WO2016136936A1

WO2016136936A1 - Coloring composition, cured film, color filter, manufacturing method for color filter, solid state imaging element, image display device and polymer

Info

Publication number: WO2016136936A1
Application number: PCT/JP2016/055788
Authority: WO
Inventors: 福田　誠; 藤田　明徳; 崇一郎長田; 晃男片山
Original assignee: 富士フイルム株式会社
Priority date: 2015-02-27
Filing date: 2016-02-26
Publication date: 2016-09-01
Also published as: TW201634592A; TWI739735B; KR101957754B1; KR20170107488A; JP6461304B2; JPWO2016136936A1

Abstract

Provided are a coloring composition having excellent heat resistance and solvent resistance, a cured film, a color filter, a manufacturing method for the color filter, a solid state imaging element, an image display device and a polymer. The coloring composition contains a polymerizable compound, and a polymer TP which includes a repeating unit A, which has a triarylmethane structure, and a repeating unit B, which has a crosslinking group. The polymer TP has a weight average molecular mass of 3,000 to 500,000. The content of the compound A, which has a triarylmethane structure and a weight average molecular mass of not more than 1500, is not more than 20 mass% with respect to the mass of the polymer TP.

Description

Colored composition, cured film, color filter, method for producing color filter, solid-state imaging device, image display device, and polymer

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, an image display device, and a polymer.

The coloring composition is used for manufacturing a color filter and the like.
In recent years, color filters tend to be used not only for monitors but also for televisions in liquid crystal display device 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.
Patent Documents 1 and 2 disclose a colored composition containing a compound having a triarylmethane structure.

US Patent Application Publication No. 2013/0141810 International Publication No. 2013/176383

A coloring composition used for a color filter or the like is required to be able to form a film having excellent heat resistance and solvent resistance.
However, the coloring compositions disclosed in Patent Documents 1 and 2 are not sufficient in heat resistance and solvent resistance.

Therefore, an object of the present invention is to provide a coloring composition, a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, an image display device, and a polymer excellent in heat resistance and solvent resistance.

Under such circumstances, the present inventors have conducted intensive studies. As a result, the polymer includes a repeating unit A having a triarylmethane structure and a repeating unit B having a crosslinkable group, and has a weight average molecular weight of 3000 to The inventors have found that the above object can be achieved by using a polymer having a triarylmethane structure having a weight average molecular weight of 1500 or less and having a triarylmethane structure of 20% by mass or less, and has completed the present invention. The present invention provides the following.
<1> Polymer TP containing at least one repeating unit A having a triarylmethane structure selected from general formula (TP1) and general formula (TP2) and a repeating unit B having a crosslinkable group, and polymerization And a sex compound,
The polymer TP has a weight average molecular weight of 3000 to 500,000, and the content of the compound A having a triarylmethane structure and a weight average molecular weight of 1500 or less is 20% by mass or less based on the mass of the polymer TP. ;

In the 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 each Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ₇₁ Rtp ₇₂ ; Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group or an aryl group; Rtp ₁₀ represents a hydrogen atom, an alkyl group or an aryl group; a, b, c and d each independently represent an integer of 0 to 4; when a, b, c and d are 2 or more, Rtp ₅ , Rtp ₆ , Rtp ₈ and Rtp ₉ may be linked to each other to form a ring; X represents an anion, or X is absent and Rtp ₁ to Rtp ₁₁ , Rtp _At least one of ₇₁ and Rtp ₇₂ contains an anion; any of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ represents a binding site to the repeating unit A.
<2> The colored composition according to <1>, wherein the polymer TP has a content of the compound A of 10% by mass or less based on the mass of the polymer TP.
<3> The colored composition according to <1> or <2>, wherein the polymer TP has a weight average molecular weight of 10,000 to 50,000.
<4> The crosslinkable group of the repeating unit B is at least one selected from a group containing an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, an oxazoline group, a group represented by —C—O—R, and a carbonate group. The coloring composition according to any one of <1> to <3>, which is a seed; wherein R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
<5> X is at least one anion selected from fluorine anion, chlorine anion, bromine anion, iodine anion, cyanide ion, perchlorate anion, borate anion, PF ⁶⁻ and SbF ⁶⁻ , and − Selected from SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , a compound having at least one structure selected from the structure represented by the following general formula (A1) and the structure represented by the following general formula (A2) A colored composition according to any one of <1> to <4>;
General formula (A1)
In general formula (A1), R ¹ and R ² each independently represents —SO ₂ — or —CO—;
General formula (A2)

