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TW200910009A - Positive type photosensitive resin composition, cured coating thereof and display element - Google Patents

Positive type photosensitive resin composition, cured coating thereof and display element Download PDF

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Publication number
TW200910009A
TW200910009A TW097112034A TW97112034A TW200910009A TW 200910009 A TW200910009 A TW 200910009A TW 097112034 A TW097112034 A TW 097112034A TW 97112034 A TW97112034 A TW 97112034A TW 200910009 A TW200910009 A TW 200910009A
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component
photosensitive resin
resin composition
group
formula
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TW097112034A
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Chinese (zh)
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TWI438571B (en
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Kazuya Ebara
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Nissan Chemical Ind Ltd
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/039Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007Filters, e.g. additive colour filters; Components for display devices
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/038Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387Polyamides or polyimides
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00Electroluminescent light sources
    • H05B33/02Details
    • H05B33/04Sealing arrangements, e.g. against humidity
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10OLED displays
    • H10K59/12Active-matrix OLED [AMOLED] displays
    • H10K59/122Pixel-defining structures or layers, e.g. banks
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10OLED displays
    • H10K59/17Passive-matrix OLED displays
    • H10K59/173Passive-matrix OLED displays comprising banks or shadow masks

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Engineering & Computer Science (AREA)
  • Materials For Photolithography (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

Disclosed is a positive photosensitive resin composition as a material for a display element which enables a sharp image display in a display device such as an organic EL device. This positive photosensitive resin composition is soluble in a low-pollution organic solvent. Specifically disclosed is a positive photosensitive resin composition containing a polyimide precursor having a structural unit represented by the formula (1) below or a polyimide obtained therefrom as a component (A), and a compound which generates an acid when irradiated with light as a component (B). The components (A) and (B) are dissolved in a solvent (C).; (1) (In the formula (1), R<1> represents an aromatic group represented by the following formula (2): (2) (wherein R<3> represents an organic group having a sulfur atom, and R<4> and R<5> independently represent a hydrogen atom or an organic group having 1-20 carbon atoms); R<2> represents an aromatic group having a fluorine atom; and n represents a natural number.)

Description

200910009 九、發明說明 【發明所屬之技術領域】 本發明係關於電性•電子裝置,特別爲半導體 顯示裝置等之表面保護膜、層間絕緣膜、鈍化膜、 護層等合適的感光性材料。更詳言之,係關於在低 有機溶劑中可溶,所得之硬化膜使用作爲有機E L 置的絕緣膜時,不會引起發光面中的發光不良之優 型感光性樹脂組成物及其硬化膜、以及使用該硬化 種材料。 【先前技術】 由具有卓越機械特性、高耐熱性之感光性聚醯 代表之感光性樹脂所製作的感光性絕緣膜,其用途 不僅於半導體領域並且於顯示器領域中已開始普及 將感光性絕緣膜作爲液晶顯示元件之薄膜電晶體( k 的保護膜、或有機EL元件之電極保護膜等之保護 於顯示裝置等之情形中,上述之性能爲當然的,並 提高目前對於絕緣膜的信賴性,並且亦要求元件步 單化、保護膜的良好形狀,更且,由生產性的觀點 要求低公害系且於生物分散性溶劑中可溶之諸種特 別’於上述裝置中,不會引起顯示不良爲重要條件 求不會因最終製品所裝入之硬化膜水分和感光劑滲 起的元件不良。 目前所提案之正型感光性樹脂組成物爲使用三 裝置和 電極保 公害系 元件裝 良的正 膜之各 亞胺所 擴大, 。特別 TFT ) 膜使用 且要求 驟的簡 而言亦 性。特 ,故要 出所引 乙胺等 -5- 200910009 之鹼性有機化合物,令聚醯胺酸的酸性度減少 顯像液之溶解速度的聚醯亞胺系正型感光性樹 專利文獻1 )。又,以提高熱硬化後之殘膜保 強度爲目的,提案由含有酚性羥基和非酚性羥 胺樹脂和醌二疊氮基化合物所構成的正型感光 物(專利文獻2 ),和以提高感度和高殘膜率 合樹脂之密黏性爲目的,提案除了聚醯亞胺前 和重氮醌化合物以外,含有酚性化合物之樹脂 利文獻3 )。此些文獻中所提案的材料雖記載 具有優良的機械特性,但擔心來自最終硬化膜 三乙胺和酚性化合物等)等的滲出造成元件發 。如上述,先前的正型感光性聚醯胺樹脂組成 提供滿足發光特性之材料作爲發光元件的間隔 專利文獻1 :美國專利第4880722號說明Ϊ 專利文獻2 :特開2004-94 1 1 8號公報 專利文獻3 :特開平9-30222 1號公報 【發明內容】 (發明所欲解決之課題) 本發明爲鑑於上述情事而完成者,於有機 之顯示裝置中,提供作爲可顯示鮮明圖像之顯 料的正型感光性樹脂組成物。更且,欲提供於 機溶劑中溶解的正型感光性樹脂組成物。 ,抑制鹼性 脂組成物( 持率和力學 基之聚醯亞 性樹脂組成 ,提高與封 體之聚醯胺 組成物(專 爲高感度且 之添加物( 光面的損傷 物中,難以 EL裝置等 示元件用材 低公害系有 200910009 (解決課題之手段) 本發明者爲了解決上述課題進行致力硏究之結果,達 到發現本發明。 即’第1觀點爲含有作爲(A)成分之具有下述式(1 )所示構造單位的聚醯亞胺前體或由其所得之聚醯亞胺、 和作爲(B )成分之經由光產生酸之化合物,並將彼等溶 解於(C )溶劑的正型感光性樹脂組成物。 [化1]BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric/electronic device, particularly a photosensitive material such as a surface protective film, an interlayer insulating film, a passivation film, or a protective layer for a semiconductor display device. More specifically, in the case of using a low-organic solvent, the obtained cured film is an excellent photosensitive resin composition and a cured film thereof which do not cause poor light-emitting in the light-emitting surface when an insulating film is used as the organic EL. And using the hardened material. [Prior Art] A photosensitive insulating film made of a photosensitive resin represented by a photosensitive polyfluorene having excellent mechanical properties and high heat resistance is used not only in the field of semiconductors but also in the field of displays. In the case where the protective film of the liquid crystal display element (the protective film of k or the electrode protective film of the organic EL element is protected by a display device or the like), the above-described performance is of course improved, and the current reliability with respect to the insulating film is improved. In addition, it is also required that the element is step-formed and the shape of the protective film is good, and that it is required to be low in pollution and soluble in a biodispersible solvent from the viewpoint of productivity, and it is not particularly difficult to cause display failure. It is important to find that the hardened film moisture and the sensitizing agent which are contained in the final product are defective. The positive photosensitive resin composition proposed at present is a positive film which is equipped with three devices and electrode-protected components. Each of the imines is expanded, and the special TFT) film is used and is required to be simple. Therefore, it is necessary to introduce a polyethylenimine-based positive photosensitive tree which is an alkaline organic compound of -5-200910009, which reduces the acidity of poly-proline. The dissolution rate of the developing solution is patent document 1). In order to improve the residual film strength after thermosetting, a positive photosensitive material comprising a phenolic hydroxyl group and a non-phenolic hydroxylamine resin and a quinonediazide compound (Patent Document 2) has been proposed, and For the purpose of sensitivity and high residual film ratio and resin adhesion, it is proposed to use a resin containing a phenolic compound in addition to polyiminamide and a diazonium compound (3). Although the materials proposed in these documents have excellent mechanical properties, they are likely to cause bleed out from the final cured film such as triethylamine and phenolic compounds. As described above, the conventional positive-type photosensitive polyimide resin composition provides a material satisfying the light-emitting property as a light-emitting element. Patent Document 1: US Pat. No. 4,880,722 Description Patent Document 2: JP-A-2004-94 1 18 CITATION LIST OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above circumstances, and is provided as an image displayable in an organic display device. A positive photosensitive resin composition of the material. Further, it is intended to provide a positive photosensitive resin composition which is dissolved in an organic solvent. It inhibits the composition of the alkaline fat (the holding ratio and the mechanical basis of the polyruthenium resin composition, and improves the polyamine composition with the sealant (specially for high sensitivity and additives (light damage, difficult EL) In the present invention, in order to solve the above problems, the inventors of the present invention have found that the present invention has been found to have a low level of pollution as a component (A). a polyimine precursor of the structural unit represented by the formula (1) or a polyimine obtained therefrom, and a compound which generates an acid via light as the component (B), and dissolves them in the solvent (C) A positive photosensitive resin composition.

⑴ (式(1)中,R1爲表示式(2) [化2] r4ooc POOR5(1) (In the formula (1), R1 is a formula (2) [Chemical 2] r4ooc POOR5

(2) (式(2)中,R3爲表示具有硫原子之有機基,R4及 R5爲分別獨立表示氫原子或碳原子數1至2〇之有機基) 所示之芳香族基,R2爲表示具有氟原子之芳香族基,η爲 表示自然數)。 第2觀點爲前述式(2)中,R3爲具有磺醯基之有機 200910009 基之第1觀點記載的正型感光性樹脂組成物。 第3觀點爲前述式(2)中,R4及R5中之至少一者爲氫 原子之第1觀點或第2觀點記載的正型感光性樹脂組成物。 第4觀點爲前述式(1)中,R2爲具有下述式(3)所 示構造之第1觀點至第3觀點中任一項記載的正型感光性 樹脂組成物。 [化3](2) In the formula (2), R3 is an aromatic group which represents an organic group having a sulfur atom, and R4 and R5 are each independently represent a hydrogen atom or an organic group having 1 to 2 carbon atoms, and R2 is It represents an aromatic group having a fluorine atom, and η represents a natural number). The second aspect is the positive photosensitive resin composition described in the first aspect of the above-mentioned formula (2), wherein R3 is an organic group having a sulfonyl group. The third aspect is the positive photosensitive resin composition described in the first aspect or the second aspect in which at least one of R4 and R5 is a hydrogen atom in the above formula (2). In the above-mentioned formula (1), R2 is a positive photosensitive resin composition according to any one of the first aspect to the third aspect of the structure of the following formula (3). [Chemical 3]

⑶ (式中’ R6爲表示經氟原子所取代之碳原子數1至8 之有機基,Χι及X2爲分別獨立表示氫原子,碳原子數1 至10之有機基、或羥基)。 第5觀點爲該(A)成分爲令含有下述式(4)所示之 化合物的四羧酸成分、與二胺成分聚合所得之聚醯亞胺前 體或由其所得之聚醯亞胺之第1觀點至第4觀點中任一項 記載的正型感光性樹脂組成物。 [化4](3) wherein R6 is an organic group having 1 to 8 carbon atoms which is substituted by a fluorine atom, and Χι and X2 are each independently represent a hydrogen atom, an organic group having 1 to 10 carbon atoms, or a hydroxyl group. According to a fifth aspect, the component (A) is a polycarboxylic acid imine obtained by polymerizing a tetracarboxylic acid component containing a compound represented by the following formula (4) or a diamine component, or a polyimine obtained therefrom. The positive photosensitive resin composition according to any one of the first aspect to the fourth aspect. [Chemical 4]

(4) (式中’ R爲表不具有硫原子之有機基)。 -8- 200910009 第6觀點爲該四羧酸成分爲該式(4)所示之化合物 ,加上含有下述式(5)至式(8)所示化合物中之至少一 種之四羧酸成分之第5觀點記載的正型感光性樹脂組成物(4) (wherein 'R is an organic group having no sulfur atom). -8- 200910009 The sixth aspect is that the tetracarboxylic acid component is a compound represented by the formula (4), and a tetracarboxylic acid component containing at least one of the compounds represented by the following formulas (5) to (8) is added. Positive photosensitive resin composition described in the fifth aspect

(式中’ m爲表示0或1,Rs爲表示碳原子數1至12 之二價有機基或直接結合至芳香環,具有氧原子之二價有 機基’ R9、R1G、R11、RU及RI3爲分別表示碳原子數1至 12之有機基)。 第7觀點爲該式(4)所示之化合物爲於該四羧酸成 分中,佔有40至99莫耳。/β之第5觀點或第6觀點記載的 正型感光性樹脂組成物。 第8觀點爲該一胺成分爲含有下述式(9)所示之二 胺化合物的一胺成分之第5觀點至第7觀點中任一項記載 的正型感光性樹脂組成物。 -9- 200910009 [化6](wherein 'm is 0 or 1, Rs is a divalent organic group representing 1 to 12 carbon atoms or directly bonded to an aromatic ring, and a divalent organic group having an oxygen atom' R9, R1G, R11, RU and RI3 To represent an organic group having 1 to 12 carbon atoms, respectively. The seventh aspect is that the compound represented by the formula (4) is 40 to 99 moles in the tetracarboxylic acid component. A positive photosensitive resin composition described in the fifth aspect or the sixth aspect of β. In the eighth aspect, the positive photosensitive resin composition according to any one of the fifth aspect to the seventh aspect of the present invention, wherein the monoamine component is a monoamine component of the diamine compound represented by the following formula (9). -9- 200910009 [Chem. 6]

(式中’ R6爲袠示經氟原子所取代之碳原子數1至8 之有機基’X3及χ4爲分別獨立表示氫原子、碳原子數i 至1 〇之有機基' 或趨基)。 第9觀點爲該二胺成分爲含有二胺基矽氧烷化合物之 二胺成分之第5觀點至第8觀點中任一項記載的正型感光 性樹脂組成物。 第10觀點爲該(B)成分爲萘醌二疊氮基磺酸酯化合 物之第1觀點至第1 〇觀點中任一項記載的正型感光性樹 脂組成物。 第11觀點爲該(C)溶劑爲由具有4個以上碳原子之 醇或烷酯所組成群中選取至少一種之第1觀點至第1 0觀 點中任一項記載的正型感光性樹脂組成物。 第12觀點爲根據(A)成分之100質量份,含有0.01 至1〇〇質量份之(B)成分之第1觀點至第π觀點中任— 項記載的正型感光性樹脂組成物。 第13觀點爲再根據(A)成分之100質量份含有5至 1 〇〇質量份下述(1 〇 )所示之馬來醯亞胺化合物作爲(D )成分之第1 2觀點記載的正型感光性樹脂組成物。 -10- (10) 200910009 [化7] R15 R16(In the formula, R6 is an organic group 'X3 and χ4 having a carbon number of 1 to 8 substituted by a fluorine atom, and is an organic group or a substituent which independently represents a hydrogen atom and has a carbon number of i to 1 Å). According to a ninth aspect, the diamine component is a positive photosensitive resin composition according to any one of the fifth aspect to the eighth aspect of the invention, wherein the diamine component is a diamine component. The ninth aspect of the present invention is the positive photosensitive resin composition according to any one of the first aspect, wherein the component (B) is a naphthoquinone diazide sulfonate compound. In the eleventh aspect, the (C) solvent is a positive photosensitive resin according to any one of the first aspect to the first aspect, wherein at least one of the group consisting of an alcohol or an alkyl ester having four or more carbon atoms; Things. The twelfth aspect is a positive photosensitive resin composition according to any one of the first aspect to the πth aspect, wherein the component (B) is contained in an amount of from 0.01 to 1 part by mass based on 100 parts by mass of the component (A). The thirteenth aspect is that the maleic imine compound represented by the following (1 〇) is contained in the first aspect of the component (D) in an amount of from 5 to 1 part by mass based on 100 parts by mass of the component (A). A photosensitive resin composition. -10- (10) 200910009 [Chem. 7] R15 R16

(式中,R14爲表二價有機基’ R15、R16、R17、R18、 R19、R2G、R21、R22、R·23、及R24爲分別獨立表示氫原子 、碳原子數1至12之有機基)。 第14觀點爲該式(10)中,R14爲具有下述式(11) 所示構造之第1 3觀點記載的正型感光性樹脂組成物。(wherein R14 is a divalent organic group of the formula: ' R15, R16, R17, R18, R19, R2G, R21, R22, R.23, and R24 are each independently represent a hydrogen atom and an organic group having 1 to 12 carbon atoms. ). In the above formula (10), R14 is a positive photosensitive resin composition described in the first aspect of the structure represented by the following formula (11).

