TW201815984A - Photosensitive resin composition, black photosensitive resin layer, and color filter - Google Patents

Photosensitive resin composition, black photosensitive resin layer, and color filter Download PDF

Info

Publication number
TW201815984A
TW201815984A TW106134109A TW106134109A TW201815984A TW 201815984 A TW201815984 A TW 201815984A TW 106134109 A TW106134109 A TW 106134109A TW 106134109 A TW106134109 A TW 106134109A TW 201815984 A TW201815984 A TW 201815984A
Authority
TW
Taiwan
Prior art keywords
photosensitive resin
black
resin composition
item
scope
Prior art date
Application number
TW106134109A
Other languages
Chinese (zh)
Other versions
TWI679251B (en
Inventor
崔玄武
朴眞佑
柳娥凜
奇承範
金光燮
金貞延
李慧旼
趙明鎬
韓圭奭
Original Assignee
三星Ｓｄｉ股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三星Ｓｄｉ股份有限公司 filed Critical 三星Ｓｄｉ股份有限公司
Publication of TW201815984A publication Critical patent/TW201815984A/en
Application granted granted Critical
Publication of TWI679251B publication Critical patent/TWI679251B/en

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • 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
    • G03F7/16—Coating processes; 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
    • G03F7/2012—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 using liquid photohardening compositions, e.g. for the production of reliefs such as flexographic plates or stamps
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Engineering & Computer Science (AREA)
  • Materials For Photolithography (AREA)

Abstract

Disclosed are a photosensitive resin composition including (A) a binder resin including a cardo-based resin and an epoxy group-containing acryl-based resin in a weight ratio of 5:5 to 9:1; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a black colorant; and (E) a solvent, a black photosensitive resin layer manufactured using the photosensitive resin composition, and a color filter including the black photosensitive resin layer.

Description

感光性樹脂組成物、黑色感光性樹脂層以及彩色濾光片Photosensitive resin composition, black photosensitive resin layer, and color filter

本發明是有關於一種感光性樹脂組成物、一種黑色感光性樹脂層以及一種彩色濾光片。The present invention relates to a photosensitive resin composition, a black photosensitive resin layer, and a color filter.

顯示裝置（例如彩色濾光片、液晶顯示材料、有機發光二極體或顯示面板材料）需要使用感光性樹脂組成物。舉例來說，彩色濾光片（例如彩色液晶顯示器等）在例如紅色、綠色、藍色等著色層之間的邊界上需要黑色矩陣來增强顯示對比度或發色團效果（chromophore effect）。擋光層可主要由感光性樹脂組成物形成。A display device (for example, a color filter, a liquid crystal display material, an organic light emitting diode, or a display panel material) requires a photosensitive resin composition. For example, a color filter (such as a color liquid crystal display, etc.) requires a black matrix on the boundary between colored layers such as red, green, and blue to enhance display contrast or chromophore effect. The light blocking layer may be mainly formed of a photosensitive resin composition.

最近，嘗試使用黑色矩陣材料作爲柱狀間隔物（column spacer）來支撑其間具有液晶層的兩個薄膜電晶體（thin film transistor，TFT）基底與C/F基底，且這個柱狀間隔物被稱爲黑色柱狀間隔物。Recently, an attempt was made to use a black matrix material as a column spacer to support two thin film transistor (TFT) substrates and C / F substrates with a liquid crystal layer in between. This column spacer is called It is a black columnar spacer.

黑色柱狀間隔物應包括因光罩的透射率差異而形成的圖案階差（pattern step），且具有擋光性質以充當一般黑色矩陣並具有壓縮位移（compression displacement）、彈性恢復率以及斷裂强度（breaking strength）以充當柱狀間隔物，並且因此具有足够高的光學密度。另外，由於黑色柱狀間隔物同時由柱狀間隔物及黑色矩陣層組成，因此應通過使用半色調遮罩（halftone mask）來實現相對高的柱狀間隔物與相對低的黑色矩陣之間的階差。黑色柱狀間隔物與一般黑色矩陣不同，其會直接接觸液晶，且因此勢必需要能够使液晶的污染最小化的可靠性特性以及對用作上層的聚醯亞胺的溶劑及再生溶液（solution for rework）的耐化學性。The black columnar spacer should include a pattern step formed by the difference in the transmittance of the photomask, and have light blocking properties to act as a general black matrix and have compression displacement, elastic recovery rate, and breaking strength. (Breaking strength) to act as a columnar spacer, and thus have a sufficiently high optical density. In addition, since the black columnar spacer is composed of a columnar spacer and a black matrix layer at the same time, a halftone mask should be used to achieve a relatively high columnar spacer and a relatively low black matrix. Step difference. The black columnar spacer is different from the general black matrix, and it directly contacts the liquid crystal, and therefore it is necessary to have reliability characteristics that can minimize the contamination of the liquid crystal, and a solvent and a regeneration solution for the polyimide used as the upper layer. rework) chemical resistance.

然而，用於黑色柱狀間隔物的傳統感光性樹脂組成物仍存在適當的顯影部分非常狹窄且對聚醯亞胺的溶劑的耐溶解性劣化的問題。However, the conventional photosensitive resin composition for a black columnar spacer still has problems in that a suitable developing portion is very narrow and the solubility resistance to a solvent of polyimide is deteriorated.

因此，已通過考慮到以上特性而進行了研究以開發一種用於黑色柱狀間隔物的感光性樹脂組成物。Therefore, research has been conducted by considering the above characteristics to develop a photosensitive resin composition for a black columnar spacer.

本發明實施例提供一種具有改善的存儲穩定性及錐度特性（taper characteristic）的感光性樹脂組成物。Embodiments of the present invention provide a photosensitive resin composition having improved storage stability and taper characteristics.

另一實施例提供一種使用所述感光性樹脂組成物製造的黑色感光性樹脂層。Another embodiment provides a black photosensitive resin layer manufactured using the photosensitive resin composition.

又一實施例提供一種包括所述感光性樹脂層的彩色濾光片。Still another embodiment provides a color filter including the photosensitive resin layer.

本發明實施例提供一種感光性樹脂組成物，所述感光性樹脂組成物包含：（A）黏合劑樹脂，以5:5至9:1的重量比包含卡多系樹脂（cardo-based resin）及含環氧基的丙烯酸系樹脂（epoxy group-containing acryl-based resin）；（B）光可聚合單體；（C）光聚合引發劑；（D）黑色著色劑；以及（E）溶劑。An embodiment of the present invention provides a photosensitive resin composition. The photosensitive resin composition includes: (A) a binder resin including a cardo-based resin in a weight ratio of 5: 5 to 9: 1. And epoxy group-containing acryl-based resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a black colorant; and (E) a solvent.

所述黏合劑樹脂可以6:4至8:2的重量比包含卡多系樹脂及含環氧基的丙烯酸系樹脂。The binder resin may include a cardo-based resin and an epoxy-based acrylic resin in a weight ratio of 6: 4 to 8: 2.

所述黑色著色劑可包含紅色顔料、藍色顔料及紫色顔料。The black colorant may include a red pigment, a blue pigment, and a purple pigment.

所述紅色顔料可包含由化學式1表示的化合物： [化學式1]在化學式1中， R1 與R2 獨立地爲經取代或未經取代的C1至C10烷基。The red pigment may include a compound represented by Chemical Formula 1: [Chemical Formula 1] In Chemical Formula 1, R 1 and R 2 are independently a substituted or unsubstituted C1 to C10 alkyl group.

以所述黑色著色劑的總量計，所述黑色著色劑可分別以40重量%至60重量%、30重量%至50重量%以及10重量%至20重量%的量包含紅色顔料、藍色顔料及紫色顔料。Based on the total amount of the black colorant, the black colorant may include a red pigment, a blue color in an amount of 40% to 60% by weight, 30% to 50% by weight, and 10% to 20% by weight, respectively. Pigments and purple pigments.

所述黑色著色劑可更包含無機黑色顔料。The black colorant may further include an inorganic black pigment.

所述無機黑色顔料可包括碳黑。The inorganic black pigment may include carbon black.

以所述黑色著色劑的總量計，可以3重量%至8重量%的量包含所述無機黑色顔料。The inorganic black pigment may be included in an amount of 3 to 8% by weight based on the total amount of the black colorant.

所述藍色顔料可包含酞菁系（phthalocyanine-based）化合物。The blue pigment may include a phthalocyanine-based compound.

所述紫色顔料可包含苝系（perylene-based）化合物。The purple pigment may include a perylene-based compound.

以所述感光性樹脂組成物的總量計，所述感光性樹脂組成物可包含：1重量%至10重量%的（A）所述黏合劑樹脂；1重量%至10重量%的（B）光可聚合單體；0.1重量%至5重量%的（C）所述光聚合引發劑；30重量%至50重量%的（D）所述黑色著色劑；以及餘量爲（E）所述溶劑。Based on the total amount of the photosensitive resin composition, the photosensitive resin composition may include: 1% to 10% by weight of (A) the binder resin; 1% to 10% by weight of (B ) A photopolymerizable monomer; 0.1 to 5% by weight of the photopolymerization initiator (C); 30 to 50% by weight of the black colorant (D); and the balance is (E) Mentioned solvents.

所述感光性樹脂組成物可更包含以下添加劑：丙二酸、3-氨基-1,2-丙二醇、矽烷系偶合劑、流平劑、氟系表面活性劑、自由基聚合引發劑或其組合。The photosensitive resin composition may further include the following additives: malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof .

另一實施例提供一種使用所述感光性樹脂組成物製造的黑色感光性樹脂層。Another embodiment provides a black photosensitive resin layer manufactured using the photosensitive resin composition.

所述黑色感光性樹脂層可爲黑色柱狀間隔物。The black photosensitive resin layer may be a black columnar spacer.

所述黑色柱狀間隔物可包括主柱狀間隔物及次柱狀間隔物。The black columnar spacer may include a primary columnar spacer and a secondary columnar spacer.

所述黑色柱狀間隔物可在所述主柱狀間隔物與所述次柱狀間隔物之間具有小於或等於1000 Å的階差。The black columnar spacer may have a step difference of less than or equal to 1000 Å between the primary columnar spacer and the secondary columnar spacer.

所述黑色柱狀間隔物可在1 μm的厚度處具有大於或等於0.8的光學密度。The black columnar spacer may have an optical density of 0.8 or more at a thickness of 1 μm.

另一實施例提供一種包括所述黑色感光性樹脂層的彩色濾光片。Another embodiment provides a color filter including the black photosensitive resin layer.

本發明的其他實施例包含在以下詳細說明中。Other embodiments of the present invention are included in the following detailed description.

根據實施例的感光性樹脂組成物以預定重量比包含卡多系樹脂及含環氧基的丙烯酸系樹脂，且由此可改善感光性樹脂組成物的存儲穩定性及錐度特性。The photosensitive resin composition according to the embodiment includes a Cardo-based resin and an epoxy-based acrylic resin in a predetermined weight ratio, and thereby the storage stability and taper characteristics of the photosensitive resin composition can be improved.

為讓本發明的上述特徵和優點能更明顯易懂，下文特舉實施例，並配合所附圖式作詳細說明如下。In order to make the above features and advantages of the present invention more comprehensible, embodiments are hereinafter described in detail with reference to the accompanying drawings.

以下，詳細闡述本發明的實施例。然而，這些實施例爲示例性的，本發明並非僅限於此且本發明是由權利要求的範圍所界定。Hereinafter, examples of the present invention will be described in detail. However, these embodiments are exemplary, and the present invention is not limited thereto and the present invention is defined by the scope of the claims.

當不另外提供具體定義時，本文中所用的“烷基”是指C1至C20烷基，術語“烯基”是指C2至C20烯基，術語“環烯基”是指C3至C20環烯基，術語“雜環烯基”是指C3至C20雜環烯基，術語“芳基”是指C6至C20芳基，術語“芳烷基”是指C6至C20芳烷基，術語“伸烷基”是指C1至C20伸烷基，術語“伸芳基”是指C6至C20伸芳基，術語“伸烷芳基”是指C6至C20伸烷芳基，術語“伸雜芳基”是指C3至C20伸雜芳基，且術語“伸烷氧基”是指C1至C20伸烷氧基。When a specific definition is not otherwise provided, "alkyl" as used herein refers to C1 to C20 alkyl, the term "alkenyl" refers to C2 to C20 alkenyl, and the term "cycloalkenyl" refers to C3 to C20 cycloolefin The term "heterocycloalkenyl" refers to a C3 to C20 heterocycloalkenyl, the term "aryl" refers to a C6 to C20 aryl, the term "aralkyl" refers to a C6 to C20 aralkyl, and the term "extended" "Alkyl" means C1 to C20 alkylene, the term "aryl" refers to C6 to C20 alkylene, the term "alkylene" refers to C6 to C20 alkylene, and the term "heteroaryl" "Refers to C3 to C20 alkaryl, and the term" alkoxy "refers to C1 to C20 alkoxy.

