TW201214044A - Black photosensitive resin composition and black matrix using the same - Google Patents
Black photosensitive resin composition and black matrix using the same Download PDFInfo
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- TW201214044A TW201214044A TW099145202A TW99145202A TW201214044A TW 201214044 A TW201214044 A TW 201214044A TW 099145202 A TW099145202 A TW 099145202A TW 99145202 A TW99145202 A TW 99145202A TW 201214044 A TW201214044 A TW 201214044A
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- G—PHYSICS
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
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- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- 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
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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Abstract
Description
201214044 六、發明說明： 【發明所屬之技術領域3 發明領域 本揭示係有關於一種黑色光敏性樹脂組成物以及使用 該組成物的遮光層。 r:先前技術】 發明背景 必需使用一種黑色光敏性樹脂組成物以製造一濾色片 的一顯示元件、一液晶顯示材料、一有機發光元件(EL)、 一顯示面板材料’及類似物。舉例而言，一渡色片（例如一 彩色液晶顯示器及類似物）需要一遮光層於彩色層（例如：紅 的、綠的、藍的，及類似物）之間的邊界上，以提升顯示對 比或顏色效應。此遮光層可以主要地由一種黑色光敏性樹 脂組成物所形成。 揭示了有關於黑色光敏性樹脂組成物之許多的專利。 曰本專利早期公開案第2002-047423號揭示了氧化鈷作為 一黑色色素來實現了具高的黑度與絕緣性質之一黑色矩 陣。此外，曰本專利早期公開案第2〇〇7 〇71994號使用包括 一茈為主的化合物之黑色矩陣材料。 近來對於-黑色矩陣材料的研究集中於增加光學密度 (OD)向上至最大值，但是減少_黑色矩陣膜的厚度使對平 度的損傷制最少，由於高_厚度，以及因而，在沒有 一保護膜的情況下確保液晶的滴注邊限。 【明内效3 201214044 發明概要 本發明的一態樣提供了一種黑色光敏性樹脂組成物， 其具有高的光學密度在沒有損害一製程的情況下、優良的 圖案化性質與解析度，以及低的介電常數。 本發明的另一態樣提供了一遮光層，其係藉由使用該 黑色光敏性樹脂組成物來製備的。 根據本發明的一態樣，提供了一種黑色光敏性樹脂組 成物，其包括(A)—有機黏結劑樹脂；（B)—反應性不飽和化 合物；（C)一光聚合化起始劑；（D)包括碳黑及一含銀錫合金 之黑色色素；以及(E)—溶劑，其中該含銀錫合金包括銀和 錫以6:4至8:2的重量比。 該碳黑及該含銀錫合金可以以1:9至9:1的重量比被包 括。 該黑色光敏性樹脂組成物可以包括0.5至20 wt%的該 有機黏結劑樹脂(A); 1至20 wt%的該反應性不飽和化合物 (B); 0.1至10 wt%的該聚合化起始劑（C) ; 1至40 wt%的包括 碳黑及一含銀錫合金之該黑色色素(D);以及差額的該溶劑 ⑻。 該有機黏結劑樹脂可以包括一β卡B朵為主之(cardo-based) 黏結劑樹脂以及該咔哚為主之黏結劑樹脂可以為含有由下 列化學式1表示的一重覆單元之一化合物。 [化學式1] 201214044201214044 VI. Description of the Invention: [Technical Field 3 of the Invention] Field of the Invention The present invention relates to a black photosensitive resin composition and a light shielding layer using the same. r: Prior Art Background of the Invention It is necessary to use a black photosensitive resin composition to produce a display element of a color filter, a liquid crystal display material, an organic light emitting element (EL), a display panel material 'and the like. For example, a color-transparent color film (such as a color liquid crystal display and the like) requires a light-shielding layer on the boundary between color layers (for example, red, green, blue, and the like) to enhance display. Contrast or color effect. This light shielding layer can be mainly formed of a black photosensitive resin composition. A number of patents relating to the composition of black photosensitive resin are disclosed. U.S. Patent Publication No. 2002-047423 discloses the use of cobalt oxide as a black pigment to achieve a black matrix having high blackness and insulating properties. In addition, Japanese Patent Laid-Open Publication No. 2-7-71994 uses a black matrix material comprising a primary compound. Recent research on -black matrix materials has focused on increasing the optical density (OD) up to the maximum, but reducing the thickness of the black matrix film to minimize the damage to the flatness due to the high_thickness, and thus, without a protection In the case of a film, the instillation margin of the liquid crystal is ensured. [Bright Internal Effect 3 201214044 SUMMARY OF THE INVENTION An aspect of the present invention provides a black photosensitive resin composition which has high optical density, excellent patterning property and resolution without damaging a process, and low Dielectric constant. Another aspect of the present invention provides a light shielding layer which is prepared by using the black photosensitive resin composition. According to an aspect of the present invention, there is provided a black photosensitive resin composition comprising (A) - an organic binder resin; (B) - a reactive unsaturated compound; (C) a photopolymerization initiator; (D) a black pigment comprising carbon black and a silver-tin alloy; and (E) a solvent, wherein the silver-containing tin alloy comprises silver and tin in a weight ratio of 6:4 to 8:2. The carbon black and the silver-containing tin alloy may be included in a weight ratio of 1:9 to 9:1. The black photosensitive resin composition may include 0.5 to 20% by weight of the organic binder resin (A); 1 to 20% by weight of the reactive unsaturated compound (B); 0.1 to 10% by weight of the polymerization Starting agent (C); 1 to 40 wt% of the black pigment (D) comprising carbon black and a silver-tin alloy; and the solvent (8) of the difference. The organic binder resin may comprise a cardo-based binder resin and the binder-based binder resin may be a compound containing a repeating unit represented by the following Chemical Formula 1. [Chemical Formula 1] 201214044
於化學式1中， R24至R27為相同或不同的，以及為氫、鹵素，或經取代 或未經取代的C1至C20烷基， 尺28與R29為相同或不同的*以及為氮或CH2〇Ra (Ra為乙 烯基、丙烯醯基(acryl)，或曱基丙烯醢基(methacryl))， R30為相同或不同的，以及為氫、經取代或未經取代的 C1至C20烷基、經取代或未經取代的C2至C20烯基、丙烯醯 基，或曱基丙烯醯基， 2!為相同或不同的，以及為一單鍵、Ο、CO、S02、 CRbRc、SiRdRe (其中，Rb至Re為相同或不同的，以及為氫， 或經取代或未經取代的C1至C20烷基），或是由下列化學式2 至12表示的官能基之一者， Z2為相同或不同的，以及為酸酐殘餘基團或酸二針殘 餘基團。 [化學式2]In Chemical Formula 1, R24 to R27 are the same or different, and are hydrogen, halogen, or a substituted or unsubstituted C1 to C20 alkyl group, and the ruler 28 and R29 are the same or different* and are nitrogen or CH2? Ra (Ra is a vinyl group, acryl, or methacryl), R30 is the same or different, and is a hydrogen, substituted or unsubstituted C1 to C20 alkyl group, Substituted or unsubstituted C2 to C20 alkenyl, propylene fluorenyl, or decyl propylene fluorenyl, 2! are the same or different, and are a single bond, hydrazine, CO, S02, CRbRc, SiRdRe (wherein Rb Z is the same or different, and is the same or different, and is a hydrogen or a substituted or unsubstituted C1 to C20 alkyl group, or one of the functional groups represented by the following Chemical Formulas 2 to 12, Z2 is the same or different, And as an acid anhydride residue or an acid two-needle residue. [Chemical Formula 2]
[化學式3] 201214044[Chemical Formula 3] 201214044
[化學式4][Chemical Formula 4]
[化學式5][Chemical Formula 5]
[化•學式6][化化学6]
於化學式6中，In Chemical Formula 6,
Rf為氫、乙基、C2H4a、C2H4OH、CH2CH=CH2，或苯 基。 [化學式7]Rf is hydrogen, ethyl, C2H4a, C2H4OH, CH2CH=CH2, or phenyl. [Chemical Formula 7]
[化學式8] 6 201214044[Chemical Formula 8] 6 201214044
[化學式9][Chemical Formula 9]
[4匕學式10][4匕学式10]
[化學式11][Chemical Formula 11]
[化學式12][Chemical Formula 12]
