TWI632204B - Colored composition, cured film, color filter, method for manufacturing color filter, solid-state image sensing device, and image display device - Google Patents

Colored composition, cured film, color filter, method for manufacturing color filter, solid-state image sensing device, and image display device Download PDF

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TWI632204B
TWI632204B TW103125025A TW103125025A TWI632204B TW I632204 B TWI632204 B TW I632204B TW 103125025 A TW103125025 A TW 103125025A TW 103125025 A TW103125025 A TW 103125025A TW I632204 B TWI632204 B TW I632204B
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compound
pigment
dye
formula
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TW201506093A (en
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田口貴規
尾田和也
室祐継
渡邉哲也
金子祐士
伊藤純一
鮫島賢
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富士軟片股份有限公司
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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
    • C09B69/10—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
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    • 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
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/205—Neutral density filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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

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Abstract

本發明提供一種於長期放置於低溫度環境下的情形時不易產生異物的著色組成物、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。本發明的著色組成物含有(A)色素多聚物及(B)溶劑，並且(A)色素多聚物具有來源於具有陽離子部位的氧雜蒽色素的部分結構及陰離子部位，著色組成物中的鈉離子濃度及鉀離子濃度的至少一者為0.1ppm~10ppm。 The present invention provides a coloring composition, a cured film, a color filter, a method of producing a color filter, a solid-state image sensor, and an image display device which are less likely to generate foreign matter when left in a low temperature environment for a long period of time. The colored composition of the present invention contains (A) a dye multimer and (B) a solvent, and (A) the dye multimer has a partial structure and an anion site derived from a xanthene dye having a cationic site, and a coloring composition At least one of the sodium ion concentration and the potassium ion concentration is 0.1 ppm to 10 ppm.

Description

著色組成物、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, cured film, color filter, color filter Manufacturing method, solid-state imaging element, and image display device

本發明是有關於一種著色組成物及使用其的硬化膜。另外，本發明是有關於一種具有硬化膜的彩色濾光片、彩色濾光片的製造方法、具有彩色濾光片的固體攝像元件及圖像顯示裝置。 The present invention relates to a colored composition and a cured film using the same. Further, the present invention relates to a color filter having a cured film, a method of manufacturing a color filter, a solid-state image sensor having a color filter, and an image display device.

關於製造液晶顯示裝置或固體攝像元件等中所用的彩色濾光片的方法之一，有顏料分散法，該顏料分散法為以下方法：使用使顏料分散於各種感光性組成物中而成的著色感光性組成物，藉由光微影法來製造彩色濾光片。即，使用旋塗機或輥塗機等將著色組成物塗佈於基板上，加以乾燥而形成塗佈膜，對塗佈膜進行圖案曝光並進行顯影，藉此獲得經著色的畫素。僅依所需的色相程度來反覆進行所述操作，由此製作彩色濾光片。 One of methods for producing a color filter used in a liquid crystal display device, a solid-state image sensor, or the like is a pigment dispersion method in which a coloring method is used in which a pigment is dispersed in various photosensitive compositions. A photosensitive composition is manufactured by a photolithography method to produce a color filter. That is, the colored composition is applied onto a substrate by a spin coater, a roll coater or the like, dried, and a coating film is formed, and the coated film is subjected to pattern exposure and developed to obtain a colored pixel. The above operation is repeated only in accordance with the degree of hue required, thereby producing a color filter.

所述方法因使用顏料，故對光或熱穩定，並且因藉由光微影法來進行圖案化，故可充分確保位置精度，被廣泛地用作適於製造彩色顯示器(color display)用彩色濾光片等的方法。 Since the method is stable to light or heat by using a pigment, and is patterned by photolithography, it can sufficiently ensure positional accuracy, and is widely used as a color suitable for color display. A method such as a filter.

於專利文獻1中揭示，於製作彩色濾光片時使用含有染料或顏料的著色感光性組成物。於專利文獻2中揭示，使用含有氧雜蒽(xanthene)骨架作為色素部位的部分結構的色素多聚物，由此改良顯影性。另外，於專利文獻2中亦揭示了色素多聚物中的陽離子部位與陰離子部位的組合。 Patent Document 1 discloses that a coloring photosensitive composition containing a dye or a pigment is used in the production of a color filter. Patent Document 2 discloses that a dye polymer containing a xanthene skeleton as a partial structure of a dye site is used, thereby improving developability. Further, Patent Document 2 also discloses a combination of a cationic site and an anionic site in a dye polymer.

[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2008-268242號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-268242

[專利文獻2]日本專利特開2012-32754號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-32754

此處得知，於將使用含有以下色素多聚物的組成物所形成的彩色濾光片長期放置於低溫度環境下的情形時，有容易產生異物的傾向，其中所述色素多聚物具有來源於具有陽離子部位的氧雜蒽色素的部分結構、及陰離子部位。 Here, it is known that when a color filter formed using a composition containing the following dye multimer is placed in a low temperature environment for a long period of time, there is a tendency that foreign matter tends to be generated, wherein the dye polymer has It is derived from a partial structure of an xanthene dye having a cationic moiety, and an anion site.

本發明的目的在於解決所述課題，且提供一種於長期放置於低溫度環境下的情形時不易產生異物的著色組成物。 An object of the present invention is to solve the above problems and to provide a coloring composition which is less likely to generate foreign matter when placed in a low temperature environment for a long period of time.

本發明者發現，藉由在含有以下色素多聚物的組成物中將鈉離子濃度及鉀離子濃度的至少一者調整至特定範圍內，可解決所述課題，其中所述色素多聚物具有來源於具有陽離子部位的氧雜蒽色素的部分結構及陰離子部位。 The present inventors have found that the problem can be solved by adjusting at least one of a sodium ion concentration and a potassium ion concentration in a composition containing a dye multimer having a pigment multimer having It is derived from a partial structure and an anion site of a xanthene pigment having a cationic moiety.

具體而言，藉由以下的手段<1>、較佳為手段<2>~手段<14>解決了所述課題。 Specifically, the above problem is solved by the following means <1>, preferably means <2>~ means <14>.

<1>一種著色組成物，含有(A)色素多聚物及(B)溶劑，並且(A)色素多聚物具有來源於具有陽離子部位的氧雜蒽色素的部分結構及陰離子部位，著色組成物中的鈉離子濃度及鉀離子濃度的至少一者為0.1ppm~10ppm。 <1> A coloring composition comprising (A) a dye polymer and (B) a solvent, and (A) a dye polymer having a partial structure and an anion site derived from a oxonium dye having a cationic site, and a coloring composition At least one of the sodium ion concentration and the potassium ion concentration in the substance is 0.1 ppm to 10 ppm.

<2>如<1>所記載的著色組成物，其中著色組成物中的甲苯濃度為1ppm~13ppm。 <2> The colored composition according to <1>, wherein the toluene concentration in the colored composition is from 1 ppm to 13 ppm.

<3>如<1>或<2>所記載的著色組成物，其中著色組成物中的含水率為0.1質量%~5質量%。 <3> The colored composition according to <1> or <2>, wherein the water content in the colored composition is from 0.1% by mass to 5% by mass.

<4>如<1>至<3>中任一項所記載的著色組成物，其中陰離子部位為低親核性的陰離子部位。 The colored composition according to any one of <1> to <3> wherein the anion site is a low nucleophilic anion site.

<5>如<1>至<4>中任一項所記載的著色組成物，更含有酞菁顏料。 <5> The colored composition according to any one of <1> to <4> further comprising a phthalocyanine pigment.

<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，更含有硬化性化合物。 <7> The colored composition according to any one of <1> to <6> further comprising a curable compound.

<8>如<1>至<7>中任一項所記載的著色組成物，其中著色組成物中的鈉離子濃度及鉀離子濃度的至少一者為3ppm~7 ppm。 The colored composition according to any one of <1> to <7>, wherein at least one of a sodium ion concentration and a potassium ion concentration in the coloring composition is 3 ppm to 7 Ppm.

<9>如<1>至<8>中任一項所記載的著色組成物，其為彩色濾光片的著色層形成用。 <9> The colored composition according to any one of <1> to <8> which is used for forming a coloring layer of a color filter.

<10>一種硬化膜，其是使如<1>至<9>中任一項所記載的著色組成物硬化而成。 <10> A cured film obtained by curing the colored composition according to any one of <1> to <9>.

<11>一種彩色濾光片的製造方法，包括以下步驟：將如<1>至<9>中任一項所記載的著色組成物應用於支持體上而形成著色組成物層的步驟；將著色組成物層以圖案狀進行曝光的步驟；以及將未曝光部顯影去除而形成著色圖案的步驟。 <11> A method of producing a color filter, comprising the step of applying the colored composition according to any one of <1> to <9> to a support to form a colored composition layer; a step of exposing the colored composition layer in a pattern; and a step of developing the unexposed portion to form a colored pattern.

<12>一種彩色濾光片的製造方法，包括以下步驟：將如<1>至<9>中任一項所記載的著色組成物應用於支持體上而形成著色組成物層，並使其硬化而形成著色層的步驟；於著色層上形成光阻層的步驟；藉由進行曝光及顯影而將光阻層圖案化，獲得抗蝕劑圖案的步驟；以及將抗蝕劑圖案作為蝕刻遮罩而對著色層進行乾式蝕刻的步驟。 <12> A method of producing a color filter, comprising the step of applying a coloring composition according to any one of <1> to <9> to a support to form a colored composition layer, and a step of forming a coloring layer by hardening; a step of forming a photoresist layer on the colored layer; a step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and using the resist pattern as an etching mask The step of dry etching the colored layer by the cover.

<13>一種彩色濾光片，其為具有如<10>所記載的硬化膜的彩色濾光片、或者藉由如<11>或<12>所記載的彩色濾光片的製造方法所製造的彩色濾光片。 <13> A color filter which is a color filter having a cured film according to <10> or a method of producing a color filter according to <11> or <12>. Color filter.

<14>一種固體攝像元件或圖像顯示裝置，具有如<13>所記載的彩色濾光片。 <14> A solid-state imaging device or image display device comprising the color filter according to <13>.

根據本發明，可提供一種於長期放置於低溫度環境下的情形時不易產生異物的著色組成物。 According to the present invention, it is possible to provide a coloring composition which is less likely to generate foreign matter when left in a low temperature environment for a long period of time.

以下記載的本發明的構成要素的說明有時是根據本發明的具代表性的實施態樣來進行，但本發明不限定於此種實施態樣。 The description of the constituent elements of the present invention described below may be carried out in accordance with a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

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)，並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 Uitraviolet，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" in the present specification 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 Uitraviolet (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.

本說明書中使用「~」表示的數值範圍是指包含「~」 的前後所記載的數值作為下限值及上限值的範圍。 The range of values indicated by "~" in this manual refers to the inclusion of "~" The numerical values described before and after are used as the range of the lower limit and the upper limit.

本說明書中，所謂總固體成分，是指自組成物的總組成中去掉溶劑所得的成分的總質量。 In the present specification, the term "total solid content" means the total mass of the components obtained by removing the solvent from the total composition of the composition.

另外，於本說明書中，「(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)acryloyl group" means either or both of an acryloyl group and a methacryloyl group.

另外，於本說明書中，「單體」與「單體(monomer)」為相同含意。本說明書中的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。於本說明書中，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 monomer in the present specification means a compound which is distinguished from an oligomer and a polymer and has a weight 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.

於本說明書中，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.

<著色組成物> <Coloring composition>

本發明的著色組成物(以下亦稱為本發明的組成物)含有(A)色素多聚物及(B)溶劑，並且所述著色組成物的特徵在於：(A)色素多聚物具有來源於具有陽離子部位的氧雜蒽色素的部分結構(以下有時稱為「色素結構」)及陰離子部位，且本發明的組成物 中的鈉離子濃度及鉀離子濃度的至少一者為0.1ppm~10ppm。 The coloring composition of the present invention (hereinafter also referred to as a composition of the present invention) contains (A) a dye polymer and (B) a solvent, and the coloring composition is characterized in that (A) the pigment polymer has a source a partial structure of a xanthene dye having a cationic site (hereinafter sometimes referred to as "pigment structure") and an anion site, and the composition of the present invention At least one of the sodium ion concentration and the potassium ion concentration is 0.1 ppm to 10 ppm.

根據本發明，可提供一種於長期(例如1個月以上)放置於低溫度環境下(例如-30℃~0℃)的情形時不易產生異物的著色組成物。 According to the present invention, it is possible to provide a coloring composition which is less likely to generate foreign matter when placed in a low temperature environment (for example, -30 ° C to 0 ° C) for a long period of time (for example, 1 month or longer).

其機制雖為推測，但藉由將鈉離子濃度及鉀離子濃度的至少一者設定為10ppm以下，可抑制色素多聚物中的陽離子、與組成物中的鈉離子及鉀離子的至少一者的離子交換反應，使色素結構與組成物中的其他成分(例如樹脂、單體、溶劑等)的相容性更良好。因此，可更有效地抑制色素結構與組成物中的其他成分的相分離。結果於將長期放置於低溫度環境下(例如冷藏保存狀態)的組成物製膜的情形時，可更有效地抑制異物的產生。 Although it is estimated that at least one of the sodium ion concentration and the potassium ion concentration is 10 ppm or less, at least one of the cation in the dye polymer and the sodium ion and potassium ion in the composition can be suppressed. The ion exchange reaction makes the dye structure more compatible with other components in the composition (for example, resin, monomer, solvent, etc.). Therefore, phase separation of the pigment structure from other components in the composition can be more effectively suppressed. As a result, in the case where the composition is placed in a low temperature environment (for example, in a refrigerated storage state) for a long period of time, the generation of foreign matter can be more effectively suppressed.

另外，藉由將鈉離子濃度及鉀離子濃度的至少一者設定為0.1ppm以上，可抑制色素結構與其他成分的相容性變得過高，結果可更有效地抑制異物的產生。 In addition, by setting at least one of the sodium ion concentration and the potassium ion concentration to 0.1 ppm or more, the compatibility between the dye structure and other components can be suppressed from being excessively high, and as a result, the generation of foreign matter can be more effectively suppressed.

尤其較佳為組成物中的鈉離子濃度及鉀離子濃度分別為1ppm~10ppm，更佳為3ppm~7ppm。藉由調整至此種範圍內，可更有效地達成本發明的效果。 It is particularly preferable that the sodium ion concentration and the potassium ion concentration in the composition are 1 ppm to 10 ppm, and more preferably 3 ppm to 7 ppm. By adjusting to such a range, the effects of the present invention can be more effectively achieved.

本發明的組成物較佳為組成物中的甲苯濃度為1ppm~13ppm，更佳為2ppm~10ppm，進而佳為3ppm~7ppm。藉由將甲苯濃度調整至此種範圍內，於將使用本發明的組成物所形成的著色圖案長時間放置的情形時，可更有效地使圖案的線寬均勻。所謂長時間放置，是指於形成著色圖案時，於使用組成物的 膜的形成後將膜長時間放置直至進行i射線曝光為止。 The composition of the present invention preferably has a toluene concentration in the composition of from 1 ppm to 13 ppm, more preferably from 2 ppm to 10 ppm, even more preferably from 3 ppm to 7 ppm. By adjusting the toluene concentration to such a range, when the colored pattern formed using the composition of the present invention is left for a long period of time, the line width of the pattern can be more effectively made uniform. The so-called long-term placement refers to the use of the composition when forming a colored pattern. After the film is formed, the film is left for a long time until i-ray exposure is performed.

藉由將甲苯濃度設定為13ppm以下，可有效地抑制以下情況：甲苯使組成物中的疏水性成分(例如硬化性化合物等)凝聚至必要程度以上。結果，即便長時間放置亦不引起相分離，可維持圖案的線寬更均勻。 By setting the toluene concentration to 13 ppm or less, it is possible to effectively suppress the condensation of a hydrophobic component (for example, a curable compound) in the composition to a required level or more. As a result, even if it is left for a long time, phase separation is not caused, and the line width of the pattern can be maintained more uniform.

另外，藉由將甲苯濃度設定為1ppm以上，可使色素結構中的陽離子部位、與組成物中的疏水性成分的相容性更良好，即便長時間放置亦不引起相分離，可維持圖案的線寬更均勻。例如即便於將放置時間設定為2天以上、將圖案尺寸設定為1.0μm、且使用1.0質量%的氫氧化四甲基銨作為曝光後的顯影液的情形時，亦可維持圖案的線寬更均勻。 Further, by setting the toluene concentration to 1 ppm or more, the compatibility between the cation site in the dye structure and the hydrophobic component in the composition is further improved, and phase separation is not caused even after standing for a long period of time, and the pattern can be maintained. The line width is more uniform. For example, even when the standing time is set to 2 days or more, the pattern size is set to 1.0 μm, and 1.0% by mass of tetramethylammonium hydroxide is used as the developer after exposure, the line width of the pattern can be maintained. Evenly.

本發明的組成物較佳為組成物中的含水率為0.1質量%~5質量%，更佳為0.1質量%~1質量%，進而佳為0.2質量%~0.5質量%。 The composition of the present invention preferably has a water content of from 0.1% by mass to 5% by mass, more preferably from 0.1% by mass to 1% by mass, even more preferably from 0.2% by mass to 0.5% by mass.

藉由將含水率設定為3質量%以下，可更有效地抑制色素多聚物中的陽離子部位與陰離子部位發生分離的情況。對於以陽離子部位與陰離子部位不易分離的狀態形成的膜而言，於低氧濃度下，經光激發的色素自由基不易被氧捕捉(trap)，色素更不易分解。 By setting the water content to 3% by mass or less, it is possible to more effectively suppress the separation of the cation site and the anion site in the dye polymer. In the film formed in a state in which the cationic site and the anion site are not easily separated, the photoexcited dye radical is less likely to be trapped by oxygen at a low oxygen concentration, and the dye is less likely to be decomposed.

另外，藉由將含水率設定為0.1質量%以上，陽離子部位與陰離子部位的距離不會過近，故不易引起光激發時的能量遷移或電子遷移，由此色素更不易分解。結果，即便長期放置於低氧濃度 下亦可維持良好的耐光性。 Further, by setting the water content to 0.1% by mass or more, the distance between the cation site and the anion site is not too close, so that energy migration or electron migration at the time of photoexcitation is less likely to occur, whereby the dye is less likely to be decomposed. As a result, even if placed in a low oxygen concentration for a long time It also maintains good light resistance.

尤其於在低氧濃度下以500勒克斯(lux)的照度照射2個月以上的情形時，亦可維持良好的耐光性。 In particular, when the illuminance of 500 lux is irradiated for 2 months or more at a low oxygen concentration, good light resistance can be maintained.

就長時間熱循環的性能的觀點而言，本發明的組成物較佳為固體成分的電壓保持率為10%~80%，較佳為60%~99%，更佳為80%~99%。 The composition of the present invention preferably has a voltage retention ratio of the solid component of 10% to 80%, preferably 60% to 99%, more preferably 80% to 99%, from the viewpoint of the performance of the long-term heat cycle. .

另外，於本發明中，藉由設定為如上所述的構成，可獲得於經過長期間後黏度的變化率小的著色組成物。例如即便於在室溫(23℃)下經過3個月以上後，亦可減小黏度的變化率。另外，本發明中，於長時間放置於各種溫度(例如-30℃~150℃)及/或高濕度(例如相對濕度80%以上)環境下的情形時，可獲得異物的產生率小的著色組成物。例如於在冷凍(-15℃以下)的環境下放置1個月以上的情形、或於在110℃85%RH的環境下放置2週以上的情形時，亦可減小異物的產生率。 Further, in the present invention, by setting the above configuration, it is possible to obtain a coloring composition having a small change rate of viscosity after a long period of time. For example, even after three months or more at room temperature (23 ° C), the rate of change in viscosity can be reduced. Further, in the present invention, when placed in an environment of various temperatures (for example, -30 ° C to 150 ° C) and/or high humidity (for example, a relative humidity of 80% or more) for a long period of time, a small color generation rate can be obtained. Composition. For example, when it is left to stand for 1 month or more in an environment of freezing (-15 ° C or lower) or when it is left in an environment of 85% RH at 110 ° C for 2 weeks or more, the rate of generation of foreign matter can be reduced.

本發明的組成物可較佳地用於彩色濾光片的著色層的形成用。本發明的著色組成物較佳為含有硬化性化合物及顏料。硬化性化合物可例示聚合性化合物或鹼可溶性樹脂(包括含有聚合性基的鹼可溶性樹脂)，可根據用途或製造方法而適當選擇。進而，本發明的著色組成物較佳為含有光聚合起始劑。 The composition of the present invention can be preferably used for the formation of a coloring layer of a color filter. The colored composition of the present invention preferably contains a curable compound and a pigment. The curable compound may, for example, be a polymerizable compound or an alkali-soluble resin (including an alkali-soluble resin containing a polymerizable group), and may be appropriately selected depending on the use or the production method. Further, the colored composition of the present invention preferably contains a photopolymerization initiator.

例如於藉由光阻來形成著色層的情形時，本發明的著色組成物較佳為含有色素多聚物、溶劑、作為硬化性化合物的鹼可溶性樹脂、顏料及光聚合起始劑。進而亦可含有界面活性劑等成分。 For example, when a coloring layer is formed by photoresist, the coloring composition of the present invention preferably contains a dye polymer, a solvent, an alkali-soluble resin as a curable compound, a pigment, and a photopolymerization initiator. Further, it may contain a component such as a surfactant.

另外，於藉由乾式蝕刻來形成著色層的情形時，較佳為含有色素多聚物、溶劑、作為硬化性化合物的聚合性化合物、顏料及光聚合起始劑。進而亦可含有界面活性劑等成分。 Further, in the case where the colored layer is formed by dry etching, a dye polymer, a solvent, a polymerizable compound as a curable compound, a pigment, and a photopolymerization initiator are preferably contained. Further, it may contain a component such as a surfactant.

<<(A)色素多聚物>> <<(A) Pigment Polymer>>

色素多聚物包含二聚物、三聚物及聚合物等結構。色素多聚物於本發明的著色組成物中例如作為著色劑發揮功能。 The dye polymer contains a structure such as a dimer, a trimer, and a polymer. The dye polymer functions as a colorant in the coloring composition of the present invention, for example.

色素多聚物較佳為最大吸收波長為420nm~700nm，更佳為450nm~650nm。 The dye multipolymer preferably has a maximum absorption wavelength of from 420 nm to 700 nm, more preferably from 450 nm to 650 nm.

色素多聚物的酸值較佳為5mgKOH/g~100mgKOH/g，更佳為15mgKOH/g~60mgKOH/g。 The acid value of the dye polymer is preferably from 5 mgKOH/g to 100 mgKOH/g, more preferably from 15 mgKOH/g to 60 mgKOH/g.

本發明中，於將重複單元的合計值設定為100mol%時，於色素多聚物中，含有來源於色素的結構的重複單元較佳為10mol%~100mol%，更佳為50mol%~100mol%，尤佳為60mol%~100mol%。 In the present invention, when the total value of the repeating unit is 100 mol%, the repeating unit containing the dye-derived structure in the dye polymer is preferably 10 mol% to 100 mol%, more preferably 50 mol% to 100 mol%. It is preferably 60 mol% to 100 mol%.

色素多聚物具有來源於具有陽離子部位的氧雜蒽色素的部分結構及陰離子部位。色素多聚物的較佳形態可列舉以下形態。 The dye multimer has a partial structure and an anion site derived from a xanthene pigment having a cationic site. A preferred form of the dye polymer is as follows.

(A1)含有以下重複單元且具有抗衡陰離子部位的色素多聚物，所述重複單元具有來源於具有陽離子部位的氧雜蒽色素的部分結構。 (A1) A dye multimer having a repeating unit having a partial structure derived from a xanthene dye having a cationic moiety, having a repeating unit.

(A2)含有以下重複單元且所述色素結構具有陰離子部位的色素多聚物，所述重複單元具有來源於具有陽離子部位的氧雜蒽 色素的部分結構。 (A2) a dye multimer having the following repeating unit and having an anionic moiety of the dye structure, the repeating unit having a xanthene derived from a cationic moiety Part of the structure of the pigment.

(A3)含有以下單體及具有抗衡陰離子部位的重複單元的色素多聚物，所述單體具有來源於具有陽離子部位的氧雜蒽色素的部分結構。 (A3) A dye multimer comprising a monomer having a repeating unit having a counter anion moiety, and the monomer having a partial structure derived from a xanthene dye having a cationic moiety.

(A4)於所述色素多聚物中，更具有其他陽離子及陰離子部位的色素多聚物。 (A4) A dye multimer having a further cation and an anion site in the dye polymer.

以下，對各形態加以詳細說明。 Hereinafter, each aspect will be described in detail.

<<<(A1)的形態>>> <<<(A1) form>>>

<<<<抗衡陰離子部位>>>> <<<<Counting anion site>>>>

色素多聚物(A)所具有的抗衡陰離子部位較佳為非親核性。所謂非親核性，是指不因加熱而對色素進行親核攻擊的性質。 The counter anion site of the dye polymer (A) is preferably non-nucleophilic. The term "non-nucleophilic" refers to the property of not subjecting a pigment to nucleophilic attack by heating.

抗衡陰離子可為有機陰離子，亦可為無機陰離子，較佳為有機陰離子。陰離子的例子可列舉日本專利特開2007-310315號公報的段落編號0075中記載者，將其內容併入至本申請案說明書中。 The counter anion may be an organic anion or an inorganic anion, preferably an organic anion. An example of the anion is described in paragraph number 0075 of JP-A-2007-310315, the contents of which are incorporated herein by reference.

較佳可列舉：雙(磺醯基)醯亞胺陰離子、三(磺醯基)甲基化物陰離子、四芳基硼酸鹽陰離子、B-(CN)n1(ORa)4-n1(Ra表示碳數1~10的烷基或碳數6~10的芳基，n1表示1~4)及PFn2RP (6-n2) -(RP表示碳數1~10的氟化烷基，n2表示1~6的整數)，更佳為選自雙(磺醯基)醯亞胺陰離子、三(磺醯基)甲基化物陰離子及四芳基硼酸鹽陰離子中，進而佳為雙(磺醯基)醯亞胺陰離子。藉由使用此種抗衡陰離子，有更有效地發揮本發明的效果的傾向。 Preferably, bis(sulfonyl) quinone imine anion, tris(sulfonyl) methide anion, tetraaryl borate anion, B - (CN) n1 (OR a ) 4-n1 (R a An alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, n1 representing 1 to 4) and PF n2 R P (6-n2) - (R P represents a fluorinated alkyl group having 1 to 10 carbon atoms , n2 represents an integer of 1 to 6), more preferably selected from the group consisting of a bis(sulfonyl) quinone imine anion, a tris(sulfonyl)methide anion, and a tetraarylborate anion, and more preferably a double ( Sulfhydryl) quinone imine. By using such a counter anion, there is a tendency that the effects of the present invention are more effectively exhibited.

雙(磺醯基)醯亞胺陰離子較佳為下述通式(AN-1)所表 示的結構。 The bis(sulfonyl) quinone imine anion is preferably represented by the following formula (AN-1) The structure shown.

(式(AN-1)中，X1及X2分別獨立地表示氟原子或含氟原子的碳數1~10的烷基。X1及X2亦可相互鍵結而形成環) (In the formula (AN-1), X 1 and X 2 each independently represent a fluorine atom or an alkyl group having a fluorine atom of 1 to 10 carbon atoms. X 1 and X 2 may be bonded to each other to form a ring)

X1及X2分別獨立地表示氟原子或含氟原子的碳數1~10的烷基，較佳為氟原子或含氟原子的碳數1~10的烷基，更佳為碳數1~10的全氟烷基，進而佳為碳數1~4的全氟烷基，尤佳為三氟甲基。 X 1 and X 2 each independently represent a fluorine atom or a fluorine atom having 1 to 10 carbon atoms, preferably a fluorine atom or a fluorine atom having 1 to 10 carbon atoms, more preferably a carbon number of 1. A perfluoroalkyl group of ~10, more preferably a perfluoroalkyl group having 1 to 4 carbon atoms, particularly preferably a trifluoromethyl group.

三(磺醯基)甲基化物陰離子較佳為下述通式(AN-2)的結構。 The tris(sulfonyl)methide anion is preferably a structure of the following formula (AN-2).

(式(AN-2)中，X3、X4及X5分別獨立地表示氟原子或碳數1~10的含氟原子的烷基) (In the formula (AN-2), X 3 , X 4 and X 5 each independently represent a fluorine atom or an alkyl group having a fluorine atom of 1 to 10 carbon atoms)

X3、X4及X5分別獨立地與X1及X2為相同含意，較佳範圍亦 為相同含意。 X 3 , X 4 and X 5 are each independently the same as X 1 and X 2 , and the preferred ranges are also the same.

四芳基硼酸鹽陰離子較佳為下述通式(AN-5)所表示的化合物。 The tetraarylborate anion is preferably a compound represented by the following formula (AN-5).

(式(AN-5)中，Ar1、Ar2、Ar3及Ar4分別獨立地表示芳基)Ar1、Ar2、Ar3及Ar4分別獨立地較佳為碳數6~20的芳基，更佳為碳數6~14的芳基，進而佳為碳數6~10的芳基。 (In the formula (AN-5), Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represent an aryl group.) Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently preferably a carbon number of 6 to 20. The aryl group is more preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms.

Ar1、Ar2、Ar3及Ar4所表示的芳基亦可具有取代基。於具有取代基的情形時，可列舉：鹵素原子、烷基、芳基、烷氧基、羰基、羰氧基、胺甲醯基、磺基、磺醯胺基、硝基等，較佳為鹵素原子及烷基，更佳為氟原子、烷基，進而佳為氟原子、碳數1~4的全氟烷基。 The aryl group represented by Ar 1 , Ar 2 , Ar 3 and Ar 4 may have a substituent. In the case of having a substituent, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, an amine carbaryl group, a sulfo group, a sulfonylamino group, a nitro group, etc. may be mentioned, and preferably The halogen atom and the alkyl group are more preferably a fluorine atom or an alkyl group, and more preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.

Ar1、Ar2、Ar3及Ar4分別獨立地更佳為具有鹵素原子及/或含鹵素原子的烷基的苯基，進而佳為具有氟原子及/或含氟的烷基的苯基。 Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently preferably a phenyl group having a halogen atom and/or a halogen atom-containing alkyl group, and more preferably a phenyl group having a fluorine atom and/or a fluorine-containing alkyl group. .

抗衡陰離子部位另較佳為-B(CN)n1(ORa)4-n1(Ra表示碳數1~10的烷基或碳數6~10的芳基，n1表示1~4的整數)。作 為碳數1~10的烷基的Ra較佳為碳數1~6的烷基，更佳為碳數1~4的烷基。作為碳數6~10的芳基的Ra較佳為苯基、萘基。 Further, the counter anion moiety is preferably -B(CN) n1 (OR a ) 4-n1 (R a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n1 represents an integer of 1 to 4) . R a of the alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. R a which is an aryl group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group.

n1較佳為1~3，更佳為1~2。 N1 is preferably from 1 to 3, more preferably from 1 to 2.

進而，抗衡陰離子部位另較佳為-PF6RP (6-n2) -(RP表示碳數1~10的氟化烷基，n2表示1~6的整數)。RP較佳為碳數1~6的含氟原子的烷基，更佳為碳數1~4的含氟的烷基，進而佳為碳數1~3的全氟烷基。 Further, the counter anion site is preferably -PF 6 R P (6-n2) - (R P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n 2 represents an integer of 1 to 6). R P is preferably a fluorine atom-containing alkyl group having 1 to 6 carbon atoms, more preferably a fluorine-containing alkyl group having 1 to 4 carbon atoms, and still more preferably a perfluoroalkyl group having 1 to 3 carbon atoms.

n2較佳為1~4的整數，更佳為1或2。 N2 is preferably an integer of 1 to 4, more preferably 1 or 2.

抗衡陰離子部位的每一分子的質量較佳為100~1,000，更佳為200~500。 The mass of each molecule in the counter anion site is preferably from 100 to 1,000, more preferably from 200 to 500.

色素多聚物可僅含有一種抗衡陰離子部位，亦可含有兩種以上。 The dye polymer may contain only one kind of counter anion site, and may contain two or more types.

以下示出抗衡陰離子部位的具體例，但本發明不限定於此。 Specific examples of the counter anion site are shown below, but the present invention is not limited thereto.

[化4] [Chemical 4]

[化6] [Chemical 6]

[化7] [Chemistry 7]

<<<<色素結構>>>> <<<<Pigment Structure>>>>

本發明所謂色素結構，為來源於具有陽離子部位的氧雜蒽色素的部分結構，且是指自可形成色素結構的具體色素(以下亦稱為色素化合物)中去掉氫原子所得的可與色素多聚物連結部(聚 合物鏈或樹枝狀聚合物(dendrimer)的核心(core)等)連結的結構。以下，對該等的詳細情況加以說明。 The dye structure of the present invention is a partial structure derived from a xanthene dye having a cationic moiety, and is a pigment which is obtained by removing a hydrogen atom from a specific pigment (hereinafter also referred to as a dye compound) capable of forming a dye structure. Polymer junction A structure in which a compound chain or a core of a dendrimer is linked. The details of these will be described below.

色素結構只要為來源於具有陽離子部位的氧雜蒽色素的結構，則並無特別限制，可應用包含公知者的各種結構。 The dye structure is not particularly limited as long as it is derived from a oxonium dye having a cationic moiety, and various structures including a known one can be applied.

色素多聚物(A)包括具有來源於下述通式(J)所表示的氧雜蒽化合物的部分結構作為色素部位的部分結構者。 The dye polymer (A) includes a partial structure having a partial structure derived from a xanthene compound represented by the following formula (J) as a dye site.

(通式(J)中，R81、R82、R83及R84分別獨立地表示氫原子或一價取代基，R85分別獨立地表示一價取代基，m表示0~5的整數。X-表示抗衡陰離子部位) (In the general formula (J), R 81 , R 82 , R 83 and R 84 each independently represent a hydrogen atom or a monovalent substituent, R 85 each independently represents a monovalent substituent, and m represents an integer of 0 to 5. X - indicates a counter anion site)

通式(J)中的R81~R84及R85可取的取代基與後述取代基組群A的項中列舉的取代基相同。 The substituents which may be taken from R 81 to R 84 and R 85 in the formula (J) are the same as those exemplified in the item of the substituent group A to be described later.

通式(J)中的R81與R82、R83與R84、及m為2以上的情形的R85彼此亦可分別獨立地相互鍵結而形成5員、6員或7員的飽和環或者5員、6員或7員的不飽和環。於所形成的5員、6 員或7員的環為可進一步經取代的基團的情形時，可經所述R81~R85中說明的取代基所取代，於經2個以上的取代基取代的情形時，該些取代基可相同亦可不同。 In the general formula (J), R 81 and R 82 , R 83 and R 84 , and R 85 in the case where m is 2 or more may be independently bonded to each other to form a saturation of 5 members, 6 members or 7 members. Ring or unsaturated ring of 5, 6 or 7 members. In the case where the ring of 5, 6 or 7 members formed is a group which may be further substituted, it may be substituted by the substituent described in R 81 to R 85 and substituted by 2 or more. In the case of a base substitution, the substituents may be the same or different.

於通式(J)中的R81與R82、R83與R84、及m為2以上的情形的R85彼此分別獨立地相互鍵結而形成不具有取代基的5員、6員及7員的飽和環或者5員、6員及7員的不飽和環的情形時，不具有取代基的5員、6員及7員的飽和環或者5員、6員及7員的不飽和環例如可列舉：吡咯環、呋喃環、噻吩環、吡唑環、咪唑環、***環(triazole ring)、噁唑環、噻唑環、吡咯啶環、哌啶環、環戊烯環、環己烯環、苯環、吡啶環、吡嗪環、噠嗪環(pyridazine)，較佳可列舉苯環、吡啶環。 In the general formula (J), R 81 and R 82 , R 83 and R 84 , and R 85 in the case where m is 2 or more are each independently bonded to each other to form 5 members and 6 members having no substituent. In the case of a saturated ring of 7 members, or an unsaturated ring of 5 members, 6 members, and 7 members, the saturation ring of 5 members, 6 members, and 7 members without substituents or the unsaturated members of 5 members, 6 members, and 7 members Examples of the ring include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, a piperidine ring, a cyclopentene ring, and a ring. The hexene ring, the benzene ring, the pyridine ring, the pyrazine ring, and the pyridazine ring are preferably a benzene ring or a pyridine ring.

尤佳為R82及R83為氫原子或者經取代或未經取代的烷基，R81及R84為經取代或未經取代的烷基或苯基。另外，R85較佳為鹵素原子、碳數1~5的直鏈或分支的烷基、磺基、磺醯胺基、羧基、醯胺基，更佳為磺基、磺醯胺基、羧基、醯胺基。R85較佳為鍵結於與氧雜蒽環連結的碳的鄰接部。R81及R84的苯基所具有的取代基尤佳為氫原子、鹵素原子、碳數1~5的直鏈或分支的烷基、磺基、磺醯胺基、羧基。 More preferably, R 82 and R 83 are a hydrogen atom or a substituted or unsubstituted alkyl group, and R 81 and R 84 are a substituted or unsubstituted alkyl group or a phenyl group. Further, R 85 is preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonylamino group, a carboxyl group or a decylamino group, more preferably a sulfo group, a sulfonylamino group or a carboxyl group. , amidino group. R 85 is preferably an abutting portion bonded to carbon bonded to the xanthene ring. The substituent of the phenyl group of R 81 and R 84 is preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonylamino group or a carboxyl group.

通式(J)所表示的具有氧雜蒽骨架的化合物可藉由文獻記載的方法來合成。具體可應用「四面體通訊(Tetrahedron Letters)」(2003年、vol.44、No.23、4355頁~4360頁)、「四面體」(2005年、vol.61、No.12、3097頁~3106頁)等中記載的方法。 The compound having a xanthene skeleton represented by the formula (J) can be synthesized by a method described in the literature. Specifically, "Tetrahedron Letters" (2003, vol. 44, No. 23, 4355 pages - 4360 pages) and "tetrahedron" can be applied (2005, vol. 61, No. 12, 3097 pages ~ The method described in 3106).

以下示出氧雜蒽化合物的具體例，但本發明不限定於此。 Specific examples of the xanthene compound are shown below, but the present invention is not limited thereto.

[表2] [Table 2]

[化10] [化10]

關於色素多聚物，只要不偏離本發明的主旨，則色素結構中的氫原子亦可經選自下述取代基組群A中的取代基所取代。 Regarding the dye polymer, the hydrogen atom in the dye structure may be substituted with a substituent selected from the following substituent group A as long as it does not deviate from the gist of the present invention.

