TW201727363A - Colored photosensitive resin composition for red pixel, color filter made using thereof and display device having the same capable of achieving high color reproduction and excellent contrast - Google Patents

Colored photosensitive resin composition for red pixel, color filter made using thereof and display device having the same capable of achieving high color reproduction and excellent contrast Download PDF

Info

Publication number
TW201727363A
TW201727363A TW105131319A TW105131319A TW201727363A TW 201727363 A TW201727363 A TW 201727363A TW 105131319 A TW105131319 A TW 105131319A TW 105131319 A TW105131319 A TW 105131319A TW 201727363 A TW201727363 A TW 201727363A
Authority
TW
Taiwan
Prior art keywords
weight
resin composition
red
photosensitive resin
dye
Prior art date
Application number
TW105131319A
Other languages
Chinese (zh)
Other versions
TWI612382B (en
Inventor
金奉奎
安大熙
池仁愛
Original Assignee
東友精細化工有限公司
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 東友精細化工有限公司 filed Critical 東友精細化工有限公司
Publication of TW201727363A publication Critical patent/TW201727363A/en
Application granted granted Critical
Publication of TWI612382B publication Critical patent/TWI612382B/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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)

Abstract

The present invention relates to a colored photosensitive resin composition for red pixel which includes a red coloring agent, an alkali soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent for achieving high color reproduction and excellent contrast, a color filter made using the composition and a display device having the color filter.

Description

紅色感光性樹脂組合物、使用其製造的濾色器和具有該濾色器的顯示裝置 Red photosensitive resin composition, color filter manufactured using the same, and display device having the same

發明領域 Field of invention

本發明涉及紅色感光性樹脂組合物，更詳細地說，涉及包含紅色著色劑、鹼可溶性樹脂、光聚合性化合物、光聚合引發劑和溶劑的紅色感光性樹脂組合物。 The present invention relates to a red photosensitive resin composition, and more particularly to a red photosensitive resin composition containing a red colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

發明背景 Background of the invention

濾色器廣泛用於攝像元件、液晶顯示元件等，其應用範圍在急速擴大。在彩色液晶顯示元件、攝像元件等中使用的濾色器通常通過以下製造：在形成了黑色矩陣圖案的基板上採用旋塗而均勻地塗布含有相當於紅色、綠色和青色的各色著色劑的著色感光性樹脂組合物後，加熱乾燥(以下有時也稱為“預燒成”)，對形成的塗膜進行曝光、顯影，根據需要進一步加熱固化(以下有時也稱為“後燒成”)，對每種顏色反複進行該操作，形成各色的像素。近年來，用 於液晶顯示器(LCD)的濾色器要求高色再現，由於背光的改變，也要求色座標改變。因此，要求色再現性良好、在背光改變的情況下色座標也可容易地改變的著色感光性樹脂組合物。 Color filters are widely used in imaging elements, liquid crystal display elements, etc., and their application range is rapidly expanding. A color filter used in a color liquid crystal display element, an image pickup element, or the like is generally manufactured by uniformly applying a coloring agent containing coloring agents corresponding to red, green, and cyan colors by spin coating on a substrate on which a black matrix pattern is formed. After the photosensitive resin composition is heated and dried (hereinafter sometimes referred to as "pre-baking"), the formed coating film is exposed and developed, and further heated and cured as necessary (hereinafter sometimes referred to as "post-firing"). ), this operation is repeated for each color to form pixels of respective colors. In recent years, Color filters for liquid crystal displays (LCDs) require high color reproduction, and color coordinates are also required to change due to backlight changes. Therefore, a colored photosensitive resin composition which is excellent in color reproducibility and can be easily changed in color coordinates in the case where the backlight is changed is required.

在彩色液晶顯示器中，色再現範圍為XYZ表色系中將紅、綠、青的各色度座標連接起來的三角形所表示的範圍，用相對於NTSC(National Television System Committee)標準的面積比表示。CRT的色再現範圍用NTSC標準比表示，為約70%。色再現性比EBU(European Broadcasting Union)標準寬，作為良好的標準，有上述的NTSC標準，紅、綠、青各色在XYZ表色系中的色度座標(x,y)分別為紅(0.670,0.330)、綠(0.210,0.710)、青(0.140,0.080)。ITU-R BT.2020播放標準的色度座標(x,y)分別為紅(0.708,0.292)、綠(0.170,0.797)、青(0.131,0.046)，DCI(Digital Cinema Initiatives)中的色度座標(x,y)分別為紅(0.680,0.320)、綠(0.265,0.690)、青(0.150,0.060)，Adobe中的色度座標(x,y)分別為紅(0.640,0.330)、綠(0.210,0.710)、青(0.150,0.060)。 In the color liquid crystal display, the color reproduction range is a range indicated by a triangle connecting the respective chromaticity coordinates of red, green, and cyan in the XYZ color system, and is expressed by an area ratio with respect to the NTSC (National Television System Committee) standard. The color reproduction range of the CRT is expressed by the NTSC standard ratio and is about 70%. The color reproducibility is wider than the EBU (European Broadcasting Union) standard. As a good standard, there are the NTSC standards mentioned above. The chromaticity coordinates (x, y) of the red, green, and cyan colors in the XYZ color system are respectively red (0.670). , 0.330), green (0.210, 0.710), cyan (0.140, 0.080). The chromaticity coordinates (x, y) of the ITU-R BT.2020 playback standard are red (0.708, 0.292), green (0.170, 0.797), cyan (0.131, 0.046), and chroma in DCI (Digital Cinema Initiatives). The coordinates (x, y) are red (0.680, 0.320), green (0.265, 0.690), cyan (0.150, 0.060), and the chromaticity coordinates (x, y) in Adobe are red (0.640, 0.330), green, respectively. (0.210, 0.710), cyan (0.150, 0.060).

近年來，液晶顯示器用濾色器要求高色再現，由此，濾色器的製造中使用的著色感光性樹脂組合物的著色劑的含量在持續提高。另外，為了製作可視性優異的高品質濾色器，不斷要求改善對比度。 In recent years, color filters for liquid crystal displays require high color reproduction, and thus the content of the coloring agent of the colored photosensitive resin composition used in the production of the color filter continues to increase. In addition, in order to produce a high-quality color filter with excellent visibility, it is required to improve the contrast.

但是，對於以往的顏料分散系，著色感光 性樹脂組合物中的顏料的含量已達到其極限，顏料的微粒化產生的對比度的改善也達到了極限。 However, for the conventional pigment dispersion system, coloring sensitivity The content of the pigment in the resin composition has reached its limit, and the improvement in contrast produced by the micronization of the pigment has reached its limit.

因此，目前在研究同時使用顏料和染料作為著色劑的方法，但如果使用包含染料作為著色劑的著色感光性樹脂組合物製造濾色器，則感度不足，有時發生在採用鹼性顯影液進行顯影工序時致使顯影的圖案剝離的問題。另外，如果用上述包含染料的著色感光性樹脂組合物製造濾色器，在後烘焙工序中染料的相容性不足，有時染料在表面析出，使對比度減小，因此很難使用足夠量的染料。 Therefore, at present, a method of simultaneously using a pigment and a dye as a colorant has been studied, but if a color filter is produced using a colored photosensitive resin composition containing a dye as a colorant, sensitivity is insufficient, and sometimes occurs with an alkaline developer. The problem of peeling off the developed pattern during the development process. Further, when the color filter is produced by using the dye-containing colored photosensitive resin composition described above, the compatibility of the dye in the post-baking step is insufficient, and the dye is sometimes precipitated on the surface to reduce the contrast, so that it is difficult to use a sufficient amount. dye.

發明概要 Summary of invention

本發明的目的在於提供顯示高色再現和高對比度的紅色感光性樹脂組合物。 An object of the present invention is to provide a red photosensitive resin composition which exhibits high color reproduction and high contrast.

另外，本發明的目的在於提供不存在染料引起的感度降低、能夠解決顯影工序中致使圖案剝離的問題的紅色感光性樹脂組合物。 Further, an object of the present invention is to provide a red photosensitive resin composition capable of solving the problem of causing peeling of a pattern in a developing process without a decrease in sensitivity by a dye.

進而，本發明的目的在於提供使用上述紅色感光性樹脂組合物製造的濾色器和包含上述濾色器的顯示裝置。 Further, an object of the present invention is to provide a color filter manufactured using the above-described red photosensitive resin composition and a display device including the above-described color filter.

為了實現上述的目的，本發明提供紅色感光性樹脂組合物，其為包含紅色著色劑、鹼可溶性樹脂、 光聚合性化合物、光聚合引發劑和溶劑的紅色感光性樹脂組合物，其特徵在於，上述紅色著色劑包含顏料和染料，上述顏料包含溴化二酮基吡咯并吡咯，上述染料包含選自下述化學式1的占噸(xanthene)系染料和偶氮系染料中的1種以上，上述光聚合引發劑包含肟酯系化合物。 In order to achieve the above object, the present invention provides a red photosensitive resin composition comprising a red colorant, an alkali soluble resin, A red photosensitive resin composition of a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the red colorant comprises a pigment and a dye, and the pigment comprises a brominated diketopyrrolopyrrole, and the dye comprises a dye selected from the group consisting of In one or more of the xanthene dyes and the azo dyes of Chemical Formula 1, the photopolymerization initiator contains an oxime ester compound.

上述R1~R6各自獨立地為氫、碳數1~5的烷基、或碳數1~5的三烷氧基甲矽烷基烷基，上述R7和R8各自獨立地為氫、COOH、COO-、SO3 -、COONa、SO3H、SO3Na、COOCH3、或COOCH2CH3。 Each of R 1 to R 6 is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a trialkoxycarbinylalkyl group having 1 to 5 carbon atoms, and each of R 7 and R 8 is independently hydrogen. COOH, COO - , SO 3 - , COONa, SO 3 H, SO 3 Na, COOCH 3 , or COOCH 2 CH 3 .

另外，本發明提供用上述紅色感光性樹脂組合物製造的紅色濾色器。 Further, the present invention provides a red color filter produced by the above red photosensitive resin composition.

進而，本發明提供包含上述紅色濾色器的顯示裝置。 Further, the present invention provides a display device including the above-described red color filter.

本發明的紅色感光性樹脂組合物產生能夠實現高色再現和高對比度的效果。 The red photosensitive resin composition of the present invention produces an effect of achieving high color reproduction and high contrast.

另外，本發明的紅色感光性樹脂組合物產 生不存在染料引起的感度降低、在顯影工序時不發生圖案剝離這樣的效果。 Further, the red photosensitive resin composition of the present invention is produced There is no effect that the sensitivity caused by the dye is lowered and the pattern peeling does not occur during the development process.

進而，使用本發明的紅色感光性樹脂組合物製造的濾色器能夠顯示高品質。 Further, the color filter manufactured using the red photosensitive resin composition of the present invention can exhibit high quality.

較佳實施例之詳細說明 Detailed description of the preferred embodiment

以下對本發明更詳細地說明。 The invention is explained in more detail below.

本發明涉及紅色感光性樹脂組合物，其為包含紅色著色劑、鹼可溶性樹脂、光聚合性化合物、光聚合引發劑和溶劑的紅色感光性樹脂組合物，其特徵在於，上述紅色著色劑包含顏料和染料，上述顏料包含溴化二酮基吡咯并吡咯，上述染料包含選自下述化學式1的占噸系染料和偶氮系染料中的1種以上，上述光聚合引發劑包含肟酯系化合物。 The present invention relates to a red photosensitive resin composition which is a red photosensitive resin composition containing a red coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the red coloring agent contains a pigment And the dye, the dye contains a brominated diketopyrrolopyrrole, and the dye contains one or more selected from the group consisting of a tonic dye and an azo dye of the following Chemical Formula 1, and the photopolymerization initiator contains an oxime ester compound. .

上述R1~R6各自獨立地為氫、碳數1~5的烷基、或碳數1~5的三烷氧基甲矽烷基烷基，上述R7和R8各自獨立地為氫、COOH、COO-、SO3 -、SO3H、COONa、SO3Na、 COOCH3、或COOCH2CH3。 Each of R 1 to R 6 is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a trialkoxycarbinylalkyl group having 1 to 5 carbon atoms, and each of R 7 and R 8 is independently hydrogen. COOH, COO - , SO 3 - , SO 3 H, COONa, SO 3 Na, COOCH 3 , or COOCH 2 CH 3 .

以下對本發明的紅色感光性樹脂組合物的各成分予以詳細說明。 Hereinafter, each component of the red photosensitive resin composition of the present invention will be described in detail.

