TW201827925A - Photosensitive composition and use thereof capable of forming a cured film excellent in transparency, heat resistance, solvent resistance, flatness, and resolution - Google Patents

Photosensitive composition and use thereof capable of forming a cured film excellent in transparency, heat resistance, solvent resistance, flatness, and resolution Download PDF

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TW201827925A
TW201827925A TW106131543A TW106131543A TW201827925A TW 201827925 A TW201827925 A TW 201827925A TW 106131543 A TW106131543 A TW 106131543A TW 106131543 A TW106131543 A TW 106131543A TW 201827925 A TW201827925 A TW 201827925A
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meth
compound
acrylate
weight
photosensitive composition
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尾崎剛史
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捷恩智股份有限公司
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/02—Homopolymers or copolymers of esters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular 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
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/16—Polyester-imides
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The present invention relates to a photosensitive composition which is a composition comprising a polyester amic acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, and an epoxy curing agent. The photosensitive composition is characterized in that the polyester amic acid is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound as essential raw material components. Through the photosensitive composition of the present invention, a cured film which is particularly excellent in transparency, heat resistance, solvent resistance, flatness, and resolution can be obtained. The cured film is suitable for being used in electronic parts and the like.

Description

感光性組成物及其用途Photosensitive composition and use thereof

本發明是有關於一種用於形成電子零件中的絕緣材料、半導體裝置中的鈍化膜、緩衝塗膜、層間絕緣膜、或平坦化膜，或顯示元件中的層間絕緣膜或彩色濾光片用保護膜等的感光性組成物。進而是有關於一種使用所述感光性組成物而形成的透明膜、及包含該膜的電子零件。The present invention relates to a method for forming an insulating material in electronic parts, a passivation film in a semiconductor device, a buffer coating film, an interlayer insulating film, or a planarizing film, or an interlayer insulating film or a color filter in a display element. A photosensitive composition such as a protective film. Furthermore, it is related with the transparent film formed using the said photosensitive composition, and the electronic component containing this film.

在顯示元件等元件的製造步驟中，有時進行有機溶劑、酸、鹼溶液等各種化學品處理，或者在通過濺射（sputtering）而成膜配線電極時，將表面局部地加熱為高溫。因此，有時為了防止各種元件的表面的劣化、損傷、變質而設置表面保護膜。對於這些保護膜，要求可耐受如上所述的製造步驟中的各種處理的各特性。具體而言，要求耐熱性、耐溶劑性/耐酸性/耐鹼性等耐化學品性、耐水性、對玻璃等基底基板的密接性、透明性、耐劃傷性、平坦性、耐光性等。而且，在推進顯示元件的高視角化、高速回應化、高精細化、廣色域化等高性能化的現狀下，在用作彩色濾光片保護膜的情況下，期望透明性、耐熱性及耐溶劑性得到提高的材料。In the manufacturing steps of elements such as display elements, various chemicals such as organic solvents, acids, and alkali solutions are sometimes treated, or when a wiring electrode is formed by sputtering, the surface is locally heated to a high temperature. Therefore, in order to prevent deterioration, damage, and deterioration of the surface of various elements, a surface protective film may be provided. These protective films are required to have characteristics that can withstand various processes in the manufacturing steps as described above. Specifically, chemical resistance such as heat resistance, solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to a base substrate such as glass, transparency, scratch resistance, flatness, and light resistance are required. . In addition, under the current situation of high performance such as high viewing angle, high speed response, high definition, and wide color gamut of display elements, when used as a color filter protective film, transparency and heat resistance are desired. And materials with improved solvent resistance.

用以形成這些保護膜的硬化性組成物的種類可大致區別為感光性組成物、熱硬化性組成物。在形成膜時通過高溫加熱使熱硬化性組成物完全硬化，因此，即使在其後的步驟中存在有加熱至高溫的情況，產生的揮發成分也少，耐熱性也優異。具有該優異特性的熱硬化性的保護膜材料存在有聚酯醯胺酸組成物（例如，參照專利文獻1）。然而，熱硬化性組成物在製造面板分割時無法形成劃痕線（scribe line）而大量地產生保護膜的細屑，因此在其後需要進行高度的面板洗淨步驟。The type of the curable composition used to form these protective films can be roughly classified into a photosensitive composition and a thermosetting composition. Since the thermosetting composition is completely hardened by high-temperature heating during film formation, even if heated to a high temperature in the subsequent steps, less volatile components are generated and the heat resistance is excellent. A thermosetting protective film material having such excellent characteristics includes a polyester amidate composition (for example, refer to Patent Document 1). However, since the thermosetting composition cannot form scribe lines during panel division, and a large amount of fine particles of the protective film are generated, a high degree of panel cleaning step is required thereafter.

另一方面，感光性組成物包含具有光聚合性基的聚合物或寡聚物或者單體與光聚合起始劑，且因以紫外線為代表的光的能量而引起化學反應，並進行硬化。感光性組成物例如可容易地形成用於製造面板分割時的劃痕線，因此存在有不產生保護膜的細屑等優點，相反的，與由熱硬化性組成物所形成的保護膜相比，由通常的感光性組成物所形成的保護膜的耐熱性不充分。On the other hand, the photosensitive composition contains a polymer or oligomer or monomer having a photopolymerizable group and a photopolymerization initiator, and causes a chemical reaction due to the energy of light represented by ultraviolet rays, and is cured. For example, a photosensitive composition can easily form a scratch line for manufacturing a panel, so there are advantages such as no generation of fine particles of the protective film. In contrast, it is compared with a protective film formed of a thermosetting composition. The heat resistance of a protective film formed of a general photosensitive composition is insufficient.

近年來，需要耐熱性、耐溶劑性的保護膜的需求逐漸增加，進而需要微細圖案形狀的保護膜的需求也逐漸增加。由此，謀求可形成耐熱性、耐溶劑性優異的保護膜且可形成微細圖案的感光性組成物。In recent years, the demand for a protective film requiring heat resistance and solvent resistance has gradually increased, and further, a demand for a protective film having a fine pattern shape has also gradually increased. Accordingly, a photosensitive composition capable of forming a protective film excellent in heat resistance and solvent resistance and capable of forming a fine pattern has been sought.

可形成具有非常優異的耐熱性的保護膜的感光性組成物存在有聚醯亞胺前驅物組成物（例如，參照專利文獻2）、可溶性聚醯亞胺組成物（例如，參照專利文獻3）。然而，即便在任何的感光性組成物中，可使所得的聚醯亞胺前驅物組成物或可溶性聚醯亞胺組成物溶解的有機溶劑也被限定，也需要極性非常高的有機溶劑。A photosensitive composition capable of forming a protective film having very excellent heat resistance includes a polyfluorene imide precursor composition (for example, refer to Patent Document 2) and a soluble polyfluorene imine composition (for example, refer to Patent Document 3). . However, even in any photosensitive composition, the organic solvent which can dissolve the obtained polyfluorene imide precursor composition or soluble polyfluorene imine composition is also limited, and a highly polar organic solvent is also required.

溶解聚醯亞胺前驅物組成物、可溶性聚醯亞胺組成物等的極性高的有機溶劑可列舉：吡咯烷酮系、亞碸系、甲醯胺系、乙醯胺系、酚系、四氫呋喃、二噁烷、γ-丁內酯等。Examples of highly polar organic solvents that dissolve the polyfluorene imide precursor composition and the soluble polyfluorene imide composition include pyrrolidone-based, fluorene-based, methylformamide-based, acetamide-based, phenol-based, tetrahydrofuran, Oxane, γ-butyrolactone, etc.

特別是在將這些感光性組成物用作彩色濾光片保護膜的情況下，如果含有這些極性高的有機溶劑，則滲入基底的彩色濾光片層，例如畫素中所含有的顏料或染料等著色材料溶出，因此難以製作高品質的顯示元件。In particular, when these photosensitive compositions are used as a color filter protective film, if these polar organic solvents are contained, the color filter layer which penetrates into the substrate, such as pigments or dyes contained in pixels It is difficult to produce a high-quality display element due to the elution of other coloring materials.

將感光性組成物用於彩色濾光片的保護膜中的例子存在有專利文獻4，但本發明者等人使用這些專利文獻中所記載的感光性組成物來形成保護膜，並對耐溶劑性進行確認的結果為耐溶劑性並非令人充分滿意，而期望進一步改良。Examples of using a photosensitive composition for a protective film of a color filter include Patent Document 4, but the present inventors and others use the photosensitive composition described in these patent documents to form a protective film, and are resistant to solvents. As a result of checking the properties, the solvent resistance was not sufficiently satisfactory, and further improvement was desired.

而且，不論感光性組成物、熱硬化性組成物，都要求這些硬化性組成物在基底基板上的塗布性優異。 [現有技術文獻] [專利文獻]In addition, the photosensitive composition and the thermosetting composition are required to have excellent coatability on a base substrate. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本專利特開2008-156546 [專利文獻2]日本專利特開昭59-068332 [專利文獻3]日本專利特開2002-003516 [專利文獻4]日本專利特開2011-090275[Patent Literature 1] Japanese Patent Laid-Open No. 2008-156546 [Patent Literature 2] Japanese Patent Laid-Open No. 59-068332 [Patent Literature 3] Japanese Patent Laid-Open No. 2002-003516 [Patent Literature 4] Japanese Patent Laid-Open No. 2011-090275

[發明所欲解決之課題] 本發明的課題在於提供一種不需要極性高的有機溶劑，而透明性、耐熱性、耐溶劑性、平坦性、及解析性特別優異的硬化膜及提供該硬化膜的感光性組成物。提供一種利用所述感光性組成物而形成的硬化膜，進而，提供一種具有所述硬化膜的電子零件。 [解決課題之手段][Problems to be Solved by the Invention] An object of the present invention is to provide a cured film which is particularly excellent in transparency, heat resistance, solvent resistance, flatness, and resolution without requiring an organic solvent having a high polarity, and to provide the cured film. Photosensitive composition. A cured film formed using the photosensitive composition is provided, and an electronic component having the cured film is provided. [Means for solving problems]

本發明者等人為了解決所述課題而進行了努力研究，結果發現通過如下的組成物、及使該組成物硬化而獲得的硬化膜可達成所述目的，從而完成了本發明，所述組成物包含聚酯醯胺酸、具有聚合性雙鍵的化合物、光聚合起始劑、環氧化合物、及環氧硬化劑，所述聚酯醯胺酸是由包含四羧酸二酐、二胺及多元羥基化合物的化合物的反應而獲得。 本發明包含以下的構成。The present inventors conducted diligent research in order to solve the above-mentioned problems, and as a result, they have found that the above-mentioned object can be achieved by the following composition and a cured film obtained by curing the composition, and have completed the present invention. The product includes polyester amidate, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, and an epoxy hardener. The polyester amidate is composed of a tetracarboxylic dianhydride and a diamine. And a polyhydroxy compound. The present invention includes the following configurations.

[1] 一種感光性組成物，其是包含聚酯醯胺酸、具有聚合性雙鍵的化合物、光聚合起始劑、環氧化合物、環氧硬化劑的感光性組成物；所述感光性組成物的特徵在於： 聚酯醯胺酸是通過使X莫耳的四羧酸二酐、Y莫耳的二胺及Z莫耳的多元羥基化合物以下述式（1）及式（2）的關係成立的比率進行反應而獲得，具有下述式（3）所表示的結構單元及式（4）所表示的結構單元； 具有聚合性雙鍵的化合物在每一分子中包含兩個以上的聚合性雙鍵； 環氧化合物的重量平均分子量是3,000以上； 相對於聚酯醯胺酸100重量份，具有聚合性雙鍵的化合物的總量為20重量份～300重量份，環氧化合物的總量為20重量份～200重量份，且光聚合起始劑的總量為1重量份～60重量份； 0.2≦Z/Y≦8.0 ·······（1） 0.2≦（Y+Z）/X≦5.0 ···（2）在式（3）及式（4）中，R1 是自四羧酸二酐除去兩個-CO-O-CO-而成的殘基，R2 是自二胺除去兩個-NH2 而成的殘基，R3 是自多元羥基化合物除去兩個-OH而成的殘基。[1] A photosensitive composition, which is a photosensitive composition comprising polyester amido acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, and an epoxy hardener; The composition is characterized in that the polyester sulfamic acid is obtained by the following formula (1) and formula (2) by making X mole's tetracarboxylic dianhydride, Y mole's diamine, and Z mole's polyhydroxy compound The ratio of the established relationship is obtained by a reaction and has a structural unit represented by the following formula (3) and a structural unit represented by the formula (4); a compound having a polymerizable double bond includes two or more polymerizations per molecule. The weight-average molecular weight of the epoxy compound is 3,000 or more; The total amount of the compound having a polymerizable double bond is 20 to 300 parts by weight based on 100 parts by weight of the polyester amidate. The amount is 20 parts by weight to 200 parts by weight, and the total amount of the photopolymerization initiator is 1 to 60 parts by weight; 0.2 ≦ Z / Y ≦ 8.0 (1) 0.2 ≦ (Y + Z) /X≦5.0 ··· (2) In formulas (3) and (4), R 1 is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, and R 2 is obtained by removing two -NH 2 from a diamine. R 3 is a residue formed by removing two -OH groups from a polyhydroxy compound.

[2] 根據[1]所述的感光性組成物，其中所述聚酯醯胺酸的原料成分進一步包含單羥基化合物。[2] The photosensitive composition according to [1], wherein a raw material component of the polyester amidate further contains a monohydroxy compound.

[3] 根據[2]所述的感光性組成物，其中所述單羥基化合物是選自異丙醇、烯丙醇、苄醇、甲基丙烯酸羥基乙酯、丙二醇單***、及3-乙基-3-羥基甲基氧雜環丁烷中的一種以上。[3] The photosensitive composition according to [2], wherein the monohydroxy compound is selected from the group consisting of isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl One or more of the methyl-3-hydroxymethyloxetane.

[4] 根據[1]至[3]中任一項所述的感光性組成物，其中所述聚酯醯胺酸的重量平均分子量是1,000～200,000。[4] The photosensitive composition according to any one of [1] to [3], wherein a weight average molecular weight of the polyester amidine is 1,000 to 200,000.

[5] 根據[1]至[4]中任一項所述的感光性組成物，其中所述四羧酸二酐是選自3,3',4,4'-二苯基碸四羧酸二酐、3,3',4,4'-二苯基醚四羧酸二酐、2,2-[雙(3,4-二羧基苯基)]六氟丙烷二酐、1,2,3,4-丁烷四羧酸二酐、及乙二醇雙(脫水偏苯三酸酯)中的一種以上； 所述二胺是選自3,3'-二胺基二苯基碸及雙[4-(3-胺基苯氧基)苯基]碸中的一種以上； 所述多元羥基化合物是選自乙二醇、丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、2,2-雙(4-羥基環己基)丙烷、4,4'-二羥基二環己基及異三聚氰酸三(2-羥基乙基)酯中的一種以上； 相對於具有聚合性雙鍵的化合物的總重量，所述具有聚合性雙鍵的化合物含有50重量%以上的選自二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇三丙烯酸酯、異三聚氰酸環氧乙烷改性三丙烯酸酯及多元酸改性(甲基)丙烯酸寡聚物中的一種以上； 所述光聚合起始劑是選自α-胺基苯烷基酮系、醯基膦氧化物系、肟酯系光聚合起始劑中的一種以上； 所述環氧化合物是通過以(甲基)丙烯酸縮水甘油酯與2官能(甲基)丙烯酸酯為必需的原料成分進行反應而獲得的含有環氧基的共聚物；而且， 所述環氧硬化劑是選自偏苯三甲酸酐、六氫偏苯三甲酸酐及2-十一烷基咪唑中的一種以上。[5] The photosensitive composition according to any one of [1] to [4], wherein the tetracarboxylic dianhydride is selected from 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic acid Acid dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2 1,3,4-butanetetracarboxylic dianhydride, and ethylene glycol bis (anhydrotrimellitate); the diamine is selected from 3,3'-diaminodiphenylsulfonium And one or more of bis [4- (3-aminophenoxy) phenyl] fluorene; the polyhydroxy compound is selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxybicyclo One or more of hexyl and tris (2-hydroxyethyl) isocyanurate; the compound having a polymerizable double bond contains 50% by weight or more of the selected compound based on the total weight of the compound having a polymerizable double bond. From dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, isotricyanic acid ethylene oxide modified triacrylate and polyvalent One or more of the modified (meth) acrylic oligomers; the photopolymerization initiator is selected from the group consisting of α-aminobenzophenone-based, fluorenylphosphine oxide-based, and oxime ester-based photopolymerization initiators One or more of the above; the epoxy compound is an epoxy group-containing copolymer obtained by reacting glycidyl (meth) acrylate and a bifunctional (meth) acrylate as an essential raw material component; and, The epoxy hardener is one or more kinds selected from trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-undecylimidazole.

[6] 根據[5]所述的感光性組成物，其中所述四羧酸二酐是選自3,3',4,4'-二苯基醚四羧酸二酐及1,2,3,4-丁烷四羧酸二酐中的一種以上； 所述二胺是3,3'-二胺基二苯基碸； 所述多元羥基化合物是1,4-丁二醇； 所述單羥基化合物是苄醇； 所述具有聚合性雙鍵的化合物是選自二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯及多元酸改性(甲基)丙烯酸寡聚物中的一種以上； 所述2官能(甲基)丙烯酸酯是選自乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯中的一種以上； 相對於光聚合起始劑的總重量，所述光聚合起始劑含有50重量%以上的選自1,2-辛二酮,1-[4-(苯硫基)苯基]-2-(O-苯甲醯基肟)、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-哢唑-3-基]-1-(O-乙醯基肟)及1,2-丙二酮,1-[4-[4-(2-羥基乙氧基)苯硫基]苯基]-2-(O-乙醯基肟)中的一種以上； 所述環氧硬化劑是選自偏苯三甲酸酐及2-十一烷基咪唑中的一種以上；而且 進一步含有選自3-甲氧基丙酸甲酯及丙二醇單甲醚乙酸酯中的一種以上作為溶劑。[6] The photosensitive composition according to [5], wherein the tetracarboxylic dianhydride is selected from 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride and 1,2, One or more of 3,4-butanetetracarboxylic dianhydrides; the diamine is 3,3'-diaminodiphenylphosphonium; the polyhydroxy compound is 1,4-butanediol; the The monohydroxy compound is benzyl alcohol; the compound having a polymerizable double bond is one or more selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polyacid-modified (meth) acrylic acid oligomers; said The bifunctional (meth) acrylate is selected from ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1 One or more of 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate; relative to the start of photopolymerization The total weight of the agent, the photopolymerization initiator contains more than 50% by weight selected from 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzidine Oxime), ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-oxazol-3-yl] -1- (O-ethyl Fluorenyl oxime) and 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetamidoxime) Above; the epoxy hardener is one or more selected from trimellitic anhydride and 2-undecylimidazole; and further contains a member selected from the group consisting of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate One or more of them are used as a solvent.

[7] 一種硬化膜，其是由根據[1]至[6]中任一項所述的感光性組成物而獲得。[7] A cured film obtained from the photosensitive composition according to any one of [1] to [6].

[8] 一種彩色濾光片，其使用根據[7]所述的硬化膜作為保護膜。[8] A color filter using the cured film according to [7] as a protective film.

[9] 一種顯示元件，其使用根據[8]所述的彩色濾光片。[9] A display element using the color filter according to [8].

[10] 一種固體攝像元件，其使用根據[8]所述的彩色濾光片。[10] A solid-state imaging element using the color filter according to [8].

[11] 一種顯示元件，其使用根據[7]所述的硬化膜作為形成在薄膜電晶體（Thin Film Transistor，TFT）與透明電極之間的透明絕緣膜。[11] A display element using the cured film according to [7] as a transparent insulating film formed between a thin film transistor (TFT) and a transparent electrode.

[12] 一種顯示元件，其使用根據[7]所述的硬化膜作為形成在透明電極與配向膜之間的透明絕緣膜。[12] A display element using the cured film according to [7] as a transparent insulating film formed between a transparent electrode and an alignment film.

