TWI667336B - Colored photosensitive resin composition suitable for both column spacer and black matrix - Google Patents

Colored photosensitive resin composition suitable for both column spacer and black matrix Download PDF

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TWI667336B
TWI667336B TW103102604A TW103102604A TWI667336B TW I667336 B TWI667336 B TW I667336B TW 103102604 A TW103102604 A TW 103102604A TW 103102604 A TW103102604 A TW 103102604A TW I667336 B TWI667336 B TW I667336B
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resin composition
photosensitive resin
colored photosensitive
meth
compound
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TW201439293A (en
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朴仟順
崔慶植
宋鎬石
李素蓏
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南韓商羅門哈斯電子材料韓國公司
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
    • G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
    • G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)
  • Electroluminescent Light Sources (AREA)
  • Epoxy Resins (AREA)

Abstract

本案提供一種有色光敏樹脂組成物，包含共聚物、環氧樹脂化合物或由其衍生的化合物、可聚合化合物、光聚合起始劑、及包括黑著色劑及藍著色劑之著色劑。當該有色光敏樹脂組成物係形成為固化層時，可獲得良好透射比及光密度，以及良好彈性回復率、解析度、化學抗性、及厚度。因此，該有色光敏樹脂組成物可成形為柱狀間隔子、黑色矩陣、或黑色柱狀間隔子，及可用於多種電子部件，諸如有機發光二極體顯示器及液晶顯示器裝置的面板。 The present invention provides a colored photosensitive resin composition including a copolymer, an epoxy resin compound or a compound derived therefrom, a polymerizable compound, a photopolymerization initiator, and a coloring agent including a black colorant and a blue colorant. When the colored photosensitive resin composition is formed as a cured layer, good transmittance and optical density, as well as good elastic recovery, resolution, chemical resistance, and thickness can be obtained. Therefore, the colored photosensitive resin composition can be formed into a columnar spacer, a black matrix, or a black columnar spacer, and can be used for a variety of electronic components such as an organic light emitting diode display and a panel of a liquid crystal display device.

Description

適用於柱狀間隔子及黑色矩陣兩者之有色光敏樹脂組成物 Colored photosensitive resin composition suitable for both column spacer and black matrix

本發明係有關於適合形成採用於有機發光二極體(OLED)顯示器或液晶顯示器(LCD)面板內的鈍化層、層間電介質、間隔子、光屏蔽部件的有色光敏樹脂組成物，及從該組成物所形成的固化層，特別為黑色柱狀間隔子(BCS)，其中柱狀間隔子與黑色矩陣結合成一體。 The present invention relates to a colored photosensitive resin composition suitable for forming a passivation layer, an interlayer dielectric, a spacer, and a light shielding member used in an organic light emitting diode (OLED) display or a liquid crystal display (LCD) panel, and from the composition The solidified layer formed by the object is a black columnar spacer (BCS), in which the columnar spacers are integrated with the black matrix.

晚近，採用從光敏組成物所形成的間隔子以維持在液晶顯示器(LCD)的液晶盒中的上與下透明基板間之距離。因LCD乃藉由施加電壓至注入兩片透明基板間恆定間隙中的液晶材料而驅動的光電裝置，故該兩片基板間之恆定間隙的維持非常重要。若透明基板間之間隙為非恆定，則施加至其上的電壓以及穿透此部分的光透射比可能改變，結果導致空間亮度不均的缺陷。鑑於晚近偏好大尺寸的LCD面板，兩片透明基板間之恆定間隙的維持甚至變得更為關鍵。 Recently, spacers formed from the photosensitive composition are used to maintain the distance between the upper and lower transparent substrates in the liquid crystal cell of a liquid crystal display (LCD). Since an LCD is a photovoltaic device driven by applying a voltage to a liquid crystal material injected into a constant gap between two transparent substrates, the maintenance of a constant gap between the two substrates is very important. If the gap between the transparent substrates is non-constant, the voltage applied to it and the light transmittance through this part may change, resulting in the defect of uneven brightness in the space. In view of the recent preference for large-sized LCD panels, the maintenance of a constant gap between two transparent substrates has become even more critical.

間隔子的形成可經由塗佈光敏樹脂組成物至基板上，及使在其上具有遮罩之經塗佈的基板其曝光於紫外光等，接著為其顯影。晚近，業經致力於使用間隔子用之光屏蔽材料，因 而，已積極地進行發展有色光敏樹脂組成物。 The spacer may be formed by applying a photosensitive resin composition to a substrate, and exposing the coated substrate having a mask thereon to ultraviolet light or the like, and then developing it. Recently, the industry has been committed to using light shielding materials for spacers, because However, development of colored photosensitive resin compositions has been actively carried out.

韓國專利案早期公開第2006-125993號揭示一種對LCD同時形成濾色器鈍化層及柱狀間隔子之方法，及可採用於該方法之負型光阻組成物，及更明確言之，揭示一種同時從具有以氧化膦為主的光聚合起始劑及以丙烯醯基為主的黏結劑的組成物形成濾色器鈍化層(亦即，絕緣層)及柱狀間隔子之方法。 Korean Patent Early Publication No. 2006-125993 discloses a method for simultaneously forming a color filter passivation layer and a columnar spacer for an LCD, and a negative photoresist composition that can be used in the method, and more specifically, discloses A method for simultaneously forming a color filter passivation layer (ie, an insulating layer) and a columnar spacer from a composition having a photopolymerization initiator mainly composed of phosphine oxide and a binder mainly composed of acryl fluorene group.

此外，晚近該方法係藉由發展黑色柱狀間隔子(BSC)而予簡化，其中柱狀間隔子與黑色矩陣係整合成一個模組。然而，BCS必須滿足黑色矩陣的性質，諸如光屏蔽性質，以及柱狀間隔子所需性質，諸如彈性回復率及化學抗性。如此，更進一步要求發展適合用於此等目的之有色光敏樹脂組成物的研究。 In addition, the method was simplified recently by developing a black columnar spacer (BSC), where the columnar spacer and the black matrix are integrated into a module. However, BCS must meet the properties of the black matrix, such as light-shielding properties, and the properties required for columnar spacers, such as elastic recovery and chemical resistance. As such, there is a further demand for research into the development of colored photosensitive resin compositions suitable for these purposes.

因此，本發明之一目的係提供一種同時滿足柱狀間隔子與黑色矩陣之性質的有色光敏樹脂組成物。 Therefore, an object of the present invention is to provide a colored photosensitive resin composition that satisfies the properties of a columnar spacer and a black matrix at the same time.

依據本發明之一態樣，提供一種有色光敏樹脂組成物，包含(a)共聚物，(b)環氧樹脂化合物或由其衍生之化合物，(c)可聚合化合物，(d)光聚合起始劑，及(e)著色劑，其包含以該有色光敏樹脂組成物中固體含量總重為基準之0至5重量%無機黑著色劑，10至40重量%有機黑著色劑，及1至15重量%藍著色劑。 According to one aspect of the present invention, there is provided a colored photosensitive resin composition comprising (a) a copolymer, (b) an epoxy resin compound or a compound derived therefrom, (c) a polymerizable compound, and (d) photopolymerization. An initiator, and (e) a colorant comprising 0 to 5% by weight of an inorganic black colorant, 10 to 40% by weight of an organic black colorant based on the total solid content of the colored photosensitive resin composition, and 1 to 15% by weight blue colorant.

依據本發明之另一態樣，提供一種從該有色光敏樹脂組成物所形成的柱狀間隔子、黑色矩陣、或黑色柱狀間隔子(BCS)。 According to another aspect of the present invention, a columnar spacer, a black matrix, or a black columnar spacer (BCS) formed from the colored photosensitive resin composition is provided.

依據本發明之又另一態樣，提供一種包含該柱狀間隔子、黑色矩陣、或黑色柱狀間隔子(BCS)的電子部件。 According to another aspect of the present invention, there is provided an electronic component including the columnar spacer, a black matrix, or a black columnar spacer (BCS).

本發明之有色光敏樹脂組成物具有良好曝光極限及顯影極限，及當形成為固化層時，針對黑色矩陣之性質諸如透射比及光密度，以及針對柱狀間隔子之性質諸如彈性回復率、解析度、化學抗性、及塗佈厚度，可提供同等滿意的性質。因此，該組成物有用以形成有色間隔子、黑色矩陣、BCS等係有用的，其可用於各種電子部件，諸如OLED顯示器及LCD的面板。 The colored photosensitive resin composition of the present invention has good exposure limit and development limit, and when formed as a cured layer, properties against a black matrix such as transmittance and optical density, and properties against a columnar spacer such as elastic recovery rate, analysis, etc. Degree, chemical resistance, and coating thickness provide equally satisfactory properties. Therefore, the composition is useful for forming colored spacers, black matrices, BCS, and the like, and it can be used for various electronic components such as OLED displays and LCD panels.

A‧‧‧柱狀間隔子部件之厚度 A‧‧‧Thickness of column spacer

B‧‧‧黑色矩陣部件之厚度 B‧‧‧Thickness of Black Matrix Parts

C‧‧‧柱狀間隔子部件之臨界維度(CD) C‧‧‧ Critical Dimensions of Columnar Spacer Subcomponents (CD)

當後文之發明說明結合附圖時，本發明之前述及其它目的及特徵將變得更為彰顯，附圖中顯示：第1圖：黑色柱狀間隔子(BCS)之橫截面之具體實施例的示意圖(A：柱狀間隔子部件之厚度；B：黑色矩陣部件之厚度；及C：柱狀間隔子部件之臨界維度(CD))。 When the following description of the invention is combined with the accompanying drawings, the foregoing and other objects and features of the present invention will become more prominent. The drawings show: Figure 1: Implementation of the cross section of the black column spacer (BCS) Schematic diagram of the example (A: thickness of the columnar spacer sub-component; B: thickness of the black matrix component; and C: critical dimension (CD) of the columnar spacer sub-component).

後文中，將以進一步細節描述本發明。 Hereinafter, the present invention will be described in further detail.

有色光敏樹脂組成物 Colored photosensitive resin composition

依據本發明之具體實施例，有色光敏樹脂組成物包含(a)共聚物，(b)環氧樹脂化合物或由其衍生之化合物，(c)可聚合化合物，(d)光聚合起始劑，及(e)著色劑，其包括黑著色劑及藍著色劑，及視需要地，(f)溶劑，(g)界面活性劑，及/或(h)矽烷偶合劑。 According to a specific embodiment of the present invention, the colored photosensitive resin composition includes (a) a copolymer, (b) an epoxy resin compound or a compound derived therefrom, (c) a polymerizable compound, (d) a photopolymerization initiator, And (e) a colorant, which includes a black colorant and a blue colorant, and (f) a solvent, (g) a surfactant, and / or (h) a silane coupling agent, if necessary.

