TW202409107A - Photosensitive resin composition resin film cured product dividing wall organic electroluminescent element wavelength conversion layer display method for producing cured product and method for producing dividing wall - Google Patents

Photosensitive resin composition resin film cured product dividing wall organic electroluminescent element wavelength conversion layer display method for producing cured product and method for producing dividing wall Download PDF

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TW202409107A
TW202409107A TW112124255A TW112124255A TW202409107A TW 202409107 A TW202409107 A TW 202409107A TW 112124255 A TW112124255 A TW 112124255A TW 112124255 A TW112124255 A TW 112124255A TW 202409107 A TW202409107 A TW 202409107A
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fluorine
group
resin composition
photosensitive resin
mass
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服部啓太
坂井田悠太
兼子譲
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日商中央硝子股份有限公司
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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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • 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
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/1201—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • H10K59/8792—Arrangements for improving contrast, e.g. preventing reflection of ambient light comprising light absorbing layers, e.g. black layers
    • 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a photosensitive resin composition, a resin film, a cured product, a barrier wall, an organic electroluminescent element, a wavelength conversion layer, a display, a method for producing the cured product, and a method for producing the barrier wall. The present invention addresses the problem of providing a photosensitive resin composition for producing a barrier wall having high uniformity in liquid repellency and/or a barrier wall having high uniformity in optical density, said photosensitive resin composition having good intermiscibility. The photosensitive resin composition according to the present invention is characterized by containing: an ethylenically unsaturated compound (A); a photopolymerization initiator (B); an alkali-soluble resin (C); and a fluorine-containing resin (D) containing a fluorine-containing resin (D1) having a fluorine atom content of 20-60% by mass and/or a fluorine-containing resin (D2) having a fluorine atom content of more than 0% by mass but less than 20% by mass. And the alkali-soluble resin (C) is a bisphenol epoxy resin having a structure represented by general formula (1). [In formula (1), each R independently represents a linear or branched alkyl group having 1-3 carbon atoms, a linear perfluoroalkyl group having 1-3 carbon atoms, or a hydrogen atom, and Z represents a monovalent organic group or a hydrogen atom].

Description

感光性樹脂組合物、樹脂膜、硬化物、阻隔壁、有機電致發光元件、波長轉換層、顯示裝置、硬化物之製造方法及阻隔壁之製造方法Photosensitive resin composition, resin film, cured product, barrier rib, organic electroluminescent element, wavelength conversion layer, display device, method for producing cured product, and method for producing barrier rib

本發明係一種感光性樹脂組合物、樹脂膜、硬化物、阻隔壁、有機電致發光元件、波長轉換層、顯示裝置、硬化物之製造方法及阻隔壁之製造方法。The present invention is a photosensitive resin composition, a resin film, a hardened material, a barrier wall, an organic electroluminescent element, a wavelength conversion layer, a display device, a method for manufacturing the hardened material, and a method for manufacturing the barrier wall.

於製造有機EL(Electroluminescence，電致發光)顯示裝置、微LED(Light Emitting Diode，發光二極體)顯示裝置、量子點顯示裝置等顯示元件時，作為具有發光等功能之有機層之形成方法，已知有噴墨法。噴墨法有一些方法，具體而言，可例舉如下方法：從噴嘴向形成於基板上之具有凹凸之圖案膜之凹部滴加墨水並使之固化；或者向作為被墨水濡濕之部位即親液部及排斥墨水之部位即撥液部之事先形成於基板上之圖案膜上滴加墨水之液滴，使墨水僅附著於親液部；等。When manufacturing organic EL (Electroluminescence, electroluminescence) display devices, micro LED (Light Emitting Diode, light emitting diode) display devices, quantum dot display devices and other display elements, as a method of forming organic layers with functions such as light emitting, The inkjet method is known. There are some methods of the inkjet method. Specifically, the following method can be exemplified: dropping ink from a nozzle onto the recessed portion of a pattern film having concavities and convexities formed on a substrate and solidifying it; The liquid part and the part that repels ink, that is, the liquid-repellent part, are dripped with ink droplets on the pattern film formed on the substrate in advance, so that the ink only adheres to the lyophilic part; etc.

尤其是前者所例舉之使從噴嘴滴加到圖案膜之凹部之墨水固化之方法中，主要採用兩種方法，以製作此種具有凹凸之圖案膜。一種方法係光微影法，其係將塗佈於基板上之感光性抗蝕膜之表面曝光成圖案狀，藉此形成曝光部及未曝光部，利用顯影液將任一部位溶解去除；另一種方法係使用印刷技術之壓印法。In particular, in the method of solidifying the ink dropped from a nozzle to the concave portion of the pattern film as exemplified in the former, two methods are mainly used to produce such a pattern film with concavities and convexities. One method is the photolithography method, which involves exposing the surface of a photosensitive resist film coated on a substrate into a pattern to form an exposed part and an unexposed part, and using a developer to dissolve and remove any part; another method is the photolithography method. One method is the imprinting method using printing technology.

所形成之具有凹凸之圖案膜之凸部稱為障壁(阻隔壁)，於將墨水滴加到圖案膜之凹部時，作為不讓墨水彼此混在一起之障壁發揮作用。為了提昇作為該障壁之效果，圖案膜凹部需要基板表面露出，該基板表面對墨水呈親液性，且障壁上表面對墨水呈撥液性。The convex part of the pattern film with concave and convex is called a barrier (blocking wall), which acts as a barrier to prevent the ink from mixing when ink is dripped into the concave part of the pattern film. In order to enhance the effect of the barrier, the concave part of the pattern film needs to be exposed on the substrate surface, the substrate surface is lyophilic to the ink, and the upper surface of the barrier is lyophilic to the ink.

作為用以形成此種障壁之樹脂，使用含氟樹脂作為撥墨水劑。藉由使用含氟樹脂，撥液性提昇。As the resin used to form such a barrier, a fluorine-containing resin is used as an ink repellent agent. By using fluorine-containing resin, liquid repellency is improved.

於專利文獻1中，揭示了一種抗蝕劑組合物作為包含含氟樹脂之抗蝕劑組合物，其特徵在於包含含氟樹脂(A)及會對波長100～600 nm之光發生反應之感光性成分，上述含氟樹脂(A)具有由下述式所表示之單體形成之單體單元且氟原子含有率為7～35質量%，上述含氟樹脂(A)相對於該抗蝕劑組合物之總固形物成分之比例為0.1～30質量%，上述感光性成分包含：光酸產生劑(B)；具有羧基及/或酚性羥基之鹼可溶性樹脂(C)；及酸交聯劑(D)，其係具有2個以上之藉由酸之作用而能與羧基或酚性羥基反應之基之化合物。 CH 2=C(R)COOXR f1(式中，R表示氫原子、甲基或三氟甲基，X表示碳數1～6之2價之不包含氟原子之有機基，R f1表示碳數4～6之全氟烷基) Patent document 1 discloses an anti-corrosion agent composition as an anti-corrosion agent composition comprising a fluorine-containing resin, wherein the anti-corrosion agent composition comprises a fluorine-containing resin (A) and a photosensitive component that reacts to light of a wavelength of 100 to 600 nm, wherein the fluorine-containing resin (A) has a monomer unit formed by a monomer represented by the following formula and a fluorine atom content of 7 to 35% by mass, and the ratio of the fluorine-containing resin (A) to the total solid content of the anti-corrosion agent composition is 0.1 to 30% by mass. The photosensitive component comprises: a photoacid generator (B); an alkali-soluble resin (C) having a carboxyl group and/or a phenolic hydroxyl group; and an acid crosslinking agent (D), which is a compound having two or more groups that can react with a carboxyl group or a phenolic hydroxyl group by the action of an acid. CH 2 =C(R)COOXR f1 (wherein R represents a hydrogen atom, a methyl group or a trifluoromethyl group, X represents a divalent organic group having 1 to 6 carbon atoms and not containing a fluorine atom, and R f1 represents a perfluoroalkyl group having 4 to 6 carbon atoms)

於專利文獻2中，揭示了一種撥墨水劑作為含有包含氟原子之聚合單元之撥墨水劑，其特徵在於包含具有聚合單元(b1)及聚合單元(b2)之聚合物，且氟含量為5～25質量%，數量平均分子量為500以上且未達10000，上述聚合單元(b1)具有氫原子至少一個被取代為氟原子之碳數20以下之烷基(其中，上述烷基包括具有醚性氧之烷基)，上述聚合單元(b2)具有乙烯性雙鍵。In Patent Document 2, an ink repellent agent is disclosed as an ink repellent agent containing a polymerized unit containing a fluorine atom, which is characterized in that it contains a polymer having a polymerized unit (b1) and a polymerized unit (b2), and the fluorine content is 5 ~25% by mass, the number average molecular weight is 500 or more and less than 10,000, and the above-mentioned polymer unit (b1) has an alkyl group with at least one carbon number of 20 or less in which at least one hydrogen atom is replaced by a fluorine atom (wherein the above-mentioned alkyl group includes an etheric group) Oxygen alkyl group), the above-mentioned polymerized unit (b2) has an ethylenic double bond.

於專利文獻3中，揭示了一種抗蝕劑組合物作為包含含氟樹脂之抗蝕劑組合物，其特徵在於包含含氟樹脂(A)及會對波長100～600 nm之光發生反應之感光性成分，上述含氟樹脂(A)具有由下述式所表示之單體形成之單體單元，並具有乙烯性雙鍵，且氟原子含有率為7～35質量%，上述含氟樹脂(A)相對於該抗蝕劑組合物之總固形物成分之比例為0.1～30質量%，上述感光性成分包含：光自由基起始劑(E)、及於1分子內具有酸性基及2個以上之乙烯性雙鍵之鹼可溶性樹脂(F)。 CH 2=C(R)COOXR f1(式中，R表示氫原子、甲基或三氟甲基，X表示碳數1～6之2價之不包含氟原子之有機基，R f1表示碳數4～6之全氟烷基) Patent document 3 discloses an anti-corrosion agent composition as an anti-corrosion agent composition comprising a fluorine-containing resin, wherein the anti-corrosion agent composition comprises a fluorine-containing resin (A) and a photosensitive component that reacts to light of a wavelength of 100 to 600 nm, wherein the fluorine-containing resin (A) has a monomer unit formed by a monomer represented by the following formula, has an ethylenic double bond, and has a fluorine atom content of 7 to 35% by mass, and the ratio of the fluorine-containing resin (A) to the total solid content of the anti-corrosion agent composition is 0.1 to 30% by mass, and the photosensitive component comprises: a photo-radical initiator (E), and an alkali-soluble resin (F) having an acidic group and two or more ethylenic double bonds in one molecule. CH 2 =C(R)COOXR f1 (wherein R represents a hydrogen atom, a methyl group or a trifluoromethyl group, X represents a divalent organic group having 1 to 6 carbon atoms and not containing a fluorine atom, and R f1 represents a perfluoroalkyl group having 4 to 6 carbon atoms)

於專利文獻4中，揭示了一種負型感光性樹脂組合物作為包含具有氟原子之撥墨水劑之負型感光性樹脂組合物，其特徵在於包含具有光硬化性之鹼可溶性樹脂或鹼可溶性單體(A)、光自由基聚合起始劑(B)、光酸產生劑(C)、酸硬化劑(D)、及具有氟原子之撥墨水劑(E)，且上述撥墨水劑(E)中之上述氟原子之含有率為1～40質量%，上述撥墨水劑(E)具有乙烯性雙鍵。 [先前技術文獻] [專利文獻] Patent document 4 discloses a negative photosensitive resin composition as a negative photosensitive resin composition containing a repellent having fluorine atoms, wherein the composition comprises a photocurable alkali-soluble resin or alkali-soluble monomer (A), a photoradical polymerization initiator (B), a photoacid generator (C), an acid curing agent (D), and a repellent having fluorine atoms (E), wherein the content of the fluorine atoms in the repellent (E) is 1 to 40% by mass, and the repellent (E) has an ethylene double bond. [Prior art document] [Patent document]

[專利文獻1]日本專利第4474991號 [專利文獻2]日本專利第4488098號 [專利文獻3]日本專利第4905563號 [專利文獻4]日本專利第6536578號 [Patent Document 1] Japanese Patent No. 4474991 [Patent Document 2] Japanese Patent No. 4488098 [Patent Document 3] Japanese Patent No. 4905563 [Patent Document 4] Japanese Patent No. 6536578

[發明所欲解決之問題][The problem the invention is trying to solve]

本發明人等經過努力研究，結果發現，當將包含乙烯性不飽和化合物、光聚合起始劑及鹼可溶性樹脂之成分、與含氟樹脂混合而製備感光性樹脂組合物時，各成分有時未充分相溶，由此種相溶性較差之感光性樹脂組合物獲得之障壁之撥液性及/或光學密度並不均勻。As a result of diligent research, the present inventors found that when a photosensitive resin composition is prepared by mixing a component including an ethylenically unsaturated compound, a photopolymerization initiator, and an alkali-soluble resin with a fluorine-containing resin, each component sometimes The liquid repellency and/or optical density of the barrier obtained from the photosensitive resin composition having poor compatibility is not uniform due to insufficient compatibility.

本發明係鑒於此種情況而完成者。本發明之一個目之在於提供一種感光性樹脂組合物，其相溶性良好，用以製造撥液性及/或光學密度之均勻性高之阻隔壁。 [解決問題之技術手段] The present invention is completed in view of this situation. One purpose of the present invention is to provide a photosensitive resin composition with good compatibility for manufacturing a barrier with high liquid repellency and/or uniform optical density. [Technical means to solve the problem]

本發明人等鑒於上述問題而進行了努力研究。結果發現，藉由使用具有規定結構之鹼可溶性樹脂，感光性樹脂組合物之相溶性會變得良好，以至本發明。The inventors of the present invention have conducted diligent research in view of the above-mentioned problems. As a result, it was found that by using an alkali-soluble resin having a prescribed structure, the compatibility of the photosensitive resin composition becomes good, leading to the present invention.

即，本發明如以下所示。That is, the present invention is as follows.

本發明(1)之感光性樹脂組合物之特徵在於：其含有乙烯性不飽和化合物(A)；光聚合起始劑(B)；鹼可溶性樹脂(C)；及含氟樹脂(D)，其包含氟原子含有率為20～60質量%之含氟樹脂(D 1)、及/或氟原子含有率超過0質量%且未達20質量%之含氟樹脂(D 2)；且上述鹼可溶性樹脂(C)係具有下述通式(1)所表示之結構之雙酚型環氧樹脂。 The photosensitive resin composition of the present invention (1) is characterized in that it contains an ethylenically unsaturated compound (A); a photopolymerization initiator (B); an alkali-soluble resin (C); and a fluorine-containing resin (D), It includes a fluorine-containing resin (D 1 ) with a fluorine atom content of 20 to 60 mass %, and/or a fluorine-containing resin (D 2 ) with a fluorine atom content exceeding 0 mass % and less than 20 mass %; and the above-mentioned alkali The soluble resin (C) is a bisphenol-type epoxy resin having a structure represented by the following general formula (1).

[化1] [式(1)中，R分別獨立地表示碳數1～3之直鏈狀或碳數3之支鏈狀之烷基、碳數1～3之直鏈狀之全氟烷基或氫原子，Z表示1價之有機基或氫原子]。 [Chemical 1] [In formula (1), R independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, a linear perfluoroalkyl group having 1 to 3 carbon atoms, or a hydrogen atom. , Z represents a univalent organic group or hydrogen atom].

本發明之感光性樹脂組合物中，鹼可溶性樹脂(C)係具有上述通式(1)所表示之結構之雙酚型環氧樹脂，因此感光性樹脂組合物之相溶性變得良好。In the photosensitive resin composition of the present invention, the alkali-soluble resin (C) is a bisphenol-type epoxy resin having a structure represented by the above general formula (1), so the compatibility of the photosensitive resin composition becomes good.

本發明(2)係本發明(1)中記載之感光性樹脂組合物，其進而含有著色顏料(E)。The present invention (2) is the photosensitive resin composition described in the present invention (1), which further contains a coloring pigment (E).

本發明(3)係本發明(1)或(2)中記載之感光性樹脂組合物，其中上述鹼可溶性樹脂(C)之氟原子含有率為10質量%以下。The present invention (3) is the photosensitive resin composition according to the present invention (1) or (2), wherein the alkali-soluble resin (C) has a fluorine atom content of 10 mass % or less.

本發明(4)係本發明(1)至(3)中任一項記載之感光性樹脂組合物，其中上述含氟樹脂(D)之氟原子含有率與上述鹼可溶性樹脂(C)之氟原子含有率之差為15～60質量%。The present invention (4) is the photosensitive resin composition according to any one of the present inventions (1) to (3), wherein the fluorine atom content rate of the above-mentioned fluorine-containing resin (D) is equal to the fluorine atom content of the above-mentioned alkali-soluble resin (C). The difference in atomic content is 15 to 60% by mass.

本發明(5)係本發明(1)至(4)中任一項記載之感光性樹脂組合物，其中上述含氟樹脂(D)之含量相對於上述感光性樹脂組合物之總固形物成分為0.01～40質量%。The present invention (5) is the photosensitive resin composition according to any one of the present inventions (1) to (4), wherein the content of the fluorine-containing resin (D) is 0.01 to 40% by mass relative to the total solid content of the photosensitive resin composition.

本發明(6)係本發明(1)至(5)中任一項記載之感光性樹脂組合物，其中上述感光性樹脂組合物中之鹼可溶性樹脂(C)之含量相對於含氟樹脂(D)100質量份為1,000質量份以上且10,000質量份以下。The present invention (6) is the photosensitive resin composition according to any one of the present invention (1) to (5), wherein the content of the alkali-soluble resin (C) in the photosensitive resin composition is relative to the fluorine-containing resin (C). D) 100 parts by mass means not less than 1,000 parts by mass and not more than 10,000 parts by mass.

本發明(7)係本發明(1)至(6)中任一項記載之感光性樹脂組合物，其進而包含選自由光自由基增感劑、鏈轉移劑、紫外線吸收劑及聚合抑制劑所組成之群中之至少1種。The present invention (7) is the photosensitive resin composition according to any one of the present invention (1) to (6), which further contains a photo radical sensitizer, a chain transfer agent, an ultraviolet absorber and a polymerization inhibitor selected from the group consisting of: At least one of the groups formed.

本發明(8)係本發明(1)至(7)中任一項記載之感光性樹脂組合物，其用於形成阻隔壁。The present invention (8) is a photosensitive resin composition according to any one of the present inventions (1) to (7), which is used to form a barrier rib.

本發明(9)係一種樹脂膜，其係由本發明(1)至(8)中任一項記載之感光性樹脂組合物獲得。The present invention (9) is a resin film obtained from the photosensitive resin composition described in any one of the present inventions (1) to (8).

本發明(10)係一種硬化物，其係使本發明(9)中記載之樹脂膜硬化而成。The present invention (10) is a cured product obtained by curing the resin film described in the present invention (9).

本發明(11)係一種阻隔壁，其係由本發明(10)中記載之硬化物構成。The present invention (11) is a barrier wall which is composed of the hardened material described in the present invention (10).

本發明(12)係一種有機電致發光元件，其具備本發明(11)中記載之阻隔壁。The present invention (12) is an organic electroluminescent element, which is provided with the barrier rib according to the present invention (11).

本發明(13)係一種波長轉換層，其具備本發明(11)中記載之阻隔壁。The present invention (13) is a wavelength conversion layer having the barrier wall described in the present invention (11).

本發明(14)係一種顯示裝置，其具備本發明(11)中記載之阻隔壁。The present invention (14) is a display device provided with the barrier rib according to the present invention (11).

本發明(15)係一種硬化物之製造方法，其特徵在於包括：成膜步驟，藉由將本發明(1)至(8)中任一項記載之感光性樹脂組合物塗佈到基板後，進行加熱而製成樹脂膜；及曝光步驟，對上述樹脂膜曝光高能量線。The present invention (15) is a method for manufacturing a cured product, which is characterized by including: a film forming step by applying the photosensitive resin composition according to any one of the present invention (1) to (8) to a substrate. , heating to form a resin film; and an exposure step, exposing the resin film to high-energy rays.

本發明(16)係一種阻隔壁之製造方法，其特徵在於包括：成膜步驟，藉由將本發明(1)至(8)中任一項記載之感光性樹脂組合物塗佈到基板後，進行加熱而製成樹脂膜；及曝光步驟，對上述樹脂膜曝光高能量線。The present invention (16) is a method for manufacturing a barrier rib, which is characterized by comprising: a film forming step, in which a photosensitive resin composition described in any one of the present inventions (1) to (8) is applied to a substrate and then heated to form a resin film; and an exposure step, in which the resin film is exposed to high energy rays.

藉由使用本發明之感光性樹脂組合物，能夠製造撥液性及/或光學密度之均勻性高之硬化物。 [發明之效果] By using the photosensitive resin composition of the present invention, it is possible to produce a hardened material with high liquid repellency and/or uniform optical density. [Effects of the invention]

根據本發明，能夠提供一種感光性樹脂組合物，其相溶性良好，用以製造撥液性均勻性高之阻隔壁及/或光學密度之均勻性高之阻隔壁。According to the present invention, it is possible to provide a photosensitive resin composition that has good compatibility and can be used to produce a barrier rib with high uniformity of liquid repellency and/or a barrier rib with high uniformity of optical density.

以下，對本發明詳細地進行說明。本發明不限定於以下之實施方式，能夠於不損害本發明之主旨之範圍內，基於業者之通常知識而適宜地實施。 再者，於本說明書中，「障壁」與「阻隔壁」係同義詞，除非另有註釋，否則就是指噴墨法中具有凹凸之圖案膜之凸部。 The present invention is described in detail below. The present invention is not limited to the following implementation methods, and can be appropriately implemented based on the common knowledge of the industry within the scope that does not damage the main purpose of the present invention. In addition, in this specification, "barrier" and "blocking wall" are synonymous, and unless otherwise noted, they refer to the convex part of the pattern film with concave and convex in the inkjet method.

本發明之感光性樹脂組合物之特徵在於含有：乙烯性不飽和化合物(A)；光聚合起始劑(B)；鹼可溶性樹脂(C)；及含氟樹脂(D)，其包含氟原子含有率為20～60質量%之含氟樹脂(D 1)、及/或氟原子含有率超過0質量%且未達20質量%之含氟樹脂(D 2)；且上述鹼可溶性樹脂(C)係具有下述通式(1)所表示之結構之雙酚型環氧樹脂。 The photosensitive resin composition of the present invention is characterized by containing: an ethylenically unsaturated compound (A); a photopolymerization initiator (B); an alkali-soluble resin (C); and a fluorine-containing resin (D), which contains fluorine atoms Fluorine-containing resin (D 1 ) with a fluorine atom content of 20 to 60 mass %, and/or fluorine-containing resin (D 2 ) with a fluorine atom content exceeding 0 mass % and less than 20 mass %; and the above-mentioned alkali-soluble resin (C ) is a bisphenol-type epoxy resin having a structure represented by the following general formula (1).

[化2] [式(1)中，R分別獨立地表示碳數1～3之直鏈狀或碳數3之支鏈狀之烷基、碳數1～3之直鏈狀之全氟烷基或氫原子，Z表示1價之有機基或氫原子] [Chemistry 2] [In formula (1), R independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, a linear perfluoroalkyl group having 1 to 3 carbon atoms, or a hydrogen atom, and Z represents a monovalent organic group or a hydrogen atom]

當R為碳數1～3之直鏈狀或碳數3之支鏈狀之烷基時，作為R之具體例，可例舉：甲基、乙基、丙基、異丙基。其中，從獲取容易性之觀點考慮，較佳為甲基。 作為碳數1～3之直鏈狀之全氟烷基之具體例，可例舉：三氟甲基、五氟乙基、七氟丙基。其中，從獲取容易性之觀點考慮，較佳為三氟甲基。 再者，各R可為相同之結構，亦可為不同之結構。 When R is a linear or branched alkyl group with 1 to 3 carbon atoms, specific examples of R include methyl, ethyl, propyl, and isopropyl. Among them, methyl is preferred from the viewpoint of easy availability. Specific examples of a linear perfluoroalkyl group with 1 to 3 carbon atoms include trifluoromethyl, pentafluoroethyl, and heptafluoropropyl. Among them, trifluoromethyl is preferred from the viewpoint of easy availability. Furthermore, each R may have the same structure or different structures.

