JP2015069052A - Coloring composition, cured film, color filter, manufacturing method of color filter, solid state imaging element, and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition having excellent heat resistance, solvent resistance, and voltage holding ratio, cured film, color filter, manufacturing method of color filter, solid state imaging element, and liquid crystal display device.SOLUTION: A coloring composition includes cations with a molecular weight of 2000 or less having a triarylmethane structure and counter anions; and the counter anions include a colorant having a repeating unit including a crosslinkable group and/or the counter anions, and a polymerizable compound.

Description

  The present invention relates to a colored composition, a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, and a liquid crystal display device.

Conventionally, a color filter is made into a colored composition by containing a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components as necessary. This is used to form a colored pattern by a photolithography method, an ink jet method or the like.
In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. Along with this trend of expanding applications, color filters are required to have high color characteristics in terms of chromaticity and contrast. Similarly, color filters for image sensors (solid-state imaging devices) are required to further improve color characteristics such as reduction of color unevenness and improvement of color resolution.
However, in conventional pigment dispersion systems, problems such as the occurrence of scattering due to coarse pigment particles and the increase in viscosity due to poor dispersion stability are likely to occur, and it is often difficult to further improve contrast and brightness.
Therefore, conventionally, as a colorant, it has been studied to use not only a pigment but also a dye (for example, see Patent Document 1). When a dye is used as a colorant, the hue and brightness of a display image when an image is displayed can be increased due to the color purity of the dye itself and the vividness of the hue, and contrast can be improved because coarse particles are eliminated. It is useful in terms.
As examples of dyes, compounds having a wide variety of chromophores such as phthalocyanine dyes, dipyrromethene dyes, pyrimidine azo dyes, pyrazole azo dyes, xanthene dyes, triarylmethane dyes are known (for example, Patent Documents 2 to 11). reference).

JP-A-6-75375 JP 2008-292970 A JP 2007-039478 A Japanese Patent Laid-Open No. 9-157536 JP 2013-25194 A JP 2012-201694 A JP 2012-108469 A JP 2000-095805 A JP 2012-072205 A International Publication WO2012 / 005203 Pamphlet JP 2003-246935 A

Here, as a coloring composition used for a color filter or the like, a composition having more excellent heat resistance, solvent resistance, and voltage holding ratio is required.
The object of the present invention is to provide a coloring composition that is excellent in heat resistance, solvent resistance, and voltage holding ratio. In particular, an object is to provide a useful coloring composition for a blue filter.

（一般式（Ａ１）中、Ｒ¹およびＲ²はそれぞれ独立して−ＳＯ₂−または−ＣＯ−を表す。）
一般式（Ａ２）

（一般式（Ａ２）中、Ｒ³は、−ＳＯ₂−または−ＣＯ−を表す。Ｒ⁴およびＲ⁵はそれぞれ独立して−ＳＯ₂−、−ＣＯ−または−ＣＮを表す。）
＜３＞対アニオンが、−ＳＯ₃ ^-、−ＣＯＯ^-、−ＰＯ₄ ^-および下記一般式（Ａ１−１）で表される構造から選択される少なくとも１種を有する、＜１＞に記載の着色組成物。
一般式（Ａ１−１）

（一般式（Ａ１−１）中、Ｒ¹およびＲ²はそれぞれ独立して−ＳＯ₂−または−ＣＯ−を表す。Ｘ¹およびＸ²は、それぞれ独立してアルキレン基またはアリーレン基を表す。）
＜４＞
前記トリアリールメタン構造を有する分子量２０００以下のカチオンが、一般式（ＴＰ１）、一般式（ＴＰ２）および一般式（ＴＰ３）の少なくともいずれかで表される、請求項１〜３のいずれか１項に記載の着色組成物。

（一般式（ＴＰ１）および（ＴＰ２）中、Ｒｔｐ₁〜Ｒｔｐ₄は、それぞれ独立して水素原子、アルキル基またはアリール基を表す。Ｒｔｐ₅、Ｒｔｐ₆、Ｒｔｐ₈、Ｒｔｐ₉およびＲｔｐ₁₁は、それぞれ独立して置換基を表す。Ｒｔｐ₇は、水素原子、アルキル基、アリール基またはＮＲｔｐ₇₁Ｒｔｐ₇₂を表す。Ｒｔｐ₇₁およびＲｔｐ₇₂は、それぞれ独立して水素原子、アルキル基またはアリール基を表す。Ｒｔｐ₁₀は、置換基を表す。ａ、ｂおよびｃは、それぞれ独立して０〜４の整数を表す。ａ、ｂおよびｃが２以上の場合、Ｒｔｐ₆、Ｒｔｐ₇およびＲｔｐ₈のうち２つは、互いに、連結して環を形成してもよい。）
一般式（ＴＰ３）

（一般式（ＴＰ３）中、Ｄｙｅは、前記一般式（ＴＰ１）または前記一般式（ＴＰ２）で表される構造を表す。Ｌ²は、２価の連結基を表し、前記一般式（ＴＰ１）または前記一般式（ＴＰ２）で表される構造中のいずれかの部位と結合している。）
＜５＞対アニオンが、アニオンを含む繰り返し単位を有する、＜１＞〜＜４＞のいずれかに記載の着色組成物。
＜６＞光重合開始剤をさらに含む、＜１＞〜＜５＞のいずれかに記載の着色組成物。
＜７＞カラーフィルタの着色層形成用である、＜１＞〜＜６＞のいずれかに記載の着色組成物。
＜８＞＜１＞〜＜７＞のいずれかに記載の着色組成物を硬化してなる着色硬化膜。
＜９＞＜８＞に記載の着色硬化膜を有するカラーフィルタ。
＜１０＞＜１＞〜＜７＞のいずれかに記載の着色組成物を支持体上に付与して着色組成物層を形成する工程と、該着色組成物層をパターン状に露光する工程と、未露光部を現像除去して着色パターンを形成する工程とを含むカラーフィルタの製造方法。
＜１１＞＜１＞〜＜７＞のいずれかに記載の着色組成物を支持体上に付与して着色組成物層を形成し、硬化して着色層を形成する工程、着色層上にフォトレジスト層を形成する工程、露光および現像することによりフォトレジスト層をパターニングしてレジストパターンを得る工程、もしくはレジストパターンをエッチングマスクとして着色層をドライエッチングする工程を含む、カラーフィルタの製造方法。
＜１２＞＜１０＞または＜１１＞に記載のカラーフィルタの製造方法によって製造したカラーフィルタ。
＜１３＞＜９＞に記載のカラーフィルタまたは＜１１＞または＜１２＞に記載のカラーフィルタの製造方法により作製されたカラーフィルタを有する固体撮像素子または画像表示装置。 Under such circumstances, the inventors of the present application have made extensive studies, and as a result, have a cation having a triarylmethane structure and a molecular weight of 2000 or less, a counter anion, the counter anion contains a crosslinkable group, and / or a counter anion. It has been found that the above-mentioned problems can be solved by blending a colorant having a repeating unit containing s in a composition.
Specifically, the above problem has been solved by the following means <1>, preferably by <2> to <13>.
<1> A colorant having a triarylmethane structure cation having a molecular weight of 2000 or less and a counter anion, wherein the counter anion contains a crosslinkable group and / or a repeating unit containing a counter anion, and a polymerizable compound A coloring composition comprising.
<2> The counter anion is at least one selected from —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , a structure represented by the following general formula (A1), and a structure represented by the following general formula (A2). The coloring composition as described in <1> which has a seed | species.
General formula (A1)

(In general formula (A1), R ¹ and R ² each independently represent —SO ₂ — or —CO—.)
General formula (A2)

(In the general formula (A2), R ³ represents —SO ₂ — or —CO—. R ⁴ and R ⁵ each independently represents —SO ₂ —, —CO— or —CN).
<3> The counter anion according to <1>, wherein the counter anion has at least one selected from the structure represented by —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ^— and the following general formula (A1-1). Coloring composition.
Formula (A1-1)

(In General Formula (A1-1), R ¹ and R ² each independently represent —SO ₂ — or —CO—, and X ¹ and X ² each independently represent an alkylene group or an arylene group. )
<4>
The cation having a triarylmethane structure and a molecular weight of 2000 or less is represented by at least one of the general formula (TP1), the general formula (TP2), and the general formula (TP3). The coloring composition as described in.

(In general formulas (TP1) and (TP2), Rtp _{1 to} Rtp ₄ each independently represents a hydrogen atom, an alkyl group, or an aryl group. Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ and Rtp ₁₁ are Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group, or NRtp ₇₁ Rtp _72. Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group, or an aryl group. Rtp ₁₀ represents a substituent, a, b and c each independently represent an integer of 0 to 4. When a, b and c are 2 or more, Rtp ₆ , Rtp ₇ and Rtp ₈ The two may be linked to each other to form a ring.)
General formula (TP3)

(In General Formula (TP3), Dye represents a structure represented by General Formula (TP1) or General Formula (TP2). L ² represents a divalent linking group, and General Formula (TP1) Or, it is bonded to any site in the structure represented by the general formula (TP2).)
<5> The colored composition according to any one of <1> to <4>, wherein the counter anion has a repeating unit containing an anion.
<6> The colored composition according to any one of <1> to <5>, further including a photopolymerization initiator.
<7> The colored composition according to any one of <1> to <6>, which is used for forming a colored layer of a color filter.
<8> A colored cured film obtained by curing the colored composition according to any one of <1> to <7>.
<9> A color filter having the colored cured film according to <8>.
<10> A step of forming a colored composition layer by applying the colored composition according to any one of <1> to <7> on a support, and a step of exposing the colored composition layer to a pattern. And a step of developing and removing the unexposed portion to form a colored pattern.
<11> A step of applying a colored composition according to any one of <1> to <7> on a support to form a colored composition layer and curing to form a colored layer, a photo on the colored layer A method for producing a color filter, comprising a step of forming a resist layer, a step of patterning a photoresist layer by exposure and development to obtain a resist pattern, or a step of dry etching a colored layer using the resist pattern as an etching mask.
<12> A color filter manufactured by the method for manufacturing a color filter according to <10> or <11>.
<13> A solid-state imaging device or an image display device having the color filter according to <9> or the color filter produced by the method for producing a color filter according to <11> or <12>.

  ADVANTAGE OF THE INVENTION According to this invention, it became possible to provide the coloring composition excellent in heat resistance, solvent resistance, and voltage holding ratio.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In this specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored composition.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have 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).
In addition, “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acrylic” ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In the present specification, “monomer” and “monomer” are synonymous. The monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having 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.
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.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
The weight average molecular weight in the present invention refers to that measured by gel permeation chromatography (GPC) unless otherwise specified. GPC was isolated by removing the solvent from the obtained polymer, and the obtained solid content was diluted to 0.1% by mass with tetrahydrofuran, and HLC-8020 GPC (manufactured by Tosoh Corporation) was used. It is possible to measure by using three TSKgel Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) connected in series as a column. The conditions can be performed using a RI detector with a sample concentration of 0.35% by mass, a flow rate of 0.35 mL / min, a sample injection amount of 10 μL, and a measurement temperature of 40 ° C.

