TW201525077A - Colored composition, method for manufacturing colored composition, cured film, color filter, method for manufacturing color filter, solid-state imaging device, and liquid crystal display device - Google Patents

Colored composition, method for manufacturing colored composition, cured film, color filter, method for manufacturing color filter, solid-state imaging device, and liquid crystal display device Download PDF

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TW201525077A
TW201525077A TW103142939A TW103142939A TW201525077A TW 201525077 A TW201525077 A TW 201525077A TW 103142939 A TW103142939 A TW 103142939A TW 103142939 A TW103142939 A TW 103142939A TW 201525077 A TW201525077 A TW 201525077A
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anion
rtp
compound
dye cation
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Soji Ishizaka
Satoshi Higuchi
Koutaro Okabe
Akinori Fujita
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
    • C09B69/06—Dyestuff salts, e.g. salts of acid dyes with basic dyes of cationic dyes with organic acids or with inorganic complex acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/103—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a diaryl- or triarylmethane dye
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

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

Abstract

The invention provides a colored composition with excellent transmittance and heat resistance, a method for manufacturing a colored composition, a cured film, a color filter, a method for manufacturing a color filter, a solid-state imaging device, and an image display device. The colored composition of the invention includes: a dye cation having a triarylmethane structure, a counter anion X and an anion Y different from the counter anion X. The dye cation has a crosslinkable group and/or a polymer structure. The anion Y may form a salt with the dye cation. A molar ratio of the anion Y to the dye cation (anion Y/dye cation) is in a range of 0.0001 to 7.0.

Description

著色組成物、著色組成物的製造方法、硬化膜、彩 色濾光片、彩色濾光片的製造方法、固體攝像元件及圖像顯示裝置 Coloring composition, method for producing colored composition, cured film, color Color filter, method of manufacturing color filter, solid-state imaging element, and image display device

本發明是有關於一種著色組成物、著色組成物的製造方法、硬化膜、彩色濾光片、彩色濾光片的製造方法、固體攝像元件及圖像顯示裝置。 The present invention relates to a coloring composition, a method for producing a colored composition, a cured film, a color filter, a method for producing a color filter, a solid-state image sensor, and an image display device.

以前，彩色濾光片是藉由以下方式來製造：藉由含有分散有有機顏料或無機顏料的顏料分散組成物與多官能單體、聚合起始劑、鹼可溶性樹脂及視需要的其他成分而製成著色組成物，使用該著色組成物藉由光微影(photolithography)法、噴墨(ink-jet)法等來形成著色圖案。 In the past, a color filter was produced by dispersing a pigment-dispersed composition containing an organic pigment or an inorganic pigment with a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components as needed. A colored composition is formed, and a colored pattern is formed by a photolithography method, an inkjet method, or the like using the colored composition.

近年來，彩色濾光片存在以下傾向：於液晶顯示元件(Liquid Crystal Display，LCD)用途中不僅用於監視器(monitor)，而且其用途向電視(Television，TV)擴大。伴隨著該用途擴大的傾向， 對彩色濾光片於色度、對比度等方面要求高度的顏色特性。另外，對於影像感測器(image sensor)(固體攝像元件)用途的彩色濾光片而言，亦同樣地要求顏色不均的減少、顏色解析度的提高等顏色特性的進一步提高。 In recent years, color filters have a tendency to be used not only for monitors in liquid crystal display (LCD) applications but also for televisions (TVs). With the tendency to expand the use, High color characteristics are required for color filters in terms of chromaticity, contrast, and the like. Further, in the color filter used for an image sensor (solid-state imaging device), color characteristics such as reduction in color unevenness and improvement in color resolution are also required to be further improved.

再者，對於以前的顏料分散系而言，容易引起由顏料的粗大粒子導致發生散射、由分散穩定性不良導致黏度上升等問題，大多情況下難以進一步提高對比度、亮度。 In addition, in the conventional pigment dispersion system, problems such as scattering due to coarse particles of the pigment and increase in viscosity due to poor dispersion stability are likely to occur, and in many cases, it is difficult to further improve contrast and brightness.

因此，一直以來作為著色劑，正在研究不僅使用顏料而且使用染料(例如參照專利文獻1)。若使用染料作為著色劑，則由於染料自身的顏色純度或其色相的鮮豔度，而可提高進行圖像顯示時的顯示圖像的色相或亮度，且由於粗大粒子消失故可提高對比度，於此方面被視為有用。 Therefore, as a coloring agent, it has been studied to use not only a pigment but also a dye (for example, refer to Patent Document 1). When a dye is used as the coloring agent, the hue or brightness of the display image at the time of image display can be improved due to the color purity of the dye itself or the vividness of the hue, and the contrast can be improved by the disappearance of the coarse particles. Aspects are considered useful.

關於染料的例子，已知有酞菁染料、二吡咯亞甲基系染料、嘧啶偶氮染料、吡唑偶氮染料、呫噸(xanthene)染料、三芳基甲烷染料等具有多種多樣的色素母體的化合物(例如參照專利文獻2~專利文獻11)。 As examples of dyes, various pigment precursors such as phthalocyanine dyes, dipyrromethene dyes, pyrimidine azo dyes, pyrazole azo dyes, xanthene dyes, and triarylmethane dyes are known. Compound (for example, refer to Patent Document 2 to Patent Document 11).

[現有技術文獻] [Prior Art Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開平6-75375號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 6-75375

[專利文獻2]日本專利特開2008-292970號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-292970

[專利文獻3]日本專利特開2007-039478號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-039478

[專利文獻4]日本專利特開平9-157536號公報 [Patent Document 4] Japanese Patent Laid-Open No. Hei 9-157536

[專利文獻5]日本專利特開2013-25194號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2013-25194

[專利文獻6]日本專利特開2012-201694號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2012-201694

[專利文獻7]日本專利特開2012-108469號公報 [Patent Document 7] Japanese Patent Laid-Open Publication No. 2012-108469

[專利文獻8]日本專利特開2000-095805號公報 [Patent Document 8] Japanese Patent Laid-Open Publication No. 2000-095805

[專利文獻9]日本專利特開2013-53240號公報 [Patent Document 9] Japanese Patent Laid-Open Publication No. 2013-53240

[專利文獻10]美國專利申請公開第2013/0141810號說明書 [Patent Document 10] US Patent Application Publication No. 2013/0141810

[專利文獻11]國際公開第2010/123071號手冊 [Patent Document 11] International Publication No. 2010/123071

此處，彩色濾光片等中所用的著色組成物需求優異的透射率，並且需求優異的耐熱性。 Here, the coloring composition used in a color filter or the like requires excellent transmittance and requires excellent heat resistance.

例如專利文獻9中記載：藉由將陽離子與染料陰離子之比率設定於特定範圍內，可提供一種透射率優異的彩色濾光片。然而，專利文獻9中記載的著色樹脂組成物的耐熱性不充分。 For example, Patent Document 9 discloses that a color filter excellent in transmittance can be provided by setting the ratio of the cation to the dye anion within a specific range. However, the colored resin composition described in Patent Document 9 is insufficient in heat resistance.

本發明的目的在於解決所述課題，且其目的在於提供一種透射率及耐熱性優異的著色組成物。尤其本發明的課題在於提供一種作為藍色濾光片(blue filter)用的著色組成物而有益的著色組成物。 An object of the present invention is to solve the above problems, and an object of the invention is to provide a coloring composition which is excellent in transmittance and heat resistance. In particular, an object of the present invention is to provide a colored composition which is advantageous as a coloring composition for a blue filter.

本申請案發明者根據所述狀況進行了努力研究，結果發現，藉由著色組成物含有具有三芳基甲烷結構的染料陽離子、相對陰離子X以及與相對陰離子X不同的陰離子Y，並且染料陽離 子含有交聯性基及/或多聚物結構，陰離子Y可與染料陽離子形成鹽，將陰離子Y相對於染料陽離子之莫耳比(陰離子Y/染料陽離子)設定於既定範圍內，可解決所述課題。 The inventors of the present application conducted diligent research based on the above conditions, and as a result, found that the coloring composition contains a dye cation having a triarylmethane structure, a relative anion X, and an anion Y different from the opposite anion X, and the dye is cationically separated. The subunit contains a crosslinkable group and/or a polymer structure, and the anion Y forms a salt with the dye cation, and the molar ratio of the anion Y to the dye cation (anion Y/dye cation) is set within a predetermined range, and the solution can be solved. The subject.

具體而言，藉由下述手段<1>、較佳為藉由下述手段<2>~下述手段<16>解決了所述課題。 Specifically, the above problem is solved by the following means <1>, preferably by the following means <2> to the following means <16>.

<1>一種著色組成物，含有具有三芳基甲烷結構的染料陽離子、相對陰離子X以及與相對陰離子X不同的陰離子Y，並且染料陽離子含有交聯性基及/或多聚物結構，陰離子Y可與染料陽離子形成鹽，陰離子Y相對於染料陽離子之莫耳比(陰離子Y/染料陽離子)為0.0001~7.0。 <1> A coloring composition comprising a dye cation having a triarylmethane structure, a relative anion X, and an anion Y different from the opposite anion X, and the dye cation contains a crosslinkable group and/or a polymer structure, and the anion Y can be Forming a salt with the dye cation, the molar ratio of the anion Y to the dye cation (anionic Y/dye cation) is 0.0001 to 7.0.

<2>如<1>所記載的著色組成物，其中染料陽離子為由通式(TP1)所表示的染料陽離子及/或由通式(TP2)所表示的染料陽離子， <2> The coloring composition according to <1>, wherein the dye cation is a dye cation represented by the formula (TP1) and/or a dye cation represented by the formula (TP2),

(通式(TP1)及通式(TP2)中，Rtp1~Rtp4分別獨立地表示氫原子、烷基或芳基；Rtp5、Rtp6、Rtp8、Rtp9及Rtp11分別獨 立地表示取代基；Rtp7表示氫原子、烷基、芳基或NRtp71Rtp72；Rtp71及Rtp72分別獨立地表示氫原子、烷基或芳基；Rtp10表示氫原子、烷基或芳基；a、b及c分別獨立地表示0~4的整數；於a、b及c為2以上的情形時，Rtp5、Rtp6、Rtp8及Rtp9中的2個亦可相互連結而形成環；Rtp1~Rtp11、Rtp71及Rtp72的至少一個含有多聚物結構或交聯性基)。 (In the general formula (TP1) and the formula (TP2), Rtp 1 to Rtp 4 each independently represent a hydrogen atom, an alkyl group or an aryl group; and Rtp 5 , Rtp 6 , Rtp 8 , Rtp 9 and Rtp 11 are each independently represented. a substituent; Rtp 7 represents a hydrogen atom, an alkyl group, an aryl group or NRtp 71 Rtp 72 ; Rtp 71 and Rtp 72 each independently represent a hydrogen atom, an alkyl group or an aryl group; and Rtp 10 represents a hydrogen atom, an alkyl group or an aryl group; a, b, and c each independently represent an integer of 0 to 4; when a, b, and c are 2 or more, two of Rtp 5 , Rtp 6 , Rtp 8 , and Rtp 9 may be linked to each other to form a ring. At least one of Rtp 1 to Rtp 11 , Rtp 71 and Rtp 72 contains a polymer structure or a crosslinkable group).

<3>如<1>或<2>所記載的著色組成物，其中陰離子Y包含：選自氟陰離子、氯陰離子、溴陰離子、碘陰離子、氰化物離子、過氯酸根陰離子、硼酸根陰離子、PF6-及SbF6-中的至少一種，以及選自-SO3 -、-COO-、-PO4 -、下述通式(A1)所表示的結構及下述通式(A2)所表示的結構中的至少一種， <3> The colored composition according to <1> or <2>, wherein the anion Y comprises: selected from the group consisting of a fluoride anion, a chloride anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, a borate anion, At least one of PF 6- and SbF 6- , and a structure selected from the group consisting of -SO 3 - , -COO - , -PO 4 - , represented by the following formula (A1) and represented by the following formula (A2) At least one of the structures,

(通式(A1)中，R1及R2分別獨立地表示-SO2-或-CO-)； (In the formula (A1), R 1 and R 2 each independently represent -SO 2 - or -CO-);

(通式(A2)中，R3表示-SO2-或-CO-；R4及R5分別獨立地表示-SO2-、-CO-或-CN)。 (In the formula (A2), R 3 represents -SO 2 - or -CO-; and R 4 and R 5 each independently represent -SO 2 -, -CO- or -CN).

<4>如<1>至<3>中任一項所記載的著色組成物，其中陰離子Y相對於染料陽離子之莫耳比(陰離子Y/染料陽離子)為0.001~5.0。 The colored composition according to any one of <1> to <3> wherein the molar ratio of the anion Y to the dye cation (anionic Y/dye cation) is 0.001 to 5.0.

<5>如<1>至<4>中任一項所記載的著色組成物，其中染料陽離子含有多聚物結構。 The colored composition according to any one of <1> to <4> wherein the dye cation contains a polymer structure.

<6>如<1>至<5>中任一項所記載的著色組成物，更含有光聚合起始劑。 <6> The colored composition according to any one of <1> to <5> further comprising a photopolymerization initiator.

<7>如<1>至<6>中任一項所記載的著色組成物，更含有聚合性化合物。 <7> The colored composition according to any one of <1> to <6> further comprising a polymerizable compound.

<8>如<1>至<7>中任一項所記載的著色組成物，其是用於形成彩色濾光片的著色層。 <8> The colored composition according to any one of <1> to <7> which is a coloring layer for forming a color filter.

<9>一種著色組成物的製造方法，包括以下步驟：於含有具有三芳基甲烷結構的染料陽離子、相對陰離子X、可與染料陽離子形成鹽且與相對陰離子X不同的陰離子Y以及溶劑的溶液中，至少調配聚合性化合物，並且染料陽離子含有交聯性基及/或多聚物結構。 <9> A method for producing a colored composition, comprising the steps of: in a solution containing a dye cation having a triarylmethane structure, a relative anion X, an anion Y which can form a salt with a dye cation and which is different from the opposite anion X, and a solvent; At least a polymerizable compound is formulated, and the dye cation contains a crosslinkable group and/or a polymer structure.

<10>如<9>所記載的著色組成物的製造方法，更包括以下步驟：將含有染料陽離子與相對陰離子X的著色劑以及陰離子Y溶解於溶劑中。 <10> The method for producing a colored composition according to <9>, further comprising the step of dissolving a coloring agent containing a dye cation and a relative anion X and an anion Y in a solvent.

<11>一種著色硬化膜，其是使如<1>至<8>中任一項所 記載的著色組成物或者藉由如<9>或<10>所記載的著色組成物的製造方法所得的著色組成物硬化而成。 <11> A colored hardening film which is obtained by any one of <1> to <8> The coloring composition described above or a colored composition obtained by the method for producing a colored composition according to <9> or <10> is cured.

<12>一種彩色濾光片，具有如<11>所記載的著色硬化膜。 <12> A color filter comprising the colored cured film according to <11>.

<13>一種彩色濾光片的製造方法，包括以下步驟：將如<1>至<8>中任一項所記載的著色組成物或者藉由如<9>或<10>所記載的著色組成物的製造方法所得的著色組成物賦予至支撐體上，形成著色組成物層；對色組成物層以圖案狀進行曝光；以及將未曝光部顯影去除而形成著色圖案。 <13> A method of producing a color filter, comprising the coloring composition according to any one of <1> to <8> or by coloring as described in <9> or <10> The colored composition obtained by the method for producing a composition is applied onto a support to form a colored composition layer; the color composition layer is exposed in a pattern; and the unexposed portion is developed and removed to form a colored pattern.

<14>如<13>所記載的彩色濾光片的製造方法，更包括以下步驟：於230℃以上對經顯影的著色圖案進行加熱。 <14> The method for producing a color filter according to <13>, further comprising the step of heating the developed coloring pattern at 230 ° C or higher.

<15>一種彩色濾光片，其是藉由如<13>或<14>所記載的彩色濾光片的製造方法所製造。 <15> A color filter produced by the method for producing a color filter according to <13> or <14>.

<16>一種固體攝像元件或液晶顯示裝置，具有如<12>或<14>所記載的彩色濾光片。 <16> A solid-state imaging device or a liquid crystal display device, comprising the color filter according to <12> or <14>.

根據本發明，可提供一種透射率及耐熱性優異的著色組成物。 According to the invention, it is possible to provide a coloring composition which is excellent in transmittance and heat resistance.

以下，對本發明的內容加以詳細說明。另外，本申請案 說明書中所謂「~」是以包含其前後所記載的數值作為下限值及上限值的含意使用。 Hereinafter, the contents of the present invention will be described in detail. In addition, this application In the specification, "~" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit.

本說明書中所謂固體成分濃度，是指將溶劑除外的其他成分的重量相對於組成物的總重量之重量百分率。另外，固體成分濃度只要無特別說明，則是指25℃下的濃度。 The solid content concentration in the present specification means the weight percentage of the weight of other components excluding the solvent with respect to the total weight of the composition. In addition, the solid content concentration means the concentration at 25 ° C unless otherwise specified.

於本說明書中的基團(原子團)的表述中，未記載經取代及未經取代的表述包含不具有取代基的基團，並且亦包含具有取代基的基團。例如所謂「烷基」，不僅包含不具有取代基的烷基(未經取代的烷基)，而且亦包含具有取代基的烷基(經取代的烷基)。 In the expression of the group (atomic group) in the present specification, it is not described that the substituted and unsubstituted expression includes a group having no substituent, and also includes a group having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

另外，本說明書中所謂「放射線」，例如是指水銀燈的明線光譜、準分子雷射所代表的遠紫外線、極紫外線((Extreme Ultraviolet，EUV)光)、X射線、電子束等。另外，本發明中所謂光，是指光化射線或放射線。本說明書中所謂「曝光」，只要無特別說明，則不僅是指利用水銀燈、準分子雷射所代表的遠紫外線、X射線、EUV光等的曝光，利用電子束、離子束等粒子束的描畫亦包括在曝光中。 In addition, the term "radiation" as used herein means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (Extreme Ultraviolet (EUV) light), an X-ray, an electron beam, or the like. Further, the term "light" as used in the present invention means actinic ray or radiation. In the present specification, the term "exposure" is used to describe not only the ultraviolet light, the X-ray, the EUV light, etc., which are represented by mercury lamps or excimer lasers, but also the use of particle beams such as electron beams and ion beams. Also included in the exposure.

另外，本說明書中，「(甲基)丙烯酸酯」表示丙烯酸酯及甲基丙烯酸酯兩者或任一者，「(甲基)丙烯酸」表示丙烯酸及甲基丙烯酸兩者或任一者，「(甲基)丙烯醯基」表示丙烯醯基及甲基丙烯醯基兩者或任一者。 In the present specification, "(meth)acrylate" means either or both of acrylate and methacrylate, and "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid," The (meth)acrylonyl group means either or both of an acryloyl group and a methacryl group.

另外，本說明書中，「單體」與「單體(monomer)」為相同含意。本說明書中所謂單體，是指與寡聚物及聚合物相區分、重量 平均分子量為2,000以下的化合物。本說明書中，所謂聚合性化合物，是指具有聚合性官能基的化合物，可為單體亦可為聚合物。所謂聚合性官能基，是指參與聚合反應的基團。 In addition, in this specification, "monomer" and "monomer" have the same meaning. The term "monomer" as used in this specification means that it is distinguished from oligomers and polymers by weight. A compound having an average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.

本說明書中，化學式中的Me表示甲基，Et表示乙基，Pr表示丙基，Bu表示丁基，Ph表示苯基。 In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.

本說明書中，「步驟」一詞不僅是指獨立的步驟，即便於無法與其他步驟明確區分的情形時，只要可達成該步驟的預期作用，則包括在該用語中。 In the present specification, the term "step" means not only an independent step, but even in the case where it cannot be clearly distinguished from other steps, it is included in the term as long as the intended effect of the step can be achieved.

本發明中的重量平均分子量只要無特別說明，則是指由凝膠滲透層析法(Gel Penetration Chromatography，GPC)所測定的重量平均分子量。關於GPC，可對所得的聚合物藉由去除溶劑而加以分離，以四氫呋喃將所得的固體成分稀釋至0.1質量%，利用HLC-8020GPC(東曹(股)製造)，將TSKgel Super Multipore HZ-H(東曹(股)製造，4.6mm內徑(ID)×15cm)串聯3根而成者作為管柱來進行測定。關於條件，可將試樣濃度設定為0.35質量%、流速設定為0.35mL/min、樣品注入量設定為10μL、測定溫度設定為40℃，使用示差折射率(Refractive Index，RI)檢測器來進行測定。 The weight average molecular weight in the present invention means a weight average molecular weight measured by Gel Penetration Chromatography (GPC) unless otherwise specified. With respect to GPC, the obtained polymer can be separated by removing the solvent, and the obtained solid component is diluted to 0.1% by mass with tetrahydrofuran, and TSKgel Super Multipore HZ-H is used by HLC-8020GPC (manufactured by Tosoh Corporation). (Manufactured by Tosoh Co., Ltd., 4.6 mm inner diameter (ID) × 15 cm) Three of them were connected in series and measured as a column. The conditions were set such that the sample concentration was set to 0.35 mass%, the flow rate was set to 0.35 mL/min, the sample injection amount was set to 10 μL, and the measurement temperature was set to 40 ° C, and the refractive index (RI) detector was used. Determination.

<著色組成物> <Coloring composition>

本發明的著色組成物的特徵在於：含有具有三芳基甲烷結構的染料陽離子、相對陰離子X及與相對陰離子X不同的陰離子Y，且染料陽離子含有交聯性基及/或多聚物結構，陰離子Y可與染料 陽離子形成鹽，陰離子Y相對於染料陽離子之莫耳比(陰離子Y/染料陽離子)為0.0001~7.0。 The coloring composition of the present invention is characterized by containing a dye cation having a triarylmethane structure, a relative anion X, and an anion Y different from the opposite anion X, and the dye cation contains a crosslinkable group and/or a polymer structure, an anion Y can be used with dyes The cation forms a salt, and the molar ratio of the anion Y to the dye cation (anionic Y/dye cation) is 0.0001 to 7.0.

藉由使用本發明的組成物，可提供一種透射率及耐熱性優異的著色組成物。另外，亦可使塗佈時的表面狀態良好。可獲得此種本發明的效果的理由雖不確定，但可如以下般推測。 By using the composition of the present invention, it is possible to provide a coloring composition excellent in transmittance and heat resistance. In addition, the surface state at the time of coating can also be made good. Although the reason why the effect of the present invention can be obtained is not certain, it can be estimated as follows.

若將含有染料陽離子及其相對陰離子、且不含其他陰離子的著色組成物加熱，則可能於著色組成物的過熱過程中，相對陰離子自染料陽離子解離，相對陰離子發生分解，其分解物昇華。結果，染料陽離子容易分解，著色組成物的顏色容易變化。 When the coloring composition containing the dye cation and its relative anion and no other anion is heated, it is possible that the anion is dissociated from the dye cation during the superheating of the coloring composition, the relative anion is decomposed, and the decomposition product is sublimated. As a result, the dye cation is easily decomposed, and the color of the colored composition is easily changed.

為了解決該問題，亦考慮到於著色組成物中過剩地調配相對陰離子。然而得知，若於著色組成物中過剩地調配相對陰離子，則著色劑於溶劑中的溶解性劣化，或組成物的耐熱性變差。 In order to solve this problem, it is also considered that the relative anion is excessively formulated in the colored composition. However, it has been found that when the relative anion is excessively mixed in the colored composition, the solubility of the colorant in the solvent is deteriorated, or the heat resistance of the composition is deteriorated.

本發明中，將與相對陰離子不同的其他陰離子以特定的比率調配至著色組成物中，藉此即便於相對陰離子自染料陽離子解離、相對陰離子發生分解的情形時，亦可藉由其他陰離子來保持著色組成物中的染料陽離子、相對陰離子及陰離子之間的平衡狀態。結果，染料陽離子不易分解，著色組成物的顏色不易變化，故可使耐熱性良好。另外，本發明的著色組成物含有不同種類的陰離子(相對陰離子及其他陰離子)，藉此與僅含有一種陰離子(相對陰離子)的情形相比較，可提高著色劑於溶劑中的溶解性。結果，可使塗佈本發明的組成物時的塗佈表面狀態更良好。 In the present invention, other anions different from the relative anions are formulated into the colored composition in a specific ratio, whereby even when the relative anion is dissociated from the dye cation and the relative anion is decomposed, it can be retained by other anions. An equilibrium state between the dye cation, the relative anion, and the anion in the colored composition. As a result, the dye cation is not easily decomposed, and the color of the colored composition is not easily changed, so that heat resistance can be improved. Further, the colored composition of the present invention contains different kinds of anions (relative anions and other anions), whereby the solubility of the colorant in a solvent can be improved as compared with the case of containing only one anion (relative anion). As a result, the coated surface state at the time of coating the composition of the present invention can be made better.

例如，本發明的著色組成物含有染料陽離子與相對陰離 子X形成鹽的化合物、染料陽離子與陰離子Y形成鹽的化合物、及相對陰離子X。此種本發明的著色組成物例如可藉由將含有染料陽離子與相對陰離子X的著色劑及陰離子Y溶解於溶劑中而獲得。下述式中，「TAM+」表示染料陽離子的一例，「X-」表示相對陰離子X的一例。「Y-」表示陰離子Y的一例。「TAM+X-」表示染料陽離子與相對陰離子X形成鹽的化合物的一例，「TAM+Y-」表示染料陽離子與陰離子Y形成鹽的化合物的一例。 For example, the colored composition of the present invention contains a compound in which a dye cation forms a salt with respect to an anion X, a compound in which a dye cation forms a salt with an anion Y, and a relative anion X. Such a colored composition of the present invention can be obtained, for example, by dissolving a coloring agent containing a dye cation and a counter anion X and an anion Y in a solvent. In the following formula, "TAM + " represents an example of a dye cation, and "X - " represents an example of a relative anion X. "Y - " represents an example of the anion Y. "TAM + X - " represents an example of a compound in which a dye cation forms a salt with respect to an anion X, and "TAM + Y - " represents an example of a compound in which a dye cation forms a salt with an anion Y.

TAM+X-+Y- TAM+X-+TAM+Y-+X- TAM + X - +Y - TAM + X - +TAM + Y - +X -

<具有三芳基甲烷結構的染料陽離子> <Dye cation having a triarylmethane structure>

染料陽離子含有三芳基甲烷結構及陽離子，且含有交聯性基及/或多聚物結構。 The dye cation contains a triarylmethane structure and a cation, and contains a crosslinkable group and/or a polymer structure.

三芳基甲烷結構為以甲烷為中心而含有3個芳基的結構。3個芳基分別較佳為苯基、萘基、將芳基與雜環縮合而成的環。該情形的雜環可例示含氮五員環或六員環。 The triarylmethane structure is a structure containing three aryl groups centered on methane. Each of the three aryl groups is preferably a phenyl group, a naphthyl group, or a ring obtained by condensing an aryl group and a hetero ring. The heterocyclic ring in this case may be a nitrogen-containing five-membered ring or a six-membered ring.

染料陽離子較佳為通式(TP1)所表示的染料陽離子及/或通式(TP2)所表示的染料陽離子。 The dye cation is preferably a dye cation represented by the formula (TP1) and/or a dye cation represented by the formula (TP2).

