TWI665520B - Colored photosensitive composition, colored spacer, color filter, and liquid crystal display - Google Patents

Colored photosensitive composition, colored spacer, color filter, and liquid crystal display Download PDF

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TWI665520B
TWI665520B TW106140131A TW106140131A TWI665520B TW I665520 B TWI665520 B TW I665520B TW 106140131 A TW106140131 A TW 106140131A TW 106140131 A TW106140131 A TW 106140131A TW I665520 B TWI665520 B TW I665520B
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photosensitive composition
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alkali
pigment
acid
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TW201812453A (en
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裴麗華
澤井良尚
福井誠
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日商三菱化學股份有限公司
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • G03F7/004—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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Structural Engineering (AREA)
  • Mathematical Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Architecture (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Optical Filters (AREA)
  • Polymerisation Methods In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本發明之課題在於提供一種著色感光性組成物，其於用以藉由光微影法而一次形成高度不同之著色間隔件之方法中，不僅確保液晶之電壓保持率，而且所需之形狀之形成、階差之控制、與基板之密接性優異。本發明係關於一種著色感光性組成物，其含有(a)著色劑、(b)鹼可溶性樹脂、(c)光聚合起始劑、(d)乙烯性不飽和化合物、(e)溶劑、及(f)分散劑，且用於藉由光微影法而一次形成高度不同之著色間隔件。 An object of the present invention is to provide a coloring photosensitive composition which, in a method for forming a coloring spacer having different heights at one time by a photolithography method, not only ensures a voltage retention ratio of a liquid crystal, but also a required shape. Formation, step control, and adhesion to the substrate are excellent. The present invention relates to a coloring photosensitive composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) A dispersant, and used to form colored spacers of different heights at one time by a photolithography method.

Description

著色感光性組成物，著色間隔件，彩色濾光片及液晶顯示裝置    Colored photosensitive composition, colored spacer, color filter and liquid crystal display device   

本發明係關於一種著色感光性組成物等。更詳細而言，係關於一種於例如液晶顯示器等之彩色濾光片中可較佳地用於著色間隔件等的著色感光性組成物、及藉由該著色感光性組成物而形成之著色間隔件、彩色濾光片、液晶顯示裝置。 The present invention relates to a colored photosensitive composition and the like. More specifically, the present invention relates to a coloring photosensitive composition which can be preferably used for a coloring spacer and the like in a color filter such as a liquid crystal display, and a coloring interval formed by the coloring photosensitive composition. Components, color filters, liquid crystal display devices.

液晶顯示器(LCD，Liquid Crystal Display)係利用藉由施加至液晶之電壓之導通-斷開而切換液晶分子之排列方式之性質。另一方面，形成LCD之單元之各構件多利用以光微影為代表之感光性組成物而形成。就易於形成微細之構造、對大畫面用之基板之處理較容易等原因而言，今後感光性組成物之應用範圍亦有進一步擴大之傾向。 Liquid crystal displays (LCDs) use the property of switching the arrangement of liquid crystal molecules by turning on and off the voltage applied to the liquid crystal. On the other hand, the various components forming the unit of the LCD are often formed using a photosensitive composition represented by photolithography. For reasons such as easy formation of a fine structure and easier handling of a substrate for a large screen, the application range of the photosensitive composition will tend to be further expanded in the future.

然而，使用感光性組成物之LCD中，由於感光性組成物本身之電氣特性、或包含於感光性組成物中之雜質之影響而未保持施加於液晶之電壓，由此產生顯示器之顯示不均等問題。尤其是於彩色液晶顯示裝置中之靠近液晶層之構件、例如液晶面板中用於將2塊基板之間隔保持為一定者、即所謂 柱狀間隔件、感光性間隔件等中，其影響較大。 However, in the LCD using the photosensitive composition, due to the electrical characteristics of the photosensitive composition itself or the influence of impurities contained in the photosensitive composition, the voltage applied to the liquid crystal is not maintained, resulting in display unevenness of the display. problem. Especially in a member near a liquid crystal layer in a color liquid crystal display device, for example, in a liquid crystal panel, a distance between two substrates is kept constant, that is, a so-called columnar spacer, a photosensitive spacer, etc., which has a great influence. .

先前，將間隔件用於TFT(Thin Film Transistor，薄膜電晶體)型LCD之情形時，存在因入射至TFT之光而使作為開關元件之TFT產生故障之情況。為防止該情況，例如於專利文獻1中記載有將間隔件設為遮光性之內容。 Previously, when a spacer was used for a TFT (Thin Film Transistor) type LCD, there was a case where a TFT as a switching element failed due to light incident on the TFT. To prevent this, for example, Patent Literature 1 describes that the spacer is made light-shielding.

又，近年來，藉由光微影法製造間隔件時，隨著面板構造之變化，提出有一次形成高度不同之間隔件之方法。專利文獻2中揭示有藉由控制曝光量與殘膜率，可實現所需之高度不同之間隔件之形狀、階差。 In addition, in recent years, when a spacer is manufactured by a photolithography method, a method of forming spacers having different heights at one time has been proposed as the structure of the panel changes. Patent Document 2 discloses that by controlling the exposure amount and the residual film rate, the shape and step of the spacers having different heights can be realized.

[先前技術文獻]     [Prior technical literature]     [專利文獻]     [Patent Literature]    

專利文獻1：日本專利特開平8-234212號公報 Patent Document 1: Japanese Patent Laid-Open No. 8-234212

專利文獻2：日本專利特開2009-31778號公報 Patent Document 2: Japanese Patent Laid-Open No. 2009-31778

然而，如專利文獻1中所記載，為將間隔件設為遮光性，通常考慮將含有顏料之著色劑等添加至感光性組成物中，但隨著著色劑之添加，由於透明成分減少而使間隔件層之硬化性降低之情況及源自顏料之雜質等之影響，有損及電氣特性之虞。 However, as described in Patent Document 1, in order to make the spacer light-shielding, it is generally considered to add a pigment-containing coloring agent or the like to the photosensitive composition. In the case where the hardenability of the spacer layer is reduced and the influence of impurities derived from the pigment, etc., the electrical characteristics may be impaired.

又，專利文獻2係關於不添加顏料之間隔件，可判明，若應用於添加顏料之著色間隔件之一次形成中，則由於顏料吸收有助於光聚合之紫外線區域之光，因此於開口部之透光率較小之圖案中，硬化性較差，難以達成所需之高度不同之間 隔件之形狀、階差之控制、與基板之密接性等特性。 In addition, Patent Document 2 relates to a spacer without adding a pigment, and it can be found that when applied to the primary formation of a colored spacer with a pigment added, the pigment absorbs light in an ultraviolet region that contributes to photopolymerization, and therefore, it is in the opening portion. In a pattern with a small light transmittance, the hardenability is poor, and it is difficult to achieve the characteristics of the spacers with different heights, the control of the step difference, and the adhesion with the substrate.

本發明係鑒於此種情況而完成者。即，本發明之主要之課題在於提供一種著色感光性組成物，其於用以藉由光微影法而一次形成高度不同之著色間隔件之方法中，不僅確保液晶之電壓保持率，而且所需之形狀之形成、階差之控制、與基板之密接性亦優異。 The present invention has been made in view of such circumstances. That is, the main object of the present invention is to provide a coloring photosensitive composition which, in a method for forming a coloring spacer having different heights at one time by a photolithography method, not only ensures the voltage retention of the liquid crystal, but also The required shape formation, step control, and adhesion to the substrate are also excellent.

又，本發明之其他課題在於提供一種藉由此種著色感光性組成物而形成之著色間隔件。 Another object of the present invention is to provide a colored spacer formed by such a colored photosensitive composition.

進而，本發明之其他課題在於提供一種具備此種著色間隔件之彩色濾光片。 Furthermore, another object of the present invention is to provide a color filter including such a coloring spacer.

進而，本發明之其他課題在於提供一種具備此種彩色濾光片之液晶顯示裝置。 Furthermore, another object of the present invention is to provide a liquid crystal display device including such a color filter.

進而，本發明之其他課題在於提供一種使用此種著色感光性組成物並藉由光微影法而一次形成高度不同之著色間隔件之方法。 Furthermore, another object of the present invention is to provide a method of using such a coloring photosensitive composition and forming a coloring spacer having different heights at one time by a photolithography method.

本發明者等人針對上述課題進行銳意研究，結果發現：藉由使用特定之鹼可溶性樹脂及分散劑，並且將鹼可溶性樹脂相對於乙烯性不飽和化合物之重量比及特定之鹼可溶性樹脂之含有比例設為特定之範圍，可解決上述課題，從而完成本發明。即，本發明之主旨如以下所述。 The present inventors conducted intensive research on the above problems, and found that by using a specific alkali-soluble resin and a dispersant, the weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound and the content of the specific alkali-soluble resin Setting the ratio to a specific range can solve the above problems and complete the present invention. That is, the gist of this invention is as follows.

[1]一種著色感光性組成物，其含有(a)著色劑、(b)鹼可溶性樹脂、(c)光聚合起始劑、(d)乙烯性不飽和化合物、(e)溶劑、及(f)分散劑，且用於藉由光微影法而一次形成高度不同 之著色間隔件；並且其含有下述鹼可溶性樹脂(A-1)及鹼可溶性樹脂(A-2)中之至少一者作為(b)鹼可溶性樹脂；含有包含氮原子之丙烯酸系嵌段共聚合體作為(f)分散劑；(b)鹼可溶性樹脂相對於(d)乙烯性不飽和化合物之重量比未滿7；且鹼可溶性樹脂(A-1)及鹼可溶性樹脂(A-2)之合計相對於著色感光性組成物中之總固形分之比例為12重量%以上； [1] A coloring photosensitive composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and ( f) a dispersant for forming colored spacers of different heights by photolithography at one time; and containing at least one of the following alkali-soluble resin (A-1) and alkali-soluble resin (A-2) Or (b) an alkali-soluble resin; an acrylic block copolymer containing a nitrogen atom as (f) a dispersant; (b) the weight ratio of the alkali-soluble resin to (d) the ethylenically unsaturated compound is less than 7; The ratio of the total of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition is 12% by weight or more;

<鹼可溶性樹脂(A-1)>      <Alkali-soluble resin (A-1)>     

藉由對環氧樹脂加成α,β-不飽和單羧酸或酯部分具有羧基之α,β-不飽和單羧酸酯，進而與多元酸酐反應而得之樹脂； A resin obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting with a polybasic acid anhydride;

<鹼可溶性樹脂(A-2)>      <Alkali soluble resin (A-2)>     

藉由對環氧樹脂加成α,β-不飽和單羧酸或酯部分具有羧基之α,β-不飽和單羧酸酯，進而與多元醇及多元酸酐反應而得之樹脂。 A resin obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting with a polyhydric alcohol and a polyacid anhydride.

[2]如上述[1]之著色感光性組成物，其中鹼可溶性樹脂(A-1)及鹼可溶性樹脂(A-2)之合計相對於著色感光性組成物中之總固形分之比例為20重量%以上。 [2] The colored photosensitive composition according to the above [1], wherein the ratio of the total of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition is 20% by weight or more.

[3]如上述[1]或[2]之著色感光性組成物，其中(a)著色劑之含有比率相對於著色感光性組成物中之總固形分未滿30重量%。 [3] The colored photosensitive composition according to the above [1] or [2], wherein (a) the content ratio of the colorant is less than 30% by weight based on the total solid content in the colored photosensitive composition.

[4]如上述[1]至[3]中任一項之著色感光性組成物，其中(a)著色劑之含有比率相對於著色感光性組成物中之總固形分 為25重量%以上。 [4] The colored photosensitive composition according to any one of the above [1] to [3], wherein (a) the content ratio of the colorant is 25% by weight or more with respect to the total solid content in the colored photosensitive composition.

[5]如上述[1]至[4]中任一項之著色感光性組成物，其含有以下(1)紅色顏料、且含有以下(2)藍色顏料及以下(3)紫色顏料中之至少一者作為(a)著色劑；(1)選自C.I.顏料紅177、254中之紅色顏料；(2)作為C.I.顏料藍15：6之藍色顏料；(3)作為C.I.顏料紫23之紫色顏料。 [5] The colored photosensitive composition according to any one of the above [1] to [4], which contains one of the following (1) a red pigment, and one of the following (2) a blue pigment and the following (3) a purple pigment At least one as (a) a colorant; (1) a red pigment selected from CI Pigment Red 177, 254; (2) a CI Pigment Blue 15: 6 blue pigment; (3) as a CI Pigment Violet 23 Purple pigment.

[6]如上述[1]至[4]中任一項之著色感光性組成物，其含有C.I.顏料紅254及C.I.顏料藍15：6作為(a)著色劑。 [6] The colored photosensitive composition according to any one of the above [1] to [4], which contains C.I. Pigment Red 254 and C.I. Pigment Blue 15: 6 as (a) a colorant.

[7]如上述[1]至[6]中任一項之著色感光性組成物，其含有A-B嵌段共聚合體及B-A-B嵌段共聚合體中之至少一者作為(f)分散劑，該A-B嵌段共聚合體及B-A-B嵌段共聚合體包含側鏈具有4級銨鹽基及胺基中之至少一者之A嵌段、與不具有4級銨鹽基及胺基之B嵌段。 [7] The colored photosensitive composition according to any one of the above [1] to [6], which contains at least one of an AB block copolymer and a BAB block copolymer as (f) a dispersant, the AB The block copolymer and the BAB block copolymer include an A block having at least one of a quaternary ammonium salt group and an amine group in a side chain, and a B block having no quaternary ammonium salt group and amine group.

[8]如上述[1]至[6]中任一項之著色感光性組成物，其含有A-B嵌段共聚合體及B-A-B嵌段共聚合體中之至少一者作為(f)分散劑，該A-B嵌段共聚合體及B-A-B嵌段共聚合體包含側鏈具有4級銨鹽基及胺基之A嵌段、與不具有4級銨鹽基及胺基之B嵌段。 [8] The colored photosensitive composition according to any one of the above [1] to [6], which contains at least one of an AB block copolymer and a BAB block copolymer as (f) a dispersant, the AB The block copolymer and the BAB block copolymer include an A block having a quaternary ammonium salt group and an amine group in a side chain, and a B block having no quaternary ammonium salt group and an amine group.

[9]如上述[1]至[6]中任一項之著色感光性組成物，其含有A-B嵌段共聚合體及B-A-B嵌段共聚合體中之至少一者作為(f)分散劑，該A-B嵌段共聚合體及B-A-B嵌段共聚合體包含側鏈不具有4級銨鹽基而具有胺基之A嵌段、與不具有4級銨鹽基及胺基之B嵌段。 [9] The colored photosensitive composition according to any one of the above [1] to [6], which contains at least one of an AB block copolymer and a BAB block copolymer as (f) a dispersant, the AB The block copolymer and the BAB block copolymer include an A block having an amine group without a quaternary ammonium salt group in the side chain, and a B block having no quaternary ammonium salt group and an amine group at the side chain.

[10]如上述[1]至[9]中任一項之著色感光性組成物，其含有肟酯化合物作為(c)光聚合起始劑。 [10] The coloring photosensitive composition according to any one of the above [1] to [9], which contains an oxime ester compound as (c) a photopolymerization initiator.

[11]一種著色間隔件，其藉由如上述[1]至[10]中任一項之著色感光性組成物而一次形成，且高度不同。 [11] A coloring spacer formed by the coloring photosensitive composition as described in any one of the above [1] to [10] at one time and having different heights.

[12]一種彩色濾光片，其具備如上述[11]之著色間隔件。 [12] A color filter including the coloring spacer according to the above [11].

[13]一種液晶顯示裝置，其具備如上述[12]之彩色濾光片。 [13] A liquid crystal display device including the color filter according to the above [12].

[14]一種著色間隔件之形成方法，其使用如上述[1]至[10]中任一項之著色感光性組成物並藉由光微影法而一次形成高度不同之著色間隔件。 [14] A method for forming a colored spacer, using the colored photosensitive composition according to any one of the above [1] to [10], and forming colored spacers of different heights at one time by a photolithography method.

根據本發明，於用以藉由光微影法而一次形成高度不同之著色間隔件之方法中，不僅確保液晶之電壓保持率，而且亦可實現所需形狀之形成、階差之控制、與基板之密接性。 According to the present invention, in a method for forming colored spacers of different heights at one time by a photolithography method, not only the voltage retention of the liquid crystal is ensured, but also the formation of a desired shape, the control of the step difference, and the The tightness of the substrate.

1‧‧‧著色間隔件圖案 1‧‧‧Colored spacer pattern

2‧‧‧玻璃基板 2‧‧‧ glass substrate

3‧‧‧中軸 3‧‧‧ bottom bracket

4‧‧‧剖面 4‧‧‧ section

41‧‧‧圖案側面部 41‧‧‧Pattern side

A、A'‧‧‧交點 A, A'‧‧‧ intersection

H‧‧‧圖案高度 H‧‧‧Pattern height

L‧‧‧下剖面直徑 L‧‧‧ bottom section diameter

圖1(A)及圖1(B)係用以說明實施例之大致圓柱狀間隔件圖案之形狀之圖，圖1(A)係間隔件圖案之平面圖，圖1(B)係間隔件圖案之剖面圖。 1 (A) and 1 (B) are diagrams for explaining the shape of a substantially cylindrical spacer pattern of the embodiment, FIG. 1 (A) is a plan view of the spacer pattern, and FIG. 1 (B) is a spacer pattern Section view.

以下對用以實施本發明之形態進行詳細之說明，以下所記載之構成要件之說明為本發明之實施態樣之一例(代表例)，本發明只要不超過其主旨，則並不特別限定於該等內容。 The following is a detailed description of the form for implementing the present invention. The description of the constituent elements described below is an example (representative example) of the embodiment of the present invention. The present invention is not particularly limited as long as it does not exceed its gist. Such content.

再者，本發明中，所謂「(甲基)丙烯酸」，意指包括丙烯酸與甲基丙烯酸兩者，(甲基)丙烯酸基、(甲基)丙烯酸酯、(甲 基)丙烯醯基等亦為相同之含義；所謂「(共)聚合體」，意指包括均聚合體(homopolymer)與共聚合體(copolymer)兩者；所謂「(酸)酐」、「(無水)...酸」，意指包括酸及其酐兩者。 In addition, in the present invention, "(meth) acrylic acid" means both acrylic acid and methacrylic acid, and (meth) acrylic acid group, (meth) acrylic acid ester, (meth) acrylic acid, etc. Have the same meaning; the so-called "(co) polymer" means including both homopolymer and copolymer; so-called "(acid) anhydride", "(anhydrous) ... acid", It is meant to include both acids and their anhydrides.

又，本發明中，所謂「單體」，係指相對於所謂之高分子物質之含義，除狹義之單體(monomer)以外，亦包括二聚物、三聚物、低聚物等。再者，此處，所謂「總固形分」，表示除本發明之著色感光性組成物所含之溶劑以外之全部成分之合計。 In addition, in the present invention, the "monomer" refers to the meaning of a so-called high molecular substance, and includes dimers, trimers, oligomers, and the like in addition to monomers in the narrow sense. Here, the "total solid content" means the total of all components other than the solvent contained in the coloring photosensitive composition of this invention.

[1]高度不同之著色間隔件之一次形成方法 [1] One-time forming method of colored spacers with different heights

用以藉由光微影法而一次形成高度不同之著色間隔件之方法之特徵主要在於曝光步驟中之曝光光罩。 The method for forming colored spacers of different heights by photolithography at one time is mainly characterized by an exposure mask in the exposure step.

已知有使用具有遮蔽光之穿透之遮光層與使光穿透之數個開口部，且一部分之開口部之平均透光率小於其他開口部之平均透光率的曝光光罩作為該曝光光罩的方法。該方法使用具有遮光層(透光率0%)與數個開口部，且具有平均透光率相對於平均透光率最高之開口部(通常透光率為100%；以下稱作完全穿透開口部)較小之開口部(平均透光率超過0%且未滿100%；較佳為超過5%且未滿50%；以下稱作中間穿透開口部)的曝光光罩。藉由該方法，例如於負型之著色感光性組成物之情形時，藉由中間穿透開口部與完全穿透開口部之平均透光率之差異、即曝光量之差異而產生形成之圖案之硬化度之差異，其後，經由顯影及熱硬化製成，可形成高度不同之著色間隔件。 It is known to use an exposure mask having a light-shielding layer that shields light from penetrating and several openings that allow light to pass through, and the average light transmittance of one of the openings is smaller than the average light transmittance of other openings as the exposure. Photomask method. This method uses an opening having a light-shielding layer (light transmittance 0%) and several openings, and having the highest average light transmittance relative to the average light transmittance (usually 100% light transmittance; hereinafter referred to as full penetration) Opening portion) An exposure mask having a small opening portion (average light transmittance exceeding 0% and less than 100%; preferably more than 5% and less than 50%; hereinafter referred to as an intermediate penetration opening portion). According to this method, for example, in the case of a negative-type colored photosensitive composition, a pattern formed is generated by a difference in average light transmittance between a middle penetrating opening portion and a completely penetrating opening portion, that is, a difference in exposure amount. The difference in the degree of hardening can be formed by development and thermal curing, so that colored spacers of different heights can be formed.

[2]著色感光性組成物 [2] Colored photosensitive composition

本發明之著色感光性組成物含有(a)著色劑、(b)鹼可溶性樹脂、(c)光聚合起始劑、(d)乙烯性不飽和化合物、(e)溶劑、及(f)分散劑，且用於藉由光微影法而一次形成高度不同之著色間隔件；其特徵在於：含有下述鹼可溶性樹脂(A-1)及鹼可溶性樹脂(A-2)中之至少一者作為(b)鹼可溶性樹脂；含有包含氮原子之丙烯酸系嵌段共聚合體作為(f)分散劑；(b)鹼可溶性樹脂相對於(d)乙烯性不飽和化合物之重量比未滿7；且鹼可溶性樹脂(A-1)及鹼可溶性樹脂(A-2)之合計相對於著色感光性組成物中之總固形分之比例為12重量%以上。 The colored photosensitive composition of the present invention contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersion. And is used to form colored spacers of different heights at one time by photolithography; characterized in that it contains at least one of the following alkali-soluble resin (A-1) and alkali-soluble resin (A-2) As (b) an alkali-soluble resin; containing an acrylic block copolymer containing a nitrogen atom as (f) a dispersant; (b) the weight ratio of the alkali-soluble resin to (d) the ethylenically unsaturated compound is less than 7; and The ratio of the total of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition is 12% by weight or more.

<鹼可溶性樹脂(A-1)>     <Alkali-soluble resin (A-1)>    

藉由對環氧樹脂加成α,β-不飽和單羧酸或酯部分具有羧基之α,β-不飽和單羧酸酯，進而與多元酸酐反應而得之樹脂。 A resin obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin and further reacting with a polybasic acid anhydride.

<鹼可溶性樹脂(A-2)>     <Alkali soluble resin (A-2)>    

藉由對環氧樹脂加成α,β-不飽和單羧酸或酯部分具有羧基之α,β-不飽和單羧酸酯，進而與多元醇及多元酸酐反應而得之樹脂。 A resin obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting with a polyhydric alcohol and a polyacid anhydride.

[2-1](a)著色劑 [2-1] (a) Colorant

通常可使用顏料作為著色劑。作為顏料，可使用藍色顏料、綠色顏料、紅色顏料、黃色顏料、紫色顏料、橙色顏料、棕色顏料、黑色顏料等各種顏色之顏料。又，作為其構造，除偶氮系、酞菁系、喹吖酮系、苯并咪唑酮系、異吲哚啉酮 系、二系、陰丹士林系、苝系等之有機顏料以外，亦可使用各種無機顏料等。以下以顏料編號例示可使用之顏料之具體例。以下所列舉之「C.I.顏料紅2」等用語意指色度指數(C.I.，Color Index)。 Pigments can often be used as colorants. As the pigment, pigments of various colors such as blue pigment, green pigment, red pigment, yellow pigment, purple pigment, orange pigment, brown pigment, and black pigment can be used. In addition, as the structure, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, In addition to organic pigments such as system-based, indanthrene-based, and osmium-based, various inorganic pigments can also be used. Specific examples of pigments that can be used are exemplified by pigment numbers. The terms "CI Pigment Red 2" and the like listed below mean the color index (CI).

作為紅色顏料，可列舉C.I.顏料紅1、2、3、4、5、6、7、8、9、12、14、15、16、17、21、22、23、31、32、37、38、41、47、48、48：1、48：2、48：3、48：4、49、49：1、49：2、50：1、52：1、52：2、53、53：1、53：2、53：3、57、57：1、57：2、58：4、60、63、63：1、63：2、64、64：1、68、69、81、81：1、81：2、81：3、81：4、83、88、90：1、101、101：1、104、108、108：1、109、112、113、114、122、123、144、146、147、149、151、166、168、169、170、172、173、174、175、176、177、178、179、181、184、185、187、188、190、193、194、200、202、206、207、208、209、210、214、216、220、221、224、230、231、232、233、235、236、237、238、239、242、243、245、247、249、250、251、253、254、255、256、257、258、259、260、262、263、264、265、266、267、268、269、270、271、272、273、274、275、276。其中，較佳可列舉C.I.顏料紅48：1、122、168、177、202、206、207、209、224、242、254，進而較佳可列舉C.I.顏料紅177、209、224、254。 Examples of the red pigment include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38 , 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1 , 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1 , 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146 , 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202 , 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250 , 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Among them, C.I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254 is preferable, and C.I. Pigment Red 177, 209, 224, 254 is more preferable.