於本說明書中，「(甲基)丙烯醯基」表示「丙烯醯基」及/或「甲基丙烯醯基」，及「(甲基)丙烯酸酯」表示「丙烯酸酯」及/或「甲基丙烯酸酯」。 In this specification, "(meth) acrylfluorenyl" means "acrylfluorenyl" and / or "methacrylfluorenyl", and "(meth) acrylate" means "acrylate" and / or "formyl" Acrylate ".

後文中，將詳細解釋有色光敏樹脂組成物的各個成分。 Hereinafter, each component of the colored photosensitive resin composition will be explained in detail.

(a)共聚物 (a) Copolymer

本發明使用的共聚物可包含(a-1)衍生自烯系不飽和羧酸、烯系不飽和羧酸酐、或其混合物之單元；及(a-2)衍生自含芳香環的烯系不飽和化合物之單元；及可進一步包含(a-3)與(a-1)及(a-2)相異之衍生自烯系不飽和化合物之單元。 The copolymer used in the present invention may include (a-1) a unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof; and (a-2) an ethylenically unsaturated compound containing an aromatic ring A unit of a saturated compound; and may further include a unit derived from an ethylenically unsaturated compound, which is different from (a-3) and (a-1) and (a-2).

該共聚物係為鹼溶性樹脂，於顯影步驟提供顯影功能，同時用作為形成塗層的基劑以及用作為形成終圖案的結構。 The copolymer is an alkali-soluble resin, which provides a developing function in the developing step, and is used as a base for forming a coating layer and as a structure for forming a final pattern.

(a-1)衍生自烯系不飽和羧酸、烯系不飽和羧酸酐、或其混合物之單元 (a-1) Units derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof

於本發明中，單元(a-1)係衍生自烯系不飽和羧酸、烯系不飽和羧酸酐、或其混合物。該烯系不飽和羧酸及烯系不飽和羧酸酐乃分子中具有至少一個羧基的可聚合不飽和單體。其實施例包括不飽和單羧酸，諸如(甲基)丙烯酸、巴豆酸、α-氯丙烯酸、桂皮酸等；不飽和二羧酸及其酐，諸如順丁烯二酸、順丁烯二酸酐、反丁烯二酸、伊康酸、伊康酸酐、檸康酸、檸康酸酐、甲基反丁烯二酸等；三價或更多價的不飽和多羧酸及其酐；二價或更多價的多羧酸之單[(甲基)丙烯醯基氧基烷基]酯，諸如丁二酸單[2-(甲基)丙烯醯基氧基乙基]酯、酞酸單[2-(甲基)丙烯醯基氧基乙基]酯等。衍生自如上例示性化合物的單元可以單一種化合物或以二種或更多種化合物之組合而含於該共聚物。 In the present invention, the unit (a-1) is derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof. The ethylenically unsaturated carboxylic acid and the ethylenically unsaturated carboxylic acid anhydride are polymerizable unsaturated monomers having at least one carboxyl group in the molecule. Examples thereof include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like; unsaturated dicarboxylic acids and their anhydrides such as maleic acid, maleic anhydride , Fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, methyl fumaric acid, etc .; unsaturated polycarboxylic acids of three or more valences and their anhydrides; divalent Mono [(meth) acrylfluorenyloxyalkyl] esters of polyvalent or higher carboxylic acids, such as succinic acid mono [2- (meth) acrylfluorenyloxyethyl] ester, phthalic acid mono [2- (meth) acrylfluorenyloxyethyl] ester and the like. The unit derived from the exemplified compound as above may be contained in the copolymer by a single compound or a combination of two or more compounds.

以組成該共聚物之單元的總莫耳數為基準，單元(a-1)之用量可為5至65莫耳%，及較佳地10至50莫耳%。在此用量範圍內容易維持顯影性質。 Based on the total number of moles of the units constituting the copolymer, the amount of the unit (a-1) may be 5 to 65 mole%, and preferably 10 to 50 mole%. It is easy to maintain the developing property within this amount range.

(a-2)衍生自含芳香環的烯系不飽和化合物之單元 (a-2) Units derived from aromatic ring-containing ethylenically unsaturated compounds

單元(a-2)係衍生自含芳香環的烯系不飽和化合物。其實施例 可包括(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-苯氧基乙酯、苯氧基二乙二醇(甲基)丙烯酸酯、對壬基苯氧基聚乙二醇(甲基)丙烯酸酯、對壬基苯氧基聚丙二醇(甲基)丙烯酸酯、(甲基)丙烯酸三溴苯酯；苯乙烯；具有烷基取代基之苯乙烯，諸如甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、二乙基苯乙烯、三乙基苯乙烯、丙基苯乙烯、丁基苯乙烯、己基苯乙烯、庚基苯乙烯、辛基苯乙烯等；具有鹵素之苯乙烯，諸如氟苯乙烯、氯苯乙烯、溴苯乙烯、碘苯乙烯等；具有烷氧基取代基之苯乙烯，諸如甲氧基苯乙烯、乙氧基苯乙烯、丙氧基苯乙烯等；4-羥基苯乙烯、對-羥基-α-甲基苯乙烯、乙醯基苯乙烯；乙烯基甲苯、二乙烯基苯、乙烯基酚、鄰-乙烯基苄基甲基醚、間-乙烯基苄基甲基醚、對-乙烯基苄基甲基醚、鄰-乙烯基苄基縮水甘油基醚、間-乙烯基苄基縮水甘油基醚、對-乙烯基苄基縮水甘油基醚等。 The unit (a-2) is derived from an aromatic ring-containing ethylenically unsaturated compound. Its examples May include phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, p-nonylphenoxy Based polyethylene glycol (meth) acrylate, p-nonylphenoxy polypropylene glycol (meth) acrylate, tribromophenyl (meth) acrylate; styrene; styrene with alkyl substituents, such as Methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptyl Styrene, octylstyrene, etc .; styrenes with halogens, such as fluorostyrene, chlorostyrene, bromostyrene, iodostyrene, etc .; styrenes with alkoxy substituents, such as methoxystyrene, Ethoxystyrene, propoxystyrene, etc .; 4-hydroxystyrene, p-hydroxy-α-methylstyrene, ethylfluorenylstyrene; vinyltoluene, divinylbenzene, vinylphenol, o -Vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl Ether, m - vinylbenzyl glycidyl ether, p - vinylbenzyl glycidyl ether.

衍生自如上例示性化合物的單元可以單一種化合物或以二種或更多種化合物之組合而含於該共聚物。 The unit derived from the exemplified compound as above may be contained in the copolymer by a single compound or a combination of two or more compounds.

鑑於其可聚合性，於該等化合物中，以苯乙烯為主的化合物為佳。 In view of its polymerizability, among these compounds, styrene-based compounds are preferred.

以組成該共聚物之單元的總莫耳數為基準，單元(a-2)之用量可為2至70莫耳%，及較佳地5至60莫耳%。在此用量範圍內，該樹脂組成物可具有有利的化學抗性。 Based on the total number of moles of the units constituting the copolymer, the amount of the unit (a-2) may be 2 to 70 mole%, and preferably 5 to 60 mole%. Within this amount range, the resin composition may have favorable chemical resistance.

(a-3)與(a-1)及(a-2)相異之衍生自烯系不飽和化合物之單元。 (a-3) A unit derived from an ethylenically unsaturated compound which is different from (a-1) and (a-2).

本發明所使用的共聚物除了(a-1)及(a-2)之外，可進一步包含與(a-1)及(a-2)相異之衍生自烯系不飽和化合物之單元。其 範例可包括不飽和羧酸酯諸如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸乙基己酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基-3-氯丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸甘油酯、α-羥基甲基丙烯酸甲酯、α-羥基甲基丙烯酸乙酯、α-羥基甲基丙烯酸丙酯、α-羥基甲基丙烯酸丁酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸3-甲氧基丁酯、乙氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、甲氧基三丙二醇(甲基)丙烯酸酯、聚(乙二醇)甲基醚(甲基)丙烯酸酯、(甲基)丙烯酸四氟丙酯、(甲基)丙烯酸1,1,1,3,3,3-六氟異丙酯、(甲基)丙烯酸八氟戊酯、(甲基)丙烯酸十七氟癸酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊烷酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烷基氧基乙酯、(甲基)丙烯酸二環戊烯基氧基乙酯等；具有N-乙烯基之三級胺，諸如N-乙烯基吡咯啶酮、N-乙烯基咔唑、N-乙烯基嗎啉等；不飽和醚，諸如乙烯基甲基醚、及乙烯基乙基醚；具有環氧基之烯系不飽和化合物，諸如(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧基丁酯、(甲基)丙烯酸4,5-環氧基戊酯、(甲基)丙烯酸5,6-環氧基己酯、(甲基)丙烯酸6,7-環氧基庚酯、(甲基)丙烯酸2,3-環氧基環戊酯、(甲基)丙烯酸3,4-環氧基環己酯、丙烯酸α-乙基縮水甘油酯、丙烯酸α-正丙基縮水甘油酯、丙烯酸α-正丁基縮水甘油酯、N-(4-(2,3-環氧基丙氧基)-3,5-二甲基苄基)丙烯醯胺、N-(4-(2,3-環氧基丙氧基)-3,5-二甲基苯基丙基)丙烯醯胺、(甲基)丙烯酸4-羥基 丁酯縮水甘油醚、烯丙基縮水甘油醚、2-甲基烯丙基縮水甘油醚等；不飽和醯亞胺，諸如N-苯基順丁烯二醯亞胺、N-(4-氯苯基)順丁烯二醯亞胺、N-(4-羥基苯基)順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺等。 In addition to (a-1) and (a-2), the copolymer used in the present invention may further include units derived from ethylenically unsaturated compounds that are different from (a-1) and (a-2). its Examples may include unsaturated carboxylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth) Isobutyl acrylate, third butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyl (meth) acrylate Ethyl ester, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glyceryl (meth) acrylate, α- Methyl hydroxymethacrylate, α-hydroxymethacrylate, α-hydroxymethacrylate, α-hydroxymethacrylate, 2-methoxyethyl (meth) acrylate, (methyl ) 3-methoxybutyl acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, Poly (ethylene glycol) methyl ether (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, ( Octafluoropentyl (meth) acrylate, 17 (meth) acrylic acid Decyl ester, isobornyl (meth) acrylate, dicyclopentane (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, ( Dicyclopentenyloxyethyl meth), etc .; tertiary amines with N-vinyl, such as N-vinylpyrrolidone, N-vinylcarbazole, N-vinylmorpholine, etc .; Saturated ethers, such as vinyl methyl ether, and vinyl ethyl ether; ethylenically unsaturated compounds with epoxy groups, such as glycidyl (meth) acrylate, 3,4-epoxy (meth) acrylate Butyl ester, 4,5-epoxypentyl (meth) acrylate, 5,6-epoxyhexyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, (formyl) Base) 2,3-epoxycyclopentyl acrylate, 3,4-epoxycyclohexyl (meth) acrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, acrylic acid α-n-butyl glycidyl ester, N- (4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl) acrylamide, N- (4- (2,3 -Epoxypropoxy) -3,5-dimethylphenylpropyl) acrylamide, 4-hydroxy (meth) acrylic acid Butyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, etc .; unsaturated fluorene imines, such as N-phenylcis butylene difluorene, N- (4-chloro Phenyl) cis-butenedifluorene imine, N- (4-hydroxyphenyl) cis-butenedifluoreneimine, N-cyclohexylcis-butenediimine, and the like.