當不另外提供具體定義時，本文所用的“經取代的”是指至少一個氫原子被以下置換：鹵素原子（F、Cl、Br或I）、羥基、C1至C20烷氧基、硝基、氰基、胺基、伸氨基、疊氮基、脒基、肼基、伸肼基、羰基、氨甲醯基、硫醇基（thiol group）、酯基、醚基、羧基或其鹽、磺酸基或其鹽、磷酸或其鹽、C1至C20烷基、C2至C20烯基、C2至C20炔基、C6至C20芳基、C3至C20環烷基、C3至C20環烯基、C3至C20環炔基、C2至C20雜環烷基、C2至C20雜環烯基、C2至C20雜環炔基、C3至C20雜芳基或其組合。When a specific definition is not otherwise provided, "substituted" as used herein means that at least one hydrogen atom is replaced with a halogen atom (F, Cl, Br or I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, Cyano, amine, amino, azido, fluorenyl, hydrazino, hydrazino, carbonyl, carbamoyl, thiol group, ester, ether, carboxyl or its salt, sulfo Acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C20 aryl, C3 to C20 cycloalkyl, C3 to C20 cycloalkenyl, C3 To C20 cycloalkynyl, C2 to C20 heterocycloalkyl, C2 to C20 heterocycloalkenyl, C2 to C20 heterocycloalkynyl, C3 to C20 heteroaryl, or a combination thereof.

當不另外提供具體定義時，本文所用的“經取代的”是指至少一個氫原子被以下置換：鹵素原子（F、Cl、Br或I）、羥基、C1至C20烷氧基、硝基、氰基、胺基、伸氨基、疊氮基、脒基、肼基、伸肼基、羰基、氨甲醯基、硫醇基（thiol group）、酯基、醚基、羧基或其鹽、磺酸基或其鹽、磷酸或其鹽、C1至C20烷基、C2至C20烯基、C2至C20炔基、C6至C20芳基、C3至C20環烷基、C3至C20環烯基、C3至C20環炔基、C2至C20雜環烷基、C2至C20雜環烯基、C2至C20雜環炔基、C3至C20雜芳基或其組合。When a specific definition is not otherwise provided, "substituted" as used herein means that at least one hydrogen atom is replaced with a halogen atom (F, Cl, Br or I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, Cyano, amine, amino, azido, fluorenyl, hydrazino, hydrazino, carbonyl, carbamoyl, thiol group, ester, ether, carboxyl or its salt, sulfo Acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C20 aryl, C3 to C20 cycloalkyl, C3 to C20 cycloalkenyl, C3 To C20 cycloalkynyl, C2 to C20 heterocycloalkyl, C2 to C20 heterocycloalkenyl, C2 to C20 heterocycloalkynyl, C3 to C20 heteroaryl, or a combination thereof.

當不另外提供具體定義時，本文所用的術語“雜”是指在化學式中包含至少一個選自N、O、S及P的雜原子。When a specific definition is not otherwise provided, the term "hetero" as used herein refers to including at least one heteroatom selected from N, O, S, and P in a chemical formula.

當不另外提供具體定義時，本文中所用的“(甲基)丙烯酸酯”是指“丙烯酸酯”和“甲基丙烯酸酯”二者，並且“(甲基)丙烯酸”是指“丙烯酸”和“甲基丙烯酸”二者。When a specific definition is not otherwise provided, "(meth) acrylate" as used herein means both "acrylate" and "methacrylate", and "(meth) acrylic acid" means "acrylic acid" and "Methacrylic" both.

當不另外提供具體定義時，本文中所用的術語“組合”是指混合或共聚合。When not specifically provided otherwise, the term "combination" as used herein refers to mixing or copolymerization.

當不另外提供具體定義時，本文中所用的不飽和鍵包括位於其他原子之間的鍵，例如羰基鍵，或偶氮鍵，以及位於碳碳原子之間的多鍵。When a specific definition is not otherwise provided, the unsaturated bond used herein includes a bond between other atoms, such as a carbonyl bond, or an azo bond, and a multiple bond between carbon atoms.

如本文所用，當不另外提供定義時，當化學式中的化學鍵並未繪製在應給出處時，氫鍵結在所述位置處。As used herein, when a definition is not otherwise provided, when a chemical bond in a chemical formula is not drawn where it should be given, a hydrogen bond is at that position.

本文所用的卡多系樹脂是指在骨架中包含至少一個選自化學式2-1至化學式2-11的官能基的樹脂。The Cardo resin as used herein refers to a resin containing at least one functional group selected from Chemical Formula 2-1 to Chemical Formula 2-11 in a skeleton.

當不另外提供具體定義時，本文中所用的“*”表示連接相同或不同的原子或化學式的點。When a specific definition is not otherwise provided, "*" as used herein means a point connecting the same or different atom or chemical formula.

根據實施例的一種感光性樹脂組成物包含：（A）黏合劑樹脂，以5:5至9:1的重量比包含卡多系樹脂及含環氧基的丙烯酸系樹脂；（B）光可聚合單體；（C）光聚合引發劑；（D）黑色著色劑；以及（E）溶劑。A photosensitive resin composition according to an embodiment includes: (A) a binder resin including a cardo-based resin and an epoxy-based acrylic resin in a weight ratio of 5: 5 to 9: 1; (B) photopolymer (C) a photopolymerization initiator; (D) a black colorant; and (E) a solvent.

一般來說，在感光性樹脂組成物中使用卡多系樹脂作爲黏合劑樹脂，但卡多系樹脂具有斷點（break point，BP）隨著時間推移而逐漸减少或在黑色柱狀間隔物的圖案化期間階差變化大且錐度低的缺點。Generally, cardo-based resins are used as binder resins in photosensitive resin compositions, but cardo-based resins have a break point (BP) that gradually decreases over time or that of black columnar spacers. Disadvantages of large step change and low taper during patterning.

然而，根據實施例的感光性樹脂組成物包含以5:5至9:1的重量比包含卡多系樹脂及含環氧基的丙烯酸系樹脂的黏合劑樹脂，且因此在低溫（0℃至10℃）下在大於或等於約3個月的時間內其存儲穩定性無斷點變化（在2秒以內），並且在黑色柱狀間隔物的圖案化期間在主柱狀間隔物與次柱狀間隔物之間以及主柱狀間隔物與黑色矩陣之間還顯示出小的階差變化（0 Å至1000 Å），且因此會實現具有優異的存儲穩定性及適當的錐度特性的黑色柱狀間隔物。However, the photosensitive resin composition according to the embodiment includes a binder resin including a Cardo-based resin and an epoxy-containing acrylic resin in a weight ratio of 5: 5 to 9: 1, and therefore is at a low temperature (0 ° C to 10 ° C), its storage stability has no breakpoint change (within 2 seconds) for a period of greater than or equal to about 3 months, and during the patterning of the black columnar spacers, between the main columnar spacers and the secondary columns Small step changes (0 Å to 1000 Å) between the spacers and between the main columnar spacers and the black matrix, and therefore a black column with excellent storage stability and appropriate taper characteristics will be realized Like spacer.

以下，具體闡述每一組分。Hereinafter, each component is explained in detail.

（A）黏合劑樹脂(A) Adhesive resin

黏合劑樹脂包含卡多系樹脂及含環氧基的丙烯酸系樹脂。The binder resin includes a Cardo resin and an epoxy-containing acrylic resin.

如上所述，當在用於黑色矩陣或黑色柱狀間隔物的組成物中使用卡多系黏合劑樹脂時，斷點（BP）隨著時間推移而减少，且因此綫寬趨於變窄，或者包括黑色柱狀間隔物的黑色矩陣的高度趨於降低。As described above, when a Cardo-based adhesive resin is used in a composition for a black matrix or a black columnar spacer, the break point (BP) decreases over time, and therefore the line width tends to become narrower, Or the height of the black matrix including the black columnar spacers tends to decrease.

爲了改善這些問題，已提出不使用卡多系黏合劑樹脂，但當使用一般丙烯酸系黏合劑樹脂時，對於黑色柱狀間隔物而言可能因缺乏精細圖案化特性（高清晰度）或缺乏對作爲聚醯亞胺膜的溶劑的N-甲基吡咯烷（N-methyl pyrrolidine，NMP）的耐化學性而存在破壞圖案等副作用。In order to improve these problems, it has been proposed not to use a Cardo-type adhesive resin, but when a general acrylic-type adhesive resin is used, the black columnar spacer may be lack of fine patterning characteristics (high definition) or lack of good The chemical resistance of N-methyl pyrrolidine (NMP), which is a solvent of a polyfluorene imine film, has side effects such as pattern damage.

爲了將所述副作用最小化，可使用包含環氧基的丙烯酸系黏合劑樹脂來替代卡多系黏合劑樹脂，且因此對N-甲基吡咯烷的耐化學性大大提高，且也會彌補因僅使用卡多系黏合劑樹脂而造成的缺點，並且因此會增强錐度特性，但因斷點（BP）隨著時間推移增多而造成儘管爲適當的顯影時間但顯影不完全（non-development）的副作用。In order to minimize the side effects, an epoxy-based acrylic resin may be used in place of the Cardo-based adhesive resin, and thus the chemical resistance to N-methylpyrrolidine is greatly improved, and the cause is also compensated. Disadvantages caused by the use of Cardo-series adhesive resin only, and consequently, the taper characteristics are enhanced, but the breakpoint (BP) increases over time, resulting in non-development, although the development time is appropriate side effect.

根據實施例的感光性樹脂組成物使用以5:5至9:1的重量比包含卡多系樹脂及含環氧基的丙烯酸系樹脂的黏合劑樹脂，且因此可通過彌補含環氧基的丙烯酸系黏合劑樹脂使斷點减少的缺點而使斷點隨著時間推移而增加，並且因此使存儲穩定性最大化且還會將錐度特性增大至適當水平。The photosensitive resin composition according to the embodiment uses a binder resin including a Cardo-based resin and an epoxy-containing acrylic resin in a weight ratio of 5: 5 to 9: 1, and therefore, it is possible to compensate for the epoxy-containing The disadvantage of the acrylic adhesive resin is that the break point is reduced and the break point is increased over time, and therefore the storage stability is maximized and the taper characteristic is also increased to an appropriate level.

舉例來說，所述黏合劑樹脂可以6:4至8:2的重量比包含卡多系樹脂及含環氧基的丙烯酸系樹脂。For example, the binder resin may include a cardo-based resin and an epoxy-based acrylic resin in a weight ratio of 6: 4 to 8: 2.

當以比含環氧基的丙烯酸系樹脂的量少的量來包含卡多系樹脂時，錐度可增大，但在低溫（0℃至10℃）下的存儲穩定性可劣化。另外，當所包含的卡多系樹脂是含環氧基的丙烯酸系樹脂的9倍時，錐度可减小，但在低溫（0℃至10℃）下的存儲穩定性可劣化很多。When the Cardo-based resin is contained in an amount smaller than the amount of the epoxy-containing acrylic resin, the taper may be increased, but storage stability at low temperatures (0 ° C to 10 ° C) may be deteriorated. In addition, when the Cardo-based resin is contained nine times as much as the epoxy-based acrylic resin, the taper can be reduced, but the storage stability at low temperatures (0 ° C to 10 ° C) can be greatly deteriorated.