當Z為1價之有機基時，Z較佳為碳數1～10之烷基。該碳數1～10之烷基可為直鏈狀，亦可為支鏈狀，還可為環狀。該碳數1～10之烷基之至少一個氫原子可被取代為羧基或羥基。 該碳數1～10之烷基所具有之羧基或羥基可以與酯化劑反應。酯化劑可例舉：醯鹵化物、酸酐、酸及縮合劑等。 當Z為氫原子時，可以使-O-Z與酯化劑反應。作為酯化劑，可例舉與上述相同之酯化劑。 作為酸酐，例如可例舉：丙烯酸酐、甲基丙烯酸酐、琥珀酸酐、鄰苯二甲酸酐、1,2,3,4-四氫鄰苯二甲酸酐等。藉由與其等酸酐反應，可向鹼可溶性樹脂導入乙烯性不飽和鍵、或羧基。 關於與酸酐反應之鹼可溶性樹脂中之羧基或羥基之量，只要考慮鹼可溶性樹脂所需要之於鹼中之溶解性來適當調整即可。 When Z is a monovalent organic group, Z is preferably an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic. At least one hydrogen atom of the alkyl group having 1 to 10 carbon atoms may be substituted with a carboxyl group or a hydroxyl group. The carboxyl group or hydroxyl group of the alkyl group having 1 to 10 carbon atoms can react with an esterification agent. Examples of the esterifying agent include acyl halide, acid anhydride, acid and condensing agent. When Z is a hydrogen atom, -O-Z can be reacted with an esterifying agent. Examples of the esterifying agent include the same esterifying agents as described above. Examples of acid anhydrides include acrylic anhydride, methacrylic anhydride, succinic anhydride, phthalic anhydride, 1,2,3,4-tetrahydrophthalic anhydride and the like. By reacting with acid anhydrides such as these, ethylenically unsaturated bonds or carboxyl groups can be introduced into alkali-soluble resins. The amount of carboxyl groups or hydroxyl groups in the alkali-soluble resin reacted with the acid anhydride may be appropriately adjusted in consideration of the solubility in alkali required for the alkali-soluble resin.

本發明之感光性樹脂組合物中，鹼可溶性樹脂(C)係具有上述通式(1)所表示之結構之雙酚型環氧樹脂，因此感光性樹脂組合物之相溶性變得良好。In the photosensitive resin composition of the present invention, the alkali-soluble resin (C) is a bisphenol-type epoxy resin having a structure represented by the above general formula (1), so the compatibility of the photosensitive resin composition becomes good.

又，若使用此種本發明之感光性樹脂組合物來製造阻隔壁等，則可製造撥液性及/或光學密度之均勻性高之阻隔壁。 可獲得此種效果之原因在於：本發明之感光性樹脂組合物之相溶性良好，含氟樹脂(D)混合得均勻。 Moreover, when the photosensitive resin composition of this invention is used to manufacture a barrier rib etc., a barrier rib with high liquid repellency and/or optical density uniformity can be manufactured. The reason why such an effect is obtained is that the photosensitive resin composition of the present invention has good compatibility and the fluorine-containing resin (D) is mixed uniformly.

以下，對本發明之感光性樹脂組合物之各成分進行詳細說明。Each component of the photosensitive resin composition of the present invention will be described in detail below.

＜乙烯性不飽和化合物(A)＞ 本發明之感光性樹脂組合物由於包含乙烯性不飽和化合物(A)，故而促進藉由光照射使感光性樹脂組合物硬化，而能以更短時間實現硬化。 作為乙烯性不飽和化合物(A)之具體例，可例舉：多官能丙烯酸酯(例如新中村化學工業股份有限公司製造之產品名：A-TMM-3、A-TMM-3L、A-TMM-3LM-N、A-TMPT、AD-TMP)、聚乙二醇二丙烯酸酯(例如新中村化學工業股份有限公司製造之產品名：A-200、A-400、A-600)、胺基甲酸酯丙烯酸酯(例如，新中村化學工業股份有限公司製造之產品名：UA-122P、UA-4HA、UA-6HA、UA-6LPA、UA-11003H、UA-53H、UA-4200、UA-200PA、UA-33H、UA-7100、UA-7200)、季戊四醇六丙烯酸酯(例如，日本化藥股份有限公司製造之產品名：DPHA)等。 <Ethylenically unsaturated compound (A)> The photosensitive resin composition of the present invention contains an ethylenically unsaturated compound (A), which promotes the curing of the photosensitive resin composition by light irradiation, and can achieve curing in a shorter time. Specific examples of the ethylenically unsaturated compound (A) include: multifunctional acrylates (e.g., product names manufactured by Shin-Nakamura Chemical Co., Ltd.: A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP), polyethylene glycol diacrylates (e.g., product names manufactured by Shin-Nakamura Chemical Co., Ltd.: A-200, A-400, A-600), urethane acrylates (e.g., product names manufactured by Shin-Nakamura Chemical Co., Ltd.: UA-122P, UA-4HA, UA-6HA, UA-6LPA, UA-11003H, UA-53H, UA-4200, UA-200PA, UA-33H, UA-7100, UA-7200), pentaerythritol hexaacrylate (e.g., product name manufactured by Nippon Kayaku Co., Ltd.: DPHA), etc.

作為多官能丙烯酸酯化合物，於以下例示較佳者。Preferred examples of the multifunctional acrylate compound are shown below.

[化3] [Chemical 3]

[化4] [Chemistry 4]

[化5] [Chemistry 5]

[化6] [Chemical 6]

關於乙烯性不飽和化合物(A)之含量，將鹼可溶性樹脂(C)及含氟樹脂(D)之合計質量設為100質量份時，較佳為10質量份以上300質量份以下，更佳為50質量份以上200質量份以下。 若乙烯性不飽和化合物(A)之含量少於10質量份，則有未充分獲得交聯效果之傾向，若超過300質量份，則有解像性、感度降低之傾向。 Regarding the content of the ethylenically unsaturated compound (A), when the total mass of the alkali-soluble resin (C) and the fluorine-containing resin (D) is 100 parts by mass, it is preferably not less than 10 parts by mass and not more than 300 parts by mass, still more preferably It is 50 parts by mass or more and 200 parts by mass or less. If the content of the ethylenically unsaturated compound (A) is less than 10 parts by mass, the crosslinking effect tends to be insufficient, and if it exceeds 300 parts by mass, the resolution and sensitivity tend to decrease.

＜光聚合起始劑(B)＞ 於本發明之感光性樹脂組合物中，光聚合起始劑(B)並無特別限定，只要可藉由電磁波或電子束等高能量線而使具有聚合性雙鍵之單體聚合即可，能夠使用公知之光聚合起始劑。 光聚合起始劑(B)可使用光自由基起始劑或光酸起始劑，其等可單獨使用，亦可併用光自由基起始劑及光酸起始劑，還可將2種以上之光自由基起始劑或光酸起始劑混合使用。又，藉由將光聚合起始劑與添加劑一同使用，還能根據情況進行活性聚合，該添加劑可使用公知者。 <Photopolymerization initiator (B)> In the photosensitive resin composition of the present invention, the photopolymerization initiator (B) is not particularly limited as long as it can polymerize a monomer having a polymerizable double bond by high-energy rays such as electromagnetic waves or electron beams. Known photopolymerization initiators can be used. As the photopolymerization initiator (B), a photoradical initiator or a photoacid initiator can be used. These can be used alone, or a photoradical initiator and a photoacid initiator can be used in combination, or both of them can be used together. The above photo radical initiators or photo acid initiators are mixed and used. Moreover, by using a photopolymerization initiator together with an additive, living polymerization can also be carried out according to circumstances, and a well-known additive can be used.

作為光自由基起始劑，具體而言，可分類為分子內斷鍵型及奪氫型等，上述分子內斷鍵型係分子內之鍵因電磁波或電子束之吸收而斷鍵從而生成自由基，上述奪氫型係藉由併用三級胺、醚等氫供體而生成自由基，可使用其中任一種。還可使用除上文例舉之類型以外之光自由基起始劑。As photo-radical initiators, specifically, they can be classified into intramolecular bond-breaking type and hydrogen-abstraction type, etc. The intramolecular bond-breaking type is that the bonds in the molecule are broken due to the absorption of electromagnetic waves or electron beams to generate free radicals, and the hydrogen-abstraction type is that free radicals are generated by the combined use of tertiary amines, ethers and other hydrogen donors, and any of them can be used. Photo-radical initiators other than the types listed above can also be used.

作為光自由基起始劑，具體而言，可例舉：二苯甲酮系、苯乙酮系、二酮系、醯基氧化膦系、醌系、偶姻系等。Specific examples of the photoradical initiator include benzophenone-based, acetophenone-based, diketone-based, acylphosphine oxide-based, quinone-based, aioin-based, and the like.

作為二苯甲酮系，具體而言，可例舉：二苯甲酮、4-羥基二苯甲酮、2-苯甲醯基苯甲酸、4-苯甲醯基苯甲酸、4,4'-雙(二甲基胺基)二苯甲酮、4,4'-雙(二乙基胺基)二苯甲酮等。其中，較佳為2-苯甲醯基苯甲酸、4-苯甲醯基苯甲酸、4,4'-雙(二乙基胺基)二苯甲酮。Specific examples of benzophenone-based compounds include benzophenone, 4-hydroxybenzophenone, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone. Among them, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and 4,4'-bis(diethylamino)benzophenone are preferred.

作為苯乙酮系，具體而言，可例舉：苯乙酮、2-(4-甲苯磺醯氧基)-2-苯基苯乙酮、對二甲基胺基苯乙酮、2,2'-二甲氧基-2-苯基苯乙酮、對甲氧基苯乙酮、2-甲基-[4-(甲硫基)苯基]-2-嗎啉基-1-丙酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁烷-1-酮等。其中，較佳為對二甲基胺基苯乙酮、對甲氧基苯乙酮。Specific examples of acetophenones include: acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2, 2'-Dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone , 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, etc. Among them, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferred.

作為二酮系，具體而言，可例舉：4,4'-二甲氧基苯偶醯、苯甲醯基甲酸甲酯、9,10-菲醌等。其中，較佳為4,4'-二甲氧基苯偶醯、苯甲醯基甲酸甲酯。Specific examples of the diketone include 4,4'-dimethoxybenzoyl, methyl benzylformate, 9,10-phenanthrenequinone, and the like. Among them, 4,4'-dimethoxybenzoylformate and methyl benzylformate are preferred.

作為醯基氧化膦系，具體而言，可例舉：雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等。Specific examples of the acylphosphine oxide-based compounds include bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide and the like.

作為醌系，具體而言，可例舉：蒽醌、2-乙基蒽醌、樟腦醌、1,4-萘醌等。其中，較佳為樟腦醌、1,4-萘醌。Specific examples of the quinone series include anthraquinone, 2-ethylanthraquinone, camphorquinone, 1,4-naphthoquinone, and the like. Among them, camphorquinone and 1,4-naphthoquinone are preferred.

作為偶姻系，具體而言，可例舉：苯偶姻、苯偶姻甲醚、苯偶姻乙醚、苯偶姻異丙醚等。其中，較佳為苯偶姻、苯偶姻甲醚。Specific examples of the azoin system include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like. Among them, benzoin and benzoin methyl ether are preferred.

作為光自由基起始劑，較佳為二苯甲酮系、苯乙酮系、二酮系，更佳為二苯甲酮系。As the photo-radical initiator, benzophenone-based, acetophenone-based, and diketone-based are preferred, and benzophenone-based are more preferred.

市售之光自由基起始劑中，較佳者可例舉：BASF公司製造之產品名：Irgacure 127、Irgacure 184、Irgacure 369、Irgacure 651、Irgacure 819、Irgacure 907、Irgacure 2959、Irgacure OXE-01、Darocure 1173、Lucirin TPO等。其中，更佳為Irgacure 651、Irgacure 369。Among the commercially available photoradical initiators, the preferred ones include: product names manufactured by BASF: Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE-01 , Darocure 1173, Lucirin TPO, etc. Among them, Irgacure 651 and Irgacure 369 are more preferred.

關於光酸起始劑，具體而言，係包含一對陽離子與陰離子之鎓鹽，上述陽離子係選自由芳香族磺酸根、芳香族碘鎓、芳香族重氮鎓、芳香族銨、噻蒽鎓、9-氧硫𠮿鎓、(2,4-環戊二烯-1-基)(1-甲基乙基苯)鐵所組成之群中之至少1種，上述陰離子係選自由四氟硼酸根、六氟磷酸根、六氟銻酸根、五氟苯基硼酸根所組成之群中之至少1種。 其中，尤佳為雙[4-(二苯基二氫硫基)苯基]硫醚雙六氟磷酸鹽、雙[4-(二苯基二氫硫基)苯基]硫醚四(五氟苯基)硼酸鹽、二苯基碘鎓六氟磷酸鹽。 The photoacid initiator specifically comprises an onium salt of a pair of cations and anions, wherein the cation is selected from aromatic sulfonates, aromatic iodoniums, aromatic diazoniums, aromatic ammoniums, thianthreniums, 9-oxysulfoniums, The anion is at least one selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroantibonate, and pentafluorophenylborate. Among them, bis[4-(diphenyldihydrothio)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenyldihydrothio)phenyl]sulfide tetrakis(pentafluorophenyl)borate, and diphenyliodonium hexafluorophosphate are particularly preferred.

作為市售之光酸起始劑，例如可例舉：San-Apro股份有限公司製造之產品名：CPI-100P、CPI-110P、CPI-101A、CPI-200K、CPI-210S、陶氏化學日本股份有限公司製造之產品名：Cyracure光硬化起始劑UVI-6990、Cyracure光硬化起始劑UVI-6992、Cyracure光硬化起始劑UVI-6976、ADEKA股份有限公司製造之產品名：Adeka Optomer SP-150、Adeka Optomer SP-152、Adeka Optomer SP-170、Adeka Optomer SP-172、Adeka Optomer SP-300、日本曹達股份有限公司製造之產品名：CI-5102、CI-2855、三新化學工業股份有限公司製造之產品名：San-Aid SI-60L、San-Aid SI-80L、San-Aid SI-100L、San-Aid SI-110L、San-Aid SI-180L、San-Aid SI-110、San-Aid SI-180、甯柏迪公司製造之產品名：Esacure 1064、Esacure 1187、汽巴精化股份有限公司製造之產品名：Irgacure 250等。Examples of commercially available photoacid initiators include: CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S manufactured by San-Apro Co., Ltd.; Cyracure Photocuring Initiator UVI-6990, Cyracure Photocuring Initiator UVI-6992, Cyracure Photocuring Initiator UVI-6976 manufactured by Dow Chemical Japan Co., Ltd.; Adeka Optomer SP-150, Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer SP-172, Adeka Optomer SP-300, CI-5102 and CI-2855 manufactured by Nippon Soda Co., Ltd., San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L, San-Aid SI-110L, San-Aid SI-180L, San-Aid SI-110 and San-Aid SI-180 manufactured by San-Aid Chemical Industry Co., Ltd., Esacure 1064 and Esacure 1187 manufactured by Nyba Chemicals Co., Ltd., Irgacure 250, etc.

關於本發明之感光性樹脂組合物中之光聚合起始劑(B)之含量，將鹼可溶性樹脂(C)及含氟樹脂(D)之合計質量設為100質量份時，較佳為0.1質量份以上30質量份以下，更佳為1質量份以上20質量份以下。若光聚合起始劑之含量少於0.1質量份，則有未充分獲得交聯效果之傾向，若超過30質量份，則有解像性、感度降低之傾向。The content of the photopolymerization initiator (B) in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total mass of the alkali-soluble resin (C) and the fluorine-containing resin (D). If the content of the photopolymerization initiator is less than 0.1 parts by mass, the crosslinking effect tends to be insufficient, and if it exceeds 30 parts by mass, the resolution and sensitivity tend to be reduced.

＜鹼可溶性樹脂(C)＞ 本發明之感光性樹脂組合物由於包含上述式(1)所表示之鹼可溶性樹脂(C)，故而感光性樹脂組合物之相溶性變得良好。又，能夠改善使用本發明之感光性樹脂組合物所製造之阻隔壁(障壁)之形狀。 <Alkali-soluble resin (C)> Since the photosensitive resin composition of the present invention contains the alkali-soluble resin (C) represented by the above formula (1), the compatibility of the photosensitive resin composition becomes good. Furthermore, the shape of the barrier rib (barrier rib) produced using the photosensitive resin composition of the present invention can be improved.

本發明之感光性樹脂組合物中，鹼可溶性樹脂(C)可包含氟原子，亦可不包含氟原子，鹼可溶性樹脂(C)之氟原子含有率較佳為10質量%以下。進而，鹼可溶性樹脂(C)更佳為不包含氟原子或者氟原子之含有率超過0質量%且為5質量%以下。 若鹼可溶性樹脂(C)包含氟原子且氟原子含有率於上述範圍內，則使用本發明之感光性樹脂組合物所製造出之阻隔壁之撥液性提昇。 又，若氟原子含有率未達10質量%，則各成分變得容易充分相溶，故而較佳。 再者，鹼可溶性樹脂(C)之氟原子含有率能夠藉由與後述含氟樹脂(D)之含氟原子含有率之測定方法相同之方法進行測定。 In the photosensitive resin composition of the present invention, the alkali-soluble resin (C) may or may not contain fluorine atoms. The fluorine atom content of the alkali-soluble resin (C) is preferably 10% by mass or less. Furthermore, it is more preferable that the alkali-soluble resin (C) does not contain a fluorine atom or the content rate of a fluorine atom exceeds 0 mass % and is 5 mass % or less. If the alkali-soluble resin (C) contains fluorine atoms and the fluorine atom content ratio is within the above range, the liquid repellency of the barrier rib produced using the photosensitive resin composition of the present invention is improved. In addition, it is preferable that the fluorine atom content is less than 10% by mass because each component becomes easily and fully soluble in each other. Furthermore, the fluorine atom content of the alkali-soluble resin (C) can be measured by the same method as the method for measuring the fluorine atom content of the fluorine-containing resin (D) described below.

作為鹼可溶性樹脂(C)，可例舉：雙酚型環氧樹脂、及由上述環氧樹脂衍生之酸改性環氧丙烯酸酯系樹脂。 作為雙酚型環氧樹脂，例如可例舉：具有上述式(1)所表示之結構單元之雙酚A型環氧樹脂。上述環氧樹脂亦可於側鏈具有羥基、甲基丙烯醯基或丙烯醯基這類之聚合性取代基。 作為具有此種結構單元之鹼可溶性樹脂(C)，可例示如下高分子化合物，其特徵在於含有以下之式(1-1)、(1-2)及(1-3)所表示之結構單元。 式(1-1)、(1-2)及(1-3)所表示之結構單元可無規共聚，亦可每個構成單元均進行嵌段共聚。 Examples of the alkali-soluble resin (C) include bisphenol-type epoxy resins and acid-modified epoxy acrylate-based resins derived from the above-mentioned epoxy resins. Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin having a structural unit represented by the above formula (1). The above-mentioned epoxy resin may also have polymerizable substituents such as hydroxyl, methacrylyl or acrylyl groups in the side chain. Examples of the alkali-soluble resin (C) having such structural units include polymer compounds characterized by containing structural units represented by the following formulas (1-1), (1-2) and (1-3). . The structural units represented by formulas (1-1), (1-2) and (1-3) can be randomly copolymerized, or each structural unit can be block copolymerized.

[化7] (於上述通式(1-1)、(1-2)及(1-3)中，a、b及c分別為1以上之整數) [Chemical 7] (In the above general formulas (1-1), (1-2) and (1-3), a, b and c are respectively integers above 1)

於上述通式(1-1)、(1-2)及(1-3)中，a＋b＋c較佳為3～100，從於顯影液中之溶解性之觀點考慮，更佳為10～50。In the above general formulas (1-1), (1-2) and (1-3), a+b+c is preferably 3 to 100, and more preferably 10 to 50 from the viewpoint of solubility in a developer.

上述高分子化合物之末端結構可例舉以下結構。再者，下述結構式中，波浪線表示與其他原子團之鍵結鍵。Examples of the terminal structure of the polymer compound include the following structures. Furthermore, in the following structural formula, wavy lines represent bonds with other atomic groups.

[化8] [Chemical 8]

當上述式(1-1)、(1-2)及(1-3)之任一結構單元成為與高分子化合物之末端鄰接之結構時，與該結構單元之氧原子鍵結之末端之結構較佳為上述式(1a)，與該結構單元之碳原子鍵結之末端之結構較佳為上述式(1c)。 再者，與高分子化合物之末端鄰接之結構單元可為相同之結構單元，亦可為不同之結構單元。 When any of the structural units of the above formulae (1-1), (1-2) and (1-3) forms a structure adjacent to the terminal of a polymer compound, the structure of the terminal bonded to the oxygen atom of the structural unit is preferably the above formula (1a), and the structure of the terminal bonded to the carbon atom of the structural unit is preferably the above formula (1c). Furthermore, the structural unit adjacent to the terminal of a polymer compound may be the same structural unit or different structural units.

從合成容易性之觀點出發，鹼可溶性樹脂較佳為末端以外之結構僅包含上述式(1)所表示之結構單元的高分子化合物。 又，鹼可溶性樹脂亦可為末端以外之結構僅包含選自上述式(1-1)、(1-2)及(1-3)所表示之結構單元中之至少1種的高分子化合物。 From the viewpoint of ease of synthesis, the alkali-soluble resin is preferably a polymer compound in which the structure other than the terminal includes only the structural unit represented by the above formula (1). In addition, the alkali-soluble resin may be a polymer compound in which the structure other than the terminal contains only at least one structural unit selected from the group consisting of the structural units represented by the above formulas (1-1), (1-2) and (1-3).

作為市售之酸改性環氧丙烯酸酯系樹脂，例如可使用日本化藥股份有限公司製造之產品名：ZAR-1035、ZAR-1494H、ZAR-2001H、ZAR-2023H、ZAR-2050H、ZAR2051H等。 其等之中，較佳為日本化藥股份有限公司製造之產品名：ZAR-2023H、ZAR-2050H。 As commercially available acid-modified epoxy acrylate resins, for example, product names manufactured by Nippon Kayaku Co., Ltd. can be used: ZAR-1035, ZAR-1494H, ZAR-2001H, ZAR-2023H, ZAR-2050H, ZAR2051H, etc. . Among them, the product names manufactured by Nippon Kayaku Co., Ltd. are preferred: ZAR-2023H, ZAR-2050H.

關於鹼可溶性樹脂(C)成分之重量平均分子量，從感光性樹脂組合物之顯影性及解像性之觀點考慮，較佳為1,000～50,000。The weight average molecular weight of the alkali-soluble resin (C) component is preferably 1,000 to 50,000 from the viewpoint of the developability and resolution of the photosensitive resin composition.

本發明之感光性樹脂組合物中之鹼可溶性樹脂(C)之含量相對於含氟樹脂(D)100質量份，較佳為1,000質量份以上且10,000質量份以下，更佳為2,000質量份以上且50,000質量份以下。 若鹼可溶性樹脂(C)之含量於上述範圍內，則使用本發明之感光性樹脂組合物形成阻隔壁時之接觸角之不均得到減少。 The content of the alkali-soluble resin (C) in the photosensitive resin composition of the present invention is preferably 1,000 parts by mass or more and 10,000 parts by mass or less, and more preferably 2,000 parts by mass or more based on 100 parts by mass of the fluorine-containing resin (D). And less than 50,000 parts by mass. When the content of the alkali-soluble resin (C) is within the above range, unevenness in the contact angle when forming a barrier rib using the photosensitive resin composition of the present invention is reduced.

再者，本發明之感光性樹脂組合物除鹼可溶性樹脂(C)以外，還可包含其他鹼可溶性樹脂。 於本發明之感光性樹脂組合物中，鹼可溶性樹脂(C)相對於全部鹼可溶性樹脂之比例較佳為10.0～100.0 wt%，更佳為30.0～100.0 wt%，進而更佳為50.0～100.0 wt%。 若鹼可溶性樹脂(C)之含量於上述範圍內，則使用本發明之感光性樹脂組合物所形成之阻隔壁之撥液性之不均得到減少。 Furthermore, the photosensitive resin composition of the present invention may contain other alkali-soluble resins in addition to the alkali-soluble resin (C). In the photosensitive resin composition of the present invention, the ratio of the alkali-soluble resin (C) to the total alkali-soluble resin is preferably 10.0 to 100.0 wt%, more preferably 30.0 to 100.0 wt%, and still more preferably 50.0 to 100.0 wt%. When the content of the alkali-soluble resin (C) is within the above range, unevenness in the liquid repellency of a barrier formed using the photosensitive resin composition of the present invention is reduced.