(A)紅色著色劑 (A) red colorant

本發明的紅色著色劑包含顏料和染料，上述顏料包含溴化二酮基吡咯并吡咯，上述染料包含選自下述化學式1的占噸系染料和偶氮系染料中的1種以上。 The red coloring agent of the present invention contains a pigment and a dye, and the pigment contains a brominated diketopyrrolopyrrole, and the dye contains one or more selected from the group consisting of a tonic dye and an azo dye of the following Chemical Formula 1.

上述R1~R6各自獨立地為氫、碳數1~5的烷基、或碳數1~5的三烷氧基甲矽烷基烷基，上述R7和R8各自獨立地為氫、COOH、COO-、SO3 -、SO3H、COONa、SO3Na、COOCH3、或COOCH2CH3。 Each of R 1 to R 6 is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a trialkoxycarbinylalkyl group having 1 to 5 carbon atoms, and each of R 7 and R 8 is independently hydrogen. COOH, COO - , SO 3 - , SO 3 H, COONa, SO 3 Na, COOCH 3 , or COOCH 2 CH 3 .

如果上述R7或R8為上述陰離子，則與上述化學式1的N+形成分子內鹽(inner salt)，在不為陰離子的情況下，可與無機或有機陰離子結合。 When R 7 or R 8 is the above anion, an inner salt of N + of the above Chemical Formula 1 can be bonded to an inorganic or organic anion without being an anion.

另外，相對於本發明的紅色感光性樹脂組合物中的固體成分總重量，含有5~60重量%的上述紅色著色劑，優選含有10~45重量%的上述紅色著色劑。 In addition, the red coloring agent is contained in an amount of 5 to 60% by weight, preferably 10 to 45% by weight, based on the total weight of the solid content of the red photosensitive resin composition of the present invention.

上述紅色著色劑為上述5~60重量%的範圍而形成薄膜時，具有如下的優點：像素的色濃度充分，顯影時非像素部的脫落性不會降低，不會產生殘渣。 When the red coloring agent is formed in a range of 5 to 60% by weight to form a film, the color density of the pixel is sufficient, and the non-pixel portion peeling property during development is not lowered, and no residue is generated.

本發明中，紅色感光性樹脂組合物中的固體成分意味著將溶劑除去了的成分的合計。 In the present invention, the solid content in the red photosensitive resin composition means the total of the components from which the solvent is removed.

(a1)顏料 (a1) pigment

作為本發明的紅色著色劑使用的顏料包含溴化二酮基吡咯并吡咯作為必要成分。 The pigment used as the red coloring agent of the present invention contains brominated diketopyrrolopyrrole as an essential component.

作為上述溴化二酮基吡咯并吡咯的製品，優選使用BASF公司的IrgaphorRed S3620CF。 As a product of the above brominated diketopyrrolopyrrole, it is preferred to use Irgaphor of BASF Corporation. Red S3620CF.

相對於紅色著色劑的總重量，包含5~95重量%的上述溴化二酮基吡咯并吡咯，優選包含30~80重量%的上述溴化二酮基吡咯并吡咯。 The above-mentioned brominated diketopyrrolopyrrole is contained in an amount of 5 to 95% by weight based on the total weight of the red colorant, preferably 30 to 80% by weight of the above-mentioned brominated diketopyrrolopyrrole.

如果包含不到5重量%的上述溴化二酮基吡咯并吡咯，則對比度的上升不充分，如果包含超過95重量%的上述溴化二酮基吡咯并吡咯，則透射率的上升不充分，不能顯示出高色再現。 If less than 5% by weight of the above-mentioned brominated diketopyrrolopyrrole is contained, the increase in contrast is insufficient, and if more than 95% by weight of the above-mentioned brominated diketopyrrolopyrrole is contained, the increase in transmittance is insufficient. High color reproduction cannot be displayed.

另外，上述顏料除了溴化二酮基吡咯并吡咯以外，可以追加地包含顏料。 Further, the above pigment may additionally contain a pigment in addition to the brominated diketopyrrolopyrrole.

上述顏料能夠使用該領域中一般使用的有機顏料或無機顏料。另外，對於上述顏料，根據需要可實施樹脂處理、使用導入了酸性基團或鹼性基團的顏料衍生物等的表面處理、採用高分子化合物等的顏料表面的接枝處理、採用硫酸微粒化法等的微粒化處理、用於將雜質除 去的採用有機溶劑、水等的清洗處理、或採用離子交換法等的離子性雜質的除去處理等。 The above pigments can use organic pigments or inorganic pigments generally used in the field. In addition, the pigment may be subjected to a resin treatment, a surface treatment using a pigment derivative or a basic group-introduced pigment derivative, a graft treatment using a polymer compound or the like, or a sulfuric acid micronization. Micronization treatment, etc., for removing impurities The cleaning treatment using an organic solvent, water, or the like, or the removal treatment of ionic impurities by an ion exchange method or the like is used.

上述有機顏料能夠使用在印刷油墨、噴墨油墨等中使用的各種的顏料，具體地，可列舉出水溶性偶氮顏料、不溶性偶氮顏料、酞菁顏料、喹吖啶酮顏料、異吲哚啉酮顏料、異吲哚啉顏料、苝顏料、苝酮顏料、二噁嗪顏料、蒽醌顏料、聯二蒽醌顏料、蒽嘧啶顏料、蒽酮顏料、陰丹酮顏料、黃蒽酮顏料、皮蒽酮顏料、二酮基吡咯并吡咯顏料等。 As the organic pigment, various pigments used in printing inks, inkjet inks, and the like can be used, and specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, and isoporphyrins. Ketone pigments, isoporphyrin pigments, anthraquinone pigments, anthrone pigments, dioxazine pigments, anthraquinone pigments, diterpene pigments, pyrimidine pigments, anthrone pigments, indanthrone pigments, xanthone pigments, skins Anthrone pigment, diketopyrrolopyrrole pigment, and the like.

另外，作為上述無機顏料，可列舉出金屬氧化物、金屬絡鹽等金屬化合物，具體地，可列舉鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、鋅、銻、炭黑、有機黑色顏料、鈦黑、和將紅色、綠色和青色混合而呈黑色的顏料等金屬的氧化物或複合金屬氧化物等。 Further, examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specific examples thereof include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, bismuth, and carbon black. An organic black pigment, titanium black, or a metal oxide such as a pigment mixed with red, green, and cyan and black, or a composite metal oxide.

特別地，作為上述有機顏料和無機顏料，具體地，可列舉出色指數(The society of Dyers and Colourists出版)中分類為顏料的化合物，更具體地，可列舉以下的色指數(C.I.)序號的顏料，但未必限定於此。 In particular, as the above-mentioned organic pigment and inorganic pigment, specifically, a compound classified as a pigment in the excellent index (published by The Society of Dyers and Colourists) can be cited, and more specifically, the following pigment of color index (CI) number can be cited. , but not necessarily limited to this.

可列舉出：C.I.顏料红9、97、105、122、123、144、149、166、168、176、177、180、192、209、215、216、224、242、254、255、264和265；C.I.顏料黃13、20、24、31、53、83、86、93、94、109、110、117、125、137、138、139、147、148、150、 153、154、166、173、180和185；C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65和71；C.I.顏料紫14、19、23、29、32、33、36、37和38等。 Can be cited: CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264 and 265 CI Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37, and 38, etc.

上述顏料可以與溴化二酮基吡咯并吡咯一起單獨使用或者將2種以上混合使用。 These pigments may be used alone or in combination of two or more kinds thereof with the brominated diketopyrrolopyrrole.

上述顏料優選使用顏料的粒徑均勻分散的顏料分散液。作為用於使顏料的粒徑均勻分散的方法的例子，可列舉出含有顏料分散劑(a2)而進行分散處理的方法等，採用上述方法，可以得到顏料在溶液中均勻分散的狀態的顏料分散液。 As the above pigment, a pigment dispersion liquid in which the particle diameter of the pigment is uniformly dispersed is preferably used. Examples of the method for uniformly dispersing the particle diameter of the pigment include a method in which a pigment dispersant (a2) is contained and a dispersion treatment is carried out, and by the above method, pigment dispersion in a state in which the pigment is uniformly dispersed in a solution can be obtained. liquid.

(a2)顏料分散劑 (a2) pigment dispersant

為了維持顏料的脫凝聚和穩定性而添加上述顏料分散劑，作為顏料分散劑的具體例，可列舉出陽離子系、陰離子系、非離子系、兩性系、聚酯系、多胺系等的界面活性劑等，這些可以各自單獨使用或者將2種以上組合使用。 In order to maintain the deagglomeration and stability of the pigment, the pigment dispersant is added. Specific examples of the pigment dispersant include an interface of a cationic system, an anionic system, a nonionic system, an amphoteric system, a polyester system, and a polyamine system. These may be used alone or in combination of two or more kinds of the active agent or the like.

作為上述陽離子系界面活性劑的具體例，可列舉出硬脂胺鹽酸鹽和月桂基三甲基氯化銨等胺鹽或季銨鹽等。 Specific examples of the cationic surfactant include an amine salt such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or a quaternary ammonium salt.

作為上述陰離子系界面活性劑的具體例，可列舉出月桂醇硫酸酯鈉和油醇硫酸酯鈉等高級醇硫酸酯鹽類、十二烷基硫酸鈉和十二烷基硫酸銨等烷基硫酸鹽 類、十二烷基苯磺酸鈉和十二烷基萘磺酸鈉等烷基芳基磺酸鹽類等。 Specific examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleyl sulfate, and alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate. salt An alkylarylsulfonate such as sodium dodecylbenzenesulfonate or sodium dodecylnaphthalenesulfonate.

作為上述非離子系界面活性劑的具體例，可列舉出聚氧乙烯烷基醚、聚氧乙烯芳基醚、聚氧乙烯烷基芳基醚、其他聚氧乙烯衍生物、環氧乙烷/環氧丙烷嵌段共聚物、山梨糖醇酐脂肪酸酯、聚氧乙烯山梨糖醇酐脂肪酸酯、聚氧乙烯山梨醇脂肪酸酯、甘油脂肪酸酯、聚氧乙烯脂肪酸酯、和聚氧乙烯烷基胺等。 Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, and ethylene oxide/ Propylene oxide block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and poly Oxyethylene alkylamine and the like.

此外，可列舉出聚氧乙烯烷基醚類、聚氧乙烯烷基苯基醚類、聚乙二醇二酯類、山梨糖醇酐脂肪酸酯類、脂肪酸改性聚酯類、叔胺改性聚胺基甲酸酯類、和聚乙烯亞胺類等。 Further, examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, and tertiary amine modifications. Polyurethanes, and polyethyleneimines.

另外，上述顏料分散劑優選含有包含甲基丙烯酸丁酯(BMA)或甲基丙烯酸N,N-二甲基胺基乙酯(DMAEMA)的丙烯酸酯系分散劑(以下稱為丙烯酸酯系分散劑)。作為上述丙烯酸酯系分散劑的市售品，可列舉出DISPER BYK-2000、DISPER BYK-2001、DISPER BYK-2070、或DISPER BYK-2150等，上述丙烯酸酯系分散劑可以各自單獨使用或者將2種以上混合使用。 Further, the pigment dispersant preferably contains an acrylate-based dispersant comprising butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA) (hereinafter referred to as an acrylate-based dispersant) ). The commercially available product of the acrylate-based dispersant may, for example, be DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150, and the above acrylate-based dispersant may be used alone or in combination. More than one kind of mixture is used.

上述顏料分散劑除了丙烯酸酯系分散劑以外，也可使用其他樹脂型的顏料分散劑。作為上述其他樹脂型的顏料分散劑，可列舉出公知的樹脂型的顏料分散劑，特別是聚胺基甲酸酯、聚丙烯酸酯為代表的聚羧酸酯、不飽和聚醯胺、聚羧酸、聚羧酸的(部分的)胺鹽、聚羧酸 的銨鹽、聚羧酸的烷基胺鹽、聚矽氧烷、長鏈聚胺基醯胺磷酸鹽、含羥基的聚羧酸的酯以及它們的改性生成物、或者通過具有游離(free)的羧基的聚酯與聚(低級烯化亞胺)的反應形成的醯胺或它們的鹽這樣的油質的分散劑；(甲基)丙烯酸-苯乙烯共聚物、(甲基)丙烯酸-(甲基)丙烯酸酯共聚物、苯乙烯-馬來酸共聚物、聚乙烯醇、或聚乙烯基吡咯烷酮這樣的水溶性樹脂或水溶性聚合物化合物；聚酯；改性聚丙烯酸酯；環氧乙烷/環氧丙烷的加成生成物；和磷酸酯等。 In addition to the acrylate-based dispersant, other pigment-type pigment dispersants may be used as the pigment dispersant. Examples of the other resin type pigment dispersant include a known resin type pigment dispersant, in particular, a polycarboxylate represented by a polyurethane or a polyacrylate, an unsaturated polyamine, or a polycarboxylate. Acid (poly)carboxylic acid (partial) amine salt, polycarboxylic acid Ammonium salt, alkylamine salt of polycarboxylic acid, polyoxyalkylene oxide, long chain polyamine guanamine phosphate, ester of hydroxyl group-containing polycarboxylic acid, and modified products thereof, or by having free (free An oily dispersant such as a guanamine or a salt thereof formed by reacting a carboxyl group of a polyester with a poly(lower alkyleneimine); (meth)acrylic acid-styrene copolymer, (meth)acrylic acid- Water-soluble resin or water-soluble polymer compound such as (meth) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, or polyvinylpyrrolidone; polyester; modified polyacrylate; epoxy An addition product of ethane/propylene oxide; and a phosphate ester or the like.