該咔哚為主之黏結劑樹脂可以具有1，000至20,000 g/mol的重量平均分子量。 該含銀錫合金可以以5至60 wt%的一量被包括，以該黑 色光敏性樹脂組成物的固體總量為基準。 該黑色光敏性樹脂組成物可以應用至一遮光層。 201214044 根據本發明的另一態樣，提供了使用該黑色光敏性樹 脂組成物來製造的一遮光層。 該遮光層於0.7 jiim或更多的膜厚度可以具有4 〇或更多 的光學密度。 下文中，其他的具體例將詳盡地予以說明。 因本發明提供了一種黑色光敏性樹脂組成物，其具有 高的光學密度在沒有損害一製程的情況下、優良的圖案化 性質與解析度，以及低的介電常數’其可以有用地腐用至 一遮光層。 圖式簡單說明 第1圖為顯示出依據實施例1之膜圖案的殘餘物之掃描 式電子顯微鏡(SEM)圖； 第2圖為顯示出依據比較實施例1之膜圖案的殘餘物之 掃描式電子顯微鏡(SEM)圖。 C實施方式3 較佳實施例之詳細說明 在下文中將詳細地說明本揭示之例示性具體例。然 而，此等具體例僅供舉例說明之用而不會限制本揭示。 當使用於本文中，當未提供特定定義時，「經取代的」 —5司係指用以下的至少一者，代替至少一個氫：鹵素(F、 C1、Br’或〗）、羥基、C1至C20烷氧基、硝基、氰基、胺基、 亞胺基、疊氮基、曱肼、基、肼基、亞肼基、羰基、胺曱醯 基、硫醇基、酯基、醚基、羧基或其鹽類、磺酸基或其鹽 類、磷酸基或其鹽類、CllC2〇烷基、€2至(：2〇烯基、C2 8 201214044 至C20炔基、C6至C30芳基、C3至C20環烷基、C3至C20環 烯基、C2至C20雜環烷基、C2至C20雜環烯基、C2至C20雜 環炔基，或其等之一組合。 當使用於本文中，當未提供特定定義時，「（甲基）丙稀 酸酯（(meth)acrylate)」係指「丙烯酸醋」與「曱基丙烯酸_」 二者。 依據一具體例之光敏性樹脂組成物包括（A)一有機黏 結劑樹脂、（B)—反應性不飽和化合物、（c)一種光聚合化起 始劑、（D)包括碳黑及一含銀錫合金之黑色色素，以及(E) 一溶劑。 (A)有機黏結劑樹脂 該有機黏結劑樹脂可以包括一咔哚為主之黏結劑樹 脂、一丙烯醯基為主之黏結劑樹脂、一聚醯亞胺為主之黏 結劑樹脂、一聚胺曱酸酯為主之黏結劑樹脂，或其等之— 組合’以及較佳地一咔哚為主之黏結劑樹脂。該咔哚為主 之黏結劑樹脂可以改善該黑色光敏性樹脂組成物的抗熱性 與耐化學性。 該有機黏結劑樹脂可以具有1，〇〇〇至150,000 g/mol的重 量平均分子量。 該咔哚為主之黏結劑樹脂可以為含有由下列化學式1 表示的一重覆單元之一化合物。 [化學式1] 9 201214044The bismuth-based binder resin may have a weight average molecular weight of 1,000 to 20,000 g/mol. The silver-containing tin alloy may be included in an amount of 5 to 60% by weight based on the total solids of the black photosensitive resin composition. The black photosensitive resin composition can be applied to a light shielding layer. 201214044 According to another aspect of the present invention, a light shielding layer produced using the black photosensitive resin composition is provided. The light shielding layer may have an optical density of 4 Torr or more at a film thickness of 0.7 jiim or more. Hereinafter, other specific examples will be described in detail. The present invention provides a black photosensitive resin composition which has high optical density without impairing a process, excellent patterning properties and resolution, and low dielectric constant 'which can be usefully used To a shade layer. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a scanning electron microscope (SEM) image showing a residue of a film pattern according to Example 1, and Fig. 2 is a scanning chart showing a residue of a film pattern according to Comparative Example 1. Electron microscopy (SEM) image. C EMBODIMENT 3 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, exemplary embodiments of the present disclosure will be described in detail. However, these specific examples are for illustrative purposes only and do not limit the disclosure. As used herein, when a specific definition is not provided, "substituted" - 5 means that at least one of the following is replaced by at least one of: halogen (F, C1, Br' or), hydroxyl, C1. To C20 alkoxy, nitro, cyano, amine, imido, azide, anthracenyl, fluorenyl, fluorenyl, carbonyl, aminyl, thiol, ester, ether a base, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, a C11C2 alkyl group, a €2 to a (2:alkenyl group, a C2 8 201214044 to a C20 alkynyl group, a C6 to C30 aromatic group) a combination of a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, or the like. Herein, when a specific definition is not provided, "(meth)acrylate" means both "acrylic acid vinegar" and "methacrylic acid _". Photosensitive resin according to a specific example The composition comprises (A) an organic binder resin, (B) a reactive unsaturated compound, (c) a photopolymerization initiator, (D) comprising carbon black and a silver-tin alloy. Color pigment, and (E) a solvent. (A) Organic binder resin The organic binder resin may include a bismuth-based binder resin, an acryl-based binder resin, and a polyimine. The main adhesive resin, a polyamine phthalate-based adhesive resin, or the like - a combination of 'and a preferred one-based adhesive resin. The bismuth-based adhesive resin The heat resistance and chemical resistance of the black photosensitive resin composition can be improved. The organic binder resin may have a weight average molecular weight of from 1, 〇〇〇 to 150,000 g/mol. The ruthenium-based binder resin may be A compound containing one of the repeating units represented by the following Chemical Formula 1. [Chemical Formula 1] 9 201214044
於化學式1中， R24至R27為相同或不同的，以及為氫、鹵素，或經取代 或未經取代的C1至C20烷基， R28與Κ·29為相同或不同的，以及為氮或CH2〇Ra (Ra為乙 烯基、丙烯醯基，或甲基丙烯醯基）， R3〇為相同或不同的，以及為氫、經取代或未經取代的 C1至C20烷基、經取代或未經取代的C2至C20烯基、丙烯醯 基，或甲基丙烯醯基， 2】為相同或不同的，以及為一單鍵、Ο、CO、S02、 CRbRc、SiRdRe(其中，Rb至1^為相同或不同的，以及為氫， 或經取代或未經取代的C1至C20烷基），或是由下列化學式2 至12表示的官能基之一者，以及 Z2為相同或不同的，以及為酸針殘餘基團或酸二酐殘 餘基團。 [化學式2]In Chemical Formula 1, R24 to R27 are the same or different, and are hydrogen, halogen, or a substituted or unsubstituted C1 to C20 alkyl group, R28 is the same or different from Κ·29, and is nitrogen or CH2. 〇Ra (Ra is a vinyl group, a propylene fluorenyl group, or a methacryl fluorenyl group), R3 is the same or different, and is a hydrogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted Substituted C2 to C20 alkenyl, propylene fluorenyl, or methacryl fluorenyl, 2] are the same or different, and are a single bond, hydrazine, CO, S02, CRbRc, SiRdRe (wherein Rb to 1^ is The same or different, and is a hydrogen, or a substituted or unsubstituted C1 to C20 alkyl group, or one of the functional groups represented by the following Chemical Formulas 2 to 12, and Z2 is the same or different, and Acid needle residual group or acid dianhydride residual group. [Chemical Formula 2]
[化學式3] 10 201214044[Chemical Formula 3] 10 201214044
[化學式4][Chemical Formula 4]
[化學式5][Chemical Formula 5]
[化學式6][Chemical Formula 6]
於化學式6中，In Chemical Formula 6,
Rf為氫、乙基、C2H4Q、C2H4OH、CH2CH=CH2，或苯 基。 [化學式7]Rf is hydrogen, ethyl, C2H4Q, C2H4OH, CH2CH=CH2, or phenyl. [Chemical Formula 7]
[化學式8] 11 201214044[Chemical Formula 8] 11 201214044
[化學式9][Chemical Formula 9]
[化< 學式10][Chemical < Formula 10]
[化學式11][Chemical Formula 11]
Η匕學式12] 該咔哚為主之黏結劑樹脂可以藉由使由下列化學式13 表示的化合物與四曱酸二酐反應而獲得。 [化學式13] 12 201214044Η匕 式 12] The ruthenium-based binder resin can be obtained by reacting a compound represented by the following Chemical Formula 13 with tetradecanoic acid dianhydride. [Chemical Formula 13] 12 201214044
四曱酸二酐可以為芳族四甲酸二酐。芳族四曱酸二酐 之實例包括焦蜜石酸二酐、3,3，，4,4，-聯苯四甲酸二酐、 2,3,3’，4-聯苯四曱酸二酐、2,2，，3,3，-聯苯四甲酸二酐、 3,3’，4,4’-二苯曱酮四甲酸二酐、3,3’，4,4，_聯苯醚四甲酸二 酐、3,3’，4,4’-二苯砜四曱酸二酐、12,3+環戊四曱酸二酐、 1，2,5,6-萘四甲酸二酐、2,3,6,7-萘四甲酸二酐、ι，4,5,8-萘四 甲酸二酐、2,3,5,6-吡啶四曱酸二酐、3,4,9,10-茈四甲酸二 酐、2,2-雙（3,4-二甲苯基）六氟丙烷二酐，及類似物，但不 限於彼等。 該咔哚為主之黏結劑樹脂可以具有L000至2〇,〇〇〇 g/mol，以及特別地3,000至1〇,〇〇〇 g/m〇l的重量平均分子 量。當該咔哚為主之黏結劑樹脂具有以上範圍内的重量平 均分子量時，一形成的遮光層具有優良的圖案化性質及顯 影性質。 該丙烯醯基為主之黏結劑樹脂為一第一乙烯屬不飽和 單體以及可與該第一乙烯屬不飽和單體共聚合的一第二乙 烯屬不飽和單體之一種共聚物，以及包括至少一丙烯醯基 為主之重覆單元的一樹脂。 該第一乙烯屬不飽和單體為包括至少一叛基之一乙烯 13 201214044 屬不飽和單體。該單體之實例包括丙烯酸、曱基丙烯酸、 馬來酸、衣康酸、反丁稀二酸，或其等之組合。 該第一乙烯屬不飽和單體以該丙烯醯基為主之黏結劑 樹脂的總量為基準，可以包括範圍由5至50〜％，以及特別 地，由10至40 wt%的一量。 該第二乙烯屬不飽和單體之實例可以包括：芳香族乙 烯基化合物，例如苯乙烯、α·曱基苯乙烯、乙烯基甲苯、 乙烯基节基甲基醚，及類似物；不飽和羧酸酯化合物，例 如：曱基丙烯酸甲酯、甲基丙烯酸乙酯、曱基丙烯酸丁酯、 甲基丙烯酸2-羥基乙酯、曱基丙烯酸2-羥基丁酯、甲基丙烯 酸苄酯、曱基丙烯酸環己酯，曱基丙烯酸苯酯，及類似物； 不飽和羧酸胺基烷基酯化合物，例如：甲基丙稀酸2_胺基 乙酯、甲基丙烯酸2-二甲基胺基乙酯，及類似物；竣酸乙 烯基酯化合物，例如：乙酸乙烯酯、苯曱酸乙烯酯，及類 似物；不飽和叛酸縮水甘油酯化合物，例如甲基丙稀酸縮 水甘油酯，及類似物；乙稀基氰化物化合物，例如曱基丙 稀腈及類似物；不飽和醯胺化合物，例如曱基丙烯醯胺及 類似物；以及類似物。其等可以單一地或如多於二個之混 合物來使用。 該丙烯醯基為主之黏結劑樹脂之實例可以包括曱基两 烯酸/甲基丙烯酸苄酯共聚物、甲基丙烯酸/甲基丙烯酸节酉旨 /苯乙烯共聚物、甲基丙烯酸/曱基丙烯酸苄酯/甲基丙烯酸 2-羥基乙酯共聚物、甲基丙烯酸/甲基丙烯酸苄酯/笨乙烯/ 甲基丙烯酸2-羥基乙酯共聚物，及類似物，但不限於彼等。 14 201214044 其等可以單一地或是如二個或更多個之混合物來使用。 該丙烯醯基為主之黏結劑樹脂可以具有範圍從3，00〇 至150,000 g/m〇i的重量平均分子量，特別地5,000至5〇,〇〇〇 g/mol的重量平均分子量，以及更特別地2,000至30,〇〇〇 g/mol的重量平均分子量。當該丙烯醯基為主之黏結劑樹脂 具有於此範圍内的重量平均分子量時，該光敏性樹脂組成 物具有良好的物理性質與化學性質、適當的黏度，以及與 一基材之緊密的接觸性質，當被應用至一遮光層時。 該丙烯醯基為主之黏結劑樹脂可以具有範圍從15至6〇 mgKOH/g的酸價，以及特別地2〇至5〇mgKOH/g的酸價。當 丙稀酿基為主之樹脂具有於此範圍内的酸價時，可以實現 優異的像素解析度。 該有機黏結劑樹脂可以以0.5至2〇 wt%，特別地丨至1〇 wt%的一量被包括，以該黑色光敏性樹脂組成物的總量為 基準。包括此範圍内的有機黏結劑樹脂，適當地維持了 — 黏度以提供具㈣案化性質、可力^以及㈣性質之 一遮光層。 —種光敏性樹脂組成物 其可以為包括至少一乙 (B)反應性不飽和化合物 該反應性不飽和化合物可以是 中之一普遍使用的單體或寡聚物。 稀屬不飽和雙鍵之單官能或多官能性曱基丙烯酸龜。 該反應性不飽和化合物之實例包括二丙烯酸乙二醇 酯、乙二醇二曱基丙烯酸酯、二丙烯酸二乙二醇酯、二^ 烯酸三乙二醇酯、三乙二醇二曱基丙烯酸酯、丄爪己二醇二 15 201214044 丙烯酸酯、1，6-己二醇二甲基丙烯酸酯、季戊四醇三丙烯酸 酯、季戊四醇四丙烯酸酯、二季戊四醇五丙稀酸酯、二季 戊四醇六丙烯酸酯、雙酚A環氧丙烯酸酯、乙二醇曱醚丙烯 酸酯、三羥甲基丙烷三丙烯酸酯、三丙烯醯基氧乙基磷酸 酉旨，及類似物。 該反應性不飽和化合物之商業上可得的實例係如下 列。單官能性曱基丙烯酸酯可以包括Aronix M-101®、 M-lll®、M-114® (TOAGOSEI CHEMICAL INDUSTRY CO.，LTD.) ; KAYARAD TC-110S®、TC-120S® (NIPPON KAYAKU CO.