(通式(TP1)及通式(TP2)中，Rtp1~Rtp4分別獨立地表示氫原子、烷基或芳基；Rtp5、Rtp6、Rtp8、Rtp9及Rtp11分別獨立地表示取代基；Rtp7表示氫原子、烷基、芳基或NRtp71Rtp72；Rtp71及Rtp72分別獨立地表示氫原子、烷基或芳基；Rtp10表示氫原子、烷基或芳基；a、b及c分別獨立地表示0~4的整數；於a、b及c為2以上的情形時，Rtp5、Rtp6、Rtp8及Rtp9中的2個亦可相互連結而形成環；Rtp1~Rtp11、Rtp71及Rtp72的至少一個含有多聚物結構或交聯性基) (In the general formula (TP1) and the formula (TP2), Rtp 1 to Rtp 4 each independently represent a hydrogen atom, an alkyl group or an aryl group; and Rtp 5 , Rtp 6 , Rtp 8 , Rtp 9 and Rtp 11 are each independently represented. a substituent; Rtp 7 represents a hydrogen atom, an alkyl group, an aryl group or NRtp 71 Rtp 72 ; Rtp 71 and Rtp 72 each independently represent a hydrogen atom, an alkyl group or an aryl group; and Rtp 10 represents a hydrogen atom, an alkyl group or an aryl group; a, b, and c each independently represent an integer of 0 to 4; when a, b, and c are 2 or more, two of Rtp 5 , Rtp 6 , Rtp 8 , and Rtp 9 may be linked to each other to form a ring. At least one of Rtp 1 to Rtp 11 , Rtp 71 and Rtp 72 contains a polymer structure or a crosslinkable group)

通式(TP1)中，Rtp1~Rtp4分別獨立地表示氫原子、烷基或芳基，較佳為氫原子或烷基。 In the formula (TP1), Rtp 1 to Rtp 4 each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom or an alkyl group.

烷基的碳數較佳為1~10，更佳為1~5，進而佳為1~3。烷基可為直鏈狀、分支狀及環狀的任一種，較佳為直鏈狀或分支狀。烷基較佳為未經取代。可列舉後述取代基組群A的項中列舉的取代基。 The carbon number of the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, and still more preferably from 1 to 3. The alkyl group may be any of a linear chain, a branched chain, and a cyclic chain, and is preferably linear or branched. The alkyl group is preferably unsubstituted. The substituents listed in the item of the substituent group A mentioned later are mentioned.

芳基的碳數較佳為6~18，更佳為6~12，進而佳為6。芳基可具有的取代基可列舉後述取代基組群A的項中列舉的取代基。 The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 12, and still more preferably 6. The substituent which the aryl group may have is a substituent listed in the item of the substituent group A mentioned later.

通式(TP1)中，Rtp7表示氫原子、烷基、芳基或NRtp71Rtp72，較佳為氫原子或NRtp71Rtp72，更佳為NRtp71Rtp72。 In the formula (TP1), Rtp 7 represents a hydrogen atom, an alkyl group, an aryl group or NRtp 71 Rtp 72 , preferably a hydrogen atom or NRtp 71 Rtp 72 , more preferably NRtp 71 Rtp 72 .

烷基的碳數較佳為1~10，更佳為1~5，進而佳為1~3。烷基可為直鏈狀、分支狀及環狀的任一種，較佳為直鏈狀。烷基可具有的取代基可列舉後述取代基組群A的項中列舉的取代基。芳基的碳數較佳為6~18，更佳為6~12，進而佳為6。 The carbon number of the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, and still more preferably from 1 to 3. The alkyl group may be any of a linear chain, a branched chain and a cyclic chain, and is preferably a linear chain. The substituent which the alkyl group may have is a substituent listed in the item of the substituent group A mentioned later. The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 12, and still more preferably 6.

Rtp71及Rtp72分別獨立地表示氫原子、烷基或芳基，較佳為氫原子或烷基。烷基的碳數較佳為1~10，更佳為1~8，進而佳為1~6。烷基可為直鏈狀、分支狀及環狀的任一種，較佳為直鏈狀或分支狀。烷基可經取代，但較佳為未經取代。烷基可具有的取代基可列舉後述取代基組群A的項中列舉的取代基。芳基的碳數較佳為6~18，更佳為6~12，進而佳為6。芳基可具有的取代基可列舉後述取代基組群A的項中列舉的取代基。 Rtp 71 and Rtp 72 each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom or an alkyl group. The carbon number of the alkyl group is preferably from 1 to 10, more preferably from 1 to 8, more preferably from 1 to 6. The alkyl group may be any of a linear chain, a branched chain, and a cyclic chain, and is preferably linear or branched. The alkyl group may be substituted, but is preferably unsubstituted. The substituent which the alkyl group may have is a substituent listed in the item of the substituent group A mentioned later. The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 12, and still more preferably 6. The substituent which the aryl group may have is a substituent listed in the item of the substituent group A mentioned later.

通式(TP1)中，Rtp5、Rtp6及Rtp8分別獨立地表示取代基。取代基可列舉後述取代基組群A的項中列舉的取代基。尤其較佳為碳數1~5的直鏈或分支的烷基、碳數1~5的烯基、碳數6~15的芳基、羧基或磺基，更佳為碳數1~5的直鏈或分支的烷基、碳數1~5的烯基、苯基或羧基。尤其Rtp5及Rtp6分別獨立地較佳為碳數1~5的烷基。另外，Rtp8較佳為2個烯基相互鍵結而形成環。環較佳為苯環。 In the formula (TP1), Rtp 5 , Rtp 6 and Rtp 8 each independently represent a substituent. Examples of the substituent include the substituents listed in the item of the substituent group A to be described later. Particularly preferred is a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, a carboxyl group or a sulfo group, and more preferably having a carbon number of 1 to 5. A linear or branched alkyl group, a carbon number of 1 to 5 alkenyl group, a phenyl group or a carboxyl group. In particular, Rtp 5 and Rtp 6 are each independently preferably an alkyl group having 1 to 5 carbon atoms. Further, Rtp 8 preferably has two alkenyl groups bonded to each other to form a ring. The ring is preferably a benzene ring.

通式(TP1)中，a、b及c分別獨立地表示0~4的整數，尤其a及b較佳為表示0或1，更佳為表示0。c較佳為表示0~2， 更佳為表示0或1。 In the formula (TP1), a, b and c each independently represent an integer of 0 to 4, and in particular, a and b preferably represent 0 or 1, more preferably 0. c preferably represents 0~2, More preferably, it means 0 or 1.

通式(TP2)中，Rtp1~Rtp4分別獨立地表示氫原子、烷基或芳基，與通式(TP1)中的Rtp1~Rtp4為相同含意，較佳範圍亦相同。 In the general formula (TP2), Rtp 1 to Rtp 4 each independently represent a hydrogen atom, an alkyl group or an aryl group, and have the same meanings as Rtp 1 to Rtp 4 in the formula (TP1), and the preferred range is also the same.

通式(TP2)中，Rtp5及Rtp6分別獨立地表示取代基，與通式(TP1)中的Rtp5及Rtp6為相同含意，較佳範圍亦相同。 In the general formula (TP2), Rtp 5 and Rtp 6 each independently represent a substituent, and have the same meanings as Rtp 5 and Rtp 6 in the formula (TP1), and the preferred range is also the same.

通式(TP2)中，Rtp9及Rtp11分別獨立地表示取代基，可使用後述取代基組群A的項中列舉的取代基。 In the general formula (TP2), Rtp 9 and Rtp 11 each independently represent a substituent, and the substituents listed in the item of the substituent group A to be described later can be used.

Rtp9較佳為芳基，更佳為碳數6~12的芳基，進而佳為苯基。 Rtp 9 is preferably an aryl group, more preferably an aryl group having 6 to 12 carbon atoms, and further preferably a phenyl group.

Rtp11較佳為烷基，更佳為碳數1~5的烷基，進而佳為碳數1~3的烷基。烷基較佳為直鏈狀或分支狀，更佳為直鏈狀。 Rtp 11 is preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group is preferably linear or branched, and more preferably linear.

通式(TP2)中，Rtp10表示取代基，可使用後述取代基組群A的項中列舉的取代基。尤其Rtp10更佳為碳數6~12的芳基，進而佳為苯基。 In the formula (TP2), Rtp 10 represents a substituent, and the substituents listed in the item of the substituent group A to be described later can be used. In particular, Rtp 10 is more preferably an aryl group having 6 to 12 carbon atoms, and further preferably a phenyl group.

通式(TP2)中，a、b及c分別獨立地表示0~4的整數，尤其a及b較佳為表示0或1，更佳為表示0。c較佳為表示0~2，更佳為表示0。 In the formula (TP2), a, b and c each independently represent an integer of 0 to 4, and in particular, a and b preferably represent 0 or 1, more preferably 0. c preferably represents 0 to 2, more preferably 0.

關於染料陽離子，陽離子如以下般非定域化而存在，下述兩種結構為相同含意，均包含在本發明中。再者，陽離子部位存在於分子中的任意位置。 Regarding the dye cation, the cation exists as follows without delocalization, and the following two structures have the same meanings and are included in the present invention. Furthermore, the cationic moiety is present at any position in the molecule.

取代基組群A： Substituent group A:

取代基可列舉：鹵素原子、烷基、環烷基、烯基、環烯基、炔基、芳基、雜環基、氰基、羥基、硝基、羧基、烷氧基、芳氧基、矽烷氧基、雜環氧基、醯氧基、胺甲醯氧基、胺基(包含烷基胺基、苯胺基)、醯基胺基、胺基羰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、胺磺醯基胺基、烷基磺醯基胺基或芳基磺醯基胺基、巰基、烷硫基、芳硫基、雜環硫基、胺磺醯基、磺基、烷基亞磺醯基或芳基亞磺醯基、烷基磺醯基或芳基磺醯基、醯基、芳氧基羰基、烷氧基羰基、胺甲醯基、芳基偶氮基或雜環偶氮基、醯亞胺基、膦基(phosphino)、氧膦基、氧膦基氧基、氧膦基胺基、矽烷基等。以下加以詳細記載。 The substituent may, for example, be a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group or an aryloxy group. a nonyloxy group, a heterocyclic oxy group, a decyloxy group, an amine methyl methoxy group, an amine group (including an alkylamino group, an anilino group), a mercaptoamine group, an aminocarbonylamino group, an alkoxycarbonylamino group, An aryloxycarbonylamino group, an amine sulfonylamino group, an alkylsulfonylamino group or an arylsulfonylamino group, a fluorenyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amine sulfonyl group, Sulfo, alkylsulfinyl or arylsulfinyl, alkylsulfonyl or arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, aminecaraki, aryl A nitrogen or heterocyclic azo group, a quinone imine group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a decyl group, and the like. The details are described below.

可列舉：鹵素原子(例如氟原子、氯原子、溴原子、碘原子)、直鏈或分支的烷基(直鏈或分支的經取代或未經取代的烷基，較佳為碳數1~30的烷基，例如甲基、乙基、正丙基、異丙 基、第三丁基、正辛基、2-氯乙基、2-氰基乙基、2-乙基己基)、環烷基(較佳為可列舉碳數3~30的經取代或未經取代的環烷基，例如環己基、環戊基，且可列舉多環烷基，例如雙環烷基(較佳為碳數5~30的經取代或未經取代的雙環烷基，例如雙環[1,2,2]庚烷-2-基、雙環[2,2,2]辛烷-3-基)或三環烷基等多環結構的基團。較佳為單環的環烷基、雙環烷基，尤佳為單環的環烷基)、直鏈或分支的烯基(直鏈或分支的經取代或未經取代的烯基，較佳為碳數2~30的烯基，例如乙烯基、烯丙基、異戊二烯基(prenyl)、香葉基、油烯基)、環烯基(較佳為碳數3~30的經取代或未經取代的環烯基，例如可列舉2-環戊烯-1-基、2-環己烯-1-基，多環烯基，例如雙環烯基(較佳為碳數5~30的經取代或未經取代的雙環烯基，例如雙環[2,2,1]庚-2-烯-1-基、雙環[2,2,2]辛-2-烯-4-基)或三環烯基，尤佳為單環的環烯基)、炔基(較佳為碳數2~30的經取代或未經取代的炔基，例如乙炔基、炔丙基、三甲基矽烷基乙炔基)、芳基(較佳為碳數6~30的經取代或未經取代的芳基，例如苯基、對甲苯基、萘基、間氯苯基、鄰十六烷醯基胺基苯基)、雜環基(較佳為5員~7員的經取代或未經取代、飽和或不飽和、芳香族或非芳香族、單環或縮環的雜環基，更佳為成環原子是選自碳原子、氮原子及硫原子中且具有至少一個氮原子、氧原子及硫原子的任一雜原子的雜環基，進而佳為碳數3~30的5員或6員的芳香族的雜環基。例如2-呋喃基、2-噻吩基、2-吡啶基、4- 吡啶基、2-嘧啶基、2-苯并噻唑基)、氰基、羥基、硝基、羧基、烷氧基(較佳為碳數1~30的經取代或未經取代的烷氧基，例如甲氧基、乙氧基、異丙氧基、第三丁氧基、正辛氧基、2-甲氧基乙氧基)、芳氧基(較佳為碳數6~30的經取代或未經取代的芳氧基，例如苯氧基、2-甲基苯氧基、2,4-二-第三戊基苯氧基、4-第三丁基苯氧基、3-硝基苯氧基、2-十四烷醯基胺基苯氧基)、矽烷氧基(較佳為碳數3~20的矽烷氧基，例如三甲基矽烷氧基、第三丁基二甲基矽烷氧基)、雜環氧基(較佳為碳數2~30的經取代或未經取代的雜環氧基，雜環部較佳為上文所述的雜環基中說明的雜環部，例如1-苯基四唑-5-氧基、2-四氫吡喃氧基)、醯氧基(較佳為甲醯氧基、碳數2~30的經取代或未經取代的烷基羰基氧基、碳數6~30的經取代或未經取代的芳基羰基氧基，例如甲醯氧基、乙醯氧基、三甲基乙醯氧基、硬脂醯氧基、苯甲醯氧基、對甲氧基苯基羰氧基)、胺甲醯氧基(較佳為碳數1~30的經取代或未經取代的胺甲醯氧基，例如N,N-二甲基胺甲醯氧基、N,N-二乙基胺甲醯氧基、嗎啉基羰氧基、N,N-二正辛基胺基羰氧基、N-正辛基胺甲醯氧基)、烷氧基羰基氧基(較佳為碳數2~30的經取代或未經取代的烷氧基羰基氧基，例如甲氧基羰氧基、乙氧基羰氧基、第三丁氧基羰氧基、正辛基羰氧基)、芳氧基羰氧基(較佳為碳數7~30的經取代或未經取代的芳氧基羰氧基，例如苯氧基羰氧基、對甲氧基苯氧基羰氧基、對正十六烷氧基苯氧基羰氧基)、 胺基(較佳為胺基、碳數1~30的經取代或未經取代的烷基胺基、碳數6~30的經取代或未經取代的芳基胺基、碳數0~30的雜環胺基，例如胺基、甲胺基、二甲胺基、苯胺基、N-甲基-苯胺基、二苯基胺基、N-1,3,5-三嗪-2-基胺基)、醯基胺基(較佳為甲醯基胺基、碳數1~30的經取代或未經取代的烷基羰基胺基、碳數6~30的經取代或未經取代的芳基羰基胺基，例如甲醯基胺基、乙醯基胺基、三甲基乙醯基胺基、月桂醯基胺基、苯甲醯基胺基、3,4,5-三-正辛氧基苯基羰基胺基)、胺基羰基胺基(較佳為碳數1~30的經取代或未經取代的胺基羰基胺基，例如胺甲醯基胺基、N,N-二甲胺基羰基胺基、N,N-二乙胺基羰基胺基、嗎啉基羰基胺基)、烷氧基羰基胺基(較佳為碳數2~30的經取代或未經取代的烷氧基羰基胺基，例如甲氧基羰基胺基、乙氧基羰基胺基、第三丁氧基羰基胺基、正十八烷氧基羰基胺基、N-甲基-甲氧基羰基胺基)、芳氧基羰基胺基(較佳為碳數7~30的經取代或未經取代的芳氧基羰基胺基，例如苯氧基羰基胺基、對氯苯氧基羰基胺基、間正辛氧基苯氧基羰基胺基)、胺磺醯基胺基(較佳為羰數0~30的經取代或未經取代的胺磺醯基胺基，例如胺磺醯基胺基、N,N-二甲基胺基磺醯基胺基、N-正辛基胺基磺醯基胺基)、烷基磺醯基胺基或芳基磺醯基胺基(較佳為碳數1~30的經取代或未經取代的烷基磺醯基胺基、碳數6~30的經取代或未經取代的芳基磺醯基胺基，例如甲基磺醯基胺基、丁基磺醯基胺基、苯基磺醯 基胺基、2,3,5-三氯苯基磺醯基胺基、對甲基苯基磺醯基胺基)、巰基、烷硫基(較佳為碳數1~30的經取代或未經取代的烷硫基，例如甲硫基、乙硫基、正十六烷硫基)、芳硫基(較佳為碳數6~30的經取代或未經取代的芳硫基，例如苯硫基、對氯苯硫基、間甲氧基苯硫基)、雜環硫基(較佳為碳數2~30的經取代或未經取代的雜環硫基，雜環部較佳為上文所述的雜環基中說明的雜環部，例如2-苯并噻唑硫基、1-苯基四唑-5-基硫基)、胺磺醯基(較佳為碳數0~30的經取代或未經取代的胺磺醯基，例如N-乙基胺磺醯基、N-(3-十二烷氧基丙基)胺磺醯基、N,N-二甲基胺磺醯基、N-乙醯基胺磺醯基、N-苯甲醯基胺磺醯基、N-(N'-苯基胺甲醯基)胺磺醯基)、磺基、烷基亞磺醯基或芳基亞磺醯基(較佳為碳數1~30的經取代或未經取代的烷基亞磺醯基、6~30的經取代或未經取代的芳基亞磺醯基，例如甲基亞磺醯基、乙基亞磺醯基、苯基亞磺醯基、對甲基苯基亞磺醯基)、烷基磺醯基或芳基磺醯基(較佳為碳數1~30的經取代或未經取代的烷基磺醯基、6~30的經取代或未經取代的芳基磺醯基，例如甲基磺醯基、乙基磺醯基、苯基磺醯基、對甲基苯基磺醯基)、醯基(較佳為甲醯基、碳數2~30的經取代或未經取代的烷基羰基、碳數7~30的經取代或未經取代的芳基羰基，例如乙醯基、三甲基乙醯基、2-氯乙醯基、硬脂醯基、苯甲醯基、對正辛氧基苯基羰基)、芳氧基羰基(較佳為碳數7~30 的經取代或未經取代的芳氧基羰基，例如苯氧基羰基、鄰氯苯氧基羰基、間硝基苯氧基羰基、對第三丁基苯氧基羰基)、烷氧基羰基(較佳為碳數2~30的經取代或未經取代的烷氧基羰基，例如甲氧基羰基、乙氧基羰基、第三丁氧基羰基、正十八烷氧基羰基)、胺甲醯基(較佳為碳數1~30的經取代或未經取代的胺甲醯基，例如胺甲醯基、N-甲基胺甲醯基、N,N-二甲基胺甲醯基、N,N-二-正辛基胺甲醯基、N-(甲基磺醯基)胺甲醯基)、芳基偶氮基或雜環偶氮基(較佳為碳數6~30的經取代或未經取代的芳基偶氮基、碳數3~30的經取代或未經取代的雜環偶氮基(雜環部較佳為上文所述的雜環基中說明的雜環部)，例如苯基偶氮、對氯苯基偶氮、5-乙硫基-1,3,4-噻二唑-2-基偶氮)、醯亞胺基(較佳為碳數2~30的經取代或未經取代的醯亞胺基，例如N-丁二醯亞胺、N-鄰苯二甲醯亞胺)、膦基(較佳為碳數2~30的經取代或未經取代的膦基，例如二甲基膦基、二苯基膦基、甲基苯氧基膦基)、氧膦基(較佳為碳數2~30的經取代或未經取代的氧膦基，例如氧膦基、二辛氧基氧膦基、二乙氧基氧膦基)、氧膦基氧基(較佳為碳數2~30的經取代或未經取代的氧膦基氧基，例如二苯氧基氧膦氧基、二辛氧基氧膦氧基)、氧膦基胺基(較佳為碳數2~30的經取代或未經取代的氧膦基胺基，例如二甲氧基氧膦基胺基、二甲基胺基氧膦基胺基)、矽烷基(較佳為碳數3~30的經取代或未經取代的矽烷基，例如三甲基矽烷基、第三丁基二甲基矽烷基、苯基二甲基矽烷基)。 The halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a linear or branched alkyl group (linear or branched substituted or unsubstituted alkyl group, preferably a carbon number of 1~) 30 alkyl, such as methyl, ethyl, n-propyl, isopropyl a group, a tributyl group, an n-octyl group, a 2-chloroethyl group, a 2-cyanoethyl group, a 2-ethylhexyl group, a cycloalkyl group (preferably, a substituted or not having a carbon number of 3 to 30) a substituted cycloalkyl group such as a cyclohexyl group or a cyclopentyl group, and a polycyclic alkyl group such as a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having a carbon number of 5 to 30, such as a bicyclic ring) a polycyclic structure group such as [1,2,2]heptan-2-yl, bicyclo[2,2,2]oct-3-yl) or tricycloalkyl. Preferred is a monocyclic naphthenic. a bis-cycloalkyl group, particularly preferably a monocyclic cycloalkyl group, a linear or branched alkenyl group (a straight or branched substituted or unsubstituted alkenyl group, preferably a olefin having 2 to 30 carbon atoms) a group such as a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group, a cycloalkenyl group (preferably a substituted or unsubstituted cycloolefin having 3 to 30 carbon atoms) Examples of the group include 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, polycycloalkenyl groups such as bicycloalkenyl groups (preferably substituted or unsubstituted having a carbon number of 5 to 30). Bicycloalkenyl, such as bicyclo[2,2,1]hept-2-en-1-yl, bicyclo[2,2,2]oct-2-en-4-yl) or tricycloalkenyl, especially Single ring Alkenyl), alkynyl (preferably substituted or unsubstituted alkynyl having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethyldecyl ethynyl), aryl (preferably carbon) a substituted or unsubstituted aryl group of 6 to 30, such as a phenyl group, a p-tolyl group, a naphthyl group, a m-chlorophenyl group, an o-hexadecanoylaminophenyl group, or a heterocyclic group (preferably a substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group of 5 to 7 members, more preferably a ring-forming atom selected from carbon atoms, nitrogen atoms and The heterocyclic group having at least one nitrogen atom, an oxygen atom and a sulfur atom in the sulfur atom is more preferably a 5-membered or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Furanyl, 2-thienyl, 2-pyridyl, 4- Pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano, hydroxy, nitro, carboxy, alkoxy (preferably substituted or unsubstituted alkoxy having 1 to 30 carbon atoms, For example, methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy (preferably substituted with 6 to 30 carbon atoms) Or unsubstituted aryloxy group, such as phenoxy, 2-methylphenoxy, 2,4-di-p-pentylphenoxy, 4-tert-butylphenoxy, 3-nitro Phenoxy, 2-tetradecylideneaminophenoxy), decyloxy (preferably a decyloxy group having 3 to 20 carbon atoms, such as trimethyldecyloxy, tert-butyldimethyl a decyloxy group), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, preferably a heterocyclic ring described in the above heterocyclic group) a moiety such as 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), a decyloxy group (preferably a methyloxy group, a substituted or unsubstituted carbon number of 2 to 30) An alkylcarbonyloxy group, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as a methyloxy group, an ethoxy group, a trimethyl group Oxyl, stearyloxy, benzhydryloxy, p-methoxyphenylcarbonyloxy), amine methoxycarbonyl (preferably substituted or unsubstituted amine A having 1 to 30 carbon atoms) Alkoxy groups, such as N,N-dimethylamine methyl methoxy, N,N-diethylamine methyl methoxy, morpholinylcarbonyloxy, N,N-di-n-octylaminocarbonyloxy a group, a N-n-octylamine methoxycarbonyl group, an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy) a substituted or unsubstituted aryl group having a carbon number of 7 to 30, preferably an ethoxycarbonyloxy group, a third butoxycarbonyloxy group, an n-octylcarbonyloxy group, or an aryloxycarbonyloxy group. An oxycarbonyloxy group, for example, a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, a p-hexadecaneoxyphenoxycarbonyloxy group, Amino group (preferably an amine group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a carbon number of 0 to 30 Heterocyclic amine groups, such as amine, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-yl Amino), mercaptoamine (preferably a mercaptoamine group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number of 6 to 30) An arylcarbonylamino group, such as a decylamino group, an ethenylamino group, a trimethyl ethylamino group, a lauryl amine group, a benzhydrylamino group, a 3,4,5-tri-positive group An octyloxyphenylcarbonylamino) group, an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as an amine formamylamine group, N,N- a dimethylaminocarbonylamino group, an N,N-diethylaminocarbonylamino group, a morpholinylcarbonylamino group, an alkoxycarbonylamino group (preferably a substituted or unsubstituted carbon number of 2 to 30) Alkoxycarbonylamino group, such as methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxy a carbonylcarbonylamino group, an N-methyl-methoxycarbonylamino group, an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as benzene) Oxycarbonylamino, p-chlorophenoxycarbonylamino, m-octyloxyphenoxycarbonylamino), aminesulfonylamino (preferably substituted or unsubstituted carbonyl number 0-30) Aminesulfonylamino group, such as amidoximeylamine, N,N-dimethylaminosulfonylamino, N-n-octylaminosulfonylamino), alkylsulfonyl Amino or arylsulfonylamino group (preferably substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms Sulfhydrylamino group, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonate Amino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), fluorenyl, alkylthio (preferably substituted with 1 to 30 carbon atoms or Unsubstituted alkylthio group, such as methylthio, ethylthio, n-hexadecylthio), arylthio (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, for example a phenylthio group, a p-chlorophenylthio group, a m-methoxyphenylthio group, a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, preferably a heterocyclic ring) It is a heterocyclic moiety illustrated in the above heterocyclic group, such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio, and sulfonyl (preferably having a carbon number of 0) ~30 substituted or unsubstituted sulfonyl, for example, N-ethylamine sulfonyl, N-(3-dodecyloxypropyl)amine sulfonyl, N,N-dimethyl Aminesulfonyl, N-ethinylsulfonyl, N-benzylidenesulfonyl, N-(N'-phenylaminecarbamimidino)sulfonyl), sulfo, alkyl A sulfinyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group of 6 to 30) Base, for example Methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkylsulfonyl or arylsulfonyl (preferably carbon number 1) ~30 substituted or unsubstituted alkylsulfonyl, 6 to 30 substituted or unsubstituted arylsulfonyl, such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl Base, p-methylphenylsulfonyl), fluorenyl (preferably formazan, substituted or unsubstituted alkylcarbonyl having 2 to 30 carbon atoms, substituted or unsubstituted with 7 to 30 carbon atoms Substituted arylcarbonyl groups, such as ethenyl, trimethylethenyl, 2-chloroethylhydrazine, stearyl, benzhydryl, p-octyloxyphenylcarbonyl, aryloxycarbonyl ( Preferably, the carbon number is 7~30 Substituted or unsubstituted aryloxycarbonyl group, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl), alkoxycarbonyl ( Preferred is a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a third butoxycarbonyl group, an n-octadecyloxycarbonyl group, and an amine group A. Mercapto group (preferably a substituted or unsubstituted amine carbenyl group having 1 to 30 carbon atoms, such as an amine methyl sulfonyl group, an N-methylamine methyl fluorenyl group, and an N,N-dimethylamine fluorenyl group. , N,N-di-n-octylamine methyl sulfonyl, N-(methylsulfonyl)amine methyl sulfhydryl), aryl azo or heterocyclic azo (preferably carbon number 6 to 30) a substituted or unsubstituted arylazo group, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocyclic ring is preferably as described above for the heterocyclic group) Heterocyclic moiety), for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo, quinone imine (preferably carbon) Number of 2 to 30 substituted or unsubstituted quinone imine groups, such as N-butanediamine, N-phthalimine, phosphino (more a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group, or a phosphinyl group (preferably a carbon number 2~) a substituted or unsubstituted phosphinyl group of 30, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl, phosphinyloxy (preferably having a carbon number of 2 to 30) Substituted or unsubstituted phosphinyloxy, for example, diphenoxyphosphinyloxy, dioctyloxyphosphoryloxy), phosphinylamino (preferably substituted with carbon number 2 to 30) Or unsubstituted phosphinylamino group, such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), decyl (preferably substituted or not having a carbon number of 3 to 30) Substituted alkylene groups, such as trimethyldecyl, tert-butyldimethylalkyl, phenyldimethylalkyl.