取代基組群A： Substituent group A:

色素多聚物可具有的取代基可列舉：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(phosphinyl)、氧膦基氧基、氧膦基胺基、矽烷基等。以下記載詳細情況。 The substituent which the dye polymer may have may 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 or an alkane. Oxyl, aryloxy, nonyloxy, heterocyclooxy, nonyloxy, amine methyloxy, amine (including alkylamino, anilino) Alkoxycarbonylamino, aryloxycarbonylamino, aminesulfonylamino, alkylsulfonylamino or arylsulfonylamino, fluorenyl, alkylthio, arylthio, heterocyclic sulfur Alkylsulfonyl, sulfo, alkylsulfinyl or arylsulfinyl, alkylsulfonyl or arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, amine A decyl group, an aryl azo group or a 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、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氮原子、氧原子及硫原子中的至少任一個雜原子的雜環基，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(benzothiazolyl))、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氧基、碳數6~30的經取代或未經取代的芳基羰氧基，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(morpholinyl carbonyloxy)、N,N-二-正辛基胺基羰氧基、N-正辛基胺甲醯氧基)、烷氧基羰氧基(較佳為碳數2~30的經取代或未經取代烷氧基羰氧基，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、甲基胺基、二甲基胺基、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-二甲基胺基羰基胺基、N,N-二乙基胺基羰基胺基、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(較佳為碳數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-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)，例如苯基偶氮基、p-氯苯基偶氮基、5-乙硫基-1,3,4-噻二唑-2-基偶氮基)、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-琥珀醯亞胺、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，例如二苯氧基氧膦基氧基、二辛氧基氧膦基氧基)、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 unsubstituted 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 bicyclo [ a group having a polycyclic structure such as heptane-2-yl, bicyclo[2.2.2]oct-3-yl) or tricycloalkyl. Preferred is a monocyclic cycloalkyl or bicycloalkyl group. More preferably, it is a monocyclic cycloalkyl group, a linear or branched alkenyl group (a linear or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as a vinyl group). , allyl, isoprenyl, geranyl, oleyl), cycloalkenyl (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, for example, a 2-ring Penten-1-yl, 2-cyclohexen-1-yl, polycycloalkenyl, such as bicycloalkenyl (preferably substituted or unsubstituted bicycloalkenyl having 5 to 30 carbon atoms, such as bicyclo [ 2.2.1] hept-2-en-1-yl, bicyclo[2.2.2]oct-2-en-4-yl) or tricycloalkenyl, especially preferably monocyclic cycloalkenyl), a base (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group, a propargyl group, a trimethyldecyl ethynyl group), an aryl group (preferably having a carbon number of 6 to 30) Substituted or unsubstituted aryl, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl, heterocyclic (preferably 5 to 7 members) a substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably a ring-forming atom is selected from the group consisting of a carbon atom, a nitrogen atom and a sulfur atom and has The heterocyclic group of at least one of a nitrogen atom, an oxygen atom and a sulfur atom is more preferably a 5-membered or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. For example, 2-furyl group, 2- Thienyl, 2-pyridyl, 4- Pyridyl, 2-pyrimidinyl, 2-benzothiazolyl, cyano, hydroxy, nitro, carboxy, alkoxy (preferably substituted or unsubstituted alkyl having 1 to 30 carbon atoms) An oxy group such as a methoxy group, an ethoxy group, an isopropoxy group, a third butoxy group, a n-octyloxy group, a 2-methoxyethoxy group, an aryloxy group (preferably having a carbon number of 6 to 30) Substituted or unsubstituted aryloxy group, such as phenoxy, 2-methylphenoxy, 2,4-di-p-pentylphenoxy, 4-tert-butylphenoxy, 3 -Nitrophenoxy, 2-tetradecylideneaminophenoxy), decyloxy (preferably a decyloxy group having a carbon number of 3 to 20, such as trimethyldecyloxy, tert-butyl a dimethyl decyloxy group, a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, preferably a heterocyclic group as described above) Heterocyclic moiety, such as 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), decyloxy (preferably methyloxy), substituted or not having a carbon number of 2 to 30 Substituted alkylcarbonyloxy group, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as methyl methoxy, ethoxylated, three Methyl ethoxylated, stearyloxy, benzhydryloxy, p-methoxyphenylcarbonyloxy), amine methoxycarbonyl (preferably substituted or not having a carbon number of 1 to 30) Substituted amine methyl methoxy, such as N,N-dimethylamine methyl methoxy, N,N-diethylamine methoxyoxy, morpholinyl carbonyloxy, N,N- Di-n-octylaminocarbonyloxy, N-n-octylaminemethyloxy), alkoxycarbonyloxy (preferably substituted or unsubstituted alkoxycarbonyl having 2 to 30 carbon atoms) a group such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, an n-octylcarbonyloxy group, an aryloxycarbonyloxy group (preferably having a carbon number of 7 to 30) Substituted or unsubstituted aryloxycarbonyloxy group, such as phenoxycarbonyloxy, p-methoxyphenoxy a carbonyloxy group, a p-hexadecaneoxyphenoxycarbonyloxy group, an amine group (preferably an amine group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a carbon number of 6) ~30 substituted or unsubstituted arylamino group, heterocyclic amino group having 0 to 30 carbon atoms, such as amino group, methylamino group, dimethylamino group, anilino group, N-methyl-aniline Substituted or diphenylamino, N-1,3,5-triazin-2-ylamino), mercaptoamine (preferably a mercaptoamine group, substituted or not having a carbon number of 1 to 30) a substituted alkylcarbonylamino group, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as a decylamino group, an ethenylamino group, a trimethylethenylamino group, Laurel-based amino group, benzhydrylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, aminocarbonylamino group (preferably substituted with carbon number 1 to 30 or Unsubstituted aminocarbonylamino group, for example, an aminomethylamino group, N,N-dimethylaminocarbonylamino group, N,N-diethylaminocarbonylamino group, morpholinylcarbonylamino group An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as a methoxycarbonylamino group, Oxycarbonylamino group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group, aryloxycarbonylamino group (preferably carbon number) 7 to 30 substituted or unsubstituted aryloxycarbonylamino groups, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m-octyloxyphenoxycarbonylamino), amine sulfonate A mercaptoamine group (preferably a substituted or unsubstituted sulfonylamino group having a carbon number of 0 to 30, such as an aminesulfonylamino group, an N,N-dimethylaminosulfonylamino group , N-n-octylaminosulfonylamino), alkylsulfonylamino or arylsulfonylamino (preferably substituted or unsubstituted alkylsulfon having 1 to 30 carbon atoms) Mercaptoamine group, substituted or unsubstituted aryl group having 6 to 30 carbon atoms Sulfhydrylamino group, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methyl Phenylsulfonylamino), mercapto, alkylthio (preferably substituted or unsubstituted alkylthio having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio , arylthio (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), heterocyclic thio (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, and the heterocyclic ring is preferably a heterocyclic moiety described in the above heterocyclic group, for example, 2-benzothiazole sulfur a group, a 1-phenyltetrazol-5-thio group, an amine sulfonyl group (preferably a substituted or unsubstituted sulfonyl group having a carbon number of 0 to 30, such as N-ethylamine sulfonyl) , N-(3-dodecyloxypropyl)amine sulfonyl, N,N-dimethylamine sulfonyl, N-acetamimidoxime, N-benzamidesulfonate , N-(N'-phenylaminocarbamimidino)sulfonyl), sulfo, alkylsulfinyl or arylsulfinyl (preferably substituted with 1 to 30 carbon atoms) Unsubstituted A sulfinyl group, a substituted or unsubstituted arylsulfinyl group of 6 to 30, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylbenzene a sulfinyl group, an alkylsulfonyl group or an arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, 6 to 30 substituted or unsubstituted Substituted arylsulfonyl, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), mercapto (preferably formazan, carbon number 2) a substituted or unsubstituted alkylcarbonyl group of ~30, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as an ethyl fluorenyl group, a trimethylethyl fluorenyl group, a 2-chloroethyl fluorenyl group, Stearic acid, benzene Mercapto, n-octyloxyphenylcarbonyl), aryloxycarbonyl (preferably substituted or unsubstituted aryloxycarbonyl having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxy) a carbonyl group, a m-nitrophenoxycarbonyl group, a p-tert-butylphenoxycarbonyl group, an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having a carbon number of 2 to 30, such as methoxy) a carbonyl group, an ethoxycarbonyl group, a third butoxycarbonyl group, an n-octadecyloxycarbonyl group, an amine carbenyl group (preferably a substituted or unsubstituted amine carbenyl group having 1 to 30 carbon atoms, For example, amine methyl sulfhydryl, N-methylamine methyl fluorenyl, N,N-dimethylamine carbhydryl, N,N-di-n-octylamine carbhydryl, N-(methylsulfonyl) Aminomethyl), arylazo or heterocyclic azo (preferably substituted or unsubstituted aryl azo having 6 to 30 carbon atoms, substituted or not having a carbon number of 3 to 30) a substituted heterocyclic azo group (the heterocyclic moiety is preferably a heterocyclic moiety described in the above heterocyclic group), for example, phenylazo, p-chlorophenylazo, 5-B Thio-1,3,4-thiadiazol-2-ylazo), quinone imine (preferably substituted or unsubstituted with 2 to 30 carbon atoms) A quinone imine group, such as N-succinimide, N-phthalimine, a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethyl a phosphinyl group, a diphenylphosphino group, a methylphenoxyphosphino group, a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as a phosphinyl group, a dioctyl group) Oxyphosphorylphosphine, diethoxyphosphinyl), phosphinyloxy (preferably substituted or unsubstituted phosphinyloxy having 2 to 30 carbon atoms, such as diphenoxy phosphine oxide a oxy group, a dioctyloxyphosphinyloxy group, a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxy phosphine oxide) Alkylamino, dimethylaminophosphinylamino), decylalkyl (preferably substituted or unsubstituted alkylene group having a carbon number of 3 to 30, such as trimethyl 矽alkyl, tert-butyldimethylmethyl, phenyldimethylalkyl).

所述官能基中，具有氫原子的官能基中的氫原子的部分亦可經所述任一基團所取代。可作為取代基而導入的官能基的例子可列舉烷基羰基胺基磺醯基、芳基羰基胺基磺醯基、烷基磺醯基胺基羰基、芳基磺醯基胺基羰基，具體可列舉甲基磺醯基胺基羰基、對甲基苯基磺醯基胺基羰基、乙醯基胺基磺醯基、苯甲醯基胺基磺醯基。 In the functional group, a portion of a hydrogen atom in a functional group having a hydrogen atom may be substituted with any of the groups. Examples of the functional group which can be introduced as a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an ethenylaminosulfonyl group, and a benzhydrylaminosulfonyl group.

<色素多聚物的結構> <Structure of Pigment Polymer>

本發明的著色組成物中所用的色素多聚物(A)並無特別限定，較佳為含有下述通式(a1-1)及通式(a1-2)所表示的重複單元的至少一個的色素多聚物、或通式(a1-3)所表示的色素多聚物。通式(a1-1)所表示的重複單元於一種色素多聚物中可僅含有一種，亦可含有兩種以上。進而，如後述，亦可含有其他重複單元。 The dye polymer (A) used in the colored composition of the present invention is not particularly limited, and preferably contains at least one repeating unit represented by the following general formula (a1-1) and formula (a1-2). A dye polymer or a dye polymer represented by the formula (a1-3). The repeating unit represented by the formula (a1-1) may be contained alone or in combination of two or more kinds. Further, as will be described later, other repeating units may be contained.

本發明中，較佳為含有通式(a1-1)所表示的色素多聚物。對該等依序進行說明。 In the present invention, it is preferred to contain the dye polymer represented by the formula (a1-1). These are described in order.

<<通式(a1-1)所表示的重複單元>> <<Repeating unit represented by the general formula (a1-1)>>

(通式(a1-1)中，X1表示形成主鏈的基團，L1表示單鍵或二價連結基。DyeI表示具有陽離子部位的色素結構) (In the formula (a1-1), X 1 represents a group forming a main chain, and L 1 represents a single bond or a divalent linking group. DyeI represents a dye structure having a cationic moiety)

以下，對通式(a1-1)加以詳細說明。 Hereinafter, the general formula (a1-1) will be described in detail.

通式(a1-1)中，X1表示形成主鏈的基團。即，是指形成相當於聚合反應中形成的主鏈的重複單元的部分。X1只要為由公知的可聚合的單體所形成的連結基，則並無特別限制，尤佳為下述(XX-1)~(X-24)所表示的連結基，更佳為選自(XX-1)及(XX-2)所表示的(甲基)丙烯酸系連結鏈、(XX-10)~(XX-17)所表示的苯乙烯系連結鏈、及(XX-24)所表示的乙烯基系連結鏈中，進而佳為(XX-1)及(XX-2)所表示的(甲基)丙烯酸系連結鏈及(XX-11)所表示的苯乙烯系連結鏈。 In the formula (a1-1), X 1 represents a group forming a main chain. That is, it means a part which forms a repeating unit corresponding to the main chain formed in a polymerization reaction. By linking groups X 1 as long as the known polymerizable monomers can be formed, is not particularly limited, particularly preferably the following (XX-1) ~ (X -24) represented by the linking group, more preferably selected from the group a (meth)acrylic linking chain represented by (XX-1) and (XX-2), a styrene-based linking chain represented by (XX-10) to (XX-17), and (XX-24) Further, among the vinyl-based linking chains, the (meth)acrylic linking chain represented by (XX-1) and (XX-2) and the styrene-based linking chain represented by (XX-11) are preferable.

(XX-1)~(XX-24)中，表示於*所表示的部位上與L1連結。 In (XX-1) to (XX-24), it is shown that it is connected to L 1 at a portion indicated by *.

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。 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.

[化12] [化12]

通式(a1-1)中，L1表示單鍵或二價連結基。於L1表示二價連結基的情形時，所述二價連結基表示碳數1~30的經取代 或未經取代的伸烷基(例如亞甲基、伸乙基、三亞甲基、伸丙基、伸丁基等)、碳數6~30的經取代或未經取代的伸芳基(例如伸苯基、伸萘基等)、經取代或未經取代的雜環連結基、-CH=CH-、-O-、-S-、-C(=O)-、-CO2-、-NR-、-CONR-、-O2C-、-SO-、-SO2-及將該等的2個以上連結而形成的連結基。L1更佳為單鍵或伸烷基，進而佳為單鍵或-(CH2)n-(n為1~5的整數)。此處，R分別獨立地表示氫原子、烷基、芳基或雜環基。 In the formula (a1-1), L 1 represents a single bond or a divalent linking group. In the case where L 1 represents a divalent linking group, the divalent linking group represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example, methylene, ethylidene, trimethylene, or exo) a propyl group, a butyl group, etc.), a substituted or unsubstituted extended aryl group having 6 to 30 carbon atoms (e.g., a phenyl group, a phenylene group, etc.), a substituted or unsubstituted heterocyclic linker, CH=CH-, -O-, -S-, -C(=O)-, -CO 2 -, -NR-, -CONR-, -O 2 C-, -SO-, -SO 2 - and Two or more of the linking groups formed by the connection. L 1 is more preferably a single bond or an alkyl group, and is preferably a single bond or -(CH 2 )n- (n is an integer of 1 to 5). Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

L1所表示的二價連結基亦可為可與DyeI形成離子鍵或配位鍵的基團。於該情形時，陰離子性基或陽離子性基均可。 The divalent linking group represented by L 1 may also be a group which can form an ionic bond or a coordinate bond with DyeI. In this case, an anionic group or a cationic group may be used.

陰離子性基可列舉-COO-、-PO3H-、-SO3 -、-SO3NH-、-SO3N-CO-等，較佳為-COO-、-PO3H-、-SO3 -。 Examples of the anionic group include -COO - , -PO 3 H - , -SO 3 - , -SO 3 NH - , -SO 3 N - CO-, etc., preferably -COO - , -PO 3 H - , -SO 3 - .

陽離子性基可列舉經取代或未經取代的鎓陽離子(例如銨、吡啶鎓、咪唑鎓(imidazolium)及鏻(phosphonium)等)，尤佳為銨陽離子。 The cationic group may, for example, be a substituted or unsubstituted phosphonium cation (for example, ammonium, pyridinium, imidazolium, and phosphonium), and particularly preferably an ammonium cation.

於L1具有可與DyeI形成離子鍵或配位鍵的基團的情形時，L1可與DyeI所具有的陰離子部(-COO-、-SO3 -、-O-等)或陽離子部(所述鎓陽離子或金屬陽離子等)鍵結。 In the case where L 1 has a group capable of forming an ionic bond or a coordinate bond with DyeI, L 1 may be an anion moiety (-COO - , -SO 3 - , -O - , etc.) or a cation moiety possessed by DyeI ( The phosphonium cation or metal cation or the like is bonded.

通式(a1-1)中，DyeI表示來源於所述色素化合物的色素結構。 In the formula (a1-1), DyeI represents a dye structure derived from the dye compound.

含有通式(a1-1)所表示的重複單元的色素多聚物可藉由以下方法合成：(1)藉由加成聚合對具有色素殘基的單體進行合成的方法；(2)使具有異氰酸酯基、酸酐基或環氧基等高反應 性官能基的聚合物，與具有可與高反應性基反應的官能基(羥基、一級或二級胺基、羧基等)的色素反應的方法。 The dye polymer containing the repeating unit represented by the formula (a1-1) can be synthesized by the following methods: (1) a method of synthesizing a monomer having a pigment residue by addition polymerization; (2) High reaction with isocyanate group, acid anhydride group or epoxy group A method of reacting a functional group-based polymer with a dye having a functional group (hydroxyl group, primary or secondary amine group, carboxyl group, etc.) reactive with a highly reactive group.

加成聚合時可應用公知的加成聚合(自由基聚合、陰離子聚合、陽離子聚合)，其中，尤其於藉由自由基聚合來進行合成的情況下，可使反應條件平穩，且不會使色素結構分解，故較佳。自由基聚合時，可應用公知的反應條件。 In the addition polymerization, a known addition polymerization (radical polymerization, anionic polymerization, cationic polymerization) can be applied. In particular, in the case of synthesis by radical polymerization, the reaction conditions can be made stable without causing the pigment. The structure is decomposed, so it is preferred. In the case of radical polymerization, well-known reaction conditions can be applied.

其中，就耐熱性的觀點而言，含有通式(a1-1)所表示的重複單元的色素多聚物較佳為使用具有乙烯性不飽和鍵的色素單體進行自由基聚合所得的自由基聚合物。 In the viewpoint of heat resistance, the dye polymer containing the repeating unit represented by the formula (a1-1) is preferably a radical obtained by radical polymerization using a dye monomer having an ethylenically unsaturated bond. polymer.

以下示出通式(a1-1)所表示的重複單元的具體例，但本發明不限定於此。 Specific examples of the repeating unit represented by the formula (a1-1) are shown below, but the present invention is not limited thereto.

[化13] [Chemistry 13]

[化14] [Chemistry 14]

<<通式(a1-2)所表示的重複單元>> <<Repeating unit represented by the general formula (a1-2)>>

繼而，對通式(a1-2)所表示的色素多聚物加以詳細說明。 Next, the dye polymer represented by the formula (a1-2) will be described in detail.

(通式(a1-2)中，L3表示單鍵或二價連結基。DyeIII表示具有陽離子部位的色素結構。m表示0或1) (In the formula (a1-2), L 3 represents a single bond or a divalent linking group. DyeIII represents a dye structure having a cationic moiety. m represents 0 or 1)

通式(a1-2)中，L3表示單鍵或二價連結基。L3所表示的二價連結基可較佳地列舉：碳數1~30的經取代或未經取代的直鏈、分支或環狀伸烷基(例如亞甲基、伸乙基、三亞甲基、伸丙基、伸丁基等)、碳數6~30的經取代或未經取代的伸芳基(例如伸苯基、伸萘基等)、經取代或未經取代的雜環連結基、-CH=CH-、-O-、-S-、-NR-(R分別獨立地表示氫原子、烷基、芳基或雜環基)、-C(=O)-、-SO-、-SO2-及將該等的2個以上連結而形成的連結基。 In the formula (a1-2), L 3 represents a single bond or a divalent linking group. The divalent linking group represented by L 3 may preferably be a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms (for example, methylene, ethylidene, and trimethylene). a substituted or unsubstituted extended aryl group having a carbon number of 6 to 30 (e.g., a phenyl group, a naphthyl group, etc.), a substituted or unsubstituted heterocyclic linker a group, -CH=CH-, -O-, -S-, -NR- (R independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group), -C(=O)-, -SO- And -SO 2 - and a linking group formed by linking two or more of these.

m表示0或1，較佳為1。 m represents 0 or 1, preferably 1.

以下記載可較佳地用作通式(a1-2)中的L3所表示的二價連結基的具體例，但本發明的L3不限定於該些具體例。再者，*所表示的部位表示與DyeIII等的連結部位。 The following description can be preferably used as a specific example of the divalent linking group represented by L 3 in the general formula (a1-2), but L 3 of the present invention is not limited to these specific examples. Further, the portion indicated by * indicates a joint portion with DyeIII or the like.

[化17] [化17]

[化18] [化18]

含有通式(a1-2)所表示的重複單元的色素多聚物是藉由逐次聚合而合成。所謂逐次聚合，可列舉複加成(polyaddition)(例如二異氰酸酯化合物與二醇的反應、二環氧化合物與二羧酸的反應、四羧酸二酐與二醇的反應等)及縮聚(例如二羧酸與二醇的反應、二羧酸與二胺的反應等)。其中，尤其於藉由複加成反應來進行合成的情況下，可使反應條件平穩，且不會使色素結構分解，故較佳。逐次聚合時可應用公知的反應條件。 The dye polymer containing the repeating unit represented by the formula (a1-2) is synthesized by sequential polymerization. The sequential polymerization may, for example, be a polyaddition (for example, a reaction of a diisocyanate compound with a diol, a reaction of a diepoxy compound with a dicarboxylic acid, a reaction of a tetracarboxylic dianhydride with a diol, etc.) and polycondensation (for example). Reaction of a dicarboxylic acid with a diol, reaction of a dicarboxylic acid with a diamine, etc.). Among them, in particular, when the synthesis is carried out by a complex addition reaction, the reaction conditions can be made stable without decomposing the dye structure, which is preferable. Well-known reaction conditions can be applied in the case of successive polymerization.

以下示出通式(a1-2)所表示的重複單元的具體例，但本發明不限定於此。 Specific examples of the repeating unit represented by the formula (a1-2) are shown below, but the present invention is not limited thereto.

[化19] [Chemistry 19]

<<通式(a1-3)所表示的色素多聚物>> <<Polymer polymer represented by the general formula (a1-3)>>

繼而，對通式(a1-3)所表示的色素多聚物加以詳細說明。 Next, the dye polymer represented by the formula (a1-3) will be described in detail.

(通式(a1-3)中，L4表示n價連結基。n表示2~20的整數。DyeIV表示具有陽離子部位的色素結構) (In the formula (a1-3), L 4 represents an n-valent linking group. n represents an integer of 2 to 20. DyeIV represents a dye structure having a cationic moiety)

通式(a1-3)中，n較佳為3~15，尤佳為3~6。 In the formula (a1-3), n is preferably from 3 to 15, more preferably from 3 to 6.

通式(a1-3)中，於n為2的情形時，L4所表示的二價連結基可較佳地列舉：碳數1~30的經取代或未經取代的伸烷基(例 如亞甲基、伸乙基、三亞甲基、伸丙基、伸丁基等)、碳數6~30的經取代或未經取代的伸芳基(例如伸苯基、伸萘基等)、經取代或未經取代的雜環連結基、-CH=CH-、-O-、-S-、-NR-(R分別獨立地表示氫原子、烷基、芳基或雜環基)、-C(=O)-、-SO-、-SO2-及將該等的2個以上連結而形成的連結基。 In the general formula (a1-3), when n is 2, the divalent linking group represented by L 4 may preferably be a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example). a methylene group, an ethylidene group, a trimethylene group, a propyl group, a butyl group, etc.), a substituted or unsubstituted aryl group having 6 to 30 carbon atoms (for example, a phenyl group, a naphthyl group, etc.), Substituted or unsubstituted heterocyclic linker, -CH=CH-, -O-, -S-, -NR- (R independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, respectively), C(=O)-, -SO-, -SO 2 - and a linking group formed by linking two or more of these.

n為3以上的n價連結基可列舉：經取代或未經取代的伸芳基(1,3,5-伸苯基、1,2,4-伸苯基、1,4,5,8-伸萘基等)、雜環連結基(例如1,3,5-三嗪基等)、以伸烷基連結基等作為中心母核且所述二價連結基進行取代而形成的連結基。 Examples of the n-valent linking group in which n is 3 or more include a substituted or unsubstituted extended aryl group (1,3,5-phenylene, 1,2,4-phenylene, 1,4,5,8). - a naphthyl group or the like), a heterocyclic linking group (for example, a 1,3,5-triazinyl group), a linking group formed by substituting a divalent linking group with an alkylene group or the like as a central core .

以下示出通式(a1-3)中的L4的具體例，但本發明不限定於此。再者，*所表示的部位表示與DyeIV的連結部位。 Specific examples of L 4 in the general formula (a1-3) are shown below, but the present invention is not limited thereto. Further, the portion indicated by * indicates the joint portion with DyeIV.

[化21] [Chem. 21]

以下示出通式(a1-3)中的DyeIV的具體例，但本發明不限定於此。 Specific examples of DyeIV in the general formula (a1-3) are shown below, but the present invention is not limited thereto.

[化22] [化22]

含有通式(a1-1)及通式(a1-2)所表示的重複單元的至少一種的色素多聚物以及通式(a1-3)所表示的色素多聚物中，含有通式(a1-1)所表示的重複單元的色素多聚物、含有通式(a1-2)所表示的重複單元的色素多聚物及通式(a1-3)所表示的色素多聚物因來源於色素的部分結構於分子結構中是以共價鍵而連結，故含有所述色素多聚物的著色組成物的耐熱性優異。因此，於將著色組成物應用於具有高溫製程的圖案形成的情形時，於抑制向鄰接的其他著色圖案的色移的方面有效，故較佳。另外，尤其通式(a1-1)所表示的化合物容易控制色素多聚物的分子量而較佳。 The dye polymer containing at least one of the repeating units represented by the formula (a1-1) and the formula (a1-2) and the dye polymer represented by the formula (a1-3) contain a formula ( a pigment polymer of a repeating unit represented by a1-1), a dye polymer containing a repeating unit represented by the formula (a1-2), and a dye polymer represented by the formula (a1-3) Since the partial structure of the dye is linked by a covalent bond in the molecular structure, the colored composition containing the dye polymer is excellent in heat resistance. Therefore, when the colored composition is applied to the pattern formation having a high-temperature process, it is effective in suppressing the color shift to the adjacent other colored patterns, which is preferable. Further, in particular, the compound represented by the formula (a1-1) is preferable because it is easy to control the molecular weight of the dye polymer.

<<其他官能基及重複單元>> <<Other functional groups and repeating units>>

色素多聚物亦可除了所述色素多聚物的色素結構部分以外具有其他官能基。其他官能基可例示聚合性基、酸基及鹼可溶性基等。 The dye polymer may have other functional groups in addition to the dye structure portion of the dye polymer. The other functional group may, for example, be a polymerizable group, an acid group or an alkali-soluble group.

另外，色素多聚物亦可除了所述含有色素結構的重複單元以外含有其他重複單元。其他重複單元亦可具有官能基。 Further, the dye polymer may contain other repeating units in addition to the repeating unit containing the dye structure. Other repeating units may also have a functional group.

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。 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.

即，色素多聚物亦可除了通式(a1-1)~通式(a1-3)所表示的重複單元以外含有其他重複單元。其他重複單元於一色素多聚物中可僅含有一種，亦可含有兩種以上。 In other words, the dye polymer may contain other repeating units in addition to the repeating unit represented by the general formulae (a1-1) to (a1-3). The other repeating unit may contain only one type in one pigment polymer, and may contain two or more types.

另外，關於色素多聚物，亦可於通式(a1-1)~通式(a1-3)所表示的色素多聚物中具有其他官能基。以下，對該等的詳細情況加以說明。 In addition, the dye polymer may have other functional groups in the dye polymer represented by the general formulae (a1-1) to (a1-3). The details of these will be described below.

<<<色素多聚物(A)所具有的聚合性基>>> <<<Polymerizable group of pigment multimer (A)>>>

色素多聚物較佳為含有聚合性基。聚合性基可僅含有一種，亦可含有兩種以上。 The dye polymer preferably contains a polymerizable group. The polymerizable group may be contained alone or in combination of two or more.

關於聚合性基，可使色素結構含有聚合性基，亦可使其他部分含有聚合性基。本發明中，較佳為色素結構含有聚合性基。藉由設定為此種構成，有耐熱性提高的傾向。 The polymerizable group may contain a polymerizable group in the dye structure, or may contain a polymerizable group in other portions. In the present invention, it is preferred that the dye structure contains a polymerizable group. By setting it as such a structure, heat resistance tends to improve.

另外，本發明中，色素結構以外的其他部分含有聚合性基的態樣亦較佳。 Further, in the present invention, a portion other than the dye structure containing a polymerizable group is also preferable.

聚合性基可使用藉由自由基、酸、熱而可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、氧雜環丁烷基)、羥甲基等，尤佳為含有乙烯性不飽和鍵的基團，進而佳為(甲基)丙烯醯基，進而更佳為來源於(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). a cyclobutane group, a hydroxymethyl group or the like is particularly preferably a group containing an ethylenically unsaturated bond, and more preferably a (meth) acrylonitrile group, and more preferably a glycidyl (meth) acrylate. (Meth)acrylonitrile group of (meth)acrylic acid-3,4-epoxy-cyclohexylmethyl ester.

聚合性基較佳為以具有聚合性基的重複單元的形式而含有於色素多聚物中，更佳為以具有乙烯性不飽和鍵的重複單元的形式而含有。即，色素多聚物的較佳實施形態的一例為色素多聚物含有含色素單體的重複單元及含聚合性基的重複單元的態樣，更佳為含有含色素單體的重複單元及含乙烯性不飽和鍵的重複單元。 The polymerizable group is preferably contained in the dye polymer in the form of a repeating unit having a polymerizable group, and more preferably in the form of a repeating unit having an ethylenically unsaturated bond. That is, an example of a preferred embodiment of the dye polymer is a state in which the dye polymer contains a repeating unit containing a dye-containing monomer and a repeating unit containing a polymerizable group, and more preferably a repeating unit containing a dye-containing monomer and A repeating unit containing an ethylenically unsaturated bond.

聚合性基的導入方法有以下方法：(1)利用含聚合性基的化合物對色素多聚物進行改質而導入聚合性基的方法、(2)使色素單體與含聚合性基的化合物進行共聚合而導入聚合性基的方法等。以下對詳細情況加以描述。 The method of introducing a polymerizable group includes (1) a method of introducing a polymerizable group by modifying a dye polymer by a polymerizable group-containing compound, and (2) a dye monomer and a polymerizable group-containing compound. A method of introducing a polymerizable group by copolymerization. The details are described below.

(1)利用含聚合性基的化合物對色素多聚物進行改質而導入聚合性基的方法： (1) A method of introducing a polymerizable group by modifying a dye polymer using a polymerizable group-containing compound:

利用含聚合性基的化合物對色素多聚物進行改質而導入聚合性基的方法可無特別限制地使用公知的方法。例如就製造上的觀點而言，較佳為以下方法：(a)使色素多聚物所具有的羧酸與含不飽和鍵的環氧化合物反應的方法、(b)使色素多聚物所具有的羥基或胺基與含不飽和鍵的異氰酸酯化合物反應的方法、(c)使色素多聚物所具有的環氧化合物與含不飽和鍵的羧酸化合物反應的方法。 A method of introducing a polymerizable group by modifying a dye polymer by a polymerizable group-containing compound can be carried out by a known method without particular limitation. For example, from the viewpoint of production, (a) a method of reacting a carboxylic acid having a dye polymer with an epoxy compound having an unsaturated bond, and (b) a dye polymer A method of reacting a hydroxyl group or an amine group with an isocyanate compound containing an unsaturated bond, and (c) a method of reacting an epoxy compound of the dye polymer with a carboxylic acid compound having an unsaturated bond.

(a)使色素多聚物所具有的羧酸與含不飽和鍵的環氧化合物反應的方法中的含不飽和鍵的環氧化合物可列舉：甲基丙烯酸縮水甘油酯、丙烯酸縮水甘油酯、烯丙基縮水甘油醚、丙烯酸-3,4-環氧-環己基甲酯、甲基丙烯酸-3,4-環氧-環己基甲酯等，尤 其甲基丙烯酸縮水甘油酯及甲基丙烯酸-3,4-環氧-環己基甲酯的交聯性及保存穩定性優異而較佳。反應條件可使用公知的條件。 (a) Examples of the unsaturated bond-containing epoxy compound in the method of reacting a carboxylic acid having a dye polymer with an unsaturated bond-containing epoxy compound include glycidyl methacrylate and glycidyl acrylate. Allyl glycidyl ether, 3,4-epoxy-cyclohexyl methyl acrylate, 3,4-epoxy-cyclohexyl methyl methacrylate, etc. Glycidyl methacrylate and 3,4-epoxy-cyclohexylmethyl methacrylate are preferred because of their excellent crosslinkability and storage stability. Well-known conditions can be used for reaction conditions.

(b)使色素多聚物所具有的羥基或胺基與含不飽和鍵的異氰酸酯化合物反應的方法中的含不飽和鍵的異氰酸酯化合物可列舉：甲基丙烯酸-2-異氰酸基乙基酯、丙烯酸2-異氰酸基乙基酯、1,1-雙(丙烯醯氧基甲基)乙基異氰酸酯等，甲基丙烯酸-2-異氰酸基乙酯的交聯性及保存穩定性優異而較佳。反應條件可使用公知的條件。 (b) An unsaturated bond-containing isocyanate compound in a method of reacting a hydroxyl group or an amine group of a dye polymer with an unsaturated bond-containing isocyanate compound: 2-ethyl isocyanatoethyl methacrylate Ester, 2-isocyanatoethyl acrylate, 1,1-bis(acryloxymethyl)ethyl isocyanate, etc., cross-linking and storage stability of 2-isocyanatoethyl methacrylate Excellent and better. Well-known conditions can be used for reaction conditions.

(c)使色素多聚物所具有的環氧化合物與含不飽和鍵的羧酸化合物反應的方法中的含不飽和鍵的羧酸化合物只要為公知的具有(甲基)丙烯醯氧基的羧酸化合物，則可無特別限制地使用，較佳為甲基丙烯酸及丙烯酸，尤其甲基丙烯酸的交聯性及保存穩定性優異而較佳。反應條件可使用公知的條件。 (c) The unsaturated bond-containing carboxylic acid compound in the method of reacting the epoxy compound of the dye polymer with the unsaturated bond-containing carboxylic acid compound, as long as it has a known (meth)acryloxy group The carboxylic acid compound can be used without particular limitation, and it is preferably methacrylic acid and acrylic acid, and particularly methacrylic acid is excellent in crosslinkability and storage stability. Well-known conditions can be used for reaction conditions.

(2)使色素單體與含聚合性基的化合物進行共聚合而導入聚合性基的方法： (2) A method of introducing a polymerizable group by copolymerizing a dye monomer and a polymerizable group-containing compound:

(2)使色素單體與含聚合性基的化合物進行共聚合而導入聚合性基的方法可無特別限制地使用公知的方法，較佳為(d)使可進行自由基聚合的色素單體與可進行自由基聚合的含聚合性基的化合物進行共聚合的方法、(e)使可進行複加成的色素單體與可進行複加成的含聚合性基的化合物進行共聚合的方法。 (2) A method of introducing a polymerizable group by copolymerizing a dye monomer and a polymerizable group-containing compound, and a known method can be used without particular limitation, and (d) a monomer monomer capable of radical polymerization is preferred. a method of copolymerizing a polymerizable group-containing compound capable of undergoing radical polymerization, and (e) a method of copolymerizing a monomer monomer capable of undergoing complex addition and a polymerizable group-containing compound capable of being subjected to re-addition .

(d)使可進行自由基聚合的色素單體與可進行自由基聚合的含聚合性基的化合物進行共聚合的方法中的可進行自由基 聚合的含聚合性基的化合物尤其可列舉：含烯丙基的化合物(例如(甲基)丙烯酸烯丙酯等)、含環氧基的化合物(例如(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸-3,4-環氧-環己基甲酯等)、含氧雜環丁烷基的化合物(例如(甲基)丙烯酸-3-甲基-3-氧雜環丁基甲酯等)、含羥甲基的化合物(例如N-(羥基甲基)丙烯醯胺等)，尤佳為環氧化合物、氧雜環丁烷化合物。反應條件可使用公知的條件。 (d) a free radical in a method of copolymerizing a pigment monomer capable of undergoing radical polymerization with a polymerizable group-containing compound capable of undergoing radical polymerization The polymerizable group-containing compound may, for example, be an allyl group-containing compound (for example, allyl (meth)acrylate) or an epoxy group-containing compound (for example, glycidyl (meth)acrylate, (A) (meth)acrylic acid-3,4-epoxy-cyclohexylmethyl ester, etc.), an oxetane group-containing compound (for example, (meth)acrylic acid-3-methyl-3-oxetanylmethyl ester, etc.), A methylol group-containing compound (for example, N-(hydroxymethyl) acrylamide or the like) is preferably an epoxy compound or an oxetane compound. Well-known conditions can be used for reaction conditions.

(e)使可進行複加成的色素單體與可進行複加成的含聚合性基的化合物進行共聚合的方法中的可進行複加成的含聚合性基的化合物可列舉含不飽和鍵的二醇化合物(例如(甲基)丙烯酸-2,3-二羥基丙酯等)。反應條件可使用公知的條件。 (e) The polymerizable group-containing compound which can be subjected to the addition addition of the monomer which can be subjected to the addition addition and the polymerizable group-containing compound which can be subjected to the addition is exemplified by the unsaturated group. A diol compound of a bond (for example, 2,3-dihydroxypropyl (meth)acrylate, etc.). Well-known conditions can be used for reaction conditions.

聚合性基的導入方法尤佳為使色素多聚物所具有的羧酸與含不飽和鍵的環氧化合物反應的方法。 The method of introducing the polymerizable group is particularly preferably a method of reacting a carboxylic acid having a dye polymer with an epoxy compound having an unsaturated bond.

相對於色素多聚物(A)1g，色素多聚物所具有的聚合性基量較佳為0.1mmol~2.0mmol，更佳為0.2mmol~1.5mmol，尤佳為0.3mmol~1.0mmol。 The amount of the polymerizable group of the dye polymer is preferably from 0.1 mmol to 2.0 mmol, more preferably from 0.2 mmol to 1.5 mmol, even more preferably from 0.3 mmol to 1.0 mmol, based on 1 g of the dye polymer (A).

另外，相對於所有重複單元100莫耳，色素多聚物含有具有聚合性基的重複單元的重複單元的比例例如較佳為5莫耳~50莫耳，更佳為10莫耳~20莫耳。 Further, the proportion of the repeating unit in which the dye polymer contains a repeating unit having a polymerizable group is, for example, preferably from 5 mol to 50 mol, more preferably from 10 mol to 20 mol, relative to all repeating units of 100 moles. .

聚合性基的導入方法尤佳為使色素多聚物所具有的羧酸與含不飽和鍵的環氧化合物反應的方法。 The method of introducing the polymerizable group is particularly preferably a method of reacting a carboxylic acid having a dye polymer with an epoxy compound having an unsaturated bond.

具有聚合性基的重複單元可列舉如下具體例。其中，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 present invention is not limited to these specific examples.

[化24] [Chem. 24]

所述具體例中，就基板密接性及表面粗糙度的觀點而言，較佳為具有乙烯性不飽和鍵的色素單體，其中較佳為甲基丙烯醯基、丙烯醯基、苯乙烯基或乙烯氧基，更佳為甲基丙烯醯基、丙烯醯基，進而佳為甲基丙烯醯基。 In the specific examples, from the viewpoint of substrate adhesion and surface roughness, a dye monomer having an ethylenically unsaturated bond is preferable, and among them, a methacryl fluorenyl group, an acryl fluorenyl group, or a styryl group is preferred. Or a vinyloxy group, more preferably a methacryl oxime group, an acryl fluorenyl group, and further preferably a methacryl oxime group.

<<<色素多聚物(A)所具有的酸基及鹼可溶性基>>> <<<Acid and alkali soluble groups of pigment multimer (A)>>>

色素多聚物可具有的酸基可例示羧酸基、磺酸基、磷酸基。另外，鹼可溶性基可例示酚性羥基、羧酸基。 The acid group which the dye polymer can have may 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 group.

本發明中，較佳為酸基及/或鹼可溶性基以如下情況為宜：以具有酸基及/或鹼可溶性基的重複單元的形式而含有於色素多聚物中。 In the present invention, it is preferred that the acid group and/or the alkali-soluble group are contained in the dye polymer in the form of a repeating unit having an acid group and/or an alkali-soluble group.

具有酸基的重複單元的酸值較佳為15mgKOH/g~110mgKOH/g，更佳為20mgKOH/g~90mgKOH/g，進而佳為30mgKOH/g~60mgKOH/g。 The acid value of the repeating unit having an acid group is preferably from 15 mgKOH/g to 110 mgKOH/g, more preferably from 20 mgKOH/g to 90 mgKOH/g, and still more preferably from 30 mgKOH/g to 60 mgKOH/g.

色素多聚物的酸值例如可根據色素多聚物中的酸基的平均含 量而算出。另外，可藉由使構成色素多聚物的含有酸基的單體單元的含量變化而獲得具有所需酸值的樹脂。 The acid value of the dye polymer can be, for example, based on the average content of the acid groups in the dye polymer. Calculated by quantity. Further, a resin having a desired acid value can be obtained by changing the content of the acid group-containing monomer unit constituting the dye polymer.

