TW201245876A - Photosensitive resin composition, color filter using the same and display device - Google Patents

Photosensitive resin composition, color filter using the same and display device Download PDF

Info

Publication number
TW201245876A
TW201245876A TW101104726A TW101104726A TW201245876A TW 201245876 A TW201245876 A TW 201245876A TW 101104726 A TW101104726 A TW 101104726A TW 101104726 A TW101104726 A TW 101104726A TW 201245876 A TW201245876 A TW 201245876A
Authority
TW
Taiwan
Prior art keywords
resin composition
photosensitive resin
group
meth
photopolymerization initiator
Prior art date
Application number
TW101104726A
Other languages
Chinese (zh)
Other versions
TWI536104B (en
Inventor
Naoto Yamaguchi
Dai Shiota
Yoshinori Tadokoro
Original Assignee
Tokyo Ohka Kogyo Co Ltd
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 Tokyo Ohka Kogyo Co Ltd filed Critical Tokyo Ohka Kogyo Co Ltd
Publication of TW201245876A publication Critical patent/TW201245876A/en
Application granted granted Critical
Publication of TWI536104B publication Critical patent/TWI536104B/en

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

This invention provides a photosensitive resin composition which has good sensitivity, a color filter using the same and a display device. Even the photosensitive resin composition contains opacifier or under condition of insufficient exposure, the photosensitive resin composition can still suppress the generation of undercut in patterns after development. The photosensitive resin composition of this invention contains (A) photopolymerizable compound and (B) oxime series photopolymerization initiator represented by the following general formula (1), and further contains (C) photopolymerization initiator with components different from the aforementioned (B).

Description

201245876 六、發明說明： 【發明所屬之技術領域】 本發明係關於感光性樹脂組成物，以及使用其之彩色 濾光片及顯示裝置。 【先前技術】 液晶顯示器等顯示裝置爲在形成相互對向相對之電極 之兩片基板之間夾持液晶層之構造。而且，於其一方之基 板之內側形成有由紅色（R )、綠色（G )、藍色（B )等 各色之像素區域所組成之彩色濾光片。該彩色濾光片中， 通常以區分成紅色、綠色、藍色等之各像素區域之方式形 成黑色基質。 一般，彩色濾光片係以微影法製造。亦即，首先將黑 色感光性樹脂組成物塗佈於基板上，經乾燥後，予以曝光 、顯像，形成黑色基質。接著，以紅色、綠色、藍色等各 色之感光性樹脂組成物重複塗佈、乾燥、曝光及顯像’在 特定位置上形成各色之像素區域，製造彩色濾光片。 黑色基質係由含有遮光劑之感光性樹脂組成物製作而 成之圖型，藉由抑制自各像素區域之光漏’有助於獲得顯 示裝置中之對比性之提高或良好之顯色。且’如上述’於 彩色濾光片製作之最初階段形成之黑色基質亦擔負著形成 用以埋入隨後對各像素區域著色之感光性樹脂組成物之凹 部，並在特定位置形成各色像素區域之角色。 近年來，液晶顯示器之製造中已嘗試利用黑色基質而 -5- 201245876 改善遮光性，進一步提高液晶顯示器所顯示之圖像之對比 性。因此，必須在用以形成黑色基質之感光性樹脂組成物 中含大量遮光劑。然而，如此感光性樹脂組成物中含大量 遮光劑時，使塗佈於基板上之感光性樹脂組成物之膜曝光 後，用以使感光性樹脂組成物硬化之光難以到達膜之底部 ，會有隨著硬化性樹脂組成物之感度顯著下降而導致硬化 不良之虞》 感光性樹脂組成物係藉由使成爲其成分之一部份而含 有之光聚合起始劑曝光而產生自由基，該自由基使感光性 樹脂組成物中所含之聚合性化合物聚合而硬化。因此。感 光性樹脂組成物之感度已知隨著其中所含之光聚合起始劑 之種類而受到影啓。又，近年來，隨著液晶顯示器之生產 台數增大，彩色濾光片之生產量亦增大，就進一步提高生 產性之觀點而言，期望可在低曝光量下形成圖型之高感度 之感光性樹脂組成物。該種情況下，作爲可使感光性樹脂 組成物之感度變良好之光聚合起始劑，在專利文獻1及2 中提案有具有環烷基之肟酯化合物。專利文獻1及2中所 記載之實施例中具體揭示以下述化學式（a)及（b)(專 利文獻1 )，以及以下述化學式（c )及（d )(專利文獻 2 )表示之化合物。 201245876 【化1】201245876 VI. [Technical Field] The present invention relates to a photosensitive resin composition, and a color filter and a display device using the same. [Prior Art] A display device such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates which are opposed to each other. Further, a color filter composed of pixel regions of respective colors such as red (R), green (G), and blue (B) is formed on the inner side of one of the substrates. In the color filter, a black matrix is usually formed so as to be distinguished from each of pixel regions of red, green, blue, and the like. Generally, color filters are manufactured by lithography. Namely, first, a black photosensitive resin composition is applied onto a substrate, dried, and exposed and developed to form a black matrix. Then, the photosensitive resin composition of each of red, green, blue, and the like is repeatedly coated, dried, exposed, and developed. A pixel region of each color is formed at a specific position to produce a color filter. The black matrix is formed of a photosensitive resin composition containing a light-shielding agent, and the light leakage from each pixel region is suppressed to contribute to improvement in contrast in the display device or good color development. And the black matrix formed as described above in the initial stage of the color filter production is also responsible for forming a concave portion for embedding the photosensitive resin composition which is subsequently colored for each pixel region, and forming pixel regions of respective colors at specific positions. Character. In recent years, in the manufacture of liquid crystal displays, attempts have been made to improve the light-shielding property by using a black matrix, and the contrast of images displayed on the liquid crystal display is further improved. Therefore, it is necessary to contain a large amount of an opacifier in the photosensitive resin composition for forming a black matrix. However, when a large amount of the light-shielding agent is contained in the photosensitive resin composition, the film for applying the photosensitive resin composition coated on the substrate is exposed, and the light for curing the photosensitive resin composition hardly reaches the bottom of the film. There is a problem that the photosensitive resin composition is formed by exposing a photopolymerization initiator contained in a part of its constituents to cause radicalization as the sensitivity of the curable resin composition is remarkably lowered. The radical polymerizes and hardens the polymerizable compound contained in the photosensitive resin composition. therefore. The sensitivity of the photosensitive resin composition is known to be affected by the kind of photopolymerization initiator contained therein. Moreover, in recent years, as the number of productions of liquid crystal displays increases, the production amount of color filters also increases, and from the viewpoint of further improving productivity, it is desired to form a high sensitivity of patterns at a low exposure amount. A photosensitive resin composition. In this case, as a photopolymerization initiator which can improve the sensitivity of the photosensitive resin composition, Patent Documents 1 and 2 propose an oxime ester compound having a cycloalkyl group. The examples described in Patent Documents 1 and 2 specifically disclose the compounds represented by the following chemical formulae (a) and (b) (Patent Document 1) and the following chemical formulas (c) and (d) (Patent Document 2). 201245876 【化1】

[先前技術文獻] [專利文獻] [專利文獻1 ]中華人民共和國公開專利公報第 101565472 號 [專利文獻2]中華人民共和國公開專利公報第 101508744 號 【發明內容】 [發明欲解決之課題] 藉由使用以上述化學式（a)〜（d)表示之化合物作 爲光聚合起始劑，可製作高感度之感光性樹脂組成物。然 而，本發明人等發現使用該等化合物作爲光聚合起始劑形 成黑色基質時雖感度良好，但相反地於形成之黑色基質之 圖型形狀會產生如下問題。 通常，使用感光性樹脂組成物形成液晶顯示器用之彩 201245876 色濾光片之圖型時，如圖1 (a)所示，一般而言會成爲該 圖型之寬度方向剖面之剖面1愈接近底邊la寬度愈寬， 愈接近頂邊lb寬度愈狹窄之梯形形狀。此時，圖型之剖 面1與彩色濾光片基板（未圖示）間所成之角度Θ成爲銳 角。 然而，使用含有以上述化學式（a)〜（d)表示之化 合物作爲光聚合起始劑之感光性樹脂組成物來形成黑色基 質時，如圖1 (b)所示，會有顯像時隨著圖型底部之一部 份溶解，該圖型寬度方向之剖面圖之剖面2中之底邊2a 兩端產生底切21之情況。此時，圖型之剖面2與彩色濾 光片基板（未圖示）間所成之角度Θ爲鈍角。該角度Θ爲 鈍角時，於形成鄰接於黑色基質之紅色、綠色、藍色等之 各色像素區域時，會於底切21部分產生氣泡。亦即，形 成鄰接黑色基質之像素區域形成用之感光性樹脂組成物之 膜後，感光性樹脂組成物不會進入存在底切2 1之空間中 ，而在該空間中殘留氣泡。該種氣泡存在於彩色濾光片中 時，由於會大幅損及液晶顯示裝置之畫質而會有問題。該 問題在黑色基質之圖型形成時之顯像於稍過量之過度顯像 時尤其顯著發生。 本發明係鑑於上述情況而完成者，其目的係提供一種 具有良好感度，且即使在感光性樹脂組成物含遮光劑，或 曝光量不足之情況下，仍可抑制顯像後之圖型發生底切之 感光性樹脂組成物，以及使用其之彩色濾光片及顯示裝置 -8 - 201245876 [用以解決課題之手段] 本發明人等爲解決上述課題而積極檢討之結果，發現 藉由組合使用以下述通式（1)表示之肟酯化合物與其他 光聚合起始劑，可維持使用肟酯化合物之良好感度，且抑 制圖型之底切，因而完成本發明。 本發明之第一樣態爲一種感光性樹脂組成物，其含有 (A)光聚合性化合物，及（B)以下述通式（1)表示之 肟系光聚合起始劑，且進而含有（C)與前述（B)成分不 同之光聚合起始劑，[Prior Art Document] [Patent Document 1] [Patent Document 1] Chinese Patent Publication No. 101565472 [Patent Document 2] Chinese Patent Publication No. 101508744 [Disclosed] A highly sensitive photosensitive resin composition can be produced by using the compound represented by the above chemical formulas (a) to (d) as a photopolymerization initiator. However, the present inventors have found that although the sensitivity is good when a black matrix is formed using these compounds as a photopolymerization initiator, the pattern of the black matrix formed in the opposite manner causes the following problems. In general, when a photosensitive resin composition is used to form a pattern of a 201245876 color filter for a liquid crystal display, as shown in FIG. 1(a), generally, the closer the profile 1 of the width direction of the pattern is. The wider the width of the bottom edge la, the closer to the trapezoidal shape of the narrower width of the top edge lb. At this time, the angle Θ formed between the cross-section 1 of the pattern and the color filter substrate (not shown) becomes an acute angle. However, when a black matrix is formed using a photosensitive resin composition containing a compound represented by the above chemical formulas (a) to (d) as a photopolymerization initiator, as shown in Fig. 1 (b), there is a development time. One of the bottom portions of the pattern is dissolved, and the bottom edge 2a of the section 2 of the cross-sectional view in the width direction of the pattern produces an undercut 21 at both ends. At this time, the angle Θ between the cross section 2 of the pattern and the color filter substrate (not shown) is an obtuse angle. When the angle Θ is an obtuse angle, when a pixel region of each of red, green, blue, or the like adjacent to the black matrix is formed, bubbles are generated in the undercut portion 21. That is, after the film of the photosensitive resin composition for forming the pixel region adjacent to the black matrix is formed, the photosensitive resin composition does not enter the space where the undercut 2 1 exists, and bubbles remain in the space. When such a bubble is present in a color filter, there is a problem in that the image quality of the liquid crystal display device is greatly impaired. This problem occurs particularly when the pattern of the black matrix is formed with a slight excess of over-exposure. The present invention has been made in view of the above circumstances, and an object thereof is to provide a good sensitivity, and even when the photosensitive resin composition contains an opacifier, or the amount of exposure is insufficient, the pattern generation after development can be suppressed. A photosensitive resin composition, and a color filter and a display device using the same - 8 - 201245876 [Means for Solving the Problems] The present inventors have actively reviewed the results to solve the above problems and found that they are used in combination. The oxime ester compound represented by the following general formula (1) and other photopolymerization initiators can maintain the good sensitivity of the oxime ester compound and suppress the undercut of the pattern, and thus the present invention has been completed. The first aspect of the present invention is a photosensitive resin composition comprising (A) a photopolymerizable compound, and (B) an oxime-based photopolymerization initiator represented by the following formula (1), and further containing ( C) a photopolymerization initiator different from the above component (B),