<<含有交聯性基的染料陽離子>> <<Dye cations containing crosslinkable groups>>

含有交聯性基的染料陽離子中，Rtp1~Rtp11、Rtp71及Rtp72的至少一個含有交聯性基，尤其較佳為Rtp71或Rtp72含有交聯性基。 In the dye cation containing a crosslinkable group, at least one of Rtp 1 to Rtp 11 , Rtp 71 and Rtp 72 contains a crosslinkable group, and it is particularly preferred that Rtp 71 or Rtp 72 contains a crosslinkable group.

含有交聯性基的基團可僅包含交聯性基，亦可除了交聯性基以外含有連結基。尤其含有交聯性基的基團較佳為-L0-P0所表示的基團。此處，L0表示單鍵或二價連結基，P1表示交聯性基。 The group containing a crosslinkable group may contain only a crosslinkable group, and may contain a linking group in addition to the crosslinkable group. Particularly, the group containing a crosslinkable group is preferably a group represented by -L 0 -P 0 . Here, L 0 represents a single bond or a divalent linking group, and P 1 represents a crosslinkable group.

交聯性基可使用可藉由自由基、酸、熱而進行交聯的交聯性基。具體可列舉：具有乙烯性不飽和雙鍵的基團、(甲基)丙烯酸基、苯乙烯基、乙烯基、烯丙基、環狀醚基等，較佳為選自(甲基)丙烯酸基、苯乙烯基、乙烯基及烯丙基中的至少一種，更佳為選自(甲基)丙烯酸基、苯乙烯基及乙烯基中的至少一種，進而佳為(甲基)丙烯酸基及苯乙烯基。環狀醚基例如較佳為環氧基、氧雜環丁基等，更佳為環氧基。 As the crosslinkable group, a crosslinkable group which can be crosslinked by a radical, an acid or a heat can be used. Specific examples thereof include a group having an ethylenically unsaturated double bond, a (meth)acrylic group, a styryl group, a vinyl group, an allyl group, a cyclic ether group, etc., preferably selected from a (meth)acrylic group. At least one of a styryl group, a vinyl group and an allyl group, more preferably at least one selected from the group consisting of a (meth)acrylic group, a styryl group and a vinyl group, and further preferably a (meth)acrylic group and a benzene group. Vinyl. The cyclic ether group is preferably, for example, an epoxy group or an oxetanyl group, and more preferably an epoxy group.

二價連結基較佳為伸烷基、伸芳基、雜環連結基、-CH=CH-、-O-、-S-、-C(=O)-、-CO-、-NR-、-CONR-、-OC-、-SO-、-SO2-及將該些基團的2個以上組合而成的基團。此處，R分別獨立地表示氫原子、烷基、芳基或雜環基。 The divalent linking group is preferably an alkylene group, an extended aryl group, a heterocyclic linking group, -CH=CH-, -O-, -S-, -C(=O)-, -CO-, -NR-, -CONR-, -OC-, -SO-, -SO 2 - and a group obtained by combining two or more of these groups. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

尤其二價連結基較佳為伸烷基。 In particular, the divalent linking group is preferably an alkylene group.

伸烷基可為直鏈狀、分支狀及環狀的任一種。伸烷基的碳數較佳為1~30，更佳為1~20，進而佳為5~20，尤佳為5~10。具體而言，較佳為亞甲基、伸乙基、伸丙基、伸丁基、伸己基、 伸庚基、伸環戊烯基、伸環己基等。 The alkylene group may be any of a linear chain, a branched chain, and a cyclic chain. The carbon number of the alkylene group is preferably from 1 to 30, more preferably from 1 to 20, further preferably from 5 to 20, and particularly preferably from 5 to 10. Specifically, it is preferably a methylene group, an ethyl group, a propyl group, a butyl group, a hexyl group, Streptylene, cyclopentenyl, cyclohexyl and the like.

伸芳基的碳數較佳為6~30，更佳為6~18，進而佳為6~12。具體而言，伸芳基較佳為伸苯基、伸萘基等。 The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 18, and even more preferably from 6 to 12. Specifically, the aryl group is preferably a phenyl group, a naphthyl group or the like.

含有交聯性基的染料陽離子的具體例可列舉以下結構，但本發明不限定於該些結構。 Specific examples of the dye cation containing a crosslinkable group include the following structures, but the present invention is not limited to these structures.

<<含有多聚物結構的染料陽離子>> <<Dye cations containing a polymer structure>>

含有多聚物結構的染料陽離子可為寡聚物亦可為聚合物。含有多聚物結構的染料陽離子較佳為具有含有重複單元的基團作為多聚物結構。 The dye cation containing the polymer structure may be an oligomer or a polymer. The dye cation having a polymer structure preferably has a group having a repeating unit as a polymer structure.

含有多聚物結構的染料陽離子較佳為含有下述通式(A)所表示的結構。 The dye cation having a polymer structure preferably contains a structure represented by the following formula (A).

(通式(A)中，X1表示重複單元的主鏈。L1表示單鍵或二價連結基。Dye表示染料陽離子中的三芳基甲烷結構) (In the general formula (A), X 1 represents a main chain of a repeating unit. L 1 represents a single bond or a divalent linking group. Dye represents a triarylmethane structure in a dye cation)

通式(A)中，X1表示重複單元的主鏈，通常表示由聚合反應所形成的連結基，例如較佳為來源於具有(甲基)丙烯酸基、苯乙烯基、乙烯基、醚基的化合物的主鏈。另外，具有主鏈環狀的伸烷基的態樣亦較佳。再者，於2個*所示的部位上與其他重複單元鍵結。 In the formula (A), X 1 represents a main chain of a repeating unit, and generally represents a linking group formed by a polymerization reaction, and is preferably derived, for example, from a (meth)acrylic group, a styryl group, a vinyl group, or an ether group. The main chain of the compound. Further, a form having an alkyl group having a main chain cyclic is also preferred. Furthermore, it is bonded to other repeating units at the positions indicated by two *.

於L1表示二價連結基的情形時，較佳為碳數1~30的伸烷基(亞甲基、伸乙基、三亞甲基、伸丙基、伸丁基等)、碳數6~30的伸芳基(伸苯基、伸萘基等)、雜環連結基、-CH=CH-、-O-、-S-、-C(=O)-、-CO-、-NR-、-CONR-、-OC-、-SO-、-SO2-及將該些基團的2個以上組合而成的連結基。此處，R分別獨立地表示氫原子、烷基、芳基或雜環基。 When L 1 represents a divalent linking group, it is preferably an alkylene group having 1 to 30 carbon atoms (methylene group, ethylidene group, trimethylene group, propyl group, butyl group, etc.), carbon number 6 ~30 of aryl (phenyl, naphthyl, etc.), heterocyclic linkage, -CH=CH-, -O-, -S-, -C(=O)-, -CO-, -NR -, -CONR-, -OC-, -SO-, -SO 2 - and a linking group in which two or more of these groups are combined. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

L1較佳為單鍵或將碳數1~30的伸烷基(較佳為碳數1~10的伸烷基，碳數5~20的伸烷基，進而佳為-(CH2)n-(n為1~10的整數))、碳數6~12的伸芳基(較佳為伸苯基、伸萘基)、-NH-、 -CO-、-O-及-SO2-組合2個以上而成的二價連結基。尤其L1較佳為-(CH2)n-(n為5~10的整數)或碳數6~12的伸芳基(較佳為伸苯基、伸萘基)。 L 1 is preferably a single bond or an alkylene group having 1 to 30 carbon atoms (preferably an alkylene group having 1 to 10 carbon atoms, an alkylene group having 5 to 20 carbon atoms, and further preferably -(CH 2 ). N-(n is an integer of 1 to 10)), an extended aryl group having 6 to 12 carbon atoms (preferably a phenyl group, a naphthyl group), -NH-, -CO-, -O-, and -SO 2 - A divalent linking group in which two or more are combined. In particular, L 1 is preferably -(CH 2 )n- (n is an integer of 5 to 10) or an extended aryl group having 6 to 12 carbon atoms (preferably a phenyl group and a naphthyl group).

於L1表示單鍵的情形時，X1與通式(TP1)及通式(TP2)中的Rtp1~Rtp11、Rtp71及Rtp72的任一個鍵結，較佳為與Rtp71或Rtp72鍵結。 In the case where L 1 represents a single bond, X 1 is bonded to any one of Rtp 1 to Rtp 11 , Rtp 71 and Rtp 72 in the formula (TP1) and the formula (TP2), preferably Rtp 71 or Rtp 72 bond.

於L1表示二價連結基的情形時，L1與通式(TP1)及通式(TP2)中的Rtp1~Rtp11、Rtp71及Rtp72的任一個鍵結，較佳為與Rtp71或Rtp72鍵結。 In the case where L 1 represents a divalent linking group, L 1 is bonded to any one of Rtp 1 to Rtp 11 , Rtp 71 and Rtp 72 in the formula (TP1) and the formula (TP2), preferably with Rtp. 71 or Rtp 72 bonding.

以下示出X1及L1的組合的具體例，但本發明不限定於該些具體例。 Specific examples of the combination of X 1 and L 1 are shown below, but the present invention is not limited to these specific examples.

尤其更佳為選自由(XX-1)及(XX-2)所表示的(甲基)丙烯酸系連結鏈、由(XX-10)~(XX-17)所表示的苯乙烯系連結鏈及由(XX-24)所表示的乙烯系連結鏈中，進而佳為由(XX-1)及(XX-2)所表示的(甲基)丙烯酸系連結鏈及由(XX-11)所表示的苯乙烯系連結鏈。 In particular, it is more preferably selected from the group consisting of (meth)acrylic linking chains represented by (XX-1) and (XX-2), and styrene-based linking chains represented by (XX-10) to (XX-17). In the ethylene-based linking chain represented by (XX-24), the (meth)acrylic linking chain represented by (XX-1) and (XX-2) is preferably represented by (XX-11) Styrene linkage chain.

(XX-1)~(X-24)中，表示於由*所示的部位上與所述三芳基甲烷結構連結。Me表示甲基。另外，(XX-18)及(XX-19)中的R表示氫原子、碳數1~5的烷基或苯基。 In (XX-1) to (X-24), it is shown that it is bonded to the triarylmethane structure at a portion indicated by *. Me represents a methyl group. Further, R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group.

另外，X1及L1的組合的具體例亦較佳為以下具體例。下述具體例中，n表示1~9的整數。另外，表示於由*所示的部位 上與三芳基甲烷結構連結。 Further, specific examples of the combination of X 1 and L 1 are also preferably the following specific examples. In the following specific examples, n represents an integer of 1 to 9. Further, it is shown to be bonded to the triarylmethane structure at a portion indicated by *.

另外，關於含有多聚物結構的染料陽離子，不論僅由具有交聯性基的染料化合物成分所構成的均聚物(homopolymer)、還是與其他聚合性化合物的共聚物(copolymer)均可較佳地使用，更佳為均聚物(homopolymer)的形態。 Further, the dye cation containing a polymer structure is preferably a homopolymer composed only of a dye compound component having a crosslinkable group or a copolymer with another polymerizable compound. It is preferably used in the form of a homopolymer.

於含有多聚物結構的染料陽離子為均聚物的情形時，相對於所有重複單元100莫耳，具有含重複單元的基團的染料陽離子的比例例如較佳為10莫耳~50莫耳，更佳為10~30莫耳。 In the case where the dye cation containing the polymer structure is a homopolymer, the proportion of the dye cation having a group having a repeating unit is preferably, for example, 10 mol to 50 mol, relative to 100 ppm of all repeating units. More preferably 10 to 30 moles.

含有多聚物結構的染料陽離子的分子量較佳為以重量平均分子量計而為3,000~30,000、且分子量分佈以Mw/Mn計而為0.8~ 3.0，更佳為以重量平均分子量計而為5,000~20,000，且分子量分佈以Mw/Mn計而為1~2.5。 The molecular weight of the dye cation having a polymer structure is preferably 3,000 to 30,000 in terms of weight average molecular weight, and the molecular weight distribution is 0.8 in terms of Mw/Mn. 3.0, more preferably 5,000 to 20,000 in terms of weight average molecular weight, and a molecular weight distribution of 1 to 2.5 in terms of Mw/Mn.

於形成含有多聚物結構的染料陽離子時，亦可添加鏈轉移劑。鏈轉移劑較佳為烷基硫醇，較佳為碳數10以下的烷基硫醇或經醚基/酯基取代的烷基硫醇。尤其更佳為logP值為5以下的烷基硫醇。 When a dye cation containing a polymer structure is formed, a chain transfer agent may also be added. The chain transfer agent is preferably an alkylthiol, preferably an alkylthiol having a carbon number of 10 or less or an alkylthiol substituted with an ether group/ester group. More preferably, it is an alkylthiol having a logP value of 5 or less.

含有多聚物結構的染料陽離子所含的作為原料的具有交聯性基的染料單體化合物的量較佳為總單體數的5%以下，更佳為1%以下。 The amount of the dye monomer compound having a crosslinkable group as a raw material contained in the dye cation having a polymer structure is preferably 5% or less, more preferably 1% or less, based on the total number of monomers.

含有多聚物結構的染料陽離子的具體例可列舉以下結構，但本發明不限定於該些結構。 Specific examples of the dye cation having a polymer structure include the following structures, but the present invention is not limited to these structures.

<相對陰離子X> <relative anion X>

相對陰離子X為染料陽離子的相對陰離子。相對陰離子X可僅包含與染料陽離子的陽離子部相對的陰離子部，亦可具有其他 部位。其他部位可例示交聯性基及/或多聚物結構。相對陰離子X可為一價陰離子，亦可為二價以上的陰離子，較佳為一價~六價的陰離子，更佳為一價或二價的陰離子，進而佳為一價陰離子。 The relative anion X is the relative anion of the dye cation. The relative anion X may contain only an anion portion opposite to the cationic portion of the dye cation, and may have other Part. Other sites may be exemplified by a crosslinkable group and/or a polymer structure. The relative anion X may be a monovalent anion, or may be a divalent or higher anion, preferably a monovalent to hexavalent anion, more preferably a monovalent or divalent anion, and more preferably a monovalent anion.

僅包含相對陰離子X的情形可列舉：氟陰離子、氯陰離子、溴陰離子、碘陰離子、氰化物離子、過氯酸根陰離子、硼酸根陰離子(BF4-等)、PF6-及SbF6-等。 Examples of the case where only the relative anion X is contained include a fluoride anion, a chloride anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, a borate anion (BF 4-, etc.), PF 6- and SbF 6-, and the like.

硼酸根陰離子為由B(R10)4-所表示的基團，R10可例示氟原子、氰基、氟化烷基、烷氧基、芳氧基等。 The borate anion is a group represented by B(R 10 ) 4- , and R 10 may, for example, be a fluorine atom, a cyano group, a fluorinated alkyl group, an alkoxy group or an aryloxy group.

相對陰離子X亦可含有選自-SO3 -、-COO-、-PO4 -、下述通式(A1)所表示的結構及下述通式(A2)所表示的結構中的至少一種。 The counter anion X may contain at least one selected from the group consisting of -SO 3 - , -COO - , -PO 4 - , a structure represented by the following formula (A1), and a structure represented by the following formula (A2).

(通式(A1)中，R1及R2分別獨立地表示-SO2-或-CO-) (In the formula (A1), R 1 and R 2 each independently represent -SO 2 - or -CO-)

通式(A1)中，較佳為R1及R2的至少一個表示-SO2-，更佳為R1及R2兩者表示-SO2-。 In the general formula (A1), preferably R 1 and R 2 represents at least one of -SO 2 -, more preferably both R 1 and indicated as R 2 -SO 2 -.

所述通式(A1)更佳為由下述通式(A1-1)表示。 The above formula (A1) is more preferably represented by the following formula (A1-1).

(通式(A1-1)中，R1及R2分別獨立地表示-SO2-或-CO-。X1及X2分別獨立地表示伸烷基或伸芳基) (In the general formula (A1-1), R 1 and R 2 each independently represent -SO 2 - or -CO-. X 1 and X 2 each independently represent an alkylene group or an extended aryl group)

通式(A1-1)中，R1及R2與通式(A1)中的R1及R2為相同含意，較佳範圍亦相同。 In the general formula (A1-1), R 1 and R 2 in the general formula (A1), R 1 and R 2 are the same meaning, the preferred range is also the same.

於X1表示伸烷基的情形時，伸烷基的碳數較佳為1~8，更佳為1~6。於X1表示伸芳基的情形時，伸芳基的碳數較佳為6~18，更佳為6~12，進而佳為6。於X1具有取代基的情形時，較佳為經氟原子取代。 When X 1 represents an alkylene group, the carbon number of the alkylene group is preferably from 1 to 8, more preferably from 1 to 6. When X 1 represents an aryl group, the carbon number of the extended aryl group is preferably from 6 to 18, more preferably from 6 to 12, and still more preferably 6. In the case where X 1 has a substituent, it is preferably substituted with a fluorine atom.

X2表示烷基或芳基，較佳為烷基。烷基的碳數較佳為1~8，更佳為1~6，進而佳為1~3，尤佳為1。於X2具有取代基的情形時，較佳為經氟原子取代。 X 2 represents an alkyl group or an aryl group, preferably an alkyl group. The carbon number of the alkyl group is preferably from 1 to 8, more preferably from 1 to 6, more preferably from 1 to 3, and still more preferably 1. In the case where X 2 has a substituent, it is preferably substituted with a fluorine atom.

(通式(A2)中，R3表示-SO2-或-CO-。R4及R5分別獨立地表示-SO2-、-CO-或-CN) (In the formula (A2), R 3 represents -SO 2 - or -CO-. R 4 and R 5 each independently represent -SO 2 -, -CO- or -CN)

通式(A2)中，較佳為R3~R5的至少一個表示-SO2-，更佳為R3~R5的至少2個表示-SO2-。 In the general formula (A2), preferably R 3 ~ R 5 represents at least one of -SO 2 -, more preferably at least 2 of R 3 ~ R 5 represents -SO 2 -.

相對陰離子X的具體例亦可例示以下情形：所述相對陰 離子X為R-SO3 -、R-COO-或R-PO4 -，且R為鹵素原子、可經鹵素原子取代的烷基、可經鹵素原子取代的芳基。 Specific examples of the relative anion X may also be exemplified by the case where the relative anion X is R-SO 3 - , R-COO - or R-PO 4 - , and R is a halogen atom, an alkyl group which may be substituted by a halogen atom, An aryl group which may be substituted by a halogen atom.

另外，含有所述通式(A1)所表示的基團的相對陰離子X的具體例可例示以下情形：R1與鹵素原子、可經鹵素原子取代的烷基、可經鹵素原子取代的芳基鍵結。 Further, specific examples of the relative anion X containing the group represented by the above formula (A1) can be exemplified by R 1 and a halogen atom, an alkyl group which may be substituted by a halogen atom, an aryl group which may be substituted by a halogen atom. Bonding.

另外，含有所述通式(A2)所表示的基團的相對陰離子X的具體例可例示以下情形：R4及R5分別為鹵素原子、可經鹵素原子取代的烷基、可經鹵素原子取代的芳基。 Further, specific examples of the relative anion X containing the group represented by the above formula (A2) include the following cases: R 4 and R 5 are each a halogen atom, an alkyl group which may be substituted by a halogen atom, and a halogen atom; Substituted aryl.

其他相對陰離子X的具體例可列舉以下具體例，但本發明不限定於該些具體例。 Specific examples of the other relative anion X include the following specific examples, but the present invention is not limited to these specific examples.

以下，對相對陰離子X含有交聯性基的情形、相對陰離子X含有多聚物結構的情形加以詳細說明。 Hereinafter, the case where the relative anion X contains a crosslinkable group and the case where the anion X contains a polymer structure will be described in detail.

相對陰離子X可含有的交聯性基可列舉：可藉由自由基、酸、熱而進行交聯的公知的聚合性基。具體可列舉：(甲基)丙烯酸基、苯乙烯基、乙烯基、環狀醚基及羥甲基，較佳為選自(甲基)丙烯酸基、苯乙烯基、乙烯基及環狀醚基中的至少一種，更佳為選自(甲基)丙烯酸基、苯乙烯基及乙烯基中的一種，進而佳為(甲基)丙烯酸基或苯乙烯基。 The crosslinkable group which can be contained in the relative anion X is a known polymerizable group which can be crosslinked by a radical, an acid, or heat. Specific examples thereof include a (meth)acrylic group, a styryl group, a vinyl group, a cyclic ether group, and a methylol group, and are preferably selected from a (meth)acrylic group, a styryl group, a vinyl group, and a cyclic ether group. At least one of them is more preferably one selected from the group consisting of a (meth)acrylic group, a styryl group and a vinyl group, and further preferably a (meth)acrylic group or a styryl group.

相對陰離子X可含有的交聯性基的個數較佳為1~3，更佳為1。 The number of the crosslinkable groups which may be contained in the relative anion X is preferably from 1 to 3, more preferably 1.

另外，交聯性基與上文所述的-SO3 -、-COO-、-PO4 -、所述通式(A1)所表示的結構及所述通式(A2)所表示的結構之間可直接鍵結，亦可經由連結基而鍵結，較佳為經由連結基而鍵結。 Further, the crosslinkable group and the above-mentioned -SO 3 - , -COO - , -PO 4 - , the structure represented by the above formula (A1) and the structure represented by the above formula (A2) The bond may be directly bonded or may be bonded via a linker, preferably via a linker.

含有交聯性基的相對陰離子X例如較佳為由下述通式(B)表示。 The relative anion X containing a crosslinkable group is preferably represented, for example, by the following formula (B).

通式(B) General formula (B)

(通式(B)中，P表示交聯性基。L表示單鍵或二價連結基。陰離子(anion)表示-SO3 -、-COO-、-PO4 -、所述通式(A1)所表示的結構及所述般式(A2)所表示的結構) (In the formula (B), P represents a crosslinkable group. L represents a single bond or a divalent linking group. Anion represents -SO 3 - , -COO - , -PO 4 - , and the formula (A1) ) the structure indicated and the structure represented by the above formula (A2)

通式(B)中，P表示交聯性基，可列舉上文所述的交聯性基。 In the general formula (B), P represents a crosslinkable group, and examples thereof include the above-mentioned crosslinkable group.

通式(B)中，於L表示二價連結基的情形時，較佳為碳數1~30的伸烷基(例如亞甲基、伸乙基、三亞甲基、伸丙基、伸丁基等)、碳數6~30的伸芳基、雜環連結基、-CH=CH-、-O-、-S-、-C(=O)-、-CO-、-NR-、-CONR-、-OC-、-SO-、-SO2-及將該些基團的2個以上組合而成的連結基。此處，R分別獨立地表示氫原子、烷基、芳基或雜環基。 In the general formula (B), when L represents a divalent linking group, it is preferably an alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an ethylidene group, a trimethylene group, a propyl group, and a butyl group). Base, etc., an extended aryl group having 6 to 30 carbon atoms, a heterocyclic linkage group, -CH=CH-, -O-, -S-, -C(=O)-, -CO-, -NR-, - CONR-, -OC-, -SO-, -SO 2 - and a linking group in which two or more of these groups are combined. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

尤其連結基較佳為將碳數1~10的伸烷基(較佳為-(CH2)n-(n為1~10的整數))、碳數6~12的伸芳基(較佳為伸苯基、伸萘基)、-NH-、-CO-、-O-及-SO2-組合2個以上而成的連結基。 In particular, the linking group is preferably an alkylene group having 1 to 10 carbon atoms (preferably -(CH 2 ) n - (n is an integer of 1 to 10)), and an extended aryl group having 6 to 12 carbon atoms. A linking group of two or more of a combination of a phenylene group, a naphthyl group, and -NH-, -CO-, -O-, and -SO 2 -.

以下示出含有交聯性基的相對陰離子X的具體例，但本發明不限定於該些具體例。 Specific examples of the relative anion X containing a crosslinkable group are shown below, but the present invention is not limited to these specific examples.

含有交聯性基的相對陰離子X的分子量較佳為1,000~100,000，更佳為5,000~50,000。 The molecular weight of the relative anion X containing a crosslinkable group is preferably from 1,000 to 100,000, more preferably from 5,000 to 50,000.

含有多聚物結構的相對陰離子X(以下亦稱為陰離子多聚物)可為寡聚物，亦可為聚合物。含有多聚物結構的相對陰離子X較佳為具有含有重複單元的基團作為多聚物結構。藉由使用含有多聚物結構的相對陰離子X，可使陰離子X與染料陽離子進 行共聚合，故可更有效地抑制陰離子X自染料陽離子解離，可進一步提高本發明的效果。 The relative anion X (hereinafter also referred to as an anionic polymer) having a polymer structure may be an oligomer or a polymer. The relative anion X containing a polymer structure preferably has a group containing a repeating unit as a polymer structure. Anion X and dye cations can be made by using a relative anion X containing a polymer structure. Since the copolymerization is carried out, the dissociation of the anion X from the dye cation can be more effectively suppressed, and the effect of the present invention can be further enhanced.

含有多聚物結構的相對陰離子X較佳為具有下述通式(C)及/或下述通式(D)所表示的結構。 The relative anion X having a polymer structure preferably has a structure represented by the following formula (C) and/or the following formula (D).

(通式(C)中，X1表示重複單元的主鏈。L1表示單鍵或二價連結基。陰離子(anion)表示-SO3 -、-COO-、-PO4 -、所述通式(A1)所表示的結構及所述般式(A2)所表示的結構) (In the general formula (C), X 1 represents a main chain of a repeating unit. L 1 represents a single bond or a divalent linking group. Anion means -SO 3 - , -COO - , -PO 4 - , said pass The structure represented by the formula (A1) and the structure represented by the above formula (A2)

通式(C)中，X1表示重複單元的主鏈，通常表示由聚合反應所形成的連結基，例如較佳為(甲基)丙烯酸系、苯乙烯系、乙烯系等。再者，由2個*所示的部位成為重複單元。 In the general formula (C), X 1 represents a main chain of a repeating unit, and usually represents a linking group formed by a polymerization reaction, and is preferably, for example, a (meth)acrylic acid, a styrene-based or an ethylene-based copolymer. Further, the portion indicated by two * is a repeating unit.

於L1表示二價連結基的情形時，較佳為碳數1~30的伸烷基(亞甲基、伸乙基、三亞甲基、伸丙基、伸丁基等)、碳數6~30的伸芳基(伸苯基、伸萘基等)、雜環連結基、-CH=CH-、-O-、-S-、-C(=O)-、-CO-、-NR-、-CONR-、-OC-、-SO-、-SO2-及將該些基團的2個以上組合而成的連結基。此處，R分別獨立地表示氫原子、烷基、芳基或雜環基。 When L 1 represents a divalent linking group, it is preferably an alkylene group having 1 to 30 carbon atoms (methylene group, ethylidene group, trimethylene group, propyl group, butyl group, etc.), carbon number 6 ~30 of aryl (phenyl, naphthyl, etc.), heterocyclic linkage, -CH=CH-, -O-, -S-, -C(=O)-, -CO-, -NR -, -CONR-, -OC-, -SO-, -SO 2 - and a linking group in which two or more of these groups are combined. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

尤其L1較佳為單鍵或將碳數1~10的伸烷基(較佳為-(CH2)n- (n為1~10的整數))、碳數6~12的伸芳基(較佳為伸苯基、伸萘基)、-NH-、-CO-、-O-及-SO2-組合2個以上而成的二價連結基。 In particular, L 1 is preferably a single bond or an alkylene group having 1 to 10 carbon atoms (preferably -(CH 2 )n- (n is an integer of 1 to 10)), and an aryl group having 6 to 12 carbon atoms. A divalent linking group obtained by combining two or more of (extended phenyl, anthranyl), -NH-, -CO-, -O-, and -SO 2 -.

X1及L1的組合的具體例可列舉上文所述的(XX-1)~(X-24)，但不限定於該些具體例。再者，陰離子多聚物於(XX-1)~(X-24)中的*所示的部位上與所述陰離子連結。 Specific examples of the combination of X 1 and L 1 include (XX-1) to (X-24) described above, but are not limited to these specific examples. Further, the anionic polymer is bonded to the anion at a position indicated by * in (XX-1) to (X-24).