作為藍色顏料，可列舉C.I.顏料藍1、1：2、9、14、15、15：1、15：2、15：3、15：4、15：6、16、17、19、25、27、28、29、33、35、36、56、56：1、60、61、61：1、62、63、66、 67、68、71、72、73、74、75、76、78、79。其中，較佳可列舉C.I.顏料藍15、15：1、15：2、15：3、15：4、15：6，進而較佳可列舉C.I.顏料藍15：6。 Examples of the blue pigment include CI Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Among them, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 are preferable, and C.I. Pigment Blue 15: 6 is more preferable.

作為綠色顏料，可列舉C.I.顏料綠1、2、4、7、8、10、13、14、15、17、18、19、26、36、45、48、50、51、54、55。其中，較佳可列舉C.I.顏料綠7、36。 Examples of the green pigment include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Among these, C.I. Pigment Green 7, 36 is preferable.

作為黃色顏料，可列舉C.I.顏料黃1、1：1、2、3、4、5、6、9、10、12、13、14、16、17、24、31、32、34、35、35：1、36、36：1、37、37：1、40、41、42、43、48、53、55、61、62、62：1、63、65、73、74、75、81、83、87、93、94、95、97、100、101、104、105、108、109、110、111、116、117、119、120、126、127、127：1、128、129、133、134、136、138、139、142、147、148、150、151、153、154、155、157、158、159、160、161、162、163、164、165、166、167、168、169、170、172、173、174、175、176、180、181、182、183、184、185、188、189、190、191、191：1、192、193、194、195、196、197、198、199、200、202、203、204、205、206、207、208。其中，較佳可列舉C.I.顏料黃83、117、129、138、139、150、154、155、180、185，進而較佳可列舉C.I.顏料黃83、138、139、150、180。 Examples of the yellow pigment include CI Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35 : 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83 , 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134 , 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170 , 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199 , 200, 202, 203, 204, 205, 206, 207, 208. Among them, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 is preferable, and C.I. Pigment Yellow 83, 138, 139, 150, 180 is more preferable.

作為橙色顏料，可列舉C.I.顏料橙1、2、5、13、16、17、19、20、21、22、23、24、34、36、38、39、43、46、48、49、61、62、64、65、67、68、69、70、71、72、73、74、75、77、78、79。其中，較佳可列舉C.I.顏料橙38、71。 作為紫色顏料，可列舉C.I.顏料紫1、1：1、2、2：2、3、3：1、3：3、5、5：1、14、15、16、19、23、25、27、29、31、32、37、39、42、44、47、49、50。其中，較佳可列舉C.I.顏料紫19、23，進而較佳可列舉C.I.顏料紫23。 Examples of the orange pigment include CI pigment orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61 , 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among these, C.I. pigment oranges 38 and 71 are preferable. Examples of the purple pigment include CI Pigment Violet 1, 1: 1,2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27 , 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among them, C.I. Pigment Violet 19 and 23 are preferred, and C.I. Pigment Violet 23 is further preferred.

作為黑色顏料，可列舉苝黑(BASF K0084、K0086)、花青黑、耐曬黑HB(C.I.26150)。 Examples of the black pigment include black (BASF K0084, K0086), cyan black, and black HB (C.I.26150).

本發明之著色感光性組成物中，可使用單獨之黑色色料，或可使用由紅、綠、藍色等之混合所產生之黑色色料。該等黑色色料可自碳黑、鈦黑等無機或有機顏料、染料中適當選擇，可單獨使用或混合多種而使用。 In the coloring photosensitive composition of the present invention, a single black colorant may be used, or a black colorant produced by a mixture of red, green, blue, and the like may be used. These black pigments can be appropriately selected from inorganic or organic pigments and dyes such as carbon black and titanium black, and can be used alone or in combination.

作為碳黑之市售品之例，可列舉如以下之商標。 Examples of commercially available products of carbon black include the following trademarks.

三菱化學公司製造：MA7、MA8、MA11、MA100、MA220、MA230、#52、#50、#47、#45、#2700、#2650、#2200、#1000、#990、#900等。 Manufactured by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA220, MA230, # 52, # 50, # 47, # 45, # 2700, # 2650, # 2200, # 1000, # 990, # 900, etc.

Degussa公司製造：Printex95、Printex90、Printex85、Printex75、Printex55、Printex45、Printex40、Printex30、Printex3、PrintexA、PrintexG、SpecialBlack550、SpecialBlack350、SpecialBlack250、SpecialBlack100等。 Made by Degussa: Printex95, Printex90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3, PrintexA, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, etc.

Cabot公司製造：Monarch460、Monarch430、Monarch280、Monarch120、Monarch800、Monarch4630、REGAL99、REGAL99R、REGAL415、REGAL415R、REGAL250、REGAL250R、REGAL330、BLACKPEARLS480、PEARLS130。 Manufactured by Cabot: Monarch460, Monarch430, Monarch280, Monarch120, Monarch800, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACKPEARLS480, PEARLS130.

Columbian Carbon公司製造：RAVEN11、RAVEN15、 RAVEN30、RAVEN35、RAVEN40、RAVEN410、RAVEN420、RAVEN450、RAVEN500、RAVEN780、RAVEN850、RAVEN890H、RAVEN1000、RAVEN1020、RAVEN1040等。 Manufactured by Columbian Carbon: RAVEN11, RAVEN15, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, etc.

作為鈦黑之市售品之例，可列舉Mitsubishi Materials公司製造之鈦黑10S、12S、13R、13M、13M-C等。 Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, and the like manufactured by Mitsubishi Materials.

就遮光性之觀點而言，本發明之著色感光性組成物較佳為含有以下(1)之紅色顏料、並且含有以下(2)之藍色顏料及以下(3)之紫色顏料中之至少一者作為(a)著色劑。 From the viewpoint of light-shielding property, the colored photosensitive composition of the present invention preferably contains at least one of the following red pigments (1), and the blue pigments (2) and the purple pigments (3) below. Or (a) a colorant.

(1)選自C.I.顏料紅177、254中之紅色顏料 (1) Red pigment selected from C.I. Pigment Red 177, 254

(2)作為C.I.顏料藍15：6之藍色顏料 (2) As a blue pigment of C.I. Pigment Blue 15: 6

(3)作為C.I.顏料紫23之紫色顏料 (3) Purple pigment as C.I.Pigment Violet 23

其中，就液晶在電壓保持率之確保、階差之控制、與基板之密接性之觀點而言，較佳為含有(1)與(2)。又，就提高可見光區域之遮光性之觀點而言，較佳為含有C.I.顏料紅254及C.I.顏料藍15：6。 Among these, (1) and (2) are preferred from the viewpoints of ensuring the voltage retention of the liquid crystal, controlling the step, and the adhesion to the substrate. From the viewpoint of improving the light-shielding property in the visible light region, it is preferable to contain C.I. Pigment Red 254 and C.I. Pigment Blue 15: 6.

本發明之著色感光性組成物中，(a)著色劑之含有比率相對於該著色感光性組成物中之總固形分，較佳為35重量%以下，更佳為未滿30重量%。若為35重量%以下，則完全穿透開口部之著色間隔件圖案之高度與中間穿透開口部之著色間隔件圖案之高度的差異(△H)較大，故而較佳。若為未滿30重量%，則完全穿透開口部之著色間隔件圖案之高度與中間穿透開口部之著色間隔件圖案之高度的差異(△H)超過0.35μm。較佳之範圍為5重量%~28重量%，進而較佳為10重量%~25重量%。若(a)著色劑之含有比率過大，則 存在著色感光性組成物之感光度降低、無法形成所需之高度不同之間隔件之形狀、階差之情況。另一方面，於著色劑之含有比率過小之情形時，存在無法確保作為著色間隔件之充分之遮光性之情況。 In the colored photosensitive composition of the present invention, the content ratio of (a) the coloring agent is preferably 35% by weight or less, and more preferably less than 30% by weight, relative to the total solid content of the colored photosensitive composition. If it is 35% by weight or less, the difference (ΔH) between the height of the colored spacer pattern completely penetrating the opening portion and the height of the colored spacer pattern penetrating the middle opening portion is large, which is preferable. If it is less than 30% by weight, the difference (ΔH) between the height of the colored spacer pattern completely penetrating the opening portion and the height of the colored spacer pattern penetrating the opening portion exceeds 0.35 μm. A preferred range is from 5 to 28% by weight, and even more preferably from 10 to 25% by weight. If (a) the content ratio of the colorant is too large, the sensitivity of the coloring photosensitive composition may be lowered, and the shapes and steps of the spacers having different heights may not be formed. On the other hand, when the content ratio of the colorant is too small, there may be cases where sufficient light-shielding properties as a colored spacer cannot be secured.

[2-2](b)鹼可溶性樹脂 [2-2] (b) Alkali-soluble resin

本發明所使用之鹼可溶性樹脂(A-1)係利用如下等方法而獲得：藉由對環氧樹脂加成α,β-不飽和單羧酸或酯部分具有羧基之α,β-不飽和單羧酸酯，進而與多元酸酐反應而賦予鹼可溶性。該反應產物於化學構造上實質上不具有環氧基。 The alkali-soluble resin (A-1) used in the present invention is obtained by adding an α, β-unsaturated monocarboxylic acid or an ester portion having an carboxyl group to an epoxy resin by an method such as: The monocarboxylic acid ester reacts with a polybasic acid anhydride to impart alkali solubility. The reaction product has substantially no epoxy group in chemical structure.

作為成為原料之環氧樹脂，可較佳地使用甲酚酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、三苯酚甲烷型環氧樹脂、聯苯酚醛清漆型環氧樹脂、萘酚醛清漆型環氧樹脂、作為二環戊二烯與苯酚或甲酚之加成聚合反應物與表鹵醇之反應產物的環氧樹脂、含金剛烷基之環氧樹脂、茀型環氧樹脂等。 As the epoxy resin used as a raw material, a cresol novolac type epoxy resin, a phenol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a triphenol methane type can be preferably used. Epoxy resin, biphenol novolac epoxy resin, naphthol novolac epoxy resin, epoxy resin as a reaction product of the addition polymerization reaction product of dicyclopentadiene and phenol or cresol and epihalohydrin, Adamantyl-containing epoxy resin, fluorene type epoxy resin, etc.

環氧樹脂之分子量係以凝膠滲透層析法(GPC，Gel Permeation Chromatography)進行測定而設為聚苯乙烯換算重量平均分子量(以下稱作「Mw」)，作為Mw，通常為200~20萬之範圍，較佳為300~10萬之範圍。於分子量未滿上述範圍之情形時，存在不易獲得較佳之Mw之鹼可溶性樹脂(A-1)之情況，反之，於超過上述範圍之情形時，有於α,β-不飽和單羧酸之加成反應時容易產生凝膠化或製造變得困難之虞。 The molecular weight of the epoxy resin is measured by gel permeation chromatography (GPC, Gel Permeation Chromatography), and is set to a polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw"). The Mw is usually 200 to 200,000. The range is preferably in the range of 300 to 100,000. When the molecular weight is less than the above range, there may be cases where it is not easy to obtain a better Mw alkali-soluble resin (A-1). On the other hand, when the molecular weight exceeds the above range, it may be caused by α, β-unsaturated monocarboxylic acid. During the addition reaction, gelation is likely to occur or production may become difficult.

作為α,β-不飽和單羧酸，可列舉丙烯酸、甲基丙烯酸、衣 康酸、丁烯酸、桂皮酸等，較佳為丙烯酸及甲基丙烯酸，尤其是由於丙烯酸富於反應性而較佳。又，作為酯部分具有羧基之α,β-不飽和單羧酸酯，可列舉丙烯酸-2-丁二醯氧基乙酯、丙烯酸-2-順丁烯二醯氧基乙酯、丙烯酸-2-鄰苯二甲醯氧基乙酯、丙烯酸-2-六氫鄰苯二甲醯氧基乙酯、甲基丙烯酸-2-丁二醯氧基乙酯、甲基丙烯酸-2-順丁烯二醯氧基乙酯、甲基丙烯酸-2-鄰苯二甲醯氧基乙酯、甲基丙烯酸-2-六氫鄰苯二甲醯氧基乙酯、丁烯酸-2-丁二醯氧基乙酯等。 Examples of the α, β-unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, itaconic acid, butenoic acid, and cinnamic acid. Acrylic acid and methacrylic acid are preferred, and acrylic acid is more reactive due to its reactivity. good. Examples of the α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion include 2-butadioxyethyl acrylate, 2-cis-butenedimethoxyethyl acrylate, and 2-acrylate -Phthalic acid ethyl ester, 2-hexahydrophthalic acid ethyl acrylate, 2-butadimethoxy ethyl methacrylate, 2-cis butene methacrylate Dimethoxyethyl, 2-phthalicyloxyethyl methacrylate, 2-hexahydrophthalicyloxyethyl methacrylate, 2-butanefluoric acid butenoic acid Oxyethyl and the like.

α,β-不飽和單羧酸或酯部分具有羧基之α,β-不飽和單羧酸酯與環氧樹脂之加成反應可使用公知之方法進行。又，α,β-不飽和單羧酸或酯部分具有羧基之α,β-不飽和單羧酸酯之使用量相對於原料環氧樹脂之環氧基1當量，較佳為0.5~1.2當量之範圍，進而較佳為0.7~1.1當量之範圍。若α,β-不飽和單羧酸或酯部分具有羧基之α,β-不飽和單羧酸酯之使用量較少，則存在不飽和基之導入量不足，後續之與多元酸酐之反應亦不充分之情況。又，殘留大量環氧基亦不利。另一方面，若該使用量較多，則存在α,β-不飽和單羧酸或其之酯作為未反應物而殘留之情況。任一情形時均存在塗膜之硬化特性惡化之可能性。 The addition reaction of an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in an ester portion and an epoxy resin can be performed by a known method. The amount of the α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably 0.5 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the raw material epoxy resin. The range is more preferably in the range of 0.7 to 1.1 equivalents. If the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic ester having a carboxyl group in the ester portion is small, the introduction amount of unsaturated group is insufficient, and the subsequent reaction with polybasic acid anhydride is also Inadequate situation. It is also disadvantageous that a large amount of epoxy groups remain. On the other hand, when this amount is large, there may be cases where α, β-unsaturated monocarboxylic acid or an ester thereof remains as an unreacted substance. In either case, there is a possibility that the hardening characteristics of the coating film are deteriorated.

再者，本發明中，若製造步驟中即便未經由環氧樹脂，最終之樹脂之構造亦相同，則於本申請案中，亦將其定義為屬於鹼可溶性樹脂(A-1)之範疇。作為其例，例如可列舉使酚醛清漆樹脂與含不飽和基之環氧化合物反應之方法。 Furthermore, in the present invention, if the final resin structure is the same even if the epoxy resin is not used in the manufacturing steps, it is also defined as belonging to the category of alkali-soluble resin (A-1) in this application. Examples thereof include a method of reacting a novolac resin with an unsaturated group-containing epoxy compound.

作為進而對使環氧樹脂與α,β-不飽和單羧酸或酯部分具 有羧基之α,β-不飽和單羧酸酯加成而得之產物加成之多元酸酐，可列舉順丁烯二酸酐、丁二酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、均苯四甲酸酐、偏苯三甲酸酐、二苯基酮四甲酸二酐、甲基六氫鄰苯二甲酸酐、內亞甲基四氫鄰苯二甲酸酐、氯菌酸酐、甲基四氫鄰苯二甲酸酐、聯苯四甲酸二酐等，較佳為順丁烯二酸酐、丁二酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、均苯四甲酸酐、偏苯三甲酸酐、聯苯四甲酸二酐，尤佳之化合物為四氫鄰苯二甲酸酐及聯苯四甲酸二酐。 Examples of the polybasic acid anhydride added to the product obtained by adding an epoxy resin to an α, β-unsaturated monocarboxylic acid or an ester portion having a carboxyl group include α, β-unsaturated monocarboxylic acid, and maleic anhydride Diacid anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, diphenylketone tetracarboxylic dianhydride, formic acid Hexahydrophthalic anhydride, internal methylenetetrahydrophthalic anhydride, chloric anhydride, methyltetrahydrophthalic anhydride, biphenyltetracarboxylic dianhydride, etc. Acid anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, biphenyltetracarboxylic dianhydride, particularly preferred compounds It is tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride.

關於多元酸酐之加成反應，亦可使用公知之方法。多元酸酐之加成量較佳為使生成之環氧丙烯酸酯系樹脂之酸值成為10mgKOH/g~150mgKOH/g之範圍，進而，尤佳為成為20mgKOH/g~140mgKOH/g之範圍。若酸值為上述範圍以下，則變得缺乏鹼性顯影性，又，若超過上述範圍，則可觀察到硬化性能劣化之傾向。 Regarding the addition reaction of a polybasic acid anhydride, a known method can also be used. The addition amount of the polybasic acid anhydride is preferably such that the acid value of the resulting epoxy acrylate resin is in a range of 10 mgKOH / g to 150 mgKOH / g, and more preferably in a range of 20 mgKOH / g to 140 mgKOH / g. If the acid value is less than the above range, the alkali developability will be insufficient, and if it exceeds the above range, the tendency of the hardening performance to be deteriorated will be observed.

本發明所使用之鹼可溶性樹脂(A-1)之以凝膠滲透層析法(GPC)所測定之聚苯乙烯換算之重量平均分子量(Mw)通常為1500以上，較佳為2000以上，通常為50000以下，較佳為30000以下，更佳為10000以下。若該鹼可溶性樹脂(A-1)之重量平均分子量過小，則有感光度降低之傾向，若過大，則存在對顯影液之溶解性不足之情況，故欠佳。 The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin (A-1) used in the present invention measured by gel permeation chromatography (GPC) is usually 1,500 or more, preferably 2,000 or more, and usually It is 50,000 or less, preferably 30,000 or less, and more preferably 10,000 or less. If the weight-average molecular weight of the alkali-soluble resin (A-1) is too small, the sensitivity tends to decrease. If the weight-average molecular weight is too large, the solubility in the developing solution may be insufficient, which is not preferable.

本發明所使用之鹼可溶性樹脂(A-2)係藉由對環氧樹脂加成α,β-不飽和單羧酸或酯部分具有羧基之α,β-不飽和單羧酸酯，進而與多元醇及多元酸酐反應而得。 The alkali-soluble resin (A-2) used in the present invention is obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having an carboxyl group to an epoxy resin, and then Polyol and polyanhydride are obtained by reaction.

鹼可溶性樹脂(A-1)之合成所使用之合成方法或除多元醇以外之成分全部可用於鹼可溶性樹脂(A-2)之合成。鹼可溶性樹脂(A-2)通常係藉由於對環氧樹脂加成α,β-不飽和單羧酸或酯部分具有羧基之α,β-不飽和單羧酸酯而成之反應物中混合多元醇及多元酸酐並加溫而得。於該情形時，多元醇與多元酸酐之混合順序並無特別限制。 All the synthesis methods used for the synthesis of the alkali-soluble resin (A-1) or the components other than the polyol can be used for the synthesis of the alkali-soluble resin (A-2). The alkali-soluble resin (A-2) is usually mixed by reacting an epoxy resin with an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in an ester portion. Polyols and polyanhydrides are obtained by heating. In this case, the mixing order of the polyol and the polyacid anhydride is not particularly limited.

作為鹼可溶性樹脂(A-2)之合成所使用之多元醇，例如較佳為選自三羥甲基丙烷、二-三羥甲基丙烷、季戊四醇、二季戊四醇、三羥甲基乙烷、1,2,3-丙三醇中之1種或2種以上之多元醇。 As the polyhydric alcohol used in the synthesis of the alkali-soluble resin (A-2), for example, it is preferably selected from the group consisting of trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1 One or two or more polyhydric alcohols in 2,3-glycerol.

藉由使用多元醇，可增大鹼可溶性樹脂(A-2)之分子量而於分子中導入分支，且可使分子量與黏度平衡。又，可增大於分子中之酸基之導入率，且可獲得感光度或密接性等平衡之有機黏合劑。 By using a polyhydric alcohol, the molecular weight of the alkali-soluble resin (A-2) can be increased to introduce branches into the molecule, and the molecular weight and viscosity can be balanced. In addition, it is possible to increase the introduction rate of the acid group in the molecule and obtain a balanced organic adhesive such as sensitivity and adhesion.

由於若多元醇之使用量過少，則效果較小，若過多，則有增黏或凝膠化之可能性，因此相對於環氧樹脂成分與α,β-不飽和單羧酸或酯部分具有羧基之α,β-不飽和單羧酸酯成分之反應物，通常為0.01~0.5倍重量左右，較佳為0.02~0.2倍重量左右。 If the amount of polyhydric alcohol is too small, the effect will be small, and if it is too large, there is a possibility of thickening or gelling. Therefore, it has a higher viscosity than the epoxy resin component and the α, β-unsaturated monocarboxylic acid or ester portion. The reactant of the carboxyl α, β-unsaturated monocarboxylic acid ester component is usually about 0.01 to 0.5 times the weight, preferably about 0.02 to 0.2 times the weight.

以上述方式獲得之鹼可溶性樹脂(A-2)之酸值通常為10mgKOH/g以上，較佳為50mgKOH/g以上。若酸值未滿10mgKOH/g，則存在顯影性不足之情況。又，若酸值過高，則存在著色感光性組成物之耐鹼性有問題(即，由鹼性顯影液導致產生圖案表面之粗化或膜減少)之情形，故酸值較佳 為200mgKOH/g以下，更佳為150mgKOH/g以下。 The acid value of the alkali-soluble resin (A-2) obtained in the above manner is usually 10 mgKOH / g or more, and preferably 50 mgKOH / g or more. If the acid value is less than 10 mgKOH / g, the developability may be insufficient. In addition, if the acid value is too high, the alkali resistance of the colored photosensitive composition may be problematic (that is, the pattern surface may be roughened or the film may be reduced by an alkaline developer). Therefore, the acid value is preferably 200 mgKOH. / g or less, more preferably 150 mgKOH / g or less.

鹼可溶性樹脂(A-2)之藉由凝膠滲透層析法(GPC)測定而得之聚苯乙烯換算之重量平均分子量(Mw)較佳為1,500以上，更佳為2,000以上。又，較佳為20,000以下，更佳為10,000以下。若重量平均分子量過小，則有感光度或塗膜強度、耐鹼性產生問題之可能性，若過大，則存在顯影性或再溶解性產生問題之情況。 The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin (A-2) measured by gel permeation chromatography (GPC) is preferably 1,500 or more, and more preferably 2,000 or more. It is preferably 20,000 or less, and more preferably 10,000 or less. If the weight average molecular weight is too small, there may be a problem in sensitivity, coating film strength, and alkali resistance. If it is too large, problems in developability or resolubility may occur.

鹼可溶性樹脂(A-1)及鹼可溶性樹脂(A-2)之合計相對於本發明之著色感光性組成物中之總固形分比例為12重量%以上，較佳為20重量以上%，更佳為30重量%以上，且通常為70重量%以下，較佳為60重量%以下，更佳為50重量%以下。若鹼可溶性樹脂之比例過於多於該範圍，則顯影性降低之同時，顏料之比例過少，故有亦無法確保必需之遮光性之傾向，另一方面，若過少，則存在無法形成所需之間隔件之形狀、階差之情況。 The total amount of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) with respect to the total solid content in the colored photosensitive composition of the present invention is 12% by weight or more, preferably 20% by weight or more, more It is preferably 30% by weight or more, and usually 70% by weight or less, preferably 60% by weight or less, and more preferably 50% by weight or less. If the ratio of the alkali-soluble resin is more than this range, the developability is lowered and the pigment ratio is too small, so there is a tendency that the necessary light-shielding property cannot be ensured. On the other hand, if it is too small, the desired The shape and step of the spacer.

作為鹼可溶性樹脂，亦可併用除鹼可溶性樹脂(A-1)、鹼可溶性樹脂(A-2)以外之其他鹼可溶性樹脂。 As the alkali-soluble resin, an alkali-soluble resin other than the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) may be used in combination.

[2-3](c)光聚合起始劑 [2-3] (c) Photopolymerization initiator

所謂本發明之光聚合起始劑，係指可藉由紫外線或熱而產生使乙烯性不飽和基聚合之自由基之化合物。 The photopolymerization initiator of the present invention refers to a compound that can generate a radical that polymerizes an ethylenically unsaturated group by ultraviolet rays or heat.

以下列舉本發明可使用之光聚合起始劑之具體之例。 Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.