(式中,1和k爲分別獨立表示〇或1,X5、X6及X7 爲分別獨立表示碳數1至12之有機基,具有氧原子、硫 原子、氮原子之二價有機基)。 第15觀點爲該式(11 )中,1和k爲1,X5和X7爲 氧原子,X6爲二甲基甲基之第14觀點記載的正型感光性 樹脂組成物。 第16觀點爲再根據(A)成分之100質量份含有5至 1 〇〇質量份交聯性化合物作爲(E )成分之第1 5觀點記載 -11 - 200910009 的正型感光性樹脂組成物。 第1 7觀點爲使用第1觀點至第1 6觀點中任一項記載 之正型感光性樹脂組成物所得的硬化膜。 第1 8觀點爲具有第1 7觀點記載之硬化膜的電子構件 〇(In the formula, 1 and k each independently represent 〇 or 1, and X5, X6 and X7 each independently represent an organic group having 1 to 12 carbon atoms, and have a divalent organic group having an oxygen atom, a sulfur atom and a nitrogen atom). According to a fifteenth aspect, in the formula (11), a positive photosensitive resin composition according to the fourteenth aspect, wherein 1 and k are 1, X5 and X7 are oxygen atoms, and X6 is a dimethylmethyl group. The sixteenth aspect is a positive photosensitive resin composition which further contains 5 to 1 part by mass of a crosslinkable compound as the (E) component in accordance with 100 parts by mass of the component (A), and is a positive photosensitive resin composition of -11 - 200910009. The cured film obtained by using the positive photosensitive resin composition according to any one of the first aspect to the sixteenth aspect. The 18th point is an electronic component having the cured film described in the 1st aspect.

第1 9觀點爲具有第1 8觀點記載之硬化膜的有機EL 元件。 第2 0觀點爲將第1觀點至第1 6觀點任一項記載的正 型感光性樹脂組成物於基板上塗佈’加熱乾燥後’照射紫 外線顯像之形成浮雕圖型的方法。 (發明之效果) 本發明之正型感光性樹脂組成物於低公害系有機溶劑 ,例如光阻材料所用之丙二醇單甲醚醋酸酯(PGMEA )等 溶劑中均勻溶解,不會發生顯像時成爲問題之未曝光部的 膜減薄,可形成微細的圖型。其上,形成圖型後使用硬化 膜之有機EL元件,可取得無影、顯示鮮明發光面的效果 【實施方式】 〔正型感光性樹脂組成物〕 本發明之正型感光性樹脂組成物爲含有(A)成分之 聚醯亞胺前體或由其所得之聚醯亞胺,(B)成分之光酸 發生劑,彼等爲溶解於(C )溶劑,且,分別根據所欲, -12- 200910009 之交聯性 含有(D)成分之馬來醢亞胺化合物、(E)成j 化合物、或界面活性劑等其他添加劑的組成物。 以下,詳細說明各成分。 &lt; (A )成分&gt; 位的聚醯 (A)成分爲具有下述式(1)所示之構造 亞胺前體或由其所得之聚醯亞胺。 [化9]The ninth aspect is an organic EL device having a cured film described in the eighteenth aspect. The twentieth aspect is a method of forming a relief pattern by irradiating an ultraviolet-ray image after applying a positive-type photosensitive resin composition according to any one of the first aspect to the sixteenth aspect to the substrate. (Effect of the Invention) The positive-type photosensitive resin composition of the present invention is uniformly dissolved in a solvent such as a low-pollution organic solvent such as propylene glycol monomethyl ether acetate (PGMEA) used for a photoresist material, and becomes a phenomenon when development does not occur. The film of the unexposed portion of the problem is thinned, and a fine pattern can be formed. In the above, an organic EL element using a cured film is formed, and an effect of eliminating the shadow and displaying a bright light-emitting surface can be obtained. [Embodiment] [Positive photosensitive resin composition] The positive photosensitive resin composition of the present invention is The polyimine precursor containing the component (A) or the polyimine obtained therefrom, the photoacid generator of the component (B), which are dissolved in the solvent (C), and respectively, as desired, The cross-linking property of 12-200910009 contains a composition of a maleic imine compound of the component (D), a compound of (E) a compound, or a surfactant, and the like. Hereinafter, each component will be described in detail. &lt;(A) Component&gt; The poly(A) component of the component (A) is a structural imine precursor represented by the following formula (1) or a polyimine obtained therefrom. [Chemistry 9]

⑴ 式(1)中’ η爲表不具有上述式(1)所: 之聚醯亞胺前體或由其所得之聚醯亞胺的聚合丨 整數。η若大於1 0 〇 〇,則對於一般有機溶劑的: 降低’樹脂組成物溶液的黏度顯著上升且操作彳 。因此,若考慮溶解性則期望η爲1 000以下丨 且特別期望爲未滿100之正整數。 又,(Α )成分之化合物,由於擔心因水^ 降低元件的信賴性’故於顯像液可溶之範圍中】 胺化。醯亞胺化的比例期望爲50至99.9%, 賴性和顯像性的觀點而言,更期望爲6 0至9 0 % 上述式(1)之R1爲表不下述式(2)所: 構造單位 。η爲正 解性極端 有時惡化 正整數, 的吸黏合 望被醯亞 由元件信 之芳香族 -13- 200910009 基,式(2)中,R3爲表示具有硫原子之有機基。 [化 10](1) In the formula (1), η is a polymerized 丨 integer representing the polyimine precursor of the above formula (1) or the polyimine obtained therefrom. If η is more than 10 〇 〇, then for general organic solvents: lowering the viscosity of the resin composition solution is significantly increased and operating 彳. Therefore, if solubility is considered, it is desirable that η is 1 000 or less and it is particularly desirable to be a positive integer of less than 100. Further, the compound of the (Α) component is aminated in the range in which the developing solution is soluble due to the fear of lowering the reliability of the device by water. The ratio of ruthenium imidation is desirably 50 to 99.9%, and more desirably 60 to 90% from the viewpoint of dependence and development. R1 of the above formula (1) is represented by the following formula (2): Construction unit. η is a positive definite extreme and sometimes deteriorates. A positive integer, the viscosity of the adsorption is expected to be entangled by the elemental aromatic -13- 200910009 base, in the formula (2), R3 is an organic group having a sulfur atom. [化10]

式(2 )中’ R3之具有硫原子之有機基並無特別限定 ’但由所得聚合物之溶解性及元件之信賴性的觀點而言, 期望爲磺醯基、硫基、或磺基。 式(2)中’ R4及R5爲分別獨立表示氫原子、或碳原 子數1至20之有機基。碳原子數1至2〇之有機基的導入 方法可採用在合成(A)成分之聚醯亞胺前體或由其所得 之聚醯亞胺時預先導入單體的方法、形成聚合物後令聚合 物與縮水甘油基化合物或丙烯酸酯化合物反應的方法、或 於反應溶液中加入一級胺類形成鹽之方法的任一種方法。 碳原子數1至20之有機基例如爲烷基、環烷基、芳 香族基、或烯丙基等,此等有機基的一部分亦可經鹵素基 所取代。此等有機基若溶解於低公害系有機溶劑則何種有 機基均可’但由所得·聚合物之溶解性觀點而言,則期望其 一部分爲經氟所取代。 上述式(1)之R2爲表示下述式(3)所示之芳香族 基。 -14- (3) 200910009 [化 11]The organic group having a sulfur atom in the formula (2) is not particularly limited. However, from the viewpoint of solubility of the obtained polymer and reliability of the element, a sulfonyl group, a sulfur group or a sulfo group is desirable. In the formula (2), R4 and R5 are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms. A method of introducing an organic group having 1 to 2 carbon atoms may be a method of preliminarily introducing a monomer when synthesizing a polyimine precursor of the component (A) or a polyimide obtained therefrom, and forming a polymer A method of reacting a polymer with a glycidyl compound or an acrylate compound, or a method of adding a primary amine to a reaction solution to form a salt. The organic group having 1 to 20 carbon atoms is, for example, an alkyl group, a cycloalkyl group, an aromatic group or an allyl group, and a part of these organic groups may be substituted with a halogen group. When these organic groups are dissolved in a low-noise organic solvent, any organic group can be used. However, from the viewpoint of solubility of the obtained polymer, it is desirable that a part thereof is substituted by fluorine. R2 in the above formula (1) is an aromatic group represented by the following formula (3). -14- (3) 200910009 [Chem. 11]

式中,R6爲表示經氟原子取代之碳原子 機基,若滿足此條件之有機基則無特別限定 氟化亞甲基、三_甲基等之氟院基’由所得 性及元件之信賴性的觀點而言,特別以三氟 式(3 )中之X !和X2爲分別獨立表示 子數1至10之有機基、或羥基。碳原子數 基可列舉烷基、環烷基、芳香族基、烯丙基 醯基、苯醯胺基或苯酯基等,但由所得聚合 感光特性之觀點而言以甲基或羥基爲佳,特 之觀點而言以羥基爲佳。 又,(A)成分(具有式(1)所示構造 胺前體或由其所得之聚醯亞胺)爲令四羧酸 選出之成分(以下,稱爲酸成分)、與二胺 將其加熱脫水,或予以化學性脫水令其醯亞 合物。 &lt;四羧酸成分&gt; 具有上述式(1)所示構造單位之聚醯 其所得之聚醯亞胺所用的酸成分爲以下述3 表示。另外,經由與後述二胺成分之反應, 數1至8之有 ,但期望爲二 聚合物之溶解 甲基爲佳。 氫原子、碳原 1至10之有機 、苄基、苯甲 物之溶解性和 別由感光特性 單位之聚醯亞 及其衍生物所 成分反應,再 胺化所得之化 亞胺前體或由 :(4 )之構造 大部分轉換成 -15- 200910009 前述式(2)所示之骨架。 W匕 12]In the formula, R6 is a carbon atom group substituted with a fluorine atom, and if the organic group satisfying the above conditions, the fluorine-based base group such as a fluorinated methylene group or a tri-methyl group is not particularly limited. From the viewpoint of the nature, X + and X 2 in the trifluoro formula (3) are each independently an organic group having a subnumber of 1 to 10 or a hydroxyl group. The carbon atom number group may, for example, be an alkyl group, a cycloalkyl group, an aromatic group, an allyl fluorenyl group, a benzoguanamine group or a phenyl ester group, but a methyl group or a hydroxyl group is preferred from the viewpoint of the obtained polymerization photosensitive property. In particular, hydroxyl is preferred. Further, the component (A) (having a structural amine precursor represented by the formula (1) or a polyimine obtained therefrom) is a component selected from a tetracarboxylic acid (hereinafter referred to as an acid component), and a diamine Heat dehydration, or chemical dehydration to make it bismuth. &lt;tetracarboxylic acid component&gt; The acid component of the polyfluorene obtained by having the structural unit represented by the above formula (1) is represented by the following three. Further, it is preferably a number of from 1 to 8 by the reaction with a diamine component described later, but it is preferred that the methyl group is dissolved in a methyl group. The solubility of a hydrogen atom, a carbonogen of 1 to 10 organic, a benzyl group, a benzene product, and a component of a polyacrylic acid and a derivative thereof in a photosensitive property unit, and a reductively obtained imine precursor or The structure of (4) is mostly converted into the skeleton shown in the above formula (2) of -15-200910009. W匕 12]

式(4)中,R7爲表示具有硫原子之有機基。若爲具 有硫原子之基則任何有機基均無妨’但由所得聚合物之溶 解性和元件之信賴性的觀點而言’則期望爲擴酿基Λ硫基 、或磺基。 具有硫原子之酸成分的具體例可列舉3,3’,4,4’-二苯 硫四羧酸成分化合物、3,3’,4,4’-二苯磺基四羧酸成分化合 物、3,3,,4,4 ’ -二苯磺醯四羧酸成分化合物等,但並非限定 於此等化合物。 又,上述具有硫原子之酸成分、與不含硫原子之酸成 分的莫耳比若爲40/60至99/1之範圍內,則上述二個酸成 分之化合物可共同使用於與二胺成分的共聚。 不含硫原子之酸成分可列舉下述式(5)至(8)之構 造所示的化合物。此等酸成分於共聚時亦可使用二種以上 。特別由兀件之信賴性的觀點而言,具有硫原子之酸成分 、與不含硫原子之酸成分的莫耳比爲5 0/5 0至8〇/2〇爲佳 -16- 200910009In the formula (4), R7 represents an organic group having a sulfur atom. Any organic group is a group having a sulfur atom, but it is expected to be a thiol group or a sulfo group from the viewpoint of solubility of the obtained polymer and reliability of the element. Specific examples of the acid component having a sulfur atom include a 3,3',4,4'-diphenylthiotetracarboxylic acid component compound, and a 3,3',4,4'-diphenylsulfotetracarboxylic acid component compound. The 3,3,4,4'-diphenylsulfonium tetracarboxylic acid component compound or the like is not limited thereto. Further, if the molar ratio of the acid component having a sulfur atom to the acid component containing no sulfur atom is in the range of 40/60 to 99/1, the compound of the two acid components may be used together with the diamine. Copolymerization of the ingredients. The acid component containing no sulfur atom may, for example, be a compound represented by the following formula (5) to (8). These acid components may be used in combination of two or more kinds. In particular, from the viewpoint of the reliability of the component, the molar ratio of the acid component having a sulfur atom to the acid component containing no sulfur atom is preferably 5 0/5 0 to 8 〇 /2 - -16- 200910009