衍生自如上例示性化合物的單元可以單一種化合物或以二種或更多種化合物之組合而含於該共聚物。 The unit derived from the exemplified compound as above may be contained in the copolymer by a single compound or a combination of two or more compounds.

鑑於其可共聚合性及用於絕緣層強度的改良，較佳地，可使用衍生自具有環氧基及/或不飽和醯亞胺之烯系不飽和化合物之單元，更佳地可使用衍生自(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸4-羥基丁酯縮水甘油醚及/或N-經取代之順丁烯二醯亞胺的單元。 In view of its copolymerizability and improvement of the strength of the insulating layer, it is preferable to use a unit derived from an ethylenically unsaturated compound having an epoxy group and / or an unsaturated fluorene imine, and it is more preferable to use a derivative Units from glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether and / or N-substituted maleimide.

以組成該共聚物之單元的總莫耳數為基準，單元(a-3)之用量可為10至80莫耳%，及較佳地20至75莫耳%。在此用量範圍內，可維持黏結劑的安定性且可改良塗層的殘留率。 Based on the total mole number of units constituting the copolymer, the amount of the unit (a-3) may be 10 to 80 mole%, and preferably 20 to 75 mole%. Within this amount range, the stability of the adhesive can be maintained and the residual rate of the coating can be improved.

具有前述單元(a-1)至(a-3)的共聚物可包括(甲基)丙烯酸/苯乙烯共聚物、(甲基)丙烯酸/(甲基)丙烯酸苄酯共聚物、(甲基)丙烯酸/苯乙烯/(甲基)丙烯酸甲酯共聚物、(甲基)丙烯酸/苯乙烯/(甲基)丙烯酸甲酯/(甲基)丙烯酸縮水甘油酯共聚物、(甲基)丙烯酸/苯乙烯/(甲基)丙烯酸甲酯/(甲基)丙烯酸縮水甘油酯/N-苯基順丁烯二醯亞胺共聚物、(甲基)丙烯酸/苯乙烯/(甲基)丙烯酸甲酯/(甲基)丙烯酸縮水甘油酯/N-環己基順丁烯二醯亞胺共聚物、(甲基)丙烯酸/苯乙烯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸縮水甘油酯/N-苯基順丁烯二醯亞胺共聚物、(甲基)丙烯酸/苯乙烯/(甲基)丙烯酸縮水甘油酯/N-苯基順丁烯二醯亞胺共聚物等。 The copolymer having the aforementioned units (a-1) to (a-3) may include (meth) acrylic acid / styrene copolymer, (meth) acrylic acid / (meth) acrylic acid benzyl copolymer, (meth) Acrylic acid / styrene / methyl (meth) acrylate copolymer, (meth) acrylic acid / styrene / methyl (meth) acrylate / glycidyl (meth) acrylate copolymer, (meth) acrylic acid / benzene Ethylene / methyl (meth) acrylate / glycidyl (meth) acrylate / N-phenylcis butylene diimide copolymer, (meth) acrylic acid / styrene / methyl (meth) acrylate / Glycidyl (meth) acrylate / N-cyclohexyl maleimide diimide copolymer, (meth) acrylic acid / styrene / n-butyl (meth) acrylate / glycidyl (meth) acrylate / N-phenyl maleimide diimide copolymer, (meth) acrylic acid / styrene / glycidyl (meth) acrylate / N-phenyl maleimide diimide copolymer, and the like.

一或多個種類的該共聚物可含在有色光敏樹脂組成物。 One or more kinds of the copolymer may be contained in the colored photosensitive resin composition.

藉由凝膠滲透層析術(洗提劑：四氫呋喃等)以聚苯乙烯為參考品測得該共聚物的重量平均分子量(Mw)可為3,000至50,000，較佳地5,000至40,000。在該範圍內，對基板的黏著性、物理/化學性質及黏度可合乎期望。 The weight average molecular weight (Mw) of the copolymer measured by gel permeation chromatography (eluent: tetrahydrofuran, etc.) using polystyrene as a reference may be 3,000 to 50,000, preferably 5,000 to 40,000. Within this range, adhesion, physical / chemical properties, and viscosity to the substrate may be desirable.

以有色光敏樹脂組成物排除溶劑後的總重為基準(亦即，以固體含量為基準)，共聚物於該有色光敏樹脂組成物中之含量可為0.5至60重量%，較佳地5至50重量%。在前述範圍內，於顯影後可獲得具有良好形狀的圖案，及可改良諸如化學抗性等性質。 Based on the total weight of the colored photosensitive resin composition after excluding the solvent (that is, based on the solid content), the content of the copolymer in the colored photosensitive resin composition may be 0.5 to 60% by weight, preferably 5 to 60% by weight. 50% by weight. Within the foregoing range, a pattern having a good shape can be obtained after development, and properties such as chemical resistance can be improved.

該共聚物之製備方式可經由將分子量控制劑、自由基聚合起始劑、溶劑、及單元(a-1)至(a-3)置於反應器內；將氮氣注入反應器內及徐緩攪拌混合物以進行聚合。 The copolymer can be prepared by placing a molecular weight control agent, a radical polymerization initiator, a solvent, and units (a-1) to (a-3) in a reactor; injecting nitrogen into the reactor and slowly stirring The mixture was subjected to polymerization.

分子量控制劑並無特殊限制，而且可包括硫醇類諸如丁基硫醇、辛基硫醇等，或α-甲基苯乙烯二元體。 The molecular weight controlling agent is not particularly limited, and may include mercaptans such as butyl mercaptan, octyl mercaptan, or the like, or α-methylstyrene binary.

自由基聚合起始劑並無特殊限制，而且可包括偶氮化合物諸如2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(4-甲氧基2,4-二甲基戊腈)等、過氧化苯甲醯、過氧化月桂醯、過氧化新戊酸第三丁酯、1,1-雙(過氧化第三丁基)環己烷等。該自由基聚合起始劑可單獨使用或組合二或多者使用。 The radical polymerization initiator is not particularly limited, and may include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-Azobis (4-methoxy2,4-dimethylvaleronitrile), etc., Benzamidine peroxide, Laurel peroxide, Tertiary butyl pivalate, 1,1 -Bis (third butyl peroxide) cyclohexane and the like. The radical polymerization initiator may be used alone or in combination of two or more.

又，用於共聚物之製備的任一種溶劑皆可使用，而且其可包括例如丙二醇單甲醚乙酸酯(PGMEA)。 Also, any solvent used for the preparation of the copolymer may be used, and it may include, for example, propylene glycol monomethyl ether acetate (PGMEA).

(b)環氧樹脂化合物或由其衍生的化合物 (b) Epoxy resin compounds or compounds derived therefrom

本發明之有色光敏樹脂組成物包含環氧樹脂化合物或由其衍生的化合物，較佳地具有二苯并吡喃(xanthene)主鏈結構的環氧樹脂化合物或由其衍生的化合物。藉由凝膠滲透層析術以聚苯乙烯為參考品測得之具有400至10,000重量平均分子量(Mw)之化合物可用作環氧樹脂化合物，及該化合物可為如下式1表示之具有二苯并吡喃主鏈結構的環氧樹脂化合物： The colored photosensitive resin composition of the present invention comprises an epoxy resin compound or a compound derived therefrom, preferably an epoxy resin compound having a xanthene main chain structure or a compound derived therefrom. A compound having a weight average molecular weight (Mw) of 400 to 10,000 measured by gel permeation chromatography with polystyrene as a reference may be used as the epoxy resin compound, and the compound may have Epoxy compound with benzopyran backbone structure:

其中標示*的各碳係獨立地以標示*且含在 ，或中之碳置 換；L1係各自獨立地為C1-10伸烷基、C3-20伸環烷基或C1-10伸烷基氧基；R1至R7各自獨立地為H、C1-10烷基、C1-10烷氧基、C2-10烯基、或C6-14芳基；R8為H、甲基、乙基、CH3CHCl-、CH3CHOH-、CH2=CHCH2-、或苯基；及n為0至10之整數。 Each carbon marked with * is independently marked with * and contained in ,or Carbon substitution in; L 1 is each independently C 1-10 alkylene, C 3-20 cycloalkyl or C 1-10 alkyleneoxy; R 1 to R 7 are each independently H, C 1-10 alkyl, C 1-10 alkoxy, C 2-10 alkenyl, or C 6-14 aryl; R 8 is H, methyl, ethyl, CH 3 CHCl-, CH 3 CHOH- , CH 2 = CHCH 2- , or phenyl; and n is an integer from 0 to 10.

C1-10伸烷基之具體實施例可包括亞甲基、伸乙基、伸丙基、伸異丙基、伸丁基、伸異丁基、伸第二丁基、伸第三丁基、伸戊基、伸異戊基、伸第三戊基、伸己基、伸庚基、伸辛基、伸異辛基、伸第三辛基、2-乙基伸己基、伸壬基、伸異壬基、伸癸 基、伸異癸基等。C3-20伸環烷基之具體實施例可包括伸環丙基、伸環丁基、伸環戊基、伸環己基、伸環庚基、伸十氫萘基、伸金剛烷基等。C1-10伸烷基氧基之具體實施例可包括亞甲基氧基、伸乙基氧基、伸丙基氧基、伸丁基氧基、伸第二丁基氧基、伸第三丁基氧基、伸戊基氧基、伸己基氧基、伸庚基氧基、伸辛基氧基、2-乙基-伸己基氧基等。C1-10烷基之具體實施例可包括甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、第三戊基、己基、庚基、辛基、異辛基、第三辛基、2-乙基己基、壬基、異壬基、癸基、異癸基等。C1-10烷氧基之具體實施例可包括甲氧基、乙氧基、丙氧基、丁氧基、第二丁氧基、第三丁氧基、戊氧基、己氧基、庚氧基、辛氧基、2-乙基-己基氧基等。C2-10烯基之具體實施例可包括乙烯基、烯丙基、丁烯基、丙烯基等。C6-14芳基之具體實施例可包括苯基、甲苯基、二甲苯基、萘基等。 Specific examples of C 1-10 alkylene may include methylene, ethylene, propyl, isopropyl, butyl, isobutyl, second butyl, and third butyl , Pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl, hexyl, hexyl Nonyl, decyl, and isodecyl. Specific examples of C 3-20 cycloalkylene may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, decalinyl, adamantyl, and the like. Specific examples of C 1-10 alkyleneoxy may include methyleneoxy, ethyleneoxy, propyloxy, butyloxy, second butyloxy, and third Butyloxy, pentenyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethyl-hexyloxy and the like. Specific examples of C 1-10 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, isopentyl, Tripentyl, hexyl, heptyl, octyl, isooctyl, third octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, and the like. Specific examples of C 1-10 alkoxy may include methoxy, ethoxy, propoxy, butoxy, second butoxy, third butoxy, pentyloxy, hexyloxy, heptyl Oxy, octyloxy, 2-ethyl-hexyloxy and the like. Specific examples of C 2-10 alkenyl may include vinyl, allyl, butenyl, propenyl, and the like. Specific examples of the C 6-14 aryl group may include phenyl, tolyl, xylyl, naphthyl, and the like.