，LTD.) ; V-158®、V-2311® (OSAKA ORGANIC CHEMICAL IND.，LTD·)，及類似物。雙官能性曱基丙烯 酸酯之實例可以包括Aronix M-210®、M-240®、M-6200® (TOAGOSEI CHEMICAL INDUSTRY CO.，LTD·)、 KAYARAD HDDA®、HX-220®、R-604® (NIPPON KAYAKU CO.，LTD·)、V-260®、V-312®、V-335 HP® (OSAKA ORGANIC CHEMICAL IND.，LTD.)，及類似物。三官能性曱基丙烯 酸酯之實例可以包括Aronix M-309®、M-400®、M-405®、 M-450®、M-7100®、M-8030®、M-8060® (TOAGOSEI CHEMICAL INDUSTRY CO.，LTD.)、KAYARAD TMPTA®、 DPCA-20®、DPCA-30®、DPCA-60®、DPCA-120® (NIPPON KAYAKU CO.，LTD.)、V-295®、V-300®、V-360®、V-GPT®、 V-3PA® ' V-400® (Osaka Yuki Kayaku Kogyo Co. > Ltd.)， 及類似物。該反應性不飽和化合物可以單一地或是如二個 或更多個之混合物來使用。 16 201214044 該反應性不飽和化合物以該光敏性樹脂組成物的總量 為基準，可以以範圍由1至4〇 wt%，以及特別地丨至2〇 wt% 的一量被包括。當包括此範圍内的反應未飽和化合物時， 與該有機黏結劑樹脂之相容性係改善的以及因而一膜的可 以提供具有優良的圖案化性質與在氧之下的敏感性，以及 在一遮光層的製造期間具有平滑的表面。 (C)光聚合化起始劑 該光聚合化起始劑可以為於一種光敏性樹脂組成物中 普遍使用的起始劑，舉例而言：苯乙酮為主的化合物、二 本基酮為主的化合物、嚷^山酮（thi〇xanth〇ne)為主的化合 物、安息香（benzoin)為主的化合物、三讲為主的化合物， 及類似物。 該苯乙酮為主的化合物包括2,2’-二乙氧基苯乙酮、 2,2’-二丁氧基苯乙銅、2-經基-2-曱基笨丙酮 (methylpropinophenone)、對-第三-丁基三氯苯乙酮、對-第 三-丁基二氣苯乙酮、4-氣苯乙酮、2,2，-二氣-4-苯氧基苯乙 酮、2-曱基-1-(4-(曱硫基)苯基)-2-嗎福啉丙-1-酮、2-苯甲基 -2-二甲基胺基-1-(4-嗎福嚇苯基)-丁-1-嗣’及類似物。 該二苯基酮為主的化合物包括二苯基酮、苯甲醯基苯 曱酸酯、苯曱醯基苯甲酸曱醋(benzoyl methyl benzoate)、 4-苯基二苯基酮、羥基二苯基酮、丙烯酸化二苯基酮 (acrylated benzophenone)、4,4’-雙(二甲基胺基)二苯基_、 4,4’-雙（二乙基胺基)二苯基酮、4,4’-二甲基胺基二苯基酮、 4,4，-二氯二苯基酮、3,3’-二甲基-2-曱氧基二苯基酮，及類 17 201214044 似物。 該噻η山酮為主的化合物包括噻咄酮、2-曱基噻《山酮、 異丙基噻'1山酮、2,4-二乙基噻0山酮、2,4-二異丙基噻11山酮、 2-氣°塞α山酮，及類似物。 該安息香為主的化合物包括安息香、安息香甲醚、安 息香***、安息香異丙醚、安息香異丁醚、安息香二曱基 縮酸(^>6112)/1(1111^1:11711<^31)，及類似物。 該三畊為主的化合物包括2,4,6-三氣-s-三畊、2-苯基 -4,6-雙（三氣曱基)-s-三讲、2-(3’，4’-二曱氧基苯乙烯基)-4,6-雙（三氣曱基）-s-三畊、2-(4’-甲氧基萘基)-4,6-雙（三氣甲 基)-s-三畊、2-(對-甲氧基苯基)-4,6-雙（三氯甲基)-s-三讲、 2-(對-甲苯基)-4,6-雙(三氣曱基)-s-三讲、2-聯苯基4,6-雙(三 氣曱基)-s-三畊、雙（三氣甲基)-6-苯乙烯基-s-三畊、2-(萘-1-基)-4,6-雙（三氣曱基)-s-三畊、2-(4-曱氧基萘-1-基)-4,6-雙 (三氣曱基)-s-三讲、2-4-三氣曱基（向日葵基)-6-三畊、2-4-三氣曱基(4’-曱氧基苯乙烯基)-6-三啡，及類似物。 該聚合化起始劑可以進一步包括叶β坐為主的化合物、 二酮為主的化合物、硼酸銃為主的化合物、重氮為主的化 合物、雙味唾為主的化合物，及類似物。 因該聚合化起始劑吸收光且予以激化以及繼而傳遞能 量，其可與一光敏劑來使用以產生一化學反應。 該聚合化起始劑可以以該黑色光敏性樹脂組成物的總 量為基準，以0.01 wt%至10 wt%的一量被包括，以及特別 地0.1至5 wt%的一量被包括。當包括此範圍内的光聚合起 18 201214044 始劑時，基(radical)的敏感性是良好的’一種黑色光敏性樹 脂組成物溶液具有所欲的色彩濃度，以及透射率降低’由 於非反應起始劑可以被抑制。 (D)黑色色素 黑色色素可以為碳黑及一含銀錫合金的混合色素。 該碳黑可以不具有特別的限制但是包括，特別地，石 墨化板、爐黑、乙快黑、科琴黑(ketjen black)，及類似物。 該含銀锡合金可以包括銀(Ag)和錫（Sn)作為主要的組 份以及具有範圍由1至3〇〇 nm的平均顆粒尺寸且特別地，由 1至10 nm的平均顆粒尺寸。當具有於此範圍内的平均顆粒 尺寸之含銀锡合金時，其可以避免細微的雜質在圖案形成 製程的期間不於―基材上產生。 "亥3銀锡合金可以為一黑色色素。於此，銀和錫可以 具有範圍由6:4至8:2的f量比以及特別地，範園由7:3至 7.5:2.5的重4比。當銀和錫具有於此範圍内的合金比率 時’-遮光層可以具有更高的光學密度、優良的光阻隔性 質，和適當的傳導性，因而容易地控制介電常數。 該含銀锡合金可以被塗覆以具有一絕緣層於表面上。 塗層可以藉由使用一石夕石為主之化合物予以執行。經塗覆 的含銀錫合金可β容易地分散於-溶射以及帶來一光學 密度給一遮光層。 該石反黑及含銀錫合金 可以以範圍由1:9至9:1的重量比 以及特別地’由1:1至1:8的重量比予以混合。當其等係以該 比率使料’其等可以帶來高的光學密度以及優良的可加 19 201214044 工性，例如圖案化性質、解析度，及類似物。 該含銀錫合金可以以1至wt%的一量被包括以及特 別地，以3G⑽wt%的—量被包括，_黑色光敏性樹脂 組成物的固體總量絲準。t包減範_的含銀錫合金 時，其相帶來高的光學密度在沒#損害可加讀的情況 下，亦即，顯影邊緣、曝光邊緣、解析度，及類似物在一 遮光層的製備期間。 田"亥”:、色色素與一分散劑、溶劑，及類似物予以混合 以製備-色素分散溶液時，討則㈣於該黑色光敏性樹 脂組成物。特別地，該含銀錫合金係與一分散劑、一溶劑， 及類似物予以混合以製備—第—色素分散溶液，.以及該碳 黑係與-分散劑、-溶劑，及類似物予以混合以製備一第 二色素分散溶液。繼而，該第—及第二色素分散溶液係被 混合在一起以及使用於該黑色光敏性樹脂組成物。否則， s亥含銀錫合金與該碳黑係同時地與一分散劑、一溶劑，及 類似物予以混合以製備-色素分散溶液。該色素分散溶液 可以使用於該黑色光敏性樹脂組成物。 S亥分散劑可以協助黑色色素均勻地分散於溶劑中。 該勿政劑可以包括非離子性化合物、陰離子性化合 物'陽離子性化合物’或其等之—組合。分散劑之實例包 括聚亞烷基二醇及其之酯、聚氧化烯(polyoxyalkylene)、多 羥基醇酯環氧烷加合產物、醇環氧烷加合產物、磺酸酯類、 磺酸鹽、羧酸酯類、羧酸鹽、烷基醯胺環氧烷加合產物、烷 基胺，及類似物。 20 201214044 該分散劑之商業上可得的實例係如下列： DISPERBYK-101、DISPERBYK-130、DISPERBYK-140、 DISPERBYK-160、DISPERBYK-161、DISPERBYK-162、 DISPERBYK-163、DISPERBYK-164、DISPERBYK-165、 DISPERBYK-166、DISPERBYK-170、DISPERBYK-171、 DISPERBYK-182、DISPERBYK-2000、DISPERBYK-2001， 及類似物（BYK) ; EFKA-47、EFKA-47EA、EFKA-48、 EFKA-49、EFKA-100、EFKA-400、EFKA-450，及類似物 (EFKA chemicals) ; Solsperse 5000、Solsperse 12000、 Solsperse 13240、Solsperse 13940、Solsperse 17000、 Solsperse 20000、Solsperse 24000GR、Solsperse 27000、 Solsperse 28000，及類似物(Zeneka);或是PB711、PB821， 及類似物（Ajinomoto)。 該分散劑可以以該黑色光敏性樹脂組成物的總量為基 準，以0.01至15 wt%的一量被包括。當包括以上範圍内的 分散劑時，該黑色光敏性樹脂組成物的分散係被改善導致 在一遮光層的製造期間優良的安定性、顯影性質，及圖案 化性質。 該溶劑係說明如下。 該黑色色素可以以該黑色光敏性樹脂組成物的總量為 基準，以1至40 wt%，以及特別地5至30 wt%的一量被包括。 當包括以上範圍内的黑色色素時，提供了具有優良的絕緣 性質、高的光學密度，和優良的顯影性質及可加工性之一 遮光層。 21 201214044 (E)溶劑 溶劑具有與該有機黏結劑樹脂、反應性不飽和化合 物、光聚合化起始劑，以及黑色色素之相容性，但是與之 不具有一反應。 溶劑之實例可以包括醇，例如曱醇、乙醇，及類似物； 醚，例如：二氣***、η-丁醚、二異戊醚、甲基苯基醚、 四氫呋喃，及類似物；二醇醚，例如：乙二醇單甲醚、乙 二醇單***，及類似物；乙酸賽璐蘇，例如：乙酸曱赛璐 蘇、乙酸乙赛璐蘇、乙酸二乙赛璐蘇，及類似物；卡必醇， 例如：曱基乙基卡必醇、二乙基卡必醇、二乙二醇單曱醚、 二乙二醇單***、二乙二醇曱醚、二乙二醇曱***、二乙 二醇***等等；丙二醇烷基醚乙酸酯，例如：丙二醇甲醚 乙酸酯、丙二醇丙醚乙酸酯，及類似物；芳烴，例如甲苯、 二甲苯，及類似物；酮，例如：曱乙酮、環己酮、4-羥基-4-曱基-2-戊酮、曱基-η-丙酮、甲基-η-丁酮、曱基-η-戊酮、 2-庚酮，及類似物；飽和脂族單羧酸烷基酯，例如：乙酸 乙酯、η-丁基乙酸酯、異丁基乙酸酯，及類似物；乳酸酯， 例如：乳酸曱酯、乳酸乙酯，及類似物；烷基氧基乙酸酯， 例如：曱基氧基乙酸酯、乙基氧基乙酸酯、丁基氧基乙酸 酯，及類似物；烷基烷氧基乙酸酯，例如：甲氧基乙酸甲 酯、甲氧基乙酸乙酯、曱氧基乙酸丁酯、乙氧基乙酸甲酯、 乙氧基乙酸乙酯，及類似物；3-氧基丙酸烷基酯（3-oxy propionate alkylesters)，例如3-氧基丙酸甲S旨、3-氧基丙酸 乙酯，及類似物；3-烷氧基丙酸烷基酯，例如：3-甲氧基丙 22 201214044 酸甲酯、3-曱氧基丙酸乙酯、3-乙氧基丙酸乙酯、3-乙氧基 丙酸曱酯，及類似物；2-氧基丙酸烷基酯，例如：2-氧基丙 酸曱醋、2-氧基丙酸乙g旨、2-氧基丙酸丙基(2-oxy propionic acid propyl)，及類似物；2-烧氧基丙酸烧基酯，例如：2-甲氧基丙酸甲酯、2-曱氧基丙酸乙酯、2-乙氧基丙酸乙酯、 2-乙氧基丙酸曱酯，及類似物；2-氧基-2-曱基丙酸酯，例 如：2-氧基-2-曱基丙酸甲酯、2-氧基-2-甲基丙酸乙酯，及 類似物；2-烷氧基-2-曱基丙酸烷基的單氧基單羧酸烷基 酯，例如：2-甲氧基-2-甲基丙酸曱酯、2-乙氧基-2-曱基丙 酸乙酯，及類似物；酯，例如：2-羥基丙酸乙酯、2-羥基-2-曱基丙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸曱酯， 及類似物；酮酯（ketonate ester)系列，例如丙酮酸乙酯，及 類似物。此外，可以進一步添加下列高沸點的溶劑：N-甲 基曱醯胺、N、N-二曱基曱醯胺、N-曱基曱醢胺、N-曱基 乙醯胺、N、N-二曱基乙醯胺、N-曱基吡咯烷酮、二曱亞 砜、苄基乙基醚、二己基醚、乙醯丙酮、異佛酮、己酸、 辛酸、1-辛醇、1-壬醇、苯甲醇、乙酸苯甲酯、苯曱酸乙酯、 草酸二乙酯、馬來酸二乙酯、Ύ-丁内酯、碳酸乙烯酯、碳 酸丙烯酯、苯基乙酸賽璐蘇，及類似物。 考慮到互溶性與反應性，二醇醚，例如乙二醇單***， 及類似物；乙二醇烷基醚乙酸酯，例如：乙酸乙赛璐蘇， 及類似物；酯，例如2-羥基丙酸乙酯，及類似物；卡必醇， 例如二乙二醇單甲醚，及類似物；丙二醇烷基醚乙酸酯， 例如丙二醇甲醚乙酸g旨、丙二醇丙醚乙酸g旨，及類似物。 23 201214044 溶劑係使用為一差額，以及特別地50至70 wt%，以該 黑色光敏性樹脂組成物的總量為基準。當包括此範圍内的 心劑時’該黑色光敏性樹脂組成物可具有適當的黏度導致 一遮光層的可加工性之改善。 (F)其他添加劑 該黑色光敏性樹脂組成物可以進一步包括具有一反應 性取代基例如羧基、曱基丙烯醯基、異氰酸酯基、環氧基， 及類似物的矽烷偶合劑俾以改善對一基材之附著。 石夕烧偶合劑之實例包括三曱氧矽烷基苯甲酸、γ-曱基 丙烯酸氧丙基三曱氧基矽烷、乙烯基三乙醯氧基矽烷、乙 烯基三甲氧基矽烷、7-異氰酸丙基三乙氧基矽烷、γ-縮水 甘油趟氧丙基三曱氧基矽烷、+(3,4-乙氧環己基）乙基三曱 氧基矽烷，及類似物。其等可以單一地或是如二個或更多 個之混合物來使用》 該矽烷偶合劑可以以該有機黏結劑樹脂的1〇〇份重量 計為基準，以0.001至5份以重量計的一量被包括。 該黑色光敏性樹脂組成物可以進一步包括一界面活性 劑俾以改善塗覆性質且抑制斑點。 該界面活性劑之實例可以包括一氟為主的界面活性 劑，舉例而言，BM-1000®，及BM-1100® (BM Chemie Inc.); MEGAFACE F 142D®、F 172®、F 173®，與F 183® DAINIPPON INK KAGAKU KOGYO CO.，LTD.) ; FULORAD FC-135®、 FULORAD FC-170C®、FULORAD FC-430®，與 FULORAD FC-431® (SUMITOMO 3M CO.，LTD.); SURFLON S-l 12®、 24 201214044 SURFLON S-113®、SURFLON S-131®、SURFLON S-141® ’ 與 SURFLON S-145® (ASAHI GLASS CO. ’ LTD·);及 SH-28PA®、SH-190®、SH-193®、SZ-6032® ’ 與SF-8428® ’ 及類似物(TORAY SILICONE CO· ’ LTD.)。 該界面活性劑可以以該有機黏結劑樹脂的10 0份重量 計為基準，以0.001至5份以重量計的一量被包括。當包括 此範圍内的界面活性劑時，可以確保塗覆均勻性，不會產 生污斑，以及一玻璃基材之潤濕性質係改善的。 該黑色光敏性樹脂組成物可以進一步其他添加劑，舉 例而言’一抗氧化劑、一安定劑，及類似物以預定量，當 其等降低性質時。 依據另一個具體例，提供了使用該光敏性樹脂組成物 來製造的一遮光層。該遮光層可以製造如下。 (1) 應用及膜形成 前述的黑色光敏性樹脂組成物係使用一旋轉塗覆法或 狹縫塗覆法、滾軸塗覆法、網板印刷法、施用器法，及類 似物而塗覆以具有一所欲的厚度，舉例而言，範圍由〇·9至 1.5 μιη的厚度於一預處理之一基材上，以及接而，於範圍 由7 0至9 0 °C的溫度下加熱歷時丨至丨〇分鐘以移除一溶劑。 該膜具有多於4.0的光學密度於〇 7 的厚度。其具有 更高的光學密度，其為更佳的。當該黑色光敏性樹脂組成 物具有於此範圍内的光學密度時，來自底部的光可以不被 照射出去。 (2) 曝光 25 201214044 將—遮罩配置於製備的膜上以形成一圖案。帶有遮罩 的膜係用範®由2GG至5GG nm的活性射料以歸。輻射係 藉由使用—光源予以執行，例如—低壓的水銀燈、一高麼 水銀垃、—超高壓水銀燈、一金屬齒化物燈、一氬氣雷射， 及類似物。然而，光源可以包括-X射線…電子束，及類 似物，取決於狀況。 ^曝光可以使用500 mJ/cm2或更少的（藉由365 nm感測器） 光劑里伴隨一高壓水銀燈，但是取決於該黑色光敏性樹脂 組成物包含的組份種類、其等之組合比例、其等之組合量， 以及一乾燥層的厚度而變化。 (3) 顯影 曝光膜係用-驗性水溶液予以顯影以溶解且移除不必 要的。p为但是保留曝光部分，形成一影像圖案。 (4) 後製程 經顯影的影像圖案可以加熱或用一活性射線予以照射 用於固化以完成優良的抗熱性、光阻性、緊密的接觸性質、 耐裂性、耐化學性、高強度、儲存安定性，及類似物。 前述的黑色光敏性樹脂組成物可以帶來—遮光層所需 要的優良的絕緣性質與光學密度。 在下文中，本發明係更詳盡地參照實施例予以闡釋。 然而’此等為本發明的例示性具體例以及為非限制性的。 實施例1至4與比較實施例1至5 依據實施例1至4以及比較實施例1至5的各黑色光敏性 樹脂組成物係使用下列的組份來製備成具有提供於表1中 26 201214044 之組成。 (A)有機黏結劑樹脂 (A-1)將159g的3,3-雙（4-羥笨基）_2-苯并呋喃-1-蜩、 426.6g的表氯醇，和160g的50%鹼性水溶液於一仏燒瓶内混 合以及接而，於95°C—起反應歷時1小時，獲得雙苯基笨并 呋喃型環氧樹脂。215g的雙苯基苯并呋喃型環氧樹脂係與 450mg的氯化三乙基苄銨、loomg的2,6-二異丁基酚，以及72g 的丙稀酸混合。