[13] 一種發光二極體（Light Emitting Diode，LED）發光體，其使用根據[7]所述的硬化膜作為保護膜。 [發明的效果][13] A light emitting diode (Light Emitting Diode, LED) light emitting body using the cured film according to [7] as a protective film. [Effect of the invention]

本發明的優選實施方式的感光性組成物是不需要極性高的有機溶劑，且可形成在透明性、耐熱性、耐溶劑性、平坦性及解析性中特別優異的硬化膜的材料，在用作彩色顯示元件的彩色濾光片保護膜的情況下，可使顯示品質及可靠性提高。根據以上所述，實用性非常高，特別是有效用作利用染色法、顏料分散法、電沉積法及印刷法而製造的彩色濾光片的保護膜。而且，還可作為各種光學材料的保護膜及透明絕緣膜而使用。The photosensitive composition according to a preferred embodiment of the present invention is a material that does not require an organic solvent with a high polarity and can form a cured film that is particularly excellent in transparency, heat resistance, solvent resistance, flatness, and resolution. When used as a color filter protective film for a color display element, display quality and reliability can be improved. As described above, practicality is very high, and it is particularly effective as a protective film for a color filter manufactured by a dyeing method, a pigment dispersion method, an electrodeposition method, and a printing method. It can also be used as a protective film and a transparent insulating film of various optical materials.

1.感光性組成物 本發明的感光性組成物是包含聚酯醯胺酸、在每一分子中包含兩個以上的聚合性雙鍵的化合物、光聚合起始劑、重量平均分子量是3,000以上的環氧化合物、環氧硬化劑的組成物，所述聚酯醯胺酸是通過以四羧酸二酐、二胺及多元羥基化合物為必需的原料成分進行反應而獲得，所述感光性組成物的特徵在於：相對於聚酯醯胺酸100重量份，具有聚合性雙鍵的化合物為20重量份～300重量份，環氧化合物為20重量份～200重量份，光聚合起始劑為1重量份～60重量份。而且，本發明的感光性組成物還可在獲得本發明的效果的範圍內進一步含有所述以外的其他成分。1. Photosensitive composition The photosensitivity composition of the present invention is a compound containing polyester glutamic acid, two or more polymerizable double bonds per molecule, a photopolymerization initiator, and a weight average molecular weight of 3,000 or more A composition of an epoxy compound and an epoxy hardener, the polyester amido acid is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound as essential raw material components, and the photosensitive composition The compound is characterized in that the compound having a polymerizable double bond is 20 to 300 parts by weight, the epoxy compound is 20 to 200 parts by weight, and the photopolymerization initiator is 100 parts by weight of polyester lysine. 1 to 60 parts by weight. The photosensitive composition of the present invention may further contain components other than those described above within a range in which the effects of the present invention are obtained.

1-1.聚酯醯胺酸 聚酯醯胺酸是通過以四羧酸二酐、二胺及多元羥基化合物為必需的原料成分進行反應而獲得。更詳細而言是通過使X莫耳的四羧酸二酐、Y莫耳的二胺及Z莫耳的多元羥基化合物以下述式（1）及式（2）的關係成立的比率進行反應而獲得。 0.2≦Z/Y≦8.0 ·······（1） 0.2≦（Y+Z）/X≦5.0 ···（2）1-1. Polyester Amidate Polyester amidate is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound as essential raw material components. More specifically, the reaction is carried out by reacting X mol tetracarboxylic dianhydride, Y mol diamine, and Z mol polyhydric hydroxy compound at a ratio where the relationship of the following formula (1) and formula (2) is established. obtain. 0.2 ≦ Z / Y ≦ 8.0 (1) 0.2 ≦ (Y + Z) /X≦5.0 (2)

聚酯醯胺酸具有下述式（3）所表示的結構單元及式（4）所表示的結構單元。在式（3）及式（4）中，R1 是自四羧酸二酐除去兩個-CO-O-CO-而成的殘基，優選為碳數2～30的有機基。R2 是自二胺除去兩個-NH2 而成的殘基，優選為碳數2～30的有機基。R3 是自多元羥基化合物除去兩個-OH而成的殘基，優選為碳數2～20的有機基。The polyester amidine has a structural unit represented by the following formula (3) and a structural unit represented by the formula (4). In the formulae (3) and (4), R 1 is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, and is preferably an organic group having 2 to 30 carbon atoms. R 2 is a diamine residue obtained by removing from the two -NH 2 formed, is preferably an organic group having a carbon number of 2 to 30. R 3 is a residue obtained by removing two -OH groups from a polyhydroxy compound, and is preferably an organic group having 2 to 20 carbon atoms.

聚酯醯胺酸的合成至少需要溶劑，可使該溶劑直接殘留而製成考慮到操作性等的液狀或凝膠狀的感光性組成物，或者也可將該溶劑除去而製成考慮到搬運性等的固體狀的組成物。而且，聚酯醯胺酸的合成也可視需要包含選自單羥基化合物及苯乙烯-馬來酸酐共聚物中的一種以上的化合物作為原料，其中，優選包含單羥基化合物。而且，聚酯醯胺酸的合成也可在不損及本發明的目的的範圍內，視需要包含所述以外的其他化合物作為原料。此種其他原料的例子可列舉含矽單胺。At least a solvent is required for the synthesis of polyester glutamic acid. The solvent can be left as it is, and it can be made into a liquid or gel-like photosensitive composition in consideration of handling properties. Alternatively, the solvent can be removed and made into consideration. Solid composition such as portability. In addition, the synthesis of the polyester glutamic acid may include one or more compounds selected from the group consisting of a monohydroxy compound and a styrene-maleic anhydride copolymer as a raw material as necessary, and among these, a monohydroxy compound is preferably contained. Moreover, the synthesis | combination of polyester glutamic acid can also contain other compounds as a raw material as needed within the range which does not impair the objective of this invention. Examples of such other raw materials include silicon-containing monoamines.

1-1-1.四羧酸二酐 在本發明中，用以獲得聚酯醯胺酸的材料使用四羧酸二酐。優選的四羧酸二酐的具體例可列舉：3,3',4,4'-二苯甲酮四羧酸二酐、2,2',3,3'-二苯甲酮四羧酸二酐、2,3,3',4'-二苯甲酮四羧酸二酐、3,3',4,4'-二苯基碸四羧酸二酐、2,2',3,3'-二苯基碸四羧酸二酐、2,3,3',4'-二苯基碸四羧酸二酐、3,3',4,4'-二苯基醚四羧酸二酐、2,2',3,3'-二苯基醚四羧酸二酐、2,3,3',4'-二苯基醚四羧酸二酐、2,2-[雙(3,4-二羧基苯基)]六氟丙烷二酐、1,2,3,4-丁烷四羧酸二酐、乙二醇雙脫水偏苯三酸酯（商品名：理家德（Rikacid）TMEG-100、新日本理化股份有限公司）、環丁烷四羧酸二酐、甲基環丁烷四羧酸二酐、環戊烷四羧酸二酐、環己烷四羧酸二酐、乙烷四羧酸二酐、及丁烷四羧酸二酐。可使用這些四羧酸二酐中的一種以上。1-1-1. Tetracarboxylic dianhydride In the present invention, a tetracarboxylic dianhydride is used as a material for obtaining polyester amidate. Specific examples of the preferred tetracarboxylic dianhydride include 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic acid Dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2 ', 3, 3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3 ', 4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid Dianhydride, 2,2 ', 3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis ( 3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, ethylene glycol dianhydrotrimellitic acid ester (Trade name: Ricardo ( Rikacid) TMEG-100, Shinnippon Physicochemical Co., Ltd.), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride Anhydride, ethanetetracarboxylic dianhydride, and butanetetracarboxylic dianhydride. One or more of these tetracarboxylic dianhydrides can be used.

這些四羧酸二酐中，更優選對硬化膜賦予良好透明性的3,3',4,4'-二苯基碸四羧酸二酐、3,3',4,4'-二苯基醚四羧酸二酐、2,2-[雙(3,4-二羧基苯基)]六氟丙烷二酐、1,2,3,4-丁烷四羧酸二酐、及理家德（Rikacid）TMEG-100，特別優選3,3',4,4'-二苯基醚四羧酸二酐、3,3',4,4'-二苯基碸四羧酸二酐及1,2,3,4-丁烷四羧酸二酐。Among these tetracarboxylic dianhydrides, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride and 3,3', 4,4'-diphenyl, which provide good transparency to the cured film, are more preferred. Ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and Ricoh German (Rikacid) TMEG-100, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic dianhydride and especially preferred 1,2,3,4-butanetetracarboxylic dianhydride.

1-1-2.二胺 在本發明中，用以獲得聚酯醯胺酸的材料使用二胺。優選的二胺的具體例可列舉：4,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸、3,4'-二胺基二苯基碸、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、雙[3-(4-胺基苯氧基)苯基]碸、[4-(4-胺基苯氧基)苯基][3-(4-胺基苯氧基)苯基]碸、[4-(3-胺基苯氧基)苯基][3-(4-胺基苯氧基)苯基]碸、及2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷。可使用這些二胺中的一種以上。1-1-2. Diamine In the present invention, a diamine is used as a material for obtaining polyester amidate. Specific examples of preferred diamines include 4,4'-diaminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 3,4'-diaminodiphenylphosphonium, and bis [4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, bis [3- (4-aminophenoxy) phenyl ] 碸, [4- (4-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] 碸, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] fluorene, and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane. One or more of these diamines can be used.

這些二胺中，更優選對硬化膜賦予良好透明性的3,3'-二胺基二苯基碸及雙[4-(3-胺基苯氧基)苯基]碸，特別優選3,3'-二胺基二苯基碸。Among these diamines, 3,3'-diaminodiphenylfluorene and bis [4- (3-aminophenoxy) phenyl] fluorene which give good transparency to the cured film are more preferable, and 3, 3'-Diaminodiphenylphosphonium.

1-1-3.多元羥基化合物 在本發明中，用以獲得聚酯醯胺酸的材料使用多元羥基化合物。優選的多元羥基化合物的具體例可列舉：乙二醇、二乙二醇、三乙二醇、四乙二醇、重量平均分子量為1,000以下的聚乙二醇、丙二醇、二丙二醇、三丙二醇、四丙二醇、重量平均分子量為1,000以下的聚丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,2-戊二醇、1,5-戊二醇、2,4-戊二醇、1,2,5-戊三醇、1,2-己二醇、1,6-己二醇、2,5-己二醇、1,2,6-己三醇、1,2-庚二醇、1,7-庚二醇、1,2,7-庚三醇、1,2-辛二醇、1,8-辛二醇、3,6-辛二醇、1,2,8-辛三醇、1,2-壬二醇、1,9-壬二醇、1,2,9-壬三醇、1,2-癸二醇、1,10-癸二醇、1,2,10-癸三醇、1,2-十二烷二醇、1,12-十二烷二醇、甘油、三羥甲基丙烷、季戊四醇、二季戊四醇、異三聚氰酸三(2-羥基乙基)酯、雙酚A（2,2-雙(4-羥基苯基)丙烷）、雙酚S（雙(4-羥基苯基)碸）、雙酚F（雙(4-羥基苯基)甲烷）、2,2-雙(4-羥基環己基)丙烷、4,4'-二羥基二環己基、二乙醇胺、及三乙醇胺。可使用這些多元羥基化合物中的一種以上。1-1-3. Polyhydric hydroxyl compound In the present invention, a polyhydric hydroxyl compound is used as a material for obtaining polyester amidate. Specific examples of preferred polyhydroxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, Tetrapropylene glycol, polypropylene glycol having a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentane Diol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6 -Hexanetriol, 1,2-heptanediol, 1,7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6 -Octanediol, 1,2,8-octantriol, 1,2-nonanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1 , 10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12-dodecanediol, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, Tris (2-hydroxyethyl) isocyanurate, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxyphenyl) fluorene), bis Phenol F (bis (4-hydroxyphenyl) methane), 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxybicyclo Group, diethanolamine, and triethanolamine. One or more of these polyhydroxy compounds can be used.

這些多元羥基化合物中，更優選在反應溶劑中的溶解性良好的乙二醇、丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、2,2-雙(4-羥基環己基)丙烷、4,4'-二羥基二環己基、及異三聚氰酸三(2-羥基乙基)酯，特別優選1,4-丁二醇、1,5-戊二醇及1,6-己二醇。Among these polyhydric hydroxy compounds, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7, which have good solubility in the reaction solvent, are more preferable. -Heptanediol, 1,8-octanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, and tris (2-hydroxyethyl isocyanurate) Ester), and 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are particularly preferred.

1-1-4.單羥基化合物 在本發明中，用以獲得聚酯醯胺酸的材料可使用單羥基化合物。通過使用單羥基化合物，可使感光性組成物的保存穩定性得到提高。優選的單羥基化合物的具體例可列舉：苄醇、丙二醇單***、丙二醇單甲醚、二丙二醇單***、二丙二醇單甲醚、乙二醇單***、乙二醇單甲醚、二乙二醇單甲醚、二乙二醇單***、甲基丙烯酸羥基乙酯、松油醇（terpineol）、3-乙基-3-羥基甲基氧雜環丁烷及二甲基苄基甲醇（dimethyl benzyl carbinol）。可使用這些單羥基化合物中的一種以上。1-1-4. Monohydroxy compound In the present invention, a monohydroxy compound can be used as a material for obtaining polyester amidate. By using a monohydroxy compound, the storage stability of a photosensitive composition can be improved. Specific examples of preferred monohydroxy compounds include benzyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, and diethylene glycol. Alcohol monomethyl ether, diethylene glycol monoethyl ether, hydroxyethyl methacrylate, terpineol, 3-ethyl-3-hydroxymethyloxetane, and dimethyl benzyl methanol benzyl carbinol). One or more of these monohydroxy compounds may be used.

這些單羥基化合物中更優選苄醇、甲基丙烯酸羥基乙酯、丙二醇單***、及3-乙基-3-羥基甲基氧雜環丁烷。如果考慮將使用這些單羥基化合物而形成的聚酯醯胺酸與含有環氧基的共聚物、環氧化合物及環氧硬化劑混合的情況下的相容性，或感光性組成物在彩色濾光片上的塗布性，則單羥基化合物特別優選使用苄醇。Among these monohydroxy compounds, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane are more preferable. Considering the compatibility of the polyester amidate formed using these monohydroxy compounds with epoxy-containing copolymers, epoxy compounds, and epoxy hardeners, or the photosensitive composition in color filters For coating properties on optical sheets, benzyl alcohol is particularly preferably used as the monohydroxy compound.

相對於四羧酸二酐、二胺、及多元羥基化合物的合計量100重量份，優選含有0重量份～300重量份的單羥基化合物而進行反應。更優選為5重量份～200重量份。The reaction is preferably carried out with respect to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyhydroxy compound, and containing 0 to 300 parts by weight of a monohydroxy compound. It is more preferably 5 to 200 parts by weight.

1-1-5.苯乙烯-馬來酸酐共聚物 而且，本發明中所使用的聚酯醯胺酸還可在所述原料中添加具有三個以上酸酐基的化合物而合成。通過如上所述地進行，可使硬化膜的透明性得到提高，因此優選。具有三個以上酸酐基的化合物的例子可列舉：苯乙烯-馬來酸酐共聚物。關於構成苯乙烯-馬來酸酐共聚物的各成分的比率，苯乙烯/馬來酸酐的莫耳比為0.5～4，優選為1～3。進一步而言，更優選1或2，特別優選1。1-1-5. Styrene-maleic anhydride copolymer In addition, the polyester amidine used in the present invention can be synthesized by adding a compound having three or more acid anhydride groups to the raw material. It is preferable to perform transparency as mentioned above because the transparency of a cured film can be improved. Examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer. As for the ratio of each component constituting the styrene-maleic anhydride copolymer, the molar ratio of styrene / maleic anhydride is 0.5 to 4, and preferably 1 to 3. Furthermore, 1 or 2 is more preferable, and 1 is especially preferable.

苯乙烯-馬來酸酐共聚物的具體例可列舉：SMA3000P、SMA2000P、SMA1000P（均為商品名；川原油化股份有限公司）。這些市售品中特別優選使硬化膜的耐熱性及耐鹼性變良好的SMA1000P。Specific examples of the styrene-maleic anhydride copolymer include SMA3000P, SMA2000P, and SMA1000P (all are trade names; Sichuan Crude Chemical Co., Ltd.). Among these commercially available products, SMA1000P, which has excellent heat resistance and alkali resistance of the cured film, is particularly preferred.

優選相對於四羧酸二酐、二胺、及多元羥基化合物的合計量100重量份而含有0重量份～500重量份的苯乙烯-馬來酸酐共聚物。更優選為10重量份～300重量份。The styrene-maleic anhydride copolymer is preferably contained in an amount of 0 to 500 parts by weight based on 100 parts by weight of the total amount of the tetracarboxylic dianhydride, diamine, and polyhydroxy compound. It is more preferably 10 to 300 parts by weight.

1-1-6.含矽單胺 在聚酯醯胺酸的合成中，還可在不損及本發明的目的的範圍內，視需要包含所述以外的其他原料作為原料，此種其他的原料的例子可列舉含矽單胺。1-1-6. In the synthesis of polyester sulfamic acid, the silicon-containing monoamine can also include other raw materials as the raw materials as needed within the range that does not impair the object of the present invention. Examples of the raw material include silicon monoamine.

本發明中所使用的優選的含矽單胺的具體例可列舉：3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-胺基丙基甲基二甲氧基矽烷、3-胺基丙基甲基二乙氧基矽烷、4-胺基丁基三甲氧基矽烷、4-胺基丁基三乙氧基矽烷、4-胺基丁基甲基二乙氧基矽烷、對胺基苯基三甲氧基矽烷、對胺基苯基三乙氧基矽烷、對胺基苯基甲基二甲氧基矽烷、對胺基苯基甲基二乙氧基矽烷、間胺基苯基三甲氧基矽烷、及間胺基苯基甲基二乙氧基矽烷。可使用這些含矽單胺中的一種以上。Specific examples of the preferred silicon-containing monoamine used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropylmethyldiamine. Methoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethyl Oxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane , M-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. One or more of these silicon-containing monoamines can be used.

這些含矽單胺中，更優選使硬化膜的耐酸性變良好的3-胺基丙基三乙氧基矽烷及對胺基苯基三甲氧基矽烷，自耐酸性、相容性的觀點考慮，特別優選3-胺基丙基三乙氧基矽烷。Among these silicon-containing monoamines, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane, which improve the acid resistance of the cured film, are more preferred, from the viewpoint of acid resistance and compatibility Especially preferred is 3-aminopropyltriethoxysilane.

優選相對於四羧酸二酐、二胺、及多元羥基化合物的合計量100重量份，含有0重量份～300重量份的含矽單胺。更優選為5重量份～200重量份。The silicon-containing monoamine is preferably contained in an amount of 0 to 300 parts by weight based on 100 parts by weight of the total amount of the tetracarboxylic dianhydride, diamine, and polyhydroxy compound. It is more preferably 5 to 200 parts by weight.

1-1-7.聚酯醯胺酸的合成反應中所使用的溶劑 用以獲得聚酯醯胺酸的合成反應中所使用的溶劑的具體例可列舉：二乙二醇二甲醚、二乙二醇甲基***、二乙二醇二***、二乙二醇單***乙酸酯、乙二醇單***乙酸酯、丙二醇單甲醚乙酸酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乳酸乙酯、環己酮。這些溶劑中優選丙二醇單甲醚乙酸酯、3-甲氧基丙酸甲酯、或二乙二醇甲基***。1-1-7. Solvents used in the synthesis reaction of polyester glutamic acid Specific examples of the solvents used in the synthesis reaction to obtain polyester glutamic acid include diethylene glycol dimethyl ether, Ethylene glycol methyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate , Ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone. Among these solvents, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, or diethylene glycol methyl ether is preferable.