衍生自式1之具有二苯并吡喃主鏈結構的環氧樹脂之化合物可藉由下述方式獲得：經由讓式1之具有二苯并吡喃主鏈結構的環氧樹脂與不飽和鹼性酸反應而製造環氧加合物，及讓如此所得的環氧加合物與多元酸酐反應；或經由另外地讓如此所得的化合物與單官能或多官能環氧化合物反應。發明所屬技術領域中已知之任一種不飽和元(unsaturated basic acid)酸例如丙烯酸、甲基丙烯酸、巴豆酸、桂皮酸、山梨酸等皆可用於本發明。發明所屬技術領域中已知之任一種多元酸酐例如丁二酸酐、順丁烯二酐、偏苯三酸酐、均苯四酸酐等皆可用於本發明。發明所屬技術領域已知之任一種單官能或多官能環氧化合物例如甲基丙烯 酸縮水甘油酯、甲基縮水甘油醚、乙基縮水甘油醚、丙基縮水甘油醚、異丙基縮水甘油醚、丁基縮水甘油醚、異丁基縮水甘油醚、雙酚Z縮水甘油醚等皆可用於本發明。 A compound derived from an epoxy resin having a dibenzopyran backbone structure of Formula 1 can be obtained by allowing an epoxy resin having a dibenzopyran backbone structure of Formula 1 and an unsaturated base to be obtained. An acid adduct is reacted to produce an epoxy adduct, and the epoxy adduct thus obtained is reacted with a polybasic acid anhydride; or the compound thus obtained is additionally reacted with a monofunctional or polyfunctional epoxy compound. Any unsaturated basic acid known in the technical field to which the invention belongs, such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, etc., can be used in the present invention. Any polybasic acid anhydride known in the technical field to which the invention belongs, such as succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, etc., can be used in the present invention. Any of the monofunctional or polyfunctional epoxy compounds known in the art to which the invention belongs, such as methacrylic acid Acid glycidyl ester, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, bisphenol Z glycidyl ether, etc. Both can be used in the present invention.

當使用衍生自式1之具有二苯并吡喃主鏈結構的環氧樹脂之化合物時，該二苯并吡喃主鏈結構可改良固化材料對基板的黏著性、抗鹼性、加工性、強度等，且一旦顯影去除未固化部分，則可形成具有精細解析度影像之圖案。 When a compound derived from an epoxy resin having a dibenzopyran backbone structure of Formula 1 is used, the dibenzopyran backbone structure can improve the adhesion, alkali resistance, processability, Strength, etc., and once the uncured portion is removed by development, a pattern with a fine resolution image can be formed.

以有色光敏樹脂組成物排除溶劑後之總量為基準(亦即，以固體含量為基準)，環氧樹脂化合物或由其衍生的化合物之用量可為1至70重量%，較佳5至50重量%。於該範圍內，可改良解析度及化學抗性，可良好維持圖案形狀，以及可有利地獲得具有期望的邊界寬度(亦即，可容許之寬度)的圖案間之恆定階差(step difference)。 Based on the total amount of the colored photosensitive resin composition after excluding the solvent (that is, based on the solid content), the amount of the epoxy resin compound or a compound derived therefrom may be 1 to 70% by weight, preferably 5 to 50%. weight%. Within this range, the resolution and chemical resistance can be improved, the pattern shape can be well maintained, and a constant step difference between patterns having a desired boundary width (that is, an allowable width) can be advantageously obtained. .

(c)可聚合化合物 (c) Polymerizable compounds

用於本發明之可聚合化合物可為任一種可藉由聚合起始劑聚合的化合物，且可為常用於有色光敏樹脂組成物的多官能單體、寡聚物或聚合物。 The polymerizable compound used in the present invention may be any compound polymerizable by a polymerization initiator, and may be a polyfunctional monomer, oligomer, or polymer commonly used in colored photosensitive resin compositions.

更明確言之，可聚合化合物可包括具有至少一個烯系不飽和雙鍵的丙烯酸或甲基丙烯酸之單官能或多官能酯化合物，且可為具有至少兩個官能基以獲得期望的化學抗性之多官能化合物。 More specifically, the polymerizable compound may include a monofunctional or polyfunctional ester compound of acrylic acid or methacrylic acid having at least one ethylenically unsaturated double bond, and may have at least two functional groups to obtain a desired chemical resistance Polyfunctional compounds.

可聚合化合物可選自於由下列所組成之組群：乙二醇二(甲基)丙烯酸酯、丙二醇二(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、1,6-己二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、甘油三 (甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯與丁二酸之單酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯與丁二酸之單酯、經己內酯改質之二季戊四醇六(甲基)丙烯酸酯、季戊四醇三丙烯酸酯六亞甲基二異氰酸酯(季戊四醇三丙烯酸酯與六亞甲基二異氰酸酯之反應產物)、三季戊四醇七(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯、雙酚A環氧基丙烯酸酯、乙二醇單甲醚丙烯酸酯、及其混合物，但非限於此。 The polymerizable compound may be selected from the group consisting of ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Alcohol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, triglyceride (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate and succinic acid monoester, pentaerythritol tetra (methyl) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, monopentaerythritol penta (meth) acrylate and succinic acid monoester, dipentaerythritol modified by caprolactone Hexa (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate (reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa Acrylate), bisphenol A epoxy acrylate, ethylene glycol monomethyl ether acrylate, and mixtures thereof, but are not limited thereto.

以有色光敏樹脂組成物排除溶劑後之總量為基準(亦即，以固體含量為基準)，可聚合化合物之用量可為1至60重量%，較佳5至45重量%。於該範圍內，容易生成圖案，且可防止顯影過程中於圖案形狀產生缺陷，諸如於底部的浮渣。 Based on the total amount of the colored photosensitive resin composition after excluding the solvent (that is, based on the solid content), the amount of the polymerizable compound may be 1 to 60% by weight, preferably 5 to 45% by weight. Within this range, patterns are easily generated, and defects such as scum on the bottom can be prevented from occurring in the pattern shape during development.

(d)光聚合起始劑 (d) Photopolymerization initiator

任何已知之聚合起始劑皆可用作為本發明之光聚合起始劑。 Any known polymerization initiator can be used as the photopolymerization initiator of the present invention.

光聚合起始劑可選自於由下列所組成之組群：苯乙酮類、非咪唑類、三類、鎓鹽類、安息香類、二苯甲酮類、二酮類、α-二酮類、多核醌類、硫雜蒽酮類(thioxanthones)、重氮化合物類、醯亞胺磺酸酯類、肟類、咔唑類、硼酸鋶類、及其混合物。 The photopolymerization initiator may be selected from the group consisting of acetophenones, non-imidazoles, Compounds, onium salts, benzoin compounds, benzophenones, diketones, α-diketones, polynuclear quinones, thioxanthones, diazonium compounds, sulfonimines , Oximes, carbazoles, lutetium borate, and mixtures thereof.

前述化合物中，較佳者為揭示於韓國專利案早期公開2004-7700、2005-84149、2008-83650、2008-80208、2007-44062、2007-91110、2007-44753、2009-9991、2009-93933、2010-97658或2011-59525號、或PCT案公開WO 2010/102502、或WO 2010/133077號之肟類。此外，較佳使用市售材料諸如歐喜(OXE)-01及歐喜 -02(汽巴公司(Ciba Co.)),N-1919(阿得卡公司(ADEKA Co.))等，而且較佳可用於獲得高敏感度及解析度。 Among the aforementioned compounds, preferred are those disclosed in the Korean Patent Early Publications 2004-7700, 2005-84149, 2008-83650, 2008-80208, 2007-44062, 2007-91110, 2007-44753, 2009-9991, 2009-93933 , 2010-97658 or 2011-59525, or PCT Publication WO 2010/102502, or WO 2010/133077 oxime. In addition, it is preferable to use commercially available materials such as OXE-01 and OXE -02 (Ciba Co.), N-1919 (ADEKA Co.), etc., and can be used to obtain high sensitivity and resolution.

以有色光敏樹脂組成物排除溶劑後之總量為基準(亦即，以固體含量為基準)，聚合起始劑之用量可為0.1至10重量%，較佳0.5至5重量%。於該範圍內，可充分進行透過曝光之固化，藉此容易形成間隔子圖案，及如此所形成的間隔子於顯影期間可充分黏著至基板。 Based on the total amount of the colored photosensitive resin composition after excluding the solvent (that is, based on the solid content), the amount of the polymerization initiator may be 0.1 to 10% by weight, preferably 0.5 to 5% by weight. Within this range, curing through exposure can be sufficiently performed, thereby easily forming spacer patterns, and the spacers thus formed can be sufficiently adhered to the substrate during development.

(e)著色劑 (e) Colorants

著色劑係含於本發明之有色光敏樹脂組成物以提供光屏蔽性質。 The colorant is contained in the colored photosensitive resin composition of the present invention to provide light shielding properties.

用於本發明之著色劑可為無機著色劑或有機著色劑中之二者或更多者的混合物，較佳為具有高發色性質及耐熱性的著色劑。特別，使用二種或更多種有機著色劑之混合物可有利於防止光洩漏從黑色矩陣逸出，及確保阻罩對齊用的透射比。 The coloring agent used in the present invention may be a mixture of two or more of an inorganic coloring agent or an organic coloring agent, and is preferably a coloring agent having high color development properties and heat resistance. In particular, the use of a mixture of two or more organic colorants can help prevent light leakage from escaping from the black matrix and ensure transmittance for mask alignment.

此外，著色劑包含黑色著色劑及藍色著色劑。黑色著色劑可為黑色無機著色劑及/或黑色有機著色劑。 The colorant includes a black colorant and a blue colorant. The black colorant may be a black inorganic colorant and / or a black organic colorant.

發明所屬技術領域中已知之任一種黑色無機著色劑、黑色有機著色劑、及藍色著色劑皆可使用，例如於顏色索引(由The Society of Dyers and Colourists(染色家及調色師學會)印刷)歸類為顏料的化合物及發明所屬技術領域中已知之任一種染料皆可使用。 Any of the black inorganic colorants, black organic colorants, and blue colorants known in the technical field to which the invention belongs can be used, for example, printed on the color index (printed by The Society of Dyers and Colourists) ) Compounds classified as pigments and any dye known in the art to which the invention pertains can be used.