卡多系黏合劑樹脂可包含由化學式2表示的重複單元。 [化學式2]在化學式2中， R11 與R12 獨立地爲氫原子或者經取代或未經取代的(甲基)丙烯醯氧基烷基（(meth)acryloyloxyalkyl group）， R13 與R14 獨立地爲氫原子、鹵素原子或者經取代或未經取代的C1至C20烷基，且 Z1 爲單鍵、O、CO、SO2 、CR7 R8 、SiR9 R10 （其中，R7 至R10 獨立地爲氫原子或者經取代或未經取代的C1至C20烷基）或由化學式2-1至化學式2-11表示的連接基中的一者， [化學式2-1][化學式2-2][化學式2-3][化學式2-4][化學式2-5]其中，在化學式2-5中， Ra 爲氫原子、乙基、C2 H4 Cl、C2 H4 OH、CH2 CH=CH2 或苯基， [化學式2-6][化學式2-7][化學式2-8][化學式2-9][化學式2-10][化學式2-11]Z2 爲酸二酐殘基，且 m1與m2獨立地爲介於0至4範圍內的整數。 卡多系黏合劑樹脂可在兩個末端中的至少一個末端處包含由化學式3表示的官能基。 [化學式3]在化學式3中， Z3 可由化學式3-1至化學式3-7表示。 [化學式3-1]在化學式3-1中，Rb 與Rc 獨立地爲氫原子、經取代或未經取代的C1至C20烷基、酯基或醚基。 [化學式3-2][化學式3-3][化學式3-4][化學式3-5]在化學式3-5中，Rd 爲O、S、NH、經取代或未經取代的C1至C20亞烷基、C1至C20烷基胺基或C2至C20烯基胺基。 [化學式3-6][化學式3-7] The Cardo-based adhesive resin may include a repeating unit represented by Chemical Formula 2. [Chemical Formula 2] In Chemical Formula 2, R 11 and R 12 are independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group, and R 13 and R 14 are independently hydrogen Atom, halogen atom or substituted or unsubstituted C1 to C20 alkyl group, and Z 1 is a single bond, O, CO, SO 2 , CR 7 R 8 , SiR 9 R 10 (wherein R 7 to R 10 are independent Ground is one of a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or a linking group represented by Chemical Formula 2-1 to Chemical Formula 2-11, [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] [Chemical Formula 2-4] [Chemical Formula 2-5] Wherein, in Chemical Formula 2-5, R a is a hydrogen atom, ethyl, C 2 H 4 Cl, C 2 H 4 OH, CH 2 CH = CH 2 or phenyl group, [Chemical Formula 2-6] [Chemical Formula 2-7] [Chemical Formula 2-8] [Chemical Formula 2-9] [Chemical Formula 2-10] [Chemical Formula 2-11] Z 2 is an acid dianhydride residue, and m1 and m2 are independently an integer ranging from 0 to 4. The Cardo-based adhesive resin may include a functional group represented by Chemical Formula 3 at at least one of two ends. [Chemical Formula 3] In Chemical Formula 3, Z 3 may be represented by Chemical Formula 3-1 to Chemical Formula 3-7. [Chemical Formula 3-1] In Chemical Formula 3-1, R b and R c are independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group. [Chemical Formula 3-2] [Chemical Formula 3-3] [Chemical Formula 3-4] [Chemical Formula 3-5] In Chemical Formulas 3-5, Rd is O, S, NH, substituted or unsubstituted C1 to C20 alkylene, C1 to C20 alkylamino, or C2 to C20 alkenylamino. [Chemical Formula 3-6] [Chemical Formula 3-7]

卡多系樹脂可通過混合以下中的至少兩種來製備：含芴化合物，例如9,9-雙(4-環氧乙烷基甲氧基苯基)芴（9,9-bis(4-oxiranylmethoxyphenyl)fluorene）等；酸酐化合物，例如苯四甲酸二酐、萘四甲酸二酐、聯苯四甲酸二酐、二苯甲酮四甲酸二酐、苯均四酸二酐、環丁烷四甲酸二酐、苝四甲酸二酐、四氫呋喃四甲酸二酐、四氫苯酐（tetrahydrophthalic anhydride）等；二醇化合物，例如乙二醇、丙二醇、聚乙二醇等；醇化合物，例如甲醇、乙醇、丙醇、正丁醇、環己醇、苯甲醇等；溶劑系化合物，例如丙二醇乙酸甲基乙酯、N-甲基吡咯烷酮等；磷化合物，例如三苯基膦等；以及胺或銨鹽化合物，例如四甲基氯化銨、四乙基溴化銨、苯甲基二乙胺、三乙胺、三丁胺、苯甲基三乙基氯化銨等。Cardo-series resins can be prepared by mixing at least two of the following: fluorene-containing compounds, such as 9,9-bis (4-oxiranylmethoxyphenyl) fluorene (9,9-bis (4- oxiranylmethoxyphenyl) fluorene) etc .; anhydride compounds, such as pyromellitic dianhydride, naphthalenetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic acid Dianhydride, pyrene tetracarboxylic dianhydride, tetrahydrofurantetracarboxylic dianhydride, tetrahydrophthalic anhydride, etc .; glycol compounds such as ethylene glycol, propylene glycol, polyethylene glycol, etc .; alcohol compounds such as methanol, ethanol, propylene Alcohols, n-butanol, cyclohexanol, benzyl alcohol, etc .; solvent compounds, such as propylene glycol methyl ethyl acetate, N-methylpyrrolidone, etc .; phosphorus compounds, such as triphenylphosphine, etc .; and amine or ammonium salt compounds, For example, tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, and the like.

卡多系黏合劑樹脂的重量平均分子量可爲500 g/mol至50,000 g/mol、例如1,000 g/mol至30,000 g/mol。當卡多系黏合劑樹脂的重量平均分子量在所述範圍內時，在製造黑色柱狀間隔物期間可很好地形成圖案而無殘留，並且在顯影期間膜厚度不會减少。The weight average molecular weight of the cardo-based adhesive resin may be 500 g / mol to 50,000 g / mol, for example, 1,000 g / mol to 30,000 g / mol. When the weight-average molecular weight of the Cardo-based adhesive resin is within the range, a pattern can be formed well without residue during the production of the black columnar spacer, and the film thickness does not decrease during development.

含環氧基的丙烯酸系黏合劑樹脂因具有環氧基而會改善耐熱性及耐化學性。含環氧基的丙烯酸系黏合劑樹脂可例如通過將含環氧基的單體與隨後將闡述的烯系不飽和單體共聚合來製備。Epoxy-based acrylic adhesive resins have epoxy groups and improve heat resistance and chemical resistance. The epoxy-group-containing acrylic adhesive resin can be produced, for example, by copolymerizing an epoxy-group-containing monomer and an ethylenically unsaturated monomer which will be described later.

此外，含環氧基的丙烯酸系黏合劑樹脂可確保隨後將闡述的顔料的分散穩定性且同時有助於形成具有所期望的解析度的像素。即使將隨後將闡述的顔料與含環氧基的丙烯酸系黏合劑樹脂一起用作黑色著色劑，不包含含環氧基的丙烯酸系樹脂的黏合劑樹脂仍與隨後將闡述的著色劑具有不適當的相容性，因而所述黏合劑樹脂必需包含含環氧基的丙烯酸系黏合劑樹脂。In addition, the epoxy-group-containing acrylic adhesive resin can ensure dispersion stability of a pigment to be described later and at the same time contribute to forming a pixel having a desired resolution. Even if a pigment to be described later is used as a black colorant together with an epoxy-containing acrylic adhesive resin, a binder resin that does not include an epoxy-containing acrylic resin still has an inappropriate coloring agent to be described later Compatibility, the adhesive resin must include an epoxy-based acrylic adhesive resin.

含環氧基的丙烯酸系黏合劑樹脂的環氧當量可爲150 g/eq至200 g/eq。當在感光性樹脂組成物中包含環氧當量處於所述範圍內的含環氧基的丙烯酸系黏合劑樹脂作爲黏合劑樹脂時，可獲得所形成的圖案的固化得以改善以及將顔料固定在已形成圖案的結構中的效果。The epoxy equivalent of the acrylic adhesive resin may have an epoxy equivalent of 150 g / eq to 200 g / eq. When the epoxy resin-containing acrylic-based adhesive resin having an epoxy equivalent in the above range is included in the photosensitive resin composition as the adhesive resin, it is possible to improve the curing of the formed pattern and fix the pigment to Effect in patterned structure.

烯系不飽和單體可包括第一烯系不飽和單體及可與其共聚合的第二烯系不飽和單體，並且可包含至少一個丙烯酸系重複單元。The ethylenically unsaturated monomer may include a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and may include at least one acrylic repeating unit.

第一烯系不飽和單體是包含至少一個羧基的烯系不飽和單體，且其具體實例可爲丙烯酸、甲基丙烯酸、順丁烯二酸、衣康酸、反丁烯二酸或其組合。The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof may be acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or the like combination.

第二烯系不飽和單體可爲芳族乙烯基化合物，例如苯乙烯、α-甲基苯乙烯、乙烯基甲苯、乙烯基苯甲基甲醚等；不飽和羧酸酯化合物，例如(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2-羥乙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸環己基酯、(甲基)丙烯酸苯酯等；不飽和羧酸氨基烷基酯化合物，例如(甲基)丙烯酸2-氨基乙酯、(甲基)丙烯酸2-二甲氨基乙酯等；羧酸乙烯基酯化合物，例如乙酸乙烯酯、苯甲酸乙烯酯等；不飽和羧酸縮水甘油基酯化合物，例如(甲基)丙烯酸縮水甘油基酯等；丙烯腈化合物，例如(甲基)丙烯腈等；不飽和醯胺化合物，例如(甲基)丙烯醯胺等；等等。這些第二烯系不飽和單體可單獨使用或以兩者或更多者的混合物形式使用。The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl methyl ether, etc .; an unsaturated carboxylic acid ester compound such as (methyl (Methyl) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzene (meth) acrylate Methyl ester, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, etc .; unsaturated alkyl carboxylic acid amino alkyl compounds, such as 2-aminoethyl (meth) acrylate, 2-methyl (meth) acrylate Dimethylaminoethyl, etc .; Vinyl carboxylic acid ester compounds, such as vinyl acetate, vinyl benzoate, etc .; Unsaturated carboxylic acid glycidyl ester compounds, such as glycidyl (meth) acrylate, etc .; acrylonitrile compounds , Such as (meth) acrylonitrile and the like; unsaturated fluorenamine compounds, such as (meth) acrylamide and the like; and so on. These second ethylenically unsaturated monomers may be used alone or as a mixture of two or more.

包含卡多系樹脂及含環氧基的丙烯酸系樹脂的黏合劑樹脂的重量平均分子量可爲6,000 g/mol至50,000 g/mol、例如6,000 g/mol至16,000 g/mol。當黏合劑樹脂的重量平均分子量處於所述範圍內時，感光性樹脂組成物在彩色濾光片的製造期間具有良好的物理性質及化學性質、適當的黏度以及與基底緊密接觸的性質。The weight average molecular weight of the binder resin including a Cardo-based resin and an epoxy-containing acrylic resin may be 6,000 g / mol to 50,000 g / mol, for example, 6,000 g / mol to 16,000 g / mol. When the weight average molecular weight of the binder resin is within the above range, the photosensitive resin composition has good physical and chemical properties, suitable viscosity, and close contact with the substrate during the manufacture of the color filter.

以所述感光性樹脂組成物的總量計，可包含1重量%至10重量%的量的所述黏合劑樹脂。當包含處於所述範圍內的黏合劑樹脂時，可改善可顯影性，並且在彩色濾光片的製造期間由於改善的交聯而可改善優異的表面光滑度。The binder resin may be included in an amount of 1 to 10% by weight based on the total amount of the photosensitive resin composition. When the binder resin is included in the range, developability can be improved, and excellent surface smoothness can be improved due to improved crosslinking during the manufacture of the color filter.

（D）黑色著色劑(D) Black colorant

黑色著色劑可包含紅色顔料、藍色顔料及紫色顔料。The black colorant may include a red pigment, a blue pigment, and a purple pigment.

黑色柱狀間隔物應阻擋從背光發出的光並支撑上部板及背板以實現黑色矩陣功能及柱狀間隔物功能兩種功能，且還具有通過半遮罩而將柱狀間隔物區與黑色矩陣區清晰地區分開的階差。然而，當使用例如無機黑色顔料（例如碳黑等）、有機黑色顔料等傳統材料來實現黑色柱狀間隔物時，傳統材料具有低透光率且因此可僅在表面上固化且幾乎不形成階差。The black columnar spacers should block the light emitted from the backlight and support the upper and back plates to achieve both the black matrix function and the columnar spacer function, and also have the columnar spacer area and the black through a half mask. The matrix area clearly distinguishes the step differences. However, when using conventional materials such as inorganic black pigments (such as carbon black, etc.), organic black pigments, and the like to realize black columnar spacers, the conventional materials have low light transmittance and therefore can be cured only on the surface and hardly form steps. difference.

然而，根據實施例，可通過不單獨使用例如碳黑等無機黑色顔料或有機黑色顔料作爲黑色著色劑而是使用紅色顔料、藍色顔料及紫色顔料的混合物並因此提高膜透射率，來容易地形成黑色柱狀間隔物的階差。However, according to the embodiment, it is possible to easily make use of a mixture of a red pigment, a blue pigment, and a purple pigment instead of using an inorganic black pigment such as carbon black or an organic black pigment alone as a black colorant and thereby increasing the film transmittance. Steps forming black columnar spacers.

舉例來說，紅色顔料可包含由化學式1表示的化合物。 [化學式1]在化學式1中， R1 與R2 獨立地爲經取代或未經取代的C1至C10烷基。For example, the red pigment may include a compound represented by Chemical Formula 1. [Chemical Formula 1] In Chemical Formula 1, R 1 and R 2 are independently a substituted or unsubstituted C1 to C10 alkyl group.

舉例來說，R1 與R2 可獨立地爲甲基。For example, R 1 and R 2 may be independently methyl.