於色素多聚物中導入鹼可溶性基的導入方法可列舉：預先於色素單體中導入鹼可溶性基的方法、及使具有鹼可溶性基的色素單體以外的單體((甲基)丙烯酸、丙烯酸的己內酯改質物、(甲基)丙烯酸2-羥基乙酯的琥珀酸酐改質物、(甲基)丙烯酸2-羥基乙酯的鄰苯二甲酸酐改質物、(甲基)丙烯酸2-羥基乙酯的1,2-環己烷二羧酸酐改質物、苯乙烯羧酸、衣康酸、馬來酸、降冰片烯羧酸等含羧酸的單體，酸式磷醯氧基乙基甲基丙烯酸酯、乙烯基膦酸等含磷酸的單體，乙烯基磺酸、2-丙烯醯胺-2-甲基磺酸等含磺酸的單體)進行共聚合的方法，進而佳為使用此兩種方法。 The method of introducing an alkali-soluble group into the dye polymer includes a method of introducing an alkali-soluble group into the dye monomer in advance, and a monomer other than the dye monomer having an alkali-soluble group ((meth)acrylic acid, Caprolactone modification of acrylic acid, succinic anhydride modification of 2-hydroxyethyl (meth)acrylate, phthalic anhydride modification of 2-hydroxyethyl (meth)acrylate, 2-(meth)acrylic acid 1,2-cyclohexanedicarboxylic anhydride modified product of hydroxyethyl ester, carboxylic acid-containing monomer such as styrene carboxylic acid, itaconic acid, maleic acid, norbornene carboxylic acid, acid phosphonium oxylate B a method of copolymerizing a phosphoric acid-containing monomer such as a methacrylic acid ester or a vinylphosphonic acid, or a sulfonic acid-containing monomer such as vinylsulfonic acid or 2-propenylamine-2-methylsulfonic acid; To use both methods.

相對於色素多聚物1g，色素多聚物所具有的鹼可溶性基量較佳為0.3mmol~2.0mmol，更佳為0.4mmol~1.5mmol，尤佳為0.5mmol~1.0mmol。 The amount of the alkali-soluble base of the dye polymer is preferably from 0.3 mmol to 2.0 mmol, more preferably from 0.4 mmol to 1.5 mmol, even more preferably from 0.5 mmol to 1.0 mmol, based on 1 g of the dye polymer.

另外，於色素多聚物含有含色素單體的重複單元及含酸基的重複單元的情形時，相對於含色素單體的重複單元100莫耳，含酸基的重複單元的比例例如較佳為5莫耳~70莫耳，更佳為10莫耳~50莫耳。 Further, in the case where the dye polymer contains a repeating unit containing a dye-containing monomer and a repeating unit containing an acid group, the ratio of the repeating unit containing an acid group is preferably, for example, relative to the repeating unit of the coloring monomer-containing monomer: It is 5 moles to 70 moles, more preferably 10 moles to 50 moles.

色素多聚物所具有的其他官能基可列舉：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 of the dye polymer include a lactone, an acid anhydride, a decylamine, a -COCH 2 CO-, a cyano group, and the like, a development promoting group, a long chain and a cyclic alkyl group, an aralkyl group, an aryl group, and a poly A hydrophilic or hydrophobicity adjusting group such as an alkylene oxide group, a hydroxyl group, a maleimide group or an amine group can be appropriately introduced.

導入方法可列舉：預先導入至色素單體中的方法、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 a dye monomer in advance, and a method of copolymerizing a monomer having the functional group.

示出色素多聚物所含有的具有其他官能基的重複單元的具體例，但本發明不限定於此。 Specific examples of the repeating unit having another functional group contained in the dye multimer are shown, but the present invention is not limited thereto.

[化25] [化25]

[化26] [Chem. 26]

[化28] [化28]

<<<(A2)的形態>>> <<<(A2) form>>>

色素多聚物(A2)的形態為含有具有色素結構的重複單元、且色素結構具有陰離子部位的色素多聚物。 The form of the dye polymer (A2) is a dye polymer containing a repeating unit having a dye structure and an anionic portion of the dye structure.

例如，色素多聚物較佳為含有通式(a2)所表示的重複單元。 For example, the dye polymer preferably contains a repeating unit represented by the formula (a2).

通式(a2)[化30] General formula (a2) [化30]

(通式(a2)中，X1表示形成主鏈的基團，L1表示單鍵或二價連結基。DyeIA表示具有陽離子部位及陰離子部位的色素結構) (In the formula (a2), X 1 represents a group forming a main chain, and L 1 represents a single bond or a divalent linking group. DyeIA represents a dye structure having a cationic moiety and an anionic moiety)

通式(a2)中，X1及L1與所述通式(a1-1)為相同含意，較佳範圍亦相同。 In the formula (a2), X 1 and L 1 have the same meanings as in the above formula (a1-1), and the preferred ranges are also the same.

通式(a2)中，DyeIA為所述通式(a1-1)中的DyeI更具有陰離子部位者。陰離子部位可列舉-SO3-、-CO2 2-等。 In the formula (a2), DyeIA is one in which the DyeI in the formula (a1-1) has an anion moiety. Examples of the anion site include -SO 3 - , -CO 2 2- and the like.

色素多聚物(A2)的形態的具體例可參考日本專利特開2012-032754號公報的段落0069中記載的A-1、A-3~A-6，將其內容併入至本說明書中。 Specific examples of the form of the dye polymer (A2) can be referred to A-1, A-3 to A-6 described in paragraph 0069 of JP-A-2012-032754, the contents of which are incorporated herein by reference. .

<<<(A3)的形態>>> <<<(A3) form>>>

色素多聚物(A3)的形態為含有具有色素結構的單體、及具有抗衡陰離子部位的重複單元的色素多聚物。 The form of the dye polymer (A3) is a dye polymer containing a monomer having a dye structure and a repeating unit having a counter anion site.

具有色素結構的單體與所述含有來源於通式(J)所表示的氧雜蒽化合物的部分結構的單體為相同含意。 The monomer having a dye structure has the same meaning as the monomer having a partial structure derived from the xanthene compound represented by the general formula (J).

具有抗衡陰離子部位的重複單元較佳為含有下述通式(a3)所表示的重複單元。 The repeating unit having a counter anion moiety preferably contains a repeating unit represented by the following formula (a3).

通式(a3)[化31] General formula (a3) [31]

(通式(a3)中，X1表示形成主鏈的基團，L2表示單鍵或二價連結基，Z表示具有抗衡陰離子部位的結構) (In the formula (a3), X 1 represents a group forming a main chain, L 2 represents a single bond or a divalent linking group, and Z represents a structure having a site for counter anion)

通式(a3)中，X1與所述通式(a1-1)為相同含意，較佳範圍亦相同。 In the formula (a3), X 1 has the same meaning as the above formula (a1-1), and the preferred range is also the same.

通式(a3)中，於L2表示二價連結基的情形時，可列舉：碳數1~20(較佳為1~10)的伸烷基、碳數6~20(較佳為6~10)的伸芳基、碳數4~20(較佳為5~10)的雜環基、碳數1~20(較佳為1~10)的烷基磺醯基、碳數6~20(較佳為6~10)的芳基磺醯基、碳數1~20(較佳為1~10)的烷基羰基、碳數6~20(較佳為6~11)的芳基羰基、碳數1~20(較佳為1~10)的烷基胺基、碳數6~20(較佳為6~10)的芳基胺基、碳數1~20(較佳為1~10)的烷基羰氧基、碳數6~20(較佳為6~11)的芳基羰氧基等。該些二價連結基較佳為經吸電子性基所取代，吸電子性基可列舉鹵素原子(氟原子、氯原子、溴原子、碘原子)、硝基、氰基、鹵化烷基(例如三氟甲基)、鹵化芳基。 In the general formula (a3), when L 2 represents a divalent linking group, an alkylene group having 1 to 20 carbon atoms (preferably 1 to 10) and a carbon number of 6 to 20 (preferably 6) are exemplified. ~10) an aryl group, a heterocyclic group having 4 to 20 carbon atoms (preferably 5 to 10), an alkylsulfonyl group having 1 to 20 carbon atoms (preferably 1 to 10), and a carbon number of 6~ 20 (preferably 6 to 10) arylsulfonyl group, alkyl group having 1 to 20 carbon atoms (preferably 1 to 10), and aryl group having 6 to 20 carbon atoms (preferably 6 to 11) a carbonyl group, an alkylamino group having 1 to 20 carbon atoms (preferably 1 to 10), an arylamino group having 6 to 20 carbon atoms (preferably 6 to 10), and a carbon number of 1 to 20 (preferably 1) The alkylcarbonyloxy group of ~10), the arylcarbonyloxy group having 6 to 20 carbon atoms (preferably 6 to 11), and the like. The divalent linking group is preferably substituted by an electron withdrawing group, and the electron withdrawing group may, for example, be a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a nitro group, a cyano group or a halogenated alkyl group (for example). Trifluoromethyl), halogenated aryl.

於後述通式(1)中的Z為所述通式(2-1)所表示的低親核性陰離子結構的情形時，L2較佳為碳數1~10的經氟原子取代的伸烷基(氟化伸烷基)。 In the case where Z in the following formula (1) is a low nucleophilic anion structure represented by the above formula (2-1), L 2 is preferably a fluorine atom substituted extension of 1 to 10 carbon atoms. Alkyl (fluorinated alkyl).

通式(a3)中，Z較佳為表示通式(2-1)所表示的基團、氟化烷基磺醯亞胺基或氟化烷基磺甲基化物基、通式(2-3)所表示的基團。 In the formula (a3), Z preferably represents a group represented by the formula (2-1), a fluorinated alkylsulfonimide group or a fluorinated alkylsulfonyl group, and a formula (2- 3) The group represented.

通式(2-1)*-Y1-A1 General formula (2-1)*-Y 1 -A 1

(通式(2-1)中，*表示與通式(a3)中的L2的鍵結部位，Y1表示氟化伸烷基，A1表示SO3 -) (In the formula (2-1), * represents a bonding site with L 2 in the formula (a3), Y 1 represents a fluorinated alkyl group, and A 1 represents SO 3 - )

(通式(2-3)中，*表示與通式(a3)中的L2的鍵結部位，R分別表示氰基或氟化烷基，較佳為氰基) (In the formula (2-3), * represents a bonding site with L 2 in the formula (a3), and R represents a cyano group or a fluorinated alkyl group, respectively, preferably a cyano group)

以下，示出本發明中所用的通式(a3)所表示的重複單元的具體例，但本發明不限定於此。再者，具體例表示陰離子部位並未解離的狀態，但陰離子部位解離的狀態亦當然在本發明的範圍內。 Specific examples of the repeating unit represented by the formula (a3) used in the present invention are shown below, but the present invention is not limited thereto. Further, the specific example shows a state in which the anion site is not dissociated, but the state in which the anion site is dissociated is of course within the scope of the present invention.

[化33] [化33]

<<<(A4)的形態>>> <<<(A4) form>>>

色素多聚物(A4)的形態為更具有其他陽離子及陰離子部位的色素多聚物。例如為具有色素結構的單體及含有具有陽離子部位的重複單元、且含色素結構的單體含有對應的陰離子部位的色素多聚物。 The form of the dye polymer (A4) is a dye polymer having more cations and anion sites. For example, it is a monomer having a dye structure and a dye polymer containing a repeating unit having a cationic moiety, and the monomer having a dye structure contains a corresponding anionic moiety.

具有陽離子部位的重複單元可參考日本專利特開2011-242752號公報的段落0018~段落0061的記載，將其內容併 入至本說明書中。 The repeating unit having a cationic moiety can be referred to the description of paragraph 0018 to paragraph 0061 of JP-A-2011-242752, and the contents thereof are Enter this manual.

含色素結構的單體含有對應的陰離子部位者可例示顏色索引(Color Index，C.I.)酸性紅289。 The color index (C.I.) acid red 289 can be exemplified as the monomer having a pigment structure containing a corresponding anion moiety.

色素多聚物(A4)的具體例可參考日本專利特開2011-242752號公報的段落0165的記載，將其內容併入至本說明書中。 Specific examples of the dye polymer (A4) can be referred to the description of paragraph 0165 of JP-A-2011-242752, the contents of which are incorporated herein by reference.

色素多聚物較佳為最大吸收波長為420nm~700nm，更佳為450nm~650nm。 The dye multipolymer preferably has a maximum absorption wavelength of from 420 nm to 700 nm, more preferably from 450 nm to 650 nm.

色素多聚物的酸值較佳為5mgKOH/g~100mgKOH/g，更佳為15mgKOH/g~60mgKOH/g。 The acid value of the dye polymer is preferably from 5 mgKOH/g to 100 mgKOH/g, more preferably from 15 mgKOH/g to 60 mgKOH/g.

於本發明中，於將重複單元的合計值設定為100mol%(莫耳百分比)時，含有來源於色素的結構的重複單元於色素多聚物中較佳為10mol%~100mol%，更佳為50mol%~100mol%，尤佳為60mol%~100mol%。 In the present invention, when the total value of the repeating unit is set to 100 mol% (% by mole), the repeating unit containing the structure derived from the dye is preferably from 10 mol% to 100 mol% in the dye polymer, more preferably 50 mol% to 100 mol%, particularly preferably 60 mol% to 100 mol%.

色素多聚物的重量平均分子量較佳為2,000~20,000，更佳為3,000~15,000，尤佳為4,000~10,000。 The weight average molecular weight of the dye polymer is preferably from 2,000 to 20,000, more preferably from 3,000 to 15,000, still more preferably from 4,000 to 10,000.

重量平均分子量及數量平均分子量可藉由凝膠滲透層析法(Gel Permeation Chromatography，GPC)來求出。 The weight average molecular weight and the number average molecular weight can be determined by gel permeation chromatography (GPC).

另外，色素多聚物的重量平均分子量(Mw)與數量平均分子量(Mn)之比[(Mw)/(Mn)]較佳為1.0~3.0，更佳為1.6~2.5，尤佳為1.6~2.0。 Further, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the dye polymer [(Mw) / (Mn)] is preferably from 1.0 to 3.0, more preferably from 1.6 to 2.5, and particularly preferably from 1.6 to 2.0.

色素多聚物的玻璃轉移溫度(Tg)較佳為50℃以上，更佳為100℃以上。另外，由熱重量分析(Thermogravimetric Analysis，TGA測定)所得的5%重量減少溫度較佳為120℃以上，更佳為150℃以上，進而佳為200℃以上。 The glass transition temperature (Tg) of the dye polymer is preferably 50 ° C or higher, more preferably 100 ° C or higher. In addition, by thermogravimetric analysis (Thermogravimetric The 5% weight loss temperature obtained by Analysis, TGA measurement is preferably 120 ° C or more, more preferably 150 ° C or more, and still more preferably 200 ° C or more.

另外，色素多聚物的每單位重量的吸光係數(以下記作ε'。ε'=ε/平均分子量，單位：L/g．cm)較佳為30以上，更佳為60以上，進而佳為100以上。藉由處於該範圍內，於應用本發明的著色組成物來製作彩色濾光片的情形時，可製作色彩再現性良好的彩色濾光片。 Further, the light absorption coefficient per unit weight of the dye polymer (hereinafter referred to as ε'. ε' = ε / average molecular weight, unit: L / g. cm) is preferably 30 or more, more preferably 60 or more, and further preferably It is 100 or more. When a color filter is produced by applying the colored composition of the present invention within this range, a color filter excellent in color reproducibility can be produced.

就著色力的觀點而言，色素多聚物的莫耳吸光係數較佳為儘可能高。 From the viewpoint of the coloring power, the molar absorption coefficient of the dye polymer is preferably as high as possible.

就色移的觀點而言，色素多聚物的還原黏度較佳為4.0~10.0，更佳為5.0~9.0，進而佳為6.0~7.0。還原黏度例如可使用烏氏黏度計(Ubbelohde viscometer)來進行測定。 From the viewpoint of color shift, the reduction viscosity of the dye polymer is preferably from 4.0 to 10.0, more preferably from 5.0 to 9.0, and even more preferably from 6.0 to 7.0. The reducing viscosity can be measured, for example, using a Ubbelohde viscometer.

色素多聚物較佳為溶解於以下溶劑中的化合物。 The dye polymer is preferably a compound dissolved in the following solvent.

溶劑可列舉：酯類(例如3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乳酸乙酯、乙酸丁酯、3-甲氧基丙酸甲酯等)、醚類(例如甲基溶纖劑乙酸酯(methyl cellosolve acetate)、乙基溶纖劑乙酸酯、丙二醇單甲醚、丙二醇單甲醚乙酸酯等)、酮類(甲基乙基酮、環己酮、2-庚酮、3-庚酮等)、芳香族烴類(例如甲苯、二甲苯等)，以如下情況為宜：相對於該些溶劑，較佳為溶解1質量%以上、50質量%以下，更佳為5質量%以上、40質量%以下，進而佳為10質量%以上、30質量%以下。藉由處於該範圍內，於將本發明的著色組成物用於製作彩色濾光片等時，可實現較佳的塗佈面狀，或 減少由塗佈其他顏色後的溶出所致的濃度降低。 Examples of the solvent include esters (for example, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, etc.), and ethers. (eg, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), ketones (methyl ethyl ketone, ring) An aromatic hydrocarbon (for example, toluene, xylene, etc.), or an aromatic hydrocarbon (for example, toluene, xylene, etc.) is preferable, and it is preferable to melt|dissolve 1 mass % or more, and 50 with respect to these solvents. The mass% or less is more preferably 5% by mass or more and 40% by mass or less, and further preferably 10% by mass or more and 30% by mass or less. By being in this range, when the coloring composition of the present invention is used for producing a color filter or the like, a preferable coating surface shape can be achieved, or Reduce the concentration reduction caused by dissolution after coating other colors.

本發明的著色組成物可單獨使用一種色素多聚物，亦可併用兩種以上。於使用兩種以上的情形時，較佳為其合計量相當於後述含量。 The coloring composition of the present invention may be used alone or in combination of two or more. When two or more cases are used, it is preferable that the total amount thereof corresponds to the content described later.

本發明的著色組成物中的色素多聚物(A)的含量較佳為考慮與後述顏料之含有比率後設定。 The content of the dye polymer (A) in the coloring composition of the present invention is preferably set in consideration of the content ratio of the pigment described later.

色素多聚物相對於顏料之質量比(色素多聚物(A)/顏料)較佳為0.1~5，更佳為0.2~2，進而佳為0.3~1。 The mass ratio of the dye polymer to the pigment (pigment polymer (A)/pigment) is preferably from 0.1 to 5, more preferably from 0.2 to 2, and still more preferably from 0.3 to 1.

本發明的著色組成物亦可含有所述色素多聚物以外的公知的染料。 The colored composition of the present invention may contain a known dye other than the dye polymer.

例如可參考：日本專利特開昭64-90403號公報、日本專利特開昭64-91102號公報、日本專利特開平1-94301號公報、日本專利特開平6-11614號公報、日本專利登記2592207號、美國專利4808501號說明書、美國專利5667920號說明書、美國專利505950號說明書、美國專利5667920號說明書、日本專利特開平5-333207號公報、日本專利特開平6-35183號公報、日本專利特開平6-51115號公報、日本專利特開平6-194828號公報、日本專利特開2010-250291號公報、日本專利特開2011-95732號公報、日本專利特開2012-13945號公報、日本專利特開2012-46708號公報、日本專利特開2012-46712號公報、日本專利特開2012-181502號公報、日本專利特開2012-208494號公報、日本專利特開2013-28764號公報、日本專利特開2013-29760號公報，將該些內容併入至本 申請案說明書中。化學結構可使用：吡唑偶氮系、吡咯亞甲基系、苯胺基偶氮系、三苯基甲烷系、蒽醌系、亞苄基系、氧喏系、吡唑并***偶氮系、吡啶酮偶氮系、花青系、啡噻嗪系、吡咯并吡唑甲亞胺系等的染料。 For example, Japanese Patent Laid-Open Publication No. Sho 64-90403, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. U.S. Patent No. 4,808, 051, U.S. Patent No. 4, 568, 850, U.S. Patent No. 5,567, 920, U.S. Patent No. 5, 505, 950, U.S. Patent No. 5,567, 920, Japanese Patent Laid-Open No. Hei No. 5-333207, Japanese Patent Laid-Open No. Hei 6-35183, Japanese Patent Laid-Open Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. 2012-46712, Japanese Patent Laid-Open Publication No. 2012-181502, Japanese Patent Laid-Open No. Hei. Publication No. 2013-29760, incorporating this content into this In the application note. The chemical structure can be used: pyrazole azo, pyrromethylene, aniline azo, triphenylmethane, lanthanide, benzylidene, oxonium, pyrazolotriazole azo A dye such as a pyridone azo, a cyanine, a phenothiazine or a pyrrolopyrazine.

<<(B)溶劑>> <<(B) Solvent>>

本發明的著色組成物含有溶劑。 The colored composition of the present invention contains a solvent.

溶劑只要滿足各成分的溶解性或著色組成物的塗佈性，則基本上無特別限制，尤佳為考慮紫外線吸收劑、鹼可溶性樹脂或分散劑等的溶解性、塗佈性、安全性而選擇。 The solvent is not particularly limited as long as it satisfies the solubility of each component or the coating property of the coloring composition, and it is particularly preferable to consider the solubility, coatability, and safety of the ultraviolet absorber, the alkali-soluble resin, or the dispersant. select.

溶劑可較佳地列舉：作為酯類的例如乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、氧基乙酸烷基酯(例如氧基乙酸甲酯、氧基乙酸乙酯、氧基乙酸丁酯(例如甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯等))、3-氧基丙酸烷基酯類(例如3-氧基丙酸甲酯、3-氧基丙酸乙酯等(例如3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯等))、2-氧基丙酸烷基酯類(例如2-氧基丙酸甲酯、2-氧基丙酸乙酯、2-氧基丙酸丙酯等(例如2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯))、2-氧基-2-甲基丙酸甲酯及2-氧基-2-甲基丙酸乙酯(例如2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯等)、丙酮酸甲酯、丙酮 酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸甲酯、2-氧代丁酸乙酯等；以及作為醚類的例如二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單***、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯等；以及作為酮類的例如甲基乙基酮、環己酮、2-庚酮、3-庚酮、環戊酮等；以及作為芳香族烴類的例如甲苯、二甲苯等。 The solvent is preferably exemplified as esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate. , ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (such as methoxyacetic acid) Methyl ester, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate (eg 3-oxyl) Methyl propionate, ethyl 3-oxypropionate, etc. (eg methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propyl propionate, etc.), alkyl 2-oxopropionate (for example, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (for example) Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate) , methyl 2-oxy-2-methylpropanoate and ethyl 2-oxy-2-methylpropionate (eg methyl 2-methoxy-2-methylpropionate) 2-ethoxy-2-methyl propionate etc.), methyl pyruvate, Ethyl acetate, propyl pyruvate, methyl acetate methyl acetate, ethyl acetate ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutanoate, etc.; and, for example, diethylene glycol as an ether Dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol single Ethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.; and as a ketone such as methyl ethyl ketone And cyclohexanone, 2-heptanone, 3-heptanone, cyclopentanone, etc.; and, as an aromatic hydrocarbon, for example, toluene, xylene, etc..

該些溶劑中，就塗佈後的乾燥的觀點而言，較佳為分子量在90~135的範圍或沸點在120℃~160℃的範圍內的溶劑。相當於該些溶劑的溶劑可列舉乙酸正丁酯、丙二醇單甲醚乙酸酯、丙二醇單甲醚、環己酮、環戊酮。 Among these solvents, from the viewpoint of drying after coating, a solvent having a molecular weight of 90 to 135 or a boiling point of 120 to 160 ° C is preferred. Examples of the solvent corresponding to the solvent include n-butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, and cyclopentanone.

就改良鹼可溶性樹脂的溶解性、塗佈面狀等的觀點而言，該些有機溶劑亦較佳為混合兩種以上。於該情形時，尤佳為由選自所述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、環戊酮、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單甲醚乙酸酯中的兩種以上所構成的混合溶液。 From the viewpoint of improving the solubility of the alkali-soluble resin, the coating surface, and the like, it is preferred to mix the organic solvents in two or more kinds. In this case, it is particularly preferred to be selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol. Dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol A mixed solution of two or more of methyl ether and propylene glycol monomethyl ether acetate.

除了所述觀點以外，該些有機溶劑藉由在溶劑中含有10%以上的氧雜蒽染料的溶解性優異的溶劑、例如環己酮、環戊酮、丙二醇單甲醚，可進一步提高放置穩定性。作為具體例，藉 由將丙二醇單甲醚乙酸酯作為主溶劑且含有10%以上的選自環己酮、環戊酮、丙二醇單甲醚中的一種以上的溶劑，可同時提高塗佈性與放置穩定性。 In addition to the above-mentioned viewpoints, the organic solvents can further improve the standing stability by containing a solvent having a solubility of 10% or more of xanthene dye in a solvent, for example, cyclohexanone, cyclopentanone, or propylene glycol monomethyl ether. Sex. As a specific example, borrow By using propylene glycol monomethyl ether acetate as a main solvent and containing at least one or more solvents selected from the group consisting of cyclohexanone, cyclopentanone, and propylene glycol monomethyl ether, coating properties and standing stability can be simultaneously improved.

就塗佈性的觀點而言，溶劑於著色組成物中的含量較佳為設定為組成物的總固體成分濃度成為5質量%~90質量%的量，更佳為5質量%~60質量%，尤佳為10質量%~50質量%。 From the viewpoint of the coating property, the content of the solvent in the coloring composition is preferably such that the total solid content concentration of the composition is from 5% by mass to 90% by mass, more preferably from 5% by mass to 60% by mass. It is preferably 10% by mass to 50% by mass.

本發明的組成物可僅含有一種溶劑，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 solvent, or may contain two or more kinds. When two or more cases are contained, it is preferable that the total amount is the said range.

<硬化性化合物> <hardening compound>

本發明的著色組成物較佳為含有硬化性化合物。 The colored composition of the present invention preferably contains a curable compound.

硬化性化合物可使用藉由自由基、酸、熱而可進行交聯的公知的聚合性化合物，例如可列舉含有乙烯性不飽和鍵、環狀醚(環氧、氧雜環丁烷)、羥甲基等的聚合性化合物。就感度的觀點而言，聚合性化合物是較佳地選自具有至少1個、較佳為2個以上的末端乙烯性不飽和鍵的化合物中。 As the curable compound, a known polymerizable compound which can be crosslinked by a radical, an acid or a heat can be used, and examples thereof include an ethylenically unsaturated bond, a cyclic ether (epoxy group, oxetane), and a hydroxyl group. A polymerizable compound such as a methyl group. From the viewpoint of sensitivity, the polymerizable compound is preferably selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds.

其中，較佳為多官能的聚合性化合物，更佳為4官能以上的多官能聚合性化合物，進而佳為5官能以上，尤佳為6官能以上。 In particular, a polyfunctional polymerizable compound is preferable, and a polyfunctional polymerizable compound having four or more functional groups is more preferable, and further preferably a pentane functional group or more, and particularly preferably a hexafunctional or higher functional group.

尤佳為多官能單體(較佳為4官能以上、更佳為6官能以上)且經環氧烷改質者。 More preferably, it is a polyfunctional monomer (preferably 4 functional or more, more preferably 6 functional or more) and is modified by alkylene oxide.

此種化合物組群於本發明的產業領域中廣為人知，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多聚物等。本發明的聚合性化合物可單獨使用一種，亦可併用兩種以上。 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. The compounds may be, for example, any of the following chemical forms: monomers, prepolymers, ie, dimers, trimers, and oligomers or Such mixtures and such polymers and the like. The polymerizable compounds of the present invention may be used alone or in combination of two or more.

更具體而言，單體及其預聚物的例子可列舉：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、以及該等的多聚物，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、以及該等的多聚物。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，或者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成不飽和膦酸、苯乙烯等乙烯基苯衍生物、乙烯醚、烯丙醚等而成的化合物組群。 More specifically, examples of the monomer and the prepolymer thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, etc.) or esters thereof. The guanamines and the polymers thereof are preferably esters of an unsaturated carboxylic acid and an aliphatic polyol compound, and guanamines of an unsaturated carboxylic acid and an aliphatic polyamine compound, and the like. Things. 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. The reactants further include a substituted carboxylic acid ester of a detachable substituent such as a halogen group or a tosyloxy group, or a substituted reactant of a monofunctional or polyfunctional alcohol, an amine or a thiol. Further, as another example, a compound group of a vinylbenzene derivative such as an unsaturated phosphonic acid or styrene, a vinyl ether or an allyl ether may be used instead of the unsaturated carboxylic acid.

作為該等的具體化合物，亦可將日本專利特開2009-288705號公報的段落0095~段落0108中記載的化合物較佳地用於本發明中。 As the specific compound, the compound described in paragraphs 0095 to 0108 of JP-A-2009-288705 can be preferably used in the present invention.

另外，聚合性化合物亦較佳為具有至少一個可進行加成聚合的乙烯基、且於常壓下具有100℃以上的沸點的具有乙烯性不 飽和基的化合物。其例子可列舉：聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、(甲基)丙烯酸苯氧基乙酯等單官能的丙烯酸酯或甲基丙烯酸酯；聚乙二醇二(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、己二醇(甲基)丙烯酸酯、三羥甲基丙烷三(丙烯醯氧基丙基)醚、異三聚氰酸三(丙烯醯氧基乙基)酯、於甘油或三羥甲基乙烷等多官能醇上加成環氧乙烷或環氧丙烷後加以(甲基)丙烯酸酯化而成者，日本專利特公昭48-41708號公報、日本專利特公昭50-6034號公報、日本專利特開昭51-37193號公報中記載般的(甲基)丙烯酸胺基甲酸酯類，日本專利特開昭48-64183號公報、日本專利特公昭49-43191號公報、日本專利特公昭52-30490號公報中記載的聚酯丙烯酸酯類，作為環氧樹脂與(甲基)丙烯酸的反應產物的環氧丙烯酸酯類等多官能的丙烯酸酯或甲基丙烯酸酯以及該等的混合物。 Further, the polymerizable compound is also preferably an ethylenic group having at least one vinyl group which can undergo addition polymerization and having a boiling point of 100 ° C or more at normal pressure. A saturated group of compounds. Examples thereof include monofunctional acrylates or methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate; Ethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(a) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tris(propylene oxypropyl) ether (Isopropyl methacrylate), (meth) acrylated by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane (Meth)acrylic acid urethanes, such as those described in Japanese Patent Laid-Open Publication No. SHO-48-41708 Japanese Patent Publication No. Sho 48-64183, Japanese Patent Publication No. Sho 49-43191, Japanese Patent Publication No. Sho 52-30490 Acrylate and methacrylate mixture of such multifunctional acrylates or polyester message described as a reaction product of an epoxy resin and (meth) acrylic acid epoxy acrylates.

亦可列舉多官能(甲基)丙烯酸酯等，所述多官能(甲基)丙烯酸酯是使(甲基)丙烯酸縮水甘油酯等具有環狀醚基及乙烯性不飽和基的化合物與多官能羧酸反應所得。 Further, a polyfunctional (meth) acrylate or the like which is a compound having a cyclic ether group and an ethylenically unsaturated group such as glycidyl (meth)acrylate, and a polyfunctional (meth) acrylate may be mentioned. The carboxylic acid is obtained by a reaction.

另外，其他較佳的聚合性化合物亦可使用：日本專利特開2010-160418號公報、日本專利特開2010-129825號公報、日本專利第4364216號說明書等中記載的具有茀環且具有2官能以上的乙烯性不飽和基的化合物，卡多樹脂(Cardo resin)。 In addition, other preferred polymerizable compounds may be used, such as those described in JP-A-2010-160418, JP-A-2010-129825, and JP-A No. 4,364,216. The above ethylenically unsaturated group compound, Cardo resin.

另外，於常壓下具有100℃以上的沸點、且具有至少一個可進行加成聚合的乙烯性不飽和基的化合物亦較佳為日本專利特開2008-292970號公報的段落編號[0254]~段落編號[0257]中記載的化合物。 Further, a compound having a boiling point of 100 ° C or higher and having at least one ethylenically unsaturated group capable of undergoing addition polymerization under normal pressure is also preferably a paragraph number [0254] of JP-A-2008-292970. The compound described in paragraph No. [0257].

除了所述以外，亦可較佳地使用下述通式(MO-1)~通式(MO-5)所表示的自由基聚合性單體。再者，式中，於T為氧伸烷基的情形時，碳原子側的末端鍵結於R。 In addition to the above, a radical polymerizable monomer represented by the following formula (MO-1) to formula (MO-5) can be preferably used. Further, in the formula, when T is an oxygen-extended alkyl group, the terminal on the carbon atom side is bonded to R.

[化34] [化34]

所述通式中，n為0~14，m為1~8。於一分子內存在多個的R、T可分別相同亦可不同。 In the above formula, n is 0 to 14, and m is 1 to 8. A plurality of R and T in one molecule may be the same or different.

於所述通式(MO-1)~通式(MO-5)所表示的各聚合性化合物中，存在多個的R的至少一個表示-OC(=O)CH=CH2或-OC(=O)C(CH3)=CH2所表示的基團。 In each of the polymerizable compounds represented by the above formula (MO-1) to formula (MO-5), at least one of a plurality of Rs represents -OC(=O)CH=CH 2 or -OC ( =O) C(CH 3 )= group represented by CH 2 .

作為所述通式(MO-1)~通式(MO-5)所表示的聚合性化合物的具體例，亦可將日本專利特開2007-269779號公報的段落編號0248~段落編號0251中記載的化合物較佳地用於本發明中。 Specific examples of the polymerizable compound represented by the above formula (MO-1) to (MO-5) can be described in paragraph number 0248 to paragraph number 0251 of JP-A-2007-269779. The compounds are preferably used in the present invention.

另外，以下化合物亦可用作聚合性化合物：於日本專利特開平10-62986號公報中作為通式(1)及通式(2)而與其具體例一併記載的所述於多官能醇上加成環氧乙烷或環氧丙烷後加以(甲基)丙烯酸酯化而成的化合物。 In addition, the following compounds can also be used as a polymerizable compound: the polyfunctional alcohol described above as a general formula (1) and a general formula (2) in the above-mentioned Japanese Patent Publication No. Hei 10-62986 A compound obtained by adding (meth)acrylic acid after addition of ethylene oxide or propylene oxide.

其中，聚合性化合物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)、及該等的(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。 Among them, the polymerizable compound is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available as Kaya) KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercial product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.) ), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and these (meth) acryloyl ruthenium-separated ethylene glycol The structure of the residue and the propylene glycol residue. These types of oligomers can also be used.

聚合性化合物亦可為多官能單體，且亦可具有羧基、磺 酸基、磷酸基等酸基。乙烯性化合物只要如上文所述為混合物的情形般具有未反應的羧基，則可直接利用，視需要亦可使非芳香族羧酸酐與所述乙烯性化合物的羥基反應而導入酸基。於該情形時，所使用的非芳香族羧酸酐的具體例可列舉：四氫鄰苯二甲酸酐、烷基化四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、烷基化六氫鄰苯二甲酸酐、琥珀酸酐、馬來酸酐。 The polymerizable compound may also be a polyfunctional monomer, and may also have a carboxyl group or a sulfonate. An acid group such as an acid group or a phosphoric acid group. When the ethylenic compound has an unreacted carboxyl group as in the case of the mixture as described above, it can be used as it is, and if necessary, a non-aromatic carboxylic anhydride can be reacted with a hydroxyl group of the ethylenic compound to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic anhydride to be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylated six. Hydrogen phthalic anhydride, succinic anhydride, maleic anhydride.

於本發明中，具有酸基的單體為脂肪族多羥基化合物與不飽和羧酸的酯，較佳為使非芳香族羧酸酐與脂肪族多羥基化合物的未反應的羥基反應而具有酸基的多官能單體，尤佳為於其酯中脂肪族多羥基化合物為季戊四醇及/或二季戊四醇者。市售品例如可列舉東亞合成股份有限公司製造的作為多元酸改質丙烯酸寡聚物的M-510、M-520等。 In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and preferably has a non-aromatic carboxylic anhydride reacting with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. The polyfunctional monomer is particularly preferably those in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. Commercially available products include M-510 and M-520 which are polybasic acid-modified acrylic oligomers manufactured by East Asia Synthetic Co., Ltd., for example.

該些單體可單獨使用一種，但於製造方面而言，難以使用單一的化合物，故亦可混合使用兩種以上。另外，視需要亦可併用不具有酸基的多官能單體與具有酸基的多官能單體作為單體。 These monomers may be used singly, but it is difficult to use a single compound in terms of production, and it is also possible to use two or more kinds in combination. Further, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as a monomer, as needed.

具有酸基的多官能單體的較佳酸值為0.1mgKOH/g~40mgKOH/g，尤佳為5mgKOH/g~30mgKOH/g。若多官能單體的酸值過低則顯影溶解特性降低，若多官能單體的酸值過高則製造或操作變困難而光聚合性能降低，畫素的表面平滑性等硬化性變差。因此，於併用兩種以上的酸基不同的多官能單體的情形時、或併用不具有酸基的多官能單體的情形時，較佳為以總體的多官 能單體的酸基在所述範圍內的方式調整。 The preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mgKOH/g to 40 mgKOH/g, particularly preferably from 5 mgKOH/g to 30 mgKOH/g. When the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are lowered. When the acid value of the polyfunctional monomer is too high, production or handling becomes difficult, photopolymerization performance is lowered, and curability such as surface smoothness of pixels is deteriorated. Therefore, in the case where a polyfunctional monomer having two or more acid groups is used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is preferred to have a general The acid group of the monomer can be adjusted in a manner within the above range.

另外，含有具有己內酯結構的多官能性單體作為聚合性化合物亦為較佳態樣。 Further, a polyfunctional monomer having a caprolactone structure is also preferable as a polymerizable compound.

具有己內酯結構的多官能性單體只要於其分子內具有己內酯結構，則並無特別限定，例如可列舉ε-己內酯改質多官能(甲基)丙烯酸酯，該ε-己內酯改質多官能(甲基)丙烯酸酯是藉由將三羥甲基乙烷、二-三羥甲基乙烷、三羥甲基丙烷、二-三羥甲基丙烷、季戊四醇、二季戊四醇、三季戊四醇、甘油、二甘油、三羥甲基三聚氰胺等多元醇與(甲基)丙烯酸及ε-己內酯進行酯化而獲得。其中，較佳為下述通式(Z-1)所表示的具有己內酯結構的多官能性單體。 The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, and examples thereof include ε-caprolactone-modified polyfunctional (meth) acrylate, and ε- Caprolactone modified polyfunctional (meth) acrylate by trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, two Polyols such as pentaerythritol, tripentaerythritol, glycerin, diglycerin, and trimethylol melamine are obtained by esterification with (meth)acrylic acid and ε-caprolactone. Among them, a polyfunctional monomer having a caprolactone structure represented by the following formula (Z-1) is preferred.

通式(Z-1)中，6個R全部為下述通式(Z-2)所表示的基團，或者6個R中的1個~5個為下述通式(Z-2)所表示的基團，且其餘為下述通式(Z-3)所表示的基團。 In the general formula (Z-1), all of the six R groups are groups represented by the following formula (Z-2), or one to five of the six R groups are represented by the following formula (Z-2). The group represented, and the rest are groups represented by the following formula (Z-3).

[化37] [化37]

通式(Z-2)中，R1表示氫原子或甲基，m表示1或2的數，「*」表示結合鍵。 In the formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bond.

通式(Z-3)中，R1表示氫原子或甲基，「*」表示結合鍵。 In the formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and "*" represents a bond.

此種具有己內酯結構的多官能性單體例如是由日本化藥(股)作為卡亞拉得(KAYARAD)DPCA系列而市售，可列舉：DPCA-20(所述式(1)~式(3)中m=1、式(2)所表示的基團的個數=2、R1全部為氫原子的化合物)、DPCA-30(所述式(1)~式(3)中m=1、式(2)所表示的基團的個數=3、R1全部為氫原子的化合物)、DPCA-60(所述式(1)~式(3)中m=1、式(2)所表示的基團的個數=6、R1全部為氫原子的化合物)、DPCA-120(所述式(1)~式(3)中m=2、式(2)所表示的基團的個數=6、R1全部為氫原子的化合物)等。 Such a polyfunctional monomer having a caprolactone structure is commercially available, for example, as a KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and may be exemplified by DPCA-20 (the formula (1)~ m in the formula (3), the number of groups represented by the formula (2) = 2, and the compound in which all R 1 are a hydrogen atom), DPCA-30 (in the formula (1) to the formula (3) m = 1, the number of groups represented by the formula (2) = 3, a compound in which all of R 1 is a hydrogen atom), DPCA-60 (in the formula (1) to the formula (3), m = 1, formula (2) The number of groups represented by the formula = 6 and the compound in which R 1 is a hydrogen atom), DPCA-120 (in the formula (1) to the formula (3), m = 2, and the formula (2) The number of groups is 6, the compound in which all of R 1 is a hydrogen atom, and the like.