作為上述其他樹脂型的顏料分散劑的市售品，作為陽離子系樹脂分散劑，例如可列舉出BYK( )公司的商品名：DISPER BYK-160、DISPER BYK-161、DISPER BYK-162、DISPER BYK-163、DISPER BYK-164、DISPER BYK-166、DISPER BYK-171、DISPER BYK-182、DISPER BYK-184；BASF公司的商品名：EFKA-44、EFKA-46、EFKA-47、EFKA-48、EFKA-4010、EFKA-4050、EFKA-4055、EFKA-4020、EFKA-4015、EFKA-4060、EFKA-4300、EFKA-4330、EFKA-4400、EFKA-4406、EFKA-4510、EFKA-4800；Lubirzol公司的商品名：SOLSPERS-24000、SOLSPERS-32550、NBZ-4204/10；川研公司的商品名：(HINOACT)T-6000、T-7000、T-8000；味之素公司的商品名： (AJISPUR)PB-821、PB-822、PB-823；共榮社化學社的商品名：(FLORENE)DOPA-17HF、DOPA-15BHF、DOPA-33、DOPA-44等。 As a commercial item of the above-mentioned other resin type pigment dispersing agent, as a cationic resin dispersing agent, BYK ( ) The company's trade name: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF's trade names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Lubirzol's trade name: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Company's product name: (HINOACT) T-6000, T-7000, T-8000; Ajinomoto's trade name: (AJISPUR) PB-821, PB-822, PB-823; Trade name of Gongrongshe Chemical Society: (FLORENE) DOPA-17HF, DOPA-15BHF, DOPA-33, DOPA-44 and so on.

除了上述丙烯酸酯系分散劑以外，其他樹脂型的顏料分散劑可以各自單獨使用或者將2種以上混合使用，可以與丙烯酸酯系分散劑並用來進行使用。 In addition to the above acrylate-based dispersant, the other resin-type pigment dispersants may be used singly or in combination of two or more kinds, and may be used together with an acrylate-based dispersant.

上述顏料分散劑，相對於顏料中的固體成分總重量，含有5~60重量%，優選含有15~50重量%。如果含有不到5重量%的上述顏料分散劑，有時顏料的微粒化困難，分散後發生凝膠化等問題，如果含有超過60重量%，則黏度可升高。 The pigment dispersant is contained in an amount of 5 to 60% by weight, preferably 15 to 50% by weight based on the total weight of the solid content in the pigment. When the pigment dispersant is contained in an amount of less than 5% by weight, the pigment may be difficult to be microparticulated, and gelation may occur after dispersion. If the content exceeds 60% by weight, the viscosity may increase.

(a3)染料 (a3) dye

作為本發明的紅色著色劑使用的染料包含選自下述化學式1的占噸系染料和偶氮系染料中的1種以上。 The dye used as the red coloring agent of the present invention contains at least one selected from the group consisting of a tonic dye and an azo dye of the following Chemical Formula 1.

上述R1~R6各自獨立地為氫、碳數1~5的烷基、或碳 數1~5的三烷氧基甲矽烷基烷基，上述R7和R8各自獨立地為氫、COOH、COO-、SO3 -、SO3H、COONa、SO3Na、COOCH3、或COOCH2CH3。 Each of R 1 to R 6 is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a trialkoxycarbinylalkyl group having 1 to 5 carbon atoms, and each of R 7 and R 8 is independently hydrogen. COOH, COO - , SO 3 - , SO 3 H, COONa, SO 3 Na, COOCH 3 , or COOCH 2 CH 3 .

如果上述R7或R8為上述的陰離子，則與上述化學式1的N+形成分子內鹽(inner salt)，不為陰離子的情況下，可與無機或有機陰離子結合。 When R 7 or R 8 is the above anion, it can form an intramolecular salt with N + of the above Chemical Formula 1, and if it is not an anion, it can be bonded to an inorganic or organic anion.

作為上述有機或無機陰離子，具體地，例如可以包含選自鹵素陰離子、高鹵酸陰離子、烷基硫酸根陰離子、磺酸鹽陰離子、和磺醯亞胺陰離子中的1種以上，但並不限定於此。 Specifically, the organic or inorganic anion may, for example, be one or more selected from the group consisting of a halogen anion, a perhalogen anion, an alkylsulfate anion, a sulfonate anion, and a sulfonimide anion, but is not limited thereto. herein.

本發明中，相對於上述紅色著色劑的總重量，以5~95重量%，優選以10~60重量%含有選自上述化學式1的占噸系染料和偶氮系染料中的1種以上的染料。 In the present invention, one or more selected from the group consisting of the xanthene dye and the azo dye selected from the above Chemical Formula 1 are contained in an amount of 5 to 95% by weight, preferably 10 to 60% by weight, based on the total weight of the red coloring agent. dye.

如果上述染料的含量不到5重量%，則透射率的上升很小，如果含有超過95重量%，有時在塗膜內容易發生析出，對比度減小，紅色感光性樹脂組合物的貯存穩定性降低。 When the content of the dye is less than 5% by weight, the increase in transmittance is small, and if it is more than 95% by weight, precipitation may easily occur in the coating film, and contrast may be reduced, and storage stability of the red photosensitive resin composition may be obtained. reduce.

上述化學式1的占噸系染料的透射率和耐熱性優異，但對於溶劑的溶解度和相容性不足，存在不能大量使用的問題。 The ton-based dye of the above Chemical Formula 1 is excellent in transmittance and heat resistance, but has insufficient solubility and compatibility with a solvent, and has a problem that it cannot be used in a large amount.

因此，本發明中，相對於紅色著色劑的總重量，優選包含3~50重量%的上述化學式1的占噸系染料，更優選包含5~20重量%。 Therefore, in the present invention, it is preferable to contain 3 to 50% by weight of the ton-based dye of the above Chemical Formula 1 with respect to the total weight of the red colorant, and more preferably 5 to 20% by weight.

如果上述化學式1的占噸系染料的含量不 到3重量%，則透射率的上升很小，如果含有超過50重量%，則有時在塗膜內容易發生析出，對比度減小，紅色感光性樹脂組合物的貯存穩定性降低。 If the content of the above-mentioned chemical formula 1 is not When the content is more than 50% by weight, the precipitation is likely to occur in the coating film, the contrast is reduced, and the storage stability of the red photosensitive resin composition is lowered.

作為上述化學式1的占噸系染料，具體地，例如可列舉出酸性紅52(Acid Red52)、鹼性紅1(Basic Red1)、鹼性紫10(Basic Violet10)、鹼性紫11(Basic Violet11)、若丹明B(Rhodamine B)、若丹明6G(Rhodamine 6G)、若丹明123(Rhodamine123)、和磺基若丹明B(Sulforhodamine B)等，但並不限定於這些，上述染料可以單獨使用或者將2種以上混合使用。 Specific examples of the oxime dye of the above Chemical Formula 1 include Acid Red 52, Basic Red 1, Basic Violet 10, and Basic Violet 11 (Basic Violet 11). ), Rhodamine B, Rhodamine 6G, Rhodamine 123, Sulforhodamine B, etc., but are not limited thereto, the above dyes They may be used alone or in combination of two or more.

上述偶氮系染料優選使用金屬絡合物結構的偶氮系染料。這是因為，與一般的偶氮系染料相比，耐熱性和溶解度優異，對比度優異，能夠提高紅色感光性樹脂組合物中的染料的含量，能夠顯示高亮度。 As the azo dye, it is preferred to use an azo dye having a metal complex structure. This is because the heat resistance and the solubility are excellent compared with the general azo dyes, and the contrast is excellent, and the content of the dye in the red photosensitive resin composition can be increased, and high luminance can be exhibited.

相對於紅色著色劑的總重量，以2~45重量%，優選以5~15重量%含有上述偶氮系染料。 The azo dye is contained in an amount of 2 to 45% by weight, preferably 5 to 15% by weight based on the total weight of the red colorant.

如果含有不到2重量%的上述偶氮系染料，則透射率的上升很小，如果含有超過45重量%，有時產生耐熱性和耐溶劑性等的可靠性的問題。 When the azo dye is less than 2% by weight, the increase in transmittance is small, and if it is more than 45% by weight, reliability such as heat resistance and solvent resistance may occur.

上述偶氮系染料，具體地，例如可列舉出C.I.溶劑黃13、C.I.溶劑黃19、C.I.溶劑黃21、C.I.溶劑黃25、C.I.溶劑黃25：1、C.I.溶劑黃81、C.I.溶劑黃82、C.I.溶劑黃88、C.I.溶劑黃89、C.I.溶劑黃90、C.I.溶劑橙5、C.I.溶劑橙20、C.I.溶劑橙40：1、C.I.溶劑橙41、C.I.溶 劑橙45、C.I.溶劑橙54、C.I.溶劑橙56、C.I.溶劑橙58、C.I.溶劑橙62、C.I.溶劑橙81、C.I.溶劑橙99、C.I.溶劑紅8、C.I.溶劑紅83：1、C.I.溶劑紅84：1、C.I.溶劑紅90、C.I.溶劑紅90：1、C.I.溶劑.紅91、C.I.溶劑紅118、C.I.溶劑紅119、C.I.溶劑紅122、C.I.溶劑紅127、C.I.溶劑紅130、C.I.溶劑紅132、C.I.溶劑紅160、C.I.溶劑紅234、C.I.溶劑紅243、C.I.溶劑橙21：1、C.I.溶劑橙58、和C.I.溶劑藍137等，但並不限定於這些。 Specific examples of the azo dyes include CI Solvent Yellow 13, CI Solvent Yellow 19, CI Solvent Yellow 21, CI Solvent Yellow 25, CI Solvent Yellow 25:1, CI Solvent Yellow 81, and CI Solvent Yellow 82. CI Solvent Yellow 88, CI Solvent Yellow 89, CI Solvent Yellow 90, CI Solvent Orange 5, CI Solvent Orange 20, CI Solvent Orange 40: 1, CI Solvent Orange 41, CI Dissolved Agent Orange 45, CI Solvent Orange 54, CI Solvent Orange 56, CI Solvent Orange 58, CI Solvent Orange 62, CI Solvent Orange 81, CI Solvent Orange 99, CI Solvent Red 8, CI Solvent Red 83:1, CI Solvent Red 84 1, CI solvent red 90, CI solvent red 90: 1, CI solvent. Red 91, CI solvent red 118, CI solvent red 119, CI solvent red 122, CI solvent red 127, CI solvent red 130, CI solvent red 132 , CI Solvent Red 160, CI Solvent Red 234, CI Solvent Red 243, CI Solvent Orange 21:1, CI Solvent Orange 58, and CI Solvent Blue 137, etc., but are not limited thereto.

(B)鹼可溶性樹脂 (B) alkali soluble resin

為了對於形成圖案時的顯影處理工序中使用的鹼顯影液具有可溶性，上述鹼可溶性樹脂以包含羧基的烯屬不飽和單體作為必要成分共聚進行製造。 The alkali-soluble resin is produced by copolymerizing an ethylenically unsaturated monomer containing a carboxyl group as an essential component in order to be soluble in the alkali developer used in the development treatment step at the time of pattern formation.

上述包含羧基的烯屬不飽和單體，作為具體例，可列舉出丙烯酸、甲基丙烯酸、巴豆酸等單羧酸類；富馬酸、中康酸、衣康酸等二羧酸類；二羧酸類的酸酐；ω-羧基聚己內酯單(甲基)丙烯酸酯等在兩末端包含羧基和羥基的聚合物的單(甲基)丙烯酸酯類等，優選丙烯酸、甲基丙烯酸。 Examples of the ethylenically unsaturated monomer containing a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; and dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and dicarboxylic acids. An acid anhydride; a mono(meth)acrylate such as a polymer containing a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate, preferably acrylic acid or methacrylic acid.