2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-均三、2-(4-甲氧基萘基)-4,6-雙(三氯甲基)-均三、2-(4-乙氧基萘基)-4,6-雙(三氯甲基)-均三、2-(4-乙氧基羰基萘基)-4,6-雙(三氯甲基)- 均三等鹵甲基化三衍生物；鹵甲基化二唑衍生物；2-(鄰氯苯基)-4,5-二苯基咪唑二聚物、2-(鄰氯苯基)-4,5-雙(3'-甲氧基苯基)咪唑二聚物、2-(鄰氟苯基)-4,5-二苯基咪唑二聚物、2-(鄰甲氧基苯基)-4,5-二苯基咪唑二聚物、2-(鄰甲氧基苯基)-4,5-二苯基咪唑二聚物等咪唑衍生物；安息香甲醚、安息香苯醚、安息香異丁醚、安息香異丙醚等安息香、安息香烷基醚類；2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、1-氯蒽醌等蒽醌衍生物；苯并蒽酮衍生物；二苯基酮、米其勒酮、2-甲基二苯基酮、3-甲基二苯基酮、4-甲基二苯基酮、2-氯二苯基酮、4-溴二苯基酮、2-羧基二苯基酮等二苯基酮衍生物；2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、1-羥基環己基苯基酮、α-羥基-2-甲基苯基丙酮、1-羥基-1-甲基乙基-(對異丙基苯基)酮、1-羥基-1-(對十二烷基苯基)酮、2-甲基-(4'-(甲硫基)苯基)-2-啉基-1-丙酮、1,1,1-三氯甲基-(對丁基苯基)酮等苯乙酮衍生物；硫雜蒽酮、2-乙基硫雜蒽酮、2-異丙基硫雜蒽酮、2-氯硫雜蒽酮、2,4-二甲基硫雜蒽酮、2,4-二乙基硫雜蒽酮、2,4-二異丙基硫雜蒽酮等硫雜蒽酮衍生物；對二甲基胺基苯甲酸乙酯、對二乙基胺基苯甲酸乙酯等苯甲酸酯衍生物； 9-苯基吖啶、9-(對甲氧基苯基)吖啶等吖啶衍生物；9,10-二甲基苯并啡等啡衍生物；二(環戊二烯基)二氯化鈦、二(環戊二烯基)雙苯基鈦、二(環戊二烯基)雙(2,3,4,5,6-五氟苯-1-基)鈦、二(環戊二烯基)雙(2,3,5,6-四氟苯-1-基)鈦、二(環戊二烯基)雙(2,4,6-三氟苯-1-基)鈦、二(環戊二烯基)2,6-二(氟苯-1-基)鈦、二(環戊二烯基)2,4-二(氟苯-1-基)鈦、二(甲基環戊二烯基)雙(2,3,4,5,6-五氟苯-1-基)鈦、二(甲基環戊二烯基)雙(2,6-二氟苯-1-基)鈦、二(環戊二烯基)2,6-二(氟-3-(吡-1-基)-苯-1-基)鈦等二茂鈦衍生物；2-甲基-1[4-(甲硫基)苯基]-2-啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-啉基苯基)-丁酮-1、2-苄基-2-二甲基胺基-1-(4-啉基苯基)丁烷-1-酮、苯甲酸4-二甲基胺基乙酯、苯甲酸4-二甲基胺基異戊酯、4-二乙基胺基苯乙酮、4-二甲基胺基苯丙酮、1,4-二甲胺基苯甲酸2-乙基己酯、2,5-雙(4-二乙基胺基苯亞甲基)環己酮、7-二乙基胺基-3-(4-二乙基胺基苯甲醯基)香豆素、4-(二乙基胺基)查爾酮等α-胺基烷基苯酮系化合物；作為光聚合起始劑，尤其是就感光度之方面而言，肟衍生物類(肟系及酮肟系化合物)較為有效，使用含有酚性羥基之鹼可溶性樹脂之情形等時，就感光度之方面而言較為不利，故尤其是此種感光度優異之肟衍生物類(肟系及酮肟系化合物)較為有用。 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -mesanthine , 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -mesanthine , 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -mesanthine , 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -mesan Isohalomethylated tris Derivatives; halomethylation Diazole derivatives; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (3'-methoxyphenyl) Imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2 -(O-methoxyphenyl) -4,5-diphenylimidazole dimer and other imidazole derivatives; benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether and other benzoin and benzoin alkyl ethers Class; Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone; benzoanthrone derivatives; diphenyl ketones, Michelin Ketone, 2-methyldiphenyl ketone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2-chlorodiphenyl ketone, 4-bromodiphenyl ketone, 2-carboxydiphenyl Diphenyl ketone derivatives such as phenyl ketone; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α -Hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2 -Methyl- (4 '-(methylthio) phenyl) -2- Acetophenone derivatives such as phosphono-1-acetone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thia anthrone, 2-ethylthio anthrone, 2-iso Propylthiaxanthone, 2-chlorothiaxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Derivatives such as thioanthrone, such as ketones; benzoate derivatives, such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (p-methyl Acridine derivatives such as acridine; 9,10-dimethylbenzophene Isorphine Derivatives; bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) bisphenyltitanium, bis (cyclopentadienyl) bis (2,3,4,5,6-penta Fluorophenyl-1-yl) titanium, bis (cyclopentadienyl) bis (2,3,5,6-tetrafluorophenyl-1-yl) titanium, bis (cyclopentadienyl) bis (2,4 , 6-trifluorophenyl-1-yl) titanium, bis (cyclopentadienyl) 2,6-bis (fluorophenyl-1-yl) titanium, bis (cyclopentadienyl) 2,4-bis ( Fluorophenyl-1-yl) titanium, bis (methylcyclopentadienyl) bis (2,3,4,5,6-pentafluorophenyl-1-yl) titanium, bis (methylcyclopentadienyl) ) Bis (2,6-difluorophenyl-1-yl) titanium, bis (cyclopentadienyl) 2,6-bis (fluoro-3- (py-1-yl) -benzene-1-yl) titanium Isotitanium derivatives; 2-methyl-1 [4- (methylthio) phenyl] -2- Linylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) butane-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4- Dimethylaminophenylacetone, 1,4-dimethylaminobenzoic acid 2-ethylhexyl, 2,5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-bis Α-Aminoalkylphenone compounds such as ethylamino-3- (4-diethylaminobenzyl) coumarin, 4- (diethylamino) chalcone; as light Polymerization initiators, particularly in terms of sensitivity, are more effective in oxime derivatives (oxime-based and ketoxime-based compounds). When using alkali-soluble resins containing phenolic hydroxyl groups, etc., in terms of sensitivity This is disadvantageous, and especially such oxime derivatives (oxime-based and ketoxime-based compounds) having excellent sensitivity are useful.

作為肟系化合物，可列舉含有下述通式(2)所示之構造部 分之化合物，較佳可列舉下述通式(3)所示之肟酯系化合物。 Examples of the oxime-based compound include compounds containing a structural portion represented by the following general formula (2), and preferably, an oxime ester-based compound represented by the following general formula (3).

(式(2)中，R2表示分別可經取代之碳數2~12之烷醯基、碳數1~20之雜芳基烷醯基、碳數3~25之烯醯基、碳數3~8之環烷醯基、碳數3~20之烷氧基羰基烷醯基、碳數8~20之苯氧基羰基烷醯基、碳數3~20之雜芳氧基羰基烷醯基、碳數2~10之胺基烷基羰基、碳數7~20之芳醯基、碳數1~20之雜芳醯基、碳數2~10之烷氧基羰基、或碳數7~20之芳氧基羰基。) (In the formula (2), R 2 represents an alkylalkyl group having 2 to 12 carbon atoms, a heteroarylalkylalkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, and carbon number, respectively, which may be substituted. 3 to 8 cycloalkanoyl groups, 3 to 20 carbon alkoxycarbonyl alkyl groups, 8 to 20 carbon phenoxy carbonyl alkyl groups, 3 to 20 carbon heteroaryloxy carbonyl groups Group, amino alkylcarbonyl group with 2 to 10 carbon atoms, arylfluorenyl group with 7 to 20 carbon atoms, heteroarylfluorenyl group with 1 to 20 carbon atoms, alkoxycarbonyl group with 2 to 10 carbon atoms, or 7 carbon number Aryloxycarbonyl group of ~ 20.)

(式(3)中，R1a表示氫、或分別可經取代之碳數1~20之烷基、碳數2~25之烯基、碳數1~20之雜芳基烷基、碳數3~20之烷氧基羰基烷基、碳數8~20之苯氧基羰基烷基、碳數1~20之雜芳氧基羰基烷基或雜芳硫基烷基、碳數1~20之胺基烷基、碳數2~12之烷醯基、碳數3~25之烯醯基、碳數3~8之環烷醯基、碳數7~20之芳醯基、碳數1~20之雜芳醯基、碳數2~10之烷氧基羰基、或碳數7~20之芳氧基羰基。 (In formula (3), R 1a represents hydrogen, or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl alkyl group having 1 to 20 carbon atoms, and carbon number, respectively, which may be substituted. Alkoxycarbonylalkyl of 3-20, phenoxycarbonylalkyl of 8-20, heteroaryloxycarbonylalkyl or heteroarylthioalkyl of 1-20, carbon of 1-20 Amine alkyl, alkanoyl having 2 to 12 carbons, alkenyl having 3 to 25 carbons, naphthene having 3 to 8 carbons, aryl fluorenyl having 7 to 20 carbons, 1 carbon A heteroarylfluorenyl group of 20 to 20, an alkoxycarbonyl group of 2 to 10 carbons, or an aryloxycarbonyl group of 7 to 20 carbons.

R1b表示包含芳香環或雜芳香環之任意取代基。 R 1b represents an arbitrary substituent including an aromatic ring or a heteroaromatic ring.

再者，R1a可與R1b共同形成環，其連結基可列舉分別可 具有取代基之碳數1~10之伸烷基、聚乙烯基(-(CH=CH)r-)、聚伸乙炔基(-(C≡C)r-)或組合該等而成之基(再者，r為0~3之整數)。 In addition, R 1a and R 1b may form a ring together, and examples of the linking group thereof include an alkylene group having 1 to 10 carbon atoms, a polyvinyl group (-(CH = CH) r- ), and a polyalkylene group which may each have a substituent. An ethynyl group (-(C≡C) r- ) or a combination of these (in addition, r is an integer of 0 to 3).

R2a表示分別可經取代之碳數2~12之烷醯基、碳數1~20之雜芳基烷醯基、碳數3~25之烯醯基、碳數3~8之環烷醯基、碳數3~20之烷氧基羰基烷醯基、碳數8~20之苯氧基羰基烷醯基、碳數3~20之雜芳氧基羰基烷醯基、碳數2~10之胺基羰基、碳數7~20之芳醯基、碳數1~20之雜芳醯基、碳數2~10之烷氧基羰基或碳數7~20之芳氧基羰基。) R 2a represents an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, and a cycloalkane group having 3 to 8 carbon atoms, respectively, which may be substituted. Group, alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, heteroaryloxycarbonylalkanoyl group having 3 to 20 carbon atoms, and 2 to 10 carbon atoms Aminocarbonyl group, arylfluorenyl group with 7 to 20 carbon atoms, heteroarylfluorenyl group with 1 to 20 carbon atoms, alkoxycarbonyl group with 2 to 10 carbon atoms or aryloxycarbonyl group with 7 to 20 carbon atoms. )

作為上述通式(2)中之R2及上述通式(3)中之R2a，較佳為列舉碳數2~12之烷醯基、碳數1~20之雜芳基烷醯基、碳數3~8之環烷醯基。 As R 2 in the general formula (2) and R 2a in the general formula (3), preferred are alkyl alkanoyl groups having 2 to 12 carbon atoms, heteroarylalkanoyl groups having 1 to 20 carbon atoms, A cycloalkanoyl group having 3 to 8 carbon atoms.

作為上述通式(3)中之R1a，較佳為列舉未經取代之甲基、乙基、丙基、或經N-乙醯基-N-乙醯氧基胺基取代之丙基。 As R 1a in the general formula (3), an unsubstituted methyl group, an ethyl group, a propyl group, or a propyl group substituted with an N-ethylfluorenyl-N-ethoxymethylamino group is preferable.

又，作為上述通式(3)中之R1b，較佳為列舉可經取代之肼甲醯基、可經取代之硫雜蒽酮基、可經取代之苯基硫醚基。 In addition, as R 1b in the general formula (3), preferred examples include a hydrazine methyl group which may be substituted, a thia anthrone group which may be substituted, and a phenyl sulfide group which may be substituted.

作為較佳用於本發明之肟酯系化合物，具體而言，可列舉如以下所例示之化合物，但並不受該等化合物任何限定。 Specific examples of the oxime ester compound to be used in the present invention include the compounds exemplified below, but they are not limited to these compounds.

[化3] [Chemical 3]

作為酮肟系化合物，可列舉含有下述通式(4)所示之構造部分之化合物，較佳為列舉下述通式(5)所示之肟酯系化合物。 Examples of the ketoxime-based compound include compounds containing a structural moiety represented by the following general formula (4), and preferably an oxime ester-based compound represented by the following general formula (5).

(上述通式(4)中，R4與上述通式(2)中之R2含義相同。) (In the general formula (4), R 4 has the same meaning as R 2 in the general formula (2).)

(上述通式(5)中，R3a表示分別可經取代之苯基、碳數1~20之烷基、碳數2~25之烯基、碳數1~20之雜芳基烷基、碳數3~20之烷氧基羰基烷基、碳數8~20之苯氧基羰基烷基、碳數2~20之烷硫基烷基、碳數1~20之雜芳氧基羰基烷基或雜芳硫基烷基、碳數1~20之胺基烷基、碳數2~12之烷醯基、碳數3~25之烯醯基、碳數3~8之環烷醯基、碳數7~20之芳醯基、碳數1~20之雜芳醯基、碳數2~10之烷氧基羰基、或碳數7~20之芳氧基羰基。 (In the general formula (5), R 3a represents a phenyl group which may be substituted, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, Alkoxycarbonylalkyl with 3 to 20 carbon atoms, phenoxycarbonylalkyl with 8 to 20 carbon atoms, alkylthioalkyl with 2 to 20 carbon atoms, and heteroaryloxycarbonylalkane with 1 to 20 carbon atoms Or heteroarylthioalkyl, amine alkyl having 1 to 20 carbons, alkanoyl having 2 to 12 carbons, alkenyl having 3 to 25 carbons, and cycloalkyl sulfonyl having 3 to 8 carbons , Arylfluorene group with 7 to 20 carbon atoms, Heteroarylarylene group with 1 to 20 carbon atoms, Alkoxycarbonyl group with 2 to 10 carbon atoms, or Aryloxycarbonyl group with 7 to 20 carbon atoms.

R3b表示包含芳香環或雜芳香環之任意取代基。 R 3b represents an arbitrary substituent including an aromatic ring or a heteroaromatic ring.

再者，R3a可與R3b共同形成環，其連結基可列舉分別可具有取代基之碳數1~10之伸烷基、聚乙烯基(-(CH=CH)r-)、聚伸乙炔基(-(C≡C)r-)或組合該等而成之基(再者，r為0~3之整數)。 In addition, R 3a and R 3b may form a ring together, and examples of the linking group thereof include an alkylene group having 1 to 10 carbon atoms, a polyvinyl group (-(CH = CH) r- ), and a polyalkylene group which may each have a substituent. An ethynyl group (-(C≡C) r- ) or a combination of these (in addition, r is an integer of 0 to 3).

R4a表示分別可經取代之碳數2~12之烷醯基、碳數3~25之烯醯基、碳數4~8之環烷醯基、碳數7~20之苯甲醯基、碳數3~20之雜芳醯基、碳數2~10之烷氧基羰基、碳數7~20之芳氧基羰基、碳數2~20之雜芳基、或碳數2~ 20之烷基胺基羰基。) R 4a represents an alkylfluorenyl group having 2 to 12 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, a cycloalkylfluorenyl group having 4 to 8 carbon atoms, a benzamidine group having 7 to 20 carbon atoms, Heteroarylfluorenyl with 3 to 20 carbons, alkoxycarbonyl with 2 to 10 carbons, aryloxycarbonyl with 7 to 20 carbons, heteroaryl with 2 to 20 carbons, or 2 to 20 with carbons Alkylaminocarbonyl. )

作為上述通式(4)中之R4及上述通式(5)中之R4a，較佳為列舉碳數2~12之烷醯基、碳數1~20之雜芳基烷醯基、碳數3~8之環烷醯基、碳數7~20之芳醯基。 As R 4 in the general formula (4) and R 4a in the general formula (5), preferred are alkyl alkanoyl groups having 2 to 12 carbon atoms, heteroaryl alkyl fluorenyl groups having 1 to 20 carbon atoms, Cycloalkylfluorenyl groups having 3 to 8 carbon atoms, and arylfluorenyl groups having 7 to 20 carbon atoms.

作為上述通式(5)中之R3a，較佳為列舉未經取代之乙基、丙基、丁基、或經甲氧基羰基取代之乙基或丙基。 As R 3a in the general formula (5), an unsubstituted ethyl group, a propyl group, a butyl group, or an ethyl group or a propyl group substituted with a methoxycarbonyl group is preferred.

又，作為上述通式(5)中之R3b，較佳為列舉可經取代之肼甲醯基、可經取代之苯基硫醚基。 Moreover, as R <3b> in said General formula (5), the hydrazine formyl group which can be substituted, and the phenyl sulfide group which can be substituted are mentioned preferably.

作為較佳用於本發明之酮肟酯系化合物，具體而言，可列舉如以下所例示之化合物，但並不受該等化合物任何限定。 Specific examples of the ketoxime ester compound to be used in the present invention include the compounds exemplified below, but they are not limited to these compounds.

該等肟及酮肟酯系化合物本身為公知之化合物，例如係於日本專利特開2000-80068號公報、日本專利特開2006-36750號公報中所記載之一系列之化合物之一種。 These oxime and ketoxime ester compounds are known compounds per se, for example, one of a series of compounds described in Japanese Patent Laid-Open No. 2000-80068 and Japanese Patent Laid-Open No. 2006-36750.

上述光聚合起始劑可單獨使用1種，亦可併用2種以上。 These photopolymerization initiators may be used individually by 1 type, and may use 2 or more types together.

本發明之遮光性感光性樹脂組成物中之光聚合起始劑之比例相對於總固形分，通常為0.4~15重量%，較佳為0.5~10重量%。若光聚合起始劑之比例過於多於該範圍，則有顯影性降低之傾向，另一方面，若過少，則存在無法形成較佳之電壓保持率或著色間隔件之形狀、階差之情況。 The proportion of the photopolymerization initiator in the light-shielding sexy light-sensitive resin composition of the present invention is usually 0.4 to 15% by weight, and preferably 0.5 to 10% by weight, relative to the total solid content. If the ratio of the photopolymerization initiator is too much more than this range, the developability tends to decrease. On the other hand, if the ratio is too small, it may not be possible to form a better voltage holding ratio or the shape and step of the colored spacer.

本發明之著色感光性組成物之特徵在於鹼可溶性樹脂相對於乙烯性不飽和化合物之重量比未滿7。該情形時之鹼可溶性樹脂意指含有鹼可溶性樹脂(A-1)及鹼可溶性樹脂(A-2)中之至少一者之全部鹼可溶性樹脂之合計。鹼可溶性樹脂相對於乙烯性不飽和化合物之重量比通常為1以上，較佳為1.5以上，進而較佳為2以上，較佳為6以下，進而更佳之範圍為5以下。若為7以上，則存在無法形成必需之階差之情況，若過少，則存在顯影性降低之情況。於大量使用對顯影液之溶解時間較長之鹼可溶性樹脂之情形時，存在即便為7以上顯影性亦降低之情況。 The colored photosensitive composition of the present invention is characterized in that the weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound is less than 7. The alkali-soluble resin in this case means the total of all alkali-soluble resins containing at least one of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2). The weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound is usually 1 or more, preferably 1.5 or more, further preferably 2 or more, preferably 6 or less, and further preferably 5 or less. If it is 7 or more, a necessary step may not be formed, and if it is too small, developability may fall. When a large amount of an alkali-soluble resin having a long dissolution time with respect to a developer is used, the developability may be reduced even if it is 7 or more.

[2-4](d)乙烯性不飽和化合物 [2-4] (d) Ethylenically unsaturated compounds

上述光聚合起始劑可與乙烯性不飽和化合物共同使用。 The photopolymerization initiator may be used together with an ethylenically unsaturated compound.

作為此處所使用之乙烯性不飽和化合物，意指分子內具有1個以上乙烯性不飽和鍵之化合物，就聚合性、交聯性及可擴大伴隨於此之曝光部與非曝光部之顯影液溶解性之差異 等方面而言，較佳為分子內具有2個以上乙烯性不飽和鍵之化合物，又，進而較佳為該不飽和鍵源自(甲基)丙烯醯氧基之(甲基)丙烯酸酯化合物。 As the ethylenically unsaturated compound used herein, it means a compound having one or more ethylenically unsaturated bonds in the molecule, in terms of polymerizability, crosslinkability, and a developing solution that can expand the exposure and non-exposure parts accompanying it. In terms of differences in solubility, a compound having two or more ethylenically unsaturated bonds in the molecule is preferred, and the (meth) acryloxy group-derived (meth) ) Acrylate compounds.

進而，若使用分子內具有3個以上乙烯性不飽和鍵之化合物，則就電壓保持率而言較佳。 Furthermore, if a compound having three or more ethylenically unsaturated bonds in the molecule is used, it is preferable in terms of voltage retention.

作為分子內具有1個以上乙烯性不飽和鍵之化合物，例如可列舉(甲基)丙烯酸、丁烯酸、異丁烯酸、順丁烯二酸、衣康酸、甲基順丁烯二酸等不飽和羧酸及其烷基酯、(甲基)丙烯腈、(甲基)丙烯醯胺、苯乙烯等。 Examples of the compound having one or more ethylenically unsaturated bonds in the molecule include (meth) acrylic acid, butenoic acid, methacrylic acid, maleic acid, itaconic acid, methyl maleic acid, and the like. Saturated carboxylic acids and their alkyl esters, (meth) acrylonitrile, (meth) acrylamide, styrene, and the like.

作為分子內具有2個以上乙烯性不飽和鍵之化合物，可代表性地列舉不飽和羧酸與聚羥基化合物之酯類、含(甲基)丙烯醯氧基之磷酸酯類、(甲基)丙烯酸羥基酯化合物與聚異氰酸酯化合物之(甲基)丙烯酸胺基甲酸酯類、及(甲基)丙烯酸或(甲基)丙烯酸羥基酯化合物與聚環氧化合物之環氧(甲基)丙烯酸酯類等。 Typical examples of compounds having two or more ethylenically unsaturated bonds in the molecule include esters of unsaturated carboxylic acids and polyhydroxy compounds, phosphates containing (meth) acryloxy groups, and (meth) (Meth) acrylate urethanes of hydroxy acrylate and polyisocyanate compounds, and epoxy (meth) acrylates of (meth) acrylic or hydroxy (meth) acrylate compounds and polyepoxides Wait.

作為不飽和羧酸與聚羥基化合物之酯類，具體而言，可列舉以下化合物。 Specific examples of the esters of the unsaturated carboxylic acid and the polyhydroxy compound include the following compounds.

不飽和羧酸與糖醇之反應物：糖醇具體而言可列舉：乙二醇、聚乙二醇(加成數2~14)、丙二醇、聚丙二醇(加成數2~14)、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、三羥甲基丙烷、甘油、季戊四醇、二季戊四醇等。 Reactants of unsaturated carboxylic acids and sugar alcohols: Specific examples of sugar alcohols include ethylene glycol, polyethylene glycol (addition number 2 to 14), propylene glycol, polypropylene glycol (addition number 2 to 14), 1, 3 -Propylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, and the like.

不飽和羧酸與糖醇之環氧烷加成物之反應物：糖醇與上述相同。所謂環氧烷加成物，具體而言，可列舉環氧乙烷加成物、或環氧丙烷加成物等。 Reactant of the alkylene oxide adduct of unsaturated carboxylic acid and sugar alcohol: Sugar alcohol is the same as above. Specific examples of the "alkylene oxide adduct" include an ethylene oxide adduct and a propylene oxide adduct.

不飽和羧酸與醇胺之反應物；所謂醇胺類，具體而言，可列舉二乙醇胺、三乙醇胺等。 Reactants of unsaturated carboxylic acids and alcohol amines; specifically, alcohol amines include diethanolamine, triethanolamine, and the like.

具體之不飽和羧酸與聚羥基化合物之酯類如以下所述。 Specific esters of unsaturated carboxylic acids and polyhydroxy compounds are described below.

乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷環氧乙烷加成三(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、甘油環氧丙烷加成三(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等，及相同之丁烯酸酯、異丁烯酸酯、順丁烯二酸酯、衣康酸酯、甲基順丁烯二酸酯等。 Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane Tris (meth) acrylate, trimethylolpropane ethylene oxide addition tris (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition Tris (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylates and the like, and the same methacrylic acid esters, methacrylic acid esters, maleic acid esters, itaconic acid esters, methyl maleic acid esters, and the like.