1-1-8.聚酯醯胺酸的合成方法 本發明中所使用的聚酯醯胺酸的合成方法是在所述溶劑中使四羧酸二酐X莫耳、二胺Y莫耳、及多元羥基化合物Z莫耳反應。此時，X、Y及Z優選設定為在這些X、Y及Z之間下述式（1）及式（2）的關係成立的比例。如果是該範圍，則聚酯醯胺酸在溶劑中的溶解性高，因此組成物的塗布性得到提高，結果可獲得平坦性優異的硬化膜。 0.2≦Z/Y≦8.0 ·······（1） 0.2≦（Y+Z）/X≦5.0 ···（2） 在式（1）中，優選0.7≦Z/Y≦7.0，更優選1.0≦Z/Y≦5.0。而且，在式（2）中，優選0.5≦（Y+Z）/X≦4.0，更優選0.6≦（Y+Z）/X≦2.0。1-1-8. Method for synthesizing polyester amidate The method for synthesizing polyester amidate used in the present invention is to make tetracarboxylic dianhydride X mole, diamine Y mole, And Z Mol reaction of polyhydroxy compounds. At this time, X, Y, and Z are preferably set to a ratio in which the relationship of the following formula (1) and formula (2) is established between these X, Y, and Z. If the content is within this range, the solubility of the polyester amidino acid in the solvent is high, so that the coatability of the composition is improved, and as a result, a cured film having excellent flatness can be obtained. 0.2 ≦ Z / Y ≦ 8.0 (1) 0.2 ≦ (Y + Z) /X≦5.0 (2) In formula (1), 0.7 ≦ Z / Y ≦ 7.0 is preferred, More preferably, 1.0 ≦ Z / Y ≦ 5.0. Further, in the formula (2), 0.5 ≦ (Y + Z) /X≦4.0 is preferred, and 0.6 ≦ (Y + Z) /X≦2.0 is more preferred.

可認為本發明中所使用的聚酯醯胺酸是在所述反應條件下，相對於Y+Z而過剩使用X的條件下，比在末端具有胺基或羥基的分子更過剩地生成在末端具有酸酐基（-CO-O-CO-）的分子。在以此種單體的構成進行反應的情況下，為了與分子末端的酸酐基反應而對末端進行酯化，可視需要添加所述的單羥基化合物。通過添加單羥基化合物進行反應而所得的聚酯醯胺酸可改善與環氧化合物及環氧硬化劑的相容性，且可改善包含這些化合物的本發明的感光性組成物的塗布性。It can be considered that the polyester amidine used in the present invention is produced in excess at the terminal under the reaction conditions described above under conditions where X is excessively used over Y + Z than molecules having an amine group or a hydroxyl group at the terminal. Molecules with acid anhydride group (-CO-O-CO-). When reacting with such a monomer structure, in order to react with an acid anhydride group at the molecular terminal to esterify the terminal, the monohydroxy compound may be added as necessary. The polyester amidine obtained by adding a monohydroxy compound for reaction can improve compatibility with epoxy compounds and epoxy hardeners, and can improve the coatability of the photosensitive composition of the present invention containing these compounds.

而且，在以所述單體的構成進行反應的情況下，為了與分子末端的酸酐基反應而在末端導入矽烷基，可添加含矽單胺。如果使用含有聚酯醯胺酸（所述聚酯醯胺酸是通過添加含矽單胺進行反應而獲得）的本發明的感光性組成物，則可改善所得的硬化膜的耐酸性。而且，在以所述單體的構成進行反應的情況下，還可添加單羥基化合物及含矽單胺此兩者而進行反應。Further, when the reaction is performed with the above-mentioned monomer configuration, a silicon-containing monoamine may be added in order to introduce a silane group at the terminal in order to react with an acid anhydride group at the molecular terminal. Use of the photosensitive composition of the present invention containing a polyester amidate (the polyester amidate is obtained by adding a silicon-containing monoamine for reaction) can improve the acid resistance of the resulting cured film. Moreover, when reacting with the said monomer structure, you may add both a monohydroxy compound and a silicon containing monoamine, and react.

如果相對於四羧酸二酐、二胺及多元羥基化合物的合計100重量份而使用100重量份以上的反應溶劑，則反應順利地進行，因此優選。反應以在40℃～200℃下反應0.2小時～20小時為宜。It is preferable to use a reaction solvent of 100 parts by weight or more with respect to 100 parts by weight of the total of tetracarboxylic dianhydride, diamine, and polyhydroxy compound, since the reaction proceeds smoothly. The reaction is preferably performed at 40 ° C to 200 ° C for 0.2 hours to 20 hours.

將反應原料添加於反應系統中的順序並無特別限定。即，也可使用以下的任意方法：將四羧酸二酐與二胺及多元羥基化合物同時加入至反應溶劑中；使二胺及多元羥基化合物溶解於反應溶劑中之後，添加四羧酸二酐；使四羧酸二酐與多元羥基化合物預先反應後，在其反應產物中添加二胺；或者使四羧酸二酐與二胺預先反應後，在其反應產物中添加多元羥基化合物等。The order in which the reaction raw materials are added to the reaction system is not particularly limited. That is, any of the following methods may be used: tetracarboxylic dianhydride is simultaneously added to the reaction solvent with the diamine and the polyhydroxy compound; after the diamine and the polyhydroxy compound is dissolved in the reaction solvent, the tetracarboxylic dianhydride is added. After the tetracarboxylic dianhydride and the polyhydroxy compound are reacted in advance, a diamine is added to the reaction product; or after the tetracarboxylic dianhydride and the diamine are reacted in advance, a polyhydroxy compound is added to the reaction product.

在使所述含矽單胺反應的情況下，在四羧酸二酐與二胺及多元羥基化合物的反應結束後，將反應液冷卻至40℃以下後，添加含矽單胺，在10℃～40℃下反應0.1小時～6小時為宜。而且，可在反應的任意時間點添加單羥基化合物。In the case of reacting the silicon-containing monoamine, after the reaction of the tetracarboxylic dianhydride with the diamine and the polyhydroxy compound is completed, the reaction solution is cooled to 40 ° C or lower, and then the silicon-containing monoamine is added at 10 ° C. The reaction at -40 ° C is preferably from 0.1 to 6 hours. Moreover, a monohydroxy compound may be added at an arbitrary time point of the reaction.

如上所述而合成的聚酯醯胺酸包含所述式（3）所表示的結構單元及式（4）所表示的結構單元，且其末端是源自作為原料的四羧酸二酐、二胺或多元羥基化合物的酸酐基、胺基或羥基，或者這些化合物以外的添加物構成其末端。通過包含此種構成，硬化性變良好。The polyester amidate synthesized as described above includes the structural unit represented by the formula (3) and the structural unit represented by the formula (4), and its terminal is derived from tetracarboxylic dianhydride and dicarboxylic acid as raw materials. An acid anhydride group, an amine group, or a hydroxyl group of an amine or a polyhydroxy compound, or an additive other than these compounds constitutes a terminal thereof. By including such a structure, hardenability becomes favorable.

所得的聚酯醯胺酸的重量平均分子量優選為1,000～200,000，更優選為3,000～50,000。如果處於這些範圍，則平坦性及耐熱性變良好。The weight average molecular weight of the obtained polyester amidine is preferably 1,000 to 200,000, and more preferably 3,000 to 50,000. If it exists in these ranges, flatness and heat resistance will become favorable.

本說明書中的重量平均分子量是利用凝膠滲透色譜（Gel Permeation Chromatography，GPC）法（管柱溫度：35℃，流速：1 ml/min）而求出的聚苯乙烯換算的值。標準的聚苯乙烯使用分子量為645～132,900的聚苯乙烯（例如，安捷倫科技（Agilent Technologies）股份有限公司的聚苯乙烯校準套組（calibration kit）PL2010-0102），管柱使用PLgel MIXED-D（安捷倫科技股份有限公司），可使用四氫呋喃（Tetrahydrofuran，THF）作為流動相而進行測定。而且，本說明書中的市售品的重量平均分子量為目錄（catalogue）記載值。The weight average molecular weight in the present specification is a polystyrene-equivalent value obtained by a gel permeation chromatography (GPC) method (column temperature: 35 ° C, flow rate: 1 ml / min). Standard polystyrene uses polystyrene with a molecular weight of 645 to 132,900 (for example, the polystyrene calibration kit PL2010-0102 from Agilent Technologies Co., Ltd.), and the column uses PLgel MIXED-D (Agilent Technology Co., Ltd.), Tetrahydrofuran (THF) can be used as the mobile phase for measurement. In addition, the weight average molecular weight of the commercial item in this specification is a catalogue value.

1-2.具有聚合性雙鍵的化合物 1-2-1.在每一分子中具有兩個以上的聚合性雙鍵的化合物 本發明中所使用的具有聚合性雙鍵的化合物並無特別限定，優選為在每一分子中具有兩個以上的聚合性雙鍵的化合物。如果具有聚合性雙鍵的化合物相對於聚酯醯胺酸100重量份而為20重量份～300重量份，則顯影後殘膜率變良好而優選。1-2. Compound having a polymerizable double bond 1-2-1. Compound having two or more polymerizable double bonds in each molecule The compound having a polymerizable double bond used in the present invention is not particularly limited It is preferably a compound having two or more polymerizable double bonds per molecule. If the compound having a polymerizable double bond is from 20 parts by weight to 300 parts by weight based on 100 parts by weight of polyester amidate, the residual film rate after development is good, which is preferable.

本發明的感光性組成物中所含有的在每一分子中具有兩個以上的聚合性雙鍵的化合物可列舉：乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、表氯醇改性乙二醇二(甲基)丙烯酸酯、表氯醇改性二乙二醇二(甲基)丙烯酸酯、表氯醇改性三乙二醇二(甲基)丙烯酸酯、表氯醇改性四乙二醇二(甲基)丙烯酸酯、表氯醇改性聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、四丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、表氯醇改性丙二醇二(甲基)丙烯酸酯、表氯醇改性二丙二醇二(甲基)丙烯酸酯、表氯醇改性三丙二醇二(甲基)丙烯酸酯、表氯醇改性四丙二醇二(甲基)丙烯酸酯、表氯醇改性聚丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷改性三羥甲基丙烷三(甲基)丙烯酸酯、環氧丙烷改性三羥甲基丙烷三(甲基)丙烯酸酯、表氯醇改性三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、甘油(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、表氯醇改性甘油三(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、表氯醇改性1,6-己二醇二(甲基)丙烯酸酯、二(甲基)丙烯酸甲氧基化環己酯、新戊二醇二(甲基)丙烯酸酯、羥基特戊酸新戊二醇二(甲基)丙烯酸酯、己內酯改性羥基特戊酸新戊二醇二(甲基)丙烯酸酯、二甘油四(甲基)丙烯酸酯、二甘油環氧乙烷改性丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、硬脂酸改性季戊四醇二(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、烷基改性二季戊四醇五(甲基)丙烯酸酯、烷基改性二季戊四醇四(甲基)丙烯酸酯、烷基改性二季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、己內酯改性二季戊四醇六(甲基)丙烯酸酯、多元酸改性(甲基)丙烯酸寡聚物、二(甲基)丙烯酸烯丙基化環己酯、雙[(甲基)丙烯醯氧基新戊二醇]己二酸酯、雙酚A二(甲基)丙烯酸酯、環氧乙烷改性雙酚A二(甲基)丙烯酸酯、雙酚F二(甲基)丙烯酸酯、環氧乙烷改性雙酚F二(甲基)丙烯酸酯、雙酚S二(甲基)丙烯酸酯、環氧乙烷改性雙酚S二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,3-丁二醇(甲基)丙烯酸酯、二丙烯酸二環戊基酯、聚酯二丙烯酸酯、聚酯三丙烯酸酯、聚酯四丙烯酸酯、聚酯五丙烯酸酯、聚酯六丙烯酸酯、環氧乙烷改性磷酸二(甲基)丙烯酸酯、環氧乙烷改性磷酸三(甲基)丙烯酸酯、環氧乙烷改性磷酸二(甲基)丙烯酸酯、環氧乙烷改性磷酸三(甲基)丙烯酸酯、表氯醇改性鄰苯二甲酸二(甲基)丙烯酸酯、四溴雙酚A二(甲基)丙烯酸酯、三甘油二(甲基)丙烯酸酯、新戊二醇改性三羥甲基丙烷二(甲基)丙烯酸酯、異三聚氰酸環氧乙烷改性二丙烯酸酯、異三聚氰酸環氧乙烷改性三丙烯酸酯、己內酯改性三[(甲基)丙烯醯氧基乙基]異三聚氰酸酯、(甲基)丙烯酸化異三聚氰酸酯、苯基縮水甘油醚丙烯酸酯/六亞甲基二異氰酸酯/胺基甲酸酯預聚物、苯基縮水甘油醚丙烯酸酯/甲苯二異氰酸酯/胺基甲酸酯預聚物、季戊四醇三丙烯酸酯/六亞甲基二異氰酸酯/胺基甲酸酯預聚物、季戊四醇三丙烯酸酯/甲苯二異氰酸酯/胺基甲酸酯預聚物、季戊四醇三丙烯酸酯/異佛爾酮二異氰酸酯/胺基甲酸酯預聚物、二季戊四醇五丙烯酸酯/六亞甲基二異氰酸酯/胺基甲酸酯預聚物、無黃變型寡聚胺基甲酸酯丙烯酸酯、及含羧酸的胺基甲酸酯丙烯酸酯寡聚物、環氧丙烯酸酯寡聚物等。Examples of the compound contained in the photosensitive composition of the present invention that has two or more polymerizable double bonds per molecule include ethylene glycol di (meth) acrylate and diethylene glycol di (methyl). Acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin modified ethylene glycol di (methyl Base) acrylate, epichlorohydrin modified diethylene glycol di (meth) acrylate, epichlorohydrin modified triethylene glycol di (meth) acrylate, epichlorohydrin modified tetraethylene glycol di ( (Meth) acrylate, epichlorohydrin modified polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylic acid Ester, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin modified propylene glycol di (meth) acrylate, epichlorohydrin modified dipropylene glycol di (meth) acrylate , Epichlorohydrin modified tripropylene glycol di (meth) acrylate, epichlorohydrin modified tetrapropylene glycol di (meth) acrylate, epichlorohydrin modified polypropylene glycol di ( Base) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (methyl) Base) acrylate, epichlorohydrin modified trimethylolpropane tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, glycerol (meth) acrylate, glycerol bis (methyl) Base) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, epichlorohydrin modified 1, 6-Hexanediol di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol dipentarate Acrylate), caprolactone-modified hydroxypivalate neopentyl glycol di (meth) acrylate, diglycerol tetra (meth) acrylate, diglycerol ethylene oxide modified acrylate, pentaerythritol tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythr Tetraol penta (meth) acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone Ester modified dipentaerythritol hexa (meth) acrylate, polyacid modified (meth) acrylic oligomer, allyl cyclohexyl di (meth) acrylate, bis [(meth) acrylic acid Neopentyl glycol] adipate, bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, cyclic Oxyethane modified bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate, ethylene oxide modified bisphenol S di (meth) acrylate, 1,4-butane Alcohol di (meth) acrylate, 1,3-butanediol (meth) acrylate, dicyclopentyl diacrylate, polyester diacrylate, polyester triacrylate, polyester tetraacrylate, poly Ester pentaacrylate, polyester hexaacrylate, ethylene oxide modified phosphate di (meth) acrylate, ethylene oxide modified phosphate tri (meth) acrylate, ethylene oxide modified phosphate di ( Methacrylate , Ethylene oxide modified phosphoric acid tri (meth) acrylate, epichlorohydrin modified phthalic acid di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, triglyceride bis ( (Meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, ethylene isocyanate modified ethylene oxide diacrylate, ethylene isocyanate modified ethylene oxide Triacrylate, caprolactone modified tri [(meth) acryloxyethyl] isotricyanate, (meth) acrylic isotricyanate, phenyl glycidyl ether acrylate / Hexamethylene diisocyanate / urethane prepolymer, phenyl glycidyl ether acrylate / toluene diisocyanate / urethane prepolymer, pentaerythritol triacrylate / hexamethylene diisocyanate / Urethane prepolymer, pentaerythritol triacrylate / toluene diisocyanate / urethane prepolymer, pentaerythritol triacrylate / isophorone diisocyanate / urethane prepolymer, dipentaerythritol Pentaacrylate / hexamethylene diisocyanate / urethane prepolymer, non-yellowing oligomeric urethane propylene Acid esters, and carboxylic acid-containing urethane acrylate oligomers, epoxy acrylate oligomers, and the like.

在每一分子中具有兩個以上的聚合性雙鍵的化合物可單獨使用所述化合物，也可混合兩種以上而使用。The compound having two or more polymerizable double bonds per molecule may be used alone, or two or more kinds may be used in combination.

自硬化膜的耐熱性、耐溶劑性的觀點考慮，在每一分子中具有兩個以上的聚合性雙鍵的化合物中優選為使用三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、多元酸改性(甲基)丙烯酸寡聚物、異三聚氰酸環氧乙烷改性二丙烯酸酯、異三聚氰酸環氧乙烷改性三丙烯酸酯、環氧丙烯酸酯寡聚物或這些的混合物。From the viewpoint of heat resistance and solvent resistance of the cured film, it is preferable to use trimethylolpropane triacrylate, pentaerythritol triacrylate, and pentaerythritol tetra among compounds having two or more polymerizable double bonds per molecule. Acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyacid modified (meth) acrylic acid oligomer, isotricyanic acid ethylene oxide modified diacrylate, isotricyanate epoxy Ethane-modified triacrylate, epoxy acrylate oligomer, or a mixture of these.

三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、多元酸改性(甲基)丙烯酸寡聚物、異三聚氰酸環氧乙烷改性二丙烯酸酯、異三聚氰酸環氧乙烷改性三丙烯酸酯、環氧丙烯酸酯寡聚物或這些的混合物可使用下述之類的市售品。三羥甲基丙烷三丙烯酸酯的具體例為亞羅尼斯（Aronix）M-309（商品名；東亞合成股份有限公司）。季戊四醇三丙烯酸酯及季戊四醇四丙烯酸酯的混合物的具體例為亞羅尼斯（Aronix）M-306（65重量%～70重量%）、亞羅尼斯（Aronix）M-305（55重量%～63重量%）、亞羅尼斯（Aronix）M-303（30重量%～60重量%）、亞羅尼斯（Aronix）M-452（25重量%～40重量%）、及亞羅尼斯（Aronix）M-450（不足10重量%）（均為商品名；東亞合成股份有限公司、括弧內的含有率是混合物中的季戊四醇三丙烯酸酯的含有率的目錄記載值）。二季戊四醇五丙烯酸酯及二季戊四醇六丙烯酸酯的混合物的具體例為亞羅尼斯（Aronix）M-403（50重量%～60重量%）、亞羅尼斯（Aronix）M-400（40重量%～50重量%）、亞羅尼斯（Aronix）M-402（30重量%～40重量%）、亞羅尼斯（Aronix）M-404（30重量%～40重量%）、亞羅尼斯（Aronix）M-406（25重量%～35重量%）、及亞羅尼斯（Aronix）M-405（10重量%～20重量%）（均為商品名；東亞合成股份有限公司、括弧內的含有率是混合物中的二季戊四醇五丙烯酸酯的含有率的目錄記載值）。多元酸改性(甲基)丙烯酸寡聚物的具體例為亞羅尼斯（Aronix）M-510及亞羅尼斯（Aronix）M-520（均為商品名；東亞合成股份有限公司）。異三聚氰酸環氧乙烷改性二丙烯酸酯的具體例為亞羅尼斯（Aronix）M-215（商品名；東亞合成股份有限公司）。異三聚氰酸環氧乙烷改性二丙烯酸酯及異三聚氰酸環氧乙烷改性三丙烯酸酯的混合物的具體例為亞羅尼斯（Aronix）M-313（30重量%～40重量%）及亞羅尼斯（Aronix）M-315（3重量%～13重量%）（均為商品名；東亞合成股份有限公司、括弧內的含有率是混合物中的異三聚氰酸環氧乙烷改性二丙烯酸酯的含有率的目錄記載值）。環氧丙烯酸酯寡聚物的具體例為TEA-100（商品名；KSM股份有限公司）。Trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyacrylic acid modified (meth) acrylic acid oligomer, isotricyanuric acid ring Commercially available products such as those described below can be used as the oxyethylene-modified diacrylate, the ethylene isocyanate-modified ethylene oxide triacrylate, the epoxy acrylate oligomer, or a mixture thereof. A specific example of trimethylolpropane triacrylate is Aronix M-309 (trade name; East Asia Synthesis Co., Ltd.). Specific examples of the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate are Aronix M-306 (65% to 70% by weight), Aronix M-305 (55% to 63% by weight). %), Aronix M-303 (30% to 60% by weight), Aronix M-452 (25% to 40% by weight), and Aronix M- 450 (less than 10% by weight) (both are trade names; the content ratios in parentheses are the catalog values of the content ratio of pentaerythritol triacrylate in the mixture). Specific examples of the mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are Aronix M-403 (50% to 60% by weight), Aronix M-400 (40% by weight to 50% by weight), Aronix M-402 (30% to 40% by weight), Aronix M-404 (30% to 40% by weight), Aronix M -406 (25% to 35% by weight) and Aronix M-405 (10% to 20% by weight) (both trade names; East Asia Synthetic Co., Ltd., and the content in parentheses is a mixture Table of Contents of Content of Dipentaerythritol Pentaacrylate in Diluent). Specific examples of the polyacid-modified (meth) acrylic acid oligomer are Aronix M-510 and Aronix M-520 (both trade names; East Asia Synthesis Co., Ltd.). A specific example of the ethylene triisocyanate-modified diacrylate is Aronix M-215 (trade name; East Asia Synthesis Co., Ltd.). A specific example of a mixture of ethylene isocyanate-modified diacrylate and ethylene isocyanate-modified triacrylate is Aronix M-313 (30% to 40% by weight). % By weight) and Aronix M-315 (3% by weight to 13% by weight) (both trade names; East Asia Synthetic Co., Ltd., and the content in parentheses is the isocyanuric epoxy in the mixture (Catalogue value of content of ethane-modified diacrylate). A specific example of the epoxy acrylate oligomer is TEA-100 (trade name; KSM Co., Ltd.).