於本發明中，具有己內酯結構的多官能性單體可單獨使用或 混合使用兩種以上。 In the present invention, the polyfunctional monomer having a caprolactone structure may be used alone or Mix two or more types.

另外，本發明的特定單體亦較佳為選自下述通式(Z-4)或通式(Z-5)所表示的化合物的組群中的至少一種。 Further, the specific monomer of the present invention is also preferably at least one selected from the group consisting of compounds represented by the following formula (Z-4) or formula (Z-5).

所述通式(Z-4)及通式(Z-5)中，E分別獨立地表示-((CH2)yCH2O)-或-((CH2)yCH(CH3)O)-，y分別獨立地表示0~10的整數，X分別獨立地表示丙烯醯基、甲基丙烯醯基、氫原子或羧基。 In the general formula (Z-4) and the general formula (Z-5), E independently represents -((CH 2 )yCH 2 O)- or -((CH 2 )yCH(CH 3 )O)- And y each independently represent an integer of 0 to 10, and X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom or a carboxyl group.

所述通式(Z-4)中，丙烯醯基及甲基丙烯醯基的合計值為3個或4個，m分別獨立地表示0~10的整數，各m的合計值為0~40的整數。其中，於各m的合計值為0的情形時，X中的任一個為羧基。 In the above formula (Z-4), the total of the acryloyl group and the methacryl fluorenyl group is 3 or 4, and m each independently represents an integer of 0 to 10, and the total value of each m is 0 to 40. The integer. In the case where the total value of each of m is 0, any one of X is a carboxyl group.

所述通式(ii)中，丙烯醯基及甲基丙烯醯基的合計值為5個或6個，n分別獨立地表示0~10的整數，各n的合計值為0~60的整數。其中，於各n的合計值為0的情形時，X中的任一個為 羧基。 In the above formula (ii), the total of the acryloyl group and the methacryl fluorenyl group is 5 or 6, and n each independently represents an integer of 0 to 10, and the total value of each n is an integer of 0 to 60. . Wherein, in the case where the total value of each n is 0, any one of X is carboxyl.

所述通式(Z-4)中，m較佳為0~6的整數，更佳為0~4的整數。另外，各m的合計值較佳為2~40的整數，更佳為2~16的整數，尤佳為4~8的整數。 In the above formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the total value of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.

所述通式(Z-5)中，n較佳為0~6的整數，更佳為0~4的整數。 In the above formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

另外，各n的合計值較佳為3~60的整數，更佳為3~24的整數，尤佳為6~12的整數。 Further, the total value of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

另外，通式(Z-4)或通式(Z-5)中的-((CH2)yCH2O)-或-((CH2)yCH(CH3)O)-較佳為氧原子側的末端鍵結於X的形態。 Further, -((CH 2 )yCH 2 O)- or -((CH 2 )yCH(CH 3 )O)- in the formula (Z-4) or the formula (Z-5) is preferably an oxygen atom. The end of the side is bonded to the form of X.

所述通式(Z-4)或通式(Z-5)所表示的化合物可單獨使用一種，亦可併用兩種以上。尤佳為通式(ii)中6個X全部為丙烯醯基的形態。 The compound represented by the formula (Z-4) or the formula (Z-5) may be used alone or in combination of two or more. More preferably, it is a form in which all six of X in the formula (ii) are an acrylonitrile group.

另外，通式(Z-4)或通式(Z-5)所表示的化合物於聚合性化合物中的總含量較佳為20質量%以上，更佳為50質量%以上。 In addition, the total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

所述通式(Z-4)或通式(Z-5)所表示的化合物可由作為以前公知的步驟的以下步驟來合成：藉由開環加成反應使環氧乙烷或環氧丙烷的開環骨架鍵結於季戊四醇或二季戊四醇的步驟；使例如(甲基)丙烯醯氯與開環骨架的末端羥基反應而導入(甲基)丙烯醯基的步驟。各步驟為廣為人知的步驟，本領域技術人員可容易地合成通式(i)或通式(ii)所表示的化合物。 The compound represented by the formula (Z-4) or the formula (Z-5) can be synthesized by the following steps as a previously known step: ethylene oxide or propylene oxide by a ring-opening addition reaction The step of bonding a ring-opening skeleton to pentaerythritol or dipentaerythritol; and introducing a (meth) acrylonitrile group by reacting, for example, (meth)acrylofluorene chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a compound represented by the formula (i) or the formula (ii) can be easily synthesized by those skilled in the art.

所述通式(Z-4)或通式(Z-5)所表示的化合物中，更佳為季戊四醇衍生物及/或二季戊四醇衍生物。 Among the compounds represented by the formula (Z-4) or the formula (Z-5), a pentaerythritol derivative and/or a dipentaerythritol derivative are more preferable.

具體可列舉下述式(a)~式(f)所表示的化合物(以下亦稱為「例示化合物(a)~例示化合物(f)」)，其中，較佳為例示化合物(a)、例示化合物(b)、例示化合物(e)、例示化合物(f)。 Specific examples thereof include the compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplary compounds (a) to exemplified compounds (f)"). Among them, preferred examples are compounds (a) and exemplified. Compound (b), exemplified compound (e), and exemplified compound (f).

[化41] [化41]

通式(Z-4)、通式(Z-5)所表示的聚合性化合物的市售品例如可列舉：沙多瑪(Sartomer)公司製造的具有4個伸乙氧基鏈的四官能丙烯酸酯SR-494，日本化藥股份有限公司製造的具有6個伸戊氧基鏈的六官能丙烯酸酯DPCA-60、具有3個伸異丁氧基鏈的三官能丙烯酸酯TPA-330等。 Commercial products of the polymerizable compound represented by the formula (Z-4) and the formula (Z-5) include, for example, a tetrafunctional acrylic acid having four ethylene oxide chains manufactured by Sartomer Co., Ltd. Ester SR-494, a hexafunctional acrylate DPCA-60 having six pentyloxy chains, three trifunctional acrylates TPA-330 having an extended isobutoxy chain, and the like, manufactured by Nippon Kayaku Co., Ltd.

另外，聚合性化合物亦較佳為日本專利特公昭48-41708號公報、日本專利特開昭51-37193號公報、日本專利特公平2-32293號公報、日本專利特公平2-16765號公報中記載般的丙烯酸胺基甲酸酯類，或日本專利特公昭58-49860號公報、日本專利特公昭56-17654號公報、日本專利特公昭62-39417號公報、日本 專利特公昭62-39418號公報記載的具有環氧乙烷系骨架的胺基甲酸酯化合物類。進而，藉由使用日本專利特開昭63-277653號公報、日本專利特開昭63-260909號公報、日本專利特開平1-105238號公報中記載的於分子內具有胺基結構或硫醚結構的加成聚合性化合物類作為聚合性化合物，可獲得感光速度非常優異的硬化性組成物。 In addition, the polymerizable compound is also preferably disclosed in Japanese Patent Publication No. Sho 48-41708, Japanese Patent Application Laid-Open No. SHO-51-37193, Japanese Patent Publication No. Hei 2-32293, and Japanese Patent Publication No. Hei 2-16765. Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. Sho 56-17654, Japanese Patent Publication No. Sho 62-39417, Japan A urethane compound having an ethylene oxide-based skeleton described in Japanese Patent Publication No. Sho 62-39418. Further, an amine group structure or a thioether structure is contained in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. As the polymerizable compound, an addition polymerizable compound can obtain a curable composition having a very excellent photospeed.

聚合性化合物的市售品可列舉：胺基甲酸酯寡聚物UAS-10、胺基甲酸酯寡聚物UAB-140(山陽國策紙漿公司製造)，「UA-7200」(新中村化學公司製造)，DPHA-40H(日本化藥公司製造)，UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600(共榮社製造)等。 Commercial products of the polymerizable compound include urethane oligomer UAS-10, urethane oligomer UAB-140 (manufactured by Shanyang Guoce Pulp Co., Ltd.), "UA-7200" (Xinzhongcun Chemical Co., Ltd.) Manufactured by the company, DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Co., Ltd.).

關於環狀醚(環氧、氧雜環丁烷)，例如作為具有環氧基者，雙酚A型環氧樹脂為JER-827、JER-828、JER-834、JER-1001、JER-1002、JER-1003、JER-1055、JER-1007、JER-1009、JER-1010(以上為日本環氧樹脂(股)製造)、艾比克隆(EPICLON)860、艾比克隆(EPICLON)1050、艾比克隆(EPICLON)1051、艾比克隆(EPICLON)1055(以上為迪愛生(DIC)(股)製造)等，雙酚F型環氧樹脂為JER-806、JER-807、JER-4004、JER-4005、JER-4007、JER-4010(以上為日本環氧樹脂(股)製造)、艾比克隆(EPICLON)830、艾比克隆(EPICLON)835(以上為迪愛生(DIC)(股)製造)、LCE-21、RE-602S(以上為日本化藥(股)製造)等，苯酚酚醛清漆型環氧樹脂為JER-152、JER-154、 JER-157S70、JER-157S65(以上為日本環氧樹脂(股)製造)、艾比克隆(EPICLON)N-740、艾比克隆(EPICLON)N-770、艾比克隆(EPICLON)N-775(以上為迪愛生(DIC)(股)製造)等，甲酚酚醛清漆型環氧樹脂可列舉艾比克隆(EPICLON)N-660、艾比克隆(EPICLON)N-665、艾比克隆(EPICLON)N-670、艾比克隆(EPICLON)N-673、艾比克隆(EPICLON)N-680、艾比克隆(EPICLON)N-690、艾比克隆(EPICLON)N-695(以上為迪愛生(DIC)(股)製造)、EOCN-1020(以上為日本化藥(股)製造)，脂肪族環氧樹脂可列舉艾迪科樹脂(ADEKA RESIN)EP-4080S、艾迪科樹脂(ADEKA RESIN)EP-4085S、艾迪科樹脂(ADEKA RESIN)EP-4088S(以上為艾迪科(ADEKA)(股)製造)、賽羅西德(Celloxide)2021P、賽羅西德(Celloxide)2081、賽羅西德(Celloxide)2083、賽羅西德(Celloxide)2085、EHPE-3150(2,2-雙(羥基甲基)-1-丁醇的1,2-環氧-4-(2-氧雜環丙基)環己烷加成物)、艾波利得(EPOLEAD)PB 3600、艾波利得(EPOLEAD)PB 4700(以上為大賽璐(Daicel)化學工業(股)製造)、代那考爾(Denacol)EX-211L、代那考爾(Denacol)EX-212L、代那考爾(Denacol)EX-214L、代那考爾(Denacol)EX-216L、代那考爾(Denacol)EX-321L、代那考爾(Denacol)EX-850L(以上為長瀨化成(Nagase Chemtex)(股)製造)、艾迪科樹脂(ADEKA RESIN)EP-4000S、艾迪科樹脂(ADEKA RESIN)EP-4003S、艾迪科樹脂(ADEKA RESIN)EP-4010S、艾迪科樹脂(ADEKA RESIN)EP-4011S(以上為艾迪科(ADEKA)(股)製造)、NC-2000、NC-3000、NC-7300、XD-1000、EPPN-501、EPPN-502(以上為艾迪科(ADEKA)(股)製造)、JER-1031S(日本環氧樹脂(股)製造)等。此種聚合性化合物適於利用乾式蝕刻法來形成圖案的情形。 Regarding a cyclic ether (epoxy or oxetane), for example, as an epoxy group, the bisphenol A type epoxy resin is JER-827, JER-828, JER-834, JER-1001, JER-1002. , JER-1003, JER-1055, JER-1007, JER-1009, JER-1010 (above is made by Japan Epoxy Resin Co., Ltd.), Abilon (EPICLON) 860, Epiclon (EPICLON) 1050, Ai Epiclon 1051, Epiclon 1055 (above is manufactured by Di Aisheng (DIC) Co., Ltd.), bisphenol F-type epoxy resin is JER-806, JER-807, JER-4004, JER -4005, JER-4007, JER-4010 (above is made by Japan Epoxy Resin Co., Ltd.), Abilon (EPICLON) 830, Epiclon (EPICLON) 835 (above is manufactured by Di Ai Sheng (DIC) Co., Ltd.) ), LCE-21, RE-602S (the above is manufactured by Nippon Chemical Co., Ltd.), etc., phenol novolac type epoxy resin is JER-152, JER-154, JER-157S70, JER-157S65 (above is made by Japan Epoxy Resin Co., Ltd.), Epiclon (EPICLON) N-740, Epiclon (NPICLON) N-770, Epiclon (EPICLON) N-775 ( The above is manufactured by Di Aisheng (DIC) Co., Ltd., etc., and the cresol novolac type epoxy resin can be exemplified by Epiclon N-660, EPICLON N-665, Epiclon. N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above is Di Aisheng (DIC) )), EOCN-1020 (above is manufactured by Nippon Kayaku Co., Ltd.), and aliphatic epoxy resins include ADEKA RESIN EP-4080S and ADEKA RESIN EP -4085S, ADEKA RESIN EP-4088S (above made by ADEKA), Celloxide 2021P, Celloxide 2081, Cyrusi Celloxide 2083, Celloxide 2085, EHPE-3150 (2,2-bis(hydroxymethyl)-1-butanol 1,2-epoxy-4-(2-oxocyclo) Propyl)cyclohexane adduct), EPOLEAD PB 3600, EPOLEAD PB 4700 (above is the big game) (Daicel) Chemical Industry (manufactured by the company), Denacol EX-211L, Denacol EX-212L, Denacol EX-214L, Denacol ) EX-216L, Denacol EX-321L, Denacol EX-850L (above manufactured by Nagase Chemtex), ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA resin RESIN)EP-4011S (above ADEKA (manufactured by ADEKA)), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above is Edico ( ADEKA) (manufactured by Japan), JER-1031S (manufactured by Japan Epoxy Co., Ltd.), etc. Such a polymerizable compound is suitable for the case where a pattern is formed by a dry etching method.

關於該些聚合性化合物，其結構、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來任意設定。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，就提高由著色組成物所形成的硬化膜的強度的觀點而言，以三官能以上者為宜，進而，藉由併用官能基數不同、聚合性基不同者(例如丙烯酸酯、甲基丙烯酸酯、苯乙烯系化合物、乙烯醚系化合物)來調節感度與強度兩者的方法亦有效。進而，併用三官能以上者且環氧乙烷鏈長不同的聚合性化合物就以下方面而言較佳：可調節著色組成物的顯影性，可獲得優異的圖案形成能力。 Regarding the polymerizable compounds, the details of the method of use, the use alone or in combination, the amount of addition, and the like 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 cured film formed by the colored composition, it is preferably a trifunctional or higher functional group, and further, a combination of different functional groups and different polymerizable groups (for example, acrylate or methacrylic acid) A method of adjusting both sensitivity and strength by an ester, a styrene compound, or a vinyl ether compound is also effective. Further, a polymerizable compound having a trifunctional or higher functional group and a different ethylene oxide chain length is preferably used in that the developability of the colored composition can be adjusted, and excellent pattern forming ability can be obtained.

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、被分散體、鹼可溶性樹脂等)的相容性、分散性而言，聚合性化合物的選擇、使用法亦為重要的原因，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，就提高與支持體等的硬質表面的密接性的觀點而言，有時亦可選擇特定的結構。 In addition, the compatibility and dispersibility of other components (for example, a photopolymerization initiator, a dispersion, an alkali-soluble resin, and the like) contained in the coloring composition are also important for the selection and use of the polymerizable compound. For example, it is sometimes possible to improve compatibility by using a low-purity compound or a combination of two or more. Further, from the viewpoint of improving the adhesion to the hard surface of the support or the like, a specific structure may be selected.

相對於組成物中的總固體成分，本發明的組成物中的硬 化性化合物的含量較佳為0.1質量%~90質量%，更佳為1.0質量%~60質量%，尤佳為2.0質量%~40質量%。 Hard in the composition of the present invention relative to the total solid content in the composition The content of the compound is preferably from 0.1% by mass to 90% by mass, more preferably from 1.0% by mass to 60% by mass, even more preferably from 2.0% by mass to 40% by mass.

本發明的組成物可僅含有一種硬化性化合物，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 curable compound, 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.

<顏料> <pigment>

本發明的著色組成物較佳為更含有(C)顏料。 The colored composition of the present invention preferably further contains (C) a pigment.

本發明中使用的顏料可使用以前公知的各種無機顏料或有機顏料，較佳為使用有機顏料。所述顏料較佳為高透射率。 As the pigment used in the present invention, various inorganic pigments or organic pigments known in the art can be used, and organic pigments are preferably used. The pigment is preferably high in transmittance.

無機顏料可列舉金屬氧化物、金屬錯鹽等所表示的金屬化合物，具體可列舉：鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、鋅、銻等的金屬氧化物，所述金屬的複合氧化物，碳黑、鈦黑等黑色顏料。 Examples of the inorganic pigment include a metal compound represented by a metal oxide or a metal salt, and specific examples thereof include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and cerium. A composite oxide of a metal, a black pigment such as carbon black or titanium black.

有機顏料例如可列舉：C.I.顏料黃11、C.I.顏料黃24、C.I.顏料黃31、C.I.顏料黃53、C.I.顏料黃83、C.I.顏料黃93、C.I.顏料黃99、C.I.顏料黃108、C.I.顏料黃109、C.I.顏料黃110、C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃147、C.I.顏料黃150、C.I.顏料黃151、C.I.顏料黃154、C.I.顏料黃155、C.I.顏料黃167、C.I.顏料黃180、C.I.顏料黃185、C.I.顏料黃199；C.I.顏料橙36、C.I.顏料橙38、C.I.顏料橙43、C.I.顏料橙71；C.I.顏料紅81、C.I.顏料紅105、C.I.顏料紅122、C.I.顏料紅149、C.I.顏料紅150、C.I.顏料紅155、C.I.顏料紅171、C.I.顏料 紅175、C.I.顏料紅176、C.I.顏料紅177、C.I.顏料紅209、C.I.顏料紅220、C.I.顏料紅224、C.I.顏料紅242、C.I.顏料紅254、C.I.顏料紅255、C.I.顏料紅264、C.I.顏料紅270；C.I.顏料紫19、C.I.顏料紫23、C.I.顏料紫32、C.I.顏料紫39；C.I.顏料藍1、C.I.顏料藍2、C.I.顏料藍15、C.I.顏料藍15：1、C.I.顏料藍15：3、C.I.顏料藍15：6、C.I.顏料藍16、C.I.顏料藍22、C.I.顏料藍60、C.I.顏料藍66；C.I.顏料綠7、C.I.顏料綠36、C.I.顏料綠37、C.I.顏料綠58；C.I.顏料棕25、C.I.顏料棕28；C.I.顏料黑1等。 Examples of the organic pigment include CI Pigment Yellow 11, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 53, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 99, CI Pigment Yellow 108, and CI Pigment Yellow 109. , CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 167, CI Pigment Yellow 180 , CI Pigment Yellow 185, CI Pigment Yellow 199; CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 71; CI Pigment Red 81, CI Pigment Red 105, CI Pigment Red 122, CI Pigment Red 149 , CI Pigment Red 150, CI Pigment Red 155, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 209, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 270; CI pigment violet 19, CI pigment violet 23, CI pigment violet 32, CI pigment violet 39; CI pigment blue 1, CI pigment blue 2, CI pigment blue 15, CI pigment blue 15: 1, CI pigment blue 15: 3. CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 66; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 58; CI Pigment Brown 25, CI Pigment Brown 28; CI Pigment Black 1 and the like.

本發明中可較佳地使用的顏料可列舉以下顏料。然而，本發明不限定於該些顏料。 The pigment which can be preferably used in the present invention is exemplified by the following pigments. However, the invention is not limited to the pigments.

C.I.顏料黃11、C.I.顏料黃24、C.I.顏料黃108、C.I.顏料黃109、C.I.顏料黃110、C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃150、C.I.顏料黃151、C.I.顏料黃154、C.I.顏料黃167、C.I.顏料黃180、C.I.顏料黃185，C.I.顏料橙36、C.I.顏料橙71，C.I.顏料紅122、C.I.顏料紅150、C.I.顏料紅171、C.I.顏料紅175、C.I.顏料紅177、C.I.顏料紅209、C.I.顏料紅224、C.I.顏料紅242、C.I.顏料紅254、C.I.顏料紅255、C.I.顏料紅264，C.I.顏料紫19、C.I.顏料紫23、C.I.顏料紫32，C.I.顏料藍15：1、C.I.顏料藍15：3、C.I.顏料藍15：6、C.I.顏料 藍16、C.I.顏料藍22、C.I.顏料藍60、C.I.顏料藍66，C.I.顏料綠7、C.I.顏料綠36、C.I.顏料綠37、C.I.顏料綠58；C.I.顏料黑1 CI Pigment Yellow 11, CI Pigment Yellow 24, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 167, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Orange 36, CI Pigment Orange 71, CI Pigment Red 122, CI Pigment Red 150, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 177, CI Pigment Red 209, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 32, CI Pigment Blue 15: 1. CI Pigment Blue 15:3, CI Pigment Blue 15:6, CI Pigment Blue 16, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 66, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Pigment Green 58; C.I. Pigment Black 1

該些有機顏料可單獨使用或為了調整分光或提高顏色純度而組合使用。以下示出所述組合的具體例。例如，紅色顏料可單獨使用蒽醌系顏料、苝系顏料、二酮吡咯并吡咯系顏料，或者使用該些顏料的至少一種與雙偶氮系黃色顏料、異吲哚啉系黃色顏料、喹酞酮系黃色顏料或苝系紅色顏料的混合等。例如，蒽醌系顏料可列舉C.I.顏料紅177，苝系顏料可列舉C.I.顏料紅155、C.I.顏料紅224，二酮吡咯并吡咯系顏料可列舉C.I.顏料紅254，就顏色分解性的方面而言，較佳為與C.I.顏料黃139的混合。另外，紅色顏料與黃色顏料之質量比較佳為100：5~100：50。若為100：4以下則難以抑制400nm~500nm的光透射率，另外若為100：51以上則有時主波長向短波長偏移，無法提高顏色分解能力。尤其所述質量比最合適的是100：10~100：30的範圍。另外，紅色顏料彼此的組合的情形下，可根據所需求的分光來進行調整。 These organic pigments may be used singly or in combination for adjusting the spectroscopic or improving the color purity. Specific examples of the combination are shown below. For example, the red pigment may be used alone as an anthraquinone pigment, an anthraquinone pigment, a diketopyrrolopyrrole pigment, or at least one of these pigments and a disazo yellow pigment, an isoporphyrin yellow pigment, a quinacridone. Mixing of a ketone-based yellow pigment or an anthraquinone-based red pigment. For example, CI pigment red 177 is exemplified, and CI pigment red 155 and CI pigment red 224 are exemplified as the ruthenium pigment, and CI pigment red 254 is exemplified as the diketopyrrolopyrrole pigment, and in terms of color decomposition property, Preferably, it is mixed with CI Pigment Yellow 139. In addition, the quality of the red pigment and the yellow pigment is preferably 100:5 to 100:50. When it is 100:4 or less, it is difficult to suppress the light transmittance of 400 nm to 500 nm, and if it is 100:51 or more, the main wavelength may be shifted to a short wavelength, and the color separation ability may not be improved. In particular, the mass ratio is most suitably in the range of 100:10 to 100:30. Further, in the case where the red pigments are combined with each other, the adjustment can be performed in accordance with the required spectroscopic light.

另外，綠色顏料可單獨使用鹵化酞菁系顏料，或使用其與雙偶氮系黃色顏料、喹酞酮(quinophthalone)系黃色顏料、甲亞胺系黃色顏料或異吲哚啉系黃色顏料的混合。例如，此種例子較佳為C.I.顏料綠7、C.I.顏料綠36、C.I.顏料綠37與C.I.顏料黃83、C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃150、C.I.顏料黃180或C.I.顏料黃185的混合。綠色顏料與黃色顏料之質量比較佳 為100：5~100：150。所述質量比尤佳為100：30~100：120的範圍。 Further, the green pigment may be a halogenated phthalocyanine-based pigment alone or a mixture with a disazo-based yellow pigment, a quinophthalone-based yellow pigment, a azomethine-based yellow pigment or an iso- porphyrin-based yellow pigment. . For example, such an example is preferably CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180 or CI Pigment. A mixture of yellow 185. The quality of green and yellow pigments is better It is 100:5~100:150. The mass ratio is particularly preferably in the range of 100:30 to 100:120.

藍色顏料可單獨使用酞菁系顏料，或使用其與二噁嗪系紫色顏料的混合。例如較佳為C.I.顏料藍15：6與C.I.顏料紫23的混合。藍色顏料與紫色顏料之質量比較佳為100：0~100：100，更佳為100：10以下。 The blue pigment may be a phthalocyanine-based pigment alone or a mixture with a dioxazine-based violet pigment. For example, a mixture of C.I. Pigment Blue 15:6 and C.I. Pigment Violet 23 is preferred. The quality of the blue pigment and the purple pigment is preferably from 100:0 to 100:100, more preferably 100:10 or less.

另外，黑色矩陣用的顏料可單獨或混合使用碳、鈦黑、氧化鐵、氧化鈦，較佳為碳與鈦黑的組合。另外，碳與鈦黑之質量比較佳為100：0~100：60的範圍。 Further, the pigment for the black matrix may be used singly or in combination of carbon, titanium black, iron oxide, titanium oxide, preferably a combination of carbon and titanium black. In addition, the quality of carbon and titanium black is preferably in the range of 100:0 to 100:60.

本發明的著色組成物較佳為調配黑色以外的顏料，適於藍色顏料。 The coloring composition of the present invention is preferably a pigment other than black, and is suitable for a blue pigment.

關於顏料的一次粒子尺寸，於用作彩色濾光片用的情形時，就色彩不均或對比度的觀點而言，較佳為100nm以下，另外，就分散穩定性的觀點而言，較佳為5nm以上。顏料的一次粒子尺寸較佳為5nm~75nm，更佳為5nm~55nm，尤佳為5nm~35nm。 When the primary particle size of the pigment is used as a color filter, it is preferably 100 nm or less from the viewpoint of color unevenness or contrast, and from the viewpoint of dispersion stability, it is preferably 5nm or more. The primary particle size of the pigment is preferably 5 nm to 75 nm, more preferably 5 nm to 55 nm, and particularly preferably 5 nm to 35 nm.

顏料的一次粒子尺寸可利用電子顯微鏡等公知的方法來測定。 The primary particle size of the pigment can be measured by a known method such as an electron microscope.

其中，顏料較佳為選自蒽醌顏料、二酮吡咯并吡咯顏料、酞菁顏料、喹酞酮顏料、異吲哚啉顏料、甲亞胺顏料及二噁嗪顏料中的顏料。尤其特佳為C.I.顏料紅177(蒽醌顏料)，C.I.顏料紅254(二酮吡咯并吡咯顏料)、C.I.顏料綠7、C.I.顏料綠36、C.I.顏料綠58、C.I.顏料藍15：6(酞菁顏料)、C.I.顏料黃138(喹 酞酮顏料)、C.I.顏料黃139、C.I.顏料黃185(異吲哚啉顏料)、C.I.顏料黃150(甲亞胺顏料)、C.I.顏料紫23(二噁嗪顏料)。 Among them, the pigment is preferably a pigment selected from the group consisting of an anthraquinone pigment, a diketopyrrolopyrrole pigment, a phthalocyanine pigment, a quinophthalone pigment, an isoporphyrin pigment, a methylimine pigment, and a dioxazine pigment. Especially preferred is CI Pigment Red 177 (蒽醌 pigment), CI Pigment Red 254 (diketopyrrolopyrrole pigment), CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Blue 15:6 (酞Cyanine pigment), CI pigment yellow 138 (quin Anthrone pigments), C.I. Pigment Yellow 139, C.I. Pigment Yellow 185 (isoporphyrin pigment), C.I. Pigment Yellow 150 (methylimine pigment), C.I. Pigment Violet 23 (dioxazine pigment).

尤其顏料較佳為酞菁顏料。 In particular, the pigment is preferably a phthalocyanine pigment.

於使用酞菁顏料作為顏料的情形時，酞菁顏料與所述色素多聚物之質量比較佳為90：10~30：70，更佳為65：35~55：45。 In the case where a phthalocyanine pigment is used as the pigment, the quality of the phthalocyanine pigment and the pigment polymer is preferably from 90:10 to 30:70, more preferably from 65:35 to 55:45.

相對於著色組成物所含有的將溶劑除外的所有成分，顏料的含量較佳為10質量%~70質量%，更佳為20質量%~60質量%，進而佳為25質量%~50質量%。 The content of the pigment is preferably from 10% by mass to 70% by mass, more preferably from 20% by mass to 60% by mass, even more preferably from 25% by mass to 50% by mass, based on the total amount of the components of the coloring composition excluding the solvent. .

關於使用酞菁顏料作為顏料的情形的含量，相對於著色組成物所含有的將溶劑除外的所有成分，所述含量較佳為25質量%~60質量%，更佳為30質量%~50質量%，進而佳為35質量%~45質量%。 The content in the case of using a phthalocyanine pigment as a pigment is preferably from 25% by mass to 60% by mass, more preferably from 30% by mass to 50% by mass based on the total amount of all components excluding the solvent contained in the coloring composition. %, and further preferably from 35 mass% to 45 mass%.

本發明的組成物可僅含有一種顏料，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 pigment, or 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就進一步提高感度的觀點而言，較佳為含有光聚合起始劑。 The coloring composition of the present invention preferably contains a photopolymerization initiator from the viewpoint of further improving the sensitivity.

光聚合起始劑只要具有引發所述聚合性化合物的聚合的能力，則並無特別限制，可自公知的光聚合起始劑中適當選擇。例如較佳為對紫外線範圍至可見光線具有感光性者。另外，亦可為與經光激發的增感劑發生某些作用而生成活性自由基的活性劑， 亦可為根據單體的種類而引發陽離子聚合般的起始劑。 The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferred to have a sensitivity to ultraviolet light to visible light. In addition, it may also be an active agent that generates a living radical by some action with a photo-excited sensitizer. It is also possible to initiate a cationic polymerization-like initiator according to the kind of the monomer.

另外，光聚合起始劑較佳為含有至少一種於約300nm~800nm(更佳為330nm~500nm)的範圍內具有至少約50的分子吸光係數的化合物。 Further, the photopolymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm, more preferably 330 nm to 500 nm.

光聚合起始劑例如可列舉：鹵化烴衍生物(例如具有三嗪骨架者、具有噁二唑骨架者等)、醯基膦氧化物等醯基膦化合物、六芳基聯咪唑、肟衍生物等肟化合物、有機過氧化物、硫化合物、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮化合物、羥基苯乙酮等，較佳為肟化合物。 Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton, a oxadiazole skeleton, etc.), a mercaptophosphine compound such as a mercaptophosphine oxide, a hexaarylbiimidazole, an anthracene derivative. The hydrazine compound, the organic peroxide, the sulfur compound, the ketone compound, the aromatic sulfonium salt, the ketoxime ether, the aminoacetophenone compound, the hydroxyacetophenone or the like is preferably an anthracene compound.

另外，就曝光感度的觀點而言，較佳為選自由三鹵代甲基三嗪化合物、苯偶醯二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、膦氧化物化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚物、鎓化合物、苯并噻唑化合物、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、鹵代甲基噁二唑化合物、3-芳基取代香豆素化合物所組成的組群中的化合物。 Further, from the viewpoint of exposure sensitivity, it is preferably selected from the group consisting of a trihalomethyltriazine compound, a benzoin dimethyl ketal compound, an α-hydroxyketone compound, an α-amino ketone compound, and a mercaptophosphine. Compound, phosphine oxide compound, metallocene compound, hydrazine compound, triaryl imidazole dimer, hydrazine compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivative thereof, cyclopentadiene-benzene a compound in a group consisting of an iron complex and a salt thereof, a halogenated methyl oxadiazole compound, and a 3-aryl substituted coumarin compound.

進而佳為三鹵代甲基三嗪化合物、α-胺基酮化合物、醯基膦化合物、膦氧化物化合物、肟化合物、三芳基咪唑二聚物、三芳基咪唑化合物、苯并咪唑化合物、鎓化合物、二苯甲酮化合物、苯乙酮化合物，尤佳為選自由三鹵代甲基三嗪化合物、α-胺基酮化合物、肟化合物、三芳基咪唑化合物、二苯甲酮化合物、三芳基咪唑化合物、苯并咪唑化合物所組成的組群中的至少一種 化合物。另外，三芳基咪唑化合物亦可為與苯并咪唑的混合物。 Further preferred are trihalomethyltriazine compounds, α-amino ketone compounds, mercaptophosphine compounds, phosphine oxide compounds, hydrazine compounds, triaryl imidazole dimers, triarylimidazole compounds, benzimidazole compounds, hydrazine The compound, the benzophenone compound, the acetophenone compound, and more preferably is selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an anthraquinone compound, a triarylimidazole compound, a benzophenone compound, and a triaryl group. At least one of a group consisting of an imidazole compound and a benzimidazole compound Compound. Further, the triarylimidazole compound may also be a mixture with benzimidazole.

具體而言，三鹵代甲基三嗪化合物可例示以下化合物。再者，Ph為苯基。 Specifically, the trihalomethyltriazine compound can be exemplified by the following compounds. Further, Ph is a phenyl group.

三芳基咪唑化合物、苯并咪唑化合物可例示以下化合物。 The triaryl imidazole compound and the benzimidazole compound can be exemplified by the following compounds.

三鹵代甲基三嗪化合物亦可使用市售品，例如可使用TAZ-107(碧化學公司製造)。 A commercially available product can also be used as the trihalomethyltriazine compound, and for example, TAZ-107 (manufactured by Biochemical Co., Ltd.) can be used.

尤其於將本發明的著色組成物用於製作固體攝像元件所具備的彩色濾光片的情形時，必須以尖銳(sharp)的形狀形成微細的圖案，因此重要的是硬化性並且於未曝光部中無殘渣地進行顯 影。就此種觀點而言，聚合起始劑尤佳為使用肟化合物。尤其於固體攝像元件中形成微細圖案的情形時，於硬化用曝光時使用步進式曝光，但有時該曝光機因鹵素而受到損傷，亦必須將聚合起始劑的添加量抑制得低，故若考慮到該些方面，則尤佳為於形成如固體攝像元件般的微細圖案時，使用肟化合物作為(D)光聚合起始劑。 In particular, when the colored composition of the present invention is used for producing a color filter provided in a solid-state image sensor, it is necessary to form a fine pattern in a sharp shape, so that it is important in hardenability and in an unexposed portion. No residue in the display Shadow. From this point of view, it is especially preferred to use a hydrazine compound for the polymerization initiator. In particular, when a fine pattern is formed in a solid-state image sensor, stepwise exposure is used for exposure for curing, but the exposure machine may be damaged by halogen, and it is necessary to suppress the addition amount of the polymerization initiator to be low. Therefore, in consideration of these aspects, it is particularly preferable to use a ruthenium compound as the (D) photopolymerization initiator when forming a fine pattern such as a solid-state image sensor.

所述具有三嗪骨架的鹵化烴化合物例如可列舉：若林等人著的「日本化學會公報(Bull.Chem.Soc.Japan)」(42、2924(1969))記載的化合物、英國專利第1388492號說明書記載的化合物、日本專利特開昭53-133428號公報記載的化合物、德國專利第3337024號說明書記載的化合物、F.C.謝弗(F.C.Schaefer)等人的「有機化學期刊(J.Org.Chem.)」(29、1527(1964))記載的化合物、日本專利特開昭62-58241號公報記載的化合物、日本專利特開平5-281728號公報記載的化合物、日本專利特開平5-34920號公報記載的化合物、美國專利第4212976號說明書中記載的化合物、特別是日本專利特開2013-077009號公報的段落編號0075中記載的化合物等。 Examples of the halogenated hydrocarbon compound having a triazine skeleton include a compound described in "Bull. Chem. Soc. Japan" (42, 2924 (1969)), and a British patent No. 1388492. The compound described in the specification, the compound described in JP-A-53-133428, the compound described in the specification of German Patent No. 3337024, and the "Journal of Organic Chemistry (J. Org. Chem) by FC Schaefer et al. The compound described in the Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compound described in the publication, the compound described in the specification of U.S. Patent No. 4,212,976, and the compound described in Paragraph No. 0075 of JP-A-2013-077009.

另外，所述以外的光聚合起始劑可例示吖啶衍生物。具體可列舉日本專利特開2013-077009號公報的段落編號0076中記載的化合物等，將該些內容併入至本申請案說明書中。 Further, the photopolymerization initiator other than the above may be an acridine derivative. Specific examples thereof include the compounds described in Paragraph No. 0076 of JP-A-2013-077009, the contents of which are incorporated herein by reference.

所述酮化合物例如可列舉日本專利特開2013-077009號公報的段落編號0077中記載的化合物等，將該些內容併入至本申 請案說明書中。 The ketone compound may, for example, be a compound described in Paragraph No. 0077 of JP-A-2013-077009, and the contents thereof are incorporated into the present application. In the case of the case.

光聚合起始劑亦可較佳地使用羥基苯乙酮化合物、胺基苯乙酮化合物及醯基膦化合物。更具體而言，例如亦可使用日本專利特開平10-291969號公報中記載的胺基苯乙酮系起始劑、日本專利第4225898號公報中記載的醯基膦氧化物系起始劑。 As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be preferably used. More specifically, for example, an amino acetophenone-based initiator as described in JP-A-10-291969, and a mercaptophosphine oxide-based initiator described in Japanese Patent No. 4,258,899 can be used.

羥基苯乙酮系起始劑可使用：豔佳固(IRGACURE)-184、達羅卡(DAROCUR)-1173、豔佳固(IRGACURE)-500、豔佳固(IRGACURE)-2959，豔佳固(IRGACURE)-127(商品名：均為巴斯夫(BASF)公司製造)。胺基苯乙酮系起始劑可使用：作為市售品的豔佳固(IRGACURE)-907、豔佳固(IRGACURE)-369及豔佳固(IRGACURE)-379(商品名：均為巴斯夫(BASF)公司製造)。胺基苯乙酮系起始劑亦可使用吸收波長與365nm或405nm等長波光源匹配(matching)的日本專利特開2009-191179號公報中記載的化合物。另外，醯基膦系起始劑亦可使用作為市售品的豔佳固(IRGACURE)-819或達羅卡(DAROCUR)-TPO(商品名：均為巴斯夫(BASF)公司製造)。 The hydroxyacetophenone-based initiator can be used: IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, Yanjiagu (IRGACURE)-127 (trade name: all manufactured by BASF). Amino acetophenone-based initiators can be used as: commercially available products such as IRGACURE-907, IRGACURE-369 and IRGACURE-379 (trade names: all BASF) (Manufactured by BASF). The amine acetophenone-based initiator may also be a compound described in JP-A-2009-191179, which has an absorption wavelength matched to a long-wavelength light source such as 365 nm or 405 nm. Further, as the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name: all manufactured by BASF) can be used as a commercial product.

光聚合起始劑更佳可列舉肟化合物。肟化合物的具體例可使用日本專利特開2001-233842號公報記載的化合物、日本專利特開2000-80068號公報記載的化合物、日本專利特開2006-342166號公報記載的化合物。 More preferably, the photopolymerization initiator is a ruthenium compound. For the specific example of the ruthenium compound, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and a compound described in JP-A-2006-342166 can be used.

可較佳地用作本發明的光聚合起始劑的肟衍生物等肟化合物例如可列舉：3-苯甲醯氧基亞胺基丁烷-2-酮、3-乙醯氧基 亞胺基丁烷-2-酮、3-丙醯氧基亞胺基丁烷-2-酮、2-乙醯氧基亞胺基戊烷-3-酮、2-乙醯氧基亞胺基-1-苯基丙烷-1-酮、2-苯甲醯氧基亞胺基-1-苯基丙烷-1-酮、3-(4-甲苯磺醯氧基)亞胺基丁烷-2-酮及2-乙氧基羰氧基亞胺基-1-苯基丙烷-1-酮等。 The hydrazine compound such as an anthracene derivative which can be preferably used as the photopolymerization initiator of the present invention is exemplified by 3-benzoyloxyiminobutan-2-one and 3-ethyloxy group. Iminobutan-2-one, 3-propenyloxyimidobutan-2-one, 2-ethyloxyiminopentan-3-one, 2-ethyloxyimide 1-phenylpropan-1-one, 2-benzylideneoxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane- 2-ketone and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

肟化合物可列舉：「英國化學會志(Journal of the Chemical Society，J.C.S.)普爾金會刊(Perkin)II」(1979年)pp.1653-1660、「英國化學會志(Journal of the Chemical Society，J.C.S.)普爾金會刊(Perkin)II」(1979年)pp.156-162、「光聚合物科學與技術期刊(Journal of Photopolymer Science and Technology)」(1995年)pp.202-232、日本專利特開2000-66385號公報記載的化合物，日本專利特開2000-80068號公報、日本專利特表2004-534797號公報、日本專利特開2006-342166號公報的各公報中記載的化合物等。 Examples of bismuth compounds include: "Journal of the Chemical Society (JCS) Perkin II (1979) pp. 1653-1660, "Journal of the Chemical Society," JCS) Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, Japanese Patent The compound described in each of the publications of JP-A-2000-86385, JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166.