作為此外之不飽和羧酸與聚羥基化合物之酯類，可列舉不飽和羧酸與對苯二酚、間苯二酚、鄰苯三酚、雙酚F、雙酚A等芳香族聚羥基化合物、或該等之環氧乙烷加成物之反應物。具體而言，例如可列舉雙酚A二(甲基)丙烯酸酯、雙酚A雙[氧乙烯(甲基)丙烯酸酯]、雙酚A雙[環氧丙醚(甲基)丙烯酸酯]等；又，可列舉如上所述之不飽和羧酸與異氰尿酸三(2-羥基乙基)酯等雜環式聚羥基化合物之反應物，例如異氰尿酸三(2-羥基乙基)酯之二(甲基)丙烯酸酯、三(甲基)丙烯酸酯等；又，可列舉不飽和羧酸與多元羧酸及聚羥基化合物之反應物，例如(甲基)丙烯酸與鄰苯二甲酸及乙二醇之縮合物、(甲基)丙烯酸與順丁烯二酸及二乙二醇之縮合物、(甲基)丙烯酸與對苯二甲酸及季戊四醇之縮合物、(甲基)丙烯酸與 己二酸與丁二醇及甘油之縮合物等。 Examples of esters of unsaturated carboxylic acids and polyhydroxy compounds include unsaturated polycarboxylic compounds such as aromatic polyhydroxy compounds such as unsaturated carboxylic acids and hydroquinone, resorcinol, catechol, bisphenol F, and bisphenol A. , Or reactants of these ethylene oxide adducts. Specific examples include bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], and the like ; Also, the reaction product of the unsaturated carboxylic acid and the heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate as mentioned above, such as tris (2-hydroxyethyl) isocyanurate Bis (meth) acrylate, tri (meth) acrylate, etc .; and examples thereof include reactants of unsaturated carboxylic acid with polycarboxylic acid and polyhydroxy compound, such as (meth) acrylic acid and phthalic acid and Condensate of ethylene glycol, (meth) acrylic acid with maleic acid and diethylene glycol, condensate of (meth) acrylic acid with terephthalic acid and pentaerythritol, (meth) acrylic acid with hexamethylene Condensates of diacid with butanediol and glycerol.

作為含(甲基)丙烯醯氧基之磷酸酯類，較佳為下述通式(6)、(7)、(8)所示者。 As the (meth) acryloxy group-containing phosphates, those represented by the following general formulae (6), (7), and (8) are preferred.

(式(6)、(7)及(8)中，R10表示氫原子或甲基，p及p'為1~25之整數，q為1、2或3。) (In the formulae (6), (7), and (8), R 10 represents a hydrogen atom or a methyl group, p and p 'are integers of 1 to 25, and q is 1, 2, or 3.)

此處，p及p'較佳為1~10，尤佳為1~4，作為該等之具體例，例如可列舉磷酸(甲基)丙烯醯氧基乙酯、磷酸雙[(甲基)丙烯醯氧基乙基]酯、(甲基)丙烯醯氧基乙二醇磷酸酯等，該等可分別單獨使用，亦可作為混合物使用。 Here, p and p 'are preferably 1 to 10, and particularly preferably 1 to 4. Specific examples of these include, for example, (meth) acrylic acid oxyethyl phosphate and bis [(methyl) phosphate Acrylic ethoxyethyl] ester, (meth) acrylic ethoxy ethylene glycol phosphate, etc. can be used individually or as a mixture.

作為(甲基)丙烯酸羥基酯化合物與聚異氰酸酯化合物之(甲基)丙烯酸胺基甲酸酯類，例如可列舉(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸羥基乙酯、四羥甲基乙烷三(甲基)丙烯酸酯等(甲基)丙烯酸羥基酯化合物與如下聚異氰酸酯化合物之反應物等：六亞甲基二異氰酸酯、1,8-二異氰酸酯-4-異氰酸酯甲基辛烷等脂肪族聚異氰酸酯，環己烷二異氰酸酯、二甲基環己烷二異氰酸酯、4,4-亞甲基雙(環己基異氰酸酯)、異佛爾酮二異氰酸酯、二環庚烷三異氰酸酯等脂環式聚異氰酸酯，4,4-二苯基甲烷二異氰酸酯、硫代磷酸三(異氰 酸酯基苯基)酯等芳香族聚異氰酸酯，異氰尿酸酯等雜環式聚異氰酸酯等。 Examples of the (meth) acrylic acid urethanes of the (meth) acrylic hydroxy ester compound and the polyisocyanate compound include, for example, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetramethylol Reactants of (meth) acrylic hydroxy ester compounds such as ethane tri (meth) acrylate and the following polyisocyanate compounds, etc .: hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, etc. Aliphatic polyisocyanate, cycloaliphatic diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, dicycloheptane triisocyanate and other alicyclics Polyisocyanates such as aromatic polyisocyanates such as 4,4-diphenylmethane diisocyanate and tris (isocyanatephenyl) thiophosphate, and heterocyclic polyisocyanates such as isocyanurate.

作為如上所述者，例如可列舉新中村化學公司製造之商品名「U-4HA」、「UA-306A」、「UA-MC340H」、「UA-MC340H」、「U6LPA」等。 As mentioned above, for example, trade names "U-4HA", "UA-306A", "UA-MC340H", "UA-MC340H", "U6LPA", etc. manufactured by Shin Nakamura Chemical Co., Ltd. may be mentioned.

該等中，較佳為1分子中具有4個以上之胺基甲酸酯鍵[-NH-CO-O-]及4個以上之(甲基)丙烯醯氧基之化合物，該化合物可藉由使如下所述之1分子中具有4個以上、較佳為6個以上異氰酸酯基之化合物等、例如旭化成工業公司製造之「Duranate ME20-100」與季戊四醇二(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯等1分子中具有1個以上羥基及2個以上、較佳為3個以上(甲基)丙烯醯氧基之化合物反應而獲得，上述1分子中具有4個以上、較佳為6個以上異氰酸酯基之化合物例如係使季戊四醇、聚甘油等1分子中具有4個以上羥基之化合物與六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、甲苯二異氰酸酯等二異氰酸酯化合物反應而得之化合物；或係使乙二醇等1分子中具有2個以上羥基之化合物與旭化成工業公司製造之「Duranate 24A-100」、旭化成工業公司製造之「Duranate 22A-75PX」、旭化成工業公司製造之「Duranate 21S-75E」、旭化成工業公司製造之「Duranate 18H-70B」等縮二脲型，旭化成工業公司製造之「Duranate P-301-75E」、旭化成工業公司製造之「Duranate E-402-90T」、旭化成工業公司製造之 「Duranate E-405-80T」等加成物型等1分子中具有3個以上異氰酸酯基之化合物反應而得之化合物；或係使異氰酸酯(甲基)丙烯酸乙酯等聚合或共聚合而得之化合物等。 Among these, a compound having 4 or more urethane bonds [-NH-CO-O-] and 4 or more (meth) acryl fluorenyloxy groups in one molecule is preferable, and the compound can be borrowed Compounds having four or more, preferably six or more isocyanate groups in one molecule as described below, for example, "Duranate ME20-100" manufactured by Asahi Kasei Corporation, pentaerythritol di (meth) acrylate, dipentaerythritol Tris (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like have one or more hydroxyl groups and two or more, preferably three or more (methyl groups) in one molecule ) Acrylic alkoxy compounds are obtained by reacting a compound having 4 or more, preferably 6 or more isocyanate groups in one molecule, for example, a compound having four or more hydroxyl groups in one molecule such as pentaerythritol and polyglycerol, and six A compound obtained by reacting a diisocyanate compound such as methylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, etc .; or two or more molecules in one molecule such as ethylene glycol Combination of hydroxyl groups With the reduction of "Duranate 24A-100" manufactured by Asahi Kasei Kogyo, "Duranate 22A-75PX" manufactured by Asahi Kasei Kogyo, "Duranate 21S-75E" manufactured by Asahi Kasei Kogyo, and "Duranate 18H-70B" manufactured by Asahi Kasei Kogyo Diurea type, "Duranate P-301-75E" manufactured by Asahi Kasei Industries, "Duranate E-402-90T" manufactured by Asahi Kasei Industries, and "Duranate E-405-80T" manufactured by Asahi Kasei Industries A compound obtained by reacting a compound having three or more isocyanate groups in one molecule; or a compound obtained by polymerizing or copolymerizing ethyl isocyanate (meth) acrylate and the like.

作為(甲基)丙烯酸或(甲基)丙烯酸羥基酯化合物與聚環氧化合物之環氧(甲基)丙烯酸酯類，例如可列舉(甲基)丙烯酸、或如上所述之(甲基)丙烯酸羥基酯化合物與如下所述之聚環氧化合物之反應物等，該聚環氧化合物有：(聚)乙二醇聚環氧丙醚、(聚)丙二醇聚環氧丙醚、(聚)1,4-丁二醇聚環氧丙醚、(聚)1,5-戊二醇聚環氧丙醚、(聚)新戊二醇聚環氧丙醚、(聚)1,6-己二醇聚環氧丙醚、(聚)三羥甲基丙烷聚環氧丙醚、(聚)甘油聚環氧丙醚、(聚)山梨醇聚環氧丙醚等脂肪族聚環氧化合物，苯酚酚醛清漆聚環氧化合物、溴化苯酚酚醛清漆聚環氧化合物、(鄰、間、對)甲酚酚醛清漆聚環氧化合物、雙酚A聚環氧化合物、雙酚F聚環氧化合物等芳香族聚環氧化合物，去水山梨醇聚環氧丙醚、異氰尿酸三環氧丙酯、異氰尿酸三環氧丙基三(2-羥基乙基)酯等雜環式聚環氧化合物等。 Examples of epoxy (meth) acrylates of (meth) acrylic acid or (meth) acrylic hydroxy ester compounds and polyepoxides include (meth) acrylic acid and (meth) acrylic acid as described above. A reactant of a hydroxy ester compound with a polyepoxide compound as described below. The polyepoxide compounds include: (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) 1 , 4-Butanediol polyglycidyl ether, (Poly) 1,5-pentanediol polyglycidyl ether, (Poly) neopentyl glycol polyglycidyl ether, (Poly) 1,6-hexanedione Aliphatic polyepoxides such as alcohol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitan polyglycidyl ether, phenol Novolac polyepoxides, brominated phenol novolac polyepoxides, (ortho, meta, p) cresol novolac polyepoxides, bisphenol A polyepoxides, bisphenol F polyepoxides, etc. Family of polyepoxides, heterocyclic polyepoxides such as sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl isocyanurate, etc. Wait.

作為其他乙烯性不飽和化合物，除上述以外，例如可列舉：乙烯雙(甲基)丙烯醯胺等(甲基)丙烯醯胺類；鄰苯二甲酸二烯丙酯等烯丙酯類；鄰苯二甲酸二乙烯酯等含乙烯基之化合物類；藉由利用五硫化二磷等使含醚鍵之乙烯性不飽和化合物之醚鍵硫化變為硫醚鍵而提高交聯速度之含硫醚鍵之化合物類；及例如日本專利第3164407號公報及日本專利特開平9-100111號公報等所記載之使用含異氰酸酯基或巰 基之矽烷偶合劑使多官能(甲基)丙烯酸酯化合物與粒徑5~30nm之矽溶膠[例如，經異丙醇分散之有機矽溶膠(日產化學公司製造之「IPA-ST」)、經甲基乙基酮分散之有機矽溶膠(日產化學公司製造之「MEK-ST」)、經甲基異丁基酮分散之有機矽溶膠(日產化學公司製造之「MIBK-ST」)等]鍵結而成之化合物等藉由經由矽烷偶合劑使乙烯性不飽和化合物與矽溶膠反應並鍵結而提高作為硬化物之強度或耐熱性之化合物類等。 Examples of other ethylenically unsaturated compounds include, in addition to the above, (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; o Vinyl-containing compounds such as diethylene phthalate; thioether-bond compounds that increase the crosslinking speed by sulfurizing the ether bonds of ethylenically unsaturated compounds containing ether bonds into thioether bonds using phosphorus pentasulfide and the like And the use of isocyanate or mercapto-containing silane coupling agents as described in Japanese Patent No. 3164407 and Japanese Patent Laid-Open No. 9-100111, etc., to make polyfunctional (meth) acrylate compounds with a particle size of 5 to 30 nm Silica sol [for example, organic silica sol dispersed by isopropanol ("IPA-ST" manufactured by Nissan Chemical Co., Ltd.), organic silica sol dispersed by methyl ethyl ketone ("MEK-ST" manufactured by Nissan Chemical Co., Ltd. ), Methyl isobutyl ketone-dispersed organosilica sol ("MIBK-ST" manufactured by Nissan Chemical Co., Ltd.), etc.), and the ethylenically unsaturated compound and silica sol are passed through a silane coupling agent. React and bond to increase Compounds such as the strength and heat resistance of hardened materials.

於本發明中，作為乙烯性不飽和化合物，較佳為酯(甲基)丙烯酸酯類、或(甲基)丙烯酸胺基甲酸酯類，其中，尤佳為二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯等5官能以上者。 In the present invention, as the ethylenically unsaturated compound, ester (meth) acrylates or (meth) acrylate urethanes are preferred, and among them, dipentaerythritol hexa (meth) acrylate is particularly preferred. , Dipentaerythritol penta (meth) acrylate, etc.

以上乙烯性不飽和化合物分別可單獨使用，亦可併用2種以上。 Each of the above ethylenically unsaturated compounds may be used alone, or two or more of them may be used in combination.

本發明之遮光性感光性樹脂組成物中之乙烯性不飽和化合物之比例相對於總固形分，通常為1~60重量%，較佳為5~40重量%，尤佳為12~30重量%。若乙烯性不飽和化合物之比例過於多於該範圍，則有顯影性降低之傾向。另一方面，若過少，則有不易確保電壓保持率或形成著色間隔件之形狀、階差之傾向。 The proportion of the ethylenically unsaturated compound in the light-shielding and sexy resin composition of the present invention is generally 1 to 60% by weight, preferably 5 to 40% by weight, and particularly preferably 12 to 30% by weight relative to the total solid content. . If the ratio of the ethylenically unsaturated compound is too much in this range, the developability tends to decrease. On the other hand, if it is too small, it tends to be difficult to ensure the voltage holding ratio or to form the shape and step of the colored spacer.

再者，本發明中，乙烯性不飽和化合物中不含有上述鹼可溶性樹脂。 In the present invention, the ethylenically unsaturated compound does not contain the alkali-soluble resin.

[2-5](e)溶劑 [2-5] (e) Solvent

通常將以上所示之本發明之著色感光性組成物中所含之 各成分溶解或分散於溶劑中，用作著色感光性組成物溶液。 Each component contained in the coloring photosensitive composition of the present invention shown above is usually dissolved or dispersed in a solvent and used as a coloring photosensitive composition solution.

作為此處所使用之溶劑，例如可列舉：二異丙醚、礦油精、正戊烷、戊醚、辛酸乙酯、正己烷、二***、異戊二烯、乙基異丁基醚、硬脂酸丁酯、正辛烷、Varsol#2、Apco#18溶劑、二異丁烯、乙酸戊酯、乙酸丁酯、Apco稀釋劑、丁醚、二異丁酮、甲基環己烯、甲基壬基酮、丙醚、十二烷、Socal溶劑No.1及No.2、甲酸戊酯、二己醚、二異丙酮、Solvesso#150、乙酸(正、第二、第三)丁酯、己烯、Shell TS28溶劑、氯丁烷、乙基戊基酮、苯甲酸乙酯、氯戊烷、乙二醇二***、原甲酸乙酯、甲氧基甲基戊酮、甲基丁基酮、甲基己基酮、異丁酸甲酯、苯甲腈、丙酸乙酯、甲基賽路蘇乙酸酯、甲基異戊基酮、甲基異丁基酮、乙酸丙酯、乙酸戊酯、甲酸戊酯、聯環己烷、二乙二醇單***乙酸酯、雙戊烯、甲氧基甲基戊醇、甲基戊基酮、甲基異丙基酮、丙酸丙酯、丙二醇第三丁醚、甲基乙基酮、甲基賽路蘇、乙基賽路蘇、乙基賽路蘇乙酸酯、卡必醇、環己酮、乙酸乙酯、丙二醇、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單***、丙二醇單***乙酸酯、二丙二醇單***、二丙二醇二甲醚、二丙二醇單甲醚、二丙二醇單甲醚乙酸酯、3-甲氧基丙酸、3-乙氧基丙酸、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、二乙二醇二甲醚、乙二醇乙酸酯、乙基卡必醇、丁基卡必醇、乙二醇單丁醚、丙二醇第三丁醚、3-甲氧基丁醇、3-甲基-3-甲氧基丁醇、三丙二醇甲醚、乙酸3-甲基-3- 甲氧基丁酯等。該等溶劑可單獨使用1種，亦可混合2種以上使用。 Examples of the solvent used herein include diisopropyl ether, mineral spirits, n-pentane, pentyl ether, ethyl octoate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, and hard Butyl fatty acid, n-octane, Varsol # 2, Apco # 18 solvent, diisobutylene, pentyl acetate, butyl acetate, Apco thinner, butyl ether, diisobutyl ketone, methyl cyclohexene, methyl nonyl Ketone, propyl ether, dodecane, Socal solvents No. 1 and No. 2, pentyl formate, dihexyl ether, diisoacetone, Solvesso # 150, acetic acid (n-, second, third) butyl ester, hexane Ene, Shell TS28 solvent, chlorobutane, ethylpentyl ketone, ethyl benzoate, chloropentane, ethylene glycol diethyl ether, ethyl orthoformate, methoxymethylpentanone, methylbutyl ketone, Methylhexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl celex acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, pentyl acetate , Pentyl formate, bicyclohexane, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methylpentyl ketone, methyl isopropyl ketone, propyl propionate, Propylene glycol tert-butyl ether Methyl ethyl ketone, methyl celex, ethyl celex, ethyl celex acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3 -Ethoxypropionic acid, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methyl Propyl oxypropionate, 3-methoxy propyl butyl ester, diethylene glycol dimethyl ether, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether , Propylene glycol third butyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate, and the like. These solvents may be used alone or in combination of two or more.

本發明之著色感光性組成物中，溶劑之含量並無特別限制，就塗膜形成時之塗佈容易性或膜厚控制之觀點而言，通常較佳為90重量%以下，且通常較佳為60重量%以上，尤佳為70重量%以上。即，較佳為以本發明之著色感光性組成物中，總固形分濃度通常成為10重量%以上且通常成為40重量%以下，尤其是成為30重量%以下之方式進行製備。 In the coloring photosensitive composition of the present invention, the content of the solvent is not particularly limited, and from the viewpoint of ease of coating or film thickness control at the time of coating film formation, it is usually preferably 90% by weight or less, and is usually preferable. It is 60% by weight or more, and particularly preferably 70% by weight or more. That is, it is preferable to prepare it in the coloring photosensitive composition of this invention so that total solid content concentration may become 10 weight% or more normally 40 weight% or less, especially 30 weight% or less.

[2-6](f)分散劑 [2-6] (f) Dispersant

為了提高著色劑之分散性，並提高分散穩定性，本發明之感光性樹脂組成物使用分散劑。 In order to improve the dispersibility of the colorant and improve the dispersion stability, the photosensitive resin composition of the present invention uses a dispersant.

本發明中，使用含有氮原子之丙烯酸系嵌段共聚合體作為分散劑。推測此種含有氮原子之丙烯酸系嵌段共聚合體由於其所含之氮原子對著色劑表面具有親和性，並且氮原子以外之部分提高對介質之親和性，故而有助於提高作為整體之分散穩定性。 In the present invention, an acrylic block copolymer containing a nitrogen atom is used as a dispersant. It is presumed that such acrylic block copolymers containing nitrogen atoms have an affinity for the surface of the colorant due to the nitrogen atoms contained therein, and the non-nitrogen atoms increase the affinity for the medium, thereby contributing to the improvement of dispersion as a whole. stability.

分散劑之性能係其對固體表面之吸附行為。關於嵌段共聚合體之吸附行為優異之原因，詳細之機制雖不明確，但推測如下。 The performance of a dispersant is its adsorption behavior on a solid surface. Although the detailed mechanism of the reason why the block copolymer has excellent adsorption behavior is not clear, it is estimated as follows.

即，於通常之無規共聚合體之情形時，構成共聚合體之單體於共聚合時，立體地及/或電性地穩定配置於共聚合體中之機率變高。由於單體穩定配置之部分(分子)立體及/或電性穩定，故吸附於著色劑上時，存在反而成為障礙之情況。與此相對，分子序列如嵌段共聚合體般得以控制之樹脂可將妨 礙分散劑之吸附之部分配置於離開顏料與分散劑之吸附部之位置。即，可於著色劑與分散劑之吸附部配置最適於吸附之部分，於需要溶劑親和性之部分配置與其相適應之部分。推測尤其是關於含有微晶尺寸較小之著色劑之色料之分散，該分子配置影響到良好之分散性。 That is, in the case of a normal random copolymer, the probability that the monomers constituting the copolymer are three-dimensionally and / or electrically stably arranged in the copolymer during copolymerization is high. Since the part (molecule) in which the monomer is stably arranged is three-dimensional and / or electrically stable, there is a case where it becomes an obstacle when adsorbed on the colorant. In contrast, a resin in which the molecular sequence is controlled like a block copolymer can arrange a portion that prevents the dispersant from being adsorbed away from the adsorption portion of the pigment and the dispersant. That is, the part that is most suitable for adsorption can be arranged in the adsorption part of the colorant and the dispersant, and the part suitable for it can be arranged in the part that requires solvent affinity. It is speculated that, especially with regard to the dispersion of colorants containing smaller coloring agents, the molecular configuration affects good dispersibility.

就可極高效地分散本發明所使用之著色劑之方面而言，較佳為含有氮原子之丙烯酸系嵌段共聚合體。其原因尚不明確，但推測其原因在於：藉由控制分子序列，分散劑吸附於著色劑時成為障礙之構造較少。作為丙烯酸系嵌段共聚合體，較佳為A-B嵌段共聚合體及B-A-B嵌段共聚合體中之至少一者，該A-B嵌段共聚合體及B-A-B嵌段共聚合體包含側鏈具有4級銨鹽基及胺基中之至少一者之A嵌段、與不具有4級銨鹽基及胺基之B嵌段。 In terms of being able to disperse the coloring agent used in the present invention extremely efficiently, an acrylic block copolymer containing a nitrogen atom is preferred. The reason is not clear, but it is presumed that by controlling the molecular sequence, the dispersant has fewer structures that become obstacles when adsorbed to the colorant. The acrylic block copolymer is preferably at least one of an AB block copolymer and a BAB block copolymer. The AB block copolymer and the BAB block copolymer include a side chain having a fourth-order ammonium salt group and The A block of at least one of the amine groups and the B block having no quaternary ammonium salt group and amine group.

於A嵌段具有4級銨鹽基之情形時，該4級銨鹽基較佳為以-N+R21R22R23‧M-(其中，R21、R22及R23分別獨立表示氫原子、或可經取代之環狀或鏈狀之烴基；或者R21、R22及R23中之兩者以上亦可相互鍵結而形成環狀構造；M-表示抗衡陰離子)表示。該4級銨鹽基可直接鍵結於主鏈上，亦可經由2價連結基而鍵結於主鏈上。 When the A block group having a quaternary ammonium salt of the case, the quaternary ammonium salt group is preferably in -N + R 21 R 22 R 23 ‧M - ( wherein, R 21, R 22 and R 23 each independently represent A hydrogen atom or a substituted cyclic or chain hydrocarbon group; or two or more of R 21 , R 22, and R 23 may be bonded to each other to form a cyclic structure; M - represents a counter anion). The quaternary ammonium salt group may be directly bonded to the main chain, or may be bonded to the main chain through a divalent linking group.

於-N+R21R22R23中，作為R21、R22及R23中之2者以上相互鍵結而形成之環狀構造，例如可列舉5~7員環之含氮雜環單環或該等中2個縮合而成之縮合環。該含氮雜環較佳為不具有芳香性者，更佳為飽和環。具體而言，例如可列舉如下所述者。該等環狀構造亦可進而具有取代基。 In -N + R 21 R 22 R 23 , as a cyclic structure formed by bonding two or more of R 21 , R 22 and R 23 to each other, for example, a nitrogen-containing heterocyclic monocyclic ring having 5 to 7 members may be mentioned Ring or two of them. The nitrogen-containing heterocyclic ring is preferably one having no aromaticity, and more preferably a saturated ring. Specific examples include the following. These cyclic structures may further have a substituent.

(上述式中，R表示R21~R23中之任一之基。) (In the above formula, R represents any one of R 21 to R 23. )

作為-N+R21R22R23中之R21~R23，更佳為可具有取代基之碳數1~3之烷基、可具有取代基之苯基、或可具有取代基之苄基。 As in the -N + R 21 R 22 R 23 R 21 ~ R 23, more preferably may have a substituent group of carbon number 1 ~ 3 alkyl group, the group may have a substituent of a phenyl or benzyl substituent may have a group of base.

又，作為具有4級銨鹽基之A嵌段，尤佳為含有下述通式(VI)所示之部分構造者。 In addition, as the A block having a quaternary ammonium salt group, it is particularly preferred to have a partial structure represented by the following general formula (VI).