In general formula (A2), R ³ represents —SO ₂ — or —CO—; R ⁴ and R ⁵ each independently represents —SO ₂ —, —CO— or —CN.
<6> The colored composition according to any one of <1> to <5>, wherein X is a compound containing a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion, or a sulfonate anion.
<7> The colored composition according to any one of <1> to <6>, wherein X is a compound containing a crosslinkable group.
<8> The colored composition according to any one of <1> to <7>, wherein X is a polymer containing a repeating unit having an anion moiety.
<9> In general formulas (TP1) and (TP2), at least one of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ is substituted with a group represented by general formula (P), <1> to <4> the colored composition according to any one of the above;
General formula (P)

In general formula (P), L represents a single bond or a divalent linking group, and X ¹ includes —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , and a structure represented by the following general formula (A1). Selected from at least one selected from a group and a group containing a structure represented by the following general formula (A2);
General formula (A1)

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

In general formula (A2), R ³ represents —SO ₂ — or —CO—; R ⁴ and R ⁵ each independently represents —SO ₂ —, —CO— or —CN.
<10> The colored composition according to any one of <1> to <9>, wherein the triarylmethane structure of the repeating unit A is represented by the following general formula (TP3);

In the general formula (TP3), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6; Rtp ₂₂ each independently represents an aryl group having 6 to 10 carbon atoms, Rtp ₇₁ is represents an alkyl group or an aryl group; X is either an anion, X is at least one contains an anion of Rtp _21, Rtp ₂₂ and Rtp ₇₁ to absent; repeated either Rtp _21, Rtp ₂₂ and Rtp ₇₁ is It represents the binding site with unit A.
<11> The colored composition according to any one of <1> to <10>, wherein the repeating unit A is represented by the following general formula (TP3-1);

In general formula (TP3-1), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Rtp ₂₂ each independently represents an aryl group having 6 to 10 carbon atoms, and Rtp _71a Represents an alkylene group or an arylene group; L ₁ represents a single bond or a divalent linking group, Rtp ₃₁ represents a hydrogen atom or a methyl group; X represents an anion, or X does not exist and Rtp _At least one of ₂₁ and Rtp ₂₂ contains an anion.
<12> The colored composition according to any one of <1> to <11>, wherein the repeating unit A is represented by the following general formula (TP3-2);

In general formula (TP3-2), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Rtp ₂₄ each independently represents an alkyl group having 1 to 4 carbon atoms, and Rtp ₂₅ Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Rtp _71a represents an alkylene group or an arylene group; Rtp ₃₁ represents a hydrogen atom or a methyl group; L ₁ represents a single bond or X represents an anion, or X does not exist and at least one of Rtp ₂₁ and Rtp ₂₄ includes an anion.
<13> The polymer TP contains a repeating unit derived from at least one of (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylic acid amide, according to any one of <1> to <12> Coloring composition.
<14> The colored composition according to any one of <1> to <13>, comprising at least one selected from a xanthene compound, a dipyrromethene metal complex compound, a dioxazine compound, and a phthalocyanine compound.
<15> The colored composition according to any one of <1> to <14>, comprising a photopolymerization initiator.
<16> The colored composition according to any one of <1> to <15>, comprising a bis (trifluoromethanesulfonyl) imide salt.
<17> The colored composition according to any one of <1> to <16>, which is used for forming a colored layer of a color filter.
<18> A cured film obtained by curing the colored composition according to any one of <1> to <17>.
<19> A color filter having the cured film according to <18>.
<20> A step of forming a colored composition layer using the colored composition according to any one of <1> to <17>, a step of exposing the colored composition layer in a pattern, and a coloring composition layer And a step of developing and removing the unexposed portion to form a colored pattern.
<21> A step of forming a colored composition layer using the colored composition according to any one of <1> to <17> and curing to form a colored layer; and forming a photoresist layer on the colored layer A method of manufacturing a color filter, comprising: a step of patterning a photoresist layer by exposure and development to obtain a resist pattern; and a step of dry etching the colored layer using the resist pattern as an etching mask.
<22> A solid-state imaging device having the color filter according to <19>.
<23> An image display device having the color filter according to <19>.
<24> A polymer comprising a repeating unit represented by the following general formula (TP-7), wherein the polymer has a weight average molecular weight of 3000 to 500,000 and a compound having a triarylmethane structure and having a weight average molecular weight of 1500 or less. A polymer having a content of 20% by mass or less based on the mass of the polymer;

