)、50質量%羥基胺水溶液(8.0g)，進行加熱回流。放冷後，添加水(50mL)，將所析出的結晶進行過濾、冷甲醇清洗後，乾燥而獲得肟化合物(2.4g)。 Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), 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).

使所得的肟化合物(1.8g)溶解於丙酮(20mL)中，於冰浴冷卻下添加三乙胺(1.5g)、對甲苯磺醯氯(2.4g)，升溫至室溫而反應1小時。於反應液中添加水(50mL)，將所析出的結晶過濾後，以甲醇(20mL)進行再漿料化，過濾、乾燥而獲得B-1的化合物(上述結構)(2.3g)。 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 for 1 hour. Water (50 mL) was added to the reaction mixture, and the precipitated crystals were filtered, and then re-slurryed with methanol (20 mL), filtered and dried to obtain a compound (the above structure) (2.3 g) of B-1.

此外，B-1的1H-NMR波譜(300MHz、CDCl3)為：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)。 Further, the 1H-NMR spectrum of B-1 (300 MHz, CDCl 3 ) was: 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).

<B-3的合成> <Synthesis of B-3>

使苯基乙腈(5.85g，東京化成公司製造)混合於四氫呋喃(50ml，和光純藥公司製造)中，於冰浴中將反應液冷卻至5℃以下。繼而，滴加SM-28(甲醇鈉28%甲醇溶液，11.6g，和光純藥公司製造)，於冰浴下攪拌30分鐘使其反應。繼而，將亞硝酸異戊酯(7.03g，東京化成公司製造)一邊保持在內溫20度以下一邊滴加，滴加結束後使反應液於室溫下反應1小時。將所得的反應液投入至溶解有氫氧化鈉(1g)的水(150mL)中，使 其完全溶解，繼而添加乙酸乙酯(100ml)進行分液，獲得具有目標物的水層約180ml。進而再次添加乙酸乙酯(100ml)，利用濃鹽酸將水層設為pH值為3以下的酸性，將生成物萃取、濃縮。若將所得的粗結晶以己烷進行清洗，則以產率63%獲得α-(羥基亞胺基)-2-苯基乙腈(4.6g)。 Phenyl acetonitrile (5.85 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with tetrahydrofuran (50 ml, manufactured by Wako Pure Chemical Industries, Ltd.), and the reaction liquid was cooled to 5 ° C or lower in an ice bath. Then, SM-28 (sodium methoxide 28% methanol solution, 11.6 g, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was stirred for 30 minutes in an ice bath to cause a reaction. Then, isoamyl nitrite (7.03 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while maintaining the internal temperature at 20 ° C. After the completion of the dropwise addition, the reaction solution was allowed to react at room temperature for 1 hour. The obtained reaction liquid was poured into water (150 mL) in which sodium hydroxide (1 g) was dissolved, so that It was completely dissolved, and then ethyl acetate (100 ml) was added for liquid separation to obtain about 180 ml of an aqueous layer having a target. Further, ethyl acetate (100 ml) was added again, and the aqueous layer was made acidic with a pH of 3 or less with concentrated hydrochloric acid, and the product was extracted and concentrated. When the obtained crude crystals were washed with hexane, α-(hydroxyimino)-2-phenylacetonitrile (4.6 g) was obtained in a yield of 63%.

(式(S)所表示的化合物) (compound represented by formula (S))

S-1：下述所示的結構 S-1: Structure shown below

S-2：下述所示的結構 S-2: Structure shown below

S-3：下述所示的結構 S-3: Structure shown below

(溶劑) (solvent)

MEDG：Hisolve EDM(東邦化學工業公司製造) MEDG: Hisolve EDM (manufactured by Toho Chemical Industry Co., Ltd.)

1,3-BGDA：1,3-丁二醇二乙酸酯(大賽璐(Daicel)(股)製造) 1,3-BGDA: 1,3-butylene glycol diacetate (manufactured by Daicel)

(烷氧基矽烷化合物) (alkoxydecane compound)

G-1：γ-縮水甘油氧基丙基三烷氧基矽烷(東京化成工業(股)製造) G-1: γ-glycidoxypropyl trialkoxy decane (manufactured by Tokyo Chemical Industry Co., Ltd.)

G-2：KBM-3103(信越化學工業(股)製造) G-2: KBM-3103 (manufactured by Shin-Etsu Chemical Co., Ltd.)

G-3：KBE-846(信越化學工業(股)製造) G-3: KBE-846 (manufactured by Shin-Etsu Chemical Co., Ltd.)

G-4：KBM-3063(信越化學工業(股)製造) G-4: KBM-3063 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(增感劑) (sensitizer)

DBA：下述結構的二丁氧基蒽(川崎化成公司製造) DBA: Dibutoxy oxime of the following structure (manufactured by Kawasaki Chemical Co., Ltd.)