混合物係於範圍由9〇至12〇。〇的溫度予以加 熱以及完全地溶解，而空氣係以每分鐘25祕的速度吹至其 内。接而’將產生的產物冷卻至室溫，來製備非彩色的透 明的固體雙苯基苯并吱喃型環氧丙烯酸@旨β將287g的所合 成之雙苯基苯并呋喃型環氧丙烯酸酯溶解於2kg的乙酸赛 路蘇之中。接而’將38g的1,2,3,6-四氫鄰苯二甲酐 (l，2,3,6-tetrahydrophthacid anhydride)、80.5g的二苯甲_四 曱酸二酐’以及lg的溴化四乙銨添加至溶液。混合物係緩 慢地予以加熱用於反應向上至110至115。(：歷時2小時，來製 備具有5,000 g/mol的重量平均分子量之一咔哚為主之點結 劑樹脂。 (A-2)將M9g的3,3-雙（4-羥苯基）_2-苯并呋喃巧-綱、 426.6g的表氣醇，以及160g的50%驗性水溶液於一 il燒瓶 内混合以及於95°C予以加熱用於反應歷時1小時，獲得雙 苯基苯并吱喃型環氧樹脂。215g的雙苯基苯并呋味型環氧 樹脂係與450mg的氯化三乙基苄銨、l〇〇mg的2,6-二異丁基 酚，以及72g的丙烯酸予以混合。將混合物加熱升高至9〇 27 201214044 至120°C以及完全地溶解，而空氣係以的速度吹至其 内。接而，將溶解的產物冷卻至室溫，來製備非彩色的透 明固體雙苯基苯并呋喃型環氧丙烯酸酯。將287g的所合成 之雙苯基苯并呋喃型環氧丙烯酸酯溶解於2kg的乙酸賽璐 蘇之中。溶液係與10g的1，2,3,6-四氫鄰苯二甲酐 (l，2,3,6-tetrahydrophthacid anhydride)、108.5g的二苯曱酉同四 甲酸二酐，以及lg的溴化四乙銨予以混合。將混合物緩慢 地加熱升高至110至115°C歷時2小時，來製備具有30,000 g/mol的重量平均分子量之一。卡°朵為主之黏結劑樹脂。 (B) 反應性不飽和化合物 使用二季戊四醇六丙烯酸自旨。 (C) 光聚合化起始劑 使用由Ciba-Geigy Co.所製造的IGR 369。 (D) 黑色色素分散 (D-1)使用包括一銀錫合金（TMP-DC-1，色素固體= 30%，銀和錫之間的重量比=7:3，Sumitomo Osaka Cement Co.，Ltd.)之一色素分散溶液。 (D-2)使用包括碳黑的一色素分散溶液（Cl-M-050， Sakata Co.) ° (E) 溶劑 使用丙二醇甲醚乙酸酯。 (F) 其他添加劑 7 -縮水甘油醚氧丙基三甲氧基石夕烧(S-510，Chisso Co.) 使用作為一妙烧偶合劑。 28 201214044 (表l) 實施例 比較實施例 1 2 3 4 1 2 3 4 5 (A)有機黏 結劑樹脂 (g) (A-l ’ g) 2 2 2 2 2 2 - 2 2 (A-2，g) - - - - - - 2 - - (B)反應性不飽和 化合物(gj 1 1 1 1 1 1 1 1 1 (C)光聚合化 起始劑(g) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (D)黑色 色素分散 (D-l ’ g) 40 (58.8*) 32.5 (53.5*) 30 49* 25 41* - 45 (74.1*) 40 (58.8*) 40 (58.8*) 35 (57.6*) (D-2，g) 5 12.5 15 20 45 - - - - (E)溶劑(g) 51.495 51.495 51.495 51.495 51.495 51.495 56.495 56.495 62.495 (F)其他添加劑 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 標記*指示出一銀錫合金固體的量，以(A)、（B)、（C)、（D)、（E)，和(F)的總固體量為基準。 評估1-光學密度 依據實施例1至4以及比較實施例1至5的黑色光敏性樹 脂組成物係各別地塗覆於一0.7 mm-厚的玻璃基材之上以 及接而，於一90°C加熱板之上乾燥歷時2.5分鐘，以製造〇 7 /xm-厚的膜。將該膜冷卻至室溫且於一23(rc強迫對流乾燥 烘箱中乾燥歷時30分鐘。接而，各膜係藉由使用_3ι〇τ^ 光學密度計(X-lite Co.)就光學密度予以測量。結果係提供 於下列的表2中。 ^ <評估參考> 〇：多於4的光學密度 △:範圍由2_5至4.0的光學密度 X :少於2_5的光學密度 29 201214044 評估2-圖案形成性質測定 依據實施例1至4以及比較實施例i至5之於評估丨中獲 得的各膜係用一圖案遮罩予以覆蓋以及藉由具40 mJ/cm2 波長365 nm來照射。產生的產物係於2；rc用經由1 wt〇/o氫氧 化鉀稀釋的一水溶液予以顯影歷時1分鐘以及接而，用純水 予以清潔歷時1分鐘。獲得的圖案係予以加熱以及於一220 °C烘箱中固化歷時30分鐘以及接而，使用一光學顯微鏡來 檢查。結果係提供於下列的表2以及第1和2圖中。 第1圖為顯示出依據實施例1之膜的圖案之掃描式電子 顯微鏡(SEM)圖。第2圖為顯示出依據比較實施例1之膜的圖 案之掃描式電子顯微鏡(SEM)圖。 <評估參考> 〇：10 μιη圖案之良好的形成 △ : 10 μπι圖案不好的形成 X : 10 μιη圖案沒有形成 評估3-解析度測量 依據實施例1至4以及比較實施例1至5之於評估2中獲 得的各圖案係用一光學顯微鏡予以檢查關於最小的圖案。 結果係提供於下列的表2中。於下列的表2中之解析度測量 指示出在曝光的期間使用的一遮罩之圖案尺寸以及係藉由 使用由KEYENCE Co.所製造的VK-855〇予以測量。 評估4-介電常數測定 依據實施例1至4以及比較實施例1至5的黑色光敏性樹 脂組成物係各別地使用來製備一遮光層。於此’至於一下 30 201214044 基材，使用一ITO(氧化銦錫）玻璃。該下基材係部分地配置 以一遮光層，但是使ΪΤΟ曝光於剩餘的部分。然後，一金(Au) 電極係被濺鍍於被製備的樣本上。所產生的產物係藉由使 用一 LCR計器裝置就電容予以測量來計算其之介電常數。 結果係提供於下列的表2中。 (表2) 實施例1 光學密度 圖案形成性質 解析度(μιη) 介電常數 〇 〇 8 20 實施例2 〇 〇 8 23 實施例3 〇 〇 8 29 實施例4 〇 〇 8 35 比較實施例1 〇 X 25 50或更多 比較實施例2 Δ X 8 17 比較實施例3 Δ X 30 17 比較實施例4 Δ X 7 17 比較實施例5 r △ X 7 17 參ft?'表2 ’依據貫施例1至4之包括一有機黏結劑樹脂、 一反應性不飽和化合物、一光聚合化起始劑、包括碳黑及 一含銀錫合金的黑色色素’以及一溶劑之黑色光敏性樹脂 組成物具有優良的解析度或優良的圖案形成性質以及光學 密度，相較於包括碳黑或含銀錫合金的任一者於依據比較 實施例1至5之黑色色素内的該等。 特別地，依據比較實施例1之僅包括碳黑的黑色光敏性 樹脂組成物具有劣化的圖案形成性質、解析度，以及介電 常數’相較於依據實施例1至4的該等。依據比較實施例2至 5之僅包括一含銀錫合金的黑色光敏性樹脂組成物具有非 常劣化的圖案形成性質。此外’參照第1與2圖，實施例1之 31 201214044 膜具有比比較實施例1之膜更佳的圖案。 再者，依據比較實施例2之包括在範圍之外的含銀錫合 金之黑色光敏性樹脂組成物具有劣化的圖案形成性質與光 學密度’相較於依據實施例1至4之包括以5至6〇 wt%的一量 (以其之總量為基準）之含銀錫合金的該等。 此外，依據比較實施例2之包括具有範圍從ιοοο至 20,000 g/m〇l的重量平均分子量之_ ^為主之黏結劑樹 脂的黑色光敏性樹脂組成物具有較佳的解析度比起依據 比較實施例3之包括在範圍之外的Μ為主之黏結劑樹脂 的該等。 儘管已以目前視為實際可行例示性具體例來說明本揭 示，但要理解到本發明不限於所揭示的具體例，而是，相 反地’欲涵蓋包括在隨”請專利範圍之精神與範_的 各種修飾與等效配置。前述的具體例為例示性的但無认士 何非限制性的。 【圖式簡單說明】 案的殘餘物之掃描 第1圖為顯示出依據實施例1之膜圖 式電子顯微鏡(SEM)圖； 第2圖為顯示出依據比較實施例1之膜圖安、 、吗系的殘餘物之 柃描式電子顯微鏡(3丑]^)圖。 【主要元件符號說明】 (無） 32The tetradecanoic dianhydride may be an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetraphthalic acid dianhydride include pyromellitic dianhydride, 3,3,4,4,-biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride , 2,2,,3,3,-biphenyltetracarboxylic dianhydride, 3,3',4,4'-dibenzophenone tetracarboxylic dianhydride, 3,3',4,4,_diphenyl ether Tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfone tetraphthalic acid dianhydride, 12,3+cyclopentanetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, iota, 4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetradecanoic acid dianhydride, 3,4,9,10 - hydrazine tetracarboxylic dianhydride, 2,2-bis(3,4-dimethylphenyl) hexafluoropropane dianhydride, and the like, but not limited to them. The bismuth-based binder resin may have a weight average molecular weight of L000 to 2 Torr, 〇〇〇 g/mol, and particularly 3,000 to 1 Torr, 〇〇〇 g/m 〇l. When the bismuth-based binder resin has a weight average molecular weight within the above range, a formed light-shielding layer has excellent patterning properties and development properties. The propylene sulfhydryl-based binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer, and A resin comprising at least one acryl-based repeating unit. The first ethylenically unsaturated monomer is an unsaturated monomer comprising at least one of a tethered ethylene 13 201214044. Examples of the monomer include acrylic acid, mercaptoacrylic acid, maleic acid, itaconic acid, butyric acid, or a combination thereof. The first ethylenically unsaturated monomer may be included in an amount ranging from 5 to 50% by weight, and particularly from 10 to 40% by weight, based on the total amount of the acrylonitrile-based binder resin. Examples of the second ethylenically unsaturated monomer may include: an aromatic vinyl compound such as styrene, α-mercaptostyrene, vinyl toluene, vinyl benzyl methyl ether, and the like; unsaturated carboxylic acid Acid ester compounds, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, benzyl methacrylate, sulfhydryl Cyclohexyl acrylate, phenyl methacrylate, and the like; an aminoalkyl ester of an unsaturated carboxylic acid, for example, 2-aminoethyl methacrylate, 2-dimethylamino methacrylate Ethyl ester, and the like; a vinyl phthalate compound such as vinyl acetate, vinyl benzoate, and the like; an unsaturated deglycidyl ester compound such as glycidyl methacrylate, and Analogs; ethylene cyanide compounds such as mercapto acrylonitrile and the like; unsaturated guanamine compounds such as mercapto acrylamide and the like; and the like. They may be used singly or as a mixture of more than two. Examples of the acryl oxime-based binder resin may include decyl enoate/benzyl methacrylate copolymer, methacrylic acid/methacrylic acid/styrene copolymer, methacrylic acid/fluorenyl group. Benzyl acrylate / 2-hydroxyethyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / stupid ethylene / 2-hydroxyethyl methacrylate copolymer, and the like, but not limited to them. 14 201214044 It may be used singly or as a mixture of two or more. The acrylonitrile-based binder resin may have a weight average molecular weight ranging from 3,00 〇 to 150,000 g/m〇i, particularly 5,000 to 5 Å, a weight average molecular weight of 〇〇〇g/mol, and In particular 2,000 to 30, 重量g/mol weight average molecular weight. When the acrylonitrile-based binder resin has a weight average molecular weight within this range, the photosensitive resin composition has good physical properties and chemical properties, appropriate viscosity, and close contact with a substrate. Nature, when applied to a shading layer. The acrylonitrile-based binder resin may have an acid value ranging from 15 to 6 〇 mgKOH/g, and particularly an acid value of 2 〇 to 5 〇 mgKOH/g. When the acryl-based resin has an acid value in this range, excellent pixel resolution can be achieved. The organic binder resin may