(上述式(VI)中，R21、R22、R23分別獨立表示氫原子、或可經取代之環狀或鏈狀之烴基；或者R21、R22及R23中之2者以上可相互鍵結而形成環狀構造；R24表示氫原子或甲基；X表示2價連結基，M-表示抗衡陰離子。) (In the above formula (VI), R 21 , R 22 , and R 23 each independently represent a hydrogen atom or a cyclic or chain hydrocarbon group which may be substituted; or two or more of R 21 , R 22, and R 23 may be Bonded to each other to form a cyclic structure; R 24 represents a hydrogen atom or a methyl group; X represents a divalent linking group, and M - represents a counter anion.)

上述通式(VI)中，R21、R22、R23之烴基較佳為分別獨立而具有碳數1~10之烷基、碳數6~20之芳香族基之取代基。具體而言，可列舉甲基、乙基、丙基、異丙基、丁基、異丁 基、苄基、苯基等。其中較佳為甲基、乙基、丙基、苄基。 In the general formula (VI), the hydrocarbon groups of R 21 , R 22 , and R 23 are each independently a substituent having an alkyl group having 1 to 10 carbon atoms and an aromatic group having 6 to 20 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, benzyl, and phenyl. Among them, methyl, ethyl, propyl and benzyl are preferred.

上述通式(VI)中，作為2價連結基X，例如可列舉碳數1~10之伸烷基、伸芳基、-CONH-R25-、-COO-R26-(其中，R25及R26表示直接鍵結、碳數1~10之伸烷基、或碳1~10之醚基(-R27-O-R28-：R27及R28各自獨立為伸烷基))等，較佳為-COO-R26-。 Examples of the divalent linking group X in the general formula (VI) include an alkylene group having 1 to 10 carbon atoms, an arylene group, -CONH-R 25- , -COO-R 26- (wherein R 25 And R 26 represents a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (-R 27 -OR 28- : R 27 and R 28 are each independently an alkylene group), etc., -COO-R 26 -is preferable.

又，作為抗衡陰離子M-，可列舉Cl-、Br-、I-、ClO4 -、BF4 -、CH3COO-、PF6 -等。 Examples of the counter anion M − include Cl − , Br − , I − , ClO 4 − , BF 4 − , CH 3 COO − , PF 6 − and the like.

1個A嵌段中亦可含有2種以上如上述含有特定之4級銨鹽基之部分構造。此種情形時，2種以上之含有4級銨鹽基之部分構造可以無規共聚合或嵌段共聚合中之任一態樣而含有於該A嵌段中。又，不含該4級銨鹽基之部分構造亦可含有於A嵌段中，作為該部分構造之例，可列舉下述源自(甲基)丙烯酸酯系單體之部分構造等。 One A block may contain two or more types of partial structures containing a specific quaternary ammonium salt group as described above. In this case, two or more types of partial structures containing a fourth-order ammonium salt group may be contained in the A block by random copolymerization or block copolymerization. In addition, a partial structure that does not include the fourth-order ammonium salt group may be contained in the A block. Examples of the partial structure include the following partial structures derived from (meth) acrylate-based monomers.

該不含4級銨鹽基之部分構造於A嵌段中之含量較佳為0~50重量%，更佳為0~20重量%，最佳為A嵌段中未包含該不含4級銨鹽基之部分構造。 The content of the fourth-stage ammonium salt-free portion structure in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, and most preferably, the A-block is not included in the A-block. Partial structure of ammonium salt.

再者，上述丙烯酸系嵌段共聚合體之A嵌段亦可具有未經4級化之未反應之3級胺基。 In addition, the A block of the acrylic block copolymer may have an unreacted tertiary amine group that has not been quaternized.

於A嵌段具有胺基之情形時，胺基可為1~3級中之任一種。該具有1~3級胺基之單體之含有比例於構成該丙烯酸系嵌段共聚合體之單體組成中，較佳為20莫耳%以上，更佳為50莫耳%以上。 When the A block has an amine group, the amine group may be any of 1 to 3 grades. The content ratio of the monomer having 1 to 3 amine groups in the monomer composition constituting the acrylic block copolymer is preferably 20 mol% or more, and more preferably 50 mol% or more.

該胺基可直接鍵結於主鏈上，亦可經由2價連結基而鍵結 於主鏈上。 This amine group may be directly bonded to the main chain, or may be bonded to the main chain via a divalent linking group.

又，作為上述1~3級胺基，較佳為以-NR41R42(其中，R41及R42分別獨立表示可具有取代基之環狀或鏈狀之烷基、可具有取代基之芳基或可具有取代基之芳烷基)表示，又，較佳作為含有其之部分構造(重複單元)者例如可列舉如下述通式所示之構造。 In addition, as the first to third amine groups, -NR 41 R 42 (wherein R 41 and R 42 each independently represent a cyclic or chain alkyl group which may have a substituent, and An aryl group or an aralkyl group which may have a substituent is represented, and a structure (repeating unit) containing a partial structure (repeating unit) preferably is, for example, a structure represented by the following general formula.

(其中，R41及R42與上述之R41及R42含義相同，R43表示碳數1以上之伸烷基，R44表示氫原子或甲基。) (Wherein R 41 and R 42 have the same meanings as R 41 and R 42 described above, R 43 represents an alkylene group having 1 or more carbon atoms, and R 44 represents a hydrogen atom or a methyl group.)

其中，R41及R42較佳為甲基，R43較佳為亞甲基、伸乙基，R44較佳為氫原子或甲基。作為此種部分構造，可尤佳地使用下述通式所示之源自丙烯酸二甲胺基乙酯或甲基丙烯酸二甲胺基乙酯之構造等。 Among them, R 41 and R 42 are preferably methyl, R 43 is preferably methylene and ethylene, and R 44 is preferably a hydrogen atom or a methyl group. As such a partial structure, a structure derived from dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate represented by the following general formula can be particularly preferably used.

(上述通式中，R44與上述含義相同。) (In the above formula, R 44 has the same meaning as above.)

進而，1個A嵌段中亦可含有2種以上之上述含有胺基之部分構造。於該情形時，2種以上之含有胺基之部分構造可以無規共聚合或嵌段共聚合中之任一態樣而含有於該A嵌段中。又，不含胺基之部分構造亦可部分含有於A嵌段中，作為此種部分構造之例，可列舉源自(甲基)丙烯酸酯系單體之部分構造等。該不含胺基之部分構造於A嵌段中之含量較佳為0~50重量%，更佳為0~20重量%，最佳為A嵌段中未包含該不含胺基之部分構造。 Furthermore, one A block may contain two or more of the above-mentioned amine group-containing partial structures. In this case, the two or more types of amine group-containing partial structures may be contained in the A block in any one of random copolymerization and block copolymerization. In addition, a partial structure that does not contain an amine group may be partially contained in the A block. Examples of such a partial structure include a partial structure derived from a (meth) acrylate-based monomer. The content of the amine group-free portion structure in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, and most preferably the A block does not include the amine group-free portion structure. .

A嵌段中可具有4級銨鹽基或胺基中之任一者，亦可具有兩者。4級銨鹽基對極性較低之溶劑之溶解性較低，胺基對極性較低之溶劑之溶解性較高。因此，於抗蝕劑中大量使用極性較低之溶劑之情形時，就提高分散劑對抗蝕劑溶劑之溶解性之觀點而言，較佳為A嵌段中具有4級銨鹽基及胺基，或者不具有4級銨鹽基而具有胺基，更佳為不具有4級銨鹽基而具有胺基。 The A block may have either a quaternary ammonium salt group or an amine group, or both. Grade 4 ammonium salts have lower solubility for solvents with lower polarity, and amine groups have higher solubility for solvents with lower polarity. Therefore, when a relatively low-polarity solvent is used in a large amount of the resist, from the viewpoint of improving the solubility of the dispersant in the resist solvent, it is preferred that the A block has a level 4 ammonium salt group and an amine group. Or it may have an amine group without having a quaternary ammonium salt group, and more preferably have an amine group without having a quaternary ammonium salt group.

另一方面，構成丙烯酸系嵌段共聚合體之B嵌段只要不具有上述4級銨鹽基及胺基，且包含可與構成上述A嵌段之單體共聚合之單體，則並無特別限制。B嵌段為不具有成為顏料吸附基之含氮原子之官能基之親溶劑性之部位，對溶劑具有親和性，故具有使吸附於分散劑中之顏料於溶劑中穩定化之功能。 On the other hand, the B block constituting the acrylic block copolymer is not particularly limited as long as it does not have the above-mentioned quaternary ammonium salt group and amine group, and contains a monomer copolymerizable with the monomer constituting the A block. limit. The B block is a solvent-free site having no nitrogen atom-containing functional group that becomes a pigment-adsorbing group, and has an affinity for the solvent. Therefore, it has the function of stabilizing the pigment adsorbed in the dispersant in the solvent.

作為B嵌段，例如可列舉使如下所述之共聚單體共聚合而成之共聚物構造，上述共聚單體為：苯乙烯、α-甲基苯乙 烯等苯乙烯系單體；(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸羥基乙酯、丙烯酸環氧丙基乙酯、(甲基)丙烯酸-N,N-二甲基胺基乙酯等(甲基)丙烯酸酯系單體；(甲基)丙烯醯氯等(甲基)丙烯酸鹽系單體；(甲基)丙烯醯胺、N,N-羥甲基丙烯醯胺、N,N-二甲基丙烯醯胺、N,N-二甲基胺基乙基丙烯醯胺等(甲基)丙烯醯胺系單體；乙酸乙烯酯；丙烯腈；烯丙基環氧丙醚、丁烯酸環氧丙醚；N-甲基丙烯醯啉等。 Examples of the B block include a copolymer structure obtained by copolymerizing a comonomer as described below. The comonomer is: a styrene-based monomer such as styrene or α-methylstyrene; (methyl ) Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, epoxypropyl ethyl acrylate, -N (meth) acrylic acid , (Meth) acrylic acid ester monomers such as N-dimethylaminoethyl ester; (meth) acrylic acid monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N, N (Meth) acrylamide-based monomers such as hydroxymethacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminoethylacrylamide; vinyl acetate; propylene Nitrile; Allyl Glycidyl Ether, Butyl Glycidyl Ether; N-Methacryl Porphyrin, etc.

作為B嵌段，尤其是較佳為含有下述式(VIII)所示之源自(甲基)丙烯酸酯系單體之部分構造者。 As the B block, a structure containing a (meth) acrylic acid ester-based monomer represented by the following formula (VIII) is particularly preferred.

(上述式(VIII)中，R41表示氫原子或甲基；R42表示可具有取代基之環狀或鏈狀之烷基、可具有取代基之烯丙基、或可具有取代基之芳烷基。) (In the above formula (VIII), R 41 represents a hydrogen atom or a methyl group; R 42 represents a cyclic or chain alkyl group which may have a substituent, an allyl group which may have a substituent, or an aromatic group which may have a substituent alkyl.)

1個B嵌段中可含有2種以上之上述源自(甲基)丙烯酸酯系單體之部分構造。當然，該B嵌段亦可進而含有該等以外之部分構造。於2種以上之源自單體之部分構造存在於不含4級銨鹽基之B嵌段中之情形時，各部分構造可以無規 共聚合或嵌段共聚合中之任一態樣而含有於該B嵌段中。 One B block may contain two or more types of the above-mentioned (meth) acrylic acid-based monomer-containing partial structures. Of course, this B block may further contain a structure other than these. When two or more types of monomer-derived partial structures are present in the B block that does not contain a level 4 ammonium salt group, each of the partial structures may be randomly copolymerized or block copolymerized. It is contained in this B block.

於B嵌段中含有上述源自(甲基)丙烯酸酯系單體之部分構造以外之部分構成之情形時，該(甲基)丙烯酸酯系單體以外之部分構造於B嵌段中之含量較佳為0~99重量%，更佳為0~85重量%。 When the B block contains a part structure other than the above-mentioned (meth) acrylate-based monomer structure, the content of the structure other than the (meth) acrylate monomer in the B block It is preferably 0 to 99% by weight, and more preferably 0 to 85% by weight.

本發明所使用之丙烯酸系分散劑為含有此種A嵌段與B嵌段之A-B嵌段或B-A-B嵌段共聚合型高分子化合物，此種嵌段共聚合體例如係藉由活性聚合法而製備。 The acrylic dispersant used in the present invention is an AB block or BAB block copolymer type polymer compound containing such A block and B block. Such a block copolymer is prepared, for example, by a living polymerization method. .

活性聚合法中有陰離子活性聚合法、陽離子活性聚合法、自由基活性聚合法。例如可列舉日本專利特開2007-270147號公報中所記載之方法。 The living polymerization method includes anionic living polymerization method, cationic living polymerization method, and radical living polymerization method. For example, the method described in Japanese Patent Laid-Open No. 2007-270147 can be cited.

再者，上述丙烯酸系嵌段共聚合體之胺值以有效固形分換算計通常為1~300mgKOH/g左右，其較佳之範圍因A嵌段具有4級銨鹽基之情形與A嵌段不具有4級銨鹽基之情形而異。再者，胺值係以與中和共聚合體1g中之胺基所需之酸之莫耳當量相對應之KOH之mg數所表示的值。 In addition, the amine value of the acrylic block copolymer is usually about 1 to 300 mgKOH / g in terms of effective solid content. The preferred range is because the A block has a level 4 ammonium salt group and the A block does not. The situation for the level 4 ammonium salt varies. The amine value is a value expressed in mg of KOH corresponding to the molar equivalent of the acid required to neutralize the amine group in 1 g of the copolymer.

即，本發明之A-B嵌段共聚合體及B-A-B嵌段共聚合體中，於A嵌段具有4級銨鹽基之情形時，該共聚合體1g中之4級銨鹽基之量通常較佳為0.1~10mmol，若於該範圍外，則存在無法兼具良好之耐熱性與分散性之情況。 That is, in the case of the AB block copolymer and the BAB block copolymer of the present invention, when the A block has a level 4 ammonium salt group, the amount of the level 4 ammonium salt group in 1 g of the copolymer is usually preferably 0.1. ~ 10mmol, if it is outside this range, there may be a case where it is impossible to have both good heat resistance and dispersibility.

再者，於此種嵌段共聚合體中，通常存在含有製造過程中所產生之胺基之情況，其胺值通常為1~100mgKOH/g左右，較佳為1~80mgKOH/g。更佳為1~50mgKOH/g。 Furthermore, in such a block copolymer, the amine group generated in the manufacturing process may be contained, and its amine value is usually about 1 to 100 mgKOH / g, and preferably 1 to 80 mgKOH / g. More preferably, it is 1 to 50 mgKOH / g.

又，於A嵌段中不含4級銨鹽基之情形時，該共聚合體 之胺值通常為50~300mgKOH/g左右，較佳為50~200mgKOH/g，更佳為80mgKOH/g以上且150mgKOH/g以下，進而較佳為90~150mgKOH/g。 In the case where the A block does not contain a level 4 ammonium salt group, the amine value of the copolymer is usually about 50 to 300 mgKOH / g, preferably 50 to 200 mgKOH / g, more preferably 80 mgKOH / g or more 150 mgKOH / g or less, and more preferably 90 to 150 mgKOH / g.

此種丙烯酸系嵌段共聚合體之酸值亦取決於成為該酸值之根源之酸性基之有無及種類，一般而言較低為宜，通常為100mgKOH/g以下，較佳為50mgKOH/g以下，更佳為40mgKOH/g以下。 The acid value of such acrylic block copolymers also depends on the presence and type of the acidic group that is the source of the acid value. Generally, a lower value is preferred, usually 100 mgKOH / g or less, and preferably 50 mgKOH / g or less. , More preferably 40 mgKOH / g or less.

又，丙烯酸系嵌段共聚合體之分子量以利用GPC測定之聚乙烯換算之重量平均分子量(Mw)計，通常為1000以上、100,000以下之範圍。若丙烯酸系嵌段共聚合體之分子量過小，則有分散穩定性降低之傾向，若過大，則有顯影性、解像性降低之傾向。 The molecular weight of the acrylic block copolymer is usually in the range of 1,000 or more and 100,000 or less as a weight average molecular weight (Mw) in terms of polyethylene measured by GPC. If the molecular weight of the acrylic block copolymer is too small, the dispersion stability tends to decrease, and if it is too large, the developability and resolution tend to decrease.

本發明中，亦可使用具有與上述者相同之構造之市售之丙烯酸系嵌段共聚合體。 In the present invention, a commercially available acrylic block copolymer having the same structure as the above may be used.

本發明中，含有氮原子之丙烯酸系嵌段共聚合體之含量相對於顏料，通常為5重量%以上且90重量%以下，較佳為5重量%以上且60重量%以下，進而較佳為5重量%以上且40重量%以下。若含有氮原子之丙烯酸系嵌段共聚合體之含量過少，則存在無法獲得充分之分散性之情況，若過多，則存在相對而言其他成分之比例減少，電壓保持率降低，並且無法形成著色間隔件之形狀、階差之情況。 In the present invention, the content of the acrylic block copolymer containing a nitrogen atom is usually 5% by weight or more and 90% by weight or less with respect to the pigment, preferably 5% by weight or more and 60% by weight or less, and further preferably 5 At least 40% by weight. If the content of the acrylic block copolymer containing a nitrogen atom is too small, sufficient dispersibility may not be obtained. If it is too large, the proportion of other components may be relatively reduced, the voltage holding ratio may be reduced, and the coloring interval may not be formed. The shape and step of the piece.

於本發明中，亦可併用含有氮原子之丙烯酸系嵌段共聚合體以外之分散劑。併用之分散劑較佳為高分子分散劑，且較佳為構造與著色劑完全不同之共聚物。 In the present invention, a dispersant other than the acrylic block copolymer containing a nitrogen atom may be used in combination. The dispersant used in combination is preferably a polymer dispersant, and a copolymer having a completely different structure from the coloring agent is preferable.

作為併用之分散劑，例如可列舉：胺基甲酸酯系分散劑、聚烯丙胺系分散劑、包含具有胺基之單體與巨單體之分散劑、聚氧乙烯烷基醚系分散劑、聚氧乙烯二酯系分散劑、聚醚磷酸系分散劑、聚酯磷酸系分散劑、去水山梨醇脂肪族酯系分散劑、脂肪族改質聚酯系分散劑等。 Examples of the dispersant used in combination include a urethane-based dispersant, a polyallylamine-based dispersant, a dispersant containing a monomer having an amine group and a macromonomer, and a polyoxyethylene alkyl ether-based dispersant. , Polyoxyethylene diester-based dispersant, polyether phosphoric acid-based dispersant, polyester phosphoric acid-based dispersant, sorbitan aliphatic ester-based dispersant, aliphatic modified polyester-based dispersant, and the like.

為了提高著色劑之分散穩定性，較佳為本發明之著色感光性組成物併用分散輔助劑。此處所謂分散輔助劑，係指用以提高著色劑之分散性之顏料衍生物等。 In order to improve the dispersion stability of the colorant, it is preferable to use a dispersion aid in combination with the coloring photosensitive composition of the present invention. The dispersing assistant herein refers to a pigment derivative or the like for improving the dispersibility of a colorant.

作為顏料衍生物，可列舉偶氮系、酞菁系、喹吖酮系、苯并咪唑酮系、喹酞酮系、異吲哚啉酮系、二系、蒽醌系、陰丹士林系、苝系、紫環酮系、二酮吡咯并吡咯系、二系等衍生物，其中較佳為喹酞酮系。作為顏料衍生物之取代基，可列舉磺酸基、磺醯胺基及其4級鹽、鄰苯二甲醯亞胺甲基、二烷基胺基烷基、羥基、羧基、醯胺基等直接或經由烷基、芳基、雜環基等鍵結於顏料骨架上者，較佳為磺酸基。又，該等取代基可對一個顏料骨架取代數個。 Examples of the pigment derivative include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, and Series, anthraquinone series, indanthrene series, stilbene series, purple ring ketone series, diketopyrrolopyrrole series, two Derivatives, such as quinolone, are preferred. Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamido group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylamino group, a hydroxyl group, a carboxyl group, and a fluorenyl group. Those bonded to the pigment skeleton directly or via an alkyl group, an aryl group, or a heterocyclic group are preferably a sulfonic acid group. In addition, these substituents may substitute several for one pigment skeleton.

作為顏料衍生物之具體例，可列舉酞菁之磺酸衍生物、喹酞酮之磺酸衍生物、蒽醌之磺酸衍生物、喹吖酮之磺酸衍生物、二酮吡咯并吡咯之磺酸衍生物、二之磺酸衍生物等。 Specific examples of the pigment derivative include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, and diketopyrrolopyrrole Sulfonic acid derivatives, di Sulfonic acid derivatives.

該等顏料衍生物可單獨使用1種或組合2種以上使用。 These pigment derivatives can be used individually by 1 type or in combination of 2 or more types.

使用顏料衍生物之情形時，其使用量相對於顏料通常為0.1~30重量%，較佳為0.1~20重量%以下，更佳為0.1~10重量%，進而較佳為0.1~5重量%。 When a pigment derivative is used, the amount used is generally 0.1 to 30% by weight relative to the pigment, preferably 0.1 to 20% by weight or less, more preferably 0.1 to 10% by weight, and still more preferably 0.1 to 5% by weight. .

[2-7]其他成分 [2-7] other ingredients

本發明之遮光性感光性樹脂組成物中，除上述成分以外，亦可進而含有聚合加速劑、增感色素、界面活性劑、光酸產生劑、交聯劑、密接性改善劑、可塑劑、保存穩定劑、表面保護劑、有機羧酸、有機羧酸酐、顯影改良劑、熱聚合抑制劑等。 The light-shielding sexy light resin composition of the present invention may further contain a polymerization accelerator, a sensitizing dye, a surfactant, a photoacid generator, a cross-linking agent, an adhesion improving agent, a plasticizer, Storage stabilizers, surface protection agents, organic carboxylic acids, organic carboxylic anhydrides, development improvers, thermal polymerization inhibitors, etc.

[2-7-1]光酸產生劑 [2-7-1] Photoacid generator

所謂光酸產生劑，係指可藉由紫外線而產生酸之化合物，藉由進行曝光時產生之酸之作用，因存在例如三聚氰胺化合物等交聯劑，故而會進行交聯反應。該光酸產生劑中，較佳為對溶劑之溶解性、尤其是對著色感光性組成物所使用之溶劑之溶解性較大者，例如可列舉：二苯基錪、二甲苯基錪、苯基對茴香基錪、雙(間硝基苯基)錪、雙(對第三丁基苯基)錪、雙(對氯苯基)錪、雙(正十二烷基)錪、對異丁基苯基對甲苯基錪、對異丙基苯基對甲苯基錪等二芳基錪；或三苯基鋶等三芳基鋶之氯化物、溴化物；或氟硼酸鹽、六氟磷酸鹽、六氟砷酸鹽、芳香族磺酸鹽、四(五氟苯基)硼酸鹽等；或正丁基三苯基硼酸二苯基苯甲醯甲基鋶等鋶有機硼錯合物類；或2-甲基-4,6-雙(三氯甲基)三、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)三等三化合物等，但並不僅限於此。 The photoacid generator refers to a compound capable of generating an acid by ultraviolet rays, and a cross-linking reaction occurs due to the presence of a crosslinking agent such as a melamine compound due to the action of an acid generated during exposure. Among the photoacid generators, those having a high solubility in a solvent, particularly those having a large solubility in a solvent used for coloring a photosensitive composition, are preferred. Examples include diphenylphosphonium, xylylphosphonium, and benzene. P-anisylfluorene, bis (m-nitrophenyl) fluorene, bis (p-thirdbutylphenyl) fluorene, bis (p-chlorophenyl) fluorene, bis (n-dodecyl) fluorene, p-isobutyl Diarylfluorene such as p-phenylphenyl p-tolylfluorene and p-isopropylphenyl p-tolylfluorene; or chlorides and bromides of triarylfluorene such as triphenylfluorene; or fluoroborate, hexafluorophosphate, Hexafluoroarsenate, aromatic sulfonate, tetrakis (pentafluorophenyl) borate, etc .; or fluorene organoborium complexes such as n-butyltriphenylborate diphenylbenzyl methyl hydrazone; or 2-methyl-4,6-bis (trichloromethyl) tri , 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) tri Wait three Compounds and the like are not limited thereto.

[2-7-2]交聯劑 [2-7-2] Crosslinking agent

亦可進而於本發明之著色感光性組成物中添加交聯劑，例如可使用三聚氰胺或胍胺系之化合物。作為該等交聯劑，例如可列舉下述通式(XI)所示之三聚氰胺或胍胺系之化合物。 You may further add a crosslinking agent to the coloring photosensitive composition of this invention, For example, a melamine or a guanamine type compound can be used. Examples of such a crosslinking agent include melamine or guanamine-based compounds represented by the following general formula (XI).

[化14] [Chemical 14]

(式中，R61表示-NR66R67基或芳基，於R61為-NR66R67基之情形時，R62、R63、R64、R65、R66及R67之一表示-CH2OR68基，並且於R61為芳基之情形時，R62、R63、R64及R65之一表示-CH2OR68基，R62、R63、R64、R65、R66及R67中剩餘者相互獨立表示氫或-CH2OR68基，此處，R68表示氫或烷基。) (In the formula, R 61 represents a -NR 66 R 67 group or an aryl group. When R 61 is a -NR 66 R 67 group, one of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 Represents a -CH 2 OR 68 group, and when R 61 is an aryl group, one of R 62 , R 63 , R 64 and R 65 represents a -CH 2 OR 68 group, R 62 , R 63 , R 64 , R (65 , R 66, and R 67 independently represent hydrogen or -CH 2 OR 68 , and R 68 represents hydrogen or alkyl.)