(其他鹼性化合物) (other basic compounds)

H-1：2,4,5-三苯基咪唑(東京化成工業(股)製造) H-1: 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

H-2：1,5-二氮雜雙環[4.3.0]-5-壬烯(東京化成工業(股)製造) H-2: 1,5-diazabicyclo[4.3.0]-5-decene (manufactured by Tokyo Chemical Industry Co., Ltd.)

(界面活性劑) (surfactant)

W-1：下述結構式所表示的含全氟烷基的非離子界面活性劑(F-554，迪愛生製造) W-1: a perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by Di Aisheng)

(其他成分) (other ingredients)

(交聯劑) (crosslinking agent)

F-1：JER828(三菱化學控股(股)製造) F-1: JER828 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.)

F-2：JER1007(三菱化學控股(股)製造) F-2: JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.)

F-3：JER157S65(三菱化學控股(股)製造) F-3: JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.)

F-4：Duranate 17B-60P(旭化成化學(股)製造) F-4: Duranate 17B-60P (made by Asahi Kasei Chemicals Co., Ltd.)

F-5：Celloxide 2021P(大賽璐(股)製造) F-5: Celloxide 2021P (made by Daicel)

F-6：Denacol EX-321L(長瀨化成(股)製造) F-6: Denacol EX-321L (manufactured by Nagase Chemical Co., Ltd.)

F-7：EPICLON EXA-4850-150(迪愛生(股)製造) F-7: EPICLON EXA-4850-150 (made by Di Aisheng (share))

F-8：Takenate B-870N(三井化學(股)製造) F-8: Takenate B-870N (manufactured by Mitsui Chemicals Co., Ltd.)

F-9：Nikalac MW-100LM(三和化學(股)製造) F-9: Nikalac MW-100LM (manufactured by Sanwa Chemical Co., Ltd.)

F-10：Nikalac MX-270(三和化學(股)製造) F-10: Nikalac MX-270 (manufactured by Sanwa Chemical Co., Ltd.)

F-11：Kayarad DPHA(日本化藥(股)製造) F-11: Kayarad DPHA (manufactured by Nippon Kayaku Co., Ltd.)

(抗氧化劑) (Antioxidants)

J-1：Adekastab AO-60(艾迪科(股)製造) J-1: Adekastab AO-60 (made by Eddy Co.)

J-2：Irganox 1035(巴斯夫製造) J-2: Irganox 1035 (made by BASF)

J-3：Irganox 1098(巴斯夫製造) J-3: Irganox 1098 (made by BASF)

<顯影時密接性評價> <Evaluation of adhesion during development>

將於基板的其中一面的一半區域(10cm×5cm)形成有Mo(鉬)薄膜且於同一面的另一半區域(10cm×5cm)形成有SiNx薄膜的玻璃基板(10cm×10cm×0.5mm)，於六甲基二矽氮烷(HMDS)蒸氣下曝露30秒，使用旋轉塗佈機，以乾燥膜厚成為3μm的方式塗佈各感光性樹脂組成物溶液後，於90℃下在加熱板上預烘烤2分鐘，使溶劑揮發。然後，隔著可再現出10μm線/10μm空間的遮罩，使用超高壓水銀燈，以累計照射量40mJ/cm2(照度：20mW/cm2，i射線)進行曝光後，以鹼顯影液(0.4質量%的TMAH水溶液)於23℃下進行60秒顯影，然後以超純水淋洗1分鐘。利用光學顯微鏡來觀察所得的基板，於Mo部及SiNx部觀察10μm線/10μm空間的圖案的缺陷、剝落。將其結果示於下述表中。剝落越少越好，較佳為A或者B。 A glass substrate (10 cm × 10 cm × 0.5 mm) in which a Mo (molybdenum) film was formed in one half of one side of the substrate (10 cm × 5 cm) and a SiNx film was formed on the other half of the same surface (10 cm × 5 cm). After exposure to hexamethyldioxane (HMDS) vapor for 30 seconds, each photosensitive resin composition solution was applied to a dry film thickness of 3 μm using a spin coater, and then dried at 90 ° C on a hot plate. Pre-bake for 2 minutes to allow the solvent to evaporate. Then, an ultra-high pressure mercury lamp was used to carry out exposure with an accumulated irradiation amount of 40 mJ/cm 2 (illuminance: 20 mW/cm 2 , i-ray) through a mask capable of reproducing a space of 10 μm line/10 μm, and then an alkali developing solution (0.4) The mass% of the TMAH aqueous solution was developed at 23 ° C for 60 seconds and then rinsed with ultrapure water for 1 minute. The obtained substrate was observed with an optical microscope, and defects and peeling of the pattern in a space of 10 μm line/10 μm were observed in the Mo portion and the SiNx portion. The results are shown in the following table. The less the peeling, the better, preferably A or B.