式(5)中,R8爲表示碳原子數1至12之有機基、或 直接結合至芳香環之具有氧原子的二價有機基。r8若爲滿 足上述條件之有機基則無特別限定’碳原子數1至12之 有機基可列舉烷基、氟烷基、環烷基或芳香族基’具有氧 原子之二價有機基可列舉醚基或甲矽烷氧基等。其中,由 溶解性和感光特性之觀點而言,以氟烷基、或醚基爲佳’ 特別由溶解性之觀點而言期望爲氟甲基。 式(6)中,m爲表示0或1之整數。滿足其之四殘 酸成分可列舉均苯四甲酸、及1,2,6,7-萘四羧酸等,但並 非限定於此。 式(7)中’R9及R1G爲表示碳原子數1至12之有機 基。R9及R1()若爲碳原子數1至12之有機基則特別爲何 種有機基均無妨。其例可列舉烷基、氟烷基、環烷基或芳 香族基等,但並非限定於此。 式(8)中’R1!爲表示碳原子數1至12之二價有機 基,R12及R13爲表示碳原子數1至丨2之有機基。R11之 -17- 200910009 碳原子數1至12之二價有機基可列舉亞甲基、醚 烷基甲矽烷基或二烷基二甲矽烷氧基等’但並非特 於此些有機基。又,R12及R13若爲碳原子數1至 機基則無特別限定,其例可列舉例如烷基、氟烷基 基或芳香族基等。 上述式(5)至(8)構造所示之不含硫原子的 具體例可列舉2,2-雙(3,4-二羧苯基)六氟異亞 4,4’-六氟異亞丙基二酞酸、均苯四甲酸、1,2,6,7-酸、3,3 ’,4,4,-聯苯羧酸、3 , 3 ’,4,4 ’ -二苯酮四_ 3,3,,4,4’-二苯醚四羧酸、3,4-二羧基-1,2,3,4-四氫. 珀酸成分所代表之芳香族四羧酸成分、或1,2,3,4-四羧酸、1,2-二甲基-1,2,3,4-環丁烷四羧酸、1,2,3 基-1,2,3,4-環丁烷四羧酸、1,2,3,4-環戊烷四; 1,2,4,5-環己烷四羧酸、5- (2,5·二氧基四氫呋喃基 基-3-環己烯-1,2-二羧酸、2,3,5-三羧基-2-環戊烷醋 環〔2.2.2〕辛-7-烯-2,3,5,6-四羧酸、2,3,4,5-四氫 羧酸-3,5,6-三羧基-2-原冰片烷醋酸等之脂環式四羧 ,但並非限定於此。 上述不含硫原子之酸成分中,由所得聚合物之 和感光特性的観點而言,特別期望使用2,2-雙(3 苯基)六氟異亞丙基、4,4’-六氟異亞丙基二酞酸' 酸、3 , 3 ’,4,4 ’ -聯苯四羧酸及其衍生物,特別由所得 之溶解性的觀點而言’期望使用4,4 ’ -六氟異亞丙 酸二酐及其二鹵化物等之化合物。 基、三 別限定 12之有 、環烷 酸成分 丙基、 萘四羧 竣酸、 -1-萘琥 環丁烷 ,4-四甲 竣酸、 )-3-甲 酸、雙 呋喃四 酸成分 溶解性 ,4-二羧 均苯四 聚合物 基二酞 -18- 200910009 具有上述式(i)所示構造單位之聚醯亞胺前體或由 其所得之聚醯亞胺所用的二胺成分’係以下述式(9 )之 構造表示。 [化 14]In the formula (5), R8 is an organic group having 1 to 12 carbon atoms or a divalent organic group having an oxygen atom directly bonded to the aromatic ring. R8 is not particularly limited as long as it is an organic group satisfying the above conditions. The organic group having 1 to 12 carbon atoms may, for example, be an alkyl group, a fluoroalkyl group, a cycloalkyl group or an aromatic group. The divalent organic group having an oxygen atom may be exemplified. Ether group or formalkoxy group and the like. Among them, from the viewpoints of solubility and photosensitivity, a fluoroalkyl group or an ether group is preferred, and a fluoromethyl group is particularly preferable from the viewpoint of solubility. In the formula (6), m is an integer representing 0 or 1. Examples of the four residual acid components satisfying are pyromellitic acid and 1,2,6,7-naphthalenetetracarboxylic acid, but are not limited thereto. In the formula (7), 'R9 and R1G are an organic group having 1 to 12 carbon atoms. When R9 and R1() are an organic group having 1 to 12 carbon atoms, it is preferable that the organic group is particularly useful. Examples thereof include an alkyl group, a fluoroalkyl group, a cycloalkyl group or an aromatic group, but are not limited thereto. In the formula (8), 'R1! is a divalent organic group having 1 to 12 carbon atoms, and R12 and R13 are an organic group having 1 to 2 carbon atoms. R11 -17- 200910009 The divalent organic group having 1 to 12 carbon atoms may, for example, be a methylene group, an ether alkylcarboxyalkyl group or a dialkyldimethyl alkoxy group, but is not particularly limited to these organic groups. Further, R12 and R13 are not particularly limited as long as the number of carbon atoms is from 1 to 1, and examples thereof include an alkyl group, a fluoroalkyl group, and an aromatic group. Specific examples of the sulfur-free atom represented by the above formulas (5) to (8) include 2,2-bis(3,4-dicarboxyphenyl)hexafluoroiso-4,4'-hexafluoroisophthalene. Propyldiphthalic acid, pyromellitic acid, 1,2,6,7-acid, 3,3 ',4,4,-biphenylcarboxylic acid, 3,3 ',4,4 '-benzophenone IV _ 3,3,,4,4'-diphenyl ether tetracarboxylic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro. Aromatic tetracarboxylic acid component represented by a peric acid component, or 1,2,3,4-tetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3 base-1,2,3,4- Cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentane tetra; 1,2,4,5-cyclohexanetetracarboxylic acid, 5-(2,5·dioxytetrahydrofuranyl-3 -cyclohexene-1,2-dicarboxylic acid, 2,3,5-tricarboxy-2-cyclopentane vinegar ring [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid An alicyclic tetracarboxylic acid such as an acid, 2,3,4,5-tetrahydrocarboxylic acid-3,5,6-tricarboxy-2-albornaneacetic acid, etc., but is not limited thereto. The above does not contain a sulfur atom Among the acid components, it is particularly desirable to use 2,2-bis(3phenyl)hexafluoroisopropylidene or 4,4'-hexafluoroisopropylidene group from the viewpoint of the photosensitive properties of the obtained polymer. Citrate 'acid, 3, 3 ', 4, 4 -Biphenyltetracarboxylic acid and its derivatives, in particular, from the viewpoint of solubility obtained, it is desirable to use a compound such as 4,4 '-hexafluoroisopropionic acid dianhydride or a dihalide thereof. Qualified 12, naphthenic acid component propyl, naphthalene tetracarboxylic acid, 1-naphthylcyclobutane, 4-tetramethyl phthalic acid, )-3-carboxylic acid, bisfuran tetracarboxylic acid component solubility, 4- Dicarboxylic pyromellityl diphenyl- 18-200910009 The diamine component of the polyimine precursor having the structural unit represented by the above formula (i) or the polyimine obtained therefrom is based on the following formula The structural representation of (9). [Chem. 14]

(9) 式(9)中,R6爲表示經氟原子所取代之碳原子數1 至8之有機基,可列舉例如二氟化亞甲基、三氟甲基或氟 苯基等,但若爲滿足上述條件的有機基,則無特別限定。 其中’由所得聚合物之溶解性和感光特性之觀點而言,期 望爲二氟甲基。 式(9)中之X3及X4爲分別獨立表示氫原子、碳原 子數至10之有機基' 或經基。碳原子數1至10之有機 基可列舉烷基、環烷基、芳香族基、烯丙基、苄基、苯甲 &quot; 釀胺基或苯酸基等’但由所得聚合物之溶解性和 感光特性之觀點命_ 而S ’以甲基或經基爲佳,特別由感光特 性之觀點而言_物 期窫爲羥基。 上述式( 具體例可列舉 、2,2-雙〔4_ 具有經氟原子取代之有機基的二胺成分 2’2 -雙〔4- (3 -胺苯氧基)苯基〕六氟丙院 4'胺苯氧基)苯基〕六氟丙烷、2,2-雙(4- -19- 200910009 苯胺基)六氟丙烷、2,2 -雙(3 -苯胺基)六氟丙烷、2,2-雙(3-胺基-4-甲苯醯)六氟丙烷、2,2-雙(3-胺基-4_羥苯 基)六氟丙烷、2,2 -雙(4 -胺基-3 -羥苯基)六氟丙院、 2,2-雙(4-胺基-3,5-二羥苯基)六氟丙烷、2,2-雙〔4_(3_ 胺基-4-羥苯氧基)苯基〕六氟丙烷、2,2 -雙〔4- (4_胺基_ 3-羧苯氧基)苯基〕六氟丙烷等之化合物,但並非限定於 此。又,由所得聚合物之溶解性和感光特性之觀點而言, 適當的化合物可列舉2,2_雙(3-胺基-4-羥苯基)六氟丙烷 及2,2-雙(3-胺基-4-甲苯醯)六氟丙烷,特別由感光特性 而言,期望爲2,2-雙(3-胺基-4-羥苯基)六氟丙烷。 又,若於後述低公害系有機溶劑((C)成分)中可 溶,則組合不含氟原子之二胺成分並且使用於共聚亦可。 不含氟原子之其他的二胺成分,若至少使用一種以上具有 經氟原子取代之有機基的二胺成分,則使用二種以上亦無 妨。 不含氟原子之二胺成分的具體例可列舉對-苯二胺、 間-苯二胺、2,4,6-三甲基-1,3 -苯二胺、2,3,5,6-四甲基-1,4-苯二胺、4,4’-二胺基二苯醚、3,4’-二胺基二苯醚、 3,3’-二胺基二苯醚、4,4’-二胺基二硫苯、4,4’-二胺基二 苯基甲烷、3,4’-二胺基二苯基甲烷、3,3’-二胺基二苯基甲 院、4,4-亞甲基-雙(2 -甲基苯胺)、4,4’-亞甲基-雙(2,6-二甲基苯胺)、4,4-亞甲基-雙(2,6-二乙基苯胺)、4,4,-亞甲基-雙(2 -異丙基-6-甲基苯胺)、4,4’-亞甲基-雙( 2,6-二異丙基苯胺)、4,4’-二胺基二苯颯、3,3,-二胺基二 -20- 200910009 苯颯、聯苯胺、鄰-聯甲苯胺、間-聯甲苯胺、3,3’,5,5’-四 甲基聯苯胺、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基 苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、雙〔4-(4-胺 苯氧基)苯基〕颯、雙〔4-(3 -胺基苯氧基)苯基〕颯、 2,2-雙〔4-(4-胺基苯氧基)苯基〕丙烷、2,2-雙〔4-(3-胺基苯氧基)苯基〕丙烷、2,4-二胺基苯酚、3,5-二胺基 苯酚、2,5-二胺基苯酚、4,6-二胺基間苯二酚、2,5-二胺基 氫醌、雙(3-胺基-4-羥苯基)醚、雙(4-胺基-3-羥苯基 )醚、雙(4-胺基- 3,5-二羥苯基)醚、雙(3-胺基-4-羥苯 基)甲烷、雙(4 -胺基-3 -羥苯基)甲烷、雙(4 -胺基-3,5 -二羥苯基)甲烷、雙(3-胺基-4-羥苯基)颯、雙(4-胺 基-3-羥苯基)碾、雙(4-胺基-3,5-二羥苯基)颯、4,4’-二胺基-3,3 ’ -二羥基聯苯、4,4 ’ -二胺基-3,3 ’ -二羥基-5,5 ’ -二甲基聯苯、4,4’-二胺基-3,3’-二羥基-5,5’-二甲氧基聯苯 、1,4-雙(3-胺基-4-羥苯氧基)苯、1,3-雙(3-胺基-4-羥 苯氧基)苯、1,4-雙(4-胺基-3-羥苯氧基)苯、1,3-雙( 4-胺基-3-羥苯氧基)苯、雙〔4-(3-胺基-4-羥苯氧基)苯 基〕颯、雙〔4- ( 3-胺基-4-羥苯氧基)苯基〕丙烷、2,4-二胺基苯甲酸、2,5-二胺基苯甲酸、3,5-二胺基苯甲酸、 4,6-二胺基-1,3-苯二羧酸、2,5-二胺基-1,4-苯二羧酸、雙 (4-胺基-3-狻苯基)醚、雙(4-胺基-3,5-二羥苯基)醚、 雙(4-胺基-3-羧苯基)颯、雙(4-胺基-3,5-二羧苯基)颯 、4,4’-二胺基-3,3、二羧基聯苯、4,4’-二胺基-3,3’-二羧 基-5,5’-二甲基聯苯、4,4’-二胺基-3,3’-二羧基-5,5’-二甲 -21 - 200910009 氧基聯苯、1,4 -雙(4 -胺基-3-殘本爭(基)本、1,3 -雙(4-胺基-3-羧苯氧基)苯、雙〔4- (4 -胺基-3-羧苯氧基)苯 基〕碾、或雙〔4-(4 -胺基-3-羧苯氧基)苯基〕丙烷等。 更且,爲了提高使用上述具有式(1)所示構造單位 之聚醯亞胺前體或含有由其所得之聚醯亞胺的正型感光性 樹脂組成物所製作之塗膜對於基板的密黏性’可組合使用 二胺基矽氧烷化合物作爲二胺成分的一部分。含此類矽氧 烷之二胺期望爲雙(3_胺烷基)3_四甲基二矽氧烷 ,由與基板之密黏性和溶解性的觀點而言’更期望爲雙( 3-胺丙基)-1,1,3,3-四甲基二矽氧烷。 前述含矽氧烷之二胺,由與基板之密黏性及顯像性的 觀點而言,期望於二胺成分之全莫耳量中使用1至30%之 莫耳比。若超過3 0莫耳%則顯像性降低,且於基板上易殘 留殘渣。更期望爲1至20莫耳%,再期望使用1至10莫 耳%。 &lt; (B )成分&gt; (B)成分之光酸發生劑,若爲經由曝光等所使用之 光照射直接或間接性發生酸,具有提高光照射部分對於鹼 顯像液之溶解性機能者’則其種類及構造等並無特別限定 。又,光酸發生劑可爲1種或組合使用二種以上亦可。 上述(B)成分之光酸發生劑可應用先前公知之任一 種光酸發生劑’其具體例可列舉鄰-醌二疊氮基化合物、 烯丙基重氮銪鹽、二烯丙基碘鐵鹽、三烯丙基鏑鹽、鄰_ -22- 200910009 硝苄酯、對-硝苄酯 '經三鹵甲基取代之s_三畊衍 或醯亞胺基磺酸酯衍生物等。 又’視需要’ (B )成分之光酸發生劑亦可倂 劑。此類增感劑可列舉例如芘、蒽、噻噸酮、蜜嗤 苯酮或芴等,但並非限定於此。 (B)成分之光酸發生劑中,於使用正型感光 組成物所得之塗膜中,由取得高感度和高解像度之 言,期望爲鄰-醌二疊氮基化合物。 鄰-醌二疊氮基化合物通常爲令鄰-醌二疊氮基 、與具有羥基及胺基中選出至少一種基之化合物’ 觸媒存在下進行縮合反應,以鄰-醌二疊氮基擴酸1 醌二疊氮基磺醯胺型式取得。 構成上述鄰-醌二疊氮基磺醯氯之鄰-醌二疊氮 成分可列舉例如,1,2-萘醌-2-二疊氮基_4_磺酸、 醌-2-二疊氮基_5_磺酸、U2-萘醌_2_二疊氮基-6_磺? 具有上述羥基之化合物的具體例可列舉苯酣 酚、間-甲酚、對-甲酚、氫醅、間苯二酚、兒氽酚 氧基苯酚' 4,4 -異亞丙基二苯酚、丨,1-雙(4_經本 己烷、4,4,-二羥苯基颯、4,4-六氟異亞丙基一 4,4,,4”·三羥基三苯基甲烷、1,1,1-三(4-羥苯基) 4,4,-〔 1-〔 4-〔 1- ( 4-羥苯棊)-1-甲基乙基〕本基 基〕雙酚、3,4,5-三羥基苯甲酸甲酯' 3,4,5-二羥基 丙酯、3,4,5 -三羥基苯曱酸異戊醋、3,4,5_二經基’ 2-乙基丁酯、2,4-二羥基二苯酮、2,3,4_三經基一 生物、 用增感 酮 '二 性樹脂 方面而 擴醯氯 於驗性 旨或鄰- 基磺酸 1,2-萘 麥等。 .鄰-甲 、鄰-甲 基)ί哀 苹酚、 乙烷、 〕亞乙 苯甲酸 £甲酸-苯酮、 -23- 200910009 2,2,4,4 -四經基二苯嗣、2,3,4,4’-四經基_苯_ 、 2,3,4,2’,4’-五羥基二苯酮等之酚化合物、乙醇、2-丙醇、 4 - 丁醇、環己醇、乙二醇、丙二醇、二乙二醇、二丙二醇 、2 -甲氧基乙醇、2 -丁氧基乙醇、2 -甲氧基丙醇、2 -丁氧 基丙醇、乳酸乙酯、乳酸丁酯等之脂肪族醇類。 又,具有上述胺基之化合物可列舉苯胺、鄰-甲苯胺 、間-甲苯胺、對-甲苯胺、4 _胺基二苯基甲烷、4 -胺基二 苯基、鄰-苯二胺、間-苯二胺、對·苯二胺、4,4’-二胺基二 苯基甲烷、4,4,-二胺基二苯醚等之苯胺類、胺基環乙烷等 〇 更且,具有羥基和胺基兩者之化合物的具體例可列舉 鄰-胺基苯酚、間-胺基苯胺、對-胺基苯胺、4_胺基間苯二 酚、2,3-二胺基苯酚、2,4-二胺基苯酚、4,4’-二胺基·4’,·經 基三苯基甲烷、4 -胺基-4,,4,,-二羥基三苯基甲烷、雙(4_ 胺基-3-羧基-5-羥苯基)醚、雙(4-胺基殘基-5-經苯基 )甲烷、雙(4-胺基-3-羧基-5-羥苯基)楓、2,2 -雙(4_胺 基_3_羧基-5-羥苯基)丙烷、2,2 -雙(4_胺基_3_知基_5-羥 胺基乙醇、3_胺基丙醇 苯基)六氟丙烷等之胺基酚類、2_ 、4-胺基環己醇等之烷醇胺類。(9) In the formula (9), R6 is an organic group having 1 to 8 carbon atoms which is substituted by a fluorine atom, and examples thereof include a methylene difluoride, a trifluoromethyl group or a fluorophenyl group. The organic group which satisfies the above conditions is not particularly limited. Among them, from the viewpoint of solubility and photosensitivity of the obtained polymer, it is expected to be difluoromethyl. X3 and X4 in the formula (9) are an organic group or a meridine which independently represent a hydrogen atom and a carbon atom number of 10. The organic group having 1 to 10 carbon atoms may, for example, be an alkyl group, a cycloalkyl group, an aromatic group, an allyl group, a benzyl group, a benzoyl group, a aryl group or a benzoic acid group, but the solubility of the obtained polymer. And the viewpoint of the sensitization property _ and S ' is preferably a methyl group or a thiol group, and particularly from the viewpoint of sensitometric properties, the 物 period is hydroxy. The above formula (specific examples include 2,2-bis[4] diamine component 2'2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropyl compound having an organic group substituted with a fluorine atom 4'Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4--19-200910009 anilino)hexafluoropropane, 2,2-bis(3-anilino)hexafluoropropane, 2, 2-bis(3-amino-4-toluene)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino- 3-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3,5-dihydroxyphenyl)hexafluoropropane, 2,2-bis[4_(3-amino-4-hydroxyl) A compound such as phenoxy)phenyl]hexafluoropropane or 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]hexafluoropropane is not limited thereto. Further, from the viewpoints of solubility and photosensitivity of the obtained polymer, suitable compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2,2-bis (3). -Amino-4-toluene)hexafluoropropane, particularly in terms of photosensitivity, is desirably 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. In addition, when it is soluble in the low-organism organic solvent (component (C)) to be described later, a diamine component having no fluorine atom may be combined and used for copolymerization. When at least one of the other diamine components having no fluorine atom is used, at least one or more kinds of the diamine component having an organic group substituted by a fluorine atom may be used. Specific examples of the diamine component having no fluorine atom include p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6. -tetramethyl-1,4-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4 , 4'-diaminodithiobenzene, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl , 4,4-methylene-bis(2-methylaniline), 4,4'-methylene-bis(2,6-dimethylaniline), 4,4-methylene-bis (2 ,6-diethylaniline), 4,4,-methylene-bis(2-isopropyl-6-methylaniline), 4,4'-methylene-bis(2,6-diiso) Propyl aniline), 4,4'-diaminodiphenyl hydrazine, 3,3,-diaminodi-20- 200910009 benzoquinone, benzidine, o-tolidine, m-toluidine, 3, 3',5,5'-tetramethylbenzidine, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3- Bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, 2,2 - bis [4-(4-amino group) Phenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,4-diaminophenol, 3,5-diaminophenol, 2 , 5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis(3-amino-4-hydroxyphenyl)ether, bis(4-amine 3-hydroxyphenyl)ether, bis(4-amino-3,5-dihydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)methane, bis(4-amino-- 3-hydroxyphenyl)methane, bis(4-amino-3,5-dihydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl)anthracene, bis(4-amino-3- Hydroxyphenyl) milled, bis(4-amino-3,5-dihydroxyphenyl)anthracene, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamine Base-3,3 '-dihydroxy-5,5 '-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis(3-amino-4-hydroxyphenoxy)benzene, 1,3-bis(3-amino-4-hydroxyphenoxy)benzene, 1,4-bis(4-amino group 3-hydroxyphenoxy)benzene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, bis[4-(3-amino-4-hydroxyphenoxy)phenyl] Bismuth, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]propane, 2,4-Diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3-benzenedicarboxylic acid, 2,5 -diamino-1,4-benzenedicarboxylic acid, bis(4-amino-3-indolylphenyl)ether, bis(4-amino-3,5-dihydroxyphenyl)ether, double (4 -amino-3-carboxyphenyl)anthracene, bis(4-amino-3,5-dicarboxyphenyl)anthracene, 4,4'-diamino-3,3,dicarboxybiphenyl, 4, 4'-Diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethyl -21 - 200910009 Oxybiphenyl, 1,4-bis(4-amino-3-residue), 1,3-bis(4-amino-3-carboxyphenoxy)benzene, Bis[4-(4-amino-3-carboxyphenoxy)phenyl]millate or bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane. Further, in order to increase the density of the coating film prepared by using the above-mentioned polyimine precursor having the structural unit represented by the formula (1) or the positive photosensitive resin composition containing the polyimine obtained therefrom The viscous 'diamine siloxane compound can be used in combination as part of the diamine component. The diamine containing such a siloxane is desirably bis(3-aminoalkyl)3-tetramethyldioxane, which is more desirable to be double (3) from the viewpoint of adhesion to a substrate and solubility. -Aminopropyl)-1,1,3,3-tetramethyldioxane. The dioxane-containing diamine is desirably used in a molar ratio of from 1 to 30% in the total molar amount of the diamine component from the viewpoint of adhesion to the substrate and development. If it exceeds 30% by mole, the developability is lowered, and residue is liable to remain on the substrate. It is more desirable to be 1 to 20 mol%, and it is desirable to use 1 to 10 mol%. &lt; (B) Component&gt; The photoacid generator of the component (B) is an acid which directly or indirectly generates light by exposure to light or the like, and has a function of improving the solubility of the light-irradiating portion with respect to the alkali developing solution. 'There is no particular limitation on the type and structure thereof. Further, the photoacid generator may be used alone or in combination of two or more. The photoacid generator of the above component (B) can be applied to any of the previously known photoacid generators. Specific examples thereof include an o-quinonediazide compound, an allyldiazonium salt, and a diallyl iron iodide. Salt, triallyl sulfonium salt, o- _ -22- 200910009 n-benzyl ester, p-n-benzyl ester 'reduced by trihalomethyl group s_three tillage or sulfhydryl sulfonate derivatives. Further, the photoacid generator of the component (B) may be used as an anthraquinone. Examples of such a sensitizer include, but are not limited to, hydrazine, hydrazine, thioxanthone, candiline benzophenone or hydrazine. Among the photo-acid generators of the component (B), a coating film obtained by using a positive-type photosensitive composition is preferably an ortho-quinonediazide compound from the viewpoint of obtaining high sensitivity and high resolution. The ortho-quinonediazide compound is usually a condensation reaction of an ortho-quinonediazide group with a compound having a hydroxyl group and at least one selected from the group consisting of a catalyst, and is excited by an o-quinonediazide group. The acid 1 quinone diazide sulfonamide type was obtained. The ortho-quinonediazide component constituting the above o-quinonediazidesulfonyl chloride may, for example, be 1,2-naphthoquinone-2-diazide-4-sulfonic acid or fluorene-2-diazepine. Base _5_sulfonic acid, U2-naphthoquinone_2_diazido-6_sulfonate? Specific examples of the compound having the above hydroxyl group include benzoquinone, m-cresol, p-cresol, hydroquinone, resorcinol, and cresylphenol phenol '4,4-isopropylidene diphenol.丨, 1-bis (4_ via hexane, 4,4,-dihydroxyphenyl hydrazine, 4,4-hexafluoroisopropylidene-4,4,,4"·trihydroxytriphenylmethane, 1 1,1-tris(4-hydroxyphenyl) 4,4,-[1-[4-[1-(4-hydroxyphenylhydra)-1-methylethyl]benyl]bisphenol, 3 , 4,5-trihydroxybenzoic acid methyl ester '3,4,5-dihydroxypropyl ester, 3,4,5-trihydroxybenzoic acid isovaleric acid, 3,4,5-di-based '2- Ethyl butyl acrylate, 2,4-dihydroxybenzophenone, 2,3,4-trisyl-based, sensitized ketone' adipic resin 1,2-naphthalene, etc.. o-methyl, o-methyl), ethane, ethane, benzoic acid, formic acid, benzophenone, -23- 200910009 2,2,4,4 -4 a phenolic compound such as bisphenylhydrazine, 2,3,4,4'-tetramyl-benzene-, 2,3,4,2',4'-pentahydroxybenzophenone, ethanol, 2-propanol , 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, An aliphatic alcohol such as propylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate or butyl lactate. Examples of the amine group compound include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, and m-benzene. An aniline such as an amine, p-phenylenediamine, 4,4'-diaminodiphenylmethane or 4,4,-diaminodiphenyl ether, or an aminocyclohexane, etc., having a hydroxyl group and Specific examples of the compound of the amine group include o-aminophenol, m-aminoaniline, p-aminoaniline, 4-aminoresorcin, 2,3-diaminophenol, 2,4. -diaminophenol, 4,4'-diamino-4', perylene triphenylmethane, 4-amino-4,4,-dihydroxytriphenylmethane, bis(4-amino 3-carboxy-5-hydroxyphenyl)ether, bis(4-amino residue-5-phenyl)methane, bis(4-amino-3-carboxy-5-hydroxyphenyl) maple, 2 ,2-bis(4-amino-3_carboxy-5-hydroxyphenyl)propane, 2,2-bis(4-amino-3- knowy-based 5-hydroxyaminoethanol, 3-aminopropyl Phenyl) hexafluoropropane group of phenol, 2_, 4-amino-cyclohexanol of alkanolamine.