另外，為了確保追加的顯影性，可以對上述鹼可溶性樹脂賦予羥基。 Further, in order to secure additional developability, a hydroxyl group may be added to the above alkali-soluble resin.

作為用於賦予上述羥基的方法，可列舉出(1)使包含羧基的烯屬不飽和單體和包含羥基的烯屬不飽和單體共聚而製造的方法、(2)使包含羧基的烯屬不飽和單體的共聚物與包含縮水甘油基的化合物追加地反應而製造 的方法、和(3)使包含羧基的烯屬不飽和單體和包含羥基的烯屬不飽和單體的共聚物追加地與具有縮水甘油基的化合物反應而製造的方法等。 Examples of the method for imparting the hydroxyl group include (1) a method of copolymerizing an ethylenically unsaturated monomer containing a carboxyl group and an ethylenically unsaturated monomer containing a hydroxyl group, and (2) an olefin containing a carboxyl group. A copolymer of an unsaturated monomer is additionally reacted with a compound containing a glycidyl group to produce And a method of (3) a method in which a copolymer of a carboxyl group-containing ethylenically unsaturated monomer and a hydroxyl group-containing ethylenically unsaturated monomer is additionally reacted with a compound having a glycidyl group, and the like.

作為上述包含羥基的烯屬不飽和單體的具體例，有(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、和N-羥基乙基丙烯醯胺等，其中優選(甲基)丙烯酸2-羥基乙酯，上述包含羥基的烯屬不飽和單體可以將2種以上組合使用。 Specific examples of the hydroxy group-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. 2-hydroxy-3-phenoxypropyl methacrylate, and N-hydroxyethyl acrylamide, etc., among which 2-hydroxyethyl (meth) acrylate, the above hydroxy group-containing ethylenically unsaturated monomer Two or more types can be used in combination.

作為上述包含縮水甘油基的化合物的具體例，有丁基縮水甘油基醚、縮水甘油基丙基醚、縮水甘油基苯基醚、2-乙基己基縮水甘油基醚、丁酸縮水甘油酯、縮水甘油基甲基醚、乙基縮水甘油基醚、縮水甘油基異丙基醚、叔丁基縮水甘油基醚、苄基縮水甘油基醚、4-叔-丁基苯甲酸縮水甘油酯、硬脂酸縮水甘油酯、芳基縮水甘油基醚、和甲基丙烯酸縮水甘油酯等，優選地，可列舉出丁基縮水甘油基醚、芳基縮水甘油基醚、和甲基丙烯酸縮水甘油酯，上述包含縮水甘油基的化合物可以將2種以上組合使用。 Specific examples of the glycidyl group-containing compound include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, and glycidyl butyrate. Glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, benzyl glycidyl ether, 4-tert-butylbenzoic acid glycidyl ester, hard Examples thereof include glycidyl sulphate, aryl glycidyl ether, and glycidyl methacrylate, and examples thereof include butyl glycidyl ether, aryl glycidyl ether, and glycidyl methacrylate. The above glycidyl group-containing compound may be used in combination of two or more kinds.

另外，上述鹼可溶性樹脂的製造時，可與包含羧基的烯屬不飽和單體共聚的不飽和單體，可列舉出芳香族乙烯基化合物、N-取代馬來醯亞胺系化合物、脂環族(甲基)丙烯酸酯類、(甲基)丙烯酸羥基乙酯類、(甲基)丙烯酸芳基酯類、和不飽和氧雜環丁烷化合物等，但並不 限定於這些。 Further, in the production of the alkali-soluble resin, an unsaturated monomer copolymerizable with a carboxyl group-containing ethylenically unsaturated monomer may, for example, be an aromatic vinyl compound, an N-substituted maleimide compound or an alicyclic ring. Group (meth) acrylates, hydroxyethyl (meth) acrylates, aryl (meth) acrylates, and unsaturated oxetane compounds, but not Limited to these.

上述芳香族乙烯基化合物，具體地，例如可列舉出苯乙烯、乙烯基甲苯、α-甲基苯乙烯、對-氯苯乙烯、鄰-甲氧基苯乙烯、間-甲氧基苯乙烯、對-甲氧基苯乙烯、鄰-乙烯基苄基甲基醚、間-乙烯基苄基甲基醚、對-乙烯基苄基甲基醚、鄰-乙烯基苄基縮水甘油基醚、間-乙烯基苄基縮水甘油基醚、和對-乙烯基苄基縮水甘油基醚等。 Specific examples of the aromatic vinyl compound include styrene, vinyl toluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, and m-methoxystyrene. p-Methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, -vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether and the like.

上述N-取代馬來醯亞胺系化合物，具體地，例如可列舉出N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、N-苯基馬來醯亞胺、N-鄰-羥基苯基馬來醯亞胺、N-間-羥基苯基馬來醯亞胺、N-對-羥基苯基馬來醯亞胺、N-鄰-甲基苯基馬來醯亞胺、N-間-甲基苯基馬來醯亞胺、N-對-甲基苯基馬來醯亞胺、N-鄰-甲氧基苯基馬來醯亞胺、N-間-甲氧基苯基馬來醯亞胺、和N-對-甲氧基苯基馬來醯亞胺等。 Specific examples of the N-substituted maleimide-based compound include N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, and N. - o-hydroxyphenyl maleimine, N-m-hydroxyphenyl maleimide, N-p-hydroxyphenyl maleimide, N-o-methylphenyl malayan Amine, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-A Oxyphenyl phenyl maleimide, and N-p-methoxyphenyl maleimide, and the like.

上述脂環族(甲基)丙烯酸酯類，具體地，例如可列舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸叔丁酯等(甲基)丙烯酸烷基酯類；(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-甲基環己酯、(甲基)丙烯酸三環[5.2.1.02,6]癸烷-8-基酯、(甲基)丙烯酸2-雙環戊氧基乙酯、和(甲基)丙烯酸異冰片酯等。 Specific examples of the alicyclic (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylate. a (meth)acrylic acid alkyl ester such as propyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate or t-butyl (meth)acrylate; Cyclo) methyl methacrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.0.1.02,6]decane-8-yl (meth) acrylate Ester, 2-biscyclopentyloxyethyl (meth)acrylate, and isobornyl (meth)acrylate.

上述(甲基)丙烯酸羥基乙酯類，具體地，例如可列舉出(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、和N-羥基乙基丙烯醯胺等。 Specific examples of the hydroxyethyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. And 2-hydroxy-3-phenoxypropyl (meth)acrylate, and N-hydroxyethyl acrylamide.

上述(甲基)丙烯酸芳基酯類，具體地，例如可列舉出(甲基)丙烯酸苯酯和(甲基)丙烯酸苄酯等。 Specific examples of the aryl (meth)acrylate include phenyl (meth)acrylate and benzyl (meth)acrylate.

上述不飽和氧雜環丁烷化合物，具體地，例如可列舉出3-(甲基丙烯醯氧基甲基)氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-3-乙基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-三氟甲基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-苯基氧雜環丁烷、2-(甲基丙烯醯氧基甲基)氧雜環丁烷、和2-(甲基丙烯醯氧基甲基)-4-三氟甲基氧雜環丁烷等。 Specific examples of the unsaturated oxetane compound include 3-(methacryloxymethyl)oxetane and 3-(methacryloxymethyl)-3- Ethyloxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-phenyl Oxetane, 2-(methacryloxymethyl)oxetane, and 2-(methacryloxymethyl)-4-trifluoromethyloxetane .

上述不飽和單體可以各自單獨使用或者將2種以上混合使用。 These unsaturated monomers may be used alone or in combination of two or more.

另外，為了確保與染料的相容性和紅色感光性樹脂組合物的貯存穩定性，上述鹼可溶性樹脂優選具有30~150mgKOH/g的酸值。上述鹼可溶性樹脂的酸值不到30mgKOH/g的情況下，紅色感光性樹脂組合物的顯影速度慢，超過150mgKOH/g的情況下，紅色感光性樹脂組合物的與基板的密合性減小，容易發生圖案的短路，產生與染料的相容性的問題，產生紅色感光性樹脂組合物中的染料析出、貯存穩定性降低、黏度上升的問題。 Further, in order to ensure compatibility with the dye and storage stability of the red photosensitive resin composition, the alkali-soluble resin preferably has an acid value of 30 to 150 mgKOH/g. When the acid value of the alkali-soluble resin is less than 30 mgKOH/g, the development speed of the red photosensitive resin composition is slow, and when it exceeds 150 mgKOH/g, the adhesion of the red photosensitive resin composition to the substrate is reduced. A problem of short-circuiting of the pattern is likely to occur, and compatibility with the dye is caused, and there is a problem that the dye is precipitated in the red photosensitive resin composition, the storage stability is lowered, and the viscosity is increased.

另外，相對於紅色感光性樹脂組合物中的 固體成分總重量，優選以10~80重量%，更優選以10~70重量%包含上述鹼可溶性樹脂。 In addition, relative to the red photosensitive resin composition The alkali-soluble resin is preferably contained in an amount of 10 to 80% by weight, and more preferably 10 to 70% by weight, based on the total weight of the solid content.

如果上述鹼可溶性樹脂的含量為10~80重量%，顯影液中的溶解性充分，圖案的形成容易，防止顯影時曝光部的像素部分的膜減少，非像素部分的脫落性變得良好。 When the content of the alkali-soluble resin is from 10 to 80% by weight, the solubility in the developer is sufficient, the formation of a pattern is easy, and the film of the pixel portion of the exposed portion during development is prevented from being reduced, and the non-pixel portion is excellent in peeling property.

(C)光聚合性化合物 (C) Photopolymerizable compound

作為本發明的紅色感光性樹脂組合物中的一者的光聚合性化合物必須是在後述的光聚合引發劑(D)的作用下可聚合的化合物。 The photopolymerizable compound which is one of the red photosensitive resin compositions of the present invention must be a compound polymerizable under the action of a photopolymerization initiator (D) to be described later.

作為光聚合性化合物，能夠使用單官能單體、2官能單體、或多官能單體，優選使用2官能單體，但並不限定於此。 As the photopolymerizable compound, a monofunctional monomer, a bifunctional monomer, or a polyfunctional monomer can be used, and a bifunctional monomer is preferably used, but is not limited thereto.

作為上述單官能單體的具體例，有壬基苯基卡必醇丙烯酸酯、丙烯酸2-羥基-3-苯氧基丙酯、2-乙基己基卡必醇丙烯酸酯、丙烯酸2-羥基乙酯、或N-乙烯基吡咯烷酮等，但並不限定於這些。 Specific examples of the above monofunctional monomer include mercaptophenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate Ester, or N-vinylpyrrolidone, etc., but is not limited thereto.

作為上述2官能單體的具體例，有1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三甘醇二(甲基)丙烯酸酯、雙酚A的雙(丙烯醯氧基乙基)醚、或3-甲基戊二醇二(甲基)丙烯酸酯等，但並不限定於這些。 Specific examples of the bifunctional monomer include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and three. Glycol di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, or 3-methylpentanediol di(meth)acrylate, etc., but it is not limited to these.

作為上述多官能單體的具體例，有三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化三羥甲基丙烷三(甲 基)丙烯酸酯、丙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、乙氧基化二季戊四醇六(甲基)丙烯酸酯、丙氧基化二季戊四醇六(甲基)丙烯酸酯、或二季戊四醇六(甲基)丙烯酸酯等，但並不限定於這些。 Specific examples of the above polyfunctional monomer include trimethylolpropane tri(meth)acrylate and ethoxylated trimethylolpropane tris(A). Acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, or dipentaerythritol hexa (meth) acrylate, etc., but is not limited thereto.

相對於本發明的紅色感光性樹脂組合物中的固體成分總重量，以5~45重量%，優選以7~45重量%含有上述光聚合性化合物。上述光聚合性化合物在上述5~45重量%的範圍內能夠使像素部的強度、平坦性變得良好。 The photopolymerizable compound is contained in an amount of 5 to 45% by weight, preferably 7 to 45% by weight, based on the total weight of the solid content in the red photosensitive resin composition of the present invention. The photopolymerizable compound can improve the strength and flatness of the pixel portion in the range of 5 to 45% by weight.

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

作為本發明的紅色感光性樹脂組合物的一成分的光聚合引發劑必須包含肟酯系化合物。 The photopolymerization initiator which is one component of the red photosensitive resin composition of the present invention must contain an oxime ester compound.