be included in an amount of 0.5 to 2% by weight, particularly 丨 to 1% by weight, based on the total amount of the black photosensitive resin composition. Including organic binder resins within this range, the viscosity is suitably maintained to provide a light-shielding layer having (4) case properties, force and (iv) properties. A photosensitive resin composition which may be at least one ethyl (B) reactive unsaturated compound. The reactive unsaturated compound may be one of the commonly used monomers or oligomers. A monofunctional or polyfunctional thioglycolic turtle with a dilute unsaturated double bond. Examples of the reactive unsaturated compound include ethylene glycol diacrylate, ethylene glycol dimercapto acrylate, diethylene glycol diacrylate, triethylene glycol dicarboxylate, and triethylene glycol didecyl. Acrylate, hexamethylene glycol diol 15 201214044 Acrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentapropionate, dipentaerythritol hexaacrylate , bisphenol A epoxy acrylate, ethylene glycol oxime ether acrylate, trimethylolpropane triacrylate, tripropylene decyl oxyethyl phosphate, and the like. Commercially available examples of such reactive unsaturated compounds are listed below. Monofunctional methacrylates may include Aronix M-101®, M-lll®, M-114® (TOAGOSEI CHEMICAL INDUSTRY CO., LTD.); KAYARAD TC-110S®, TC-120S® (NIPPON KAYAKU CO.). , LTD.); V-158®, V-2311® (OSAKA ORGANIC CHEMICAL IND., LTD.), and the like. Examples of the bifunctional methacrylate may include Aronix M-210®, M-240®, M-6200® (TOAGOSEI CHEMICAL INDUSTRY CO., LTD.), KAYARAD HDDA®, HX-220®, R-604®. (NIPPON KAYAKU CO., LTD.), V-260®, V-312®, V-335 HP® (OSAKA ORGANIC CHEMICAL IND., LTD.), and the like. Examples of trifunctional methacrylates may include Aronix M-309®, M-400®, M-405®, M-450®, M-7100®, M-8030®, M-8060® (TOAGOSEI CHEMICAL INDUSTRY) CO., LTD.), KAYARAD TMPTA®, DPCA-20®, DPCA-30®, DPCA-60®, DPCA-120® (NIPPON KAYAKU CO., LTD.), V-295®, V-300®, V-360®, V-GPT®, V-3PA® 'V-400® (Osaka Yuki Kayaku Kogyo Co. > Ltd.), and the like. The reactive unsaturated compound may be used singly or as a mixture of two or more. 16 201214044 The reactive unsaturated compound may be included in an amount ranging from 1 to 4% by weight, and particularly from 2% to 2% by weight based on the total amount of the photosensitive resin composition. When a reactive unsaturated compound in this range is included, the compatibility with the organic binder resin is improved and thus a film can provide excellent patterning properties and sensitivity under oxygen, and The light-shielding layer has a smooth surface during its manufacture. (C) Photopolymerization initiator The photopolymerization initiator may be an initiator commonly used in a photosensitive resin composition, for example, an acetophenone-based compound and a bis-ketone. The main compound, a compound mainly composed of thi嚷xanth〇ne, a compound mainly composed of benzoin, a compound of three main compounds, and the like. The acetophenone-based compound includes 2,2'-diethoxyacetophenone, 2,2'-dibutoxyphenethyl copper, 2-methyl-2-mercaptoacetone (methylpropinophenone), p-T-butyltrichloroacetophenone, p-tert-butyldiacetophenone, 4-acetophenone, 2,2,-dioxa-4-phenoxyacetophenone, 2-mercapto-1-(4-(indolyl)phenyl)-2-morpholinepropan-1-one, 2-benzyl-2-dimethylamino-1-(4-? Beneficial phenyl)-butyl-1-anthracene and analogs. The diphenyl ketone-based compound includes diphenyl ketone, benzhydryl benzoate, benzoyl methyl benzoate, 4-phenyl diphenyl ketone, hydroxy diphenyl Acetone, acrylated benzophenone, 4,4'-bis(dimethylamino)diphenyl-, 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-dimethylaminodiphenyl ketone, 4,4,-dichlorodiphenyl ketone, 3,3'-dimethyl-2-decyloxydiphenyl ketone, and class 17 201214044 Like things. The timolone-based compound includes thiazolone, 2-mercaptothioxanthene, isopropyl thiophene 1 ketone, 2,4-diethylthioxanthone, 2,4-diiso Propyl thia-11 ketone, 2-gas stagnation alpha ketone, and the like. The benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin dimercapto acid (^> 6112)/1 (1111^1:11711<^31) , and the like. The three-till-based compounds include 2,4,6-tri-gas-s-three-plow, 2-phenyl-4,6-bis (tris-methyl)-s-three, 2-(3', 4'-dimethoxyoxystyryl-4,6-bis(triseodecyl)-s-trin, 2-(4'-methoxynaphthyl)-4,6-bis (three gas Methyl)-s-three tillage, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tris, 2-(p-tolyl)-4,6 - bis (tri-gas fluorenyl)-s-three-speaking, 2-biphenyl 4,6-bis (trimethyl fluorenyl)-s-three tillage, bis(trimethyl)-6-styrylyl- S-three tillage, 2-(naphthalen-1-yl)-4,6-bis(triseodecyl)-s-three tillage, 2-(4-decyloxynaphthalen-1-yl)-4,6 - double (three gas sulfhydryl)-s-three, 2-4-trimethyl sulfhydryl (sunflower based)-6-three tillage, 2-4-trimethyl sulfhydryl (4'-nonyloxy styryl) )-6-trione, and the like. The polymerization initiator may further include a compound having a leaf β-based composition, a diketone-based compound, a bismuth borate-based compound, a diazo-based compound, a bis-salt-based compound, and the like. Since the polymerization initiator absorbs light and amplifies and then transfers energy, it can be used with a photosensitizer to produce a chemical reaction. The polymerization initiator may be included in an amount of 0.01 wt% to 10 wt%, and particularly an amount of 0.1 to 5 wt%, based on the total amount of the black photosensitive resin composition. When photopolymerization in this range is included, the radical sensitivity is good. 'A black photosensitive resin composition solution has a desired color density, and the transmittance is lowered' due to non-reaction The initiator can be inhibited. (D) Black Pigment The black pigment may be a carbon black and a mixed pigment containing a silver tin alloy. The carbon black may not be particularly limited but includes, in particular, a graphite plate, furnace black, B-black, ketjen black, and the like. The silver-containing tin alloy may include silver (Ag) and tin (Sn) as main components and an average particle size ranging from 1 to 3 Å nm and, in particular, from 1 to 10 nm. When a silver-containing tin alloy having an average particle size within this range is used, it is possible to prevent fine impurities from being generated on the substrate during the pattern forming process. "Hai 3 silver tin alloy can be a black pigment. Here, silver and tin may have a ratio of the amount of f ranging from 6:4 to 8:2 and, in particular, a weight ratio of from 7:3 to 7.5:2.5. When silver and tin have an alloy ratio in this range, the light-shielding layer can have a higher optical density, excellent light-blocking properties, and appropriate conductivity, and thus the dielectric constant can be easily controlled. The silver-containing tin alloy may be coated to have an insulating layer on the surface. The coating can be carried out by using a compound based on a stone. The coated silver-containing tin alloy is readily dispersible in -solubilization and imparts an optical density to a light-shielding layer. The stone anti-black and silver-containing tin alloys may be mixed in a weight ratio ranging from 1:9 to 9:1 and particularly in a weight ratio of 1:1 to 1:8. When they are at this ratio, they can bring high optical density and excellent workability, such as patterning properties, resolution, and the like. The silver-containing tin alloy may