或五取代體的鄰-醌二疊氮基化合物。 。將此類鄰-醌二疊氮 -24- 200910009 基化合物使用作爲正型感光性樹脂組成物之一成分 般將上述多取代體之鄰-醌二疊氮基化合物單獨、 述多取代體中選取二種以上之多取代體的混合物型 用。 上述之鄰-醌二疊氮基化合物中,由使用正型 樹脂組成物所得之塗膜中,曝光部與未曝光部的顯 度差的平衡良好’且顯像時圖型底部無顯像殘渣( 緣部之殘渣)的觀點而言,期望爲對-甲酚的鄰-醌 基磺酸酯、4,4’-〔 1-〔 4_〔 1- (4_羥苯基)-1-甲基 苯基〕亞乙基〕雙酚的鄰-醌二疊氮基磺酸酯、3,4: 基苯甲酸甲酯的鄰-醌二疊氮基磺酸酯、2,3,4·三羥 酮的鄰-醌二疊氮基磺酸酯、或2,3,4,4’-四羥基二 鄰-醌二疊氮基磺酸酯等,且此等化合物可分別單 ’又,亦可由此等化合物中任意選取二種以上混合彳 本發明所用(B)成分之光酸發生劑的含量爲枝 )成分之100質量份以0.01至100質量份。由本 正型感光性樹脂組成物所得之塗膜中,就曝光部與 部之顯像液溶解度差之平衡良好方面,更且,由該 感度及由該塗膜所得之硬化膜的機械特性的觀點而 B)成分之光酸發生劑的含量特別期望爲50質量份 且更期望爲3 0質量份以下。 &lt; (C )成分&gt; 本發明之正型感光性樹脂組成物所用之(C ) 時,— 或由上 式供使 感光性 像溶解 圖型邊 二疊氮 乙基〕 ,5 ·三羥 基二苯 苯酮的 獨使用 吏用。 【據(A 發明之 未曝光 塗膜之 言,( 以下, 溶劑, -25- 200910009 由(A)成分(具有式(1)所示之構造單位之聚醯 體或由其所得之聚醯亞胺)的溶解性高方面、與( 分(光酸發生劑)及後述其他成分之相溶性良好方 正型感光性樹脂組成物中操作容易方面、以及係爲 系有機溶劑方面而言’期望具有4個以上碳原子之 酯。其中代表性溶劑可列舉丁基溶纖劑、丙二醇單 丙二醇單甲醚醋酸酯、二丙二醇單甲醚、r-丁內 酸乙酯及乳酸丁酯、正丁醇、第二丁醇、第三丁醇 基甲基戊醇、甲基溶纖劑、乙基溶纖劑、丁基卡必 基卡必醇醋酸酯、乙基卡必醇、乙基卡必醇醋酸酯 醇單異丙醚、乙二醇單丁醚、二丙二醇單醋酸酯單 二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單醋 乙醚、二丙二醇單丙醚、二丙二醇單醋酸酯單丙醚 氧基乙醇、2-丁氧基乙醇、乳酸甲酯、乳酸乙酯、 酯、醋酸甲酯、醋酸乙酯、醋酸正丁酯、丙二醇單 酸酯、丙酮酸甲醋、丙酮酸乙酯、3 -甲氧基丙酸甲 乙氧基丙酸甲基乙酯、3_甲氧基丙酸乙酯、3_甲氧 丙酯、3_甲氧基丙酸丁酯或丁酸丁酯。此等溶劑爲 上之混合溶劑亦無妨。 特別於正型感光性樹脂組成物中操作最容易之 言,期望使用丁基溶纖劑、丙二醇單甲醚、丙二醇 醋酸酯、二丙二醇單甲醚、r-丁內酯、乳酸乙酯 丁酯所組成群中選出一種或二種以上之混合物。 又,上述溶劑以外’亦可混合使用丙酮、甲醇 亞胺前 :B )成 面、及 低公害 醇或烷 甲醚、 酯、乳 、甲氧 醇、丁 、乙二 甲醚、 酸酯單 、2-乙 乳酸丁 乙醚醋 酯、3-基丙酸 二種以 觀點而 單甲醚 及乳酸 、乙醇 -26- 200910009 、異丙醇、二戊烯、乙基戊基酮、甲基壬基酮、甲基乙基 酮、甲基異戊基酮、甲基異丙基酮、乙二醇、乙二醇單醋 酸酯、丙二醇、二乙二醇、二乙二醇單醋酸酯、二乙二醇 二甲醚、3-甲基-3-甲氧基丁基醋酸酯、三丙二醇單甲醚、 3-甲基-3-甲氧基丁醇、二異丙醚、乙基二異丁醚、二異丁 烯、戊基醋酸酯、丁醚、二異丁基酮、甲基環己烯、丙醚 、二己醚、二of烷、Ν,Ν-二甲基乙醯胺、N,N-二甲基甲醯 胺、N-甲基-2-吡略烷酮、N-乙烯基吡咯烷酮、二甲基亞 颯、N-甲基叱咯烷酮、正己烷、正戊烷 '正辛烷、2-甲氧 基乙醇、二乙醚、環己酮、3 -乙氧基丙酸、3 -甲氧基丙酸 或二甘醇二甲醚等之溶劑。但,此等其他溶劑由先前之正 型感光性樹脂組成物所使用(非低公害系有機溶劑)之觀 點而言,其使用量愈少愈佳。 &lt; (D )成分&gt; 本發明之正型感光性樹脂組成物可含有馬來醯亞胺化 合物作爲(D )成分。(D )成分之馬來醯亞胺化合物於 使用本發明之正型感光性樹脂組成物所得塗膜之顯像步驟 中,若爲可溶於鹼性顯像液之化合物,則無特別限定。( D )成分之馬來醯亞胺化合物若爲馬來醯亞胺部位直接結 合至芳香環,且氫原子直接結合至鄰接的芳香族碳,則其 構造並無特別限定。 上述之具有馬來醯亞胺部位直接結合至芳香環,且氫 原子直接結合至鄰接之芳香族碳構造的馬來醯亞胺化合物 -27- 200910009 ,可列舉下述式(1 〇)所示之化合物。 [化 15]Or a penta-substituted ortho-quinonediazide compound. . The ortho-quinonediazide-24-200910009-based compound is used as a component of a positive photosensitive resin composition, and the above-mentioned polysubstituted ortho-quinonediazide compound is selected as a single or multiple substituent. A mixture of two or more types of substituents. In the ortho-quinonediazide compound described above, the coating film obtained by using the positive resin composition has a good balance of the difference in the difference between the exposed portion and the unexposed portion, and there is no image residue at the bottom of the pattern at the time of development. From the viewpoint of (residue of the edge), it is expected to be o-mercaptosulfonate of p-cresol, 4,4'-[ 1-[ 4_[ 1-(4-hydroxyphenyl)-1-methyl O-quinonediazide sulfonate of phenyl]ethylidene bisphenol, o-quinonediazide sulfonate of methyl 3,4: benzoate, 2,3,4·3 O-nonyldiazide sulfonate of hydroxyketone, or 2,3,4,4'-tetrahydroxydi-o-quinonediazide sulfonate, etc., and these compounds can be separately The photoacid generator of the component (B) used in the present invention may be arbitrarily selected from the above-mentioned compounds in an amount of from 0.01 to 100 parts by mass per 100 parts by mass of the component of the component. In the coating film obtained from the positive photosensitive resin composition, the balance between the solubility of the developing solution of the exposed portion and the portion is good, and the sensitivity and the mechanical properties of the cured film obtained from the coating film are also improved. The content of the photoacid generator of the component B) is particularly desirably 50 parts by mass and more desirably 30 parts by mass or less. &lt;(C) component&gt; When (C) is used for the positive photosensitive resin composition of the present invention, or by the above formula, the photosensitive image is dissolved in the pattern of bis-azidoethyl], 5 · trihydroxyl The use of benzophenone alone. (According to the unexposed coating film of the invention A, (hereinafter, solvent, -25- 200910009) (A) component (a polyorganism having a structural unit represented by formula (1) or a polyaluminum obtained therefrom In view of the high solubility of the amine, the compatibility with the (photoacid generator) and other components described later is easy to handle, and it is desirable to have an organic solvent. Examples of the solvent include butyl cellosolve, propylene glycol monopropylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, ethyl r-butyrolate and butyl lactate, n-butanol, and second. Butanol, tert-butanylmethylpentanol, methyl cellosolve, ethyl cellosolve, butyl carbitol carbitol acetate, ethyl carbitol, ethyl carbitol acetate Monoisopropyl ether, ethylene glycol monobutyl ether, dipropylene glycol monoacetate monodipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether oxygen Ethanol, 2-butoxyethanol, methyl lactate, milk Ethyl ester, ester, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoester, methyl acetonate, ethyl pyruvate, methyl 3-ethoxypropionate methyl ethoxypropionate, 3_Methyl methoxypropionate, 3-methoxypropionate, butyl 3-methoxypropionate or butyl butyrate. These solvents are also suitable solvents. Especially for positive photosensitive resins. It is easiest to operate in the composition. It is desirable to select one or two of the group consisting of butyl cellosolve, propylene glycol monomethyl ether, propylene glycol acetate, dipropylene glycol monomethyl ether, r-butyrolactone, and ethyl lactate. Mixture of the above. In addition to the above solvents, 'may be mixed with acetone, methanol imine before: B) faceted, and low-harm alcohol or alkyl ether, ester, milk, methoxy alcohol, butyl, ethyl dimethyl ether, Acid ester monomer, 2-ethyl lactate butyl ether acetate, 3-propyl propionic acid from the viewpoint of monomethyl ether and lactic acid, ethanol-26- 200910009, isopropanol, dipentene, ethyl amyl ketone, A Pyridyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, ethylene glycol, ethylene glycol Acetate, propylene glycol, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol monomethyl ether, 3-methyl 3-methoxybutanol, diisopropyl ether, ethyl diisobutyl ether, diisobutylene, pentyl acetate, dibutyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, di-, alkane, hydrazine, hydrazine-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, dimethyl飒, N-methylpyrrolidone, n-hexane, n-pentane 'n-octane, 2-methoxyethanol, diethyl ether, cyclohexanone, 3-ethoxypropionic acid, 3-methoxypropane A solvent such as an acid or diglyme. However, these other solvents are used in the form of a conventional positive photosensitive resin composition (non-low pollution organic solvent), and the smaller the amount is, the better. . &lt;Component (D)&gt; The positive photosensitive resin composition of the present invention may contain a maleimide compound as the component (D). The maleic imine compound of the component (D) is not particularly limited as long as it is a compound soluble in an alkaline developing solution in the developing step of the coating film obtained by using the positive photosensitive resin composition of the present invention. When the maleidide compound of the component (D) is directly bonded to the aromatic ring and the hydrogen atom is directly bonded to the adjacent aromatic carbon, the structure is not particularly limited. The above-described maleated imine compound -27-200910009 having a maleimine moiety directly bonded to an aromatic ring and having a hydrogen atom bonded directly to an adjacent aromatic carbon structure is exemplified by the following formula (1 〇) Compound. [化15]