(上述通式（1)中’ 1爲1~5之整數’ m爲0〜（1 + 3 )之整數，η爲1〜8之整數’ R1爲可具有取代基之碳數 1~11之烷基，或可具有取代基之芳基’ r2爲以下述通式 (2)〜（4)表示之取代基之任一種’ r3爲碳數1〜11之院 基、或芳基）， 201245876 【化3】(In the above formula (1), '1 is an integer of 1 to 5', m is an integer of 0 to (1 + 3), and η is an integer of 1 to 8', and R1 is a carbon number which may have a substituent, 1 to 11. The alkyl group or the aryl group which may have a substituent 'r2 is any one of the substituents represented by the following general formulae (2) to (4) 'r3 is a hospital group having a carbon number of 1 to 11, or an aryl group), 201245876 [化3]

(上述通式（2)及（3)中，R4爲可具有取代基之芳 基，R5爲氫原子、可具有取代基之碳數1〜1〇之烷基、或 芳基，上述通式（4)中，R6爲可具有取代基之芳基）。 且本發明之第二樣態爲使用上述感光性樹脂組成物形 成之彩色濾光片。 又本發明之第三樣態爲使用上述彩色濾光片之顯示裝 置。 [發明效果] 依據本發明，提供一種具有良好感度’且即使在感光 性樹脂組成物含遮光劑，或曝光量不足之情況，仍可抑制 顯像後之圖型出現底切之感光性樹脂組成物，以及使用該 等之彩色濾光片及顯示裝置。 【實施方式】 《感光性樹脂組成物》 本發明之感光性樹脂組成物至少含有（A )光聚合性 化合物，（B)肟系光聚合起始劑，及（C)與上述（B) -10- 201245876 成分不同之光聚合起始劑。以下，針對本發明之 脂組成物中含有之各成分加以詳細說明。 〈（A)光聚合性化合物〉 本發明之感光性樹脂組成物中所含有之（A 性化合物（以下亦稱爲「（A)成分」）並無特 可使用過去習知之光聚合性化合物。其中，較好 烯性不飽和基之樹脂或單體，更好爲組合該等者 合具有乙烯性不飽和基之樹脂與具有乙烯性不飽 體’可提高感光性樹脂組成物之硬化性，而使圖 易。 [具有乙烯性不飽和基之樹脂] 具有乙烯性不飽和基之樹脂列舉爲使（甲基 、富馬酸、馬來酸、富馬酸單甲酯、富馬酸單乙 基）丙烯酸2-羥基乙酯、乙二醇單甲醚（甲基） 、乙二醇單乙醚（甲基）丙烯酸酯、丙三醇（甲 酸酯、（甲基）丙烯醯胺、丙烯腈、甲基丙烯腈 )丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基） 丁酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙 、乙二醇二（甲基）丙烯酸酯、二乙二醇二（甲 酸酯、三乙二醇二（甲基）丙烯酸酯、四乙二醇 )丙烯酸酯、丁二醇二（甲基）丙烯酸酯、丙二 基）丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸 感光性樹 )光聚合 別限制， 爲具有乙 。藉由組 和基之單 型形成容 )丙烯酸 酯、（甲 丙烯酸酯 基）丙烯 、（甲基 丙烯酸異 烯酸苄酯 基）丙烯 二（甲基 醇二（甲 酯、四羥 -11 - 201245876 甲基丙烷四（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、二季戊四醇六（甲基）丙烯酸酯、1，6-己 二醇二（甲基）丙烯酸酯、cardo環氧二丙烯酸酯等聚合 而成之寡聚物類；使多元醇類與單元酸或多元酸縮合獲得 之聚酯預聚物再與（甲基）丙烯酸反應獲得之聚酯（甲基 )丙烯酸酯；使多元醇與帶有兩個異氰酸酯基之化合物反 應後，再與（甲基）丙烯酸反應獲得之聚胺基甲酸酯（甲 基）丙烯酸酯；使雙酚A型環氧樹脂、雙酚F型環氧樹脂 、雙酚S型環氧樹脂、酚或甲酚酚醛清漆型環氧樹脂、甲 階型環氧樹脂、三酚甲烷型環氧樹脂、聚碳酸聚縮水甘油 酯、多元醇聚縮水甘油酯、脂肪族或脂環式環氧樹脂、胺 環氧樹脂、二羥基苯型環氧樹脂等之環氧樹脂，與（甲基 )丙烯酸反應獲得之環氧（甲基）丙烯酸酯樹脂等。另外 ，可使用使環氧（甲基）丙烯酸酯樹脂與多元酸酐反應而 成之樹脂。又，本說明書中之「（甲基）丙烯酸」意指「 丙烯酸或甲基丙烯酸」。 另外，具有乙烯性不飽和基之樹脂可較好地使用藉由 使環氧化合物與含有不飽和基之羧酸化合物之反應物再與 多元酸酐反應而得之樹脂。 其中，較好爲以下述式（al)表示之化合物。以該式 (al)表示之化合物其本身由於光硬化性高故較佳。 -12- 201245876 【化4】(In the above formulae (2) and (3), R4 is an aryl group which may have a substituent, R5 is a hydrogen atom, an alkyl group having 1 to 1 ring of a carbon group which may have a substituent, or an aryl group, and the above formula In (4), R6 is an aryl group which may have a substituent). Further, the second aspect of the present invention is a color filter formed using the above photosensitive resin composition. Further, the third aspect of the present invention is a display device using the above color filter. [Effect of the Invention] According to the present invention, it is possible to provide a photosensitive resin composition which has a good sensitivity and which can suppress the undercut of the pattern after development even when the photosensitive resin composition contains an opacifier or the amount of exposure is insufficient. And the use of such color filters and display devices. [Embodiment] "Photosensitive resin composition" The photosensitive resin composition of the present invention contains at least (A) a photopolymerizable compound, (B) an anthracene photopolymerization initiator, and (C) and (B) above. 10- 201245876 Photopolymerization initiators with different compositions. Hereinafter, each component contained in the fat composition of the present invention will be described in detail. <(A) Photopolymerizable Compound> The (A compound (hereinafter also referred to as "(A) component)) contained in the photosensitive resin composition of the present invention is not particularly limited to a conventional photopolymerizable compound. Among them, a resin or a monomer having a preferred ethylenically unsaturated group, more preferably a combination of the resin having an ethylenically unsaturated group and having an ethylenic unsaturated group can improve the hardenability of the photosensitive resin composition. [Fig. [Resin having ethylenically unsaturated group] The resin having an ethylenically unsaturated group is exemplified as (methyl, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate) 2-hydroxyethyl acrylate, ethylene glycol monomethyl ether (methyl), ethylene glycol monoethyl ether (meth) acrylate, glycerol (formate, (meth) acrylamide, acrylonitrile , methacrylonitrile) methyl acrylate, ethyl (meth) acrylate, (meth) butyl acrylate, 2-ethylhexyl (meth) acrylate, (methyl) propyl, ethylene glycol di (methyl) Acrylate, diethylene glycol di(formate, triethylene glycol di(meth)acrylic acid) , tetraethylene glycol) acrylate, butanediol di(meth) acrylate, propylene diacrylate), trimethylolpropane tri (meth) acrylate photosensitive tree) photopolymerization is limited, with B . Acrylate, (methacrylate) propylene, (benzyl methacrylate) propylene (methyl alcohol bis(methyl ester, tetrahydroxy-11 - 201245876) formed by the group and the base type Methylpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1 An oligomer obtained by polymerizing 6-hexanediol di(meth)acrylate or cardo epoxy diacrylate; and a polyester prepolymer obtained by condensing a polyol with a unit acid or a polybasic acid A polyester (meth) acrylate obtained by reacting (meth)acrylic acid; a polyurethane obtained by reacting a polyhydric alcohol with a compound having two isocyanate groups, and then reacting with (meth)acrylic acid (A) Acrylate; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, trisphenol Methane type epoxy resin, poly carbon Epoxy resin such as polyglycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxybenzene type epoxy resin, etc., obtained by reacting with (meth)acrylic acid An oxygen (meth) acrylate resin, etc. Further, a resin obtained by reacting an epoxy (meth) acrylate resin with a polybasic acid anhydride can be used. Further, in the present specification, "(meth)acrylic acid" means "acrylic acid". Further, the resin having an ethylenically unsaturated group can be preferably a resin obtained by reacting an epoxy compound with a reaction product of an unsaturated group-containing carboxylic acid compound with a polybasic acid anhydride. It is preferably a compound represented by the following formula (al). The compound represented by the formula (al) itself is preferably high in photocurability. -12- 201245876 [Chemical 4]

HOOC 一 Y-CO-OHOOC-Y-CO-O

&lt;p〇OH Χ·0·(：0 十 C〇-〇_ COOH&lt;p〇OH Χ·0·(:0 ten C〇-〇_ COOH

_X 一 O-CO-Y—COOH (a1) 上述式（al)中，x表示以下述式（a2)表示之基。_X - O-CO-Y-COOH (a1) In the above formula (al), x represents a group represented by the following formula (a2).

【化5 I[Chemical 5 I

02) 上述式（a2)中，各獨立表示氫原子、碳數1〜6 之烴基、或鹵素原子，R2a各獨立表示氫原子或甲基，w 表示單鍵或以下述式（a3)表示之基。02) In the above formula (a2), each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R2a each independently represents a hydrogen atom or a methyl group, and w represents a single bond or is represented by the following formula (a3). base.