一般來說，關於黑色柱狀間隔物，由於在黑色柱狀間隔物上形成有聚醯亞胺膜，因此黑色柱狀間隔物應具有對作爲聚醯亞胺的溶劑的N-甲基吡咯烷的優異耐溶解性。可通過在紅色顔料中包含由化學式1表示的化合物（例如使用由化學式1表示的化合物作爲紅色顔料）而容易地控制對N-甲基吡咯烷的耐溶解性（可提高液晶耐溶解性）。In general, regarding a black columnar spacer, since a polyimide film is formed on the black columnar spacer, the black columnar spacer should have N-methylpyrrolidine as a solvent for the polyimide. Excellent solubility resistance. By including the compound represented by Chemical Formula 1 in the red pigment (for example, using the compound represented by Chemical Formula 1 as a red pigment), the solubility resistance to N-methylpyrrolidine can be easily controlled (the solubility resistance of the liquid crystal can be improved).

以所述黑色著色劑的總量計，所述黑色著色劑可分別以40重量%至60重量%、30重量%至50重量%以及10重量%至20重量%的量包含紅色顔料、藍色顔料及紫色顔料。當包含處於所述含量範圍內的紅色顔料、藍色顔料及紫色顔料時，由於短波長區中的透射率最大化，因此可獲得能够容易形成階差的圖案，且由於可見光區中的透射率最小化，因此可將黑色柱狀間隔物的光學密度這一固有特性最大化。Based on the total amount of the black colorant, the black colorant may include a red pigment, a blue color in an amount of 40% to 60% by weight, 30% to 50% by weight, and 10% to 20% by weight, respectively. Pigments and purple pigments. When a red pigment, a blue pigment, and a purple pigment within the content range are included, since the transmittance in the short wavelength region is maximized, a pattern capable of easily forming a step difference can be obtained, and since the transmittance in the visible light region is obtained Minimized, thus maximizing the inherent characteristic of the optical density of the black columnar spacer.

所述藍色顔料可包含酞菁系化合物。舉例來說，所述藍色顔料可包含酞菁系化合物。The blue pigment may include a phthalocyanine-based compound. For example, the blue pigment may include a phthalocyanine-based compound.

舉例來說，所述藍色顔料可由化學式4表示。 [化學式4]所述紫色顔料可包含苝系化合物。舉例來說，所述紫色顔料可由化學式5表示。 [化學式5] For example, the blue pigment may be represented by Chemical Formula 4. [Chemical Formula 4] The purple pigment may include a fluorene-based compound. For example, the purple pigment may be represented by Chemical Formula 5. [Chemical Formula 5]

所述黑色著色劑可進一步包含無機黑色顔料。The black colorant may further include an inorganic black pigment.

舉例來說，無機黑色顔料可包括碳黑、鈦黑、苝黑、苯胺黑或其組合。舉例來說，所述無機黑色顔料可爲碳黑。For example, the inorganic black pigment may include carbon black, titanium black, perylene black, aniline black, or a combination thereof. For example, the inorganic black pigment may be carbon black.

以所述黑色著色劑的總量計，可以3重量%至8重量%的量包含所述無機黑色顔料。由於例如碳黑等無機黑色顔料具有導電性且因此可存在使用所述黑色感光性樹脂組成物形成的黑色感光性樹脂層的介電常數增大且其電性質劣化的問題，因此所包含的無機黑色顔料（例如，碳黑）可適宜處於所述含量範圍內。The inorganic black pigment may be included in an amount of 3 to 8% by weight based on the total amount of the black colorant. Inorganic black pigments such as carbon black have conductivity and, therefore, there is a problem that the dielectric constant of a black photosensitive resin layer formed using the black photosensitive resin composition is increased and its electrical properties are deteriorated. A black pigment (for example, carbon black) may suitably be in the content range.

可使用分散劑來分散所述顔料。A dispersant may be used to disperse the pigment.

具體來說，可使用分散劑來預處理顔料的表面，或將顔料與分散劑一起添加來製備組成物。Specifically, a dispersant may be used to pretreat the surface of a pigment, or a pigment may be added together with a dispersant to prepare a composition.

分散劑可爲非離子分散劑、陰離子分散劑、陽離子分散劑等。分散劑的具體實例可爲聚亞烷基二醇及其酯、聚氧化烯、多元醇酯環氧烷加成産物、醇環氧烷加成産物、磺酸酯、磺酸鹽、羧酸酯、羧酸鹽、烷基醯胺環氧烷加成産物、烷基胺等，且這些分散劑可單獨使用或作爲兩者或更多者的混合物形式使用。The dispersant may be a nonionic dispersant, an anionic dispersant, a cationic dispersant, or the like. Specific examples of the dispersant may be polyalkylene glycol and its ester, polyoxyalkylene, polyol ester alkylene oxide addition product, alcohol alkylene oxide addition product, sulfonate, sulfonate, carboxylic acid ester , Carboxylate, alkylamidoalkylene oxide addition products, alkylamines, etc., and these dispersants can be used alone or as a mixture of two or more.

分散劑的市售實例可包括畢克化學有限公司（BYK Co., Ltd.）製成的迪斯帕畢克（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；埃夫卡化學公司（EFKA Chemicals Co.）製造的埃夫卡（EFKA）-47、EFKA-47EA、EFKA-48、EFKA-49、EFKA-100、EFKA-400、EFKA-450；捷利康公司（Zeneka Co.）製造的索思帕（Solsperse）5000、Solsperse 12000、Solsperse 13240、Solsperse 13940、Solsperse 17000、Solsperse 20000、Solsperse 24000GR、Solsperse 27000、Solsperse 28000等；或味之素公司（Ajinomoto Inc.）製造的PB711、PB821等。Commercial examples of the dispersant may include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161 made by BYK Co., Ltd. , DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001; EFKA Chemicals Co. (EFKA Chemicals Co .) Manufactured by EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450; Sospa manufactured by Zeneka Co. (Solsperse) 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc .; or PB711 and PB821 manufactured by Ajinomoto Inc.

以所述感光性樹脂組成物的總量計，可以0.1重量%至15重量%的量包含所述分散劑。當包含處於所述範圍內的分散劑時，組成物在製造黑色柱狀間隔物期間因爲分散性提高而具有優異的穩定性、可顯影性及圖案形成能力。The dispersant may be included in an amount of 0.1 to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant is included in the range, the composition has excellent stability, developability, and pattern forming ability due to improved dispersibility during the production of the black columnar spacer.

顔料可用水溶性無機鹽和潤濕劑預處理。當顔料經過預處理後，顔料的平均粒徑可變得更細。Pigments can be pretreated with water-soluble inorganic salts and wetting agents. When the pigment is pretreated, the average particle size of the pigment can be made finer.

預處理可如下進行：用水溶性無機鹽及潤濕劑揉捏顔料，且然後過濾並洗滌揉捏後的顔料。The pretreatment may be performed as follows: the pigment is kneaded with a water-soluble inorganic salt and a wetting agent, and then the kneaded pigment is filtered and washed.

揉捏可在40℃至100℃的溫度下執行，且可通過在用水等洗滌掉無機鹽後過濾顔料執行過濾及洗滌。Kneading may be performed at a temperature of 40 ° C to 100 ° C, and filtration and washing may be performed by filtering the pigment after washing off the inorganic salt with water or the like.

水溶性無機鹽的實例可爲氯化鈉、氯化鉀等，但並非僅限於此。潤濕劑可使顔料與水溶性無機鹽均勻地混合並粉碎。潤濕劑的實例包括亞烷基二醇單烷基醚（alkylene glycol monoalkyl ether），例如乙二醇單乙醚、丙二醇單甲醚、二乙二醇單甲醚等；以及醇，例如乙醇、異丙醇、丁醇、己醇、環己醇、乙二醇、二乙二醇、聚乙二醇、甘油聚乙二醇等。這些潤濕劑可單獨使用或以兩者或更多者的混合物形式使用。Examples of the water-soluble inorganic salt may be, but are not limited to, sodium chloride, potassium chloride, and the like. The wetting agent can uniformly mix and pulverize the pigment with the water-soluble inorganic salt. Examples of wetting agents include alkylene glycol monoalkyl ethers, such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and the like; and alcohols such as ethanol, isopropyl ether, Propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol polyethylene glycol, and the like. These wetting agents may be used alone or in the form of a mixture of two or more.

揉捏後顔料的平均粒徑可介於5 nm至200 nm之間，例如5 nm至150 nm。當顔料的平均粒徑在所述範圍內時，顔料分散的穩定性可提高，並且可不劣化像素解析度。The average particle size of the pigment after kneading can be between 5 nm and 200 nm, such as 5 nm to 150 nm. When the average particle diameter of the pigment is within the range, the stability of pigment dispersion may be improved, and pixel resolution may not be deteriorated.

具體來說，顔料可以包含分散劑及溶劑（稍後將進行闡述）的顔料分散液的形式使用，且顔料分散液可包含固體顔料、分散劑及溶劑。以顔料分散液的總量計，可以5重量%至20重量%、例如8重量%至15重量%的量包含固體顔料。Specifically, the pigment may be used in the form of a pigment dispersion including a dispersant and a solvent (explained later), and the pigment dispersion may include a solid pigment, a dispersant, and a solvent. The solid pigment may be contained in an amount of 5 to 20% by weight, for example, 8 to 15% by weight based on the total amount of the pigment dispersion liquid.

以所述感光性樹脂組成物的總量計，可以30重量%至50重量%、例如35重量%至45重量%的量包含黑色著色劑。當包含處於所述範圍內的黑色著色劑時，可改善著色效果及顯影性能。The black colorant may be contained in an amount of 30% to 50% by weight, for example, 35% to 45% by weight based on the total amount of the photosensitive resin composition. When the black colorant is included in the range, the coloring effect and developing performance can be improved.

（B）光可聚合單體(B) Photopolymerizable monomer

光可聚合單體可爲包含至少一個烯系不飽和雙鍵的(甲基)丙烯酸的單官能或多官能酯。The photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth) acrylic acid containing at least one ethylenically unsaturated double bond.

所述光可聚合單體可因烯系不飽和雙鍵而在圖案形成過程的曝光期間引起足够的聚合並形成具有優異的耐熱性、耐光性及耐化學性的圖案。The photopolymerizable monomer may cause sufficient polymerization during exposure of the patterning process due to the ethylenically unsaturated double bond and form a pattern having excellent heat resistance, light resistance, and chemical resistance.

光可聚合單體的具體實例可爲乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、雙酚A二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、季異戊四醇六(甲基)丙烯酸酯、二季戊四醇二(甲基)丙烯酸酯、二季戊四醇三(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、雙酚A環氧基(甲基)丙烯酸酯、乙二醇單甲醚(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、磷酸三(甲基)丙烯醯氧基乙酯、酚醛環氧(甲基)丙烯酸酯等。Specific examples of the photopolymerizable monomer may be ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (methyl) ) Acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (Meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaisopentaerythritol hexa (meth) acrylate, dipentaerythritol di (Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, Ethylene glycol monomethyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri (meth) acryloxyethyl phosphate, phenolic epoxy (meth) acrylate, and the like.

所述光可聚合單體的市售實例可如下。單官能(甲基)丙烯酸酯可包括亞羅尼斯（Aronix）M-101®、M-111®、M-114®（東亞合成化工有限公司（Toagosei Chemistry Industry Co., Ltd.））；卡亞拉得（KAYARAD）TC-110S®、TC-120S®（日本化藥有限公司（Nippon Kayaku Co., Ltd.））；V-158®、V-2311®（大阪有機化工有限公司（Osaka Organic Chemical Ind., Ltd.））等。二官能(甲基)丙烯酸酯的實例可包括亞羅尼斯（Aronix）M-210®、M-240®、M-6200®（東亞化工有限公司）、卡亞拉得（KAYARAD）HDDA®、HX-220®、R-604®（日本化藥有限公司）、V-260®、V-312®、V-335 HP®（大阪有機化工有限公司）等。三官能(甲基)丙烯酸酯的實例可包括亞羅尼斯（Aronix）M-309®、M-400®、M-405®、M-450®、M-7100®、M-8030®、M-8060®（東亞化工有限公司）、卡亞拉得（KAYARAD）TMPTA®、DPCA-20®、DPCA-30®、DPCA-60®、DPCA-120®（日本化藥有限公司）、V-295®、V-300®、V-360®、V-GPT®、V-3PA®、V-400®（大阪有機化工有限公司（Osaka Yuki Kayaku Kogyo Co. Ltd.））等。這些光可聚合單體可單獨使用或以兩者或更多者的混合物形式使用。Commercial examples of the photopolymerizable monomer may be as follows. Monofunctional (meth) acrylates may include Aronix M-101®, M-111®, M-114® (Toagosei Chemistry Industry Co., Ltd.); Kaya KAYARAD TC-110S®, TC-120S® (Nippon Kayaku Co., Ltd.); V-158®, V-2311® (Osaka Organic Chemical Co., Ltd.) Ind., Ltd.)) and so on. Examples of difunctional (meth) acrylates may include Aronix M-210®, M-240®, M-6200® (East Asia Chemical Co., Ltd.), KAYARAD HDDA®, HX -220®, R-604® (Nippon Kayaku Co., Ltd.), V-260®, V-312®, V-335 HP® (Osaka Organic Chemical Co., Ltd.), etc. Examples of trifunctional (meth) acrylates may include Aronix M-309®, M-400®, M-405®, M-450®, M-7100®, M-8030®, M- 8060® (East Asia Chemical 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.), etc. These photopolymerizable monomers may be used alone or as a mixture of two or more.