(通式(D)中，L2及L3分別獨立地表示單鍵或二價連結基。陰離子表示-SO3 -、-COO-、-PO4 -、所述通式(A1)所表示的結構及所述般式(A2)所表示的結構) (In the formula (D), L 2 and L 3 each independently represent a single bond or a divalent linking group. The anions represent -SO 3 - , -COO - , -PO 4 - , represented by the above formula (A1) Structure and structure represented by the above formula (A2)

通式(D)中，於L2及L3表示二價連結基的情形時，較佳為碳數1~30的伸烷基、碳數6~30的伸芳基、雜環連結基、-CH=CH-、-O-、-S-、-C(=O)-、-CO-、-NR-、-CONR-、-O2C-、-SO-、-SO2-及將該些基團的2個以上組合而成的連結基。此處，R分別獨立地表示氫原子、烷基、芳基或雜環基。 In the case of the general formula (D), when L 2 and L 3 represent a divalent linking group, an alkylene group having 1 to 30 carbon atoms, an extended aryl group having 6 to 30 carbon atoms, a heterocyclic linking group, and -CH=CH-, -O-, -S-, -C(=O)-, -CO-, -NR-, -CONR-, -O 2 C-, -SO-, -SO 2 - and A linking group in which two or more of these groups are combined. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

L2較佳為碳數6~12的伸芳基(尤其是伸苯基)。碳數6~30的伸芳基較佳為經氟原子取代。 L 2 is preferably a aryl group having 6 to 12 carbon atoms (especially a phenyl group). The aryl group having 6 to 30 carbon atoms is preferably substituted by a fluorine atom.

L3較佳為包含碳數6~12的伸芳基(尤其是伸苯基)與-O-的組合的基團，較佳為至少一種碳數6~12的伸芳基經氟原子取代。 L 3 is preferably a group containing a combination of a aryl group (particularly a phenyl group) having a carbon number of 6 to 12 and -O-, and preferably at least one exoaryl group having a carbon number of 6 to 12 is substituted by a fluorine atom. .

關於形成陰離子多聚物的高分子，不論僅由具有交聯性 基的染料化合物成分所構成的均聚物(homopolymer)、還是與其他聚合性化合物的共聚物(copolymer)均可較佳地使用，更佳為均聚物(homopolymer)。 Regarding the polymer forming the anionic polymer, whether it is only cross-linkable A homopolymer composed of a dye component of the base or a copolymer with another polymerizable compound can be preferably used, and more preferably a homopolymer.

陰離子多聚物的分子量較佳為以重量平均分子量計而為3,000~30,000且分子量分佈以Mw/Mn計而為0.8~3.0，更佳為以重量平均分子量計而為5,000~20,000且分子量分佈以Mw/Mn計而為1~2.5。 The molecular weight of the anionic polymer is preferably from 3,000 to 30,000 by weight average molecular weight, and the molecular weight distribution is from 0.8 to 3.0 in terms of Mw/Mn, more preferably from 5,000 to 20,000 by weight average molecular weight, and the molecular weight distribution is Mw/Mn is 1 to 2.5.

於形成陰離子多聚物的情形時，亦可添加鏈轉移劑。鏈轉移劑較佳為烷基硫醇，較佳為碳數10以下的烷基硫醇或經醚基/酯基取代的烷基硫醇。尤其更佳為logP值為5以下的烷基硫醇。 In the case of forming an anionic polymer, a chain transfer agent may also be added. The chain transfer agent is preferably an alkylthiol, preferably an alkylthiol having a carbon number of 10 or less or an alkylthiol substituted with an ether group/ester group. More preferably, it is an alkylthiol having a logP value of 5 or less.

陰離子多聚物所含的作為陰離子多聚物的原料的具有交聯性基的陰離子單體化合物的量較佳為5%以下，更佳為1%以下。 The amount of the anionic monomer compound having a crosslinkable group as a raw material of the anionic polymer contained in the anionic polymer is preferably 5% or less, more preferably 1% or less.

陰離子多聚物所含的鹵素離子含量較佳為10ppm~3000ppm以下，更佳為10ppm~2000ppm，進而佳為10ppm~1000ppm。 The content of the halogen ion contained in the anionic polymer is preferably from 10 ppm to 3,000 ppm, more preferably from 10 ppm to 2,000 ppm, and still more preferably from 10 ppm to 1,000 ppm.

以下示出陰離子多聚物的具體例，但本發明不限定於該些具體例。 Specific examples of the anionic polymer are shown below, but the present invention is not limited to these specific examples.

以下的具體例表示陰離子結構未解離的狀態，但陰離子結構解離的狀態亦當然在本發明的範圍內。 The following specific examples show a state in which the anion structure is not dissociated, but the state in which the anion structure is dissociated is of course within the scope of the present invention.

<<其他官能基或其他重複單元>> <<Other functional groups or other repeating units>>

本發明中所用的著色劑亦可含有所述以外的其他官能基或其他重複單元。 The color former used in the present invention may also contain other functional groups or other repeating units other than those described above.

具體而言，本發明所用的著色劑的染料陽離子可具有其他官能基，亦可含有陰離子多聚物以外的其他重複單元。 Specifically, the dye cation of the color former used in the present invention may have other functional groups, and may further contain other repeating units than the anionic polymer.

其他官能基可例示聚合性基、酸基及鹼可溶性基等。另外，其他重複單元可例示：含有聚合性基、酸基及鹼可溶性基的至少一種的重複單元。 The other functional group may, for example, be a polymerizable group, an acid group or an alkali-soluble group. Further, the other repeating unit may be a repeating unit containing at least one of a polymerizable group, an acid group, and an alkali-soluble group.

以下，對該等的詳細情況加以說明。 The details of these will be described below.

相對陰離子X亦可含有聚合性基。聚合性基可僅含有一種，亦可含有兩種以上。 The counter anion X may also contain a polymerizable group. The polymerizable group may be contained alone or in combination of two or more.

聚合性基可使用可藉由自由基、酸、熱而進行交聯的公知的聚合性基，例如可列舉：含有乙烯性不飽和鍵的基團、環狀醚基(環氧基、氧雜環丁基)等，尤其較佳為含有乙烯性不飽和鍵的基團，更佳為(甲基)丙烯醯基，進而佳為來源於(甲基)丙烯酸縮水甘油酯及(甲基)丙烯酸-3,4-環氧-環己基甲酯的(甲基)丙烯醯基。 As the polymerizable group, a known polymerizable group which can be crosslinked by a radical, an acid or a heat can be used, and examples thereof include a group containing an ethylenically unsaturated bond, and a cyclic ether group (epoxy group, oxa group). Particularly preferred is a group containing an ethylenically unsaturated bond, more preferably a (meth)acryl fluorenyl group, and further preferably derived from glycidyl (meth)acrylate and (meth)acrylic acid. a (meth) acrylonitrile group of -3,4-epoxy-cyclohexylmethyl ester.

聚合性基亦較佳為以具有聚合性基的重複單元的形式而組入。 The polymerizable group is also preferably incorporated in the form of a repeating unit having a polymerizable group.

另外，於陰離子多聚物更含有具有聚合性基的重複單元的情形時，相對於所有重複單元100莫耳，其量例如較佳為50莫耳~90莫耳，更佳為70莫耳~90莫耳。 Further, in the case where the anionic polymer further contains a repeating unit having a polymerizable group, the amount thereof is, for example, preferably from 50 mol to 90 mol, more preferably 70 mol, relative to 100 mol of all repeating units. 90 moles.

具有聚合性基的重複單元可列舉如下具體例。然而，本發明不限定於該些具體例。 Specific examples of the repeating unit having a polymerizable group are as follows. However, the invention is not limited to the specific examples.

酸基可例示羧酸基、磺酸基、磷酸基。另外，鹼可溶性基可例示酚性羥基、羧酸。 The acid group may, for example, be a carboxylic acid group, a sulfonic acid group or a phosphoric acid group. Further, the alkali-soluble group can be exemplified by a phenolic hydroxyl group or a carboxylic acid.

另外，於陰離子多聚物含有具有酸基的重複單元的情形時，相對於所有重複單元100莫耳，含有具有酸基的重複單元的重複單元的比例例如較佳為10莫耳~50莫耳，更佳為10莫耳~30莫耳。 Further, in the case where the anionic polymer contains a repeating unit having an acid group, the proportion of the repeating unit containing a repeating unit having an acid group is preferably, for example, 10 mol to 50 mol per 100 mol of all repeating units. More preferably 10 moles to 30 moles.

其他官能基可列舉：內酯、酸酐、醯胺、-COCH2CO-、氰基等顯影促進基，長鏈烷基及環狀烷基、芳烷基、芳基、聚環氧烷基、羥基、馬來醯亞胺基、胺基等親疏水性調整基等，可適當導入。 Examples of other functional groups include a lactone, an acid anhydride, a decylamine, a -COCH 2 CO-, a cyano group, and the like, a long-chain alkyl group and a cyclic alkyl group, an aralkyl group, an aryl group, a polyalkylene oxide group, and the like. A hydrophilic or hydrophobicity adjusting group such as a hydroxyl group, a maleimide group or an amine group can be appropriately introduced.

導入方法可列舉：預先導入至所述三芳基甲烷結構中的方法、及使具有所述官能基的單體進行共聚合的方法。 The introduction method includes a method of introducing into the triarylmethane structure in advance, and a method of copolymerizing a monomer having the functional group.

以下示出其他重複單元的具體例，但本發明不限定於此。 Specific examples of other repeating units are shown below, but the present invention is not limited thereto.

以下示出含有染料陽離子與相對陰離子X的化合物的具體例，但不限定於此。 Specific examples of the compound containing a dye cation and a counter anion X are shown below, but are not limited thereto.

下述化合物中的染料陽離子以相當於含有重複單元的相對陰離子X的個數而存在。 The dye cations in the following compounds exist in a number corresponding to the relative anion X containing a repeating unit.

於含有染料陽離子與相對陰離子X的化合物具有含有多聚物結構的相對陰離子X的情形時，重量平均分子量較佳為1,000~100,000，更佳為5,000~50,000。 In the case where the compound containing the dye cation and the opposite anion X has a relative anion X having a polymer structure, the weight average molecular weight is preferably from 1,000 to 100,000, more preferably from 5,000 to 50,000.

含有染料陽離子與相對陰離子X的化合物可單獨含有一種或組合含有兩種以上。 The compound containing a dye cation and a counter anion X may be contained alone or in combination of two or more.

相對於本發明的著色組成物的總固體成分，含有染料陽離子與相對陰離子X的化合物的含量較佳為5質量%~40質量%，更佳為10質量%~30質量%。 The content of the compound containing the dye cation and the counter anion X is preferably from 5% by mass to 40% by mass, and more preferably from 10% by mass to 30% by mass based on the total solid content of the colored composition of the present invention.

<<陰離子Y>> <<Anion Y>>

陰離子Y可與染料陽離子形成鹽，且與相對陰離子X不同。例如陰離子Y只要於相對陰離子X因加熱等而與染料陽離子解離的情形時與染料陽離子形成鹽，使著色劑成為穩定的狀態，藉此提高耐熱性，則並無特別限定。相對陰離子Y可為一價陰離子，亦可為二價以上的陰離子。 The anion Y can form a salt with the dye cation and is different from the opposite anion X. For example, the anion Y is not particularly limited as long as it forms a salt with the dye cation when the anion X is dissociated from the dye cation by heating or the like, and the colorant is stabilized. The relative anion Y may be a monovalent anion or may be a divalent or higher anion.

具體而言，陰離子Y可應用上文所述的相對陰離子X中說明的陰離子。 In particular, the anion Y can be applied to the anions described above for the relative anion X.

本發明的組成物中的陰離子Y相對於染料陽離子之莫耳比(陰離子Y/染料陽離子)為0.0001~7.0，較佳為0.001~5.0，更佳為0.01~3.0，進而佳為0.1~1.0。 The molar ratio of the anion Y to the dye cation (anionic Y/dye cation) in the composition of the present invention is 0.0001 to 7.0, preferably 0.001 to 5.0, more preferably 0.01 to 3.0, and still more preferably 0.1 to 1.0.

陰離子Y含有至少一種，可單獨使用一種，亦可組合使用兩種以上。於使用兩種以上的陰離子Y的情形時，較佳為以莫耳比(陰離子Y/染料陽離子)成為所述範圍內的方式設定。 The anion Y contains at least one kind, and they may be used alone or in combination of two or more. When two or more kinds of anions Y are used, it is preferable to set such that the molar ratio (anionic Y/dye cation) is within the above range.

<<其他著色化合物>> <<Other coloring compounds>>

本發明的著色組成物亦可含有一種或兩種以上的上文所述的著色劑、即染料陽離子以外的其他著色化合物。其他著色化合物可列舉染料化合物、顏料化合物及該些化合物的分散物。 The colored composition of the present invention may also contain one or two or more of the coloring agents described above, that is, other coloring compounds other than the dye cations. Other coloring compounds include dye compounds, pigment compounds, and dispersions of these compounds.

染料化合物只要不影響著色圖像的色相，則可為任意結構，例如可列舉：偶氮系(例如溶劑黃162)、蒽醌系(例如日本專利特開2001-10881號公報中記載的蒽醌化合物)、酞菁系(例如美國專利2008/0076044A1中記載的酞菁化合物)、呫噸系(例如顏色索引(Color Index，C.I.)酸性紅289(C.I.Acid.Red 289))、三芳基甲烷系(例如C.I.酸性藍7(C.I.Acid Blue 7)、C.I.酸性藍83(C.I.Acid Blue 83)、C.I.酸性藍90(C.I.Acid Blue 90)、C.I.溶劑藍38(C.I.Solvent Blue 38)、C.I.酸性紫17(C.I.Acid Violet 17)、C.I.酸性紫49(C.I.Acid Violet 49)、C.I.酸性綠3(C.I.Acid Green 3))、次甲基染料等。 The dye compound may have any structure as long as it does not affect the hue of the colored image, and examples thereof include an azo system (for example, Solvent Yellow 162) and a lanthanide system (for example, those described in JP-A-2001-10881). a compound), a phthalocyanine system (for example, a phthalocyanine compound described in US Pat. No. 2008/0076044 A1), a xanthene system (for example, Color Index (CI) Acid Red 289 (CIAcid. Red 289)), a triarylmethane system (eg CI Acid Blue 7), CI Acid Blue 83, CI Acid Blue 90, CI Solvent Blue 38, CI Acid Violet 17 (CIAcid Violet 17), CI Acid Violet 49 (CIAcid Violet 49), CI Acid Green 3), methine dye, and the like.

顏料化合物可列舉：苝、紫環酮(perinone)、喹吖啶酮、喹吖啶酮醌(quinacridonequinone)、蒽醌、花蒽酮 (anthoanthrone)、苯并咪唑酮、雙偶氮(disazo)縮合、雙偶氮、偶氮、陰丹士林(indanthrone)、酞菁、三芳基碳鎓、二噁嗪、胺基蒽醌、二酮基吡咯并吡咯、靛藍、硫靛藍、異吲哚啉、異吲哚啉酮、皮蒽酮(pyranthrone)或異紫蒽酮(Isoviolanthrone)等。更詳細而言，例如可列舉：顏料紅190、顏料紅224、顏料紫29等苝化合物顏料，顏料橙43或顏料紅194等紫環酮化合物顏料，顏料紫19、顏料紫42、顏料紅122、顏料紅192、顏料紅202、顏料紅207或顏料紅209等喹吖啶酮化合物顏料，顏料紅206、顏料橙48或顏料橙49等喹吖啶酮醌化合物顏料，顏料黃147等蒽醌化合物顏料，顏料紅168等花蒽酮化合物顏料，顏料棕25、顏料紫32、顏料橙36、顏料黃120、顏料黃180、顏料黃181、顏料橙62或顏料紅185等苯并咪唑酮化合物顏料，顏料黃93、顏料黃94、顏料黃95、顏料黃128、顏料黃166、顏料橙34、顏料橙13、顏料橙31、顏料紅144、顏料紅166、顏料紅220、顏料紅221、顏料紅242、顏料紅248、顏料紅262或顏料棕23等雙偶氮縮合化合物顏料，顏料黃13、顏料黃83或顏料黃188等雙偶氮化合物顏料，顏料紅187、顏料紅170、顏料黃74、顏料黃150、顏料紅48、顏料紅53、顏料橙64或顏料紅247等偶氮化合物顏料，顏料藍60等陰丹士林化合物顏料，顏料綠7、顏料綠36、顏料綠37、顏料綠58、顏料藍16、顏料藍75或顏料藍15等酞菁化合物顏料，顏料藍56或顏料藍61等三芳基碳鎓化合物顏料，顏料紫23或顏料紫37等二噁嗪化合物顏料，顏料紅177等胺基蒽醌化合物顏 料，顏料紅254、顏料紅255、顏料紅264、顏料紅272、顏料橙71或顏料橙73等二酮基吡咯并吡咯化合物顏料，顏料紅88等硫靛藍化合物顏料，顏料黃139、顏料橙66等異吲哚啉化合物顏料，顏料黃109或顏料橙61等異吲哚啉酮化合物顏料，顏料橙40或顏料紅216等皮蒽酮化合物顏料，或顏料紫31等異紫蒽酮化合物顏料。 Examples of the pigment compound include hydrazine, perinone, quinacridone, quinacridonequinone, anthraquinone, and decyl ketone. (anthoanthrone), benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbenium, dioxazine, amine guanidine, two Ketopyrrolopyrrole, indigo, thioindigo, isoindoline, isoindolinone, pyranthrone or isosolanone (Isoviolanthrone) and the like. More specifically, examples thereof include an anthraquinone compound pigment such as Pigment Red 190, Pigment Red 224, and Pigment Violet 29, and a purple ketone compound pigment such as Pigment Orange 43 or Pigment Red 194, Pigment Violet 19, Pigment Violet 42, and Pigment Red 122. Quinacridone compound pigment such as Pigment Red 192, Pigment Red 202, Pigment Red 207 or Pigment Red 209, quinacridone oxime compound pigment such as Pigment Red 206, Pigment Orange 48 or Pigment Orange 49, Pigment Yellow 147, etc. Compound pigment, pigment red 168 and other flower ketone compound pigment, pigment brown 25, pigment purple 32, pigment orange 36, pigment yellow 120, pigment yellow 180, pigment yellow 181, pigment orange 62 or pigment red 185 and other benzimidazolone compounds Pigment, Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 166, Pigment Orange 34, Pigment Orange 13, Pigment Orange 31, Pigment Red 144, Pigment Red 166, Pigment Red 220, Pigment Red 221, Bis-azo condensation compound pigments such as Pigment Red 242, Pigment Red 248, Pigment Red 262 or Pigment Brown 23, disazo compound pigments such as Pigment Yellow 13, Pigment Yellow 83 or Pigment Yellow 188, Pigment Red 187, Pigment Red 170, Pigment Yellow 74, Pigment Yellow 150, Pigment Red 48. Pigment red 53, pigment orange 64 or pigment red 247 and other azo compound pigments, pigment blue 60 and other indanthrene compound pigments, pigment green 7, pigment green 36, pigment green 37, pigment green 58, pigment blue 16, a phthalocyanine compound pigment such as Pigment Blue 75 or Pigment Blue 15, a triarylcarbamate compound pigment such as Pigment Blue 56 or Pigment Blue 61, a dioxazine compound pigment such as Pigment Violet 23 or Pigment Violet 37, and an amine group such as Pigment Red 177 Compound , pigment red 254, pigment red 255, pigment red 264, pigment red 272, pigment orange 71 or pigment orange 73 and other diketopyrrolopyrrole compound pigment, pigment red 88 and other sulfur indigo compound pigment, pigment yellow 139, pigment orange 66 iso-porphyrin compound pigment, isophthalone compound pigment such as pigment yellow 109 or pigment orange 61, dermatone compound pigment such as pigment orange 40 or pigment red 216, or isopurinone pigment such as pigment purple 31 .

本發明中較佳為綠色至青色(cyan)的有色材料，較佳為顏料綠7、顏料綠36、顏料綠37、顏料綠58、顏料藍16、顏料藍75、顏料藍15、顏料藍15：6等酞菁化合物顏料，顏料藍56或顏料藍61等三芳基碳鎓化合物顏料，顏料紫23或顏料紫37等二噁嗪化合物顏料，顏料紅177等胺基蒽醌化合物顏料，顏料紅254、顏料紅255、顏料紅264、顏料紅272、顏料橙71或顏料橙73等二酮基吡咯并吡咯化合物顏料，顏料紅88等硫靛藍化合物顏料，顏料黃139、顏料橙66等異吲哚啉化合物顏料，顏料黃109或顏料橙61等異吲哚啉酮化合物顏料，顏料橙40或顏料紅216等皮蒽酮化合物顏料，或顏料紫31等異紫蒽酮化合物顏料。 Preferred in the present invention are green to cyan colored materials, preferably Pigment Green 7, Pigment Green 36, Pigment Green 37, Pigment Green 58, Pigment Blue 16, Pigment Blue 75, Pigment Blue 15, Pigment Blue 15 : 6 such as phthalocyanine compound pigment, triarylcarbazone compound pigment such as Pigment Blue 56 or Pigment Blue 61, dioxazine compound pigment such as Pigment Violet 23 or Pigment Violet 37, Amine based compound pigment such as Pigment Red 177, Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 272, Pigment Orange 71 or Pigment Orange 73 and other diketopyrrolopyrrole compound pigments, Pigment Red 88 and other sulfur indigo compound pigments, Pigment Yellow 139, Pigment Orange 66, etc. A porphyrin compound pigment, an isoindolinone compound pigment such as Pigment Yellow 109 or Pigment Orange 61, a Pipione compound pigment such as Pigment Orange 40 or Pigment Red 216, or an isopurinone pigment such as Pigment Violet 31.

於將所述染料或顏料調配成分散物的情形時，可依照日本專利特開平9-197118號公報、日本專利特開2000-239544號公報的記載來調整。 In the case where the dye or the pigment is blended into a dispersion, it can be adjusted in accordance with the description of JP-A-H09-197118, JP-A-2000-239544.

關於所述料或顏料的含量，可於不損及本發明的效果的範圍內使用，相對於本發明的著色組成物的總固體成分，較佳為0.5質量%~70質量%。另外，較佳為以吸收強度比(450nm的吸收 /650nm的吸收)成為0.95~1.05的範圍的方式添加至著色組成物中。 The content of the material or the pigment can be used within the range not detracting from the effects of the present invention, and is preferably from 0.5% by mass to 70% by mass based on the total solid content of the coloring composition of the present invention. In addition, it is preferably an absorption intensity ratio (absorption at 450 nm) The absorption at /650 nm is added to the coloring composition in such a manner as to be in the range of 0.95 to 1.05.

<<聚合性化合物>> <<Polymerized compound>>

本發明的著色組成物含有聚合性化合物。聚合性化合物例如可列舉：具有至少1個乙烯性不飽和雙鍵的加成聚合性化合物。 The colored composition of the present invention contains a polymerizable compound. The polymerizable compound is, for example, an addition polymerizable compound having at least one ethylenically unsaturated double bond.

具體而言，所述聚合性化合物是選自具有至少1個、較佳為2個以上的末端乙烯性不飽和鍵的化合物中。此種化合物組群於本發明的產業領域中已廣為人知，本發明中可無特別限定地使用該些化合物。該些化合物例如可為以下化學形態的任一種：單體，預聚物即二聚物、三聚物及寡聚物，或該等的混合物以及該等的(共)聚合物等。 Specifically, the polymerizable compound is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such a compound group is widely known in the industrial field of the present invention, and these compounds can be used without particular limitation in the present invention. These compounds may be, for example, any of the following chemical forms: monomers, prepolymers, i.e., dimers, trimers, and oligomers, or mixtures thereof, and such (co)polymers.

單體及其(共)聚合物的例子可列舉：不飽和羧酸(例如丙烯酸、甲基丙烯酸、衣康酸、丁烯酸、異丁烯酸、馬來酸等)或其酯類、醯胺類、以及該等的(共)聚合物，較佳為不飽和羧酸與脂肪族多元醇化合物的酯、及不飽和羧酸與脂肪族多元胺化合物的醯胺類、以及該等的(共)聚合物。另外，亦可較佳地使用以下反應物：具有羥基或胺基、巰基等親核性取代基的不飽和羧酸酯或醯胺類與單官能或多官能異氰酸酯類或環氧類的加成反應物，或與單官能或多官能的羧酸的脫水縮合反應物等。另外，以下反應物亦較佳：具有異氰酸酯基或環氧基等親電子性取代基的不飽和羧酸酯或醯胺類與單官能或多官能的醇類、胺類、硫醇類的加成反應物，進而具有鹵素基或甲苯磺醯氧基等脫離性取代 基的不飽和羧酸酯或醯胺類與單官能或多官能的醇類、胺類、硫醇類的取代反應物。另外，作為其他例，亦可使用代替所述不飽和羧酸而替換為不飽和膦酸、苯乙烯、乙烯醚等而成的化合物組群。 Examples of the monomer and its (co)polymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, etc.) or esters thereof, guanamines. And the (co)polymer, preferably an ester of an unsaturated carboxylic acid and an aliphatic polyol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound, and the (co) polymer. Further, it is also preferred to use the following reactants: an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, or an addition of a monofunctional or polyfunctional isocyanate or epoxy group. a reactant, or a dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid, or the like. Further, the following reactants are also preferred: an unsaturated carboxylic acid ester or a guanamine having an electrophilic substituent such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol. a reactant, which in turn has a detachment substitution such as a halogen group or a toluenesulfonyloxy group Substituted reactants of a group of unsaturated carboxylic acid esters or guanamines with monofunctional or polyfunctional alcohols, amines, thiols. Further, as another example, a compound group obtained by replacing the unsaturated carboxylic acid with unsaturated phosphonic acid, styrene, vinyl ether or the like may be used.

關於脂肪族多元醇化合物與不飽和羧酸的酯的單體的具體例，丙烯酸酯例如可列舉：乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、1,3-丁二醇二丙烯酸酯、四亞甲基二醇二丙烯酸酯、丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三(丙烯醯氧基丙基)醚、三羥甲基乙烷三丙烯酸酯、己二醇二丙烯酸酯、1,4-環己二醇二丙烯酸酯、四乙二醇二丙烯酸酯、季戊四醇二丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇二丙烯酸酯、二季戊四醇六丙烯酸酯、山梨醇三丙烯酸酯、山梨醇四丙烯酸酯、山梨醇五丙烯酸酯、山梨醇六丙烯酸酯、三(丙烯醯基氧基乙基)異氰脲酸酯、聚酯丙烯酸酯寡聚物、異氰脲酸環氧乙烷(Ethylene Oxide，EO)改質三丙烯酸酯等。 Specific examples of the monomer of the ester of the aliphatic polyol compound and the unsaturated carboxylic acid include, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butylene glycol diacrylate. Ester, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene methoxypropyl) ether, Trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate Ester, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(propylene decyloxyethyl) isocyanide Urea ester, polyester acrylate oligomer, Ethylene Oxide (EO) modified triacrylate, and the like.

另外，甲基丙烯酸酯例如可列舉：四亞甲基二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、新戊二醇二甲基丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、三羥甲基乙烷三甲基丙烯酸酯、乙二醇二甲基丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、己二醇二甲基丙烯酸酯、季戊四醇二甲基丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇四甲基丙烯酸酯、二季戊四醇二甲基丙烯酸酯、二 季戊四醇六甲基丙烯酸酯、山梨醇三甲基丙烯酸酯、山梨醇四甲基丙烯酸酯、雙[對-(3-甲基丙烯醯氧基-2-羥基丙氧基)苯基]二甲基甲烷、雙-[對-(甲基丙烯醯氧基乙氧基)苯基]二甲基甲烷等。 Further, examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimethylolpropane trimethyl. Acrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethyl Acrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, two Pentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis[p-(3-methylpropenyloxy-2-hydroxypropoxy)phenyl]dimethyl Methane, bis-[p-(methacryloxyethoxy)phenyl]dimethylmethane, and the like.