(a3) 又，上述式（al)中，Y表示由二羧酸酐去除酸酐基 (-C0-0-C0-)之殘基。二羧酸酐之例列舉爲馬來酸酐、 琥珀酸酐、衣康酸酐、苯二甲酸酐、四氫苯二甲酸酐、六 氫苯二甲酸酐、甲基橋-亞甲基四氫苯二甲酸酐、氯菌酸 ff ( chlorendic anhydride)、甲基四氫苯二甲酸酉干、戊二 酸酐等。 且，上述式（al)中，Z表示自四羧酸二酐去除兩個 -13- 201245876 酸酐基之殘基》四羧酸二酐之例列舉爲均苯四酸酐、二苯 甲酮四羧酸二酐、聯苯四羧酸二酐、聯苯醚四羧酸二酐等 0 又，上述式（al)中，m表示0〜20之整數。 具有乙烯性不飽和基之樹脂之酸價以樹脂固體成分計 ，較好爲 10〜150mgKOH/g，更好爲 70~110mgICOH/g。藉 由使酸價成爲10mgKOH/g以上，可獲得對顯像液足夠之 溶解性故較佳。且，藉由使酸價爲150mgKOH/g以下，可 獲得充分硬化性，可使表面性良好故較佳。 又，具有乙烯性不飽和基之樹脂之質量平均分子量較 好爲 1 000〜40000，更好爲 2000〜30000。藉由使質量平均 分子量爲1 000以上，可獲得良好之耐熱性、膜強度故而 較佳。且，藉由使質量平均分子量爲40000以下，可獲得 良好顯像性故而較佳。 [具有乙烯性不飽和基之單體] 具有乙烯性不飽和基之單體有單官能單體與多官能單 體。 單官能單體列舉爲（甲基）丙烯醯胺、羥甲基（甲基 )丙烯醯胺、甲氧基甲基（甲基）丙烯醯胺、乙氧基甲基 (甲基）丙烯醯胺、丙氧基甲基（甲基）丙烯醯胺、丁氧 基甲氧基甲基（甲基）丙烯醯胺、N-羥甲基（甲基）丙烯 醯胺、N-羥基甲基（甲基）丙烯醯胺、（甲基）丙烯酸、 富馬酸、馬來酸、馬來酸酐、衣康酸、衣康酸酐、檸康酸 -14- 201245876 、檸康酸酐、巴豆酸、2-丙烯醯胺-2-甲基丙烷磺酸、第三 丁基丙烯醯胺磺酸、（甲基）丙烯酸甲酯、（甲基）丙烯 酸乙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸2-乙基己 酯、（甲基)丙烯酸環己醋、（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2-羥基丁 酯、（甲基）丙烯酸2-苯氧基-2-羥基丙酯、2-(甲基） 丙烯醯氧基-2-羥基丙基苯二甲酸酯、甘油單（甲基）丙烯 酸酯、（甲基）丙烯酸四氫糠酯、二甲胺基（甲基）丙烯 酸酯、縮水甘油基（甲基）丙烯酸酯、（甲基）丙烯酸 2,2,2-三氟乙酯、（甲基）丙烯酸2,2，3,3-四氟丙酯、苯二 甲酸衍生物之半（甲基）丙烯酸酯等。該等單官能單體可 單獨使用，亦可組合兩種以上使用。 另一方面，多官能單體列舉爲乙二醇二（甲基）丙烯 酸酯、二乙二醇二（甲基）丙烯酸酯 '四乙二醇二（甲基 )丙烯酸酯、丙二醇二（甲基）丙烯酸酯、聚丙二醇二（ 甲基）丙烯酸酯、丁二醇二（甲基）丙烯酸酯、新戊二醇 二（甲基）丙烯酸酯、1,6-己二醇二（甲基）丙烯酸酯、 二經甲基丙院三（甲基）丙嫌酸醋、丙三醇二（甲基）丙 烯酸酯 '季戊四醇三丙烯酸酯、季戊四醇四丙烯酸醋、二 季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、季戊四醇 二（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、季 戊四醇四（甲基）丙烯酸酯、二季戊四醇五（甲基）丙稀 酸酯、二季戊四醇六（甲基）丙烯酸酯、2,2_雙（4_ (甲 基）丙烯氧基二乙氧基苯基）丙烷、2，2·雙（4-(甲基） -15- 201245876 丙烯氧基聚乙氧基苯基）丙烷、2-羥基- 3-(甲基）丙烯醯 氧基丙基（甲基）丙烯酸酯、乙二醇二縮水甘油基醚二（ 甲基）丙烯酸酯、二乙二醇二縮水甘油醚二（甲基）丙烯 酸酯、苯二甲酸二縮水甘油酯二（甲基）丙烯酸酯、丙三 醇三丙烯酸酯、丙三醇聚縮水甘油醚聚（甲基）丙烯酸酯 、胺基甲酸酯（甲基）丙烯酸酯（亦即，甲苯二異氰酸酯 )、三甲基六亞甲基二異氰酸酯與六亞甲基二異氰酸酯及 (甲基）丙烯酸2-羥基乙酯之反應物、亞甲基雙（甲基） 丙烯醯胺、（甲基）丙烯醯胺亞甲基醚、多元醇與N-羥 甲基（甲基）丙烯醯胺之縮合物等之多官能單體，或三丙 烯酸甲縮醛等。該等多官能單體可簞獨使用，亦可組合兩 種以上使用。 (Α)成分的光聚合性化合物之含量相對於感光性樹 脂組成物之固體成分之合計100質量份較好爲10-99.9質 量份。藉由使（Α)成分之含量相對於固體成分之合計 100質量份爲10質量份以上，可期待形成之圖型之足夠耐 熱性及耐藥品性。 〈（Β)肟系光聚合起始劑〉 本發明之感光性樹脂組成物中含有之（Β )肟系光聚 合起始劑（以下亦稱爲「（Β)成分」）爲以下述通式（1 )表示之化合物。如先前所述，肟系光聚合起始劑尤其在 如黑色基質形成用之感光性樹脂組成物之組成物含遮光劑 時雖亦具有良好之感度，但另一方面會有在形成之圖型中 -16- 201245876 產生底切之情況。本發明人發現尤其藉由組合使用下述通 式（1)之肟系光聚合起始劑與後述之（c)成分作爲感光 性樹脂組成物之光聚合起始劑，可對感光性樹脂組成物賦 予良好感度，同時可抑制形成之圖型中之底切’因而完成 本發明。(a3) Further, in the above formula (al), Y represents a residue obtained by removing an acid anhydride group (-C0-0-C0-) from a dicarboxylic acid anhydride. Examples of the dicarboxylic anhydride are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl bridge-methylenetetrahydrophthalic anhydride , chlorendic acid ff (chlorendic anhydride), methyl tetrahydrophthalic acid hydrazine, glutaric anhydride and the like. Further, in the above formula (al), Z represents a residue from which two-13-201245876 acid anhydride groups are removed from the tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride are pyromellitic anhydride and benzophenone tetracarboxylic acid. Oxalic anhydride, biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, etc. Further, in the above formula (al), m represents an integer of 0 to 20. The acid value of the resin having an ethylenically unsaturated group is preferably from 10 to 150 mgKOH/g, more preferably from 70 to 110 mg ICOH/g, based on the solid content of the resin. By setting the acid value to 10 mgKOH/g or more, it is preferable to obtain sufficient solubility for the developing liquid. Further, by setting the acid value to 150 mgKOH/g or less, sufficient hardenability can be obtained, and surface properties are good, which is preferable. Further, the resin having an ethylenically unsaturated group preferably has a mass average molecular weight of from 1,000 to 40,000, more preferably from 2,000 to 30,000. By setting the mass average molecular weight to 1,000 or more, good heat resistance and film strength can be obtained, which is preferable. Further, by setting the mass average molecular weight to 40000 or less, good development performance can be obtained, which is preferable. [Monomer having an ethylenically unsaturated group] The monomer having an ethylenically unsaturated group has a monofunctional monomer and a polyfunctional monomer. Monofunctional monomers are exemplified by (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide , propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (A Base) acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid-14-201245876, citraconic anhydride, crotonic acid, 2-propene Indole-2-methylpropanesulfonic acid, tert-butylacrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid 2-ethylhexyl ester, cyclohexanic acid (meth)acrylate, 2-hydroxyethyl (meth)acrylate 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( 2-phenoxy-2-hydroxypropyl methacrylate, 2-(methyl) propylene fluorenyl-2-hydroxypropyl phthalate, glycerol mono(meth) acrylate, (methyl) Propylene Tetrahydrofurfuryl ester, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, (meth) acrylate 2, 2,3,3-tetrafluoropropyl ester, a half (meth) acrylate of a phthalic acid derivative, or the like. These monofunctional monomers may be used singly or in combination of two or more. On the other hand, polyfunctional monomers are exemplified by ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate 'tetraethylene glycol di(meth)acrylate, propylene glycol di(methyl) Acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylic acid Ester, dimethicone, tris(methyl)propyl citrate, glycerol di(meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate Pentaerythritol di(meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2_bis(4_(meth)acryloxydiethoxyphenyl)propane, 2,2·bis(4-(methyl)-15- 201245876 propyleneoxypolyethoxyphenyl)propane 2-hydroxy-3-(meth)acryloxypropyl ( Acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylic acid Ester, glycerol triacrylate, glycerol polyglycidyl ether poly(meth) acrylate, urethane (meth) acrylate (ie, toluene diisocyanate), trimethyl hexamethylene Reaction of bis-isocyanate with hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylene bis(methyl) acrylamide, (meth) acrylamide, methylene ether, dimer A polyfunctional monomer such as a condensate of an alcohol and N-methylol (meth) acrylamide, or a methyl acetal or the like. These polyfunctional monomers may be used singly or in combination of two or more. The content of the photopolymerizable compound of the (Α) component is preferably from 10 to 99.9 parts by mass based on 100 parts by mass of the total of the solid components of the photosensitive resin composition. When the content of the (Α) component is 10 parts by mass or more based on 100 parts by mass of the total of the solid components, sufficient heat resistance and chemical resistance of the formed pattern can be expected. <(Β)肟-based photopolymerization initiator> The (Β)-based photopolymerization initiator (hereinafter also referred to as "(Β) component)) contained in the photosensitive resin composition of the present invention has the following general formula (1) A compound represented. As described above, the oxime-based photopolymerization initiator particularly has a good sensitivity even when the composition of the photosensitive resin composition for forming a black matrix contains an opacifier, but on the other hand, there is a pattern formed.中-16- 201245876 The situation of undercutting. The present inventors have found that a photosensitive polymerization resin can be used, in particular, by using a combination of an oxime-based photopolymerization initiator of the following formula (1) and a component (c) described later as a photopolymerization initiator of a photosensitive resin composition. The article imparts good sensitivity while inhibiting the undercut in the formed pattern' thus completing the present invention.

上述通式（1)中，1爲1〜5之整數，爪爲0~(1 + 3) 之整數，η爲1~8之整數，R1爲可具有取代基之碳數1~11 之烷基，或爲可具有取代基之芳基，R2·爲以下述通式（2 )〜（4)表示之取代基之任一種，R3爲碳數1〜11之烷基 、或芳基。R1爲烷基時可具有之取代基較佳之例示爲苯基 、萘基等。又，R1爲芳基時可具有之取代基較佳之例示爲 碳數1~5之烷基、烷氧基、鹵素原子等。 上述通式（1 )中，作爲R1較好例示爲甲基、乙基、 丙基、異丙基、丁基、苯基、苄基、甲基苯基、萘基等。 其中，更好爲甲基或苯基。又，上述通式（1)中，R3較 佳例示爲甲基、乙基、丙基、異丙基、丁基、苯基等。該 等中，更好爲甲基。 -17- 201245876 【化8】In the above formula (1), 1 is an integer of 1 to 5, the claw is an integer of 0 to (1 + 3), η is an integer of 1 to 8, and R1 is an alkyl group having 1 to 11 carbon atoms which may have a substituent The group may be an aryl group which may have a substituent, and R2· is any one of the substituents represented by the following formulas (2) to (4), and R3 is an alkyl group having 1 to 11 carbon atoms or an aryl group. The substituent which may be possessed when R1 is an alkyl group is preferably exemplified by a phenyl group, a naphthyl group or the like. Further, a substituent which may be contained when R1 is an aryl group is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom or the like. In the above formula (1), R1 is preferably exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a phenyl group, a benzyl group, a methylphenyl group or a naphthyl group. Among them, it is more preferably a methyl group or a phenyl group. Further, in the above formula (1), R3 is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a phenyl group. Among these, it is more preferably a methyl group. -17- 201245876 【化8】

ReRe

上述通式（2)及（3)中，R4爲可具有取代基之芳基 ，R5爲氫原子、可具有取代基之碳數1〜10之烷基、或芳 基。R4之芳基可具有之取代基較佳例示爲碳數1〜5之烷基 、碳數1〜5之烷氧基、鹵素原子等。又，R5爲烷基時可具 有之取代基較佳例示爲碳數.1〜5之烷氧基、苯基、萘基等 〇 上述通式（2 ) ·及（3 )中，作爲R4較佳例示爲苯基 、2-甲基苯基、3-甲基苯基、4-甲基苯基、2-乙基苯基、 3-乙基苯基、4-乙基苯基、2，3-二甲基苯基、2,4-二甲基苯 基、2,5-二甲基苯基、2,6-二甲基苯基、萘基、2-甲氧基_ 1-萘基、9-蒽基等。上述通式（2)及（3)中，R5較佳例 示爲氫原子、甲基、乙基、正丙基、異丙基、正丁基、異 丁基、第二丁基、第三丁基、正戊基、正己基、苯基、3· 甲基丁基、3 -甲氧基丁基等，該等中，更好爲乙基。 上述通式（4)中，R6爲可具有取代基之芳基。R6之 芳基可具有之取代基較佳例示爲碳數1〜5之烷基、碳數 1〜5之烷氧基、鹵素原子等》 該等R6較佳例示爲苯基、2-甲基苯基、3·甲基苯基、 -18- 201245876 4-甲基苯基、2-乙基苯基、3-乙基苯基、4-乙基苯基、2，3-二甲基苯基、2,4-二甲基苯基、2,5-二甲基苯基、2,6-二甲 基苯基、萘基、對-第三丁基苯基、對-甲氧基苯基等，該 等中，更好例示爲苯基。 更具體而言，可較好例示下述式之化合物作爲（B ) 肟系光聚合起始劑。 【化9 wch3In the above formulae (2) and (3), R4 is an aryl group which may have a substituent, and R5 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group. The substituent which the aryl group of R4 may have is preferably exemplified by an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom or the like. Further, the substituent which may be present when R5 is an alkyl group is preferably an alkoxy group having a carbon number of from 1 to 5, a phenyl group, a naphthyl group or the like, and the above formula (2) and (3) are used as R4. Preferred examples are phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2, 3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, naphthyl, 2-methoxy-1-naphthalene Base, 9-mercapto and the like. In the above formulae (2) and (3), R5 is preferably exemplified as a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group, and a third butyl group. A group, a n-pentyl group, a n-hexyl group, a phenyl group, a trimethyl butyl group, a 3-methoxy butyl group, etc., among these, an ethyl group is more preferable. In the above formula (4), R6 is an aryl group which may have a substituent. The substituent which the aryl group of R6 may have is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom or the like. These R6 are preferably exemplified as a phenyl group or a 2-methyl group. Phenyl, 3·methylphenyl, -18- 201245876 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-dimethylbenzene Base, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, naphthyl, p-tert-butylphenyl, p-methoxybenzene The base, etc., is more preferably exemplified as phenyl. More specifically, a compound of the following formula can be preferably exemplified as the (B) fluorene-based photopolymerization initiator. [化9 wch3

ch2ch3 1 丫 ch3Ch2ch3 1 丫 ch3

【化1 0】[化1 0]