上述肟酯系化合物優選包含選自1,2-辛二酮、1-[4-(苯硫基)苯基]-，2-(O-苯甲醯基肟)(1,2-Octanedione，1-[4-(phenylthio)phenyl]-，2-(O-benzoyloxime))、和1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮1-(O-乙醯基肟)(1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanonel-(O-acetyloxime))中的1種以上。另外，作為製品，可列舉出BASF公司的IrgacureOXE01、IrgacureOXE02、IrgacureOXE03等，由於各自的吸光度和產生的自由基的種類多樣，因此優選將2種以上混合而使用。 The above oxime ester-based compound preferably comprises a compound selected from the group consisting of 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzhydrylhydrazine) (1,2-Octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime)), and 1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazole-3- One of 1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanonel-(O-acetyloxime)) the above. In addition, as a product, the Irgacure of BASF Corporation can be cited. OXE01, Irgacure OXE02, Irgacure OXE03 and the like are preferably used in combination of two or more types because of the various absorbances and the types of radicals generated.

上述肟酯系化合物，相對於光聚合引發劑的總重量，包含10~100重量%，優選包含20~100重量%。 The oxime ester-based compound is contained in an amount of 10 to 100% by weight, preferably 20 to 100% by weight based on the total weight of the photopolymerization initiator.

如果包含不到10重量%的上述肟酯系化合物，則不能解決染料引起的感度降低的問題，在顯影工序中容易發生圖案的短路。 When less than 10% by weight of the above-mentioned oxime ester-based compound is contained, the problem of deterioration in sensitivity due to the dye cannot be solved, and a short circuit of the pattern is likely to occur in the development step.

另外，在不損害本發明的效果的範圍內，除了上述肟酯系化合物以外，可以追加地使用選自苯乙酮系化合物、二苯甲酮系化合物、三嗪系化合物、聯咪唑系化合物、和噻噸酮系化合物中的1種以上的化合物。 In addition, the acetophenone-based compound, the benzophenone-based compound, the triazine-based compound, and the biimidazole-based compound may be additionally used in addition to the above-described oxime ester-based compound, in addition to the above-described oxime ester-based compound. And one or more compounds among the thioxanthone compounds.

上述苯乙酮系化合物，具體地，例如可列舉出二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、苯偶醯二甲基縮酮、2-羥基-1-[4-(2-羥基乙氧基)苯基]-2-甲基丙烷-1-酮、1-羥基環己基苯基酮、2-甲基-1-(4-甲硫基苯基)-2-嗎啉代丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基)丁烷-1-酮、2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙烷-1-酮、和2-(4-甲基苄基)-2-(二甲基胺基)-1-(4-嗎啉代苯基)丁烷-1-酮等。 Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzoin dimethyl ketal. 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4- Methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2 -hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, and 2-(4-methylbenzyl)-2-(dimethylamino) )-1-(4-morpholinophenyl)butan-1-one and the like.

上述二苯甲酮系化合物，具體地，例如可列舉出二苯甲酮、O-苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4’-甲基二苯基硫醚、3,3’,4,4’-四(叔-丁基過氧羰基)二苯甲酮、和2,4,6-三甲基二苯甲酮等。 Specific examples of the benzophenone-based compound include benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, and 4-benzylidene-4'- Methyl diphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone.

上述三嗪系化合物，具體地，例如可列舉出2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三嗪、2,4-雙(三氯 甲基)-6-胡椒基-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三嗪、和2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三嗪等。 Specific examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-. Bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloro) Methyl)-6-piperidin-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three Pyrazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis (three Chloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4- Diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,4-di Methoxyphenyl)vinyl]-1,3,5-triazine, and the like.

上述聯咪唑化合物，具體地，例如可列舉出2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基聯咪唑、2,2’-雙(2,3-二氯苯基)-4,4’,5,5’-四苯基聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(烷氧基苯基)聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(三烷氧基苯基)聯咪唑、2,2-雙(2,6-二氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、或4,4’,5,5’位的苯基被烷氧羰基取代的咪唑化合物等。這些中，優選使用2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基聯咪唑、2,2’-雙(2,3-二氯苯基)-4,4’,5,5’-四苯基聯咪唑、和2,2-雙(2,6-二氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑。 The biimidazole compound, specifically, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis (2) ,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-four (alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole, 2,2- Bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, or 4,4',5,5' phenyl group An oxycarbonyl-substituted imidazole compound or the like. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) is preferably used. -4,4',5,5'-tetraphenylbiimidazole, and 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1 , 2'-biimidazole.

上述噻噸酮系化合物，具體地，例如可列舉出2-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮、和1-氯-4-丙氧基噻噸酮等。 The above thioxanthone-based compound, specifically, for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4 - propoxy thioxanthone and the like.

上述光聚合引發劑可以單獨使用或者將2種以上混合使用。 These photopolymerization initiators may be used alone or in combination of two or more.

本發明中，上述光聚合引發劑，相對於紅色感光性樹脂組合物中的固體成分總重量，含有0.1~40 重量%，優選含有1~10重量%。 In the present invention, the photopolymerization initiator contains 0.1 to 40 based on the total weight of the solid component in the red photosensitive resin composition. The weight % preferably contains 1 to 10% by weight.

在上述0.1~40重量%的範圍內，紅色感光性樹脂組合物高感度化，使曝光時間縮短，因此生產率提高，能夠維持高的解析度。另外，使用上述紅色感光性樹脂組合物形成的像素部的強度和上述像素部的表面的平滑性變得良好。 In the range of 0.1 to 40% by weight, the red photosensitive resin composition has high sensitivity and shortens the exposure time, so that productivity is improved and high resolution can be maintained. In addition, the strength of the pixel portion formed using the red photosensitive resin composition and the smoothness of the surface of the pixel portion are improved.

另外，上述光聚合引發劑(D)，為了提高本發明的紅色感光性樹脂組合物的感度，可以進一步包含光聚合引發輔助劑(d1)。本發明涉及的紅色感光性樹脂組合物通過含有光聚合引發輔助劑(d1)，感度進一步提高，能夠提高生產率。 In addition, the photopolymerization initiator (D) may further contain a photopolymerization initiation aid (d1) in order to improve the sensitivity of the red photosensitive resin composition of the present invention. When the red photosensitive resin composition of the present invention contains a photopolymerization initiation aid (d1), the sensitivity is further improved, and productivity can be improved.

上述光聚合引發輔助劑，能夠包含例如選自胺化合物、羧酸化合物、和多官能硫醇化合物中的1種以上。 The photopolymerization initiation auxiliary agent may contain, for example, one or more selected from the group consisting of an amine compound, a carboxylic acid compound, and a polyfunctional thiol compound.

作為上述胺化合物，優選使用芳香族胺化合物，具體地，能夠使用三乙醇胺、甲基二乙醇胺、和三異丙醇胺等脂肪族胺化合物；4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、4-二甲基胺基苯甲酸2-乙基己酯、苯甲酸2-二甲基胺基乙酯、N,N-二甲基對甲苯胺、4,4’-雙(二甲基胺基)二苯甲酮(通稱：米蚩酮)、和4,4’-雙(二乙基胺基)二苯甲酮等。 As the above amine compound, an aromatic amine compound is preferably used, and specifically, an aliphatic amine compound such as triethanolamine, methyldiethanolamine or triisopropanolamine; methyl 4-dimethylaminobenzoate, 4 can be used. -ethyl dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylamino B-benzoate Ester, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (general name: Michler's ketone), and 4,4'-bis(diethylamine) Base) benzophenone and the like.

上述羧酸化合物優選為芳香族雜醋酸類，具體地，可列舉出苯基硫代醋酸、甲基苯基硫代醋酸、乙基苯基硫代醋酸、甲基乙基苯基硫代醋酸、二甲基苯基硫 代醋酸、甲氧基苯基硫代醋酸、二甲氧基苯基硫代醋酸、氯苯基硫代醋酸、二氯苯基硫代醋酸、N-苯基甘胺酸、苯氧基醋酸、萘基硫代醋酸、N-萘基甘胺酸、和萘氧基醋酸等。 The carboxylic acid compound is preferably an aromatic heteroacetic acid, and specific examples thereof include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, and methylethylphenylthioacetic acid. Dimethylphenyl sulfide Acetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, Naphthylthioacetic acid, N-naphthylglycine, and naphthyloxyacetic acid, and the like.

作為上述多官能硫醇化合物，可列舉出三-[(3-巰基丙醯氧基)-乙基]-異氰脲酸酯(Tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate)、三羥甲基丙烷三-3-巰基丙酸酯(Trimethylolpropane tris-3-mercaptopropionate)、季戊四醇四-3-巰基丙酸酯(Pentaerythritol tetrakis-3-mercaptopropionate)、和二季戊四醇六-3-巰基丙酸酯(Dipentaerythritol hexa-3-mercaptopropionate)等。 The polyfunctional thiol compound may, for example, be tris-[(3-mercaptopropoxyl)-ethyl]-isocyanurate (Tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate), Trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate (Dipentaerythritol hexa-3-mercaptopropionate) and the like.

使用上述光聚合引發輔助劑的情況下，上述光聚合引發輔助劑，相對於本發明的紅色感光性樹脂組合物中的固體成分總重量，含有0.1~40重量%，優選含有1~30重量%。 When the photopolymerization initiation auxiliary agent is used, the photopolymerization initiation auxiliary agent is contained in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight based on the total weight of the solid content of the red photosensitive resin composition of the present invention. .

如果含有0.1~40重量%的上述光聚合引發輔助劑，則紅色感光性樹脂組合物的感度上升，使用其製造的濾色器的生產率提高。 When 0.1 to 40% by weight of the photopolymerization initiation aid is contained, the sensitivity of the red photosensitive resin composition increases, and the productivity of the color filter produced using the same increases.

(E)溶劑 (E) solvent

上述溶劑只要對於使紅色感光性樹脂組合物中所含的其他成分溶解有效，則可以無特別限制地使用通常的紅色感光性樹脂組合物中使用的溶劑，特別優選醚類、乙酸酯類、芳香族烴類、酮類、醇類或酯類等。 When the solvent is effective for dissolving other components contained in the red photosensitive resin composition, the solvent used in the usual red photosensitive resin composition can be used without particular limitation, and ethers, acetates, and aromatics are particularly preferable. Hydrocarbons, ketones, alcohols or esters, and the like.

作為上述醚類，例如可列舉出乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、和乙二醇單丁基醚等乙二醇單烷基醚類；二甘醇二甲基醚、二甘醇二乙基醚、二甘醇二丙基醚、和二甘醇二丁基醚等二甘醇二烷基醚類等。 Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether.

作為上述乙酸酯類，例如可列舉出甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、乙酸乙酯、乙酸丁酯、乙酸戊酯、乳酸甲酯、乳酸乙酯、乳酸丁酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基-1-丁基乙酸酯、甲氧基戊基乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、甲基3-甲氧基丙酸酯、丙二醇甲基醚乙酸酯、3-甲氧基-1-丁基乙酸酯、1,2-丙二醇二乙酸酯、乙二醇單丁基醚乙酸酯、二甘醇單乙基醚乙酸酯、二丙二醇甲基醚乙酸酯、1,3-丁二醇二乙酸酯、二甘醇單丁基醚乙酸酯、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二甘醇單乙酸酯、二甘醇二乙酸酯、二甘醇單丁基醚乙酸酯、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、碳酸亞乙酯、和碳酸亞丙酯等。 Examples of the acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, and lactic acid. Ester, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, B Glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1-butyl acetate, 1,2-propylene glycol diacetate, Ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether An acid ester, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, and propylene carbonate.

作為上述芳香族烴類，例如可列舉出苯、甲苯、二甲苯、和均三甲苯等。 Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

作為上述酮類，例如可列舉出甲基乙基酮、丙酮、甲基戊基酮、甲基異丁基酮、和環己酮等。 Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

作為上述醇類，例如可列舉出乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、甘油、和4-羥基-4-甲基-2- 戊酮等。 Examples of the above alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, and 4-hydroxy-4-methyl-2- Pentanone and the like.

作為上述酯類，例如可列舉出3-乙氧基丙酸乙酯、3-甲氧基丙酸甲酯、和γ-丁內酯等。 Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and γ-butyrolactone.

上述溶劑可各自單獨使用或者將2種以上混合使用。 These solvents may be used alone or in combination of two or more.

上述溶劑在塗布性和乾燥性的方面，優選使用沸點為100℃~200℃的有機溶劑，其中，使用丙二醇單甲基醚乙酸酯和4-羥基-4-甲基-2-戊酮能夠使染料充分地溶解，因此最優選。 The solvent is preferably an organic solvent having a boiling point of from 100 ° C to 200 ° C in terms of coatability and drying properties, wherein propylene glycol monomethyl ether acetate and 4-hydroxy-4-methyl-2-pentanone can be used. It is most preferred to dissolve the dye sufficiently.