光可聚合單體可用酸酐處理以改善可顯影性。The photopolymerizable monomer may be treated with an acid anhydride to improve developability.

以感光性樹脂組成物的總量計，可以1重量%至15重量%、例如5重量%至10重量%的量包含光可聚合單體。當包含處於所述範圍內的光可聚合單體時，光可聚合單體在圖案形成過程的曝光期間充分固化且具有優異的可靠性，並且可改善鹼性顯影液的可顯影性。The photopolymerizable monomer may be contained in an amount of 1 to 15% by weight, for example, 5 to 10% by weight based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included in the range, the photopolymerizable monomer is sufficiently cured during the exposure of the pattern forming process and has excellent reliability, and the developability of the alkaline developer can be improved.

（C）光聚合引發劑(C) Photopolymerization initiator

光聚合引發劑可爲例如二苯甲酮系化合物（benzophenone-based）、噻噸酮系（thioxanthone-based）化合物、安息香系（benzoin-based）化合物、三嗪系化合物（triazine-based）、肟系（oxime-based）化合物、苯乙酮系（acetophenone-based）化合物等。The photopolymerization initiator may be, for example, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, or an oxime Oxime-based compounds, acetophenone-based compounds, etc.

二苯甲酮系化合物的實例可爲二苯甲酮、苯甲醯基苯甲酸、苯甲醯基苯甲酸甲酯（benzoylbenzoic acidmethyl）、4-苯基二苯甲酮、羥基二苯甲酮、丙烯酸化二苯甲酮、4,4'-雙(二甲基氨基)二苯甲酮、4,4'-雙(二乙基氨基)二苯甲酮、4,4'-二甲基氨基二苯甲酮、4,4'-二氯二苯甲酮、3,3'-二甲基-2-甲氧基二苯甲酮等。Examples of the benzophenone-based compound may be benzophenone, benzophenone benzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, Acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-dimethylamino Benzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.

噻噸酮系化合物的實例可爲噻噸酮、2-甲基噻噸酮、異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮、2-氯噻噸酮等。Examples of the thioxanthone-based compound may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone , 2-chlorothioxanthone and so on.

安息香系化合物的實例可爲安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚、苯甲基二甲基縮酮（benzyldimethylketal）等。Examples of the benzoin-based compound may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethylketal, and the like.

三嗪系化合物的實例可爲2,4,6-三氯-s-三嗪、2-苯基-4,6-雙(三氯甲基)-s-三嗪、2-(3',4'-二甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三嗪、2-(4'-甲氧基萘基)-4,6-雙(三氯甲基)-s-三嗪、2-(對甲氧基苯基)-4,6-雙(三氯甲基)-s-三嗪、2-(對甲苯基)-4,6-雙(三氯甲基)-s-三嗪、2-聯苯基-4,6-雙(三氯甲基)-s-三嗪、雙(三氯甲基)-6-苯乙烯基-s-三嗪、2-(萘酚-基)-4,6-雙(三氯甲基)-s-三嗪、2-(4-甲氧基萘酚-基)-4,6-雙(三氯甲基)-s-三嗪、2-4-雙(三氯甲基)-6-胡椒基-s-三嗪、2-4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-s-三嗪、2-[4-(4-乙基苯基)-苯基]-4,6-雙(三氯甲基)-1,3,5-三嗪等。Examples of the triazine-based compound may be 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloro (Methyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (Trichloromethyl) -s-triazine, 2-biphenyl-4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s -Triazine, 2- (naphthol-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol-yl) -4,6-bis ( (Trichloromethyl) -s-triazine, 2-4-bis (trichloromethyl) -6-piperidyl-s-triazine, 2-4-bis (trichloromethyl) -6- (4- Methoxystyryl) -s-triazine, 2- [4- (4-ethylphenyl) -phenyl] -4,6-bis (trichloromethyl) -1,3,5-tris Hydrazine, etc.

所述肟系化合物的實例可爲O-醯基肟系化合物、2-(O-苯甲醯基肟)-1-[4-(苯硫基)苯基]-1,2-辛二酮、1-(O-乙醯基肟)-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-哢唑-3-基]乙酮、O-乙氧基羰基-α-氧氨基-1-苯基丙-1-酮等。O-醯基肟系化合物的具體實例可爲1,2-辛二酮、2-二甲基氨基-2-(4-甲基苯甲基)-1-(4-嗎啉-4-基-苯基)-丁-1-酮、1-(4-苯硫基苯基)-丁-1,2-二酮-2-肟-O-苯甲酸酯、1-(4-苯硫基苯基)-辛-1,2-二酮-2-肟-O-苯甲酸酯、1-(4-苯硫基苯基)-辛-1-酮肟-O-乙酸酯、1-(4-苯硫基苯基)-丁-1-酮肟-O-乙酸酯等。Examples of the oxime-based compound may be an O-fluorenyl oxime-based compound, 2- (O-benzylidene oxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione , 1- (O-ethylamidoxime) -1- [9-ethyl-6- (2-methylbenzyl) -9H-oxazol-3-yl] ethanone, O-ethoxy Carbonyl-α-oxoamino-1-phenylpropan-1-one and the like. Specific examples of the O-fluorenyl oxime-based compound may be 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl -Phenyl) -butan-1-one, 1- (4-phenylthiophenyl) -butan-1,2-dione-2-oxime-O-benzoate, 1- (4-phenylthio Phenyl) -octyl-1,2-dione-2-oxime-O-benzoate, 1- (4-phenylthiophenyl) -oct-1-oneoxime-O-acetate, 1- (4-phenylthiophenyl) -butan-1-oneoxime-O-acetate and the like.

苯乙酮系化合物的實例可爲2,2'-二乙氧基苯乙酮、2,2'-二丁氧基苯乙酮、2-羥基-2-甲基苯丙酮、對叔丁基三氯苯乙酮、對叔丁基二氯苯乙酮、4-氯苯乙酮、2,2'-二氯-4-苯氧基苯乙酮、2-甲基-1-(4-(甲硫基)苯基)-2-嗎啉並丙-1-酮、2-苯甲基-2-二甲基氨基-1-(4-嗎啉並苯基)-丁-1-酮等。Examples of the acetophenone-based compound may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylacetophenone, p-tert-butyl Trichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (Methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -but-1-one Wait.

除包含所述化合物之外，所述光聚合引發劑可進一步包含哢唑系化合物、二酮系化合物、硼酸鋶系化合物、重氮系化合物、咪唑系化合物、聯咪唑系化合物、芴系化合物等。In addition to including the compound, the photopolymerization initiator may further include an oxazole-based compound, a dione-based compound, a boron fluorene-based compound, a diazonium-based compound, an imidazole-based compound, a biimidazole-based compound, a fluorene-based compound, and the like .

所述光聚合引發劑可與能够通過吸收光且被激發並隨後傳輸其能量而引起化學反應的光敏劑一起使用。The photopolymerization initiator may be used with a photosensitizer capable of causing a chemical reaction by absorbing light and being excited and then transmitting its energy.

所述光敏劑的實例可爲四乙二醇雙-3-巰基丙酸酯、季戊四醇四-3-巰基丙酸酯、二季戊四醇四-3-巰基丙酸酯等。Examples of the photosensitizer may be tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, dipentaerythritol tetra-3-mercaptopropionate, and the like.

以感光性樹脂組成物的總量計，可包含0.1重量%至5重量%、例如0.1重量%至3重量%的量的光聚合引發劑。當包含處於所述範圍內的光聚合引發劑時，可由於在圖案形成過程的曝光期間充分固化而確保優異的可靠性，圖案可具有優異的解析度和緊密接觸性質以及優異的耐熱性、耐光性和耐化學性，且可由於非反應引發劑而防止透射率劣化。The photopolymerization initiator may be contained in an amount of 0.1 to 5% by weight, for example, 0.1 to 3% by weight based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included in the range, excellent reliability can be ensured due to sufficient curing during the exposure of the pattern forming process, the pattern can have excellent resolution and close contact properties, and excellent heat resistance and light resistance. And chemical resistance, and can prevent deterioration of transmittance due to non-reactive initiators.

（E）溶劑(E) Solvent

溶劑是一種與黑色著色劑、光聚合引發劑、光可聚合單體及黏合劑樹脂具有相容性但不與其反應的材料。A solvent is a material that is compatible with, but does not react with, a black colorant, a photopolymerization initiator, a photopolymerizable monomer, and a binder resin.

所述溶劑的實例可包括醇，例如甲醇、乙醇等；醚，例如二氯乙醚、正丁醚、二異戊醚、苯甲醚、四氫呋喃等；二醇醚，例如乙二醇單甲醚、乙二醇單乙醚、乙二醇二甲醚（ethylene glycoldimethylether，EDM）等；乙酸溶纖劑，例如乙酸甲基溶纖劑、乙酸乙基溶纖劑、乙酸二乙基溶纖劑等；卡必醇（carbitol），例如甲基乙基卡必醇、二乙基卡必醇、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇二甲醚、二乙二醇甲乙醚、二乙二醇二乙醚等；丙二醇烷基醚乙酸酯，例如丙二醇甲醚乙酸酯、丙二醇丙醚乙酸酯等；芳香族烴，例如甲苯、二甲苯等；酮，例如甲乙酮、環己酮、4-羥基-4-甲基-2-戊酮、甲基-正丙基酮、甲基-正丁基酮、甲基-正戊基酮、2-庚酮等；飽和脂肪族單羧酸烷基酯，例如乙酸乙酯、乙酸正丁酯、乙酸異丁酯等；乳酸酯，例如乳酸甲酯、乳酸乙酯等；氧基乙酸烷基酯，例如氧基乙酸甲酯、氧基乙酸乙酯、氧基乙酸丁酯等；烷氧基乙酸烷基酯，例如甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯等；3-氧基丙酸烷基酯，例如3-氧基丙酸甲酯、3-氧基丙酸乙酯等；3-烷氧基丙酸烷基酯，例如3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲酯等；2-氧基丙酸烷基酯，例如2-氧基丙酸甲酯、2-氧基丙酸乙酯、2-氧基丙酸丙酯等；2-烷氧基丙酸烷基酯，例如2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸甲酯等；2-氧基-2-甲基丙酸酯，例如2-氧基-2-甲基丙酸甲酯、2-氧基-2-甲基丙酸乙酯等；2-烷氧基-2-甲基丙酸烷基酯的單氧基單羧酸烷基酯，例如2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯等；酯，例如2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯等；酮酸酯，例如丙酮酸乙酯等。此外，也可使用高沸點溶劑，例如N-甲基甲醯胺、N,N-二甲基甲醯胺、N-甲基甲醯苯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基吡咯烷酮、二甲基亞碸、苯甲基乙基醚、二己基醚、乙醯丙酮、異佛爾酮、己酸、辛酸、1-辛醇、1-壬醇、苯甲基醇、乙酸苯甲酯、苯甲酸乙酯、草酸二乙酯、馬來酸二乙酯、γ-丁內酯、碳酸乙烯酯、碳酸丙烯酯、乙酸苯基溶纖劑等。Examples of the solvent may include alcohols such as methanol, ethanol, and the like; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, anisole, tetrahydrofuran, and the like; glycol ethers such as ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol dimethyl ether (EDM), etc .; acetic acid cellosolve, such as methyl acetate cellosolve, ethyl acetate cellosolve, diethyl cellosolve, etc .; card Carbitol, such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ester Diethyl ether, diethylene glycol diethyl ether, etc .; propylene glycol alkyl ether acetates, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc .; aromatic hydrocarbons, such as toluene, xylene, etc .; ketones, such as methyl ethyl ketone, Cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-pentyl ketone, 2-heptanone, etc .; saturated fat Alkyl monocarboxylic acid esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc .; lactates, such as methyl lactate, ethyl lactate, etc. ; Alkyl oxyacetate, such as methyl oxyacetate, ethyl ethoxylate, butyl acetate, etc .; alkyl alkoxyacetate, such as methyl methoxyacetate, ethyl methoxyacetate , Butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .; alkyl 3-oxypropionate, such as methyl 3-oxypropionate, ethyl 3-oxypropionate Esters, etc .; alkyl 3-alkoxypropionates, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxy Methyl propionate, etc .; alkyl 2-oxypropionate, such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc .; 2-alkoxy Alkyl propionate, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc .; 2- Oxy-2-methylpropionate, such as methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, etc .; 2-alkoxy-2-methyl Monooxy monocarboxylic acid alkyl esters of alkyl propionate, such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc .; esters , Such as 2-hydroxypropionic acid Ester, 2-hydroxy-ethyl, hydroxy-ethyl, 2-hydroxy-3-methylbutanoate; a ketone esters such as ethyl pyruvate. In addition, high boiling point solvents such as N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-diamine Methylacetamide, N-methylpyrrolidone, dimethylsulfenyl, benzylethyl ether, dihexyl ether, acetamone, isophorone, hexanoic acid, caprylic acid, 1-octanol, 1- Nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, vinyl carbonate, propylene carbonate, phenyl acetate cellosolve Wait.