A：完全無缺陷、剝落 A: completely defect free, peeling off

B：缺陷、剝落為30%以下 B: Defects and peeling are less than 30%

C：缺陷、剝落超過30%且60%以下 C: Defects, peeling more than 30% and less than 60%

D：缺陷、剝落超過60%且100%以下 D: Defect, peeling more than 60% and less than 100%

<硬化膜密接性：Mo> <hardened film adhesion: Mo>

將形成有Mo(鉬)薄膜的玻璃基板(10cm×10cm×0.5mm)，於六甲基二矽氮烷(HMDS)蒸氣下曝露30秒，然後，旋轉塗佈各感光性樹脂組成物後，於90℃下在加熱板上預烘烤2分 鐘，使溶劑揮發，形成膜厚為3μm的感光性樹脂組成物層。繼而，使用超高壓水銀燈，以累計照射量成為300mJ/cm2(照度：20mW/cm2，i射線)的方式進行全面曝光，然後，於烘箱中在230℃下將該基板加熱30分鐘而獲得硬化膜。 A glass substrate (10 cm × 10 cm × 0.5 mm) in which a Mo (molybdenum) film was formed was exposed to hexamethyldioxane (HMDS) vapor for 30 seconds, and then each of the photosensitive resin compositions was spin-coated. The film was prebaked on a hot plate at 90 ° C for 2 minutes to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3 μm. Then, using an ultrahigh pressure mercury lamp, the total exposure was 300 mJ/cm 2 (illuminance: 20 mW/cm 2 , i-ray), and then the substrate was heated at 230 ° C for 30 minutes in an oven. Hardened film.

繼而，使用切割機，於硬化膜上以縱橫1mm的間隔切割出切口，使用思高膠帶(Scotch tape)進行膠帶剝離試驗(依據100整體交叉切割法(100 mass cross cut method)：JIS5600)。根據轉印於膠帶背面的硬化膜的面積來評價硬化膜與基板間的密接性。將其結果示於下述表中。數值越小，與基底基板的密接性越高，較佳為A或者B。 Then, using a cutter, the slit was cut at intervals of 1 mm in the longitudinal direction and the transverse direction on the cured film, and the tape peeling test was performed using Scotch tape (100 mass cross cut method: JIS 5600). The adhesion between the cured film and the substrate was evaluated based on the area of the cured film transferred to the back surface of the tape. The results are shown in the following table. The smaller the value, the higher the adhesion to the base substrate, and it is preferably A or B.

A：所轉印的面積小於10% A: The transferred area is less than 10%

B：所轉印的面積為1%以上且小於5% B: The transferred area is 1% or more and less than 5%

C：所轉印的面積為5%以上且小於10% C: The transferred area is 5% or more and less than 10%

D：所轉印的面積為10%以上且小於50% D: The transferred area is 10% or more and less than 50%

E：所轉印的面積為50%以上 E: The transferred area is 50% or more

<硬化膜密接性：Ti> <hardened film adhesion: Ti>

將形成有Ti(鈦)薄膜的玻璃基板(10cm×10cm×0.5mm)，於六甲基二矽氮烷(HMDS)蒸氣下曝露30秒，然後，旋轉塗佈各感光性樹脂組成物後，於90℃下在加熱板上預烘烤2分鐘，使溶劑揮發，形成膜厚為3μm的感光性樹脂組成物層。繼而，使用超高壓水銀燈，以累計照射量成為300mJ/cm2(照度：20 mW/cm2，i射線)的方式進行全面曝光，然後，於烘箱中在230℃下將該基板加熱30分鐘而獲得硬化膜。 A glass substrate (10 cm × 10 cm × 0.5 mm) on which a Ti (titanium) film was formed was exposed to hexamethyldiaziridine (HMDS) vapor for 30 seconds, and then each of the photosensitive resin compositions was spin-coated. The film was prebaked on a hot plate at 90 ° C for 2 minutes to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3 μm. Then, using an ultrahigh pressure mercury lamp, the total exposure was 300 mJ/cm 2 (illuminance: 20 mW/cm 2 , i-ray), and then the substrate was heated at 230 ° C for 30 minutes in an oven. A cured film is obtained.

繼而，使用切割機，於硬化膜上以縱橫1mm的間隔切割出切口，使用思高膠帶進行膠帶剝離試驗(依據100整體交叉切割法：JIS5600)。根據轉印於膠帶背面的硬化膜的面積來評價硬化膜與基板間的密接性。將其結果示於下述表中。數值越小，與基底基板的密接性越高，較佳為A或者B。 Then, using a cutter, the slit was cut at intervals of 1 mm in the longitudinal direction and the transverse direction on the cured film, and the tape peeling test was performed using the Scotch tape (in accordance with the 100 overall cross-cut method: JIS 5600). The adhesion between the cured film and the substrate was evaluated based on the area of the cured film transferred to the back surface of the tape. The results are shown in the following table. The smaller the value, the higher the adhesion to the base substrate, and it is preferably A or B.