＜含氟樹脂(D)＞ 於本發明之感光性樹脂組合物中，含氟樹脂(D)包含氟原子含有率為20～60質量%之含氟樹脂(D 1)、及/或氟原子含有率超過0質量%且未達20質量%之含氟樹脂(D 2)。 其等之中，從提昇使用本發明之感光性樹脂組合物所製造之阻隔壁之撥液性之觀點考慮，含氟樹脂(D)較佳為包含氟原子含有率為20～60質量%之含氟樹脂(D 1)。 <Fluorine-containing resin (D)> In the photosensitive resin composition of the present invention, the fluorine-containing resin (D) contains a fluorine-containing resin (D 1 ) with a fluorine atom content of 20 to 60 mass %, and/or fluorine atoms. Fluorine-containing resin (D 2 ) with a content exceeding 0% by mass and less than 20% by mass. Among them, from the viewpoint of improving the liquid repellency of the barrier rib produced using the photosensitive resin composition of the present invention, the fluorine-containing resin (D) preferably contains a fluorine atom content of 20 to 60 mass %. Fluorine-containing resin (D 1 ).

再者，本發明之感光性樹脂組合物中，含氟樹脂(D)亦可包含多種含氟樹脂，例如可包含氟原子含有率為20～60質量%之含氟樹脂(D 1)、及氟原子含有率超過0質量%且未達20質量%之含氟樹脂(D 2)這兩種含氟樹脂。 Furthermore, in the photosensitive resin composition of the present invention, the fluorine-containing resin (D) may include a plurality of fluorine-containing resins, for example, a fluorine-containing resin (D 1 ) having a fluorine atom content of 20 to 60 mass % and a fluorine-containing resin (D 2 ) having a fluorine atom content of more than 0 mass % and less than 20 mass %.

於本說明書中，「含氟樹脂(D)之氟原子含有率」能夠根據藉由NMR(核磁共振波譜法)測得之構成含氟樹脂(D)之單體之莫耳比、構成含氟樹脂(D)之單體之分子量、單體所包含之氟之含量等算出。 此處，作為一例，對當含氟樹脂(D)為包含1,1-雙三氟甲基丁二烯、4-羥基苯乙烯及甲基丙烯酸2-(全氟己基)乙酯之樹脂時之氟之含量之測定方法進行說明。 (i)首先，對含氟樹脂(D)進行NMR測定，藉此算出各組成之比例(莫耳比)。 (ii)將含氟樹脂(D)之各組成之單體之分子量(Mw)乘以莫耳比，將得到之值相加而求出合計值。根據該合計值算出各組成之質量比(wt%)。 再者，1,1-雙三氟甲基丁二烯之分子量為190，4-羥基苯乙烯之分子量為120，甲基丙烯酸2-(全氟己基)乙酯之分子量為432。 (iii)繼而，於含有氟之組成中，計算單體中之氟原子含有率。 (iv)算出各成分中之「單體中之氟原子含有率÷單體分子量(Mw)×質量比(wt%)」之值，將得到之數值相加。 (v)算出「上述(iv)中所得到之數值」/「上述(ii)中所得到之合計值」，而算出含氟樹脂(D)之氟原子含有率。 藉此，判定含氟樹脂(D)為氟原子含有率為20～60質量%之含氟樹脂(D 1)，或為氟原子含有率超過0質量%且未達20質量%之含氟樹脂(D 2)。 In this specification, "the fluorine atom content rate of the fluorine-containing resin (D)" can be based on the molar ratio of the monomers constituting the fluorine-containing resin (D) measured by NMR (nuclear magnetic resonance spectroscopy), and the fluorine-containing resin (D). The molecular weight of the monomer of the resin (D), the fluorine content contained in the monomer, etc. are calculated. Here, as an example, when the fluorine-containing resin (D) is a resin containing 1,1-bistrifluoromethylbutadiene, 4-hydroxystyrene, and 2-(perfluorohexyl)ethyl methacrylate The method for determining the fluorine content is explained. (i) First, NMR measurement is performed on the fluorine-containing resin (D) to calculate the ratio (molar ratio) of each composition. (ii) Multiply the molecular weight (Mw) of the monomers of each component of the fluorine-containing resin (D) by the molar ratio, and add the obtained values to obtain a total value. The mass ratio (wt%) of each component was calculated based on this total value. Furthermore, the molecular weight of 1,1-bistrifluoromethylbutadiene is 190, the molecular weight of 4-hydroxystyrene is 120, and the molecular weight of 2-(perfluorohexyl)ethyl methacrylate is 432. (iii) Next, in the composition containing fluorine, calculate the fluorine atom content rate in the monomer. (iv) Calculate the value of "fluorine atom content in the monomer ÷ monomer molecular weight (Mw) × mass ratio (wt%)" in each component, and add the obtained values. (v) Calculate "the numerical value obtained in the above (iv)" / "the total value obtained in the above (ii)" to calculate the fluorine atom content rate of the fluorine-containing resin (D). From this, it is determined that the fluorine-containing resin (D) is a fluorine-containing resin (D 1 ) with a fluorine atom content of 20 to 60 mass %, or a fluorine-containing resin with a fluorine atom content exceeding 0 mass % and less than 20 mass %. ( D2 ).

以下，對含氟樹脂(D)之較佳結構進行說明。 再者，氟原子含有率為20～60質量%之含氟樹脂(D 1)、與氟原子含有率超過0質量%且未達20質量%之含氟樹脂(D 2)於氟原子含有率上有所不同，除非特別說明，否則較佳結構共通。 The preferred structure of the fluorine-containing resin (D) is described below. The fluorine-containing resin (D 1 ) having a fluorine atom content of 20 to 60 mass % and the fluorine-containing resin (D 2 ) having a fluorine atom content of more than 0 mass % and less than 20 mass % differ in fluorine atom content, but unless otherwise specified, the preferred structure is the same.

於本發明之感光性樹脂組合物中，含氟樹脂(D)可具有下述化學式(2)所示之結構，亦可具有下述式(3)所表示之結構。In the photosensitive resin composition of the present invention, the fluorine-containing resin (D) may have a structure represented by the following chemical formula (2), or may have a structure represented by the following formula (3).

[化9] (式(2)中，Rb分別獨立地表示碳數1～6之直鏈狀、碳數3～6之支鏈狀或碳數3～6之環狀之烷基或氟原子，該烷基中之任意數量之氫原子被取代為氟原子。R 2表示氫原子、碳數1～6之直鏈狀、碳數3～6之支鏈狀或碳數3～6之環狀之烷基)。 [Chemistry 9] (In formula (2), Rb independently represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a fluorine atom, wherein any number of hydrogen atoms in the alkyl group are replaced by fluorine atoms. R2 represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a fluorine atom).

[化10] (式(3)中，Rb分別獨立地表示碳數1～6之直鏈狀、碳數3～6之支鏈狀或碳數3～6之環狀之烷基或氟原子，該烷基中之任意數量之氫原子被取代為氟原子。R 1表示氫原子、氟原子或甲基。R 2表示氫原子、碳數1～6之直鏈狀、碳數3～6之支鏈狀或碳數3～6之環狀之烷基)。 [Chemical 10] (In formula (3), Rb independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched chain alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom. The alkyl group Any number of hydrogen atoms in are replaced by fluorine atoms. R 1 represents a hydrogen atom, a fluorine atom or a methyl group. R 2 represents a hydrogen atom, a linear chain with 1 to 6 carbon atoms, or a branched chain with 3 to 6 carbon atoms. Or a cyclic alkyl group with 3 to 6 carbon atoms).

於式(3)中，R 1較佳為氫原子、甲基。又，作為R 2，例如可例舉：氫原子、甲基、乙基、正丙基、異丙基、正丁基、1-甲基丙基、2-甲基丙基、第三丁基、正戊基、異戊基、1,1-二甲基丙基、1-甲基丁基、1,1-二甲基丁基、正己基、環戊基、環己基等，較佳為氫原子、甲基、乙基、正丙基、異丙基，更佳為氫原子、甲基。 又，式(2)或式(3)中之Rb較佳為氟原子、三氟甲基、二氟甲基、五氟乙基、2,2,2-三氟乙基、七氟正丙基、2,2,3,3,3-五氟丙基、3,3,3-三氟丙基、六氟異丙基、七氟異丙基、九氟正丁基、九氟異丁基、九氟第三丁基，更佳為氟原子、三氟甲基、二氟甲基、五氟乙基、2,2,2-三氟乙基、七氟正丙基、2,2,3,3,3-五氟丙基、3,3,3-三氟丙基、六氟異丙基，尤佳為氟原子、二氟甲基、三氟甲基。 In formula (3), R 1 is preferably a hydrogen atom or a methyl group. R 2 may be, for example, a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a t-butyl group, a n-pentyl group, an isopentyl group, a 1,1-dimethylpropyl group, a 1-methylbutyl group, a 1,1-dimethylbutyl group, a n-hexyl group, a cyclopentyl group, a cyclohexyl group, etc., preferably a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and more preferably a hydrogen atom or a methyl group. In addition, Rb in formula (2) or formula (3) is preferably a fluorine atom, a trifluoromethyl group, a difluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoro-n-propyl group, a 2,2,3,3,3-pentafluoropropyl group, a 3,3,3-trifluoropropyl group, a hexafluoroisopropyl group, a heptafluoroisopropyl group, a nonafluoro-n-butyl group, a nonafluoroisobutyl group, or a nonafluoro-t-butyl group; more preferably a fluorine atom, a trifluoromethyl group, a difluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoro-n-propyl group, a 2,2,3,3,3-pentafluoropropyl group, a 3,3,3-trifluoropropyl group, or a hexafluoroisopropyl group; and particularly preferably a fluorine atom, a difluoromethyl group, or a trifluoromethyl group.

關於本發明之感光性樹脂組合物中之含氟樹脂(D)所包含之式(3)所表示之重複單元，較佳者可例示以下之結構。Regarding the repeating unit represented by formula (3) contained in the fluorine-containing resin (D) in the photosensitive resin composition of the present invention, the following structures can be preferably exemplified.

[化11] [Chemical 11]

[化12] [Chemistry 12]

式(3)所表示之重複單元於含氟樹脂(D)中之含量相對於構成含氟樹脂(D)之總重複單元100莫耳%，較佳為5莫耳%以上70莫耳%以下，更佳為10莫耳%以上50莫耳%以下，尤佳為10莫耳%以上30莫耳%以下。The content of the repeating unit represented by formula (3) in the fluorine-containing resin (D) is preferably 5 mol% or more and 70 mol% or less based on 100 mol% of the total repeating units constituting the fluorine-containing resin (D). , more preferably not less than 10 mol% and not more than 50 mol%, particularly preferably not less than 10 mol% and not more than 30 mol%.

若式(3)之重複單元之含量多於70莫耳%，則有含氟樹脂(D)變得難溶於溶劑中之傾向。If the content of the repeating unit of formula (3) exceeds 70 mol%, the fluororesin (D) tends to become poorly soluble in the solvent.

又，於本發明之感光性樹脂組合物中，含氟樹脂(D)亦可為包含下述(4)式所表示之結構。Furthermore, in the photosensitive resin composition of the present invention, the fluororesin (D) may have a structure represented by the following formula (4).

[化13] [Chemical 13]

於式(4)中，R 3、R 4分別獨立地表示氫原子或甲基。 In formula (4), R 3 and R 4 each independently represent a hydrogen atom or a methyl group.

於式(4)中，W 1表示2價之連結基，表示-O-、-O-C(=O)-、-C(=O)-O-、-O-C(=O)-NH-、-C(=O)-O-C(=O)-NH-或-C(=O)-NH-。其中，較佳為-O-C(=O)-NH-、-C(=O)-O-C(=O)-NH-或-C(=O)-NH-。 In formula (4), W 1 represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, - C(=O)-OC(=O)-NH- or -C(=O)-NH-. Among them, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH- is preferred.

於式(4)中，A 1表示2～4價之連結基，表示碳數1～10之直鏈狀、碳數3～10之支鏈狀或碳數3～10之環狀之烴基，該烴基中之任意數量之氫原子可被取代為羥基或-O-C(=O)-CH 3。 In formula (4), A1 represents a divalent to tetravalent linking group, and represents a linear, branched, or cyclic carbon group having 1 to 10 carbon atoms, wherein any number of hydrogen atoms in the carbon group may be replaced by hydroxyl groups or -OC(=O) -CH3 .

當2價之連結基A 1為碳數1～10之直鏈狀之伸烷基時，例如可例舉：亞甲基、伸乙基、伸丙基、伸正丁基、伸正戊基、伸正己基、伸正庚基、伸正辛基、伸正壬基、伸正癸基。 When the divalent linking group A1 is a linear alkylene group having 1 to 10 carbon atoms, examples thereof include methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene and n-decylene.

當2價之連結基A 1為碳數3～10之支鏈狀之伸烷基時，例如可例舉：伸異丙基、伸異丁基、伸第二丁基、伸第三丁基、伸異戊基、伸異己基等。 When the divalent linking group A1 is a branched alkylene group having 3 to 10 carbon atoms, examples thereof include isopropylene, isobutylene, sec-butylene, t-butylene, isopentylene, isohexylene and the like.

當2價之連結基A 1為碳數3～10之環狀之伸烷基時，例如可例舉：二取代環丙烷、二取代環丁烷、二取代環戊烷、二取代環己烷、二取代環庚烷、二取代環辛烷、二取代環癸烷、二取代4-第三丁基環己烷等。 When the divalent linking group A 1 is a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, and disubstituted cyclohexane. , disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, disubstituted 4-tert-butylcyclohexane, etc.

當該等伸烷基中之任意數量之氫原子被取代為羥基時，作為該經羥基取代之伸烷基，例如可例舉：羥基伸乙基、1-羥基伸正丙基、2-羥基伸正丙基、羥基伸異丙基(-CH(CH 2OH)CH 2-)、1-羥基伸正丁基、2-羥基伸正丁基、羥基伸第二丁基(-CH(CH 2OH)CH 2CH 2-)、羥基伸異丁基(-CH 2CH(CH 2OH)CH 2-)、羥基伸第三丁基(-C(CH 2OH)(CH 3)CH 2-)等。 When any number of hydrogen atoms in the alkylene groups are substituted with hydroxyl groups, examples of the alkylene groups substituted with hydroxyl groups include hydroxyethylene, 1-hydroxyn-propylene, 2-hydroxyn-propylene, hydroxyi-propylene (-CH( CH2OH ) CH2- ), 1-hydroxyn-butylene, 2-hydroxyn - butylene, hydroxyi-butylene (-CH(CH2OH)CH2CH2-), hydroxyi-butylene (-CH2CH(CH2OH)CH2- ) , hydroxyi - butylene (-C( CH2OH )( CH3 ) CH2- ), and the like.

又，當該等伸烷基中之任意數量之氫原子被取代為-O-C(=O)-CH 3時，作為該經取代之伸烷基，可例舉：上文中例示之經羥基取代之伸烷基之羥基被取代為-O-C(=O)-CH 3者。 Furthermore, when any number of hydrogen atoms in the alkylene group is substituted by -OC(=O)-CH 3 , examples of the substituted alkylene group include: the hydroxyl-substituted ones exemplified above The hydroxyl group of the alkylene group is substituted by -OC(=O)-CH 3 .

其中，2價之連結基A 1較佳為亞甲基、伸乙基、伸丙基、伸正丁基、伸異丁基、伸第二丁基、環己基、2-羥基伸正丙基、羥基伸異丙基(-CH(CH 2OH)CH 2-)、2-羥基伸正丁基、羥基伸第二丁基(-CH(CH 2OH)CH 2CH 2-)，更佳為伸乙基、伸丙基、2-羥基伸正丙基、羥基伸異丙基(-CH(CH 2OH)CH 2-)，尤佳為伸乙基、2-羥基伸正丙基。 作為3價之連結基A 1，可例舉-C(CH 2-) 2CH 3等，作為4價之連結基A 1，可例舉C(CH 2-) 4等。 Among them, the divalent linking group A 1 is preferably methylene, ethylidene, propylene, n-butyl, isobutyl, di-butyl, cyclohexyl, 2-hydroxyl-n-propyl, or hydroxyl. isopropyl (-CH(CH 2 OH)CH 2 -), 2-hydroxy-n-butyl, hydroxyl-butyl (-CH(CH 2 OH)CH 2 CH 2 -), more preferably ethylene-butyl base, propylene group, 2-hydroxyl-n-propyl group, hydroxyl-isopropyl group (-CH(CH 2 OH) CH 2 -), particularly preferably ethyl-ylene group and 2-hydroxyl-n-propyl group. Examples of the trivalent coupling group A 1 include -C(CH 2 -) 2 CH 3 and the like, and examples of the tetravalent coupling group A 1 include C(CH 2 -) 4 and the like.

於式(4)中，Y 1表示2價之連結基，表示-O-或-NH-，更佳為-O-。 In formula (4), Y 1 represents a divalent linking group, and represents -O- or -NH-, and more preferably -O-.

於通式(4)中，u表示1～3之整數，u尤佳為1。In the general formula (4), u represents an integer from 1 to 3, and u is preferably 1.

於式(4)中，n表示1～3之整數，n尤佳為1。 芳香環之取代位置分別獨立地表示鄰位、間位、對位，較佳為對位。 In formula (4), n represents an integer from 1 to 3, and n is preferably 1. The substitution positions of the aromatic ring independently represent the ortho position, meta position, and para position, and the preferred position is the para position.

關於式(4)所表示之重複單元，較佳者可例示以下之結構。再者，雖對芳香環之取代位置為對位者進行例示，但取代位置亦可分別獨立地為鄰位、間位。The repeating unit represented by formula (4) preferably has the following structure. In addition, although the substitution position on the aromatic ring is para-position, the substitution position may be ortho-position or meta-position, respectively.

[化14] [Chemistry 14]

[化15] [Chemistry 15]

[化16] [Chemistry 16]

[化17] [Chemistry 17]

式(4)所表示之重複單元之含氟樹脂(D)中之含量相對於構成含氟樹脂(D)之總重複單元100莫耳%，較佳為5莫耳%以上70莫耳%以下，更佳為10莫耳%以上50莫耳%以下，尤佳為10莫耳%以上30莫耳%以下。The content of the repeating unit represented by the formula (4) in the fluorine-containing resin (D) is preferably 5 mol% or more and 70 mol% or less based on 100 mol% of the total repeating units constituting the fluorine-containing resin (D). , more preferably not less than 10 mol% and not more than 50 mol%, particularly preferably not less than 10 mol% and not more than 30 mol%.

若式(4)之重複單元之含量多於70莫耳%，則有含氟樹脂(D)變得難溶於溶劑中之傾向。If the content of the repeating unit of formula (4) is more than 70 mol %, the fluorinated resin (D) tends to become difficult to dissolve in the solvent.

含氟樹脂(D)亦可為如上文所示包含上述式(3)所表示之重複單元及上述式(4)所表示之重複單元之共聚物、與包含上述式(3)所表示之重複單元及上述式(4)所表示之重複單元之另一種共聚物的混合體(摻合物)。尤其是含氟樹脂(D)係包含式(4)中之W 1為-O-C(=O)-NH-之重複單元之含氟樹脂、與包含式(4)中之W 1為-C(=O)-NH-之重複單元之含氟樹脂的混合體為本發明之一較佳形態。 The fluorinated resin (D) may also be a mixture (blend) of a copolymer comprising a repeating unit represented by the above formula (3) and a repeating unit represented by the above formula (4) as shown above, and another copolymer comprising a repeating unit represented by the above formula (3) and a repeating unit represented by the above formula (4). In particular, a mixture of a fluorinated resin (D) comprising a repeating unit in which W1 in the formula (4) is -OC(=O)-NH- and a fluorinated resin comprising a repeating unit in which W1 in the formula (4) is -C(=O)-NH- is a preferred embodiment of the present invention.

又，於本發明之感光性樹脂組合物中，含氟樹脂(D)亦可包含下述(5)式所表示之結構。Furthermore, in the photosensitive resin composition of the present invention, the fluorine-containing resin (D) may also include a structure represented by the following formula (5).

[化18] [Chemistry 18]

於式(5)中，R 5、R 6分別獨立地表示氫原子或甲基。 In formula (5), R 5 and R 6 each independently represent a hydrogen atom or a methyl group.

於式(5)中，W 2表示2價之連結基，表示-O-、-O-C(=O)-、-C(=O)-O-、-O-C(=O)-NH-、-C(=O)-O-C(=O)-NH-或-C(=O)-NH-。其中，較佳為-O-C(=O)-NH-、-C(=O)-O-C(=O)-NH-或-C(=O)-NH-。 In formula (5), W 2 represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, - C(=O)-OC(=O)-NH- or -C(=O)-NH-. Among them, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH- is preferred.

於式(5)中，A 2表示2價之連結基，表示碳數1～10之直鏈狀、碳數3～10之支鏈狀或碳數3～10之環狀之伸烷基，該伸烷基中之任意數量之氫原子可被取代為羥基或-O-C(=O)-CH 3。 In formula (5), A 2 represents a divalent linking group, which represents a linear alkylene group having 1 to 10 carbon atoms, a branched chain having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group may be substituted with hydroxyl groups or -OC(=O)-CH 3 .

於通式(5)中，A 3表示2～4價之連結基，表示碳數1～10之直鏈狀、碳數3～10之支鏈狀或碳數3～10之環狀之烴基，該烴基中之任意數量之氫原子可被取代為羥基或-O-C(=O)-CH 3。 In the general formula (5), A 3 represents a 2- to 4-valent linking group, and represents a linear hydrocarbon group having 1 to 10 carbon atoms, a branched chain having 3 to 10 carbon atoms, or a cyclic hydrocarbon group having 3 to 10 carbon atoms. , any number of hydrogen atoms in the hydrocarbon group can be substituted with hydroxyl groups or -OC(=O)-CH 3 .

當2價之連結基A 2、A 3分別獨立地為碳數1～10之直鏈狀之伸烷基時，例如可例舉：亞甲基、伸乙基、伸丙基、伸正丁基、伸正戊基、伸正己基、伸正庚基、伸正辛基、伸正壬基、伸正癸基。 When the divalent linking groups A 2 and A 3 are independently linear alkylene groups having 1 to 10 carbon atoms, examples thereof include methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene and n-decylene.

當2價之連結基A 2、A 3分別獨立地為碳數3～10之支鏈狀之伸烷基時，例如可例舉：伸異丙基、伸異丁基、伸第二丁基、伸第三丁基、伸異戊基、伸異己基等。 When the divalent linking groups A 2 and A 3 are independently branched alkylene groups having 3 to 10 carbon atoms, examples thereof include isopropylene, isobutylene, sec-butylene, t-butylene, isopentylene, isohexylene and the like.

當2價之連結基A 2、A 3分別獨立地為碳數3～10之環狀之伸烷基時，例如可例舉：二取代環丙烷、二取代環丁烷、二取代環戊烷、二取代環己烷、二取代環庚烷、二取代環辛烷、二取代環癸烷、二取代4-第三丁基環己烷等。 When the divalent linking groups A 2 and A 3 are each independently a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include: disubstituted cyclopropane, disubstituted cyclobutane, and disubstituted cyclopentane. , disubstituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, disubstituted 4-tert-butylcyclohexane, etc.

當該等伸烷基中之任意數量之氫原子被取代為羥基時，作為該經羥基取代之伸烷基，例如可例舉：1-羥基伸乙基(-CH(OH)CH 2-)、2-羥基伸乙基(-CH 2CH(OH)-)、1-羥基伸正丙基、2-羥基伸正丙基、羥基伸異丙基(-CH(CH 2OH)CH 2-)、1-羥基伸正丁基、2-羥基伸正丁基、羥基伸第二丁基(-CH(CH 2OH)CH 2CH 2-)、羥基伸異丁基(-CH 2CH(CH 2OH)CH 2-)、羥基伸第三丁基(-C(CH 2OH)(CH 3)CH 2-)等。 When any number of hydrogen atoms in the alkylene groups are substituted with hydroxyl groups, examples of the alkylene groups substituted with hydroxyl groups include 1-hydroxyethylene (—CH(OH) CH2— ), 2-hydroxyethylene ( —CH2CH (OH)—), 1-hydroxyn-propylene, 2-hydroxyn-propylene, hydroxyi-propylene (—CH( CH2OH ) CH2— ), 1-hydroxyn-butylene, 2- hydroxyn-butylene, hydroxyi-butylene (—CH(CH2OH)CH2CH2—), hydroxyi-butylene (—CH2CH(CH2OH)CH2— ) , hydroxyi - butylene (—C( CH2OH )( CH3 ) CH2— ) , and the like.

又，當該等伸烷基中之任意數量之氫原子被取代為-O-C(=O)-CH 3時，作為該經取代之伸烷基，可例舉：上文中例示之經羥基取代之伸烷基之羥基被取代為-O-C(=O)-CH 3者。 When any number of hydrogen atoms in the alkylene groups are substituted with -OC(=O)-CH 3 , the substituted alkylene groups include those in which the hydroxyl group of the alkylene groups substituted with hydroxyl groups exemplified above is substituted with -OC(=O)-CH 3 .