The coloring composition of the present invention has a cation having a triarylmethane structure with a molecular weight of 2000 or less and a counter anion, and the counter anion contains a crosslinkable group and / or has a repeating unit containing a counter anion, And a polymerizable compound.
By setting it as such a structure, the coloring composition excellent in heat resistance, solvent resistance, and voltage holding ratio can be provided.

（一般式（ＴＰ１）および（ＴＰ２）中、Ｒｔｐ₁〜Ｒｔｐ₄は、それぞれ独立して水素原子、アルキル基またはアリール基を表す。Ｒｔｐ₅、Ｒｔｐ₆、Ｒｔｐ₈、Ｒｔｐ₉およびＲｔｐ₁₁は、それぞれ独立して置換基を表す。Ｒｔｐ₇は、水素原子、アルキル基、アリール基またはＮＲｔｐ₇₁Ｒｔｐ₇₂を表す。Ｒｔｐ₇₁およびＲｔｐ₇₂は、それぞれ独立して水素原子、アルキル基またはアリール基を表す。Ｒｔｐ₁₀は、置換基を表す。ａ、ｂおよびｃは、それぞれ独立して０〜４の整数を表す。ａ、ｂおよびｃが２以上の場合、Ｒｔｐ₆、Ｒｔｐ₇およびＲｔｐ₈のうち２つは、互いに、連結して環を形成してもよい。） <Colorant (triarylmethane dye)>
<< Cation having a triarylmethane structure and a molecular weight of 2000 or less >>
The colorant contains a cation having a triarylmethane structure and a molecular weight of 2000 or less, and preferably has a molecular weight of 300 to 800.
The cation having a molecular weight of 2000 or less having a triarylmethane structure is preferably a structure represented by at least one of general formula (TP1), general formula (TP2) and general formula (TP3).

(In general formulas (TP1) and (TP2), Rtp _{1 to} Rtp ₄ each independently represents a hydrogen atom, an alkyl group, or an aryl group. Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ and Rtp ₁₁ are Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group, or NRtp ₇₁ Rtp _72. Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group, or an aryl group. Rtp ₁₀ represents a substituent, a, b and c each independently represent an integer of 0 to 4. When a, b and c are 2 or more, Rtp ₆ , Rtp ₇ and Rtp ₈ The two may be linked to each other to form a ring.)

In General Formula (TP1), Rtp _{1 to} Rtp ₄ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and preferably a hydrogen atom or an alkyl group.
1-10 are preferable, as for carbon number of an alkyl group, 1-5 are more preferable, and 1-3 are more preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. The alkyl group is preferably unsubstituted. As the substituent that the alkyl group may have, the substituents mentioned in the section of Substituent Group A described later can be used, and an aryl group having 6 to 12 carbon atoms is preferable.
6-18 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6 is more preferable. As the substituent that the aryl group may have, the substituents mentioned in the section of Substituent group A described later can be used.

In General Formula (TP1), Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group, or NRtp ₇₁ Rtp ₇₂ , preferably a hydrogen atom or NRtp ₇₁ Rtp ₇₂ , and more preferably NRtp ₇₁ Rtp ₇₂ .
1-10 are preferable, as for carbon number of an alkyl group, 1-5 are more preferable, and 1-3 are more preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear. As the substituent that the alkyl group may have, an aryl group having 6 to 12 carbon atoms and the like are preferable.
6-18 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6 is more preferable.
Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group or an aryl group.
1-10 are preferable, as for carbon number of an alkyl group, 1-8 are more preferable, and 1-6 are more preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. As the substituent that the alkyl group may have, an aryl group having 6 to 12 carbon atoms and the like are preferable.
6-18 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6 is more preferable. Examples of the substituent that the aryl group may have include the substituents mentioned in the section of Substituent Group A described later, and an alkoxy group having 1 to 6 carbon atoms (particularly an alkoxy group having 1 to 3 carbon atoms) is preferable.

In general formula (TP1), Rtp ₅ , Rtp ₆ and Rtp ₈ each independently represent a substituent. As the substituent, the substituents mentioned in the section of the substituent group A described later can be used. In particular, a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, a carboxyl group, or a sulfo group is preferable, and a linear chain having 1 to 5 carbon atoms. Or a branched alkyl group, a C1-C5 alkenyl group, a phenyl group, or a carboxyl group is more preferable. In particular, Rtp ₅ and Rtp ₆ are preferably each independently an alkyl group having 1 to 5 carbon atoms. Rtp ₈ preferably has two alkenyl groups bonded to each other to form a ring. The ring is preferably a benzene ring.

  In the general formula (TP1), a, b and c each independently represent an integer of 0 to 4, and a and b preferably represent 0 or 1, and more preferably represent 0. c preferably represents 0 to 2, more preferably 0 or 1.

In General Formula (TP2), Rtp _{1 to} Rtp ₄ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and have the same meaning as Rtp _{1 to} Rtp ₄ in General Formula (TP1).
1-10 are preferable, as for carbon number of an alkyl group, 1-5 are more preferable, and 1-3 are more preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. As the substituent that the alkyl group may have, the substituents mentioned in the section of Substituent Group A described later can be used. The alkoxy group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms can be used. A hydroxy group is preferred.
6-18 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6 is more preferable. As the substituent that the aryl group may have, the substituents mentioned in the section of Substituent group A described later can be used, and an alkyl group having 1 to 4 carbon atoms is preferable.
Rtp ₁ and Rtp ₂ and / or Rtp ₃ and Rtp ₄ may be bonded to each other to form a ring. The formed ring is preferably a 4- to 7-membered ring, more preferably a 5- or 6-membered ring.

In general formula (TP2), Rtp ₅ and Rtp ₆ each independently represent a substituent, and are synonymous with Rtp ₅ and Rtp ₆ in general formula (TP1), and their preferred ranges are also the same.

In General Formula (TP2), Rtp ₉ and Rtp ₁₁ each independently represent a substituent, and the substituents mentioned in the section of Substituent Group A described later can be used.
Rtp ₉ is preferably an aryl group, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. The substituent that the aryl group may have is preferably a halogen atom.
Rtp ₁₁ is preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group is preferably linear or branched, and more preferably linear. The substituent that the alkyl group may have is preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group.

In General Formula (TP2), Rtp ₁₀ represents a substituent, and the substituents mentioned in the section of Substituent Group A described later can be used. In particular, Rtp ₁₀ is more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group.

  In general formula (TP2), a, b and c each independently represent an integer of 0 to 4, and a and b preferably represent 0 or 1, and more preferably represent 0. c preferably represents 0 to 2, more preferably 0 or 1.

The cations having a molecular weight of 2000 or less having a triarylmethane structure are present in a delocalized manner as follows, and the following two structures are synonymous and both are included in the present invention. The cation moiety may be at any position in the molecule, but is preferably located on the nitrogen atom. When substituted on a nitrogen atom, the color tends to be further improved.

（一般式（ＴＰ３）中、Ｄｙｅは、上記一般式（ＴＰ１）または一般式（ＴＰ２）で表される構造を表す。Ｌ²は、２価の連結基を表し、上記一般式（ＴＰ１）または一般式（ＴＰ２）で表される構造中のいずれかの部位と結合している。）
一般式（ＴＰ３）中、Ｄｙｅは、上記一般式（ＴＰ１）または一般式（ＴＰ２）で表される構造を表し、上記一般式（ＴＰ１）で表される構造が好ましい。
Ｌ²は、２価の連結基を表し、脂肪族炭化水素基または芳香族炭化水素基が好ましい。脂肪族炭化水素基は、直鎖状、分岐状および環状のいずれであってもよいが、環状が好ましい。脂肪族炭化水素基の炭素数は、１〜１０が好ましく、１〜８がより好ましい。芳香族炭化水素基の炭素数は、６〜１８が好ましく、６〜１２がより好ましく、６がさらに好ましい。
Ｌ²は、上記一般式（ＴＰ１）または一般式（ＴＰ２）で表される構造中のいずれかの部位と結合しており、上記一般式（ＴＰ１）中のＲｔｐ₇がＮＲｔｐ₇₁Ｒｔｐ₇₂を表す場合のＲｔｐ₇₁またはＲｔｐ₇₂と結合していることが好ましい。 General formula (TP3)

(In General Formula (TP3), Dye represents a structure represented by General Formula (TP1) or General Formula (TP2). L ² represents a divalent linking group, and General Formula (TP1) or It is bonded to any site in the structure represented by the general formula (TP2).)
In General Formula (TP3), Dye represents a structure represented by General Formula (TP1) or General Formula (TP2), and a structure represented by General Formula (TP1) is preferable.
L ² represents a divalent linking group, and is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched or cyclic, but is preferably cyclic. 1-10 are preferable and, as for carbon number of an aliphatic hydrocarbon group, 1-8 are more preferable. 6-18 are preferable, as for carbon number of an aromatic hydrocarbon group, 6-12 are more preferable, and 6 is more preferable.
L ² is bonded to any part of the structure represented by the general formula (TP1) or (TP2), and Rtp ₇ in the general formula (TP1) represents NRtp ₇₁ Rtp ₇₂ . It is preferable to bind to Rtp ₇₁ or Rtp _{72 of the} case.

Substituent group A:
Substituents include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups Silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfa Moylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group Groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl or heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, silyl groups, etc. It is done. Details are described below.

  A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms) For example, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably having 3 to 30 carbon atoms substituted or Examples thereof include unsubstituted cycloalkyl groups such as cyclohexyl and cyclopentyl, and polycycloalkyl groups such as bicycloalkyl groups (preferably substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms such as bicyclo [ 1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3 Yl) or group of polycyclic structures such as tricycloalkyl groups. Preferably monocyclic cycloalkyl group, a bicycloalkyl group, a monocyclic cycloalkyl group is particularly preferred.)