考慮到混溶性及反應性，可優選地使用酮，例如環己酮等；二醇醚，例如乙二醇單乙醚、乙二醇二甲醚、乙二醇二乙醚等；乙二醇烷基醚乙酸酯，例如乙酸乙基溶纖劑等；酯，例如2-羥基丙酸乙酯等；卡必醇，例如二乙二醇單甲醚等；丙二醇烷基醚乙酸酯，例如丙二醇甲醚乙酸酯、丙二醇丙醚乙酸酯等。Considering miscibility and reactivity, ketones such as cyclohexanone and the like can be preferably used; glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, etc .; ethylene glycol alkyl Ether acetate, such as ethyl acetate cellosolve, etc .; esters, such as ethyl 2-hydroxypropionate, etc .; carbitol, such as diethylene glycol monomethyl ether, etc .; propylene glycol alkyl ether acetate, such as propylene glycol Methyl ether acetate, propylene glycol propyl ether acetate, and the like.

以所述感光性樹脂組成物的總量計，所述溶劑是以餘量使用，例如爲30重量%至70重量%。當包含處於所述範圍內的溶劑時，所述感光性樹脂組成物可具有適當的黏度，從而改善黑色柱狀間隔物的塗佈特性。The solvent is used in the balance based on the total amount of the photosensitive resin composition, for example, 30 to 70% by weight. When a solvent in the range is included, the photosensitive resin composition may have an appropriate viscosity, thereby improving the coating characteristics of the black columnar spacer.

（F）其他添加劑(F) Other additives

所述感光性樹脂組成物可進一步包含以下添加劑：丙二酸；3-氨基-1,2-丙二醇；矽烷系偶合劑；流平劑；氟系表面活性劑；自由基聚合引發劑；或其組合。The photosensitive resin composition may further include the following additives: malonic acid; 3-amino-1,2-propanediol; a silane-based coupling agent; a leveling agent; a fluorine-based surfactant; a radical polymerization initiator; or combination.

矽烷系偶合劑可具有以下反應性取代基：乙烯基、羧基、甲基丙烯醯氧基、異氰酸酯基（isocyanate group）、環氧基等，以改善與基底的緊密接觸性質。The silane-based coupling agent may have the following reactive substituents: a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, an epoxy group, etc. to improve the close contact property with the substrate.

矽烷系偶合劑的實例可包括三甲氧基甲矽烷基苯甲酸（trimethoxysilylbenzoic acid）、γ-甲基丙烯醯氧基丙基三甲氧基矽烷（γ-methacryloxypropyltrimethoxysilane）、乙烯基三乙醯氧基矽烷（vinyltriacetoxysilane）、乙烯基三甲氧基矽烷（vinyltrimethoxysilane）、γ-異氰酸酯丙基三乙氧基矽烷（γ-isocyanatepropyltriethoxysilane）、γ-縮水甘油氧基丙基三甲氧基矽烷（γ-glycidoxypropyltrimethoxysilane）、β-(3,4-環氧環己基)乙基三甲氧基矽烷（β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane）等。這些矽烷系偶合劑可單獨使用或以兩者或更多者的混合物形式使用。Examples of the silane-based coupling agent may include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and vinyltriethoxysilane ( vinyltriacetoxysilane), vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane (β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane) and the like. These silane-based coupling agents may be used alone or as a mixture of two or more.

以100重量份的所述感光性樹脂組成物計，可以0.01重量份至10重量份的量包含所述矽烷系偶合劑。當包含處於所述範圍內的矽烷系偶合劑時，可改善緊密接觸性質、存儲性質等。The silane-based coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When a silane-based coupling agent is included in the range, close contact properties, storage properties, and the like can be improved.

感光性樹脂組成物可進一步包含表面活性劑，例如氟系表面活性劑，以在需要時改善塗佈性質並預防缺陷。The photosensitive resin composition may further include a surfactant, such as a fluorine-based surfactant, to improve coating properties and prevent defects when necessary.

氟系表面活性劑的實例可爲市售的氟系表面活性劑，例如 BM-1000®和BM-1100®（BM化學有限公司（BM Chemie Inc.））；MEGAFACE F 142D®、F 172®、F 173®、F 183®和F 554® （大日本油墨化學工業股份有限公司（Dainippon Ink Kagaku Kogyo Co., Ltd.））；弗洛拉德（FULORAD）FC-135®、FULORAD FC-170C®、FULORAD FC-430®和FULORAD FC-431®（住友（Sumitomo）3M股份有限公司）；沙福隆（SURFLON）S-112®、SURFLON S-113®、SURFLON S-131®、SURFLON S-141®和SURFLON S-145®（旭硝子玻璃（Asahi Glass）股份有限公司）；以及SH-28PA®、SH-190®、SH-193®、SZ-6032®和SF-8428®等（東麗矽膠（Toray Silicone）股份有限公司）。Examples of the fluorine-based surfactant may be commercially available fluorine-based surfactants, such as BM-1000® and BM-1100® (BM Chemie Inc.); MEGAFACE F 142D®, F 172®, F 173®, F 183® and F 554® (Dainippon Ink Kagaku Kogyo Co., Ltd.); FULORAD FC-135®, FULORAD FC-170C® , FULORAD FC-430® and FULORAD FC-431® (Sumitomo 3M Co., Ltd.); SURFLON S-112®, SURFLON S-113®, SURFLON S-131®, SURFLON S-141 ® and SURFLON S-145® (Asahi Glass Co., Ltd.); and SH-28PA®, SH-190®, SH-193®, SZ-6032®, and SF-8428® (Toray Silicone ( Toray Silicone), Inc.).

以100重量份的感光性樹脂組成物計，可以0.001重量份至5重量份的量使用氟系表面活性劑。當包含處於所述範圍內的表面活性劑時，可確保在氧化銦鋅（Indium Zinc Oxide，IZO）基底或玻璃基底上具有優異的潤濕性以及塗佈均勻度，可不産生污點（stain）。The fluorine-based surfactant may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included in the range, it can ensure excellent wettability and coating uniformity on an Indium Zinc Oxide (IZO) substrate or a glass substrate, and a stain may not be generated.

此外，感光性樹脂組成物可包含預定量的其他添加劑，例如抗氧化劑、穩定劑等，除非這些添加劑使感光性樹脂組成物的性質劣化。In addition, the photosensitive resin composition may include other additives in a predetermined amount, such as an antioxidant, a stabilizer, and the like, unless these additives degrade the properties of the photosensitive resin composition.

另一實施例提供一種黑色感光性樹脂層，所述黑色感光性樹脂層通過將感光性樹脂組成物曝光、顯影及固化而製造。Another embodiment provides a black photosensitive resin layer, which is manufactured by exposing, developing, and curing a photosensitive resin composition.

所述黑色感光性樹脂層可爲黑色柱狀間隔物。The black photosensitive resin layer may be a black columnar spacer.

黑色柱狀間隔物可包含主柱狀間隔物及次柱狀間隔物，其中所述黑色柱狀間隔物可在主柱狀間隔物與次柱狀間隔物之間（在0℃至10℃下達0天至10天）具有小於或等於1000 Å、例如處於0 Å至1000 Å範圍內的階差。The black columnar spacer may include a primary columnar spacer and a secondary columnar spacer, wherein the black columnar spacer may be between the primary columnar spacer and the secondary columnar spacer (at 0 ° C to 10 ° C). 0 days to 10 days) with a step less than or equal to 1000 Å, for example in the range of 0 Å to 1000 Å.

黑色柱狀間隔物還充當黑色矩陣且因此可在大於或等於1 μm的厚度下具有0.8的光學密度。The black columnar spacer also functions as a black matrix and thus may have an optical density of 0.8 at a thickness of 1 μm or more.

製造黑色感光性樹脂層的方法如下。The method for producing a black photosensitive resin layer is as follows.

（1）塗佈及膜形成(1) Coating and film formation

在經過預定預處理的基底（例如玻璃基底或氧化銦鋅基底）上，使用旋轉或狹縫塗佈法、輥塗法、網版印刷法、敷料器法等，將感光性樹脂組成物塗佈至具有所期望的厚度，在70℃至100℃下加熱1分鐘至10分鐘以移除溶劑，從而形成層。The photosensitive resin composition is coated on a predetermined pretreated substrate (for example, a glass substrate or an indium zinc oxide substrate) by a spin or slit coating method, a roll coating method, a screen printing method, an applicator method, or the like. To have a desired thickness, heating is performed at 70 ° C. to 100 ° C. for 1 to 10 minutes to remove the solvent, thereby forming a layer.

（2）曝光(2) Exposure

通過以下步驟將所述層圖案化：設置由用於實現黑色矩陣圖案及次柱狀間隔物圖案的半色調部分及用於實現主柱狀間隔物圖案的全色調組成的遮罩，且然後照射介於200 nm至500 nm範圍的光化射綫（actinic ray）。所述照射是使用例如具有低壓、高壓或超高壓的汞燈、金屬鹵化物燈、氬氣雷射等光源來執行。也可使用X射綫、電子束等。The layer is patterned by setting a mask consisting of a halftone portion for realizing a black matrix pattern and a sub-column spacer pattern and a full tone for realizing a main columnar spacer pattern, and then irradiating Actinic ray in the 200 nm to 500 nm range. The irradiation is performed using a light source such as a mercury lamp, a metal halide lamp, an argon laser, or the like having a low pressure, a high pressure, or an ultra high pressure. X-rays, electron beams, and the like can also be used.

光劑量可依據每一組分的種類、其組合比及幹膜厚度而不同，但當使用高壓汞燈時，光劑量可爲500 mJ/cm2或小於500 mJ/cm2（使用365 nm傳感器）。The light dose may vary depending on the type of each component, its combination ratio and dry film thickness, but when using a high-pressure mercury lamp, the light dose may be 500 mJ / cm2 or less (using a 365 nm sensor).

（3）顯影(3) Development

在曝光製程後，使用鹼性水溶液通過溶解並移除除被曝光部分以外的不需要的部分來將被曝光膜顯影以形成圖案，且同時對斷點（BP）進行測量。After the exposure process, the exposed film is developed to form a pattern by dissolving and removing unnecessary portions other than the exposed portion using an alkaline aqueous solution, and at the same time measuring the break point (BP).

（4）後處理(4) Post-processing

可對經顯影圖像圖案進行後處理，以在耐熱性、耐光性、緊密接觸性質、抗裂性、耐化學性、高强度、存儲穩定性等方面實現優異的品質。舉例來說，在顯影之後，可在250℃的對流烘箱中將圖案加熱1小時。The developed image pattern can be post-processed to achieve excellent quality in terms of heat resistance, light resistance, close contact properties, crack resistance, chemical resistance, high strength, storage stability, and the like. For example, after development, the pattern may be heated in a convection oven at 250 ° C. for 1 hour.

另一實施例提供一種包括所述黑色感光性樹脂層的彩色濾光片。Another embodiment provides a color filter including the black photosensitive resin layer.

以下，參考實例更詳細地說明本發明。然而，這些實例不應在任何意義上被解釋爲限制本發明的範圍。Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples should not be interpreted in any sense as limiting the scope of the invention.

（實例）(Example)

（感光性樹脂組成物的製備）(Preparation of photosensitive resin composition)

實例Examples 11 至實例To example 88 以及比較例And comparative examples 11 及比較例And comparative examples 22

通過將具有表1及表2所示組成的以下組分進行混合而製備了根據實例1至實例8以及比較例1及比較例2的感光性樹脂組成物。The photosensitive resin compositions according to Examples 1 to 8 and Comparative Examples 1 and 2 were prepared by mixing the following components having the compositions shown in Tables 1 and 2.