其中，2價之連結基A 2、A 3分別獨立地較佳為亞甲基、伸乙基、伸丙基、伸正丁基、伸異丁基、伸第二丁基、環己基、1-羥基伸乙基(-CH(OH)CH 2-)、2-羥基伸乙基(-CH 2CH(OH)-)、2-羥基伸正丙基、羥基伸異丙基(-CH(CH 2OH)CH 2-)、2-羥基伸正丁基、羥基伸第二丁基(-CH(CH 2OH)CH 2CH 2-)，更佳為伸乙基、伸丙基、1-羥基伸乙基(-CH(OH)CH 2-)、2-羥基伸乙基(-CH 2CH(OH)-)、2-羥基伸正丙基、羥基伸異丙基(-CH(CH 2OH)CH 2-)，尤佳為伸乙基、1-羥基伸乙基(-CH(OH)CH 2-)、2-羥基伸乙基(-CH 2CH(OH)-)。 作為3價之連結基A 3，可例舉-C(CH 2-) 2CH 3等，作為4價之連結基A 3，可例舉C(CH 2-) 4等。 Among them, the divalent linking groups A 2 and A 3 are each independently preferably a methylene group, an ethylene group, a propylene group, a n-butylene group, an isobutylene group, a sec-butylene group, a cyclohexyl group, a 1-hydroxyethylene group (—CH(OH)CH 2 —), a 2-hydroxyethylene group (—CH 2 CH(OH)-), a 2-hydroxyn-propylene group, an isopropylene group (—CH(CH 2 OH)CH 2 —), a 2-hydroxyn-butylene group, a sec-butylene group (—CH(CH 2 OH)CH 2 CH 2 —), and more preferably an ethylene group, a propylene group, a 1-hydroxyethylene group (—CH(OH)CH 2 —), a 2-hydroxyethylene group (—CH 2 CH(OH)-), a 2-hydroxyn-propylene group, an isopropylene group (—CH(CH 2 OH)CH 2 —), a 2 -), particularly preferably ethylene, 1-hydroxyethylene (-CH(OH)CH 2 -), 2-hydroxyethylene (-CH 2 CH(OH)-). Examples of the trivalent linking group A 3 include -C(CH 2 -) 2 CH 3 , and examples of the tetravalent linking group A 3 include C(CH 2 -) 4 , etc.

於式(5)中，Y 2、Y 3表示2價之連結基，分別獨立地表示-O-或-NH-，更佳為-O-。 In formula (5), Y 2 and Y 3 represent a divalent linking group, and each independently represents -O- or -NH-, more preferably -O-.

於式(5)中，n表示1～3之整數，n尤佳為1。In formula (5), n represents an integer from 1 to 3, and n is preferably 1.

於式(5)中，r表示0或1。r為0時「(-C(=O)-) r」之部分表示單鍵。 In formula (5), r represents 0 or 1. When r is 0, the part of "(-C(=O)-) r " represents a single bond.

關於式(5)所表示之重複單元，較佳者可例示以下之結構。Regarding the repeating unit represented by formula (5), the following structures can be preferably exemplified.

[化19] [Chemical 19]

[化20] [Chemistry 20]

[化21] [Chemistry 21]

[化22] [Chemistry 22]

[化23] [Chemistry 23]

式(5)所表示之重複單元於含氟樹脂(D)中之含量相對於構成含氟樹脂(D)之總重複單元100莫耳%，較佳為5莫耳%以上70莫耳%以下，更佳為10莫耳%以上50莫耳%以下，尤佳為10莫耳%以上30莫耳%以下。The content of the repeating unit represented by formula (5) in the fluorinated resin (D) is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and particularly preferably 10 mol% to 30 mol%, based on 100 mol% of the total repeating units constituting the fluorinated resin (D).

若式(5)之重複單元之含量多於70莫耳%，則有含氟樹脂(D)變得難溶於溶劑中之傾向。另一方面，若式(5)之重複單元之含量少於5莫耳%，則有由含氟樹脂(D)獲得之含氟樹脂膜或障壁對於基板之密接性降低之傾向。If the content of the repeating unit of formula (5) is more than 70 mol%, the fluorinated resin (D) tends to become difficult to dissolve in the solvent. On the other hand, if the content of the repeating unit of formula (5) is less than 5 mol%, the adhesion of the fluorinated resin film or barrier obtained from the fluorinated resin (D) to the substrate tends to decrease.

式(5)所表示之重複單元所具有之效果並不明確，但推測，藉由使含氟樹脂(D)包含式(5)所表示之重複單元，可以提昇所獲得之含氟樹脂膜或障壁對於基板之密接性。但，本發明之效果並不限定於此處所描述之效果。The effect of the repeating unit represented by formula (5) is not clear, but it is speculated that by making the fluorine-containing resin (D) contain the repeating unit represented by formula (5), the adhesion of the obtained fluorine-containing resin film or barrier to the substrate can be improved. However, the effect of the present invention is not limited to the effect described here.

含氟樹脂(D)亦可為包含上述式(3)所表示之重複單元及上述式(5)所表示之重複單元之共聚物、與包含上述式(3)所表示之重複單元及上述式(5)所表示之重複單元之另一種共聚物的混合體(摻合物)。尤其是含氟樹脂(D)係包含式(5)中之W 2為-O-C(=O)-NH-之重複單元之含氟樹脂、與包含式(5)中之W 2為-C(=O)-NH-之重複單元之含氟樹脂的混合體為本發明之一較佳形態。 The fluorine-containing resin (D) may be a copolymer containing a repeating unit represented by the above formula (3) and a repeating unit represented by the above formula (5), or a copolymer containing a repeating unit represented by the above formula (3) and the above formula (5) A mixture (blend) of another copolymer of the repeating units indicated. In particular, the fluorine-containing resin (D) is a fluorine-containing resin containing a repeating unit in which W 2 in the formula (5) is -OC(=O)-NH-, and a fluorine-containing resin containing a repeating unit in which W 2 in the formula (5) is -C( A mixture of fluorine-containing resins with repeating units of =O)-NH- is a preferred embodiment of the present invention.

又，於本發明之感光性樹脂組合物中，含氟樹脂(D)亦可包含下述(6)式所表示之結構。Moreover, in the photosensitive resin composition of this invention, the fluorine-containing resin (D) may contain the structure represented by following formula (6).

[化24] [Chemistry 24]

式(6)中，R 7表示氫原子或甲基。 In formula (6), R7 represents a hydrogen atom or a methyl group.

式(6)中，R 8表示碳數1～15之直鏈狀、碳數3～15之支鏈狀或碳數3～15之環狀之烷基，該烷基中之任意數量之氫原子被取代為氟原子，重複單元中之氟原子含有率為30質量%以上。 In formula (6), R8 represents a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, wherein any number of hydrogen atoms in the alkyl group are substituted with fluorine atoms, and the fluorine atom content in the repeating unit is 30 mass % or more.

R 8為直鏈狀之烷基時，具體而言，可例舉：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基或碳數10～14之直鏈狀烷基之任意數量之氫原子被取代為氟原子之重複單元。 When R8 is a linear alkyl group, specifically, it can be exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or a linear alkyl group having 10 to 14 carbon atoms in which any number of hydrogen atoms are replaced by repeated units of fluorine atoms.

當R 8為直鏈狀之烷基時，上述式(6)所表示之重複單元較佳為下述式(6-1)所表示之重複單元。 When R 8 is a linear alkyl group, the repeating unit represented by the above formula (6) is preferably a repeating unit represented by the following formula (6-1).

[化25] [Chemical 25]

式(6-1)中，R 9與式(6)之R 7含義相同。 In formula (6-1), R 9 has the same meaning as R 7 in formula (6).

式(6-1)中，X為氫原子或氟原子。In formula (6-1), X is a hydrogen atom or a fluorine atom.

式(6-1)中，p為1～4之整數。q為1～14之整數。尤佳為p為1～2之整數且q為2～8之整數，並且X為氟原子。In formula (6-1), p is an integer of 1 to 4. q is an integer of 1 to 14. It is particularly preferred that p is an integer of 1 to 2 and q is an integer of 2 to 8, and X is a fluorine atom.

關於式(6)所表示之重複單元，較佳者可例示以下之結構。Regarding the repeating unit represented by formula (6), the following structures can be preferably exemplified.

[化26] [Chemistry 26]

[化27] [Chemistry 27]

[化28] [Chemical 28]

[化29] [Chemistry 29]

式(6)所表示之重複單元之含量相對於構成含氟樹脂(D)之總重複單元100莫耳%，較佳為5莫耳%以上70莫耳%以下，更佳為10莫耳%以上50莫耳%以下，尤佳為10莫耳%以上30莫耳%以下。The content of the repeating unit represented by formula (6) is preferably 5 mol% or more and 70 mol% or less, more preferably 10 mol%, based on 100 mol% of the total repeating units constituting the fluorine-containing resin (D). More than 50 mol% and less, preferably more than 10 mol% and less than 30 mol%.

若式(6)之重複單元之含量多於70莫耳%，則有含氟樹脂(D)變得難溶於溶劑中之傾向。If the content of the repeating unit of formula (6) exceeds 70 mol%, the fluororesin (D) tends to become poorly soluble in the solvent.

又，於本發明之感光性樹脂組合物中，含氟樹脂(D)亦可為包含下述(7)式所表示之結構。Furthermore, in the photosensitive resin composition of the present invention, the fluorine-containing resin (D) may also have a structure represented by the following formula (7).

[化30] [Chemistry 30]

式(7)中，R 10表示氫原子或甲基。 In formula (7), R 10 represents a hydrogen atom or a methyl group.

式(7)中，B分別獨立地表示羥基、羧基、-C(=O)-O-R 11(R 11表示碳數1～15之直鏈狀、碳數3～15之支鏈狀或碳數3～15之環狀之烷基，該烷基中之任意數量之氫原子被取代為氟原子，且R 11中之氟原子含有率為30質量%以上)或-O-C(=O)-R 12(R 12表示碳數1～6之直鏈狀、碳數3～6之支鏈狀或碳數3～6之環狀之烷基)。又，m表示0～3之整數。 In formula (7), B independently represents a hydroxyl group, a carboxyl group, -C(=O)-OR 11 (R 11 represents a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, an arbitrary number of hydrogen atoms in the alkyl group are substituted with fluorine atoms, and the fluorine atom content in R 11 is 30 mass % or more), or -OC(=O)-R 12 (R 12 represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. Furthermore, m represents an integer from 0 to 3.

關於式(7)所表示之重複單元，較佳者可例示以下之結構。Regarding the repeating unit represented by formula (7), the following structures can be preferably exemplified.

[化31] [Chemistry 31]

[化32] [Chemistry 32]

式(7)所表示之重複單元之含量相對於構成含氟樹脂(D)之總重複單元100莫耳%，較佳為5莫耳%以上70莫耳%以下，更佳為10莫耳%以上50莫耳%以下，尤佳為20莫耳%以上40莫耳%以下。The content of the repeating unit represented by formula (7) is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and particularly preferably 20 mol% to 40 mol%, based on 100 mol% of the total repeating units constituting the fluorinated resin (D).

若式(7)之重複單元之含量多於70莫耳%，則有含氟樹脂(D)變得難溶於溶劑中之傾向。If the content of the repeating unit of formula (7) is more than 70 mol %, the fluorinated resin (D) tends to become difficult to dissolve in the solvent.

於式(7)中，當B為羥基或羧基時，式(7)所表示之重複單元具有於鹼性顯影液中之溶解性。因此，當想要向由含氟樹脂(D)獲得之膜賦予鹼性顯影性時，較佳為含氟樹脂(D)中包含B為羥基或羧基之情形時之式(7)所表示之重複單元。In formula (7), when B is a hydroxyl group or a carboxyl group, the repeating unit represented by formula (7) has solubility in an alkaline developer. Therefore, when it is desired to impart alkaline developability to a film obtained from a fluorine-containing resin (D), it is preferable that the fluorine-containing resin (D) include the case where B is a hydroxyl group or a carboxyl group, represented by formula (7) Repeating unit.

又，於本發明之感光性樹脂組合物中，含氟樹脂(D)亦可包含下述(8)式所表示之結構。Moreover, in the photosensitive resin composition of this invention, the fluorine-containing resin (D) may contain the structure represented by following formula (8).

[化33] [Chemistry 33]

於式(8)中，R 13表示氫原子或甲基。 In formula (8), R 13 represents a hydrogen atom or a methyl group.

於式(8)中，A 4表示2價之連結基，表示碳數1～10之直鏈狀、碳數3～10之支鏈狀或碳數3～10之環狀之伸烷基，該伸烷基中之任意數量之氫原子可被取代為羥基或-O-C(=O)-CH 3。 In formula (8), A 4 represents a divalent linking group, which represents a linear alkylene group having 1 to 10 carbon atoms, a branched chain having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group may be substituted with hydroxyl groups or -OC(=O)-CH 3 .

當2價之連結基A 4為碳數1～10之直鏈狀之伸烷基時，例如可例舉：亞甲基、伸乙基、伸丙基、伸正丁基、伸正戊基、伸正己基、伸正庚基、伸正辛基、伸正壬基、伸正癸基。 When the divalent linking group A 4 is a straight-chain alkylene group having 1 to 10 carbon atoms, examples thereof include methylene, ethylene, propylene, n-butyl, n-pentyl, and n-pentyl. Hexyl, heptyl, octyl, nonyl, decyl.

當2價之連結基A 4為碳數3～10之支鏈狀之伸烷基時，例如可例舉：伸異丙基、伸異丁基、伸第二丁基、伸第三丁基、伸異戊基、伸異己基等。 When the divalent linking group A 4 is a branched alkylene group having 3 to 10 carbon atoms, examples thereof include: isopropyl group, isobutyl group, second butylene group, and third butylene group. , isopentyl, isohexyl, etc.

當2價之連結基A 4為碳數3～10之環狀之伸烷基時，例如可例舉：二取代環丙烷、二取代環丁烷、二取代環戊烷、二取代環己烷、二取代環庚烷、二取代環辛烷、二取代環癸烷、二取代4-第三丁基環己烷等。 When the divalent linking group A 4 is a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, and disubstituted cyclohexane. , disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, disubstituted 4-tert-butylcyclohexane, etc.

當該等伸烷基中之任意數量之氫原子被取代為羥基時，作為該經羥基取代之伸烷基，例如可例舉：1-羥基伸乙基(-CH(OH)CH 2-)、2-羥基伸乙基(-CH 2CH(OH)-)、1-羥基伸正丙基、2-羥基伸正丙基、羥基伸異丙基(-CH(CH 2OH)CH 2-)、1-羥基伸正丁基、2-羥基伸正丁基、羥基伸第二丁基(-CH(CH 2OH)CH 2CH 2-)、羥基伸異丁基(-CH 2CH(CH 2OH)CH 2-)、羥基伸第三丁基(-C(CH 2OH)(CH 3)CH 2-)等。 When any number of hydrogen atoms in the alkylene group are substituted with hydroxyl groups, examples of the hydroxyl-substituted alkylene group include: 1-hydroxyethylene group (-CH(OH)CH 2 -) , 2-hydroxyethylidene (-CH 2 CH(OH)-), 1-hydroxypropyl propyl, 2-hydroxypropyl propyl, hydroxyisopropyl (-CH(CH 2 OH)CH 2 -), 1-hydroxy-n-butyl, 2-hydroxy-n-butyl, hydroxyl-butyl (-CH(CH 2 OH)CH 2 CH 2 -), hydroxyl-isobutyl (-CH 2 CH(CH 2 OH) CH 2 -), hydroxyl-tert-butyl (-C(CH 2 OH)(CH 3 )CH 2 -), etc.

又，當該等伸烷基中之任意數量之氫原子被取代為-O-C(=O)-CH 3時，作為該經取代之伸烷基，可例舉：上文中例示之經羥基取代之伸烷基之羥基被取代為-O-C(=O)-CH 3者。 When any number of hydrogen atoms in the alkylene groups are substituted with -OC(=O)-CH 3 , the substituted alkylene groups include those in which the hydroxyl group of the alkylene groups substituted with hydroxyl groups exemplified above is substituted with -OC(=O)-CH 3 .

其中，2價之連結基A 4較佳為亞甲基、伸乙基、伸丙基、伸正丁基、伸異丁基、伸第二丁基、環己基、1-羥基伸乙基(-CH(OH)CH 2-)、2-羥基伸乙基(-CH 2CH(OH)-)、2-羥基伸正丙基、羥基伸異丙基(-CH(CH 2OH)CH 2-)、2-羥基伸正丁基、羥基伸第二丁基(-CH(CH 2OH)CH 2CH 2-)，更佳為伸乙基、伸丙基、1-羥基伸乙基(-CH(OH)CH 2-)、2-羥基伸乙基(-CH 2CH(OH)-)、2-羥基伸正丙基、羥基伸異丙基(-CH(CH 2OH)CH 2-)，尤佳為伸乙基、1-羥基伸乙基(-CH(OH)CH 2-)、2-羥基伸乙基(-CH 2CH(OH)-)。 Among them, the divalent linking group A 4 is preferably methylene, ethylidene, propylene, n-butyl, isobutyl, second-butylene, cyclohexyl, or 1-hydroxyethylidene (- CH(OH)CH 2 -), 2-hydroxyethylidene (-CH 2 CH(OH)-), 2-hydroxypropylene, hydroxyisopropyl (-CH(CH 2 OH)CH 2 -) , 2-hydroxyl-n-butyl group, hydroxyl-n-butyl group (-CH(CH 2 OH) CH 2 CH 2 -), more preferably ethyl-ylidene group, propyl-ylidene group, 1-hydroxyl-butylene ethyl group (-CH( OH)CH 2 -), 2-hydroxyethyl (-CH 2 CH(OH)-), 2-hydroxypropyl, hydroxyisopropyl (-CH(CH 2 OH)CH 2 -), especially Preferred ones are ethylidene, 1-hydroxyethylidene (-CH(OH)CH 2 -), and 2-hydroxyethylidene (-CH 2 CH(OH)-).

於式(8)中，Y 4表示2價之連結基，表示-O-或-NH-，更佳為-O-。 In formula (8), Y 4 represents a divalent linking group, and represents -O- or -NH-, and more preferably -O-.

於式(8)中，r表示0或1。r為0時「(-C(=O)-) r」之部分表示單鍵。 In formula (8), r represents 0 or 1. When r is 0, the part of "(-C(=O)-) r " represents a single bond.

於式(8)中，E 1表示羥基、羧基或氧雜環丙烷基。 E 1為氧雜環丙烷基時，例如可例舉：環氧乙烷基、1,2-環氧丙烷基、1,3-環氧丙烷基等。其中，較佳為環氧乙烷基。 In formula (8), E 1 represents a hydroxyl group, a carboxyl group or an oxadiazole group. When E 1 is an oxadiazole group, examples thereof include an oxadiazole group, a 1,2-oxadiazole group, a 1,3-oxadiazole group and the like. Among them, an oxadiazole group is preferred.

於式(8)中，s表示0或1。s為0時「(-Y 4-A 4-) s」之部分表示單鍵。r為0且s為0時，成為於重複單元之主鏈上鍵結有E 1之結構。 In formula (8), s represents 0 or 1. When s is 0, the portion of "(-Y 4 -A 4 -) s " represents a single bond. When r is 0 and s is 0, a structure is formed in which E 1 is bonded to the main chain of the repeating unit.

關於式(8)所表示之重複單元，較佳者可例示以下之結構。Regarding the repeating unit represented by formula (8), the following structures can be preferably exemplified.

[化34] [Chemical 34]

於式(8)中，當E 1為羥基或羧基時，式(8)所表示之重複單元賦予含氟樹脂(D)於鹼性顯影液中之溶解性。因此，當想要向由含氟樹脂(D)獲得之膜賦予鹼性顯影性時，較佳為於含氟樹脂(D)中包含E 1為羥基或羧基之情形時之式(8)所表示之重複單元。 In formula (8), when E1 is a hydroxyl group or a carboxyl group, the repeating unit represented by formula (8) imparts solubility to the fluorinated resin (D) in an alkaline developer. Therefore, when it is desired to impart alkaline developing properties to a film obtained from the fluorinated resin (D), it is preferred that the repeating unit represented by formula (8) includes the case where E1 is a hydroxyl group or a carboxyl group in the fluorinated resin (D).

關於具有交聯部位之含氟樹脂(D)，例如使單體聚合而獲得具有包含上述式(3)、(6)～(8)所示之結構之重複單元之含氟樹脂前體，繼而使含氟樹脂前體與光聚合性基衍生物進行反應，藉此向聚合物之側鏈導入光聚合性基，而能夠合成具有包含上述式(4)、(5)所示之結構之重複單元之含氟樹脂(D)。 作為要導入含氟樹脂前體之光聚合性基，較佳為丙烯醯基、甲基丙烯醯基、乙烯基、烯丙基，更佳為丙烯醯基。 當導入丙烯醯基作為光聚合性基時，作為光聚合性基衍生物，例如可例舉：具有丙烯醯基之異氰酸酯單體、具有丙烯醯基之環氧單體等丙烯酸衍生物。 作為具有丙烯醯基之異氰酸酯單體，例如可例舉：甲基丙烯酸2-異氰酸基乙酯、丙烯酸2-異氰酸基乙酯、異氰酸2-(2-甲基丙烯醯氧基乙基氧基)乙酯、異氰酸1,1-(雙丙烯醯氧基甲基)乙酯等。較佳為丙烯酸2-異氰酸基乙酯。 作為具有丙烯醯基之環氧單體，例如可例舉：丙烯酸環氧丙酯、4-羥基丁基丙烯酸酯環氧丙基醚(4HBAGE，三菱化學股份有限公司製造)等。 Regarding the fluorine-containing resin (D) having a cross-linked site, for example, a monomer is polymerized to obtain a fluorine-containing resin precursor having a repeating unit including a structure represented by the above formulas (3), (6) to (8), and then By reacting a fluororesin precursor with a photopolymerizable group derivative, a photopolymerizable group is introduced into the side chain of the polymer, and a repeating structure including the structures represented by the above formulas (4) and (5) can be synthesized. Unit of fluorine-containing resin (D). As the photopolymerizable group to be introduced into the fluorine-containing resin precursor, an acrylic group, a methacrylic group, a vinyl group, and an allyl group are preferred, and an acryl group is more preferred. When an acryl group is introduced as a photopolymerizable group, examples of the photopolymerizable group derivative include acrylic acid derivatives such as an isocyanate monomer having an acryl group and an epoxy monomer having an acryl group. Examples of the isocyanate monomer having an acryl group include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, and 2-(2-methacrylyl isocyanate). ethyloxy)ethyl ester, 1,1-(bisacrylyloxymethyl)ethyl isocyanate, etc. Preferred is 2-isocyanatoethyl acrylate. Examples of the epoxy monomer having an acryl group include glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether (4HBAGE, manufactured by Mitsubishi Chemical Co., Ltd.), and the like.

藉由含氟樹脂前體所具有之羥基與光聚合性基衍生物之加成反應，而向含氟樹脂前體導入光聚合性基。 含氟樹脂(D)中之光聚合性基之比例於含氟樹脂(D)中，較佳為10莫耳%以上且70莫耳%以下。若光聚合性基之比例未達10莫耳%，則有樹脂膜、阻隔壁之強度降低之傾向。若光聚合性基之比例超過70莫耳%，則有時難以藉由塗佈形成樹脂膜。更佳為15莫耳%～60莫耳%。 The photopolymerizable group is introduced into the fluororesin precursor through an addition reaction between the hydroxyl group of the fluororesin precursor and the photopolymerizable group derivative. The proportion of the photopolymerizable group in the fluorine-containing resin (D) is preferably 10 mol% or more and 70 mol% or less in the fluorine-containing resin (D). If the proportion of the photopolymerizable group is less than 10 mol%, the strength of the resin film and barrier ribs tends to decrease. If the proportion of the photopolymerizable group exceeds 70 mol%, it may be difficult to form a resin film by coating. More preferably, it is 15 mol% to 60 mol%.

於本發明之感光性樹脂組合物中，含氟樹脂(D)之分子量係藉由以聚苯乙烯作為標準物質之凝膠滲透層析法(GPC)測得之重量平均分子量，較佳為1,000以上且1,000,000以下，更佳為2,000以上且500,000以下，尤佳為3,000以上且100,000以下。若分子量小於1,000，則有所形成之含氟樹脂膜或障壁之強度降低之傾向，若分子量大於1,000,000，則有時於溶劑中之溶解性不足而難以藉由塗佈形成含氟樹脂膜。In the photosensitive resin composition of the present invention, the molecular weight of the fluorine-containing resin (D) is the weight average molecular weight measured by gel permeation chromatography (GPC) using polystyrene as a standard material, and is preferably 1,000. More than 1,000,000 and less, more preferably not less than 2,000 and not more than 500,000, particularly preferably not less than 3,000 and not more than 100,000. If the molecular weight is less than 1,000, the strength of the formed fluororesin film or barrier tends to decrease. If the molecular weight exceeds 1,000,000, the solubility in a solvent may be insufficient, making it difficult to form a fluororesin film by coating.