In general formula (TP-7), each R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, and R ^1a represents an alkylene group or an arylene group. L ¹¹ represents a single bond or a divalent linking group having 1 to 30 carbon atoms; L ¹² and L ¹³ represent a single bond or a divalent linking group having 1 to 30 carbon atoms. R ² represents a hydrocarbon group having 1 to 10 carbon atoms; R ³ represents a crosslinkable group; X represents a compound containing a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion or a sulfonate anion A to d are mass ratios of repeating units, a and d each represent a number exceeding 0, and b and c each independently represent a number of 0 or more.

According to the present invention, it has become possible to provide a colored composition, a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, an image display device, and a polymer excellent in heat resistance and solvent resistance.

Hereinafter, the contents of the present invention will be described in detail.
In the present specification, “˜” 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).
The “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an 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 refers not only to exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also particle beams such as electron beams and ion beams. This drawing is also included in the exposure.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”. ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
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 refers to a compound having a polymerizable functional group. 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 and the number average molecular weight in the present invention are defined as polystyrene conversion values in gel permeation chromatography (GPC) measurement unless otherwise specified.

<Coloring composition>
The colored composition of the present invention includes a repeating unit A having a triarylmethane structure, which will be described later, and a polymer TP containing a repeating unit B having a crosslinkable group, and a polymerizable compound. The content of Compound A having a molecular weight of 3000 to 500,000 and having a triarylmethane structure and a weight average molecular weight of 1500 or less is 20% by mass or less based on the mass of the polymer TP.
By setting it as such a structure, the coloring composition excellent in heat resistance and solvent resistance can be provided. Furthermore, a film having a good voltage holding ratio can be formed. As a mechanism for obtaining such an effect, it is considered that the use of the polymer TP makes it difficult for the polymer TP to elute from the film when the film is formed, and the solvent resistance and heat resistance are improved. Hereinafter, each component of the coloring composition of this invention is demonstrated in detail.

<< Polymer TP >>
<<< Repeating unit A >>>
The polymer TP includes a repeating unit A having a triarylmethane structure.
The repeating unit A preferably has a structure represented by the following general formula (A). The repeating unit A is preferably contained at 1 to 99% by mass in all the repeating units of the polymer TP. The upper limit is more preferably 95% by mass or less, and still more preferably 90% by mass or less. The lower limit is more preferably 5% by mass or more. If content of the repeating unit A is the said range, color value will become more favorable.

In the general formula (A), X ¹ represents a main chain of repeating units. L ¹ represents a single bond or a divalent linking group. DyeI represents a triarylmethane structure represented by general formula (TP1) or general formula (TP2) described later.
In the general formula (A), X ¹ represents a main chain of repeating units, usually represents a linking group formed by polymerization reaction, for example, having a (meth) acrylic group, styrene group, a vinyl group, an ether group A main chain derived from a compound is preferred. An embodiment having a main chain cyclic alkylene group is also preferred. In addition, it has couple | bonded with the other repeating unit in the site | part represented by two *.
X ¹ is not particularly limited as long as it is a linking group formed from a known polymerizable monomer, but is particularly preferably a linking group represented by the following (XX-1) to (XX-24), (XX— 1) (meth) acrylic linking chains represented by (XX-2), styrene linking chains represented by (XX-10) to (XX-17), (XX-18) and (XX-19) ) And a vinyl-based linking chain represented by (XX-24), and (meth) acrylic linking chains represented by (XX-1) and (XX-2), ( More preferably selected from styrene-based linking chains represented by (XX-10) to (XX-17) and vinyl-based linking chains represented by (XX-24), and (XX-1) and (XX- (Meth) acrylic connecting chain represented by 2) and (XX-11) In styrene linking chain represented are especially preferred.
In (XX-1) to (XX-24), this represents that L1 is linked 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.