此處，芳基典型而言為苯基、1-萘基或2-萘基，於該等苯基或萘基上可鍵結有烷基、烷氧基、鹵素等取代基。烷基及烷氧基可分別為碳數1~6左右。R68所表示之烷基通常為上述中之甲基或乙基，特別是甲基。 Here, the aryl group is typically a phenyl group, a 1-naphthyl group, or a 2-naphthyl group, and substituents such as an alkyl group, an alkoxy group, and a halogen group may be bonded to the phenyl or naphthyl group. The alkyl group and the alkoxy group may each have about 1 to 6 carbon atoms. The alkyl group represented by R 68 is usually a methyl group or an ethyl group, especially a methyl group.

相當於通式(XI)之三聚氰胺系化合物、即下述通式(XI-1)之化合物中包含六羥甲基三聚氰胺、五羥甲基三聚氰胺、四羥甲基三聚氰胺、六甲氧基甲基三聚氰胺、五甲氧基甲基三聚氰胺、四甲氧基甲基三聚氰胺、六乙氧基甲基三聚氰胺等。 The melamine-based compound corresponding to the general formula (XI), that is, the compound of the following general formula (XI-1) includes hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, and hexamethoxymethylmelamine , Pentamethoxymethyl melamine, tetramethoxymethyl melamine, hexaethoxymethyl melamine, etc.

(式中，於R62、R63、R64、R65、R66及R67之一為芳基之 情形時，R62、R63、R64及R65之一表示-CH2OR68基，R62、R63、R64、R65、R66及R67中剩餘者相互獨立表示氫或-CH2OR68基，此處R68表示氫或烷基。) (In the formula, when one of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 is an aryl group, one of R 62 , R 63 , R 64 and R 65 represents -CH 2 OR 68 Group , the rest of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 independently represent a hydrogen or -CH 2 OR 68 group, where R 68 represents hydrogen or an alkyl group.)

又，相當於通式(XI)之胍胺系化合物、即通式(XI)中之R61為芳基之化合物中包含四羥甲基苯并胍胺、四甲氧基甲基苯并胍胺、三甲氧基甲基苯并胍胺、四乙氧基甲基苯并胍胺等。 In addition, guanamine-based compounds corresponding to the general formula (XI), that is, compounds in which R 61 in the general formula (XI) is an aryl group, include tetramethylolbenzoguanamine and tetramethoxymethylbenzoguanidine. Amine, trimethoxymethylbenzoguanamine, tetraethoxymethylbenzoguanamine, and the like.

進而，亦可使用具有羥甲基或羥甲基烷基醚基之交聯劑。以下列舉其例。 Furthermore, a crosslinking agent having a methylol group or a methylol alkyl ether group may be used. Examples are given below.

2,6-雙(羥基甲基)-4-甲基苯酚、4-第三丁基-2,6-雙(羥基甲基)苯酚、5-乙基-1,3-雙(羥基甲基)全氫-1,3,5-三-2-酮(通稱為N-乙基二羥甲基三酮)或其二甲醚體、二羥甲基三亞甲基脲或其二甲醚體、3,5-雙(羥基甲基)全氫-1,3,5-二-4-酮(通稱為dimethyloluron)或其二甲醚體、四羥甲基乙二醛二烷基脲或其四甲醚體。 2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) Perhydro-1,3,5-tri -2-one (commonly known as N-ethyldimethyloltriol Ketone) or its dimethyl ether body, dimethyloltrimethylene urea or its dimethyl ether body, 3,5-bis (hydroxymethyl) perhydro-1,3,5- two 4-ketone (commonly known as dimethyloluron) or its dimethyl ether body, tetramethylol glyoxal dialkyl urea or its tetramethyl ether body.

再者，該等交聯劑可單獨使用1種，亦可組合2種以上使用。使用交聯劑時之量相對於遮光性感光性樹脂組成物之總固形分較佳為0.1~15重量%，尤佳為0.5~10重量%。 In addition, these crosslinking agents may be used individually by 1 type, and may be used in combination of 2 or more type. The amount when the crosslinking agent is used is preferably 0.1 to 15% by weight, and more preferably 0.5 to 10% by weight, relative to the total solids content of the light-shielding photosensitive resin composition.

[2-7-3]密接改善劑 [2-7-3] Adhesion improving agent

為使較細之線或點充分密接，亦可於本發明之遮光性感光性樹脂組成物中含有密接改善劑。 In order to make the thinner threads or dots sufficiently close to each other, an adhesion improving agent may be contained in the light-shielding and sexy light-sensitive resin composition of the present invention.

作為密接改善劑，較佳為含有氮原子之化合物或含磷酸基之化合物、矽烷偶合劑等，作為含有氮原子之化合物，例如較佳為二胺類(日本專利特開平11-184080號公報記載之密接增強劑等)或唑類。其中較佳為唑類，尤佳為咪唑類(日本 專利特開平9-236923號公報記載之密接改善劑等)、苯并咪唑類、苯并***類(日本專利特開2000-171968號公報記載之密接改善劑等)，最佳為咪唑類與苯并咪唑類。該等中，就難以產生灰霧、可大幅提高密接性之方面而言，較佳為2-羥基苯并咪唑、2-羥基乙基苯并咪唑、苯并咪唑、2-羥基咪唑、咪唑、2-巰基咪唑、2-胺基咪唑，尤佳為2-羥基苯并咪唑、苯并咪唑、2-羥基咪唑、咪唑。作為矽烷偶合劑之種類，可使用環氧系、甲基丙烯酸系、胺基系等各者，尤佳為環氧系之矽烷偶合劑。 The adhesion improving agent is preferably a compound containing a nitrogen atom, a compound containing a phosphate group, a silane coupling agent, and the like, and a compound containing a nitrogen atom is, for example, a diamine (Japanese Patent Application Laid-Open No. 11-184080) (Tightening enhancer, etc.) or azoles. Among them, azoles are preferred, and imidazoles (adhesion improvers described in Japanese Patent Laid-Open No. 9-236923) are particularly preferred, benzimidazoles, and benzotriazoles (Japanese Patent Laid-Open No. 2000-171968). As described in the adhesion improving agent, etc.), the most preferred are imidazoles and benzimidazoles. Among these, 2-hydroxybenzimidazole, 2-hydroxyethyl benzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, 2-aminoimidazole, particularly preferably 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole. As the type of the silane coupling agent, each of epoxy-based, methacrylic-based, and amine-based can be used, and an epoxy-based silane coupling agent is particularly preferred.

該等可單獨使用1種或組合2種以上使用。 These can be used individually by 1 type or in combination of 2 or more types.

於調配該等密接改善劑之情形時，其調配比例根據所使用之密接改善劑之種類而有所不同，相對於著色感光性組成物之總固形分，較佳為設為0.01~5重量%，尤佳為設為0.05~3重量%。若少於此，則存在無法獲得充分提高密接性之效果之情況，若過多，則存在顯影性降低之情況。 When blending these adhesion improving agents, the blending ratio varies depending on the type of adhesion improving agent used, and it is preferably set to 0.01 to 5% by weight relative to the total solid content of the coloring photosensitive composition. It is particularly preferably set to 0.05 to 3% by weight. If it is less than this, the effect which fully improves adhesiveness may not be acquired, and when it is too much, developability may fall.

[2-7-4]增感色素 [2-7-4] sensitizing pigment

作為增感色素，例如可列舉：日本專利特開平4-221958號公報、日本專利特開平4-219756號公報中所記載之色素，日本專利特開平3-239703號公報、日本專利特開平5-289335號公報中所記載之具有雜環之香豆素色素，日本專利特開平3-239703號公報、日本專利特開平5-289335號公報中所記載之3-酮香豆素化合物，日本專利特開平6-19240號公報中所記載之吡咯亞甲基色素，除此以外，可列舉日本專利特開昭47-2528號公報、日本專利特開昭 54-155292號公報、日本專利特公昭45-37377號公報、日本專利特開昭48-84183號公報、日本專利特開昭52-112681號公報、日本專利特開昭58-15503號公報、日本專利特開昭60-88005號公報、日本專利特開昭59-56403號公報、日本專利特開平2-69號公報、日本專利特開昭57-168088號公報、日本專利特開平5-107761號公報、日本專利特開平5-210240號公報、日本專利特開平4-288818號公報中所記載之具有二烷基胺基苯骨架之色素等。 Examples of the sensitizing dye include those described in Japanese Patent Laid-Open No. 4-221958 and Japanese Patent Laid-Open No. 4-219756. Pigments, coumarin pigments having heterocyclic rings described in Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335, Japanese Patent Laid-Open No. 3-239703, and Japanese Patent Laid-Open No. 5-239703. In addition to the 3-ketocoumarin compounds described in Japanese Patent Publication No. 289335 and the pyrrole methylene pigment described in Japanese Patent Application Laid-Open No. 6-19240, Japanese Patent Application Laid-Open No. 47-2528 can be cited. Japanese Patent Laid-Open No. 54-155292, Japanese Patent Laid-Open No. 45-37377, Japanese Patent Laid-Open No. 48-84183, Japanese Patent Laid-Open No. 52-112681, Japanese Patent Laid-Open No. 58 -15503, Japanese Patent Laid-Open No. 60-88005, Japanese Patent Laid-Open No. 59-56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, Japanese Patent A pigment having a dialkylaminobenzene skeleton described in Japanese Patent Application Laid-Open No. 5-107761, Japanese Patent Application Laid-Open No. 5-210240, and Japanese Patent Laid-Open No. 4-288818.

該等可單獨使用1種或組合2種以上使用。 These can be used individually by 1 type or in combination of 2 or more types.

於調配增感色素之情形時，著色感光性組成物中之總固形分中之增感色素之含有率通常為0.01~5重量%，較佳為0.05~3重量%。若少於此，則存在無法發揮增感效果之情況，若過多，則存在顯影性降低之情況。 When the sensitizing dye is blended, the content ratio of the sensitizing dye in the total solid content in the colored photosensitive composition is usually 0.01 to 5% by weight, preferably 0.05 to 3% by weight. If it is less than this, a sensitization effect may not be exhibited, and if it is too much, developability may fall.

[2-7-5]界面活性劑 [2-7-5] Surfactants

作為界面活性劑，可使用陰離子系、陽離子系、非離子系、兩性界面活性劑等各種界面活性劑之1種或2種以上，就對各特性造成不良影響之可能性較低之方面而言，較佳為使用非離子系界面活性劑。又，氟系或矽系界面活性劑就塗佈性方面而言較為有效。 As the surfactant, one or more kinds of various surfactants, such as anionic, cationic, nonionic, and amphoteric surfactants, can be used, and the possibility of adversely affecting each characteristic is low. Preferably, a non-ionic surfactant is used. Further, a fluorine-based or silicon-based surfactant is more effective in terms of coatability.

作為界面活性劑之調配比例，相對於著色感光性組成物中之總固形分，通常為0.001~10重量%之範圍，較佳為0.005~1重量%之範圍，進而較佳為0.01~0.5重量%之範圍，最佳為0.03~0.3重量%之範圍。若界面活性劑之添加量少於上述範圍，則存在無法表現塗佈膜之平滑性、均勻性之情 況，若多於上述範圍，則除存在塗佈膜之平滑性、均勻性無法表現之情況以外，亦存在其他特性惡化之情況。 The blending ratio of the surfactant is generally in the range of 0.001 to 10% by weight, preferably in the range of 0.005 to 1% by weight, and more preferably 0.01 to 0.5% by weight relative to the total solid content in the colored photosensitive composition. The range of% is preferably in the range of 0.03 to 0.3% by weight. If the amount of the surfactant added is less than the above range, there may be cases where the smoothness and uniformity of the coating film cannot be expressed. If it is more than the above range, there may be cases where the smoothness and uniformity of the coating film cannot be expressed. In addition, other characteristics may deteriorate.

[2-7-6]有機羧酸、有機羧酸酐 [2-7-6] organic carboxylic acid, organic carboxylic anhydride

為提高顯影性或改善版污，本發明之著色感光性組成物亦可包含有機羧酸及有機羧酸酐中之至少一者。 The coloring photosensitive composition of the present invention may contain at least one of an organic carboxylic acid and an organic carboxylic anhydride in order to improve developability or improve plate stain.

作為有機羧酸，可列舉脂肪族羧酸及芳香族羧酸中之至少一者。 Examples of the organic carboxylic acid include at least one of an aliphatic carboxylic acid and an aromatic carboxylic acid.

作為脂肪族羧酸，具體而言，可列舉甲酸、乙酸、丙酸、丁酸、戊酸、特戊酸、己酸、二乙基乙酸、庚酸、辛酸、乙醇酸、丙烯酸、甲基丙烯酸等單羧酸，草酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十三烷二酸、甲基丙二酸、乙基丙二酸、二甲基丙二酸、甲基丁二酸、四甲基丁二酸、環己烷二甲酸、環己烯二甲酸、衣康酸、甲基順丁烯二酸、順丁烯二酸、反丁烯二酸等二羧酸，1,2,3-丙三甲酸、烏頭酸、降三酸等三羧酸等。又，作為芳香族羧酸，具體而言，可列舉苯甲酸、甲苯甲酸、小茴香酸、2,3-二甲基苯甲酸、3,5-二甲基苯甲酸、鄰苯二甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、偏苯三甲酸、均苯三甲酸、1,2,3,5-苯四甲酸、均苯四甲酸、苯乙酸、氫阿托酸、氫桂皮酸、苦杏仁酸、苯基丁二酸、阿托酸、桂皮酸、桂皮酸甲酯、桂皮酸苄酯、亞桂皮基乙酸、香豆酸、傘形酸等苯基上直接鍵結有羧基之羧酸、及苯基上經由碳鍵而鍵結有羧基之羧酸等。 Specific examples of the aliphatic carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, hexanoic acid, diethylacetic acid, heptanoic acid, caprylic acid, glycolic acid, acrylic acid, and methacrylic acid. Monocarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid, methylmalonic acid , Ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, methylmaleic acid , Maleic acid, fumaric acid and other dicarboxylic acids, 1, 2, 3-malonic acid, aconitic acid, Tricarboxylic acids and the like. Specific examples of the aromatic carboxylic acid include benzoic acid, toluic acid, cuminic acid, 2,3-dimethylbenzoic acid, 3,5-dimethylbenzoic acid, phthalic acid, and o-phthalic acid. Phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 1,2,3,5-benzenetetracarboxylic acid, pyromellitic acid, phenylacetic acid, hydrogen attoric acid, hydrogen Cinamic acid, picric acid, phenylsuccinic acid, atoric acid, cinnamic acid, methyl cinnamic acid, benzyl cinnamic acid, cinnamic acid, coumaric acid, umbellic acid, etc. Carboxylic acid, carboxylic acid having carboxyl group bonded to the phenyl group via a carbon bond, and the like.

上述有機羧酸中，較佳為單羧酸、二羧酸，其中進而較佳 為丙二酸、戊二酸、乙醇酸，尤佳為丙二酸。 Among the above-mentioned organic carboxylic acids, monocarboxylic acids and dicarboxylic acids are preferred, and among them, malonic acid, glutaric acid, and glycolic acid are more preferred, and malonic acid is particularly preferred.

上述有機羧酸之分子量通常為1000以下，且通常為50以上。若上述有機羧酸之分子量過大，則存在版污改善效果不充分之情況，若過少，則有因昇華、揮發等而引起添加量之減少或步驟污染之虞。 The molecular weight of the organic carboxylic acid is usually 1,000 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid is too large, the effect of improving plate stain may be insufficient. If it is too small, the amount of addition may be reduced due to sublimation, volatilization, etc., or the step may be polluted.

作為有機羧酸酐，可列舉脂肪族羧酸酐及芳香族羧酸酐中之至少一者，作為脂肪族羧酸酐，具體而言，可列舉乙酸酐、三氯乙酸酐、三氟乙酸酐、四氫鄰苯二甲酸酐、丁二酸酐、順丁烯二酸酐、衣康酸酐、甲基順丁烯二酸酐、戊二酸酐、1,2-環己烯二甲酸酐、正十八烷基丁二酸酐、5-降烯-2,3-二甲酸酐等脂肪族羧酸酐。作為芳香族羧酸酐，具體而言，可列舉鄰苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸酐、萘二甲酸酐等。 Examples of the organic carboxylic acid anhydride include at least one of an aliphatic carboxylic acid anhydride and an aromatic carboxylic acid anhydride. Examples of the aliphatic carboxylic acid anhydride include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, and tetrahydroortho. Phthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, methyl maleic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride 5-down Aliphatic carboxylic anhydrides such as ene-2,3-dicarboxylic anhydride. Specific examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalenedicarboxylic anhydride.

上述有機羧酸酐中，較佳為順丁烯二酸酐、丁二酸酐、衣康酸酐、甲基順丁烯二酸酐，進而較佳為順丁烯二酸酐。 Among the organic carboxylic anhydrides, maleic anhydride, succinic anhydride, itaconic anhydride, and methyl maleic anhydride are preferred, and maleic anhydride is further preferred.

上述有機羧酸酐之分子量通常為800以下，較佳為600以下，進而較佳為500以下，且通常為50以上。若上述有機羧酸酐之分子量過大，則存在版污改善效果不充分之情況，若過少，則有因昇華、揮發等而引起添加量之減少或步驟污染之虞。 The molecular weight of the organic carboxylic anhydride is usually 800 or less, preferably 600 or less, more preferably 500 or less, and usually 50 or more. If the molecular weight of the organic carboxylic anhydride is too large, there may be cases where the effect of improving plate staining is insufficient. If it is too small, the amount of addition may be reduced due to sublimation, volatilization, etc., or the step may be contaminated.

該等有機羧酸及有機羧酸酐分別可單獨使用1種，亦可混合2種以上使用。 These organic carboxylic acids and organic carboxylic anhydrides may be used singly or in combination of two or more kinds.

該等有機羧酸及有機羧酸酐之添加量分別於本發明之遮光性感光性樹脂組成物之總固形分中，通常為0.01重量% ~5重量%，較佳為0.03重量%~3重量%。若其添加量過少，則存在無法獲得充分之添加效果之情況，若過多，則存在表面平滑性或感光度惡化，產生未溶解剝離片之情況。 The addition amounts of these organic carboxylic acids and organic carboxylic anhydrides are respectively in the total solid content of the light-shielding and photosensitive resin composition of the present invention, usually 0.01% to 5% by weight, preferably 0.03% to 3% by weight. . If the added amount is too small, a sufficient addition effect may not be obtained, and if it is too large, surface smoothness or sensitivity may be deteriorated, and an undissolved release sheet may be generated.

[2-7-7]熱聚合抑制劑 [2-7-7] Thermal polymerization inhibitor

作為熱聚合抑制劑，例如可使用對苯二酚、對甲氧基苯酚、鄰苯三酚、鄰苯二酚、2,6-第三丁基對甲酚、β-萘酚等中之1種或2種以上。 As the thermal polymerization inhibitor, for example, one of hydroquinone, p-methoxyphenol, catechol, catechol, 2,6-tert-butyl-p-cresol, and β-naphthol can be used. One or two or more.

熱聚合抑制劑之調配比例相對於遮光性感光性樹脂組成物中之總固形分，較佳為於0~2重量%之範圍，若多於此，則存在降低遮光性、感光性樹脂組成物之感光度之情況。 The blending ratio of the thermal polymerization inhibitor is preferably in the range of 0 to 2% by weight relative to the total solid content in the light-shielding photosensitive resin composition. If it is more than this, the light-shielding and photosensitive resin composition may be reduced The sensitivity of the situation.

[2-7-8]可塑劑 [2-7-8] Plasticizer

作為可塑劑，例如可使用鄰苯二甲酸二辛酯、鄰苯二甲酸二(十二烷基)酯、三乙二醇二辛酸酯、二甲基乙二醇鄰苯二甲酸酯、磷酸三甲酚酯、己二酸二辛酯、癸二酸二丁酯、三乙醯甘油等中之1種或2種以上。 As the plasticizer, for example, dioctyl phthalate, di (dodecyl) phthalate, triethylene glycol dicaprylate, dimethyl ethylene glycol phthalate, One or two or more of tricresol phosphate, dioctyl adipate, dibutyl sebacate, triacetin, and glycerol.

該等可塑劑之調配比例相對於遮光性感光性樹脂組成物中之總固形分，較佳為5重量%以下之範圍，若多於此，則樹脂黑矩陣之硬化點降低。 The blending ratio of these plasticizers is preferably in the range of 5% by weight or less relative to the total solid content in the light-shielding and sexy resin composition. If more than this, the hardening point of the resin black matrix is reduced.

[3]著色感光性組成物之製造方法 [3] Manufacturing method of colored photosensitive composition

繼而，對本發明之著色感光性組成物之製造方法進行說明。 Next, the manufacturing method of the coloring photosensitive composition of this invention is demonstrated.

以下，對使用顏料作為著色劑之著色感光性組成物進行說明。 Hereinafter, a coloring photosensitive composition using a pigment as a colorant will be described.

首先，使用(a)顏料與(f)分散劑以及必需之成分，製造顏 料分散液。繼而，將上述所得之顏料分散液、(b)鹼可溶性樹脂、(c)光聚合起始劑、(d)乙烯性不飽和化合物及(e)溶劑混合而製造著色感光性組成物。亦可視需要而混合上述其他成分。 First, a pigment dispersion is produced using (a) a pigment and (f) a dispersant and necessary components. Then, the pigment dispersion liquid obtained above, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, and (e) a solvent are mixed to produce a colored photosensitive composition. If necessary, the other ingredients mentioned above can also be mixed.

[3-1](a)顏料分散液之製造方法 [3-1] (a) Manufacturing method of pigment dispersion

作為本發明之顏料分散液之製造方法，可採用各種方法。以下表示其中一例。 As a method for producing the pigment dispersion liquid of the present invention, various methods can be adopted. One example is shown below.

首先，分別稱量特定量之顏料、溶劑及分散劑/分散輔助劑，於分散處理步驟中，使顏料分散而製成液狀之顏料分散液。作為顏料、溶劑及分散劑/分散輔助劑，可使用作為上述著色感光性組成物之構成成分而記載者。 First, a specific amount of a pigment, a solvent, and a dispersant / dispersion aid are weighed separately, and the pigment is dispersed in a dispersion treatment step to prepare a liquid pigment dispersion. As a pigment, a solvent, and a dispersing agent / dispersion adjuvant, what is described as a component of the said coloring photosensitive composition can be used.

於該分散處理步驟中，可使用塗料調節機、砂磨機、球磨機、輥磨機、石磨機、噴射磨機、均質機等。於使用砂磨機進行分散處理之情形時，較佳為使用0.1至數毫米直徑之玻璃珠、或氧化鋯珠。 In this dispersion treatment step, a paint conditioner, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, and the like can be used. When using a sand mill for dispersion treatment, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several millimeters.

由於藉由進行該分散處理而將顏料微粒化，故使用該顏料分散液之著色感光性組成物之塗佈特性及直線性等製版性能提高。 Since the pigment is micronized by performing the dispersion treatment, the plate-making properties such as coating characteristics and linearity of the coloring photosensitive composition using the pigment dispersion liquid are improved.

於對顏料進行分散處理時，可適當併用上述鹼可溶性樹脂等。 When dispersing a pigment, the said alkali-soluble resin etc. can be used together suitably.

分散處理時之溫度通常設定為0℃~100℃之範圍，較佳為設定為室溫~80℃之範圍。再者，由於分散時間根據顏料分散液之組成(顏料、溶劑、分散劑/分散輔助劑等)及砂磨機之裝置之大小等不同而準確時間有所不同，故必需適當調 整。 The temperature during the dispersion treatment is usually set in a range of 0 ° C to 100 ° C, and preferably in a range of room temperature to 80 ° C. In addition, since the dispersion time varies depending on the composition of the pigment dispersion liquid (pigment, solvent, dispersant / dispersion aid, etc.) and the size of the device of the sand mill, etc., the exact time must be appropriately adjusted.

顏料分散液中之(a)顏料之含量通常為5重量%以上且50重量%以下，較佳為10重量%以上且40重量%以下。 The content of the (a) pigment in the pigment dispersion liquid is usually 5% by weight or more and 50% by weight or less, preferably 10% by weight or more and 40% by weight or less.

顏料分散液中之(f)分散劑之含量相對於顏料通常為5重量%以上且90重量%以下，較佳為5重量%以上且60重量%以下，進而較佳為5重量%以上且40重量以下。 The content of the (f) dispersant in the pigment dispersion liquid is usually 5 wt% or more and 90 wt% or less, preferably 5 wt% or more and 60 wt% or less, and more preferably 5 wt% or more and 40% with respect to the pigment. Below weight.

顏料分散液中之分散輔助劑之含量相對於顏料通常為0.1~30重量%，較佳為0.1~20重量%以下，更佳為0.1~10重量%，進而較佳為0.1~5重量%。 The content of the dispersion aid in the pigment dispersion liquid is generally 0.1 to 30% by weight, preferably 0.1 to 20% by weight or less, more preferably 0.1 to 10% by weight, and still more preferably 0.1 to 5% by weight relative to the pigment.