含氟樹脂(D)之分散指數(Mw/Mn)較佳為1.01～5.00，更佳為1.01～4.00，尤佳為1.01～3.00。The dispersion index (Mw/Mn) of the fluorinated resin (D) is preferably 1.01 to 5.00, more preferably 1.01 to 4.00, and particularly preferably 1.01 to 3.00.

含氟樹脂(D)可為無規共聚物，亦可為交替共聚物，亦可為嵌段共聚物，還可為接枝共聚物。從適度分散各特性而並非局部分散之觀點考慮，較佳為無規共聚物。The fluorinated resin (D) may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. From the viewpoint of appropriately dispersing various properties without partial dispersion, a random copolymer is preferred.

本發明之感光性樹脂組合物中之含氟樹脂(D)之較佳為形態如以下所示。 ＜形態1＞ 包含以下之式(3)所表示之重複單元、式(5)所表示之重複單元、式(6-1)所表示之重複單元及式(7)所表示之重複單元之含氟樹脂(D) 式(3)：R 1及R 2為氫原子，Rb分別獨立地為氟原子、二氟甲基或三氟甲基 式(5)：R 5及R 6分別獨立地為氫原子或甲基，W 2為-O-C(=O)-NH-、-C(=O)-O-C(=O)-NH-或-C(=O)-NH-，A 2、A 3分別獨立地為伸乙基，Y 2及Y 3為-O-，n為1，r為1 式(6-1)：R 9為甲基，p為2之整數，q為4～8之整數，X為氟原子 式(7)：R 10為氫原子，B為羥基或羧基，m為1。 The preferred form of the fluorine-containing resin (D) in the photosensitive resin composition of the present invention is as follows. <Form 1> A fluorinated resin (D) comprising the following repeating units represented by formula (3), repeating units represented by formula (5), repeating units represented by formula (6-1), and repeating units represented by formula (7): Formula (3): R1 and R2 are hydrogen atoms, Rb are independently fluorine atoms, difluoromethyl groups, or trifluoromethyl groups. Formula (5): R5 and R6 are independently hydrogen atoms or methyl groups, W2 is -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH-, A2 and A3 are independently ethylidene groups, Y2 and Y3 are -O-, n is 1, and r is 1. Formula (6-1): R9 is methyl, p is an integer of 2, q is an integer of 4 to 8, and X is a fluorine atom. Formula (7): R 10 is a hydrogen atom, B is a hydroxyl group or a carboxyl group, and m is 1.

＜形態2＞ 包含以下之式(5)所表示之重複單元、式(6)所表示之重複單元、式(6-1)所表示之重複單元及式(8)所表示之重複單元之含氟樹脂(D) 式(5)：R 5及R 6分別獨立地為氫原子或甲基，W 2為-O-C(=O)-NH-、-C(=O)-O-C(=O)-NH-或-C(=O)-NH-，A 2、A 3分別獨立地為伸乙基，Y 2及Y 3為-O-，n為1，r為1 式(6)：R 7為甲基，R 8為碳數3～15之支鏈狀之全氟烷基 式(6-1)：R 9為甲基，p為2之整數，q為4～8之整數，X為氟原子 式(8)：R 13為甲基，A 4為伸乙基，Y 4為-O-，r為1，s為0或1，E 1為羥基或羧基。 <Form 2> A fluorinated resin (D) comprising the repeating unit represented by the following formula (5), the repeating unit represented by the following formula (6), the repeating unit represented by the following formula (6-1), and the repeating unit represented by the following formula (8): Formula (5): R5 and R6 are each independently a hydrogen atom or a methyl group, W2 is -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH-, A2 and A3 are each independently an ethylidene group, Y2 and Y3 are -O-, n is 1, and r is 1. Formula (6): R7 is a methyl group, R8 is a branched perfluoroalkyl group having 3 to 15 carbon atoms. Formula (6-1): R9 is a methyl group, p is an integer of 2 , q is an integer of 4 to 8, and X is a fluorine atom. Formula (8): R13 is a methyl group, A Y4 is ethylidene, Y4 is -O-, r is 1, s is 0 or 1, and E1 is hydroxyl or carboxyl.

本發明之感光性樹脂組合物之含氟樹脂(D)相對於總固形物成分之含量較佳為0.01～40質量%，更佳為20～40質量%。若為該範圍，則樹脂膜之撥水撥油性、基材密接性變得良好。The content of the fluororesin (D) in the photosensitive resin composition of the present invention is preferably 0.01 to 40 mass%, more preferably 20 to 40 mass% relative to the total solid content. If it is within this range, the water and oil repellency of the resin film and the substrate adhesion will become good.

於本發明之感光性樹脂組合物中，含氟樹脂(D)之氟原子含有率與鹼可溶性樹脂(C)之氟原子含有率之差([含氟樹脂(D)之氟原子含有率]－[鹼可溶性樹脂(C)之氟原子含有率])較佳為15～60質量%，較佳為20～50質量%，更佳為25～40質量%。 若為上述範圍，則本發明之感光性樹脂組合物之相溶性變得更加良好。 In the photosensitive resin composition of the present invention, the difference between the fluorine atom content of the fluorine-containing resin (D) and the fluorine atom content of the alkali-soluble resin (C) ([fluorine atom content of the fluorine-containing resin (D)] - [fluorine atom content of the alkali-soluble resin (C)]) is preferably 15 to 60% by mass, more preferably 20 to 50% by mass, and more preferably 25 to 40% by mass. If it is within the above range, the compatibility of the photosensitive resin composition of the present invention becomes better.

＜其他成分＞ 本發明之感光性樹脂組合物亦可為包含溶劑、著色顏料(E)、光自由基增感劑、鏈轉移劑、紫外線吸收劑、聚合抑制劑等作為其他成分。 其等其他成分之較佳形態如以下所示。 ＜Other ingredients＞ The photosensitive resin composition of the present invention may also contain a solvent, a color pigment (E), a photoradical sensitizer, a chain transfer agent, an ultraviolet absorber, a polymerization inhibitor, etc. as other components. Preferable forms of these and other components are as follows.

＜溶劑＞ 於本發明之感光性樹脂組合物中，溶劑並無特別限制，只要可溶解乙烯性不飽和化合物(A)、光聚合起始劑(B)、鹼可溶性樹脂(C)及含氟樹脂(D)即可，例如可例舉：甲基乙基酮、丙二醇單甲醚乙酸酯(PGMEA)、丙二醇單甲醚(PGME)、環己酮、乳酸乙酯、乙酸丁酯、γ-丁內酯。 <Solvent> In the photosensitive resin composition of the present invention, the solvent is not particularly limited, as long as it can dissolve the ethylenically unsaturated compound (A), the photopolymerization initiator (B), the alkali-soluble resin (C) and the fluorine-containing resin (D). Examples thereof include: methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, and γ-butyrolactone.

關於本發明之感光性樹脂組合物中之溶劑之量，將鹼可溶性樹脂(C)及含氟樹脂(D)之合計質量設為100質量份時，較佳為成為50質量份以上且2,000質量份以下之範圍。更佳為100質量份以上且1,000質量份以下。藉由調整溶劑之量，可調節所形成之樹脂膜之膜厚，若於上述範圍內，則能夠獲得尤其是適合獲得障壁之樹脂膜之膜厚。Regarding the amount of solvent in the photosensitive resin composition of the present invention, when the total mass of the alkali-soluble resin (C) and the fluorine-containing resin (D) is set to 100 parts by mass, it is preferably in the range of 50 parts by mass or more and 2,000 parts by mass or less. It is more preferably in the range of 100 parts by mass or more and 1,000 parts by mass or less. By adjusting the amount of solvent, the film thickness of the formed resin film can be adjusted. If it is within the above range, the film thickness of the resin film that is particularly suitable for obtaining a barrier rib can be obtained.

＜著色顏料(E)＞ 著色顏料(E)會導致包含含氟樹脂之感光性樹脂組合物之相溶性降低。然而，本發明之感光性樹脂組合物由於包含上述鹼可溶性樹脂(C)，故而即便包含著色顏料(E)，相溶性也會變得足夠高。 <Coloring pigment (E)> The coloring pigment (E) reduces the compatibility of the photosensitive resin composition containing the fluorine-containing resin. However, since the photosensitive resin composition of the present invention contains the above-mentioned alkali-soluble resin (C), the compatibility becomes sufficiently high even if the coloring pigment (E) is contained.

作為著色顏料(E)，可為有機顏料，亦可為無機顏料，較佳為黑色顏料、白色顏料、其他著色顏料。The color pigment (E) may be an organic pigment or an inorganic pigment, and is preferably a black pigment, a white pigment, or other color pigments.

作為黑色顏料，從相溶性之觀點考慮，較佳為有機顏料，更佳為苯并二呋喃酮系黑色顏料、苝系黑色顏料、偶氮系黑色顏料及其等之異構物。異構物亦包括互變異構物。異構物可以多種顏料粉末之混合物之形式包含，亦可在構成1個一次粒子之基礎上以混晶之形式包含。As the black pigment, from the viewpoint of compatibility, an organic pigment is preferred, and a benzodifuranone-based black pigment, a perylene-based black pigment, an azo-based black pigment, and isomers thereof are more preferred. Isomers also include tautomeric isomers. Isomers may be included in the form of a mixture of a plurality of pigment powders, or in the form of a mixed crystal on the basis of constituting one primary particle.

作為苯并二呋喃酮系黑色顏料，可例舉下述通式(9)或下述通式(10)所表示之顏料，下述通式(9)所表示之顏料相當於被分類為所謂內醯胺黑之顏料。As the benzodifuranone-based black pigment, there can be mentioned the pigment represented by the following general formula (9) or the following general formula (10). The pigment represented by the following general formula (9) is equivalent to a pigment classified as so-called lactamide black.

[化35] [Chemical 35]

[化36] [Chemistry 36]

通式(9)及(10)中，R 14及R 19分別獨立地表示氫原子、CH 3、CF 3、氟原子或氯原子。R 15、R 16、R 17、R 18、R 20、R 21、R 22及R 23分別獨立地表示氫原子、鹵素原子、碳數1～12之烷基、碳數1～12之環烷基、碳數1～12之烯基、碳數1～12之環烯基、碳數1～12之炔基、COOH、COOR 24、COO -、CONH 2、CONHR 24、CONR 24R 25、CN、OH、OR 24、OCOR 24、OCONH 2、OCONHR 24、OCONR 24R 25、NO 2、NH 2、NHR 24、NR 24R 25、NHCOR 24、NR 24COR 25、N=CH 2、N=CHR 24、N=CR 24R 25、SH、SR 24、SOR 24、SO 2R 24、SO 3R 24、SO 3H、SO 3-、SO 2NH 2、SO 2NHR 19或SO 2NR 24R 25。R 15及R 16、R 16及R 17、R 17及R 18、R 20及R 21、R 21及R 22、以及R 22及R 23可以直接鍵結或者藉由O、S、NH或NR 24來鍵結。R 24及R 25分別獨立地表示碳數1～12之烷基、碳數1～12之環烷基、碳數1～12之烯基、碳數1～12之環烯基或碳數1～12之炔基。 In general formulas (9) and (10), R 14 and R 19 each independently represent a hydrogen atom, CH 3 , CF 3 , fluorine atom or chlorine atom. R 15 , R 16 , R 17 , R 18 , R 20 , R 21 , R 22 and R 23 respectively independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a cycloalkane having 1 to 12 carbon atoms. Base, alkenyl group with 1 to 12 carbon atoms, cycloalkenyl group with 1 to 12 carbon atoms, alkynyl group with 1 to 12 carbon atoms, COOH, COOR 24 , COO - , CONH 2 , CONHR 24 , CONR 24 R 25 , CN , OH, OR 24 , OCOR 24 , OCONH 2 , OCONHR 24 , OCONR 24 R 25 , NO 2 , NH 2 , NHR 24 , NR 24 R 25 , NHCOR 24 , NR 24 COR 25 , N=CH 2 , N=CHR 24 , N=CR 24 R 25 , SH, SR 24 , SOR 24 , SO 2 R 24 , SO 3 R 24 , SO 3 H, SO 3 -, SO 2 NH 2 , SO 2 NHR 19 or SO 2 NR 24 R 25 . R 15 and R 16 , R 16 and R 17 , R 17 and R 18 , R 20 and R 21 , R 21 and R 22 , and R 22 and R 23 can be bonded directly or through O, S, NH or NR 24 to bond. R 24 and R 25 each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, a cycloalkenyl group having 1 to 12 carbon atoms, or 1 carbon group. ~12 alkynyl.

其中，從相溶性及光學密度之均勻性之觀點考慮，更佳為R 14～R 23為氫原子者，即，可較佳地使用下述結構式(11)所表示之苯并二呋喃酮系黑色顏料。 藉由使用下述結構式(11)之黑色顏料，感光性樹脂組合物中之著色顏料濃度變得均勻，可獲得用以製造光學密度之均勻性更高之阻隔壁之感光性樹脂組合物。作為下述結構式(11)所表示之苯并二呋喃酮系黑色顏料，亦可為使用市售品，例如可例舉：BASF製造之「Irgaphor」(註冊商標)Black S0100。 Among them, from the viewpoint of compatibility and uniformity of optical density, those in which R 14 to R 23 are hydrogen atoms are more preferred, that is, benzodifuranone represented by the following structural formula (11) can be preferably used. Made of black paint. By using the black pigment of the following structural formula (11), the concentration of the colored pigment in the photosensitive resin composition becomes uniform, and a photosensitive resin composition for producing a barrier rib with higher uniformity in optical density can be obtained. As the benzodifuranone-based black pigment represented by the following structural formula (11), a commercially available product may be used, for example, "Irgaphor" (registered trademark) Black S0100 manufactured by BASF.

[化37] [Chemistry 37]

苝系黑色顏料係指下述通式(12)或(13)所表示之顏料及C.I.顏料黑31、32。相當於被分類為所謂苝黑之顏料。其中，從光學密度之均勻性之觀點考慮，較佳為下述通式(12)或(13)所表示之顏料。Perylene-based black pigments refer to pigments represented by the following general formula (12) or (13) and C.I. Pigment Black 31 and 32. It is equivalent to a pigment classified as so-called perylene black. Among them, from the viewpoint of uniformity of optical density, a pigment represented by the following general formula (12) or (13) is preferred.

[化38] [Chemistry 38]

[化39] [Chemistry 39]

通式(12)及(13)中，R 26～R 33分別獨立地表示氫原子、碳數1～12之烷基、碳數1～6之烷氧基或羥基。其中，從光學密度之均勻性之觀點考慮，較佳為R 26～R 33為氫原子者，即，可較佳地使用下述結構式(14)及/或(15)所表示之苝系黑色顏料。作為下述結構式(14)及(15)所表示之苝系黑色顏料(順反異構物混合物)，亦可使用市售品，例如可例舉：BASF製造之FK4280。 In the general formulas (12) and (13), R 26 to R 33 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydroxyl group. Among them, from the viewpoint of uniformity of optical density, those in which R 26 to R 33 are hydrogen atoms are preferred, that is, the perylene system represented by the following structural formulas (14) and/or (15) can be preferably used. Black pigment. As the perylene-based black pigment (cis-trans isomer mixture) represented by the following structural formulas (14) and (15), commercially available products can also be used, for example, FK4280 manufactured by BASF.

[化40] [Chemistry 40]

[化41] [Chemistry 41]

偶氮系黑色顏料係指下述通式(16)所表示之顏料。相當於被分類為所謂甲亞胺黑之顏料。The azo black pigment refers to a pigment represented by the following general formula (16). It is equivalent to a pigment classified as so-called methamine black.

[化42] [Chemistry 42]

通式(16)中，R 34表示具有異吲哚啉酮結構之有機基或具有異吲哚啉結構之有機基，R 35表示選自由碳數1～3之烷基及碳數1～3之烷氧基所組成之群中之至少1種有機基，n表示1～5之整數。 In the general formula (16), R 34 represents an organic group having an isoindolinone structure or an organic group having an isoindoline structure, and R 35 represents an alkyl group having 1 to 3 carbon atoms and an alkyl group having 1 to 3 carbon atoms. At least one organic group in the group consisting of alkoxy groups, n represents an integer from 1 to 5.

作為白色顏料，較佳為選自由氧化鋁、氧化鎂、氧化銻、氧化鈦、氧化鋯、氫氧化鋁、氫氧化鎂、硫酸鋇、碳酸鎂及碳酸鋇所組成之群中之至少1種無機物。該等無機物由於具有高折射率，故而使用本發明之感光性樹脂組合物所製造之阻隔壁可以提昇光反射性。尤其是從高折射率及於感光性樹脂組合物中之分散性之觀點考慮，更佳為氧化鈦。The white pigment is preferably at least one inorganic substance selected from the group consisting of aluminum oxide, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate. . Since these inorganic substances have high refractive index, the barrier ribs manufactured using the photosensitive resin composition of the present invention can improve the light reflectivity. In particular, titanium oxide is more preferred from the viewpoint of high refractive index and dispersibility in the photosensitive resin composition.

作為其他著色顏料，可以使用黃色、橙色、藍色、紅色、綠色、紫色、棕色等各種有機顏料，亦可製成含有2種以上有機顏料之顏料分散體。藉由調整所含有之顏料之種類、量比，可控制溶解性、遮光性等光學特性。尤其是從相溶性及光學密度之均勻性之觀點考慮，較佳為藍色、紫色、橙色之組合。 又，顏料分散體可包含鹼可溶性樹脂，該鹼可溶性樹脂亦可包含具有上述通式(1)所表示之結構之雙酚型環氧樹脂。 As other coloring pigments, various organic pigments such as yellow, orange, blue, red, green, purple, and brown can be used, and a pigment dispersion containing two or more organic pigments can also be prepared. By adjusting the type and amount ratio of the pigments contained, the optical properties such as solubility and light shielding can be controlled. In particular, from the perspective of compatibility and uniformity of optical density, a combination of blue, purple, and orange is preferred. In addition, the pigment dispersion may contain an alkali-soluble resin, and the alkali-soluble resin may also contain a bisphenol-type epoxy resin having a structure represented by the above general formula (1).

作為有機橙色顏料，例如可例舉：C.I.顏料橙1、2、5、13、16、17、19、20、21、22、23、24、34、36、38、39、43、46、48、49、61、62、64、65、67、68、69、70、71、72、73、74、75、77、78、79。其中，從分散性、遮光性之觀點考慮，較佳為C.I.顏料橙43。Examples of organic orange pigments include: C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48 ,49,61,62,64,65,67,68,69,70,71,72,73,74,75,77,78,79. Among them, C.I. Pigment Orange 43 is preferred from the viewpoint of dispersibility and light-shielding properties.

作為有機藍色顏料，例如可例舉：C.I.顏料藍15、15：1、15：2、15：3、15：4、15：6、16、17、60、64、65、75、79、80。其中，從分散性、遮光性之觀點考慮，較佳為C.I.顏料藍60。Examples of organic blue pigments include: C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 60, 64, 65, 75, 79, 80. Among them, C.I. Pigment Blue 60 is preferred from the viewpoint of dispersibility and light-shielding properties.

作為有機紫色顏料，例如可例舉：C.I.顏料紫1、1：1、2、2：2、3、3：1、3：3、5、5：1、14、15、16、19、23、25、27、29、31、32、37、39、42、44、47、49、50。其中，從分散性、遮光性之觀點考慮，較佳為C.I.顏料紫23。Examples of organic purple pigments include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among them, C.I. Pigment Violet 23 is preferred from the viewpoint of dispersibility and light-shielding properties.

於本發明之感光性樹脂組合物中，著色顏料(E)相對於總固形物成分量，較佳為3質量%以上且未達70質量%，更佳為5～70質量%。 藉由設為上述範圍，本發明之感光性樹脂組合物之相溶性變得良好，而對於使用本發明之感光性樹脂組合物所製造之硬化物之著色變得良好。 In the photosensitive resin composition of the present invention, the color pigment (E) is preferably 3 mass % or more and less than 70 mass % with respect to the total solid content, and more preferably 5 to 70 mass %. By setting it as the said range, the compatibility of the photosensitive resin composition of this invention becomes good, and the coloring of the hardened|cured material produced using the photosensitive resin composition of this invention becomes good.

於本發明之感光性樹脂組合物中，著色顏料(E)之粒徑D 50較佳為50～700 nm，更佳為200～500 nm，進而較佳為200～400 nm。 若著色顏料(E)之粒徑D 50為上述範圍，則對於使用本發明之感光性樹脂組合物所製造之阻隔壁而言，能夠降低阻隔壁部分之光學密度值之不均。 In the photosensitive resin composition of the present invention, the particle diameter D 50 of the color pigment (E) is preferably 50 to 700 nm, more preferably 200 to 500 nm, and still more preferably 200 to 400 nm. If the particle diameter D 50 of the color pigment (E) is within the above range, the unevenness in the optical density value of the barrier rib portion of the barrier rib produced using the photosensitive resin composition of the present invention can be reduced.

再者，本發明之感光性樹脂組合物亦可不包含著色顏料(E)。Furthermore, the photosensitive resin composition of the present invention may not contain the coloring pigment (E).

＜光自由基增感劑＞ 若本發明之感光性樹脂組合物包含光自由基增感劑，則能夠更為提昇本發明之感光性樹脂組合物之曝光感度。光自由基增感劑較佳為吸收光線或放射線而成為激發狀態之化合物。光自由基增感劑因成為激發狀態而在與光聚合起始劑接觸時產生電子轉移、能量轉移或放熱等，藉此光聚合起始劑分解而變得容易生成酸。光自由基增感劑只要於350 nm～450 nm之區域內具有吸收波長即可，可例舉：多核芳香族類、𠮿類、𠮿酮類、花青類、部花青類、噻𠯤類、吖啶類、吖啶酮類、蒽醌類、方酸菁類、苯乙烯基類、基礎苯乙烯基類、或香豆素類。 <Photoradical sensitizer> If the photosensitive resin composition of the present invention contains a photoradical sensitizer, the exposure sensitivity of the photosensitive resin composition of the present invention can be further improved. The photoradical sensitizer is preferably a compound that absorbs light or radiation and becomes an excited state. The photoradical sensitizer enters an excited state and generates electron transfer, energy transfer, heat generation, etc. when it comes into contact with the photopolymerization initiator. As a result, the photopolymerization initiator decomposes and easily generates an acid. The photoradical sensitizer only needs to have an absorption wavelength in the region of 350 nm to 450 nm. Examples include: polynuclear aromatics, 𠮿 Classes, ketones, cyanines, merocyanines, thiocyanines, acridines, acridinones, anthraquinones, squaraine, styryls, basic styrenes, or aromatics Legumes.

作為多核芳香族類，可例示芘、苝、三亞苯、蒽、9,10-二丁氧基蒽、9,10-二乙氧基蒽，3,7-二甲氧基蒽、或9,10-二丙氧基蒽。Examples of the polynuclear aromatics include pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, and 9,10-dipropoxyanthracene.

作為𠮿類，可例示螢光素、曙紅、赤蘚紅、若丹明B、孟加拉玫瑰紅。 作為𠮿酮類，可例示𠮿酮、9-氧硫𠮿、二甲基9-氧硫𠮿、二乙基9-氧硫𠮿、或異丙基9-氧硫𠮿。 as 𠮿 Examples of the category include luciferin, eosin, erythrosine, rhodamine B, and Rose Bengal. Examples of 𠮿ketones include 𠮿ketone and 9-oxysulfur 𠮿 , dimethyl 9-oxosulfide𠮿 , diethyl 9-oxosulfide𠮿 , or isopropyl 9-oxosulfide𠮿 .

作為花青類，可例示噻碳菁、惡碳菁。 作為部花青類，可例示部花青、碳部花青。 作為噻𠯤類，可例示硫堇、亞甲基藍、甲苯胺藍。 Examples of cyanines include thiocyanine and oxacocyanine. Examples of merocyanine include merocyanine and carbonocyanine. Examples of thioxins include thionine, methylene blue, and toluidine blue.

作為吖啶類，可例示吖啶橙、氯黃素、吖啶黃素。 作為吖啶酮類，可例示吖啶酮、10-丁基-2-氯吖啶酮。 Examples of acridines include acridine orange, chloroflavin, and acriflavin. Examples of acridones include acridone and 10-butyl-2-chloroacridone.