19- 201245876 (B )成分的肟系光聚合起始劑之含量相對於感光性 樹脂組成物之固體成分之合計100質量份，較好爲0.1〜50 質量份’更好爲1~45質量份。藉由成爲上述範圍內，可 獲得足夠之耐熱性、耐藥品性，同時可提高塗膜形成能力 ，抑制光硬化不良。 〈（C)與上述（B)成分不同之光聚合起始劑〉 本發明之感光性樹脂組成物中含有之（C)光聚合起 始劑（以下亦稱爲「（C)成分」）爲與作爲上述（b)成 分使用之光聚合起始劑不同之光聚合起始劑。（C)成分 只要爲與上述（B)成分不同之化合物即可，且與上述（b )成分同樣，亦可爲聘系光聚合起始劑。 (C)成分只要是藉由紫外線或電子束等之活性能量 線之照射而產生自由基之化合物即無特別限制。該種光聚 合起始劑例不爲2 -节基-2-二甲胺基-1- ( 4_嗎啉基苯基） 丁酮-1、2 -甲基-1-[4-(甲硫基）苯基]_2 -嗎啉基两-1_酮、 2-苄基-2-二甲胺基-1- ( 4-二甲胺基苯基）丁酮_丨、2_ ( 4_ 甲基苄基）-2 -二乙胺基-1-( 4 -嗎啉基苯基）丁酮.丨、2_甲 基-1-苯基-2-嗎啉基丙-1-酮、2 -甲基- i_[4-(己基）苯基]_ 2 -嗎啉基丙-1-酮、2 -乙基-2-二甲胺基嗎啉基苯基 )丁酮-1等之α-胺基酮系光聚合起始劑；卜苯基·2_羥基· 2 -甲基丙-1-酮、1-(4-異丙基苯基）-2·羥基-2_甲基丙 酮、4- (2-羥基乙氧基）苯基-(2-羥基-2_丙基）酮、丨·經 基環己基本基酮等之α-經基酮系光聚合起始劑；苯偶因、 -20- 201245876 苯偶因甲基醚、苯偶因乙基醚、苯偶因丙基醚、苄基甲基 縮酮等苯偶因系光聚合起始劑；二苯甲酮、苯甲醯基苯甲 酸、本甲醯基苯甲酸甲酯、4-苯基二苯甲酮、羥基二苯甲 酮、丙烯酸化一苯甲酮、4·苯甲醯、4，_甲基二苯基硫醚、 4,4’-雙一乙胺基—苯甲酮等二苯甲酮系光聚合起始劑；噻 噸酮、2-氯噻噸酮、2-甲基噻噸酮、異丙基噻噸酮、2,4_ 二異丙基噻噸酮等噻噸酮系光聚合起始劑；2,4,6_三氯-s_ 二嗪、2 -本基-4,6 -雙（二氯甲基）_s•三嗪、2_ (對-甲氧 基本基）-4,6-雙（二氯甲基）-3_三嗪、2_(對-甲苯基）_ 4,6-雙（三氯甲基）-s-三嗪、2·胡椒基_4,6_雙（三氯甲基 )-s-二嗪、2,4 -雙（二氯甲基）_6_苯乙烯基_s·三嗪、2 ( 萘-1-基）-4,6-雙（二氯甲基）-3_三嗪、2_(4_甲氧基_萘_ 1-基）-4,6-雙（二氯甲基）_3_三嗪、2,4_三氯甲基_(胡椒 基）-6-二嗪、2,4-二氯甲基.（4，-甲氧基苯乙烯基）_6_三 嗪、2-[4-(4·甲氧基苯乙烯基）苯基]_4,6_雙（三氯甲基 )-1,3,5-一曉等—嚷系光聚合起始劑；咔· η坐系光聚合起始 劑；2,2’-雙（2-氯苯基）_4,4，，5,5，·肆（4_乙氧基羰基苯 基）-1，2’-聯咪唑、2,2’-雙（2_溴苯基）_4,4，，5,5，_肆（4_ 乙氧基戴基本基）_1，2，-聯味哗、2,2’ -雙（2 -氯苯基）-4,4 ,5,5 ·四本基-1,2 _聯味π坐、2,2’_雙（2,4 -二氯苯基） 4,4’，5,5’-四苯基-1,2’-聯咪唑、2,2’_雙（2,4,6_三氯苯基 )-4,4,5,5-四本基-1，2'-聯味哩、2,2' -雙（2 -漠苯基） 4,4’，5,5_ -四苯基-1，2·-聯咪唑、2,2，-雙（2,4 -二溴苯基） 4,4，，5,5，-四苯基-1，2，-聯咪唑、2,2__雙（2,4,6-三溴苯基） -21 - 201245876 4,4·，5,5·-四苯基-1，2’_聯咪唑等聯咪唑系光聚合起始劑； 2- ( 0 -苯甲醯基肟）·ΐ-[4-(苯硫基）苯基]_i，2_辛二醇、 1- ( 4 -甲基胺磺醯基苯基）丁烷_1、2 -丁烷-2-肟-0-乙酸酯 、1-(4 -甲基胺磺醯基苯基）丁烷-i-酮肟_〇_乙酸酯、羥 基亞胺基（4-甲基胺磺醯基苯基）乙酸乙酯-〇_乙酸酯、 羥基亞胺基（4 -甲基胺磺醯基苯基）乙酸乙酯-〇·苯甲酸 酯等肟系光聚合起始劑；以下式表示之苯并咪唑系光聚合 起始劑等。 【化1 1】19 to 201245876 The content of the oxime-based photopolymerization initiator of the component (B) is preferably 0.1 to 50 parts by mass, more preferably 1 to 45 parts by mass, based on 100 parts by mass of the total of the solid content of the photosensitive resin composition. . When it is within the above range, sufficient heat resistance and chemical resistance can be obtained, and the coating film forming ability can be improved to suppress photohardening failure. <(C) Photopolymerization initiator which is different from the component (B)> The (C) photopolymerization initiator (hereinafter also referred to as "(C) component)) contained in the photosensitive resin composition of the present invention is A photopolymerization initiator different from the photopolymerization initiator used as the component (b). (C) A component may be a compound different from the component (B), and may be a photopolymerization initiator similar to the component (b). The component (C) is not particularly limited as long as it is a compound which generates radicals by irradiation with an active energy ray such as ultraviolet rays or electron beams. The photopolymerization initiator is not 2-phenyl-2-methylamino-1-(4-morpholinylphenyl)butanone-1, 2-methyl-1-[4-(A Thio)phenyl]_2-morpholinyl 2--1-one, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl)butanone 丨, 2_ (4_A Benzyl)-2-diethylamino-1-(4-morpholinylphenyl)butanone. Anthracene, 2-methyl-1-phenyl-2-morpholinylpropan-1-one, 2 -Methyl-i_[4-(hexyl)phenyl]-2-ylmorpholinylpropan-1-one, 2-ethyl-2-dimethylaminomorpholinophenyl)butanone-1, etc. - aminoketone photopolymerization initiator; phenyl phenyl 2 - hydroxy-2-methyl propan-1-one, 1-(4-isopropylphenyl)-2 hydroxy-2-methylacetone , α-pyridyl ketone photopolymerization initiator, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, fluorene-cyclohexyl ketone ketone, etc.; benzene Occasion, -20- 201245876 Benzene methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl methyl ketal and other benzoin photopolymerization initiator; benzophenone, Benzyl benzoic acid, methyl methionine, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzoyl , benzophenone, 4,-methyldiphenyl sulfide, 4,4'-bis-ethylamino-benzophenone and other benzophenone photopolymerization initiator; thioxanthone, 2- Thiophenone photopolymerization initiator such as chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone; 2,4,6-trichloro- S_ diazine, 2-n-benzyl-4,6-bis(dichloromethyl)_s•triazine, 2_(p-methoxybenyl)-4,6-bis(dichloromethyl)-3_three Oxazine, 2_(p-tolyl)_ 4,6-bis(trichloromethyl)-s-triazine, 2·piperonyl-4,6-bis(trichloromethyl)-s-diazine, 2 ,4-bis(dichloromethyl)_6-styryl-s-triazine, 2 (naphthalen-1-yl)-4,6-bis(dichloromethyl)-3-triazine, 2_(4 _Methoxy-naphthalene-1-yl)-4,6-bis(dichloromethyl)_3_triazine, 2,4-trichloromethyl-(piperidinyl)-6-diazine, 2,4 -Dichloromethyl.(4,-methoxystyryl)_6_triazine, 2-[4-(4.methoxystyryl)phenyl]_4,6-bis(trichloromethyl) )-1,3,5-一晓等—嚷 photopolymerization initiator; 咔· η sitting photopolymerization initiator; 2,2′-bis(2-chlorophenyl)_4,4,,5 ,5,·肆(4_ethoxycarbonylbenzene) 1,1,2'-biimidazole, 2,2'-bis(2-bromophenyl)_4,4,5,5,_肆(4_ethoxydoradyl)_1,2,-linked Miso, 2,2'-bis(2-chlorophenyl)-4,4,5,5 ·tetrabenyl-1,2 _ _ π sitting, 2,2' _ double (2,4 - two Chlorophenyl) 4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4,5 , 5-tetrabenyl-1,2'-linked miso, 2,2'-bis(2-indolyl) 4,4',5,5--tetraphenyl-1,2--biimidazole, 2,2,-bis(2,4-dibromophenyl) 4,4,5,5,-tetraphenyl-1,2,-biimidazole, 2,2__bis (2,4,6- Tribromophenyl) -21 - 201245876 4,4·,5,5·-tetraphenyl-1,2'-biimidazole and other biimidazole photopolymerization initiator; 2-(0-benzhydrylhydrazine )·ΐ-[4-(phenylthio)phenyl]_i,2-octanediol, 1-(4-methylaminesulfonylphenyl)butane-1,2-butane-2-anthracene -0-acetate, 1-(4-methylaminosulfonylphenyl)butane-i-ketooxime-acetate, hydroxyimino (4-methylaminesulfonylphenyl) Ethyl acetate-〇-acetate, hydroxyimino(4-methylaminesulfonylphenyl)acetate-oxime-benzoic acid An anthracene photopolymerization initiator such as an ester; a benzimidazole photopolymerization initiator represented by the following formula. [1 1]