進而，衣康酸酯例如可列舉：乙二醇二衣康酸酯、丙二醇二衣康酸酯、1,3-丁二醇二衣康酸酯、1,4-丁二醇二衣康酸酯、四亞甲基二醇二衣康酸酯、季戊四醇二衣康酸酯、山梨醇四衣康酸酯等，另外，丁烯酸酯例如可列舉：乙二醇二丁烯酸酯、四亞甲基二醇二丁烯酸酯、季戊四醇二丁烯酸酯、山梨醇四二丁烯酸酯等，異丁烯酸酯例如可列舉：乙二醇二異丁烯酸酯、季戊四醇二異丁烯酸酯、山梨醇四異丁烯酸酯等，另外，馬來酸酯例如可列舉：乙二醇二馬來酸酯、三乙二醇二馬來酸酯、季戊四醇二馬來酸酯、山梨醇四馬來酸酯等。 Further, examples of the itaconate include, for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butylene glycol diitaconate, and 1,4-butanediol diitaconic acid. Ethyl ester, tetramethylene glycol bisitaconate, pentaerythritol diitaconate, sorbitol tetraconate, etc., and examples of the butenoate include ethylene glycol bisacrylate, and Methylene glycol bis methacrylate, pentaerythritol dimethyl acrylate, sorbitol tetra bis acrylate or the like, and examples of the methacrylate include ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, and sorbitol. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Wait.

其他酯的例子例如亦可較佳地使用：日本專利特公昭51-47334號公報、日本專利特開昭57-196231號公報記載的脂肪族醇系酯類，或日本專利特開昭59-5240號公報、日本專利特開昭59-5241號公報、日本專利特開平2-226149號公報記載的具有芳香族系骨架的酯，日本專利特開平1-165613號公報記載的含有胺基的酯等。進而，上文所述的酯單體亦能以混合物的形式使用。 For example, an aliphatic alcohol-based ester described in Japanese Patent Laid-Open Publication No. Sho 57-196231, or Japanese Patent Laid-Open No. Sho 57-196231, or Japanese Patent Laid-Open No. 59-5240 An ester having an aromatic skeleton, which is described in Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. . Further, the above ester monomers can also be used in the form of a mixture.

另外，使用異氰酸酯與羥基的加成反應所製造的胺基甲酸酯系加成聚合性化合物亦較佳，此種具體例例如可列舉：日本專利特公昭48-41708號公報中記載的一分子中含有2個以上的聚合性乙烯基的乙烯基胺基甲酸酯化合物等，該乙烯基胺基甲酸酯 化合物是使下述通式(A)所表示的含羥基的乙烯系單體加成於一分子內具有2個以上的異氰酸酯基的聚異氰酸酯化合物上而成。 In addition, a urethane-based addition polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group is also preferable, and a specific example thereof is exemplified by a molecule described in Japanese Patent Publication No. Sho 48-41708. a vinyl urethane compound containing two or more polymerizable vinyl groups, etc., the vinyl urethane The compound is obtained by adding a hydroxyl group-containing vinyl monomer represented by the following formula (A) to a polyisocyanate compound having two or more isocyanate groups in one molecule.

CH2=C(R)COOCH2CH(R')OH…(A) CH 2 =C(R)COOCH 2 CH(R')OH...(A)

[通式(A)中，R及R'分別獨立地表示H或CH3] [In the general formula (A), R and R' each independently represent H or CH 3 ]

另外，聚合性化合物亦較佳為二季戊四醇三丙烯酸酯(市售品為卡亞拉得(KAYARAD)D-330；日本化藥股份有限公司製造)、二季戊四醇四丙烯酸酯(市售品為卡亞拉得(KAYARAD)D-320；日本化藥股份有限公司製造)、二季戊四醇五(甲基)丙烯酸酯(市售品為卡亞拉得(KAYARAD)D-310；日本化藥股份有限公司製造)、二季戊四醇六(甲基)丙烯酸酯(市售品為卡亞拉得(KAYARAD)DPHA；日本化藥股份有限公司製造)、及該些化合物的(甲基)丙烯醯基介隔乙二醇殘基、丙二醇殘基的結構。亦可使用該等的寡聚物類型。 Further, the polymerizable compound is also preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available as card) KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercial product is KAYARAD D-310; Nippon Chemical Co., Ltd.) Manufactured, dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and (meth)acryloyl thiol group of these compounds The structure of the diol residue and the propylene glycol residue. These types of oligomers can also be used.

關於該些聚合性化合物，其結構或者單獨使用或併用、添加量等使用方法的詳細情況可根據著色組成物的最終的性能設計而任意設定。例如就感度的觀點而言，較佳為每一分子的不飽和基含量多的結構，多的情況下較佳為二官能以上。另外，就提高著色硬化膜的強度的觀點而言，以三官能以上者為宜，進而，藉由併用官能數不同、聚合性基不同(例如丙烯酸酯、甲基丙烯酸酯、苯乙烯化合物、乙烯基醚化合物)者來調節感度與強度兩 者的方法亦有效。另外，對於與著色組成物所含有的其他成分(例如光聚合起始劑、著色劑(顏料)、黏合劑聚合物等)的相容性、分散性而言，聚合性化合物的選擇、使用法為重要的原因，例如有時可藉由使用低純度化合物或併用兩種以上來提高相容性。另外，就提高與基板等硬質表面的密接性的觀點而言，有時亦可選擇特定的結構。 Regarding the polymerizable compounds, the details of the structure or the method of use, either alone or in combination, and the amount of addition can be arbitrarily set depending on the final performance design of the coloring composition. For example, from the viewpoint of sensitivity, it is preferred that the structure has a large content of unsaturated groups per molecule, and in many cases, it is preferably a difunctional or higher. In addition, from the viewpoint of improving the strength of the colored cured film, it is preferably a trifunctional or higher functional group, and further, the functional group is different and the polymerizable group is different (for example, acrylate, methacrylate, styrene compound, ethylene). (ether ether compound) to adjust the sensitivity and strength The method is also effective. In addition, the compatibility and dispersibility of other components (for example, a photopolymerization initiator, a colorant (pigment), a binder polymer, etc.) contained in the coloring composition, the selection and use of the polymerizable compound For important reasons, for example, compatibility may be improved by using a low-purity compound or a combination of two or more. Further, from the viewpoint of improving the adhesion to a hard surface such as a substrate, a specific structure may be selected.

就更有效地獲得本發明的效果的觀點而言，著色組成物的總固體成分中的聚合性化合物的含量較佳為10質量%~80質量%，更佳為15質量%~75質量%，尤佳為20質量%~60質量%。 The content of the polymerizable compound in the total solid content of the colored composition is preferably from 10% by mass to 80% by mass, and more preferably from 15% by mass to 75% by mass, from the viewpoint of more effectively obtaining the effect of the present invention. More preferably, it is 20% by mass to 60% by mass.

本發明的組成物可僅含有一種聚合性化合物，亦可含有兩種以上。於含有兩種以上的情形時，較佳為其合計量成為所述範圍。 The composition of the present invention may contain only one kind of polymerizable compound, and may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

<<光聚合起始劑>> <<Photopolymerization initiator>>

本發明的著色組成物較佳為含有至少一種光聚合起始劑。光聚合起始劑只要可使聚合性化合物或含有交聯性基的著色劑進行聚合，則並無特別限制，較佳為自特性、起始效率、吸收波長、獲取性、成本等觀點來選擇。 The colored composition of the present invention preferably contains at least one photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can polymerize a polymerizable compound or a crosslinkable group-containing coloring agent, and is preferably selected from the viewpoints of characteristics, initial efficiency, absorption wavelength, availability, cost, and the like. .

光聚合起始劑例如可列舉：選自鹵代甲基噁二唑化合物及鹵代甲基-均三嗪化合物中的至少一種活性鹵素化合物、3-芳基取代香豆素化合物、咯吩二聚物、二苯甲酮化合物、苯乙酮化合物及其衍生物、環戊二烯-苯-鐵錯合物及其鹽、肟化合物等。關於光聚合起始劑的具體例，可列舉日本專利特開2004-295116號公報的段落[0070]~段落[0077]中記載者。其中，就聚合反應迅速的方 面等而言，較佳為肟化合物或聯咪唑系化合物。 The photopolymerization initiator may, for example, be at least one active halogen compound selected from the group consisting of a halogenated methyl oxadiazole compound and a halogenated methyl-s-triazine compound, a 3-aryl-substituted coumarin compound, and a phenanthrene a polymer, a benzophenone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron complex, a salt thereof, a hydrazine compound, and the like. Specific examples of the photopolymerization initiator include those described in paragraphs [0070] to [0077] of JP-A-2004-295116. Among them, the party with rapid polymerization The surface or the like is preferably an anthracene compound or a biimidazole compound.

肟系化合物(以下亦稱為「肟系光聚合起始劑」)並無特別限定，例如可列舉日本專利特開2000-80068號公報、WO02/100903A1、日本專利特開2001-233842號公報等中記載的肟系化合物。 The oxime compound (hereinafter also referred to as "an oxime photopolymerization initiator") is not particularly limited, and examples thereof include, for example, JP-A-2000-80068, WO02/100903A1, JP-A-2001-233842, and the like. The lanthanide compound described in the above.

肟系化合物的具體例可參照日本專利特開2013-182215號公報的段落0053的記載，將其內容併入至本申請案說明書中。 Specific examples of the lanthanoid compound can be referred to the description of paragraph 0053 of JP-A-2013-182215, the contents of which are incorporated herein by reference.

另外，本發明中，就感度、徑時穩定性、後加熱時的著色的觀點而言，肟化合物更佳為下述通式(1)或通式(2)所表示的化合物。 In the present invention, the ruthenium compound is more preferably a compound represented by the following formula (1) or (2) from the viewpoints of sensitivity, stability at the time of the run, and coloration at the time of post-heating.

(通式(1)中，R及X分別表示一價取代基，A表示二價有機基，Ar表示芳基。n為1~5的整數) (In the formula (1), R and X each represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1 to 5)

就高感度化的方面而言，R較佳為醯基，具體而言，較佳為乙醯基、丙醯基、苯甲醯基、甲苯甲醯基。 In terms of high sensitivity, R is preferably a mercapto group, and specifically, is preferably an ethyl fluorenyl group, a propyl fluorenyl group, a benzamidine group or a tolylmethyl group.

就提高感度、抑制由加熱經時所致的著色的方面而言，A較佳為未經取代的伸烷基、經烷基(例如甲基、乙基、第三丁基、十二烷基)取代的伸烷基、經烯基(例如乙烯基、烯丙基) 取代的伸烷基、經芳基(例如苯基、對甲苯基、二甲苯基、枯烯基、萘基、蒽基、菲基、苯乙烯基)取代的伸烷基。 A is preferably an unsubstituted alkylene group, an alkyl group (for example, methyl group, ethyl group, tert-butyl group, dodecyl group) in terms of improving sensitivity and suppressing coloring caused by heating over time. Substituted alkyl, alkenyl (eg vinyl, allyl) A substituted alkylene group, an alkylene group substituted with an aryl group (e.g., phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthracenyl, phenanthryl, styryl).

就提高感度、抑制由加熱經時所致的著色的方面而言，Ar較佳為經取代或未經取代的苯基。經取代的苯基的情況下，其取代基例如較佳為氟原子、氯原子、溴原子、碘原子等鹵素基。 Ar is preferably a substituted or unsubstituted phenyl group in terms of improving sensitivity and suppressing coloring caused by heating over time. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

就提高溶劑溶解性及長波長範圍的吸收效率的方面而言，X較佳為可具有取代基的烷基、可具有取代基的芳基、可具有取代基的烯基、可具有取代基的炔基、可具有取代基的烷氧基、可具有取代基的芳氧基、可具有取代基的烷基硫氧基(alkylthioxy)、可具有取代基的芳基硫氧基、可具有取代基的胺基。另外，通式(1)中的n較佳為1~2的整數。 X is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, may have a substituent, in terms of improving solvent solubility and absorption efficiency in a long wavelength range. An alkynyl group, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthiooxy group which may have a substituent, an arylthiooxy group which may have a substituent, may have a substituent Amino group. Further, n in the formula (1) is preferably an integer of 1 to 2.

通式(2)中，R101表示烷基、烷醯基、烯醯基、芳醯基、烷氧基羰基、芳氧基羰基、雜環氧基羰基、雜芳氧基羰基、烷硫基羰基、芳硫基羰基、雜環硫基羰基、雜芳硫基羰基或CO-CO-Rf。Rf表示碳環式芳香族基或雜環式芳香族基。 In the formula (2), R 101 represents an alkyl group, an alkyl fluorenyl group, an olefin group, an aryl fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, a heteroaryloxycarbonyl group, an alkylthio group. Carbonyl, arylthiocarbonyl, heterocyclic thiocarbonyl, heteroarylthiocarbonyl or CO-CO-Rf. Rf represents a carbocyclic aromatic group or a heterocyclic aromatic group.

R102表示烷基、芳基或雜環基，該些基團亦可經取代。 R 102 represents an alkyl group, an aryl group or a heterocyclic group, and these groups may also be substituted.

R103及R104分別獨立地表示烷基、芳基或雜環基，該些基團亦可進一步經鹵素原子、烷基、芳基、烷氧基、烷基羰基等取代。 R 103 and R 104 each independently represent an alkyl group, an aryl group or a heterocyclic group, and these groups may be further substituted with a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylcarbonyl group or the like.

R105~R111分別獨立地表示氫原子、鹵素原子、烷基、芳基、雜環基、烷氧基、芳醯基、雜芳醯基、烷硫基、芳醯基硫基、雜芳醯基、烷基羰基、芳基羰基、雜芳基羰基、烷氧基羰基、芳氧基羰基、雜環氧基羰基、硝基、胺基、磺酸基、羥基、羧酸基、醯胺基、胺甲醯基或氰基。 R 105 to R 111 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an arylsulfonyl group, a heteroarylsulfonyl group, an alkylthio group, an arylsulfonylthio group, or a heteroaryl group. Mercapto, alkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, heterocyclooxycarbonyl, nitro, amine, sulfonate, hydroxy, carboxylic acid, decylamine Base, amine carbenyl or cyano group.

R105~R111中的一個或兩個為電子吸引性的取代基、即硝基、氰基、鹵代基、烷基羰基或芳基羰基的情況下，可獲得具有更高的硬化性的著色組成物，故較佳。 In the case where one or both of R 105 to R 111 is an electron-attracting substituent, that is, a nitro group, a cyano group, a halogeno group, an alkylcarbonyl group or an arylcarbonyl group, a higher hardenability can be obtained. It is preferred to color the composition.

以下列舉所述通式(2)所表示的具有茀結構的化合物的具體例。然而，不限定於該些化合物。 Specific examples of the compound having a fluorene structure represented by the above formula (2) are listed below. However, it is not limited to these compounds.

所述通式(2)所表示的具有茀結構的化合物例如可依據日本專利特開2008-292970號公報中記載的合成方法來合成。 The compound having a fluorene structure represented by the above formula (2) can be synthesized, for example, according to the synthesis method described in JP-A-2008-292970.

聯咪唑系化合物的具體例可參照日本專利特開2013-182213號公報段落0061~段落0070的記載，將其內容併入至本申請案說明書中。 Specific examples of the biimidazole-based compound can be referred to the description of paragraphs 0061 to 0070 of JP-A-2013-182213, the contents of which are incorporated herein by reference.

另外，本發明的著色組成物中，除了所述光聚合起始劑以外，亦可使用日本專利特開2004-295116號公報的段落編號0079 中記載的其他公知的光聚合起始劑。 Further, in the coloring composition of the present invention, in addition to the photopolymerization initiator, paragraph number 0079 of JP-A-2004-295116 may be used. Other known photopolymerization initiators described therein.

就更有效地獲得本發明的效果的觀點而言，光聚合起始劑於著色組成物的總固體成分中的含量較佳為3質量%~20質量%，更佳為4質量%~19質量%，尤佳為5質量%~18質量%。 The content of the photopolymerization initiator in the total solid content of the coloring composition is preferably from 3% by mass to 20% by mass, more preferably from 4% by mass to 19% by mass, from the viewpoint of more effectively obtaining the effect of the present invention. %, particularly preferably from 5% by mass to 18% by mass.

本發明的組成物可僅含有一種光聚合起始劑，亦可含有兩種以上。於含有兩種以上的情形時，較佳為其合計量成為所述範圍。 The composition of the present invention may contain only one photopolymerization initiator, and may contain two or more kinds. When two or more cases are contained, it is preferable that the total amount is the said range.

<<有機溶劑>> <<Organic solvent>>

本發明的著色組成物較佳為含有至少一種有機溶劑。 The colored composition of the present invention preferably contains at least one organic solvent.

有機溶劑只要可滿足並存的各成分的溶解性或製成著色組成物時的塗佈性，則基本上無特別限制，尤其較佳為考慮到黏合劑的溶解性、塗佈性、安全性而選擇。 The organic solvent is not particularly limited as long as it satisfies the solubility of each component and the coating property when the coloring composition is formed, and it is particularly preferable to consider the solubility, coatability, and safety of the binder. select.

有機溶劑可使用酯類、醚類、酮類、芳香族烴類，具體可例示日本專利特開2012-032754號公報的段落編號0161~段落編號0162中記載的溶劑。 As the organic solvent, esters, ethers, ketones, and aromatic hydrocarbons can be used. Specific examples thereof include the solvents described in Paragraph No. 0161 to Paragraph No. 0162 of JP-A-2012-032754.

就上文所述的各成分的溶解性、及含有鹼可溶性聚合物的情形時的其溶解性、塗佈表面狀態的改良等觀點而言，該些有機溶劑亦較佳為混合兩種以上。於該情形時，尤佳為由選自以下溶劑中的兩種以上所構成的混合溶液：3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙基溶纖劑乙酸酯、乳酸乙酯、二乙二醇二甲醚、乙酸丁酯、3-甲氧基丙酸甲酯、2-庚酮、環己酮、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇甲醚及丙二醇甲醚乙酸酯。 The organic solvent is preferably mixed in two or more kinds from the viewpoints of the solubility of each component described above, the solubility in the case of containing an alkali-soluble polymer, and the improvement of the coating surface state. In this case, a mixed solution composed of two or more selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl cellosolve B is particularly preferred. Acid ester, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl card Alcohol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate.

有機溶劑於著色組成物中的含量較佳為組成物中的總 固體成分濃度成為10質量%~80質量%的量，更佳為成為15質量%~60質量%的量。 The content of the organic solvent in the coloring composition is preferably the total amount in the composition The solid content concentration is from 10% by mass to 80% by mass, more preferably from 15% by mass to 60% by mass.

本發明的組成物可僅含有一種有機溶劑，亦可含有兩種以上。於含有兩種以上的情形時，較佳為其合計量成為所述範圍。 The composition of the present invention may contain only one kind of organic solvent, and may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

<<鹼可溶性黏合劑>> <<Alkali Soluble Binder>>

本發明的著色組成物較佳為含有鹼可溶性黏合劑。鹼可溶性黏合劑除了具有鹼可溶性以外，並無特別限定，較佳為自耐熱性、顯影性、獲取性等觀點而選擇。 The colored composition of the present invention preferably contains an alkali-soluble binder. The alkali-soluble binder is not particularly limited as long as it has alkali solubility, and is preferably selected from the viewpoints of heat resistance, developability, and availability.

鹼可溶性黏合劑較佳為線狀有機高分子聚合物，且可溶於有機溶劑中，可利用弱鹼性水溶液來進行顯影者。此種線性有機高分子聚合物可列舉：側鏈上具有羧酸的聚合物，例如日本專利特開昭59-44615號、日本專利特公昭54-34327號、日本專利特公昭58-12577號、日本專利特公昭54-25957號、日本專利特開昭59-53836號、日本專利特開昭59-71048號的各公報中記載般的甲基丙烯酸共聚物、丙烯酸共聚物、衣康酸共聚物、丁烯酸共聚物、馬來酸共聚物、部分酯化馬來酸共聚物等，同樣地於側鏈上具有羧酸的酸性纖維素衍生物有用。 The alkali-soluble binder is preferably a linear organic high molecular polymer, and is soluble in an organic solvent, and can be developed by using a weakly alkaline aqueous solution. Examples of such a linear organic high molecular polymer include a polymer having a carboxylic acid in a side chain, for example, Japanese Patent Laid-Open No. Sho 59-44615, Japanese Patent Publication No. Sho 54-34327, and Japanese Patent Publication No. Sho 58-12577. A methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer as described in each of the publications of Japanese Patent Laid-Open Publication No. Sho 54-25957, JP-A-59-53836, and JP-A-59-71048 A crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer or the like is similarly useful as an acidic cellulose derivative having a carboxylic acid in a side chain.

除了所述鹼可溶性黏合劑以外，作為本發明的鹼可溶性黏合劑，於具有羥基的聚合物上加成酸酐而成者等、或聚羥基苯乙烯系樹脂、聚矽氧烷系樹脂、聚((甲基)丙烯酸-2-羥基乙酯)、聚乙烯基吡咯啶酮或聚環氧乙烷、聚乙烯醇等亦有用。另外，線狀有機高分子聚合物亦可為使具有親水性的單體進行共聚合而成 者。其例子可列舉：(甲基)丙烯酸烷氧基烷基酯、(甲基)丙烯酸羥基烷基酯、甘油(甲基)丙烯酸酯、(甲基)丙烯醯胺、N-羥甲基丙烯醯胺、二級或三級的烷基丙烯醯胺、(甲基)丙烯酸二烷基胺基烷基酯、嗎啉(甲基)丙烯酸酯、N-乙烯基吡咯啶酮、N-乙烯基己內醯胺、乙烯基咪唑、乙烯基***、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、分支或直鏈的(甲基)丙烯酸丙酯、分支或直鏈的(甲基)丙烯酸丁酯或(甲基)丙烯酸苯氧基羥基丙酯等。除此以外，作為具有親水性的單體，含有四氫糠基、磷酸基、磷酸酯基、四級銨鹽基、伸乙氧基鏈、伸丙氧基鏈、磺酸基及來源於其鹽的基團、嗎啉基乙基等而成的單體等亦有用。 In addition to the alkali-soluble binder, the alkali-soluble binder of the present invention is obtained by adding an acid anhydride to a polymer having a hydroxyl group, or a polyhydroxystyrene resin, a polyoxyalkylene resin, or a poly( (2-hydroxyethyl (meth)acrylate), polyvinylpyrrolidone or polyethylene oxide, polyvinyl alcohol and the like are also useful. In addition, the linear organic high molecular polymer may also be obtained by copolymerizing a monomer having hydrophilicity. By. Examples thereof include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, glycerol (meth) acrylate, (meth) acrylamide, and N-methylol propylene oxime. Amine, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinyl pyrrolidone, N-vinyl hexanyl Indoleamine, vinylimidazole, vinyltriazole, methyl (meth)acrylate, ethyl (meth)acrylate, branched or linear propyl (meth)acrylate, branched or linear (methyl Butyl acrylate or phenoxy hydroxypropyl (meth) acrylate or the like. In addition, as a hydrophilic monomer, it contains a tetrahydroindenyl group, a phosphoric acid group, a phosphate group, a quaternary ammonium salt group, an extended ethoxy chain, a propoxy chain, a sulfonic acid group, and a derived therefrom. A monomer such as a salt group or a morpholinylethyl group is also useful.

鹼可溶性黏合劑亦可較佳地使用下述式(b1)及式(b2)所示般的馬來醯亞胺與環氧乙烷的共聚物。 As the alkali-soluble binder, a copolymer of maleimide and ethylene oxide represented by the following formula (b1) and formula (b2) can be preferably used.

(式(b1)中，R1表示氫原子、芳基或烷基) (In the formula (b1), R 1 represents a hydrogen atom, an aryl group or an alkyl group)

R1表示烷基的情形的烷基可列舉：碳數1~10的直鏈狀烷基、碳數3~10的具有分支鏈的烷基、碳數5~20的環狀烷基等，更具體可列舉甲基、乙基、第三丁基、環己基等。 Examples of the alkyl group in the case where R 1 represents an alkyl group include a linear alkyl group having 1 to 10 carbon atoms, an alkyl group having a branched chain of 3 to 10 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. More specifically, a methyl group, an ethyl group, a tributyl group, a cyclohexyl group, etc. are mentioned.

烷基亦可具有取代基，可導入至烷基中的取代基可列舉苯基、羰基、烷氧基、羥基、胺基等。 The alkyl group may have a substituent, and examples of the substituent which may be introduced into the alkyl group include a phenyl group, a carbonyl group, an alkoxy group, a hydroxyl group, an amine group and the like.

R1表示芳基的情形的芳基可列舉：單環結構的芳基、多環結構的芳基、縮環結構的芳基、含雜原子的雜芳基等。更具體可列舉：苯基、萘基、聯苯基、苯并咪唑基、吡啶基、呋喃基等。 Examples of the aryl group in the case where R 1 represents an aryl group include an aryl group having a monocyclic structure, an aryl group having a polycyclic structure, an aryl group having a condensed ring structure, a heteroaryl group containing a hetero atom, and the like. More specifically, a phenyl group, a naphthyl group, a biphenyl group, a benzimidazolyl group, a pyridyl group, a furyl group, etc. are mentioned.

芳基亦可具有取代基，可導入至芳基中的取代基可列舉：甲基、乙基、第三丁基、環己基等烷基，甲氧基等烷氧基，羧基，羥基，胺基，硝基，氯基，溴基等。 The aryl group may have a substituent, and the substituent which may be introduced into the aryl group may, for example, be an alkyl group such as a methyl group, an ethyl group, a tributyl group or a cyclohexyl group, an alkoxy group such as a methoxy group, a carboxyl group, a hydroxyl group or an amine group. Base, nitro, chloro, bromo and the like.

(式(b2)中，R2表示氫原子或甲基。R3為碳數2或3的伸烷基，R4表示氫原子、芳基或烷基，m表示1~15的整數) (In the formula (b2), R 2 represents a hydrogen atom or a methyl group. R 3 is an alkylene group having 2 or 3 carbon atoms, R 4 represents a hydrogen atom, an aryl group or an alkyl group, and m represents an integer of 1 to 15)

R4表示烷基的情形的烷基可列舉：碳數1~20的直鏈狀烷基、碳數1~20的具有分支鏈的烷基、碳數5~20的環狀烷基等，更具體可列舉：甲基、乙基、第三丁基、環己基、2-乙基己基等。 Examples of the alkyl group in the case where R 4 represents an alkyl group include a linear alkyl group having 1 to 20 carbon atoms, an alkyl group having a branched chain of 1 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. More specifically, a methyl group, an ethyl group, a tert-butyl group, a cyclohexyl group, a 2-ethylhexyl group, etc. are mentioned.

烷基亦可具有取代基，可導入至烷基中的取代基可列舉苯基、羰基、烷氧基等。 The alkyl group may have a substituent, and examples of the substituent which may be introduced into the alkyl group include a phenyl group, a carbonyl group, an alkoxy group and the like.

R4表示芳基的情形的芳基可列舉：單環結構的芳基、多環結 構的芳基、縮環結構的芳基、含雜原子的雜芳基等。更具體可列舉：苯基、萘基、蒽基、聯苯基、苯并咪唑基、吲哚基、咪唑基、噁唑基、咔唑基、吡啶基、呋喃基等。 Examples of the aryl group in the case where R 4 represents an aryl group include an aryl group having a monocyclic structure, an aryl group having a polycyclic structure, an aryl group having a condensed ring structure, a heteroaryl group containing a hetero atom, and the like. More specifically, a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, a benzimidazolyl group, a fluorenyl group, an imidazolyl group, an oxazolyl group, a carbazolyl group, a pyridyl group, a furyl group, etc. are mentioned.

芳基亦可具有取代基，可導入至芳基中的取代基可列舉：壬基、甲基、乙基、第三丁基、環己基等烷基，甲氧基等烷氧基，羧基，羥基，胺基，硝基，氯基，溴基等。 The aryl group may have a substituent, and examples of the substituent which may be introduced into the aryl group include an alkyl group such as a mercapto group, a methyl group, an ethyl group, a tributyl group, and a cyclohexyl group; an alkoxy group such as a methoxy group; and a carboxyl group; Hydroxy, amine, nitro, chloro, bromo and the like.