市售品中亦可較佳地使用豔佳固(IRGACURE)-OXE01(巴斯夫(BASF)公司製造)、豔佳固(IRGACURE)-OXE02(巴斯夫(BASF)公司製造)。 In the commercial product, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can be preferably used.

另外，亦可使用以下化合物作為所述記載以外的肟化合物：肟連結於咔唑N位上的日本專利特表2009-519904號公報中記載的化合物、於二苯甲酮部位上導入有雜取代基的美國專利第7626957號公報中記載的化合物、於色素部位上導入有硝基的日本專利特開2010-15025號公報及美國專利公開2009-292039號記載的化合物、國際公開專利2009-131189號公報中記載的酮肟化合 物、於同一分子內含有三嗪骨架與肟骨架的美國專利7556910號公報中記載的化合物、於405nm處具有最大吸收且對g射線光源具有良好的感度的日本專利特開2009-221114號公報記載的化合物等。 In addition, the following compound may be used as a compound other than the above-mentioned compound: a compound described in Japanese Patent Laid-Open Publication No. 2009-519904, which is attached to the N-position of the carbazole, and a hetero-substrate introduced into the benzophenone moiety. The compound described in the U.S. Patent No. 7,626,957, the compound of the Japanese Patent Publication No. 2010-15025, and the U.S. Patent Publication No. 2009-292039, the International Patent Publication No. 2009-131189 Ketone oxime combination described in the bulletin The compound described in the U.S. Patent No. 7,569,910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, has a maximum absorption at 405 nm and has a good sensitivity to a g-ray source, and is described in JP-A-2009-221114. Compounds, etc.

較佳為進而亦可較佳地使用日本專利特開2007-231000號公報及日本專利特開2007-322744號公報中記載的環狀肟化合物。環狀肟化合物中，尤其就具有高的光吸收性而高感度化的觀點而言，較佳為日本專利特開2010-32985號公報、日本專利特開2010-185072號公報中記載的縮環於咔唑色素上的環狀肟化合物。 The cyclic ruthenium compound described in JP-A-2007-2318 and JP-A-2007-322744 is preferably used. In the case of the cyclic ruthenium compound, the condensed ring described in Japanese Patent Laid-Open Publication No. 2010-185072, and the Japanese Patent Publication No. 2010-185072, and the like. a cyclic guanidine compound on a carbazole dye.

另外，於肟化合物的特定部位上具有不飽和鍵的日本專利特開2009-242469號公報中記載的化合物亦由聚合非活性自由基來再生活性自由基，由此可達成高感度化而可較佳地使用。 In addition, the compound described in JP-A-2009-242469, which has an unsaturated bond at a specific site of a ruthenium compound, also regenerates an active radical by polymerizing an inactive radical, thereby achieving high sensitivity and being comparable. Good to use.

尤佳可列舉：日本專利特開2007-269779號公報中揭示的具有特定取代基的肟化合物、或日本專利特開2009-191061號公報中揭示的具有硫代芳基的肟化合物。 In particular, an anthracene compound having a specific substituent disclosed in Japanese Laid-Open Patent Publication No. 2007-269779, or a ruthenium compound having a thioaryl group disclosed in Japanese Laid-Open Patent Publication No. 2009-191061.

具體而言，作為光聚合起始劑的肟化合物較佳為下述通式(OX-1)所表示的化合物。再者，可為肟的N-O鍵為(E)體的肟化合物，亦可為(Z)體的肟化合物，亦可為(E)體與(Z)體的混合物。 Specifically, the ruthenium compound as a photopolymerization initiator is preferably a compound represented by the following formula (OX-1). Further, the ruthenium compound in which the N-O bond of ruthenium is (E), the ruthenium compound of the (Z) form, or a mixture of the (E) form and the (Z) form may be used.

[化44] [化44]

通式(OX-1)中，R及B分別獨立地表示一價取代基，A表示二價有機基，Ar表示芳基。 In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

通式(OX-1)中，R所表示的一價取代基較佳為一價的非金屬原子團。 In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metal atomic group.

所述一價的非金屬原子團可列舉：烷基、芳基、醯基、烷氧基羰基、芳氧基羰基、雜環基、烷硫基羰基、芳硫基羰基等。另外，該些基團亦可具有一個以上的取代基。另外，所述取代基亦可進一步經其他取代基所取代。 The monovalent non-metal atomic group may, for example, be an alkyl group, an aryl group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group or an arylthiocarbonyl group. In addition, the groups may have more than one substituent. Further, the substituent may be further substituted with other substituents.

取代基可列舉鹵素原子、芳氧基、烷氧基羰基或芳氧基羰基、醯氧基、醯基、烷基、芳基等。 The substituent may, for example, be a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group or an aryl group.

烷基較佳為碳數1~30的烷基，具體可參考日本專利特開2009-191061號公報的段落0025，將其內容併入至本說明書中。 The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms. For details, refer to paragraph 0025 of JP-A-2009-191061, the contents of which are incorporated herein by reference.

芳基較佳為碳數6~30的芳基，具體可參考日本專利特開2009-191061號公報的段落0026，將其內容併入至本說明書中。 The aryl group is preferably an aryl group having a carbon number of 6 to 30. For details, refer to paragraph 0026 of Japanese Patent Laid-Open Publication No. 2009-191061, the entire contents of which is incorporated herein.

醯基較佳為碳數2~20的醯基，具體可參考日本專利特開2009-191061號公報的段落0033，將其內容併入至本說明書中。 The fluorenyl group is preferably a fluorenyl group having a carbon number of 2 to 20, and specific reference is made to paragraph 0033 of Japanese Patent Laid-Open Publication No. 2009-191061, the contents of which are incorporated herein.

烷氧基羰基較佳為碳數2~20的烷氧基羰基，具體可參考日本專利特開2009-191061號公報的段落0034，將其內容併入 至本說明書中。 The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and the content thereof can be specifically incorporated by referring to paragraph 0034 of JP-A-2009-191061. To this manual.

芳氧基羰基具體而言較佳為碳數6~30的芳氧基羰基，可參考日本專利特開2009-191061號公報的段落0035，將其內容併入至本說明書中。 The aryloxycarbonyl group is preferably an aryloxycarbonyl group having a carbon number of 6 to 30, and the content of the aryloxycarbonyl group is incorporated in the present specification by referring to paragraph 0035 of JP-A-2009-191061.

雜環基較佳為含有氮原子、氧原子、硫原子或磷原子的芳香族或脂肪族的雜環基。 The heterocyclic group is preferably an aromatic or aliphatic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

具體可參考日本專利特開2009-191061號公報的段落0037，將其內容併入至本說明書中。 For details, refer to paragraph 0037 of Japanese Patent Laid-Open Publication No. 2009-191061, the contents of which are incorporated herein.

烷硫基羰基具體而言較佳為碳數1~20的烷硫基羰基，可參考日本專利特開2009-191061號公報的段落0038，將其內容併入至本說明書中。 The alkylthiocarbonyl group is preferably an alkylthiocarbonyl group having 1 to 20 carbon atoms, and the content of the alkylthiocarbonyl group of JP-A-2009-191061 is incorporated herein by reference.

芳硫基羰基具體而言較佳為碳數6~30的芳硫基羰基，可參考日本專利特開2009-191061號公報的段落0039，將其內容併入至本說明書中。 The arylthiocarbonyl group is preferably an arylthiocarbonyl group having a carbon number of 6 to 30, and the contents thereof are incorporated in the present specification by referring to paragraph 0039 of JP-A-2009-191061.

通式(OX-1)中，B所表示的一價取代基表示芳基、雜環基、芳基羰基或雜環羰基。另外，該些基團亦可具有一個以上的取代基。取代基可例示上文所述的取代基。另外，上文所述的取代基亦可進一步經其他取代基所取代。 In the formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. In addition, the groups may have more than one substituent. The substituents described above can be exemplified as the substituents described above. Further, the substituents described above may be further substituted with other substituents.

其中，尤佳可參考日本專利特開2009-191061號公報的段落0044，將其內容併入至本說明書中。 In particular, the content of the above-mentioned Japanese Patent Laid-Open Publication No. 2009-191061, the disclosure of which is incorporated herein by reference.

所述式(OX-1)中，A所表示的二價有機基可列舉碳數1~12的伸烷基、伸環烷基、伸炔基。另外，該些基團亦可具有一 個以上的取代基。取代基可例示上文所述的取代基。另外，上文所述的取代基亦可進一步經其他取代基所取代。 In the formula (OX-1), the divalent organic group represented by A may, for example, be an alkylene group having a carbon number of 1 to 12, a cycloalkylene group or an alkynylene group. In addition, the groups may also have one More than one substituent. The substituents described above can be exemplified as the substituents described above. Further, the substituents described above may be further substituted with other substituents.

其中，就提高感度、抑制由加熱經時所致的著色的方面而言，式(OX-1)中的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(cumenyl)、萘基、蒽基、菲基、苯乙烯基)取代的伸烷基。 Among them, in terms of improving sensitivity and suppressing coloring caused by heating over time, A in the formula (OX-1) is preferably an unsubstituted alkylene group or an alkyl group (e.g., methyl group, ethyl group). , a tert-butyl, dodecyl) substituted alkylene group, an alkyl group substituted by an alkenyl group (e.g., a vinyl group, an allyl group), an aryl group (e.g., phenyl, p-tolyl, xylyl) , cumenyl, naphthyl, anthracenyl, phenanthryl, styryl) substituted alkyl.

所述式(OX-1)中，Ar所表示的芳基較佳為碳數6~30的芳基，另外，亦可具有取代基。取代基可例示：與上文中作為可具有取代基的芳基的具體例而列舉的導入至經取代的芳基中的取代基相同的基團。 In the formula (OX-1), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. The substituent may be exemplified by the same group as the substituent introduced into the substituted aryl group as exemplified above as a specific example of the aryl group which may have a substituent.

其中，就提高感度、抑制由加熱經時所致的著色的方面而言，較佳為經取代或未經取代的苯基。 Among them, a substituted or unsubstituted phenyl group is preferred in terms of improving sensitivity and suppressing coloration caused by heating over time.

式(OX-1)中，由所述式(OX-1)中的Ar及與之鄰接的S所形成的「SAr」的較佳結構可參考日本專利特開2009-191061號公報的段落0049的記載，將其內容併入至本說明書中。 In the formula (OX-1), a preferred structure of "SAr" formed by Ar in the formula (OX-1) and S adjacent thereto can be referred to paragraph 0049 of JP-A-2009-191061. The contents are incorporated into the present specification.

肟化合物可參考日本專利特開2009-191061號公報的段落0050~段落0106的記載，將其內容併入至本說明書中。 The ruthenium compound can be referred to the description of paragraphs 0050 to 0106 of JP-A-2009-191061, the contents of which are incorporated herein by reference.

肟化合物於350nm~500nm的波長範圍內具有最大吸收波長，較佳為於360nm~480nm的波長範圍內具有吸收波長，尤佳為365nm及455nm的吸光度高。 The ruthenium compound has a maximum absorption wavelength in a wavelength range of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength range of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 455 nm.

就感度的觀點而言，肟化合物於365nm或405nm下的莫耳吸光係數較佳為1,000~300,000，更佳為2,000~300,000，尤佳為5,000~200,000。 From the viewpoint of sensitivity, the molar absorption coefficient of the cerium compound at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, particularly preferably from 5,000 to 200,000.

化合物的莫耳吸光係數可使用公知的方法，具體而言，例如較佳為利用紫外可見分光光度計(瓦里安(Varian)公司製造的卡里-5(Carry-5)分光光度計(spectrophotometer))，使用乙酸乙酯溶劑以0.01g/L的濃度進行測定。 A known method can be used for the molar absorption coefficient of the compound. Specifically, for example, a UV-visible spectrophotometer (Carry-5) spectrophotometer manufactured by Varian Co., Ltd. is preferably used. )), using an ethyl acetate solvent to measure at a concentration of 0.01 g/L.

於本發明的著色組成物中含有光聚合起始劑的情形時，相對於著色組成物的總固體成分，光聚合起始劑的含量較佳為0.1質量%~50質量%，更佳為0.5質量%~30質量%，進而佳為1質量%~20質量%。於該範圍內可獲得更良好的感度及圖案形成性。 In the case where the coloring composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably from 0.1% by mass to 50% by mass, more preferably 0.5%, based on the total solid content of the coloring composition. The mass % to 30% by mass, and more preferably 1% by mass to 20% by mass. Better sensitivity and pattern formation can be obtained within this range.

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.

<顏料分散劑> <Pigment Dispersant>

於本發明的著色組成物含有顏料的情形時，可視需要而併用顏料分散劑。 In the case where the colored composition of the present invention contains a pigment, a pigment dispersant may be used in combination as needed.

本發明中可使用的顏料分散劑可列舉：高分子分散劑[例如聚醯胺-胺及其鹽、聚羧酸及其鹽、高分子量不飽和酸酯、改質聚胺基甲酸酯、改質聚酯、改質聚(甲基)丙烯酸酯、(甲基)丙烯酸系共聚物、萘磺酸福馬林縮合物]、及聚氧伸乙基烷基磷酸酯、聚氧伸乙基烷基胺、烷醇胺等界面活性劑及顏料衍生物等。 The pigment dispersant which can be used in the present invention may, for example, be a polymer dispersant [for example, polyamine-amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, Modified polyester, modified poly(meth)acrylate, (meth)acrylic copolymer, formalin condensate naphthalenesulfonate, and polyoxyalkylene phosphate, polyoxyalkylene oxide Surfactants such as base amines and alkanolamines, and pigment derivatives.

高分子分散劑可根據其結構而進一步分類為直鏈狀高分子、末端改質型高分子、接枝型高分子、嵌段型高分子。 The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer according to the structure thereof.

具有對顏料表面的固定(anchor)部位的末端改質型高分子例如可列舉：日本專利特開平3-112992號公報、日本專利特表2003-533455號公報等中記載的於末端具有磷酸基的高分子，日本專利特開2002-273191號公報等中記載的於末端具有磺酸基的高分子，日本專利特開平9-77994號公報等中記載的具有有機色素的部分骨架或雜環的高分子等。另外，日本專利特開2007-277514號公報中記載的於高分子末端導入2個以上的對顏料表面的固定部位(酸基、鹼性基、有機色素的部分骨架或雜環等)的高分子亦分散穩定性優異而較佳。 For example, the terminal-modified polymer having an anchor portion on the surface of the pigment has a phosphate group at the terminal, as described in JP-A-3-112992, JP-A-2003-533455, and the like. The polymer having a sulfonic acid group at the terminal described in JP-A-2002-273191, and the like, and the high molecular weight of the partial skeleton or heterocyclic ring having an organic dye described in Japanese Laid-Open Patent Publication No. Hei 9-77994 Molecules, etc. In addition, a polymer which introduces two or more fixed sites (acid groups, basic groups, partial skeletons of organic dyes, heterocyclic rings, etc.) to the surface of the pigment at the end of the polymer described in JP-A-2007-277514 It is also excellent in dispersion stability and is preferred.

具有對顏料表面的固定部位的接枝型高分子例如可列舉聚酯系分散劑等，具體可列舉：日本專利特開昭54-37082號公報、日本專利特表平8-507960號公報、日本專利特開2009-258668號公報等中記載的聚(低級伸烷基亞胺)與聚酯的反應產物，日本專利特開平9-169821號公報等中記載的聚烯丙胺與聚酯的反應產物，日本專利特開平10-339949號公報、日本專利特開2004-37986號公報、國際公開手冊WO2010/110491等中記載的巨單體與氮原子單體的共聚物，日本專利特開2003-238837號公報、日本專利特開2008-9426號公報、日本專利特開2008-81732號公報等中記載的具有有機色素的部分骨架或雜環的接枝型高分子，日本專利特開2010-106268號公報等中記載的巨單體與含酸基的單體的共 聚物等。尤其就顏料分散物的分散性、分散穩定性及使用顏料分散物的著色組成物所顯示出的顯影性的觀點而言，尤佳為日本專利特開2009-203462號公報中記載的具有鹼性基及酸性基的兩性分散樹脂。 The graft-type polymer having a fixed portion on the surface of the pigment is, for example, a polyester-based dispersant, and the like, and a Japanese Patent Laid-Open Publication No. Hei 54-37082, Japanese Patent Publication No. Hei 8-507960, and Japan The reaction product of the polyallylamine and the polyester described in JP-A-H09-169821, and the like, and the reaction product of the poly(lower alkylene imine) and the polyester described in JP-A-H09-169821, and the like. a copolymer of a macromonomer and a nitrogen atom monomer described in Japanese Patent Laid-Open No. Hei 10-339949, Japanese Patent Laid-Open No. 2004-37986, and International Publication No. WO2010/110491, Japanese Patent Laid-Open No. 2003-238837 A graft-type polymer having a partial skeleton or a heterocyclic ring of an organic dye described in Japanese Laid-Open Patent Publication No. 2008-81732, and the like. Japanese Patent Laid-Open No. 2010-106268 A total of macromonomers and acid group-containing monomers described in the publication Polymer, etc. In particular, in view of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the coloring composition using the pigment dispersion, it is preferable to be alkaline as described in JP-A-2009-203462. Amphoteric dispersion resin with a base and an acidic group.

藉由自由基聚合來製造具有對顏料表面的固定部位的接枝型高分子時所用的巨單體可使用公知的巨單體，可列舉：東亞合成(股)製造的巨單體AA-6(末端基為甲基丙烯醯基的聚甲基丙烯酸甲酯)、AS-6(末端基為甲基丙烯醯基的聚苯乙烯)、AN-6S(末端基為甲基丙烯醯基的苯乙烯與丙烯腈的共聚物)、AB-6(末端基為甲基丙烯醯基的聚丙烯酸丁酯)、大賽璐(Daicel)化學工業(股)製造的普拉克塞爾(Placcel)FM5(甲基丙烯酸2-羥基乙酯的ε-己內酯5莫耳當量加成品)、FA10L(丙烯酸2-羥基乙酯的ε-己內酯10莫耳當量加成品)、及日本專利特開平2-272009號公報中記載的聚酯系巨單體等。該些巨單體中，尤其就顏料分散物的分散性、分散穩定性及使用顏料分散物的著色組成物所顯示出的顯影性的觀點而言，尤佳為柔軟性且親溶劑性優異的聚酯系巨單體，進而尤佳為日本專利特開平2-272009號公報中記載的聚酯系巨單體所表示的聚酯系巨單體。 A known macromonomer can be used as the macromonomer used for the production of the graft-type polymer having a fixed portion on the surface of the pigment by radical polymerization, and examples thereof include a macromonomer AA-6 manufactured by East Asia Synthetic Co., Ltd. (polymethyl methacrylate with terminal group being methacryl fluorenyl), AS-6 (polystyrene with terminal group of methacryl fluorenyl), AN-6S (benzene with terminal group of methacryl fluorenyl) Copolymer of ethylene and acrylonitrile), AB-6 (polybutyl acrylate of methacryl fluorenyl group), Placcel FM5 manufactured by Daicel Chemical Industry Co., Ltd. 2-hydroxyethyl acrylate ε-caprolactone 5 molar equivalent plus finished product), FA10L (2-hydroxyethyl acrylate ε-caprolactone 10 molar equivalent plus finished product), and Japanese Patent Laid-Open 2- The polyester-based macromonomer described in the publication No. 272009. Among these macromonomers, in particular, from the viewpoint of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the coloring composition using the pigment dispersion, it is particularly preferable that it is excellent in flexibility and solvophilicity. The polyester-based macromonomer is a polyester-based macromonomer represented by the polyester-based macromonomer described in Japanese Laid-Open Patent Publication No. Hei 2-272009.

具有對顏料表面的固定部位的嵌段型高分子較佳為日本專利特開2003-49110號公報、日本專利特開2009-52010號公報等中記載的嵌段型高分子。 The block type polymer which has a fixed part to the surface of the pigment is preferably a block type polymer described in JP-A-2003-49110, JP-A-2009-52010, and the like.

本發明中可使用的顏料分散劑亦可作為市售品而獲 取，此種具體例可列舉：楠木化成股份有限公司製造的「DA-7301」，畢克化學(BYK Chemie)公司製造「迪斯帕畢克(Disperbyk)-101(聚醯胺-胺磷酸鹽)、迪斯帕畢克(Disperbyk)-107(羧酸酯)、迪斯帕畢克(Disperbyk)-110、迪斯帕畢克(Disperbyk)-111(含酸基的共聚物)、迪斯帕畢克(Disperbyk)-130(聚醯胺)、迪斯帕畢克(Disperbyk)-161、迪斯帕畢克(Disperbyk)-162、迪斯帕畢克(Disperbyk)-163、迪斯帕畢克(Disperbyk)-164、迪斯帕畢克(Disperbyk)-165、迪斯帕畢克(Disperbyk)-166、迪斯帕畢克(Disperbyk)-170(高分子共聚物)」、「畢克(BYK)-P104、畢克(BYK)-P105(高分子量不飽和多羧酸)」、埃夫卡(EFKA)公司製造的「埃夫卡(EFKA)4047、埃夫卡(EFKA)4050、埃夫卡(EFKA)4010、埃夫卡(EFKA)4165(聚胺基甲酸酯系)、埃夫卡(EFKA)4330~埃夫卡(EFKA)4340(嵌段共聚物)、埃夫卡(EFKA)4400~埃夫卡(EFKA)4402(改質聚丙烯酸酯)、埃夫卡(EFKA)5010(聚酯醯胺)、埃夫卡(EFKA)5765(高分子量多羧酸鹽)、埃夫卡(EFKA)6220(脂肪酸聚酯)、埃夫卡(EFKA)6745(酞菁衍生物)、埃夫卡(EFKA)6750(偶氮顏料衍生物)」、味之素精密技術(Ajinomoto Fine-Techno)公司製造的「阿吉斯帕(Ajisper)PB821、阿吉斯帕(Ajisper)PB822、阿吉斯帕(Ajisper)PB880、阿吉斯帕(Ajisper)PB881」，共榮社化學公司製造的「弗洛蘭(Flowlen)TG-710(胺基甲酸酯寡聚物)」、「波利弗洛(Polyflow)No.50E、波利弗洛 (Polyflow)No.300(丙烯酸系共聚物)」，楠本化成公司製造的「迪斯帕隆(Disperlon)KS-860、迪斯帕隆(Disperlon)873SN、迪斯帕隆(Disperlon)874、迪斯帕隆(Disperlon)#2150(脂肪族多元羧酸)、迪斯帕隆(Disperlon)#7004(聚醚酯)、迪斯帕隆(Disperlon)DA-703-50、迪斯帕隆(Disperlon)DA-705、迪斯帕隆(Disperlon)DA-725」、花王公司製造的「德莫耳(Demol)RN、德莫耳(Demol)N(萘磺酸福馬林縮聚物)、德莫耳(Demol)MS、德莫耳(Demol)C、德莫耳(Demol)SN-B(芳香族磺酸福馬林縮聚物)」、「火莫格諾(Homogenol)L-18(高分子多羧酸)」、「愛慕根(Emulgen)920、愛慕根(Emulgen)930、愛慕根(Emulgen)935、愛慕根(Emulgen)985(聚氧伸乙基壬基苯基醚)」、「阿塞他命(Acetamin)86(硬脂基胺乙酸酯)」，日本路博潤(Lubrizol)(股)製造的「索努帕斯(Solsperse)5000(酞菁衍生物)、索努帕斯(Solsperse)22000(偶氮顏料衍生物)、索努帕斯(Solsperse)13240(聚酯胺)、索努帕斯(Solsperse)3000、索努帕斯(Solsperse)17000、索努帕斯(Solsperse)27000(於末端部具有功能部的高分子)、索努帕斯(Solsperse)24000、索努帕斯(Solsperse)28000、索努帕斯(Solsperse)32000、索努帕斯(Solsperse)38500(接枝型高分子)」，日光化學公司製造的「尼克爾(Nikkol)T106(聚氧伸乙基山梨醇酐單油酸酯)、尼克爾(Nikkol)MYS-IEX(聚氧伸乙基單硬脂酸酯)」，川研精化(股)製造的海諾埃克特(Hinoact)T-8000E等，信越化學工業(股)製造的有機矽氧烷聚合物KP341， 裕商(股)製造的「W001：陽離子系界面活性劑」，聚氧伸乙基月桂基醚、聚氧伸乙基硬脂基醚、聚氧伸乙基油烯基醚、聚氧伸乙基辛基苯基醚、聚氧伸乙基壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、山梨醇酐脂肪酸酯等非離子系界面活性劑，「W004、W005、W017」等陰離子系界面活性劑，森下產業(股)製造的「埃夫卡(EFKA)-46、埃夫卡(EFKA)-47、埃夫卡(EFKA)-47EA、埃夫卡(EFKA)聚合物100、埃夫卡(EFKA)聚合物400、埃夫卡(EFKA)聚合物401、埃夫卡(EFKA)聚合物450」，聖諾普科(Sannopco)(股)製造的「迪斯帕斯艾德(Disperse-aid)6、迪斯帕斯艾德(Disperse-aid)8、迪斯帕斯艾德(Disperse-aid)15、迪斯帕斯艾德(Disperse-aid)9100」等高分子分散劑，艾迪科(ADEKA)(股)製造的「艾迪科普羅尼克(Adeka Pluronic)L31、艾迪科普羅尼克(Adeka Pluronic)F38、艾迪科普羅尼克(Adeka Pluronic)L42、艾迪科普羅尼克(Adeka Pluronic)L44、艾迪科普羅尼克(Adeka Pluronic)L61、艾迪科普羅尼克(Adeka Pluronic)L64、艾迪科普羅尼克(Adeka Pluronic)F68、艾迪科普羅尼克(Adeka Pluronic)L72、艾迪科普羅尼克(Adeka Pluronic)P95、艾迪科普羅尼克(Adeka Pluronic)F77、艾迪科普羅尼克(Adeka Pluronic)P84、艾迪科普羅尼克(Adeka Pluronic)F87、艾迪科普羅尼克(Adeka Pluronic)P94、艾迪科普羅尼克(Adeka Pluronic)L101、艾迪科普羅尼克(Adeka Pluronic)P103、艾迪科普羅尼克(Adeka Pluronic)F108、艾迪科普羅尼克(Adeka Pluronic)L121、艾迪科普羅尼克(Adeka Pluronic)P-123」，及三洋化成(股)製造的「伊奧奈特(Eonet)(商品名)S-20」等。 The pigment dispersant which can be used in the present invention can also be obtained as a commercial product. Take such a specific example: "DA-7301" manufactured by Nanmu Chemical Co., Ltd., and Disperbyk-101 (polyamide-amine phosphate manufactured by BYK Chemie) ), Disperbyk-107 (carboxylate), Disperbyk-110, Disperbyk-111 (acid-containing copolymer), Diss Disperbyk-130 (polyamide), Disperbyk-161, Disperbyk-162, Disperbyk-163, Dispa Disperbyk-164, Disperbyk-165, Disperbyk-166, Disperbyk-170 (polymer copolymer), "Bi克 (BYK)-P104, BYK-P105 (high molecular weight unsaturated polycarboxylic acid), Efka (EFKA) 4047, EFKA 4050, manufactured by EFKA , EFKA 4010, EFKA 4165 (polyurethane), Efka (EFKA) 4330~Evka (EFKA) 4340 (block copolymer), Eve Card (EFKA) 4400~Evka (EFKA) 4402 (modified polyacrylate), Efka (EFKA) 5010 (polyester phthalamide), angstrom Card (EFKA) 5765 (high molecular weight polycarboxylate), Efka (EFKA) 6220 (fatty acid polyester), Efka (EFKA) 6745 (phthalocyanine derivative), Efka (EFKA) 6750 (even Nitrogen pigment derivatives), Ajisper PB821, Ajisper PB822, Ajisper PB880, manufactured by Ajinomoto Fine-Techno "Ajisper PB881", "Flowlen TG-710 (urethane oligomer)" and "Polyflow No. 50E" manufactured by Kyoritsu Chemical Co., Ltd. Polyflo (Polyflow) No. 300 (Acrylic Copolymer), "Disperlon KS-860, Disperlon 873SN, Disperlon 874, Di, manufactured by Nanben Chemical Co., Ltd." Disperlon #2150 (aliphatic polycarboxylic acid), Disperlon #7004 (polyether ester), Disperlon DA-703-50, Disperlon ) DA-705, Disperlon DA-725", Demol RN, Demol N (naphthoic acid formalin polycondensate), Demol (Demol) MS, Demol C, Demol SN-B (aromatic sulfonate fumarate polycondensate), and "Homogenol L-18 (polymer polycarboxylate) Acid)", "Emulgen 920, Emulgen 930, Emulgen 935, Emulgen 985 (polyoxyethyl phenyl ether)", "Aceta Acetamin 86 (stearylamine acetate), manufactured by Lubrizol, Japan, Solsperse 5000 (phthalocyanine derivative), Solsperse 22000 (azo pigment derivative), Solsperse 13240 (polyesteramine), Sonu Solsperse 3000, Solsperse 17000, Solsperse 27000 (polymer with functional part at the end), Solsperse 24000, Solsperse 28000, Solsperse 32000, Solsperse 38500 (grafted polymer), "Nikkol T106 (polyoxyethylene ethyl sorbitol) manufactured by Nikko Chemical Co., Ltd. Monooleate), Nikkol MYS-IEX (polyoxyethylidene monostearate), Hinoact T-8000E manufactured by Kawasaki Seiki Co., Ltd., etc. An organic siloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd., "W001: Cationic surfactant" manufactured by Yushang Co., Ltd., polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl alkenyl ether, polyoxyethylene Nonionic surfactants such as octyl phenyl ether, polyoxyethylene ethyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester , "W004, W005, W017" and other anionic surfactants, "Efka (EFKA)-46, Efka (EFKA)-47, Efka (EFKA)-47EA, manufactured by Morishita Industries Co., Ltd." EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450", Sannopco ) Made by Disperse-aid 6, Disperse-aid 8, Disperse-aid 15, Despas Eide ( A polymer dispersant such as Disperse-aid) 9100", Adeka Pluronic L31, Adeka Pluronic F38, Adi Copro, made by ADEKA Adeka Pluronic L42, Eddie Copro Adeka Pluronic L44, Adeka Pluronic L61, Adeka Pluronic L64, Adeka Pluronic F68, Adeka Pluronic L72 , Adeka Pluronic P95, Adeka Pluronic F77, Adeka Pluronic P84, Adeka Pluronic F87, Eddie Pronick (Adeka Pluronic) P94, Adeka Pluronic L101, Adeka Pluronic P103, Adeka Pluronic F108, Adeka Pronik Pluronic) L121, Adeka Pluronic P-123, and Eonet (trade name) S-20 manufactured by Sanyo Chemicals Co., Ltd.

該些顏料分散劑可單獨使用，亦可組合使用兩種以上。於本發明中，尤其較佳為將顏料衍生物與高分子分散劑組合使用。另外，關於顏料分散劑，亦可與具有對所述顏料表面的固定部位的末端改質型高分子、接枝型高分子、嵌段型高分子一起而併用鹼可溶性樹脂。鹼可溶性樹脂可列舉：(甲基)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，以及於側鏈上具有羧酸的酸性纖維素衍生物，尤佳為(甲基)丙烯酸共聚物。另外，日本專利特開平10-300922號公報中記載的N位取代馬來醯亞胺單體共聚物、日本專利特開2004-300204號公報中記載的醚二聚物共聚物、日本專利特開平7-319161號公報中記載的含有聚合性基的鹼可溶性樹脂亦較佳。具體可例示鹼可溶性樹脂：甲基丙烯酸苄酯/甲基丙烯酸/甲基丙烯酸-2-羥基乙酯共聚物。 These pigment dispersants may be used singly or in combination of two or more. In the present invention, it is particularly preferred to use a pigment derivative in combination with a polymer dispersant. Further, the pigment dispersant may be used together with an end-modified polymer having a fixed portion on the surface of the pigment, a graft polymer, or a block-type polymer, together with an alkali-soluble resin. Examples of the alkali-soluble resin include a (meth)acrylic copolymer, an itaconic acid copolymer, a butenoic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like, and a carboxylic acid in a side chain. An acidic cellulose derivative, particularly preferably a (meth)acrylic copolymer. In addition, the N-substituted maleimide monomer copolymer described in Japanese Laid-Open Patent Publication No. Hei 10-300922, the ether dimer copolymer described in Japanese Patent Laid-Open Publication No. 2004-300204, and the Japanese Patent Laid-Open The alkali-soluble resin containing a polymerizable group described in Japanese Patent Publication No. 7-319161 is also preferable. Specifically, an alkali-soluble resin: benzyl methacrylate/methacrylic acid/-2-hydroxyethyl methacrylate copolymer can be exemplified.

於著色組成物中含有顏料分散劑的情形時，相對於顏料100質量份，顏料分散劑的總含量較佳為1質量份~80質量份，更佳為5質量份~70質量份，進而佳為20質量份~40質量份。 When the coloring composition contains a pigment dispersant, the total content of the pigment dispersant is preferably from 1 part by mass to 80 parts by mass, more preferably from 5 parts by mass to 70 parts by mass, based on 100 parts by mass of the pigment. It is 20 parts by mass to 40 parts by mass.

本發明的組成物可分別僅含有一種顏料分散劑，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 pigment dispersant, 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.

具體而言，若為使用高分子分散劑的情形，則相對於顏 料100質量份，其使用量以質量換算計而較佳為5質量份~100質量份的範圍，更佳為10質量份~80質量份的範圍。 Specifically, in the case of using a polymer dispersant, it is relative to the face. 100 parts by mass of the material is used, and the amount thereof is preferably in the range of 5 parts by mass to 100 parts by mass, more preferably 10 parts by mass to 80 parts by mass.

另外，於併用顏料衍生物的情形時，相對於顏料100質量份，顏料衍生物的使用量以質量換算計而較佳為在1質量份~30質量份的範圍內，更佳為在3質量份~20質量份的範圍內，尤佳為在5質量份~15質量份的範圍內。 In the case of using a pigment derivative in combination, the amount of the pigment derivative used is preferably in the range of 1 part by mass to 30 parts by mass, more preferably 3 parts by mass, based on 100 parts by mass of the pigment. In the range of up to 20 parts by mass, it is particularly preferably in the range of 5 parts by mass to 15 parts by mass.

於著色組成物中，就硬化感度、顏色濃度的觀點而言，相對於構成著色組成物的總固體成分，著色劑及分散劑成分的含量的總和較佳為50質量%以上、90質量%以下，更佳為55質量%以上、85質量%以下，進而佳為60質量%以上、80質量%以下。 In the coloring composition, the total content of the colorant and the dispersant component is preferably 50% by mass or more and 90% by mass or less based on the total solid content of the coloring composition in terms of the hardening sensitivity and the color density. More preferably, it is 55 mass % or more, 85 mass % or less, and further preferably 60 mass % or more and 80 mass % or less.

<鹼可溶性樹脂> <alkali soluble resin>

本發明的著色組成物較佳為更含有鹼可溶性樹脂。 The colored composition of the present invention preferably further contains an alkali-soluble resin.

鹼可溶性樹脂的分子量並無特別限定，Mw較佳為5000~100,000。另外，Mn較佳為1000~20,000。 The molecular weight of the alkali-soluble resin is not particularly limited, and Mw is preferably from 5,000 to 100,000. Further, Mn is preferably from 1,000 to 20,000.

本發明中所用的化合物的重量平均分子量是以由GPC測定所得的聚苯乙烯換算值來定義。重量平均分子量及數量平均分子量例如可藉由以下方式求出：使用HLC-8220(東曹(股)製造)，使用TSKgel Super AWM-H(東曹(股)製造，6.0mm ID×15.0cm)作為管柱，且使用10mmol/L的溴化鋰N-甲基吡咯啶酮(N-methyl Pyrrolidinone，NMP)溶液作為溶離液。 The weight average molecular weight of the compound used in the present invention is defined by a polystyrene-converted value obtained by GPC measurement. The weight average molecular weight and the number average molecular weight can be obtained, for example, by using HLC-8220 (manufactured by Tosoh Corporation), using TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm). As a column, a 10 mmol/L lithium bromide N-methyl Pyrrolidinone (NMP) solution was used as a solution.

鹼可溶性樹脂可自以下鹼可溶性樹脂中適當選擇，所述鹼可溶性樹脂為線性有機高分子聚合物，且於分子(較佳為以丙 烯酸系共聚物、苯乙烯系共聚物作為主鏈的分子)中具有至少一個促進鹼可溶性的基團。就耐熱性的觀點而言，較佳為多羥基苯乙烯系樹脂、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。 The alkali-soluble resin can be appropriately selected from the following alkali-soluble resins, which are linear organic high molecular polymers, and are molecules (preferably The olefinic copolymer and the styrene copolymer as a molecule of the main chain have at least one group which promotes alkali solubility. From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic acid/acrylamide copolymer resin is preferred in terms of controlling developability. In particular, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable.

促進鹼可溶性的基團(以下亦稱為酸基)例如可列舉羧基、磷酸基、磺酸基、酚性羥基等，較佳為可溶於有機溶劑中且可藉由弱鹼性水溶液進行顯影的基團，可列舉(甲基)丙烯酸基作為尤佳者。該些酸基可僅為一種，亦可為兩種以上。 Examples of the group which promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group and the like, and are preferably soluble in an organic solvent and can be developed by a weakly basic aqueous solution. As the group, a (meth)acrylic group is exemplified as a preferred one. These acid groups may be used alone or in combination of two or more.

所述可於聚合後賦予酸基的單體例如可列舉：(甲基)丙烯酸-2-羥基乙酯等具有羥基的單體、(甲基)丙烯酸縮水甘油酯等具有環氧基的單體、(甲基)丙烯酸-2-異氰酸酯乙酯等具有異氰酸基的單體等。該些用以導入酸基的單體可僅為一種，亦可為兩種以上。為了於鹼可溶性樹脂中導入酸基，例如只要將具有酸基的單體及/或可於聚合後賦予酸基的單體(以下有時亦稱為「用以導入酸基的單體」)作為單體成分來進行聚合即可。 Examples of the monomer which can give an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or a monomer having an epoxy group such as glycidyl (meth)acrylate. A monomer having an isocyanate group such as 2-isocyanate ethyl (meth)acrylate. These monomers for introducing an acid group may be used alone or in combination of two or more. In order to introduce an acid group into the alkali-soluble resin, for example, a monomer having an acid group and/or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as "a monomer for introducing an acid group") may be used. The polymerization may be carried out as a monomer component.

再者，於將可於聚合後賦予酸基的單體作為單體成分來導入酸基的情形時，必須於聚合後進行例如後述般的用以賦予酸基的處理。 In the case where a monomer capable of imparting an acid group after polymerization is introduced as a monomer component, it is necessary to carry out a treatment for imparting an acid group as described later after the polymerization.

製造鹼可溶性樹脂時，例如可應用公知的利用自由基聚合法的方法。藉由自由基聚合法來製造鹼可溶性樹脂時的溫度、壓力、自由基起始劑的種類及其量、溶劑的種類等聚合條件可由 本領域技術人員容易地設定，亦能以實驗方式來決定條件。 When the alkali-soluble resin is produced, for example, a known method using a radical polymerization method can be applied. The polymerization conditions such as the temperature, the pressure, the type and amount of the radical initiator, and the kind of the solvent when the alkali-soluble resin is produced by the radical polymerization method may be Those skilled in the art can easily set the conditions and determine the conditions experimentally.