When L ¹ represents a divalent linking group, an alkylene group, an arylene group, a heterocyclic group, —CH═CH—, —O—, —S—, —CO—, —NR—, —CONR—, —COO —, —OCO—, —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.
The alkylene group preferably has 1 to 30 carbon atoms. The upper limit is more preferably 25 or less, and still more preferably 20 or less. The lower limit is more preferably 2 or more, and still more preferably 3 or more. The alkylene group may be linear, branched or cyclic.
The carbon number of the arylene group is preferably 6 to 20, and more preferably 6 to 12.
L ¹ is preferably an alkylene group, an arylene group, —NH—, —CO—, —O—, —COO—, —OCO— or a linking group in which two or more thereof are combined, and includes an alkylene group, an arylene group, and , —O—, —COO—, and a divalent group formed by combining one or more selected from —OCO— are more preferable, and an alkylene group or alkylene groups are —O—, —COO—, and —OCO. More preferred is a linking group linked via one or more selected from-.
In L ¹ , the number of atoms constituting the chain connecting X ¹ and Dye I is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and particularly preferably 5 or more. The upper limit is preferably 20 or less, for example. According to this aspect, in the synthesis of the polymer TP, a low-molecular triarylmethane compound that is unreacted or insufficiently reacted can be effectively suppressed. For example, in the following case, the number of atoms constituting the chain connecting X ¹ and Dye I is ten. The numbers written in the structural formula are the number of atoms constituting the chain connecting X ¹ and DyeI.

When L ¹ represents a single bond, X ¹ is bonded to any one of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp _{72 in} the general formulas (TP1) and (TP2), and Rtp ₇₁ or Rtp ₇₂ It is preferable that it is couple | bonded with.
When L ¹ represents a divalent linking group, L ¹ is bonded to any one of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp _{72 in} the general formulas (TP1) and (TP2), and Rtp ₇₁ or Rtp ₇₂ is preferably bonded.

<<<<< Triarylmethane Structure >>>>
Next, the triarylmethane structure that the repeating unit A has will be described.
The repeating unit A has a triarylmethane structure selected from the general formula (TP1) and the general formula (TP2).

In the 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 each Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ₇₁ Rtp ₇₂ ; Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group or an aryl group; Rtp ₁₀ represents a hydrogen atom, an alkyl group or an aryl group; a, b, c and d each independently represent an integer of 0 to 4; when a, b, c and d are 2 or more, Rtp ₅ , Rtp ₆ , Rtp ₈ and Rtp ₉ may be linked to each other to form a ring; X represents an anion, or X is absent and Rtp ₁ to Rtp ₁₁ , Rtp _At least one of ₇₁ and Rtp ₇₂ contains an anion; any of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ represents a binding site to the repeating unit A.

In general formula (TP1), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group, or an aryl group. It is preferable that _one of Rtp ₁ and Rtp ₂ is an alkyl group and the other is an aryl group. It is preferable that one of Rtp ₃ and Rtp ₄ is an alkyl group and the other is an aryl group.

The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. The alkyl group is preferably unsubstituted. Examples of the substituent include the substituents mentioned in the section of the substituent group A described later.
The aryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 carbon atoms. Examples of the substituent that the aryl group may have include the substituents mentioned in the section of the substituent group A described later.

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 .
The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably linear. Examples of the substituent that the alkyl group may have include the substituents mentioned in the section of Substituent Group A described later. The aryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 carbon atoms.
Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom or an alkyl group.
The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably cyclic. The alkyl group may be substituted. Examples of the substituent that the alkyl group may have include the substituents mentioned in the section of Substituent Group A described later.
The aryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 carbon atoms. Examples of the substituent that the aryl group may have include the substituents mentioned in the section of the substituent group A described later.

In general formula (TP1), Rtp ₅ , Rtp ₆ and Rtp ₈ each independently represent a substituent. Examples of the substituent include the substituents mentioned in the section of the substituent group A described later. 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 carboxy group, or a sulfo group is preferable, and a linear chain having 1 to 5 carbon atoms. Or a branched alkyl group, an alkenyl group having 1 to 5 carbon atoms, a phenyl group, or a carboxy 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, more preferably 0. c preferably represents 0-2.

In general formula (TP2), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group or an aryl group, and are synonymous with Rtp ₁ to Rtp ₄ in general formula (TP1), and the preferred ranges are also the same. It is.

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.
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.