黑色無機著色劑之具體實施例可包括碳黑、鈦黑、金屬氧化物諸如以Cu-Fe-Mn為主的氧化物及合成鐵黑等。其中較佳者為用於獲得期望的圖案性質及化學抗性之碳黑。 Specific examples of the black inorganic colorant may include carbon black, titanium black, metal oxides such as Cu-Fe-Mn-based oxides, and synthetic iron black. Among them, preferred is carbon black for obtaining desired pattern properties and chemical resistance.

此外，黑色有機著色劑之具體實施例可包括苯胺黑、內醯胺黑、苝黑等。其中較佳為用於獲得期望的光密度、穿透性、透射比等之內醯胺黑(例如FASF公司的黑色582)。 In addition, specific examples of the black organic colorant may include aniline black, lactam black, perylene black, and the like. Among them, it is preferable to use fluorenamine black (for example, FASF Black 582) for obtaining desired optical density, transmittance, and transmittance.

藍色著色劑之具體實施例可包括C.I.顏料藍15：6，C.I.顏料藍15：4，C.I.顏料藍60，C.I.顏料藍16等。其中較佳者為用以預防光逸出之C.I.顏料藍15：6。 Specific examples of the blue colorant may include C.I. Pigment Blue 15: 6, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 60, C.I. Pigment Blue 16 and the like. The preferred one is C.I. Pigment Blue 15: 6 to prevent light from escaping.

以有色光敏樹脂組成物排除溶劑後之總量為基準(亦即，以固體含量為基準)，黑色無機著色劑、黑色有機著色劑、及藍色著色劑之用量分別可為0至5重量%，10至40重量%及1至15重量%。於此範圍內，可具有高光密度，因而可防止光逸出，及阻罩對齊所需的透射比也合乎期望，例如於730奈米小於15%及於900奈米小於15%。 Based on the total amount of the colored photosensitive resin composition after excluding the solvent (that is, based on the solid content), the amount of the black inorganic colorant, the black organic colorant, and the blue colorant may be 0 to 5 wt%, respectively 10 to 40% by weight and 1 to 15% by weight. Within this range, it can have a high optical density, which can prevent light from escaping, and the transmittance required for mask alignment is also desirable, such as less than 15% at 730 nm and less than 15% at 900 nm.

同時，用於分散著色劑之分散劑可用於本發明之有色光敏樹脂組成物。分散劑之實施例可包括著色劑之任一種已知之分散劑。具體實施例可包括陽離子性界面活性劑、陰離子性界面活性劑、非離子性界面活性劑、兩性離子性界面活性劑、以矽為主的界面活性劑、以氟為主的界面活性劑等。市售分散劑可為得自比克公司(BYK Co.)的迪斯比克(Disperbyk)-182、-183、-184、-185、-2000、-2150、-2150、-2155、-2163或-2164。此等化合物可單獨使用或以二者或更多者組合使用。分散劑可透過使用分散劑進行著色劑的表面處理而添加至該著色劑，或於有色光敏樹脂組成物之製備期間與著色劑一起添加。 Meanwhile, a dispersant for dispersing a colorant can be used for the colored photosensitive resin composition of the present invention. Examples of the dispersant may include any known dispersant of a colorant. Specific embodiments may include cationic surfactants, anionic surfactants, non-ionic surfactants, zwitterionic surfactants, silicon-based surfactants, fluorine-based surfactants, and the like. Commercially available dispersants may be Disperbyk-182, -183, -184, -185, -2000, -2150, -2150, -2155, -2163 from BYK Co. Or -2164. These compounds may be used alone or in combination of two or more. The dispersant may be added to the colorant by surface treatment of the colorant using the dispersant, or added together with the colorant during the preparation of the colored photosensitive resin composition.

或者，著色劑可與黏結劑混合而用於有色光敏樹脂組成物之製備。此種情況下，黏結劑可為本發明描述的共聚物(a)、已知的 共聚物、或其混合物。 Alternatively, the colorant may be mixed with a binder to prepare a colored photosensitive resin composition. In this case, the binder may be the copolymer (a) described in the present invention, a known Copolymer, or a mixture thereof.

因此，本發明使用的著色劑可以經由混合著色劑與分散劑、黏結劑、溶劑等獲得的有色分散液(有色研磨基劑)之形式而添加於有色光敏樹脂組成物。 Therefore, the coloring agent used in the present invention can be added to the colored photosensitive resin composition in the form of a colored dispersion (colored grinding base) obtained by mixing a coloring agent with a dispersant, a binder, a solvent, and the like.

(f)溶劑 (f) Solvent

本發明之有色光敏樹脂組成物較佳係經由混合前述成分與溶劑而製備成液體組成物。發明所屬技術領域中已知之任一種溶劑皆可用於有色光敏樹脂組成物，該溶劑係與該有色光敏樹脂組成物中之成分為可相容性，但非反應性。 The colored photosensitive resin composition of the present invention is preferably prepared as a liquid composition by mixing the aforementioned components and a solvent. Any solvent known in the technical field to which the invention belongs can be used in the colored photosensitive resin composition. The solvent is compatible with the components in the colored photosensitive resin composition, but is non-reactive.

溶劑之實施例可包括二醇醚類諸如乙二醇單***等；乙二醇烷基醚乙酸酯諸如乙基溶纖素乙酸酯等；酯類諸如2-羥基丙酸乙酯等；二乙二醇類諸如二乙二醇單甲醚等；及丙二醇烷基醚乙酸酯類諸如丙二醇單甲醚乙酸酯；丙二醇丙基醚乙酸酯等。溶劑可單獨使用或以二種或更多種組合使用。 Examples of the solvent may include glycol ethers such as ethylene glycol monoethyl ether, etc .; ethylene glycol alkyl ether acetates such as ethyl cellolysin acetate, etc .; esters such as ethyl 2-hydroxypropionate, etc .; Diethylene glycols such as diethylene glycol monomethyl ether and the like; and propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate; propylene glycol propyl ether acetate and the like. The solvent may be used alone or in a combination of two or more.

溶劑之用量並無特殊限制，反而可決定成使得組成物內(亦即，以固體含量為基準)溶劑除外的各個成分之總濃度常見為5至70重量%，較佳為10至55重量%，以最終獲得有色光敏樹脂組成物的分散性及安定性。 The amount of the solvent is not particularly limited, but may be determined so that the total concentration of each component except the solvent in the composition (that is, based on the solid content) is usually 5 to 70% by weight, preferably 10 to 55% by weight In order to finally obtain the dispersibility and stability of the colored photosensitive resin composition.

(g)界面活性劑 (g) Surfactant

若有所需，本發明之有色光敏樹脂組成物可進一步包含界面活性劑以改良塗佈性質及防止缺陷的生成。 If necessary, the colored photosensitive resin composition of the present invention may further include a surfactant to improve coating properties and prevent generation of defects.

界面活性劑的種類並無特殊限制，例如可使用以氟為主的界面活性劑或以矽為主的界面活性劑。 The type of the surfactant is not particularly limited. For example, a fluorine-based surfactant or a silicon-based surfactant can be used.

市售以矽為主的界面活性劑為得自道康寧東麗聚矽氧公司 (Dow Corning Toray Silicone Co.)的DC3PA、DC7PA、SH11PA、SH21PA及SH8400、得自奇異東芝聚矽氧公司(GE Toshiba Silicones Co.)的TSF-4440、TSF-4300、TSF-4445、TSF-4446、TSF-4460及TSF-4452，得自比克公司之比克333等。此等化合物可單獨使用或以二者或更多者之組合使用。市售以氟為主的界面活性劑為得自大日本油墨化學工業公司(Dainippon Ink Kagaku Kogyo Co.)的美加菲(Megafac)F-470、F-471、F-475、F-482、F-489等。其中，得自比克公司之比克333可較佳用於獲得分散性。 Commercially available silicon-based surfactants are available from Dow Corning Toray Polysilicon (Dow Corning Toray Silicone Co.) DC3PA, DC7PA, SH11PA, SH21PA and SH8400, TSF-4440, TSF-4300, TSF-4445, TSF-4446 from GE Toshiba Silicones Co. , TSF-4460 and TSF-4452, BAK 333 from BAK, etc. These compounds may be used alone or in combination of two or more. The commercially available fluorine-based surfactants are Megafac F-470, F-471, F-475, F-482, F from Dainippon Ink Kagaku Kogyo Co. -489 etc. Among them, BAK 333 from BAK can be preferably used to obtain dispersion.

以有色光敏樹脂組成物排除溶劑後之總量為基準(亦即，以固體含量為基準)，界面活性劑之用量可為0.01至10重量%，較佳為0.05至5重量%。於該範圍內，容易塗佈有色光敏樹脂組成物。 Based on the total amount of the colored photosensitive resin composition after excluding the solvent (that is, based on the solid content), the amount of the surfactant may be 0.01 to 10% by weight, preferably 0.05 to 5% by weight. Within this range, the colored photosensitive resin composition can be easily applied.

(h)矽烷偶合劑 (h) Silane coupling agent

若有所需，本發明之有色光敏樹脂組成物可進一步包含矽烷偶合劑，其具有選自於由羧基、(甲基)丙烯醯基、異氰酸基、胺基、巰基、乙烯基、環氧基、及其組合所組成之組群的一個反應性取代基來改良與基板的黏著性。 If necessary, the colored photosensitive resin composition of the present invention may further include a silane coupling agent having a group selected from the group consisting of carboxyl, (meth) acrylfluorenyl, isocyanate, amine, mercapto, vinyl, and cyclic A reactive substituent of a group consisting of an oxy group and a combination thereof to improve adhesion to a substrate.

矽烷偶合劑之種類並無特殊限制，但較佳係選自於由下列所組成之組群：三甲氧基矽基苯甲酸、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三甲氧基矽烷、γ-異氰酸基丙基三乙氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基三乙氧基矽烷、β-(3,4-環氧基環己基)乙基三甲氧基矽烷、苯基胺基三甲氧基矽烷及其混合物。其中，以具有異氰酸基的γ-異氰酸基丙基三乙氧基矽烷(例如得自新越公司(Shin-Etsu Co.)的KBE-9007)或苯基胺基三甲氧基矽烷為較 佳，其可具有良好化學抗性及與基板的黏著性。 The type of the silane coupling agent is not particularly limited, but it is preferably selected from the group consisting of trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyl Triethoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrisiloxane Ethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, phenylaminotrimethoxysilane, and mixtures thereof. Among them, γ-isocyanatopropyltriethoxysilane (for example, KBE-9007 available from Shin-Etsu Co.) having an isocyanate group or phenylaminotrimethoxysilane For comparison Good, it can have good chemical resistance and adhesion to the substrate.