用作鹼可溶性樹脂的線性有機高分子聚合物較佳為於側鏈上具有羧酸的聚合物，可列舉：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、酚醛清漆型樹脂等鹼可溶性酚樹脂等，以及於側鏈上具有羧酸的酸性纖維素衍生物、對具有羥基的聚合物加成酸酐而成者。尤其(甲基)丙烯酸與可與其共聚合的其他單體的共聚物適合作為鹼可溶性樹脂。可與(甲基)丙烯酸共聚合的其他單體可列舉：(甲基)丙烯酸烷基酯、(甲基)丙烯酸芳基酯、乙烯系化合物等。(甲基)丙烯酸烷基酯及(甲基)丙烯酸芳基酯可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸甲苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸環己酯等，乙烯系化合物可列舉：苯乙烯、α-甲基苯乙烯、乙烯基甲苯、甲基丙烯酸縮水甘油酯、丙烯腈、乙酸乙烯酯、N-乙烯基吡咯啶酮、甲基丙烯酸四氫糠酯、聚苯乙烯巨單體、聚甲基丙烯酸甲酯巨單體等，日本專利特開平10-300922號公報中記載的作為N位取代馬來醯亞胺單體的N-苯基馬來醯亞胺、N-環己基馬來醯亞胺等。再者，該些可與(甲基)丙烯酸共聚合的其他單體可僅為一種，亦可為兩種以上。 The linear organic high molecular polymer used as the alkali-soluble resin is preferably a polymer having a carboxylic acid in a side chain, and examples thereof include a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, and a butenoic acid copolymer. , an alkali-soluble phenol resin such as a maleic acid copolymer, a partially esterified maleic acid copolymer, or a novolac type resin, and an acidic cellulose derivative having a carboxylic acid in a side chain, and a polymer addition to a hydroxyl group Anhydride is the only one. In particular, copolymers of (meth)acrylic acid with other monomers copolymerizable therewith are suitable as alkali-soluble resins. Examples of the other monomer copolymerizable with (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, and a vinyl compound. Examples of the alkyl (meth)acrylate and the aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Ester, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate , (methyl) methacrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc., and examples of the vinyl compound include styrene, α-methyl styrene, vinyl toluene, and methacrylic acid. Glycidyl ester, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc., Japanese Patent Laid-Open 10 N-phenylmaleimide, N-cyclohexylmaleimide, which is a N-substituted maleimide monomer described in the publication No. -300922. Further, these other monomers copolymerizable with (meth)acrylic acid may be used alone or in combination of two or more.

鹼可溶性樹脂亦較佳為含有聚合物(a)，該聚合物(a) 是使必需下述通式(ED)所表示的化合物(以下有時亦稱為「醚二聚物」)的單體成分進行聚合而成。 The alkali-soluble resin preferably also contains the polymer (a), the polymer (a) The monomer component which is required to be represented by the following formula (ED) (hereinafter sometimes referred to as "ether dimer") is polymerized.

通式(ED)中，R1及R2分別獨立地表示氫原子或可具有取代基的碳數1~25的烴基。 In the general formula (ED), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

藉此，本發明的著色組成物可形成耐熱性與透明性均極為優異的硬化塗膜。表示所述醚二聚物的所述通式(1)中，R1及R2所表示的可具有取代基的碳數1~25的烴基並無特別限制，例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、第三戊基、硬脂基、月桂基、2-乙基己基等直鏈狀或分支狀的烷基；苯基等芳基；環己基、第三丁基環己基、二環戊二烯基、三環癸基、異冰片基、金剛烷基、2-甲基-2-金剛烷基等脂環式基；1-甲氧基乙基、1-乙氧基乙基等經烷氧基取代的烷基；苄基等經芳基取代的烷基等。該些基團中，尤其就耐熱性的方面而言，較佳為甲基、乙基、環己基、苄基等般的不易因酸或熱而脫離的一級或二級碳的取代基。 Thereby, the colored composition of the present invention can form a cured coating film which is extremely excellent in heat resistance and transparency. In the above formula (1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R 1 and R 2 in the above-mentioned ether dimer is not particularly limited, and examples thereof include methyl group and ethyl group. Linear or branched alkyl such as n-propyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-pentyl, stearyl, lauryl or 2-ethylhexyl An aryl group such as a phenyl group; an alicyclic ring such as a cyclohexyl group, a tert-butylcyclohexyl group, a dicyclopentadienyl group, a tricyclodecanyl group, an isobornyl group, an adamantyl group or a 2-methyl-2-adamantyl group; An alkyl group substituted with an alkoxy group such as a 1-methoxyethyl group or a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as a benzyl group; and the like. Among these groups, in particular, in terms of heat resistance, a substituent of a primary or secondary carbon which is not easily removed by acid or heat such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group is preferable.

所述醚二聚物的具體例例如可列舉：二甲基-2,2'-[氧基 雙(亞甲基)]雙-2-丙烯酸酯(dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate)、二乙基-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(正丙基)-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(異丙基)-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(正丁基)-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(異丁基)-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(第三丁基)-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(第三戊基)-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(硬脂基)-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(月桂基)-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(2-乙基己基)-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(1-甲氧基乙基)-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(1-乙氧基乙基)-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二苄基-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二苯基-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二環己基-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(第三丁基環己基)-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(二環戊二烯基)-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(三環癸基)-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(異冰片基)-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二金剛烷基-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(2-甲基-2-金剛烷基)-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯等。該些具體例中，尤佳為二甲基-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二乙基-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二環己基-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二苄基-2,2'-[氧基雙(亞甲 基)]雙-2-丙烯酸酯。該些醚二聚物可僅為一種，亦可為兩種以上。來源於所述通式(ED)所表示的化合物的結構體亦可使其他單體進行共聚合。 Specific examples of the ether dimer include, for example, dimethyl-2,2'-[oxy Dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate), diethyl-2,2'-[oxybis(- Base]] bis-2-acrylate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(isopropyl)-2,2' -[oxybis(methylene)]bis-2-acrylate, di(n-butyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(iso) Butyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(t-butyl)-2,2'-[oxybis(methylene)] double 2-acrylate, bis(third amyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(stearyl)-2,2'-[oxygen Bis(methylene)]bis-2-acrylate, bis(lauryl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(2-ethylhexyl) -2,2'-[oxybis(methylene)]bis-2-acrylate, bis(1-methoxyethyl)-2,2'-[oxybis(methylene)] Bi-2-acrylate, bis(1-ethoxyethyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, dibenzyl-2,2'-[ Oxyxybis(methylene)]bis-2-acrylate, diphenyl-2,2'-[oxybis(methylene)]bis-2-acrylate, dicyclohexyl-2,2' -[ Oxyxybis(methylene)]bis-2-acrylate, bis(t-butylcyclohexyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di( Dicyclopentadienyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(tricycloindenyl)-2,2'-[oxybis(methylene) Base]] bis-2-acrylate, bis(isobornyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, diamantyl-2,2'-[ Oxyxybis(methylene)]bis-2-acrylate, bis(2-methyl-2-adamantyl)-2,2'-[oxybis(methylene)]bis-2-acrylic acid Ester and the like. In these specific examples, dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxybis(Asian) is especially preferred. Methyl)]bis-2-acrylate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-acrylate, dibenzyl-2,2'-[oxy double (Asia Base)] bis-2-acrylate. These ether dimers may be used alone or in combination of two or more. The structure derived from the compound represented by the above formula (ED) may also copolymerize other monomers.

另外，為了提高本發明的著色組成物的交聯效率，較佳為使用具有聚合性基的鹼可溶性樹脂。具有聚合性基的鹼可溶性樹脂有用的是於側鏈上含有烯丙基、(甲基)丙烯酸基、烯丙氧基烷基等的鹼可溶性樹脂等。 Further, in order to improve the crosslinking efficiency of the colored composition of the present invention, it is preferred to use an alkali-soluble resin having a polymerizable group. The alkali-soluble resin having a polymerizable group is preferably an alkali-soluble resin containing an allyl group, a (meth)acrylic group, an allyloxyalkyl group or the like in a side chain.

含有聚合性基的聚合物的例子可列舉：蒂阿諾(Dianal)NR系列(三菱麗陽股份有限公司製造)、Photomer 6173(含COOH的丙烯酸聚胺基甲酸酯寡聚物(polyurethane acrylic oligomer)，鑽石三葉草股份有限公司(Diamond Shamrock Co.Ltd.,)製造)、比斯克(Biscoat)R-264、KS抗蝕劑(KS Resist)106(均為大阪有機化學工業股份有限公司製造)，賽克羅馬(Cyclomer)P系列、普拉克塞爾(Placcel)CF200系列(均為大賽璐(Daicel)化學工業股份有限公司製造)、艾***(Ebecryl)3800(大賽璐UCB(Daicel UCB)股份有限公司製造)等。該些含有聚合性基的鹼可溶性樹脂較佳為以下樹脂：經胺基甲酸酯改質的含聚合性雙鍵的丙烯酸系樹脂，其是藉由預先使異氰酸酯基與OH基反應而殘留一個未反應的異氰酸酯基且含有(甲基)丙烯醯基的化合物、與含有羧基的丙烯酸系樹脂的反應而獲得；含不飽和基的丙烯酸系樹脂，其是藉由含有羧基的丙烯酸系樹脂與分子內一併具有環氧基及聚合性雙鍵的化合物的反應而獲得；酸側位型環氧丙烯酸酯樹 脂；使含有OH基的丙烯酸系樹脂與具有聚合性雙鍵的二元酸酐反應而成的含聚合性雙鍵的丙烯酸系樹脂；使含有OH基的丙烯酸系樹脂、異氰酸酯及具有聚合性基的化合物反應而成的樹脂；日本專利特開2002-229207號公報及日本專利特開2003-335814號公報中記載的藉由對以下樹脂進行鹼性處理所得的樹脂等，所述樹脂於側鏈上具有在α位或β位上具有鹵素原子或磺酸酯基等脫離基的酯基。 Examples of the polymer containing a polymerizable group include Dianan NR series (manufactured by Mitsubishi Rayon Co., Ltd.) and Photomer 6173 (polyurethane acrylate oligomer containing COOH). ), Diamond Shamrock Co., Ltd., Biscoat R-264, KS Resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Placcel CF200 series (all manufactured by Daicel Chemical Industry Co., Ltd.), Ebecryl 3800 (Daicel UCB) Company manufacturing) and so on. The alkali-soluble resin containing a polymerizable group is preferably a resin containing a polymerizable double bond modified by a urethane, which is left by reacting an isocyanate group with an OH group in advance. An unreacted isocyanate group containing a (meth) acrylonitrile group-containing compound and a reaction with a carboxyl group-containing acrylic resin; and an unsaturated group-containing acrylic resin which is a carboxyl group-containing acrylic resin and a molecule Obtained by a reaction of a compound having an epoxy group and a polymerizable double bond; an acid side-type epoxy acrylate tree An acrylic resin containing a polymerizable double bond obtained by reacting an OH group-containing acrylic resin with a dibasic acid anhydride having a polymerizable double bond; and an OH group-containing acrylic resin, an isocyanate, and a polymerizable group; A resin obtained by reacting a compound, and a resin obtained by subjecting the following resin to alkaline treatment as described in JP-A-2002-229207, wherein the resin is on a side chain. An ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or the β-position.

鹼可溶性樹脂尤佳為(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物或包含(甲基)丙烯酸苄酯/(甲基)丙烯酸/其他單體的多元共聚物。除此以外，可列舉：使甲基丙烯酸-2-羥基乙酯進行共聚合而成的(甲基)丙烯酸苄酯/(甲基)丙烯酸/(甲基)丙烯酸-2-羥基乙酯共聚物、日本專利特開平7-140654號公報中記載的(甲基)丙烯酸-2-羥基丙酯/聚苯乙烯巨單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物、丙烯酸-2-羥基-3-苯氧基丙酯/聚甲基丙烯酸甲酯巨單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物、甲基丙烯酸-2-羥基乙酯/聚苯乙烯巨單體/甲基丙烯酸甲酯/甲基丙烯酸共聚物、甲基丙烯酸-2-羥基乙酯/聚苯乙烯巨單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物等，尤佳可列舉甲基丙烯酸苄酯/甲基丙烯酸的共聚物等。 The alkali-soluble resin is particularly preferably a benzyl (meth)acrylate/(meth)acrylic copolymer or a multicomponent copolymer comprising benzyl (meth)acrylate/(meth)acrylic acid/other monomer. In addition, benzyl (meth)acrylate/(meth)acrylic acid/(meth)acrylic acid-2-hydroxyethyl ester copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate may be mentioned. Japanese Patent Publication No. 7-140654, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-2-acrylate- 3-phenoxypropyl ester/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methacrylic acid Methyl ester/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, etc., especially benzyl methacrylate/methyl A copolymer of acrylic acid or the like.

鹼可溶性樹脂可參考日本專利特開2012-208494號公報的段落0558~段落0571(對應的美國專利申請案公開第2012/0235099號說明書的[0685]~[0700])以後的記載，將該些內容併入至本申請案說明書中。 The alkali-soluble resin can be referred to the following paragraphs 0558 to 5571 of the Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to U.S. Patent Application Publication No. 2012/0235099, the specification of [0685] to [0700]). The content is incorporated into the specification of the present application.

進而較佳為使用以下樹脂：日本專利特開2012-32767號公報中記載的段落編號0029~段落編號0063所記載的共聚物(B)及實施例中所用的鹼可溶性樹脂、日本專利特開2012-208474號公報的段落編號0088~段落編號0098中記載的黏合劑樹脂及實施例中所用的黏合劑樹脂、日本專利特開2012-137531號公報的段落編號0022~段落編號0032中記載的黏合劑樹脂及實施例中所用的黏合劑樹脂、日本專利特開2013-024934號公報的段落編號0132~段落編號0143中記載的黏合劑樹脂及實施例中所用的黏合劑樹脂、日本專利特開2011-242752號公報的段落編號0092~段落編號0098及實施例中所用的黏合劑樹脂、日本專利特開2012-032770號公報的段落編號0030~段落編號0072的記載的黏合劑樹脂。將該些內容併入至本申請案說明書中。更具體而言，較佳為下述樹脂。 Further, it is preferable to use the following resin: the copolymer (B) described in Paragraph No. 0029 to Paragraph No. 0063 described in JP-A-2012-32767, and the alkali-soluble resin used in the examples, Japanese Patent Laid-Open No. 2012 The adhesive resin described in Paragraph No. 0088 to Paragraph No. 0098 of the Japanese Patent Publication No. 208474, and the adhesive resin used in the examples, and the adhesive described in Paragraph No. 0022 to Paragraph No. 0032 of JP-A-2012-137531 The binder resin used in the resin and the examples, the binder resin described in paragraph No. 0132 to paragraph number 0143 of JP-A-2013-024934, and the binder resin used in the examples, Japanese Patent Laid-Open No. 2011- The adhesive resin described in Paragraph No. 0092 to Paragraph No. 0098 of the Japanese Patent Publication No. 242752, and the adhesive resin used in the examples, and the paragraph number 0030 to paragraph 0072 of JP-A-2012-032770. This is incorporated into the specification of the present application. More specifically, the following resins are preferred.

[化46] [Chem. 46]

鹼可溶性樹脂的酸值較佳為30mgKOH/g~200mgKOH/g，更佳為以50mgKOH/g~150mgKOH/g為宜，尤佳為70mgKOH/g~120mgKOH/g。 The acid value of the alkali-soluble resin is preferably from 30 mgKOH/g to 200 mgKOH/g, more preferably from 50 mgKOH/g to 150 mgKOH/g, still more preferably from 70 mgKOH/g to 120 mgKOH/g.

另外，鹼可溶性樹脂的重量平均分子量(Mw)較佳為2,000~50,000，更佳為5,000~30,000，尤佳為7,000~20,000。 Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000, still more preferably from 7,000 to 20,000.

於著色組成物中含有鹼可溶性樹脂的情形時，相對於著色組成物的總固體成分，鹼可溶性樹脂的含量較佳為1質量%~15質量%，更佳為2質量%~12質量%，尤佳為3質量%~10質量%。 When the alkali-soluble resin is contained in the coloring composition, the content of the alkali-soluble resin is preferably from 1% by mass to 15% by mass, more preferably from 2% by mass to 12% by mass, based on the total solid content of the coloring composition. More preferably, it is 3 mass% to 10 mass%.

本發明的組成物可僅含有一種鹼可溶性樹脂，亦可含有兩種以上，較佳為含有兩種以上，更佳為至少一種具有聚合性基。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 resin, or may contain two or more kinds, preferably two or more, and more preferably at least one polymerizable group. When two or more cases are contained, it is preferable that the total amount is the said range.

<其他成分> <Other ingredients>

本發明的著色組成物除了含有所述各成分以外，亦可於不損及本發明的效果的範圍內，更含有界面活性劑、交聯劑、聚合抑制劑、有機羧酸、有機羧酸酐等其他成分。 In addition to the above-mentioned respective components, the coloring composition of the present invention may further contain a surfactant, a crosslinking agent, a polymerization inhibitor, an organic carboxylic acid, an organic carboxylic anhydride, etc., within a range that does not impair the effects of the present invention. Other ingredients.

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

本發明的著色組成物中，就進一步提高塗佈性的觀點而言，亦可添加各種界面活性劑。界面活性劑可使用氟系界面活性劑、非離子系界面活性劑、陽離子系界面活性劑、陰離子系界面活性劑、矽酮系界面活性劑等各種界面活性劑。 In the colored composition of the present invention, various surfactants may be added from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used.

尤其本發明的著色組成物藉由含有氟系界面活性劑，於製備成塗佈液時的溶液特性(特別是流動性)進一步提高，故可 進一步改善塗佈厚度的均勻性或省液性。 In particular, the colored composition of the present invention further contains a fluorine-based surfactant, and the solution characteristics (particularly fluidity) when the coating liquid is prepared are further improved. The uniformity of the coating thickness or the liquid-saving property are further improved.

即，於使用應用含有氟系界面活性劑的著色組成物的塗佈液來進行膜形成的情形時，藉由使被塗佈面與塗佈液的界面張力減小，對被塗佈面的濡濕性得到改善，對被塗佈面的塗佈性提高。因此，即便於以少量的液量形成幾微米(μm)左右的薄膜的情形時，亦可更佳地進行厚度不均小的均勻厚度的膜形成，就此方面而言有效。 In other words, when the film formation is carried out using a coating liquid using a coloring composition containing a fluorine-based surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the surface to be coated is applied. The wettability is improved, and the coatability to the coated surface is improved. Therefore, even when a film having a thickness of a few micrometers (μm) is formed with a small amount of liquid, it is possible to more preferably form a film having a uniform thickness having a small thickness unevenness, which is effective in this respect.

氟系界面活性劑中的氟含有率較佳為3質量%~40質量%，更佳為5質量%~30質量%，尤佳為7質量%~25質量%。氟含有率為該範圍內的氟系界面活性劑於塗佈膜的厚度的均勻性或省液性的方面有效，於著色組成物中的溶解性亦良好。 The fluorine content in the fluorine-based surfactant is preferably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, even more preferably from 7% by mass to 25% by mass. The fluorine-containing surfactant is effective in the uniformity of the thickness of the coating film or the liquid-saving property in the fluorine-based surfactant in this range, and the solubility in the colored composition is also good.

氟系界面活性劑例如可列舉：美佳法(Megafac)F171、美佳法(Megafac)F172、美佳法(Megafac)F173、美佳法(Megafac)F176、美佳法(Megafac)F177、美佳法(Megafac)F141、美佳法(Megafac)F142、美佳法(Megafac)F143、美佳法(Megafac)F144、美佳法(Megafac)R30、美佳法(Megafac)F437、美佳法(Megafac)F475、美佳法(Megafac)F479、美佳法(Megafac)F482、美佳法(Megafac)F554、美佳法(Megafac)F780、美佳法(Megafac)F781(以上為迪愛生(DIC)(股)製造)，弗拉德(Fluorad)FC430、弗拉德(Fluorad)FC431、弗拉德(Fluorad)FC171(以上為住友3M(股)製造)，沙福隆(Surflon)S-382、沙福隆(Surflon)SC-101、沙福隆(Surflon)SC-103、沙福隆(Surflon) SC-104、沙福隆(Surflon)SC-105、沙福隆(Surflon)SC1068、沙福隆(Surflon)SC-381、沙福隆(Surflon)SC-383、沙福隆(Surflon)S393、沙福隆(Surflon)KH-40(以上為旭硝子(股)製造)等。 Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, and Megafac F141. , Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781 (above produced by Di Aisheng (DIC)), Fluorad FC430, Fu Fluorad FC431, Fluorad FC171 (above Sumitomo 3M), Surflon S-382, Surflon SC-101, Surflon ) SC-103, Surflon (Surflon) SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above is manufactured by Asahi Glass Co., Ltd.).

非離子系界面活性劑具體可列舉：甘油、三羥甲基丙烷、三羥甲基乙烷以及該等的乙氧基化物及丙氧基化物(例如丙氧基化甘油、乙氧基化甘油等)、聚氧伸乙基月桂基醚、聚氧伸乙基硬脂基醚、聚氧伸乙基油烯基醚、聚氧伸乙基辛基苯基醚、聚氧伸乙基壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、山梨醇酐脂肪酸酯(巴斯夫(BASF)公司製造的普羅尼克(Pluronic)L10、普羅尼克(Pluronic)L31、普羅尼克(Pluronic)L61、普羅尼克(Pluronic)L62、普羅尼克(Pluronic)10R5、普羅尼克(Pluronic)17R2、普羅尼克(Pluronic)25R2、特羅尼克(Tetronic)304、特羅尼克(Tetronic)701、特羅尼克(Tetronic)704、特羅尼克(Tetronic)901、特羅尼克(Tetronic)904、特羅尼克(Tetronic)150R1)、索努帕斯(Solsperse)20000(日本路博潤(Lubrizol)(股))等。 Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates (for example, propoxylated glycerin, ethoxylated glycerin). Etc.), polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl olefin ether, polyoxyethyl octyl phenyl ether, polyoxyethyl thiol Phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, manufactured by BASF), Pluronic L31 , Pluronic L61, Pluronic L62, Pluronic 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304, Tetronic 701, Tetronic 704, Tetronic 901, Tetronic 904, Tetronic 150R1), Solsperse 20000 (Lubrizol, Japan) ) (shares)) and so on.

陽離子系界面活性劑具體可列舉：酞菁衍生物(商品名：埃夫卡(EFKA)-745，森下產業(股)製造)，有機矽氧烷聚合物KP341(信越化學工業(股)製造)，(甲基)丙烯酸系(共)聚合物波利弗洛(Polyflow)No.75、波利弗洛(Polyflow)No.90、波利弗洛(Polyflow)No.95(共榮社化學(股)製造)，W001(裕商(股)製造)等。 Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: Efka (EFKA)-745, manufactured by Morishita Industries Co., Ltd.), and an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). , (meth)acrylic (co)polymer Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (Kyoeisha Chemicals ( () manufacturing), W001 (Yu Shang (share) manufacturing) and so on.

陰離子系界面活性劑具體可列舉：W004、W005、W017(裕商(股)公司製造)等。 Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusei Co., Ltd.).

矽酮系界面活性劑例如可列舉：東麗道康寧(Toray-Dow corning)(股)製造的「東麗矽酮(Toray Silicone)DC3PA」、「東麗矽酮(Toray Silicone)SH7PA」、「東麗矽酮(Toray Silicone)DC11PA」、「東麗矽酮(Toray Silicone)SH21PA」、「東麗矽酮(Toray Silicone)SH28PA」、「東麗矽酮(Toray Silicone)SH29PA」、「東麗矽酮(Toray Silicone)SH30PA」、「東麗矽酮(Toray Silicone)SH8400」，邁圖高新材料(Momentive Performance Materials)公司製造的「TSF-4440」、「TSF-4300」、「TSF-4445」、「TSF-4460」、「TSF-4452」，信越矽酮股份有限公司製造的「KP341」、「KF6001」、「KF6002」，畢克化學(BYK Chemie)公司製造的「畢克(BYK)307」、「畢克(BYK)323」、「畢克(BYK)330」等。 Examples of the fluorenone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, and East, manufactured by Toray-Dow Corning Co., Ltd. Toray Silicone DC11PA", "Toray Silicone SH21PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Dong Lizhen" Toray Silicone SH30PA", "Toray Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445" manufactured by Momentive Performance Materials "TSF-4460" and "TSF-4452", "KP341", "KF6001" and "KF6002" manufactured by Shin-Etsu Chemical Co., Ltd., "BYK 307" manufactured by BYK Chemie , "BYK 323", "BYK" 330, etc.

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質量，界面活性劑的添加量較佳為0.001質量%~2.0質量%，更佳為0.05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 from 0.001% by mass to 2.0% by mass, more preferably from 0.05% by mass to 1.0%, based on the total mass of the coloring composition. quality%.

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.

<<交聯劑>> <<Crosslinker>>

亦可於本發明的著色組成物中補充使用交聯劑，進一步提高使著色組成物硬化而成的硬化膜的硬度。 Further, the crosslinking agent may be additionally used in the colored composition of the present invention to further increase the hardness of the cured film obtained by curing the colored composition.

交聯劑只要藉由交聯反應可進行膜硬化，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取代的三聚氰胺化合物、胍胺化合物、甘脲化合物(glycoluryl compound)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. For example, (a) an epoxy resin; (b) a melamine compound, a guanamine compound, a glycoluril compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and a decyloxymethyl group; (glycoluryl compound) or a urea compound; (c) a phenol compound, a naphthol compound or a hydroxyquinone compound substituted with at least one substituent selected from the group consisting of a methylol group, an alkoxymethyl group and a decyloxymethyl group. 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。 For details of specific examples of the crosslinking agent, the descriptions of paragraphs 0134 to 0147 of JP-A-2004-295116 can be referred to.

於本發明的著色組成物中含有交聯劑的情形時，交聯劑的調配量並無特別限定，較佳為組成物的總固體成分的2質量%~30質量%，更佳為3質量%~20質量%。 In the case where the coloring composition of the present invention contains a crosslinking agent, the amount of the crosslinking agent to be added is not particularly limited, but is preferably 2% by mass to 30% by mass, more preferably 3% by mass based on the total solid content of the composition. %~20% by mass.

本發明的組成物可僅含有一種交聯劑，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 crosslinking agent, 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.

<<聚合抑制劑>> <<Polymerization inhibitor>>

於本發明的著色組成物中，為了於著色組成物的製造中或保存中阻止聚合性化合物的不需要的熱聚合，理想的是添加少量的聚合抑制劑。 In the colored composition of the present invention, in order to prevent unnecessary thermal polymerization of the polymerizable compound during or during storage of the colored composition, it is preferred to add a small amount of a polymerization inhibitor.

本發明中可使用的聚合抑制劑可列舉：對苯二酚、對甲氧基苯酚、二-第三丁基對甲酚、鄰苯三酚、第三丁基鄰苯二酚、苯醌、4,4'-硫代雙(3-甲基-6-第三丁基苯酚)、2,2'-亞甲基雙(4-甲基-6-第三丁基苯酚)、N-亞硝基苯基羥基胺亞鈰鹽等。 The polymerization inhibitor which can be used in the present invention may, for example, be hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-Asia Nitrophenylhydroxylamine sulfonium salt and the like.

於本發明的著色組成物中含有聚合抑制劑的情形時，相對於 所有組成物的質量，聚合抑制劑的添加量較佳為0.01質量%~5質量%。 In the case where the coloring composition of the present invention contains a polymerization inhibitor, The mass of all the components and the amount of the polymerization inhibitor added are preferably from 0.01% by mass to 5% by mass.

本發明的組成物可僅含有一種聚合抑制劑，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 polymerization inhibitor, 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.

<<有機羧酸、有機羧酸酐>> <<Organic carboxylic acid, organic carboxylic anhydride>>

本發明的著色組成物亦可含有分子量為1000以下的有機羧酸及/或有機羧酸酐。 The colored composition of the present invention may also contain an organic carboxylic acid having a molecular weight of 1,000 or less and/or an organic carboxylic anhydride.

有機羧酸化合物具體可列舉脂肪族羧酸或芳香族羧酸。脂肪族羧酸例如可列舉：甲酸、乙酸、丙酸、丁酸、戊酸、三甲基乙酸、己酸、甘醇酸、丙烯酸、甲基丙烯酸等單羧酸，草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、環己烷二羧酸、環己烯二羧酸、衣康酸、檸康酸、馬來酸、富馬酸等二羧酸，1,2,3-丙三甲酸、烏頭酸等三羧酸等。另外，芳香族羧酸例如可列舉：苯甲酸、鄰苯二甲酸等羧基直接鍵結於苯基的羧酸，及自苯基經由碳鍵而鍵結羧基的羧酸類。該等中，尤佳為分子量600以下、特別是分子量50~500者，具體而言，例如較佳為馬來酸、丙二酸、琥珀酸、衣康酸。 Specific examples of the organic carboxylic acid compound include an aliphatic carboxylic acid or an aromatic carboxylic acid. Examples of the aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, glycolic acid, acrylic acid, and methacrylic acid, and oxalic acid, malonic acid, and amber. Dicarboxylic acids such as acid, glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, etc. Tricarboxylic acid such as 2,3-propanetricarboxylic acid or aconitic acid. Further, examples of the aromatic carboxylic acid include a carboxylic acid in which a carboxyl group such as benzoic acid or phthalic acid is directly bonded to a phenyl group, and a carboxylic acid in which a carboxyl group is bonded to a carboxyl group via a carbon bond. Among these, a molecular weight of 600 or less, particularly a molecular weight of 50 to 500 is particularly preferable, and specific examples thereof include maleic acid, malonic acid, succinic acid, and itaconic acid.

有機羧酸酐例如可列舉脂肪族羧酸酐、芳香族羧酸酐，具體而言，例如可列舉：乙酸酐、三氯乙酸酐、三氟乙酸酐、四氫鄰苯二甲酸酐、琥珀酸酐、馬來酸酐、檸康酸酐、衣康酸酐、戊二酸酐、1,2-環己烯二羧酸酐、正十八烷基琥珀酸酐、5-降冰片烯-2,3-二羧酸酐等脂肪族羧酸酐。芳香族羧酸酐例如可列舉：鄰 苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸酐、萘二甲酸酐等。該等中，尤佳為分子量600以下、特別是分子量50~500者，具體而言，例如較佳為馬來酸酐、琥珀酸酐、檸康酸酐、衣康酸酐。 Examples of the organic carboxylic acid anhydride include an aliphatic carboxylic acid anhydride and an aromatic carboxylic acid anhydride. Specific examples thereof include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, and Malay. An aliphatic carboxylic acid such as an acid anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride Anhydride. Examples of the aromatic carboxylic acid anhydride include: Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride, and the like. Among these, a molecular weight of 600 or less, particularly a molecular weight of 50 to 500 is particularly preferable, and specific examples thereof include maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride.

於本發明的著色組成物中含有有機羧酸、有機羧酸酐的情形時，有機羧酸及/或有機羧酸酐的添加量通常於總固體成分中為0.01重量%~10重量%、較佳為0.03重量%~5重量%、更佳為0.05重量%~3重量%的範圍。 When the colored composition of the present invention contains an organic carboxylic acid or an organic carboxylic anhydride, the amount of the organic carboxylic acid and/or the organic carboxylic anhydride to be added is usually 0.01% by weight to 10% by weight based on the total solid content, preferably It is in the range of 0.03 wt% to 5% by weight, more preferably 0.05 wt% to 3% by weight.

本發明的組成物可分別僅含有一種有機羧酸及/或有機羧酸酐，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 organic carboxylic acid and/or organic carboxylic acid anhydride, 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.

藉由添加該些分子量為1000以下的有機羧酸及/或有機羧酸酐，可保持高的圖案密接性，並且進一步減少著色組成物的未溶解物的殘存。 By adding these organic carboxylic acids and/or organic carboxylic anhydrides having a molecular weight of 1,000 or less, high pattern adhesion can be maintained, and the remaining of the colored composition can be further reduced.

除了所述添加劑以外，著色組成物中視需要可調配各種添加物、例如填充劑、密接促進劑、抗氧化劑、紫外線吸收劑、抗凝聚劑等。該些添加物可列舉日本專利特開2004-295116號公報的段落0155~段落0156中記載者，將該些內容併入至本申請案說明書中。 In addition to the additives, various additives such as a filler, a adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, and the like may be blended as needed in the coloring composition. The additives are described in paragraphs 0155 to 0156 of JP-A-2004-295116, the contents of which are incorporated herein by reference.

於本發明的著色組成物中，可含有日本專利特開2004-295116號公報的段落0078中記載的增感劑或光穩定劑、該公報的段落0081中記載的防熱聚合劑。 The coloring composition of the present invention may contain the sensitizer or light stabilizer described in paragraph 0078 of JP-A-2004-295116, and the heat-resistant polymerization agent described in paragraph 0081 of the publication.

本發明的組成物可分別僅含有一種所述成分，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 of the above components, and may also contain two types. the above. When two or more cases are contained, it is preferable that the total amount is the said range.

<著色組成物的製備方法> <Method for Preparing Colored Composition>

本發明的著色組成物是藉由將上文所述的成分混合而製備。 The colored composition of the present invention is prepared by mixing the above-described ingredients.

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、分散於溶劑中後逐次調配。另外，調配時的投入順序或作業條件不受特別限制。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)將該等混合而製備成組成物。 Further, when preparing a colored composition, each component constituting the colored composition may be formulated at once, or each component may be dissolved and dispersed in a solvent, and then successively 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 mixed at the time of use (at the time of coating). It was prepared into a composition.

如上所述般製備的著色組成物可使用較佳為孔徑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 using a filter having a pore diameter of preferably 0.01 μm to 3.0 μm, more preferably a pore diameter of 0.05 μm to 0.5 μm, or the like.

另外，於在本發明的組成物中調配顏料的情形時，較佳為使用經清洗的顏料。藉由使用經清洗的顏料，可進一步減少組成物中的異物。清洗顏料的方法可參考日本專利特開2010-83997號公報的段落0011~段落0099，將其內容併入至本說明書中。 Further, in the case of formulating a pigment in the composition of the present invention, it is preferred to use a washed pigment. Foreign matter in the composition can be further reduced by using the washed pigment. The method of cleaning the pigment can be referred to the paragraphs 0011 to 0099 of Japanese Patent Laid-Open No. 2010-83997, the contents of which are incorporated herein.

本發明的著色組成物可較佳地用於彩色濾光片的著色層形成用。更具體而言，本發明的著色組成物由於可形成耐熱性及顏色特性優異的硬化膜，故可較佳地用於形成彩色濾光片的著色圖案(著色層)。另外，本發明的著色組成物可較佳地用於固體攝像元件(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)或液晶顯示裝置(LCD)等圖像顯示裝置中所用的彩色濾光片等著色圖案形成用。進而，亦可較佳地用於印刷油墨、噴墨油墨及塗料等的製作用途。其中，可較佳地使用CCD及CMOS等固體攝像元件用的彩色濾光片作為製作用途。 The colored composition of the present invention can be preferably used for the formation of a coloring layer of a color filter. More specifically, since the colored composition of the present invention can form a cured film excellent in heat resistance and color characteristics, it can be preferably used for forming a colored pattern (colored layer) of a color filter. Further, the coloring composition of the present invention can be preferably used for a solid-state imaging device (for example, a charge-coupled device (CCD), a complementary metal oxide semiconductor (Complementary Metal Oxide). Semiconductor, CMOS, etc.) or a color filter such as a color filter used in an image display device such as a liquid crystal display device (LCD). Further, it can also be preferably used for production of printing inks, inkjet inks, paints, and the like. Among them, a color filter for a solid-state imaging device such as a CCD or a CMOS can be preferably used as a production.

<硬化膜、圖案形成方法、彩色濾光片及彩色濾光片的製造方法> <Method for Producing Cured Film, Pattern Forming Method, Color Filter, and Color Filter>

繼而，對本發明的硬化膜、圖案形成方法及彩色濾光片藉由其製造方法加以詳述。 Next, the cured film, the pattern forming method, and the color filter of the present invention will be described in detail by a method for producing the same.

本發明的硬化膜是使本發明的著色組成物硬化而成。該硬化膜可較佳地用於彩色濾光片。 The cured film of the present invention is obtained by hardening the colored composition of the present invention. The cured film can be preferably used for a color filter.

本發明的圖案形成方法將本發明的著色組成物應用於支持體上而形成著色組成物層，將不需要的部分去除而形成著色圖案。 The pattern forming method of the present invention applies the colored composition of the present invention to a support to form a colored composition layer, and removes an unnecessary portion to form a colored pattern.

本發明的圖案形成方法可較佳地用於形成彩色濾光片所具有的著色圖案(畫素)。 The pattern forming method of the present invention can be preferably used to form a color pattern (pixel) which the color filter has.

本發明的組成物可利用所謂光微影法藉由圖案形成來製造彩色濾光片，亦可藉由乾式蝕刻法來形成圖案。 The composition of the present invention can be used to form a color filter by pattern formation by a so-called photolithography method, or can be formed by a dry etching method.

即，本發明的彩色濾光片的第一製造方法可例示包括以下步驟的彩色濾光片的製造方法：將著色組成物應用於支持體上而形成著色組成物層的步驟；將所述著色組成物層以圖案狀進行曝光的步驟；以及將未曝光部顯影去除而形成著色圖案的步驟。 That is, the first manufacturing method of the color filter of the present invention can exemplify a method of producing a color filter including the following steps: a step of applying a colored composition to a support to form a colored composition layer; a step of exposing the composition layer in a pattern; and a step of developing and removing the unexposed portion to form a colored pattern.

另外，本發明的彩色濾光片的第二製造方法可例示包括以下步驟的彩色濾光片的製造方法：將著色組成物應用於支持體上而形成著色組成物層，並使其硬化而形成著色層的步驟；於所述著色層上形成光阻層的步驟；藉由曝光及顯影將所述光阻層圖案化而獲得抗蝕劑圖案的步驟；以及將所述抗蝕劑圖案作為蝕刻遮罩來對所述著色層進行乾式蝕刻的步驟。 Further, the second method for producing a color filter of the present invention can be exemplified by a method of producing a color filter comprising the steps of applying a colored composition to a support to form a colored composition layer, and hardening it to form a color filter. a step of forming a photoresist layer; a step of forming a photoresist layer on the colored layer; a step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and using the resist pattern as an etch A step of dry etching the colored layer by a mask.

於本發明中，更佳為利用光微影法來製造。 In the present invention, it is more preferably produced by photolithography.

以下對該些方法加以詳細描述。 The methods are described in detail below.

以下，對本發明的圖案形成方法的各步驟藉由固體攝像元件用彩色濾光片的製造方法來加以詳細說明，但本發明不限定於該方法。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, each step of the pattern forming method of the present invention will be described in detail by a method of producing a color filter for a solid-state image sensor, but the present invention is not limited to this method. 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>> <<Steps of forming a colored composition layer>>

於形成著色組成物層的步驟中，於支持體上應用本發明的著色組成物而形成著色組成物層。 In the step of forming the colored composition layer, the colored composition of the present invention is applied to the support to form a colored composition layer.

該步驟中可使用的支持體例如可使用：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攝像元件形成面側(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 imaging element forming surface side (surface) of the solid-state imaging device substrate, or can be formed on the surface side (back surface) where the imaging element is not formed.

亦可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，於支持體上，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。底塗層中可調配溶劑、鹼可溶性樹脂、聚合性化合物、聚合抑制劑、界面活性劑、光聚合起始劑等，該些各成分較佳為自調配至所述本發明的組成物中的成分中適當選擇。 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. The primer layer may be formulated with a solvent, an alkali-soluble resin, a polymerizable compound, a polymerization inhibitor, a surfactant, a photopolymerization initiator, etc., and the components are preferably self-adapted into the composition of the present invention. Appropriate choice of ingredients.

於支持體上賦予本發明的著色組成物的賦予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。 Various methods of applying the coloring composition of the present invention to the support can be applied by various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing.

塗佈於支持體上的著色組成物層的乾燥(預烘烤)可利用熱板、烘箱等在50℃~140℃的溫度下進行10秒鐘~300秒鐘。 The drying (prebaking) of the colored composition layer applied to the support can be carried out at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds using a hot plate, an oven or the like.