相對於溶劑的總重量，以15~80重量%，優選以30~60重量%含有上述丙二醇單甲基醚乙酸酯。在上述15~80重量%的範圍內，能夠確保紅色感光性樹脂組合物的黏度穩定性。 The propylene glycol monomethyl ether acetate is contained in an amount of 15 to 80% by weight, preferably 30 to 60% by weight, based on the total weight of the solvent. The viscosity stability of the red photosensitive resin composition can be ensured in the range of 15 to 80% by weight.

另外，上述4-羥基-4-甲基-2-戊酮，相對於溶劑的總重量，含有20~85重量%，優選含有20~40重量%。在上述20~85重量%的範圍內，不出現紅色感光性樹脂組合物的染料的析出引起的異物產生、對比度的減小，紅色感光性樹脂組合物的分散性適當，能夠確保黏度穩定性。 Further, the 4-hydroxy-4-methyl-2-pentanone is contained in an amount of 20 to 85% by weight, preferably 20 to 40% by weight based on the total mass of the solvent. In the range of 20 to 85% by weight, foreign matter generation and contrast reduction due to precipitation of the dye of the red photosensitive resin composition do not occur, and the dispersibility of the red photosensitive resin composition is appropriate, and viscosity stability can be ensured.

本發明中，相對於紅色感光性樹脂組合物的總重量，以60~90重量%，優選以70~85重量%含有上述溶劑。如果在上述60~90重量%的範圍內含有上述溶劑，則採用輥塗機、旋塗機、狹縫和旋轉塗布機、狹縫塗布機(有時也稱為模壓塗布機)、和噴墨等塗布裝置塗布 時，塗布性變得良好。 In the present invention, the solvent is contained in an amount of 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the red photosensitive resin composition. If the solvent is contained in the above range of 60 to 90% by weight, a roll coater, a spin coater, a slit and a spin coater, a slit coater (sometimes referred to as a press coater), and an ink jet are used. Coating device At the time, the coating property became good.

(F)添加劑 (F) additive

上述添加劑可以根據需要選擇性地添加，例如可以包含選自填充劑、其他高分子化合物、固化劑、界面活性劑、密合促進劑、抗氧化劑、紫外線吸收劑、和防凝聚劑中的1種以上。 The above additives may be selectively added as needed, and for example, may include one selected from the group consisting of a filler, another polymer compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-agglomerating agent. the above.

作為上述填充劑的具體例，可列舉出玻璃、二氧化矽、和氧化鋁等。 Specific examples of the above filler include glass, cerium oxide, aluminum oxide, and the like.

作為上述其他高分子化合物的具體例，可列舉出環氧樹脂、馬來醯亞胺樹脂等固化性樹脂、聚乙烯醇、聚丙烯酸、聚乙二醇單烷基醚、聚丙烯酸氟烷基酯、聚酯、和聚胺基甲酸酯等热塑性樹脂等。 Specific examples of the other polymer compound include curable resins such as epoxy resins and maleic imine resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. , thermoplastic resins such as polyester, and polyurethane, and the like.

上述固化劑為了提高深部固化和機械強度而使用，作為固化劑的具體例，可列舉出環氧化合物、多官能異氰酸酯化合物、蜜胺化合物、和氧雜環丁烷化合物等。 The curing agent is used to improve deep curing and mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

上述固化劑中，作為環氧化合物的具體例，可列舉出雙酚A系環氧樹脂、氫化雙酚A系環氧樹脂、雙酚F系環氧樹脂、氫化雙酚F系環氧樹脂、酚醛清漆型環氧樹脂、其他芳香族系環氧樹脂、脂環族系環氧樹脂、縮水甘油酯系樹脂、縮水甘油胺系樹脂、或上述環氧樹脂的溴化衍生物、環氧樹脂、及其溴化衍生物以外的脂肪族、脂環族或芳香族環氧化合物、丁二烯(共)聚合物環氧化物、異戊二烯(共)聚合物環氧化物、(甲基)丙烯酸縮水甘 油酯(共)聚合物、和異氰脲酸三縮水甘油酯等。 In the above curing agent, specific examples of the epoxy compound include a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, and a hydrogenated bisphenol F epoxy resin. A novolak type epoxy resin, another aromatic epoxy resin, an alicyclic epoxy resin, a glycidyl ester resin, a glycidylamine resin, a brominated derivative of the above epoxy resin, an epoxy resin, An aliphatic, alicyclic or aromatic epoxy compound other than its brominated derivative, butadiene (co)polymer epoxide, isoprene (co)polymer epoxide, (methyl) Acrylic glycam Oil ester (co)polymer, and triglycidyl isocyanurate.

上述固化劑中，作為氧雜環丁烷化合物的具體例，可列舉出碳酸酯雙氧雜環丁烷、二甲苯雙氧雜環丁烷、己二酸酯雙氧雜環丁烷、對苯二甲酸酯雙氧雜環丁烷、和環己烷二羧酸雙氧雜環丁烷等。 Among the above curing agents, specific examples of the oxetane compound include carbonate dioxetane, xylene dioxetane, adipate dioxetane, and benzene. Dicarboxylate dioxetane, cyclohexanedicarboxylic acid dioxetane, and the like.

就上述固化劑而言，可以與固化劑一起將可以使環氧化合物的環氧基、氧雜環丁烷化合物的氧雜環丁烷骨架進行開環聚合的固化輔助化合物並用。 In the above curing agent, a curing auxiliary compound capable of ring-opening polymerization of an epoxy group of an epoxy compound or an oxetane skeleton of an oxetane compound may be used together with a curing agent.

上述固化輔助化合物例如有多元羧酸類、多元羧酸酐類、和產酸劑等。上述多元羧酸酐類可以使用作為環氧樹脂固化劑市售的產品。作為上述市售品，可列舉出EH-700(工業(株)製造)、 HH(新日本理化(株)製造)和MH-700(新日本理化(株)製造)等。上述例示的固化劑可以單獨使用或者將2種以上混合使用。 Examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic acid anhydrides, and acid generators. As the above polyvalent carboxylic acid anhydride, a commercially available product as an epoxy resin curing agent can be used. As the above-mentioned commercial products, it can be cited EH-700( Industrial Co., Ltd.), HH (manufactured by Shin-Nippon Chemical Co., Ltd.) and MH-700 (manufactured by Shin-Nippon Chemical Co., Ltd.). The curing agents exemplified above may be used singly or in combination of two or more.

為了進一步提高紅色感光性樹脂組合物的被膜形成，能夠使用上述界面活性劑，優選使用有機矽系、氟系、酯系、陽離子系、陰離子系、非離子系、兩性界面活性劑等。 In order to further increase the formation of the film of the red photosensitive resin composition, the above surfactant may be used, and an organic fluorene-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, amphoteric surfactant or the like is preferably used.

上述有機矽系界面活性劑，例如，作為市售品，有道康寧東麗有機矽公司的DC3PA、DC7PA、SH11PA、SH21PA和SH8400等，GE東芝有機矽公司的TSF-4440、TSF-4300、TSF-4445、TSF-4446、TSF-4460和TSF-4452等。 The above organic lanthanide surfactants are, for example, commercially available products, such as DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 of Dow Corning Toray Organic Co., Ltd., and TSF-4440, TSF-4300, and TSF of GE Toshiba Organic Corporation. 4445, TSF-4446, TSF-4460, and TSF-4452.

上述氟系界面活性劑，例如，作為市售品，有大日本油墨化學工業公司的F-470、F-471、F-475、F-482和F-489等。 The fluorine-based surfactant is, for example, a commercially available product, and is manufactured by Dainippon Ink Chemical Industry Co., Ltd. F-470, F-471, F-475, F-482 and F-489.

另外，作為其他可使用的市售品，可列舉出KP(信越化學工業(株))、(POLYFLOW)(共榮社化學(株))、(EFTOP)( 社)、(MEGAFAC)(大日本油墨化學工業(株))、(Flourad)(住友(株))、 (Asahi guard)、(Surflon)(以上為旭硝子(株))、(SOLSPERSE)(Lubrisol)、EFKA(EFKA公司)、PB821(味之素(株))、和Disperbyk系列(BYK-chemi)等。上述例示的界面活性劑可以各自單獨使用或者將2種以上組合使用。 In addition, as another commercially available product, KP (Shin-Etsu Chemical Co., Ltd.), (POLYFLOW) (Kyoeisha Chemical Co., Ltd.), (EFTOP)( Society), (MEGAFAC) (Japan Japan Ink Chemical Industry Co., Ltd.), (Flourad) (Sumitomo ()), (Asahi guard), (Surflon) (above is Asahi Glass Co., Ltd.), (SOLSPERSE) (Lubrisol), EFKA (EFKA Company), PB821 (Ajinomoto Co., Ltd.), and Disperbyk series (BYK-chemi). The above-exemplified surfactants may be used alone or in combination of two or more.

對上述密合促進劑的種類並無特別限定，作為可使用的密合促進劑的具體例，可列舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-異氰酸酯基丙基三甲氧基矽烷、和3-異氰酸酯基丙基三乙氧基矽烷等。 The type of the adhesion promoter is not particularly limited, and specific examples of the adhesion promoter that can be used include vinyl trimethoxy decane, vinyl triethoxy decane, and vinyl tris(2-methyl). Oxyethoxy) decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyl Trimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3 , 4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxy Basear, 3-mercaptopropyltrimethoxydecane, 3-isocyanatepropyltrimethoxydecane, and 3-isocyanatepropyltriethoxydecane.

上述例示的密合促進劑可以各自單獨使用或者將2種以上組合使用。相對於紅色感光性樹脂組合物中的固體成分總重量，通常以0.01~10重量%，優選以0.05~2重量%含有上述密合促進劑。 The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter is usually contained in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of the solid content in the red photosensitive resin composition.

對上述抗氧化劑的種類並無特別限定，可列舉出2,2’-硫代雙(4-甲基-6-叔-丁基苯酚)、2,6-二-叔-丁基-4-甲基苯酚等。 The type of the above antioxidant is not particularly limited, and examples thereof include 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-. Methyl phenol and the like.

對上述紫外線吸收劑的種類並無特別限定，作為可使用的具體例，可列舉出2-(3-叔-丁基-2-羥基-5-甲基苯基)-5-氯苯并***、烷氧基二苯甲酮等。 The type of the ultraviolet absorber is not particularly limited, and specific examples thereof include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriene Azole, alkoxybenzophenone, and the like.

對上述防凝聚劑的種類並無特別限定，作為可使用的具體例，可列舉出聚丙烯酸鈉等。 The type of the anti-agglomeration agent is not particularly limited, and specific examples of the usable agent include sodium polyacrylate.

本發明的紅色感光性樹脂組合物的製造方法如下所述。 The method for producing the red photosensitive resin composition of the present invention is as follows.

首先，將上述紅色顏料(A)與溶劑(E)混合，使用珠磨機等進行分散直至顏料的平均粒徑成為0.2μm以下左右。此時，根據需要，可以使顏料分散劑(a1)、鹼可溶性樹脂(B)的一部分或全部與染料(a3)和溶劑(E)一起混合、溶解或分散。 First, the red pigment (A) and the solvent (E) are mixed and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, a part or all of the pigment dispersant (a1) and the alkali-soluble resin (B) may be mixed, dissolved or dispersed together with the dye (a3) and the solvent (E) as needed.

在上述混合的分散液中進一步添加染料的剩餘部分(a3)、鹼可溶性樹脂的剩餘部分(B)、光聚合性化合物(C)、光聚合引發劑(D)、和根據需要使用的添加劑(F)和溶劑(E)以致成為規定的濃度，能夠製造本發明涉及的紅色感光性樹脂組合物。 Further, the remaining portion (a3) of the dye, the remaining portion (B) of the alkali-soluble resin, the photopolymerizable compound (C), the photopolymerization initiator (D), and the additive used as needed are further added to the above-mentioned mixed dispersion liquid ( F) and the solvent (E) are at a predetermined concentration, and the red photosensitive resin composition of the present invention can be produced.

另外，本發明提供用紅色感光性樹脂組合物製造的紅色濾色器和具有其的顯示裝置。 Further, the present invention provides a red color filter manufactured using a red photosensitive resin composition and a display device having the same.