另外，為了提高交聯效率，鹼可溶性黏合劑亦可於側鏈上具有聚合性基，例如側鏈上含有烯丙基、(甲基)丙烯酸基、烯丙氧基烷基等的聚合物等亦有用。上文所述含有聚合性基的聚合物的例子可列舉：市售品的KS抗蝕劑(KS Resist)-106(大阪有機化學工業(股)製造)、賽克羅馬(Cyclomer)P系列(大賽璐(Daicel)化學工業(股)製造)等。另外，為了提高硬化皮膜的強度，醇可溶性尼龍或2,2-雙-(4-羥基苯基)-丙烷與表氯醇的聚醚等亦有用。 Further, in order to improve the crosslinking efficiency, the alkali-soluble binder may have a polymerizable group in the side chain, for example, a polymer having an allyl group, a (meth)acrylic group, an allyloxyalkyl group or the like in the side chain. Also useful. Examples of the polymerizable group-containing polymer described above include a commercially available KS resist (KS Resist)-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and a Cyclomer P series ( Daicel Chemical Manufacturing Co., Ltd., etc. Further, in order to increase the strength of the hardened film, alcohol-soluble nylon or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin or the like is also useful.

該些各種鹼可溶性黏合劑中，就耐熱性的觀點而言，較佳為聚羥基苯乙烯系樹脂、聚矽氧烷系樹脂、丙烯酸系樹脂、丙烯醯胺系樹脂、丙烯酸/丙烯醯胺共聚物樹脂，就控制顯影性的觀點而言，較佳為丙烯酸系樹脂、丙烯醯胺系樹脂、丙烯酸/丙烯醯胺共聚物樹脂。 Among these various alkali-soluble binders, polyhydroxystyrene resin, polyoxyalkylene resin, acrylic resin, acrylamide resin, acrylic acid/acrylamide copolymerization are preferred from the viewpoint of heat resistance. The resin is preferably an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin from the viewpoint of controlling developability.

尤其較佳為具有下述通式(2)所示般的重複單元及酸性基的共聚物，更佳可列舉除了通式(2)及酸性基以外還具有通式(3)所表示的結構單元的共聚物。 In particular, a copolymer having a repeating unit and an acidic group represented by the following formula (2) is preferable, and a structure represented by the formula (3) in addition to the formula (2) and the acidic group is more preferable. Copolymer of the unit.

(通式(2)中，R20表示氫原子或甲基，R21~R25分別獨立地表示氫原子、鹵素原子、氰基、烷基或芳基) (In the formula (2), R 20 represents a hydrogen atom or a methyl group, and R 21 to R 25 each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group)

(通式(3)中，R11表示氫原子或甲基。R12及R13分別獨立地表示氫原子或含有不飽和雙鍵作為部分結構的碳數3~20的羰基，R12及R13兩者為氫原子的情況不存在。於R12及R13的至少一個表示含有不飽和雙鍵作為部分結構的碳數3~20的羰基的情形時，亦可更含有羧基作為部分結構) (In the formula (3), R 11 represents a hydrogen atom or a methyl group. R 12 and R 13 each independently represent a hydrogen atom or a carbonyl group having a carbon number of 3 to 20 containing an unsaturated double bond as a partial structure, R 12 and R 13 When both of them are hydrogen atoms, when at least one of R 12 and R 13 represents a carbon group having 3 to 20 carbon atoms having an unsaturated double bond as a partial structure, a carboxyl group may be further contained as a partial structure)

丙烯酸系樹脂較佳為：包含選自(甲基)丙烯酸苄酯、(甲基)丙烯酸、(甲基)丙烯酸羥基乙酯、(甲基)丙烯醯胺等中的單體的共聚物，或市售品的KS抗蝕劑(KS Resist)-106(大阪有機化學工業(股)製造)、賽克羅馬(Cyclomer)P系列(大賽璐(Daicel) 化學工業(股)製造)等。 The acrylic resin is preferably a copolymer containing a monomer selected from the group consisting of benzyl (meth)acrylate, (meth)acrylic acid, hydroxyethyl (meth)acrylate, (meth)acrylamide, and the like, or Commercially available KS Resist-106 (Manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P Series (Daicel) Chemical industry (stock) manufacturing) and so on.

另外，鹼可溶性黏合劑亦可含有來源於下述式(X)所表示的乙烯性不飽和單量體的結構單元。 Further, the alkali-soluble binder may also contain a structural unit derived from an ethylenically unsaturated monomer represented by the following formula (X).

(式(X)中，R1表示氫原子或甲基，R2表示碳數2~10的伸烷基，R3表示氫原子或可含有苯環的碳數1~20的烷基。n表示1~15的整數) (In the formula (X), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 2 to 10 carbon atoms, and R 3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. Indicates an integer from 1 to 15)

所述式(X)中，R2的伸烷基的碳數較佳為2~3。另外，R3的烷基的碳數為1~20，更佳為1~10，R3的烷基亦可含有苯環。R3所表示的含有苯環的烷基可列舉苄基、2-苯基(異)丙基等。 In the formula (X), the alkyl group of R 2 preferably has 2 to 3 carbon atoms. Further, the alkyl group of R 3 has a carbon number of 1 to 20, more preferably 1 to 10, and the alkyl group of R 3 may further contain a benzene ring. The benzene ring-containing alkyl group represented by R 3 may, for example, be a benzyl group or a 2-phenyl(iso)propyl group.

就顯影性、液體黏度等觀點而言，鹼可溶性黏合劑較佳為重量平均分子量(利用GPC法測定的聚苯乙烯換算值)為1,000~200,000的聚合物，更佳為2,000~100,000的聚合物，尤佳為5,000~50,000的聚合物。 The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1,000 to 200,000, more preferably 2,000 to 100,000, from the viewpoints of developability, liquid viscosity, and the like. Particularly preferred is a polymer of 5,000 to 50,000.

鹼可溶性黏合劑的調配量較佳為著色組成物的總固體成分的10質量%~80質量%，更佳為20質量%~60質量%。 The amount of the alkali-soluble binder to be added is preferably from 10% by mass to 80% by mass, and more preferably from 20% by mass to 60% by mass based on the total solid content of the coloring composition.

另外，鹼可溶性黏合劑的酸值較佳為10mg/KOH~1000mg/KOH，更佳為50mg/KOH~300mg/KOH，進而佳為50mg/KOH ~200mg/KOH，尤佳為105mg/KOH~200mg/KOH。 Further, the acid value of the alkali-soluble binder is preferably from 10 mg/KOH to 1000 mg/KOH, more preferably from 50 mg/KOH to 300 mg/KOH, and further preferably from 50 mg/KOH. ~200 mg / KOH, particularly preferably 105 mg / KOH ~ 200 mg / KOH.

本發明的組成物可僅含有一種鹼可溶性黏合劑，亦可含有兩種以上。於含有兩種以上的情形時，較佳為其合計量成為所述範圍。 The composition of the present invention may contain only one alkali-soluble binder, and may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

<<交聯劑>> <<Crosslinker>>

本發明的著色組成物亦可更含有交聯劑。 The colored composition of the present invention may further contain a crosslinking agent.

交聯劑只要可藉由交聯反應來進行膜硬化，則並無特別限定，例如可列舉：(a)環氧樹脂；(b)經選自羥甲基、烷氧基甲基及醯氧基甲基中的至少一個取代基所取代的三聚氰胺化合物、胍胺化合物、甘脲化合物或脲化合物；(c)經選自羥甲基、烷氧基甲基及醯氧基甲基中的至少一個取代基取代的苯酚化合物、萘酚化合物或羥基蒽化合物。其中，較佳為多官能環氧樹脂。 The crosslinking agent is not particularly limited as long as it can be cured by a crosslinking reaction, and examples thereof include (a) an epoxy resin; and (b) a selected from the group consisting of a methylol group, an alkoxymethyl group, and an anthracene oxygen group. a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent in the methyl group; (c) at least selected from the group consisting of a methylol group, an alkoxymethyl group and a decyloxymethyl group A substituted phenol compound, a naphthol compound or a hydroxy hydrazine compound. Among them, a polyfunctional epoxy resin is preferred.

關於交聯劑的具體例等詳細情況，可參照日本專利特開2004-295116號公報的段落0134~段落0147的記載，將其內容併入至本說明書中。 For details of specific examples of the crosslinking agent, etc., the descriptions of paragraphs 0134 to 0147 of JP-A-2004-295116 can be referred to, and the contents thereof are incorporated herein by reference.

<<界面活性劑>> <<Interfacial active agent>>

本發明的著色組成物亦可含有界面活性劑。界面活性劑可為非離子系、陽離子系、陰離子系的任一種，較佳為具有環氧乙烷結構的界面活性劑、含氟界面活性劑。尤其較佳為親水親油平衡(Hydrophile-Lipophile Balance，HLB)值在9.2~15.5的範圍內的具有環氧乙烷結構的界面活性劑或日本專利特開平2-54202號公報記載的氟系界面活性劑。 The colored composition of the present invention may also contain a surfactant. The surfactant may be any of a nonionic, cationic or anionic system, and is preferably a surfactant having an ethylene oxide structure or a fluorine-containing surfactant. In particular, a surfactant having an ethylene oxide structure having a Hydrophile-Lipophile Balance (HLB) value of 9.2 to 15.5 or a fluorine-based interface described in JP-A No. 2-54202 is preferred. Active agent.

於本發明的著色組成物中含有界面活性劑的情形時，相對於著色組成物的總固體成分，界面活性劑的添加量較佳為0.0001質量%~2.0質量%，更佳為0.005質量%~1.0質量%。 When the coloring composition of the present invention contains a surfactant, the amount of the surfactant added is preferably 0.0001% by mass to 2.0% by mass, more preferably 0.005% by mass, based on the total solid content of the coloring composition. 1.0% by mass.

本發明的組成物可僅含有一種界面活性劑，亦可含有兩種以上。於含有兩種以上的情形時，較佳為其合計量成為所述範圍。 The composition of the present invention may contain only one type of surfactant, and may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

本發明的著色組成物進而視需要亦可含有熱酸產生劑、填充材料、抗氧化劑、紫外線吸收劑、抗凝聚劑、增感劑或光穩定劑等各種添加劑。 The colored composition of the present invention may further contain various additives such as a thermal acid generator, a filler, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, a sensitizer, or a light stabilizer, as needed.

<<熱酸產生劑>> <<Thermal acid generator>>

酸產生劑可於抗蝕劑膜中藉由產生酸而將因鹼顯影滲透至膜中的鹼中和，更有效地抑制染料陽離子與相對陰離子X的解離。 The acid generator can neutralize the alkali which is infiltrated into the film by alkali development in the resist film by generating an acid, and more effectively suppress the dissociation of the dye cation from the relative anion X.

酸產生劑較佳為熱酸產生劑。熱酸產生劑中包括離子性化合物及非離子性化合物。 The acid generator is preferably a thermal acid generator. The thermal acid generator includes an ionic compound and a nonionic compound.

離子性化合物較佳為不含重金屬或鹵素離子。離子性的熱酸產生劑例如可列舉：三苯基鋶、1-二甲硫基萘、1-二甲硫基-4-羥基萘、1-二甲硫基-4,7-二羥基萘、4-羥基苯基二甲基鋶、苄基-4-羥基苯基甲基鋶、2-甲基苄基-4-羥基苯基甲基鋶、2-甲基苄基-4-乙醯基苯基甲基鋶、2-甲基苄基-4-苯甲醯氧基苯基甲基鋶、該些化合物的甲磺酸鹽、三氟甲磺酸鹽、樟腦磺酸鹽、對甲苯磺酸鹽、六氟膦酸鹽等。 The ionic compound is preferably free of heavy metals or halide ions. Examples of the ionic thermal acid generator include triphenylsulfonium, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, and 1-dimethylthio-4,7-dihydroxynaphthalene. , 4-hydroxyphenyldimethylhydrazine, benzyl-4-hydroxyphenylmethylhydrazine, 2-methylbenzyl-4-hydroxyphenylmethylhydrazine, 2-methylbenzyl-4-acetamidine Phenylmethyl hydrazine, 2-methylbenzyl-4-benzylideneoxyphenylmethyl hydrazine, mesylate salt of these compounds, triflate, camphor sulfonate, p-toluene Sulfonate, hexafluorophosphonate, and the like.

較佳的脂肪族磺酸及/或芳香族磺酸可列舉：對甲苯磺酸(PTS)、苯磺酸(BS)、對十二烷基苯磺酸(DBS)、對氯苯磺酸 (CBS)、1,4-萘二磺酸(NDS)、甲磺酸(MsOH)、九氟丁烷-1-磺酸(NFBS)等，均可較佳地使用。所述括弧內的記載表示簡稱。 Preferred aliphatic sulfonic acids and/or aromatic sulfonic acids include p-toluenesulfonic acid (PTS), benzenesulfonic acid (BS), p-dodecylbenzenesulfonic acid (DBS), and p-chlorobenzenesulfonic acid. (CBS), 1,4-naphthalene disulfonic acid (NDS), methanesulfonic acid (MsOH), nonafluorobutane-1-sulfonic acid (NFBS), and the like can be preferably used. The description in the brackets indicates an abbreviation.

非離子性的熱酸產生劑例如可列舉：含鹵素的化合物、重氮甲烷化合物、碸化合物、磺酸酯化合物、羧酸酯化合物、磷酸酯化合物、磺醯亞胺化合物、磺苯并***化合物等。該些化合物中，尤其較佳為磺醯亞胺化合物。 Examples of the nonionic thermal acid generator include a halogen-containing compound, a diazomethane compound, a hydrazine compound, a sulfonate compound, a carboxylate compound, a phosphate compound, a sulfonimide compound, and a sulfotriazole. Compounds, etc. Among these compounds, a sulfonimide compound is particularly preferred.

磺醯亞胺化合物例如可列舉：N-(三氟甲基磺醯氧基)丁二醯亞胺(商品名「SI-105」，綠化學公司)、N-(樟腦磺醯氧基)丁二醯亞胺(商品名「SI-106」，綠化學公司)、N-(4-甲基苯基磺醯氧基)丁二醯亞胺(商品名「SI-101」，綠化學公司)、N-(2-三氟甲基苯基磺醯氧基)丁二醯亞胺、N-(4-氟苯基磺醯氧基)丁二醯亞胺、N-(三氟甲基磺醯氧基)鄰苯二甲醯亞胺、N-(樟腦磺醯氧基)鄰苯二甲醯亞胺、N-(2-三氟甲基苯基磺醯氧基)鄰苯二甲醯亞胺、N-(2-氟苯基磺醯氧基)鄰苯二甲醯亞胺、N-(三氟甲基磺醯氧基)二苯基馬來醯亞胺(商品名「PI-105」，綠化學公司)、N-(樟腦磺醯氧基)二苯基馬來醯亞胺、4-甲基苯基磺醯氧基)二苯基馬來醯亞胺、N-(2-三氟甲基苯基磺醯氧基)二苯基馬來醯亞胺、N-(4-氟苯基磺醯氧基)二苯基馬來醯亞胺、N-(4-氟苯基磺醯氧基)二苯基馬來醯亞胺、N-(苯基磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺(商品名「NDI-100」，綠化學公司)、N-(4-甲基苯基磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺(商品名「NDI-101」，綠化學公司)、N-(三氟甲烷磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺(商品 名「NDI-105」，綠化學公司)、N-(九氟丁烷磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺(商品名「NDI-109」，綠化學公司)、N-(樟腦磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺(商品名「NDI-106」，綠化學公司)、N-(樟腦磺醯氧基)-7-氧雜雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(三氟甲基磺醯氧基)-7-氧雜雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4-甲基苯基磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4-甲基苯基磺醯氧基)-7-氧雜雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2-三氟甲基苯基磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2-三氟甲基苯基磺醯氧基)-7-氧雜雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4-氟苯基磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4-氟苯基磺醯氧基)-7-氧雜雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(三氟甲基磺醯氧基)雙環[2.2.1]庚烷-5,6-氧基-2,3-二羧基醯亞胺、N-(樟腦磺醯氧基)雙環[2.2.1]庚烷-5,6-氧基-2,3-二羧基醯亞胺、N-(4-甲基苯基磺醯氧基)雙環[2.2.1]庚烷-5,6-氧基-2,3-二羧基醯亞胺、N-(2-三氟甲基苯基磺醯氧基)雙環[2.2.1]庚烷-5,6-氧基-2,3-二羧基醯亞胺、N-(4-氟苯基磺醯氧基)雙環[2.2.1]庚烷-5,6-氧基-2,3-二羧基醯亞胺、N-(三氟甲基磺醯氧基)萘基二羧基醯亞胺(商品名「NAI-105」，綠化學公司)、N-(樟腦磺醯氧基)萘基二羧基醯亞胺(商品名「NAI-106」，綠化學公司)、N-(4-甲基苯基磺醯氧基)萘基二羧基醯亞胺(商品名「NAI-101」，綠化學公司)、N-(苯基磺醯氧基)萘基二羧基醯亞胺(商品名「NAI-100」，綠化學公司)、 N-(2-三氟甲基苯基磺醯氧基)萘基二羧基醯亞胺、N-(4-氟苯基磺醯氧基)萘基二羧基醯亞胺、N-(五氟乙基磺醯氧基)萘基二羧基醯亞胺、N-(七氟丙基磺醯氧基)萘基二羧基醯亞胺、N-(九氟丁基磺醯氧基)萘基二羧基醯亞胺(商品名「NAI-109」，綠化學公司)、N-(乙基磺醯氧基)萘基二羧基醯亞胺、N-(丙基磺醯氧基)萘基二羧基醯亞胺、N-(丁基磺醯氧基)萘基二羧基醯亞胺(商品名「NAI-1004」，綠化學公司)、N-(戊基磺醯氧基)萘基二羧基醯亞胺、N-(己基磺醯氧基)萘基二羧基醯亞胺、N-(庚基磺醯氧基)萘基二羧基醯亞胺、N-(辛基磺醯氧基)萘基二羧基醯亞胺、N-(壬基磺醯氧基)萘基二羧基醯亞胺等。 Examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy)butaneimine (trade name "SI-105", Green Chemical Co., Ltd.), and N-(camphorsulfonyloxy) butyl Diimine (trade name "SI-106", Green Chemical Company), N-(4-methylphenylsulfonyloxy) butadiene imide (trade name "SI-101", Green Chemical Company) , N-(2-trifluoromethylphenylsulfonyloxy)butaneimine, N-(4-fluorophenylsulfonyloxy)butaneimine, N-(trifluoromethylsulfonate醯oxy)phthalic acid imide, N-(camphorsulfonyloxy) phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalic acid Imine, N-(2-fluorophenylsulfonyloxy) phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide (trade name "PI- 105", Green Chemical Company), N-(camphorsulfonyloxy)diphenylmaleimide, 4-methylphenylsulfonyloxy)diphenylmaleimide, N-(2 -trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(4-fluorobenzene Sulfosulfonyloxy)diphenylmaleimide, N-(phenylsulfonyloxy) double [2.2.1] G--5-ene-2,3-dicarboxy quinone imine (trade name "NDI-100", Green Chemical Co., Ltd.), N-(4-methylphenylsulfonyloxy) bicyclo [ 2.2.1] G--5-ene-2,3-dicarboxy quinone imine (trade name "NDI-101", Green Chemical Company), N-(trifluoromethanesulfonyloxy) bicyclo [2.2.1] Gh-5-ene-2,3-dicarboxy quinone imine (commodity "NDI-105", Green Chemical Company), N-(nonafluorobutanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine (trade name "NDI" -109", Green Chemical Co., Ltd., N-(camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine (trade name "NDI-106", Green Chemistry Company), N-(camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-(trifluoromethylsulfonyloxy) - 7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine, N-(4-methylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-(2-trifluoro Methylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4-fluorophenylsulfonyloxy)bicyclo [2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-di Base imine, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxy quinone imine, N-(4-methylphenyl sulfonate醯oxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxy quinone imine, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2. 1] heptane-5,6-oxy-2,3-dicarboxy quinone imine, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxyl -2,3-dicarboxy quinone imine, N-(trifluoromethylsulfonyloxy)naphthyl dicarboxy quinone imine (trade name "NAI-105", Green Chemical Company), N-( camphor sulfonate) Oxy)naphthyldicarboxy quinone imine (trade name "NAI-106", Green Chemical Co., Ltd.), N-(4-methylphenylsulfonyloxy)naphthyldicarboxy quinone imine (trade name "NAI" -101", Green Chemical Co., Ltd.), N-(phenylsulfonyloxy)naphthyldicarboxyimine (trade name "NAI-100", Green Chemical Co., Ltd.), N-(2-trifluoromethylphenylsulfonyloxy)naphthyldicarboxy quinone imine, N-(4-fluorophenylsulfonyloxy)naphthyldicarboxy quinone imine, N-(pentafluoro Ethylsulfonyloxy)naphthyldicarboxyarsenine, N-(heptafluoropropylsulfonyloxy)naphthyldicarboxyanilide, N-(nonafluorobutoxysulfonyloxy)naphthyl Carboxylimine (trade name "NAI-109", Green Chemical Co., Ltd.), N-(ethylsulfonyloxy)naphthyldicarboxyimine, N-(propylsulfonyloxy)naphthyldicarboxyl Yttrium, N-(butylsulfonyloxy)naphthyldicarboxy quinone imine (trade name "NAI-1004", Green Chemical Company), N-(pentylsulfonyloxy)naphthyldicarboxyfluorene Imine, N-(hexylsulfonyloxy)naphthyldicarboxy quinone imine, N-(heptylsulfonyloxy)naphthyldicarboxy quinone imine, N-(octylsulfonyloxy)naphthyl Dicarboxy quinone imine, N-(decyl sulfonyloxy) naphthyl dicarboxy quinone imine, and the like.

其他熱酸產生劑例如可列舉：1-(4-正丁氧基萘-1-基)四氫噻吩鎓三氟甲磺酸鹽、1-(4,7-二丁氧基-1-萘基)四氫噻吩鎓三氟甲磺酸鹽等四氫噻吩鎓鹽。 Examples of other thermal acid generators include 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate and 1-(4,7-dibutoxy-1-naphthalene). A tetrahydrothiophene sulfonium salt such as tetrahydrothiophene trifluoromethanesulfonate.

該些熱酸產生劑中，就鹼可溶性樹脂的硬化反應的觸媒作用的方面而言，更佳為苄基-4-羥基苯基甲基鋶六氟磷酸鹽、1-(4,7-二丁氧基-1-萘基)四氫噻吩鎓三氟甲磺酸鹽、N-(三氟甲基磺醯氧基)萘基二羧基醯亞胺。 Among the thermal acid generators, in terms of the catalytic action of the hardening reaction of the alkali-soluble resin, benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate and 1-(4,7- are more preferable. Dibutoxy-1-naphthyl)tetrahydrothiophene fluorene triflate, N-(trifluoromethylsulfonyloxy)naphthyldicarboxy quinone imine.

熱酸產生劑可單獨使用或混合使用兩種以上。相對於著色組成物的總固體成分，熱酸產生劑的含量較佳為0.001質量%~5.0質量%，更佳為0.01質量%~3.0質量%。 The thermal acid generator may be used singly or in combination of two or more. The content of the thermal acid generator is preferably 0.001% by mass to 5.0% by mass, and more preferably 0.01% by mass to 3.0% by mass based on the total solid content of the coloring composition.

<<染料穩定劑>> <<Dye Stabilizer>>

本發明的組成物中，較佳為除了染料陽離子以外添加染料穩 定劑。穩定劑例如可使用陽離子系、陰離子系、非離子系、兩性、矽酮系、氟系等的界面活性劑。界面活性劑中，就可均勻地微細地分散的方面而言，較佳為高分子界面活性劑(高分子分散劑)。 In the composition of the present invention, it is preferred to add a dye in addition to the dye cation. A fixative. As the stabilizer, for example, a surfactant such as a cationic system, an anionic system, a nonionic system, an amphoteric, an anthrone or a fluorine-based surfactant can be used. Among the surfactants, a polymer surfactant (polymer dispersant) is preferred in terms of being uniformly finely dispersed.

高分子分散劑例如可列舉：聚丙烯酸酯等不飽和羧酸酯的(共)聚合物類；聚丙烯酸等不飽和羧酸的(共)聚合物的(部分)胺鹽、(部分)銨鹽或(部分)烷基胺鹽類；含羥基的聚丙烯酸酯等含羥基的不飽和羧酸酯的(共)聚合物或該等的編成物；具有交聯性基的磺酸或磷酸的聚合物等。 Examples of the polymer dispersant include (co)polymers of unsaturated carboxylic acid esters such as polyacrylate; (partial) amine salts and (partial) ammonium salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid. Or (partially) alkylamine salts; (co)polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates or such sizing agents; polymerization of sulfonic acid or phosphoric acid having crosslinkable groups Things and so on.

交聯性基可使用可藉由自由基、酸、熱而進行交聯的交聯性基。具體可列舉：(甲基)丙烯酸基、苯乙烯基、乙烯基、環狀醚基、羥甲基，較佳為(甲基)丙烯酸基、苯乙烯基、乙烯基，更佳為(甲基)丙烯酸基及苯乙烯基。 As the crosslinkable group, a crosslinkable group which can be crosslinked by a radical, an acid or a heat can be used. Specific examples thereof include a (meth)acrylic group, a styryl group, a vinyl group, a cyclic ether group, and a methylol group, preferably a (meth)acrylic group, a styryl group, a vinyl group, and more preferably a (methyl group). ) Acrylic and styryl groups.

另外，除了該些界面活性劑以外，添加雙三氟甲磺醯亞胺鈉鹽或下述陰離子的鹽(鈉鹽、鉀鹽等)亦有效。 Further, in addition to the surfactants, addition of a sodium bistrifluoromethanesulfonimide salt or a salt of the following anion (sodium salt, potassium salt, etc.) is also effective.

<抗氧化劑> <antioxidant>

本發明的組成物亦可含有抗氧化劑。抗氧化劑例如可列舉：自由基捕捉劑、過氧化物分解劑、紫外線吸收劑、單重態氧淬滅劑等。 The composition of the present invention may also contain an antioxidant. Examples of the antioxidant include a radical scavenger, a peroxide decomposer, an ultraviolet absorber, and a singlet oxygen quencher.

自由基捕捉劑例如可列舉：酚系抗氧化劑、受阻胺系抗氧化劑等。酚系抗氧化劑例如可列舉：羥基苯基丙酸酯系化合物、羥基苄基系化合物、硫代雙酚系化合物、硫代甲基酚系化合物、烷烴二基酚系化合物等。其中，就顏色特性的穩定性的觀點而言，較佳為羥基苯基丙酸酯系化合物。 Examples of the radical scavenger include a phenol-based antioxidant and a hindered amine-based antioxidant. Examples of the phenolic antioxidant include a hydroxyphenylpropionate compound, a hydroxybenzyl compound, a thiobisphenol compound, a thiomethylphenol compound, and an alkanediylphenol compound. Among them, from the viewpoint of stability of color characteristics, a hydroxyphenylpropionate-based compound is preferred.

過氧化物分解劑為將因暴露於光下等而產生的過氧化物分解成無害的物質、不產生新的自由基的化合物，例如可列舉磷系抗氧化劑、硫系抗氧化劑等。其中，就顏色特性的穩定性的觀點而言，較佳為硫系抗氧化劑。 The peroxide decomposing agent is a compound which decomposes the peroxide generated by exposure to light or the like into a harmless substance and does not generate a new radical. Examples thereof include a phosphorus-based antioxidant and a sulfur-based antioxidant. Among them, a sulfur-based antioxidant is preferred from the viewpoint of stability of color characteristics.

紫外線吸收劑例如可列舉：水楊酸酯系抗氧化劑、二苯甲酮系抗氧化劑。 Examples of the ultraviolet absorber include a salicylate-based antioxidant and a benzophenone-based antioxidant.