<利用光微影法來進行圖案形成的步驟> <Step of pattern formation by photolithography>

<<進行曝光的步驟>> <<Steps for exposure>>

於曝光步驟中，對著色組成物層形成步驟中形成的著色組成物層使用例如步進機等曝光裝置，介隔具有既定的遮罩圖案的遮罩來進行圖案曝光。藉此可獲得硬化膜。 In the exposure step, an exposure device such as a stepper is used for the colored composition layer formed in the colored composition layer forming step, and a mask having a predetermined mask pattern is interposed to perform pattern exposure. 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30mJ/cm2~1500mJ/cm2，更佳為50mJ/cm2~1000mJ/cm2，尤佳為80mJ/cm2~500mJ/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. Irradiation amount (exposure amount) is preferably 30mJ / cm 2 ~ 1500mJ / cm 2, more preferably 50mJ / cm 2 ~ 1000mJ / cm 2, and particularly preferably 80mJ / cm 2 ~ 500mJ / cm 2.

硬化膜(著色膜)的膜厚較佳為1.0μm以下，更佳為 0.1μm~0.9μm，進而佳為0.2μm~0.8μm。 The film thickness of the cured film (colored film) is preferably 1.0 μm or less, more preferably 0.1 μm to 0.9 μm, and more preferably 0.2 μm to 0.8 μm.

藉由將膜厚設定為1.0μm以下，可獲得高解析性、高密接性，故較佳。 By setting the film thickness to 1.0 μm or less, high resolution and high adhesion can be obtained, which is preferable.

另外，於該步驟中，亦可較佳地形成具有0.7μm以下的薄的膜厚的硬化膜，藉由利用後述圖案形成步驟對所得的硬化膜進行顯影處理，可獲得即便為薄膜，顯影性、表面粗糙抑制及圖案形狀亦優異的著色圖案。 Further, in this step, a cured film having a thin film thickness of 0.7 μm or less can be preferably formed, and the obtained cured film can be developed by a pattern forming step described later, whereby a film can be obtained, and developability can be obtained. A coloring pattern excellent in surface roughness suppression and pattern shape.

<<顯影步驟>> <<Development step>>

繼而進行鹼顯影處理，藉此曝光步驟中的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, an alkali development treatment is performed, whereby 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底層的攝像元件或電路等造成損傷(damage)的有機鹼顯影液。顯影溫度通常為20℃~30℃，顯影時間以前為20秒~90秒。為了進一步去除殘渣，近年來有時亦有實施120秒~180秒的情況。進而，為了進一步提高殘渣去除性，有時亦重複以下步驟幾次：每隔60秒甩去顯影液，進一步重新供給顯影液。 The developer is desirably an organic alkali developer which does not cause damage to the underlying imaging element or circuit. 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 some cases, 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 the developer is further supplied again.

顯影液中所用的鹼劑例如可列舉：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、氫氧化三甲基苄基銨、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 tetrabutylammonium hydroxide. Preferably, an organic basic compound such as a solution of a solution such as ammonium amide, trimethylbenzylammonium hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5.4.0]-7-undecene is preferred. An alkaline aqueous solution obtained by diluting the alkali agent in a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass, using pure water is used as an Shadow liquid.

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，較佳為於實施了乾燥後進行加熱處理(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. 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進行的顯影後的加熱處理，通常於100℃~240℃、較佳為200℃~240℃下進行熱硬化處理。 The post-baking is a heat treatment after development for completely curing, and is usually subjected to a heat hardening treatment at 100 ° C to 240 ° C, preferably 200 ° C to 240 ° C.

可使用熱板或對流式烘箱(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 by using a heating mechanism such as a hot plate or a convection oven (hot air circulation dryer) or a high-frequency heating machine in such a manner as to achieve the above conditions. Baked.

<利用乾式蝕刻法來進行圖案形成的情形> <Scenario of Patterning by Dry Etching Method>

乾式蝕刻可對著色層使用經圖案化的光阻層作為遮罩使用蝕刻氣體來進行。具體而言，於著色層上塗佈正型或負型的感放射線性組成物並使其乾燥，藉此形成光阻層。於光阻層的形成時，較佳為進一步實施預烘烤處理。光阻的形成製程尤其理想的是實施曝光後的加熱處理(曝光後烘烤(Post-Exposure Bake，PEB))、顯影後的加熱處理(後烘烤處理)的形態。 Dry etching can be performed using a patterned photoresist layer as a mask for the colored layer using an etching gas. Specifically, a positive or negative radiation sensitive composition is applied onto the colored layer and dried to form a photoresist layer. At the time of formation of the photoresist layer, it is preferred to further carry out the prebaking treatment. The formation process of the photoresist is particularly preferably a form in which heat treatment (Post-Exposure Bake (PEB)) after exposure and heat treatment (post-baking treatment) after development are performed.

光阻例如可使用正型的感放射線性組成物。該正型的感放射線性組成物可使用感應紫外線(g射線、h射線、i射線)、包 含準分子雷射等的遠紫外線、電子束、離子束及X射線等放射線的適於正型光阻用的正型抗蝕劑組成物。放射線中，較佳為g射線、h射線、i射線，其中較佳為i射線。 For the photoresist, for example, a positive type radiation sensitive composition can be used. The positive radiation sensitive composition can be used to induce ultraviolet rays (g rays, h rays, i rays), and packages. A positive resist composition suitable for positive resists such as far ultraviolet rays, electron beams, ion beams, and X-rays, such as excimer lasers. In the radiation, it is preferably g-ray, h-ray, or i-ray, and among them, i-ray is preferable.

具體而言，正型的感放射線性組成物較佳為含有醌二疊氮化合物及鹼可溶性樹脂的組成物。含有醌二疊氮化合物及鹼可溶性樹脂的正型的感放射線性組成物利用以下情況：藉由500nm以下的波長的光照射而醌二疊氮基發生分解產生羧基，結果由鹼不溶狀態變為鹼可溶性。該正型光阻的解析力明顯優異，故可用於製作積體電路(Integrated Circuit，IC)或大規模積體電路(Large Scale Integration，LSI)等積體電路。醌二疊氮化合物可列舉萘醌二疊氮化合物。市售品例如可列舉「FHi622BC」(富士膠片電子材料(Fujifilm Electronic Materials)公司製造)等。 Specifically, the positive radiation sensitive composition is preferably a composition containing a quinonediazide compound and an alkali-soluble resin. A positive-type radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin is obtained by decomposing a quinonediazide group by light irradiation at a wavelength of 500 nm or less to produce a carboxyl group, and the result is changed from an alkali-insoluble state. Alkali soluble. Since the positive resist has an excellent resolving power, it can be used to form an integrated circuit such as an integrated circuit (IC) or a large scale integrated circuit (LSI). The quinonediazide compound may be a naphthoquinonediazide compound. For example, "FHi622BC" (made by Fujifilm Electronic Materials Co., Ltd.), etc. are mentioned as a commercial item.

光阻層的厚度較佳為0.1μm~3μm，較佳為0.2μm~2.5μm，進而佳為0.3μm~2μm。再者，光阻層的塗佈可使用上文已述的著色層的塗佈方法來較佳地進行。 The thickness of the photoresist layer is preferably from 0.1 μm to 3 μm, preferably from 0.2 μm to 2.5 μm, and more preferably from 0.3 μm to 2 μm. Further, the coating of the photoresist layer can be preferably carried out using the coating method of the coloring layer described above.

繼而，對光阻層進行曝光、顯影，藉此形成設有抗蝕劑貫通孔組群的抗蝕劑圖案(經圖案化的光阻層)。抗蝕劑圖案的形成並無特別限制，可將以前公知的光微影技術適當地最適化來進行。藉由曝光、顯影而於光阻層中設置抗蝕劑貫通孔組群，藉此將作為後續的蝕刻中所用的蝕刻遮罩的抗蝕劑圖案設置於著色層上。 Then, the photoresist layer is exposed and developed to form a resist pattern (patterned photoresist layer) provided with a resist through-hole group. The formation of the resist pattern is not particularly limited, and the conventionally known photolithography technique can be appropriately optimized. A resist through-hole group is provided in the photoresist layer by exposure and development, whereby a resist pattern as an etching mask used for subsequent etching is provided on the colored layer.

光阻層的曝光可藉由以下方式來進行：介隔既定的遮罩 圖案，對正型或負型的感放射線性組成物利用g射線、h射線、i射線等、較佳為i射線實施曝光。曝光後，藉由利用顯影液進行顯影處理，而與欲形成著色圖案的區域相對應地將光阻去除。 The exposure of the photoresist layer can be performed by interposing a predetermined mask The pattern, the positive or negative radiation sensitive composition is exposed by g-ray, h-ray, i-ray, or the like, preferably i-ray. After the exposure, the photoresist is removed by performing development processing using a developer to correspond to a region where the colored pattern is to be formed.

所述顯影液只要對含有著色劑的著色層不造成影響，且將正型抗蝕劑的曝光部及負型抗蝕劑的未硬化部溶解，則均可使用，例如可使用各種有機溶劑的組合或鹼性水溶液。鹼性水溶液較佳為將鹼性化合物以濃度成為0.001質量%~10質量%、較佳為0.01質量%~5質量%的方式溶解而製備的鹼性水溶液。鹼性化合物例如可列舉：氫氧化鈉、氫氧化鉀、碳酸鈉，矽酸鈉、偏矽酸鈉、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、膽鹼、吡咯、哌啶、1,8-二氮雜雙環[5.4.0]-7-十一烯等。另外，於使用鹼性水溶液作為顯影液的情形時，通常於顯影後利用水實施清洗處理。 The developer may be used as long as it does not affect the coloring layer containing the coloring agent, and the exposed portion of the positive resist and the uncured portion of the negative resist may be used. For example, various organic solvents may be used. Combination or alkaline aqueous solution. The alkaline aqueous solution is preferably an alkaline aqueous solution prepared by dissolving a basic compound in a concentration of from 0.001% by mass to 10% by mass, preferably from 0.01% by mass to 5% by mass. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and hydroxide. Tetraethylammonium, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and the like. Further, when an alkaline aqueous solution is used as the developing solution, the cleaning treatment is usually performed by water after development.

繼而，將抗蝕劑圖案作為蝕刻遮罩，以於著色層中形成貫通孔組群的方式藉由乾式蝕刻進行圖案化。藉此形成著色圖案。貫通孔組群是以棋盤格狀設置於著色層中。因此，於著色層中設有貫通孔組群而成的第1著色圖案以棋盤格狀而具有多個四角形狀的第1著色畫素。 Then, the resist pattern is used as an etching mask, and patterning is performed by dry etching so that the through-hole group is formed in the colored layer. Thereby a colored pattern is formed. The through hole group is disposed in the colored layer in a checkerboard pattern. Therefore, the first colored pattern in which the through-hole group is provided in the colored layer has a plurality of square-shaped first colored pixels in a checkerboard pattern.

具體而言，乾式蝕刻時，將抗蝕劑圖案作為蝕刻遮罩來對著色層進行乾式蝕刻。乾式蝕刻的代表例有日本專利特開昭59-126506號、日本專利特開昭59-46628號、日本專利特開昭58-9108號、日本專利特開昭58-2809號、日本專利特開昭 57-148706號、日本專利特開昭61-41102號等各公報中記載的方法。 Specifically, in the dry etching, the colored layer is dry-etched using the resist pattern as an etching mask. Representative examples of dry etching include Japanese Patent Laid-Open No. 59-126506, Japanese Patent Laid-Open No. Sho 59-46628, Japanese Patent Laid-Open No. Sho 58-9108, Japanese Patent Laid-Open No. Sho 58-2809, and Japanese Patent Laid-Open Zhao The method described in each of the publications of JP-A-61-41102, and the like.

就使圖案剖面形成得更接近矩形的觀點或進一步減少對支持體的損傷的觀點而言，乾式蝕刻較佳為按以下形態來進行。 From the viewpoint of forming the pattern cross section closer to a rectangular shape or further reducing the damage to the support, the dry etching is preferably carried out in the following form.

較佳為包括第1階段的蝕刻、第2階段的蝕刻及過蝕刻的形態，所述第1階段的蝕刻使用氟系氣體與氧氣(O2)的混合氣體，進行蝕刻直至支持體不露出的區域(深度)為止，所述第2階段的蝕刻於所述第1階段的蝕刻後，使用氮氣(N2)與氧氣(O2)的混合氣體，進行蝕刻直至較佳為支持體露出的區域(深度)附近為止，所述過蝕刻是於支持體露出後進行。以下，對乾式蝕刻的具體方法以及第1階段的蝕刻、第2階段的蝕刻及過蝕刻加以說明。 It is preferable to include a first-stage etching, a second-stage etching, and an over-etching. The first-stage etching uses a mixed gas of a fluorine-based gas and oxygen (O 2 ), and etching is performed until the support is not exposed. In the region (depth), the second-stage etching is performed after the etching in the first step, and etching is performed using a mixed gas of nitrogen (N 2 ) and oxygen (O 2 ) until it is preferable that the support is exposed. The over-etching is performed after the support is exposed, in the vicinity of (depth). Hereinafter, a specific method of dry etching, etching in the first stage, etching in the second stage, and over etching will be described.

乾式蝕刻是藉由下述方法預先求出蝕刻條件來進行。 The dry etching is performed by previously obtaining etching conditions by the following method.

(1)分別算出第1階段的蝕刻的蝕刻速率(nm/min)、及第2階段的蝕刻的蝕刻速率(nm/min)。(2)分別算出於第1階段的蝕刻中蝕刻所需厚度的時間、及於第2階段的蝕刻中蝕刻所需厚度的時間。(3)依照所述(2)中算出的蝕刻時間來實施第1階段的蝕刻。(4)依照所述(2)中算出的蝕刻時間來實施第2階段的蝕刻。或者，藉由終點(end point)檢測來決定蝕刻時間，根據所決定的蝕刻時間來實施第2階段的蝕刻。(5)針對所述(3)、(4)的合計時間算出過蝕刻時間，實施過蝕刻。 (1) The etching rate (nm/min) of the etching in the first stage and the etching rate (nm/min) in the etching in the second stage were respectively calculated. (2) Calculate the time required for etching in the etching of the first stage and the time required to etch the required thickness in the etching of the second stage. (3) The first-stage etching is performed in accordance with the etching time calculated in the above (2). (4) The second-stage etching is performed in accordance with the etching time calculated in the above (2). Alternatively, the etching time is determined by end point detection, and the second etching is performed in accordance with the determined etching time. (5) The over-etching time is calculated for the total time of the above (3) and (4), and over-etching is performed.

就將作為被蝕刻膜的有機材料加工成矩形的觀點而 言，所述第1階段的蝕刻步驟中所用的混合氣體較佳為含有氟系氣體及氧氣(O2)。另外，第1階段的蝕刻步驟藉由設定為進行蝕刻直至支持體不露出的區域為止的形態，可避免支持體的損傷。另外，就避免支持體的損傷的觀點而言，所述第2階段的蝕刻步驟及所述過蝕刻步驟較佳為於第1階段的蝕刻步驟中藉由氟系氣體及氧氣的混合氣體實施蝕刻直至支持體不露出的區域為止後，使用氮氣及氧氣的混合氣體來進行蝕刻處理。 The mixed gas used in the first-stage etching step preferably contains a fluorine-based gas and oxygen (O 2 ) from the viewpoint of processing the organic material as the film to be processed into a rectangular shape. Further, the etching step of the first step can be prevented from being damaged by the support so as to be etched until the region where the support is not exposed. Further, from the viewpoint of avoiding damage of the support, the etching step and the over-etching step in the second step are preferably performed by a mixed gas of a fluorine-based gas and oxygen in the etching step of the first-stage etching step. After the region where the support is not exposed, the etching treatment is performed using a mixed gas of nitrogen gas and oxygen gas.

第1階段的蝕刻步驟中的蝕刻量、與第2階段的蝕刻步驟中的蝕刻量之比率重要的是以不損及由第1階段的蝕刻步驟中的蝕刻處理所得的矩形性的方式來決定。再者，總蝕刻量(第1階段的蝕刻步驟中的蝕刻量與第2階段的蝕刻步驟中的蝕刻量的總和)中的後者的比率較佳為大於0%且為50%以下的範圍，更佳為10%~20%。所謂蝕刻量，是指根據被蝕刻膜的殘存的膜厚與蝕刻前的膜厚之差所算出的量。 The ratio of the amount of etching in the etching step in the first step to the amount of etching in the etching step in the second step is important in such a manner as not to impair the squareness obtained by the etching treatment in the etching step of the first step. . Further, the ratio of the latter in the total etching amount (the total of the etching amount in the etching step in the first step and the etching amount in the etching step in the second step) is preferably in a range of more than 0% and not more than 50%. More preferably 10% to 20%. The amount of etching refers to an amount calculated from the difference between the film thickness remaining in the film to be etched and the film thickness before etching.

另外，蝕刻較佳為包括過蝕刻處理。過蝕刻處理較佳為設定過蝕刻比率來進行。另外，過蝕刻比率較佳為根據最初進行的蝕刻處理時間來算出。過蝕刻比率可任意設定，就維持光阻的耐蝕刻性及被蝕刻圖案的矩形性的方面而言，較佳為蝕刻步驟中的蝕刻處理時間的30%以下，更佳為5%~25%，尤佳為10%~15%。 In addition, the etching preferably includes an overetching process. The overetching treatment is preferably performed by setting an overetch ratio. Further, the overetch ratio is preferably calculated based on the etching processing time that is initially performed. The overetching ratio can be arbitrarily set, and it is preferably 30% or less, more preferably 5% to 25%, of the etching treatment time in the etching step in terms of maintaining the etching resistance of the photoresist and the rectangularity of the etching pattern. , especially good for 10% to 15%.

繼而，將蝕刻後殘存的抗蝕劑圖案(即蝕刻遮罩)去除。抗蝕劑圖案的去除較佳為包括以下步驟：於抗蝕劑圖案上賦予剝離液或溶劑而將抗蝕劑圖案調整為可去除的狀態的步驟；以及使 用清洗水將抗蝕劑圖案去除的步驟。 Then, the resist pattern remaining after the etching (ie, the etching mask) is removed. The removal of the resist pattern preferably includes the steps of: applying a stripping liquid or a solvent to the resist pattern to adjust the resist pattern to a removable state; and The step of removing the resist pattern with washing water.

於抗蝕劑圖案上賦予剝離液或溶劑而將抗蝕劑圖案調整為可去除的狀態的步驟例如可列舉：至少於抗蝕劑圖案上賦予剝離液或溶劑，使之停滯既定的時間而進行浸置顯影的步驟。使剝離液或溶劑停滯的時間並無特別限制，較佳為幾十秒鐘至幾分鐘。 The step of applying a peeling liquid or a solvent to the resist pattern to adjust the resist pattern to a removable state includes, for example, applying a peeling liquid or a solvent to at least the resist pattern, and stopping the film for a predetermined period of time. The step of immersing the development. The time for stopping the stripping solution or the solvent is not particularly limited, and is preferably from several tens of seconds to several minutes.

另外，使用清洗水將抗蝕劑圖案去除的步驟例如可列舉：自噴射式或噴淋式的噴射噴嘴對抗蝕劑圖案噴射清洗水，將抗蝕劑圖案去除的步驟。清洗水可較佳地使用純水。另外，噴射噴嘴可列舉：於其噴射範圍內包含整個支持體的噴射噴嘴、或為可動式的噴射噴嘴且其可動範圍包含整個支持體的噴射噴嘴。於噴射噴嘴為可動式的情形時，可於去除抗蝕劑圖案的步驟中自支持體中心部至支持體端部為止移動2次以上來噴射清洗水，藉此更有效地去除抗蝕劑圖案。 Further, the step of removing the resist pattern by using the washing water may, for example, be a step of ejecting the washing water from the resist pattern by a spray type or a spray type spray nozzle to remove the resist pattern. Pure water can be preferably used for the washing water. Further, the injection nozzle may be an injection nozzle that includes the entire support in the injection range thereof, or an injection nozzle that is a movable injection nozzle and whose movable range includes the entire support. When the ejection nozzle is movable, the cleaning water can be sprayed two times or more from the center of the support to the end of the support in the step of removing the resist pattern, thereby more effectively removing the resist pattern. .

剝離液通常含有有機溶劑，亦可更含有無機溶劑。有機溶劑例如可列舉：1)烴系化合物、2)鹵化烴系化合物、3)醇系化合物、4)醚或縮醛系化合物、5)酮或醛系化合物、6)酯系化合物、7)多元醇系化合物、8)羧酸或其酸酐系化合物、9)酚系化合物、10)含氮化合物、11)含硫化合物、12)含氟化合物。剝離液較佳為含有含氮化合物，更佳為含有非環狀含氮化合物及環狀含氮化合物。 The stripping solution usually contains an organic solvent, and may further contain an inorganic solvent. Examples of the organic solvent include 1) a hydrocarbon-based compound, 2) a halogenated hydrocarbon-based compound, 3) an alcohol-based compound, 4) an ether or an acetal-based compound, 5) a ketone or an aldehyde-based compound, and 6) an ester-based compound, and 7) A polyol compound, 8) a carboxylic acid or an anhydride thereof, 9) a phenol compound, 10) a nitrogen-containing compound, 11) a sulfur-containing compound, and 12) a fluorine-containing compound. The stripper preferably contains a nitrogen-containing compound, more preferably an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

非環狀含氮化合物較佳為具有羥基的非環狀含氮化合 物。具體而言，例如可列舉：單異丙醇胺、二異丙醇胺、三異丙醇胺、N-乙基乙醇胺、N,N-二丁基乙醇胺、N-丁基乙醇胺、單乙醇胺、二乙醇胺、三乙醇胺等，較佳為單乙醇胺、二乙醇胺、三乙醇胺，更佳為單乙醇胺(H2NCH2CH2OH)。另外，環狀含氮化合物可列舉：異喹啉、咪唑、N-乙基嗎啉、ε-己內醯胺、喹啉、1,3-二甲基-2-咪唑啶酮、α-甲基吡啶、β-甲基吡啶、γ-甲基吡啶、2-甲基哌啶、3-甲基哌啶、4-甲基哌啶、哌嗪、哌啶、吡嗪、吡啶、吡咯啶、N-甲基-2-吡咯啶酮、N-苯基嗎啉、2,4-二甲基吡啶、2,6-二甲基吡啶等，較佳為N-甲基-2-吡咯啶酮、N-乙基嗎啉，更佳為N-甲基-2-吡咯啶酮(NMP)。 The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specific examples thereof include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N,N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, and the like. Diethanolamine, triethanolamine or the like is preferably monoethanolamine, diethanolamine or triethanolamine, more preferably monoethanolamine (H 2 NCH 2 CH 2 OH). Further, examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, and α-A. Pyridine, β-methylpyridine, γ-methylpyridine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-dimethylpyridine, 2,6-lutidine, etc., preferably N-methyl-2-pyrrolidone N-ethylmorpholine, more preferably N-methyl-2-pyrrolidone (NMP).

剝離液較佳為含有非環狀含氮化合物及環狀含氮化合物，其中，更佳為含有作為非環狀含氮化合物的選自單乙醇胺、二乙醇胺及三乙醇胺中的至少一種與作為環狀含氮化合物的選自N-甲基-2-吡咯啶酮及N-乙基嗎啉中的至少一種，進而佳為含有單乙醇胺與N-甲基-2-吡咯啶酮。 The stripping liquid preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound, and more preferably contains at least one selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine as acyclic nitrogen-containing compound. The nitrogen-containing compound is at least one selected from the group consisting of N-methyl-2-pyrrolidone and N-ethylmorpholine, and further preferably contains monoethanolamine and N-methyl-2-pyrrolidone.

於利用剝離液來進行去除時，只要將形成於第1著色圖案12上的抗蝕劑圖案52去除即可，即便於在第1著色圖案12的側壁上附著有作為蝕刻產物的堆積物的情形時，所述堆積物亦可未完全被去除。所謂堆積物，是指蝕刻產物附著堆積於著色層的側壁上而成者。 When the removal is performed by the peeling liquid, the resist pattern 52 formed on the first colored pattern 12 may be removed, and even if deposits as etching products adhere to the side walls of the first colored pattern 12, The deposit may also not be completely removed. The term "deposited material" means that the etching product adheres to the side wall of the colored layer.

剝離液理想的是相對於剝離液100質量份而非環狀含氮化合物的含量為9質量份以上、11質量份以下，且相對於剝離液 100質量份而環狀含氮化合物的含量為65質量份以上、70質量份以下。另外，剝離液較佳為利用純水將非環狀含氮化合物與環狀含氮化合物的混合物稀釋而成者。 It is preferable that the peeling liquid is contained in an amount of 9 parts by mass or more and 11 parts by mass or less with respect to 100 parts by mass of the peeling liquid instead of the cyclic nitrogen-containing compound, and is relative to the stripping liquid. The content of the cyclic nitrogen-containing compound is 100 parts by mass or more and 70 parts by mass or less. Further, the peeling liquid is preferably one obtained by diluting a mixture of the acyclic nitrogen-containing compound and the cyclic nitrogen-containing compound with pure water.

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來作為所述以外的步驟。例如於進行所述著色組成物層形成步驟、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。 Furthermore, the manufacturing method of the present invention may include a step known as a method of producing a color filter for a solid-state image sensor as a step other than the above. For example, after the coloring composition layer forming step, the exposing step, and the pattern forming step, a hardening step of hardening the formed coloring pattern by heating and/or exposure may be included as needed.

另外，於使用本發明的著色組成物的情形時，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著色組成物所致的污染，較佳為將與上文所述的本組成物有關的溶劑用作清洗液。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著色組成物的清洗去除。 Further, in the case of using the colored composition of the present invention, for example, clogging of the nozzle or the piping portion of the coating device discharge portion or adhesion, sedimentation, and drying of the colored composition or pigment in the coater may occur. Pollution and so on. Therefore, in order to efficiently clean the contamination caused by the coloring 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 colored 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，更佳為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. Mixed in two In the above case, 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, more preferably from 20/80 to 80/20. More preferably, it is a mixed solvent of Propyleneglycol monomethylether acetate (PGMEA) and Propyleneglycol monomethylether (PGME) in a ratio of 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因使用本發明的著色組成物，故可進行曝光容限(margin)優異的曝光，且所形成的著色圖案(著色畫素)的圖案形狀優異，圖案表面的粗糙或顯影部的殘渣得到抑制，故顏色特性變優異。 Since the color filter of the present invention uses the coloring composition of the present invention, it is possible to perform exposure with excellent exposure margin, and the pattern shape of the formed color pattern (colored pixel) is excellent, and the surface of the pattern is rough or Since the residue of the developing unit is suppressed, the color characteristics are excellent.

本發明的彩色濾光片可較佳地用於CCD、CMOS等固體攝像元件，特別適於超過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 preferably used for 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2.0μm以下，更佳為1.0μm以下，進而佳為0.7μm以下。 In addition, the thickness of the colored pattern (colored pixel) of the color filter of the present invention is preferably 2.0 μm or less, more preferably 1.0 μm or less, and still more preferably 0.7 μm or less.

另外，著色圖案(著色畫素)的尺寸(圖案寬度)較佳為2.5μm以下，更佳為2.0μm以下，尤佳為1.7μm以下。 Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and still more preferably 1.7 μm or less.

<固體攝像元件> <Solid image sensor>

本發明的固體攝像元件具備上文已述的本發明的彩色濾光片。本發明的固體攝像元件的構成為具備本發明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 solid-state imaging device of the present invention includes the color filter of the present invention described above. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has a configuration that functions as a solid-state imaging device, and the configuration is as follows.

所述固體攝像元件為以下構成：於支持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元件保護膜，於所述元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, etc.) and a polycrystalline germanium or the like are provided on a 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 An element protective film containing tantalum nitride or the like is formed, and the color filter for a solid-state imaging device of the present invention is provided on the element protective film.

進而，亦可為於所述元件保護層上且彩色濾光片之下(靠近支持體之側)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 element protective layer 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.

<圖像顯示裝置> <Image display device>

本發明的彩色濾光片不僅可用於所述固體攝像元件，而且可用於液晶顯示裝置或有機EL顯示裝置等圖像顯示裝置，特別適於液晶顯示裝置的用途。具備本發明的彩色濾光片的液晶顯示裝置可顯示以下圖像：顯示圖像的色調良好且顯示特性優異的高畫質圖像。 The color filter of the present invention can be used not only for the solid-state imaging device but also for an image display device such as a liquid crystal display device or an organic EL display device, and is particularly suitable for use in a liquid crystal display device. The liquid crystal display device including the color filter of the present invention can display a high-quality image in which the hue of the display image is good and the display characteristics are excellent.

關於顯示裝置的定義或各顯示裝置的詳細情況，例如是記載於「電子顯示器元件(佐佐木昭夫著，工業調查會(股)，1990 年發行)」、「顯示器元件(伊吹順章著，產業圖書(股)，平成元年發行)」等中。另外，關於液晶顯示裝置，例如是記載於「下一代液晶顯示技術(內田龍男編輯，工業調查會(股)，1994年發行)」中。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「下一代液晶顯示技術」中記載的各種方式的液晶顯示裝置。 The definition of the display device or the details of each display device is described, for example, in "Electronic display components" (Sasaki Sasaki, Industrial Investigation Association, 1990) "Annual release", "display components (Ibuki Shun, industrial books (shares), issued in the first year of Heisei)" and so on. In addition, the liquid crystal display device is described in, for example, "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 applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "next-generation liquid crystal display technology".

本發明的彩色濾光片亦可用於彩色薄膜電晶體(Thin Film Transistor，TFT)方式的液晶顯示裝置。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)」中。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(Optically Compensated Splay，OCS)、邊緣場切換(Fringe Field Switching，FFS)及反射光學補償彎曲(Reflective-Optically Compensated Bend，R-OCB)等中。 The color filter of the present invention can also be used in 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 an enlarged liquid crystal display such as a transverse electric field driving method such as In-Plane Switching (IPS) or a pixel division method such as multi-domain vertical alignment (MVA). Device or Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optically Compensated Splay (OCS), 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。於COA方式的液晶顯示裝置中，對彩色濾光片層的要求特性除了上文所述般的通常的要求特性以外，有時還需要對層間絕緣膜的要求特性、即低介電常數及耐剝離液性。於本發明的彩色濾光片中，因使用色相優異的色素多聚物，故顏色純度、光透射性等良好且著色圖案(畫 素)的色調優異，故可提供一種解析度高且長期耐久性優異的COA方式的液晶顯示裝置。再者，為了滿足低介電常數的要求特性，亦可於彩色濾光片層上設置樹脂被膜。 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. In the liquid crystal display device of the COA type, in addition to the usual required characteristics as described above, the required characteristics of the color filter layer may require characteristics of the interlayer insulating film, that is, low dielectric constant and resistance. Stripping liquidity. In the color filter of the present invention, since a coloring matter polymer excellent in hue is used, color purity, light transmittance, and the like are good and a coloring pattern is drawn. Since the color tone is excellent, it is possible to provide a COA liquid crystal display device having high resolution and excellent long-term durability. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

關於該些圖像顯示方式，例如是記載於「電致發光(Electroluminescence，EL)、電漿顯示面板(Plasma Display Panel，PDP)、液晶顯示器(Liquid Crystal Display，LCD)顯示器-技術與市場的最新動向-(東麗研究中心(Toray Research Center)調查研究部門，2001年發行)」的43頁等中。 These image display methods are described, for example, in "Electroluminescence (EL), Plasma Display Panel (PDP), Liquid Crystal Display (LCD) displays - technology and market. Trends - (Toray Research Center, Research and Research Department, issued in 2001), 43 pages, etc.

具備本發明的彩色濾光片的液晶顯示裝置除了本發明的彩色濾光片以外，是由電極基板、偏光膜、相位差膜、背光、間隔件(spacer)、視角保障膜等各種構件所構成。本發明的彩色濾光片可應用於由該些公知的構件所構成的液晶顯示裝置中。關於該些構件，例如是記載於「'94液晶顯示器周邊材料-化學品的市場(島健太郎，CMC(股)，1994年發行)」、「2003液晶相關市場的現狀與將來展望(下卷)(表良吉，富士凱美萊總研(股)，2003年發行)」中。 The liquid crystal display device including the color filter of the present invention comprises, in addition to the color filter of the present invention, an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle securing film. . The color filter of the present invention can be applied to a liquid crystal display device composed of such known members. For example, the "94 liquid crystal display peripheral materials - chemicals market (Ichishima Kentaro, CMC (share), issued in 1994)", "2003 liquid crystal related market status and future prospects (volume) (Former Liangji, Fuji Kamelai Institute (share), issued in 2003).

關於背光，是記載於「國際信息顯示學會會議記錄(SID meeting Digest)」(1380(2005))(A.今野(A.Konno)等人)或月刊顯示器的2005年12月號的18頁~24頁(島康裕)及該文獻25頁~30頁(八木隆明)等中。 The backlight is recorded on the 18th page of the December 2005 issue of the "SID meeting Digest" (1380 (2005)) (A. Konno et al.) or the monthly display. 24 pages (Island Kang Yu) and the document 25 to 30 pages (Yamu Longming) and so on.

若將本發明的彩色濾光片用於液晶顯示裝置，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 in a liquid crystal display device, high contrast can be achieved when combined with a three-wavelength tube of a conventionally known cold cathode tube, and By setting the red, green, and blue LED light sources (RGB-LEDs) as backlights, it is possible to provide a liquid crystal display device having high brightness and high color reproducibility.

[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。 The invention is more specifically illustrated by the following examples. The materials, the amounts, the ratios, the treatment contents, the treatment procedures, 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.

色素多聚物的合成例 Synthesis example of pigment polymer

下述氧雜蒽1~氧雜蒽4包括在所述色素多聚物的較佳形態(A1)中。下述氧雜蒽5包括在所述色素多聚物的較佳形態(A2)中。下述氧雜蒽6包括在所述色素多聚物的較佳形態(A3)中。下述氧雜蒽7、氧雜蒽8包括在所述色素多聚物的較佳形態(A4)中。 The following xanthene 1 to xanthene 4 is included in the preferred form (A1) of the dye polymer. The following xanthene 5 is included in the preferred form (A2) of the dye polymer. The following oxonium 6 is included in the preferred form (A3) of the dye polymer. The following xanthene 7 and xanthene 8 are included in the preferred form (A4) of the dye polymer.

<氧雜蒽1的合成> <Synthesis of xanthene 1>

使玫瑰紅(Rhodamine)B 20.0g(41.8mmol)溶解於 氯仿125g中後，一面利用冰浴進行冷卻一面滴加***9.6g(62.6mmol)。其後，於外溫65℃下加熱3小時間。冷卻至20℃為止後，一面利用冰浴進行冷卻一面添加甲基丙烯酸2-羥基乙酯9.8g(75.2mmol)，添加三乙胺30.8g(304mmol)。將內溫調整為20℃並攪拌3小時後添加氯仿100g，利用水進行分液後，將氯仿層濃縮。將所得的濃縮物添加至甲醇100mL中，添加三氟甲基磺酸四丁基銨鹽16.4g(41.8mmol)。利用乙酸乙酯200mL、水100mL進行分液，將乙酸乙酯層濃縮，由此獲得18.0g的單體X。 Rhodamine B 20.0g (41.8mmol) was dissolved in After 125 g of chloroform, 9.6 g (62.6 mmol) of phosphorus oxychloride was added dropwise while cooling with an ice bath. Thereafter, it was heated at an external temperature of 65 ° C for 3 hours. After cooling to 20 ° C, 9.8 g (75.2 mmol) of 2-hydroxyethyl methacrylate was added while cooling with an ice bath, and 30.8 g (304 mmol) of triethylamine was added. The internal temperature was adjusted to 20 ° C and stirred for 3 hours, and then 100 g of chloroform was added thereto, and the mixture was separated by water, and then the chloroform layer was concentrated. The obtained concentrate was added to 100 mL of methanol, and 16.4 g (41.8 mmol) of tetrabutylammonium trifluoromethanesulfonate was added. The mixture was separated by ethyl acetate (200 mL) and water (100 mL), and the ethyl acetate layer was concentrated to obtain 18.0 g of the monomer X.

於三口燒瓶中添加單體X(8.2g)、甲基丙烯酸(0.46g)、十二烷基硫醇(0.255g)、丙二醇1-單甲醚2-乙酸酯(以下亦稱為「PGMEA」)(23.3g)，於氮氣環境下加熱至80℃。於該溶液中用3小時滴加單體X(8.2g)、甲基丙烯酸(1.075g)、十二烷基硫醇(0.255g)、2,2'-偶氮雙(異丁酸)二甲酯[商品名：V601，和光純藥工業(股)製造](0.58g)、PGMEA(23.3g)的混合溶液。其後攪拌4小時後，升溫至90℃，加熱攪拌2小時後，放置冷卻而獲得中間體(MD-1)的PGMEA溶液。冷卻後滴加至甲醇/離子交換水=100mL/10mL的混合溶劑中進行再沈澱。於40℃下進行2天送風乾燥後，獲得色素多聚物(氧雜蒽1)7.9g。 Monomer X (8.2 g), methacrylic acid (0.46 g), dodecyl mercaptan (0.255 g), and propylene glycol 1-monomethyl ether 2-acetate were added to a three-necked flask (hereinafter also referred to as "PGMEA". () (23.3 g), heated to 80 ° C under a nitrogen atmosphere. In this solution, monomer X (8.2 g), methacrylic acid (1.075 g), dodecyl mercaptan (0.255 g), 2,2'-azobis(isobutyric acid) were added dropwise over 3 hours. A mixed solution of a methyl ester [trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.] (0.58 g) and PGMEA (23.3 g). After stirring for 4 hours, the temperature was raised to 90 ° C, and the mixture was heated and stirred for 2 hours, and then left to cool to obtain a PGMEA solution of the intermediate (MD-1). After cooling, it was added dropwise to a mixed solvent of methanol/ion exchanged water = 100 mL/10 mL to carry out reprecipitation. After air drying at 40 ° C for 2 days, 7.9 g of a pigment polymer (oxaxene 1) was obtained.

藉由GPC測定所確認的色素多聚物(氧雜蒽1)的重量平均分子量(Mw)為7,700。另外，根據使用0.1N氫氧化鈉水溶液的滴定，酸值為37mgKOH/g。 The weight average molecular weight (Mw) of the dye polymer (xanthene 1) confirmed by GPC measurement was 7,700. Further, the acid value was 37 mgKOH/g according to the titration using a 0.1 N aqueous sodium hydroxide solution.

<氧雜蒽2~氧雜蒽4的合成> <Synthesis of xanthene 2~oxaxene 4>

如下述表所記載般變更合成例1中的單體X的抗衡陰離子，除此以外進行相同的操作，合成色素多聚物(氧雜蒽2~氧雜蒽4)。 The dye polymer (xanthene 2 to xanthene 4) was synthesized by performing the same operation except that the counter anion of the monomer X in Synthesis Example 1 was changed as described in the following table.

<氧雜蒽5的合成> <Synthesis of xanthene 5>

將以下單體(氧雜蒽單體55mol%與甲基丙烯酸45mol%)共聚合而合成氧雜蒽5。 Xanthanium 5 was synthesized by copolymerizing the following monomers (55 mol% of xanthene monomer and 45 mol% of methacrylic acid).

使C.I.酸性紅289 27.4g(41.8mmol)溶解於氯仿125g中後，一面利用冰浴進行冷卻一面滴加***9.6g(62.6mmol)。其後，於外溫65℃下攪拌3小時。冷卻至20℃為止後，一面利用冰浴進行冷卻一面添加4-胺基苯乙烯9.0g(75.2mmol)，添加三乙胺30.8g(304mmol)。將內溫調整為20℃並攪拌3小時後添加氯仿100g，利用水進行分液後，將氯仿層濃縮，由此獲得15.0g的單體Z。再者，此時自水層獲得10.0g的單體 Z2。 After dissolving 27.4 g (41.8 mmol) of C.I. Acid Red 289 in 125 g of chloroform, 9.6 g (62.6 mmol) of phosphorus oxychloride was added dropwise while cooling with an ice bath. Thereafter, the mixture was stirred at an external temperature of 65 ° C for 3 hours. After cooling to 20 ° C, 9.0 g (75.2 mmol) of 4-aminostyrene was added while cooling with an ice bath, and 30.8 g (304 mmol) of triethylamine was added. The internal temperature was adjusted to 20 ° C and stirred for 3 hours, and then 100 g of chloroform was added thereto, and the mixture was separated by water, and then the chloroform layer was concentrated to obtain 15.0 g of the monomer Z. Furthermore, at this time, 10.0 g of monomer was obtained from the water layer. Z2.