首先，將紅色感光性樹脂組合物在基板(通常為玻璃)或在先形成的紅色感光性樹脂組合物的固體成分構成的層上塗布後，進行加熱乾燥，從而將溶劑等揮發成分除去，得到平滑的塗膜。 First, the red photosensitive resin composition is applied onto a layer composed of a solid component of a substrate (usually glass) or a previously formed red photosensitive resin composition, and then dried by heating to remove volatile components such as a solvent. Smooth coating.

作為塗布方法，例如可以採用旋塗、流延塗布法、輥塗布法、狹縫和旋轉塗布、或狹縫塗布法等進行。塗布後加熱乾燥(預烘焙)，或者減壓乾燥後進行加熱，使溶劑等揮發成分揮發。其中，加熱溫度通常為70~200℃，優選為80~130℃。加熱乾燥後的塗膜厚度通常為1~8μm左右。對這樣得到的塗膜，經由用於形成目標圖案的掩模照射紫外線。此時，對曝光部全體均勻地照射平行光線，另外，為了進行掩模與基板的正確的對位，優選使用掩模對準器、步進器等裝置。如果照射紫外線，則進行照射了紫外線的部位的固化。 The coating method can be carried out, for example, by spin coating, cast coating, roll coating, slit and spin coating, or slit coating. After coating, it is dried by heating (prebaking), or dried under reduced pressure, and then heated to volatilize volatile components such as a solvent. Among them, the heating temperature is usually 70 to 200 ° C, preferably 80 to 130 ° C. The thickness of the coating film after heat drying is usually about 1 to 8 μm. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, the entire exposed portion is uniformly irradiated with parallel rays, and in order to perform accurate alignment of the mask and the substrate, it is preferable to use a device such as a mask aligner or a stepper. When ultraviolet rays are irradiated, curing of a portion irradiated with ultraviolet rays is performed.

作為上述紫外線，能夠使用g線(波長：436nm)、h線、i線(波長：365nm)等。紫外線的照射量根據需要適當地選擇，在本發明中對其沒有限定。通過使固化完成的塗膜與顯影液接觸，使非曝光部溶解，進行顯影，從而能夠得到具有目標的圖案形狀的間隔物。 As the ultraviolet rays, a g line (wavelength: 436 nm), an h line, an i line (wavelength: 365 nm), or the like can be used. The amount of irradiation of ultraviolet rays is appropriately selected as needed, and is not limited in the present invention. By bringing the cured coating film into contact with the developer, the non-exposed portion is dissolved and developed, and a spacer having a desired pattern shape can be obtained.

上述顯影方法，可以列舉液添加法、浸漬法、噴霧法等，並無特別限定。另外，顯影時可以使基板傾斜任意的角度。上述顯影液通常為含有鹼性化合物和界 面活性劑的水溶液。 The development method is not particularly limited, and examples thereof include a liquid addition method, a dipping method, and a spray method. In addition, the substrate can be tilted at an arbitrary angle during development. The above developer usually contains a basic compound and a boundary An aqueous solution of a surfactant.

上述鹼性化合物並不特別限定於無機或有機鹼性化合物。作為上述無機鹼性化合物，例如可列舉出氫氧化鈉、氫氧化鉀、磷酸氫二鈉、磷酸二氫鈉、磷酸氫二銨、磷酸二氫銨、磷酸二氫鉀、矽酸鈉、矽酸鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、硼酸鈉、硼酸鉀、和氨等。 The above basic compound is not particularly limited to an inorganic or organic basic compound. Examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, and citric acid. Potassium, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia.

另外，作為有機鹼性化合物，例如可列舉出四甲基氫氧化銨、2-羥基乙基三甲基氫氧化銨、一甲胺、二甲胺、三甲胺、一乙胺、二乙胺、三乙胺、一異丙胺、二異丙胺、和乙醇胺等。 Further, examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, and diethylamine. Triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine.

上述無機或有機鹼性化合物可以各自單獨使用或者將2種以上混合使用。上述顯影液中的鹼性化合物的濃度，相對於顯影液的總重量，為0.01~10重量%，優選為0.03~5重量%。 These inorganic or organic basic compounds may be used alone or in combination of two or more. The concentration of the basic compound in the developer is from 0.01 to 10% by weight, preferably from 0.03 to 5% by weight, based on the total weight of the developer.

上述顯影液中的界面活性劑能夠使用選自上述的非離子系界面活性劑、陰離子系界面活性劑、和陽離子系界面活性劑中的1種以上。上述顯影液中的界面活性劑的濃度，相對於顯影液的總重量，含有0.01~10重量%，優選含有0.05~8重量%，更優選含有0.1~5重量%。顯影後，進行水洗，根據需要可以在150~230℃下實施10~60分鐘的後烘焙。 One or more types selected from the above-mentioned nonionic surfactants, anionic surfactants, and cationic surfactants can be used as the surfactant in the developer. The concentration of the surfactant in the developer is 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 5% by weight based on the total weight of the developer. After development, it is washed with water, and may be subjected to post-baking at 150 to 230 ° C for 10 to 60 minutes as needed.

使用本發明的紅色感光性樹脂組合物，經過上述這樣的各工序，能夠在基板上形成特定的圖案。 By using the red photosensitive resin composition of the present invention, a specific pattern can be formed on the substrate through the above-described respective steps.

以下為了具體地說明本發明，列舉實施例詳細地說明。但是，本發明涉及的實施例可以變形為各種不同的形態，不應解釋為將本發明的範圍限定於以下詳述的實施例。本發明的實施例是為了更為完全地說明本發明而提供給本領域中的普通技術人員。 Hereinafter, the present invention will be specifically described by way of specific examples. However, the embodiments of the present invention may be modified in various different forms and should not be construed as limiting the scope of the present invention to the embodiments described below. The embodiments of the present invention are provided to provide a more complete description of the present invention to those of ordinary skill in the art.

合成例1.鹼可溶性樹脂的製造 Synthesis Example 1. Production of alkali-soluble resin

在具有攪拌器、溫度計、回流冷凝管、滴液漏斗和氮導入管的燒瓶中，投入丙二醇單甲基醚乙酸酯120重量份、丙二醇單甲基醚80重量份、AIBN 2重量份、丙烯酸13重量份、甲基丙烯酸苄酯10重量份、苯乙烯57重量份、甲基丙烯酸甲酯20重量份、和正-十二烷基硫醇3重量份，進行氮置換。 In a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, and acrylic acid were placed. 13 parts by weight, 10 parts by weight of benzyl methacrylate, 57 parts by weight of styrene, 20 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecylmercaptan were replaced with nitrogen.

然後攪拌，使反應液的溫度上升到110℃，使其反應6小時。這樣合成的鹼可溶性樹脂的固體成分酸值為100.2mgKOH/g，通過GPC測定的重均分子量Mw為約15110。 Then, the temperature of the reaction liquid was raised to 110 ° C with stirring, and the reaction was allowed to proceed for 6 hours. The alkali-soluble resin thus synthesized had a solid content acid value of 100.2 mgKOH/g, and a weight average molecular weight Mw measured by GPC of about 15,110.

<紅色感光性樹脂組合物的製造> <Manufacture of Red Photosensitive Resin Composition> 實施例1~3、比較例1~6 Examples 1 to 3 and Comparative Examples 1 to 6

採用下述表1的組成製造實施例1~3和比較例1~6的紅色感光性樹脂組合物。 The red photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 6 were produced by using the compositions shown in Table 1 below.

A1：Irgaphor® Red S3620CF(BASF公司製造) A1: Irgaphor® Red S3620CF (manufactured by BASF)

A2：DISPERBYK-2001(BYK公司製造) A2: DISPERBYK-2001 (manufactured by BYK)

A3：酸性紅52 A3: Acid Red 52

A4：C.I.溶劑紅122 A4: C.I. Solvent Red 122

B：合成例1中製造的鹼可溶性樹脂 B: alkali-soluble resin produced in Synthesis Example 1.

C：KAYARAD DPHA(日本化藥製造) C: KAYARAD DPHA (Nippon Chemical Manufacturing)

D1：Irgacure®OXE02(BASF公司製造) D1: Irgacure® OXE02 (manufactured by BASF)

D2：Irgacure®369(BASF公司製造) D2: Irgacure® 369 (manufactured by BASF)

E1：4-羥基-4-甲基-2-戊酮 E1: 4-hydroxy-4-methyl-2-pentanone

E2：丙二醇單甲基醚乙酸酯 E2: propylene glycol monomethyl ether acetate

實驗例1.密合性評價 Experimental Example 1. Adhesion evaluation

採用旋塗法將上述實施例1~3和比較例1~6中製造的各個紅色感光性樹脂組合物塗布到2英寸見方的玻璃基板(康寧公司製造、“EAGLE XG”)上後，放置到加熱板上，在100℃的溫度下維持3分鐘，形成薄膜。 Each of the red photosensitive resin compositions produced in the above Examples 1 to 3 and Comparative Examples 1 to 6 was applied onto a 2 inch square glass substrate (manufactured by Corning Incorporated, "EAGLE XG") by a spin coating method, and then placed. The film was maintained on a hot plate at a temperature of 100 ° C for 3 minutes.

接下來，在上述薄膜上放置具有1μm~ 100μm的線/間隙圖案的試驗光掩模，使與試驗光掩模的間隔為300μm，照射紫外線。此時，紫外線光源使用包含g、h、i線的全部的1KW的高壓汞燈，以60mJ/cm2進行照射，沒有使用特別的光學濾波器。 Next, a test photomask having a line/gap pattern of 1 μm to 100 μm was placed on the film so that the distance from the test photomask was 300 μm, and ultraviolet rays were irradiated. At this time, the ultraviolet light source was irradiated at 60 mJ/cm 2 using all 1 KW high-pressure mercury lamps including g, h, and i lines, and no special optical filter was used.

將上述照射了紫外線的薄膜在pH 10.5的KOH水溶液顯影溶液中浸漬2分鐘而顯影。使用蒸餾水將塗布了上述薄膜的玻璃板清洗後，噴射氮氣而將其乾燥，用230℃的加熱烘箱加熱25分鐘，製造了紅色濾色器。 The above ultraviolet ray-irradiated film was immersed in a KOH aqueous solution developing solution of pH 10.5 for 2 minutes to develop. The glass plate coated with the above film was washed with distilled water, and then nitrogen gas was sprayed, dried, and heated in a heating oven at 230 ° C for 25 minutes to produce a red color filter.

上述製造的紅色濾色器的厚度為2.4μm。 The red color filter manufactured above had a thickness of 2.4 μm.

利用光學顯微鏡觀察上述紅色濾色器的圖案，根據下述評價標準對圖案上的缺損現象的程度進行評價，將結果示於下述表2中。 The pattern of the red color filter was observed with an optical microscope, and the degree of the defect on the pattern was evaluated according to the following evaluation criteria. The results are shown in Table 2 below.

<密合性的評價標準> <Evaluation criteria for adhesion>

○：沒有圖案上的缺損 ○: no defect on the pattern

△：圖案上的缺損為1~4個 △: The defect on the pattern is 1~4

×：圖案上的缺損為5個以上 ×: The defect on the pattern is 5 or more

實驗例2.透射率和對比度的測定 Experimental Example 2. Measurement of Transmittance and Contrast

除了沒有使用試驗光掩模，沒有形成圖案以外，與上述實驗例1同樣地實施，製造了沒有圖案的紅色濾色器。 A red color filter having no pattern was produced in the same manner as in Experimental Example 1 except that the test photomask was not used and no pattern was formed.

將上述製造的紅色濾色器夾持於2個偏光板之間，一邊從後側用螢光燈(波長380~780nm)照明，一邊使前面側偏光板旋轉，使用CS-2000亮度計(KONICA MINOLTA公司)測定透過的光強度的最大值和最小值。然 後，用最大值除以最小值，測定紅色濾色器的對比度。 The red color filter manufactured above was sandwiched between two polarizing plates, and the front side polarizing plate was rotated while being illuminated by a fluorescent lamp (wavelength: 380 to 780 nm) from the rear side, and a CS-2000 luminance meter (KONICA) was used. MINOLTA, Inc.) measures the maximum and minimum values of transmitted light intensity. Of course After that, the maximum value is divided by the minimum value to determine the contrast of the red color filter.

另外，使用色度計(奧林巴斯公司製造、OSP-200)測定透射率，將對比度和透射率的測定值示於下述表2中。 In addition, the transmittance was measured using a colorimeter (manufactured by Olympus Corporation, OSP-200), and the measured values of contrast and transmittance were shown in Table 2 below.

由上述表2的結果可知，作為本發明的紅色感光性樹脂組合物的實施例1~3的透射率、對比度和密合性均優異。 As a result of the above-mentioned Table 2, it is understood that Examples 1 to 3 which are red photosensitive resin compositions of the present invention are excellent in transmittance, contrast, and adhesion.