  Linear or branched alkenyl group (straight or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl Group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, and a polycycloalkenyl group such as bicyclo An alkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group 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) and tricycloalkenyl groups, with monocyclic cycloalkenyl groups being particularly preferred. Le group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, e.g., ethynyl, propargyl, trimethylsilylethynyl group),

  An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 to 5 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably the ring-constituting atom is selected from carbon atom, nitrogen atom and sulfur atom And a heterocyclic group having at least one heteroatom of any one of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. For example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydride Hexyl group, a nitro group, a carboxyl group,

  An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably Is a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, tert-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 2 to 2 carbon atoms) 30 substituted or unsubstituted heterocyclic oxy groups Heterocyclic portion is preferably described in the heterocyclic portion described above heterocyclic group, e.g., 1-phenyl-5-oxy, 2-tetrahydropyranyloxy),

  An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably having 2 to 30 carbon atoms) Or an unsubstituted alkoxycarbonyloxy group such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted group having 7 to 30 carbon atoms). Substituted aryloxycarbonyloxy groups such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

  An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 0 to 30 carbon atoms); For example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino), acylamino group (preferably formylamino group, carbon number A substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3, 4,5-tri-n-octyloxyphenylcarbonylamino), amino A rubonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl- Methoxycarbonylamino),

  Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) A sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino Sulfonylamino), alkyl or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methyl Sulfonyla Bruno, butyl sulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenyl sulfonylamino, p- methylphenyl sulfonylamino), a mercapto group,

  An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms). , For example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, wherein the heterocyclic portion is the above-described heterocyclic group The heterocyclic moiety described in the above is preferable, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfa Yl, N, N- dimethylsulfamoyl, N- acetyl sulfamoyl, N- benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), a sulfo group,

  An alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl , Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbocycle having 7 to 30 carbon atoms) D Groups such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), aryloxycarbonyl groups (preferably substituted or unsubstituted aryloxy having 7 to 30 carbon atoms) A carbonyl group, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl),

  An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably having a carbon number) 1-30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl or hetero A ring azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocycle portion is the heterocycle described in the above heterocyclic group); Ring portion is preferred), for example, phenyl Zo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms such as N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably 2 carbon atoms). -30 substituted or unsubstituted phosphinyl groups such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl)

  A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino group ( Preferably, it is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably substituted with 3 to 30 carbon atoms) Or an unsubstituted silyl group, for example, trimethylsilyl, tert-butyldimethylsilyl, phenyldimethylsilyl).

  Specific examples of the cation having a triarylmethane structure and a molecular weight of 2000 or less are shown below, but the present invention is not limited thereto.

<< Counter anion >>
The counter anion has a repeating unit containing a crosslinkable group and / or containing a counter anion, and preferably has a repeating unit containing a counter anion.

（一般式（Ａ１）中、Ｒ¹およびＲ²はそれぞれ独立して−ＳＯ₂−または−ＣＯ−を表す。）
一般式（Ａ１）中、Ｒ¹およびＲ²の少なくとも１つが−ＳＯ₂−を表すことが好ましく、Ｒ¹およびＲ²の両方が−ＳＯ₂−を表すことがより好ましい。 The counter anion has at least one selected from —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , a structure represented by the following general formula (A1) and a structure represented by the following general formula (A2). It is preferable.
General formula (A1)

(In general formula (A1), R ¹ and R ² each independently represent —SO ₂ — or —CO—.)
In formula (A1), at least one of R ¹ and R ² -SO ₂ - preferably represents an, both R ¹ and R ² are -SO ₂ - and more preferably represents.

（一般式（Ａ２）中、Ｒ³は、−ＳＯ₂−または−ＣＯ−を表す。Ｒ⁴およびＲ⁵はそれぞれ独立して−ＳＯ₂−、−ＣＯ−または−ＣＮを表す。）
一般式（Ａ２）中、Ｒ³〜Ｒ⁵の少なくとも１つが−ＳＯ₂−を表すことが好ましく、Ｒ³〜Ｒ⁵の少なくとも２つが−ＳＯ₂−を表すことがより好ましい。 General formula (A2)

(In the general formula (A2), R ³ represents —SO ₂ — or —CO—. R ⁴ and R ⁵ each independently represents —SO ₂ —, —CO— or —CN).
Preferably representing the at least two R ³ to R ⁵ is -SO ₂ - - In formula (A2), at least one of R ³ to R ⁵ -SO ₂ more preferably represents.

（一般式（Ａ１−１）中、Ｒ¹およびＲ²はそれぞれ独立して−ＳＯ₂−または−ＣＯ−を表す。Ｘ¹およびＸ²は、それぞれ独立してアルキレン基またはアリーレン基を表す。）
一般式（Ａ１−１）中、Ｒ¹およびＲ²は、一般式（Ａ１）中のＲ¹およびＲ²と同義であり、好ましい範囲も同様である。
Ｘ¹がアルキレン基を表す場合、アルキレン基の炭素数は、１〜８が好ましく、１〜６がより好ましい。Ｘ¹がアリーレン基を表す場合、アリーレン基の炭素数は、６〜１８が好ましく、６〜１２がより好ましく、６がさらに好ましい。Ｘ¹が置換基を有する場合、フッ素原子で置換されていることが好ましい。
Ｘ²は、アルキル基またはアリール基を表し、アルキル基が好ましい。アルキル基の炭素数は、１〜８が好ましく、１〜６がより好ましく、１〜３がさらに好ましく、１が特に好ましい。Ｘ²が置換基を有する場合、フッ素原子で置換されていることが好ましい。 The counter anion more preferably has at least one selected from the structure represented by —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ^— and the following general formula (A1-1).
Formula (A1-1)

(In General Formula (A1-1), R ¹ and R ² each independently represent —SO ₂ — or —CO—, and X ¹ and X ² each independently represent an alkylene group or an arylene group. )
In formula (A1-1), R ¹ and R ² of the general formula (A1) in the same meaning as R ¹ and R ^2, and preferred ranges are also the same.
When X < ¹ > represents an alkylene group, 1-8 are preferable and, as for carbon number of an alkylene group, 1-6 are more preferable. When X < ¹ > represents an arylene group, 6-18 are preferable, as for carbon number of an arylene group, 6-12 are more preferable, and 6 is more preferable. When X ¹ has a substituent, it is preferably substituted with a fluorine atom.
X ² represents an alkyl group or an aryl group, and an alkyl group is preferable. 1-8 are preferable, as for carbon number of an alkyl group, 1-6 are more preferable, 1-3 are more preferable, and 1 is especially preferable. When X ² has a substituent, it is preferably substituted with a fluorine atom.

<<< Counter anion containing a crosslinkable group >>>
Examples of the crosslinkable group that the counter anion may contain include known polymerizable groups that can be cross-linked by radicals, acids, and heat. Specific examples include a (meth) acryl group, a styrene group, a vinyl group, a cyclic ether group, and a methylol group, and at least one selected from a (meth) acryl group, a styrene group, a vinyl group, and a cyclic ether group. Preferably, one selected from a (meth) acryl group, a styrene group, and a vinyl group is more preferable, and a (meth) acryl group or a styrene group is more preferable.
The number of crosslinkable groups that the counter anion may contain is preferably 1 to 3, and more preferably 1.

In addition, between the crosslinkable group and the above-described —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , the structure represented by the following general formula (A1) and the structure represented by the following general formula (A2) These may be directly bonded or may be bonded via a linking group, but are preferably bonded via a linking group.
The counter anion containing a crosslinkable group is preferably represented by, for example, the following general formula (B).

（一般式（Ｂ）中、Ｐは架橋性基を表す。Ｌは単結合または２価の連結基を表す。ａｎｉｏｎは、−ＳＯ₃ ^-、−ＣＯＯ^-、−ＰＯ₄ ^-、上記一般式（Ａ１）で表される構造および上記般式（Ａ２）で表される構造を表す。） General formula (B)

(In general formula (B), P represents a crosslinkable group. L represents a single bond or a divalent linking group. Anion represents —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , the above general formula ( The structure represented by A1) and the structure represented by the general formula (A2) are represented.)

In general formula (B), P represents a crosslinkable group, and examples thereof include the crosslinkable groups described above.
In the general formula (B), when L represents a divalent linking group, an alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group, etc.), a carbon number of 6 to 30 arylene groups, heterocyclic linking groups, —CH═CH—, —O—, —S—, —C (═O) —, —CO—, —NR—, —CONR—, —OC—, —SO —, —SO ₂ — and a linking group obtained by combining two or more thereof are preferred. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
In particular, the linking group is an alkylene group having 1 to 10 carbon atoms (preferably — (CH ₂ ) n — (n is an integer of 1 to 10), an arylene group having 6 to 12 carbon atoms (preferably a phenylene group or naphthalene). Group), —NH—, —CO—, —O— and —SO ₂ — are preferably combined.

  Specific examples of the counter anion containing a crosslinkable group are shown below, but the present invention is not limited thereto.

  The molecular weight of the counter anion containing a crosslinkable group is preferably from 1,000 to 100,000, more preferably from 5,000 to 50,000.

<<< Repeating unit containing counter anion (hereinafter also referred to as anion multimer) >>>
The repeating unit containing a counter anion may have an anion structure in the side chain, an anion structure in the main chain, or an anion structure in both the main chain and the side chain. Also good.
The repeating unit containing a counter anion preferably has a structure represented by the following general formula (C) and / or the following general formula (D).

（一般式（Ｃ）中、Ｘ¹は、繰り返し単位の主鎖を表す。Ｌ¹は単結合または２価の連結基を表す。ａｎｉｏｎは、−ＳＯ₃ ^-、−ＣＯＯ^-、−ＰＯ₄ ^-、上記一般式（Ａ１）で表される構造および上記般式（Ａ２）で表される構造を表す。） General formula (C)

(In General Formula (C), X ¹ represents the main chain of the repeating unit. L ¹ represents a single bond or a divalent linking group. Anion represents —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ^−. The structure represented by the general formula (A1) and the structure represented by the general formula (A2) are represented.)

In the general formula (C), X ¹ represents a main chain of repeating units, usually represents a linking group formed by polymerization reaction, for example, (meth) acrylic, styrene, vinyl and the like are preferable. Two sites represented by * are repeating units.

When L ¹ represents a divalent linking group, an alkylene group having 1 to 30 carbon atoms (methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.), an arylene group having 6 to 30 carbon atoms (phenylene group, Naphthalene group, etc.), heterocyclic linking group, -CH = CH-, -O-, -S-, -C (= O)-, -CO-, -NR-, -CONR-, -OC-, -SO —, —SO ₂ — and a linking group obtained by combining two or more thereof are preferred. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
In particular, L ¹ is a single bond or an alkylene group having 1 to 10 carbon atoms (preferably — (CH ₂ ) n — (n is an integer of 1 to 10), an arylene group having 6 to 12 carbon atoms (preferably Is preferably a divalent linking group in which two or more of —NH—, —CO—, —O— and —SO ₂ — are combined.

Specific examples of combinations of X ¹ and L ¹ are shown below, but the present invention is not limited to these.
In particular, a (meth) acrylic linking chain represented by (XX-1) and (XX-2), a styrene linking chain represented by (XX-10) to (XX-17), and (XX-24) More preferably, it is selected from vinyl-based linking chains represented by (XX-1) and (XX-1) and (XX-2) (meth) acrylic linking chains and (XX-11). Styrenic linkage chains are more preferred.
In (XX-1) to (X-24), it represents that it is linked to the above anion at the site indicated by *. Me represents a methyl group. R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

Moreover, the following is also preferable as a specific example of the combination of X ¹ and L ¹ . In the following specific examples, n represents an integer of 1 to 9. Moreover, it represents having connected with the said anion in the site | part shown by *.

（一般式（Ｄ）中、Ｌ²およびＬ³は、それぞれ独立して単結合または２価の連結基を表す。ａｎｉｏｎは、−ＳＯ₃ ^-、−ＣＯＯ^-、−ＰＯ₄ ^-、上記一般式（Ａ１）で表される構造および上記般式（Ａ２）で表される構造を表す。） Formula (D)

(In General Formula (D), L ² and L ³ each independently represent a single bond or a divalent linking group. Anion represents —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , (The structure represented by (A1) and the structure represented by the general formula (A2) are represented.)