以有色光敏樹脂組成物排除溶劑後之總量為基準(亦即，以固體含量為基準)，矽烷偶合劑用量可為0.01至10重量%，較佳0.05至5重量%。於此範圍內，可改良有色光敏樹脂組成物之黏著性。 Based on the total amount of the colored photosensitive resin composition after excluding the solvent (that is, based on the solid content), the amount of the silane coupling agent may be 0.01 to 10% by weight, preferably 0.05 to 5% by weight. Within this range, the adhesion of the colored photosensitive resin composition can be improved.

又復，唯有當有色光敏樹脂組成物之物理性質不會劣化時才可含括其它添加劑諸如抗氧化劑、安定劑等。 Furthermore, other additives such as antioxidants, stabilizers, etc. may be included only when the physical properties of the colored photosensitive resin composition do not deteriorate.

當從本發明之有色光敏樹脂組成物形成固化層時，黑色矩陣之性質諸如透射比及光密度，以及柱狀間隔子性質諸如彈性回復率、解析度、化學抗性及塗覆厚度皆可同樣地令人滿意。如此，曝光極限及顯影極限二者可合乎所需。特別，當從本發明之有色光敏樹脂組成物形成具有1微米厚度之固化層時，可達成0.6至1.5之光密度，更精確言之，0.6至1.4之光密度。此外，當形成具有1.5至2.5微米之固化層時，可於730奈米波長達成小於15%之透射比；而當形成具有3.5至4.5微米之固化層時，可於900奈米波長達成小於15%之透射比。因此，本發明之有色光敏樹脂組成物可同時形成柱狀間隔子及黑色矩陣，因而縮短加工時間。 When a cured layer is formed from the colored photosensitive resin composition of the present invention, the properties of the black matrix such as transmittance and optical density, and the properties of the columnar spacers such as elastic recovery rate, resolution, chemical resistance, and coating thickness may be the same. To be satisfactory. As such, both the exposure limit and the development limit may be desirable. In particular, when a cured layer having a thickness of 1 micron is formed from the colored photosensitive resin composition of the present invention, an optical density of 0.6 to 1.5, and more specifically, an optical density of 0.6 to 1.4 can be achieved. In addition, when a cured layer having a thickness of 1.5 to 2.5 microns is formed, a transmittance of less than 15% can be achieved at a wavelength of 730 nm; and when a cured layer having a wavelength of 3.5 to 4.5 microns is formed, a wavelength of less than 15 can be achieved at a wavelength of 900 nm % Transmittance. Therefore, the colored photosensitive resin composition of the present invention can simultaneously form a columnar spacer and a black matrix, thereby shortening the processing time.

有色光敏樹脂組成物之製法 Method for producing colored photosensitive resin composition

依據本發明之包含前述成分的有色光敏樹脂組成物可藉由習知方法製備，其中一個具體實施例說明如下。 The colored photosensitive resin composition containing the foregoing components according to the present invention can be prepared by a conventional method, and a specific example is described below.

首先，預先混合著色劑與溶劑，及於球磨機等內分散直到著色劑的平均直徑變成期望大小為止。於此階段，若有期望則可添加界面活性劑，及可添加部分或全部共聚物。共聚物、環氧樹脂化合物或由其衍生之化合物、可聚合化合物、及光聚合起始劑等其餘成分添加至該分散液。若期望，可添加添加劑諸如矽烷偶合 劑或額外溶劑以調整混合物之濃度。然後充分攪拌該混合物以獲得期望的有色光敏樹脂組成物。 First, a colorant and a solvent are mixed in advance, and dispersed in a ball mill or the like until the average diameter of the colorant becomes a desired size. At this stage, surfactants can be added if desired, and some or all copolymers can be added. Copolymers, epoxy resin compounds or compounds derived therefrom, polymerizable compounds, and other components such as photopolymerization initiators are added to the dispersion. Addition of additives such as silane coupling if desired Agent or additional solvent to adjust the concentration of the mixture. The mixture was then sufficiently stirred to obtain a desired colored photosensitive resin composition.

柱狀間隔子、黑色矩陣、及BCS Columnar spacer, black matrix, and BCS

依據本發明，提供從有色光敏樹脂組成物所形成的柱狀間隔子及黑色矩陣。特別，本發明提供從有色光敏樹脂組成物形成的整合型黑色柱狀間隔子(BCS)。該BCS圖案之具體實施例係示例說明於第1圖。 According to the present invention, a columnar spacer and a black matrix formed from a colored photosensitive resin composition are provided. In particular, the present invention provides an integrated black columnar spacer (BCS) formed from a colored photosensitive resin composition. A specific embodiment of the BCS pattern is illustrated in FIG. 1 as an example.

柱狀間隔子、黑色矩陣或BCS可經由形成塗層、曝光、顯影及加熱處理等步驟製成。 The columnar spacer, black matrix, or BCS can be made through steps such as coating formation, exposure, development, and heat treatment.

於塗層形成步驟中，本發明之有色光敏樹脂組成物係利用旋塗法或縫塗法、輥塗法、網印法、施用器法等塗覆於經前處理的基板上至期望厚度，例如2至25微米，然後於70至100℃預固化1至10分鐘以去除溶劑及形成塗層。 In the coating forming step, the colored photosensitive resin composition of the present invention is applied on a pre-treated substrate to a desired thickness by a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, or the like, For example, 2 to 25 microns, and then pre-cured at 70 to 100 ° C for 1 to 10 minutes to remove the solvent and form a coating.

為了形成如此所得的塗層之圖案，在具有某種形狀的阻罩已經放置於其上之後照射200至500奈米的活化光。於此階段，為了獲得整合型BCS，可使用具有不同透射比之圖案的阻罩來同時形成柱狀間隔子及黑色矩陣。作為用於曝光的光源，可使用低壓汞燈、高壓汞燈、超高壓汞燈、金屬鹵素燈、氬氣雷射等；及若期望，也可使用X光、電子射線等。劑量可根據該組成物之成分的種類及混合比及乾燥層厚度而改變。當使用高壓汞燈時，劑量可為500毫焦耳/平方厘米(mJ/cm2)或更低(於365奈米波長)。 To form the pattern of the coating thus obtained, 200 to 500 nanometers of activating light is irradiated after a mask having a certain shape has been placed thereon. At this stage, in order to obtain an integrated BCS, a columnar spacer and a black matrix can be formed at the same time by using a mask with a pattern having different transmittances. As a light source for exposure, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon laser, and the like can be used; and if desired, X-rays, electron rays, and the like can also be used. The dose can be changed according to the type and mixing ratio of the components of the composition and the thickness of the dry layer. When a high-pressure mercury lamp is used, the dose may be 500 millijoules per square centimeter (mJ / cm 2 ) or less (at a wavelength of 365 nanometers).

於曝光步驟後，進行使用鹼性水溶液諸如碳酸鈉、氫氧化鈉、氫氧化鉀、氫氧化四甲基銨等的顯影步驟來經由溶解不需要部分而將其去除，藉此允許留下之曝光部分形成圖案。藉由顯影獲得 的影像圖案經冷卻至室溫，及於180至250℃的熱空氣循環型乾燥烤爐內後烤乾10至60分鐘，藉此獲得最終圖案。 After the exposure step, a developing step using an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, etc. is performed to remove unnecessary portions by dissolving them, thereby allowing the remaining exposure Partly formed a pattern. Obtained by development The image pattern is cooled to room temperature and dried in a hot air circulation type drying oven at 180 to 250 ° C for 10 to 60 minutes to obtain the final pattern.

如此製造的柱狀間隔子、黑色矩陣或BCS由於其良好物理性質，因此可有用地用在電子部件諸如OLED顯示器、LCD等。如此，包括該柱狀間隔子、黑色矩陣、或BCS的電子部件可提供於本發明。 The column spacer, black matrix or BCS thus manufactured can be usefully used in electronic components such as OLED displays, LCDs, etc. due to its good physical properties. As such, an electronic component including the columnar spacer, the black matrix, or the BCS can be provided in the present invention.

除了依據本發明之間隔子之外，OLED顯示器、LCD等可包括熟悉發明所屬技術領域者已知之元件。換言之，其中可採用本發明之柱狀間隔子、黑色矩陣或BCS的OLED顯示器、LCD等可含括於本發明。 In addition to the spacer according to the present invention, OLED displays, LCDs, etc. may include elements known to those skilled in the art to which the invention belongs. In other words, OLED displays, LCDs, etc. in which the column spacers, black matrix or BCS of the present invention can be used can be included in the present invention.

後文中，將藉由下列實施例更特定描述本發明，但此等實施例僅用於示例說明目的，本發明並非侷限於其中。 Hereinafter, the present invention will be more specifically described by the following examples, but these examples are for illustrative purposes only, and the present invention is not limited thereto.

製備例1：共聚物之製備 Preparation Example 1: Preparation of copolymer

100克具有下表1顯示之用量比的單體混合物，300克(g)作為溶劑之PGMEA，及2克作為自由基聚合起始劑之2,2’-偶氮(2,4-二甲基戊腈)放置於裝配有迴流冷凝器及攪拌器的500毫升圓底瓶內。溫度升高至70℃，及將混合物攪拌5小時進行聚合以產生共聚物。如此產生的共聚物具有80毫克氫氧化鉀/克(mgKOH/g)之酸值及藉由凝膠滲透層析術以聚苯乙烯為參考品測得為11,000之重量平均分子量(Mw)。 100 grams of a monomer mixture having the dosage ratio shown in Table 1 below, 300 grams (g) of PGMEA as a solvent, and 2 grams of 2,2'-azo (2,4-dimethyl) as a radical polymerization initiator Valeronitrile) was placed in a 500 ml round bottom flask equipped with a reflux condenser and a stirrer. The temperature was raised to 70 ° C, and the mixture was stirred for 5 hours to perform polymerization to produce a copolymer. The copolymer thus produced had an acid value of 80 milligrams of potassium hydroxide / gram (mgKOH / g) and a weight average molecular weight (Mw) of 11,000 as measured by gel permeation chromatography using polystyrene as a reference.

共聚物之各組成單元的用量及共聚物之重量平均分子量係示例說明於下表1。 Examples of the amount of each constituent unit of the copolymer and the weight average molecular weight of the copolymer are shown in Table 1 below.