具體來說，精確地測量光聚合引發劑的量並添加在溶劑中，且對所述混合物進行了攪拌直到光聚合引發劑完全溶解（30分鐘或大於30分鐘）。向其中依序添加了黏合劑樹脂及光可聚合單體，且接著將所述混合物攪拌了約1小時。隨後，添加了黑色著色劑（顔料分散液）且添加了其他添加劑，並且接著將所得組成物攪拌了約2小時以製備感光性樹脂組成物。Specifically, the amount of the photopolymerization initiator was accurately measured and added to the solvent, and the mixture was stirred until the photopolymerization initiator was completely dissolved (30 minutes or more). A binder resin and a photopolymerizable monomer were sequentially added thereto, and then the mixture was stirred for about 1 hour. Subsequently, a black colorant (pigment dispersion liquid) was added and other additives were added, and then the resulting composition was stirred for about 2 hours to prepare a photosensitive resin composition.

用於感光性樹脂組成物中的每一組分如下。 （A）黏合劑樹脂 （A-1）卡多系黏合劑樹脂（V259ME，日本鋼鐵化學有限公司（Nippon Steel Chemical.Co., Ltd.）） （A-2）含環氧基的丙烯酸系黏合劑樹脂（RY20-2，昭和電工有限公司（Showa Denco K. K.）） （B）光可聚合單體 二季戊四醇六(甲基)丙烯酸酯（dipentaerythritol hexa(meth)acrylate，DPHA，沙多瑪公司（Sartomer）） （C）光聚合引發劑 OXE02，巴斯夫公司（BASF Corporation） （D）黑色著色劑 （D-1）包含比色指數（color index，C.I.）紅色顔料179的漆漿分散液（阪田公司（SAKATA）） （D-2）包含C.I.藍色顔料15:6的漆漿分散液（阪田公司） （D-3）包含C.I.紫色顔料29的漆漿分散液（阪田公司） （D-4）碳黑漆漿（BK-6925）分散液（阪田公司） （D-5）包含C.I.紅色顔料254的漆漿分散液（阪田公司） （D-6）包含有機黑色顔料的漆漿分散液（巴斯夫公司） （E）溶劑 （E-1）丙二醇單甲醚乙酸酯（propylene glycol monomethylether acetate，PGMEA，西格瑪-奧德裏奇有限公司（Sigma-Aldrich Co. LLC.）） （E-2）乙二醇二甲醚（EDM，西格瑪-奧德裏奇有限公司） （F）其他添加劑 γ-縮水甘油氧基丙基三甲氧基矽烷（S-510，智索公司（Chisso Corporation））Each component used in the photosensitive resin composition is as follows. (A) Adhesive resin (A-1) Cardo-based adhesive resin (V259ME, Nippon Steel Chemical. Co., Ltd.) (A-2) Epoxy-based acrylic adhesive Resin (RY20-2, Showa Denco KK) (B) Photopolymerizable monomer dipentaerythritol hexa (meth) acrylate, DPHA, Sartomer )) (C) Photopolymerization initiator OXE02, BASF Corporation (D) Black colorant (D-1) A paint slurry dispersion containing a color index (CI) red pigment 179 (Sakata Corporation ( SAKATA)) (D-2) Paint slurry dispersion containing CI blue pigment 15: 6 (Sakata Corporation) (D-3) Paint slurry dispersion containing CI purple pigment 29 (Sakata Corporation) (D-4) Carbon Black paint paste (BK-6925) dispersion (Sakata Corporation) (D-5) paint paste dispersion containing CI red pigment 254 (Sakata Corporation) (D-6) paint paste dispersion containing organic black pigment (BASF) ) (E) Solvent (E-1) Propylene glycol monomethyl ether Ester (propylene glycol monomethylether acetate, PGMEA, Sigma-Aldrich Co. LLC.) (E-2) ethylene glycol dimethyl ether (EDM, Sigma-Aldrich Co., Ltd.) ( F) Other additives γ-glycidoxypropyltrimethoxysilane (S-510, Chisso Corporation)

[表1] （單位：g） [Table 1] (Unit: g)

[表2] （單位：g） [Table 2] (Unit: g)

（評估）(Evaluation)

錐度及存儲穩定性Taper and storage stability

對根據實例1至實例8以及比較例1及比較例2的每一感光性樹脂組成物進行塗佈、曝光、顯影及後烘烤以獲得圖案化樣本，利用非接觸型厚度計（3-D廓綫儀；奈米圖（nanoview），奈米系統有限公司（NanoSystem Co., Ltd.））對樣本的黑色柱狀間隔物圖案進行了測量且在10天后再次進行了測量，並且結果示於表3及圖2中。Each photosensitive resin composition according to Examples 1 to 8 and Comparative Examples 1 and 2 was coated, exposed, developed, and post-baked to obtain a patterned sample, and a non-contact thickness gauge (3-D Profiler; nanoview, NanoSystem Co., Ltd.) measured the black columnar spacer pattern of the sample and measured it again after 10 days, and the results are shown in Table 3 and Figure 2.

另外，利用掃描電子顯微鏡對樣本的錐度角進行了測量，且結果示於表3及圖4至圖13中。In addition, the taper angle of the sample was measured with a scanning electron microscope, and the results are shown in Table 3 and FIGS. 4 to 13.

[表3] [table 3]

參考表3，根據實施例的感光性樹脂組成物可提供具有優異的存儲穩定性以及適當的錐度角的黑色感光性樹脂層（例如，黑色柱狀間隔物）。當以較高的比率包含卡多系黏合劑樹脂時，斷點變短，但當以較高的比率包含含環氧基的丙烯酸黏合劑樹脂時，斷點變長，且在本文中，當斷點變得太短或太長時，難以實現階差。換句話說，可對卡多系黏合劑樹脂與含環氧基的丙烯酸系黏合劑樹脂之間的比率進行適當限制，以使得根據實施例的感光性樹脂組成物可具有適當的斷點以實現階差。Referring to Table 3, the photosensitive resin composition according to the example can provide a black photosensitive resin layer (for example, a black columnar spacer) having excellent storage stability and an appropriate taper angle. When a Cardo-based adhesive resin is included at a higher ratio, the break point becomes shorter, but when an epoxy-group-containing acrylic adhesive resin is included at a higher ratio, the break point becomes longer, and in this paper, when When the breakpoint becomes too short or too long, it is difficult to achieve a step. In other words, the ratio between the Cardo-based adhesive resin and the epoxy-containing acrylic adhesive resin may be appropriately limited so that the photosensitive resin composition according to the embodiment may have an appropriate break point to achieve Step difference.

光學密度及耐Optical density and resistance N-N- 甲基吡咯烷（Methylpyrrolidine NMPNMP ）溶解性) Solubility

對根據實例1至實例8以及比較例1及比較例2的每一感光性樹脂組成物進行塗佈、曝光、顯影及後烘烤以獲得圖案化樣本，利用光學密度計（愛色麗（X-rite）361T）對樣本的黑色柱狀間隔物圖案測量了兩次且求平均，並且結果示於表5中。Each photosensitive resin composition according to Examples 1 to 8 and Comparative Examples 1 and 2 was coated, exposed, developed, and post-baked to obtain a patterned sample, and an optical density meter (X-Rite (X -rite) 361T) The black columnar spacer pattern of the sample was measured twice and averaged, and the results are shown in Table 5.

另外，將樣本切割成1.5 cm×3.0 cm的大小，且在瓶中浸入10 g N-甲基吡咯烷中。將瓶維持在100℃下達60分鐘，且接著僅收集N-甲基吡咯烷。利用0.2 μm注射器過濾器（syringe filter）對所收集的N-甲基吡咯烷（洗出液）進行了過濾並放入瓶中以進行高效液相色譜分析（High Performance Liquid Chromatography，HPLC），並接著對高效液相色譜分析進行了測量，且其結果示於表5中。In addition, the sample was cut into a size of 1.5 cm × 3.0 cm, and immersed in 10 g of N-methylpyrrolidine in a bottle. The bottle was maintained at 100 ° C for 60 minutes, and then only N-methylpyrrolidine was collected. The collected N-methylpyrrolidine (eluate) was filtered using a 0.2 μm syringe filter and placed in a bottle for high performance liquid chromatography (HPLC) analysis, and The high-performance liquid chromatography analysis was then performed, and the results are shown in Table 5.

高效液相色譜分析測量條件在表4中進行了闡述。The measurement conditions for HPLC analysis are described in Table 4.

[表4] [Table 4]

[表5] [table 5]

參考表5，根據實施例的感光性樹脂組成物可提供具有優異的耐N-甲基吡咯烷溶解性以及大於或等於0.8的光學密度的黑色感光性樹脂層（例如，黑色柱狀間隔物）。Referring to Table 5, the photosensitive resin composition according to the example can provide a black photosensitive resin layer (for example, a black columnar spacer) having excellent resistance to N-methylpyrrolidine solubility and an optical density of 0.8 or more. .

儘管已結合目前被認爲是實用的示例性實施例對本發明進行了闡述，但應理解，本發明幷非僅限于所公開的實施例，而是相反，本發明旨在涵蓋包含在隨附申請專利範圍的精神及範圍內的各種修改形式及等效配置。因此，上述實施例應理解爲示例性的，而非以任何方式限制本發明。Although the invention has been described in connection with exemplary embodiments that are presently considered to be practical, it should be understood that the invention is not limited to the disclosed embodiments, but rather, the invention is intended to cover The spirit of the patent scope and various modifications and equivalent configurations within the scope. Therefore, the above-mentioned embodiments are to be construed as exemplary and not limiting the present invention in any way.

無no

圖1說明黑色柱狀間隔物的主柱狀間隔物及次柱狀間隔物以及其階差。MG階差表示主柱狀間隔物和閘極黑色矩陣的階差。MS階差表示主柱狀間隔物和次柱狀間隔物的階差。 圖2是使用根據比較例1的感光性樹脂組成物製造的包括主柱狀間隔物及次柱狀間隔物的黑色柱狀間隔物的照片。 圖3是曲綫圖，其示出利用三維（3D）測量設備在使用根據實例1的感光性樹脂組成物製造的黑色柱狀間隔物的主柱狀間隔物與次柱狀間隔物之間測量的階差。 圖4是用於測量使用根據實例1的感光性樹脂組成物製造的黑色柱狀間隔物的錐度的掃描電子顯微鏡照片。 圖5是用於測量使用根據實例2的感光性樹脂組成物製造的黑色柱狀間隔物的錐度的掃描電子顯微鏡照片。 圖6是用於測量使用根據實例3的感光性樹脂組成物製造的黑色柱狀間隔物的錐度的掃描電子顯微鏡照片。 圖7是用於測量使用根據實例4的感光性樹脂組成物製造的黑色柱狀間隔物的錐度的掃描電子顯微鏡照片。 圖8是用於測量使用根據實例5的感光性樹脂組成物製造的黑色柱狀間隔物的錐度的掃描電子顯微鏡照片。 圖9是用於測量使用根據實例6的感光性樹脂組成物製造的黑色柱狀間隔物的錐度的掃描電子顯微鏡照片。 圖10是用於測量使用根據實例7的感光性樹脂組成物製造的黑色柱狀間隔物的錐度的掃描電子顯微鏡照片。 圖11是用於測量使用根據實例8的感光性樹脂組成物製造的黑色柱狀間隔物的錐度的掃描電子顯微鏡照片。 圖12是用於測量使用根據比較例1的感光性樹脂組成物製造的黑色柱狀間隔物的錐度的掃描電子顯微鏡照片。 圖13是用於測量使用根據比較例2的感光性樹脂組成物製造的黑色柱狀間隔物的錐度的掃描電子顯微鏡照片。FIG. 1 illustrates a main columnar spacer and a secondary columnar spacer of a black columnar spacer, and their steps. The MG step indicates the step between the main columnar spacer and the gate black matrix. The MS step indicates the step difference between the primary columnar spacer and the secondary columnar spacer. FIG. 2 is a photograph of a black columnar spacer including a primary columnar spacer and a secondary columnar spacer manufactured using the photosensitive resin composition according to Comparative Example 1. FIG. FIG. 3 is a graph showing a measurement using a three-dimensional (3D) measuring device between a main columnar spacer and a secondary columnar spacer of a black columnar spacer manufactured using the photosensitive resin composition according to Example 1. FIG. Step difference. FIG. 4 is a scanning electron microscope photograph for measuring a taper of a black columnar spacer manufactured using the photosensitive resin composition according to Example 1. FIG. FIG. 5 is a scanning electron microscope photograph for measuring a taper of a black columnar spacer manufactured using the photosensitive resin composition according to Example 2. FIG. FIG. 6 is a scanning electron microscope photograph for measuring a taper of a black columnar spacer manufactured using the photosensitive resin composition according to Example 3. FIG. FIG. 7 is a scanning electron microscope photograph for measuring a taper of a black columnar spacer manufactured using the photosensitive resin composition according to Example 4. FIG. FIG. 8 is a scanning electron microscope photograph for measuring a taper of a black columnar spacer manufactured using the photosensitive resin composition according to Example 5. FIG. FIG. 9 is a scanning electron microscope photograph for measuring a taper of a black columnar spacer manufactured using the photosensitive resin composition according to Example 6. FIG. FIG. 10 is a scanning electron microscope photograph for measuring a taper of a black columnar spacer manufactured using the photosensitive resin composition according to Example 7. FIG. FIG. 11 is a scanning electron microscope photograph for measuring a taper of a black columnar spacer manufactured using the photosensitive resin composition according to Example 8. FIG. FIG. 12 is a scanning electron microscope photograph for measuring a taper of a black columnar spacer manufactured using the photosensitive resin composition according to Comparative Example 1. FIG. 13 is a scanning electron microscope photograph for measuring a taper of a black columnar spacer manufactured using the photosensitive resin composition according to Comparative Example 2. FIG.