In the general formula (D), when L ² and L ³ represent a divalent linking group, an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, —CH═CH— , —O—, —S—, —C (═O) —, —CO—, —NR—, —CONR—, —O ₂ C—, —SO—, —SO ₂ — and combinations of two or more thereof A linking group is preferred. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
L ² is preferably an arylene group having 6 to 12 carbon atoms (particularly a phenylene group). The arylene group having 6 to 30 carbon atoms is preferably substituted with a fluorine atom.
L ³ is preferably a group composed of a combination of an arylene group having 6 to 12 carbon atoms (particularly a phenylene group) and —O—, and at least one arylene group having 6 to 12 carbon atoms is substituted with a fluorine atom. It is preferable.

As a polymer that forms an anion multimer, a homopolymer (homopolymer) composed only of a dye compound component having a crosslinkable group or a copolymer (copolymer) with other polymerizable compound is preferably used. A homopolymer (homopolymer) is more preferable.
As the molecular weight of the anionic multimer, the weight average molecular weight is preferably 3,000 to 30,000, and the molecular weight distribution is preferably 0.8 to 3.0 in terms of Mw / Mn, more preferably the weight average molecular weight is 5, The molecular weight distribution is 1 to 2.5 in terms of Mw / Mn.

When forming an anionic multimer, a chain transfer agent may be added. The chain transfer agent is preferably an alkyl mercaptan, and is preferably an alkyl mercaptan having 10 or less carbon atoms or an alkyl mercaptan substituted with an ether group / ester group. In particular, an alkyl mercaptan having a log P value of 5 or less is more preferable.
The amount of the anionic monomer compound having a crosslinkable group that is a raw material of the anionic multimer contained in the anionic multimer is preferably 5% or less, more preferably 1% or less.
The halogen ion content contained in the anionic multimer is preferably 10 to 3000 ppm, more preferably 10 to 2000 ppm, and still more preferably 10 to 1000 ppm.
Specific examples of the anion multimer are shown below, but the present invention is not limited thereto.

The following specific examples show a state where the anion structure is not dissociated, but it goes without saying that the state where the anion structure is dissociated is also within the scope of the present invention.

<< Other functional groups or other repeating units >>
The colorant used in the present invention may have other functional groups other than those described above and other repeating units.
Specifically, in the colorant used in the present invention, a cation having a triarylmethane structure and having a molecular weight of 2000 or less may have another functional group, and includes other repeating units other than the anion multimer. You may go out.
Examples of other functional groups include polymerizable groups, acid groups, and alkali-soluble groups. Moreover, as another repeating unit, the repeating unit containing at least 1 sort (s) of a polymeric group, an acid group, and an alkali-soluble group is illustrated.
Details of these will be described below.

The counter anion preferably contains a polymerizable group. One type of polymerizable group may be included, or two or more types may be included.
As the polymerizable group, a known polymerizable group that can be cross-linked by a radical, acid, or heat can be used, and examples thereof include a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetanyl group) and the like. In particular, a group containing an ethylenically unsaturated bond is preferred, a (meth) acryloyl group is more preferred, and a (meth) acryloyl group derived from glycidyl (meth) acrylate and 3,4-epoxy-cyclohexylmethyl (meth) acrylate is preferred. Further preferred.
The polymerizable group is also preferably incorporated as a repeating unit having a polymerizable group. More preferably, the anionic multimer contains a repeating unit having an anionic structure and a repeating unit having an ethylenically unsaturated bond.

  Moreover, when an anion multimer further contains the repeating unit which has a polymeric group, 50-90 mol is preferable with respect to 100 mol of all the repeating units, and 70-90 mol is more preferable.

  Specific examples of the repeating unit having a polymerizable group include the following. However, the present invention is not limited to these.

Examples of the acid group include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. Examples of the alkali-soluble group include phenolic hydroxyl groups and carboxylic acids.
In addition, when the anionic multimer contains a repeating unit having an acid group, the ratio of the repeating unit containing a repeating unit having an acid group is preferably, for example, 10 to 50 mol with respect to 100 mol of all repeating units. 10-30 mol is more preferable.

Other functional groups include development accelerators such as lactones, acid anhydrides, amides, —COCH ₂ CO—, cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups, hydroxyl groups, maleimides And an aqueous affinity adjusting group such as an amino group and the like, and can be appropriately introduced.
Examples of the introduction method include a method in which the triarylmethane structure is introduced in advance and a method in which the monomer having the functional group is copolymerized.

  Specific examples of other repeating units are shown below, but the present invention is not limited thereto.

Although the specific example of the coloring agent used for this invention below is shown, it is not limited to these.

The cation in the following compound has a number corresponding to the repeating unit of the counter anion.

The molar ratio of each repeating unit in the following compounds represents 10:50:40 to 30:35:35.

When the triarylmethane dye has a repeating unit containing a counter anion, the weight average molecular weight is preferably 1,000 to 100,000, and more preferably 5,000 to 50,000.
The triarylmethane dye can be used alone or in combination of two or more.
5-40 mass% is preferable with respect to the total solid of the coloring composition of this invention, and, as for content of the said triarylmethane dye, 10-30 mass% is more preferable.

<< Other colored compounds >>
The coloring composition of the present invention may contain one or more coloring compounds other than the triarylmethane dye described above as a coloring agent. Examples of other coloring compounds include dye compounds, pigment compounds, and dispersions thereof.

  The dye compound may have any structure as long as it does not affect the hue of the colored image. For example, azo (for example, Solvent Yellow 162), anthraquinone (for example, JP 2001-10881 A). Anthraquinone compounds), phthalocyanine compounds (for example, phthalocyanine compounds described in US Patent 2008 / 0076044A1), xanthene compounds (for example, CI Acid Red 289)) , Triarylmethane-based (for example, CI Acid Blue 7), CI Acid Blue 83, CI Acid Blue 90 (C.I. Acid Blue 7). I. Acid Blue 90), C.I. Solvent Blue 38 (CI Solvent Blue 38), CI Acid Violet 17 (CI Acid Violet 17), CI Acid Violet 49 (CI Acid Violet 49), CI Eye Acid 49 -Green 3 (CI Acid Green3), a methine dye, etc. are mentioned.

Examples of pigment compounds include perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, Indigo, thioindigo, isoindoline, isoindolinone, pyranthrone, isoviolanthrone and the like. More specifically, for example, perylene compound pigments such as Pigment Red 190, Pigment Red 224, and Pigment Violet 29, perinone compound pigments such as Pigment Orange 43, and Pigment Red 194, Pigment Violet 19, and Pigment Violet. 42, quinacridone such as Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 207, or Pigment Red 209, quinacridone compound pigment, Pigment Red 206, Pigment Orange 48, or Pigment Orange 49 Quinone compound pigment, anthraquinone compound pigment such as pigment yellow 147, anthanthrone compound pigment such as pigment red 168, pigment Benzimidazolone compound pigments such as Pigment Brown 25, Pigment Violet 32, Pigment Orange 36, Pigment Yellow 120, Pigment Yellow 180, Pigment Yellow 181, Pigment Orange 62, or Pigment Red 185; Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 166, Pigment Orange 34, Pigment Orange 13, Pigment Orange 31, Pigment Red 144, Pigment Red 166, Pigment Red Red 220, Pigment Red 221, Pigment Red 242, Pigment Red 248, Pigment Red 262, or Pigment Disazo condensation compound pigments such as Brown 23, Pigment Yellow 13, Pigment Yellow 83, or Disazo Compound Pigments such as Pigment Yellow 188, Pigment Red 187, Pigment Red 170, Pigment Yellow 74, Pigment Yellow 150, Pigment Red 48, Pigment Red 53, Pigment Orange 64, Pigment Red 247 and other azo compound pigments, Pigment Blue 60 and other indanthrone compound pigments, Pigment Green 7, Pigment Green 36, Pigment Green 37, phthalocyanine compound pigments such as Pigment Green 58, Pigment Blue 16, Pigment Blue 75, and Pigment Blue 15, Pigment Blue 56 Or triarylcarbonium compound pigments such as Pigment Blue 61, dioxazine compound pigments such as Pigment Violet 23 or Pigment Violet 37, aminoanthraquinone compound pigments such as Pigment Red 177, Pigment Red 254, Pigment Red 255, pigment red 264, pigment red 272, pigment orange 71, or diketopyrrolopyrrole compound pigment such as pigment orange 73, thioindigo compound pigment such as pigment red 88, pigment yellow 139, pigment orange 66 Isoindoline compound pigments such as Pigment Yellow 109, Pigment Orange 61, and Pigment Oren 40, or pyranthrone compound pigments such as Pigment Red 216 or isoviolanthrone compound pigments, such as Pigment Violet 31, and the like.
In the present invention, a color material of green to cyan is preferable, such as Pigment Green 7, Pigment Green 36, Pigment Green 37, Pigment Green 58, Pigment Blue 16, Pigment Blue 75, or Pigment Blue 15. Phthalocyanine compound pigments, triarylcarbonium compound pigments such as pigment blue 56 or pigment blue 61, dioxazine compound pigments such as pigment violet 23 or pigment violet 37, aminoanthraquinone compound pigments such as pigment red 177, Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 272, Pigment Orange 71, Pigment Orange 73, etc. Ketopyrrolopyrrole compound pigments, thioindigo compound pigments such as Pigment Red 88, isoindolin compound pigments such as Pigment Yellow 139 and Pigment Orange 66, isoindolinone compound pigments such as Pigment Yellow 109 or Pigment Orange 61, Pyranthrone compound pigments such as CI Pigment Orange 40 or CI Pigment Red 216, or isoviolanthrone compound pigments such as CI Pigment Violet 31 are preferred.

When the dye or pigment is blended as a dispersion, it can be adjusted according to the descriptions in JP-A-9-197118 and JP-A-2000-239544.
The content of the above-mentioned material or pigment can be used within a range not impairing the effects of the present invention, and is preferably 0.5% by mass to 70% by mass with respect to the total solid content of the colored composition of the present invention. Moreover, it is preferable to add to a coloring composition so that absorption intensity ratio (absorption of 450 nm / absorption of 650 nm) may be in the range of 0.95 to 1.05.

<< polymerizable compound >>
The coloring composition of the present invention contains a polymerizable compound. Examples of the polymerizable compound include addition polymerizable compounds having at least one ethylenically unsaturated double bond.

  Specifically, it is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and their (co) polymers.

  Examples of monomers and their (co) polymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, amides, and these (Co) polymers, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and these (co) polymers It is a polymer. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the ester monomer of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetra Methylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol Diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol tria Relate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanur Examples include acid EO-modified triacrylate.

  Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethylmethane bis - [p- (methacryloxyethoxy) phenyl] dimethylmethane.

  Further, as itaconic acid ester, for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol Diitaconate, sorbitol tetritaconate, etc., and crotonic acid esters such as ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate, etc. For example, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc. As, for example, ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetra malate, and the like.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613. Furthermore, the ester monomers described above can also be used as a mixture.

Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. Vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups Compounds and the like.
CH ₂ = C (R) COOCH ₂ CH (R ′) OH (A)
[In General Formula (A), R and R ′ each independently represent H or CH ₃ . ]

  Moreover, as a polymeric compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial item; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial item, KAYARAD D-320; Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (manufactured by company) KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (manufactured by KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are interposed via ethylene glycol and propylene glycol residues. These oligomer types can also be used.

  About these polymerizable compounds, the structure, details of usage such as single use or combination, addition amount, etc. can be arbitrarily set according to the final performance design of the colored composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Also, from the viewpoint of increasing the strength of the colored cured film, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound) are used in combination. Thus, a method of adjusting both sensitivity and intensity is also effective. In addition, selection and use of polymerizable compounds for compatibility and dispersibility with other components (for example, photopolymerization initiator, colorant (pigment), binder polymer, etc.) contained in the colored composition Is an important factor. For example, compatibility may be improved by the use of a low-purity compound or a combination of two or more. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a substrate.

The content of the polymerizable compound in the total solid content of the colored composition is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, from the viewpoint of more effectively obtaining the effects of the present invention. Mass% is particularly preferred.
The composition of the present invention may contain only one type of polymerizable compound or two or more types. When two or more types are included, the total amount is preferably within the above range.

<< photopolymerization initiator >>
The colored composition of the present invention preferably contains at least one photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can polymerize a polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyl oxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds, and the like. Specific examples of the photopolymerization initiator include those described in paragraphs [0070] to [0077] of JP-A No. 2004-295116. Among these, an oxime compound or a biimidazole compound is preferable from the viewpoint of rapid polymerization reaction.

The oxime compound (hereinafter also referred to as “oxime photopolymerization initiator”) is not particularly limited, and is described in, for example, JP-A No. 2000-80068, WO 02 / 100903A1, and JP-A No. 2001-233842. These oxime compounds are mentioned.
As specific examples of the oxime compound, the description in paragraph 0053 of JP2013-182215A can be referred to, and the contents thereof are incorporated in the present specification.

  Moreover, in this invention, the compound represented by the following general formula (1) or general formula (2) is more preferable as an oxime compound from a viewpoint of a sensitivity, the time stability, and the coloring at the time of post-heating.

（一般式（１）中、ＲおよびＸは、それぞれ、１価の置換基を表し、Ａは、２価の有機基を表し、Ａｒは、アリール基を表す。ｎは、１〜５の整数である。）

(In general formula (1), R and X each represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 1 to 5. .)

  R is preferably an acyl group from the viewpoint of increasing sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.

  A is an alkylene group substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heat aging, An alkylene group substituted with an alkenyl group (for example, vinyl group, allyl group), an aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) A substituted alkylene group is preferred.

  Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring due to heating. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

  X is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl that may have a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. Group, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, a substituent An arylthioxy group which may have a substituent and an amino group which may have a substituent are preferred. Moreover, n in General formula (1) has a preferable integer of 1-2.

一般式（２）中、Ｒ¹⁰¹はアルキル基、アルカノイル基、アルケノイル基、アリーロイル基、アルコキシカルボニル基、アリーロキシカルボニル基、ヘテロ環オキシカルボニル基、ヘテロアリールオキシカルボニル基、アルキルチオカルボニル基、アリールチオカルボニル基、ヘテロ環チオカルボニル基、ヘテロアリールチオカルボニル基またはＣＯ−ＣＯ−Ｒｆを表す。Ｒｆは炭素環式芳香族基またはヘテロ環式芳香族基を表す。

In general formula (2), R ¹⁰¹ represents an alkyl group, an alkanoyl group, an alkenoyl group, an aryloyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, a heteroaryloxycarbonyl group, an alkylthiocarbonyl group, an arylthiocarbonyl. Represents a group, a heterocyclic thiocarbonyl group, a heteroarylthiocarbonyl group or CO-CO-Rf. Rf represents a carbocyclic aromatic group or a heterocyclic aromatic group.

^R102 represents an alkyl group, an aryl group or a heterocyclic group, which may be substituted.
R ¹⁰³ and R ¹⁰⁴ each independently represents an alkyl group, an aryl group or a heterocyclic group, and these groups are further substituted with a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylcarbonyl group or the like. Also good.

R ^{105 to} R ¹¹¹ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloyl group, a heteroaryloyl group, an alkylthio group, an aryloylthio group, or a heteroaryloyl group. , Alkylcarbonyl group, arylcarbonyl group, heteroarylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, nitro group, amino group, sulfonic acid group, hydroxy group, carboxylic acid group, amide group, carbamoyl Represents a group or a cyano group.
One or two of R ^{105 to} R ¹¹¹ are electron-withdrawing substituents, that is, a nitro group, a cyano group, a halogeno group, an alkylcarbonyl group or an arylcarbonyl group, which has a much higher curability. Since a coloring composition is obtained, it is preferable.

  Specific examples of the compound having a fluorene structure represented by the general formula (2) are given below. However, it is not limited to these compounds.

上記一般式（２）で表されるフルオレン構造を有する化合物は、例えば特開２００８−２９２９７０号公報に記載された合成方法に準じて合成することができる。

The compound having a fluorene structure represented by the general formula (2) can be synthesized according to a synthesis method described in, for example, JP-A-2008-292970.

  As specific examples of the biimidazole compound, the description in paragraphs 0061 to 0070 of JP2013-182213A can be referred to, and the contents thereof are incorporated in the present specification.

  In addition to the above photopolymerization initiator, other known photopolymerization initiators described in paragraph No. 0079 of JP-A No. 2004-295116 may be used in the colored composition of the present invention.

The content of the photopolymerization initiator in the total solid content of the colored composition is preferably 3% by mass to 20% by mass and more preferably 4% by mass to 19% by mass from the viewpoint of obtaining the effect of the present invention more effectively. Preferably, 5% by mass to 18% by mass is particularly preferable.
The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Organic solvent >>
The coloring composition of the present invention preferably contains at least one organic solvent.
The organic solvent is basically not particularly limited as long as it can satisfy the solubility of each coexisting component and the coating property when it is a colored composition, and in particular, the solubility, coating property, and safety of the binder. Is preferably selected in consideration of

  As the organic solvent, esters, ethers, ketones, and aromatic hydrocarbons are used, and specific examples thereof include those described in JP-A-2012-032754, paragraph numbers 0161 to 0162.

  It is also preferable to mix two or more of these organic solvents from the viewpoints of the solubility of each of the above-described components, and the solubility of the above-described components and the improvement of the coating surface state when an alkali-soluble polymer is included. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol It is a mixed solution composed of two or more selected from acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

The content of the organic solvent in the colored composition is preferably such that the total solid concentration in the composition is 10% by mass to 80% by mass, and more preferably 15% by mass to 60% by mass.
The composition of the present invention may contain only one type of organic solvent or two or more types of organic solvents. When two or more types are included, the total amount is preferably within the above range.

<< Alkali-soluble binder >>
It is preferable that the coloring composition of this invention contains the alkali-soluble binder. The alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble binder is preferably a linear organic high molecular polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

  In addition to the above, the alkali-soluble binder in the present invention includes a polymer having a hydroxyl group added with an acid anhydride, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth)), and the like. Acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include chain butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.

  As the alkali-soluble binder, a copolymer of maleimide and ethylene oxide as shown in the following formulas (b1) and (b2) can also be preferably used.

（式（ｂ１）中、Ｒ¹は、水素原子、アリール基、またはアルキル基を表す。）
Ｒ¹がアルキル基を表す場合のアルキル基としては、炭素数１〜１０の直鎖状アルキル基、炭素数３〜１０の分岐鎖を有するアルキル基、炭素数５〜２０の環状アルキル基などが挙げられ、より具体的には、メチル基、エチル基、ｔ−ブチル基、シクロヘキシル基などが挙げられる。
アルキル基は、置換基を有していてもよく、アルキル基に導入可能な置換基としては、フェニル基、カルボニル基、アルコキシ基、ヒドロキシ基、アミノ基などが挙げられる。
Ｒ¹がアリール基を表す場合のアリール基としては、単環構造のアリール基、多環構造のアリール基、縮環構造のアリール基、ヘテロ原子を含むヘテロアリール基などが挙げられる。より具体的には、フェニル基、ナフチル基、ビフェニル基、ベンゾイミダゾリル基、ピリジル基、フリル基などが挙げられる。
アリール基は、置換基を有していてもよく、アリール基に導入可能な置換基としては、メチル基、エチル基、ｔ−ブチル基、シクロヘキシル基等のアルキル基、メトキシ基等のアルコキシ基、カルボキシ基、ヒドロキシ基、アミノ基、ニトロ基、クロロ基、ブロモ基などが挙げられる。 Formula (b1)

(In formula (b1), R ¹ represents a hydrogen atom, an aryl group, or an alkyl group.)
Examples of the alkyl group when R ¹ represents an alkyl group include a linear alkyl group having 1 to 10 carbon atoms, an alkyl group having a branched chain having 3 to 10 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. More specifically, a methyl group, an ethyl group, a t-butyl group, a cyclohexyl group and the like can be mentioned.
The alkyl group may have a substituent, and examples of the substituent that can be introduced into the alkyl group include a phenyl group, a carbonyl group, an alkoxy group, a hydroxy group, and an amino group.
When R ¹ represents an aryl group, examples of the aryl group include a monocyclic aryl group, a polycyclic aryl group, a condensed ring aryl group, a heteroaryl group containing a hetero atom, and the like. More specifically, a phenyl group, a naphthyl group, a biphenyl group, a benzimidazolyl group, a pyridyl group, a furyl group, and the like can be given.
The aryl group may have a substituent, and examples of the substituent that can be introduced into the aryl group include an alkyl group such as a methyl group, an ethyl group, a t-butyl group, and a cyclohexyl group, an alkoxy group such as a methoxy group, Examples thereof include a carboxy group, a hydroxy group, an amino group, a nitro group, a chloro group, and a bromo group.

（式（ｂ２）中、Ｒ²は、水素原子またはメチル基を表す。Ｒ³は、炭素数２または３のアルキレン基であり、Ｒ⁴は、水素原子、アリール基、またはアルキル基を表し、ｍは、１〜１５の整数を表す。） Formula (b2)

(In formula (b2), R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group having 2 or 3 carbon atoms, R ⁴ represents a hydrogen atom, an aryl group, or an alkyl group, m represents an integer of 1 to 15.)