作為蒽醌類，可例示蒽醌。 作為方酸菁類，可例示方酸菁。作為基礎苯乙烯基類，可例示2-[2-[4-(二甲基胺基)苯基]次乙基]苯并㗁唑。 Examples of the anthraquinones include anthraquinone. An example of squaraine is squaraine. As the basic styrene group, 2-[2-[4-(dimethylamino)phenyl]ethylidene]benzoethazole can be exemplified.

作為香豆素類，可例示7-二乙基胺基4-甲基香豆素、7-羥基4-甲基香豆素、或2,3,6,7-四氫-9-甲基-1H,5H,11H[l]苯并吡喃[6,7,8-ij]喹嗪-11-酮。 該等光自由基增感劑可單獨使用，或組合2種以上使用。 Examples of coumarins include 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, or 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H[l]benzopyrano[6,7,8-ij]quinolizin-11-one. These photoradical sensitizers can be used alone or in combination of two or more.

作為本發明之感光性樹脂組合物所使用之光自由基增感劑，基於提昇曝光感度之效果較大之方面考慮，較佳為多核芳香族類、吖啶酮類、苯乙烯基類、基礎苯乙烯基類、香豆素類、或𠮿酮類，尤佳為𠮿酮類。𠮿酮類中，較佳為二乙基9-氧硫𠮿及異丙基9-氧硫𠮿。As the photo-radical sensitizer used in the photosensitive resin composition of the present invention, based on the consideration of the greater effect of improving exposure sensitivity, polynuclear aromatics, acridones, styryls, base styryls, coumarins, or ketones are preferred, and ketones are particularly preferred. Among ketones, diethyl 9-thiothiothioate is preferred. and isopropyl 9-oxysulfide .

於本發明之感光性樹脂組合物中，光自由基增感劑之含量相對於鹼可溶性樹脂(C)及含氟樹脂(D)100質量份，較佳為0.1質量份～8質量份，更佳為1質量份～4質量份。藉由將光自由基增感劑之含量設為上述範圍，而使感光性樹脂組合物之曝光感度提昇，於曝光本發明之感光性樹脂組合物後之圖案形成膜中撥液部位與親液部位之邊界變得清楚，從而墨水塗佈後之墨水圖案之對比度提昇，可獲得精緻之圖案。In the photosensitive resin composition of the present invention, the content of the photoradical sensitizer is preferably 0.1 to 8 parts by weight, and more preferably 1 to 4 parts by weight, relative to 100 parts by weight of the alkali-soluble resin (C) and the fluorine-containing resin (D). By setting the content of the photoradical sensitizer to the above range, the exposure sensitivity of the photosensitive resin composition is increased, and the boundary between the liquid-repellent part and the lyophilic part in the pattern-forming film after exposure to the photosensitive resin composition of the present invention becomes clear, thereby improving the contrast of the ink pattern after ink coating, and obtaining a fine pattern.

＜鏈轉移劑＞ 本發明之感光性樹脂組合物亦可根據需要包含鏈轉移劑。 作為鏈轉移劑，可例舉：與上述含氟樹脂(D)之合成中可使用者相同之化合物等。 ＜Chain transfer agent＞ The photosensitive resin composition of the present invention may also contain a chain transfer agent if necessary. Examples of the chain transfer agent include the same compounds that can be used in the synthesis of the above-mentioned fluorine-containing resin (D).

＜紫外線吸收劑＞ 本發明之感光性樹脂組合物亦可根據需要包含紫外線吸收劑。作為紫外線吸收劑，可例舉：水楊酸系、二苯甲酮系、三唑系等。 紫外線吸收劑之含量於感光性樹脂組合物中較佳為0.5～5質量%，更佳為1～3質量%。 <Ultraviolet absorber> The photosensitive resin composition of the present invention may also contain a ultraviolet absorber as needed. Examples of ultraviolet absorbers include salicylic acid-based, benzophenone-based, triazole-based, etc. The content of the ultraviolet absorber in the photosensitive resin composition is preferably 0.5 to 5% by mass, and more preferably 1 to 3% by mass.

＜聚合抑制劑＞ 本發明之感光性樹脂組合物亦可包含聚合抑制劑。 作為聚合抑制劑，可例示：鄰甲酚、間甲酚、對甲酚、6-第三丁基-2,4-二甲苯酚、2,6-二第三丁基對甲酚、對苯二酚、鄰苯二酚、4-第三丁基鄰苯二酚、2,5-雙四甲基丁基對苯二酚、2,5-二第三丁基對苯二酚、對甲氧基苯酚、1,2,4-三羥基苯、1,2-苯醌、1,3-苯醌、1,4-苯醌、醌茜隱色體、啡噻𠯤、2-甲氧基啡噻𠯤、二硫化四甲基秋蘭姆、1,1-二苯基-2-苦基肼基或1,1-二苯基-2-苦基肼。 ＜Polymerization inhibitor＞ The photosensitive resin composition of the present invention may also contain a polymerization inhibitor. Examples of the polymerization inhibitor include: o-cresol, m-cresol, p-cresol, 6-tert-butyl-2,4-xylenol, 2,6-di-tert-butylp-cresol, p-benzene Diphenol, catechol, 4-tert-butylcatechol, 2,5-bis-tetramethylbutylhydroquinone, 2,5-di-tert-butylhydroquinone, p-methyl Oxyphenol, 1,2,4-trihydroxybenzene, 1,2-benzoquinone, 1,3-benzoquinone, 1,4-benzoquinone, quinocyanine leucosome, thiophene, 2-methoxy Phenthiol, tetramethylthiuram disulfide, 1,1-diphenyl-2-picrylhydrazyl or 1,1-diphenyl-2-picrylhydrazyl.

作為市售之聚合抑制劑，可例示：精工化學股份有限公司製造之N,N'-二-2-萘基對苯二胺(商品名，Nonflex F)、N,N-二苯基對苯二胺(商品名，Nonflex H)、4,4'-雙(a,a-二甲基苄基)二苯基胺(商品名，Nonflex DCD)、2,2'-亞甲基-雙(4-甲基-6-第三丁基苯酚)(商品名，Nonflex MBP)、N-(1-甲基庚基)-N'-苯基對苯二胺(商品名，Ozonone 35)或和光純藥工業股份有限公司製造之N-亞硝基苯基羥胺銨鹽(商品名，Q-1300)或N-亞硝基苯基羥胺鋁鹽(商品名，Q-1301)。Examples of commercially available polymerization inhibitors include N,N'-di-2-naphthyl-p-phenylenediamine (trade name, Nonflex F), N,N-diphenyl-p-phenylenediamine (trade name, Nonflex H), 4,4'-bis(a,a-dimethylbenzyl)diphenylamine (trade name, Nonflex DCD), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol) (trade name, Nonflex MBP), N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine (trade name, Ozonone 35) manufactured by Seiko Chemical Industries, Ltd., or N-nitrosophenylhydroxylamine ammonium salt (trade name, Q-1300) or N-nitrosophenylhydroxylamine aluminum salt (trade name, Q-1301) manufactured by Wako Pure Chemical Industries, Ltd.

本發明之感光性樹脂組合物中總固形物成分中之聚合抑制劑之含有比例較佳為0.001～20質量%，更佳為0.005～10質量%，尤佳為0.01～5質量%。若含有比例為上述範圍，則使得感光性樹脂組合物之顯影殘渣得到減少，圖案直線性良好。The content ratio of the polymerization inhibitor in the total solid content of the photosensitive resin composition of the present invention is preferably 0.001 to 20 mass %, more preferably 0.005 to 10 mass %, and particularly preferably 0.01 to 5 mass %. When the content ratio is in the above range, the development residue of the photosensitive resin composition is reduced, and the pattern linearity is good.

本發明之感光性樹脂組合物亦可為根據需要，進而包含溶解抑制劑、塑化劑、穩定劑、增黏劑、密接劑、抗氧化劑等各種添加劑。該等其他添加劑亦可為公知者。The photosensitive resin composition of the present invention may further contain various additives such as dissolution inhibitors, plasticizers, stabilizers, thickeners, adhesives, and antioxidants as needed. These other additives may also be known ones.

本發明之感光性樹脂組合物能夠用以製造本發明之硬化物。 本發明之硬化物之製造方法包括：(1)成膜步驟，藉由將上述本發明之感光性樹脂組合物塗佈到基板後，進行加熱而製成樹脂膜；及(2)曝光步驟，對該樹脂膜曝光高能量線。 The photosensitive resin composition of the present invention can be used to produce the cured product of the present invention. The manufacturing method of the cured product of the present invention includes: (1) a film forming step, in which the photosensitive resin composition of the present invention is coated on a substrate and then heated to form a resin film; and (2) an exposure step, The resin film is exposed to high energy rays.

針對使用本發明之感光性樹脂組合物之硬化物之製造方法，例舉製造包含該硬化物之阻隔壁之方法為例進行說明。 形成該阻隔壁之方法除(1)成膜步驟及(2)曝光步驟以外，還可包括(3)顯影步驟。 以下，對各步驟進行說明。 The method for producing a cured product using the photosensitive resin composition of the present invention is described by taking as an example a method for producing a barrier wall including the cured product. The method for forming the barrier wall may include (1) a film forming step and (2) an exposure step, and may also include (3) a development step. Each step is described below.

(1)成膜步驟 首先，藉由將上述本發明之感光性樹脂組合物塗佈到基板後，進行加熱而將上述感光性樹脂組合物製成含氟樹脂膜。 加熱條件並無特別限定，較佳為80～100℃且60～200秒。 藉此，可將感光性樹脂組合物中所包含之溶劑等去除。 再者，該含氟樹脂膜亦為本發明之樹脂膜。 (1) Film formation step First, the photosensitive resin composition of the present invention is applied to a substrate and then heated to form a fluororesin film from the photosensitive resin composition. The heating conditions are not particularly limited, but are preferably 80 to 100°C and 60 to 200 seconds. Thereby, the solvent etc. contained in the photosensitive resin composition can be removed. Furthermore, the fluorine-containing resin film is also the resin film of the present invention.

基板可使用矽晶圓、金屬、玻璃、ITO基板等。 又，亦可為於基板上事先設置有機系或無機系之膜。例如抗反射膜、多層抗蝕層可以為下層，於其上形成圖案。又，亦可事先清洗基板。例如可使用超純水、丙酮、醇(甲醇、乙醇、異丙醇)等進行清洗。 The substrate may be a silicon wafer, metal, glass, ITO substrate, etc. In addition, an organic or inorganic film may be provided on the substrate in advance. For example, an anti-reflection film or a multi-layer anti-corrosion layer may be the lower layer, and a pattern may be formed thereon. In addition, the substrate may be cleaned in advance. For example, ultrapure water, acetone, alcohol (methanol, ethanol, isopropyl alcohol), etc. may be used for cleaning.

作為於基板塗佈本發明之感光性樹脂組合物之方法，可使用旋轉塗佈等公知方法。As a method for coating the photosensitive resin composition of the present invention on a substrate, a known method such as spin coating can be used.

(2)曝光步驟 繼而，將所需之光罩放到曝光裝置上，隔著該光罩對上述含氟樹脂膜曝光高能量線。 高能量線較佳為選自由紫外線、伽瑪射線、X射線、及α射線所組成之群中之至少1種。 (2) Exposure step Then, the required photomask is placed on the exposure device, and the fluorine-containing resin film is exposed to high energy rays through the photomask. The high energy rays are preferably at least one selected from the group consisting of ultraviolet rays, gamma rays, X-rays, and alpha rays.

高能量線之曝光量較佳為1 mJ/cm 2以上且200 mJ/cm 2以下，更佳為10 mJ/cm 2以上且100 mJ/cm 2以下。 The exposure dose of high-energy rays is preferably 1 mJ/cm 2 or more and 200 mJ/cm 2 or less, and more preferably 10 mJ/cm 2 or more and 100 mJ/cm 2 or less.

藉由該步驟，含氟樹脂膜之曝光部發生硬化而成為硬化物。該硬化物亦為本發明之硬化物。Through this step, the exposed portion of the fluorine-containing resin film is cured and becomes a cured product. This hardened material is also the hardened material of this invention.

(3)顯影步驟 繼而，將曝光步驟後之含氟樹脂膜利用鹼性水溶液進行顯影而製成含氟樹脂圖案膜。 即，藉由使含氟樹脂膜曝光部或膜未曝光部之任一部位溶解於鹼性水溶液中而製成含氟樹脂圖案膜。 (3)Development step Then, the fluorine-containing resin film after the exposure step is developed using an alkaline aqueous solution to form a fluorine-containing resin pattern film. That is, the fluororesin pattern film is produced by dissolving either the exposed portion of the fluororesin film or the unexposed portion of the film in an alkaline aqueous solution.

作為鹼性水溶液，可使用氫氧化四甲基銨(TMAH)水溶液、氫氧化四丁基銨(TBAH)水溶液等。當鹼性水溶液為氫氧化四甲基銨(TMAH)水溶液時，其濃度較佳為0.1質量%以上且5質量%以下，更佳為2質量%以上且3質量%以下。As the alkaline aqueous solution, tetramethylammonium hydroxide (TMAH) aqueous solution, tetrabutylammonium hydroxide (TBAH) aqueous solution, etc. can be used. When the alkaline aqueous solution is a tetramethylammonium hydroxide (TMAH) aqueous solution, its concentration is preferably 0.1 mass% or more and 5 mass% or less, and more preferably 2 mass% or more and 3 mass% or less.

顯影方法可使用公知之方法，例如可例舉：浸漬法、覆液法、噴霧法等。As the development method, a known method may be used, for example, dipping method, liquid coating method, spray method, etc. can be used.

顯影時間(顯影液與含氟樹脂膜接觸之時間)較佳為10秒以上3分鐘以下，更佳為30秒以上2分鐘以下。The development time (the time during which the developer contacts the fluororesin film) is preferably not less than 10 seconds and not more than 3 minutes, more preferably not less than 30 seconds and not more than 2 minutes.

顯影後，亦可根據需要，設置使用去離子水等將含氟樹脂圖案膜清洗之步驟。關於清洗方法及清洗時間，較佳為10秒以上3分鐘以下，更佳為30秒以上2分鐘以下。After development, a step of cleaning the fluororesin pattern film using deionized water or the like can also be set as needed. Regarding the cleaning method and cleaning time, it is preferably not less than 10 seconds and not more than 3 minutes, and more preferably not less than 30 seconds and not more than 2 minutes.

可經過以上之步驟而製造阻隔壁。該阻隔壁亦為本發明之阻隔壁。The barrier ribs can be manufactured through the above steps. This barrier wall is also a barrier wall of the present invention.

使用本發明之感光性樹脂組合物製造之硬化物(包括上述阻隔壁)之撥液性之均勻性高。 例如藉由下述＜硬化物之形成方法＞於基板上形成硬化物，將形成有該硬化物之基板於230℃下進行60分鐘加熱後，於該硬化物之任意20個位置測定與丙二醇單甲醚乙酸酯(PGMEA)之接觸角，此時接觸角之最大值與最小值之差較佳為0～2°，更佳為0°。 ＜硬化物之形成方法＞ 將ITO基板利用超純水清洗，繼而利用丙酮進行清洗後，使用UV臭氧處理裝置，對該基板進行5分鐘UV臭氧處理。 繼而，使用本發明之感光性組合物，於所獲得之UV臭氧處理後之基板上使用旋轉塗佈機以轉速400 rpm進行塗佈，於加熱板上以100℃進行150秒鐘加熱，形成膜厚3 μm之硬化物。 其後，對所獲得之硬化物照射i射線(波長365 nm)來進行曝光。 The hardened material (including the above-mentioned barrier rib) made using the photosensitive resin composition of the present invention has high uniformity of liquid repellency. For example, a hardened material is formed on a substrate by the following <hardened material formation method>, and the substrate formed with the hardened material is heated at 230°C for 60 minutes, and the contact angle with propylene glycol monomethyl ether acetate (PGMEA) is measured at any 20 positions of the hardened material. At this time, the difference between the maximum and minimum values of the contact angle is preferably 0 to 2°, and more preferably 0°. <hardened material formation method> The ITO substrate is cleaned with ultrapure water, and then cleaned with acetone, and then the substrate is treated with UV ozone for 5 minutes using a UV ozone treatment device. Next, the photosensitive composition of the present invention was applied to the substrate after UV ozone treatment using a spin coater at a rotation speed of 400 rpm, and heated on a heating plate at 100°C for 150 seconds to form a cured product with a film thickness of 3 μm. Thereafter, the cured product was exposed by irradiating i-rays (wavelength 365 nm).

又，如此製造出之硬化物(阻隔壁)之光學密度(OD值)之均勻性高。 例如，藉由上述＜硬化物之形成方法＞於基板上形成硬化物，將形成有該硬化物之基板以230℃進行60分鐘加熱後，於該硬化物之任意20個位置，利用黑白透射密度計(光源：鹵素燈、測定波長：400～700 nm之全波長區域)測定硬化物之光學密度，此時OD值之最大值與最小值之差較佳為0.00～0.01 μm -1，更佳為0.00 μm -1。 Moreover, the optical density (OD value) of the hardened material (barrier) thus manufactured is highly uniform. For example, a hardened material is formed on a substrate by the above-mentioned <hardened material forming method>, and the substrate with the hardened material formed thereon is heated at 230°C for 60 minutes, and then the optical density of the hardened material is measured at any 20 positions of the hardened material using a black and white transmission densitometer (light source: halogen lamp, measurement wavelength: full wavelength range of 400 to 700 nm). At this time, the difference between the maximum and minimum OD values is preferably 0.00 to 0.01 μm -1 , and more preferably 0.00 μm -1 .

如此製造出之阻隔壁可用作有機電致發光元件、波長轉換層或顯示裝置用之障壁。 具備本發明之阻隔壁之有機電致發光元件、波長轉換層或顯示裝置亦為本發明之有機電致發光元件、波長轉換層或顯示裝置。 作為顯示裝置，可例舉：有機EL顯示裝置、量子點顯示裝置等。 [實施例] The barrier wall manufactured in this way can be used as a barrier for an organic electroluminescent element, a wavelength conversion layer or a display device. The organic electroluminescent element, wavelength conversion layer or display device having the barrier wall of the present invention is also the organic electroluminescent element, wavelength conversion layer or display device of the present invention. As a display device, there can be cited: an organic EL display device, a quantum dot display device, etc. [Example]

以下，藉由實施例對本發明詳細地進行說明，但本發明並不限於該等實施例。The present invention is described in detail below by way of embodiments, but the present invention is not limited to these embodiments.

1.含氟樹脂(D)之參數之測定方法 [各重複單元之莫耳比之測定]聚合物中之各重複單元之莫耳比由 1H-NMR、 19F-NMR或 13C-NMR之測定值決定。 1. Method for determining parameters of fluorinated resin (D) [Determination of molar ratio of each repeating unit] The molar ratio of each repeating unit in the polymer is determined by the measured value of 1 H-NMR, 19 F-NMR or 13 C-NMR.

[聚合物之分子量之測定]聚合物之重量平均分子量Mw及分子量分散度(數量平均分子量Mn與重量平均分子量Mw之比；Mw/Mn)可使用高效凝膠滲透層析法(以下，有時稱為GPC。東曹股份有限公司製造，型號HLC-8320GPC)，將ALPHA-M色譜柱與ALPHA-2500色譜柱(均為東曹股份有限公司製造)各1根串聯連接，並使用四氫呋喃(THF)作為展開溶劑而測定。檢測器係使用折射率差測定檢測器。[Measurement of the molecular weight of the polymer] The weight average molecular weight Mw and molecular weight dispersion (ratio of the number average molecular weight Mn and the weight average molecular weight Mw; Mw/Mn) of the polymer can be determined by high-efficiency gel permeation chromatography (hereinafter, sometimes Called GPC. Manufactured by Tosoh Co., Ltd., model number HLC-8320GPC), connect one ALPHA-M column and ALPHA-2500 column (both manufactured by Tosoh Co., Ltd.) in series, and use tetrahydrofuran (THF ) is measured as a developing solvent. The detector uses a refractive index difference measuring detector.

2.撥液劑用含氟樹脂之合成 [撥液劑前體1之合成]於室溫(約20℃)下，將2.9 g(0.015 mol)之1,1-雙(三氟甲基)-1,3-丁二烯(中央硝子股份有限公司製造。以下記載為BTFBE)、3.2 g(0.02 mol)之4-乙醯氧基苯乙烯(東京化成工業股份有限公司產品。以下，記載為p-AcO-St)、13.0 g(0.03 mol)之甲基丙烯酸2-(全氟己基)乙酯(東京化成工業股份有限公司產品。以下，記載為MA-C6F)、4.6 g(0.035 mol)之甲基丙烯酸羥基乙酯(東京化成工業股份有限公司產品。以下，記載為HEMA)、47.2 g之甲基乙基酮(以下記載為MEK)採取到附帶攪拌機之500 ml玻璃製燒瓶內，添加0.84 g(0.005 mol)之偶氮雙(2-甲基丁腈)(東京化成工業股份有限公司產品。以下記載為AIBN)，一邊攪拌一邊脫氣後，對燒瓶內進行氮氣置換，內溫升溫至79℃，徹夜進行了反應。向反應系滴加200 g之正庚烷，結果得到白色沈澱物。將該沈澱物進行過濾分離，於溫度45℃下進行減壓乾燥，以產率88%獲得20.7 g作為白色固體之撥液劑前體1。 2. Synthesis of fluorinated resin for repellent [Synthesis of repellent precursor 1] At room temperature (about 20°C), 2.9 g (0.015 mol) of 1,1-bis(trifluoromethyl)-1,3-butadiene (produced by Central Glass Co., Ltd., hereinafter referred to as BTFBE), 3.2 g (0.02 mol) of 4-acetoxystyrene (produced by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as p-AcO-St), 13.0 g (0.03 mol) of 2-(perfluorohexyl)ethyl methacrylate (produced by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as MA-C6F), 4.6 g (0.035 mol) of hydroxyethyl methacrylate (produced by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as HEMA), 47.2 0.84 g (0.005 mol) of azobis(2-methylbutyronitrile) (Tokyo Chemical Industry Co., Ltd., hereinafter referred to as AIBN) was added to a 500 ml glass flask equipped with a stirrer. After degassing while stirring, the flask was replaced with nitrogen, the internal temperature was raised to 79°C, and the reaction was carried out overnight. 200 g of n-heptane was added dropwise to the reaction system to obtain a white precipitate. The precipitate was separated by filtration and dried under reduced pressure at 45°C to obtain 20.7 g of the hydrophobic agent precursor 1 as a white solid with a yield of 88%.

＜NMR測定結果＞撥液劑前體1之各重複單元之組成比用mol比來表示，基於BTFBE之重複單元：基於p-AcO-St之重複單元：基於MA-C6F之重複單元：基於HEMA之重複單元＝15：20：30：35。<NMR measurement results> The composition ratio of each repeating unit of the repellent precursor 1 is expressed as a mol ratio, repeating unit based on BTFBE: repeating unit based on p-AcO-St: repeating unit based on MA-C6F: repeating unit based on HEMA = 15:20:30:35.

[化43] [Chemical 43]

＜GPC測定結果＞ Mw＝8,900、Mw/Mn=1.5 ＜GPC measurement results＞ Mw=8,900, Mw/Mn=1.5

[撥液劑1之合成]向附帶攪拌機之500 ml玻璃製燒瓶內加入20 g(羥基當量0.035 mol)之撥液劑前體1、0.20 g(羥基當量0.0021 mol)之三乙胺、60 g之丙二醇單甲醚乙酸酯(以下，記載為PGMEA)、4.9 g(羥基當量0.035mol)之丙烯酸2-異氰酸基乙酯(昭和電工股份有限公司產品。產品名：Karenz AOI)，於45℃下反應4小時。將反應結束後之反應液濃縮後，加入200 g之正庚烷，使沈澱物析出。將該沈澱物進行過濾分離，於40℃下進行減壓乾燥，以產率80%獲得19.9 g作為白色固體之撥液劑1。[Synthesis of repellent 1] 20 g (hydroxyl equivalent 0.035 mol) of repellent precursor 1, 0.20 g (hydroxyl equivalent 0.0021 mol) of triethylamine, 60 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), and 4.9 g (hydroxyl equivalent 0.035 mol) of 2-isocyanatoethyl acrylate (Showa Denko Co., Ltd. product name: Karenz AOI) were added to a 500 ml glass flask equipped with a stirrer, and reacted at 45°C for 4 hours. After the reaction was completed, the reaction solution was concentrated, and 200 g of n-heptane was added to precipitate the precipitate. The precipitate was separated by filtration and dried under reduced pressure at 40°C to obtain 19.9 g of the hydrophobic agent 1 as a white solid with a yield of 80%.