於三口燒瓶中添加單體Z(8.2g)、甲基丙烯酸(0.46g)、十二烷基硫醇(0.255g)、PGMEA(23.3g)，於氮氣環境下加熱至80℃。於該溶液中用4小時滴加單體Z(8.2g)、甲基丙烯酸(1.075g)、十二烷基硫醇(0.255g)、2,2'-偶氮雙(異丁酸)二甲酯[商品名：V601，和光純藥工業(股)製造](0.58g)、PGMEA(23.3g)的混合溶液。其後攪拌4小時後，升溫至93℃，加熱攪拌2小時後，放置冷卻而獲得中間體(MD-1)的PGMEA溶液。冷卻後，滴加至甲醇/離子交換水=100mL/10mL的混合溶劑中進行再沈澱。於40℃下進行2天送風乾燥後，獲得色素多聚物(氧雜蒽5)7.4g。 Monomer Z (8.2 g), methacrylic acid (0.46 g), dodecyl mercaptan (0.255 g), and PGMEA (23.3 g) were added to a three-necked flask, and the mixture was heated to 80 ° C under a nitrogen atmosphere. In this solution, monomer Z (8.2 g), methacrylic acid (1.075 g), dodecyl mercaptan (0.255 g), 2,2'-azobis(isobutyric acid) were added dropwise over 4 hours. A mixed solution of a methyl ester [trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.] (0.58 g) and PGMEA (23.3 g). After stirring for 4 hours, the temperature was raised to 93 ° C, and the mixture was heated and stirred for 2 hours, and then left to cool to obtain a PGMEA solution of the intermediate (MD-1). After cooling, it was added dropwise to a mixed solvent of methanol/ion exchanged water = 100 mL/10 mL to carry out reprecipitation. After air drying at 40 ° C for 2 days, 7.4 g of a pigment polymer (xanthene 5) was obtained.

藉由GPC測定所確認的色素多聚物(氧雜蒽5)的重量平均分子量(Mw)為6,500。另外，根據使用0.1N氫氧化鈉水溶液的滴定，酸值為38mgKOH/g。 The weight average molecular weight (Mw) of the dye polymer (xanthene 5) confirmed by GPC measurement was 6,500. Further, the acid value was 38 mgKOH/g according to the titration using a 0.1 N aqueous sodium hydroxide solution.

<氧雜蒽6的合成> <Synthesis of xanthene 6>

氧雜蒽單體Y 61mol%與甲基丙烯酸39mol% Xanthene monomer Y 61 mol% and methacrylic acid 39 mol%

[化50] [化50]

將玫瑰紅B 20.0g(41.8mmol)與下述聚合性陰離子的鉀鹽24.3g(41.8mmol)於甲醇200ml中進行鹽交換，添加水1L並利用氯仿500ml進行萃取，加以濃縮，獲得25g的單體Y。 20.0 g (41.8 mmol) of rose bengal B was salt-exchanged with 24.3 g (41.8 mmol) of the potassium salt of the following polymeric anion in 200 ml of methanol, and 1 L of water was added thereto, and the mixture was extracted with 500 ml of chloroform, and concentrated to obtain a 25 g single. Body Y.

於三口燒瓶中添加單體Y(8.2g)、甲基丙烯酸(0.46g)、十二烷基硫醇(0.255g)、PGMEA(23.3g)，於氮氣環境下加熱至80℃。於該溶液中用5小時滴加單體Y(8.2g)、甲基丙烯酸(1.075g)、十二烷基硫醇(0.255g)、2,2'-偶氮雙(異丁酸)二甲酯[商品名：V601，和光純藥工業(股)製造](0.58g)、PGMEA(23.3g)的混合溶液。其後攪拌5小時後，升溫至93℃，加熱攪拌2小時後，放置冷卻而獲得中間體(MD-1)的PGMEA溶液。冷卻後，滴加至甲醇/離子交換水=100mL/10mL的混合溶劑中進行再沈澱。於40℃下進行2天送風乾燥後，獲得色素多聚物(氧雜蒽6)4.8g。 Monomer Y (8.2 g), methacrylic acid (0.46 g), dodecyl mercaptan (0.255 g), and PGMEA (23.3 g) were added to a three-necked flask, and the mixture was heated to 80 ° C under a nitrogen atmosphere. In this solution, monomer Y (8.2 g), methacrylic acid (1.075 g), dodecyl mercaptan (0.255 g), 2,2'-azobis(isobutyric acid) II were added dropwise over 5 hours. A mixed solution of a methyl ester [trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.] (0.58 g) and PGMEA (23.3 g). After stirring for 5 hours, the temperature was raised to 93 ° C, and the mixture was heated and stirred for 2 hours, and then left to cool to obtain a PGMEA solution of the intermediate (MD-1). After cooling, it was added dropwise to a mixed solvent of methanol/ion exchanged water = 100 mL/10 mL to carry out reprecipitation. After air drying at 40 ° C for 2 days, 4.8 g of a pigment polymer (oxaxene 6) was obtained.

藉由GPC測定所確認的色素多聚物(氧雜蒽6)的重量平均分子量(Mw)為6,900。 The weight average molecular weight (Mw) of the dye polymer (xanthene 6) confirmed by GPC measurement was 6,900.

<氧雜蒽7的合成> <Synthesis of xanthene 7>

將以下單體(氧雜蒽單體Z2(51mol%)與甲基丙烯酸(49mol%))共聚合而合成氧雜蒽7。 Xanthan 7 was synthesized by copolymerizing the following monomer (xanthene monomer Z2 (51 mol%) with methacrylic acid (49 mol%)).

於三口燒瓶中添加氧雜蒽5的合成中所得的單體Z2(8.2 g)、甲基丙烯酸(0.46g)、十二烷基硫醇(0.255g)、丙二醇1-單甲醚2-乙酸酯(以下亦稱為「PGMEA」)(23.3g)，於氮氣環境下加熱至80℃。於該溶液中用3小時滴加單體Z2(8.2g)、甲基丙烯酸(1.075g)、十二烷基硫醇(0.255g)、2,2'-偶氮雙(異丁酸)二甲酯[商品名：V601，和光純藥工業(股)製造](0.58g)、PGMEA(23.3g)的混合溶液。其後攪拌4小時後，升溫至90℃，加熱攪拌2小時後，放置冷卻而獲得中間體(MD-1)的PGMEA溶液。冷卻後，滴加至甲醇/離子交換水=100mL/10mL的混合溶劑中進行再沈澱。於40℃下進行2天送風乾燥後，獲得色素多聚物(氧雜蒽7)7.8g。 The monomer Z2 obtained in the synthesis of xanthene 5 was added to a three-necked flask (8.2 g), methacrylic acid (0.46g), dodecyl mercaptan (0.255g), propylene glycol 1-monomethyl ether 2-acetate (hereinafter also referred to as "PGMEA") (23.3g), in a nitrogen atmosphere Heat to 80 ° C under. In this solution, monomer Z2 (8.2 g), methacrylic acid (1.075 g), dodecyl mercaptan (0.255 g), 2,2'-azobis(isobutyric acid) were added dropwise over 3 hours. A mixed solution of a methyl ester [trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.] (0.58 g) and PGMEA (23.3 g). After stirring for 4 hours, the temperature was raised to 90 ° C, and the mixture was heated and stirred for 2 hours, and then left to cool to obtain a PGMEA solution of the intermediate (MD-1). After cooling, it was added dropwise to a mixed solvent of methanol/ion exchanged water = 100 mL/10 mL to carry out reprecipitation. After air drying at 40 ° C for 2 days, 7.8 g of a pigment polymer (oxaxene 7) was obtained.

藉由GPC測定所確認的色素多聚物(氧雜蒽7)的重量平均分子量(Mw)為8,200。另外，根據使用0.1N氫氧化鈉水溶液的滴定，酸值為38mgKOH/g。 The weight average molecular weight (Mw) of the dye polymer (oxaxene 7) confirmed by GPC measurement was 8,200. Further, the acid value was 38 mgKOH/g according to the titration using a 0.1 N aqueous sodium hydroxide solution.

<氧雜蒽8的合成> <Synthesis of xanthene 8>

(以下單體的共聚物) (copolymer of the following monomers)

依照日本專利特開2011-242752號公報的段落0165中記載的造鹽化合物(A-1)的製造方法，獲得色素多聚物(氧雜蒽8)。藉由GPC測定所確認的色素多聚物(氧雜蒽7)的重量平均分子量(Mw)為15,000。 A dye multimer (oxaxene 8) is obtained according to the method for producing a salt-forming compound (A-1) described in paragraph 0165 of JP-A-2011-242752. The weight average molecular weight (Mw) of the dye polymer (oxaxene 7) confirmed by GPC measurement was 15,000.

[化53] [化53]

著色組成物的製備 Preparation of coloring composition

藍色顏料分散液的製備 Preparation of blue pigment dispersion

如以下般製備藍色顏料分散液1。 The blue pigment dispersion 1 was prepared as follows.

藉由珠磨機(氧化鋯珠，直徑為0.3mm)將包含10.0份的C.I.顏料藍(Pigment Blue)15：6(藍色顏料，平均粒子尺寸為55nm)、及3.0份的作為顏料分散劑的迪斯帕畢克(Disperbyk)111、70.0份的PGMEA及17.0份的環己酮的混合液混合、分散3小時，製備顏料分散液。其後，進而使用帶有減壓機構的高壓分散機NANO-3000-10(日本BEE(股)製造)於2000kg/cm3的壓力下將流量設定為500g/min來進行分散處理。將該分散處理反覆10次，獲得實施例或比較例的著色組成物中所用的藍色用顏料分散液1(C.I.顏料藍15：6分散液，顏料濃度為10質量%)。 10.0 parts of CI Pigment Blue 15:6 (blue pigment, average particle size 55 nm) and 3.0 parts as a pigment dispersant by a bead mill (zirconia beads, diameter 0.3 mm) A mixture of Disperbyk 111, 70.0 parts of PGMEA and 17.0 parts of cyclohexanone was mixed and dispersed for 3 hours to prepare a pigment dispersion. Thereafter, a high-pressure disperser NANO-3000-10 (manufactured by BEE Co., Ltd.) equipped with a pressure reducing mechanism was used to carry out a dispersion treatment by setting the flow rate to 500 g/min under a pressure of 2000 kg/cm 3 . This dispersion treatment was repeated 10 times, and the blue pigment dispersion liquid 1 (CI Pigment Blue 15:6 dispersion liquid having a pigment concentration of 10% by mass) used in the colored composition of the example or the comparative example was obtained.

實施例0的製備 Preparation of Example 0

將下述各成分混合並加以分散、溶解，獲得實施例0的著色組成物。 The following components were mixed, dispersed, and dissolved to obtain the colored composition of Example 0.

再者，於製備實施例0之前，進行使用溶劑的蒸餾及使用乾燥劑將系中的甲苯、水分去除，對染料、顏料利用蒸餾水反覆進 行清洗、乾燥，將系中的Na離子、K離子去除。關於其他單體等原材料，於使用前進行純化而去除雜質(甲苯、Na離子、K離子等)後，進行製備。 Further, before the preparation of Example 0, distillation using a solvent and removal of toluene and water in the system using a desiccant were carried out, and the dye and the pigment were repeatedly fed with distilled water. The cells are washed and dried to remove Na ions and K ions from the system. Raw materials such as other monomers are purified by purification to remove impurities (toluene, Na ions, K ions, etc.) before use, and then prepared.

．所述藍色用顏料分散液1 390.0份 . The blue pigment dispersion 1 390.0 parts

．鹼可溶性樹脂1(甲基丙烯酸苄酯55mol%與甲基丙烯酸45mol%的共聚物，重量平均分子量為10,000，以下稱為「B1」) 3.8份 . Alkali-soluble resin 1 (copolymer of benzyl methacrylate 55 mol% and methacrylic acid 45 mol%, weight average molecular weight 10,000, hereinafter referred to as "B1") 3.8 parts

．鹼可溶性樹脂2(以下樹脂，重量平均分子量為11,000，以下稱為「B2」) 1.0份 . Alkali-soluble resin 2 (the following resin, weight average molecular weight is 11,000, hereinafter referred to as "B2") 1.0 part

．硬化性化合物(以下結構的六官能單體，以下稱為「m1」) 9.0份 . Hardening compound (hexafunctional monomer of the following structure, hereinafter referred to as "m1") 9.0 parts

．光聚合起始劑(以下結構，以下稱為「I-1」，日本專利特開2011-158654號公報中記載) 8.5份 . Photopolymerization initiator (the following structure, hereinafter referred to as "I-1", Japanese Patent Laid-Open No. 2011-158654) 8.5 parts

．色素多聚物(氧雜蒽1) 固體成分為25份 . Pigment polymer (oxaxan 1) solid content of 25 parts

．氟系界面活性劑(迪愛生(DIC)(股)製造，F-475) 0.2份 . Fluorine-based surfactant (manufactured by Di Aisheng (DIC) Co., Ltd., F-475) 0.2 parts

．PGMEA 260份 . PGMEA 260 copies

示出對實施例0的組成物中的以下成分的濃度進行測定所得的結果。 The results of measuring the concentrations of the following components in the composition of Example 0 are shown.

含水率：0.01質量%以下 Moisture content: 0.01% by mass or less

甲苯濃度：0.005ppm以下 Toluene concentration: 0.005ppm or less

Na離子濃度：0.005ppm以下 Na ion concentration: 0.005ppm or less

K離子濃度：0.005ppm以下 K ion concentration: 0.005ppm or less

含水率是藉由卡爾-費歇爾(Karl Fisher)法依據公知的方法進行測定。具體而言，使用卡爾-費歇爾水分計(三菱化學控股(Mitsubishi Chemical Holdings)公司製造的KF-06)對測定資料的水分量進行測定，以水分量/測定資料的質量×100的形式測定 含水率。 The water content is measured by a Karl Fisher method according to a known method. Specifically, the moisture content of the measurement data was measured using a Karl Fischer moisture meter (KF-06 manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the mass of the water content/measurement data was measured in the form of ×100. Moisture content.

甲苯濃度是依據公知的方法利用氣相層析儀製作校準曲線後進行定量。於本申請案中，將組成物的各原材料真空乾燥，確認到甲苯含量為0.005ppm以下後，於組成物的製備時另添加甲苯，由此製作甲苯濃度不同的組成物。 The toluene concentration was quantified by preparing a calibration curve by a gas chromatograph according to a known method. In the present application, each of the raw materials of the composition was vacuum dried, and it was confirmed that the toluene content was 0.005 ppm or less, and then toluene was additionally added during the preparation of the composition to prepare a composition having a different toluene concentration.

於實施例0的組成物中追加水、甲苯、Na離子源(具體而言製備氯化鈉的甲醇溶液並添加該溶液，藉此進行製備)、K離子源(具體而言製備溴化鉀的甲醇溶液並添加該溶液，藉此進行製備)，製作實施例1~實施例6的樣品。 To the composition of Example 0, water, toluene, and a source of Na ions (specifically, a methanol solution of sodium chloride was prepared and the solution was added thereto to prepare), and a source of K ions (specifically, potassium bromide was prepared). The samples of Examples 1 to 6 were prepared by adding the solution in methanol and preparing the mixture.

另外，除了如下述表般變更色素多聚物、硬化性化合物(單體)、光聚合起始劑以外，與實施例0同樣地製作實施例7~實施例77及比較例1~比較例16的組成物。 Further, Example 7 to Example 77 and Comparative Example 1 to Comparative Example 16 were produced in the same manner as in Example 0 except that the dye polymer, the curable compound (monomer), and the photopolymerization initiator were changed as shown in the following Table. Composition.

硬化性化合物(單體(m-2)) Hardening compound (monomer (m-2))

硬化性化合物(單體(m-3)) Hardening compound (monomer (m-3))

[化58] [化58]

硬化性化合物(單體(m-4)) Hardening compound (monomer (m-4))

光聚合起始劑(I-2，巴斯夫(BASF)製造的OXE-02) Photopolymerization initiator (I-2, OXE-02 manufactured by BASF)

光聚合起始劑(I-3，巴斯夫(BASF)製造的豔佳固(Irgacure)907) Photopolymerization initiator (I-3, Irgacure 907, manufactured by BASF)

[化61] [化61]

<長期經時穩定性的評價> <Evaluation of long-term stability over time>

對實施例及比較例中所得的組成物的初期的黏度(Vi)進行測定，於密閉容器中於23℃下經時100天。另外，測定經時後的黏度(Vd)。計算| Vi-Vd |/Vi×100%的值，根據該值進行評價。實用上理想的是判定基準3以上。將結果示於下述表中。 The initial viscosity (Vi) of the compositions obtained in the examples and the comparative examples was measured and passed through a sealed container at 23 ° C for 100 days. Further, the viscosity (Vd) after the passage of time was measured. Calculate | Vi-Vd | / Vi × 100% of the value, based on this value for evaluation. It is desirable to use the criterion 3 or more in practical use. The results are shown in the following table.

6：黏度變化率為0.5%以下(特別良好) 6: The viscosity change rate is 0.5% or less (especially good)

5：黏度變化率高於0.5%且為3%以下(良好) 5: viscosity change rate is higher than 0.5% and less than 3% (good)

4：黏度變化率高於3%且為7%以下(稍良好) 4: The viscosity change rate is higher than 3% and less than 7% (slightly good)

3：黏度變化率高於7%且為8%以下(容許範圍內) 3: The viscosity change rate is higher than 7% and less than 8% (within the allowable range)

2：黏度變化率高於8%且為12%以下(容許範圍外) 2: The viscosity change rate is higher than 8% and less than 12% (outside the allowable range)

1：黏度變化率高於12%(容許範圍外) 1: viscosity change rate is higher than 12% (outside the allowable range)

利用著色組成物的彩色濾光片的製作 Production of color filters using coloring compositions

<圖案形成> <pattern formation>

將如上文所述般製備的實施例及比較例的著色組成物分別塗佈於玻璃基板上，形成著色組成物層(塗佈膜)。繼而，以該塗佈膜的乾燥膜厚成為0.6μm的方式，利用100℃的熱板進行120秒鐘的加熱處理(預烘烤)。 The colored compositions of the examples and the comparative examples prepared as described above were respectively applied onto a glass substrate to form a colored composition layer (coating film). Then, heat treatment (prebaking) was performed for 120 seconds using a hot plate of 100 ° C so that the dry film thickness of the coating film was 0.6 μm.

<低氧濃度下的長時間耐光性> <Long-term light resistance at low oxygen concentration>

於實施例及比較例中所得的成膜品(圖案)上被覆蓋玻片 (glass cover)，(成為供氧被阻斷的低氧狀態)使用作為氙氣燈光源的耐光性試驗器的須賀試驗機(股)製造的SX75F，以500勒克斯的照度照射2000小時而進行耐光性試驗。 Covered slides on film-forming articles (patterns) obtained in the examples and comparative examples (glass cover), (slow-oxygen state in which oxygen is blocked). SX75F manufactured by Suga Tester Co., Ltd., which is a light-resistance tester for a xenon lamp source, is irradiated with illumination at 500 lux for 2000 hours for light resistance. test.

藉由大塚電子(股)製造的MCPD-2000來測定照射前後的色差(△E*ab)，進行評價。實用上理想的是判定基準3以上。將結果示於下述表中。 The color difference (ΔE*ab) before and after the irradiation was measured by MCPD-2000 manufactured by Otsuka Electronics Co., Ltd., and evaluated. It is desirable to use the criterion 3 or more in practical use. The results are shown in the following table.

6：0.5%以下(特別良好) 6: 0.5% or less (especially good)

5：高於0.5%且為1%以下(良好) 5: higher than 0.5% and less than 1% (good)

4：高於1%且為2%以下(稍良好) 4: above 1% and below 2% (slightly good)

3：高於2%且為3%以下(容許範圍內) 3: higher than 2% and less than 3% (within the allowable range)

2：高於3%且為5%以下(容許範圍外) 2: higher than 3% and less than 5% (outside the allowable range)

1：高於5%(容許範圍外) 1: higher than 5% (outside the allowable range)

<長期經時後的缺陷評價(異物增加率評價)> <Determination of defects after long-term transit time (evaluation of foreign body increase rate)>

將所述獲得的各感放射線性組成物以塗佈後的膜厚成為0.6μm的方式塗佈於矽晶圓上，其後於熱板上於100℃下加熱2分鐘而獲得著色組成物層。 Each of the obtained radiation sensitive compositions was applied onto a ruthenium wafer so that the film thickness after coating was 0.6 μm, and then heated on a hot plate at 100 ° C for 2 minutes to obtain a colored composition layer. .

對形成有著色組成物層的基板使用缺陷評價裝置ComPLUS(應用材料(Applied Materials)公司製造)，對大小為1.0μm以上的異物進行計數。 To the substrate on which the colored composition layer was formed, a defect evaluation device ComPLUS (manufactured by Applied Materials Co., Ltd.) was used, and foreign matter having a size of 1.0 μm or more was counted.

於著色組成物層的製備直後、及冷凍(-18℃)經時1個月後分別實施所述評價，按照下述判定基準來評價異物增加率。 The evaluation was carried out after the preparation of the colored composition layer and after freezing (-18 ° C) for one month, and the increase rate of the foreign matter was evaluated according to the following criteria.

再者，異物增加率是以(冷凍1個月後的異物數/剛製備後的 異物數)來算出。實用上理想的是判定基準3以上。將結果示於表中。 Furthermore, the increase rate of foreign matter is (the number of foreign objects after freezing for 1 month / just after preparation) The number of foreign objects is calculated. It is desirable to use the criterion 3 or more in practical use. The results are shown in the table.

(判定基準) (judgment basis)

6：小於1.1 6: Less than 1.1

5：1.1以上且小於1.3 5: 1.1 or more and less than 1.3

4：1.3以上且小於1.5 4: 1.3 or more and less than 1.5

3：1.5以上且小於2.0 3: 1.5 or more and less than 2.0

2：2.0以上且小於3.0 2: 2.0 or more and less than 3.0

1：3.0以上 1:3.0 or more

<長時間放置評價> <Long time evaluation>

(帶有底塗層的矽晶圓的製作) (Production of tantalum wafer with undercoat)

使用旋塗機將抗蝕劑CT-4000L溶液(富士膠片電子材料(Fujifilm Electronic Materials)(股)製造；基底透明劑)以膜厚成為0.1μm的方式塗佈於矽晶圓上，於220℃下加熱乾燥1小時而形成底塗層，獲得帶有底塗層的矽晶圓。 A resist CT-4000L solution (manufactured by Fujifilm Electronic Materials Co., Ltd.; base transparent agent) was applied onto a tantalum wafer at a film thickness of 0.1 μm using a spin coater at 220 ° C. The undercoat layer was formed by heating and drying for 1 hour to obtain a ruthenium wafer with an undercoat layer.

(著色圖案的製作) (production of coloring pattern)

利用旋塗法將實施例及比較例的著色組成物以塗佈後的膜厚成為0.6μm的方式塗佈於帶有底塗層的矽晶圓上，其後於熱板上於90℃下加熱2分鐘，獲得著色組成物層。 The coloring compositions of the examples and the comparative examples were applied onto a ruthenium wafer with an undercoat layer by a spin coating method so as to have a film thickness of 0.6 μm after coating, and then applied to a hot plate at 90 ° C. The mixture was heated for 2 minutes to obtain a colored composition layer.

繼而，對所得的著色組成物層使用i射線步進機曝光裝置FPA-3000i5+(佳能(Canon)(股)製造)，介隔遮罩以300mi/cm2來曝光1.0μm的島狀圖案。繼而，對曝光後的著色組成物層使用 氫氧化四甲基銨(TMAH)1.0%水溶液，於23℃下進行60秒鐘浸置顯影。其後，藉由旋轉噴淋(spin shower)來進行淋洗，進而以純水進行水洗，獲得著色圖案。 Then, the obtained coloring composition layer was irradiated with an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon), and an island pattern of 1.0 μm was exposed at 300 μm/cm 2 through a mask. Then, a 1.0% aqueous solution of tetramethylammonium hydroxide (TMAH) was used for the exposed coloring composition layer, and immersion development was carried out at 23 ° C for 60 seconds. Thereafter, the mixture was rinsed by a spin shower, and further washed with pure water to obtain a colored pattern.

使用測長掃描式電子顯微鏡(Scanning Electron Microscope，SEM)(商品名：S-7800H，日立製作所(股)製造)對所得的著色圖案的線寬進行觀察。對放置時間為72小時的情形的一畫素內的線寬的最大值與最小值之差於晶圓內測定任意10點並求出平均值。再者，於放置時間為0小時的情形時，於實施例、比較例中平均值均為<0.02μm。 The line width of the obtained colored pattern was observed using a Scanning Electron Microscope (SEM) (trade name: S-7800H, manufactured by Hitachi, Ltd.). The difference between the maximum value and the minimum value of the line width in one pixel in the case where the standing time was 72 hours was measured at the arbitrary 10 points in the wafer, and the average value was obtained. Further, in the case where the standing time was 0 hours, the average value in the examples and the comparative examples was <0.02 μm.

實用上理想的是判定基準3以上。將結果示於表中。 It is desirable to use the criterion 3 or more in practical use. The results are shown in the table.

(判定基準) (judgment basis)

6：小於0.02μm(最良好) 6: less than 0.02 μm (best)

5：0.02μm以上且小於0.04μm(良好) 5: 0.02 μm or more and less than 0.04 μm (good)

4：0.04μm以上且小於0.06μm(稍良好) 4: 0.04 μm or more and less than 0.06 μm (slightly good)

3：0.06μm以上且小於0.10μm(容許範圍內) 3: 0.06 μm or more and less than 0.10 μm (within the allowable range)

2：0.10μm以上且小於0.20μm(容許範圍外) 2: 0.10 μm or more and less than 0.20 μm (outside the allowable range)

1：0.20μm以上(容許範圍外) 1:0.20 μm or more (outside the allowable range)

<耐濕試驗後的缺陷評價(異物增加率評價)> <Determination of defects after moisture resistance test (evaluation of foreign matter increase rate)>

將實施例及比較例的組成物以塗佈後的膜厚成為0.6μm的方式塗佈於矽晶圓上，於熱板上於100℃下進行2分鐘加熱而獲得著色組成物層。其後，以1000mJ/cm2的曝光量進行全面i射線曝光，於熱板上進行200℃、10分鐘的追加加熱而製成初期樣品。 The composition of the examples and the comparative examples was applied onto a ruthenium wafer so as to have a film thickness of 0.6 μm after application, and heated on a hot plate at 100 ° C for 2 minutes to obtain a colored composition layer. Thereafter, total i-ray exposure was performed at an exposure amount of 1000 mJ/cm 2 , and additional heating was performed on a hot plate at 200 ° C for 10 minutes to prepare an initial sample.

將對初期樣品於110℃85%RH的條件下進行408小時的耐濕所得的樣品作為耐濕試驗後的樣品。 A sample obtained by subjecting the initial sample to moisture resistance under conditions of 110 ° C and 85% RH for 408 hours was used as a sample after the moisture resistance test.

對各樣品使用缺陷評價裝置ComPLUS(應用材料(Applied Materials)公司製造)，對大小為1.0μm以上的異物進行計數。按照下述判定基準來評價異物增加率。 For each sample, a foreign matter having a size of 1.0 μm or more was counted using a defect evaluation device ComPLUS (manufactured by Applied Materials). The foreign matter increase rate was evaluated in accordance with the following criteria.

再者，異物增加率是以(耐濕試驗後的樣品的異物數/初期樣品的異物數)來算出。實用上理想的是判定基準3以上。將結果示於表中。 Further, the increase rate of the foreign matter was calculated by (the number of foreign matter of the sample after the moisture resistance test/the number of foreign matter of the initial sample). It is desirable to use the criterion 3 or more in practical use. The results are shown in the table.

(判定基準) (judgment basis)

6：小於1.1 6: Less than 1.1

5：1.1以上且小於1.3 5: 1.1 or more and less than 1.3

4：1.3以上且小於1.5 4: 1.3 or more and less than 1.5

3：1.5以上且小於2.0 3: 1.5 or more and less than 2.0

2：2.0以上且小於3.0 2: 2.0 or more and less than 3.0

1：3.0以上 1:3.0 or more

<長時間熱循環試驗> <Long-term thermal cycle test>

對將實施例及比較例的組成物於以下的溫度條件下保管後的塗佈異物的增加率進行評價。 The rate of increase of the coated foreign matter after storage of the compositions of the examples and the comparative examples under the following temperature conditions was evaluated.

溫度條件(1)：30℃/72hr Temperature condition (1): 30 ° C / 72 hr

溫度條件(2)：23℃/72hr Temperature condition (2): 23 ° C / 72 hr

溫度條件(3)：5℃/72hr Temperature condition (3): 5 ° C / 72 hr

以溫度條件(1)、溫度條件(2)及溫度條件(3)的順序反 覆2次後對塗佈異物進行評價。 In the order of temperature condition (1), temperature condition (2) and temperature condition (3) The coated foreign matter was evaluated after covering twice.

<塗佈異物評價> <Coating foreign matter evaluation>

將著色組成物以塗佈後的膜厚成為0.6μm的方式塗佈於矽晶圓上，其後於熱板上於90℃下加熱2分鐘而獲得著色組成物層。 The colored composition was applied onto a ruthenium wafer so that the film thickness after coating was 0.6 μm, and then heated on a hot plate at 90 ° C for 2 minutes to obtain a colored composition layer.

對形成有著色組成物層的基板使用缺陷評價裝置ComPLUS(應用材料(Applied Materials)公司製造)，對大小為2.0μm以上的異物進行計數。 To the substrate on which the colored composition layer was formed, a defect evaluation device ComPLUS (manufactured by Applied Materials Co., Ltd.) was used, and foreign matter having a size of 2.0 μm or more was counted.

再者，異物增加率是以(熱循環試驗後的異物數/剛製備後的異物數)來算出，並按照以下分類進行評價。 Further, the increase rate of the foreign matter was calculated (the number of foreign matter after the heat cycle test/the number of foreign matter immediately after the heat cycle test), and was evaluated according to the following classification.

(判定基準) (judgment basis)

6：小於1.1(最良好) 6: less than 1.1 (best)

5：1.1以上且小於1.3(良好) 5: 1.1 or more and less than 1.3 (good)

4：1.3以上且小於1.5(稍良好) 4: 1.3 or more and less than 1.5 (slightly good)

3：1.5以上且小於2.0(容許範圍內) 3: 1.5 or more and less than 2.0 (within the allowable range)

2：2.0以上且小於4.0(容許範圍外) 2: 2.0 or more and less than 4.0 (outside the allowable range)

1：4.0以上(容許範圍外) 1:4.0 or above (outside the allowable range)

根據所述表所示的結果得知，藉由著色組成物中的鈉離子濃度及鉀離子濃度的至少一者為0.1ppm~10ppm，於長期放置於低溫度環境下的情形時，不易產生異物。 According to the results shown in the above table, at least one of the sodium ion concentration and the potassium ion concentration in the colored composition is 0.1 ppm to 10 ppm, and it is less likely to generate foreign matter when left in a low temperature environment for a long period of time. .

另外得知，藉由著色組成物中的含水率為0.1質量%~5質量%，即便長期放置於低氧濃度下亦可維持良好的耐光性。 Further, it has been found that the water content in the colored composition is from 0.1% by mass to 5% by mass, and good light resistance can be maintained even when placed at a low oxygen concentration for a long period of time.

另外得知，藉由著色組成物中的甲苯濃度為1ppm~13ppm，即便長時間放置，亦可維持著色圖案的線寬均勻性更良好。 Further, it has been found that the toluene concentration in the colored composition is from 1 ppm to 13 ppm, and even if it is left for a long period of time, the uniformity of the line width of the colored pattern can be maintained.

另外得知，實施例70~實施例77中，長時間熱循環試驗的評價以外的任一評價結果均良好。 Further, in Examples 70 to 77, the evaluation results other than the evaluation of the long-term heat cycle test were good.

Claims (21)

一種著色組成物，含有(A)色素多聚物及(B)溶劑，並且(A)色素多聚物具有來源於具有陽離子部位的氧雜蒽色素的部分結構及陰離子部位，著色組成物中的鈉離子濃度及鉀離子濃度的至少一者為0.1ppm~10ppm，所述(B)溶劑於所述著色組成物中的含量設定為所述著色組成物的總固體成分濃度成為5質量%~90質量%的量。 A colored composition comprising (A) a dye multimer and (B) a solvent, and (A) a dye multimer having a partial structure and an anion site derived from a xanthene dye having a cationic site, in a colored composition At least one of the sodium ion concentration and the potassium ion concentration is 0.1 ppm to 10 ppm, and the content of the solvent (B) in the coloring composition is set such that the total solid content concentration of the coloring composition is 5% by mass to 90%. The amount of mass %. 如申請專利範圍第1項所述的著色組成物，其中著色組成物中的甲苯濃度為1ppm~13ppm。 The coloring composition according to claim 1, wherein the toluene concentration in the coloring composition is from 1 ppm to 13 ppm. 如申請專利範圍第1項所述的著色組成物，其中著色組成物中的含水率為0.1質量%~5質量%。 The colored composition according to claim 1, wherein the water content in the colored composition is from 0.1% by mass to 5% by mass. 如申請專利範圍第1項所述的著色組成物，其中所述陰離子部位為低親核性的陰離子部位。 The colored composition according to claim 1, wherein the anion site is a low nucleophilic anion site. 如申請專利範圍第1項所述的著色組成物，更含有酞菁顏料。 The coloring composition as described in claim 1 further contains a phthalocyanine pigment. 如申請專利範圍第1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 further contains a photopolymerization initiator. 如申請專利範圍第1項所述的著色組成物，更含有硬化性化合物。 The colored composition according to Item 1 of the patent application further contains a curable compound. 如申請專利範圍第1項所述的著色組成物，其中著色組成 物中的鈉離子濃度及鉀離子濃度的至少一者為3ppm~7ppm。 The coloring composition as described in claim 1, wherein the coloring composition At least one of the sodium ion concentration and the potassium ion concentration in the substance is 3 ppm to 7 ppm. 如申請專利範圍第1項所述的著色組成物，其中所述(A)色素多聚物為含有通式(a1-1)所表示的重複單元及通式(a1-2)所表示的重複單元的至少一個的色素多聚物、或通式(a1-3)所表示的色素多聚物， 通式(a1-1)中，X1表示形成主鏈的基團，L1表示單鍵或二價連結基，DyeI表示具有陽離子部位的色素結構， 通式(a1-2)中，L3表示單鍵或二價連結基，DyeIII表示具有陽離子部位的色素結構，m表示0或1， 通式(a1-3)中，L4表示n價連結基，n表示2~20的整數，DyeIV表示具有陽離子部位的色素結構。 The colored composition according to claim 1, wherein the (A) dye polymer contains a repeating unit represented by the formula (a1-1) and a repeat represented by the formula (a1-2) a dye polymer of at least one of the units or a dye polymer represented by the formula (a1-3), In the formula (a1-1), X 1 represents a group forming a main chain, L 1 represents a single bond or a divalent linking group, and DyeI represents a dye structure having a cationic moiety. In the formula (a1-2), L 3 represents a single bond or a divalent linking group, DyeIII represents a dye structure having a cationic moiety, and m represents 0 or 1, In the formula (a1-3), L 4 represents an n-valent linking group, n represents an integer of 2 to 20, and DyeIV represents a dye structure having a cationic moiety. 如申請專利範圍第1項所述的著色組成物，其中所述(A)色素多聚物為含有通式(a1-1)所表示的重複單元的色素多聚物， 通式(a1-1)中，X1表示形成主鏈的基團，L1表示單鍵或二價連結基，DyeI表示具有陽離子部位的色素結構。 The colored composition according to claim 1, wherein the (A) dye polymer is a dye polymer containing a repeating unit represented by the formula (a1-1). In the formula (a1-1), X 1 represents a group forming a main chain, L 1 represents a single bond or a divalent linking group, and DyeI represents a dye structure having a cationic moiety. 如申請專利範圍第1項所述的著色組成物，其中所述(A)色素多聚物包括來源於具有陽離子部位的下述通式(J’)所表示的氧雜蒽化合物的結構， 通式(J’)中，R81、R82、R83及R84分別獨立地表示氫原子或一價取代基，R85分別獨立地表示一價取代基，m表示0~5的整數。 The coloring composition according to claim 1, wherein the (A) dye polymer comprises a structure derived from a xanthene compound represented by the following formula (J') having a cationic moiety. In the formula (J'), R 81 , R 82 , R 83 and R 84 each independently represent a hydrogen atom or a monovalent substituent, R 85 each independently represents a monovalent substituent, and m represents an integer of 0 to 5. 如申請專利範圍第11項所述的著色組成物，其中所述(A) 色素多聚物為選自(A1)、(A2)、(A3)及(A4)中的至少一者，(A1)具有具有來源於所述通式(J’)所表示的氧雜蒽化合物的部分結構的重複單元及抗衡陰離子的色素多聚物；(A2)含有具有來源於所述通式(J’)所表示的氧雜蒽化合物的部分結構的重複單元且來源於所述氧雜蒽化合物的部分結構更具有陰離子部位的色素多聚物；(A3)含有所述通式(J’)所表示的氧雜蒽化合物及具有抗衡陰離子部位的重複單元的色素多聚物；(A4)含有所述通式(J’)所表示的氧雜蒽化合物及具有陽離子部位的重複單元且所述氧雜蒽化合物更具有陰離子部位的色素多聚物。 The colored composition according to claim 11, wherein the (A) The dye polymer is at least one selected from the group consisting of (A1), (A2), (A3) and (A4), and (A1) has a oxonium compound derived from the above formula (J') a repeating unit of a partial structure and a dye polymer of a counter anion; (A2) containing a repeating unit having a partial structure derived from the xanthene compound represented by the general formula (J') and derived from the oxygen a partial polymer having a partial structure of an anthracene compound; (A3) comprising a xanthene compound represented by the above formula (J') and a dye polymer having a repeating unit of a counter anion moiety; (A4) A dye polymer comprising the xanthene compound represented by the above formula (J') and a repeating unit having a cationic moiety and the xanthene compound further having an anionic moiety. 如申請專利範圍第1項所述的著色組成物，其更含有硬化性化合物、鹼可溶性樹脂及光聚合起始劑。 The colored composition according to claim 1, further comprising a curable compound, an alkali-soluble resin, and a photopolymerization initiator. 如申請專利範圍第1項所述的著色組成物，其中所述(A)色素多聚物相對於(B)溶劑為溶解1質量%以上、50質量%以下。 The coloring composition according to the first aspect of the invention, wherein the (A) dye polymer is dissolved in an amount of 1% by mass or more and 50% by mass or less based on the solvent (B). 如申請專利範圍第1項至第14項中任一項所述的著色組成物，其為彩色濾光片的著色層形成用。 The coloring composition according to any one of claims 1 to 14, which is used for forming a coloring layer of a color filter. 一種硬化膜，其是使如申請專利範圍第1項至第15項中任一項所述的著色組成物硬化而成。 A cured film obtained by hardening the coloring composition according to any one of the items 1 to 15. 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15項中任一項所述的著色組成物應用於支持體上而形成著色組成物層的步驟；將著色組成物層以圖案狀進行曝 光的步驟；以及將未曝光部顯影去除而形成著色圖案的步驟。 A method of producing a color filter, comprising the steps of: applying a colored composition according to any one of claims 1 to 15 to a support to form a colored composition layer; The colored composition layer is exposed in a pattern a step of light; and a step of developing the unexposed portion to form a colored pattern. 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15項中任一項所述的著色組成物應用於支持體上而形成著色組成物層，並使其硬化而形成著色層的步驟；於著色層上形成光阻層的步驟；藉由進行曝光及顯影而將光阻層圖案化，獲得抗蝕劑圖案的步驟；以及將抗蝕劑圖案作為蝕刻遮罩來對著色層進行乾式蝕刻的步驟。 A method of producing a color filter, comprising the steps of: applying a colored composition according to any one of claims 1 to 15 to a support to form a colored composition layer, and a step of forming a coloring layer by hardening; a step of forming a photoresist layer on the colored layer; a step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and using the resist pattern as an etching mask A cover to dry-etch the colored layer. 一種彩色濾光片，其為具有如申請專利範圍第16項所述的硬化膜的彩色濾光片、或者藉由如申請專利範圍第17項或第18項所述的彩色濾光片的製造方法所製造的彩色濾光片。 A color filter which is a color filter having a cured film as described in claim 16 or a color filter as described in claim 17 or 18. Method of manufacturing a color filter. 一種固體攝像元件，具有如申請專利範圍第19項所述的彩色濾光片。 A solid-state image sensor having a color filter as described in claim 19. 一種圖像顯示裝置，具有如申請專利範圍第19項所述的彩色濾光片。 An image display device having the color filter according to claim 19 of the patent application.
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