單重態氧淬滅劑為可藉由自單重態狀態的氧的能量移動使單重態氧失活的化合物，例如可列舉：四甲基乙烯、環戊烯等乙烯性化合物；二乙胺、三乙胺、1,4-二氮雜雙環辛烷(1,4-Diazabicyclooctane，DABCO)、N-乙基咪唑等胺類；可經取代的萘、二甲基萘、二甲氧基蒽、蒽、二苯基蒽等縮合多環芳香族化合物；1,3-二苯基異苯并呋喃、1,2,3,4-四苯基-1,3-環戊二烯、五苯基環戊二烯等芳香族化合物，除此以外可列舉：哈利H.沃瑟曼(Harry H.wasserman)的「單重態氧(Singlet Oxygen)」(5章， 學術出版社(Academic Press)(1979))、尼古拉斯J.塔羅(Nicholas J.Turro)的「現代分子光化學(Modern Molecular Photochemistry)」(14章，本傑明/卡明斯出版公司(The Benjamin Cummings Publishing Co.,Inc.)(1978))、及CMC公司發行的「彩色照片感光材料用高功能化學品」(7章(2002))中作為單重態氧淬滅劑而例示的化合物。 The singlet oxygen quencher is a compound which can inactivate singlet oxygen by energy transfer of oxygen from a singlet state, and examples thereof include an ethylenic compound such as tetramethylethylene or cyclopentene; diethylamine and trisole; Amines such as ethylamine, 1,4-diazabicyclooctane (DABCO), N-ethylimidazole, etc.; substituted naphthalene, dimethylnaphthalene, dimethoxyanthracene, anthracene a condensed polycyclic aromatic compound such as diphenylphosphonium; 1,3-diphenylisobenzofuran, 1,2,3,4-tetraphenyl-1,3-cyclopentadiene, pentaphenyl ring An aromatic compound such as pentadiene may be exemplified by Harry H. Wasserman's "Singlet Oxygen" (Chapter 5, Academic Press (1979)), Nicholas J. Turro, "Modern Molecular Photochemistry" (Chapter 14, Benjamin Cummings, The Benjamin Cummings) Publishing Co., Inc. (1978)), and a compound exemplified as a singlet oxygen quencher in "High-performance chemicals for color photo-sensitive materials" (Chapter 7 (2002)) issued by CMC Corporation.

除此以外，可列舉以具有硫原子的化合物作為配位體的金屬錯合物。此種化合物可列舉：以雙二硫代-α-二酮、雙苯基二硫醇及硫代雙酚作為配位體的鎳錯合物、鈷錯合物、銅錯合物、錳錯合物、鉑錯合物等過渡金屬螯合化合物。 Other than this, a metal complex which has a compound having a sulfur atom as a ligand can be cited. Such a compound may be exemplified by a nickel complex, a cobalt complex, a copper complex, and an manganese wrong with bisdithio-α-diketone, bisphenyldithiol and thiobisphenol as ligands. Transition metal chelate compound such as a compound or a platinum complex.

硫系抗氧化劑可列舉硫代丙酸酯系化合物、巰基苯并咪唑系化合物。其中，就顏色特性的穩定性的觀點而言，較佳為硫代丙酸酯系化合物。 Examples of the sulfur-based antioxidant include a thiopropionate-based compound and a mercaptobenzimidazole-based compound. Among them, from the viewpoint of stability of color characteristics, a thiopropionate-based compound is preferred.

本發明中，抗氧化劑可單獨使用或混合使用兩種以上。相對於著色劑100質量，抗氧化劑的含量較佳為0.01質量份~20質量份，尤佳為0.1質量份~10質量份。 In the present invention, the antioxidant may be used singly or in combination of two or more. The content of the antioxidant is preferably from 0.01 part by mass to 20 parts by mass, particularly preferably from 0.1 part by mass to 10 parts by mass, per 100 parts by mass of the colorant.

<硬化劑> <hardener>

本發明的著色組成物可含有作為硬化劑而發揮功能的化合物。 The colored composition of the present invention may contain a compound that functions as a curing agent.

例如可使用：選自由芳香族胺化合物、三級胺化合物、胺鹽、鏻鹽、脒鹽、醯胺化合物、硫醇化合物、嵌段異氰酸酯化合物及含咪唑環的化合物所組成的組群中的至少一種化合物。 For example, a group selected from the group consisting of an aromatic amine compound, a tertiary amine compound, an amine salt, a phosphonium salt, a phosphonium salt, a guanamine compound, a thiol compound, a blocked isocyanate compound, and an imidazole ring-containing compound can be used. At least one compound.

藉由著色組成物含有此種硬化劑，可更有效地實現著色圖案的低溫硬化。並且可進一步提高著色組成物的保存穩定性。 By including such a hardening agent in the colored composition, the low-temperature hardening of the colored pattern can be more effectively achieved. Further, the storage stability of the colored composition can be further improved.

<抗還原劑> <anti-reducing agent>

本發明的著色組成物亦可添加較所述染料而更易被還原的化合物作為染料的抗還原劑。藉此，可於畫素形成後的氧化銦錫(Indium Tin Oxide，ITO)濺鍍時進一步抑制染料的還原褪色。具體而言，較佳為醌化合物，較佳為分子量100~800左右的以下結構的醌化合物。 The coloring composition of the present invention may also add a compound which is more easily reduced than the dye as an anti-reducing agent for the dye. Thereby, the reduction fading of the dye can be further suppressed during the sputtering of Indium Tin Oxide (ITO) after the formation of the pixel. Specifically, a ruthenium compound is preferred, and a ruthenium compound having the following structure having a molecular weight of about 100 to 800 is preferred.

本發明的著色組成物進而視需要亦可含有填充材料、紫外線吸收劑、抗凝聚劑、增感劑或光穩定劑等各種添加劑。 The colored composition of the present invention may further contain various additives such as a filler, an ultraviolet absorber, an anti-agglomerating agent, a sensitizer, or a light stabilizer, as needed.

[著色組成物的製備方法] [Preparation method of coloring composition]

本發明的著色組成物是藉由將上文所述的各成分及視需要的任意成分混合而製備。 The colored composition of the present invention is prepared by mixing the above-described respective components and optionally any of the components.

再者，於製備著色組成物時，可將構成著色組成物的各成分一次性調配，亦可將各成分溶解、分散於溶劑中後依序調配。另外，進行調配時的投入順序或作業條件不特別受限制。例如可將所有成分同時溶解、分散於溶劑中而製備組成物，視需要亦可預先將各成分適當製成兩種以上的溶液、分散液，並於使用時(塗佈時)將該些溶液、分散液混合而製備成組成物。 Further, in the preparation of the colored composition, the components constituting the colored composition may be formulated at once, or the components may be dissolved and dispersed in a solvent, and then sequentially formulated. In addition, the order of input or the working conditions at the time of preparation are not particularly limited. For example, all the components may be simultaneously dissolved and dispersed in a solvent to prepare a composition, and if necessary, each component may be appropriately prepared into two or more kinds of solutions and dispersions, and these solutions may be used at the time of application (at the time of coating). The dispersion was mixed to prepare a composition.

本發明的著色組成物的製造方法的特徵在於包括以下步驟：於含有具有三芳基甲烷結構的染料陽離子、相對陰離子X、與陰離子X不同的陰離子Y以及溶劑的溶液中，至少調配聚合性 化合物，且染料陽離子含有交聯性基及/或多聚物結構。具體而言，本發明的著色組成物的製造方法較佳為更包括以下步驟：將含有染料陽離子與相對陰離子X的著色劑及陰離子Y溶解於溶劑中的步驟。 The method for producing a colored composition of the present invention is characterized by comprising the steps of: at least formulating a polymerizable property in a solution containing a dye cation having a triarylmethane structure, a relative anion X, an anion Y different from an anion X, and a solvent; a compound, and the dye cation contains a crosslinkable group and/or a polymer structure. Specifically, the method for producing a colored composition of the present invention preferably further comprises the step of dissolving a coloring agent containing a dye cation and a relative anion X and an anion Y in a solvent.

藉由設定為此種構成，而使陰離子Y更穩定地溶解於溶劑中，故可進一步提高著色劑於溶劑中的溶解性。結果，可使塗佈本發明的組成物時的塗佈表面狀態更良好。 By setting such a configuration, the anion Y is more stably dissolved in the solvent, so that the solubility of the colorant in the solvent can be further improved. As a result, the coated surface state at the time of coating the composition of the present invention can be made better.

如上文所述般製備的著色組成物可於使用較佳為孔徑0.01μm~3.0μm、更佳為孔徑0.05μm~0.5μm左右的過濾器等進行過濾分離後供使用。 The colored composition prepared as described above can be used by filtration and separation using a filter having a pore diameter of preferably 0.01 μm to 3.0 μm, more preferably 0.05 μm to 0.5 μm.

本發明的著色組成物可形成色相及對比度優異的著色硬化膜，故可較佳地用於形成液晶顯示裝置(LCD)或固體攝像元件(例如電荷耦合元件(Charge Coupled Device，CCD)、互補式金屬氧化物半導體(Complementary Metal-Oxide-Semiconductor，CMOS)等)中所用的彩色濾光片等的著色畫素形成用著色組成物，另外可較佳地用於印刷油墨、噴墨油墨及塗料等的製作用途。尤其適於液晶顯示裝置用的著色畫素形成用途。 The colored composition of the present invention can form a colored cured film having excellent hue and contrast, and thus can be preferably used for forming a liquid crystal display device (LCD) or a solid-state imaging device (for example, a charge coupled device (CCD), a complementary type. A coloring composition for forming a color pixel such as a color filter used in a metal oxide semiconductor (CMOS) or the like, and preferably used for printing ink, inkjet ink, paint, etc. Production use. It is especially suitable for the formation of colored pixels for liquid crystal display devices.

[彩色濾光片及其製造方法] [Color filter and method of manufacturing the same]

本發明的彩色濾光片是設置基板、及於該基板上設置含有本發明的著色組成物的著色區域而構成者。基板上的著色區域是由形成彩色濾光片的各畫素的例如紅色(R)、綠色(G)、藍色(B) 等的著色膜所構成。 The color filter of the present invention is configured by providing a substrate and providing a colored region containing the colored composition of the present invention on the substrate. The colored areas on the substrate are, for example, red (R), green (G), and blue (B) of the respective pixels forming the color filter. It is composed of a colored film.

關於本發明的彩色濾光片，只要為可形成將本發明的著色組成物應用於基板上並使之硬化而成的著色區域(著色圖案)的方法，則可利用任意方法來形成。較佳為使用本發明的著色組成物而製作。 The color filter of the present invention can be formed by any method as long as it can form a colored region (colored pattern) obtained by applying the colored composition of the present invention to a substrate and curing it. It is preferably produced by using the colored composition of the present invention.

另外，於使用本發明的著色組成物來製造固體攝像元件用的彩色濾光片的情形時，可採用日本專利特開2011-252065號公報的段落0359~段落0371中記載的製造方法。 In the case of producing a color filter for a solid-state image sensor using the coloring composition of the present invention, the production method described in paragraph 0359 to paragraph 0371 of JP-A-2011-252065 can be employed.

本發明的彩色濾光片的製造方法的特徵在於包括以下步驟：將本發明的著色組成物賦予至支撐體上而形成著色組成物層；將所述著色組成物層以圖案狀進行曝光；以及將未曝光部顯影去除而形成著色圖案。 The method for producing a color filter of the present invention is characterized by comprising the steps of: applying a colored composition of the present invention to a support to form a colored composition layer; and exposing the colored composition layer in a pattern; The unexposed portion is developed and removed to form a colored pattern.

進而，視需要亦可設置對著色組成物層進行烘烤的步驟(預烘烤步驟)、及對經顯影的著色圖案進行烘烤的步驟(後烘烤步驟)。以下，有時將該些步驟統稱為圖案形成步驟。 Further, a step of baking the colored composition layer (prebaking step) and a step of baking the developed colored pattern (post baking step) may be provided as needed. Hereinafter, these steps are collectively referred to as a pattern forming step.

本發明的彩色濾光片的製造方法較佳為包括於230℃以上對經顯影的著色圖案進行加熱的步驟。 The method for producing a color filter of the present invention preferably includes a step of heating the developed coloring pattern at 230 ° C or higher.

本發明的彩色濾光片可藉由所述製造方法而較佳地獲得。 The color filter of the present invention can be preferably obtained by the above manufacturing method.

以下，有時將固體攝像元件用彩色濾光片簡稱為「彩色濾光片」。 Hereinafter, the color filter for a solid-state imaging device may be simply referred to as a "color filter".

<形成著色組成物層的步驟> <Step of forming colored composition layer>

於形成著色組成物層的步驟中，於支撐體上賦予本發明的組 成物而形成著色組成物層。 In the step of forming the colored composition layer, the group of the present invention is imparted to the support The object forms a colored composition layer.

本步驟中可使用的支撐體例如可使用：於基板(例如矽基板)上設有電荷耦合元件(Charge Coupled Device，CCD)或互補式金屬氧化物半導體(Complementary Metal-Oxide Semiconductor，CMOS)等攝像元件(受光元件)的固體攝像元件用基板。 For the support which can be used in this step, for example, a substrate (for example, a germanium substrate) may be provided with a charge coupled device (CCD) or a complementary metal-oxide semiconductor (CMOS). A substrate for a solid-state image sensor of an element (light receiving element).

本發明的著色圖案可形成於固體攝像元件用基板的形成有攝像元件的面側(表面)，亦可形成於未形成攝像元件的面側(背面)。 The colored pattern of the present invention can be formed on the surface side (surface) on which the image pickup element is formed on the solid-state image sensor substrate, or on the surface side (back surface) on which the image pickup element is not formed.

於固體攝像元件的著色圖案之間或固體攝像元件用基板的背面上，亦可設有遮光膜。 A light shielding film may be provided between the colored patterns of the solid-state image sensor or the back surface of the solid-state image sensor substrate.

另外，於支撐體上，視需要亦可設置底塗層以改良與上部的層的密接、防止物質的擴散或實現基板表面的平坦化。 Further, on the support, an undercoat layer may be provided as needed to improve adhesion to the upper layer, to prevent diffusion of substances, or to planarize the surface of the substrate.

對支撐體上賦予本發明的組成物的方法可應用：狹縫塗佈、噴墨法、旋轉塗佈、流延塗佈、輥塗佈、網版印刷法等各種塗佈方法。 A method of imparting the composition of the present invention to a support can be applied to various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing.

塗佈於支撐體上的著色感光性組成物層的乾燥(預烘烤)可利用加熱板、烘箱等在50℃~140℃的溫度下進行10秒鐘~900秒鐘。 The drying (prebaking) of the colored photosensitive composition layer coated on the support can be carried out at a temperature of 50 ° C to 140 ° C for 10 seconds to 900 seconds using a hot plate, an oven or the like.

<<利用光微影法來進行圖案形成的情形>> <<The situation of pattern formation by light lithography>>

-曝光步驟- - Exposure step -

曝光步驟中，例如使用步進機(stepper)等曝光裝置，介隔 具有既定的遮罩圖案的遮罩對形成著色組成物層的步驟中形成的著色成物層進行圖案曝光。藉此可獲得硬化膜。 In the exposure step, for example, using an exposure device such as a stepper, the spacer is separated. The mask having a predetermined mask pattern is patterned to expose the coloring layer formed in the step of forming the coloring composition layer. Thereby, a cured film can be obtained.

曝光時可使用的放射線(光)尤其可較佳地使用g射線、i射線等紫外線(尤佳為i射線)。照射量(曝光量)較佳為5mJ/cm2~500mJ/cm2，更佳為10mJ/cm2~400mJ/cm2，最佳為20mJ/cm2~300mJ/cm2。 In particular, it is preferable to use ultraviolet rays (especially i-rays) such as g-rays and i-rays for radiation (light) which can be used for exposure. The irradiation amount (exposure amount) is preferably 5 mJ/cm 2 to 500 mJ/cm 2 , more preferably 10 mJ/cm 2 to 400 mJ/cm 2 , and most preferably 20 mJ/cm 2 to 300 mJ/cm 2 .

硬化膜的膜厚較佳為0.1μm~5.0μm，更佳為0.5μm~4.0μm，進而佳為1.0μm~3.0μm。 The film thickness of the cured film is preferably from 0.1 μm to 5.0 μm, more preferably from 0.5 μm to 4.0 μm, still more preferably from 1.0 μm to 3.0 μm.

藉由將膜厚設定為3.0μm以下，可獲得高解析性、高密接性，故較佳。 By setting the film thickness to 3.0 μm or less, high resolution and high adhesion can be obtained, which is preferable.

<<<圖案形成步驟>>> <<<pattern forming step>>

繼而，藉由進行鹼顯影處理，曝光步驟中未經光照射的部分的著色組成物層溶出至鹼性水溶液中，僅經光硬化的部分殘留。 Then, by performing the alkali development treatment, the colored composition layer of the portion which is not irradiated with light in the exposure step is eluted into the alkaline aqueous solution, and only the photohardened portion remains.

顯影液理想的是不對基底的攝像元件或電路等造成損傷的有機鹼性顯影液。顯影溫度通常為20℃~30℃，顯影時間以前為20秒鐘~90秒鐘。為了進一步去除殘渣，近年來亦有實施120秒鐘~180秒鐘的情形。進而，為了進一步提高殘渣去除性，有時亦將以下步驟反覆進行幾次：每隔60秒鐘甩去顯影液，進而供給新的顯影液。 The developer is preferably an organic alkaline developer which does not cause damage to an image pickup element or a circuit of the substrate. The development temperature is usually 20 ° C to 30 ° C, and the development time is 20 seconds to 90 seconds. In order to further remove the residue, in recent years, it has been carried out for 120 seconds to 180 seconds. Further, in order to further improve the residue removal property, the following steps may be repeated several times: the developer is removed every 60 seconds, and a new developer is supplied.

顯影液中所用的鹼性劑例如可列舉：氨水、乙胺、二乙胺、二甲基乙醇胺、氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化苄基三甲基銨、膽鹼、吡咯、 哌啶、1,8-二氮雜雙環-[5,4,0]-7-十一烯等有機鹼性化合物，可較佳地使用利用純水將該些鹼性劑以濃度成為0.001質量%~10質量%、較佳為0.01質量%~1質量%的方式稀釋而成的鹼性水溶液作為顯影液。 Examples of the alkaline agent used in the developing solution include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrahydric hydroxide. Butyl ammonium, benzyltrimethylammonium hydroxide, choline, pyrrole, An organic basic compound such as piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene can be preferably used in a concentration of 0.001 by mass using pure water. An alkaline aqueous solution diluted in a range of from 0.01 to 10% by mass, preferably from 0.01% by mass to 1% by mass, is used as a developing solution.

再者，顯影液中亦可使用無機鹼，無機鹼例如較佳為氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、矽酸鈉、偏矽酸鈉等。 Further, an inorganic base may be used in the developer. The inorganic base is preferably, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate or sodium metasilicate.

再者，於使用包含此種鹼性水溶液的顯影液的情形時，通常於顯影後利用純水進行清洗(淋洗)。 Further, in the case of using a developing solution containing such an alkaline aqueous solution, it is usually washed (rinsed) with pure water after development.

繼而，較佳為於實施乾燥之後進行加熱處理(後烘烤)。若形成多種顏色的著色圖案，則可每種顏色逐一依序重複所述步驟來製造硬化皮膜。藉此可獲得彩色濾光片。 Then, it is preferred to carry out heat treatment (post-baking) after drying is carried out. If a color pattern of a plurality of colors is formed, the steps may be repeated one by one for each color to produce a hardened film. Thereby, a color filter can be obtained.

後烘烤為用以使硬化完全者進行的顯影後的加熱處理，通常進行100℃~240℃、較佳為200℃~240℃、更佳為230℃~240℃的熱硬化處理。 The post-baking is a heat curing treatment after development for curing, and is usually subjected to a heat hardening treatment at 100 ° C to 240 ° C, preferably 200 ° C to 240 ° C, more preferably 230 ° C to 240 ° C.

可使用加熱板或對流烘箱(熱風循環式乾燥機)、高頻加熱機等加熱機構，以成為所述條件的方式以連續式或批次式對顯影後的塗佈膜進行所述後烘烤處理。 The post-baking of the developed coating film may be carried out in a continuous or batch manner using a heating plate or a convection oven (hot air circulation dryer), a high-frequency heating machine or the like in a heating mechanism. deal with.

利用乾式蝕刻法來形成圖案的情形的方法例如可參考日本專利特開2013-054080號公報的段落0287~段落0356，將其內容併入至本說明書中。 A method of forming a pattern by a dry etching method can be referred to, for example, paragraphs 0287 to 0356 of Japanese Patent Laid-Open Publication No. 2013-054080, the contents of which are incorporated herein.

再者，本發明的製造方法視需要亦可包括作為固體攝像元件用彩色濾光片的製造方法而公知的步驟作為所述以外的步 驟。例如於進行如上所述的形成著色組成物層的步驟、曝光步驟及圖案形成步驟後，視需要亦可包括藉由加熱及/或曝光使所形成的著色圖案硬化的硬化步驟。 In addition, the manufacturing method of the present invention may include a step known as a method of manufacturing a color filter for a solid-state image sensor as a step other than the above. Step. For example, after the step of forming the colored composition layer, the exposing step, and the pattern forming step as described above, a hardening step of hardening the formed colored pattern by heating and/or exposure may be included as needed.

另外，於使用本發明的組成物的情形時，例如有時產生塗佈裝置噴出部的噴嘴或配管部的堵塞或者因著色組成物或顏料於塗佈機內的附著．沈降．乾燥所致的污染等。因此，為了高效地清洗由本發明的組成物所致的污染，較佳為將與上文所述的本組成物有關的溶劑作為清洗液。另外，日本專利特開平7-128867號公報、日本專利特開平7-146562號公報、日本專利特開平8-278637號公報、日本專利特開2000-273370號公報、日本專利特開2006-85140號公報、日本專利特開2006-291191號公報、日本專利特開2007-2101號公報、日本專利特開2007-2102號公報、日本專利特開2007-281523號公報等中記載的清洗液亦可較佳地用於本發明的組成物的清洗去除。 Further, in the case of using the composition of the present invention, for example, clogging of the nozzle or the piping portion of the coating device discharge portion or adhesion of the coloring composition or pigment to the coater may occur. settlement. Pollution caused by drying, etc. Therefore, in order to efficiently clean the contamination caused by the composition of the present invention, it is preferred to use a solvent related to the present composition described above as a cleaning liquid. In addition, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The cleaning liquids described in the Japanese Patent Publication No. 2007-291191, the Japanese Patent Publication No. 2007-2101, the Japanese Patent Publication No. 2007-2102, and the Japanese Patent Publication No. 2007-281523 can also be used. It is preferably used for cleaning and removal of the composition of the present invention.

所述中，較佳為伸烷基二醇單烷基醚羧酸酯及伸烷基二醇單烷基醚。 Among them, an alkylene glycol monoalkyl ether carboxylate and an alkylene glycol monoalkyl ether are preferred.

該些溶劑可單獨使用亦可混合使用兩種以上。於混合兩種以上的情形時，較佳為將具有羥基的溶劑與不具有羥基的溶劑混合。具有羥基的溶劑與不具有羥基的溶劑之質量比為1/99~99/1，較佳為10/90~90/10，進而佳為20/80~80/20。尤佳為丙二醇單甲醚乙酸酯(Propyleneglycol monomethylether acetate，PGMEA)與丙二醇單甲醚(Propyleneglycol monomethylether，PGME)的混合 溶劑且其比率為60/40。再者，為了提高清洗液對污染物的滲透性，亦可於清洗液中添加與上文所述的本組成物有關的界面活性劑。 These solvents may be used singly or in combination of two or more. In the case of mixing two or more kinds, it is preferred to mix a solvent having a hydroxyl group with a solvent having no hydroxyl group. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 80/20. Especially preferred is a mixture of Propyleneglycol monomethylether acetate (PGMEA) and Propyleneglycol monomethylether (PGME). Solvent and its ratio is 60/40. Further, in order to increase the permeability of the cleaning liquid to the contaminants, a surfactant related to the above-described composition may be added to the cleaning liquid.

本發明的彩色濾光片可較佳地用於液晶顯示裝置(LCD)或CCD、CMOS等固體攝像元件，尤其適於超過100萬畫素般的高解析度的CCD或CMOS等。本發明的固體攝像元件用彩色濾光片例如可用作配置於構成CCD或CMOS的各畫素的受光部、與用以進行聚光的微透鏡(microlens)之間的彩色濾光片。 The color filter of the present invention can be suitably used for a liquid crystal display device (LCD), a solid-state imaging device such as a CCD or a CMOS, and is particularly suitable for a high-resolution CCD or CMOS of more than one million pixels. The color filter for a solid-state image sensor of the present invention can be used, for example, as a color filter disposed between a light receiving portion of each pixel constituting the CCD or CMOS and a microlens for collecting light.

再者，本發明的彩色濾光片的著色圖案(著色畫素)的膜厚較佳為3.0μm以下，更佳為2.5μm以下。 Further, the coloring pattern (coloring pixel) of the color filter of the present invention has a film thickness of preferably 3.0 μm or less, more preferably 2.5 μm or less.

[液晶顯示裝置] [Liquid Crystal Display Device]

本發明的液晶顯示元件及固體攝像元件是具備本發明的彩色濾光片而成。更具體而言，例如於彩色濾光片的內面側形成配向膜，使之與電極基板相對向，於間隙部中填滿液晶並加以密封，藉此可獲得作為本發明的液晶顯示元件的面板。另外，例如藉由在受光元件上形成彩色濾光片，可獲得本發明的固體攝像元件。 The liquid crystal display element and the solid-state imaging element of the present invention are provided with the color filter of the present invention. More specifically, for example, an alignment film is formed on the inner surface side of the color filter so as to face the electrode substrate, and the liquid crystal is filled in the gap portion and sealed, whereby the liquid crystal display element of the present invention can be obtained. panel. Further, the solid-state imaging element of the present invention can be obtained, for example, by forming a color filter on the light-receiving element.

關於液晶顯示裝置的定義或各顯示裝置的詳細情況，例如是記載於「電子顯示器器件(佐佐木昭夫著，工業調查會(股)，1990年發行)」、「顯示器器件(伊吹順章著，產業圖書(股)，1989年發行)」等。另外，關於液晶顯示裝置，例如是記載於「下一代液晶顯示器技術(內田龍男編輯，工業調查會(股)，1994年發行)」。本發明可應用的液晶顯示裝置並無特別限制，例如可應用 於所述「下一代液晶顯示器技術」中記載的各種方式的液晶顯示裝置。 The definition of the liquid crystal display device or the details of each display device is described in, for example, "Electronic display device (Sasaki Sasaki, Industrial Research Association, issued in 1990)", "Display device (Ibuki Shunzhang, industry) Books (shares), issued in 1989) and so on. In addition, the liquid crystal display device is described, for example, in "Next-Generation Liquid Crystal Display Technology (Editor Uchida Natsuo, Industrial Research Association, issued in 1994)." The liquid crystal display device to which the present invention is applicable is not particularly limited, and may be applied, for example. Various types of liquid crystal display devices described in the "Next Generation Liquid Crystal Display Technology".

其中，本發明的彩色濾光片尤其對彩色薄膜電晶體(Thin Film Transistor，TFT)方式的液晶顯示裝置而言有效。關於彩色TFT方式的液晶顯示裝置，例如是記載於「彩色TFT液晶顯示器(共立出版(股)，1996年發行)」。進而，本發明亦可應用於共面切換(In-Plane Switching，IPS)等橫向電場驅動方式、多象限垂直配向(Multi-domain Vertical Alignment，MVA)等畫素分割方式等視場角經擴大的液晶顯示裝置或超扭轉向列(Super Twisted Nematic，STN)、扭轉向列(Twisted Nematic，TN)、垂直配向(Vertical Alignment，VA)、光學補償傾斜(Fringe Field Switching，OCS)、邊緣場切換(Fringe Field Switching，FFS)及反射式光學補償彎曲(Reflective-Optically Compensated Bend，R-OCB)等。 Among them, the color filter of the present invention is particularly effective for a liquid crystal display device of a Thin Film Transistor (TFT) type. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)". Furthermore, the present invention can also be applied to a field of view such as a transverse electric field driving method such as In-Plane Switching (IPS), a multi-domain vertical alignment (MVA), and the like. Liquid crystal display device or Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Fringe Field Switching (OCS), fringe field switching ( Fringe Field Switching (FFS) and Reflective-Optically Compensated Bend (R-OCB).