上述例示之光聚合起始劑中，可較好地使用α-胺基酮 系光聚合起始劑、二苯甲酮系光聚合起始劑、三嗪系光聚 合起始劑、咔唑系光聚合起始劑。又，上述光聚合起始劑 可單獨使用，亦可組合兩種以上使用。 (C)成分之含量相對於感光性樹脂組成物之固體成 分之合計100質量份，較好爲0.1〜50質量份，更好爲 1~4 5質量份。又，上述（Β)成分與（C)成分之比率以 質量比計較好爲（Β)成分/(C)成分=100/1〜1/100之範 圍’更好爲（Β)成分/ (C)成分=10/1〜1/1〇之範圍。藉 由使（Β)成分與（C)成分之比率在上述範圍內，可維持 感光性樹脂組成物之良好感度，同時可抑制由感光性樹脂 組成物所形成之圖型中之底切發生。 -22- 201245876 〈（D)著色劑〉 本發明之感光性樹脂組成物亦可進而含有（D ) 劑（以下亦稱爲「（ D )成分」）。感光性樹脂組成 由含有（D )成分的著色劑，可較好地使用作爲例如 顯示器之彩色濾光片形成用途。又’本發明之感光性 組成物藉由含遮光劑作爲（D)成分，可較好地使用 例如顯示裝置之彩色濾光片中之黑色基質形成用途。 本發明之感光性樹脂組成物中所含有之（D )成 無特別限制，但較好使用例如色彩指數（C.I.; Society of Dyers and Colourists 公司發行）中歸類爲 (pigment )之化合物，具體爲如下述之附加色彩指 C.I.)編號者。 C.I.顔料黃1(以下，同樣爲「C.I.顏料黃」，僅 編號）、3、11、12、13、14、15、16、17、20、24 、53、55、60、61、65、71、73、74、81、83、86、 95、97、98、99、100 &gt; ι〇ι、104、106、108、109、 、113、 114、 116、 117、 119、 120、 125、 126、 127、 、129、 137、 138、 139、 147、 148、 150、 151、 152、 、154、 155、 156、 166、 167、 168、 175、 180、 185; C . I ·顏料橙1 (以下，同樣爲「C . I.顏料橙」，僅 編號）、5、 13、 14、 16、 17、 24、 34、 36、 38、 4〇 、46、 49、 51、 55、 59、 61、 63、 64、 71、 73; C.I.顏料紫1(以下，同樣爲「C I顏料紫 著色 物藉 液晶 樹脂 作爲 分並 The 顏料 數（ 列出 、3 1 93、 1 10 128 153 列出 、43 ，僅列出 -23- 201245876 編號）、19、 23、 29、 30、 32、 36、 37、 38' 39' 40、 50 ， C.I.顏料紅1 (以下，同樣爲「C.I.顔料紅」，僅列出 編 號） 、2、3 、4、 5、6 、7、 8、 9、 10 ' 11' 12 、14 、15 16、 17、18 、19 、21、 22、 23 、30 ' 3 1、32 &gt; 37、 38 ' 40 、4 1 [' 42 ' 48:1 、48:2 、48 :3 &gt; 48: 4、 49:1' 49:2、 50:1 52:1 ' 53:1 &gt; 57 、57:1 、57 :2、 58: 2、 58:4、 60:1、 63:1 、 63:2 '64:1 '81: 1 ' 83 ' 88 、90:1 、 97 、101 102、 104 &gt; 105 、10 6、 108、 112、 113 ' 1 ] 14、 122 、123 、 144、 146 149 、150、 151、 155、 166 、168、 170 、171 、 172 ' 174 175 '176' 177 ' 178 ' 179 、180、 185 、187 、 188 ' 190 192 、193、 194、 202 ' 206 、207、 208 ' 209 、 215、 2 16 、 2 17 、220、 223、 224、 226 、227、 228 、240 、 242、 243 245 、254、 2 5 5、 264、 2 65 ； C. I.顏料藍1 ( :以下 ，同樣爲 「C .1.顏料藍 j ，僅 列出 編 號） 、2、1 5、1 5:3、1 5:4、 15 :6、 16、 22、 60 '64 ' 6 6 ， C. I.顏料綠7、 C · I.顏 料綠 36 ' C. I.顏 料綠 37 、 C. I.顏料棕23 ' C.I. 顏料 棕 25、 C.I .顏料; 踪 26、 C.I. 顏料棕28 ; C.I.顏料黑1、C.I.顔料黑7。 又，以成分（D )作爲遮光劑時，遮光劑較好使用黑 色顏料。作爲黑色顏料可列舉爲碳黑、鈦黑、銅、鐵、錳 、鈷、鉻、鎳、鋅、鈣、銀等金屬氧化物、複合氧化物、 -24- 201245876 金屬硫化物、金屬硫酸鹽或金屬碳酸鹽等，無論 、無機物之各種顏料。該等中，較好使用具有高 碳黑。藉由倂用上述（B)成分與（C)成分作爲 始劑，即使使用遮光性高之黑色顔料，亦可抑制 圖型出現底切之問題。 至於碳黑可使用槽黑（channel black )、爐 碳黑、燈黑等習知之碳黑，但較好使用遮光性優 &quot;又，亦可使用被覆樹脂之碳黑。 被覆樹脂之碳黑相較於未被覆樹脂之碳黑， 性較低，故使用作爲如液晶顯示器之液晶顯示元 基質時，電流洩漏較少，可製造信賴性高且電力 顯不器。 又，爲了調整碳黑之色調，亦可適當添加上 料作爲輔助顏料。 爲使上述（D)成分均勻分散於感光性樹脂 ，可進而使用分散劑。該種分散劑較好使用聚乙 、胺基甲酸酯樹脂系、丙烯酸樹脂系高分子分散 ，使用碳黑作爲（D)成分時，較好使用丙烯酸 分散劑作爲分散劑。 又，無機顔料與有機顏料可分別單獨使用或 以上，但倂用時，相對於無機顏料與有機顏料之 質量份，較好使用10〜80質量份範圍之有機顏料 用20〜40質量份之範圍。 感光性樹脂組成物中之著色劑之使用量只要 是有機物 遮光性之 光聚合起 顯像後之 黑、熱裂 異之槽黑 由於導電 件之黑色 消耗低之 述有機顏 組成物中 烯亞胺系 劑。尤其 樹脂系之 倂用兩種 總量1 〇 〇 ，更好使 依據感光 -25- 201245876 性樹脂組成物之用途適當決定即可，但其一例’爲相對於 感光性樹脂組成物之固體成分之合計100質量份1較好爲 5〜70質量份，更好爲25~60質量份。藉由在上述範圍內 ，可以目標圖型形成黑色基質或各著色層而較佳。 尤其，使用感光性樹脂組成物形成黑色基質時，較好 以使黑色基質之被膜每Ιμιη之OD値爲4以上之方式調整 感光性樹脂組成物中之遮光劑之量。黑色基質中被膜每 Ιμηι之OD値若爲4以上，則使用於液晶顯示器之黑色基 質中時，可獲得足夠之顯示對比性。 (D)成分較好使用分散劑以適當濃度分散成分散液 後，添加於感光性樹脂組成物中。 &lt;其他成分&gt; 本發明之感光性樹脂組成物中，可視需要添加各種添 加劑。具體例示爲溶劑、增感劑、硬化促進劑、光交聯劑 、光增感劑、分散助劑、塡充劑、密合促進劑、抗氧化劑 、紫外線吸收劑、抗凝聚劑、熱聚合抑制劑、消泡劑、界 面活性劑等。 本發明之感光性樹脂組成物中使用之溶劑列舉爲例如 乙二醇單甲醚、乙二醇單乙醚、乙二醇正丙醚、乙二醇單 正丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單 正丙醚、二乙二醇單正丁醚、三乙二醇單甲醚、三乙二醇 單乙醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單正丙醚 、丙二醇單正丁醚、二丙二醇單甲醚、二丙二醇單乙醚、 -26- 201245876 二丙二醇單正丙醚、二丙二醇單正丁醚、三丙二醇單甲醚 、三丙二醇單乙醚等之（聚）烷二醇單烷基醚類；乙二醇 單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二醇單甲醚乙 酸酯、二乙二醇單乙醚乙酸酯、丙二醇單甲醚乙酸酯、丙 二醇單乙醚乙酸酯等之（聚）烷二醇單烷基醚乙酸酯類； 二乙二醇二甲醚、二乙二醇甲基乙基醚、二乙二醇二乙醚 、四氫呋喃等之其他醚類；甲基乙基酮、環己酮、2-庚酮 、3-庚酮等酮類；2_羥基丙酸甲酯、2-羥基丙酸乙酯等之 乳酸烷酯類；2-羥基-2-甲基丙酸乙酯' 3-甲氧基丙酸甲酯 、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸 乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁 酸甲酯、乙酸3-甲基-3-甲氧基丁基酯、丙酸3-甲基-3-甲 氧基丁基酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸 正丁酯、乙酸異丁酯 '甲酸正戊酯、乙酸異戊酯、丙酸正 丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯 、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯基乙酸 甲酯、乙醯基乙酸乙酯、2-氧代丁酸乙酯等其他酯類；甲 苯、二甲苯等芳香族烴類；N-甲基吡咯烷酮、ν，Ν·二甲基 甲醯胺、Ν，Ν-二甲基乙醯胺等醯胺類等。該等溶劑可單獨 使用，亦可組合兩種以上使用&quot; 上述溶劑中’丙二醇單甲醚、乙二醇單甲醚乙酸酯、 丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、二乙二醇二 甲醚、二乙二醇甲基乙基醚、環己酮、乙酸3-甲氧基丁基 酯對於上述之（Α)成分、（Β)成分及（C)成分顯示優 -27- 201245876 異之溶解性，同時可使上述之（D)成分之分散性良好故 而較佳，最好使用丙二醇單甲醚乙酸酯、乙酸3-甲氧基丁 基酯。溶劑較好依據感光性樹脂組成物之用途適當決定， 其一例，列舉爲相對於感光性樹脂組成物之固體成分之合 計100質量份爲50〜900質量份左右。 本發明之感光性樹脂組成物中使用之熱聚合抑制劑可 列舉爲例如氫醌、氫醌單乙醚等。另外，消泡劑分別例示 爲矽氧系、氟系等化合物，界面活性劑例示爲陰離子系、 陽離子系、非離子系等之化合物》 《感光性樹脂組成物之調製方法》 本發明之感光性樹脂組成物可藉攪拌機混合上述各成 分全部而調製。又，亦可使用過濾器過濾使經調製之感光 性樹脂組成物成爲均勻者。 《圖型形成方法》 使用本發明之感光性樹脂組成物形成圖型首先係使用 輥塗佈器、逆轉塗佈器、棒塗佈器等接觸轉印型塗佈裝置 或旋轉塗佈器（旋轉式塗佈裝置）、簾流式塗佈器等非接 觸型塗佈裝置，將感光性樹脂組成物塗佈於基板上。 接著，使經塗佈之感光性樹脂組成物乾燥形成塗膜。 乾燥方法並無特別限制，列舉爲例如（1 )以加熱板在80〜 120 °C，較好90〜100 °C之溫度乾燥60〜120秒之方法，（2 )在室溫放置數小時至數天之方法，（3)在溫風加熱器 -28- 201245876 或紅外線加熱器中放置數十分鐘至數小時而去除溶劑之方 法等。 接著，透過負型光罩對該塗膜照射紫外線、準分子雷 射光等活性能量線予以部分曝光。照射之能量線之量係依 據感光性樹脂組成物之組成而不同，但較好爲例如30〜200 mJ/cm2 左右。 接著，以顯像液使曝光後之膜顯像，圖型化成期望形 狀。顯像方法並無特別限制，可使用例如浸漬法、噴霧法 等》顯像液列舉爲單乙醇胺、二乙醇胺、三乙醇胺等有機 系者，或氫氧化鈉、氫氧化鉀、碳酸鈉、氨、四級銨鹽等 水溶液。如先前說明，藉由使用本發明之感光性樹脂組成 物，顯像後形成之圖型中之底切受到抑制。因此，若使用 本發明之感光性樹脂組成物，則製作例如顯示裝置用之彩 色濾光片時，可抑制氣泡進入到各像素邊界部附近故較佳 〇 接著，較好在200°C~25 0°C左右對經顯像圖型進行後 烘烤。 如此形成之圖型可適當地使用作爲例如液晶顯示器等 之顯示裝置中之彩色濾光片之像素或黑色基質。該彩色濾 光片或使用該彩色濾光片之顯示裝置亦爲本發明之一。 [實施例] 以下例示實施例更具體說明本發明，但本發明之範圍 並不受限於該等實施例。 -29- 201245876 [感光性樹脂組成物之調製] [實施例1〜20，及比較例1〜15] 使用下述式B1〜B12之化合物作爲肟系光聚合起始劑 ，且使用下述式C1~C9之化合物作爲其他光聚合起始劑， 調製實施例1~20及比較例1〜15之感光性樹脂組成物。下 述式B1~B12之肟系光聚合起始劑中，式B1〜B8之化合物 相當於上述通式（1)之肟系光聚合起始劑。各實施例及 比較例之感光性樹脂組成物中之光聚合起始劑如表1〜3所 示》又，表1〜3中，「肟/其他之比」該項所示之比率表 示感光性樹脂組成物所含光聚合起始劑中，肟系之光聚合 起始劑與其他光聚合起始劑之質量比。 各感光性樹脂組成物之調製係在光聚合起始劑（肟系 及其他光聚合起始劑之合計）100質量份、下述樹脂A( 固體成分55質量％，溶劑乙酸3 -甲氧基丁酯）310質量 份、二季戊四醇六丙烯酸酯（DPHA，日本化藥股份有限 公司製造）175質量份、及碳黑分散液（碳黑含量20質 量％， 「CF Black」，御國色素股份有限公司製造）450 質量份之混合物中，以使固體成分成爲15質量％之方式添 加乙酸3-甲氧基丁基酯/環己酮/丙二醇單甲醚乙酸酯（ PGMEA ) =60/20/20 (重量比），且攪拌直至均勻而進行 〇 上述感光性樹脂之調製中使用之樹脂 A爲與特開 2〇1 0-3 2940號公報之段落006 3〜0064中記載之樹脂A-1相 -30- 201245876 同者。 【化1 2】Among the photopolymerization initiators exemplified above, an α-amino ketone photopolymerization initiator, a benzophenone photopolymerization initiator, a triazine photopolymerization initiator, and an oxazole system can be preferably used. Photopolymerization initiator. Further, the photopolymerization initiator may be used singly or in combination of two or more. The content of the component (C) is preferably from 0.1 to 50 parts by mass, more preferably from 1 to 45 parts by mass, per 100 parts by mass of the total solid content of the photosensitive resin composition. Further, the ratio of the above (Β) component to the component (C) is preferably in the range of (Β) component / (C) component = 100/1 to 1/100 by mass ratio, and more preferably (Β) component / (C) ) The range of the components = 10/1 to 1/1〇. By setting the ratio of the (Β) component to the component (C) within the above range, the sensitivity of the photosensitive resin composition can be maintained, and undercutting in the pattern formed by the photosensitive resin composition can be suppressed. -22-201245876 <(D) Colorant> The photosensitive resin composition of the present invention may further contain a (D) agent (hereinafter also referred to as "(D) component"). Photosensitive resin composition The coloring agent containing the component (D) can be preferably used as a color filter for display, for example. Further, the photosensitive composition of the present invention can be preferably used as a component (D) containing a light-shielding agent, for example, a black matrix in a color filter of a display device. The (D) contained in the photosensitive resin composition of the present invention is not particularly limited, but a compound which is classified as a pigment in a color index (CI; issued by Society of Dyers and Colourists) is preferably used, specifically The additional color as described below refers to the CI) number. CI Pigment Yellow 1 (hereinafter, also referred to as "CI Pigment Yellow", number only), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 53, 55, 60, 61, 65, 71 , 73, 74, 81, 83, 86, 95, 97, 98, 99, 100 &gt; ι〇ι, 104, 106, 108, 109, 113, 114, 116, 117, 119, 120, 125, 126 , 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 154, 155, 156, 166, 167, 168, 175, 180, 185; C. I · Pigment Orange 1 (below , also "C. I. Pigment Orange", only number), 5, 13, 14, 16, 17, 24, 34, 36, 38, 4, 46, 49, 51, 55, 59, 61, 63 , 64, 71, 73; CI Pigment Violet 1 (hereinafter, also the same as "CI Pigment Violet Colorant by Liquid Crystal Resin as the Part and The Pigment Number (listed, 3 1 93, 1 10 128 153 listed, 43, only listed -23- 201245876 No.), 19, 23, 29, 30, 32, 36, 37, 38' 39' 40, 50, CI Pigment Red 1 (hereinafter, also "CI Pigment Red", only the number is listed) , 2, 3, 4, 5, 6, 7, 8, 9, 10 ' 11' 12 , 14 , 15 16 , 17 , 18 , 19 , 21 , 22 , 23 , 30 ' 3 1 , 32 &gt; 37, 38 ' 40 , 4 1 [' 42 ' 48:1 48:2, 48:3 &gt; 48: 4, 49:1' 49:2, 50:1 52:1 '53:1 &gt; 57, 57:1, 57:2, 58: 2, 58: 4, 60:1, 63:1, 63:2 '64:1 '81: 1 '83 '88, 90:1, 97, 101 102, 104 &gt; 105, 10 6, 108, 112, 113 ' 1 14, 122, 123, 144, 146 149, 150, 151, 155, 166, 168, 170, 171, 172 ' 174 175 '176' 177 ' 178 ' 179 , 180 , 185 , 187 , 188 ' 190 192 , 193, 194, 202 '206, 207, 208' 209, 215, 2 16 , 2 17 , 220 , 223 , 224 , 226 , 227 , 228 , 240 , 242 , 243 245 , 254 , 2 5 5 , 264 , 2 65 ; CI Pigment Blue 1 (: The following is also the same as "C.1. Pigment Blue j, only the number is listed", 2, 1 5, 1 5:3, 1 5:4, 15:6, 16, 22, 60 '64 ' 6 6 , CI Pigment Green 7, C · I. Pigment Green 36 ' CI Pigment Green 37 , CI Pigment Brown 23 ' CI Pigment Brown 25 , CI . Pigment; 26, C.I. Pigment Brown 28; C.I. Pigment Black 1, C.I Pigment Black 7. Further, when the component (D) is used as the light-shielding agent, a black pigment is preferably used as the light-shieling agent. Examples of the black pigment include metal oxides such as carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, composite oxides, -24-201245876 metal sulfides, metal sulfates, or Metal carbonates, etc., regardless of the inorganic pigments. Among these, it is preferred to use a high carbon black. By using the above-mentioned components (B) and (C) as a starting agent, even if a black pigment having a high light-shielding property is used, the problem of undercutting of the pattern can be suppressed. As the carbon black, a