Examples of the alkyl group when R ⁴ represents an alkyl group include a linear alkyl group having 1 to 20 carbon atoms, an alkyl group having a branched chain having 1 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. More specifically, a methyl group, an ethyl group, a t-butyl group, a cyclohexyl group, a 2-ethylhexyl group, and the like can be given.
The alkyl group may have a substituent, and examples of the substituent that can be introduced into the alkyl group include a phenyl group, a carbonyl group, and an alkoxy group.
Examples of the aryl group when R ⁴ represents an aryl group include a monocyclic aryl group, a polycyclic aryl group, a condensed ring aryl group, and a heteroaryl group containing a heteroatom. More specifically, a phenyl group, a naphthyl group, an anthranyl group, a biphenyl group, a benzimidazolyl group, an indolyl group, an imidazolyl group, an oxazolyl group, a carbazolyl group, a pyridyl group, a furyl group, and the like can be given.
The aryl group may have a substituent, and examples of the substituent that can be introduced into the aryl group include an alkyl group such as a nonyl group, a methyl group, an ethyl group, a t-butyl group, and a cyclohexyl group, and a methoxy group. Examples thereof include an alkoxy group, a carboxy group, a hydroxy group, an amino group, a nitro group, a chloro group, and a bromo group.

  The alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. Examples of the polymer containing the above-described polymerizable group include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  In particular, a copolymer having a repeating unit represented by the following general formula (2) and an acidic group is preferred, and more preferably a structural unit represented by the general formula (3) in addition to the general formula (2) and the acidic group. And a copolymer having.

（一般式（２）中、Ｒ²⁰は、水素原子またはメチル基を表し、Ｒ²¹〜Ｒ²⁵は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、アルキル基、またはアリール基を表す。）

(In General Formula (2), R ²⁰ represents a hydrogen atom or a methyl group, and R ^{21 to} R ²⁵ each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an aryl group. )

（一般式（３）中、Ｒ¹¹は、水素原子またはメチル基を表す。Ｒ¹²およびＲ¹³は、それぞれ独立して、水素原子または不飽和二重結合を部分構造として含む炭素数３〜２０のカルボニル基を表し、Ｒ¹²およびＲ¹³の双方が水素原子であることはない。Ｒ¹²およびＲ¹³の少なくとも一方が不飽和二重結合を部分構造として含む炭素数３〜２０のカルボニル基を表す場合、さらにカルボキシ基を部分構造として含んでいてもよい。）

(In General Formula (3), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or an unsaturated double bond having 3 to 20 carbon atoms as a partial structure. R ¹² and R ¹³ are not both hydrogen atoms, and at least one of R ¹² and R ^{13 is} a C 3-20 carbonyl group containing an unsaturated double bond as a partial structure. When represented, it may further contain a carboxy group as a partial structure.)

  Examples of the acrylic resin include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and commercially available KS resist 106 (Osaka). Organic Chemical Industry Co., Ltd.), Cyclomer P Series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable.

（式（Ｘ）において、Ｒ¹は、水素原子またはメチル基を表し、Ｒ²は炭素数２〜１０のアルキレン基を表し、Ｒ³は、水素原子またはベンゼン環を含んでもよい炭素数１〜２０のアルキル基を表す。ｎは１〜１５の整数を表す。） Moreover, the alkali-soluble binder may contain a structural unit derived from an ethylenically unsaturated monomer represented by the following formula (X).
Formula (X)

(In Formula (X), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 10 carbon atoms, and R ³ represents a hydrogen atom or a benzene ring that may contain a benzene ring. Represents an alkyl group of 20. n represents an integer of 1 to 15.)

In the formula (X), the number of carbon atoms of the alkylene group R ² is preferably 2-3. Although the carbon number of the alkyl group of R ³ is 1 to 20, more preferably 1 to 10, alkyl group of R ³ may include a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ³ include a benzyl group and a 2-phenyl (iso) propyl group.

  The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1,000 to 200,000 from the viewpoint of developability, liquid viscosity, etc., and 2,000 to 100,000. More preferably, the polymer of 5,000-50,000 is especially preferable.

The blending amount of the alkali-soluble binder is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, based on the total solid content of the coloring composition.
The acid value of the alkali-soluble binder is preferably 10 to 1000 mg / KOH, more preferably 50 to 300 mg / KOH, still more preferably 50 to 200 mg / KOH, and particularly preferably 105 to 200 mg / KOH.
The composition of the present invention may contain only one kind of alkali-soluble binder or two or more kinds. When two or more types are included, the total amount is preferably within the above range.

<< Crosslinking agent >>
The coloring composition of the present invention may further contain a crosslinking agent.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with one substituent; Phenol compounds, naphthol compounds or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are preferred.
For details such as specific examples of the crosslinking agent, reference can be made to the descriptions in paragraphs 0134 to 0147 of JP-A No. 2004-295116, the contents of which are incorporated herein.

<< Surfactant >>
The coloring composition of the present invention may contain a surfactant. The surfactant may be nonionic, cationic or anionic, but surfactants having an ethylene oxide structure and fluorine-containing surfactants are preferred. In particular, a surfactant having an ethylene oxide structure having an HLB value in the range of 9.2 to 15.5 or a fluorosurfactant described in JP-A-2-54202 is preferred.
When the coloring composition of the present invention contains a surfactant, the addition amount of the surfactant is preferably 0.0001% by mass to 2.0% by mass, more preferably, based on the total solid content of the coloring composition. Is 0.005% by mass to 1.0% by mass.
The composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.

  The coloring composition of the present invention may further contain various additives such as a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a sensitizer, and a light stabilizer as necessary.

<< Dye stabilizer >>
In addition to the triarylmethane dye, a dye stabilizer is preferably added to the composition of the present invention. As the stabilizer, for example, cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants can be used. Among the surfactants, a polymer surfactant (polymer dispersant) is preferable because it can be uniformly and finely dispersed.
Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; (Partial) ammonium salt and (partial) alkylamine salt; (co) polymer of hydroxyl group-containing unsaturated carboxylic acid ester such as hydroxyl group-containing polyacrylic acid ester or knitted product thereof; sulfonic acid or phosphoric acid having a crosslinkable group And the like.
As the crosslinkable group, a known polymerizable group that can be cross-linked by a radical, an acid, or heat can be used. Specific examples include (meth) acryl groups, styrene groups, vinyl groups, cyclic ether groups, and methylol groups, with (meth) acryl groups, styrene groups, and vinyl groups being preferred, and (meth) acryl groups and styrene groups being preferred. More preferred.

<Antioxidant>
The composition of the present invention may contain an antioxidant. Examples of the antioxidant include a radical scavenger, a peroxide decomposer, an ultraviolet absorber, and a singlet oxygen quencher.
Examples of the radical scavenger include phenolic antioxidants and hindered amine antioxidants. Examples of phenolic antioxidants include hydroxyphenylpropionate compounds, hydroxybenzyl compounds, thiobisphenol compounds, thiomethylphenol compounds, alkanediylphenol compounds, and the like. Of these, hydroxyphenylpropionate compounds are preferred from the viewpoint of the stability of color characteristics.
A peroxide decomposer is a compound that decomposes peroxides generated by exposure to light into harmless substances and prevents the generation of new radicals. For example, phosphorus antioxidants, sulfur And system antioxidants. Among these, sulfur-based antioxidants are preferable from the viewpoint of the stability of color characteristics.
Examples of the ultraviolet absorber include salicylate-based antioxidants and benzophenone-based antioxidants.
A singlet oxygen quencher is a compound that can deactivate singlet oxygen by energy transfer from oxygen in a singlet state. For example, ethylenic compounds such as tetramethylethylene and cyclopentene, diethylamine, triethylamine, Amines such as diazabicyclooctane (DABCO), N-ethylimidazole, condensed polycyclic aromatic compounds such as optionally substituted naphthalene, dimethylnaphthalene, dimethoxyanthracene, anthracene, diphenylanthracene; 1,3-diphenylisobenzofuran In addition to aromatic compounds such as 1,2,3,4-tetraphenyl-1,3-cyclopentadiene, pentaphenylcyclopentadiene, Harry H. et al. wasserman, “Single Oxygen”, Chapter 5, Academic Press (1979), Nicholas J. et al. Turro, ““ Modern Molecular Photochemistry ””, Chapter 14, The Benjamin Cummings Publishing Co. , Inc. (1978), and CMC Co., Ltd., High Performance Chemicals for Color Photosensitive Materials, Chapter 7 (2002) can include compounds exemplified as singlet oxygen quenchers.
In addition, a metal complex having a sulfur atom-containing compound as a ligand can be exemplified. Examples of such compounds include transition metal chelate compounds such as nickel complexes, cobalt complexes, copper complexes, manganese complexes, and platinum complexes having bisdithio-α-diketone, bisphenyldithiol, and thiobisphenol as ligands. .
Examples of the sulfur antioxidant include thiopropionate compounds and mercaptobenzimidazole compounds. Of these, thiopropionate compounds are preferred from the viewpoint of the stability of color characteristics.

  In this invention, antioxidant can be used individually or in mixture of 2 or more types. The content of the antioxidant is preferably 0.01 to 20 parts by mass, particularly preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant.

<Curing agent>
The coloring composition of the present invention can contain a compound that functions as a curing agent.
For example, at least one compound selected from the group consisting of aromatic amine compounds, tertiary amine compounds, amine salts, phosphonium salts, amidine salts, amide compounds, thiol compounds, blocked isocyanate compounds, and imidazole ring-containing compounds can be used. .
When the coloring composition contains such a curing agent, the low-temperature curing of the coloring pattern can be more effectively realized. In addition, the storage stability of the colored composition can be further improved.

<Reducing inhibitor>
In the coloring composition of the present invention, a compound that is more easily reduced than the triarylmethane dye can be added as a reduction inhibitor of the triarylmethane dye. Thereby, dye reduction fading can be further suppressed during ITO sputtering after pixel formation. Specifically, a quinone compound is preferable, and a quinone compound having a molecular weight of about 100 to 800 and having the following structure is preferable.

  The coloring composition of the present invention may further contain various additives such as a filler, an ultraviolet absorber, an aggregation inhibitor, a sensitizer and a light stabilizer, as necessary.

[Preparation method of coloring composition]
The coloring composition of the present invention is prepared by mixing the above-described components and optional components as necessary.
In preparation of the colored composition, the components constituting the colored composition may be combined at once, or may be sequentially added after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
The colored composition prepared as described above is preferably used after being filtered using a filter having a pore size of about 0.01 μm to 3.0 μm, more preferably about 0.05 μm to 0.5 μm. Can be provided.

  Since the colored composition of the present invention can form a colored cured film excellent in hue and contrast, it can be used in liquid crystal display devices (LCD) and color filters used in solid-state imaging devices (for example, CCD, CMOS, etc.). It can be suitably used for forming colored pixels and for producing printing ink, inkjet ink, paint, and the like. In particular, it is suitable for use in forming colored pixels for liquid crystal display devices.

[Color filter and manufacturing method thereof]
The color filter of the present invention is configured by providing a substrate and a colored region containing the colored composition of the present invention on the substrate. The colored region on the substrate is composed of colored films such as red (R), green (G), and blue (B) that form each pixel of the color filter.

The color filter of the present invention may be formed by any method as long as it can form a colored region (colored pattern) cured by applying the colored composition of the present invention on a substrate. Preferably, it is produced using the coloring composition of the present invention.
Moreover, when manufacturing the color filter for solid-state image sensors using the coloring composition of this invention, the manufacturing method described in Paragraph 0359-0371 of Unexamined-Japanese-Patent No. 2011-252065 can also be employ | adopted. .