1-2-2.在每一分子中具有一個聚合性雙鍵且在每一分子中具有至少一個選自-OH及-COOH中的官能基的化合物 自解析性的觀點考慮，本發明的感光性組成物中也可進一步含有在每一分子中具有一個聚合性雙鍵且在每一分子中具有至少一個選自-OH及-COOH中的官能基的化合物。如果在每一分子中具有一個聚合性雙鍵且在每一分子中具有至少一個選自-OH及-COOH中的官能基的化合物相對於聚酯醯胺酸100重量份而為1重量份～50重量份，則解析性變良好而優選。1-2-2. A compound having one polymerizable double bond in each molecule and at least one functional group selected from -OH and -COOH in each molecule. From the viewpoint of self-resolvability, the photosensitivity of the present invention The sexual composition may further contain a compound having one polymerizable double bond per molecule and having at least one functional group selected from -OH and -COOH per molecule. If the compound having one polymerizable double bond in each molecule and at least one functional group selected from -OH and -COOH in each molecule is 1 part by weight to 100 parts by weight of polyester amidate. 50 parts by weight is preferred because the resolvability is improved.

此種在每一分子中具有一個聚合性雙鍵且在每一分子中具有至少一個選自-OH及-COOH中的官能基的化合物例如可列舉：(甲基)丙烯酸、(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯、(甲基)丙烯酸-2-羥基-3-苯氧基丙酯、丁二酸-2-(甲基)丙烯醯氧基乙酯、六氫鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯、鄰苯二甲酸-2-(甲基)丙烯醯氧基乙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基乙基-2-羥基乙酯、(甲基)丙烯酸-4-羥基苯基酯、對羥基(甲基)丙烯酸苯胺化物、(甲基)丙烯酸-4-羥基丁酯、1,4-環己烷二甲醇單(甲基)丙烯酸酯、甘油單(甲基)丙烯酸酯、丙烯酸-3-(2-羥基苯基)酯、及(甲基)丙烯酸-β-羧基乙酯。Examples of such a compound having one polymerizable double bond in each molecule and at least one functional group selected from -OH and -COOH in each molecule include (meth) acrylic acid and (meth) acrylic acid. Hydroxyethyl ester, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (methyl) succinate Acrylic ethoxy ethyl ester, 2- (meth) acrylic ethoxy ethyl hexahydrophthalate, 2- (meth) acrylic ethoxy ethyl phthalate, 2-phthalic acid 2- (Meth) acryloxyethyl-2-hydroxyethyl, (meth) acrylic acid 4-hydroxyphenyl ester, p-hydroxy (meth) acrylic acid anilide, (meth) acrylic acid 4-hydroxybutyl Esters, 1,4-cyclohexanedimethanol mono (meth) acrylate, glycerol mono (meth) acrylate, 3- (2-hydroxyphenyl) acrylate, and (meth) acrylic acid-β- Carboxyethyl.

這些化合物中，(甲基)丙烯酸-4-羥基苯基酯及對羥基(甲基)丙烯酸苯胺化物的解析性變良好而優選。Among these compounds, 4-hydroxyphenyl (meth) acrylate and anilide of p-hydroxy (meth) acrylic acid are preferred because they have better resolvability.

1-3.光聚合起始劑 本發明的感光性組成物中所含有的光聚合起始劑只要為可使如下組成物的聚合開始者，則並無特別限定，所述組成物含有聚酯醯胺酸、具有聚合性雙鍵的化合物、光聚合起始劑、環氧化合物、環氧硬化劑。1-3. Photopolymerization initiator The photopolymerization initiator contained in the photosensitive composition of the present invention is not particularly limited as long as it can start polymerization of the following composition, and the composition contains polyester Amines, compounds having polymerizable double bonds, photopolymerization initiators, epoxy compounds, epoxy hardeners.

本發明的感光性組成物中所含有的光聚合起始劑可列舉：二苯甲酮、米其勒酮、4,4'-雙(二乙基胺基)二苯甲酮、氧雜蒽酮、硫雜蒽酮、異丙基氧雜蒽酮、2,4-二乙基硫雜蒽酮、2-乙基蒽醌、苯乙酮、2-羥基-2-甲基苯丙酮、2-羥基-2-甲基-4'-異丙基苯丙酮、1-羥基環己基苯基酮、異丙基安息香醚、異丁基安息香醚、2,2-二乙氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、樟腦醌、苯並蒽酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代丙烷-1-酮（例如，商品名：豔佳固（IRGACURE）907、日本巴斯夫（BASF Japan）股份有限公司）、2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基)-丁酮-1（例如，商品名：豔佳固（IRGACURE）369、日本巴斯夫（BASF Japan）股份有限公司）、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、4,4'-二(叔丁基過氧化羰基)二苯甲酮、3,4,4'-三(叔丁基過氧化羰基)二苯甲酮、1,2-辛二酮,1-[4-(苯硫基)苯基]-2-(O-苯甲醯基肟)（例如，商品名：豔佳固（IRGACURE）OXE-01、日本巴斯夫（BASF Japan）股份有限公司）、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-哢唑-3-基]-1-(O-乙醯基肟)（例如，商品名：豔佳固（IRGACURE）OXE-02、日本巴斯夫（BASF Japan）股份有限公司）、OXE-03（商品名；日本巴斯夫（BASF Japan）股份有限公司）、OXE-04（商品名；日本巴斯夫（BASF Japan）股份有限公司）、1,2-丙二酮-,1-[4-[4-(2-羥基乙氧基)苯硫基]苯基]-2-(O-乙醯基肟)（例如，商品名：艾迪科亞庫魯茲（ADEKA ARKLS）NCI-930、艾迪科（ADEKA）股份有限公司）、艾迪科亞庫魯茲（ADEKA ARKLS）NCI-831（商品名；艾迪科（ADEKA）股份有限公司）、艾迪科奧托馬（ADEKA OPTOMER）N-1919（商品名；艾迪科（ADEKA）股份有限公司）、2,4,6-三甲基苯甲醯基二苯基膦氧化物、2-(4'-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-均三嗪、2-(3',4'-二甲氧基苯乙烯基)-4,6-雙(三氯甲基)-均三嗪、2-(2',4'-二甲氧基苯乙烯基)-4,6-雙(三氯甲基)-均三嗪、2-(2'-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-均三嗪、2-(4'-戊氧基苯乙烯基)-4,6-雙(三氯甲基)-均三嗪、4-[對-N,N-二(乙氧基羰基甲基)]-2,6-二(三氯甲基)-均三嗪、1,3-雙(三氯甲基)-5-(2'-氯苯基)-均三嗪、1,3-雙(三氯甲基)-5-(4'-甲氧基苯基)-均三嗪、2-(對二甲基胺基苯乙烯基)苯並噁唑、2-(對二甲基胺基苯乙烯基)苯並噻唑、2-疏基苯並噻唑、3,3'-羰基雙(7-二乙基胺基香豆素)、2-(鄰氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(4-乙氧基羰基苯基)-1,2'-聯咪唑、2,2'-雙(2,4-二氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2,4-二溴苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2,4,6-三氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、3-(2-甲基-2-二甲基胺基丙醯基)哢唑、3,6-雙(2-甲基-2-嗎啉代丙醯基)-9-正十二烷基哢唑、1-羥基環己基苯基酮、及雙(h5 -2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦等。Examples of the photopolymerization initiator contained in the photosensitive composition of the present invention include benzophenone, Michelin, 4,4'-bis (diethylamino) benzophenone, and xanthracene. Ketone, thiaxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylphenylacetone, 2 -Hydroxy-2-methyl-4'-isopropylphenylacetone, 1-hydroxycyclohexylphenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzoxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane -1-one (for example, trade name: IRGACURE 907, BASF Japan Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1 (for example, trade name: IRGACURE 369, BASF Japan Co., Ltd.), 4-dimethylaminobenzoic acid ethyl ester, 4-dimethyl Isoamyl aminobenzoate, 4,4'-bis (tert-butylperoxycarbonyl) benzophenone, 3,4,4'-tris (tert-butylperoxycarbonyl) benzophenone, 1, 2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzylideneoxime) (for example, trade name: IRGACURE OXE-01, BASF Japan ( BASF Japan) Co., Ltd.), ethyl ketone, 1- [9-ethyl-6- (2-methylbenzyl) -9H-oxazol-3-yl] -1- (O-ethylfluorenyl Oxime) (for example, trade name: IRGACURE OXE-02, BASF Japan Co., Ltd.), OXE-03 (trade name; BASF Japan Co., Ltd.), OXE-04 (Trade name; BASF Japan Co., Ltd.), 1,2-propanedione-, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetylamoxime) (for example, trade name: ADEKA ARKLS NCI-930, ADEKA Co., Ltd.), ADEKA ARKLS ) NCI-831 (trade name; ADEKA) Co., Ltd., ADEKA OPTOMER N-1919 (trade name; ADEKA) Co., Ltd., 2, 4 , 6-trimethylbenzylidene diphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis ( Chloromethyl) -mesytriazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -mesytriazine, 2- (2', 4 '-Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) ) -Mesytriazine, 2- (4'-pentoxystyryl) -4,6-bis (trichloromethyl) -mesytriazine, 4- [p-N, N-bis (ethoxy) Carbonylmethyl)]-2,6-bis (trichloromethyl) -mesytriazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -mesytriazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -mesytriazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- ( P-dimethylaminostyryl) benzothiazole, 2-sulfobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (4 -Ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1, 2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylamine (Propanyl) Oxazole, 3,6-bis (2-methyl-2-morpholinopropylfluorenyl) -9-n-dodecyloxazole, 1-hydroxycyclohexylphenyl ketone, and bis (h 5 -2 , 4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium and the like.

光聚合起始劑可單獨使用，也可混合兩種以上而使用。自曝光時的塗膜的感度及硬化膜的透明性的觀點考慮，在光聚合起始劑中，優選為α-胺基苯烷基酮系、醯基膦氧化物系、肟酯系光聚合起始劑。另外，在本說明書中，將如下薄膜稱為「塗膜」，所述薄膜是將在基板上利用旋塗、印刷及其他方法所形成的感光性組成物的薄膜預備乾燥（預烘烤）而獲得。該塗膜經過後續的曝光-顯影-洗淨-乾燥等步驟後，通過正式煆燒（後烘烤）而成為硬化膜。在本說明書中，將自所述預備加熱起至乾燥的步驟中的薄膜均稱為「塗膜」，例如，通過表述為「曝光時的塗膜」、「顯影後的塗膜」來表示成膜步驟的何種階段的塗膜。The photopolymerization initiator may be used alone or as a mixture of two or more. From the viewpoint of the sensitivity of the coating film at the time of exposure and the transparency of the cured film, among the photopolymerization initiators, α-aminobenzoyl ketone, fluorenylphosphine oxide, and oxime ester photopolymerization are preferred. Initiator. In addition, in this specification, a thin film is referred to as a "coating film". The thin film is prepared by pre-drying (pre-baking) a thin film of a photosensitive composition formed on a substrate by spin coating, printing, or other methods. obtain. The coating film is subjected to subsequent steps of exposure, development, washing, and drying, and then is formally cured (post-baking) to form a cured film. In this specification, the thin films in the steps from the preliminary heating to the drying are referred to as "coating films", and are expressed, for example, as "coating films during exposure" and "coating films after development". What stage of the film coating step?

自塗膜的感度及硬化膜的透明性的觀點考慮，在光聚合起始劑中，更優選為，1,2-辛二酮,1-[4-(苯硫基)苯基]-2-(O-苯甲醯基肟)或1,2-丙二酮,1-[4-[4-(2-羥基乙氧基)苯硫基]苯基]-2-(O-乙醯基肟)相對於光聚合起始劑的總重量而為20重量%以上。而且，如果為50重量%以上，則進而更優選。光聚合起始劑也可僅包含1,2-辛二酮,1-[4-(苯硫基)苯基]-2-(O-苯甲醯基肟)或1,2-丙二酮,1-[4-[4-(2-羥基乙氧基)苯硫基]苯基]-2-(O-乙醯基肟)。From the viewpoint of the sensitivity of the coating film and the transparency of the cured film, among the photopolymerization initiators, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2 is more preferred. -(O-benzylidene oxime) or 1,2-propionedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetamidine The oxime) is 20% by weight or more based on the total weight of the photopolymerization initiator. Furthermore, if it is 50 weight% or more, it is still more preferable. The photopolymerization initiator may also contain only 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzylideneoxime), or 1,2-propanedione , 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetamidooxime).

1-4.環氧化合物 本發明中所使用的環氧化合物的重量平均分子量是3,000以上。通過在本發明的感光性組成物中添加環氧化合物，可提高硬化膜的耐熱性、耐溶劑性。1-4. Epoxy compound The epoxy compound used in the present invention has a weight average molecular weight of 3,000 or more. By adding an epoxy compound to the photosensitive composition of this invention, the heat resistance and solvent resistance of a cured film can be improved.

本發明中所使用的環氧化合物的具體例為含有環氧基的共聚物。所述含有環氧基的共聚物可通過使(甲基)丙烯酸縮水甘油酯與其他自由基聚合性單體反應而獲得。由於由感光性組成物所得的硬化膜的透明性變高，且可抑制UV臭氧處理步驟或紫外線曝光步驟中的透明性下降，因此優選為使用含有環氧基的共聚物。自平坦性、耐熱性、耐溶劑性的觀點考慮，在構成含有環氧基的共聚物的所有單體中，(甲基)丙烯酸縮水甘油酯優選為占50重量%～99重量%。A specific example of the epoxy compound used in the present invention is an epoxy group-containing copolymer. The epoxy group-containing copolymer can be obtained by reacting glycidyl (meth) acrylate with another radical polymerizable monomer. Since the transparency of the cured film obtained from the photosensitive composition is high, and it is possible to suppress a decrease in transparency in the UV ozone treatment step or the ultraviolet exposure step, it is preferable to use a copolymer containing an epoxy group. From the viewpoints of flatness, heat resistance, and solvent resistance, glycidyl (meth) acrylate is preferably 50 to 99% by weight of all monomers constituting the epoxy group-containing copolymer.

其他自由基聚合性單體可例示單官能(甲基)丙烯酸酯、2官能(甲基)丙烯酸酯及3官能以上的多官能(甲基)丙烯酸酯。為了提高由感光性組成物所得的硬化膜的耐熱性、耐溶劑性，優選為使用3官能以上的多官能(甲基)丙烯酸酯，另一方面，為了提高硬化膜的平坦性、與組成物中的聚酯醯胺酸的相容性，優選為使用單官能(甲基)丙烯酸酯。然而，硬化膜的耐熱性、耐溶劑性及硬化膜的平坦性、與組成物中的聚酯醯胺酸的相容性存在折衷的傾向，因此為了平衡性良好地發揮這些性能，優選為使用2官能(甲基)丙烯酸酯。Examples of the other radical polymerizable monomer include a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, and a trifunctional or higher polyfunctional (meth) acrylate. In order to improve the heat resistance and solvent resistance of the cured film obtained from the photosensitive composition, it is preferable to use a trifunctional or higher polyfunctional (meth) acrylate. On the other hand, in order to improve the flatness of the cured film and the composition The compatibility of the polyester amidine in the resin is preferably a monofunctional (meth) acrylate. However, the heat resistance, solvent resistance, flatness of the cured film, and compatibility with the polyester amidate in the composition tend to be compromised. Therefore, in order to exert these properties in a balanced manner, it is preferable to use Bifunctional (meth) acrylate.

2官能(甲基)丙烯酸酯的優選例可列舉：乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯。由於這些2官能(甲基)丙烯酸酯與(甲基)丙烯酸縮水甘油酯反應而獲得的含有環氧基的共聚物和聚酯醯胺酸的相容性變得良好，因此優選。自平坦性、耐熱性、耐溶劑性的觀點考慮，在構成含有環氧基的共聚物的所有單體中，2官能(甲基)丙烯酸酯優選為含有1重量%～30重量%。Preferred examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and 1,4-butanediol di (meth) acrylic acid. Esters, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate. These difunctional (meth) acrylic acid esters and glycidyl (meth) acrylic acid react, and the compatibility of the epoxy-group-containing copolymer and polyester amidate becomes favorable, and it is preferable. From the viewpoints of flatness, heat resistance, and solvent resistance, the bifunctional (meth) acrylate is preferably contained in an amount of 1 to 30% by weight in all the monomers constituting the epoxy group-containing copolymer.

所述環氧化合物還可包含(甲基)丙烯酸縮水甘油酯與2官能(甲基)丙烯酸酯以外的自由基聚合性單體作為原料成分。自不損及本發明的效果，顯現出所述其他自由基聚合性單體的特性的觀點考慮，此種其他的自由基聚合性單體優選為含有0重量%～20重量%。其他自由基聚合性單體可使用所述單官能(甲基)丙烯酸酯及3官能以上的多官能(甲基)丙烯酸酯。The epoxy compound may further contain, as a raw material component, a radical polymerizable monomer other than glycidyl (meth) acrylate and a bifunctional (meth) acrylate. From the viewpoint of exhibiting the characteristics of the other radical polymerizable monomer without impairing the effects of the present invention, such other radical polymerizable monomer is preferably contained in an amount of 0 to 20% by weight. As the other radically polymerizable monomer, the monofunctional (meth) acrylate and a trifunctional or higher polyfunctional (meth) acrylate can be used.

單官能(甲基)丙烯酸酯的具體例為(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯、甲氧基聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、甘油單(甲基)丙烯酸酯、(甲基)丙烯酸間苯氧基苄酯、及(甲基)丙烯酸四氫糠酯。Specific examples of the monofunctional (meth) acrylate are methyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) Dicyclopentyl acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, methoxy Polyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, m-phenoxy (meth) acrylate Benzyl ester and tetrahydrofurfuryl (meth) acrylate.

3官能以上的多官能(甲基)丙烯酸酯的具體例為三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三丙烯酸酯、三羥甲基丙烷乙氧基三丙烯酸酯、三羥甲基丙烷丙氧基三丙烯酸酯、乙氧基化異三聚氰酸三丙烯酸酯、ε-己內酯改性三-(2-丙烯醯氧基乙基)異三聚氰酸酯、甘油乙氧基三丙烯酸酯、甘油丙氧基三丙烯酸酯、二-三羥甲基丙烷四丙烯酸酯、季戊四醇四丙烯酸酯、乙氧基化季戊四醇四丙烯酸酯。Specific examples of the trifunctional or higher polyfunctional (meth) acrylate are trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate, trimethylolpropane ethoxy triacrylate, and trimethylol. Propane propoxy triacrylate, ethoxylated isotricyanate triacrylate, ε-caprolactone modified tri- (2-propenyloxyethyl) isotricyanate, glyceryl ethoxylate Triacrylate, glyceryl propoxy triacrylate, di-trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate.