上述式(10)中,R14爲表示二價有機基,R15、R16 、:R17、R18、R19、R2C)、R21、R22、R23、及 R24 爲分別獨 立表示氫原子、碳原子數1至12之有機基。 其中,前述式(10)中,期望使用R14爲具有下述式 (1 Π所示構造之馬來醯亞胺化合物作爲(D )成分。 [化 16]In the above formula (10), R14 represents a divalent organic group, and R15, R16, R17, R18, R19, R2C), R21, R22, R23, and R24 each independently represent a hydrogen atom and have 1 to 12 carbon atoms. Organic base. In the above formula (10), it is desirable to use R14 as a component (D) having a structure represented by the following formula (1). [Chem. 16]

(11) 上述式(11)中,1與k爲分別獨立表示0或1,Χ5 、Χ6及Χ7爲分別獨立表示碳1至12之有機基、具有氧原 子、硫原子、氮原子之二價有機基。 特別,前述式(11)中,1與k爲1,Χ5與Χ7爲氧原 子,χ6爲二甲基。 上述式(1 〇 )所示(D )成分之馬來醯亞胺化合物的 -28- 200910009 具體例可列舉2,2-雙(3-胺基-4-馬來醯亞胺)六氟丙烷、 4,4’ -二馬來醯亞胺二苯醚、3,4’ -二馬來醯亞胺二苯醚、 3,3’-二馬來醯亞胺二苯醚、4,4’-二馬來醢亞胺二硫苯、 4,4’-二馬來醯亞胺二苯基甲烷、3,4’-二馬來醯亞胺二苯基 甲烷、3,3’-二馬來醯亞胺二苯基甲烷、4,4-亞甲基-雙(2-甲基馬來醯亞胺)、4,4’-二馬來醯亞胺二苯楓、3,3’-二馬 來醯亞胺二苯碾、雙(4-馬來醯亞胺苯氧基)苯、 1,3’-雙(4 -馬來醯亞胺苯氧基)苯、1,3’-雙(4 -馬來醯亞 胺苯氧基)苯、雙〔4- (4-馬來醯亞胺苯氧基)苯基〕楓 、雙〔4-(3 -馬來醯亞胺苯氧基)苯基〕颯、雙〔3-(4-馬來醯亞胺苯氧基)苯基〕颯、雙〔3-(3 -馬來醯亞胺苯 氧基)苯基〕颯、2,2’-雙〔4-(4-馬來醯亞胺苯氧基)苯 基〕丙烷、2,2-雙〔4- ( 3-胺基苯氧基)苯基〕丙烷等之 化合物,但並非限定於此。 另外,上述化合物中,由取得容易度方面而言期望爲 4,4’·二馬來醯亞胺二苯基甲烷及2,2’-雙〔4- (4-馬來醯亞 胺苯氧基)苯基〕丙烷’更且由感光特性之觀點而言,更 佳爲2,2’-雙〔4-(4-馬來醯亞胺苯氧基)苯基〕丙烷。 本發明中(D )成分之馬來醯亞胺化合物可組合使用 二種以上。 本發明之正型感光性樹脂組成物中’ (D )成分之馬 來醯亞胺化合物的含量並無特別限定’但根據(A )成分 之聚醯亞胺前體100質量份期望以5至1〇〇質量份,且更 期望爲5至20質量份。 -29- 200910009 &lt; (E )成分&gt; 本發明之正型感光性樹脂組成物可含有交聯性化合物 作爲(E)成分。(E)成分之交聯性化合物爲於使用本發 明之正型感光性樹脂組成物所得之塗膜轉換成硬化膜的步 驟(以下,稱爲最終硬化時)中,若爲具有令(A )成分 之聚醯亞胺前體、或(B)成分之光酸發生劑中之至少一 者所含之有機基反應所得基之化合物,則無特別限定。 (E)成分之交聯性化合物可列舉例如含有2個以上 環氧基之化合物、或、胺基之氫原子爲具有經羥甲基、烷 氧甲基或其兩者取代基之蜜胺衍生物、苯并胍胺衍生物或 二元醇脲等。此蜜胺衍生物及苯并胍胺衍生物可爲二聚物 或三聚物,又,亦可爲由單體、二聚物及三聚物中任意選 出之混合物。此些蜜胺衍生物及苯并胍胺衍生物爲每1個 三愕環’期望具有平均3個以上且未達6個羥甲基或烷氧 甲基者。 又,本發明中(E )成分的交聯性化合物可組合使用 二種以上。 (E )成分之交聯性化合物由容易取得之方面而言, 期望使用市售品之化合物。以下列舉其具體例(商品名) ,但並非限定於此。 含有2個以上環氧基之化合物可列舉Ep〇lid GT-401 、Epolid GT-403 ' Epolid GT-3〇i、Epolid GT-302、 Seroxide 2021、Seroxide 3000 (以下,Diacel 化學工業( -30- 200910009 股)製)等之具有環己烯構造的環氧化合物、Epicoat 1001 、 Epicoat 1002 、 Epicoat 1003 、 Epicoat 1004 、 Epicoat 1007 、 Epicoat 1009 、 Epicoat 1010 、 Epicoat 828 (以上,Japan Epoxy Resin (股)製)等之雙酣A型環氧 化合物、Epicoat 807 ( Japan Epoxy Resin (股)製)等之 雙酣F型環氧化合物、Epicoat 152、Epicoat 154 (以上, Japan Epoxy Resin (股)製)、EPPN 201、EPPN 202 (以 上,日本化藥(股)製)等之苯酚酚醛清漆型環氧化合物 、ECON-1 02、ECON-103S、ECON-104S、ECON- 1 020、 ECON- 1 025、ECON- 1 027 (以上,日本化藥(股)製)、 Epicoat 180S75 ( Japan Epoxy Resin (股)製)等之甲酣 酌醒清漆型環氧化合物、Denacol EX-252 (Nagasekemtex (股)製)、CY175、CY177、CY179、Ararudite CY-182 、Ararudite CY-192、Ararudite CY-184 (以上,CIBA-GEIGY A.G 製)、Epiclone 2 00、Epiclone 400 (以上,大 曰本油墨化學工業(股)製)Epieoat 87 1、Epicoat 8 72 ( 以上,Japan Epoxy Resin (股)製)ED-5661、ED-5662 ( 以上,Ceraneeds Coating (股)製)等之脂環式環氧化合 物、Denacol EX-611、Denacol EX-612、Denacol EX-614 、Denacol EX-622、Denacol EX-411、Denacol EX-512、 Denacol EX-5 22、Denacol EX-421、Denacol EX-313、 Denacol EX-314、Denacol EX-312 (以上,Nagasekemtex (股)製)等之脂肪族聚縮水甘油醚化合物。 胺基之氫原子爲具有經羥甲基、烷氧甲基或其兩者所 -31 - 200910009 取代基之虽' fee衍生物、本并胍I女衍生物或二元醇脲可列舉 每1個二Π并環之甲氧甲基爲平均經取代3 7個的μΧ·750 、每1個二U并ϊ哀之甲氧甲基爲平均經取代5.8個的mW-30 (以上’二和 Chemical 製)、或 Cymei 3〇〇、Cymel 301 、C y m e 1 3 0 3、C y m e 1 3 5 0、C y m e 1 3 7 0、C y m e 1 7 7 1、 Cymel 3 25、Cymel 3 27、Cymel 703、Cymel 712 等之甲氧 甲基化蜜胺、Cymel 235、Cymel 236、Cymel 238、Cymel 212、Cymel 253、Cymel 254等之甲氧甲基化丁氧甲基化 蜜胺、Cymel 506、Cymel 5〇8等之丁氧甲基化蜜胺、 Cymel 1141等之含有羧基的甲氧甲基化異丁氧甲基化蜜胺 、Cymel 1123般之甲氧甲基化乙氧甲基化苯并胍胺、 Cymel 1123-10般之甲氧甲基化丁氧甲基化苯并胍胺、 Cymel 1128般之丁氧甲基化苯并胍胺、Cymel 1125-80般 之含有羧基之甲氧甲基化乙氧甲基化苯并胍胺(以上,曰 本 Cytic Industries (股)(舊:三井 Cyanamide)製)、 Cymel 1170般之丁氧甲基化二元醇脲、Cymel 1172般之 羥甲基化二元醇脲等。 本發明之正型感光性樹脂組成物中,(E )成分之交 聯性化合物的含量並無特別限定,但由正型感光性樹脂組 成物之保存安定性、所得硬化膜之吸水性的低度及耐熱性 及耐藥品性的觀點而言,根據(A )成分之聚醯亞胺前體 1 〇 〇質量份期望以5至1 0 0質量份,且由保存安定性之觀 點而言更期望以5至20質量份。 -32- 200910009 &lt;其他添加劑&gt; 更且,本發明之正型感光性樹脂組成物只要不損害本 發明之效果,視需要,可含有界面活性劑、流變調整劑、 矽烷偶合劑等之接黏輔助劑、顏料、染料、保存安定劑、 消泡劑、或多價苯酚、多價羧酸等之溶解促進劑等。 本發明之正型感光性樹脂組成物於提高其塗佈性之目 的下所使用的界面活性劑,可列舉氟系界面活性劑、矽系 界面活性劑、非離子系界面活性劑等。此種界面活性劑可 使用例如住友3 Μ (股)製、大日本油墨化學工業(股) 製或旭硝子(股)製等之市售品。此些市售品因爲可輕易 取得,故爲合適。其具體例可列舉Efutop EF301、EF303 、EF352((股)Gemco 製)'Megafac F171、F173(大 日本油墨化學工業(股)製)、Florad FC43 0、FC431 ( 住友 3M (股)製)、Asahiguard AG710、Surfuron S-382 、SC101、SC102、SC103、SC104、SC 105 ' SC106(旭硝 子(股)製)等之氟系界面活性劑。 上述界面活性劑可單獨一種、或組合使用二種以上。 又,使用界面活性劑時,其含量爲於正型感光性樹脂 組成物1 〇 〇質量%中通常爲〇 · 2質量%以下,較佳爲〇. 1質 量%以下。即使將界面活性劑的使用量設定成超過0.2質 量%之份量,亦令上述塗佈性的改良效果鈍化,非經濟的 &lt;正型感光性樹脂組成物&gt; -33- 200910009 本發明之正型感光性樹脂組成物爲含有(A )成分之 聚醯亞胺前體或由其所得之聚醯亞胺、(B)成分之光酸 發生劑及(C )溶劑,且分別視所欲’可進一步含有(D ) 成分之馬來醯亞胺化合物、(E )成分之交聯性化合物及 界面活性劑等之其他添加劑中之一種以上的組成物。 其中,本發明之正型感光性樹脂組成物的較佳例爲如 下。 〔1〕:根據(A)成分100質量份’含有〇.〇1至1〇〇 質量份之(B)成分,且此等成分爲溶解於(C)溶劑的正 型感光性樹脂組成物。 〔2〕:於上述〔1〕之組成物中,再令(D)成分根 據(A)成分100質量份含有5至100質量份之正型感光 性樹脂組成物。 〔3〕:於上述〔2〕之組成物中,再令(E )成分根 據(A)成分100質量份含有5至100質量份之正型感光 性樹脂組成物。 本發明之正型感光性樹脂組成物中固形成分的比例只 要可令各成分均勻溶解於溶劑中,則無特別限定,一般作 成可由固形成分濃度1至50質量%範圍中任意選擇濃度之 正型感光性樹脂組成物的溶液,可輕易形成塗膜。此處, 所謂固形成分,係指由正型感光性樹脂組成物之全成分中 除去(C )溶劑者。 本發明之正型感光性樹脂組成物的調製方法無特別限 定。此種組成物通常以溶液之形態供使用,故本發明之正 -34- 200910009 型感光性樹脂組成物一般可列舉將(A )成分 、及、視所欲之(D )成分及(E )成分溶解方 ,作成均勻溶液之方法,或者於此調製法的適 添加混合其他添加劑的方法。 又,調製本發明之正型感光性樹脂組成杉 )成分的製造時,即,令四羧酸及其衍生物所 二胺成分於有機溶劑中聚合反應,且所得之反 其原樣使用。另外此時所使用之有機溶劑可歹 )溶劑中記載的溶劑。此時,於此(A )成分 中同前述加入(B)成分等作成均勻溶液時, 爲目的下亦可進一步追加投入(C )溶劑,此日: )成分時所用之有機溶劑、與調整濃度所用;^ 可爲相同,或爲相異亦可。 又,使用數種有機溶劑時,不僅於最初混 有機溶劑,將數種有機溶劑任意分別添加亦可 所調製之正型感光性樹脂組成物的溶液, 〇. 2 μιη左右的濾紙過濾後,供使用爲佳。 &lt;塗膜及硬化膜&gt; 一般,根據旋塗、浸漬、印刷等公知方法 本發明之正型感光性樹脂組成物於ΙΤΟ基板、 璃板、陶瓷基板、或具有氧化膜或氮化膜等之 ,其後,以溫度6 0 °c至1 6 0 °c,期望爲7 0 °c至 乾燥,則可形成本發明之正型感光性樹脂組成 (B )成分 &gt; (C )溶劑 當階段中再 I時,於(A 選出成分與 應溶液可就 丨舉前述(C 之反應溶液 以調製濃度 ,,製造(A .(C )溶劑 合使用數種 〇 使用孔徑爲 ,例如,將 矽晶圓、玻 基材上塗佈 130°C下預 物所構成的 -35- 200910009 塗膜。 形成塗膜後,例如經由紫外線等,使用具有 之光罩將塗膜曝光,並以鹼顯像液予以顯像,將 淨除去,如此可於基板上形成邊緣面爲鮮明的浮 此處所用之鹼顯像液若爲鹼性水溶液,則無 ,可列舉例如,氫氧化鉀、氫氧化鈉、碳酸鉀、 之鹼金屬氫氧化物的水溶液、氫氧化四甲基銨、 乙基銨、膽鹼等之氫氧化四級銨的水溶液、乙醇 、乙二胺等之胺水溶液。 上述鹼顯像液之濃度一般爲1 〇質量%以下, 用0.1至3 . 0質量%的鹼性水溶液。又,鹼顯像 有醇類或界面活性劑等,且期望分別含有0.05 3 %左右。 於顯像步驟中,可任意選擇鹼顯像液的溫度 本發明之正型感光性樹脂組成物時,因曝光部的 ,故於室溫下可輕易以鹼顯像液進行顯像。 如此處理所得之具有浮雕圖型的基板以溫度 400 °C熱處理(锻燒),使得吸水性低,因此可 特性優良,且耐熱性及耐藥品性亦良好,具有浮 硬化膜。 由本發明之正型感光性樹脂組成物所得的硬 爲具有此類優良之效果,故可使用於電氣•電子 導體裝置及顯示裝置等。特別,由本發明之正型 脂組成物所得的硬化膜,因爲具有有機EL元 指定圖型 曝光部洗 雕圖型。 特別限定 碳酸鈉等 氫氧化四 胺、丙胺 工業上使 .液亦可含 ξ 10質量 ,但使用 溶解性高 180。。至 取得電氣 雕圖型的 化膜,因 裝置、半 感光性樹 -(LED ( -36- 200910009(11) In the above formula (11), 1 and k each independently represent 0 or 1, and Χ5, Χ6 and Χ7 are respectively an organic group independently representing carbons 1 to 12, and have a valence of an oxygen atom, a sulfur atom, and a nitrogen atom. Organic base. In particular, in the above formula (11), 1 and k are 1, Χ5 and Χ7 are oxygen atoms, and χ6 is dimethyl. Specific examples of the maleidinolide compound of the component (D) represented by the above formula (1) can be exemplified by 2,2-bis(3-amino-4-maleimide)hexafluoropropane. , 4,4' - dimaleimide diphenyl ether, 3,4'-dimaleimide diphenyl ether, 3,3'-domalidene diphenyl ether, 4,4' - dimaleimide dithiobenzene, 4,4'-dimaleimide diphenylmethane, 3,4'-dimaleimide diphenylmethane, 3,3'-two horse醯iminodiphenylmethane, 4,4-methylene-bis(2-methylmaleimide), 4,4'-dismaleimide diphenyl maple, 3,3'- Dimaleimide diphenyl milling, bis(4-maleimidophenoxy)benzene, 1,3'-bis(4-maleimidophenoxy)benzene, 1,3'- Bis(4-maleimide phenoxy)benzene, bis[4-(4-maleimidophenoxy)phenyl] maple, bis[4-(3-maleimide phenoxy) Phenyl]indole, bis[3-(4-maleimidophenoxy)phenyl]indole, bis[3-(3-maleimidophenoxy)phenyl]pyrene, 2 , 2'-bis[4-(4-maleimide phenoxy)phenyl]propane, 2,2-dual A compound such as 4-(3-aminophenoxy)phenyl]propane, but is not limited thereto. Further, among the above compounds, 4,4'·dimaleimide diphenylmethane and 2,2'-bis[4-(4-maleimide phenoxy) are desirable in terms of ease of availability. The phenyl]propanol propane is more preferably 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane from the viewpoint of photosensitivity. In the present invention, the maleic imine compound of the component (D) may be used in combination of two or more kinds. The content of the maleic imine compound of the '(D) component in the positive photosensitive resin composition of the present invention is not particularly limited, but it is desirable to use 5 to 5 parts by mass of the polyimine precursor of the component (A). 1 part by mass, and more desirably 5 to 20 parts by mass. -29-200910009 &lt;(E) component&gt; The positive photosensitive resin composition of the present invention may contain a crosslinkable compound as the component (E). The cross-linking compound of the component (E) is a step of converting the coating film obtained by using the positive-type photosensitive resin composition of the present invention into a cured film (hereinafter, referred to as final hardening), if it has the order (A) The compound obtained by reacting the organic group contained in at least one of the polyimine precursor of the component or the photoacid generator of the component (B) is not particularly limited. The crosslinkable compound of the component (E) may, for example, be a compound containing two or more epoxy groups, or a hydrogen atom of an amine group may be derived from melamine having a methylol group, an alkoxymethyl group or a substituent thereof. a substance, a benzoguanamine derivative or a glycol urea or the like. The melamine derivative and the benzoguanamine derivative may be a dimer or a trimer, or may be a mixture of any one selected from the group consisting of a monomer, a dimer and a trimer. Such melamine derivatives and benzoguanamine derivatives are each desired to have an average of 3 or more and less than 6 methylol groups or alkoxymethyl groups per one triterpene ring. Further, in the present invention, the crosslinkable compound of the component (E) may be used in combination of two or more kinds. The crosslinkable compound of the component (E) is preferably a compound of a commercial product from the viewpoint of easy availability. The specific examples (trade names) are listed below, but are not limited thereto. Examples of the compound containing two or more epoxy groups include Ep〇lid GT-401, Epolid GT-403 'Epolid GT-3〇i, Epolid GT-302, Seroxide 2021, and Seroxide 3000 (hereinafter, Diacel Chemical Industry (-30-) 200910009, etc., epoxy compound with cyclohexene structure, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (above, Japan Epoxy Resin) ), such as a bismuth A type epoxy compound, a double 酣F type epoxy compound such as Epicoat 807 (made by Japan Epoxy Resin Co., Ltd.), Epicoat 152, Epicoat 154 (above, Japan Epoxy Resin Co., Ltd.), EPPN 201. EPPN 202 (above, manufactured by Nippon Chemical Co., Ltd.), etc., phenol novolak type epoxy compound, ECON-1 02, ECON-103S, ECON-104S, ECON-1 020, ECON-1 025, ECON- 1 027 (above, Nippon Chemical Co., Ltd.), Epicoat 180S75 (made by Japan Epoxy Resin Co., Ltd.), etc. Awakening varnish-type epoxy compound, Denacol EX-252 (made by Nagasekemtex Co., Ltd.), CY175 , CY177, CY179, Ara Rudite CY-182, Ararudite CY-192, Ararudite CY-184 (above, manufactured by CIBA-GEIGY AG), Epiclione 2 00, Epiclione 400 (above, manufactured by Otsuka Ink Chemical Industry Co., Ltd.) Epiioat 87 1, Epicoat 8 72 (above, Japan Epoxy Resin Co., Ltd.) ED-5661, ED-5662 (above, manufactured by Ceraneeds Coating Co., Ltd.), alicyclic epoxy compounds, Denacol EX-611, Denacol EX-612, Denacol EX -614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-5 22, Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX-312 (above, Nagasekemtex) An aliphatic polyglycidyl ether compound. The hydrogen atom of the amine group is a substituent having a hydroxymethyl group, an alkoxymethyl group or both of them - 31 - 200910009, although the 'fee derivative, the indole I derivative or the diol urea can be enumerated per 1 The methoxymethyl group of the diindole is an average of 3 7 μΧ·750, and each of the 2 U and methoxymethyl groups is an average of 5.8 mW-30 (above 'II and Chemical), or Cymei 3〇〇, Cymel 301, C yme 1 3 0 3, C yme 1 3 5 0, C yme 1 3 7 0, C yme 1 7 7 1 , Cymel 3 25, Cymel 3 27, Cymel Methoxyl methylated melamine melamine, Cymel 506, Cymel, such as methoxyl, melamine melamine, Cymel 235, Cymel 236, Cymel 238, Cymel 212, Cymel 253, Cymel 254, etc. a methoxymethylated melamine of 5〇8, etc., a methoxymethylated isobutoxymethylated melamine containing a carboxyl group such as Cymel 1141, and a methoxymethylated ethoxylated benzophenone of Cymel 1123 Indoleamine, Cymel 1123-10, methoxymethylated butoxymethylated benzoguanamine, Cymel 1128-like butoxymethylated benzoguanamine, Cymel 1125-80, carboxyl-containing methoxyl Ethoxylated Benzobenzamide (above, 曰本 Cytic Industries (sold) (old: Mitsui Cyanamide)), Cymel 1170-like butoxymethylated glycol urea, Cymel 1172-like methylolated diol Urea, etc. In the positive photosensitive resin composition of the present invention, the content of the crosslinkable compound of the component (E) is not particularly limited, but the storage stability of the positive photosensitive resin composition and the water absorption of the obtained cured film are low. From the viewpoint of the degree of heat resistance and chemical resistance, it is desirable to use 5 to 1000 parts by mass of the polybenzamine precursor according to the component (A), and it is more preferable from the viewpoint of preservation stability. It is desirable to be 5 to 20 parts by mass. -32-200910009 &lt;Other Additives&gt; Further, the positive photosensitive resin composition of the present invention may contain a surfactant, a rheology modifier, a decane coupling agent, etc. as long as it does not impair the effects of the present invention. A adhesion aid, a pigment, a dye, a storage stabilizer, an antifoaming agent, or a dissolution promoter such as a polyvalent phenol or a polyvalent carboxylic acid. The surfactant used for the purpose of improving the coatability of the positive photosensitive resin composition of the present invention includes a fluorine-based surfactant, a ruthenium-based surfactant, and a nonionic surfactant. As such a surfactant, a commercially available product such as Sumitomo 3 Co., Ltd., Dainippon Ink Chemical Industry Co., Ltd., or Asahi Glass Co., Ltd. can be used. These commercial products are suitable because they are easily available. Specific examples thereof include Efutop EF301, EF303, EF352 (manufactured by Gemco), 'Megafac F171, F173 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Florad FC43 0, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahiguard A fluorine-based surfactant such as AG710, Surfuron S-382, SC101, SC102, SC103, SC104, SC 105 'SC106 (made by Asahi Glass Co., Ltd.). The above surfactants may be used alone or in combination of two or more. Further, when the surfactant is used, the content thereof is usually 〇 2 % by mass or less, preferably 〇 1 % by mass or less, based on 1% by mass of the positive photosensitive resin composition. Even if the amount of the surfactant to be used is more than 0.2% by mass, the above-mentioned improvement effect of the coating property is inactivated, and the non-economical &lt;positive type photosensitive resin composition&gt; -33- 200910009 The photosensitive resin composition is a polyimine precursor containing the component (A), a polyimine obtained therefrom, a photoacid generator of the component (B), and (C) a solvent, and respectively, as desired. Further, one or more of the maleimide compound of the component (D), the crosslinkable compound of the component (E), and other additives such as a surfactant may be contained. Among them, preferred examples of the positive photosensitive resin composition of the present invention are as follows. [1]: The component (B) is contained in an amount of 质量1 to 1 part by mass based on 100 parts by mass of the component (A), and these components are a positive photosensitive resin composition dissolved in the solvent (C). [2] In the composition of the above [1], the component (D) is further contained in an amount of 5 to 100 parts by mass based on 100 parts by mass of the component (A). [3]: In the composition of the above [2], the component (E) is further contained in an amount of 5 to 100 parts by mass based on 100 parts by mass of the component (A). The proportion of the solid component in the positive photosensitive resin composition of the present invention is not particularly limited as long as the components are uniformly dissolved in the solvent, and generally, a positive type which can be arbitrarily selected from the range of 1 to 50% by mass of the solid component concentration is prepared. A solution of the photosensitive resin composition can easily form a coating film. Here, the solid component means a solvent (C) which is removed from the entire composition of the positive photosensitive resin composition. The preparation method of the positive photosensitive resin composition of the present invention is not particularly limited. Such a composition is usually used in the form of a solution. Therefore, the composition of the positive-34-200910009 photosensitive resin of the present invention generally includes the component (A), and the component (D) and (E) as desired. A method in which a component is dissolved, a uniform solution is prepared, or a method in which other additives are appropriately added to the preparation method. Further, in the production of the component of the positive photosensitive resin composition of the present invention, that is, the diamine component of the tetracarboxylic acid and its derivative is polymerized in an organic solvent, and the obtained product is used as it is. Further, the organic solvent used at this time may be a solvent described in the solvent. In this case, when the component (B) is added to the component (B) or the like as a homogeneous solution, the solvent (C) may be further added for the purpose of using the organic solvent and the adjusted concentration for the component: Used; ^ can be the same, or can be different. Further, when a plurality of organic solvents are used, not only the first organic solvent but also a plurality of organic solvents may be added to the solution of the positive photosensitive resin composition prepared, and the filter paper of about 2 μιη may be filtered. Use is better. &lt;Coating film and cured film&gt; Generally, the positive photosensitive resin composition of the present invention is applied to a ruthenium substrate, a glass plate, a ceramic substrate, or an oxide film or a nitride film, etc., according to a known method such as spin coating, immersion, or printing. Then, at a temperature of 60 ° C to 160 ° C, desirably 70 ° C to dry, the positive photosensitive resin composition (B) of the present invention can be formed &gt; (C) solvent In the case of further I in the stage, (A, the component and the solution are selected, and the above-mentioned reaction solution can be used to prepare the concentration, and the production is carried out. (A. (C) The solvent is used in combination with several kinds of enthalpy, for example, 矽Applying a coating film of -35 to 200910009 composed of a preform at 130 ° C on a wafer or a glass substrate. After forming a coating film, the coating film is exposed by using a photomask, for example, by ultraviolet light, and alkali imaging is performed. The liquid is imaged and removed, so that the surface of the substrate can be formed into a clear floating surface. If the alkali developing solution is used as an alkaline aqueous solution, it may be, for example, potassium hydroxide or sodium hydroxide. An aqueous solution of potassium carbonate, an alkali metal hydroxide, tetramethyl hydroxide An aqueous solution of a quaternary ammonium hydroxide such as ethylammonium or choline, or an aqueous solution of an amine such as ethanol or ethylenediamine. The concentration of the alkali developing solution is generally 1% by mass or less, and 0.1 to 3.0% by mass. An alkaline aqueous solution. Further, the alkali imaging has an alcohol or a surfactant, and is desirably about 0.05% by weight. In the developing step, the temperature of the alkali developing solution can be arbitrarily selected. The positive photosensitive property of the present invention. In the case of the resin composition, it is easy to develop with an alkali developing solution at room temperature due to the exposed portion. The substrate having the relief pattern thus obtained is heat-treated (calcined) at a temperature of 400 ° C to make water absorption. Since it is low, it has excellent characteristics, and is excellent in heat resistance and chemical resistance, and has a float-hardened film. The hardness obtained from the positive-type photosensitive resin composition of this invention has such an excellent effect, and can be used for electrical and electronic In particular, the cured film obtained from the positive-type fat composition of the present invention has an organic EL element designation type exposed portion, and is particularly limited to tetraamine hydroxide such as sodium carbonate. The propylamine industry can also contain ξ 10 mass, but the solubility is high 180. To obtain the electric pattern of the film, because of the device, semi-photosensitive tree - (LED (-36- 200910009)