相反，沒有使用染料的比較例1的紅色感光性樹脂組合物顯示出對比度不良、密合性不良的結果。 On the contrary, the red photosensitive resin composition of Comparative Example 1 which did not use a dye showed poor contrast and poor adhesion.

另外，沒有使用顏料的比較例2~4的紅色感光性樹脂組合物顯示出如下結果：只在比較例2中由於染料的析出，對比度和透射率不良，比較例3和4的對比度優異。但是，在比較例2~4中，由於染料引起的密合性的降低，密合性顯示出一般或不良的結果。 Further, the red photosensitive resin compositions of Comparative Examples 2 to 4 in which no pigment was used showed the following results: In Comparative Example 2, the contrast and the transmittance were poor due to the precipitation of the dye, and the contrast ratios of Comparative Examples 3 and 4 were excellent. However, in Comparative Examples 2 to 4, the adhesion was lowered by the dye, and the adhesion showed a general or poor result.

沒有使用染料和肟酯系化合物作為光聚合 引發劑的比較例5的紅色感光性樹脂組合物顯示出密合性不良的結果，沒有使用肟酯系化合物作為光聚合引發劑的比較例6的紅色感光性樹脂組合物顯示出對比度和密合性不良的結果。 No dyes and oxime esters are used as photopolymerization The red photosensitive resin composition of Comparative Example 5 of the initiator showed poor adhesion, and the red photosensitive resin composition of Comparative Example 6 which did not use an oxime ester-based compound as a photopolymerization initiator exhibited contrast and adhesion. Poor sexual outcome.

因此，本發明的紅色感光性樹脂組合物產生如下效果：能夠顯示出高的對比度，不存在染料引起的感度降低，在顯影工序時不發生圖案的剝離，密合性極優。 Therefore, the red photosensitive resin composition of the present invention has an effect of exhibiting high contrast, no deterioration in sensitivity due to dye, and no peeling of the pattern during the development step, and the adhesion is excellent.

Claims (10)

一種紅色感光性樹脂組合物，其為包含紅色著色劑、鹼可溶性樹脂、光聚合性化合物、光聚合引發劑和溶劑的紅色感光性樹脂組合物，其特徵在於，所述紅色著色劑包含顏料和染料，所述顏料包含溴化二酮基吡咯并吡咯，所述染料包含選自下述化學式1的占噸(xanthene)系染料和偶氮系染料中的1種以上，所述光聚合引發劑包含肟酯系化合物： 所述R1~R6各自獨立地為氫、碳數1~5的烷基、或碳數1~5的三烷氧基甲矽烷基烷基，所述R7和R8各自獨立地為氫、COOH、COO-、SO3 -、SO3H、COONa、SO3Na、COOCH3、或COOCH2CH3。 A red photosensitive resin composition which is a red photosensitive resin composition containing a red coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the red coloring agent contains a pigment and a dye comprising a brominated diketopyrrolopyrrole, the dye comprising one or more selected from the group consisting of a xanthene dye and an azo dye of the following Chemical Formula 1, the photopolymerization initiator Contains oxime ester compounds: Each of R 1 to R 6 is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a trialkoxycarboxalkylalkyl group having 1 to 5 carbon atoms, and each of R 7 and R 8 is independently Hydrogen, COOH, COO - , SO 3 - , SO 3 H, COONa, SO 3 Na, COOCH 3 , or COOCH 2 CH 3 . 如請求項1之紅色感光性樹脂組合物，其中，相對於紅色著色劑的總重量，包含5~95重量%的所述溴化二酮基吡咯并吡咯顏料、和5~95重量%的選自所述化學式1的占噸系染料和偶氮系染料中的1種以上的染料。 The red photosensitive resin composition of claim 1, which comprises 5 to 95% by weight of the brominated diketopyrrolopyrrole pigment, and 5 to 95% by weight, based on the total weight of the red colorant. One or more dyes of the ton dye and the azo dye of Chemical Formula 1. 如請求項2之紅色感光性樹脂組合物，其中，相對於紅色著色劑的總重量，包含5~95重量%的所述溴化二酮基吡咯并吡咯顏料、3~50重量%的所述化學式1的占噸系染料、和2~45重量%的偶氮系染料。 The red photosensitive resin composition of claim 2, wherein the brominated diketopyrrolopyrrole pigment is contained in an amount of 5 to 95% by weight based on the total weight of the red colorant, and 3 to 50% by weight of the The ton dye of Chemical Formula 1 and the azo dye of 2 to 45% by weight. 如請求項1之紅色感光性樹脂組合物，其特徵在於，相對於紅色感光性樹脂組合物中的固體成分總重量，包含紅色著色劑5~60重量%、鹼可溶性樹脂10~80重量%、光聚合性化合物5~45重量%、和光聚合引發劑0.1~40重量%，相對於所述紅色感光性樹脂組合物的總重量，包含溶劑60~90重量%。 The red photosensitive resin composition of claim 1, which comprises 5 to 60% by weight of a red coloring agent and 10 to 80% by weight of an alkali-soluble resin, based on the total weight of the solid content of the red photosensitive resin composition. The photopolymerizable compound is 5 to 45% by weight, and the photopolymerization initiator is 0.1 to 40% by weight, and the solvent is contained in an amount of 60 to 90% by weight based on the total weight of the red photosensitive resin composition. 如請求項1之紅色感光性樹脂組合物，其特徵在於，肟酯系化合物包含選自1,2-辛二酮、1-[4-(苯硫基)苯基]-，2-(O-苯甲醯基肟)、和1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮1-(O-乙醯基肟)中的1種以上。 The red photosensitive resin composition of claim 1, wherein the oxime ester compound comprises a compound selected from the group consisting of 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O) -benzimidoxime), and 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone 1-(O-ethylindenyl) One or more of them. 如請求項1之紅色感光性樹脂組合物，其特徵在於，相對於光聚合引發劑的總重量，包含10~100重量%的所述肟酯系化合物。 The red photosensitive resin composition of claim 1, which comprises 10 to 100% by weight of the oxime ester compound based on the total weight of the photopolymerization initiator. 如請求項1之紅色感光性樹脂組合物，其特徵在於，所述溶劑包含選自丙二醇單甲基醚乙酸酯和4-羥基-4-甲基-2-戊酮中的1種以上。 The red photosensitive resin composition of claim 1, wherein the solvent contains one or more selected from the group consisting of propylene glycol monomethyl ether acetate and 4-hydroxy-4-methyl-2-pentanone. 如請求項7之紅色感光性樹脂組合物，其特徵在於，相對於溶劑的總重量，包含丙二醇單甲基醚乙酸酯15~80重量%和4-羥基-4-甲基-2-戊酮20~85重量 %。 The red photosensitive resin composition of claim 7, which comprises propylene glycol monomethyl ether acetate in an amount of 15 to 80% by weight and 4-hydroxy-4-methyl-2-pentane based on the total weight of the solvent. Ketone 20~85 weight %. 一種紅色濾色器，其係使用如請求項1至8中任一項之紅色感光性樹脂組合物而製造。 A red color filter manufactured by using the red photosensitive resin composition according to any one of claims 1 to 8. 一種顯示裝置，其包含如請求項9之紅色濾色器。 A display device comprising a red color filter as in claim 9.
TW105131319A 2016-01-15 2016-09-29 Colored photosensitive resin composition for red pixel, color filter using thereof and display device having the same TWI612382B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
??10-2016-0005108 2016-01-15
KR1020160005108A KR20170085687A (en) 2016-01-15 2016-01-15 Colored photosensitive resin composition for red pixel

Publications (2)

Publication Number Publication Date
TW201727363A true TW201727363A (en) 2017-08-01
TWI612382B TWI612382B (en) 2018-01-21

Family

ID=59340356

Family Applications (1)

Application Number Title Priority Date Filing Date
TW105131319A TWI612382B (en) 2016-01-15 2016-09-29 Colored photosensitive resin composition for red pixel, color filter using thereof and display device having the same

Country Status (4)

Country Link
JP (1) JP2017126058A (en)
KR (1) KR20170085687A (en)
CN (1) CN106980231A (en)
TW (1) TWI612382B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI766152B (en) * 2018-03-19 2022-06-01 南韓商東友精細化工有限公司 Colored curable resin composition, color filter, and display device

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102456397B1 (en) * 2018-03-08 2022-10-19 동우 화인켐 주식회사 Red colored photosensitive resin composition and color filter comprising the same
KR102558491B1 (en) * 2019-03-12 2023-07-21 동우 화인켐 주식회사 A blue color photosensitive resin composition for organic light emitting diodes, a color filter and an image display device comprising the same
JP7497998B2 (en) 2019-03-25 2024-06-11 住友化学株式会社 Colored curable resin composition, color filter and solid-state imaging device
KR102596395B1 (en) * 2019-03-26 2023-10-31 동우 화인켐 주식회사 Colored photosensitive resin composition, color filter and image display device produced using the same
KR102539091B1 (en) * 2019-03-27 2023-06-01 동우 화인켐 주식회사 Red colored photosensitive resin composition and color filter comprising the same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102105622B1 (en) * 2011-06-09 2020-04-29 스미또모 가가꾸 가부시키가이샤 Colored composition
JP2014149506A (en) * 2013-02-04 2014-08-21 Toyo Ink Sc Holdings Co Ltd Red coloring composition for color filter, and color filter
JP6194671B2 (en) * 2013-06-12 2017-09-13 東洋インキＳｃホールディングス株式会社 Coloring composition for color filter and color filter
TWI644174B (en) * 2013-07-16 2018-12-11 南韓商東友精細化工有限公司 Colored curable resin composition
JP6251208B2 (en) * 2014-04-02 2017-12-20 富士フイルム株式会社 Coloring composition, cured film, color filter, method for producing color filter, solid-state imaging device, and liquid crystal display device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI766152B (en) * 2018-03-19 2022-06-01 南韓商東友精細化工有限公司 Colored curable resin composition, color filter, and display device

Also Published As

Publication number Publication date
TWI612382B (en) 2018-01-21
JP2017126058A (en) 2017-07-20
CN106980231A (en) 2017-07-25
KR20170085687A (en) 2017-07-25

Similar Documents

Publication Publication Date Title
TWI719016B (en) Colored photosensitive resin composition, color filter, and image display apparatus comprising the same
TWI579271B (en) A color photosensitive resin composition, color filter and display device comprising the same
TWI612382B (en) Colored photosensitive resin composition for red pixel, color filter using thereof and display device having the same
TWI675254B (en) Blue photosensitive resin composition, blue color filter and display device having the same
TW201531513A (en) Color photosensitive resin composition, color filter and display device comprising the same
TW201727371A (en) Colored photosensitive resin composition, color filter and image display device produced using the same including an alkali soluble resin, a photopolymerizable compound, and a photopolymerization initiator
JP6625511B2 (en) Colored photosensitive resin composition, color filter and display device including the same
TW201723638A (en) Colored photosensitive resin composition, color filter, and image display device comprising same in which the colored photosensitive resin composition comprises a colorant, alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent
KR102335628B1 (en) Colored photosensitive resin composition, color filter and image display device produced using the same
TWI672560B (en) A blue photosensitive resin composition, blue color filter and display device comprising the same
CN111752103B (en) Red photosensitive resin composition and color filter comprising same
TW201504756A (en) A colored photosensitive resin composition, color filter and display device comprising the same
TWI724045B (en) A blue photosensitive resin composition, blue color filter and display device comprising the same
KR102012523B1 (en) Colored photosensitive resin composition, color filter and liquid crystal display having the same
KR102319892B1 (en) Colored photosensitive resin composition, color filter and image display device using the same
CN104914669B (en) Blue photosensitive resin composition, blue filter and display device having the same
KR102179956B1 (en) Colored photosensitive resin composition, color filter, and liquid crystal display device apparatus comprising the same
CN110244512B (en) Red photosensitive resin composition and color filter comprising same
KR102456390B1 (en) Colored photo sensitive resin composition, a color filter comprising the same, and a display devide comprising the color filter
KR102195690B1 (en) Photosensitive resin comopsition, photocurable pattern formed from the same and image display comprising the pattern
TW201537291A (en) Photosensitive resin composition, color filter with high color reproducing and liquid crystal display device using the same
KR102206495B1 (en) A colored photosensitive resin comopsition
KR102222403B1 (en) Colored photosensitive resin composition for green pixel
TWI705077B (en) Colored photosensitive resin composition, color filter and image display device produced using the same
TW201626107A (en) Colored photosensitive resin composition, color filter and image display device