通過以(甲基)丙烯酸縮水甘油酯與2官能(甲基)丙烯酸酯為必需的原料成分進行反應而獲得的含有環氧基的共聚物的重量平均分子量優選為3,000～50,000，更優選為3,000～20,000。如果分子量為這些範圍，則可獲得充分的解析性、平坦性、耐熱性、耐溶劑性。The weight-average molecular weight of the epoxy-group-containing copolymer obtained by reacting glycidyl (meth) acrylate and difunctional (meth) acrylate as an essential raw material component is preferably 3,000 to 50,000, and more preferably 3,000. ~ 20,000. When the molecular weight is in these ranges, sufficient resolution, flatness, heat resistance, and solvent resistance can be obtained.

1-5.環氧硬化劑 在本發明的感光性組成物中，為了使平坦性、耐熱性、耐溶劑性提高而使用環氧硬化劑。環氧硬化劑存在有酸酐系硬化劑、胺系硬化劑、酚系硬化劑、咪唑系硬化劑、催化劑型硬化劑、及鋶鹽、苯並噻唑鎓鹽、銨鹽、鏻鹽等感熱性酸產生劑等，自避免硬化膜的著色及硬化膜的耐熱性的觀點考慮，優選酸酐系硬化劑或咪唑系硬化劑。1-5. Epoxy hardener In the photosensitive composition of the present invention, an epoxy hardener is used in order to improve flatness, heat resistance, and solvent resistance. Epoxy hardeners include acid anhydride-based hardeners, amine-based hardeners, phenol-based hardeners, imidazole-based hardeners, catalyst-based hardeners, and thermostable acids such as sulfonium salts, benzothiazolium salts, ammonium salts, and sulfonium salts. The generator and the like are preferably an acid anhydride-based hardener or an imidazole-based hardener from the viewpoint of avoiding the coloration of the cured film and the heat resistance of the cured film.

酸酐系硬化劑的具體例可列舉：脂肪族二羧酸酐（例如，馬來酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、六氫偏苯三甲酸酐等）、芳香族多元羧酸酐（例如，鄰苯二甲酸酐、偏苯三甲酸酐等）。這些酸酐系硬化劑中特別優選可提高硬化膜的耐熱性而不損及感光性組成物對溶劑的溶解性的偏苯三甲酸酐及六氫偏苯三甲酸酐。Specific examples of the acid anhydride-based hardener include aliphatic dicarboxylic acid anhydrides (for example, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydro Trimellitic anhydride, etc.), aromatic polycarboxylic anhydride (for example, phthalic anhydride, trimellitic anhydride, etc.). Among these acid anhydride-based hardeners, trimellitic anhydride and hexahydrotrimellitic anhydride which can improve the heat resistance of the cured film without impairing the solubility of the photosensitive composition to the solvent are preferred.

咪唑系硬化劑的具體例可列舉：2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2,3-二氫-1H-吡咯並[1,2-a]苯並咪唑、1-氰基乙基-2-十一烷基咪唑鎓偏苯三酸鹽。這些咪唑系硬化劑中特別優選可提高硬化膜的硬化性而不損及感光性組成物對溶劑的溶解性的2-十一烷基咪唑。Specific examples of the imidazole-based hardener include 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2,3-dihydro- 1H-pyrrolo [1,2-a] benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate. Among these imidazole-based hardeners, 2-undecylimidazole, which can improve the hardenability of the cured film without impairing the solubility of the photosensitive composition in a solvent, is particularly preferred.

1-6.聚酯醯胺酸、具有聚合性雙鍵的化合物、光聚合起始劑、環氧化合物、及環氧硬化劑的比例 在本發明的感光性組成物中，相對於聚酯醯胺酸100重量份，具有聚合性雙鍵的化合物的比例為20重量份～300重量份。如果具有聚合性雙鍵的化合物的比例為該範圍，則耐熱性、平坦性、耐化學品性、顯影後殘膜率的平衡良好。如果具有聚合性雙鍵的化合物為50重量份～200重量份的範圍，則進而更優選。1-6. The ratio of polyester sulfamic acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, and an epoxy hardener is in the photosensitive composition of the present invention relative to polyester. The proportion of the compound having a polymerizable double bond is 100 parts by weight of amino acid and 20 to 300 parts by weight. When the ratio of the compound having a polymerizable double bond is within this range, the balance of heat resistance, flatness, chemical resistance, and residual film rate after development is good. The compound which has a polymerizable double bond is more preferable if it is the range of 50 weight part-200 weight part.

相對於聚酯醯胺酸100重量份，光聚合起始劑的比例為1重量份～60重量份。自曝光時的塗膜的感度的觀點考慮，優選為光聚合起始劑的比例為所述範圍。而且，自曝光時的塗膜的感度及硬化膜的透明性的觀點考慮，在光聚合起始劑中，如果1,2-辛二酮,1-[4-(苯硫基)苯基]-2-(O-苯甲醯基肟)或1,2-丙二酮,1-[4-[4-(2-羥基乙氧基)苯硫基]苯基]-2-(O-乙醯基肟)相對於光聚合起始劑的總重量而為20重量%以上，則更優選。而且，如果為50重量%以上，則進而更優選。The ratio of the photopolymerization initiator to 100 parts by weight of the polyester lysine is 1 to 60 parts by weight. From the viewpoint of the sensitivity of the coating film at the time of exposure, it is preferable that the ratio of the photopolymerization initiator is within the above range. Furthermore, from the viewpoints of the sensitivity of the coating film at the time of exposure and the transparency of the cured film, in the photopolymerization initiator, if 1,2-octanedione, 1- [4- (phenylthio) phenyl] 2- (O-benzylideneoxime) or 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O- Acetyl oxime) is more preferably 20% by weight or more based on the total weight of the photopolymerization initiator. Furthermore, if it is 50 weight% or more, it is still more preferable.

在本發明的感光性組成物中，相對於聚酯醯胺酸100重量份，環氧化合物的比例為20重量份～200重量份。如果環氧化合物的比例為該範圍，則耐熱性、平坦性的平衡良好。如果環氧化合物為20重量份～150重量份的範圍，則進而更優選。In the photosensitive composition of this invention, the ratio of an epoxy compound is 20 weight part-200 weight part with respect to 100 weight part of polyester glutamic acids. When the ratio of the epoxy compound is within this range, the balance between heat resistance and flatness is good. An epoxy compound is more preferable if it is the range of 20 weight part-150 weight part.

環氧硬化劑相對於環氧化合物的比例是相對於環氧化合物100重量份，環氧硬化劑為0.1重量份～60重量份。例如，關於環氧硬化劑為酸酐系硬化劑的情況下的添加量，更詳細而言，優選以相對於環氧基而言，環氧硬化劑中的羧酸酐基或羧基成為0.1倍當量～1.5倍當量的方式進行添加。此時，羧酸酐基以2價進行計算。如果以成為0.15倍當量～0.8倍當量的方式添加羧酸酐基或羧基，則耐溶劑性進一步提高，因此進而更優選。The ratio of the epoxy curing agent to the epoxy compound is 100 parts by weight relative to the epoxy compound, and the epoxy curing agent is 0.1 to 60 parts by weight. For example, in the case where the epoxy hardener is an acid anhydride-based hardener, more specifically, it is preferable that the carboxylic anhydride group or carboxyl group in the epoxy hardener is 0.1 times equivalent to the epoxy group. Add 1.5 times equivalent. At this time, the carboxylic acid anhydride group is calculated at a divalent value. If a carboxylic anhydride group or a carboxyl group is added so that it may become 0.15-times equivalent to 0.8-times equivalent, since solvent resistance will improve further, it is further more preferable.

1-7.其他成分 本發明的感光性組成物中，可添加各種添加劑以提高解析性、塗布均勻性、黏接性。添加劑主要可列舉：溶劑，分子量調整劑，光酸產生劑，陰離子系、陽離子系、非離子系、氟系或矽系的表面活性劑，矽烷偶合劑等偶合劑，受阻酚系、受阻胺系、磷系、硫系化合物等抗氧化劑。1-7. Other components Various additives can be added to the photosensitive composition of the present invention to improve the resolution, uniformity of coating, and adhesion. Examples of additives include solvents, molecular weight modifiers, photoacid generators, anionic, cationic, nonionic, fluorine or silicon surfactants, coupling agents such as silane coupling agents, hindered phenols, hindered amines , Phosphorus-based, sulfur-based compounds and other antioxidants.

1-7-1.溶劑 在本發明的感光性組成物中，也可添加溶劑。本發明的感光性組成物中所任意添加的溶劑優選可溶解聚酯醯胺酸、具有聚合性雙鍵的化合物、環氧化合物、環氧硬化劑等的溶劑。該溶劑的具體例是乙酸乙酯、乙酸丁酯、乙酸丙酯、丙酸丁酯、乳酸乙酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-氧基丙酸甲酯、3-羥基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-羥基丙酸甲酯、2-羥基丙酸丙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸甲酯、2-氧代丁酸乙酯、4-羥基-4-甲基-2-戊酮、1,4-丁二醇、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、乙二醇單丁醚乙酸酯、環己酮、環戊酮、二乙二醇單甲醚、二乙二醇單甲醚乙酸酯、二乙二醇單***、二乙二醇單***乙酸酯、二乙二醇單丁醚、二乙二醇單丁醚乙酸酯、二乙二醇二甲醚、二乙二醇二***、及二乙二醇甲基***。溶劑可為這些溶劑的一種，也可為這些溶劑的兩種以上的混合物。1-7-1. Solvent A solvent may be added to the photosensitive composition of the present invention. The solvent arbitrarily added to the photosensitive composition of the present invention is preferably a solvent capable of dissolving polyester amidate, a compound having a polymerizable double bond, an epoxy compound, an epoxy hardener, and the like. Specific examples of the solvent are ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, and ethoxylate. Methyl acetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3 -Methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, 2- Ethyl hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate Propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether ethyl Ester, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol Monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ether. The solvent may be one kind of these solvents or a mixture of two or more kinds of these solvents.

1-7-2.分子量調整劑 為了抑制因聚合而分子量變高、且顯現出優異的解析性，在本發明的感光性組成物中，還可添加分子量調整劑。分子量調整劑可列舉：硫醇類、黃原酸類、醌類、氫醌類、苯酚類、兒茶酚（catechol）類、甲酚類、2,4-二苯基-4-甲基-1-戊烯、啡噻嗪等。1-7-2. Molecular weight adjuster In order to suppress the increase in molecular weight due to polymerization and to exhibit excellent resolution, a molecular weight adjuster may be added to the photosensitive composition of the present invention. Examples of molecular weight modifiers include thiols, xanthates, quinones, hydroquinones, phenols, catechols, cresols, 2,4-diphenyl-4-methyl-1 -Pentene, phenothiazine and the like.

分子量調整劑的具體例可列舉：1,4-萘醌、2-羥基-1,4-萘醌、1,2-苯醌、1,4-苯醌、甲基-對苯醌、蒽醌、氫醌、甲基氫醌、叔丁基氫醌、2,5-二-叔丁基氫醌、2,5-二-叔戊基氫醌、1,4-二羥基萘、3,6-二羥基苯並降冰片烷、4-甲氧基苯酚、2,2',6,6'-四-叔丁基-4,4'-二羥基聯苯、3-(3,5-二-叔丁基-4-羥基苯基)丙酸硬脂酯、2,2'-亞甲基雙(6-叔丁基-4-乙基苯酚)、2,4,6-三(3',5'-二-叔丁基-4'-羥基苄基)1,3,5-三甲苯、季戊四醇四[3-(3,5-二-叔丁基-4-羥基苯基)丙酸酯]、4-叔丁基鄰苯二酚（4-t-butyl pyrocatechol）、正己基硫醇、正辛基硫醇、正十二烷基硫醇、叔十二烷基硫醇、硫代乙醇酸、二甲基黃原酸硫醚、二異丙基黃原酸二硫醚、2,6-二-叔丁基-對甲酚、4,4'-亞丁基雙(6-叔丁基-間甲酚)、4,4'-硫代雙(6-叔丁基-間甲酚)、2,4-二苯基-4-甲基-1-戊烯、啡噻嗪等。Specific examples of the molecular weight modifier include 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, 1,2-benzoquinone, 1,4-benzoquinone, methyl-p-benzoquinone, and anthraquinone. , Hydroquinone, methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 1,4-dihydroxynaphthalene, 3,6 -Dihydroxybenzonorbornane, 4-methoxyphenol, 2,2 ', 6,6'-tetra-tert-butyl-4,4'-dihydroxybiphenyl, 3- (3,5-di -Tert-butyl-4-hydroxyphenyl) stearyl propionate, 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,4,6-tris (3 ' , 5'-di-tert-butyl-4'-hydroxybenzyl) 1,3,5-trimethylbenzene, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid [Ester], 4-t-butyl pyrocatechol, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, thio Glycolic acid, dimethyl xanthate sulfide, diisopropylxanthate disulfide, 2,6-di-tert-butyl-p-cresol, 4,4'-butylene bis (6-tert-butyl -M-cresol), 4,4'-thiobis (6-tert-butyl-m-cresol), 2,4-diphenyl-4-methyl-1-pentene, phenothiazine, and the like.

1-7-3.光酸產生劑 為了顯現出優異的解析性，在本發明的感光性組成物中，還可添加光酸產生劑。光酸產生劑可列舉1,2-醌二疊氮化合物。1-7-3. Photoacid generator In order to exhibit excellent resolution, a photoacid generator may be added to the photosensitive composition of the present invention. Examples of the photoacid generator include 1,2-quinonediazide compounds.

1,2-醌二疊氮化合物的具體例為2,3,4-三羥基二苯甲酮-1,2-萘醌二疊氮-4-磺酸酯、2,3,4-三羥基二苯甲酮-1,2-萘醌二疊氮-5-磺酸酯（例如，商品名：NT-200、東洋合成化學工業）、2,4,6-三羥基二苯甲酮-1,2-萘醌二疊氮-4-磺酸酯、2,4,6-三羥基二苯甲酮-1,2-萘醌二疊氮-5-磺酸酯；2,2',4,4'-四羥基二苯甲酮-1,2-萘醌二疊氮-4-磺酸酯、2,2',4,4'-四羥基二苯甲酮-1,2-萘醌二疊氮-5-磺酸酯、2,3,3',4-四羥基二苯甲酮-1,2-萘醌二疊氮-4-磺酸酯、2,3,3',4-四羥基二苯甲酮-1,2-萘醌二疊氮-5-磺酸酯、2,3,4,4'-四羥基二苯甲酮-1,2-萘醌二疊氮-4-磺酸酯、2,3,4,4'-四羥基二苯甲酮-1,2-萘醌二疊氮-5-磺酸酯；雙(2,4-二羥基苯基)甲烷-1,2-萘醌二疊氮-4-磺酸酯、雙(2,4-二羥基苯基)甲烷-1,2-萘醌二疊氮-5-磺酸酯、雙(對羥基苯基)甲烷-1,2-萘醌二疊氮-4-磺酸酯、雙(對羥基苯基)甲烷-1,2-萘醌二疊氮-5-磺酸酯；三(對羥基苯基)甲烷-1,2-萘醌二疊氮-4-磺酸酯、三(對羥基苯基)甲烷-1,2-萘醌二疊氮-5-磺酸酯、1,1,1-三(對羥基苯基)乙烷-1,2-萘醌二疊氮-4-磺酸酯、1,1,1-三(對羥基苯基)乙烷-1,2-萘醌二疊氮-5-磺酸酯；雙(2,3,4-三羥基苯基)甲烷-1,2-萘醌二疊氮-4-磺酸酯、雙(2,3,4-三羥基苯基)甲烷-1,2-萘醌二疊氮-5-磺酸酯、2,2-雙(2,3,4-三羥基苯基)丙烷-1,2-萘醌二疊氮-4-磺酸酯、2,2-雙(2,3,4-三羥基苯基)丙烷-1,2-萘醌二疊氮-5-磺酸酯；1,1,3-三(2,5-二甲基-4-羥基苯基)-3-苯基丙烷-1,2-萘醌二疊氮-4-磺酸酯、1,1,3-三(2,5-二甲基-4-羥基苯基)-3-苯基丙烷-1,2-萘醌二疊氮-5-磺酸酯、4,4'-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚-1,2-萘醌二疊氮-4-磺酸酯、4,4'-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚-1,2-萘醌二疊氮-5-磺酸酯；雙(2,5-二甲基-4-羥基苯基)-2-羥基苯基甲烷-1,2-萘醌二疊氮-4-磺酸酯、雙(2,5-二甲基-4-羥基苯基)-2-羥基苯基甲烷-1,2-萘醌二疊氮-5-磺酸酯、3,3,3',3'-四甲基-1,1'-螺雙茚-5,6,7,5',6',7'-己醇-1,2-萘醌二疊氮-4-磺酸酯、3,3,3',3'-四甲基-1,1'-螺雙茚-5,6,7,5',6',7'-己醇-1,2-萘醌二疊氮-5-磺酸酯；2,2,4-三甲基-7,2',4'-三羥基黃烷-1,2-萘醌二疊氮-4-磺酸酯、及2,2,4-三甲基-7,2',4'-三羥基黃烷-1,2-萘醌二疊氮-5-磺酸酯。Specific examples of the 1,2-quinonediazide compound are 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4-trihydroxy Benzophenone-1,2-naphthoquinonediazide-5-sulfonate (for example, trade name: NT-200, Toyo Synthetic Chemical Industry), 2,4,6-trihydroxybenzophenone-1 , 2-naphthoquinonediazide-4-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate; 2,2 ', 4 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone Diazide-5-sulfonate, 2,3,3 ', 4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,3', 4 -Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide- 4-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate; bis (2,4-dihydroxyphenyl) methane -1,2-naphthoquinonediazide-4-sulfonate, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate, bis (p-hydroxyl Phenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate; Phenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, tris (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate, 1,1 1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonate, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthalene Quinonediazide-5-sulfonate; bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, bis (2,3,4- Trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinone diazide Aza-4-sulfonate, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonate; 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonate, 1,1,3-tris (2,5- Dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonate, 4,4 '-[1- [4- [1- [4- Hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol-1,2-naphthoquinonediazide-4-sulfonate, 4,4 '-[1- [4- [ 1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol-1,2-naphthoquinonediazide-5-sulfonate; bis (2,5-bis (Methyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonate, (2,5-Dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonate, 3,3,3 ', 3'-tetra Methyl-1,1'-spirobisindene-5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-4-sulfonate, 3,3, 3 ', 3'-tetramethyl-1,1'-spirobisindene-5,6,7,5', 6 ', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfonate Acid esters; 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonate, and 2,2,4-tri Methyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonate.