A：所轉印的面積小於1% A: The transferred area is less than 1%

B：所轉印的面積為1%以上且小於5% B: The transferred area is 1% or more and less than 5%

C：所轉印的面積為5%以上且小於10% C: The transferred area is 5% or more and less than 10%

D：所轉印的面積為10%以上且小於50% D: The transferred area is 10% or more and less than 50%

E：所轉印的面積為50%以上 E: The transferred area is 50% or more

<硬化膜密接性：SiNx> <hardened film adhesion: SiNx>

將形成有SiNx(氮化矽)薄膜的玻璃基板(10cm×10cm×0.5mm)，於六甲基二矽氮烷(HMDS)蒸氣下曝露30秒，然後，旋轉塗佈各感光性樹脂組成物後，於90℃下在加熱板上預烘烤2分鐘，使溶劑揮發，形成膜厚為3μm的感光性樹脂組成物層。繼而，使用超高壓水銀燈，以累計照射量成為300mJ/cm2(照度120mW/cm2，i射線)的方式進行全面曝光，然後，於烘箱中在230℃下將該基板加熱30分鐘而獲得硬化膜。 A glass substrate (10 cm × 10 cm × 0.5 mm) on which a SiNx (tantalum nitride) film was formed was exposed to hexamethyldioxane (HMDS) vapor for 30 seconds, and then each photosensitive resin composition was spin-coated. Thereafter, the film was prebaked on a hot plate at 90 ° C for 2 minutes to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3 μm. Then, using an ultrahigh pressure mercury lamp, the total exposure was 300 mJ/cm 2 (illuminance 120 mW/cm 2 , i-ray), and then the substrate was heated in an oven at 230 ° C for 30 minutes to obtain hardening. membrane.

繼而，使用切割機，於硬化膜上以縱橫1mm的間隔切 割出切口，使用思高膠帶進行膠帶剝離試驗(依據100整體交叉切割法：JIS5600)。根據轉印於膠帶背面的硬化膜的面積來評價硬化膜與基板間的密接性。將其結果示於下述表中。數值越小，與基底基板的密接性越高，較佳為A或者B。 Then, using a cutter, cut on the hardened film at intervals of 1 mm in length and width. The incision was cut out, and the tape peeling test was performed using the Scotch tape (in accordance with the 100 overall cross-cut method: JIS 5600). The adhesion between the cured film and the substrate was evaluated based on the area of the cured film transferred to the back surface of the tape. The results are shown in the following table. The smaller the value, the higher the adhesion to the base substrate, and it is preferably A or B.

A：所轉印的面積小於1% A: The transferred area is less than 1%

B：所轉印的面積為1%以上且小於5% B: The transferred area is 1% or more and less than 5%

C：所轉印的面積為5%以上且小於10% C: The transferred area is 5% or more and less than 10%

D：所轉印的面積為10%以上且小於50% D: The transferred area is 10% or more and less than 50%

E：所轉印的面積為50%以上 E: The transferred area is 50% or more

<耐化學品性的評價> <Evaluation of chemical resistance>

將玻璃基板(10cm×10cm×0.5mm)，於六甲基二矽氮烷(HMDS)蒸氣下曝露30秒，然後，旋轉塗佈各感光性樹脂組成物後，於90℃下在加熱板上預烘烤2分鐘，使溶劑揮發，形成膜厚為3μm的感光性樹脂組成物層。繼而，使用超高壓水銀燈，以累計照射量成為300mJ/cm2(照度：20mW/cm2，i射線)的方式進行全面曝光，然後，於烘箱中在230℃下將該基板加熱30分鐘而獲得硬化膜。 The glass substrate (10 cm × 10 cm × 0.5 mm) was exposed to hexamethyldioxane (HMDS) vapor for 30 seconds, and then each photosensitive resin composition was spin-coated, and then heated at 90 ° C on a hot plate. The mixture was prebaked for 2 minutes, and the solvent was volatilized to form a photosensitive resin composition layer having a film thickness of 3 μm. Then, using an ultrahigh pressure mercury lamp, the total exposure was 300 mJ/cm 2 (illuminance: 20 mW/cm 2 , i-ray), and then the substrate was heated at 230 ° C for 30 minutes in an oven. Hardened film.