Claims (18)

一種感光性樹脂組成物，包括： （A）黏合劑樹脂，以5:5至9:1的重量比包含卡多系樹脂及含環氧基的丙烯酸系樹脂； （B）光可聚合單體； （C）光聚合引發劑； （D）黑色著色劑；以及 （E）溶劑。A photosensitive resin composition comprising: (A) a binder resin comprising a cardo-based resin and an epoxy-based acrylic resin in a weight ratio of 5: 5 to 9: 1; (B) a photopolymerizable monomer (C) a photopolymerization initiator; (D) a black colorant; and (E) a solvent. 如申請專利範圍第1項所述的感光性樹脂組成物，其中所述黏合劑樹脂以6:4至8:2的重量比包含所述卡多系樹脂及所述含環氧基的丙烯酸系樹脂。The photosensitive resin composition according to item 1 of the scope of patent application, wherein the binder resin comprises the cardo-based resin and the epoxy-containing acrylic resin in a weight ratio of 6: 4 to 8: 2. Resin. 如申請專利範圍第1項所述的感光性樹脂組成物，其中所述黑色著色劑包含紅色顔料、藍色顔料及紫色顔料。The photosensitive resin composition according to item 1 of the patent application scope, wherein the black colorant includes a red pigment, a blue pigment, and a purple pigment. 如申請專利範圍第3項所述的感光性樹脂組成物，其中所述紅色顔料包含由化學式1表示的化合物： [化學式1]其中，在化學式1中， R1與R2獨立地爲經取代或未經取代的C1至C10烷基。The photosensitive resin composition according to item 3 of the scope of patent application, wherein the red pigment contains a compound represented by Chemical Formula 1: [Chemical Formula 1] Wherein, in Chemical Formula 1, R1 and R2 are independently a substituted or unsubstituted C1 to C10 alkyl group. 如申請專利範圍第3項所述的感光性樹脂組成物，其中以所述黑色著色劑的總量計，所述黑色著色劑分別以40重量%至60重量%、30重量%至50重量%以及10重量%至20重量%的量包含紅色顔料、藍色顔料及紫色顔料。The photosensitive resin composition according to item 3 of the scope of application for a patent, wherein the black colorant is 40% to 60% by weight and 30% to 50% by weight based on the total amount of the black colorant. And the amount of 10 to 20% by weight contains a red pigment, a blue pigment, and a purple pigment. 如申請專利範圍第3項所述的感光性樹脂組成物，其中所述黑色著色劑更包含無機黑色顔料。The photosensitive resin composition according to item 3 of the scope of patent application, wherein the black colorant further includes an inorganic black pigment. 如申請專利範圍第6項所述的感光性樹脂組成物，其中所述無機黑色顔料包括碳黑。The photosensitive resin composition according to item 6 of the scope of patent application, wherein the inorganic black pigment includes carbon black. 如申請專利範圍第6項所述的感光性樹脂組成物，其中以所述黑色著色劑的總量計，以3重量%至8重量%的量包含所述無機黑色顔料。The photosensitive resin composition according to item 6 of the patent application scope, wherein the inorganic black pigment is contained in an amount of 3 to 8% by weight based on the total amount of the black colorant. 如申請專利範圍第3項所述的感光性樹脂組成物，其中所述藍色顔料包含酞菁系化合物。The photosensitive resin composition as described in claim 3, wherein the blue pigment contains a phthalocyanine compound. 如申請專利範圍第3項所述的感光性樹脂組成物，其中所述紫色顔料包含苝系化合物。The photosensitive resin composition according to item 3 of the scope of patent application, wherein the purple pigment contains a fluorene-based compound. 如申請專利範圍第1項所述的感光性樹脂組成物，其中以所述感光性樹脂組成物的總量計，所述感光性樹脂組成物包含： 1重量%至10重量%的（A）所述黏合劑樹脂； 1重量%至10重量%的（B）所述光可聚合單體； 0.1重量%至5重量%的（C）所述光聚合引發劑； 30重量%至50重量%的（D）所述黑色著色劑；以及 餘量爲（E）所述溶劑。The photosensitive resin composition according to item 1 of the scope of the patent application, wherein the photosensitive resin composition comprises: 1% to 10% by weight (A) based on the total amount of the photosensitive resin composition The binder resin; 1 to 10% by weight (B) of the photopolymerizable monomer; 0.1 to 5% by weight of (C) the photopolymerization initiator; 30 to 50% by weight (D) the black colorant; and the balance is the solvent (E). 如申請專利範圍第1項所述的感光性樹脂組成物，其中所述感光性樹脂組成物更包含以下添加劑：丙二酸、3-氨基-1,2-丙二醇、矽烷系偶合劑、流平劑、氟系表面活性劑、自由基聚合引發劑或其組合。The photosensitive resin composition according to item 1 of the scope of the patent application, wherein the photosensitive resin composition further includes the following additives: malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, and leveling Agent, fluorine-based surfactant, radical polymerization initiator, or a combination thereof. 一種黑色感光性樹脂層，使用如申請專利範圍第1項至第12項中任一項所述的感光性樹脂組成物製造。A black photosensitive resin layer is manufactured using the photosensitive resin composition according to any one of claims 1 to 12 of the scope of patent application. 如申請專利範圍第13項所述的黑色感光性樹脂層，其中所述黑色感光性樹脂層是黑色柱狀間隔物。The black photosensitive resin layer according to item 13 of the patent application scope, wherein the black photosensitive resin layer is a black columnar spacer. 如申請專利範圍第14項所述的黑色感光性樹脂層，其中所述黑色柱狀間隔物包括主柱狀間隔物及次柱狀間隔物。The black photosensitive resin layer according to item 14 of the scope of patent application, wherein the black columnar spacers include a main columnar spacer and a sub-column spacer. 如申請專利範圍第15項所述的黑色感光性樹脂層，其中所述黑色柱狀間隔物在所述主柱狀間隔物與所述次柱狀間隔物之間具有小於或等於1000 Å的階差。The black photosensitive resin layer according to item 15 of the scope of patent application, wherein the black columnar spacer has a step less than or equal to 1000 Å between the primary columnar spacer and the secondary columnar spacer. difference. 如申請專利範圍第14項所述的黑色感光性樹脂層，其中所述黑色柱狀間隔物在1 μm的厚度處具有大於或等於0.8的光學密度。The black photosensitive resin layer according to item 14 of the scope of patent application, wherein the black columnar spacer has an optical density of 0.8 or more at a thickness of 1 μm. 一種彩色濾光片，包括如申請專利範圍第13項所述的黑色感光性樹脂層。A color filter includes the black photosensitive resin layer according to item 13 of the patent application scope.
TW106134109A 2016-10-28 2017-10-03 Photosensitive resin composition, black photosensitive resin layer, and color filter TWI679251B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR1020160142171A KR102080235B1 (en) 2016-10-28 2016-10-28 Photosensitive resin composition, black photosensitive resin layer using the same and color filter
KR10-2016-0142171 2016-10-28
??10-2016-0142171 2016-10-28

Publications (2)

Publication Number Publication Date
TW201815984A true TW201815984A (en) 2018-05-01
TWI679251B TWI679251B (en) 2019-12-11

Family

ID=62050857

Family Applications (1)

Application Number Title Priority Date Filing Date
TW106134109A TWI679251B (en) 2016-10-28 2017-10-03 Photosensitive resin composition, black photosensitive resin layer, and color filter

Country Status (3)

Country Link
KR (1) KR102080235B1 (en)
CN (1) CN108003593B (en)
TW (1) TWI679251B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102349083B1 (en) * 2018-07-27 2022-01-07 코오롱인더스트리 주식회사 Photosensitive Resin Composition
KR102432808B1 (en) * 2018-08-31 2022-08-16 동우 화인켐 주식회사 A white resin composition, a back light unit prepared using the same, and a display devide comprising the same

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101148548B1 (en) * 2008-09-30 2012-05-21 코오롱인더스트리 주식회사 Photopolymerizable resin composition
JP5306952B2 (en) * 2009-09-29 2013-10-02 太陽ホールディングス株式会社 Photosensitive resin composition and cured product thereof, and printed wiring board
KR20110054887A (en) * 2009-11-18 2011-05-25 코오롱인더스트리 주식회사 Photopolymerizable resin composition
KR101288564B1 (en) * 2009-12-17 2013-07-22 제일모직주식회사 Resin composition for color filter, and color filter produced by using same
KR101333713B1 (en) * 2010-12-21 2013-11-28 제일모직주식회사 Black photosensitive resin composition, and black matrix and column spacer using the same
KR101910674B1 (en) * 2013-06-25 2018-10-22 동우 화인켐 주식회사 A black photosensitive resin composition, color filter and display device comprising the same
KR20150134191A (en) * 2014-05-21 2015-12-01 제일모직주식회사 Photosensitive resin compositionand color filter using the same
KR101825545B1 (en) * 2014-09-25 2018-02-05 삼성에스디아이 주식회사 Photosensitive resin composition and color filter using the same
JP7131907B2 (en) * 2015-03-11 2022-09-06 三菱ケミカル株式会社 Photosensitive coloring composition, cured product, colored spacer, image display device
KR101804259B1 (en) * 2015-03-24 2017-12-04 삼성에스디아이 주식회사 Photosensitive resin composition, black column spacerusing the same and color filter

Also Published As

Publication number Publication date
TWI679251B (en) 2019-12-11
KR20180046688A (en) 2018-05-09
CN108003593A (en) 2018-05-08
KR102080235B1 (en) 2020-02-21
CN108003593B (en) 2020-08-18

Similar Documents

Publication Publication Date Title
JP6527319B2 (en) Method of manufacturing black column spacer, and black column spacer and color filter
KR101804259B1 (en) Photosensitive resin composition, black column spacerusing the same and color filter
TWI657100B (en) Photosensitive resin composition, black pixel defining layer using the same and display device
TWI655260B (en) Photosensitive resin composition, photosensitive resin layer and color filter using the same
TWI592747B (en) Black photosensitive resin composition and light blocking layer using the same
TWI679251B (en) Photosensitive resin composition, black photosensitive resin layer, and color filter
KR101812579B1 (en) Photosensitive double resin layer, black column spacer using the same, and color filter
TWI655504B (en) Photosensitive resin composition, black pixel defining layer using the same, and display device
KR102243364B1 (en) Photosensitive resin composition, photosensitive resin layer using the same, color filter and display device
TW201619671A (en) Liquid crystal display
TWI615678B (en) Photosensitive resin composition, black column spacer using the same, and color filter
KR20160063836A (en) Photosensitive resin layer, black column spacer using the same and color filter
JP7461491B2 (en) Photosensitive resin composition, photosensitive resin film manufactured using the same, and display device
KR102682916B1 (en) Photosensitive resin composition, photosensitive resin layer using the same and display device
KR102586092B1 (en) Photosensitive resin composition, photosensitive resin layer using the same and display device
KR102216426B1 (en) Photosensitive resin composition, photosensitive resin layer using the same, color filter and display device
TWI629565B (en) Photosensitive resin composition, photosensitive resin layer using the same and black column spacer
KR102036683B1 (en) Photosensitive resin composition, black photosensitive resin layer using the same and color filter
KR20160140227A (en) Photosensitive double resin layer, black column spacer using the same, and color filter
KR101776264B1 (en) Photosensitive resin composition layer, black column spacer using the same, and color filter
KR101724607B1 (en) Method of manufacturing black column spacer, black column spacer, and color filter
TW202305064A (en) Pigment dispersion, photosensitive resin composition comprising the same, photosensitive resin layer, color filter, and display device
KR20150075998A (en) Photosensitive resin composition and light blocking layer using the same
KR20160066353A (en) Photosensitive resin layer, black column spacerusing the sameand color filter
KR20160068387A (en) Photosensitive resin layer, black column spacerusing the sameand color filter