be included in an amount of from 1 to wt% and, in particular, in an amount of 3 G (10) wt%, the total amount of solids of the black photosensitive resin composition is predetermined. When a silver-containing tin alloy is used, the phase brings a high optical density in the case where no damage can be read, that is, the development edge, the exposure edge, the resolution, and the like are in a light shielding layer. During the preparation. Field "Hai": When the coloring matter is mixed with a dispersing agent, a solvent, and the like to prepare a pigment dispersion solution, the black photosensitive resin composition is specifically (four). In particular, the silver-containing tin alloy system The mixture is mixed with a dispersant, a solvent, and the like to prepare a first-pigment dispersion solution, and the carbon black-and-dispersant, -solvent, and the like are mixed to prepare a second dye dispersion solution. Then, the first and second pigment dispersion solutions are mixed together and used in the black photosensitive resin composition. Otherwise, the silver-tin alloy and the carbon black are simultaneously mixed with a dispersant and a solvent. And the analog is mixed to prepare a pigment dispersion solution. The pigment dispersion solution can be used for the black photosensitive resin composition. The S-dispersing agent can assist the black pigment to be uniformly dispersed in the solvent. The non-governmental agent can include non-ion. a compound, an anionic compound 'cationic compound' or a combination thereof, etc. Examples of the dispersing agent include polyalkylene glycol and esters thereof, polyoxyalky (polyoxyalky) Lene), polyhydric alcohol ester alkylene oxide adduct product, alcohol alkylene oxide adduct product, sulfonate ester, sulfonate, carboxylate, carboxylate, alkylguanamine alkylene oxide adduct product , alkylamines, and the like. 20 201214044 Commercially available examples of the dispersant are as follows: DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK -163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, and the like (BYK); EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, and the like (EFKA chemicals); Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, and the like (Zeneka); or PB711, PB821, and the like (Ajinomoto). The dispersant may be 0.01 to 15 wt% based on the total amount of the black photosensitive resin composition. One quantity is included. When the dispersant in the above range is included, the dispersion of the black photosensitive resin composition is improved to cause excellent stability, developing properties, and patterning properties during the production of a light shielding layer. This solvent is explained below. The black pigment may be included in an amount of 1 to 40% by weight, and particularly 5 to 30% by weight based on the total amount of the black photosensitive resin composition. When a black pigment in the above range is included, a light-shielding layer having excellent insulating properties, high optical density, and excellent developing property and workability is provided. 21 201214044 (E) Solvent The solvent has compatibility with the organic binder resin, reactive unsaturated compound, photopolymerization initiator, and black pigment, but does not have a reaction therewith. Examples of the solvent may include alcohols such as decyl alcohol, ethanol, and the like; ethers such as dioxyl ether, η-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran, and the like; glycol ether For example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the like; acetaminophen acetate, for example: acesulfame acetate, acesulfame acetate, dicetaxel acetate, and the like; Carbitol, for example: mercaptoethyl carbitol, diethyl carbitol, diethylene glycol monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol oxime ether, diethylene glycol oxime ether, Diethylene glycol ethyl ether, etc.; propylene glycol alkyl ether acetate, such as: propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, and the like; aromatic hydrocarbons such as toluene, xylene, and the like; ketone, For example: acetophenone, cyclohexanone, 4-hydroxy-4-mercapto-2-pentanone, decyl-η-acetone, methyl-η-butanone, decyl-η-pentanone, 2-g Ketones, and the like; saturated aliphatic monocarboxylic acid alkyl esters, for example: ethyl acetate, η-butyl acetate, isobutyl acetate, and the like; lactate, examples Such as: decyl lactate, ethyl lactate, and the like; alkyloxy acetate, such as: mercaptooxyacetate, ethyloxy acetate, butyloxy acetate, and the like Alkyl alkoxy acetate, for example: methyl methoxyacetate, ethyl methoxyacetate, butyl oxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and the like 3-oxy propionate alkylesters, such as 3-oxopropionate, ethyl 3-oxypropionate, and the like; 3-alkoxypropionic acid Alkyl esters, for example: 3-methoxypropene 22 201214044 methyl ester, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, decyl 3-ethoxypropionate, and the like An alkyl 2-oxopropionate such as 2-oxopropionic acid vinegar, 2-oxypropionic acid propyl, 2-oxy propionic acid propyl, And analogs; 2-alkoxypropionate, for example: methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, 2-B Ethyl oxypropionate, and the like; 2-oxy-2-mercaptopropionate, for example: 2-oxyl Methyl 2-mercaptopropionate, ethyl 2-oxy-2-methylpropanoate, and the like; monooxymonocarboxylic acid alkyl of 2-alkoxy-2-mercaptopropionic acid alkyl Base esters, for example: decyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-mercaptopropionate, and the like; esters, for example: ethyl 2-hydroxypropionate , 2-hydroxy-2-mercaptopropionate ethyl ester, ethyl hydroxyethyl acetate, 2-hydroxy-3-methylbutyrate decyl ester, and the like; a ketonate ester series, such as ethyl pyruvate, And similar. Further, the following high boiling solvents may be further added: N-methyl decylamine, N, N-didecyl decylamine, N-mercapto decylamine, N-mercaptoacetamide, N, N- Dimercaptoacetamide, N-decylpyrrolidone, disulfoxide, benzyl ethyl ether, dihexyl ether, acetamidine, isophorone, caproic acid, octanoic acid, 1-octanol, 1-nonanol , benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, decyl-butyrolactone, ethylene carbonate, propylene carbonate, phenylacetic acid cyanisol, and the like Things. In view of mutual solubility and reactivity, glycol ethers such as ethylene glycol monoethyl ether, and the like; ethylene glycol alkyl ether acetates, for example, ethyl acesulfame acetate, and the like; esters such as 2- Ethyl hydroxypropionate, and the like; carbitol, such as diethylene glycol monomethyl ether, and the like; propylene glycol alkyl ether acetate, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetic acid, And similar. 