測定所得硬化膜的膜厚(T1)。接著，將形成有該硬化膜的基板於溫度被控制為60℃的二甲基亞碸：單乙醇胺=7：3溶液中浸漬10分鐘後，測定浸漬後的硬化膜的膜厚(t1)，算出由浸漬引起的膜厚變化率{|t1-T1|/T1}×100[%]。將結果示於下述表中。 變化率越小越好，A、B為實用上無問題的水準。 The film thickness (T 1 ) of the obtained cured film was measured. Next, the substrate on which the cured film was formed was immersed in a solution of dimethyl hydrazine:monoethanolamine=7:3 whose temperature was controlled to 60° C. for 10 minutes, and then the film thickness (t 1 ) of the cured film after immersion was measured. The film thickness change rate {|t 1 -T 1 |/T 1 }×100 [%] caused by the immersion was calculated. The results are shown in the following table. The smaller the change rate, the better. A and B are practically problem-free.

A：小於2% A: less than 2%

B：2%以上且小於3% B: 2% or more and less than 3%

C：3%以上且小於4% C: 3% or more and less than 4%

D：4%以上且小於6% D: 4% or more and less than 6%

E：6%以上 E: 6% or more

如上述結果所明示，可知，本發明的感光性樹脂組成物 的顯影時的密接性優異，另外，本發明的感光性樹脂組成物的硬化膜與基板的密接性亦優異。尤其於多種基板中，均為硬化膜密接性極其優異，因此可較佳地用於顯示裝置等的配線基板。進而，鉬基板具有評價為「A」的密接性，是價值極高者。 As apparent from the above results, it is understood that the photosensitive resin composition of the present invention In the development of the photosensitive resin composition of the present invention, the cured film is excellent in adhesion to the substrate. In particular, in a variety of substrates, since the cured film is extremely excellent in adhesion, it can be preferably used for a wiring board such as a display device. Further, the molybdenum substrate has adhesion evaluated as "A" and is extremely valuable.

此外，本發明的感光性樹脂組成物的硬化膜具有耐化學品性亦高的優點。 Further, the cured film of the photosensitive resin composition of the present invention has an advantage of high chemical resistance.

<實施例65> <Example 65>

於實施例1中，實施例65除了將曝光機由佳能(Canon)(股)製造的MPA 5500CF變更為尼康(Nikon)(股)製造的FX-803M(gh-Line步進器)以外，以相同的方式進行。顯影時與硬化膜的密接性的評價是與實施例1相同的水準。 In Example 1, Example 65 was changed except that the exposure machine was changed from MPA 5500CF manufactured by Canon (Canon) to FX-803M (gh-Line stepper) manufactured by Nikon. The same way. The evaluation of the adhesion to the cured film at the time of development was the same as that of Example 1.

<實施例66> <Example 66>

於實施例1中，實施例66除了將顯影液由鹼顯影液(0.4質量%的TMAH水溶液)變更為鹼顯影液(2.38質量%的TMAH水溶液)以外，以相同的方式進行。顯影時的密接性的評價是與實施例1相同的水準。 In Example 1, Example 66 was carried out in the same manner except that the developer was changed from an alkali developer (0.4% by mass aqueous TMAH solution) to an alkali developer (2.38 mass% TMAH aqueous solution). The evaluation of the adhesion at the time of development was the same as that of Example 1.

<實施例67> <Example 67>

於實施例1中，實施例67除了省略利用烘箱進行加熱前的使用超高壓水銀燈的全面曝光的步驟以外，以相同的方式進行。硬化膜的密接性與耐化學品性的評價是與實施例1相同的水準。 In Example 1, Example 67 was carried out in the same manner except that the step of using the ultra-high pressure mercury lamp before the heating by the oven was omitted. The evaluation of the adhesion and chemical resistance of the cured film was the same as that of Example 1.

<實施例68> <Example 68>

於實施例1中，實施例68除了將曝光機由佳能(股)製造的MPA 5500CF變更為355nm雷射曝光機，來進行355nm雷射曝光以外，以相同的方式進行。此處，355nm雷射曝光機是使用V科技(V-Technology)公司股份有限公司製造的「AEGIS」(波長為355nm，脈衝寬度為6nsec)，曝光量是使用OPHIR公司製造的「PE10B-V2」來測定。 In Example 1, Example 68 was carried out in the same manner except that the exposure machine was changed from a MPA 5500CF manufactured by Canon Co., Ltd. to a 355 nm laser exposure machine to perform 355 nm laser exposure. Here, the 355 nm laser exposure machine is "AEGIS" (wavelength: 355 nm, pulse width: 6 nsec) manufactured by V-Technology Co., Ltd., and the exposure amount is "PE10B-V2" manufactured by OPHIR Corporation. To determine.

顯影時與硬化膜的密接性的評價是與實施例1相同的水準。 The evaluation of the adhesion to the cured film at the time of development was the same as that of Example 1.