1-7-4.表面活性劑 在本發明的感光性組成物中，還可添加表面活性劑以提高塗布均勻性。表面活性劑的具體例可列舉：波利弗洛（Polyflow）No.45、波利弗洛（Polyflow）KL-245、波利弗洛（Polyflow）No.75、波利弗洛（Polyflow）No.90、波利弗洛（Polyflow）No.95（均為商品名；共榮社化學股份有限公司）、迪斯帕畢克（Disperbyk）161、迪斯帕畢克（Disperbyk）162、迪斯帕畢克（Disperbyk）163、迪斯帕畢克（Disperbyk）164、迪斯帕畢克（Disperbyk）166、迪斯帕畢克（Disperbyk）170、迪斯帕畢克（Disperbyk）180、迪斯帕畢克（Disperbyk）181、迪斯帕畢克（Disperbyk）182、BYK300、BYK306、BYK310、BYK320、BYK330、BYK342、BYK346、BYK361N、BYK-UV3500、BYK-UV3570（均為商品名；日本畢克化學（BYK Chemie Japan）股份有限公司）、KP-341、KP-358、KP-368、KF-96-50CS、KF-50-100CS（均為商品名；信越化學工業股份有限公司）、沙福隆（Surflon）SC-101、沙福隆（Surflon）KH-40、沙福隆（Surflon）S611（均為商品名；AGC清美化學（AGC Seimi Chemical）股份有限公司）、福吉特（Ftergent）222F、福吉特（Ftergent）208G、福吉特（Ftergent）251、福吉特（Ftergent）710FL、福吉特（Ftergent）710FM、福吉特（Ftergent）710FS、福吉特（Ftergent）601AD、福吉特（Ftergent）602A、福吉特（Ftergent）650A、FTX-218（均為商品名；尼奧斯（Neos）股份有限公司）、艾福拓（EFTOP）EF-351、艾福拓（EFTOP）EF-352、艾福拓（EFTOP）EF-601、艾福拓（EFTOP）EF-801、艾福拓（EFTOP）EF-802（均為商品名；三菱材料（Mitsubishi Material）股份有限公司）、美佳法（Megafac）F-171、美佳法（Megafac）F-177、美佳法（Megafac）F-410、美佳法（Megafac）F-430、美佳法（Megafac）F-444、美佳法（Megafac）F-472SF、美佳法（Megafac）F-475、美佳法（Megafac）F-477、美佳法（Megafac）F-552、美佳法（Megafac）F-553、美佳法（Megafac）F-554、美佳法（Megafac）F-555、美佳法（Megafac）F-556、美佳法（Megafac）F-558、美佳法（Megafac）F-559、美佳法（Megafac）R-30、美佳法（Megafac）R-94、美佳法（Megafac）RS-75、美佳法（Megafac）RS-72-K、美佳法（Megafac）RS-76-NS、美佳法（Megafac）DS-21（均為商品名；迪愛生（DIC）股份有限公司）、迪高屯（TEGO Twin）4000、迪高屯（TEGO Twin）4100、迪高弗洛（TEGO Flow）370、迪高格萊德（TEGO Glide）420、迪高格萊德（TEGO Glide）440、迪高格萊德（TEGO Glide）450、迪高拉德（TEGO Rad）2200N、迪高拉德（TEGO Rad）2250N（均為商品名，日本贏創德固賽（Evonik-Degussa Japan）股份有限公司）、氟烷基苯磺酸鹽、氟烷基羧酸鹽、氟烷基聚氧乙烯醚、氟烷基碘化銨、氟烷基甜菜鹼、氟烷基磺酸鹽、二甘油四(氟烷基聚氧乙烯醚)、氟烷基三甲基銨鹽、氟烷基胺基磺酸鹽、聚氧乙烯壬基苯基醚、聚氧乙烯辛基苯基醚、聚氧乙烯烷基醚、聚氧乙烯月桂基醚、聚氧乙烯油烯基醚、聚氧乙烯十三烷基醚、聚氧乙烯鯨蠟基醚、聚氧乙烯硬脂基醚、聚氧乙烯月桂酸酯、聚氧乙烯油酸酯、聚氧乙烯硬脂酸酯、聚氧乙烯月桂基胺、山梨醇酐月桂酸酯、山梨醇酐棕櫚酸酯、山梨醇酐硬脂酸酯、山梨醇酐油酸酯、山梨醇酐脂肪酸酯、聚氧乙烯山梨醇酐月桂酸酯、聚氧乙烯山梨醇酐棕櫚酸酯、聚氧乙烯山梨醇酐硬脂酸酯、聚氧乙烯山梨醇酐油酸酯、聚氧乙烯萘基醚、烷基苯磺酸鹽、及烷基二苯基醚二磺酸鹽。優選使用選自這些化合物中的至少一種。1-7-4. Surfactant A surfactant may be added to the photosensitive composition of the present invention to improve coating uniformity. Specific examples of the surfactant include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, and Polyflow No. .90, Polyflow No.95 (both trade names; Kyoeisha Chemical Co., Ltd.), Disperbyk 161, Disperbyk 162, Diss Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Dis Disperbyk 181, Disperbyk 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346, BYK361N, BYK-UV3500, BYK-UV3570 (all product names; Japan's BYK) Chemical (BYK Chemie Japan) Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (both trade names; Shin-Etsu Chemical Industry Co., Ltd.), Shafu Surflon SC-101, Surflon KH-40, Surflon S611 (both trade names; AGC clear AGC Seimi Chemical Co., Ltd.), Ftergent 222F, Ftergent 208G, Ftergent 251, Ftergent 710FL, Ftergent 710FM, Fudge ( Ftergent 710FS, Ftergent 601AD, Ftergent 602A, Ftergent 650A, FTX-218 (both trade names; Neos Co., Ltd.), Eftop (EFTOP ) EF-351, Eftop (EFTOP) EF-352, Eftop (EFTOP) EF-601, Eftop (EFTOP) EF-801, Eftop (EFTOP) EF-802 (all are trade names; Mitsubishi Material Co., Ltd.), Megafac F-171, Megafac F-177, Megafac F-410, Megafac F-430, Megafac ( Megafac) F-444, Megafac F-472SF, Megafac F-475, Megafac F-477, Megafac F-552, Megafac F-553 , Megafac F-554, Megafac F-555, Megafac egafac) F-556, Megafac F-558, Megafac F-559, Megafac R-30, Megafac R-94, Megafac RS-75 , Megafac RS-72-K, Megafac RS-76-NS, Megafac DS-21 (both trade names; DIC Corporation), Digotun (TEGO Twin) 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGOG TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2250N (both trade names, Evonik-Degussa Japan Co., Ltd.), Fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetra (fluoroalkyl (Polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, poly Oxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oil Acid ester, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan Fatty acid esters, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl Ethers, alkylbenzene sulfonates, and alkyl diphenyl ether disulfonates. It is preferable to use at least one selected from these compounds.

這些表面活性劑中，如果是選自BYK306、BYK342、BYK346、KP-341、KP-358、KP-368、沙福隆（Surflon）S611、福吉特（Ftergent）710FL、福吉特（Ftergent）710FM、福吉特（Ftergent）710FS、福吉特（Ftergent）601AD、福吉特（Ftergent）650A、美佳法（Megafac）F-477、美佳法（Megafac）F-556、美佳法（Megafac）F-559、美佳法（Megafac）RS-72-K、美佳法（Megafac）DS-21、迪高屯（TEGO Twin）4000、氟烷基苯磺酸鹽、氟烷基羧酸鹽、氟烷基聚氧乙烯醚、氟烷基磺酸鹽、氟烷基三甲基銨鹽、及氟烷基胺基磺酸鹽中的至少一種，則感光性組成物的塗布均勻性變高，因此優選。Among these surfactants, if selected from BYK306, BYK342, BYK346, KP-341, KP-358, KP-368, Surflon S611, Ftergent 710FL, Ftergent 710FM, Fetergent 710FS, Ftergent 601AD, Ftergent 650A, Megafac F-477, Megafac F-556, Megafac F-559, Megafac (Megafac) RS-72-K, Megafac DS-21, TEGO Twin 4000, fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, At least one of a fluoroalkylsulfonic acid salt, a fluoroalkyltrimethylammonium salt, and a fluoroalkylaminosulfonic acid salt is preferable because the uniformity of application of the photosensitive composition is improved.

本發明的感光性組成物中的表面活性劑的含量優選相對於感光性組成物總量而為0.01重量%～10重量%。The content of the surfactant in the photosensitive composition of the present invention is preferably 0.01 to 10% by weight based on the total amount of the photosensitive composition.

1-7-5.偶合劑 自使所形成的硬化膜與基板的密接性進一步提高的觀點考慮，本發明的感光性組成物還可進一步含有偶合劑。1-7-5. Coupling agent From the viewpoint of further improving the adhesion between the formed cured film and the substrate, the photosensitive composition of the present invention may further contain a coupling agent.

此種偶合劑例如可使用矽烷系、鋁系或鈦酸酯系的偶合劑。具體而言可列舉：3-縮水甘油氧基丙基二甲基乙氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷（例如，商品名：薩拉艾斯（Sila-Ace）S510、捷恩智（JNC）股份有限公司）、2-(3,4-環氧環己基)乙基三甲氧基矽烷（例如，商品名：薩拉艾斯（Sila-Ace）S530、捷恩智（JNC）股份有限公司）、3-巰基丙基三甲氧基矽烷（例如，商品名：薩拉艾斯（Sila-Ace）S810、捷恩智（JNC）股份有限公司）、3-縮水甘油氧基丙基三甲氧基矽烷的共聚物（例如，商品名：考特奧斯陸（CoatOSil）MP200、邁圖高新材料（Momentive Performance Materials）合同公司）等矽烷系偶合劑，乙醯烷氧基二異丙醇鋁等鋁系偶合劑、及四異丙基雙(二辛基亞磷酸酯)鈦酸酯等鈦酸酯系偶合劑。As such a coupling agent, for example, a silane-based, aluminum-based, or titanate-based coupling agent can be used. Specific examples include 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (For example, trade name: Sila-Ace S510, JNC Co., Ltd.), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (for example, trade name : Sila-Ace S530, JNC Co., Ltd., 3-Mercaptopropyltrimethoxysilane (for example, trade name: Sila-Ace S810, Jensen (JNC) Co., Ltd.), a copolymer of 3-glycidyloxypropyltrimethoxysilane (for example, trade name: CoatOSil MP200, Momentive Performance Materials contract company), etc. Silane-based coupling agents, aluminum-based coupling agents such as aluminum acetoxy aluminum diisopropoxide, and titanate-based coupling agents such as tetraisopropylbis (dioctyl phosphite) titanate.

這些偶合劑中，3-縮水甘油氧基丙基三甲氧基矽烷由於使密接性提升的效果大而優選。Among these coupling agents, 3-glycidoxypropyltrimethoxysilane is preferred because of its large effect of improving adhesion.

偶合劑的含量相對於感光性組成物總量而為0.01重量%以上、10重量%以下，可提高所形成的硬化膜與基板的密接性，故優選。The content of the coupling agent is preferably 0.01% by weight or more and 10% by weight or less based on the total amount of the photosensitive composition, and it is preferable because the adhesion between the formed cured film and the substrate can be improved.

1-7-6.抗氧化劑 自提高透明性、防止硬化膜暴露在高溫的情況下的黃變的觀點考慮，本發明的感光性組成物還可進一步含有抗氧化劑。1-7-6. Antioxidant From the viewpoint of improving transparency and preventing yellowing of the cured film when exposed to high temperatures, the photosensitive composition of the present invention may further contain an antioxidant.

本發明的感光性組成物中還可添加受阻酚系、受阻胺系、磷系、硫系化合物等抗氧化劑。其中，自耐候性的觀點考慮，優選受阻酚系。具體例可列舉：易璐佳諾斯（Irganox）1010、易璐佳諾斯（Irganox）FF、易璐佳諾斯（Irganox）1035、易璐佳諾斯（Irganox）1035FF、易璐佳諾斯（Irganox）1076、易璐佳諾斯（Irganox）1076FD、易璐佳諾斯（Irganox）1076DWJ、易璐佳諾斯（Irganox）1098、易璐佳諾斯（Irganox）1135、易璐佳諾斯（Irganox）1330、易璐佳諾斯（Irganox）1726、易璐佳諾斯（Irganox）1425 WL、易璐佳諾斯（Irganox）1520L、易璐佳諾斯（Irganox）245、易璐佳諾斯（Irganox）245FF、易璐佳諾斯（Irganox）245DWJ、易璐佳諾斯（Irganox）259、易璐佳諾斯（Irganox）3114、易璐佳諾斯（Irganox）565、易璐佳諾斯（Irganox）565DD、易璐佳諾斯（Irganox）295（均為商品名；日本巴斯夫（BASF Japan）股份有限公司）、艾迪科斯塔波（ADK STAB）AO-20、艾迪科斯塔波（ADK STAB）AO-30、艾迪科斯塔波（ADK STAB）AO-50、艾迪科斯塔波（ADK STAB）AO-60、艾迪科斯塔波（ADK STAB）AO-70、艾迪科斯塔波（ADK STAB）AO-80（均為商品名；艾迪科（ADEKA）股份有限公司）。其中更優選易璐佳諾斯（Irganox）1010、艾迪科斯塔波（ADK STAB）AO-60。Antioxidants such as hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds may be added to the photosensitive composition of the present invention. Among them, from the viewpoint of weather resistance, a hindered phenol type is preferred. Specific examples include: Irganox 1010, Irganox FF, Irganox 1035, Irganox 1035FF, Yiluganox (Irganox) 1076, Irganox 1076FD, Irganox 1076DWJ, Irganox 1098, Irganox 1135, Ilganox (Irganox) 1330, Irganox 1726, Irganox 1425 WL, Irganox 1520L, Irganox 245, Irganox (Irganox) 245FF, Irganox (245DWJ), Irganox (259), Irganox (3114), Irganox (565), Yiluganuo (Irganox) 565DD, Irganox (295) (both trade names; BASF Japan Co., Ltd.), ADK STAB AO-20, Edko Costa (ADK STAB) AO-30, ADK STAB AO-50, ADK STAB AO-60,迪科斯塔波 (ADK STAB) AO-70, Addison Costa wave (ADK STAB) AO-80 (both trade names; manufactured by ADEKA (ADEKA) Ltd.). Among them, Irganox 1010 and ADK STAB AO-60 are more preferred.

相對於感光性組成物總量，添加0.1重量份～10重量份的抗氧化劑而使用。An antioxidant is used in an amount of 0.1 to 10 parts by weight based on the total amount of the photosensitive composition.

相對於感光性組成物總量，添加0.1重量份～20重量份的其他添加劑而使用。Based on the total amount of the photosensitive composition, 0.1 to 20 parts by weight of other additives are added and used.

1-8.感光性組成物的保存 本發明的感光性組成物如果在-30℃～25℃的範圍內保存，則組成物的經時穩定性變良好而優選。如果保存溫度是-20℃～10℃，則並無析出物而更優選。1-8. Storage of Photosensitive Composition The photosensitive composition of the present invention is preferably stored because it is stored within a range of -30 ° C to 25 ° C because the stability over time of the composition is improved. If the storage temperature is -20 ° C to 10 ° C, no precipitates are present and it is more preferable.

2.由感光性組成物所得的硬化膜 本發明的感光性組成物可通過如下方式而獲得：將聚酯醯胺酸、具有聚合性雙鍵的化合物、環氧化合物、環氧硬化劑及分子量調整劑加以混合，根據目標特性，進一步視需要而選擇性添加溶劑、偶合劑、表面活性劑、及其他添加劑，將這些化合物均勻地混合溶解。2. A hardened film obtained from a photosensitive composition The photosensitive composition of the present invention can be obtained by polyester polyester amino acid, a compound having a polymerizable double bond, an epoxy compound, an epoxy hardener, and a molecular weight. The modifier is mixed, and a solvent, a coupling agent, a surfactant, and other additives are further optionally added according to the target characteristics, and these compounds are uniformly mixed and dissolved.

如果將如上所述而製備的感光性組成物（並無溶劑的固體狀態的情況下，溶解在溶劑中之後）塗布在基體表面上，通過例如加熱等而將溶劑除去，則可形成塗膜。在基體表面塗布感光性組成物可使用旋塗法、輥塗法、浸漬法、柔版印刷法、噴霧法、及狹縫塗布法等現有公知的方法。其次，利用加熱板（hot plate）或烘箱（oven）等對該塗膜進行加熱（預烘烤）。加熱條件因各成分的種類及調配比例而異，通常在70℃～150℃下，如果使用烘箱則為5分鐘～15分鐘，如果使用加熱板則為1分鐘～5分鐘。A coating film can be formed by applying the photosensitive composition prepared as described above (in a solid state without a solvent, after dissolving in a solvent) to the surface of a substrate and removing the solvent by, for example, heating. A conventionally known method such as a spin coating method, a roll coating method, a dipping method, a flexographic printing method, a spray method, and a slit coating method can be used for coating the photosensitive composition on the substrate surface. Next, the coating film is heated (pre-baked) using a hot plate, an oven, or the like. The heating conditions vary depending on the type of each component and the blending ratio. Generally, it is 5 minutes to 15 minutes if an oven is used at 70 ° C to 150 ° C, and 1 minute to 5 minutes if a heating plate is used.

其後，介隔所期望的圖案形狀的遮罩對塗膜照射紫外線。適當的是紫外線照射量以i射線計為5 mJ/cm2 ～1000 mJ/cm2 。經紫外線照射的感光性組成物通過具有聚合性雙鍵的化合物的聚合而成為三維交聯體，在鹼性顯影液中進行不溶化。Thereafter, the coating film is irradiated with ultraviolet rays through a mask having a desired pattern shape. It is suitable that the amount of ultraviolet irradiation is 5 mJ / cm 2 to 1000 mJ / cm 2 in terms of i-rays. The photosensitive composition irradiated with ultraviolet rays becomes a three-dimensional crosslinked body by polymerization of a compound having a polymerizable double bond, and is insoluble in an alkaline developing solution.

其次，通過噴淋顯影、噴霧顯影、覆液顯影、浸漬顯影等而將塗膜浸漬於鹼性顯影液中，將不需要的部分溶解除去。鹼性顯影液的具體例為碳酸鈉、氫氧化鈉、氫氧化鉀等無機鹼類的水溶液，以及氫氧化四甲基銨、氫氧化四乙基銨等有機鹼類的水溶液。而且，也可在所述鹼性顯影液中添加適當量的甲醇、乙醇、及表面活性劑等而使用。Next, the coating film is immersed in an alkaline developing solution by spray development, spray development, coating development, dip development, or the like, and unnecessary portions are dissolved and removed. Specific examples of the alkaline developer are aqueous solutions of inorganic bases such as sodium carbonate, sodium hydroxide, and potassium hydroxide, and aqueous solutions of organic bases such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Further, an appropriate amount of methanol, ethanol, a surfactant, and the like may be added to the alkaline developing solution and used.

最後，為了使塗膜完全硬化，可通過加熱處理而獲得硬化膜，所述加熱處理是在180℃～250℃、優選200℃～250℃下，如果是烘箱則進行30分鐘～90分鐘，如果是加熱板則進行5分鐘～30分鐘。Finally, in order to completely harden the coating film, a hardened film can be obtained by heat treatment at 180 ° C to 250 ° C, preferably 200 ° C to 250 ° C, and in an oven, for 30 minutes to 90 minutes, if If it is a hot plate, it is performed for 5 to 30 minutes.

如上所述而所得的硬化膜在加熱時，進而1）聚酯醯胺酸的聚醯胺酸部分脫水環化而形成醯亞胺鍵，及2）聚酯醯胺酸的羧酸與含有環氧基的共聚物反應而高分子量化，因此非常強韌，且透明性、耐熱性、耐化學品性、平坦性、密接性、耐光性、及耐濺射性優異。因此，本發明的硬化膜如果用作彩色濾光片用的保護膜則有效，可使用該彩色濾光片來製造液晶顯示元件或固體攝像元件。而且，除了彩色濾光片用的保護膜以外，本發明的硬化膜如果用作形成在TFT與透明電極之間的透明絕緣膜或形成在透明電極與配向膜之間的透明絕緣膜則有效。進而，本發明的硬化膜即便用作LED發光體的保護膜也有效。 [實施例]When the cured film obtained as described above is further heated, 1) the polyamidic acid of the polyester pseudoamic acid is partially dehydrated and cyclized to form an imine bond, and 2) the carboxylic acid of the polyester pseudoamino acid and the ring The copolymer of an oxy group reacts and has a high molecular weight, so it is very tough, and has excellent transparency, heat resistance, chemical resistance, flatness, adhesion, light resistance, and sputtering resistance. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a liquid crystal display element or a solid-state imaging element can be manufactured using the color filter. In addition to the protective film for a color filter, the cured film of the present invention is effective if used as a transparent insulating film formed between a TFT and a transparent electrode or a transparent insulating film formed between a transparent electrode and an alignment film. Furthermore, the cured film of this invention is effective even if it is used as a protective film of LED light emitting body. [Example]

其次，通過合成例、參考例、實施例、及比較例對本發明加以具體說明，但本發明並不受這些實施例任何限定。另外，關於表1～表2中的添加劑的略稱，M-520為具有聚合性雙鍵的化合物亞羅尼斯（Aronix）M-520（商品名；東亞合成股份有限公司），NCI-930為光聚合起始劑艾迪科亞庫魯茲（ADEKA ARKLS）NCI-930（商品名；艾迪科（ADEKA）股份有限公司），VG3101L為環氧化合物泰克莫（TECHMORE）VG3101L（商品名；普林泰克（Printec）股份有限公司），EHPE3150為環氧化合物EHPE3150（商品名；大賽璐（Daicel）股份有限公司）、TMA為環氧硬化劑偏苯三甲酸酐，S510為偶合劑薩拉艾斯（Sila-Ace）S510（商品名；捷恩智（JNC）股份有限公司），AO-60為抗氧化劑艾迪科斯塔波（ADK STAB）AO-60（商品名；艾迪科（ADEKA）股份有限公司），F-556為表面活性劑美佳法（Megafac）F-556（商品名；迪愛生（DIC）股份有限公司），MMP為溶劑3-甲氧基丙酸甲酯，EDM為溶劑二乙二醇乙基甲醚，PGMEA為溶劑丙二醇單甲醚乙酸酯。Next, the present invention will be specifically described through synthesis examples, reference examples, examples, and comparative examples, but the present invention is not limited to these examples at all. In addition, regarding the abbreviations of the additives in Tables 1 to 2, M-520 is a compound having a polymerizable double bond, Aronix M-520 (trade name; Toa Synthetic Co., Ltd.), and NCI-930 is Photopolymerization initiator ADEKA ARKLS NCI-930 (trade name; ADEKA) Co., Ltd., VG3101L is epoxy compound TECHMORE VG3101L (trade name; general Lintec (Printec Co., Ltd.), EHPE3150 is the epoxy compound EHPE3150 (trade name; Daicel Co., Ltd.), TMA is the epoxy hardener trimellitic anhydride, S510 is the coupling agent Sara Eis ( Sila-Ace) S510 (Trade name; JNC Co., Ltd.), AO-60 is the antioxidant ADK STAB AO-60 (Trade name; ADEKA) Co., Ltd. ), F-556 is surfactant Megafac F-556 (trade name; DIC), MMP is methyl 3-methoxypropionate, and EDM is diethylene glycol. Alcohol ethyl methyl ether, PGMEA is a solvent of propylene glycol monomethyl ether B Ester.