conventional black carbon such as channel black, furnace carbon black or lamp black can be used, but it is preferable to use a light-shielding property. Further, a carbon black coated with a resin can also be used. Since the carbon black of the resin is less inferior to the carbon black which is not coated with the resin, when it is used as a liquid crystal display element substrate such as a liquid crystal display, current leakage is small, and a high reliability and power display can be manufactured. Further, in order to adjust the color tone of carbon black, it is also possible to appropriately add a binder as an auxiliary pigment. In order to uniformly disperse the component (D) in the photosensitive resin, a dispersant may be further used. When the dispersant is preferably a polyethylene, a urethane resin or an acrylic polymer, and a carbon black is used as the component (D), an acrylic dispersant is preferably used as the dispersant. Further, the inorganic pigment and the organic pigment may be used singly or in combination, and in the case of use, the amount of the organic pigment in the range of 10 to 80 parts by mass is preferably 20 to 40 parts by mass based on the mass part of the inorganic pigment and the organic pigment. . The amount of the coloring agent used in the photosensitive resin composition is as long as it is a blackening of the organic light-shielding light, and the blackening of the thermal cracking is caused by the low black consumption of the conductive member. Reagents. In particular, the resin is used in two total amounts of 1 〇〇, and it is preferable to appropriately determine the use according to the photosensitive resin composition of the photosensitive sensitizer, but an example thereof is a solid component with respect to the photosensitive resin composition. The total amount of 100 parts by mass 1 is preferably 5 to 70 parts by mass, more preferably 25 to 60 parts by mass. It is preferable to form a black matrix or a colored layer by a target pattern within the above range. In particular, when a black matrix is formed using the photosensitive resin composition, it is preferred to adjust the amount of the light-shielding agent in the photosensitive resin composition so that the OD値 of the coating of the black matrix is 4 or more. When the OD of the film in the black matrix is 4 or more per Ιμηι, when used in a black matrix of a liquid crystal display, sufficient display contrast can be obtained. The component (D) is preferably dispersed in a dispersion at a suitable concentration using a dispersant, and then added to the photosensitive resin composition. &lt;Other components&gt; In the photosensitive resin composition of the present invention, various additives may be added as needed. Specific examples are a solvent, a sensitizer, a hardening accelerator, a photocrosslinking agent, a photosensitizer, a dispersing aid, a chelating agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, and a thermal polymerization inhibition. Agent, defoamer, surfactant, and the like. The solvent used in the photosensitive resin composition of the present invention is exemplified by, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, -26- 201245876 dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (poly)alkylene glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether (poly)alkylene glycol monoalkyl ether acetates such as acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl Other ethers such as ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3 a ketone such as heptanone; an alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate 3-methoxypropionic acid Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3- Methyl methyl butyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate Ester, n-butyl acetate, isobutyl acetate 'n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate , other esters such as methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoxyacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, etc.; aromatics such as toluene and xylene Alkaloids; amides such as N-methylpyrrolidone, ν, dimethyl dimethyl carbamide, hydrazine, hydrazine-dimethylacetamide, and the like. These solvents may be used singly or in combination of two or more of the above solvents: 'propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, and 3-methoxybutyl acetate show excellent properties for the above (Α) component, (Β) component, and (C) component. -27- 201245876 It is preferable to use the propylene glycol monomethyl ether acetate or 3-methoxybutyl acetate in order to make the dispersibility of the above component (D) good. The solvent is preferably determined in accordance with the use of the photosensitive resin composition, and an example thereof is about 50 to 900 parts by mass based on 100 parts by mass of the total solid content of the photosensitive resin composition. The thermal polymerization inhibitor used in the photosensitive resin composition of the present invention may, for example, be hydroquinone or hydroquinone monoethyl ether. In addition, the antifoaming agent is exemplified by a compound such as an anthracene-based or a fluorine-based compound, and the surfactant is exemplified by an anionic, cationic, or nonionic compound. <<Method for Preparing Photosensitive Resin Composition>> Photosensitivity of the Invention The resin composition can be prepared by mixing all of the above components by a stirrer. Further, it is also possible to use a filter to filter the prepared photosensitive resin composition to be uniform. <<Forming Method of Forming Pattern>> The photosensitive resin composition forming pattern of the present invention is first formed by using a contact transfer type coating device or a spin coater such as a roll coater, a reverse coater, or a bar coater. A non-contact type coating device such as a coating device or a curtain flow applicator applies a photosensitive resin composition onto a substrate. Next, the applied photosensitive resin composition is dried to form a coating film. The drying method is not particularly limited, and is, for example, (1) drying at a temperature of 80 to 120 ° C, preferably 90 to 100 ° C for 60 to 120 seconds, and (2) leaving at room temperature for several hours until The method of several days, (3) the method of removing the solvent by placing the temperate heater -28-201245876 or the infrared heater for tens of minutes to several hours. Next, the coating film is partially exposed by irradiation with an active energy ray such as ultraviolet rays or excimer laser light through a negative mask. The amount of the energy ray to be irradiated varies depending on the composition of the photosensitive resin composition, but is preferably, for example, about 30 to 200 mJ/cm2. Next, the exposed film was developed with a developing liquid to form a desired shape. The development method is not particularly limited, and for example, a dip method, a spray method, or the like can be used. The developing solution is exemplified by an organic system such as monoethanolamine, diethanolamine or triethanolamine, or sodium hydroxide, potassium hydroxide, sodium carbonate or ammonia. An aqueous solution such as a quaternary ammonium salt. As described above, by using the photosensitive resin composition of the present invention, undercut in the pattern formed after development is suppressed. Therefore, when the photosensitive resin composition of the present invention is used, when a color filter for a display device is produced, for example, it is possible to suppress bubbles from entering the vicinity of the boundary portion of each pixel, which is preferable, preferably 200 ° C to 25 Post-baking of the developed image pattern at around 0 °C. The pattern thus formed can be suitably used as a pixel or a black matrix of a color filter in a display device such as a liquid crystal display. The color filter or the display device using the color filter is also one of the inventions. [Examples] The present invention will be more specifically described by the following examples, but the scope of the invention is not limited to the examples. -29-201245876 [Preparation of photosensitive resin composition] [Examples 1 to 20, and Comparative Examples 1 to 15] The compounds of the following formulas B1 to B12 were used as the oxime-based photopolymerization initiator, and the following formula was used. The compounds of C1 to C9 were used as other photopolymerization initiators, and the photosensitive resin compositions of Examples 1 to 20 and Comparative Examples 1 to 15 were prepared. In the oxime-based photopolymerization initiator of the above formulae B1 to B12, the compounds of the formulae B1 to B8 correspond to the oxime-based photopolymerization initiator of the above formula (1). The photopolymerization initiator in the photosensitive resin composition of each of the examples and the comparative examples is shown in Tables 1 to 3. Further, in Tables 1 to 3, the ratio of the ratio of "肟/other ratio" indicates photosensitive. In the photopolymerization initiator contained in the resin composition, the mass ratio of the lanthanide photopolymerization initiator to other photopolymerization initiators. The photosensitive resin composition is prepared by using 100 parts by mass of a photopolymerization initiator (total of a fluorene-based and other photopolymerization initiator), and the following resin A (solid content: 55 mass%, solvent acetic acid 3-methoxy group) Butyl ester) 310 parts by mass, dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) 175 parts by mass, and carbon black dispersion (carbon black content 20% by mass, "CF Black", limited by Royal Chinese Co., Ltd. In a mixture of 450 parts by mass, 3-methoxybutyl acetate/cyclohexanone/propylene glycol monomethyl ether acetate (PGMEA) = 60/20/ was added in such a manner that the solid content became 15% by mass. 20 (weight ratio), and the mixture is stirred until uniform. The resin A used in the preparation of the above-mentioned photosensitive resin is the resin A-1 described in paragraphs 006 3 to 0064 of JP-A No. 2 0-3 2940.相-30- 201245876 The same. [1 2]