<實施例69> <Example 69>

日本專利第3321003號公報的圖1中記載的主動矩陣型液晶顯示裝置中，以如下方式形成硬化膜17作為層間絕緣膜，獲得實施例68的液晶顯示裝置。即，使用實施例1的感光性樹脂組成物，形成硬化膜17作為層間絕緣膜。 In the active matrix liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3,321,003, a cured film 17 is formed as an interlayer insulating film in the following manner, and a liquid crystal display device of Example 68 is obtained. That is, using the photosensitive resin composition of Example 1, the cured film 17 was formed as an interlayer insulating film.

對所得的液晶顯示裝置施加驅動電壓，結果可知為表現出良好的顯示特性且可靠性高的液晶顯示裝置。 When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device exhibited excellent display characteristics and high reliability.

<實施例70> <Example 70>

與實施例69相比僅變更以下的塗佈製程，獲得同樣的液晶顯示裝置。即，利用狹縫塗佈法來塗佈實施例1的感光性樹脂組成物後，於90℃/120秒加熱板上藉由加熱而去除溶劑，形成膜厚為3.0μm的感光性樹脂組成物層。所得的塗膜為平坦且無不 均的良好面狀。另外，作為液晶顯示裝置的性能亦與實施例69同樣地良好。 The same coating process was changed as compared with Example 69, and the same liquid crystal display device was obtained. In other words, the photosensitive resin composition of Example 1 was applied by a slit coating method, and then the solvent was removed by heating on a hot plate at 90 ° C / 120 seconds to form a photosensitive resin composition having a film thickness of 3.0 μm. Floor. The resulting coating film is flat and all Good good shape. Further, the performance as a liquid crystal display device was also good as in Example 69.

<實施例71> <Example 71>

於實施例1中，實施例71除了將曝光機由佳能(股)製造的MPA 5500CF變更為UV-LED光源曝光機以外，以相同的方式進行。顯影時與硬化膜的密接性的評價是與實施例1相同的水準。 In Example 1, Example 71 was carried out in the same manner except that the exposure machine was changed from the MPA 5500CF manufactured by Canon to the UV-LED source exposure machine. The evaluation of the adhesion to the cured film at the time of development was the same as that of Example 1.

如上所述，可知，實施例的感光性樹脂組成物不論基板、曝光機如何，所形成的圖案的形狀均優異。 As described above, it is understood that the photosensitive resin composition of the examples is excellent in shape of the formed pattern regardless of the substrate or the exposure machine.

<實施例72> <Example 72>

與實施例69相比僅變更以下的塗佈製程，獲得同樣的液晶顯示裝置。即，利用狹縫及旋轉法來塗佈實施例1的感光性樹脂組成物後，於90℃/120秒加熱板上藉由加熱而去除溶劑，形成膜厚為3.0μm的感光性樹脂組成物層。所得的塗膜為平坦且無不均的良好面狀。另外，作為液晶顯示裝置的性能亦與實施例69同樣地良好。 The same coating process was changed as compared with Example 69, and the same liquid crystal display device was obtained. In other words, the photosensitive resin composition of Example 1 was applied by a slit and a spin method, and then the solvent was removed by heating on a hot plate at 90 ° C / 120 seconds to form a photosensitive resin composition having a film thickness of 3.0 μm. Floor. The obtained coating film was a flat surface which was flat and had no unevenness. Further, the performance as a liquid crystal display device was also good as in Example 69.

<實施例73> <Example 73>

利用以下方法來製作使用薄膜電晶體(TFT)的有機EL顯示裝置(參照圖2)。 An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).

於玻璃基板6上形成底閘極型的TFT 1，以覆蓋該TFT 1的狀態形成包含Si3N4的絕緣膜3。繼而，於該絕緣膜3上形成此 處省略圖示的接觸孔後，於絕緣膜3上形成經由該接觸孔而連接於TFT 1的配線2(高度為1.0μm)。該配線2用以將TFT 1間或者後述步驟中形成的有機EL元件與TFT 1連接。 A bottom gate type TFT 1 is formed on the glass substrate 6 to cover the TFT 1 to form an insulating film 3 containing Si 3 N 4 . Then, after the contact hole (not shown) is formed on the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 via the contact hole is formed on the insulating film 3. This wiring 2 is for connecting the organic EL element formed in the TFT 1 or in the step described later to the TFT 1.

進而，為了使由配線2的形成所引起的凹凸平坦化，而以埋入由配線2引起的凹凸的狀態於絕緣膜3上形成平坦化膜4。於絕緣膜3上形成平坦化膜4，是將實施例16的感光性樹脂組成物旋轉塗佈於基板上，於加熱板上進行預烘烤(90℃/120秒)後，自遮罩上，使用高壓水銀燈照射45mJ/cm2(照度20mW/cm2)的i射線(365nm)後，利用鹼水溶液進行顯影而形成圖案，進行230℃/30分鐘的加熱處理。 Further, in order to planarize the unevenness caused by the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness caused by the wiring 2 is buried. The planarizing film 4 was formed on the insulating film 3, and the photosensitive resin composition of Example 16 was spin-coated on a substrate, prebaked on a hot plate (90 ° C / 120 seconds), and then self-masked. After irradiating an i-ray (365 nm) of 45 mJ/cm 2 (illuminance: 20 mW/cm 2 ) with a high-pressure mercury lamp, development was carried out by an aqueous alkali solution to form a pattern, and heat treatment was performed at 230 ° C for 30 minutes.