The method for producing a color filter of the present invention includes a step (A) of applying (preferably coating) the above-described colored composition on a substrate to form a colored layer (also referred to as a colored composition layer), and a step It has the process (B) which hardens the coloring composition layer formed in (A).
The curing step is preferably performed in a pattern (preferably through a mask), and the uncured portion of the coating film is developed and removed with a developer to form a colored region (colored pattern). By passing through these steps, a colored pattern composed of pixels of each color (3 colors or 4 colors) is formed, and a color filter can be obtained. In the method for producing a color filter of the present invention, in particular, the step (C) of irradiating the colored pattern formed in the step (B) with ultraviolet rays and the colored pattern irradiated with the ultraviolet rays in the step (C) are applied. On the other hand, the aspect which further provided the process (D) which heat-processes is preferable.
By such a method, a color filter used for a liquid crystal display element or a solid-state imaging element can be manufactured with low process difficulty, high quality, and low cost.
Hereinafter, the manufacturing method of the color filter of the present invention will be described more specifically.

-Process (A)-
In the method for producing a color filter of the present invention, first, the above-described colored composition of the present invention is coated on a substrate directly or via another layer by a desired coating method to form a coating film comprising the colored composition. (Coloring composition layer) is formed, and then pre-curing (pre-baking) is performed as necessary, and the coloring composition layer is dried.

As the substrate, for example, alkali-free glass, sodium glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film thereto, solid-state imaging elements, and the like are used. Examples of the photoelectric conversion element substrate include a silicone substrate and a plastic substrate. On these substrates, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion. Further, if necessary, an undercoat layer may be provided on the substrate in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

In addition, a driving substrate on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed (hereinafter referred to as “TFT type liquid crystal driving substrate”) is used as the substrate. A color filter using the colored composition of the present invention can also be formed on the top to produce a color filter.
Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate can be used.

  The coloring composition of the present invention is applied to the substrate directly or through other layers. As a method to be applied, coating is preferable, and coating is preferably performed by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, and inkjet.

In the coating step, the method for applying the colored composition of the present invention to the substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin method or a spinless coating method (hereinafter referred to as slit nozzle). The application method is preferred.
In the slit nozzle coating method, the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the spinless coating method. In this case, the discharge amount of the coloring composition from the slit nozzle is usually 500 microliters / second to 2000 microliters / second, preferably 800 microliters / second to 1500 microliters / second, and the coating speed is Usually, it is 50 mm / second to 300 mm / second, preferably 100 mm / second to 200 mm / second.
Moreover, as solid content of the coloring composition used at an application | coating process, it is 10%-20% normally, Preferably it is 13%-18%.

When forming the coating film by the coloring composition of this invention on a board | substrate, as thickness (after a prebaking process) of this coating film, it is generally 0.3 micrometer-5.0 micrometers, Desirably 0.5 micrometer-4.0 micrometers. Most desirably, the thickness is 0.5 μm to 3.0 μm.
In the case of a color filter for a solid-state image sensor, the thickness of the coating film (after pre-baking) is preferably in the range of 0.5 μm to 5.0 μm.

In the application process, usually, a pre-bake treatment is performed after application. If necessary, vacuum treatment can be performed before pre-baking. The vacuum drying conditions are such that the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.
The pre-bake treatment is performed in a temperature range of 50 ° C. to 140 ° C., preferably about 70 ° C. to 110 ° C. using a hot plate, an oven, etc., and can be performed under conditions of 10 seconds to 300 seconds. Note that high-frequency treatment or the like may be used in combination with the pre-bake treatment. The high frequency treatment can be used alone.

Examples of the pre-baking condition include a condition of heating at 70 ° C. to 130 ° C. for about 0.5 minutes to 15 minutes using a hot plate or an oven.
Moreover, the thickness of the colored composition layer formed of the colored composition is appropriately selected according to the purpose. In the color filter for liquid crystal display devices, the range of 0.2 μm to 5.0 μm is preferable, the range of 1.0 μm to 4.0 μm is more preferable, and the range of 1.5 μm to 3.5 μm is most preferable. Moreover, in the color filter for solid-state image sensors, the range of 0.2 micrometer-5.0 micrometers is preferable, The range of 0.3 micrometer-2.5 micrometers is more preferable, The range of 0.3 micrometer-1.5 micrometers is the most preferable.
In addition, the thickness of a coloring composition layer is a film thickness after prebaking.

-Process (B)-
Subsequently, in the method for producing a color filter of the present invention, the film (colored composition layer) made of the colored composition formed on the substrate as described above is exposed through, for example, a photomask. As light or radiation applicable to exposure, g-line, h-line, i-line, j-line, KrF light and ArF light are preferable, and i-line is particularly preferable. When using the i-line to the irradiation light is preferably irradiated at an exposure dose of ^{100mJ / cm 2 ~10000mJ / cm 2} .

  Other exposure rays include ultra high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser light sources, fluorescent lamps, tungsten lamps, solar Light or the like can also be used.

Exposure process using a laser light source In an exposure method using a laser light source, an ultraviolet laser is used as the light source.
The irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm matches the photosensitive wavelength of the resist. Is preferable. Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
The exposure amount of the exposure object (pattern), in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm ² is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

There are no particular restrictions on the exposure apparatus, but commercially available devices such as Callisto (buoy technology), EGIS (buoy technology), DF2200G (Dainippon Screen) can be used. It is. Further, devices other than those described above are also preferably used.
When manufacturing a color filter for a liquid crystal display device, exposure using mainly h-line and i-line is preferably used by a proximity exposure machine and a mirror projection exposure machine. Further, when manufacturing a color filter for a solid-state image sensor, it is preferable to mainly use i-line in a stepper exposure machine. When manufacturing a color filter using a TFT type liquid crystal driving substrate, the photomask used has a through hole or a U-shaped depression in addition to a pattern for forming a pixel (colored pattern). The thing in which the pattern for forming is provided is used.

The colored composition layer exposed as described above can be heated.
The exposure can be performed while flowing a nitrogen gas in the chamber in order to suppress oxidation fading of the coloring material in the colored composition layer.

Subsequently, development is performed with a developer on the colored composition layer after exposure. Thereby, a negative type or positive type coloring pattern (resist pattern) can be formed. In the development step, the uncured portion of the coating film after exposure is eluted in the developer, and only the cured portion remains on the substrate.
Any developer can be used as long as it dissolves the coating film (colored composition layer) of the colored composition in the uncured part, but does not dissolve the cured part. For example, combinations of various organic solvents and alkaline aqueous solutions can be used.
Examples of the organic solvent used for development include the above-described solvents that can be used when preparing the colored composition of the present invention.
Examples of the alkaline aqueous solution include tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, benzyltrimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate Sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0 ] Concentration of an alkaline compound such as -7-undecene is 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass. And alkali aqueous solution was dissolved at a. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to be pH 11 to 13, more preferably pH 11.5 to 12.5.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 seconds to 90 seconds.
Development may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. It is also possible to prevent development unevenness by previously moistening the surface to be developed with water or the like before touching the developer. It is also possible to develop with the substrate tilted.
Further, when manufacturing a color filter for a solid-state image sensor, paddle development is also used.

After the development process, a rinsing process for washing and removing excess developer is performed, followed by drying, followed by heat treatment (post-baking) to complete the curing.
The rinsing process is usually performed with pure water, but in order to save liquid, pure water is used in the final cleaning, and used pure water is used in the initial stage of cleaning, or the substrate is inclined and cleaned. Alternatively, a method of using ultrasonic irradiation together may be used.

  After the rinse treatment, after draining and drying, a heat treatment of about 200 ° C. to 250 ° C. is usually performed. In this heat treatment (post-bake), the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with an expression.

By sequentially repeating the above steps for each color according to the desired number of hues, it is possible to produce a color filter in which a cured film (colored pattern) colored in a plurality of colors is formed.
Since the color filter of the present invention has high contrast, small color density unevenness, and good color characteristics, it can be suitably used for a solid-state imaging device or a liquid crystal display device.

-Step (C)-
In the method for producing a color filter of the present invention, in particular, post-exposure by ultraviolet irradiation can be performed on a colored pattern (pixel) formed using a colored composition.

-Process (D)-
It is preferable to further heat-treat the colored pattern that has been post-exposed by ultraviolet irradiation as described above. The colored pattern can be further cured by subjecting the formed colored pattern to heat treatment (so-called post-bake treatment). This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
As temperature in the case of heat processing, it is preferable that it is 100 to 300 degreeC, More preferably, it is 150 to 250 degreeC. The heating time is preferably about 10 minutes to 120 minutes.

The colored pattern thus obtained constitutes a pixel in the color filter. In the production of a color filter having a plurality of hue pixels, the above steps (A), (B), and if necessary, the steps (C) and (D) are repeated according to the desired number of colors. Good.
It should be noted that the above step (C) and / or step (D) may be performed each time the formation, exposure, and development of the monochromatic coloring composition layer is completed (for each color) After all the colored composition layers have been formed, exposed, and developed, the step (C) and / or the step (D) may be performed collectively.

  Moreover, the coloring composition of this invention is applicable also to the manufacturing method of the color filter containing a dry etching process. As an example of such a manufacturing method, the step of forming a colored layer using the colored composition of the present invention, the step of forming a photoresist layer on the colored layer, the photoresist layer by exposing and developing. Examples of the manufacturing method include a step of patterning to obtain a resist pattern, and a step of dry etching the colored layer using the resist pattern as an etching mask. When the colored composition of the present invention is used in a method for producing a color filter including a dry etching step, it may be a photocurable composition or a thermosetting composition. In the case of a thermosetting composition, a thermosetting agent can be used. As the thermosetting agent, a compound having two or more epoxy groups in one molecule is preferable.

The color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) is excellent in hue and contrast because the colored composition of the present invention is used.
The color filter of the present invention can be used for a liquid crystal display element or a solid-state image sensor, and is particularly suitable for use in a liquid crystal display device. When used in a liquid crystal display device, it is possible to display an image with excellent spectral characteristics and contrast while achieving a good hue using a triarylmethane dye as a colorant.

As for the use of the coloring composition of the present invention, the description has mainly focused on the use for forming the color pattern of the color filter in the above, but it is also applicable to the formation of a black matrix for isolating the color pattern (pixel) constituting the color filter. can do.
For the black matrix on the substrate, a coloring composition containing a black pigment processed pigment such as carbon black or titanium black is used, followed by coating, exposure, and development, and then post-baking as necessary. Can be formed.

[Liquid Crystal Display]
The liquid crystal display element and the solid-state image sensor of the present invention are provided with the color filter of the present invention. More specifically, for example, by forming an alignment film on the inner surface side of the color filter, facing the electrode substrate, and filling the gap with liquid crystal and sealing, a panel which is the liquid crystal display element of the present invention is obtained. . For example, the solid-state image sensor of this invention is obtained by forming a color filter on a light receiving element.