23 201214044 The solvent is used as a difference, and particularly 50 to 70 wt%, based on the total amount of the black photosensitive resin composition. When the core agent in this range is included, the black photosensitive resin composition can have an appropriate viscosity to cause an improvement in workability of a light shielding layer. (F) Other Additives The black photosensitive resin composition may further include a decane coupling agent having a reactive substituent such as a carboxyl group, a mercaptopropenyl group, an isocyanate group, an epoxy group, and the like to improve a pair of groups. The attachment of the material. Examples of the sulphur coupling agent include trioxanyl benzoic acid, γ-mercapto oxypropyltrimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, and 7-isocyanide. Acid propyl triethoxy decane, γ-glycidyl methoxypropyl tridecyloxy decane, + (3,4-ethoxycyclohexyl)ethyltrimethoxy decane, and the like. The decane coupling agent may be used singly or as a mixture of two or more. The decane coupling agent may be 0.001 to 5 parts by weight based on 1 part by weight of the organic binder resin. The amount is included. The black photosensitive resin composition may further include an surfactant 俾 to improve coating properties and to suppress spots. Examples of the surfactant may include a fluorine-based surfactant, for example, BM-1000®, and BM-1100® (BM Chemie Inc.); MEGAFACE F 142D®, F 172®, F 173® , with F 183® DAINIPPON INK KAGAKU KOGYO CO.,LTD.) ; FULORAD FC-135®, FULORAD FC-170C®, FULORAD FC-430®, and FULORAD FC-431® (SUMITOMO 3M CO.,LTD.); SURFLON Sl 12®, 24 201214044 SURFLON S-113®, SURFLON S-131®, SURFLON S-141® ' with SURFLON S-145® (ASAHI GLASS CO. ' LTD·); and SH-28PA®, SH-190 ®, SH-193®, SZ-6032® 'with SF-8428® ' and similar (TORAY SILICONE CO· ' LTD.). The surfactant may be included in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the organic binder resin. When the surfactant in this range is included, coating uniformity can be ensured without staining, and the wetting property of a glass substrate is improved. The black photosensitive resin composition may further contain other additives, for example, an antioxidant, a stabilizer, and the like in a predetermined amount, when they lower the properties. According to another specific example, a light shielding layer produced using the photosensitive resin composition is provided. The light shielding layer can be manufactured as follows. (1) Application and film formation The black photosensitive resin composition described above is coated by a spin coating method or a slit coating method, a roller coating method, a screen printing method, an applicator method, and the like. Having a desired thickness, for example, ranging from 〇·9 to 1.5 μηη on a pretreated substrate, and then heating at a temperature ranging from 70 to 90 ° C It takes about 丨〇 to remove a solvent. The film has an optical density of more than 4.0 at a thickness of 〇7. It has a higher optical density, which is better. When the black photosensitive resin composition has an optical density within this range, light from the bottom may not be irradiated. (2) Exposure 25 201214044 A mask is placed on the prepared film to form a pattern. Membrane-coated membranes are graded from 2GG to 5GG nm active shots. The radiation system is performed by using a light source such as a low pressure mercury lamp, a high mercury lamp, an ultra high pressure mercury lamp, a metal toothed lamp, an argon laser, and the like. However, the light source may include an -X ray ... electron beam, and the like, depending on the condition. ^Exposure can be used with 500 mJ/cm2 or less (by 365 nm sensor). A high-pressure mercury lamp is included in the photoreceptor, but depends on the type of component contained in the black photosensitive resin composition, and the combination ratio thereof. The combined amount of the materials, and the thickness of a dry layer vary. (3) Development The exposure film is developed with an aqueous test solution to dissolve and remove unnecessary. p is but the exposed portion is retained to form an image pattern. (4) The post-process developed image pattern can be heated or irradiated with an active ray for curing to achieve excellent heat resistance, photoresist resistance, tight contact properties, crack resistance, chemical resistance, high strength, and storage stability. Sex, and the like. The aforementioned black photosensitive resin composition can bring about excellent insulating properties and optical density required for the light shielding layer. In the following, the invention is explained in more detail with reference to the examples. However, these are exemplary embodiments of the invention and are non-limiting. Examples 1 to 4 and Comparative Examples 1 to 5 Each of the black photosensitive resin compositions according to Examples 1 to 4 and Comparative Examples 1 to 5 was prepared by using the following components to have the contents provided in Table 1 26 201214044 The composition. (A) Organic binder resin (A-1) 159 g of 3,3-bis(4-hydroxyphenyl)_2-benzofuran-1-oxime, 426.6 g of epichlorohydrin, and 160 g of 50% alkali The aqueous solution was mixed and stirred in a flask, and the reaction was carried out at 95 ° C for 1 hour to obtain a bisphenyl benzofuran type epoxy resin. 215 g of a bisphenylbenzofuran type epoxy resin was mixed with 450 mg of triethylbenzylammonium chloride, loomg of 2,6-diisobutylphenol, and 72 g of acrylic acid. The mixture is in the range of 9 to 12 inches. The temperature of the crucible is heated and completely dissolved, and the air is blown into it at a rate of 25 secrets per minute. Then, the resulting product was cooled to room temperature to prepare an achromatic transparent solid bisphenylbenzofuran-type epoxy acrylate. The 287 g of the synthesized bisphenylbenzofuran-type epoxy acrylate was prepared. The ester was dissolved in 2 kg of celecoxib acetate. Then, '38g of 1,2,3,6-tetrahydrophthacid anhydride, 80.5g of diphenyltetramethane dianhydride' and lg Tetraethylammonium bromide was added to the solution. The mixture is slowly heated for the reaction up to 110 to 115. (: 2 hours to prepare a point-and-point resin having a weight average molecular weight of 5,000 g/mol. (A-2) M9g of 3,3-bis(4-hydroxyphenyl)_2 - benzofuran, 426.6 g of surface gas alcohol, and 160 g of a 50% aqueous solution in an il flask and heated at 95 ° C for 1 hour to obtain bisphenylbenzindole An epoxy resin. 215 g of a bisphenylbenzofuran type epoxy resin with 450 mg of triethylbenzylammonium chloride, 1 mg of 2,6-diisobutylphenol, and 72 g of acrylic acid Mixing. The mixture is heated to 9〇27 201214044 to 120°C and completely dissolved, and air is blown into it at a rate. Then, the dissolved product is cooled to room temperature to prepare achromatic color. Transparent solid bisphenylbenzofuran type epoxy acrylate. 287 g of the synthesized bisphenylbenzofuran type epoxy acrylate was dissolved in 2 kg of ceramide acetate. The solution was combined with 10 g of 1,2 , 3,6-tetrahydrophthacid anhydride, 108.5 g of diphenyl hydrazine with tetracarboxylic dianhydride, and lg Tetraethylammonium bromide was mixed. The mixture was slowly heated to 110 to 115 ° C for 2 hours to prepare one of the weight average molecular weights of 30,000 g/mol. B) The reactive unsaturated compound is dipentaerythritol hexaacrylic acid. (C) The photopolymerization initiator is IGR 369 manufactured by Ciba-Geigy Co. (D) Black pigment dispersion (D-1) is used. A pigment dispersion solution of a silver tin alloy (TMP-DC-1, pigment solid = 30%, weight ratio between silver and tin = 7:3, Sumitomo Osaka Cement Co., Ltd.) (D-2) Propylene glycol methyl ether acetate was used using a pigment dispersion solution (C-M-050, Sakata Co.) ° (E) solvent including carbon black. (F) Other additives 7 - glycidyloxypropyl trimethoxy stone Burning (S-510, Chisso Co.) was used as a wonderful coupling agent. 