製備例2：衍生自具有二苯并吡喃主鏈結構之環氧樹脂之化合物 Preparation Example 2: Compound derived from epoxy resin having main structure of dibenzopyran

將125.4克螺[茀-9,9’-二苯并吡喃]-3’,6’-二醇及0.1386克溴化第三丁基銨置於3000毫升圓底瓶內及混合。在其中額外添加78.6克表氯醇，及將該混合物加熱至90℃以進行反應。於使用液相層析術分析而確保螺[茀-9,9’-二苯并吡喃]-3’,6’-二醇完全消耗後，使反應物冷卻至30℃，及緩慢添加50%氫氧化鈉水溶液(3當量)。藉由使用液相層析術分析而確保表氯醇完全耗盡之後，將反應物用二氯甲烷萃取及洗滌三次。將有機層用硫酸鎂乾燥，及於減壓下蒸餾去除二氯甲烷。將粗產物用二氯甲烷/甲醇混合溶劑(50：50，v/v)再結晶。 125.4 g of spiro [茀 -9,9'-dibenzopyran] -3 ', 6'-diol and 0.1386 g of tert-butylammonium bromide were placed in a 3000 ml round bottom bottle and mixed. An additional 78.6 g of epichlorohydrin was added thereto, and the mixture was heated to 90 ° C to perform a reaction. After using liquid chromatography analysis to ensure the complete consumption of spiron [茀 -9,9'-dibenzopyran] -3 ', 6'-diol, cool the reaction to 30 ° C and slowly add 50 % Sodium hydroxide aqueous solution (3 equivalents). After ensuring that epichlorohydrin was completely consumed by analysis using liquid chromatography, the reaction was extracted and washed three times with dichloromethane. The organic layer was dried over magnesium sulfate, and dichloromethane was distilled off under reduced pressure. The crude product was recrystallized from a dichloromethane / methanol mixed solvent (50:50, v / v).

在1當量之如此所得以環氧基為主的化合物中添加0.004當量之溴化第三丁基銨，0.001當量之2,6-二異丁基酚，及2.2當量之丙烯酸。隨後在其中添加8.29克之PGMEA溶劑，接著混合溶液。以25毫升/分鐘吹送空氣至如此製備之溶液，將溶液加熱至90至100℃以溶解反應物。當溶液為白色混濁時，溫度升高至120℃以完全溶解反應物。當溶液變澄清及黏度升高時測量其酸值，及攪拌溶液直到酸值達到小於1.0mgKOH/g為止。直到酸值達到目標值(0.8)為止，持續攪拌了11小時。反應完成後，將反應器溫 度降至室溫，及獲得無色透明固體。 To one equivalent of the epoxy-based compound thus obtained, 0.004 equivalent of tertiary butyl ammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of acrylic acid were added. Then, 8.29 g of PGMEA solvent was added thereto, followed by mixing the solutions. Air was blown at 25 ml / minute to the solution thus prepared, and the solution was heated to 90 to 100 ° C to dissolve the reactants. When the solution was white and cloudy, the temperature was raised to 120 ° C to completely dissolve the reactants. When the solution becomes clear and the viscosity increases, measure its acid value, and stir the solution until the acid value reaches less than 1.0 mgKOH / g. The stirring was continued for 11 hours until the acid value reached the target value (0.8). After the reaction is completed, the reactor temperature The temperature was reduced to room temperature, and a colorless transparent solid was obtained.

將43克如此所得固體產物，33.6克之丙烯酸，0.04克之2,6-二-第三丁基-對-甲酚，0.21克之乙酸四丁基銨，及18克之PGMEA置於反應瓶內，及將該混合物於120℃攪拌13小時。其後，使反應物冷卻至室溫，及在其中添加24克之PGMEA及10克之丁二酸酐，接著於100℃攪拌混合物3小時。在該混合物中額外添加8克之雙酚Z縮水甘油醚，及將該混合物於120℃攪拌4小時，於90℃攪拌3小時，於60℃攪拌2小時，及於40℃攪拌5小時。於水及醇中進行再沈澱而獲得粉末態之最終樹脂。然後，添加PGMEA以使得固體含量變成48%。如此所得樹脂之酸值為105mgKOH/g，而且利用凝膠滲透層析術以聚苯乙烯為參考品之方式測量之重量平均分子量(Mw)為5,500。 43 g of the solid product thus obtained, 33.6 g of acrylic acid, 0.04 g of 2,6-di-third-butyl-p-cresol, 0.21 g of tetrabutylammonium acetate, and 18 g of PGMEA were placed in a reaction flask, and The mixture was stirred at 120 ° C for 13 hours. Thereafter, the reaction was cooled to room temperature, and 24 g of PGMEA and 10 g of succinic anhydride were added thereto, followed by stirring the mixture at 100 ° C for 3 hours. An additional 8 grams of bisphenol Z glycidyl ether was added to the mixture, and the mixture was stirred at 120 ° C for 4 hours, 90 ° C for 3 hours, 60 ° C for 2 hours, and 40 ° C for 5 hours. It is reprecipitated in water and alcohol to obtain the final resin in powder form. Then, PGMEA was added so that the solid content became 48%. The acid value of the resin thus obtained was 105 mgKOH / g, and the weight average molecular weight (Mw) measured by gel permeation chromatography using polystyrene as a reference was 5,500.

製備例3：有色分散液之製備 Preparation Example 3: Preparation of colored dispersion

將下表2顯示用量之各成分混合。此種情況下，使用製備例1所得之共聚物作為共聚物，使用巴斯夫公司(BASF Co.)之內醯胺黑(黑色582)作為有機黑色，使用聚合物分散劑(迪斯比克-2000)作為分散劑，及使用PGMEA作為溶劑。將如此所得混合物分散於25至60℃之塗料振盪器內6小時。使用0.3毫米氧化鋯珠進行分散步驟。於分散步驟完成後，分開珠粒及分散液，藉此分別製造有色分散液A至C。 The ingredients in the amounts shown in Table 2 below are mixed. In this case, use the copolymer obtained in Preparation Example 1 as a copolymer, use BASF Co.'s linalamide black (Black 582) as an organic black, and use a polymer dispersant (Discobe-2000 ) As a dispersant and PGMEA as a solvent. The thus-obtained mixture was dispersed in a paint shaker at 25 to 60 ° C for 6 hours. The dispersion step was performed using 0.3 mm zirconia beads. After the dispersing step is completed, the beads and the dispersion liquid are separated, thereby producing colored dispersion liquids A to C, respectively.

實施例1至6及比較例1至3：有色光敏樹脂組成物之製備 Examples 1 to 6 and Comparative Examples 1 to 3: Preparation of colored photosensitive resin composition

製備例1所得具有31%固體含量之共聚物A、製備例2所得衍生自具有二苯并吡喃結構之環氧樹脂之化合物、作為可聚合化合物之二季戊四醇六丙烯酸酯(DPHA，日本化藥公司(Nippon Kayaku Co.))，及製備例3所得有色分散液A至C以下表3描述之用量混合。此外，藉由習知方法混合0.04克之作為光聚合起始劑之以肟為主的光起始劑(歐喜(OXE)-02，汽巴公司)，0.0082克之界面活性劑(比克-333，比克公司)，及7.5176克之作為溶劑之PGMEA，及攪拌5小時以製備各有色光敏樹脂組成物(實施例1至6及比較例1至3)。 Copolymer A having a solid content of 31% obtained in Preparation Example 1, a compound derived from an epoxy resin having a dibenzopyran structure obtained in Preparation Example 2, dipentaerythritol hexaacrylate (DPHA, a Japanese chemical) as a polymerizable compound (Nippon Kayaku Co.), and the colored dispersions A to C obtained in Preparation Example 3 were mixed in the amounts described in Table 3 below. In addition, 0.04 g of an oxime-based photoinitiator (OXE-02, Ciba) as a photopolymerization initiator was mixed by a conventional method, and 0.0082 g of a surfactant (Bike-333 , BAK Corporation), and 7.5176 g of PGMEA as a solvent, and stirred for 5 hours to prepare each colored photosensitive resin composition (Examples 1 to 6 and Comparative Examples 1 to 3).

實施例及比較例中如此所製備之組成物之各成分之用量示例說明於下表3。 Examples of the amount of each component of the composition thus prepared in the examples and comparative examples are shown in Table 3 below.

實驗例1：從有色光敏樹脂組成物形成的固化層之物理性質之測量 Experimental Example 1: Measurement of physical properties of a cured layer formed from a colored photosensitive resin composition

於玻璃基板上，藉由使用旋塗機塗佈實施例及比較例中所製備之各種有色光敏樹脂組成物，及於100℃預先固化150秒而形成塗層。將具有100%全調性柱狀間隔子(CS)圖案及30%半調性黑色矩陣圖案的圖案阻罩設置於如此所得之塗層上，然後藉由40毫焦耳/平方厘米曝光於具有365奈米波長之光。然後，藉由使用以1重量%氫氧化鉀稀釋的水溶液於23℃檢查斷裂點時間(BP)，並且額外顯影15秒。以純水洗滌1分鐘後，將如此形成的圖案於230℃烤爐中後固化30分鐘以獲得固化層。 On the glass substrate, various colored photosensitive resin compositions prepared in Examples and Comparative Examples were coated by using a spin coater, and cured at 100 ° C. for 150 seconds to form a coating layer. A pattern mask having a 100% full-toned column spacer (CS) pattern and a 30% half-toned black matrix pattern was set on the coating thus obtained, and then exposed to a film having a wavelength of 365 by 40 mJ / cm2. Nano-wavelength light. Then, the break point time (BP) was checked by using an aqueous solution diluted with 1% by weight potassium hydroxide at 23 ° C, and development was performed for an additional 15 seconds. After washing with pure water for 1 minute, the pattern thus formed was post-cured in an oven at 230 ° C. for 30 minutes to obtain a cured layer.

(1)彈性回復率之測量 (1) Measurement of elastic recovery rate

依據前述形成固化層之方法，於後固化之後形成具有4.0(±0.2)微米之總厚度及35(±1)微米之圖案寬度之固化層，及將該固化層設定為用以測量物理性質，亦即壓縮位移及彈性回復率之基本參考形狀。壓縮位移及彈性回復率係根據如下測量條件使用彈性測 量裝置(杜何(DUH)-W201S，日本島津公司(Simadzu Co.))測量。 According to the aforementioned method for forming a cured layer, a cured layer having a total thickness of 4.0 (± 0.2) microns and a pattern width of 35 (± 1) microns is formed after post-curing, and the cured layer is set to measure physical properties, That is, the basic reference shape for compression displacement and elastic recovery rate. Compression displacement and elastic recovery rate Measuring device (DUH-W201S, Simadzu Co., Japan).

作為壓縮圖案的阻尼器，以重量載荷-卸載方式採用具有50微米直徑的平坦阻尼器。彈性回復率係於300毫牛頓(mN)之測試傳遞負荷測量而在比較組間獲得可區別的結果。恆常維持3克力/秒(gf/sec)之載荷率及3秒之停留時間。至於彈性回復率，恆常載荷平坦阻尼器歷時3秒，然後藉由使用三維厚度測量裝置測量載荷之前及之後該圖案的實際彈性回復率。彈性回復率表示當施加恆定力時，在經過10分鐘回復時間後，回復距離相對於壓縮距離(壓縮位移)之比，係以如下方程式1表示。 As the damper of the compression pattern, a flat damper having a diameter of 50 micrometers was used in a weight-loading-unloading manner. The elastic recovery rate is measured at 300 millinewtons (mN) of the test transfer load to obtain distinguishable results between the comparison groups. Constantly maintain a load rate of 3 grams force per second (gf / sec) and a dwell time of 3 seconds. As for the elastic recovery rate, the constant load flat damper lasted 3 seconds, and then the actual elastic recovery rate of the pattern before and after the load was measured by using a three-dimensional thickness measuring device. The elastic recovery rate represents the ratio of the recovery distance to the compression distance (compression displacement) after a 10-minute recovery time has elapsed when a constant force is applied, and is expressed by Equation 1 below.