顏料分散液中之鹼可溶性樹脂(b)之含量相對於顏料通常為0重量%以上且100重量%以下，較佳為5重量%以上且80重量%以下，進而較佳為5重量%以上且60重量%以下。 The content of the alkali-soluble resin (b) in the pigment dispersion liquid is usually 0% by weight or more and 100% by weight or less with respect to the pigment, preferably 5% by weight or more and 80% by weight or less, and further preferably 5% by weight or more and 60% by weight or less.

[3-2]著色感光性組成物之製造方法 [3-2] Manufacturing method of colored photosensitive composition

繼而，添加藉由上述分散處理而得之顏料分散液(油墨)與作為著色感光性組成物成分所需之上述其他成分並攪拌混合，製成均勻之著色感光性組成物溶液。於該製造步驟中，由於溶液中混有較多微細之雜物，故較理想為藉由過濾器等對著色感光性組成物溶液進行過濾處理。 Next, the pigment dispersion liquid (ink) obtained by the above-mentioned dispersion treatment and the above-mentioned other components required for coloring the photosensitive composition component are added and mixed to prepare a uniform colored photosensitive composition solution. In this manufacturing step, since a lot of fine impurities are mixed in the solution, it is preferable to filter the colored photosensitive composition solution with a filter or the like.

再者，使用除顏料以外(例如染料)作為著色劑之著色感光性組成物可利用公知之方法製造。 In addition, the coloring photosensitive composition using other than a pigment (for example, a dye) as a colorant can be manufactured by a well-known method.

[4]著色間隔件之形成方法 [4] Method for forming colored spacers

本實施形態之著色感光性組成物可利用與公知之彩色濾光片用著色感光性組成物相同之方法而使用，以下，對用作著色間隔件之情形進行說明。 The colored photosensitive composition of this embodiment can be used in the same manner as the known colored photosensitive composition for color filters, and the case where it is used as a colored spacer will be described below.

通常，藉由塗佈等方法，將著色感光性組成物溶液膜狀或圖案狀地供給至應設置著色間隔件之基板上，並使溶劑乾燥。繼而，藉由進行曝光-顯影之光微影法形成圖案。其後，視需要進行追加曝光或熱硬化處理，藉此於該基板上形成著色間隔件。 Generally, the colored photosensitive composition solution is supplied in a film or pattern form to a substrate to be provided with a colored spacer by a method such as coating, and the solvent is dried. Then, a pattern is formed by a photolithography method in which exposure-development is performed. Thereafter, if necessary, additional exposure or thermosetting treatment is performed to form a colored spacer on the substrate.

[4-1]對基板之供給方法 [4-1] Supply method to substrate

通常本實施形態之著色感光性組成物係以溶解或分散於溶劑中之狀態供給至基板上。作為其供給方法，可藉由先前公知之方法、例如旋轉塗佈法、線棒塗佈法、流塗法、模塗法、輥塗法、噴塗法等。其中，若利用擠壓式塗佈法，則就可大幅削減塗佈液之使用量，且全無利用旋轉塗佈法時附著之霧等之影響，可抑制雜質產生等綜合觀點而言較佳。 The colored photosensitive composition of this embodiment is usually supplied to a substrate in a state of being dissolved or dispersed in a solvent. As a supply method thereof, a conventionally known method such as a spin coating method, a bar coating method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be used. Among them, if the extrusion coating method is used, the amount of coating liquid used can be greatly reduced, and there is no effect of fog and the like attached when the spin coating method is used, and it is preferable to comprehensively suppress the generation of impurities and the like. .

塗佈量根據用途而有所不同，例如於著色間隔件之情形時，乾燥膜厚通常為0.5μm~10μm之範圍，較佳為1μm~9μm之範圍，尤佳為1μm~7μm之範圍。又，重要的是乾燥膜厚或最終形成之著色間隔件之高度於基板全域上均勻。於偏差較大之情形時，有於液晶面板上產生不均缺陷之情況。又，亦可藉由噴墨法或印刷法等圖案狀地供給。 The coating amount varies depending on the application. For example, in the case of a colored spacer, the dry film thickness is usually in a range of 0.5 μm to 10 μm, preferably in a range of 1 μm to 9 μm, and particularly preferably in a range of 1 μm to 7 μm. In addition, it is important that the thickness of the dried film or the height of the colored spacer to be finally formed is uniform over the entire area of the substrate. When the deviation is large, uneven defects may occur in the liquid crystal panel. It can also be supplied in a pattern form by an inkjet method or a printing method.

再者，可使用玻璃基板等公知之基板作為基板。又，基板表面較佳為平面。 Further, a known substrate such as a glass substrate can be used as the substrate. The surface of the substrate is preferably flat.

[4-2]乾燥方法 [4-2] Drying method

將著色感光性組成物溶液供給至基板上後之乾燥較佳為利用使用加熱板、IR(infrared，紅外線)烘箱、對流烘箱之乾燥方法。又，亦可組合不提高溫度而於減壓腔室內進行乾燥 之減壓乾燥法。 The drying method after the colored photosensitive composition solution is supplied onto the substrate is preferably a drying method using a hot plate, an IR (infrared) oven, or a convection oven. Further, a reduced-pressure drying method in which drying is performed in a decompression chamber without increasing the temperature may be combined.

乾燥之條件可根據溶劑成分之種類、所使用之乾燥機之性能等而適當選擇。乾燥時間根據溶劑成分之種類、所使用之乾燥機之性能等，通常可於40℃~130℃之溫度下15秒~5分鐘之範圍內選擇，較佳為於50℃~110℃之溫度下30秒~3分鐘之範圍內選擇。 The drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. Drying time can be selected within the range of 15 seconds to 5 minutes at a temperature of 40 ° C to 130 ° C, and preferably at a temperature of 50 ° C to 110 ° C, depending on the type of solvent composition and the performance of the dryer used. Choose from 30 seconds to 3 minutes.

[4-3]曝光方法 [4-3] Exposure method

曝光係於著色感光性組成物之塗佈膜上重疊負光罩圖案，經由該光罩圖案照射紫外線或可見光線之光源而進行。於使用曝光光罩進行曝光之情形時，可利用使曝光光罩靠近著色感光性組成物之塗佈膜之方法，或將曝光光罩配置於離開著色感光性組成物之塗佈膜之位置，並投影經由該曝光光罩之曝光之光的方法。又，亦可利用不使用光罩圖案之藉由雷射光之掃描曝光方式。此時，為防止由氧所導致之光聚合性層之感光度之降低，可視需要於脫氧環境下進行，或於在光聚合性層上形成聚乙烯醇層等氧遮斷層後進行曝光。 The exposure is performed by superposing a negative mask pattern on the coating film of the colored photosensitive composition, and irradiating a light source of ultraviolet rays or visible rays through the mask pattern. In the case of using an exposure mask for exposure, a method of bringing the exposure mask close to the coating film of the colored photosensitive composition, or arranging the exposure mask at a position away from the coating film of the colored photosensitive composition, A method of projecting light that is exposed through the exposure mask. In addition, a scanning exposure method using laser light without using a mask pattern may be used. At this time, in order to prevent a decrease in the sensitivity of the photopolymerizable layer caused by oxygen, it may be performed in a deoxidizing environment, or exposed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer.

上述曝光所使用之光源並無特別限定。作為光源，例如可列舉氙氣燈、鹵素燈、鎢絲燈、高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、中壓水銀燈、低壓水銀燈、碳弧燈、螢光燈等燈光源，或氬離子雷射、YAG(Yttrium Aluminum Garnet，釔-鋁-石榴石)雷射、準分子雷射、氮雷射、氦-鎘雷射、藍紫色半導體雷射、近紅外線半導體雷射等雷射光源等。於照射特定波長之光而使用之情形時，亦可利用光學濾光片。 The light source used for the above exposure is not particularly limited. Examples of the light source include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, and fluorescent lamps, or argon ion lightning Laser, YAG (Yttrium Aluminum Garnet) laser, excimer laser, nitrogen laser, helium-cadmium laser, blue-violet semiconductor laser, near-infrared semiconductor laser and other laser light sources. When using light of a specific wavelength, an optical filter can also be used.

作為光學濾光片，例如可為可利用薄膜控制曝光波長中之 透光率之類型，作為該情形時之材質，例如可列舉Cr化合物(Cr之氧化物、氮化物、氧氮化物、氟化物等)、MoSi、Si、W、Al等。 The optical filter may be, for example, a type in which the light transmittance at the exposure wavelength can be controlled by a thin film. As a material in this case, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride) Etc.), MoSi, Si, W, Al, etc.

又，於用以藉由光微影法而一次形成高度不同之著色間隔件之方法中，可利用以下方法：使用具有遮蔽光之穿透之遮光層與使光穿透之開口部，且一部分開口部之平均透光率小於其他開口部之平均透光率之曝光光罩作為曝光光罩的方法，即，使用具有遮光層(透光率0%)與數個開口部，相對於平均透光率最高之開口部(通常透光率為100%；以下稱作完全穿透開口部)具有平均透光率較小之開口部(中間穿透開口部)之曝光光罩的方法。 In addition, in the method for forming colored spacers of different heights at one time by a photolithography method, the following methods may be used: a light-shielding layer having a light-shielding layer and an opening through which light is transmitted, and a part thereof As an exposure mask, an exposure mask having an average transmittance smaller than the average transmittance of other openings is used as the exposure mask. That is, a light-shielding layer (light transmittance 0%) and several openings are used as the exposure mask. A method of exposing a mask having an opening portion (middle penetration opening portion) having a small average light transmittance (usually a light transmittance of 100%; hereinafter referred to as a fully penetrating opening portion).

作為中間穿透開口部之形成方法，可採用使用如下光罩之方法：上述光罩於光罩圖案之開口部(透光部)上任意配置有上述光學濾光片，即，適當配置設置有光學濾光片之開口部(中間穿透開口部)與未設置光學濾光片之開口部(完全穿透開口部)。藉此，可藉由一次曝光步驟而形成與開口部之透光率相對應之光聚合率不同之圖案，例如可藉由一次曝光步驟而同時一次形成高度不同之圖案。 As a method of forming the intermediate penetrating opening portion, a method using a mask may be adopted in which the above-mentioned optical filter is arbitrarily arranged on the opening portion (light transmitting portion) of the mask pattern, that is, appropriately arranged with The opening portion (middle penetration opening portion) of the optical filter and the opening portion (complete penetration opening portion) where no optical filter is provided. Thereby, a pattern having a different photopolymerization rate corresponding to the light transmittance of the opening portion can be formed by one exposure step, for example, patterns having different heights can be formed at the same time by one exposure step.

又，作為另一中間穿透開口部之形成方法，亦可進行日本專利特開2003-344860號公報所記載之藉由將遮光部與完全穿透部配置為微小之矩陣圖案狀或微細之狹縫圖案狀，從而形成具有平均透光率經調整之(透光率相對於完全穿透開口部較小)中間穿透開口部之曝光光罩。 Also, as another method for forming the intermediate penetrating opening portion, it is also possible to arrange the light-shielding portion and the fully penetrating portion described in Japanese Patent Application Laid-Open No. 2003-344860 into a small matrix pattern shape or a narrow slit. The slit pattern is formed to form an exposure mask having an average light transmittance adjusted (the light transmittance is smaller than that of the full penetration opening) with an intermediate penetration opening.

作為本實施形態中之曝光量，通常為1mJ/cm2以上，較 佳為5mJ/cm2以上，更佳為10mJ/cm2以上，且通常為300mJ/cm2以下，較佳為200mJ/cm2以下，更佳為150mJ/cm2以下。 As the exposure amount of the present embodiment, generally 1mJ / cm 2 or more, preferably from 5mJ / cm 2 or more, more preferably 10mJ / cm 2 or more, and usually 2 or less 300mJ / cm, preferably 200mJ / cm 2 or less, more preferably 150 mJ / cm 2 or less.

又，於靠近曝光方式之情形時，曝光對象與光罩圖案之距離通常為10μm以上，較佳為50μm以上，更佳為75μm以上，且通常為500μm以下，較佳為400μm以下，更佳為300μm以下。 In the case of approaching the exposure method, the distance between the exposure object and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm or less, and more preferably 300 μm or less.

[4-4]顯影方法 [4-4] Development method

進行上述曝光後，藉由使用鹼性化合物之水溶液、或有機溶劑之顯影，可於基板上形成圖像圖案。該水溶液中可進而含有界面活性劑、有機溶劑、緩衝劑、錯合劑、染料或顏料。 After the exposure is performed, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution may further contain a surfactant, an organic solvent, a buffering agent, a complexing agent, a dye, or a pigment.

作為鹼性化合物，可列舉氫氧化鈉、氫氧化鉀、氫氧化鋰、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、矽酸鈉、矽酸鉀、偏矽酸鈉、磷酸鈉、磷酸鉀、磷酸氫鈉、磷酸氫鉀、磷酸二氫鈉、磷酸二氫鉀、氫氧化銨等無機鹼性化合物，或單/二/三乙醇胺、單/二/三甲胺、單/二/三乙胺、單/二異丙胺、正丁胺、單/二/三異丙醇胺、伸乙基亞胺、伸乙基二亞胺、四甲基氫氧化銨(TMAH，tetramethyl ammonium hydroxide)、膽鹼等有機鹼性化合物。該等鹼性化合物可為2種以上之混合物。 Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and phosphoric acid. Inorganic basic compounds such as potassium, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, or mono / di / triethanolamine, mono / di / trimethylamine, mono / di / triethyl Amine, mono / diisopropylamine, n-butylamine, mono / di / triisopropanolamine, ethyleneimine, ethylenediimine, tetramethyl ammonium hydroxide (TMAH), bile Organic basic compounds such as alkali. These basic compounds may be a mixture of two or more kinds.

作為上述界面活性劑，例如可列舉：聚氧乙烯烷基醚類、聚氧乙烯烷基芳基醚類、聚氧乙烯烷基酯類、去水山梨醇烷基酯類、單甘油酯烷基酯類等非離子系界面活性劑；烷基苯磺酸鹽類、烷基萘磺酸鹽類、烷基硫酸鹽類、烷基磺酸鹽類、 磺基丁二酸酯鹽類等陰離子性界面活性劑；烷基甜菜鹼類、胺基酸類等兩性界面活性劑。 Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceryl alkyl groups. Nonionic surfactants such as esters; anionic properties such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, sulfosuccinates, etc. Surfactants; Ampholytic surfactants such as alkyl betaines and amino acids.

作為有機溶劑，例如可列舉異丙醇、苄醇、乙基賽路蘇、丁基賽路蘇、苯基賽路蘇、丙二醇、二丙酮醇等。有機溶劑可單獨使用，亦可與水溶液併用而使用。 Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cyrus, butyl cyrus, phenyl cyrus, propylene glycol, and diacetone alcohol. The organic solvent may be used alone or in combination with an aqueous solution.

關於顯影處理之方法並無特別限制，通常於10℃~50℃、較佳為15℃~45℃之顯影溫度下，藉由浸漬顯影、噴射顯影、毛刷顯影、超音波顯影等方法進行。 There is no particular limitation on the method of the development treatment, and it is usually carried out at a development temperature of 10 ° C to 50 ° C, preferably 15 ° C to 45 ° C, by immersion development, jet development, brush development, ultrasonic development, or the like.

[4-5]追加曝光及熱硬化處理 [4-5] Additional exposure and thermal hardening

可視需要藉由與上述曝光方法相同之方法對顯影後之基板進行追加曝光，又，亦可進行熱硬化處理。關於此時之熱硬化處理條件，溫度可於100℃~280℃之範圍、較佳為150℃~250℃之範圍內選擇，時間可於5分鐘~60分鐘之範圍內選擇。 If necessary, additional exposure may be performed on the substrate after development by the same method as the above-mentioned exposure method, and a thermosetting treatment may also be performed. Regarding the heat curing treatment conditions at this time, the temperature can be selected in the range of 100 ° C to 280 ° C, preferably 150 ° C to 250 ° C, and the time can be selected in the range of 5 minutes to 60 minutes.

本實施形態之著色感光性組成物於液晶顯示器等之彩色濾光片等中，可較佳地用於形成黑矩陣、表塗層、阻隔壁及著色間隔件等時。又，尤其可提供適於用以藉由光微影法而同時形成尤其是高度不同之著色間隔件之方法之著色感光性組成物。又，根據本實施形態，可提供高品質之彩色濾光片或液晶顯示裝置等。 The colored photosensitive composition of this embodiment is preferably used for forming a black matrix, a surface coating layer, a barrier rib, a colored spacer, and the like in a color filter or the like in a liquid crystal display. In addition, it is possible to provide a coloring photosensitive composition suitable for a method for simultaneously forming a coloring spacer having particularly different heights by a photolithography method. In addition, according to this embodiment, a high-quality color filter, a liquid crystal display device, and the like can be provided.

[5]著色間隔件 [5] colored spacers

藉由本發明之著色感光性組成物而形成之著色間隔件較佳為大致圓柱狀間隔件圖案。 The colored spacer formed by the colored photosensitive composition of the present invention is preferably a substantially cylindrical spacer pattern.

完全穿透開口部之著色間隔件圖案之下剖面直徑通常為 超過15μm且未滿45μm，較佳為超過18μm且未滿40μm。於低於該範圍之情形時，有壓縮特性變差之傾向，於高於該範圍之情形時，基板上之面積增加，故於面板構造方面而言欠佳。 The diameter of the cross section under the pattern of the colored spacer which completely penetrates the opening is usually more than 15 m and less than 45 m, preferably more than 18 m and less than 40 m. When it is lower than this range, there is a tendency that the compression characteristics are deteriorated. When it is higher than this range, the area on the substrate is increased, so it is not good in terms of panel structure.

中間穿透開口部之著色間隔件圖案之下剖面直徑通常為超過20μm且未滿50μm，較佳為超過30μm且未滿40μm。於低於該範圍其情形時，有壓縮特性變差之傾向，於高於該範圍之情形時，基板上之面積增加，故於面板構造方面而言欠佳。 The cross-sectional diameter under the colored spacer pattern of the intermediate penetration opening is usually more than 20 μm and less than 50 μm, and preferably more than 30 μm and less than 40 μm. If the range is lower than this range, the compression characteristics tend to be deteriorated. If the range is higher than this range, the area on the substrate is increased, which is not good in terms of panel structure.

關於完全穿透開口部之著色間隔件圖案之高度與中間穿透開口部之著色間隔件圖案之高度的差異(△H)，於完全穿透開口部之著色間隔件圖案之高度超過2.8μm且未滿3.2μm之情形時，通常為0.25μm以上且1.0μm以下，較佳為超過0.35μm且為0.80μm以下，更佳為超過0.4μm且為0.6μm以下。於低於該範圍之情形時，有耐負荷性變差之傾向，於高於該範圍之情形時，有超過壓縮極限之傾向。 Regarding the difference (△ H) between the height of the colored spacer pattern that completely penetrates the opening and the height of the colored spacer pattern that penetrates the opening, the height of the colored spacer pattern that completely penetrates the opening exceeds 2.8 μm and When it is less than 3.2 μm, it is usually 0.25 μm or more and 1.0 μm or less, preferably 0.35 μm or more and 0.80 μm or less, and more preferably 0.4 μm or more and 0.6 μm or less. When it falls below this range, the load resistance tends to deteriorate, and when it falls above this range, the compression limit tends to be exceeded.

[6]彩色濾光片 [6] Color filters

本發明之彩色濾光片具備如上所述之本發明之著色間隔件，例如係於作為透明基板之玻璃基板上積層黑矩陣與紅色、綠色、藍色之像素著色層、及表塗層，並形成著色間隔件後形成配向膜而製造。作為配向膜，較佳為聚醯亞胺等樹脂膜。 The color filter of the present invention includes the coloring spacer of the present invention as described above, for example, a black matrix and red, green, and blue pixel coloring layers are laminated on a glass substrate as a transparent substrate, and a surface coating layer, and An alignment film is formed after the colored spacers are formed. The alignment film is preferably a resin film such as polyimide.

[7]液晶顯示裝置 [7] Liquid crystal display device

本發明之液晶顯示裝置具備如上所述之具有本發明之著 色間隔件之彩色濾光片，例如係貼合如上所述之彩色濾光片與液晶驅動側基板而形成液晶單元。於形成之液晶單元中注入液晶而製造。 The liquid crystal display device of the present invention includes the color filter having the color spacer of the present invention as described above, and for example, the color filter and the liquid crystal driving side substrate are bonded together to form a liquid crystal cell. It is manufactured by injecting liquid crystal into the formed liquid crystal cell.

實施例 Examples

繼而，列舉實施例及比較例更具體地說明本實施形態，本實施態形只要不超過其主旨，則並不限定於以下實施例。 Next, the present embodiment will be described more specifically by citing examples and comparative examples. The present embodiment is not limited to the following examples as long as it does not exceed the gist thereof.

以下之實施例及比較例所使用之著色感光性組成物之構成成分如下所述。 The constituents of the colored photosensitive composition used in the following examples and comparative examples are as follows.

再者，以下，「份」表示「重量份」。 In the following, "part" means "part by weight".

<鹼可溶性樹脂-1>     <Alkali soluble resin-1>    

新中村化學工業股份有限公司製造之「ADEP02」(MW=3500~4500，酸值=約110mg-KOH/g，相當於鹼可溶性樹脂(A-2)) "ADEP02" (MW = 3500 ~ 4500, acid value = about 110mg-KOH / g, equivalent to alkali-soluble resin (A-2)) manufactured by Shin Nakamura Chemical Industry Co., Ltd.

<鹼可溶性樹脂-2>     <Alkali soluble resin-2>    

日本化藥股份有限公司製造之「ZCR-1664H」(MW=5000~6000，酸值=約60mg-KOH/g，相當於鹼可溶性樹脂(A-1)) "ZCR-1664H" (MW = 5000 ~ 6000, acid value = about 60mg-KOH / g, equivalent to alkali-soluble resin (A-1)) manufactured by Nippon Kayaku Co., Ltd.

<鹼可溶性樹脂-3>     <Alkali soluble resin-3>    

昭和高分子股份有限公司製造之「SPCM-82」(MW=約10000，酸值=約24mg-KOH/g，丙烯酸酯系鹼可溶性樹脂) "SPCM-82" manufactured by Showa Polymer Co., Ltd. (MW = approximately 10,000, acid value = approximately 24mg-KOH / g, acrylate-based alkali-soluble resin)

<鹼可溶性樹脂-4>     <Alkali soluble resin-4>    

於500mL四口燒瓶中，在80℃下，將苯乙烯-丙烯酸樹脂、Joncryl 680(BASF JAPAN股份有限公司)61.2g均勻溶解於丙二醇單甲醚乙酸酯138.6g中。於其中添加四氯化銨0.24g、對甲氧基苯酚0.09g並加以溶解，花費40分鐘滴 加丙二醇單甲醚乙酸酯71.4g與丙烯酸3,4-環氧環己基甲酯(Cyclomer A400，Daicel Chemical股份有限公司)19.9g之混合液。將反應溶液於保持為80℃之狀態下攪拌32小時，獲得重量平均分子量6700、酸值106mgKOH/g之樹脂。 In a 500 mL four-necked flask, 61.2 g of styrene-acrylic resin and Joncryl 680 (BASF JAPAN Co., Ltd.) were uniformly dissolved in 138.6 g of propylene glycol monomethyl ether acetate at 80 ° C. 0.24 g of ammonium tetrachloride and 0.09 g of p-methoxyphenol were added and dissolved therein, and 71.4 g of propylene glycol monomethyl ether acetate and 3,4-epoxycyclohexyl methyl acrylate (Cyclomer A400) were added dropwise over 40 minutes. , Daicel Chemical Co., Ltd.) 19.9 g of the mixed liquid. The reaction solution was stirred for 32 hours while maintaining the temperature at 80 ° C to obtain a resin having a weight average molecular weight of 6700 and an acid value of 106 mgKOH / g.