【化1 3】【化1 3】

-31 - 201245876 【化1 4】-31 - 201245876 [Chem. 1 4]

【化1 5】[化1 5]

-32- 201245876 【表1】 光聚合起始劑 感度 錐角 肟系 其他 肟/其他之比 (mj/cm2) (·) 實施例1 Bt C1 80/20 100 48 實施例2 B1 C2 80/20 100 52 實施例3 B1 C3 80/20 100 51 實施例4 B1 C4 80/20 109 76 實施例5 B1 C5 80/20 102 54 實施例6 B1 C6 80/20 152 75 實施例7 B1 C7 80/20 109 74 實施例8 B1 C8 80/20 105 55 實施例9 B1 C9 80/20 156 75 比較例1 B9 - 100/- 114 155 比較例2 B10 - 100/- 115 157 比較例3 B11 - 100/- 115 154 比較例4 B12 - 100/- 208 125 比較例5 B9 C1 80/20 125 134 比較例6 B12 C1 80/20 210 157 【表2】 光聚合起始劑 感度 錐角 肟系 其他 肟/其他之比 (mJ/cm2) (。） 實施例1 B1 C1 80/20 100 48 實施例10 B2 C1 80/20 111 75 實施例11 B3 C1 80/20 117 74 實施例12 B4 C1 80/20 101 50 實施例13 B5 C1 80/20 107 75 實施例14 B6 C1 80/20 118 60 實施例15 B7 C1 80/20 199 70 實施例16 B8 C1 80/20 192 65 比較例7 B2 - 100/- 104 112 比較例8 B3 - 100/- 114 113 比較例9 B5 - 100/- 104 110 比較例10 B7 - 100/- 198 97 比較例11 68 - 100/- 192 91 -33- 201245876 【表3】 光聚合起始劑 感度 錐角 肟系 其他 肟淇他之比 (mJ/cm2) (·) Η施例1 Β1 C1 80/20 100 48 龍例17 Θ1 C1 70/30 106 45 ΪΪ施例18 Β1 C1 60/40 120 47 龍例19 Β1 C1 50/50 125 46 0施例20 Β1 C1 90/10 100 65 比較例5 Β9 CI 80/20 125 134 比較例12 Β9 C1 70/30 130 133 比較例13 Β9 C1 60/40 剝離 無PTN 比較例14 Β9 C1 50/50 剝離 無PTN 比較例15 Θ9 C1 90/10 111 145 比較例1 Β9 - 100/- 114 155 [感度評價] 分別針對實施例1~20及比較例1〜15之感光性樹脂組 成物，以下述順序進行感度評價。首先，將感光性樹脂組 成物旋轉塗佈於玻璃基板（lOcmxlOcm)上，在90°C加熱 120秒，藉以於玻璃基板之表面形成Ι.Ομηι之塗佈膜。隨 後，使用鏡面投射分析儀（製品名：TME-150RTO， TOPCON股份有限公司製造），透過形成線寬ΙΟμτη之直 線圖型之負型光罩，使間距爲 50μηι，以 30mJ/cm2、 60mJ/cm2、120m】/cm2三種曝光量使塗佈膜曝光。曝光後 之膜以26eC之0.04質量％ KOH水溶液顯像50秒後，在 23 0°C進行燒成處理30分鐘，使用掃描電子顯微鏡，分別 針對30mJ/cm2、60mJ/cm2、120mJ/cm2三種曝光量求得形 成之直線圖型之線寬。使用所得結果，自各線寬與曝光量 以最小平方法之近似計算，算出獲得1 Ομηι之線寬時之曝 光量》其結果，作爲感度列於表1〜3 »又，感度數値愈小 意指感光性樹脂組成物之感度愈高。且，表中’爲了 -34- 201245876 使各實施例及比較例之對比變得容易，故重複列 實施例及比較例之內容。 [圖型形狀評估] 分別針對實施例1〜20及比較例1〜15之感光 成物，以下述順序進行曝光，接著進行顯像後之 無底切，亦即圖型形狀之評價。首先，將感光性 物旋轉塗佈於玻璃基板（lOcmxlOcm)上，在 120秒，而於玻璃基板表面形成Ι.Ομιη之塗佈膜 使用鏡面投射分析儀（製品名：TME-150RTO， 股份有限公司製造），透過形成線寬1 〇μηι之直 負型光罩，以曝光量l〇〇mJ/cm2 (間距50μιη )曝 後之膜以26°C之0.04質量％ ΚΟΗ水溶液顯像50 230 °C進行燒成處理30分鐘，以掃描電子顯微鏡 與基板間之接合角度（錐角）。該錐角係對應於丨 及（b )中之角度Θ。測定之錐角列於表1 ~ 3。若 角，則意指圖型中不存在底切，若錐角爲鈍角’ 型中存在底切。 如由表1〜3所了解，具備本發明中之（B) ^ )成分之實施例1 ~ 2 0之感光性樹脂組成物爲具 度者。 又，若對實施例1〇、11、13、15及16之感 組成物與比較例7 ~ 1 1之感光性樹脂組成物進行 可知藉由組合上述（B)成分及（C)成分作爲光 出一部份 性樹脂組 圖型中有 樹脂組成 90°C加熱 。隨後， TOPCON 線圖型之 光。曝光 秒後，在 測定圖型 圖 1 ( a ) 錐角爲銳 則意指圖 5分及（C 有實用感 光性樹脂 比較時， 聚合起始 -35- 201245876 劑，所形成之圖型之錐角成爲銳角，可有效地抑制圖型底 切。 【圖式簡單說明】 圖1爲顯示由感光性樹脂組成物形成之圖型之寬度方 向之剖面形狀之示意圖，（a )爲顯示通常圖型剖面形狀 之圖，（b)爲顯示產生底切21之圖型之剖面形狀之圖。 【主要元件符號說明】 1:不存在底切之圖型中之寬度方向之剖面 la :底邊 1 b :頂邊 2:存在底切之圖型中之寬度方向之剖面 2a :底邊 2b :頂邊 21 :底切 -36--32- 201245876 [Table 1] Photopolymerization initiator sensitivity cone angle 肟 other 肟/other ratio (mj/cm2) (·) Example 1 Bt C1 80/20 100 48 Example 2 B1 C2 80/20 100 52 Example 3 B1 C3 80/20 100 51 Example 4 B1 C4 80/20 109 76 Example 5 B1 C5 80/20 102 54 Example 6 B1 C6 80/20 152 75 Example 7 B1 C7 80/20 109 74 Example 8 B1 C8 80/20 105 55 Example 9 B1 C9 80/20 156 75 Comparative Example 1 B9 - 100/- 114 155 Comparative Example 2 B10 - 100/- 115 157 Comparative Example 3 B11 - 100/- 115 154 Comparative Example 4 B12 - 100/- 208 125 Comparative Example 5 B9 C1 80/20 125 134 Comparative Example 6 B12 C1 80/20 210 157 [Table 2] Photopolymerization initiator sensitivity cone angle 肟 other 肟/other Ratio (mJ/cm2) (.) Example 1 B1 C1 80/20 100 48 Example 10 B2 C1 80/20 111 75 Example 11 B3 C1 80/20 117 74 Example 12 B4 C1 80/20 101 50 Example 13 B5 C1 80/20 107 75 Example 14 B6 C1 80/20 118 60 Example 15 B7 C1 80/20 199 70 Example 16 B8 C1 80/20 192 65 Comparative Example 7 B2 - 100/- 104 112 Comparative Example 8 B3 - 100/- 114 113 Comparative Example 9 B5 - 100/- 104 110 Comparative Example 10 B7 - 100/- 198 97 Comparative Example 11 68 - 100/- 192 91 -33- 201245876 [Table 3] Photopolymerization initiator sensitivity cone angle 肟 Other 肟qi Ratio (mJ/cm2) (·) ΗExample 1 Β1 C1 80/20 100 48 Dragon Case 17 Θ1 C1 70/30 106 45 ΪΪExample 18 Β1 C1 60/40 120 47 Dragon Case 19 Β1 C1 50/50 125 46 0 Example 20 Β1 C1 90/10 100 65 Comparative Example 5 Β9 CI 80/20 125 134 Comparative Example 12 Β9 C1 70/30 130 133 Comparative Example 13 Β9 C1 60/40 Peel-free PTN Comparative Example 14 Β9 C1 50/ 50 peeling-free PTN Comparative Example 15 Θ9 C1 90/10 111 145 Comparative Example 1 Β9 - 100/- 114 155 [Sensitivity evaluation] The photosensitive resin compositions of Examples 1 to 20 and Comparative Examples 1 to 15 were respectively described below. Sensitivity evaluation was performed sequentially. First, a photosensitive resin composition was spin-coated on a glass substrate (10 cm x 10 cm) and heated at 90 ° C for 120 seconds to form a coating film of Ι.Οηηι on the surface of the glass substrate. Subsequently, using a specular projection analyzer (product name: TME-150RTO, manufactured by TOPCON Co., Ltd.), the negative-type mask of a straight line pattern forming a line width ΙΟμτη was used, and the pitch was 50 μm, at 30 mJ/cm 2 , 60 mJ/cm 2 . The exposure amount of 120 m]/cm2 was exposed to the coating film. The film after exposure was developed with a 0.04 mass% KOH aqueous solution of 26 eC for 50 seconds, and then subjected to a baking treatment at 30 ° C for 30 minutes, and three exposures of 30 mJ/cm 2 , 60 mJ/cm 2 , and 120 mJ/cm 2 were respectively performed using a scanning electron microscope. The line width of the formed straight line pattern is obtained. Using the obtained results, the exposure amount obtained by obtaining the line width of 1 Ομηι is calculated from the approximate calculation of the line width and the exposure amount by the least square method. The results are shown in Tables 1 to 3 as the sensitivity, and the sensitivity is less. It means that the sensitivity of the photosensitive resin composition is higher. Further, in the table, the comparison between the respective examples and the comparative examples was made easy for -34-201245876, and the contents of the examples and comparative examples were repeated. [Evaluation of Pattern Shape] The photosensitive materials of Examples 1 to 20 and Comparative Examples 1 to 15 were exposed in the following order, and then the undercut after development, that is, the evaluation of the shape of the pattern was carried out. First, a photosensitive material was spin-coated on a glass substrate (10 cm×10 cm) for 120 seconds, and a coating film of Ι.Ομιη was formed on the surface of the glass substrate using a mirror projection analyzer (product name: TME-150RTO, Co., Ltd. Manufactured by a straight-line type mask having a line width of 1 〇μηι, the film exposed at an exposure amount of l〇〇mJ/cm2 (pitch 50 μm) was developed at a concentration of 0.04% by mass at 26 ° C in an aqueous solution of 50 230 ° C. The firing treatment was performed for 30 minutes to scan the angle (taper angle) between the electron microscope and the substrate. The cone angle corresponds to the angle Θ in 丨 and (b). The taper angles of the measurements are shown in Tables 1 to 3. If it is an angle, it means that there is no undercut in the pattern, and if there is an undercut in the cone angle. As is understood from Tables 1 to 3, the photosensitive resin compositions of Examples 1 to 20 having the components (B) in the present invention are preferred. Further, when the photosensitive resin compositions of Examples 1〇, 11, 13, 15 and 16 and the photosensitive resin compositions of Comparative Examples 7 to 1 1 were used, it was found that the components (B) and (C) were combined as light. A part of the resin group pattern has a resin composition heated at 90 ° C. Subsequently, the TOPCON line pattern light. After the exposure seconds, in the measurement pattern Figure 1 (a) cone angle is sharp means that Figure 5 points and (C has a practical photosensitive resin comparison, polymerization start -35-201245876 agent, the formed pattern cone The angle becomes an acute angle, and the undercut of the pattern can be effectively suppressed. [Simplified illustration of the drawing] Fig. 1 is a schematic view showing the cross-sectional shape in the width direction of a pattern formed of a photosensitive resin composition, and (a) shows the normal pattern. (b) is a diagram showing the cross-sectional shape of the pattern in which the undercut 21 is generated. [Description of main component symbols] 1: A section in the width direction in the pattern without undercut: la: bottom edge 1 b : Top edge 2: Profile in the width direction in the undercut pattern 2a: bottom edge 2b: top edge 21: undercut -36-