[化44] [Chemistry 44]

＜ 13C-NMR測定結果＞於撥液劑1中，來自AOI之丙烯酸衍生物導入量(反應率)及剩餘羥基量(未反應率)以mol比表示為99：1。又，確認到未與交聯基部位反應之各重複單元(基於BTFBE之重複單元、基於p-AcO-St之重複單元、基於MA-C6F之重複單元)之組成比與所使用之撥液劑前體1相比並無變化(與導入交聯基前相同)。相較於重複單元，撥液劑1中之含氟原子含有率為27.6質量%。因此，撥液劑1為含氟樹脂(D)。 < 13 C-NMR measurement results> In the liquid repellent agent 1, the molar ratio of the introduced amount of the acrylic acid derivative derived from the AOI (reaction rate) and the amount of remaining hydroxyl groups (unreacted rate) was 99:1. Furthermore, the composition ratio of each repeating unit (repeating unit based on BTFBE, repeating unit based on p-AcO-St, repeating unit based on MA-C6F) that has not reacted with the crosslinking group site and the liquid repellent used were confirmed There is no change compared to Precursor 1 (the same as before introduction of the cross-linking group). Compared with the repeating units, the fluorine-containing atom content in the liquid repellent agent 1 is 27.6% by mass. Therefore, the liquid repellent agent 1 is a fluororesin (D).

＜GPC測定結果＞ Mw＝12,800、Mw/Mn=1.5 ＜GPC measurement results＞ Mw＝12,800、Mw/Mn=1.5

[撥液劑前體2之合成]於室溫(約20℃)，將2.7 g(0.014 mol)之BTFBE、2.3 g(0.042 mol)之p-AcO-St、18.2 g(0.042 mol)之MA-C6F、3.9 g(0.03 mol)之HEMA(東京化成工業股份有限公司產品)、54.0 g之MEK採取到附帶攪拌機之500 ml玻璃製燒瓶內，加入0.84 g(0.005 mol)之AIBN，一邊攪拌一邊脫氣後，對燒瓶內進行氮氣置換，內溫升溫至79℃，徹夜進行了反應。向反應系滴加300 g之正庚烷，結果得到白色沈澱物。將該沈澱物進行過濾分離，於溫度45℃下進行減壓乾燥，以產率89%獲得24.0 g作為白色固體之撥液劑前體2。[Synthesis of repellent precursor 2] At room temperature (about 20°C), 2.7 g (0.014 mol) of BTFBE, 2.3 g (0.042 mol) of p-AcO-St, 18.2 g (0.042 mol) of MA-C6F, 3.9 g (0.03 mol) of HEMA (Tokyo Chemical Industry Co., Ltd.), and 54.0 g of MEK were placed in a 500 ml glass flask with a stirrer, and 0.84 g (0.005 mol) of AIBN was added. After degassing while stirring, the flask was replaced with nitrogen, the internal temperature was raised to 79°C, and the reaction was carried out overnight. 300 g of n-heptane was added dropwise to the reaction system, and a white precipitate was obtained. The precipitate was separated by filtration and dried under reduced pressure at 45°C to obtain 24.0 g of the hydrophobic agent precursor 2 as a white solid with a yield of 89%.

＜NMR測定結果＞撥液劑前體2之各重複單元之組成比係用mol比來表示，為基於BTFBE之重複單元：基於p-AcO-St之重複單元：基於MA-C6F之重複單元：基於HEMA之重複單元＝14：14：42：30。<NMR measurement results> The composition ratio of each repeating unit of the repellent precursor 2 is expressed as a mol ratio, which is repeating unit based on BTFBE: repeating unit based on p-AcO-St: repeating unit based on MA-C6F: repeating unit based on HEMA = 14:14:42:30.

[化45] [Chemistry 45]

＜GPC測定結果＞ Mw＝9,200、Mw/Mn=1.5 <GPC measurement results> Mw=9,200, Mw/Mn=1.5

[撥液劑2之合成]將20 g(羥基當量0.03 mol)之撥液劑前體2、0.21g(羥基當量0.0021 mol)之三乙胺、60 g之PGMEA採取到附帶攪拌機之500 ml玻璃製燒瓶內，加入4.26 g(羥基當量0.03 mol)之Karenz AOI，於45℃下反應4小時。將反應結束後之反應液濃縮後，加入200 g正庚烷，使沈澱物析出。將該沈澱物進行過濾分離，於40℃下進行減壓乾燥，以產率90%獲得21.6 g作為白色固體之撥液劑2。[Synthesis of repellent 2] 20 g (hydroxyl equivalent 0.03 mol) of repellent precursor 2, 0.21 g (hydroxyl equivalent 0.0021 mol) of triethylamine, and 60 g of PGMEA were placed in a 500 ml glass flask with a stirrer, and 4.26 g (hydroxyl equivalent 0.03 mol) of Karenz AOI was added, and the mixture was reacted at 45°C for 4 hours. After the reaction was completed, the reaction solution was concentrated, and 200 g of n-heptane was added to precipitate the precipitate. The precipitate was separated by filtration and dried under reduced pressure at 40°C to obtain 21.6 g of repellent 2 as a white solid with a yield of 90%.

[化46] [Chemistry 46]

＜ 13C-NMR測定結果＞於撥液劑2中，來自AOI之丙烯酸衍生物導入量(反應率)及剩餘羥基量(未反應率)以mol比表示為99：1。又，確認到未與交聯基部位反應之各重複單元(基於BTFBE之重複單元、基於p-AcO-St之重複單元、基於MA-C6F之重複單元)之組成比與所使用之撥液劑前體2相比並無變化(與導入交聯基前相同)。相較於重複單元，撥液劑2中之含氟原子含有率為38.6質量%。因此，撥液劑2係含氟樹脂(D)。 < 13C -NMR measurement results> In repellent 2, the amount of acrylic acid derivative introduced from AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were expressed as 99:1 in molar ratio. In addition, it was confirmed that the composition ratio of each repeating unit (repeating unit based on BTFBE, repeating unit based on p-AcO-St, repeating unit based on MA-C6F) that did not react with the crosslinking group site did not change compared with the repellent precursor 2 used (the same as before the introduction of the crosslinking group). Compared with the repeating unit, the fluorine atom content in repellent 2 was 38.6 mass%. Therefore, repellent 2 is a fluorine-containing resin (D).

＜GPC測定結果＞ Mw＝13,100、Mw/Mn=1.7 ＜GPC measurement results＞ Mw=13,100, Mw/Mn=1.7

[撥液劑前體3之合成]於室溫(約20℃)下，將2.3 g(0.012 mol)之BTFBE、4.9 g(0.03 mol)之p-AcO-St、5.6 g(0.013 mol)之MA-C6F、5.9 g(0.045 mol)之HEMA(東京化成工業股份有限公司產品)、37.2 g之MEK採取到附帶攪拌機之500 ml玻璃製燒瓶內，加入0.84 g(0.005 mol)之AIBN，一邊攪拌一邊脫氣後，對燒瓶內進行氮氣置換，內溫升溫至79℃，徹夜進行了反應。向反應系滴加250 g之正庚烷，結果獲得白色沈澱物。將該沈澱物進行過濾分離，於溫度45℃下進行減壓乾燥，以產率90%獲得16.7 g作為白色固體之撥液劑前體3。[Synthesis of hydrophobic agent precursor 3] At room temperature (about 20°C), 2.3 g (0.012 mol) of BTFBE, 4.9 g (0.03 mol) of p-AcO-St, 5.6 g (0.013 mol) of MA-C6F, 5.9 g (0.045 mol) of HEMA (Tokyo Chemical Industry Co., Ltd.), and 37.2 g of MEK were placed in a 500 ml glass flask with a stirrer, and 0.84 g (0.005 mol) of AIBN was added. After degassing while stirring, the flask was replaced with nitrogen, the internal temperature was raised to 79°C, and the reaction was carried out overnight. 250 g of n-heptane was added dropwise to the reaction system, and a white precipitate was obtained. The precipitate was separated by filtration and dried under reduced pressure at 45°C to obtain 16.7 g of the hydrophobic agent precursor 3 as a white solid with a yield of 90%.

＜NMR測定結果＞撥液劑前體3之各重複單元之組成比係用mol比來表示，為基於BTFBE之重複單元：基於p-AcO-St之重複單元：基於MA-C6F之重複單元：基於HEMA之重複單元＝12：30：13：45。<NMR measurement results> The composition ratio of each repeating unit of the repellent precursor 3 is expressed as a mol ratio, which is repeating unit based on BTFBE: repeating unit based on p-AcO-St: repeating unit based on MA-C6F: repeating unit based on HEMA = 12:30:13:45.

[化47] [Chemistry 47]

＜GPC測定結果＞ Mw＝9,800、Mw/Mn=1.5 <GPC measurement results> Mw=9,800, Mw/Mn=1.5

[撥液劑3之合成]將16.5g(羥基當量0.045 mol)之撥液劑前體3、0.45g(羥基當量0.0045 mol)之三乙胺、60 g之PGMEA採取到附帶攪拌機之500 ml玻璃製燒瓶內，加入6.4 g(羥基當量0.045 mol)之Karenz AOI，並於45℃下反應4小時。將反應結束後之反應液濃縮後，加入200 g正庚烷，使沈澱物析出。將該沈澱物進行過濾分離，於40℃下進行減壓乾燥，以產率85%獲得19.4 g作為白色固體之撥液劑3。[Synthesis of repellent 3] 16.5 g (hydroxyl equivalent 0.045 mol) of repellent precursor 3, 0.45 g (hydroxyl equivalent 0.0045 mol) of triethylamine, and 60 g of PGMEA were placed in a 500 ml glass flask with a stirrer, and 6.4 g (hydroxyl equivalent 0.045 mol) of Karenz AOI was added, and the mixture was reacted at 45°C for 4 hours. After the reaction was completed, the reaction solution was concentrated, and 200 g of n-heptane was added to precipitate the precipitate. The precipitate was separated by filtration and dried under reduced pressure at 40°C to obtain 19.4 g of repellent 3 as a white solid with a yield of 85%.

[化48] [Chemistry 48]

＜ 13C-NMR測定結果＞於撥液劑3中，來自AOI之丙烯酸衍生物導入量(反應率)及剩餘羥基量(未反應率)以mol比表示為99：1。又，確認到未與交聯基部位反應之各重複單元(基於BTFBE之重複單元、基於p-AcO-St之重複單元、基於MA-C6F之重複單元)之組成比與所使用之撥液劑前體3相比並無變化(與導入交聯基前相同)。相較於重複單元，撥液劑3中之含氟原子含有率為18.5質量%。因此，撥液劑3為含氟樹脂(D)。 < 13 C-NMR measurement results> In the liquid repellent agent 3, the molar ratio of the introduced amount of the acrylic acid derivative derived from the AOI (reaction rate) and the amount of remaining hydroxyl groups (unreacted rate) was 99:1. Furthermore, the composition ratio of each repeating unit (repeating unit based on BTFBE, repeating unit based on p-AcO-St, repeating unit based on MA-C6F) that has not reacted with the crosslinking group site and the liquid repellent used were confirmed There is no change compared to Precursor 3 (the same as before introduction of the cross-linking group). Compared with the repeating unit, the fluorine-containing atom content in the liquid repellent 3 is 18.5% by mass. Therefore, the liquid repellent agent 3 is fluorine-containing resin (D).

＜GPC測定結果＞ Mw＝14,300、Mw/Mn=1.7 ＜GPC measurement results＞ Mw=14,300, Mw/Mn=1.7

3.著色顏料分散體1之製備 將表1中記載之顏料、分散劑、鹼可溶性樹脂及溶劑以成為表1中記載之質量比之方式進行混合。於25℃下，使用0.5 mm 之氧化鋯珠，利用珠磨機對該溶液進行12小時分散處理。分散處理結束後，藉由過濾將氧化鋯珠去除，而製備著色顏料分散體1。 3. Preparation of Colored Pigment Dispersion 1 The pigment, dispersant, alkali-soluble resin and solvent described in Table 1 were mixed so as to have the mass ratio described in Table 1. At 25°C, use 0.5 mm zirconia beads, and the solution was dispersed using a bead mill for 12 hours. After the dispersion treatment is completed, the zirconia beads are removed by filtration, and a colored pigment dispersion 1 is prepared.

[表1] 成分 產品 使用量 (質量份) 固形物成分含量 (質量%) 顏料1 顏料藍60(東京化成工業股份有限公司製造) 56 32 顏料2 顏料紫23(東京化成工業股份有限公司製造) 57 33 顏料3 顏料橙43(東京化成工業股份有限公司製造) 1 1 分散劑 BYK-167(畢克化學股份有限公司製造) 23 13 鹼可溶性樹脂 ZAR-2050H(日本化藥股份有限公司製造) 38 22 溶劑 PGMEA 42 - [Table 1] Element product Usage (quantity) Solid content (mass%) Pigment 1 Pigment Blue 60 (manufactured by Tokyo Chemical Industry Co., Ltd.) 56 32 Pigment 2 Pigment Purple 23 (manufactured by Tokyo Chemical Industry Co., Ltd.) 57 33 Pigment 3 Pigment Orange 43 (manufactured by Tokyo Chemical Industry Co., Ltd.) 1 1 Dispersants BYK-167 (manufactured by BYK Chemical Co., Ltd.) twenty three 13 Alkaline soluble resin ZAR-2050H (manufactured by Nippon Kayaku Co., Ltd.) 38 twenty two Solvent PGMEA 42 -

4.感光性樹脂組合物之製備 以下表示各實施例及各比較例中所使用之各成分。 ＜鹼可溶性樹脂＞ 鹼可溶性樹脂1：日本化藥公司製造之「ZAR-2050H」(特殊BIS-A型環氧樹脂，包含上文所述之通式(1)所表示之結構單元。不包含氟原子) 鹼可溶性樹脂2：日本化藥公司製造之「ZCR-1569H」(聯苯型環氧樹脂，不包含上文所述之通式(1)所表示之結構單元) 鹼可溶性樹脂3：日本化藥公司製造之「CCR-1171H」(甲酚酚醛清漆型環氧樹脂，不包含上文所述之通式(1)所表示之結構單元) 鹼可溶性樹脂4：雙酚B衍生物，包含上文所述之通式(1)所表示之結構單元。R為甲基、乙基。不包含氟原子) 鹼可溶性樹脂5：雙酚E衍生物，包含上文所述之通式(1)所表示之結構單元。R為甲基、氫。不包含氟原子) 4. Preparation of photosensitive resin composition Each component used in each Example and each Comparative Example is shown below. ＜Alkali-soluble resin＞ Alkali-soluble resin 1: "ZAR-2050H" manufactured by Nippon Kayaku Co., Ltd. (special BIS-A type epoxy resin, containing the structural unit represented by the general formula (1) mentioned above. Does not contain fluorine atoms) Alkali-soluble resin 2: "ZCR-1569H" manufactured by Nippon Kayaku Co., Ltd. (biphenyl-type epoxy resin, does not contain the structural unit represented by the general formula (1) mentioned above) Alkali-soluble resin 3: "CCR-1171H" manufactured by Nippon Kayaku Co., Ltd. (cresol novolak type epoxy resin, does not contain the structural unit represented by the general formula (1) mentioned above) Alkali-soluble resin 4: a bisphenol B derivative, including the structural unit represented by the general formula (1) described above. R is methyl or ethyl. Does not contain fluorine atoms) Alkali-soluble resin 5: a bisphenol E derivative, containing the structural unit represented by the general formula (1) described above. R is methyl and hydrogen. Does not contain fluorine atoms)

鹼可溶性樹脂4之合成： 於附帶溫度計、帶冷凝器之傾析器之四口燒瓶中，向24.3 g(0.1 mol)之雙酚B(東京化成工業試劑)添加表氯醇(東京化成工業試劑)92.52 g(10 mol)並使之溶解。於80℃下歷時1小時滴加16.7 g(0.2 mol)之48質量%NaOH水溶液。進行加熱，蒸餾出表氯醇及水，將表氯醇與水分離，並使表氯醇持續回到上述燒瓶內。進而繼續攪拌2小時。其後，向上述燒瓶內添加水50 g並進行靜置。將下層(水層)捨棄，回收殘留於有機層中之表氯醇而獲得粗樹脂。向粗樹脂添加50 g之甲基異丁基酮(以下，稱為MIBK)，進而添加30 g之3質量%NaOH水溶液，於70℃下攪拌30分鐘。然後將下層之水層捨棄。其後，將MIBK層利用30 g之水進行水洗，將水層捨棄。將MIBK層濃縮後，獲得目標環氧樹脂35 g。該樹脂呈液狀且環氧當量為180 g/eq。 所獲得之環氧樹脂係下述通式(11-1)及(11-2)所示之雙酚B型環氧化合物。 Synthesis of alkali soluble resin 4: In a four-necked flask with a thermometer and a decanter equipped with a condenser, add 92.52 g (10 mol) of epichlorohydrin (Tokyo Chemical Industry Reagent) to 24.3 g (0.1 mol) of bisphenol B (Tokyo Chemical Industry Reagent). and make it dissolve. 16.7 g (0.2 mol) of 48 mass % NaOH aqueous solution was added dropwise at 80° C. for 1 hour. Heating is performed to distill out epichlorohydrin and water, separate epichlorohydrin from water, and continuously return epichlorohydrin to the above-mentioned flask. Further stirring was continued for 2 hours. Thereafter, 50 g of water was added to the above-mentioned flask and allowed to stand. The lower layer (aqueous layer) was discarded, and the epichlorohydrin remaining in the organic layer was recovered to obtain a crude resin. To the crude resin, 50 g of methyl isobutyl ketone (hereinafter referred to as MIBK) was added, and further, 30 g of a 3 mass % NaOH aqueous solution was added, and the mixture was stirred at 70° C. for 30 minutes. Then discard the lower water layer. Thereafter, the MIBK layer was washed with 30 g of water, and the water layer was discarded. After concentrating the MIBK layer, 35 g of the target epoxy resin was obtained. The resin is liquid and has an epoxy equivalent weight of 180 g/eq. The obtained epoxy resin is a bisphenol B-type epoxy compound represented by the following general formulas (11-1) and (11-2).

[化49] (通式(11-1)及(11-2)中，n分別獨立地為1～20) [Chemistry 49] (In general formulas (11-1) and (11-2), n is independently 1 to 20)

將上文中所獲得之30 g之雙酚B型環氧化合物(環氧當量180 g/eq)、10 g之丙烯酸(東京化成工業試劑)、0.1 g之作為聚合抑制劑之6-第三丁基-2,4二甲苯酚(東京化成工業試劑)、1.0 g之三苯基膦(東京化成工業試劑)、40 g之丙二醇單甲醚乙酸酯添加到反應容器中，於90℃下進行攪拌直到酸值成為3 mgKOH/g以下。繼而，向藉由上述反應獲得之反應液添加1.0 g之順-4-環己烯-1,2-二羧酸酐，並於90℃下反應3小時。 然後，獲得固形物成分酸值50 mgKOH/g且藉由GPC測得之聚苯乙烯換算之重量平均分子量(Mw)為7,200之鹼可溶性樹脂4之50質量%PGMEA溶液。 鹼可溶性樹脂4係特徵在於含有以下通式(1-4)、(1-5)及(1-6)所示之結構單元之高分子化合物。 30 g of the bisphenol B type epoxy compound (epoxy equivalent 180 g/eq) obtained above, 10 g of acrylic acid (Tokyo Chemical Industry reagent), 0.1 g of 6-tert-butyl-2,4-xylenol (Tokyo Chemical Industry reagent) as a polymerization inhibitor, 1.0 g of triphenylphosphine (Tokyo Chemical Industry reagent), and 40 g of propylene glycol monomethyl ether acetate were added to a reaction vessel and stirred at 90°C until the acid value became less than 3 mgKOH/g. Then, 1.0 g of cis-4-cyclohexene-1,2-dicarboxylic anhydride was added to the reaction solution obtained by the above reaction, and the reaction was carried out at 90°C for 3 hours. Then, a 50 mass% PGMEA solution of alkali-soluble resin 4 having a solid acid value of 50 mgKOH/g and a polystyrene-equivalent weight average molecular weight (Mw) of 7,200 measured by GPC was obtained. Alkali-soluble resin 4 is a polymer compound characterized by containing structural units represented by the following general formulas (1-4), (1-5) and (1-6).

[化50] (上述通式(1-4)、(1-5)及(1-6)中，a、b及c分別為1以上之整數)。 [Chemistry 50] (In the above general formulas (1-4), (1-5) and (1-6), a, b and c are integers greater than 1, respectively).

鹼可溶性樹脂5之合成： 於附帶溫度計、帶冷凝器之傾析器之四口燒瓶中，向21.4 g(0.1 mol)之雙酚E(東京化成工業試劑)加入92.52 g(10 mol)之表氯醇並使之溶解。於80℃下歷時1小時滴加16.7 g(0.2 mol)之48質量%NaOH水溶液。進行加熱，蒸餾出表氯醇及水，將表氯醇與水分離，並使表氯醇持續回到上述燒瓶內。進而繼續攪拌2小時，其後，向上述燒瓶內加入水50 g並進行靜置。將下層(水層)捨棄，回收殘留於有機層中之表氯醇而獲得粗樹脂。向粗樹脂加入50 g之MIBK，進而加入30 g之3質量%NaOH水溶液，於70℃下攪拌30分鐘。然後將下層之水層捨棄。其後，將MIBK層利用30 g之水進行水洗，將水層捨棄。將MIBK層濃縮後，獲得目標環氧樹脂30 g。該樹脂呈液狀且環氧當量為185 g/eq。 所獲得之環氧樹脂係下述通式(12-1)及(12-2)所示之雙酚E型環氧化合物。 Synthesis of alkali soluble resin 5: In a four-necked flask equipped with a thermometer and a decanter equipped with a condenser, add 92.52 g (10 mol) of epichlorohydrin to 21.4 g (0.1 mol) of bisphenol E (Tokyo Chemical Industry Reagent) and dissolve it. 16.7 g (0.2 mol) of 48 mass % NaOH aqueous solution was added dropwise at 80° C. for 1 hour. Heating is performed to distill out epichlorohydrin and water, separate epichlorohydrin from water, and continuously return epichlorohydrin to the above-mentioned flask. Stirring was continued for 2 hours, and then 50 g of water was added to the above-mentioned flask and allowed to stand. The lower layer (aqueous layer) was discarded, and the epichlorohydrin remaining in the organic layer was recovered to obtain a crude resin. 50 g of MIBK was added to the crude resin, and then 30 g of 3 mass % NaOH aqueous solution was added, and the mixture was stirred at 70° C. for 30 minutes. Then discard the lower water layer. Thereafter, the MIBK layer was washed with 30 g of water, and the water layer was discarded. After concentrating the MIBK layer, 30 g of the target epoxy resin was obtained. The resin is liquid and has an epoxy equivalent weight of 185 g/eq. The obtained epoxy resin is a bisphenol E-type epoxy compound represented by the following general formulas (12-1) and (12-2).

[化51] (通式(12-1)及(12-2)中，n分別獨立地為1～20) [Chemistry 51] (In general formulas (12-1) and (12-2), n is independently 1 to 20.)

將上文中所獲得之25 g之下述式所表示之雙酚E型環氧化合物(環氧當量185 g/eq)、8 g之丙烯酸(東京化成工業試劑)、0.1 g之作為聚合抑制劑之6-第三丁基-2,4二甲苯酚(東京化成工業試劑)、0.8 g之三苯基膦(東京化成工業試劑)、33 g之丙二醇單甲醚乙酸酯加入到反應容器中，於90℃下進行攪拌直到酸值成為3 mgKOH/g以下。繼而，向藉由上述反應獲得之反應液添加0.8 g之順-4-環己烯-1,2-二羧酸酐，於90℃下反應3小時。 然後，獲得固形物成分酸值50 mgKOH/g且藉由GPC測得之聚苯乙烯換算之重量平均分子量(Mw)為7,500之鹼可溶性樹脂5之50質量%PGMEA溶液。 鹼可溶性樹脂5係特徵在於含有以下之通式(1-7)、(1-8)及(1-9)所示之結構單元之高分子化合物。 25 g of the bisphenol E type epoxy compound represented by the following formula obtained above (epoxy equivalent 185 g/eq), 8 g of acrylic acid (Tokyo Chemical Industry reagent), 0.1 g of 6-tert-butyl-2,4-xylenol (Tokyo Chemical Industry reagent) as a polymerization inhibitor, 0.8 g of triphenylphosphine (Tokyo Chemical Industry reagent), and 33 g of propylene glycol monomethyl ether acetate were added to a reaction vessel and stirred at 90°C until the acid value became less than 3 mgKOH/g. Then, 0.8 g of cis-4-cyclohexene-1,2-dicarboxylic anhydride was added to the reaction solution obtained by the above reaction and reacted at 90°C for 3 hours. Then, a 50 mass% PGMEA solution of alkali-soluble resin 5 having a solid acid value of 50 mgKOH/g and a polystyrene-equivalent weight average molecular weight (Mw) of 7,500 measured by GPC was obtained. Alkali-soluble resin 5 is a polymer compound characterized by containing structural units represented by the following general formulas (1-7), (1-8) and (1-9).