28 201214044 (Table 1) Example Comparative Example 1 2 3 4 1 2 3 4 5 (A) Organic Adhesive Resin (g) (Al ' g) 2 2 2 2 2 2 - 2 2 (A-2, g) - - - - - - 2 - - (B) Reactive unsaturated compound (gj 1 1 1 1 1 1 1 1 1 (C) Photopolymerization initiation Agent (g) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (D) Black pigment dispersion (Dl 'g) 40 (58.8*) 32.5 (53.5*) 30 49* 25 41* - 45 (74.1*) 40 (58.8* 40 (58.8*) 35 (57.6*) (D-2, g) 5 12.5 15 20 45 - - - - (E) Solvent (g) 51.495 51.495 51.495 51.495 51.495 51.495 56.495 56.495 62.495 (F) Other additives 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 Mark * indicates the amount of a silver tin alloy solid, based on the total solids of (A), (B), (C), (D), (E), and (F) . Evaluation 1 - Optical Density The black photosensitive resin compositions according to Examples 1 to 4 and Comparative Examples 1 to 5 were individually coated on a 0.7 mm-thick glass substrate and connected to each other at 90. Drying on a °C heating plate lasted 2.5 minutes to produce a 〇7/xm-thick film. The film was cooled to room temperature and dried in a convection drying oven for 30 minutes at rc. In turn, each film was optically densified by using a _3ι〇τ^ optical density meter (X-lite Co.). The results are provided in the following Table 2. ^ <Evaluation Reference> 〇: Optical density more than 4 Δ: Optical density ranging from 2_5 to 4.0 X: Optical density less than 2_5 29 201214044 Evaluation 2 - Pattern formation property measurement Each film obtained in the evaluation crucible according to Examples 1 to 4 and Comparative Examples i to 5 was covered with a pattern mask and irradiated with a wavelength of 365 nm at 40 mJ/cm 2 . The product was developed at 2; rc was developed with an aqueous solution diluted with 1 wt〇/o potassium hydroxide for 1 minute and then cleaned with pure water for 1 minute. The obtained pattern was heated and at 220 ° The curing in the C oven lasted for 30 minutes and was followed by inspection using an optical microscope. The results are provided in Table 2 below and in Figures 1 and 2. Figure 1 is a scan showing the pattern of the film according to Example 1. Electron microscopy (SEM) image. Figure 2 shows Scanning electron microscope (SEM) image according to the pattern of the film of Comparative Example 1. <Evaluation Reference> 〇: Good formation of 10 μιη pattern △ : 10 μπι pattern was not formed well X : 10 μιη pattern was not formed Evaluation 3 - Resolution Measurement Each pattern obtained in Evaluation 2 according to Examples 1 to 4 and Comparative Examples 1 to 5 was examined with an optical microscope for the smallest pattern. The results are provided in Table 2 below. The resolution measurements in Table 2 below indicate the pattern size of a mask used during exposure and are measured by using VK-855® manufactured by KEYENCE Co. Evaluation 4-Dielectric Constant Measurement The black photosensitive resin compositions according to Examples 1 to 4 and Comparative Examples 1 to 5 were each used separately to prepare a light-shielding layer. Here, as for the 30 201214044 substrate, an ITO (Indium Tin Oxide) glass was used. The lower substrate is partially disposed with a light shielding layer, but exposes the germanium to the remaining portion. Then, a gold (Au) electrode is sputtered onto the prepared sample. The resulting product isThe capacitance was measured by an LCR meter device to calculate the dielectric constant. The results are provided in the following Table 2. (Table 2) Example 1 Optical density pattern formation property resolution (μιη) Dielectric constant 〇〇 8 20 Example 2 〇〇 8 23 Example 3 〇〇 8 29 Example 4 〇〇 8 35 Comparative Example 1 〇X 25 50 or more Comparative Example 2 Δ X 8 17 Comparative Example 3 Δ X 30 17 Comparative Example 4 ΔX 7 17 Comparative Example 5 r △ X 7 17 Ref?' Table 2 'According to Examples 1 to 4, including an organic binder resin, a reactive unsaturated compound, and a photopolymerization The initiator, the black pigment comprising carbon black and a silver-tin alloy, and the black photosensitive resin composition of a solvent have excellent resolution or excellent pattern formation properties and optical density, as compared with carbon black or Any of the silver tin alloys are in the black pigments according to Comparative Examples 1 to 5. Specifically, the black photosensitive resin composition including only carbon black according to Comparative Example 1 had deteriorated pattern formation properties, resolution, and dielectric constant' as compared with those according to Examples 1 to 4. The black photosensitive resin composition containing only a silver-tin alloy according to Comparative Examples 2 to 5 had a very deteriorated pattern forming property. Further, referring to Figs. 1 and 2, the film of 2012 201244 of Example 1 has a pattern better than that of the film of Comparative Example 1. Further, the black photosensitive resin composition containing silver tin alloy included in the outside of the range according to Comparative Example 2 has deteriorated pattern forming properties and optical density' as compared with Examples 1 to 4 including 5 to 6 〇 wt% of an amount (based on the total amount thereof) of such a silver-containing tin alloy. Further, the black photosensitive resin composition comprising the binder resin having a weight average molecular weight ranging from ιοοο to 20,000 g/m〇1 according to Comparative Example 2 has a better resolution than the comparison. The third embodiment includes the bismuth-based binder resin outside the range. Although the present disclosure has been described in what is considered to be a practical illustrative embodiment, it is understood that the invention is not limited to the specific examples disclosed, but rather, Various modifications and equivalent configurations of _. The foregoing specific examples are illustrative but not restrictive. [Simplified Schematic Description] Scanning of Residues of the Case FIG. 1 shows the basis of Example 1. A film-based electron microscope (SEM) image; Fig. 2 is a scanning electron microscope (3 ugly) image showing the residue of the film according to Comparative Example 1. [Main component symbol] Description] (none) 32
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| TWI493288B (en) * | 2012-04-13 | 2015-07-21 | Ism Co Ltd | Photosensitive polymer resin for thick layer and resin composition including the same |
| CN113140950A (en) * | 2021-03-29 | 2021-07-20 | 常州莱特康光电科技有限公司 | Laser gain unit, manufacturing method of laser gain unit and laser gain module |
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| JP2008051934A (en) | 2006-08-23 | 2008-03-06 | Fujifilm Corp | Photosensitive composition and photosensitive transfer material using the same, light-shielding film for display device and method for producing the same, substrate with the light-shielding film, and the display device |
| KR20100066197A (en) * | 2008-12-09 | 2010-06-17 | 제일모직주식회사 | Black photosensitive resin composition, and black matrix and column spacer using the same |
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| TWI493288B (en) * | 2012-04-13 | 2015-07-21 | Ism Co Ltd | Photosensitive polymer resin for thick layer and resin composition including the same |
| CN113140950A (en) * | 2021-03-29 | 2021-07-20 | 常州莱特康光电科技有限公司 | Laser gain unit, manufacturing method of laser gain unit and laser gain module |
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