VG3101L為2-[4-(2,3-環氧丙氧基)苯基]-2-[4-[1,1-雙[4-(2,3-環氧丙氧基)苯基]乙基]苯基]丙烷（分子量=593）90重量%及1,3-雙[4-[1-[4-(2,3-環氧丙氧基)苯基]-1-[4-[1-[4-(2,3-環氧丙氧基)苯基]-1-甲基乙基]苯基]乙基]苯氧基]-2-丙醇（分子量=1,129）10重量%的混合物，EHPE3150為分子式C126 H194 O33 所表示的化合物，分子量為2,237（均參照製品的安全資料表）。VG3101L is 2- [4- (2,3-glycidoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-glycidoxy) phenyl] Ethyl] phenyl] propane (molecular weight = 593) 90% by weight and 1,3-bis [4- [1- [4- (2,3-glycidyloxy) phenyl] -1- [4- [1- [4- (2,3-glycidoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol (molecular weight = 1,129) 10 weight % Mixture, EHPE3150 is a compound represented by the molecular formula C 126 H 194 O 33 , and the molecular weight is 2,237 (both refer to the product safety data sheet).

首先，如下所示地合成包含四羧酸二酐、二胺、多元羥基化合物等的反應產物的聚酯醯胺酸溶液（合成例1）。First, a polyester amidic acid solution containing a reaction product of a tetracarboxylic dianhydride, a diamine, a polyhydroxy compound, and the like was synthesized as follows (Synthesis Example 1).

[合成例1]聚酯醯胺酸（A）溶液的合成 在帶有攪拌機的四口燒瓶中，以下述重量依序裝入進行了脫水純化的PGMEA、二乙二醇乙基甲醚（以下略記為「EDM」）、4,4'-二苯基醚四羧酸二酐（以下略記為「ODPA」）、SMA1000P、1,4-丁二醇、苄醇，在乾燥氮氣流下、120℃下進行3小時攪拌。 PGMEA 504.00 g EDM 96.32 g ODPA 47.70 g SMA1000P 144.97 g 1,4-丁二醇 9.23 g 苄醇 55.40 g[Synthesis Example 1] Synthesis of Polyester Amino Acid (A) Solution A four-necked flask equipped with a stirrer was charged with PGMEA, diethylene glycol ethyl methyl ether (hereinafter, dehydrated and purified) in the following weight order. Abbreviated as "EDM"), 4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as "ODPA"), SMA1000P, 1,4-butanediol, benzyl alcohol, 120 ° C under a stream of dry nitrogen Stir for 3 hours. PGMEA 504.00 g EDM 96.32 g ODPA 47.70 g SMA1000P 144.97 g 1,4-butanediol 9.23 g benzyl alcohol 55.40 g

其後，將反應液冷卻至25℃，以下述重量投入3,3'-二胺基二苯基碸（以下略記為「DDS」）、EDM，在20℃～30℃下進行2小時攪拌後，在120℃下進行2小時攪拌。 DDS 12.72 g EDM 29.68 g [Z/Y=2.0、（Y+Z）/X=1.0]Thereafter, the reaction solution was cooled to 25 ° C, and 3,3'-diaminodiphenylphosphonium (hereinafter abbreviated as "DDS") and EDM were added at the following weights, and the mixture was stirred at 20 ° C to 30 ° C for 2 hours. Stir at 120 ° C for 2 hours. DDS 12.72 g EDM 29.68 g [Z / Y = 2.0, (Y + Z) /X=1.0]

將溶液冷卻至室溫，獲得淡黃色透明的聚酯醯胺酸（A）的30重量%溶液。對溶液的一部分進行取樣，利用GPC分析（聚苯乙烯標準）測定重量平均分子量。其結果，所得的聚酯醯胺酸（A）的重量平均分子量是21,000。The solution was cooled to room temperature to obtain a 30% by weight solution of pale yellow transparent polyester amidine (A). A part of the solution was sampled, and the weight-average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polyester amidine (A) was 21,000.

[合成例2]含有環氧基的共聚物（B-1）溶液的合成 在帶有攪拌器的四口燒瓶中，以下述重量裝入作為聚合溶劑的進行了脫水純化的MMP、作為具有環氧基的自由基聚合性化合物（a1）的甲基丙烯酸縮水甘油酯、作為其他聚合性化合物（a2）的二乙二醇二甲基丙烯酸酯（NK酯2G；商品名；新中村化學工業股份有限公司），進而以下述重量裝入作為聚合引發劑的二甲基-2,2'-偶氮雙(2-甲基丙酸酯)（V-601；商品名；和光純藥工業股份有限公司），在乾燥氮氣流下、110℃下進行2小時攪拌。 MMP 31.50 g 甲基丙烯酸縮水甘油酯 12.15 g 二乙二醇二甲基丙烯酸酯 1.35 g V-601 2.03 g[Synthesis Example 2] Synthesis of epoxy group-containing copolymer (B-1) solution A four-necked flask equipped with a stirrer was charged with the following weight as a polymerization solvent, dehydrated and purified MMP, and Glycidyl methacrylate, a radically polymerizable compound (a1) of oxy group, and diethylene glycol dimethacrylate (NK ester 2G; trade name; Shin Nakamura Chemical Industry Co., Ltd.) as another polymerizable compound (a2) Co., Ltd.), and further charged dimethyl-2,2'-azobis (2-methylpropionate) (V-601; trade name; Wako Pure Chemical Industries, Ltd.) as a polymerization initiator at the following weight. Company), and stirred at 110 ° C for 2 hours under a stream of dry nitrogen. MMP 31.50 g glycidyl methacrylate 12.15 g diethylene glycol dimethacrylate 1.35 g V-601 2.03 g

將溶液冷卻至室溫，獲得含有環氧基的共聚物（B-1）的30.0重量%溶液。對溶液的一部分進行取樣，利用GPC分析（聚苯乙烯標準）測定重量平均分子量。其結果，所得的含有環氧基的共聚物（B-1）的重量平均分子量是4,000。The solution was cooled to room temperature to obtain a 30.0% by weight solution of the epoxy group-containing copolymer (B-1). A part of the solution was sampled, and the weight-average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained epoxy group-containing copolymer (B-1) was 4,000.

[合成例3]含有環氧基的共聚物（B-2）溶液的合成 在帶有攪拌器的四口燒瓶中，以下述重量裝入作為聚合溶劑的進行了脫水純化的MMP、作為具有環氧基的自由基聚合性化合物（a1）的甲基丙烯酸縮水甘油酯、作為其他聚合性化合物（a2）的二乙二醇二甲基丙烯酸酯（NK酯2G；商品名；新中村化學工業股份有限公司），進而以下述重量裝入作為聚合引發劑的二甲基-2,2'-偶氮雙(2-甲基丙酸酯)（V-601；商品名；和光純藥工業股份有限公司），在乾燥氮氣流下、90℃下進行2小時攪拌。 MMP 31.50 g 甲基丙烯酸縮水甘油酯 12.15 g 二乙二醇二甲基丙烯酸酯 1.35 g V-601 0.68 g[Synthesis Example 3] Synthesis of epoxy group-containing copolymer (B-2) solution A four-necked flask equipped with a stirrer was charged with the following weight as a polymerization solvent, dehydrated and purified MMP, and Glycidyl methacrylate, a radically polymerizable compound (a1) of oxy group, and diethylene glycol dimethacrylate (NK ester 2G; trade name; Shin Nakamura Chemical Industry Co., Ltd.) as another polymerizable compound (a2) Co., Ltd.), and further charged dimethyl-2,2'-azobis (2-methylpropionate) (V-601; trade name; Wako Pure Chemical Industries, Ltd.) as a polymerization initiator at the following weight. Company), and stirred under a dry nitrogen stream at 90 ° C for 2 hours. MMP 31.50 g glycidyl methacrylate 12.15 g diethylene glycol dimethacrylate 1.35 g V-601 0.68 g

將溶液冷卻至室溫，獲得含有環氧基的共聚物（B-2）的30.0重量%溶液。對溶液的一部分進行取樣，利用GPC分析（聚苯乙烯標準）測定重量平均分子量。其結果，所得的含有環氧基的共聚物（B-2）的重量平均分子量是10,000。The solution was cooled to room temperature to obtain a 30.0% by weight solution of the epoxy group-containing copolymer (B-2). A part of the solution was sampled, and the weight-average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight-average molecular weight of the obtained epoxy group-containing copolymer (B-2) was 10,000.

[合成例4]含有環氧基的共聚物（B-3）溶液的合成 在帶有攪拌器的四口燒瓶中，以下述重量裝入作為聚合溶劑的進行了脫水純化的MMP、作為具有環氧基的自由基聚合性化合物（a1）的甲基丙烯酸縮水甘油酯、作為其他聚合性化合物（a2）的1,4-丁二醇二甲基丙烯酸酯，進而以下述重量裝入作為聚合引發劑的二甲基-2,2'-偶氮雙(2-甲基丙酸酯)（V-601；商品名；和光純藥工業股份有限公司），在乾燥氮氣流下、110℃下進行2小時攪拌。 MMP 31.50 g 甲基丙烯酸縮水甘油酯 12.15 g 1,4-丁二醇二甲基丙烯酸酯 1.35 g V-601 2.03 g[Synthesis Example 4] Synthesis of epoxy group-containing copolymer (B-3) solution In a four-necked flask equipped with a stirrer, dehydration-purified MMP as a polymerization solvent was charged at the following weight as A glycidyl methacrylate of a radically polymerizable compound (a1) of oxy group and 1,4-butanediol dimethacrylate as another polymerizable compound (a2) are further charged in the following weight as a polymerization initiator Agent dimethyl-2,2'-azobis (2-methylpropionate) (V-601; trade name; Wako Pure Chemical Industries, Ltd.), under a dry nitrogen stream at 110 ° C for 2 Stir for hours. MMP 31.50 g glycidyl methacrylate 12.15 g 1,4-butanediol dimethacrylate 1.35 g V-601 2.03 g

將溶液冷卻至室溫，獲得含有環氧基的共聚物（B-3）的30.0重量%溶液。對溶液的一部分進行取樣，利用GPC分析（聚苯乙烯標準）測定重量平均分子量。其結果，所得的含有環氧基的共聚物（B-3）的重量平均分子量是4,200。The solution was cooled to room temperature to obtain a 30.0% by weight solution of the epoxy group-containing copolymer (B-3). A part of the solution was sampled, and the weight-average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight-average molecular weight of the obtained epoxy-group-containing copolymer (B-3) was 4,200.

[合成例5]含有環氧基的共聚物（B-4）溶液的合成 在帶有攪拌器的四口燒瓶中，以下述重量裝入作為聚合溶劑的進行了脫水純化的MMP、作為具有環氧基的自由基聚合性化合物（a1）的甲基丙烯酸縮水甘油酯、作為其他聚合性化合物（a2）的二乙二醇二甲基丙烯酸酯，進而以下述重量裝入作為聚合引發劑的二甲基-2,2'-偶氮雙(2-甲基丙酸酯)（V-601；商品名；和光純藥工業股份有限公司），在乾燥氮氣流下、130℃下進行2小時攪拌。 MMP 31.50 g 甲基丙烯酸縮水甘油酯 12.15 g 二乙二醇二甲基丙烯酸酯 1.35 g V-601 2.03 g[Synthesis Example 5] Synthesis of epoxy group-containing copolymer (B-4) solution A four-necked flask equipped with a stirrer was charged with the following weight as a polymerization solvent, dehydrated and purified MMP, and An oxy radical polymerizable compound (a1) of glycidyl methacrylate and diethylene glycol dimethacrylate as another polymerizable compound (a2) are further charged in the following weight as a polymerization initiator. Methyl-2,2'-azobis (2-methylpropionate) (V-601; trade name; Wako Pure Chemical Industries, Ltd.) was stirred under a stream of dry nitrogen at 130 ° C for 2 hours. MMP 31.50 g glycidyl methacrylate 12.15 g diethylene glycol dimethacrylate 1.35 g V-601 2.03 g

將溶液冷卻至室溫，獲得含有環氧基的共聚物（B-4）的30.0重量%溶液。對溶液的一部分進行取樣，利用GPC分析（聚苯乙烯標準）測定重量平均分子量。其結果，所得的含有環氧基的共聚物（B-4）的重量平均分子量是2,000。The solution was cooled to room temperature to obtain a 30.0% by weight solution of the epoxy group-containing copolymer (B-4). A part of the solution was sampled, and the weight-average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained epoxy group-containing copolymer (B-4) was 2,000.

[實施例1] 對帶有攪拌翼的1000 ml的可分離式燒瓶進行氮氣置換，在該燒瓶中裝入40.00 g的合成例1中所得的聚酯醯胺酸（A）溶液、12.00 g的作為具有聚合性雙鍵的化合物的M-520、0.96 g的作為光聚合起始劑的NCI-930、48.00 g的作為環氧化合物的含有環氧基的共聚物（B-1）、3.24 g的作為環氧硬化劑的偏苯三甲酸酐（以下略記為「TMA」）、1.92 g的作為添加劑的3-縮水甘油氧基丙基三甲氧基矽烷（例如，商品名：薩拉艾斯（Sila-Ace）S510、捷恩智（JNC）股份有限公司）、0.12 g的NT-200（商品名；東洋合成工業股份有限公司）、及0.20 g的艾迪科斯塔波（ADK STAB）AO-60（商品名；艾迪科（ADEKA）股份有限公司）、18.8 g的作為溶劑的進行了脫水純化的MMP、15.4 g的EDM、及9.0 g的PGMEA，在室溫下進行3 hr攪拌，使其均勻地溶解。其次，投入0.06 g的美佳法（Megafac）F-556（商品名；迪愛生（DIC）股份有限公司），在室溫下進行1小時攪拌，利用膜濾器（0.2 μm）進行過濾而製備感光性組成物。[Example 1] A 1000 ml separable flask equipped with a stirring blade was purged with nitrogen, and 40.00 g of the polyester amidine (A) solution obtained in Synthesis Example 1 and 12.00 g of the M-520 as a compound having a polymerizable double bond, 0.96 g of NCI-930 as a photopolymerization initiator, 48.00 g of epoxy-group-containing copolymer (B-1) as an epoxy compound, 3.24 g Of trimellitic anhydride (hereinafter referred to as "TMA") as an epoxy hardener, and 1.92 g of 3-glycidoxypropyltrimethoxysilane as an additive (for example, trade name: Sila -Ace) S510, JNC (JNC) Co., Ltd., 0.12 g of NT-200 (trade name; Toyo Kogyo Co., Ltd.), and 0.20 g of ADK STAB AO-60 ( Trade name; ADEKA Co., Ltd.), 18.8 g of dehydrated and purified MMP, 15.4 g of EDM, and 9.0 g of PGMEA, stirred at room temperature for 3 hr to make uniform To dissolve. Next, put 0.06 g of Megafac F-556 (trade name; DIC) Co., Ltd., stir at room temperature for 1 hour, and filter with a membrane filter (0.2 μm) to prepare photosensitivity.组合 物。 Composition.

以900 rpm歷時10秒將該感光性組成物旋塗於玻璃基板上，在80℃的加熱板上進行2分鐘預烘烤。其次，在空氣中，使用接近式曝光機TME-150PRC（商品名；拓普康（Topcon）股份有限公司），並進行曝光。曝光量是利用累計光量計UIT-102（商品名；牛尾（USHIO）股份有限公司）、光接收器UVD-365PD（商品名；牛尾（USHIO）股份有限公司）進行測定而設為30 mJ/cm2 。使用25℃的氫氧化鉀水溶液對曝光後的塗膜進行1分鐘的覆液顯影後，利用純水將塗膜清洗20秒後，利用100℃的加熱板進行2分鐘乾燥。進而以230℃進行30分鐘後烘烤，獲得膜厚為1.5 μm的帶有硬化膜的玻璃基板。This photosensitive composition was spin-coated on a glass substrate at 900 rpm for 10 seconds, and pre-baked on a hot plate at 80 ° C for 2 minutes. Next, exposure was performed in the air using a proximity exposure machine TME-150PRC (trade name; Topcon Co., Ltd.). The exposure amount was measured using a cumulative light meter UIT-102 (trade name; Ushio (USHIO) Co., Ltd.) and a light receiver UVD-365PD (trade name; Ushio (USHIO) Co., Ltd.) to measure 30 mJ / cm 2 . The exposed coating film was subjected to liquid-covering development using a 25 ° C potassium hydroxide aqueous solution for 1 minute, and then the coating film was washed with pure water for 20 seconds, and then dried on a hot plate at 100 ° C for 2 minutes. After further baking at 230 ° C. for 30 minutes, a glass substrate with a cured film having a film thickness of 1.5 μm was obtained.

關於如上所述而獲得的硬化膜，針對顯影後殘膜率、耐熱性、耐溶劑性、透明性、解析性、及平坦性而評價特性。With respect to the cured film obtained as described above, characteristics were evaluated with respect to the residual film rate, heat resistance, solvent resistance, transparency, resolution, and flatness after development.

[顯影後殘膜率的評價方法] 使用階差·表面粗糙度·微細形狀測定裝置（商品名：P-16、科磊（KLA TENCOR）股份有限公司）測定顯影前膜厚及顯影後膜厚，利用下述計算式而算出殘膜率。將顯影後的殘膜率為80%以上的情況評價為○，將顯影後的殘膜率不足80%的情況評價為×。 顯影後的殘膜率=（顯影後的膜厚/顯影前的膜厚）×100[Evaluation method of residual film rate after development] Measurement of film thickness before and after development using a step, surface roughness, and fine shape measuring device (trade name: P-16, KLA TENCOR Co., Ltd.) The residual film rate was calculated using the following calculation formula. A case where the residual film rate after development was 80% or more was evaluated as ○, and a case where the residual film rate after development was less than 80% was evaluated as x. Residual film rate after development = (film thickness after development / film thickness before development) × 100

[耐熱性的評價方法] 將所得的帶有硬化膜的玻璃基板在230℃下進行1小時的再加熱後，測定加熱前的膜厚及加熱後的膜厚，利用下述計算式而算出殘膜率。膜厚的測定使用P-16。將加熱後的殘膜率為95%以上的情況評價為○，將加熱後的殘膜率不足95%的情況評價為×。 殘膜率=（加熱後的膜厚/加熱前的膜厚）×100[Evaluation method of heat resistance] After the obtained glass substrate with a cured film was reheated at 230 ° C for 1 hour, the film thickness before heating and the film thickness after heating were measured, and the residual was calculated using the following calculation formula. Film rate. The film thickness was measured using P-16. A case where the residual film rate after heating was 95% or more was evaluated as ○, and a case where the residual film rate after heating was less than 95% was evaluated as x. Residual film rate = (film thickness after heating / film thickness before heating) × 100

[透明性的評價方法] 在所得的帶有硬化膜的玻璃基板中，利用紫外可見近紅外分光光度計（商品名：V-670、日本分光股份有限公司）測定僅僅硬化膜的波長為400 nm的光下的透射率。將透射率為95%以上的情況評價為○，將不足95%的情況評價為×。[Evaluation method of transparency] In the obtained glass substrate with a cured film, the wavelength of only the cured film was measured with an ultraviolet-visible near-infrared spectrophotometer (trade name: V-670, Japan Spectroscopy Corporation) to be 400 nm Transmittance of light. A case where the transmittance was 95% or more was evaluated as ○, and a case where the transmittance was less than 95% was evaluated as ×.