Light-Emitting Diode)元件之一種)之信賴性高的特徵性 效果,故作爲發光元件之損傷成爲大問題之有機EL元件 的絕緣膜及間隔壁材,或者,於半導體包裝中銅配線之離 子遷移作用大受絕緣膜之吸水性影響時的緩衝塗敷中,大 爲有用。 以下列舉實施例,進一步詳細說明本發明,但本發明 並非限定於此。 實施例 〔實施例所用之簡略記號〕 下列實施例所用之簡略記號的意義爲如下。 &lt;二胺成分&gt; BAHF: 2,2,-雙(3-胺基-4-羥苯基)六氟丙烷 BATF: 2,2’-雙(3-胺基-4-甲苯甲酿)六氟丙垸 DDM: 4,4’-二胺基二苯基甲烷 APDS:雙(3-胺丙基)-1,1,3,3-四甲基二矽氧烷 DBA : 1,3-二胺基-5-羧基苯 TFMB : 2,2’-雙(三氟甲基)聯苯胺 &lt;四羧酸成分&gt; 6FDA: 4,4,-六氟異亞丙基二酞酸酐 DSDA : 3,3,- 4,4,-二苯颯四羧酸酐 PMDA:均苯四酸酐 ODPA: 3,3,,4,4,-二苯醚四羧酸酐 -37- 200910009 &lt;溶劑&gt; PGMEA :丙二醇單甲醚醋酸酯 PGME:丙二醇單甲醚 NMP : N-甲基吡咯烷酮 7· -BL : r -丁內酯 &lt;光酸發生劑&gt; 名) 亞乙 莫耳 P20 0 :經由東洋合成工業(股)製P-200 (商品 4,4’-〔1-〔 4-〔 1-(4-羥苯基)-1-甲基乙基〕苯基〕 基〕雙酚1莫耳與1,2-萘醌-2-二疊氮基-5-磺醯氯2 之縮合反應所合成的感光劑 &lt;馬來醯亞胺成分&gt; 基〕 BMI-80: 2,2’-雙〔4-(4-馬來醯亞胺苯氧基)苯 丙烷 〔數平均分子量及重量平均分子量的測定〕 以下 GPC 作爲 流過 爲以 根據以下之合成例,聚合物之重量平均分子量( 簡稱爲Mw)與分子量分佈爲使用日本分光(股)製 裝置(Shodex (註冊商標)柱KF803L及KF805L,將 溶出溶劑之二甲基甲醯胺以流量1毫升/分鐘於柱中 (柱溫:5 0 °C )令其溶離的條件下測定。另外,μ w 聚苯乙烯換算値表示。 -38- 200910009 〔醯亞胺化率之測定〕 醯亞胺化率爲使用NMR裝置(JNM-LA系列,日本電 子(股)製)測定H-NMR,並由聚合物骨架之芳香族的 質子比與聚醯胺酸之NH部位的質子比算出。 〔合成例〕 &lt;聚醯胺酸溶液之製造(合成例1 ) &gt; 令 BAHF 26.6 克(0.199 莫耳)、APDS 5.51 克( 0.0022莫耳)、DSDA 71_5克(0.199莫耳)溶解於 PGME 8 5 0克作成濃度1 5wt%後,以60°C反應24小時。 所得聚合物之Mw爲8600、分子量分佈1.55。將此所得聚 合物溶液之1.00克移至鋁杯,並以熱板加熱2小時,算 出固形成分。所得固形成分之固形成分濃度爲16.39 wt% 。又,令此聚合物於聚合物溶液8倍量(4000克)之 5 Owt%甲醇水溶液中沈澱,並且減壓乾燥取得聚醯胺酸粉 末。所得聚合物之產率爲9 1 %,醯亞胺化率爲62%。另外 ,所得聚合物爲於PGME與PGMEA中可溶。 &lt;各種聚醯胺酸溶液之製造(合成例2至5 ) &gt; 令各種二胺與酸二酐與P G Μ E中以濃度1 5 wt %般溶解 ’並使用與合成例1同樣之方法合成聚合物。此時所用之 二胺' 酸二酐、溶劑之使用量,所得聚合物之Mw與分子 量分佈、所得聚合物溶液之固形成分濃度、及醯亞胺率示 於表1。另外,此些聚合物爲於PGMEA中可溶。 -39- 200910009 &lt;聚醯胺酸溶液之製造(合成例6)〉 添加令各種二胺溶解的NMP無水物 合成聚合物。其後,將反應溶液5 0克投J ,將沈澱物過濾後,減壓乾燥取得聚醯胺 二胺、酸二酐、溶劑之使用量,所得聚合 量分佈、固形成分濃度、及醯亞胺化率示 合物爲於PGME或PGMEA之任一者中均 液就其原樣使用於調製後述的正型感光性 另外’同合成例1,於溶解各種二胺. 聚合物之結果,反應後1小時析出聚合物 ,反應4小時, k純水1 0 0 0毫升 酸。此時所用之 物之Mw與分子 於表1。所得聚 不溶,故反應溶 樹脂組成物。 之PGME中合成 -40- 200910009 〔表1〕 表1 聚合物組成 合成例1 合成例2 合成例3 合成例4 合成例5 合成例6 聚醯胺酸(一部分醯亞胺化) PI P2 HP1 HP2 HP3 HP4 二胺成分 BAHF(g) 26.6 58.4 59.8 BATF(g) 68.0 DDM(g) 7.11 6.07 21.6 APDS(g) 5.51 1.00 2.53 3.89 2.46 DBA⑻ 16.7 12.0 TFMB(g) 79.8 四羧酸 成分 6FDA(g) 62.0 77.1 DSDA(g) 71.5 34.1 PMDA(g) 4.46 61.4 38.9 〇DPA(g) 70.2 溶劑*1 PGME(g) 850 850 850 850 850 NMP(g) 425 重量平均分子量(Mw) 8600 8400 12500 7900 8500 9040 分子量分佈 1.55 1.93 1.96 1.46 1.66 1.88 固形成分濃度*2(質量%) 16.39 15.81 15.52 15.91 15.52 15.00*2 醯亞胺化率(%) 62 78 45 43 75 9 * 1 :調製時所用之溶劑 * 2 :反應溶液之固形成分濃度 〔正型感光性樹脂組成物之製造:實施例1至3、比 較例1至4〕 根據下表2所不之組成,將(A)成分、(B)成分、 (C )溶劑、(D )成分、及氟系界面活性劑(大日本油墨 化學工業(股)製,Megafac R-3 0 ) 0.0002克以指定之比 例混合,並以室溫攪拌3小時以上作成均勻之溶液,則可 調製各實施例及各比較例的正型感光性樹脂組成物。 -41 - 200910009 〔表2〕 表2 正型感光性/ 樹脂組成物之組成 No. (A)成分 (B)成分 (C)成分 (D)成分 界面活性劑 (s) (S) (s) (g) (g) 實施例1 P1 P200 PGME R-30 3.0 0.246 1.07 0.0002 實施例2 P2 P200 PGME R-30 3.0 0.238 0.92 0.0002 實施例3 P1 P200 PGME/1.07 BMI-80 R-30 3.0 0.246 7 -BL/1.26 0.246 0.0002 比較例1 HP1 P200 PGME R-30 3.0 0.233 1.411 0.0002 比較例2 HP2 P200 PGME R-30 3.0 0.143 0.487 0.0002 比較例3 HP3 P200 PGME R-30 3.0 0.140 0.401 0.0002 比較例4 HP4 P200 NMP R-30 3.0 0.135 0.287 0.0002 〔感光性特性評價:實施例1至3、比較例1至4〕 關於所得之實施例1至3及比較例1至4之各正型感 光性樹脂組成物,以下列手法評價感光性特性。所得之結 果示於表3。 &lt; 1 ·熱處理(煅燒)前膜厚&gt; 將正型感光性樹脂組成物於段差25mmx25mm的ITO 基板(山容真空工業(股)製)上,使用旋塗器塗佈後, 以溫度1 〇〇°C於熱板上進行預烘烤1 20秒鐘,形成塗膜。 另外,膜厚爲使用接觸式膜厚測定器(股)ULVAC製 Dektak 3 ST )測定。 -42- 200910009 &lt;2 ·顯像後膜厚、解像度(線寬)&gt; 對所得之塗膜透過1 0 〇 # m /2 0 0 // m之線/空間光罩, 以Cannon (股)製紫外線照射裝置Pla-501,照射紫外光 1 1秒鐘(7〇mJ/cm2 )。曝光後,於2 3 °C之氫氧化四甲基 銨水溶液(各實施例所使用之水溶液濃度爲記載於表3 ) 中浸漬3 0秒鐘進行顯像’並且測定顯像後的膜厚。 又,以光學顯微鏡觀察顯像後之塗膜,將圖型未剝離 且形成線/空間的最小線寬視爲解像度。 &lt;3.熱處理(煅燒)後膜厚&gt; 同&lt; 1 &gt;之手續’將段差1 τ 0基板所形成的感光性樹脂 塗膜於熱板上以100°c加熱丨20秒鐘。其次,未曝光以 2 3 0 °C加熱3 0分鐘後’測定膜厚。 〔表3〕 表3 感光特 π No. 熱處理前 膜厚(μηι) 顯像液濃度 (23〇C ,質量%) 顯像後膜厚 (μιη) 解像度 (μηι) 熱處理後 膜厚 (μιη) 實施例1 0.9 0.8 ___ 3 0.8 實施例2 1.0 0.8 3 0.9 實施例3 1.2 2.4 3 1.0 比較例1 0.9 2.4 一一- -~~~LL_ 5 0.9 比較例2 1.1 0.4 1.0 3 1.0 比較例3 1.0 0.2 10 0.9 比較例4 2.2 ——一 —~~— - 1.9 -43- 200910009 &lt;4.元件特性評價:實施例1至3、比較例}至4&gt; 將&lt;2&gt;所得之聚醯亞胺圖型(另外,比較例4爲於顯 像後圖型完全溶解,故於段差IT0基板上塗佈後,取得無 法威像之聚酿亞胺薄膜)以UV臭氧洗淨裝置((股) Tecnovision製)洗淨40分鐘,其後,將ND_1〇32 (日產 化學工業(股)製)以旋塗塗佈,於熱板上以2 〇 〇 〇C熱處 理(煅燒)1小時,取得厚度3 0nm的薄膜。其後,由中 央以殘留1 5 m m2正方削取,於真空條件下,以元件成分 a -NPD、Alq3、FLi、A1的順序蒸餾’製作元件。蒸鍍成 分爲以晶振動式成膜Controller CRTM-6000 (日本真空技 術(股)製)測定。其後,對元件通以9V的電流並以光 學顯微鏡觀察發光面。元件成分,蒸鍍量、及發光面的觀 察評價結果示於表4。 -44- 200910009Light-Emitting Diode (a type of component) has a highly reliable characteristic effect, so that the insulating film and the partition wall material of the organic EL element, which is a problem of the light-emitting element damage, or the ion migration of the copper wiring in the semiconductor package It is useful in buffer coating when the effect is greatly affected by the water absorption of the insulating film. The present invention will be described in further detail below by way of examples, but the invention is not limited thereto. EXAMPLES [Simplified Symbols Used in the Examples] The meanings of the abbreviations used in the following examples are as follows. &lt;Diamine component&gt; BAHF: 2,2,-bis(3-amino-4-hydroxyphenyl)hexafluoropropane BATF: 2,2'-bis(3-amino-4-toluene) Hexafluoropropane DDM: 4,4'-diaminodiphenylmethane APDS: bis(3-aminopropyl)-1,1,3,3-tetramethyldioxane DBA: 1,3- Diamino-5-carboxybenzene TFMB: 2,2'-bis(trifluoromethyl)benzidine &lt;tetracarboxylic acid component&gt; 6FDA: 4,4,-hexafluoroisopropylidene dicarboxylic anhydride DSDA: 3,3,- 4,4,-diphenylfluorene tetracarboxylic anhydride PMDA: pyromellitic anhydride ODPA: 3,3,,4,4,-diphenyl ether tetracarboxylic anhydride-37- 200910009 &lt;solvent&gt; PGMEA : propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether NMP : N-methylpyrrolidone 7 · -BL : r - butyrolactone &lt; photoacid generator &gt; Name) Ethylene P20 0 : via Toyo synthesis Industrial (stock) P-200 (commodity 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl)phenyl] yl] bisphenol 1 molar A sensitizer synthesized by the condensation reaction of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride 2 &lt;maleimide component&gt; base] BMI-80: 2,2'-double [4-(4-maleimide phenoxy) phenylpropane [number Measurement of Average Molecular Weight and Weight Average Molecular Weight] The following GPC is used as a device for synthesizing the weight average molecular weight (abbreviated as Mw) and molecular weight distribution of the polymer according to the following synthesis example (Shodex (registered trademark) Column KF803L and KF805L were measured by dissolving dimethylformamide in a solvent at a flow rate of 1 ml/min in a column (column temperature: 50 ° C). In addition, μ w polystyrene conversion 38 。 - - - - - - - - - - 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定The proton ratio of the group is calculated from the proton ratio of the NH moiety of the poly-proline. [Synthesis Example] &lt;Production of Polyproline Solution (Synthesis Example 1) &gt; BAHF 26.6 g (0.199 mol), APDS 5.51 g (0.0022 mol), DSDA 71_5 g (0.199 mol) dissolved in PGME 8 50 g to a concentration of 15 wt%, and then reacted at 60 ° C for 24 hours. The obtained polymer had a Mw of 8600 and a molecular weight distribution of 1.55. 1.00 g of the obtained polymer solution To an aluminum cup, and heated for 2 hours to a hot plate, a solid component count. The solid content of the obtained solid component was 16.39 wt%. Further, this polymer was precipitated in an aqueous solution of 8 times by weight (4000 g) of 5 wt% methanol in a polymer solution, and dried under reduced pressure to obtain a polyamic acid powder. The yield of the obtained polymer was 91%, and the oxime imidization ratio was 62%. In addition, the obtained polymer is soluble in PGME and PGMEA. &lt;Production of various polyaminic acid solutions (Synthesis Examples 2 to 5) &gt; Dissolving various diamines and acid dianhydrides in PG Μ E at a concentration of 15 wt%' and using the same method as in Synthesis Example 1. Synthetic polymer. The amount of the diamine 'acid dianhydride and the solvent used at this time, the Mw and molecular weight distribution of the obtained polymer, the solid content concentration of the obtained polymer solution, and the quinone imine ratio are shown in Table 1. Additionally, such polymers are soluble in PGMEA. -39- 200910009 &lt;Production of Polyproline Solution (Synthesis Example 6)> Addition of NMP anhydrate which dissolves various diamines Synthesizes a polymer. Thereafter, 50 g of the reaction solution was added, and the precipitate was filtered, and dried under reduced pressure to obtain a polyamine amine diamine, an acid dianhydride, and a solvent, and the obtained polymerization amount distribution, solid content concentration, and quinone imine. The conversion rate is a solution of either PGME or PGMEA used as it is in the preparation of the positive photosensitive property described later. In the same manner as in Synthesis Example 1, in dissolving various diamines, the result of the polymer, after the reaction 1 The polymer was precipitated in an hour, and reacted for 4 hours, k pure water of 1 0 0 ml of acid. The Mw and molecular weight of the materials used at this time are shown in Table 1. The resulting polymer is insoluble, so the reaction dissolves the resin composition. Synthesis in PGME-40-200910009 [Table 1] Table 1 Polymer Composition Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Polylysine (partially ruthenium) PI P2 HP1 HP2 HP3 HP4 diamine component BAHF (g) 26.6 58.4 59.8 BATF (g) 68.0 DDM (g) 7.11 6.07 21.6 APDS (g) 5.51 1.00 2.53 3.89 2.46 DBA (8) 16.7 12.0 TFMB (g) 79.8 tetracarboxylic acid component 6FDA (g) 62.0 77.1 DSDA(g) 71.5 34.1 PMDA(g) 4.46 61.4 38.9 〇DPA(g) 70.2 Solvent*1 PGME(g) 850 850 850 850 850 NMP(g) 425 Weight average molecular weight (Mw) 8600 8400 12500 7900 8500 9040 Molecular weight Distribution 1.55 1.93 1.96 1.46 1.66 1.88 Solid content concentration *2 (% by mass) 16.39 15.81 15.52 15.91 15.52 15.00*2 醯 imidization ratio (%) 62 78 45 43 75 9 * 1 : Solvent used in preparation * 2 : Reaction Solid content concentration of solution [Production of positive photosensitive resin composition: Examples 1 to 3, Comparative Examples 1 to 4] According to the composition of Table 2 below, (A) component, (B) component, (C ) solvent, (D) component, and fluorine-based surfactant Dainippon Ink Chemical Industry Co., Ltd., Megafac R-3 0 ) 0.0002 g is mixed in a specified ratio and stirred at room temperature for 3 hours or more to form a homogeneous solution. The positive examples of the respective examples and comparative examples can be prepared. A photosensitive resin composition. -41 - 200910009 [Table 2] Table 2 Composition of positive photosensitive/resin composition No. (A) Component (B) Component (C) Component (D) Component Surfactant (s) (S) (s) (g) (g) Example 1 P1 P200 PGME R-30 3.0 0.246 1.07 0.0002 Example 2 P2 P200 PGME R-30 3.0 0.238 0.92 0.0002 Example 3 P1 P200 PGME/1.07 BMI-80 R-30 3.0 0.246 7 - BL/1.26 0.246 0.0002 Comparative Example 1 HP1 P200 PGME R-30 3.0 0.233 1.411 0.0002 Comparative Example 2 HP2 P200 PGME R-30 3.0 0.143 0.487 0.0002 Comparative Example 3 HP3 P200 PGME R-30 3.0 0.140 0.401 0.0002 Comparative Example 4 HP4 P200 NMP R-30 3.0 0.135 0.287 0.0002 [Evaluation of Photosensitive Properties: Examples 1 to 3, Comparative Examples 1 to 4] With respect to the obtained positive photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 4, the following The column method evaluates the photosensitivity characteristics. The results obtained are shown in Table 3. &lt;1. Pre-heat treatment (calcination) film thickness> The positive-type photosensitive resin composition was applied onto a ITO substrate (manufactured by Yamato Vacuum Industries Co., Ltd.) having a step of 25 mm x 25 mm, and coated with a spin coater at a temperature of 1 〇. 〇 ° C was prebaked on a hot plate for 1 20 seconds to form a coating film. Further, the film thickness was measured using a contact film thickness measuring device (manufactured by ULVAC Dektak 3 ST). -42- 200910009 &lt;2 · Film thickness after development, resolution (line width)&gt; The resulting film was passed through a line of 10 〇# m /2 0 0 // m/space mask, with Cannon (shares) The ultraviolet irradiation device Pla-501 was irradiated with ultraviolet light for 1 second (7 〇 mJ/cm 2 ). After the exposure, the aqueous solution of tetramethylammonium hydroxide (the concentration of the aqueous solution used in each example is described in Table 3) was immersed for 30 seconds to carry out development, and the film thickness after development was measured. Further, the coating film after development was observed with an optical microscope, and the minimum line width in which the pattern was not peeled off and the line/space was formed was regarded as the resolution. &lt;3. Film thickness after heat treatment (calcination) &gt; Procedure of &lt;1 &gt; The photosensitive resin coating film formed on the substrate of step τ 0 was heated on a hot plate at 100 ° C for 20 seconds. Next, the film thickness was measured after heating for 30 minutes without exposure at 203 °C. [Table 3] Table 3 Photosensitive π No. Film thickness before heat treatment (μηι) Development solution concentration (23〇C, mass%) Film thickness after development (μιη) Resolution (μηι) Film thickness after heat treatment (μιη) Example 1 0.9 0.8 ___ 3 0.8 Example 2 1.0 0.8 3 0.9 Example 3 1.2 2.4 3 1.0 Comparative Example 1 0.9 2.4 One--~~~LL_ 5 0.9 Comparative Example 2 1.1 0.4 1.0 3 1.0 Comparative Example 3 1.0 0.2 10 0.9 Comparative Example 4 2.2 -1 -~~- - 1.9 -43- 200910009 &lt;4. Evaluation of element characteristics: Examples 1 to 3, Comparative Examples} to 4&gt; Polyimine obtained from &lt;2&gt; Type (In addition, in Comparative Example 4, the pattern was completely dissolved after development, so that the film was coated on the step of the IT0 substrate, and the film was obtained.) The UV ozone cleaning device (manufactured by Tecnovision) After washing for 40 minutes, ND_1〇32 (manufactured by Nissan Chemical Industries Co., Ltd.) was spin-coated and heat-treated (calcined) on a hot plate at 2 〇〇〇C for 1 hour to obtain a thickness of 30 nm. film. Thereafter, the center was cut with a residual of 15 m m2 in the center, and the elements were produced by vacuum distillation under the condition of component components a - NPD, Alq3, FLi, and A1. The vapor deposition was measured by a crystal vibration type film formation controller CRTM-6000 (manufactured by Nippon Vacuum Technology Co., Ltd.). Thereafter, a current of 9 V was applied to the element, and the light-emitting surface was observed with an optical microscope. The results of observation of the component components, the amount of vapor deposition, and the light-emitting surface are shown in Table 4. -44- 200910009