[方程式1]彈性回復率(%)=[(回復距離/壓縮位移)x100] [Equation 1] Elastic recovery rate (%) = [(recovery distance / compression displacement) x100]

(2)解析度之測量 (2) Measurement of resolution

依據形成固化層之方法，形成具有3.5(±0.2)微米厚度之預固化層，然後於顯影固化層所用的相同條件下進行以光罩(具有8、10、12、14微米等圖案大小)曝光及顯影。測量固化層之圖案臨界維度，及評估解析度(微米)。 According to the method of forming a cured layer, a pre-cured layer having a thickness of 3.5 (± 0.2) microns is formed, and then exposed with a photomask (having a pattern size of 8, 10, 12, 14 microns, etc.) under the same conditions used for developing the cured layer And development. Measure the critical dimension of the pattern of the cured layer and evaluate the resolution (micron).

(3)化學抗性之測量 (3) Measurement of chemical resistance

藉由形成固化層之方法不使用阻罩製備於後固化之後具有3.0(±0.2)微米厚度之固化層，及測量如此所製備之固化層之初厚度。然後，將試樣浸沒於1克之100% N-甲基吡咯啶酮(NMP)中，在恆溫器中於100℃沸騰5分鐘，及在烤爐中於100℃烤乾2分鐘，及測量第二厚度。試樣最終在烤爐中於230℃烤乾20分鐘，及測量終厚度。根據如此測得的數值，藉由如下方程式2計算化學抗性。化學抗性(%)愈低，固化層的性質愈佳。 A cured layer having a thickness of 3.0 (± 0.2) microns after post-curing was prepared by using a method of forming a cured layer without using a mask, and the initial thickness of the cured layer thus prepared was measured. Then, the sample was immersed in 1 g of 100% N-methylpyrrolidone (NMP), boiled at 100 ° C for 5 minutes in a thermostat, and dried at 100 ° C for 2 minutes in an oven, and Two thicknesses. The samples were finally dried in an oven at 230 ° C for 20 minutes, and the final thickness was measured. Based on the values thus measured, chemical resistance was calculated by Equation 2 below. The lower the chemical resistance (%), the better the properties of the cured layer.

[方程式2]化學抗性(%)=[(最終厚度/初厚度)x100]-100 [Equation 2] Chemical resistance (%) = [(final thickness / initial thickness) x100] -100

(4)BCS的厚度之測量 (4) Measurement of BCS thickness

類似於彈性回復率之測量方法，製備BCS圖案(參考第1圖)，其中黑色矩陣與柱狀間隔子整合為一體。使用高度測量裝置(希斯(SIS)-2000，首爾國立大學)測量BCS總厚度(A+B)、柱狀間隔子部分厚度(A)、及黑色矩陣部分厚度(B)。當黑色矩陣部分厚度(A)係於2.0±0.5微米之範圍時，光屏蔽性質合乎期望。 Similar to the method of measuring the elastic recovery rate, a BCS pattern is prepared (refer to FIG. 1), in which a black matrix is integrated with a column spacer. The height measurement device (SIS-2000, Seoul National University) was used to measure the total thickness of the BCS (A + B), the thickness of the columnar spacer portion (A), and the thickness of the black matrix portion (B). When the thickness (A) of the black matrix portion is in the range of 2.0 ± 0.5 μm, the light shielding property is desirable.

(5)不同波長之透射比之測量 (5) Measurement of transmittance at different wavelengths

藉由形成固化層之方法不使用阻罩製備於後固化之後具有2.0微米及4.0微米厚度的固化層，及使用分光光度分析儀(開瑞(Cary)100，亞吉蘭公司(Agilent Co.))針對具有個別厚度的固化層測量於730奈米波長之透射比及於900奈米波長之透射比。當於2.0(±0.5)微米厚度和730奈米之透射比係低於15%及最低透射比(其不會造成對齊的任何缺陷)於4.0(±0.5)微米之厚度和900奈米波長為至少15%時，可防止光逸出。 A cured layer having a thickness of 2.0 μm and 4.0 μm after post-curing is prepared by using a method of forming a cured layer without using a mask, and a spectrophotometer (Cary 100, Agilent Co.) is used. ) The transmittance at a wavelength of 730 nanometers and the transmittance at a wavelength of 900 nanometers are measured for a cured layer having an individual thickness. When the thickness is 2.0 (± 0.5) microns and the transmittance of 730 nm is less than 15% and the minimum transmittance (which does not cause any defects in alignment) is at a thickness of 4.0 (± 0.5) microns and a wavelength of 900 nm At least 15% prevents light from escaping.

(6)光密度之測量 (6) Measurement of optical density

藉由形成固化層之方法不使用阻罩製備於後固化之後具有3.0微米厚度的固化層。藉由使用光密度系統(361T，愛力特公司(X-lite Co.))測量該固化層於550奈米之透射比，及獲得1微米厚度之光密度。 A cured layer having a thickness of 3.0 micrometers after post-curing was prepared by a method of forming a cured layer without using a mask. By using an optical density system (361T, X-lite Co.) to measure the transmittance of the cured layer at 550 nm, and obtain an optical density of 1 micron thickness.

如上獲得之測量結果示例說明於下表4及5。 Examples of the measurement results obtained above are illustrated in Tables 4 and 5 below.

如表4及5顯示，根據實施例1至6之從有色光敏樹脂組成物製備的固化層諸如柱狀間隔子、黑色矩陣及BCS顯示同 等良好的彈性回復率、解析度、化學抗性、厚度、透射比及光密度。相反地，從根據比較例1至3之有色光敏樹脂組成物形成的固化層之前述性質中的至少一種性質顯示令人不滿意的結果。更明確言之，比較例1至3之固化層的於2微米厚度以730奈米波長測得的透射比係高，不適合用作為BCS。同時，比較例2之固化層於4微米厚度以900奈米波長測得的透射比係低，不適合用作為BCS。因此，根據本發明之有色光敏樹脂組成物可用作為包括LCD之各種電子部件的間隔子及/或黑色矩陣。 As shown in Tables 4 and 5, the cured layers, such as columnar spacers, black matrix, and BCS, prepared from the colored photosensitive resin composition according to Examples 1 to 6 show the same Such as good elastic recovery, resolution, chemical resistance, thickness, transmittance and optical density. In contrast, at least one of the foregoing properties of the cured layer formed from the colored photosensitive resin composition according to Comparative Examples 1 to 3 showed unsatisfactory results. More specifically, the cured layers of Comparative Examples 1 to 3 had high transmittances measured at a wavelength of 730 nm at a thickness of 2 microns, and were not suitable for use as BCS. At the same time, the cured layer of Comparative Example 2 had a low transmittance measured at a thickness of 4 microns at a wavelength of 900 nanometers, and was not suitable for use as a BCS. Therefore, the colored photosensitive resin composition according to the present invention can be used as a spacer and / or a black matrix for various electronic parts including an LCD.

Claims (6)

一種有色光敏樹脂組成物，其係包含：(a)共聚物；(b)環氧樹脂化合物或經由讓環氧樹脂與不飽和鹼性酸反應而製造環氧加合物，及讓如此所得的環氧加合物與多元酸酐反應；以及讓如此所得的化合物與單官能或多官能環氧化合物反應之化合物；(c)可聚合化合物；(d)光聚合起始劑；及(e)著色劑，其包含以該有色光敏樹脂組成物中固體含量總重為基準，0至5重量%之無機黑著色劑，10至40重量%之有機黑著色劑，及1至15重量%之藍著色劑。A colored photosensitive resin composition comprising: (a) a copolymer; (b) an epoxy resin compound or an epoxy adduct produced by reacting an epoxy resin with an unsaturated basic acid, and allowing the thus obtained An epoxy adduct is reacted with a polybasic acid anhydride; and a compound obtained by reacting a compound thus obtained with a monofunctional or polyfunctional epoxy compound; (c) a polymerizable compound; (d) a photopolymerization initiator; and (e) coloring An agent comprising an inorganic black colorant in an amount of 0 to 5% by weight, an organic black colorant in an amount of 10 to 40% by weight, and a blue coloration in an amount of 1 to 15% by weight based on the total solid content of the colored photosensitive resin composition Agent. 如申請專利範圍第1項所述之有色光敏樹脂組成物，其中，該共聚物係包含：(a-1)衍生自烯系不飽和羧酸、烯系不飽和羧酸酐、或其混合物之單元；(a-2)衍生自含芳香環的烯系不飽和化合物之單元；及(a-3)與(a-1)及(a-2)相異之衍生自烯系不飽和化合物之單元。The colored photosensitive resin composition according to item 1 of the scope of the patent application, wherein the copolymer system comprises: (a-1) units derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof (A-2) units derived from ethylenically unsaturated compounds containing aromatic rings; and (a-3) units derived from ethylenically unsaturated compounds that are different from (a-1) and (a-2) . 如申請專利範圍第1項所述之有色光敏樹脂組成物，其中，該環氧樹脂化合物係包含二苯并吡喃主鏈結構。The colored photosensitive resin composition according to item 1 of the scope of patent application, wherein the epoxy resin compound contains a dibenzopyran main chain structure. 如申請專利範圍第1項所述之有色光敏樹脂組成物，其中，該藍著色劑係為C.I.顏料藍15：6。The colored photosensitive resin composition according to item 1 of the scope of the patent application, wherein the blue colorant is C.I. Pigment Blue 15: 6. 如申請專利範圍第1項所述之有色光敏樹脂組成物，當形成為1微米(μm)厚度的固化層時，其係具有0.6至1.4的光密度。When the colored photosensitive resin composition described in item 1 of the patent application range is formed into a cured layer having a thickness of 1 micrometer (μm), it has an optical density of 0.6 to 1.4. 如申請專利範圍第1項所述之有色光敏樹脂組成物，當形成為1.5至2.5微米厚度的固化層時，其係於730奈米具有低於15%之光透射比，而當形成為3.5至4.5微米厚度的固化層時，其係於900奈米(nm)具有至少15%之光透射比。The colored photosensitive resin composition described in item 1 of the scope of patent application, when formed into a cured layer having a thickness of 1.5 to 2.5 microns, has a light transmittance of less than 15% at 730 nm, and when formed to 3.5 When the cured layer has a thickness of 4.5 microns, it has a light transmittance of at least 15% at 900 nanometers (nm).
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