<鹼可溶性樹脂-5>     <Alkali soluble resin-5>    

昭和高分子股份有限公司製造之「SPCM-121B」(MW=約8300，酸值=約80mg-KOH/g，丙烯酸酯系鹼可溶性樹脂) "SPCM-121B" manufactured by Showa Polymer Co., Ltd. (MW = approximately 8300, acid value = approximately 80mg-KOH / g, acrylate-based alkali-soluble resin)

<分散劑-1>     <Dispersant-1>    

BYK-Chemie公司製造之「DisperBYK-2000」(包含側鏈具有4級銨鹽基之A嵌段與不具有4級銨鹽基之B嵌段的丙烯酸系A-B嵌段共聚合體) "DisperBYK-2000" manufactured by BYK-Chemie (acrylic A-B block copolymer containing an A block with a 4th level ammonium salt group and a B block without a 4th ammonium salt group in the side chain)

<分散劑-2>     <Dispersant-2>    

BYK-Chemie公司製造之「DisperBYK-LPN21116」(包含側鏈具有4級銨鹽基及胺基之A嵌段與不具有4級銨鹽基及胺基之B嵌段的丙烯酸系A-B嵌段共聚合體) "DisperBYK-LPN21116" manufactured by BYK-Chemie (including A-blocks with side-chain ammonium salt and amine groups in the side chain and acrylic AB blocks without B-blocks with quaternary ammonium salt and amine groups Fit

<分散劑-3>     <Dispersant-3>    

BYK-Chemie公司製造之「DisperBYK-167」(胺基甲酸酯系分散劑) "DisperBYK-167" (urethane-based dispersant) manufactured by BYK-Chemie

<分散輔助劑>     <Dispersion aid>    

Lubrizol公司製造之「S12000」 "S12000" made by Lubrizol

<界面活性劑>     <Surfactant>    

Dainippon Ink and Chemicals公司製造之Megafac F-475 Megafac F-475 manufactured by Dainippon Ink and Chemicals

<溶劑-1>     <Solvent-1>    

PGMEA(propylene glycol methyl ether acetate)：丙二醇單甲醚乙酸酯 PGMEA (propylene glycol methyl ether acetate): propylene glycol methyl ether acetate

<溶劑-2>     <Solvent-2>    

MB(3-methoxybutanol)：3-甲氧基丁醇 MB (3-methoxybutanol): 3-methoxybutanol

<溶劑-3>     <Solvent-3>    

MBA(3-methoxybutyl acetate)：乙酸3-甲氧基丁酯 MBA (3-methoxybutyl acetate): 3-methoxybutyl acetate

<溶劑-4>     <Solvent-4>    

CHN(cyclohexanone)：環己酮 CHN (cyclohexanone): cyclohexanone

<光聚合起始劑>     <Photopolymerization initiator>    

下述式所示之化合物。 A compound represented by the following formula.

<乙烯性不飽和化合物>     <Ethylene unsaturated compound>    

DPHA(dipentaerythritol hexaacrylate)：日本化藥股份有限公司製造之二季戊四醇六丙烯酸酯 DPHA (dipentaerythritol hexaacrylate): Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.

<顏料分散液-1~4之製備>     <Preparation of Pigment Dispersion Liquids 1-4>    

以表1所記載之重量比混合表1所記載之顏料、分散劑、分散輔助劑、鹼可溶性樹脂及作為溶劑之丙二醇單甲醚乙酸酯(PGMEA)與乙酸甲氧基丁酯(MBA)。於其中混合分散容器之容積之80%之氧化鋯珠後，填充至PICO MILL分散容器中，於所需之滯留時間加以分散，製備各顏料分散液。 The pigments, dispersants, dispersion aids, alkali-soluble resins, and propylene glycol monomethyl ether acetate (PGMEA) and methoxybutyl acetate (MBA) described in Table 1 are mixed in a weight ratio described in Table 1. . After mixing 80% of the volume of the dispersion container with zirconia beads, it was filled into the PICO MILL dispersion container and dispersed for the required residence time to prepare each pigment dispersion.

[實施例1~3、比較例1~4]     [Examples 1 to 3, Comparative Examples 1 to 4]    

以表2所示之比例調配上述所製備之顏料分散液與表2所示之成分並加以攪拌，分別製備著色感光性組成物塗佈液。使用所得之著色感光性組成物溶液，並藉由下述方法，形成大致圓柱狀間隔件圖案，對形狀、階差、與基板之密接性及電壓保持率(VHR，Voltage Holding Ratio)進行評價。將結果合併記於表2中。 The pigment dispersion liquid prepared above and the components shown in Table 2 were blended at the ratios shown in Table 2 and stirred to prepare colored photosensitive composition coating liquids, respectively. Using the obtained colored photosensitive composition solution, a substantially cylindrical spacer pattern was formed by the following method, and the shape, step, adhesion to the substrate, and voltage holding ratio (VHR, Voltage Holding Ratio) were evaluated. The results are shown in Table 2.

[一次形成高度不同之著色間隔件之方法]     [Method for forming colored spacers of different heights at one time]    

使用旋轉塗佈機於表面形成有ITO(Indium Tin Oxide，氧化銦錫)膜之玻璃基板之該ITO膜上塗佈上述感光性組成物。繼而，於110℃下，在加熱板上加熱乾燥70s，形成塗佈膜。乾燥膜厚為3.5μm。 The photosensitive composition was coated on the ITO film of a glass substrate having an ITO (Indium Tin Oxide) film formed on the surface using a spin coater. Then, it was heated and dried on a hot plate at 110 ° C. for 70 s to form a coating film. The dry film thickness was 3.5 μm.

使用具有直徑15μm之圓形圖案之完全穿透開口部及直徑35μm之圓形圖案之中間穿透開口部的曝光光罩，對所得之塗佈膜實施曝光處理。中間穿透開口部以Cr氧化物之薄膜將波長365nm中之透光率設為12.1%，將405nm中之透光率設為16.5%，將436nm中之透光率設為19.6%。再者，上述3點之前後及其間之透光率連續，不存在反曲點。曝光間距(光罩與塗佈面之間之距離)為250μm。 The obtained coating film was subjected to an exposure treatment using an exposure mask having a full penetration opening portion having a circular pattern with a diameter of 15 μm and a middle penetration opening portion having a circular pattern with a diameter of 35 μm. A thin film of Cr oxide was used in the middle penetration opening to set the light transmittance at a wavelength of 365 nm to 12.1%, the light transmittance at 405 nm to 16.5%, and the light transmittance at 436 nm to 19.6%. In addition, the light transmittance before and after the three points is continuous, and there is no inflection point. The exposure pitch (distance between the mask and the coating surface) was 250 μm.

又，使用365nm下之強度為32mW/cm2之紫外線。將曝光量設為50mJ/cm2。又，紫外線照射係於空氣下進行。繼而，使用25℃之0.1%氫氧化鉀水溶液，進行最小顯影時間之1.6倍時間之噴射顯影，進而以純水清洗。將120秒亦無法溶解者設為無法顯影。 In addition, ultraviolet rays having an intensity of 32 mW / cm 2 at 365 nm were used. The exposure amount was set to 50 mJ / cm 2 . The ultraviolet irradiation was performed in the air. Then, using a 0.1% potassium hydroxide aqueous solution at 25 ° C., jet development was performed at 1.6 times the minimum development time, and then washed with pure water. Those who cannot dissolve even after 120 seconds are set as undeveloped.

藉由該等操作，獲得去除不需要部分之圖案。將形成有該圖案之基板於烘箱中、230℃下加熱20分鐘而使圖案硬化，獲得大致圓柱狀之間隔件圖案。 With these operations, a pattern for removing unnecessary portions is obtained. The substrate on which the pattern was formed was heated in an oven at 230 ° C. for 20 minutes to harden the pattern to obtain a substantially cylindrical spacer pattern.

[著色間隔件圖案之形狀測量]     [Shape measurement of colored spacer pattern]    

關於上述大致圓柱狀之著色間隔件圖案，縱剖通過著色間隔件圖案之中軸之縱剖面，測量著色間隔件圖案之高度與上、下底面之剖面直徑。測量時，使用Ryoka Systems股份有限公司製造之立體非接觸表面形狀測量系統Micromap MM3500-M100。 Regarding the above-mentioned substantially cylindrical colored spacer pattern, the longitudinal section was passed through the longitudinal section of the central axis of the colored spacer pattern, and the height of the colored spacer pattern and the cross-sectional diameters of the upper and lower bottom surfaces were measured. For measurement, a three-dimensional non-contact surface shape measuring system Micromap MM3500-M100 manufactured by Ryoka Systems Co., Ltd. was used.

圖1(A)及圖1(B)係用以說明上述大致圓柱狀間隔件圖案之形狀之圖。圖1(A)中，著色間隔件圖案1凸狀地形成於玻璃基板2上，具有俯視大致圓形狀之輪廓。圖1(B)為通過圖1(A)之著色間隔件圖案1之中軸3之X-X剖面圖。圖1(B)中，著色間隔件圖案1具有大致矩形狀之輪廓。將該輪廓設為著色間隔件圖案1之剖面4，將剖面4之圖案側面部41與玻璃基板2之交點設為交點A、A'。自玻璃基板2之表面至剖面4之最高位置點之距離為圖案高度H，交點A與交點A'之距離為下剖面直徑L。 1 (A) and 1 (B) are diagrams for explaining the shape of the above-mentioned substantially cylindrical spacer pattern. In FIG. 1 (A), the colored spacer pattern 1 is convexly formed on the glass substrate 2 and has a substantially circular shape in plan view. FIG. 1 (B) is an X-X cross-sectional view of the axis 3 passing through the colored spacer pattern 1 of FIG. 1 (A). In FIG. 1 (B), the colored spacer pattern 1 has a substantially rectangular outline. Let this outline be the cross section 4 of the colored spacer pattern 1, and let the intersection point of the pattern side surface part 41 of the cross section 4 and the glass substrate 2 be the intersection A, A '. The distance from the surface of the glass substrate 2 to the highest position point of the section 4 is the pattern height H, and the distance between the intersection point A and the intersection point A ′ is the lower section diameter L.

[階差之評價]     [Evaluation of step]    

將完全穿透開口部之著色間隔件圖案之高度與中間穿透開口部之著色間隔件圖案之高度的差異(△H)超過0.35μm且為0.8μm以下者設為○，將0.25μm以上且0.4μm以下者設為△，將未滿0.25μm者設為×。將結果示於表2。 The difference (ΔH) between the height of the colored spacer pattern that completely penetrates the opening and the height of the colored spacer pattern that penetrates the middle of the opening is more than 0.35 μm and 0.8 μm or less. ○, and 0.25 μm or more and A value of 0.4 μm or less is Δ, and a value of less than 0.25 μm is X. The results are shown in Table 2.

[密接性之評價]     [Evaluation of tightness]    

以上述之方式，使用設置有中間穿透開口部之尺寸為5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、25、30、35、40、45、50μm之中間穿透開口部各24個之光罩，形成尺寸不同之圖案各24個。測定24個圖案均未消失之最小之中間穿透開口部之尺寸(直徑)。將其尺寸為15μm以下者設為○，將超過15μm者設為×。將結果示於表2。 In the manner described above, the sizes provided with the intermediate penetration openings are 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50 μm each has 24 photomasks in the middle penetrating openings, each forming 24 patterns with different sizes. The size (diameter) of the smallest intermediate penetrating opening where 24 patterns did not disappear was measured. A size of 15 μm or less is ○, and a size of more than 15 μm is X. The results are shown in Table 2.

[電壓保持率(VHR)之評價]     [Evaluation of Voltage Holding Rate (VHR)]    

藉由以下所說明之方法，進行電壓保持率(VHR)之評價，將結果示於表2。 The voltage retention ratio (VHR) was evaluated by the method described below, and the results are shown in Table 2.

<液晶單元之製作>     <Creating a liquid crystal cell>    

準備5cm見方之單面整面上形成有ITO膜之電極基板A(EHC製造，評價用玻璃ITO整面)，及2.5cm見方之相同玻璃基板之單面中央部形成有連接有2mm寬度之提取電極之1cm見方之ITO膜的電極基板B(EHC，評價用玻璃SZ-B111MIN(B))。 An electrode substrate A (made of EHC, glass ITO entire surface) with an ITO film formed on one side of 5 cm square was prepared, and an extraction of 2 mm width was formed at the center of one side of the same glass substrate of 2.5 cm square. Electrode substrate B (EHC, evaluation glass SZ-B111MIN (B)) of 1 cm square ITO film of the electrode.

於電極基板A上塗佈各著色感光性組成物溶液，於1分鐘真空乾燥後，於110℃下在加熱板上預烘烤70s，獲得乾燥膜厚3.5μm之塗佈膜。其後，遮蔽外周部2mm，分別使用3kW高壓水銀，於50mJ/cm2之曝光條件下實施圖像曝光。繼而，使用25℃之約0.1重量%之氫氧化鉀水溶液，於25℃下實施水壓0.15MPa之噴淋顯影後，利用純水停止顯影，並利用水洗噴射進行清洗。噴淋顯影時間於10~120秒間加以調整，設為溶解去除感光層之時間(分斷時間)之約 1.6倍。將120秒亦無法溶解者判斷為無法顯影。 Each colored photosensitive composition solution was coated on the electrode substrate A, and dried under vacuum for 1 minute, and then pre-baked on a hot plate at 110 ° C. for 70 s to obtain a coating film having a dry film thickness of 3.5 μm. Thereafter, the outer peripheral portion was shielded by 2 mm, and 3 kW high-pressure mercury was used to perform image exposure under an exposure condition of 50 mJ / cm 2 . Then, using a 0.1% by weight potassium hydroxide aqueous solution at 25 ° C., spray development was performed at 25 ° C. with a water pressure of 0.15 MPa, development was stopped by pure water, and washing was performed by water jetting. The spray development time is adjusted from 10 to 120 seconds, and is set to about 1.6 times the time (break time) for dissolving and removing the photosensitive layer. Those who could not dissolve for 120 seconds were judged to be unable to develop.

於230℃下將以上述方式形成有圖像之電極基板後烘烤20分鐘，獲得施有抗蝕劑之電極基板(抗蝕劑基板)。其後，於抗蝕劑基板上塗佈聚醯亞胺溶液，在加熱板上於70℃下預烘烤2分鐘，於220℃下後烘烤24分鐘。將以上述方式獲得之抗蝕劑基板切割為2.5cm見方之基板，完成評價用電極基板A。 The electrode substrate on which the image was formed as described above was baked at 230 ° C. for 20 minutes to obtain an electrode substrate (resist substrate) to which a resist was applied. Thereafter, a polyimide solution was coated on the resist substrate, pre-baked at 70 ° C for 2 minutes on a hot plate, and post-baked at 220 ° C for 24 minutes. The resist substrate obtained in the above manner was cut into a 2.5 cm square substrate to complete the electrode substrate A for evaluation.

另一方面，亦於電極基板B上塗佈聚醯亞胺溶液，在加熱板上於70℃下預烘烤2分鐘，於220℃下後烘烤24分鐘，完成評價用電極基板B。 On the other hand, the polyimide solution was also coated on the electrode substrate B, pre-baked at 70 ° C. for 2 minutes on a hot plate, and post-baked at 220 ° C. for 24 minutes to complete the electrode substrate B for evaluation.

其後，使用分注器，於電極基板B之外周上塗佈含有直徑5μm之二氧化矽珠之環氧樹脂系密封劑後，將評價用電極基板A之塗佈面壓接之狀態貼附於電極基板B之表側(密封劑側)，完成空單元。在熱風循環爐內，於180℃下加熱2小時。 Thereafter, an epoxy resin-based sealant containing silicon dioxide beads having a diameter of 5 μm was coated on the outer periphery of the electrode substrate B using a dispenser, and then the coated surface of the electrode substrate A for evaluation was pressure-bonded. On the front side (sealant side) of the electrode substrate B, an empty cell is completed. In a hot-air circulation furnace, it was heated at 180 ° C for 2 hours.

於以上述方式而得之空單元中注入液晶(Merck Japan公司製造之MLC-6608)，藉由UV(Ultraviolet，紫外線)硬化型密封劑密封周邊部，完成電壓保持率測定用液晶單元。 Liquid crystal (MLC-6608 manufactured by Merck Japan) was injected into the empty cell obtained in the above manner, and a peripheral portion was sealed with a UV (Ultraviolet) hardening sealant to complete a liquid crystal cell for measuring a voltage holding ratio.

<電壓保持率(VHR)之評價>     <Evaluation of Voltage Holding Rate (VHR)>    

對上述液晶單元進行退火處理(在熱風循環爐內，於105℃下加熱2.5小時)後，於0.6Hz、幀時間1667msec之條件下對評價用電極基板A、B施加5V之電壓，藉由Toyo Corporation股份有限公司製造之「VHR-6254型」測定電壓保持率。 After the above liquid crystal cell was annealed (heated in a hot air circulation furnace at 105 ° C. for 2.5 hours), a voltage of 5 V was applied to the electrode substrates A and B for evaluation at 0.6 Hz and a frame time of 1667 msec. "VHR-6254" manufactured by Corporation Co., Ltd. measures the voltage holding ratio.

由表2之結果可知，藉由本發明之著色感光性組成物，可獲得完全穿透開口部與中間穿透開口部圖案之形狀之形成、階差之控制、密接性較佳，且液晶之電壓保持率優異之著色間隔件，可用於一次形成高度不同之著色間隔件之方法。 From the results in Table 2, it can be seen that with the colored photosensitive composition of the present invention, it is possible to obtain the shape of the pattern of completely penetrating openings and intermediate penetrating openings, control of step difference, better adhesion, and the voltage of the liquid crystal. The colored spacer with excellent retention can be used for a method of forming colored spacers of different heights at one time.

對本發明詳細地且參照特定之實施態樣進行了說明，但業者應明白，可不脫離本發明之精神與範圍而施加各種變更或修正。本申請案基於2011年10月25日申請之日本專利申請案(日本專利特願2011-233900)，其內容係作為參照而引用於此。 The present invention has been described in detail and with reference to specific implementation aspects, but it should be understood by those skilled in the art that various changes or modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application filed on October 25, 2011 (Japanese Patent Application No. 2011-233900), the contents of which are incorporated herein by reference.

(產業上之可利用性)     (Industrial availability)    

本發明之著色感光性組成物可較佳地用於在液晶顯示器等之彩色濾光片中形成著色間隔件等時，尤其是於藉由光微影法而一次形成高度不同之著色間隔件之情形時，形狀之形成、階差、密接性及液晶之電性可靠性優異。本發明可提供高品質之彩色濾光片或液晶顯示裝置等。 The coloring photosensitive composition of the present invention can be preferably used when forming a coloring spacer or the like in a color filter of a liquid crystal display or the like, especially when forming coloring spacers of different heights at one time by a photolithography method. In this case, the shape formation, step difference, adhesion, and electrical reliability of the liquid crystal are excellent. The invention can provide a high-quality color filter or a liquid crystal display device.

Claims (14)

一種著色感光性組成物，其含有(a)著色劑、(b)鹼可溶性樹脂、(c)光聚合起始劑、(d)乙烯性不飽和化合物、(e)溶劑及(f)分散劑，且用於藉由光微影法而一次形成高度不同之著色間隔件；(a)著色劑之含有比率相對於著色感光性組成物中之總固形分係未滿30重量%；含有下述鹼可溶性樹脂(A-1)及鹼可溶性樹脂(A-2)中之至少一者作為(b)鹼可溶性樹脂；含有包含氮原子之丙烯酸系嵌段共聚合體作為(f)分散劑；(b)鹼可溶性樹脂相對於(d)乙烯性不飽和化合物之重量比為未滿7；鹼可溶性樹脂(A-1)及鹼可溶性樹脂(A-2)之合計相對於著色感光性組成物中之總固形分之比例為12重量%以上；<鹼可溶性樹脂(A-1)>藉由對環氧樹脂加成α,β-不飽和單羧酸或酯部分具有羧基之α,β-不飽和單羧酸酯，進而與多元酸酐反應而得之樹脂；<鹼可溶性樹脂(A-2)>藉由對環氧樹脂加成α,β-不飽和單羧酸或酯部分具有羧基之α,β-不飽和單羧酸酯，進而與多元醇及多元酸酐反應而得之樹脂。A colored photosensitive composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant And used to form colored spacers of different heights at one time by photolithography; (a) the content ratio of the colorant is less than 30% by weight relative to the total solid content of the coloring photosensitive composition; it contains the following At least one of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) is (b) an alkali-soluble resin; an acrylic block copolymer containing a nitrogen atom is used as (f) a dispersant; (b) ) The weight ratio of the alkali-soluble resin to the (d) ethylenically unsaturated compound is less than 7; the total of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) is relative to that of the colored photosensitive composition. The proportion of the total solid content is 12% by weight or more; <Alkali-soluble resin (A-1)> By adding α, β-unsaturated monocarboxylic acid or ester portion to the epoxy resin, α, β-unsaturation Monocarboxylic acid ester, which is obtained by reacting with polybasic acid anhydride; <alkali soluble resin (A-2)> By adding α, β-unsaturated monocarboxylic acid to epoxy resin Or carboxyl ester moiety having α, [beta] unsaturated monocarboxylic acid esters, in turn obtained by reacting the resin with a polyol and polybasic acid anhydride. 如請求項1之著色感光性組成物，其中，鹼可溶性樹脂(A-1)及鹼可溶性樹脂(A-2)之合計相對於著色感光性組成物中之總固形分之比例為20重量%以上。The colored photosensitive composition according to claim 1, wherein the ratio of the total of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition is 20% by weight the above. 如請求項1之著色感光性組成物，其中，鹼可溶性樹脂(A-1)及鹼可溶性樹脂(A-2)之合計相對於著色感光性組成物中之總固形分之比例為20~60重量%。For example, the colored photosensitive composition of claim 1, wherein the ratio of the total of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition is 20 to 60. weight%. 如請求項1至3中任一項之著色感光性組成物，其中，(a)著色劑之含有比率相對於著色感光性組成物中之總固形分為25重量%以上。The colored photosensitive composition according to any one of claims 1 to 3, wherein (a) the content ratio of the colorant is 25% by weight or more with respect to the total solid content in the colored photosensitive composition. 如請求項1至3中任一項之著色感光性組成物，其中，作為(a)著色劑，係含有以下之(1)紅色顏料，且含有以下之(2)藍色顏料及以下之(3)紫色顏料中之至少一者；(1)選自C.I.顏料紅177、254之紅色顏料；(2)屬於C.I.顏料藍15：6之藍色顏料；(3)屬於C.I.顏料紫23之紫色顏料。The coloring photosensitive composition according to any one of claims 1 to 3, wherein (a) the colorant contains the following (1) red pigment, and the following (2) blue pigment and ( 3) At least one of the purple pigments; (1) a red pigment selected from CI Pigment Red 177 and 254; (2) a blue pigment belonging to CI Pigment Blue 15: 6; (3) a violet belonging to CI Pigment Violet 23 pigment. 如請求項1至3中任一項之著色感光性組成物，其中，含有C.I.顏料紅254及C.I.顏料藍15：6作為(a)著色劑。The colored photosensitive composition according to any one of claims 1 to 3, which contains C.I. Pigment Red 254 and C.I. Pigment Blue 15: 6 as (a) a colorant. 如請求項1至3中任一項之著色感光性組成物，其中，含有A-B嵌段共聚合體及B-A-B嵌段共聚合體中之至少一者作為(f)分散劑，該A-B嵌段共聚合體及B-A-B嵌段共聚合體包含側鏈具有4級銨鹽基及胺基中之至少一者之A嵌段、與不具有4級銨鹽基及胺基之B嵌段。The colored photosensitive composition according to any one of claims 1 to 3, which contains at least one of an AB block copolymer and a BAB block copolymer as (f) a dispersant, the AB block copolymer and The BAB block copolymer includes an A block having at least one of a quaternary ammonium salt group and an amine group in a side chain, and a B block having no quaternary ammonium salt group and amine group. 如請求項1至3中任一項之著色感光性組成物，其中，含有A-B嵌段共聚合體及B-A-B嵌段共聚合體中之至少一者作為(f)分散劑，該A-B嵌段共聚合體及B-A-B嵌段共聚合體包含側鏈具有4級銨鹽基及胺基之A嵌段、與不具有4級銨鹽基及胺基之B嵌段。The colored photosensitive composition according to any one of claims 1 to 3, which contains at least one of an AB block copolymer and a BAB block copolymer as (f) a dispersant, the AB block copolymer and The BAB block copolymer includes an A block having a quaternary ammonium salt group and an amine group in a side chain, and a B block having no quaternary ammonium salt group and an amine group. 如請求項1至3中任一項之著色感光性組成物，其中，含有A-B嵌段共聚合體及B-A-B嵌段共聚合體中之至少一者作為(f)分散劑，該A-B嵌段共聚合體及B-A-B嵌段共聚合體包含側鏈不具有4級銨鹽基而具有胺基之A嵌段、與不具有4級銨鹽基及胺基之B嵌段。The colored photosensitive composition according to any one of claims 1 to 3, which contains at least one of an AB block copolymer and a BAB block copolymer as (f) a dispersant, the AB block copolymer and The BAB block copolymer includes an A block having an amine group without a quaternary ammonium salt group in the side chain, and a B block having no quaternary ammonium salt group and an amine group at the side chain. 如請求項1至3中任一項之著色感光性組成物，其中，含有肟酯化合物作為(c)光聚合起始劑。The coloring photosensitive composition according to any one of claims 1 to 3, which contains an oxime ester compound as (c) a photopolymerization initiator. 一種著色間隔件，其係藉由請求項1至10中任一項之著色感光性組成物而一次形成，且高度不同。A coloring spacer, which is formed at one time by the coloring photosensitive composition according to any one of claims 1 to 10 and has different heights. 一種彩色濾光片，其具備請求項11之著色間隔件。A color filter including the coloring spacer of claim 11. 一種液晶顯示裝置，其具備請求項12之彩色濾光片。A liquid crystal display device includes a color filter according to claim 12. 一種著色間隔件之一次形成方法，其使用請求項1至10中任一項之著色感光性組成物並藉由光微影法而一次形成高度不同之著色間隔件。A one-time forming method of a colored spacer, using the colored photosensitive composition of any one of claims 1 to 10, and forming colored spacers of different heights at one time by a photolithography method.
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