表4 元件特性察 P價結果 例 聚醯亞胺 a-NPD (nm) Alq3 (nm) FLi (nm) A1 (nm) 發光面 之評價※ 實施例1 P1 35 50 0.5 100 ◎ 實施例2 P2 35 50 0.5 100 ◎ 實施例3 P1 35 50 1.5 100 ◎ 比較例1 HP1 35 50 0.5 100 X 比較例2 HP2 35 50 0.5 100 X 比較例3 HP3 35 50 0.5 100 X 比較例4 HP4 35 50 0.5 100 X ※發光面之評價 ◎:於邊緣部察見鮮明的發光。 〇:於邊緣部與發光面的一部分界面存在滲出。 △:於邊緣部與發光面的界面全體存在滲出。 X: S令邊緣部與發光面的界面存在影子。 〔元件評價結果〕 使用P1或P2的元件中,於聚醯亞胺圖型邊緣部亦察 見鮮明的發光。此情事顯示使用實施例1至3之聚醯亞胺 的間隔壁元件,可在不會對發光面造成不良影響下製作畫 素。 另一方面,使用HP 1至HP4的元件中,於聚醯亞胺 圖型邊緣部與發光面的界面存在影子,察見發光不良,故 將比較例1至4之聚醯亞胺使用於元件時,擔心引起發光 面不良之結果。 -45 -Table 4 Component characteristics P-valence results Example Polyimine a-NPD (nm) Alq3 (nm) FLi (nm) A1 (nm) Evaluation of light-emitting surface ※ Example 1 P1 35 50 0.5 100 ◎ Example 2 P2 35 50 0.5 100 ◎ Example 3 P1 35 50 1.5 100 ◎ Comparative Example 1 HP1 35 50 0.5 100 X Comparative Example 2 HP2 35 50 0.5 100 X Comparative Example 3 HP3 35 50 0.5 100 X Comparative Example 4 HP4 35 50 0.5 100 X ※ Evaluation of the luminescent surface ◎: The bright luminescence was observed at the edge portion. 〇: There is bleeding at the interface between the edge portion and a part of the light-emitting surface. △: Exudation occurred in the entire interface between the edge portion and the light-emitting surface. X: S has a shadow at the interface between the edge portion and the light-emitting surface. [Results of component evaluation] In the element using P1 or P2, bright luminescence was also observed at the edge of the polyimine pattern. This case shows that the partition member using the polyimine of Examples 1 to 3 can produce a picture without adversely affecting the light-emitting surface. On the other hand, in the elements using HP 1 to HP 4, there is a shadow at the interface between the edge portion of the polyimine pattern and the light-emitting surface, and it is found that the light emission is poor, so the polyimine of Comparative Examples 1 to 4 is used for the element. At the time, there is a fear of causing a defective light-emitting surface. -45 -

Claims (1)

200910009 十、申請專利範圍 1 · 一種正型感光性樹脂組成物,其特徵爲含有作爲 (A)成分之具有下述式(丨)所示構造單位的聚醯亞胺前 體或由其所得之聚醯亞胺、和作爲(B)成分之經由光產 生酸之化合物,並將彼等溶解於(C )溶劑, [化1]200910009 X. Patent Application No. 1 A positive photosensitive resin composition characterized by containing or obtaining a polyimide precursor having a structural unit represented by the following formula (丨) as the component (A). Polyimine, and a compound which produces an acid via light as component (B), and dissolves them in (C) solvent, [Chemical 1] [化2][Chemical 2] (式(2)中,R3爲表示具有硫原子之有機基,R4及 R5爲分別獨立表示氫原子或碳原子數1至20之有機基) 所示之芳香族基,R2爲表示具有氟原子之芳香族基,η爲 表示自然數)。 2. 如申請專利範圍第1項之正型感光性樹脂組成物 ,其中,該式(2)中,R3爲具有磺醯基之有機基。 3. 如申請專利範圍第1項或第2項之正型感光性樹 脂組成物,其中,該式(2 )中,R4及R5中之至少一者爲 氫原子。 4. 如申請專利範圍第1項至第3項中任一項之正型 感光性樹脂組成物,其中,該式(1 )中,R2爲具有下述 -46- 200910009 式(3)所示之構造, [化3](In the formula (2), R3 represents an organic group having a sulfur atom, R4 and R5 are each an aromatic group independently represented by a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R2 represents a fluorine atom; The aromatic group, η is a natural number). 2. The positive photosensitive resin composition of claim 1, wherein in the formula (2), R3 is an organic group having a sulfonyl group. 3. The positive photosensitive resin composition of claim 1 or 2, wherein in the formula (2), at least one of R4 and R5 is a hydrogen atom. 4. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein, in the formula (1), R2 has the following formula -46-200910009 (3) Structure, [3] (式中’ R&amp;爲表示經氟原子所取代之碳原子數1至8 之有機基’乂!及X2爲分別獨立表示氫原子,碳原子數1 至10之有機基、或羥基)。 5 ·如申請專利範圍第1項至第4項中任一項之正型 感光性樹Ih組成物’其中’該(A)成分爲令含有下述式 (4)所示之化合物之四羧酸成分、與二胺成分聚合所得 之聚醯亞胺前體或由其所得之聚醯亞胺, [化4] 9 〇(In the formula, R&amp; is an organic group having a number of carbon atoms of 1 to 8 substituted with a fluorine atom; and X2 is an organic group or a hydroxyl group each independently representing a hydrogen atom and having 1 to 10 carbon atoms). 5. The positive-type photosensitive tree Ih composition of any one of the first to fourth aspects of the patent application, wherein the component (A) is a tetracarboxylic acid containing a compound represented by the following formula (4) An acid component, a polyimine precursor obtained by polymerizing a diamine component, or a polyimine obtained therefrom, [Chemical 4] 9 〇 (4) (式中’R7爲表示具有硫原子之有機基)。 6·如申請專利範圍第5項之正型感光性樹脂組成物 ’其中’該四羧酸成分爲該式(4)所示之化合物,加上 含有下述式(5)至式(8)所示化合物中之至少一種之四 羧酸成分, -47- 200910009 [化5](4) (wherein 'R7 is an organic group having a sulfur atom). 6. The positive photosensitive resin composition as described in claim 5, wherein the tetracarboxylic acid component is a compound represented by the formula (4), and the following formulas (5) to (8) are added. a tetracarboxylic acid component of at least one of the compounds shown, -47- 200910009 [Chemical 5] (8) (式中’ m爲表示〇或丨,R8爲表示碳原子數1 之一價有機基或直接結合至芳香環,具有氧原子之二 機基,R9、R10、R11、Ri2及r13爲分別表示碳原子數 1 2之有機基)。 7 ·如申請專利範圍第5項或第6項之正型感光 脂組成物,其中’該式(4 )所示之化合物爲於該四 成分中,佔有40至99莫耳%。 8.如申請專利範圍第5項至第7項中任一項之 感光性樹脂組成物,其中,該二胺成分爲含有下述5 )所不之—胺化合物的二胺成分, [化6] 至12 價有 1至 性樹 羧酸 正型(8) (where m is 〇 or 丨, R8 is a one-valent organic group representing a carbon number of 1 or directly bonded to an aromatic ring, a two-membered group having an oxygen atom, R9, R10, R11, Ri2 and r13 It is an organic group having a carbon number of 12). 7. The positive-type photosensitive resin composition of claim 5 or 6, wherein the compound represented by the formula (4) is 40 to 99 mol% of the four components. The photosensitive resin composition according to any one of the items 5 to 7 wherein the diamine component is a diamine component containing an amine compound which is not the following 5). ] to 12 valence 1 to sex tree carboxylic acid positive type (式中,R6爲表示經氟原子所取代之碳原子數1 之有機基,X3及X4爲分別獨立表示氫原子、碳原子 至1 〇之有機基、或羥基)。 9.如申請專利範圍第5項至第8項中任一項之 至8 數1 正型 -48- 200910009 感光性樹脂組成物,其中,該二胺成分爲含有二胺基 院化合物的二胺成分。 10.如申請專利範圍第1項至第9項中任一項之 感光性樹脂組成物,其中,該(B )成分爲萘醌二疊 磺酸酯化合物。 1 1 ·如申請專利範圍第1項至第1 0項中任一項 型感光性樹脂組成物,其中,該(C )溶劑爲由具有 以上碳原子之醇或烷酯所組成群中選取至少一種。 1 2.如申請專利範圍第1項至第1 1項中任一項 型感光性樹脂組成物,其中,根據(A )成分之100 份,含有0.01至100質量份的(B )成分。 1 3 ·如申請專利範圍第1 2項之正型感光性樹脂 物,其中,再根據(A)成分之100質量份含有5至 質量份下述(1 〇 )所示之馬來醯亞胺化合物作爲(D 分, [化7] 砂氧 正型 氮基 之正 4個 之正 質量 組成 100 )成 R15 r16(wherein R6 is an organic group having 1 carbon atom substituted by a fluorine atom, and X3 and X4 are each an organic group or a hydroxyl group independently representing a hydrogen atom or a carbon atom to 1 Å). 9. The photosensitive resin composition according to any one of claims 5 to 8 to 8 to 1 positive type -48 to 200910009, wherein the diamine component is a diamine containing a diamine compound compound ingredient. The photosensitive resin composition according to any one of claims 1 to 9, wherein the component (B) is a naphthoquinone bissulfonate compound. 1 1 . The photosensitive resin composition according to any one of claims 1 to 10, wherein the (C) solvent is at least selected from the group consisting of alcohols or alkyl esters having the above carbon atoms; One. 1. The photosensitive resin composition according to any one of the above-mentioned items, wherein the component (B) contains 0.01 to 100 parts by mass of the component (B) based on 100 parts of the component (A). In the case of the positive photosensitive resin of the first aspect of the invention, the maleic imide represented by the following (1 〇) is contained in an amount of 5 parts by mass based on 100 parts by mass of the component (A). The compound as (D, [Chemical 7] sand-oxygen-type nitrogen-based positive positive mass composition 100) into R15 r16 (式中,R14爲表示二價有機基,R15、RW、 、:R19、、R21、R22、r23、及 R24 爲分別獨立表示 子、碳原子數1至12之有機基)。 1 4 .如申請專利範圍第1 3項之正型感光性樹脂 物,其中,該式(10)中,R14爲具有下述式(n) -49- ,R&quot; 氫原 組成 所示 200910009 之構造, [化8](wherein R14 represents a divalent organic group, and R15, RW, :: R19, R21, R22, r23, and R24 are independently an organic group having 1 to 12 carbon atoms). In the formula (10), R14 has the following formula (n) -49-, and the R&quot; hydrogen original composition is shown in 200910009. Construction, [8] (式中,1和k爲分別獨立表示〇或1,X5、X6 : 爲分別獨立表示碳數1至12之有機基,具有氧原子 原子、氮原子之二價有機基)。 1 5 ·如申請專利範圍第丨4項之正型感光性樹脂 物’其中,該式(11)中,1和k爲1,X5和X7爲氧 ,Χ6爲二甲基甲基。 1 6 .如申請專利範圍第1 5項之正型感光性樹脂 物’其中,再根據(Α)成分之100質量份含有5至 質量份交聯性化合物作爲(Ε )成分。 17. 一種硬化膜,其特徵爲使用如申請專利範圍 項至第1 6項中任一項之正型感光性樹脂組成物所得。 18. 一種電子構件,其特徵爲具有如申請專利範 1 7項之硬化膜。 19. 一種有機EL元件,其特徵爲具有如申請專 圍第1 8項之硬化膜。 20. 一種形成浮雕圖型的方法,其特徵爲將如申 利範圍第1項至第1 6項中任一項之正型感光性樹脂 物於基板上塗佈,加熱乾燥後,照射紫外線進行顯像 έ Χ7 、硫 組成 原子 組成 100 第1 圍第 利範 請專 組成 -50- 200910009 七 無 • · 明 說 單 簡 號 為代 圖件 表元 代之 定圖 指表 :案代 圖本本 表、、 代 r-s 定一二 八、本案若有化學式時,請揭示最能顯示發明特徵的化學 式:無(In the formula, 1 and k each independently represent 〇 or 1, and X5 and X6 are each an organic group having a carbon number of 1 to 12 and a divalent organic group having an oxygen atom and a nitrogen atom, respectively). 1 5 - The positive photosensitive resin of the fourth aspect of the patent application' wherein, in the formula (11), 1 and k are 1, X5 and X7 are oxygen, and Χ6 is a dimethylmethyl group. In the case of the positive photosensitive resin of the fifteenth aspect of the invention, 5 parts by mass of the crosslinkable compound is contained as the (Ε) component based on 100 parts by mass of the (Α) component. A cured film obtained by using a positive photosensitive resin composition according to any one of claims 1 to 6. 18. An electronic component characterized by having a cured film as in the patent application. An organic EL device characterized by having a cured film as disclosed in claim 18. 20. A method of forming a relief pattern, characterized in that a positive photosensitive resin such as any one of items 1 to 16 of the application range is coated on a substrate, dried by heating, and irradiated with ultraviolet rays. Imaging έ 7, sulphur composition atomic composition 100 1st circumference Di Li Fan Please make up -50- 200910009 七无• · Ming said single simple number is the generation of map elements on behalf of the map reference table: the case map of this table, If you have a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none
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