Claims (1)

201245876 七'申請專利範圍： 1 · 一種感光性樹脂組成物，其含有（A )光聚合性化 #物’及（B )以下述通式（1 )表示之肟系光聚合起始劑 ’·§·進而含有（C)與前述（B)成分不同之光聚合起始劑 【化1】 k/R1201245876 VII's patent application range: 1 · A photosensitive resin composition containing (A) photopolymerizable #物' and (B) an oxime-based photopolymerization initiator represented by the following formula (1) §· Further contains (C) a photopolymerization initiator different from the above component (B) [Chemical 1] k/R1 (上述通式（1)中，1爲1〜5之整數，m爲0〜（1 + 3 )之整數’η爲1〜8之整數，Ri爲可具有取代基之碳數 1〜Π之院基’或可具有取代基之芳基，R2爲以下述通式 (2)〜（4)表示之取代基之任—者，R3爲碳數之烷 基、或芳基），(In the above formula (1), 1 is an integer of 1 to 5, m is an integer of 0 to (1 + 3) 'n is an integer of 1 to 8, and Ri is a carbon number 1 to 可 which may have a substituent Ordinary group ' or an aryl group which may have a substituent, and R 2 is any one of the substituents represented by the following general formulae (2) to (4), and R 3 is an alkyl group having an alkyl group or an aryl group), (上述通式（2)及（3)中，r4爲可具有取代基之芳 -37· 201245876 基，R5爲氫原子、可具有取代基之碳數1~10之烷基、或 芳基，上述通式（4)中，R6爲可具有取代基之芳基）° 2 .如申請專利範圍第1項之感光性樹脂組成物’其進 而含有著色劑（D )。 3 .如申請專利範圍第2項之感光性樹脂組成物’其中 前述著色劑爲遮光劑β 4.一種彩色濾光片，其係使用如申請專利範圍第2或 3項之感光性樹脂組成物而形成。 5·—種顯示裝置，其係使用如申請專利範圍第4項之 彩色濾光片。 -38-(In the above formulae (2) and (3), r4 is a aryl-37·201245876 group which may have a substituent, and R5 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group. In the above formula (4), R6 is an aryl group which may have a substituent). The photosensitive resin composition of the first aspect of the invention is further contained a coloring agent (D). 3. The photosensitive resin composition of claim 2, wherein the coloring agent is an opacifier β. 4. A color filter using a photosensitive resin composition as claimed in claim 2 or 3. And formed. A display device using a color filter as in the fourth aspect of the patent application. -38-
TW101104726A 2011-02-22 2012-02-14 A photosensitive resin composition, and a color filter and a display device using the same TWI536104B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2011036212 2011-02-22

Publications (2)

Publication Number Publication Date
TW201245876A true TW201245876A (en) 2012-11-16
TWI536104B TWI536104B (en) 2016-06-01

Family

ID=46658739

Family Applications (1)

Application Number Title Priority Date Filing Date
TW101104726A TWI536104B (en) 2011-02-22 2012-02-14 A photosensitive resin composition, and a color filter and a display device using the same

Country Status (4)

Country Link
JP (1) JP6009774B2 (en)
KR (2) KR101851798B1 (en)
CN (2) CN102645843B (en)
TW (1) TWI536104B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI723061B (en) * 2015-11-04 2021-04-01 南韓商羅門哈斯電子材料韓國公司 Colored photosensitive resin composition and light shielding spacer prepared therefrom

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5793924B2 (en) * 2011-04-11 2015-10-14 日立化成株式会社 Photosensitive resin composition, photosensitive element, method for producing resist pattern, and method for producing printed wiring board
KR102130430B1 (en) * 2012-08-08 2020-07-07 아사히 가세이 이-매터리얼즈 가부시키가이샤 Photosensitive film laminate, flexible printed wiring board, and method for manufacturing same
KR101968510B1 (en) * 2013-02-06 2019-04-12 동우 화인켐 주식회사 Photosensitive resin composition for forming red pixel pattern
KR101852509B1 (en) * 2013-03-15 2018-04-26 동우 화인켐 주식회사 Colored photosensitive resin composition
JP6375236B2 (en) * 2014-02-04 2018-08-15 新日鉄住金化学株式会社 Photosensitive composition for light shielding film and cured product thereof
JP6401529B2 (en) * 2014-07-15 2018-10-10 東京応化工業株式会社 Photosensitive composition
JP2016090797A (en) * 2014-11-05 2016-05-23 株式会社Adeka Curable composition
JP6788971B2 (en) * 2016-01-14 2020-11-25 東京応化工業株式会社 Photosensitive composition
KR101991699B1 (en) 2016-09-26 2019-06-21 삼성에스디아이 주식회사 Photosensitive resin composition, black pixel defining layer using the same and display device
JP6785122B2 (en) 2016-10-24 2020-11-18 東京応化工業株式会社 Method for forming a photosensitive composition and a cured film
TWI766941B (en) * 2017-03-31 2022-06-11 南韓商東友精細化工有限公司 Blue photosensitive resin composition and color filter and image display device manufactured using the same
CN111656277A (en) 2018-01-31 2020-09-11 东丽株式会社 Negative photosensitive resin composition, cured film, element and display device provided with cured film, and method for producing same
KR102029733B1 (en) * 2018-08-23 2019-10-08 주식회사 삼양사 photosensitive resin composition
JP2021167905A (en) 2020-04-10 2021-10-21 東京応化工業株式会社 Photosensitive composition, patterned cured film production method, and patterned cured film
JP2021167906A (en) 2020-04-10 2021-10-21 東京応化工業株式会社 Photosensitive composition, method for producing patterned cured film and patterned cured film

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090010158A (en) * 2006-05-18 2009-01-29 미쓰비시 가가꾸 가부시키가이샤 Curable composition, cured product, color filter, and liquid crystal display device
JP5030527B2 (en) * 2006-10-20 2012-09-19 株式会社Ａｄｅｋａ Oxime ester compound and photopolymerization initiator containing the compound
JP5298653B2 (en) * 2007-07-06 2013-09-25 Ｊｓｒ株式会社 Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element
JP5249588B2 (en) * 2008-01-11 2013-07-31 東京応化工業株式会社 Colored photosensitive resin composition
JP2009300642A (en) * 2008-06-12 2009-12-24 Tokyo Ohka Kogyo Co Ltd Colored photosensitive resin composition
JP5291405B2 (en) * 2008-07-31 2013-09-18 東京応化工業株式会社 Colored photosensitive resin composition, color filter, and liquid crystal display
JP5577659B2 (en) * 2008-09-18 2014-08-27 東レ株式会社 Photosensitive black resin composition, resin black matrix substrate, color filter substrate, and liquid crystal display device
CN101508744B (en) * 2009-03-11 2011-04-06 常州强力电子新材料有限公司 Carbazole oxime ester lightlike initiating agent
CN101565472B (en) 2009-05-19 2011-05-04 常州强力电子新材料有限公司 Ketoxime ester photoinitiator
JP5673111B2 (en) * 2011-01-12 2015-02-18 東洋インキＳｃホールディングス株式会社 Photosensitive coloring composition and color filter
TWI438570B (en) * 2010-03-11 2014-05-21 Toyo Ink Mfg Co Photosensitive coloring composition and color filter
JP5657452B2 (en) * 2010-05-07 2015-01-21 富士フイルム株式会社 Colored photosensitive composition, method for producing color filter, color filter, and liquid crystal display device
CN101891845B (en) * 2010-07-15 2013-08-07 常州强力电子新材料有限公司 Application of carbazole oxime ester compound serving as photoinitiator in photopolymerisable acrylate composition
CN101923287B (en) * 2010-08-31 2011-11-30 常州强力电子新材料有限公司 Photosensitive composition containing photoinitiator of diphenyl sulfide based ketoxime esters and application thereof
JP5121912B2 (en) * 2010-11-24 2013-01-16 富士フイルム株式会社 Colored photosensitive resin composition, pattern forming method, color filter manufacturing method, color filter, and display device including the same
JP5929496B2 (en) * 2011-06-30 2016-06-08 Jsr株式会社 Radiation-sensitive resin composition, cured film for display element, method for forming cured film for display element, and display element

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI723061B (en) * 2015-11-04 2021-04-01 南韓商羅門哈斯電子材料韓國公司 Colored photosensitive resin composition and light shielding spacer prepared therefrom

Also Published As

Publication number Publication date
KR20120097462A (en) 2012-09-04
CN102645843A (en) 2012-08-22
JP2012189996A (en) 2012-10-04
TWI536104B (en) 2016-06-01
CN106980230B (en) 2020-05-19
KR20170099817A (en) 2017-09-01
CN102645843B (en) 2018-05-08
JP6009774B2 (en) 2016-10-19
KR101851798B1 (en) 2018-04-24
CN106980230A (en) 2017-07-25
KR101976268B1 (en) 2019-05-07

Similar Documents

Publication Publication Date Title
TW201245876A (en) Photosensitive resin composition, color filter using the same and display device
JP6134037B2 (en) Photosensitive resin composition, and color filter and display device using the same
KR101291480B1 (en) Photosensitive composition and color filter formed from photosensitive composition
JP6026757B2 (en) Photosensitive resin composition, color filter, display device, photopolymerization initiator, and compound
JP5096814B2 (en) Colored photosensitive composition
JP2020118971A (en) Quantum dot, curable composition containing the same, cured film produced using curable composition, color filter including cured film, display device, and method of fabricating cured film
KR20150055417A (en) Colored Photosensitive Resin Composition
CN107272341B (en) Photosensitive resin composition for light-shielding film, substrate for display, and method for producing same
JP4745146B2 (en) Colored photosensitive resin composition
JP2014134813A (en) Colored photosensitive resin composition, black matrix, color filter, and liquid crystal display
JP2008003299A (en) Colored photosensitive resin composition
TWI377441B (en)
JP5510050B2 (en) Coloring composition for color filter, color filter, color liquid crystal display element, and method for producing color filter
JP2008052069A (en) Colored photosensitive resin composition
JP2009173560A (en) Oxime ester-based compound and photosensitive composition
JP2010262027A (en) Colored radiation-sensitive composition, color filter and color liquid crystal display element
TWI676862B (en) Photosensitive resin composition
JP5336274B2 (en) Colored photosensitive resin composition and oxime photopolymerization initiator
JP7359559B2 (en) Light-shielding film, photosensitive resin composition for obtaining the same, and method for producing light-shielding film
TWI539235B (en) Photosensitive resin composition, color filter and method for manufacturing the same, liquid crystal display device
KR20100006538A (en) Colored photosensitive resin composition and oxime-based photopolymerization initiator