  For the definition of liquid crystal display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Devices (written by Junaki Ibuki, Sangyo Tosho) Issued in 1989). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be 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”.

The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a horizontal electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
The color filter of the present invention can also be used for a bright and fine COA (Color-filter On Array) system.

  When the color filter of the present invention is used for a liquid crystal display element, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and further, red, green and blue LED light sources (RGB-LED). By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

[Solid-state imaging device]
The colored composition of the present invention can be preferably used for a solid-state imaging device. The configuration of the solid-state imaging device is a configuration provided with a color filter manufactured using the colored composition of the present invention, and is not particularly limited as long as the configuration functions as a solid-state imaging device. Such a structure is mentioned.

A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on a support, and the photodiode and the transfer electrode are provided on the support. A light-shielding film made of tungsten or the like having an opening only in the light-receiving portion of the photodiode, and a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion. It is the structure which has the color filter for solid-state image sensors of this invention on a device protective film.
Further, a configuration having a light condensing means (for example, a microlens, etc., the same applies hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light condensing means on the color filter. Etc.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “%” and “parts” are based on mass.

<Example 1>
(Preparation of coloring composition (coating solution))
Components in the following composition were mixed to prepare a colored composition.
<Composition>
The following triarylmethane dye (I-1): 2 parts by mass The following photopolymerizable compound: (T-1) 10.3 parts by mass The following alkali-soluble binder (U-1)
... 21.2 parts by mass (converted to solids: 8.5 parts by mass)
The following photopolymerization initiator (V-3): 1.0 part by mass The following solvent (X-1): 7.2 parts by weight The following solvent (X-2): 0.4 parts by mass-Surfactant (Z-1) shown below--0.006 parts by mass

Triarylmethane dye (I-1): Compound having the following structure

溶剤（Ｘ−１）：プロピレングリコールモノメチルエーテルアセテート
溶剤（Ｘ−２）：３−エトキシプロピオン酸エチル
界面活性剤（Ｚ−１）：メガファックＦ７８１−Ｆ（大日本インキ化学工業（株）製） Photopolymerizable compound (T-1): Kayalad DPHA (Nippon Kayaku Co., Ltd., mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
Alkali-soluble binder (U-1): benzyl methacrylate / methacrylic acid (85/15 [mass ratio] copolymer (weight average molecular weight: 12,000) in propylene glycol monomethyl ether acetate solution (solid content: 40.0 mass%) Acid value (100mgKOH / g)
Photopolymerization initiator (V-3): an oxime compound having the following structure

Solvent (X-1): Propylene glycol monomethyl ether acetate Solvent (X-2): Ethyl 3-ethoxypropionate Surfactant (Z-1): Megafac F781-F (manufactured by Dainippon Ink & Chemicals, Inc.)

<Examples 2 to 12>
A colored composition was prepared in the same manner as in Example 1 except that the triarylmethane dye was changed to (I-2) to (I-12) below.

N in the following compound (I-11) represents the number of repeating units, and in this case represents 200. Moreover, the molar ratio (a: b: c) of each repeating unit in the following compound (I-12) represents 20:50:30.

<Example 13>
A colored composition was prepared in the same manner as in Example 1 except that the alkali-soluble binder (U-1) used in Example 1 was changed to the following alkali-soluble binder (U-1-1).
Alkali-soluble binder (U-1-1): benzyl methacrylate / methacrylic acid / allyl methacrylate (20/60/20) [mass ratio] copolymer (weight average molecular weight: 20,000) in propylene glycol monomethyl ether acetate solution ( Solid content 40.0% by mass) Acid value (250 mgKOH / g)

<Example 14>
A colored composition was prepared in the same manner as in Example 1 except that the alkali-soluble binder (U-1) used in Example 1 was changed to the following alkali-soluble binder (U-2-1).
Alkali-soluble binder (U-2-1): GMA-MAA / methacrylic acid / cyclohexyl methacrylate (26/38/36) [mass ratio] copolymer (weight average molecular weight: 3,000) propylene glycol monomethyl ether acetate solution (Solid content: 40.0% by mass) Acid value (125 mgKOH / g)
GMA-MAA has the following structure.

<Example 15>
A colored composition was prepared in the same manner as in Example 1 except that the alkali-soluble binder (U-1) used in Example 1 was changed to the following alkali-soluble binder (U-1-2).
Alkali-soluble binder (U-1-2): benzyl methacrylate / methacrylic acid / allyl methacrylate / N-phenylmaleimide (15/20/30/35) [mass ratio] copolymer (weight average molecular weight: 20,000) Propylene glycol monomethyl ether acetate solution (solid content: 40.0% by mass) Acid value (110 mgKOH / g)

<Comparative Example 1>
A colored composition was prepared in the same manner as in Example 1 except that the triarylmethane dye was changed to the following Comparative Compound 1 described in Example 2 of WO2010-127301.
Comparative compound 1

<Comparative Example 2>
A colored composition was prepared in the same manner as in Example 1 except that the triarylmethane dye was changed to the following Comparative Compound 2.
Comparative compound 2: (manufactured by Tokyo Chemical Industry Co., Ltd., product name Basic Blue 7)

<Preparation of colored film with colored composition>
The colored composition obtained above was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the maximum absorbance at 600 to 700 nm was 1.5 to 2.0. It was dried in an oven for 180 seconds to produce a colored film on the substrate.

The following evaluation was performed about the colored film obtained above.
<Heat resistance>
The colored film was heated at 230 ° C. for 40 minutes, and then the chromaticity change, that is, the ΔEab value was measured. The ΔEab value was calculated from UV-Vis spectra before and after heating. A smaller ΔEab value indicates better light resistance.

<Solvent resistance (color difference)>
The colored film heated at 230 ° C. for 20 minutes was immersed in NMP (N-methylpyrrolidone) at 25 ° C. for 10 minutes, and the chromaticity before and after the immersion was measured to calculate a color change index ΔEab. . The ΔEab value was calculated from UV-Vis spectra before and after heating. In addition, when the value of ΔEab was 3 or less, the hue change was small and the solvent resistance was excellent.

<Voltage holding ratio>
The colored composition was applied onto a glass substrate with an ITO electrode (trade name: 1737 manufactured by Corning) to a thickness of 2.0 μm after drying, and dried (prebaked) in an oven at 90 ° C. for 60 seconds. Then, exposure is performed at 100 mJ / cm ² without using a mask (illuminance is 20 mW / cm ² ), and a 1% aqueous solution of an alkali developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) is used. It was developed at 25 ° C., washed with water and dried, and the coated film was heat-treated (post-baked) in an oven at 230 ° C. for 30 minutes to form a colored cured film. Next, the substrate on which this colored cured film is formed and the substrate on which ITO electrodes are simply deposited in a predetermined shape are bonded together with a sealant mixed with 5 μm glass beads, and then Merck liquid crystal MJ971118 (trade name) ) Was injected to prepare a liquid crystal cell.
Next, after putting the liquid crystal cell in a constant temperature layer at 70 ° C. for 48 hours, the voltage holding ratio of the liquid crystal cell was measured using the liquid crystal voltage holding ratio measuring system VHR-1A type (trade name) manufactured by Toyo Technica under the following measurement conditions. It measured and evaluated by the score shown to the following reference | standard. The higher the score, the better the voltage holding ratio.
Measurement conditions / Distance between electrodes: 5 μm to 15 μm
・ Applied voltage pulse amplitude: 5V
・ Applied voltage pulse frequency: 60 Hz
・ Applied voltage pulse width: 16.67 msec
* Voltage holding ratio: liquid crystal cell potential difference after 16.7 milliseconds / value of voltage applied in 0 milliseconds * judgment method 90% or more: 5
85% or more and less than 90%: 4
80% or more and less than 85%: 3
75% or more and less than 80%: 2
Less than 75%: 1

From the above results, it was found that the present invention can provide a colored composition having excellent heat resistance, solvent resistance and voltage holding ratio.
On the other hand, it was found that the heat resistance, solvent resistance, and voltage holding ratio were not good in the colored composition of the comparative example.

Claims (13)

Coloring comprising a cation having a triarylmethane structure with a molecular weight of 2000 or less and a counter anion, wherein the counter anion contains a crosslinkable group and / or a repeating unit containing a counter anion and a polymerizable compound Composition. The counter anion has at least one selected from —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , a structure represented by the following general formula (A1) and a structure represented by the following general formula (A2). The coloring composition according to claim 1.
General formula (A1)

(In general formula (A1), R ¹ and R ² each independently represent —SO ₂ — or —CO—.)
General formula (A2)

(In the general formula (A2), R ³ represents —SO ₂ — or —CO—. R ⁴ and R ⁵ each independently represents —SO ₂ —, —CO— or —CN). The coloring composition according to claim 1, wherein the counter anion has at least one selected from the structure represented by —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ^— and the following general formula (A1-1). .
Formula (A1-1)

(In General Formula (A1-1), R ¹ and R ² each independently represent —SO ₂ — or —CO—, and X ¹ and X ² each independently represent an alkylene group or an arylene group. ) The cation having a triarylmethane structure and a molecular weight of 2000 or less is represented by at least one of the general formula (TP1), the general formula (TP2), and the general formula (TP3). The coloring composition as described in.

(In general formulas (TP1) and (TP2), Rtp _{1 to} Rtp ₄ each independently represents a hydrogen atom, an alkyl group, or an aryl group. Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ and Rtp ₁₁ are Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group, or NRtp ₇₁ Rtp _72. Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group, or an aryl group. Rtp ₁₀ represents a substituent, a, b and c each independently represent an integer of 0 to 4. When a, b and c are 2 or more, Rtp ₆ , Rtp ₇ and Rtp ₈ The two may be linked to each other to form a ring.)
General formula (TP3)

(In General Formula (TP3), Dye represents a structure represented by General Formula (TP1) or General Formula (TP2). L ² represents a divalent linking group, and General Formula (TP1) Or, it is bonded to any site in the structure represented by the general formula (TP2).) The coloring composition of any one of Claims 1-4 in which the said counter anion has a repeating unit containing an anion. The coloring composition of any one of Claims 1-5 which further contains a photoinitiator. The colored composition according to any one of claims 1 to 6, which is used for forming a colored layer of a color filter. The colored cured film formed by hardening | curing the coloring composition of any one of Claims 1-7. A color filter having the colored cured film according to claim 8. A step of applying the colored composition according to any one of claims 1 to 7 on a support to form a colored composition layer, a step of exposing the colored composition layer in a pattern, and an unexposed state And a step of developing and removing the portion to form a colored pattern. A step of applying the colored composition according to any one of claims 1 to 7 on a support to form a colored composition layer and curing to form a colored layer, a photoresist layer on the colored layer A method for producing a color filter, comprising: a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, or a step of dry etching the colored layer using the resist pattern as an etching mask. The color filter manufactured by the manufacturing method of the color filter of Claim 10 or 11. A solid-state imaging device or an image display device having the color filter according to claim 9 or the color filter produced by the method for producing a color filter according to claim 10 or 11.