塗佈感光性樹脂組成物時的塗佈性良好，曝光、顯影、煅燒後所獲得的硬化膜上未確認到皺褶或龜裂的產生。進而，配線2的平均階差為500nm，所製作的平坦化膜4的膜厚為2,000nm。 When the photosensitive resin composition was applied, the coating property was good, and no occurrence of wrinkles or cracks was observed on the cured film obtained after exposure, development, and firing. Further, the average step of the wiring 2 was 500 nm, and the thickness of the produced planarizing film 4 was 2,000 nm.

繼而，於所得的平坦化膜4上形成底部發光型的有機EL元件。首先，於平坦化膜4上，使包含ITO的第一電極5經由接觸孔7而連接於配線2來形成。然後，塗佈抗蝕劑進行預烘烤，隔著所需圖案的遮罩進行曝光、顯影。將該抗蝕劑圖案作為遮罩，藉由使用ITO蝕刻劑的濕式蝕刻來進行圖案加工。然後，使用抗蝕劑剝離液(Remover 100，安智電子材料(AZ Electronic Materials)公司製造)，於50℃下剝離上述抗蝕劑圖案。以上述方式獲得的第 一電極5相當於有機EL元件的陽極。 Then, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, the first electrode 5 including ITO is connected to the wiring 2 via the contact hole 7 on the planarizing film 4. Then, the resist is applied for prebaking, and exposure and development are performed through a mask of a desired pattern. This resist pattern was used as a mask, and pattern processing was performed by wet etching using an ITO etchant. Then, the resist pattern was peeled off at 50 ° C using a resist stripper (Remover 100, manufactured by AZ Electronic Materials Co., Ltd.). The first obtained in the above manner One electrode 5 corresponds to the anode of the organic EL element.

繼而，形成覆蓋第一電極5的周緣的形狀的絕緣膜8。於絕緣膜8上，使用實施例1的感光性樹脂組成物，以與上述相同的方法形成絕緣膜8。藉由設置該絕緣膜8，可防止第一電極5與其後的步驟中形成的第二電極之間短路。 Then, an insulating film 8 covering the shape of the periphery of the first electrode 5 is formed. The insulating film 8 was formed on the insulating film 8 by using the photosensitive resin composition of Example 1 in the same manner as described above. By providing the insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent step.

進而，於真空蒸鍍裝置內隔著所需的圖案遮罩，依次蒸鍍而設置電洞傳輸層、有機發光層、電子傳輸層。繼而，於基板上方的整個面形成包含Al的第二電極。藉由自蒸鍍機中取出所得的上述基板，使用密封用玻璃板與紫外線硬化型環氧樹脂進行貼合來密封。 Further, a hole transport layer, an organic light-emitting layer, and an electron transport layer are provided by sequentially depositing a mask in a vacuum vapor deposition apparatus with a desired pattern. Then, a second electrode containing Al is formed on the entire surface above the substrate. The obtained substrate was taken out from a vapor deposition machine, and sealed with a glass plate for sealing and an ultraviolet curable epoxy resin.

以上述方式，獲得於各有機EL元件上連接用於將其驅動的TFT 1而成的主動矩陣型有機EL顯示裝置。經由驅動電路來施加電壓，結果可知為表現出良好的顯示特性且可靠性高的有機EL顯示裝置。 In the above manner, an active matrix organic EL display device in which the TFTs 1 for driving the organic EL elements are connected to each other is obtained. When a voltage was applied via a drive circuit, it was found that the organic EL display device exhibits excellent display characteristics and high reliability.

Claims (11)