[化52] (上述通式(1-7)、(1-8)及(1-9)中，a、b及c分別為1以上之整數)。 ＜著色顏料分散體＞ 著色顏料分散體1：按上述著色顏料分散體1之製備順序調整之著色顏料分散體。 (顏料混合、相對於總固形物成分之顏料含量：66質量%、粒徑：D 50為320 nm) 著色顏料分散體2：包含作為內醯胺黑之以下化合物之顏料(相對於總固形物成分之顏料含量：75質量%、粒徑：D 50為300 nm) [Chemistry 52] (In the above general formulas (1-7), (1-8) and (1-9), a, b and c are each an integer of 1 or more). <Colored Pigment Dispersion> Colored Pigment Dispersion 1: A colored pigment dispersion adjusted according to the preparation procedure of the above-mentioned colored pigment dispersion 1. (Pigment mixture, pigment content relative to total solid content: 66 mass %, particle size: D 50 is 320 nm) Colored pigment dispersion 2: Pigment containing the following compound as lactam black (relative to total solid content Ingredients: Pigment content: 75% by mass, particle size: D 50 is 300 nm)

[化53] [Chemistry 53]

著色顏料分散體3：大日精化工業公司製造「NX-501」(氧化鈦顏料、顏料含量：73質量%、粒徑：D 50為270 nm) ＜乙烯性不飽和化合物＞ 乙烯性不飽和化合物1：日本化藥公司製造「DPHA」(二季戊四醇六丙烯酸酯) ＜光聚合起始劑＞ 光聚合起始劑1：BASF公司製造「Irgacure OXE-01」 ＜添加劑＞ 添加劑1：日本化藥公司製造「KAYAMER PM-21」(己內酯改性磷酸單甲基丙烯酸酯與己內酯改性磷酸二甲基丙烯酸酯之混合物) Colored pigment dispersion 3: "NX-501" manufactured by Dainichi Chemical Industry Co., Ltd. (titanium oxide pigment, pigment content: 73% by mass, particle size: D 50 is 270 nm) <ethylenically unsaturated compound> ethylenically unsaturated compound 1: "DPHA" (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd. <Photopolymerization initiator> Photopolymerization initiator 1: "Irgacure OXE-01" manufactured by BASF Co., Ltd. <Additive> Additive 1: Nippon Kayaku Co., Ltd. Manufacture of "KAYAMER PM-21" (a mixture of caprolactone-modified phosphate monomethacrylate and caprolactone-modified phosphate dimethacrylate)

5.評價 ＜感光性樹脂組合物之製備＞ 以總固形物成分中之各成分之固形物成分之含有比例成為表2及表3中記載之方式加入各成分(表2中，調配比之數值意味著質量調配比)，進而以總固形物成分之含有比例達到30質量%之方式加入PGMEA，進行攪拌並使之溶解，而製備實施例1～21及比較例1～11之感光性樹脂組合物。使用所獲得之感光性樹脂組合物，藉由後述方法進行評價。 5.Evaluation <Preparation of photosensitive resin composition> Add each component so that the solid content ratio of each component in the total solid component becomes as described in Table 2 and Table 3 (in Table 2, the numerical value of the blending ratio means the mass blending ratio), and then the total solid content is PGMEA was added so that the content ratio of the component reached 30 mass %, and it was stirred and dissolved, and the photosensitive resin composition of Examples 1-21 and Comparative Examples 1-11 was prepared. Using the obtained photosensitive resin composition, it evaluated by the method mentioned later.

[表2]    實施例 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 調配比 鹼可溶性樹脂1 47.2 47.2 47.2 43.1 34.5 25.9 43.1 28.2 43.1 20.5 16.8 43.1 43.1 - - - - - - - - 鹼可溶性樹脂2 - - - - - - - - - - - - - - - - - - - - - 鹼可溶性樹脂3 - - - - - - - - - - - - - - - - - - - - - 鹼可溶性樹脂4 - - - - - - - - - - - - - 43.1 28.2 43.1 20.5 - - - - 鹼可溶性樹脂5 - - - - - - - - - - - - - - - - - 43.1 28.2 43.1 20.5 著色顏料分散體1 - - - - - - - - 8.6 51.3 - - - - - 8.6 51.3 - - 8.6 51.3 著色顏料分散體2 - - - 8.6 8.6 8.6 8.6 38.3 - - - 8.6 8.6 8.6 38.3 - - 8.6 38.3 - - 著色顏料分散體3 - - - - - - - - - - 64.0 - - - - - - - - - - 撥液劑1 1.9 - - 1.7 1.7 1.7 1.7 1.2 1.7 0.9 1.0 - - 1.7 1.2 1.7 0.9 1.7 1.2 1.7 0.9 撥液劑2 - 1.9 - - - - - - - - - 1.7 - - - - - - - - - 撥液劑3 - - 1.9 - - - - - - - - - 1.7 - - - - - - - - 乙烯性不飽和化合物1 47.2 47.2 47.2 43.1 51.7 60.3 43.1 28.2 43.1 20.5 16.8 43.1 43.1 43.1 28.2 43.1 20.5 43.1 28.2 43.1 20.5 光聚合起始劑 1.9 1.9 1.9 1.7 1.7 1.7 1.7 2.8 1.7 1.2 0.4 1.7 1.7 1.7 2.8 1.7 1.2 1.7 2.8 1.7 1.2 添加劑1 1.9 1.9 1.9 1.7 1.7 1.7 1.7 1.2 1.7 2 1.0 1.7 1.7 1.7 1.2 1.7 2 1.7 1.2 1.7 2 鹼可溶性樹脂(C)相對於全部鹼可溶性樹脂之含有比例(wt%) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 鹼可溶性樹脂(C)相對於含氟樹脂(D)100質量份之含量(質量份) 2484 2484 2484 2535 2028 1524 2535 2350 2535 2278 1680 2535 2535 2535 2350 2535 2278 2535 2350 2535 2278 PGMEA 接觸角 (°) 平均值 44 47 31 45 46 45 45 44 44 42 44 48 33 44 45 45 43 44 44 44 43 最大值 45 47 32 46 46 45 46 44 44 43 44 48 34 45 45 45 44 45 45 45 44 最小值 44 46 30 45 45 45 45 44 43 42 43 47 32 44 45 45 43 44 44 43 43 最大值－最小值 1 1 2 1 1 1 1 0 1 1 1 1 2 1 0 0 1 1 1 2 1 OD值 (µm -1) 平均值 - - - 0.23 0.23 0.23 0.23 1.10 0.20 1.00 0.08 0.23 0.23 0.23 1.10 0.20 1.00 0.23 1.10 0.20 1.00 最大值 - - - 0.23 0.23 0.23 0.23 1.10 0.21 1.00 0.08 0.23 0.23 0.23 1.10 0.20 1.00 0.23 1.10 0.21 1.01 最小值 - - - 0.23 0.23 0.23 0.23 1.10 0.20 1.00 0.08 0.23 0.22 0.22 1.09 0.20 1.00 0.23 1.09 0.21 1.00 最大值－最小值 - - - 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.01 0.00 0.01 [Table 2] Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 twenty one Mixing ratio Alkali soluble resin 1 47.2 47.2 47.2 43.1 34.5 25.9 43.1 28.2 43.1 20.5 16.8 43.1 43.1 - - - - - - - - Alkali soluble resin 2 - - - - - - - - - - - - - - - - - - - - - Alkali soluble resin 3 - - - - - - - - - - - - - - - - - - - - - Alkali soluble resin 4 - - - - - - - - - - - - - 43.1 28.2 43.1 20.5 - - - - Alkali soluble resin 5 - - - - - - - - - - - - - - - - - 43.1 28.2 43.1 20.5 Colored Pigment Dispersions 1 - - - - - - - - 8.6 51.3 - - - - - 8.6 51.3 - - 8.6 51.3 Colored Pigment Dispersions 2 - - - 8.6 8.6 8.6 8.6 38.3 - - - 8.6 8.6 8.6 38.3 - - 8.6 38.3 - - Colored Pigment Dispersion 3 - - - - - - - - - - 64.0 - - - - - - - - - - Liquid repellent 1 1.9 - - 1.7 1.7 1.7 1.7 1.2 1.7 0.9 1.0 - - 1.7 1.2 1.7 0.9 1.7 1.2 1.7 0.9 Liquid repellent 2 - 1.9 - - - - - - - - - 1.7 - - - - - - - - - Liquid repellent 3 - - 1.9 - - - - - - - - - 1.7 - - - - - - - - Ethylenically unsaturated compounds 1 47.2 47.2 47.2 43.1 51.7 60.3 43.1 28.2 43.1 20.5 16.8 43.1 43.1 43.1 28.2 43.1 20.5 43.1 28.2 43.1 20.5 Photopolymerization initiator 1.9 1.9 1.9 1.7 1.7 1.7 1.7 2.8 1.7 1.2 0.4 1.7 1.7 1.7 2.8 1.7 1.2 1.7 2.8 1.7 1.2 Additive 1 1.9 1.9 1.9 1.7 1.7 1.7 1.7 1.2 1.7 2 1.0 1.7 1.7 1.7 1.2 1.7 2 1.7 1.2 1.7 2 Content ratio of alkali-soluble resin (C) to all alkali-soluble resins (wt%) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Content of alkali-soluble resin (C) relative to 100 parts by mass of fluorine-containing resin (D) (parts by mass) 2484 2484 2484 2535 2028 1524 2535 2350 2535 2278 1680 2535 2535 2535 2350 2535 2278 2535 2350 2535 2278 PGMEA contact angle (°) average value 44 47 31 45 46 45 45 44 44 42 44 48 33 44 45 45 43 44 44 44 43 maximum value 45 47 32 46 46 45 46 44 44 43 44 48 34 45 45 45 44 45 45 45 44 minimum value 44 46 30 45 45 45 45 44 43 42 43 47 32 44 45 45 43 44 44 43 43 maximum value minimum value 1 1 2 1 1 1 1 0 1 1 1 1 2 1 0 0 1 1 1 2 1 OD value (µm -1 ) average value - - - 0.23 0.23 0.23 0.23 1.10 0.20 1.00 0.08 0.23 0.23 0.23 1.10 0.20 1.00 0.23 1.10 0.20 1.00 maximum value - - - 0.23 0.23 0.23 0.23 1.10 0.21 1.00 0.08 0.23 0.23 0.23 1.10 0.20 1.00 0.23 1.10 0.21 1.01 minimum value - - - 0.23 0.23 0.23 0.23 1.10 0.20 1.00 0.08 0.23 0.22 0.22 1.09 0.20 1.00 0.23 1.09 0.21 1.00 maximum value minimum value - - - 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.01 0.00 0.01

[表3]    比較例 1 2 3 4 5 6 7 8 9 10 11 調配比 鹼可溶性樹脂1 - - - - - - - - - - - 鹼可溶性樹脂2 47.2 47.2 47.2 - 43.1 34.5 25.9 43.1 16.8 43.1 43.1 鹼可溶性樹脂3 - - - 47.2 - - - - - - - 鹼可溶性樹脂4 - - - - - - - - - - - 鹼可溶性樹脂5 - - - - - - - - - - - 著色顏料分散體1 - - - - - - - 8.6 - - - 著色顏料分散體2 - - - - 8.6 8.6 8.6 - - 8.6 - 著色顏料分散體3 - - - - - - - - 64.0 - - 撥液劑1 1.9 - - 1.9 1.7 1.7 1.7 1.7 1.0 - - 撥液劑2 - 1.9 - - - - - - - 1.7 - 撥液劑3 - - 1.9 - - - - - - - 1.7 乙烯性不飽和化合物1 47.2 47.2 47.2 47.2 43.1 51.7 60.3 43.1 16.8 43.1 43.1 光聚合起始劑 1.9 1.9 1.9 1.9 1.7 1.7 1.7 1.7 0.4 1.7 1.7 添加劑1 1.9 1.9 1.9 1.9 1.7 1.7 1.7 1.7 1.0 1.7 1.7 鹼可溶性樹脂(C)相對於全部鹼可溶性樹脂之含有比例(wt%) 0.0 0.0 0.0 0.0 0.0 0.0 0.0 4.2 0.0 0.0 0.0 鹼可溶性樹脂(C)相對於含氟樹脂(D)100質量份之含量(質量份) 0 0 0 0 0 0 0 110 0 0 0 PGMEA 接觸角 (°) 平均值 43 45 31 43 43 43 43 44 42 45 30 最大值 47 49 31 48 49 49 49 48 47 48 33 最小值 36 39 28 39 38 38 38 39 38 39 30 最大值－最小值 11 10 3 9 11 11 11 9 9 9 3 OD值 (µm -1) 平均值 - - - - 0.23 0.25 0.24 0.22 0.08 0.22 0.17 最大值 - - - - 0.26 0.27 0.26 0.24 0.11 0.26 0.18 最小值 - - - - 0.19 0.18 0.18 0.15 0.06 0.21 0.16 最大值－最小值 - - - - 0.07 0.09 0.08 0.09 0.05 0.05 0.02 [table 3] Comparison Example 1 2 3 4 5 6 7 8 9 10 11 Allocation ratio Alkaline soluble resin 1 - - - - - - - - - - - Alkaline soluble resin 2 47.2 47.2 47.2 - 43.1 34.5 25.9 43.1 16.8 43.1 43.1 Alkaline soluble resin 3 - - - 47.2 - - - - - - - Alkaline soluble resin 4 - - - - - - - - - - - Alkaline soluble resin 5 - - - - - - - - - - - Coloring pigment dispersion 1 - - - - - - - 8.6 - - - Coloring pigment dispersion 2 - - - - 8.6 8.6 8.6 - - 8.6 - Coloring pigment dispersion 3 - - - - - - - - 64.0 - - Lotion 1 1.9 - - 1.9 1.7 1.7 1.7 1.7 1.0 - - Repellent 2 - 1.9 - - - - - - - 1.7 - Repellent 3 - - 1.9 - - - - - - - 1.7 Ethylenically unsaturated compound 1 47.2 47.2 47.2 47.2 43.1 51.7 60.3 43.1 16.8 43.1 43.1 Photopolymerization initiator 1.9 1.9 1.9 1.9 1.7 1.7 1.7 1.7 0.4 1.7 1.7 Additive 1 1.9 1.9 1.9 1.9 1.7 1.7 1.7 1.7 1.0 1.7 1.7 Content ratio of alkali-soluble resin (C) to total alkali-soluble resin (wt%) 0.0 0.0 0.0 0.0 0.0 0.0 0.0 4.2 0.0 0.0 0.0 Content of alkali-soluble resin (C) relative to 100 parts by mass of fluorinated resin (D) (parts by mass) 0 0 0 0 0 0 0 110 0 0 0 PGMEA contact angle (°) average value 43 45 31 43 43 43 43 44 42 45 30 Maximum 47 49 31 48 49 49 49 48 47 48 33 Minimum 36 39 28 39 38 38 38 39 38 39 30 maximum value minimum value 11 10 3 9 11 11 11 9 9 9 3 OD value (µm -1 ) average value - - - - 0.23 0.25 0.24 0.22 0.08 0.22 0.17 Maximum - - - - 0.26 0.27 0.26 0.24 0.11 0.26 0.18 Minimum - - - - 0.19 0.18 0.18 0.15 0.06 0.21 0.16 maximum value minimum value - - - - 0.07 0.09 0.08 0.09 0.05 0.05 0.02

[評價測定用基板之形成] 將10 cm見方之ITO基板利用超純水清洗後，繼而利用丙酮清洗後，使用UV臭氧處理裝置(SEN特殊光源股份有限公司製造，型號PL17-110)，對該基板進行5分鐘UV臭氧處理。繼而，使用各實施例及各比較例之感光性組合物，於所獲得之UV臭氧處理後之基板上使用旋轉塗佈機以轉速400 rpm進行塗佈，於加熱板上以100℃加熱150秒鐘，形成膜厚3 μm之含氟塗膜及比較含氟塗膜。使用光罩對準曝光機(蘇斯微技術股份有限公司產品)對所獲得之樹脂膜照射i射線(波長365 nm)而進行曝光。對於所獲得之曝光後之硬化塗膜進行接觸角及光學密度之測定。 [Formation of substrate for evaluation measurement] After cleaning the 10 cm square ITO substrate with ultrapure water and then with acetone, the substrate was subjected to UV ozone treatment for 5 minutes using a UV ozone treatment device (manufactured by SEN Special Light Source Co., Ltd., model PL17-110). Then, the photosensitive composition of each example and each comparative example was used to coat the obtained substrate after UV ozone treatment using a spin coater at a rotation speed of 400 rpm, and heated on a hot plate at 100°C for 150 seconds. Within minutes, a fluorine-containing coating with a film thickness of 3 μm and a comparative fluorine-containing coating were formed. The obtained resin film was irradiated with i-rays (wavelength 365 nm) using a mask alignment exposure machine (product of Seuss Microtechnology Co., Ltd.) and exposed. The contact angle and optical density of the obtained hardened coating film after exposure were measured.

[接觸角] 將具有藉由上述步驟獲得之硬化物之基板於230℃下加熱60分鐘後，針對硬化物表面之與丙二醇單甲醚乙酸酯(PGMEA)之接觸角，使用接觸角計(共和介面化學股份有限公司製造之GMs-601)，於塗膜上之20個部位測定PGMEA接觸角。 將所測得之數值之平均值、最大值、最小值及最大值與最小值之差示於表2及表3。 [Contact angle] After heating the substrate with the cured product obtained by the above steps at 230°C for 60 minutes, the contact angle between the cured product surface and propylene glycol monomethyl ether acetate (PGMEA) was measured at 20 locations on the coating using a contact angle meter (GMs-601 manufactured by Kyowa Interface Chemical Co., Ltd.). The average value, maximum value, minimum value, and difference between the maximum value and the minimum value of the measured values are shown in Tables 2 and 3.

[光學密度] 將具有藉由上述步驟獲得之實施例4～21及比較例5～11之硬化物之基板於230℃下進行60分鐘加熱後，針對硬化物之光學密度，使用黑白透射密度計(伊原電子製造之T5plus)，於塗膜上之20個部位測定OD值。 將所測得之數值之平均值、最大值、最小值及最大值與最小值之差示於表2及表3。 [Optical density] After heating the substrates with the cured products of Examples 4 to 21 and Comparative Examples 5 to 11 obtained by the above steps at 230°C for 60 minutes, the optical density of the cured products was measured at 20 locations on the coating using a black and white transmission densitometer (T5plus manufactured by Ihara Electronics). The average value, maximum value, minimum value, and difference between the maximum value and the minimum value of the measured values are shown in Tables 2 and 3.

於實施例中，確認到PGMEA接觸角及OD值於膜面內之不均較小。 又，於比較例中，確認到PGMEA接觸角或OD值於硬化物內之不均較大，其原因或許在於與實施例中使用之鹼可溶性樹脂相比，與其他成分之相溶性低。 In the examples, it was confirmed that the unevenness of PGMEA contact angle and OD value within the film surface was small. In addition, in the comparative examples, it was confirmed that the PGMEA contact angle or OD value varied greatly within the cured product. The reason may be that the alkali-soluble resin used in the examples has lower compatibility with other components than the alkali-soluble resin used in the examples.

Claims (16)

一種感光性樹脂組合物，其特徵在於含有： 乙烯性不飽和化合物(A)； 光聚合起始劑(B)； 鹼可溶性樹脂(C)；及 含氟樹脂(D)，其包含氟原子含有率為20～60質量%之含氟樹脂(D 1)、及/或氟原子含有率超過0質量%且未達20質量%之含氟樹脂(D 2)；且 上述鹼可溶性樹脂(C)係具有下述通式(1)所表示之結構之雙酚型環氧樹脂， [化1] [式(1)中，R分別獨立地表示碳數1～3之直鏈狀或碳數3之支鏈狀之烷基、碳數1～3之直鏈狀之全氟烷基或氫原子，Z表示1價之有機基或氫原子]。 A photosensitive resin composition, characterized by containing: an ethylenically unsaturated compound (A); a photopolymerization initiator (B); an alkali-soluble resin (C); and a fluorine-containing resin (D), which contains fluorine atoms. Fluorine-containing resin (D 1 ) with a fluorine atom content of 20 to 60 mass %, and/or fluorine-containing resin (D 2 ) with a fluorine atom content exceeding 0 mass % and less than 20 mass %; and the above-mentioned alkali-soluble resin (C) It is a bisphenol type epoxy resin having a structure represented by the following general formula (1), [Chemical 1] [In formula (1), R independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, a linear perfluoroalkyl group having 1 to 3 carbon atoms, or a hydrogen atom. , Z represents a univalent organic group or hydrogen atom]. 如請求項1之感光性樹脂組合物，其進而含有著色顏料(E)。The photosensitive resin composition of claim 1 further contains a coloring pigment (E). 如請求項1或2之感光性樹脂組合物，其中上述鹼可溶性樹脂(C)之氟原子含有率為10質量%以下。The photosensitive resin composition of claim 1 or 2, wherein the fluorine atom content of the alkali-soluble resin (C) is 10 mass % or less. 如請求項1或2之感光性樹脂組合物，其中上述含氟樹脂(D)之氟原子含有率與上述鹼可溶性樹脂(C)之氟原子含有率之差為15～60質量%。The photosensitive resin composition according to claim 1 or 2, wherein the difference between the fluorine atom content of the fluorine-containing resin (D) and the fluorine atom content of the alkali-soluble resin (C) is 15 to 60 mass %. 如請求項1或2之感光性樹脂組合物，其中上述含氟樹脂(D)相對於上述感光性樹脂組合物之總固形物成分之含量為0.01～40質量%。The photosensitive resin composition according to claim 1 or 2, wherein the content of the fluorine-containing resin (D) relative to the total solid content of the photosensitive resin composition is 0.01 to 40 mass %. 如請求項1或2之感光性樹脂組合物，其中上述感光性樹脂組合物中之鹼可溶性樹脂(C)之含量相對於含氟樹脂(D)100質量份為1,000質量份以上且10,000質量份以下。The photosensitive resin composition of claim 1 or 2, wherein the content of the alkali-soluble resin (C) in the photosensitive resin composition is 1,000 parts by mass or more and 10,000 parts by mass relative to 100 parts by mass of the fluorine-containing resin (D) the following. 如請求項1或2之感光性樹脂組合物，其進而包含選自由光自由基增感劑、鏈轉移劑、紫外線吸收劑及聚合抑制劑所組成之群中之至少1種。The photosensitive resin composition of claim 1 or 2 further comprises at least one selected from the group consisting of a photo-radical sensitizer, a chain transfer agent, an ultraviolet absorber and a polymerization inhibitor. 如請求項1或2之感光性樹脂組合物，其用於形成阻隔壁。The photosensitive resin composition of claim 1 or 2 is used to form a barrier wall. 一種樹脂膜，其係由如請求項1至8中任一項之感光性樹脂組合物獲得。A resin film obtained from the photosensitive resin composition of any one of claims 1 to 8. 一種硬化物，其係使如請求項9之樹脂膜硬化而成。A hardened material is obtained by hardening the resin film as claimed in claim 9. 一種阻隔壁，其係由如請求項10之硬化物構成。A barrier wall is formed of the hardened material as claimed in claim 10. 一種有機電致發光元件，其具備如請求項11之阻隔壁。An organic electroluminescent element comprises the barrier rib as claimed in claim 11. 一種波長轉換層，其具備如請求項11之阻隔壁。A wavelength conversion layer having a barrier as claimed in claim 11. 一種顯示裝置，其具備如請求項11之阻隔壁。A display device provided with the barrier wall according to claim 11. 一種硬化物之製造方法，其特徵在於包括： 成膜步驟，藉由將如請求項1至8中任一項之感光性樹脂組合物塗佈到基板後，進行加熱而製成樹脂膜；及 曝光步驟，對上述樹脂膜曝光高能量線。 A method for manufacturing a hardened product, characterized by comprising: a film-forming step, in which a photosensitive resin composition as described in any one of claims 1 to 8 is applied to a substrate and then heated to form a resin film; and an exposure step, in which the resin film is exposed to high energy rays. 一種阻隔壁之製造方法，其特徵在於包括： 成膜步驟，藉由將如請求項1至8中任一項之感光性樹脂組合物塗佈到基板後，進行加熱而製成樹脂膜；及 曝光步驟，對上述樹脂膜曝光高能量線。 A method for manufacturing barrier walls, which is characterized by including: In the film forming step, the photosensitive resin composition according to any one of claims 1 to 8 is applied to the substrate and then heated to form a resin film; and In the exposure step, the resin film is exposed to high-energy rays.
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