[耐溶劑性的評價方法] 將所得的帶有硬化膜的玻璃基板在50℃的N-甲基吡咯烷酮（N-Methyl Pyrrolidone，NMP）中浸漬30分鐘後，測定浸漬前的膜厚及浸漬後的膜厚，利用下述計算式而算出膨潤率。膜厚的測定使用P-16。將NMP浸漬後的膨潤率不足5%的情況評價為○，將NMP浸漬後的膨潤率為5%以上的情況評價為×。 膨潤率=｛（NMP浸漬後的膜厚-NMP浸漬前的膜厚）/NMP浸漬前的膜厚｝×100[Evaluation method of solvent resistance] The obtained glass substrate with a cured film was immersed in N-Methyl Pyrrolidone (NMP) at 50 ° C for 30 minutes, and the film thickness before immersion and after immersion were measured. The film thickness is calculated by the following calculation formula. The film thickness was measured using P-16. A case where the swelling ratio after NMP immersion was less than 5% was evaluated as ○, and a case where the swelling ratio after NMP immersion was 5% or more was evaluated as ×. Swelling ratio = ｛(film thickness after NMP immersion-film thickness before NMP immersion) / film thickness before NMP immersion｝ 100

[解析性評價用基板的製作] 其次，以900 rpm歷時10秒將感光性組成物旋塗於玻璃基板上，在80℃的加熱板上進行2分鐘預烘烤。其次，在空氣中，介隔寬為50 μm的具有孔及線圖案的遮罩，使用接近式曝光機TME-150PRC以曝光間隙100 μm進行曝光。曝光量是利用累計光量計UIT-102、光接收器UVD-365PD進行測定而設為30 mJ/cm2 。使用氫氧化鉀水溶液在25℃下對曝光後的塗膜進行1分鐘的覆液顯影，將未曝光部除去。利用純水將顯影後的塗膜清洗20秒後，利用100℃的加熱板進行2分鐘乾燥。進而在烘箱中以230℃進行30分鐘後烘烤，獲得帶有膜厚為1.5 μm的圖案狀硬化膜的玻璃基板。[Preparation of a substrate for analytical evaluation] Next, a photosensitive composition was spin-coated on a glass substrate at 900 rpm for 10 seconds, and pre-baked on a hot plate at 80 ° C for 2 minutes. Next, in the air, a mask with holes and line patterns with a width of 50 μm was used to perform exposure using a proximity exposure machine TME-150PRC with an exposure gap of 100 μm. The exposure amount was measured using a cumulative light meter UIT-102 and a light receiver UVD-365PD, and was set to 30 mJ / cm 2 . The coating film after exposure was subjected to liquid-cover development using a potassium hydroxide aqueous solution at 25 ° C. for 1 minute, and the unexposed portion was removed. The developed coating film was washed with pure water for 20 seconds, and then dried on a hot plate at 100 ° C. for 2 minutes. After further baking in an oven at 230 ° C. for 30 minutes, a glass substrate with a pattern-shaped cured film having a film thickness of 1.5 μm was obtained.

關於如上所述而獲得的硬化膜，針對解析性而評價特性。With respect to the cured film obtained as described above, the characteristics were evaluated for resolvability.

[解析性的評價方法] 利用1,000倍的光學顯微鏡對所得的帶有圖案狀硬化膜的玻璃基板進行觀察，並評價與遮罩尺寸50 μm寬相對應的孔及線圖案的解析性。將孔及線圖案經解析的情況評價為「○」，將未解析的情況評價為「×」。[Analytical Evaluation Method] The obtained glass substrate with a patterned cured film was observed with a 1,000-fold optical microscope, and the resolvability of holes and line patterns corresponding to a mask size of 50 μm was evaluated. The case where the hole and the line pattern were analyzed was evaluated as "○", and the case where the pattern was not analyzed was evaluated as "×".

[平坦性評價用基板的製作] 其次，以900 rpm歷時10秒將感光性組成物旋塗於使用最大階差約0.8 μm的樹脂黑色矩陣的顏料分散彩色濾光片（以下略記為CF）基板上，在80℃的加熱板上進行2分鐘預烘烤。其次，使用接近式曝光機TME-150PRC（商品名；拓普康（Topcon）股份有限公司）進行曝光。曝光量是利用累計光量計UIT-102（商品名；牛尾（USHIO）股份有限公司）、光接收器UVD-365PD（商品名；牛尾（USHIO）股份有限公司）進行測定而設為30 mJ/cm2 。使用氫氧化鉀水溶液在25℃下對曝光後的塗膜進行1分鐘的覆液顯影後，利用純水將塗膜清洗20秒後，利用100℃的加熱板進行2分鐘乾燥。進而在烘箱中以230℃進行30分鐘後烘烤，獲得帶有膜厚為1.5 μm的硬化膜的CF。[Production of substrate for flatness evaluation] Next, a photosensitive composition was spin-coated on a pigment-dispersed color filter (hereinafter abbreviated as CF) substrate using a resin black matrix with a maximum step difference of about 0.8 μm at 900 rpm for 10 seconds. On a hot plate at 80 ° C. for 2 minutes. Next, exposure was performed using a proximity exposure machine TME-150PRC (trade name; Topcon Co., Ltd.). The exposure amount was measured using a cumulative light meter UIT-102 (trade name; Ushio (USHIO) Co., Ltd.) and a light receiver UVD-365PD (trade name; Ushio (USHIO) Co., Ltd.) to measure 30 mJ / cm 2 . After the exposed coating film was subjected to liquid-cover development using a potassium hydroxide aqueous solution at 25 ° C for 1 minute, the coating film was washed with pure water for 20 seconds, and then dried on a hot plate at 100 ° C for 2 minutes. Further, it was post-baked at 230 ° C. for 30 minutes in an oven to obtain CF with a cured film having a film thickness of 1.5 μm.

關於如上所述而獲得的硬化膜，針對平坦性而評價特性。The cured film obtained as described above was evaluated for its flatness.

[平坦性的評價方法] 使用階差·表面粗糙度·微細形狀測定裝置（商品名：P-16、科磊（KLA TENCOR）股份有限公司）測定所得的帶有硬化膜的彩色濾光片基板的硬化膜表面的階差。將包含黑色矩陣的R、G、B畫素間的階差的最大值（以下略記為最大階差）不足0.16 μm的情況評價為○，將0.16 μm以上的情況評價為×。[Evaluation method of flatness] The color filter substrate with a cured film was measured using a step, surface roughness, and fine shape measuring device (trade name: P-16, KLA TENCOR Co., Ltd.) The step of the hardened film surface. A case where the maximum value of the step difference between R, G, and B pixels including the black matrix (hereinafter referred to as the maximum step difference) is less than 0.16 μm is evaluated as ○, and a case where the maximum value is 0.16 μm or more is evaluated as ×.

[實施例2～實施例3] 依照實施例1的方法，以表1中所記載的比例（單位：g）將各成分混合溶解而獲得感光性組成物。[Example 2 to Example 3] According to the method of Example 1, each component was mixed and dissolved at the ratio (unit: g) shown in Table 1 to obtain a photosensitive composition.

表1 Table 1

[比較例1～比較例3] 依據實施例1的方法，以表2的比例（單位：g）將各成分混合溶解而獲得感光性組成物。 表2 [Comparative Example 1 to Comparative Example 3] According to the method of Example 1, each component was mixed and dissolved at the ratio (unit: g) in Table 2 to obtain a photosensitive composition. Table 2

以下，將實施例1～實施例3的硬化膜的評價結果分別匯總記載於表3中，將比較例1～比較例3的硬化膜的評價結果分別匯總記載於表4中。 表3 Hereinafter, the evaluation results of the cured films of Examples 1 to 3 are collectively described in Table 3, and the evaluation results of the cured films of Comparative Examples 1 to 3 are collectively described in Table 4. table 3

表4 Table 4

根據表3～表4所示的結果而明確般，可知：實施例1～實施例3的硬化膜的耐熱性、透明性、耐溶劑性優異，進而在包含顯影後殘膜率及解析性的所有方面取得平衡。另一方面，比較例1～比較例3的硬化膜的各評價項目並非均為「○」。比較例1～比較例3的硬化膜的耐溶劑性及顯影後殘膜率差。如上所述，在使用如下聚酯醯胺酸，環氧化合物的分子量為本發明的範圍內的情況下，可滿足所有特性，所述聚酯醯胺酸是通過以四羧酸二酐、二胺及多元羥基化合物為必需的原料成分進行反應而獲得。 [產業上的可利用性]As is clear from the results shown in Tables 3 to 4, it is understood that the cured films of Examples 1 to 3 are excellent in heat resistance, transparency, and solvent resistance, and further include a residual film rate and resolution after development. All aspects are balanced. On the other hand, each of the evaluation items of the cured films of Comparative Examples 1 to 3 is not all "○". The cured films of Comparative Examples 1 to 3 were inferior in solvent resistance and residual film rate after development. As described above, when the following polyester amidate is used and the molecular weight of the epoxy compound is within the range of the present invention, all the characteristics can be satisfied. The polyester amidate is obtained by using tetracarboxylic dianhydride, An amine and a polyhydroxy compound are obtained by reacting as essential raw material components. [Industrial availability]

由本發明的感光性組成物所得的硬化膜的耐溶劑性、耐熱性、透明性、平坦性及解析性等作為光學材料的特性均優異，自此方面考慮，可用作彩色濾光片、LED發光元件及光接收元件等的各種光學材料等的保護膜、以及形成在TFT與透明電極之間及透明電極與配向膜之間的透明絕緣膜。The cured film obtained from the photosensitive composition of the present invention has excellent properties such as solvent resistance, heat resistance, transparency, flatness, and resolution as optical materials. From this aspect, it can be used as a color filter and LED. A protective film of various optical materials such as a light emitting element and a light receiving element, and a transparent insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

無no

無。no.

Claims (13)

一種感光性組成物，其是包含聚酯醯胺酸、具有聚合性雙鍵的化合物、光聚合起始劑、環氧化合物、環氧硬化劑的感光性組成物；所述感光性組成物的特徵在於： 所述聚酯醯胺酸是通過使X莫耳的四羧酸二酐、Y莫耳的二胺及Z莫耳的多元羥基化合物以下述式（1）及式（2）的關係成立的比率進行反應而獲得，具有下述式（3）所表示的結構單元及式（4）所表示的結構單元； 所述具有聚合性雙鍵的化合物在每一分子中包含兩個以上的聚合性雙鍵； 所述環氧化合物的重量平均分子量是3,000以上； 相對於所述聚酯醯胺酸100重量份，所述具有聚合性雙鍵的化合物的總量為20重量份～300重量份，所述環氧化合物的總量為20重量份～200重量份，且所述光聚合起始劑的總量為1重量份～60重量份； 0.2≦Z/Y≦8.0 ·······（1） 0.2≦（Y+Z）/X≦5.0 ···（2）在式（3）及式（4）中，R1 是自四羧酸二酐除去兩個-CO-O-CO-而成的殘基，R2 是自二胺除去兩個-NH2 而成的殘基，R3 是自多元羥基化合物除去兩個-OH而成的殘基。A photosensitive composition comprising a polyester sulfamic acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, and an epoxy hardener; The polyester amidate is characterized in that the X-Mole tetracarboxylic dianhydride, the Y-Mole diamine, and the Z-Mole polyhydroxy compound are related by the following formulae (1) and (2): It is obtained by reacting at a established ratio, and has a structural unit represented by the following formula (3) and a structural unit represented by the formula (4); The compound having a polymerizable double bond includes two or more in each molecule. Polymerizable double bond; the weight average molecular weight of the epoxy compound is 3,000 or more; the total amount of the compound having a polymerizable double bond is 20 parts by weight to 300 weight based on 100 parts by weight of the polyester amidine Parts, the total amount of the epoxy compound is 20 parts by weight to 200 parts by weight, and the total amount of the photopolymerization initiator is 1 part by weight to 60 parts by weight; 0.2 ≦ Z / Y ≦ 8.0 ····· (1) 0.2 ≦ (Y + Z) /X≦5.0 (2) In formulas (3) and (4), R 1 is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, and R 2 is obtained by removing two -NH 2 from a diamine. R 3 is a residue formed by removing two -OH groups from a polyhydroxy compound. 如申請專利範圍第1項所述的感光性組成物，其中所述聚酯醯胺酸的原料成分進一步包含單羥基化合物。The photosensitive composition according to item 1 of the scope of patent application, wherein a raw material component of the polyester amidate further comprises a monohydroxy compound. 如申請專利範圍第2項所述的感光性組成物，其中所述單羥基化合物是選自異丙醇、烯丙醇、苄醇、甲基丙烯酸羥基乙酯、丙二醇單***、及3-乙基-3-羥基甲基氧雜環丁烷中的一種以上。The photosensitive composition according to item 2 of the scope of patent application, wherein the monohydroxy compound is selected from the group consisting of isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl One or more of the methyl-3-hydroxymethyloxetane. 如申請專利範圍第1項至第3項中任一項所述的感光性組成物，其中所述聚酯醯胺酸的重量平均分子量是1,000～200,000。The photosensitive composition according to any one of claims 1 to 3, wherein the weight average molecular weight of the polyester amidine is 1,000 to 200,000. 如申請專利範圍第1項至第4項中任一項所述的感光性組成物，其中所述四羧酸二酐是選自3,3',4,4'-二苯基碸四羧酸二酐、3,3',4,4'-二苯基醚四羧酸二酐、2,2-[雙(3,4-二羧基苯基)]六氟丙烷二酐、1,2,3,4-丁烷四羧酸二酐、及乙二醇雙(脫水偏苯三酸酯)中的一種以上； 所述二胺是選自3,3'-二胺基二苯基碸及雙[4-(3-胺基苯氧基)苯基]碸中的一種以上； 所述多元羥基化合物是選自乙二醇、丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、2,2-雙(4-羥基環己基)丙烷、4,4'-二羥基二環己基及異三聚氰酸三(2-羥基乙基)酯中的一種以上； 相對於所述具有聚合性雙鍵的化合物的總重量，所述具有聚合性雙鍵的化合物含有50重量%以上的選自二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇三丙烯酸酯、異三聚氰酸環氧乙烷改性三丙烯酸酯及多元酸改性(甲基)丙烯酸寡聚物中的一種以上； 所述光聚合起始劑是選自α-胺基苯烷基酮系、醯基膦氧化物系、肟酯系光聚合起始劑中的一種以上； 所述環氧化合物是通過以(甲基)丙烯酸縮水甘油酯與2官能(甲基)丙烯酸酯為必需的原料成分進行反應而獲得的含有環氧基的共聚物；而且， 所述環氧硬化劑是選自偏苯三甲酸酐、六氫偏苯三甲酸酐及2-十一烷基咪唑中的一種以上。The photosensitive composition according to any one of claims 1 to 4, wherein the tetracarboxylic dianhydride is selected from 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic acid Acid dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2 1,3,4-butanetetracarboxylic dianhydride, and ethylene glycol bis (anhydrotrimellitate); the diamine is selected from 3,3'-diaminodiphenylsulfonium And one or more of bis [4- (3-aminophenoxy) phenyl] fluorene; the polyhydroxy compound is selected from ethylene glycol, propylene glycol, 1,4-butanediol, and 1,5-pentane Diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxybicyclo One or more of hexyl and tris (2-hydroxyethyl) isocyanurate; the compound having a polymerizable double bond contains 50% by weight or more of the total weight of the compound having a polymerizable double bond Selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ethylene isocyanate modified ethylene oxide One or more of a triacrylate and a polyacid-modified (meth) acrylic oligomer; the photopolymerization initiator is selected from the group consisting of an α-aminobenzoyl ketone system, a fluorenyl phosphine oxide system, and an oxime ester One or more of the photopolymerization initiators; the epoxy compound is an epoxy group-containing compound obtained by reacting glycidyl (meth) acrylate and a bifunctional (meth) acrylate as an essential raw material component In addition, the epoxy hardener is one or more selected from the group consisting of trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-undecylimidazole. 如申請專利範圍第5項所述的感光性組成物，其中所述四羧酸二酐是選自3,3',4,4'-二苯基醚四羧酸二酐及1,2,3,4-丁烷四羧酸二酐中的一種以上； 所述二胺是3,3'-二胺基二苯基碸； 所述多元羥基化合物是1,4-丁二醇； 所述單羥基化合物是苄醇； 所述具有聚合性雙鍵的化合物是選自二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯及多元酸改性(甲基)丙烯酸寡聚物中的一種以上； 所述2官能(甲基)丙烯酸酯是選自乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯中的一種以上； 相對於所述光聚合起始劑的總重量，所述光聚合起始劑含有50重量%以上的選自1,2-辛二酮,1-[4-(苯硫基)苯基]-2-(O-苯甲醯基肟)、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-哢唑-3-基]-1-(O-乙醯基肟)及1,2-丙二酮,1-[4-[4-(2-羥基乙氧基)苯硫基]苯基]-2-(O-乙醯基肟)中的一種以上； 所述環氧硬化劑是選自偏苯三甲酸酐及2-十一烷基咪唑中的一種以上；而且 進一步含有選自3-甲氧基丙酸甲酯及丙二醇單甲醚乙酸酯中的一種以上作為溶劑。The photosensitive composition according to item 5 of the scope of patent application, wherein the tetracarboxylic dianhydride is selected from 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride and 1,2, One or more of 3,4-butanetetracarboxylic dianhydride; the diamine is 3,3'-diaminodiphenylphosphonium; the polyhydroxy compound is 1,4-butanediol; the The monohydroxy compound is benzyl alcohol; the compound having a polymerizable double bond is one or more selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polyacid-modified (meth) acrylic acid oligomers; said The bifunctional (meth) acrylate is selected from ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1 One or more of 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate; with respect to the photopolymerization The total weight of the initiator, the photopolymerization initiator contains more than 50% by weight selected from 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzene (Formamyl oxime), ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H- Azol-3-yl] -1- (O-ethylammonium oxime) and 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl]- One or more of 2- (O-acetamidooxime); the epoxy hardener is one or more selected from trimellitic anhydride and 2-undecylimidazole; and further contains 3-methoxy One or more of methyl propionate and propylene glycol monomethyl ether acetate are used as a solvent. 一種硬化膜，其特徵在於：其是由如申請專利範圍第1項至第6項中任一項所述的感光性組成物而獲得。A cured film obtained from the photosensitive composition according to any one of claims 1 to 6 of the scope of patent application. 一種彩色濾光片，其特徵在於：其使用如申請專利範圍第7項所述的硬化膜作為保護膜。A color filter is characterized in that it uses a cured film as described in item 7 of the scope of patent application as a protective film. 一種顯示元件，其特徵在於：其使用如申請專利範圍第8項所述的彩色濾光片。A display element is characterized in that it uses a color filter as described in item 8 of the scope of patent application. 一種固體攝像元件，其特徵在於：其使用如申請專利範圍第8項所述的彩色濾光片。A solid-state imaging element, characterized in that it uses a color filter as described in item 8 of the patent application scope. 一種顯示元件，其特徵在於：其使用如申請專利範圍第7項所述的硬化膜作為形成在薄膜電晶體與透明電極之間的透明絕緣膜。A display element is characterized in that it uses a cured film as described in item 7 of the scope of patent application as a transparent insulating film formed between a thin film transistor and a transparent electrode. 一種顯示元件，其特徵在於：其使用如申請專利範圍第7項所述的硬化膜作為形成在透明電極與配向膜之間的透明絕緣膜。A display element is characterized in that it uses a cured film as described in item 7 of the scope of patent application as a transparent insulating film formed between a transparent electrode and an alignment film. 一種發光二極體發光體，其特徵在於：其使用如申請專利範圍第7項所述的硬化膜作為保護膜。A light-emitting diode light-emitting body is characterized in that it uses a cured film as described in item 7 of the scope of patent application as a protective film.
TW106131543A 2017-01-23 2017-09-14 Photosensitive composition and use thereof capable of forming a cured film excellent in transparency, heat resistance, solvent resistance, flatness, and resolution TW201827925A (en)

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