一種感光性樹脂組成物，其含有：(A)包含滿足下述(1)及(2)的至少一者的聚合物的聚合物成分：(1)包括(a1)具有酸基由酸分解性基保護的基團的構成單元、(a2)具有交聯性基的構成單元、以及(a3)具有(甲基)丙烯酸烷基酯的構成單元的聚合物，(2)包括(a1)具有酸基由酸分解性基保護的基團的構成單元的聚合物、包括(a2)具有交聯性基的構成單元的聚合物、以及包括(a3)具有(甲基)丙烯酸烷基酯的構成單元的聚合物；(B)非離子性光酸產生劑；(C)下述通式(S)所表示的化合物： (通式(S)中，R1表示肼基、吡啶基、咪唑基、喹啉基、哌啶基、吡咯啶基、吡唑基、噁唑基、噻唑基、苯并噁唑基、苯并咪唑基、苯并噻唑基、吡嗪基或二乙胺基，A表示2價連結基，R2表示有機基)； (D)溶劑；以及(E)烷氧基矽烷化合物。 A photosensitive resin composition comprising: (A) a polymer component comprising a polymer satisfying at least one of the following (1) and (2): (1) comprising (a1) having an acid group decomposable by acid a constituent unit of the group-protected group, (a2) a structural unit having a crosslinkable group, and (a3) a polymer having a constituent unit of an alkyl (meth)acrylate, and (2) including (a1) having an acid a polymer of a constituent unit of a group protected by an acid-decomposable group, a polymer comprising (a2) a constituent unit having a crosslinkable group, and a constituent unit comprising (a3) an alkyl (meth)acrylate (B) a nonionic photoacid generator; (C) a compound represented by the following formula (S): (In the general formula (S), R 1 represents a decyl group, a pyridyl group, an imidazolyl group, a quinolyl group, a piperidinyl group, a pyrrolidinyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, a benzoxazolyl group, a benzene group. And imidazolyl, benzothiazolyl, pyrazinyl or diethylamino, A represents a divalent linking group, R 2 represents an organic group; (D) a solvent; and (E) an alkoxydecane compound. 如申請專利範圍第1項所述的感光性樹脂組成物，其中上述(B)非離子性光酸產生劑為肟磺酸酯化合物。 The photosensitive resin composition according to claim 1, wherein the (B) nonionic photoacid generator is an oxime sulfonate compound. 如申請專利範圍第1項或第2項所述的感光性樹脂組成物，其中上述烷氧基矽烷化合物為二烷氧基矽烷化合物或者三烷氧基矽烷化合物。 The photosensitive resin composition according to claim 1 or 2, wherein the alkoxydecane compound is a dialkoxy decane compound or a trialkoxy decane compound. 如申請專利範圍第1項或第2項所述的感光性樹脂組成物，其包含(F)交聯劑。 The photosensitive resin composition according to claim 1 or 2, which comprises (F) a crosslinking agent. 如申請專利範圍第1項或第2項所述的感光性樹脂組成物，其包含(F)交聯劑，且上述(B)非離子性光酸產生劑為肟磺酸酯化合物，上述烷氧基矽烷化合物為二烷氧基矽烷化合物或者三烷氧基矽烷化合物。 The photosensitive resin composition according to claim 1 or 2, comprising (F) a crosslinking agent, wherein the (B) nonionic photoacid generator is an oxime sulfonate compound, the alkane The oxydecane compound is a dialkoxy decane compound or a trialkoxy decane compound. 一種硬化膜的製造方法，其包括：(1)將如申請專利範圍第1項至第5項中任一項所述的感光性樹脂組成物塗佈於基板上的步驟；(2)自所塗佈的感光性樹脂組成物中去除溶劑的步驟；(3)利用光化射線對去除了溶劑的感光性樹脂組成物進行曝光的步驟；(4)利用水性顯影液對經曝光的感光性樹脂組成物進行顯影的步驟；以及 (5)對經顯影的感光性樹脂組成物進行熱硬化的後烘烤步驟。 A method for producing a cured film, comprising: (1) a step of applying a photosensitive resin composition according to any one of claims 1 to 5 to a substrate; (2) a step of removing a solvent in the applied photosensitive resin composition; (3) a step of exposing the solvent-removed photosensitive resin composition by actinic rays; (4) using an aqueous developing solution to expose the photosensitive resin a step of developing the composition; (5) A post-baking step of thermally curing the developed photosensitive resin composition. 如申請專利範圍第6項所述的硬化膜的製造方法，其中於上述顯影步驟後、上述後烘烤步驟前，包括對經顯影的感光性樹脂組成物進行全面曝光的步驟。 The method for producing a cured film according to claim 6, wherein the step of performing the full exposure of the developed photosensitive resin composition is performed after the developing step and before the post-baking step. 一種硬化膜，其是由如申請專利範圍第1項至第5項中任一項所述的感光性樹脂組成物所形成。 A cured film formed of the photosensitive resin composition according to any one of claims 1 to 5. 如申請專利範圍第8項所述的硬化膜，其為層間絕緣膜。 The cured film according to claim 8, which is an interlayer insulating film. 一種有機電激發光顯示裝置，其包括如申請專利範圍第8項或第9項所述的硬化膜。 An organic electroluminescence display device comprising the cured film according to item 8 or claim 9 of the patent application. 一種液晶顯示裝置，其包括如申請專利範圍第8項或第9項所述的硬化膜。 A liquid crystal display device comprising the cured film according to item 8 or claim 9 of the patent application.
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