另外，本發明的彩色濾光片亦可用於明亮且高精細的彩色濾光片陣列(Color-filter On Array，COA)方式。 In addition, the color filter of the present invention can also be used in a bright and high-definition Color-filter On Array (COA) mode.

若將本發明的彩色濾光片用於液晶顯示元件，則於與以前公知的冷陰極管的三波長管組合時可實現高的對比度，進而藉由將紅色、綠色、藍色的發光二極體(Light Emitting Diode，LED)光源(RGB-LED)設定為背光，可提供亮度高、另外顏色純度高的色彩再現性良好的液晶顯示裝置。 When the color filter of the present invention is used for a liquid crystal display element, high contrast can be achieved when combined with a three-wavelength tube of a conventionally known cold cathode tube, and the red, green, and blue light-emitting diodes can be realized. A Light Emitting Diode (LED) light source (RGB-LED) is set as a backlight, and can provide a liquid crystal display device having high brightness and high color reproducibility.

[固體攝像元件] [Solid image sensor]

本發明的著色組成物亦可較佳地用於固體攝像元件用途。固體攝像元件的構成為具備使用本發明的著色組成物所製造的彩色濾光片的構成，只要為作為固體攝像元件而發揮功能的構成，則並無特別限定，例如可列舉如下構成。 The colored composition of the present invention can also be preferably used for solid-state imaging device applications. The configuration of the solid-state imaging device is not particularly limited as long as it has a configuration in which the color filter is produced by using the colored composition of the present invention, and the configuration is as follows.

所述固體攝像元件為以下構成：於支撐體上具有構成固體攝像元件(CCD影像感測器、CMOS影像感測器等)的受光區域的多個光二極體(photodiode)及包含多晶矽等的傳輸電極，於所述光二極體及所述傳輸電極上具有僅光二極體的受光部開口的包含鎢等的遮光膜，於遮光膜上具有以覆蓋遮光膜整個面及光二極體受光部的方式形成的包含氮化矽等的器件保護膜，於所述器件保護膜上具有本發明的固體攝像元件用彩色濾光片。 The solid-state imaging device has a configuration in which a plurality of photodiodes (photodiodes) constituting a light receiving region of a solid-state imaging device (a CCD image sensor, a CMOS image sensor, or the like) and a polycrystalline germanium or the like are provided on the support. The electrode includes a light-shielding film containing tungsten or the like on the light-receiving portion of the photodiode and the light-transmitting film, and the light-shielding film has a surface covering the entire surface of the light-shielding film and the light-receiving portion of the photodiode A device protective film containing tantalum nitride or the like is formed, and the color filter for a solid-state image sensor of the present invention is provided on the device protective film.

進而，亦可為於所述器件保護層上且彩色濾光片之下(靠近支撐體之側)具有聚光機構(例如微透鏡等。以下相同)的構成、或於彩色濾光片上具有聚光機構的構成等。 Furthermore, it may be configured to have a light collecting means (for example, a microlens or the like, the same below) on the protective layer of the device and under the color filter (on the side close to the support), or may have a color filter. The composition of the concentrating mechanism, and the like.

[實施例] [Examples]

以下，列舉實施例對本發明加以更具體說明。以下的實施例中所示的材料、使用量、比例、處理內容、處理順序等只要不偏離本發明的主旨，則可適當變更。因此，本發明的範圍不限定於以下所示的具體例。再者，只要無特別說明，則「%」及「份」為質量基準。 Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "%" and "parts" are quality standards unless otherwise specified.

<實施例1> <Example 1>

藍色著色膜的製作 Blue color film production

著色組成物(塗佈液)的製備 Preparation of coloring composition (coating liquid)

將下述組成中的成分混合，製備染料溶液1。 The dye solution 1 was prepared by mixing the components in the following compositions.

<組成> <composition>

繼而，將下述組成中的成分混合，製備著色組成物。 Then, the components in the following compositions were mixed to prepare a colored composition.

<組成> <composition>

三芳基甲烷染料(I-1)：下述結構的化合物 Triarylmethane dye (I-1): a compound of the following structure

<可與染料陽離子形成鹽、且與相對陰離子X不同的陰離子Y> <Anion Y which can form a salt with a dye cation and which is different from the opposite anion X>

三芳基甲烷染料(I-1)的合成例 Synthesis example of triarylmethane dye (I-1)

三芳基甲烷染料(I-1)是依照以下的路徑來合成。 The triarylmethane dye (I-1) was synthesized according to the following route.

(化合物3的合成) (Synthesis of Compound 3)

使化合物1(1-萘基胺)17.0g(118.8mmol)及1,2-環氧環己烷11.65g(118.7mmol)溶解於六氟異丙醇50mL中後，加熱回流5小時。確認到反應結束後，藉由乙酸乙酯50mL及水、食鹽水將目標物萃取至有機層中及加以清洗後，使之濃縮。利用己烷使該粗產物溶解、再結晶後，進行過濾，藉此獲得19.2g的化合物3(產率為67%)。 17.0 g (118.8 mmol) of the compound 1 (1-naphthylamine) and 11.65 g (118.7 mmol) of 1,2-epoxycyclohexane were dissolved in 50 mL of hexafluoroisopropanol, and the mixture was heated under reflux for 5 hours. After confirming the completion of the reaction, the target was extracted into an organic layer and washed with 50 mL of ethyl acetate and water and brine, and then concentrated. This crude product was dissolved and recrystallized with hexane, and filtered, whereby 19.2 g of Compound 3 (yield: 67%) was obtained.

(化合物4的合成) (Synthesis of Compound 4)

使化合物3(2.4g(10mmol))及三乙胺1.5g(15mmol)溶解於10mL的四氫呋喃(Tetrahydrofuran，THF)中。將該溶液冷卻至0℃後，滴加甲基丙烯醯氯1.15g(11mol)。確認到反應結束後，藉由乙酸乙酯20mL及水、食鹽水將目標物萃取至有機層中及加以清洗後，進行濃縮。藉由管柱層析法將該粗產物純化，藉此獲得1.8g的化合物4(產率為58%)。 Compound 3 (2.4 g (10 mmol)) and triethylamine 1.5 g (15 mmol) were dissolved in 10 mL of tetrahydrofuran (THF). After the solution was cooled to 0 ° C, 1.15 g (11 mol) of methacrylonitrile chloride was added dropwise. After confirming the completion of the reaction, the target product was extracted into an organic layer and washed with 20 mL of ethyl acetate and water and brine, and then concentrated. This crude product was purified by column chromatography, whereby 1.8 g of Compound 4 (yield: 58%) was obtained.

(化合物I-1的合成) (Synthesis of Compound I-1)

將化合物4(1.9g(5.8mmol))、化合物5(1.8g(5.8mmol))、***1.0g(6.4mmol)溶解於甲苯6mL中，加溫至90℃並攪拌1小時。確認到反應結束後，於該溶液中添加乙酸乙酯10mL並將目標物以上清液的形式取出，將該操作重複3次，將化合物6以乙酸乙酯溶液的形式取出。於該溶液中添加另行調整的雙三氟甲磺醯亞胺鋰鹽2.0g(7.0mmol)的甲醇20mL溶液。確認到鹽交換反應結束後，添加水50mL，將化合物萃取至乙酸乙酯層中並進行濃縮後，藉由管柱層析法進行純化，藉此獲得目標化合物I-1(1.7g(33%))。 Compound 4 (1.9 g (5.8 mmol)), Compound 5 (1.8 g (5.8 mmol)), and 1.0 g (6.4 mmol) of phosphorus oxychloride were dissolved in 6 mL of toluene, and the mixture was warmed to 90 ° C and stirred for 1 hour. After confirming the completion of the reaction, 10 mL of ethyl acetate was added to the solution, and the target supernatant was taken out. This operation was repeated three times, and the compound 6 was taken out as an ethyl acetate solution. To the solution was added a solution of 2.0 g (7.0 mmol) of a separately adjusted bistrifluoromethanesulfonimide lithium salt in 20 mL of methanol. After confirming that the salt exchange reaction was completed, 50 mL of water was added, and the compound was extracted into an ethyl acetate layer and concentrated, and then purified by column chromatography to obtain the target compound I-1 (1.7 g (33%) )).

1H核磁共振(Nuclear Magnetic Resonance，NMR)(CHCl3)：1.25(m,16H),1.8(s,3H),3.6(t,8H),3.75(bs,1H),5.2(dt,1H),5.55(s,1H),6.1(s,1H),6.2(d,1H),6.75(d,4H),7.2-7.5(m,9H),7.8(d,1H) 1 H Nuclear Magnetic Resonance (NMR) (CHCl 3 ): 1.25 (m, 16H), 1.8 (s, 3H), 3.6 (t, 8H), 3.75 (bs, 1H), 5.2 (dt, 1H) , 5.55 (s, 1H), 6.1 (s, 1H), 6.2 (d, 1H), 6.75 (d, 4H), 7.2-7.5 (m, 9H), 7.8 (d, 1H)

光聚合性化合物(T-1)：卡亞拉得(Kayarad)DPHA(日本化藥(股)製造，二季戊四醇五丙烯酸酯與二季戊四醇六丙烯 酸酯的混合物) Photopolymerizable compound (T-1): Kayarad DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol pentaacrylate and dipentaerythritol hexapropylene) Mixture of acid esters)

黏合劑樹脂(U-1)：甲基丙烯酸苄酯/甲基丙烯酸(85/15[質量比]共聚物(重量平均分子量：12,000)酸值(100mgKOH/g)) Adhesive resin (U-1): benzyl methacrylate/methacrylic acid (85/15 [mass ratio] copolymer (weight average molecular weight: 12,000) acid value (100 mgKOH/g))

光聚合起始劑(V-3)：下述結構的肟系化合物 Photopolymerization initiator (V-3): a lanthanide compound of the following structure

溶劑(X-1)：丙二醇單甲醚乙酸酯 Solvent (X-1): propylene glycol monomethyl ether acetate

溶劑(X-2)：3-乙氧基丙酸乙酯 Solvent (X-2): ethyl 3-ethoxypropionate

界面活性劑(Z-1)：美佳法(Mega fuck)F781-F(迪愛生(DIC)(股)製造) Surfactant (Z-1): Mega fuck F781-F (made by Di Love (DIC))

<實施例2~實施例7、比較例4> <Example 2 to Example 7 and Comparative Example 4>

除了如下述表中般變更三芳基甲烷染料(I-1)中的相對陰離子X以外，與實施例1同樣地進行操作，製備著色組成物。 A colored composition was prepared in the same manner as in Example 1 except that the relative anion X in the triarylmethane dye (I-1) was changed as shown in the following table.

<實施例8~實施例10> <Example 8 to Example 10>

除了如下述表中般變更含有與(b)相對陰離子X不同的陰離子Y的化合物相對於染料陽離子之莫耳比((b)化合物/染料陽離子)以外，與實施例1同樣地進行操作，製備著色組成物。 The operation was carried out in the same manner as in Example 1 except that the compound containing the anion Y different from (b) the opposite anion X was changed to the molar ratio of the dye cation ((b) compound/dye cation) as in the following table. Coloring composition.

<實施例11> <Example 11>

除了將三芳基甲烷染料(I-1)變更為下述三芳基甲烷染料 (I-2)以外，與實施例1同樣地進行操作，製備著色組成物。 In addition to changing the triarylmethane dye (I-1) to the following triarylmethane dye A coloring composition was prepared in the same manner as in Example 1 except for (I-2).

三芳基甲烷染料(I-2)：下述化合物，Mw=6000 Triarylmethane dye (I-2): the following compound, Mw=6000

三芳基甲烷染料(I-2)的合成例 Synthesis example of triarylmethane dye (I-2)

三芳基甲烷染料(I-2)是依照以下的路徑來合成。 The triarylmethane dye (I-2) was synthesized according to the following route.

於氮氣環境下，加入甲基乙基酮30g並加熱至70℃。於該溶液中歷時3小時滴加化合物I-1(17.9g)及偶氮雙異丁腈(Azobisisobutyronitrile，AIBN)(0.16g)的甲基乙基酮20mL溶液。滴加結束後攪拌15小時，將甲基乙基酮濃縮後，於己烷中投入反應液。將所得的個體乾固，藉此獲得17.0g的三芳基甲烷染料I-2。 Under a nitrogen atmosphere, 30 g of methyl ethyl ketone was added and heated to 70 °C. To the solution was added dropwise a solution of compound I-1 (17.9 g) and azobisisobutyronitrile (AIBN) (0.16 g) in methyl ethyl ketone in 20 mL over 3 hours. After completion of the dropwise addition, the mixture was stirred for 15 hours, and methyl ethyl ketone was concentrated, and then the reaction liquid was poured into hexane. The obtained individual was dried to thereby obtain 17.0 g of a triarylmethane dye I-2.

<實施例12、實施例13> <Example 12, Example 13>

除了將三芳基甲烷染料(I-1)的陰離子X變更為a-14或a-21以外，與實施例1同樣地進行操作，製備著色組成物。 A colored composition was prepared in the same manner as in Example 1 except that the anion X of the triarylmethane dye (I-1) was changed to a-14 or a-21.

<實施例14> <Example 14>

除了將三芳基甲烷染料(I-1)變更為下述三芳基甲烷染料(I-3)以外，與實施例1同樣地進行操作，製備著色組成物。 A colored composition was prepared in the same manner as in Example 1 except that the triarylmethane dye (I-1) was changed to the following triarylmethane dye (I-3).

三芳基甲烷染料(I-3)：下述化合物，Mw=6000，下述三芳基甲烷染料(I-3)的結構中，右側的結構單元相當於相對陰離子X(陰離子多聚物)。 Triarylmethane dye (I-3): The following compound, Mw = 6000, in the structure of the following triarylmethane dye (I-3), the structural unit on the right side corresponds to the relative anion X (anionic polymer).

三芳基甲烷染料(I-3)的合成例 Synthesis example of triarylmethane dye (I-3)

除了將化合物I-1(17.9g)變更為化合物I-1(12.6g)及下述化合物0.76g以外，同樣地進行操作，藉此獲得13.0g的三芳基甲烷染料I-3。 The same procedure was carried out except that the compound I-1 (17.9 g) was changed to the compound I-1 (12.6 g) and the following compound 0.76 g, whereby 13.0 g of the triarylmethane dye I-3 was obtained.

<實施例15> <Example 15>

於調整著色組成物時，利用將所有成分同時混合的方法來進行調整，除此以外，與實施例1同樣地進行操作，調整著色組成物。 In the same manner as in Example 1, except that the coloring composition was adjusted, the coloring composition was adjusted in the same manner as in Example 1.

<實施例16、實施例17> <Example 16, Example 17>

除了添加兩種可與染料陽離子形成鹽、且與相對陰離子X不同的陰離子Y以外，與實施例1同樣地進行操作，調整著色組成物。兩種陰離子Y是分別添加0.05質量份。 The coloring composition was adjusted in the same manner as in Example 1 except that two kinds of anions Y which can form a salt with the dye cation and which are different from the opposite anion X were added. The two anions Y were added in an amount of 0.05 parts by mass, respectively.

<實施例18> <Example 18>

除了併用顏料PB15：6(顏料藍15：6)作為有色材料以外，與實施例1同樣地進行操作，調整著色組成物。 The coloring composition was adjusted in the same manner as in Example 1 except that the pigment PB15:6 (Pigment Blue 15:6) was used in combination as a colored material.

<比較例1> <Comparative Example 1>

除了不使用與相對陰離子X不同的陰離子Y以外，與實施例1同樣地進行操作，製備著色組成物。 A colored composition was prepared in the same manner as in Example 1 except that the anion Y different from the counter anion X was not used.

<比較例2> <Comparative Example 2>

除了將三芳基甲烷染料(I-1)變更為WO2010-123071號公報的實施例2中記載的下述比較化合物1以外，與實施例1同樣地 進行操作，製備著色組成物。 In the same manner as in Example 1, except that the triarylmethane dye (I-1) was changed to the following comparative compound 1 described in Example 2 of WO2010-123071. The operation was carried out to prepare a colored composition.

<比較例3> <Comparative Example 3>

除了將三芳基甲烷染料變更為下述比較化合物2以外，與實施例1同樣地進行操作，製備著色組成物。 A colored composition was prepared in the same manner as in Example 1 except that the triarylmethane dye was changed to the following Comparative Compound 2.

比較化合物2：(東京化成工業公司製造，產品名：鹼性藍(Basic Blue)7) Comparative Compound 2: (manufactured by Tokyo Chemical Industry Co., Ltd., product name: Basic Blue 7)

所述表中，a-10、a-21、a-23、a-28表示以下的結構。 In the table, a-10, a-21, a-23, and a-28 represent the following structures.

<利用著色組成物的著色膜的製作> <Production of Colored Film Using Colored Composition>

以600nm~700nm下的最大吸光度成為1.5~2.0的方式將所述獲得的著色組成物塗佈於100mm×100mm的玻璃基板(1737，康寧(Corning)公司製造)上，利用100℃的烘箱乾燥180秒鐘，於基板上製作著色膜。 The obtained coloring composition was applied to a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) at a maximum absorbance at 600 nm to 700 nm of 1.5 to 2.0, and dried in an oven at 100 ° C. In seconds, a colored film was formed on the substrate.

對所述獲得的著色膜進行下述評價。 The obtained coloring film was subjected to the following evaluation.

<耐熱性> <heat resistance>

對著色膜於230℃下加熱80分鐘後，測定色度變化、即△Eab值。△Eab值是根據加熱前後的紫外線-可見(Ultraviolet-Visable，UV-Vis)光譜而算出。△Eab值小的情況下表示耐熱性優異。 After the colored film was heated at 230 ° C for 80 minutes, the change in chromaticity, that is, the ΔEab value was measured. The ΔEab value was calculated from the ultraviolet-Visable (UV-Vis) spectrum before and after heating. When the ΔEab value is small, the heat resistance is excellent.

<亮度(透射率)> <Brightness (transmittance)>

對著色膜於230℃下加熱80分鐘後，利用分光光度計(MCPD-3700，大塚電子製造)來測定色度，算出亮度。亮度的數值高的情況下，透射率高而良好。 After the colored film was heated at 230 ° C for 80 minutes, the chromaticity was measured by a spectrophotometer (MCPD-3700, manufactured by Otsuka Electronics Co., Ltd.) to calculate the luminance. When the value of the luminance is high, the transmittance is high and good.

<表面狀態> <surface state>

對塗佈後的著色膜進行藉由目測的粗大異物(10μm以上的異物)的觀察、及利用雷射干涉計(zygo)的觀察，評價表面粗糙度Ra。Ra測定值小的情況下表示表面狀態良好，3以上可加以實用。 The surface roughness Ra was evaluated by observing a large foreign matter (a foreign matter of 10 μm or more) visually observed and a observation by a laser interferometer (zygo) on the colored film after coating. When the Ra measurement value is small, the surface state is good, and 3 or more can be used.

表面狀態評價5：Ra為0.001μm以下 Surface state evaluation 5: Ra is 0.001 μm or less

表面狀態評價4：Ra超過0.001μm、且為0.0015μm以下 Surface state evaluation 4: Ra exceeded 0.001 μm and was 0.0015 μm or less

表面狀態評價3：Ra超過0.0015μm、且為0.002μm以下 Surface state evaluation 3: Ra exceeds 0.0015 μm and is 0.002 μm or less

表面狀態評價2：Ra超過0.002μ、且為0.005μm以下，或大量觀察到粗大異物 Surface state evaluation 2: Ra exceeds 0.002 μ and is 0.005 μm or less, or a large amount of foreign matter is observed in a large amount.

表面狀態評價1：Ra超過0.005μm，或大量觀察到粗大異物 Surface state evaluation 1: Ra exceeds 0.005 μm, or a large amount of foreign matter is observed

由所述結果得知，本發明中，可提供透射率及耐熱性優異的著色組成物。另外，得知可使塗佈時的表面狀態亦良好。 From the results, it is understood that in the present invention, a coloring composition excellent in transmittance and heat resistance can be provided. Further, it was found that the surface state at the time of coating was also good.

另一方面得知，比較例的著色組成物難以提供透射率及耐熱性優異的著色組成物。另外得知，難以使塗佈時的表面狀態亦良好。 On the other hand, it was found that the coloring composition of the comparative example is difficult to provide a coloring composition excellent in transmittance and heat resistance. Further, it was found that it was difficult to make the surface state at the time of coating good.

Claims (17)

一種著色組成物，含有：具有三芳基甲烷結構的染料陽離子、相對陰離子X以及與所述相對陰離子X不同的陰離子Y，並且所述染料陽離子含有交聯性基及多聚物結構的至少一種，所述陰離子Y可與所述染料陽離子形成鹽，所述陰離子Y相對於所述染料陽離子之莫耳比，即陰離子Y/染料陽離子，為0.0001~7.0。 A colored composition comprising: a dye cation having a triarylmethane structure, a relative anion X, and an anion Y different from the opposite anion X, and the dye cation contains at least one of a crosslinkable group and a polymer structure, The anion Y may form a salt with the dye cation, and the molar ratio of the anion Y to the dye cation, that is, the anion Y/dye cation, is 0.0001 to 7.0. 如申請專利範圍第1項所述的著色組成物，其中所述染料陽離子為通式(TP1)所表示的染料陽離子及通式(TP2)所表示的染料陽離子的至少一種； 通式(TP1)及通式(TP2)中，Rtp1~Rtp4分別獨立地表示氫原子、烷基或芳基；Rtp5、Rtp6、Rtp8、Rtp9及Rtp11分別獨立地表示取代基；Rtp7表示氫原子、烷基、芳基或NRtp71Rtp72；Rtp71及Rtp72分別獨立地表示氫原子、烷基或芳基；Rtp10表示氫原子、 烷基或芳基；a、b及c分別獨立地表示0~4的整數；於a、b及c為2以上的情形時，Rtp5、Rtp6、Rtp8及Rtp9中的2個亦可相互連結而形成環；Rtp1~Rtp11、Rtp71及Rtp72的至少一個含有多聚物結構或交聯性基。 The coloring composition according to claim 1, wherein the dye cation is at least one of a dye cation represented by the formula (TP1) and a dye cation represented by the formula (TP2); In the general formula (TP1) and the formula (TP2), Rtp 1 to Rtp 4 each independently represent a hydrogen atom, an alkyl group or an aryl group; and Rtp 5 , Rtp 6 , Rtp 8 , Rtp 9 and Rtp 11 each independently represent a substitution. Rtp 7 represents a hydrogen atom, an alkyl group, an aryl group or NRtp 71 Rtp 72 ; Rtp 71 and Rtp 72 each independently represent a hydrogen atom, an alkyl group or an aryl group; Rtp 10 represents a hydrogen atom, an alkyl group or an aryl group; , b and c each independently represent an integer of 0 to 4; when a, b, and c are 2 or more, two of Rtp 5 , Rtp 6 , Rtp 8 , and Rtp 9 may be connected to each other to form a ring; At least one of Rtp 1 to Rtp 11 , Rtp 71 and Rtp 72 contains a polymer structure or a crosslinkable group. 如申請專利範圍第1項或第2項所述的著色組成物，其中所述陰離子Y包含：選自氟陰離子、氯陰離子、溴陰離子、碘陰離子、氰化物離子、過氯酸根陰離子、硼酸根陰離子、PF6-及SbF6-中的至少一種，以及選自-SO3 -、-COO-、-PO4 -、下述通式(A1)所表示的結構及下述通式(A2)所表示的結構中的至少一種； 通式(A1)中，R1及R2分別獨立地表示-SO2-或-CO-； 通式(A2)中，R3表示-SO2-或-CO-；R4及R5分別獨立地表示-SO2-、-CO-或-CN。 The colored composition according to claim 1 or 2, wherein the anion Y comprises: selected from the group consisting of a fluoride anion, a chloride anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, and a borate At least one of an anion, PF 6- and SbF 6- , and a structure selected from the group consisting of -SO 3 - , -COO - , -PO 4 - , the following formula (A1), and the following formula (A2) At least one of the structures represented; In the formula (A1), R 1 and R 2 each independently represent -SO 2 - or -CO-; In the formula (A2), R 3 represents -SO 2 - or -CO-; and R 4 and R 5 each independently represent -SO 2 -, -CO- or -CN. 如申請專利範圍第1項或第2項所述的著色組成物，其中 所述陰離子Y相對於所述染料陽離子之莫耳比即陰離子Y/染料陽離子為0.001~5.0。 The colored composition as described in claim 1 or 2, wherein The molar ratio of the anion Y to the dye cation, i.e., the anionic Y/dye cation, is from 0.001 to 5.0. 如申請專利範圍第1項或第2項所述的著色組成物，其中所述染料陽離子含有多聚物結構。 The coloring composition of claim 1 or 2, wherein the dye cation comprises a polymer structure. 如申請專利範圍第1項或第2項所述的著色組成物，更含有光聚合起始劑。 The coloring composition as described in claim 1 or 2 further contains a photopolymerization initiator. 如申請專利範圍第1項或第2項所述的著色組成物，更含有聚合性化合物。 The colored composition according to Item 1 or Item 2 of the patent application further contains a polymerizable compound. 如申請專利範圍第1項或第2項所述的著色組成物，其是用於形成彩色濾光片的著色層。 The colored composition according to claim 1 or 2, which is a coloring layer for forming a color filter. 一種著色組成物的製造方法，包括以下步驟：於含有具有三芳基甲烷結構的染料陽離子、相對陰離子X、可與所述染料陽離子形成鹽且與所述相對陰離子X不同的陰離子Y以及溶劑的溶液中，至少調配聚合性化合物，並且所述染料陽離子含有交聯性基及多聚物結構的至少一種。 A method for producing a colored composition comprising the steps of: a solution containing a dye cation having a triarylmethane structure, a relative anion X, an anion Y which forms a salt with the dye cation and which is different from the opposite anion X, and a solvent At least one of the polymerizable compounds is formulated, and the dye cation contains at least one of a crosslinkable group and a polymer structure. 如申請專利範圍第9項所述的著色組成物的製造方法，更包括以下步驟：將含有所述染料陽離子與所述相對陰離子X的著色劑以及所述陰離子Y溶解於所述溶劑中。 The method for producing a colored composition according to claim 9, further comprising the step of dissolving a coloring agent containing the dye cation and the opposite anion X and the anion Y in the solvent. 一種著色硬化膜，其是使如申請專利範圍第1項至第8項中任一項所述的著色組成物或者藉由如申請專利範圍第9項或第10項所述的著色組成物的製造方法所得的著色組成物硬化而成。 A colored hardening film which is a coloring composition according to any one of claims 1 to 8 or a coloring composition as described in claim 9 or 10 The colored composition obtained by the production method is cured. 一種彩色濾光片，具有如申請專利範圍第11項所述的著色硬化膜。 A color filter having a colored cured film as described in claim 11 of the patent application. 一種彩色濾光片的製造方法，包括以下步驟：將如申請專利範圍第1項至第8項中任一項所述的著色組成物或者藉由如申請專利範圍第9項或第10項所述的著色組成物的製造方法所得的著色組成物賦予至支撐體上，形成著色組成物層；將所述色組成物層以圖案狀進行曝光；以及將未曝光部顯影去除而形成著色圖案。 A method of manufacturing a color filter, comprising the steps of: applying the coloring composition according to any one of claims 1 to 8 or by claim 9 or 10; The colored composition obtained by the method for producing a colored composition is applied onto a support to form a colored composition layer; the color composition layer is exposed in a pattern; and the unexposed portion is developed and removed to form a colored pattern. 如申請專利範圍第13項所述的彩色濾光片的製造方法，更包括以下步驟：於230℃以上對所述經顯影的著色圖案進行加熱。 The method for producing a color filter according to claim 13, further comprising the step of heating the developed coloring pattern at 230 ° C or higher. 一種彩色濾光片，其是藉由如申請專利範圍第13項或第14項所述的彩色濾光片的製造方法所製造。 A color filter manufactured by the method of producing a color filter according to claim 13 or 14. 一種固體攝像元件，具有如申請專利範圍第12項或第14項所述的彩色濾光片。 A solid-state image sensor having a color filter as described in claim 12 or 14. 一種液晶顯示裝置，具有如申請專利範圍第12項或第14項所述的彩色濾光片。 A liquid crystal display device having a color filter as described in claim 12 or 14.
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