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

In the general formula (TP1) and the general formula (TP2), any _one of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ represents a binding site to the repeating unit, and in particular, Rtp ₇₁ or Rtp ₇₂ is bonded to the repeating unit. A site is preferred.

In the general formula (TP1) and the general formula (TP2), at least one of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ may contain an anion.
As the anion, —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , bis (sulfonyl) imide anion, tris (sulfonyl) methide anion and tetraarylborate anion are preferable, and bis (sulfonyl) imide anion and tris (sulfonyl) methide anion And tetraarylborate anions are more preferable, and bis (sulfonyl) imide anions and tris (sulfonyl) methide anions are more preferable.
Specifically, a structure in which at least one of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ is substituted with the general formula (P) can be mentioned.
General formula (P)

In general formula (P), L represents a single bond or a divalent linking group, and X ¹ represents an anion.

In general formula (P), L represents a single bond or a divalent linking group. The divalent linking group preferably represents —NR ¹⁰ —, —O—, —SO ₂ —, an alkylene group containing a fluorine atom, an arylene group containing a fluorine atom, or a combination thereof. In particular, a group consisting of a combination of —NR ¹⁰ —, —SO ₂ and an alkylene group containing a fluorine atom, a group consisting of a combination of —O— and an arylene group containing a fluorine atom, or —NR ¹⁰ — and —SO _A group consisting of a combination of ₂ and an alkylene group containing a fluorine atom is preferred.
In —NR ¹⁰ —, R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom.
The number of carbon atoms of the alkylene group containing a fluorine atom is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3. These alkylene groups are more preferably perfluoroalkylene groups. Specific examples of the fluorine-substituted alkylene group include a difluoromethylene group, a tetrafluoroethylene group, and a hexafluoropropylene group.
The number of carbon atoms of the arylene group containing a fluorine atom is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10. Specific examples of the arylene group containing a fluorine atom include a tetrafluorophenylene group, a hexafluoro-1-naphthylene group, and a hexafluoro-2-naphthylene group.

In the general formula (P), X ¹ represents an anion, —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , a group containing a structure represented by the following general formula (A1), and the following general formula (A2) It is preferable to be selected from at least one selected from a group containing a structure represented by:
General formula (A1)

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

In general formula (A2), R ³ represents —SO ₂ — or —CO—. R ⁴ and R ⁵ each independently represents —SO ₂ —, —CO— or —CN.

Group containing a structure represented by the general formula (A1), in the general formula (A1), to one end of R ¹ and R ^2, preferably has a fluorine-substituted alkyl group, one of R ¹ and R ² More preferably, is directly bonded to a fluorine-substituted alkyl group. The number of carbon atoms in the fluorine-substituted alkyl group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 1. These alkyl groups are more preferably perfluoroalkyl groups. As a specific example of the fluorine-substituted alkyl group, a trifluoromethyl group is preferable.
The group containing the structure represented by the general formula (A2) preferably has a fluorine-substituted alkyl group at least at any terminal of R ³ to R ^{5 in} the general formula (A2), and R ³ to R ⁵ More preferably, at least one of the above is directly bonded to the fluorine-substituted alkyl group. In particular, at least two ends of R ³ ~ R ^5, preferably has a fluorine-substituted alkyl group, and more preferably at least two of R ³ ~ R ⁵ are attached directly to a fluorine-substituted alkyl group. A fluorine-substituted alkyl group is synonymous with what was demonstrated by group containing the structure represented by general formula (A1), and its preferable range is also the same.
Other specific examples of X ¹ include counter anion A described later. In this case, any one hydrogen atom or halogen atom constituting the counter anion A is bonded to L in the general formula (P).

In the general formulas (TP1) and (TP2), the portion substituted with the general formula (P) may be present only at one place, or may be present at two or more places. When there are two or more moieties substituted with the general formula (P), the polymer TP has a number of cations corresponding to the number of anions in addition to the cations contained in the triarylmethane structure. Is preferred.

In general formula (TP1) and general formula (TP2), X represents an anion. In the general formula (TP1) and general formula (TP2), X may or may not exist.
In the general formulas (TP1) and (TP2), when X is present, it means that the anion is outside the molecule of the triarylmethane structure. The term “an anion outside the molecule of the triarylmethane structure” means that the triarylmethane structure and the anion are not bonded via a covalent bond but exist as a separate compound. Hereinafter, an anion outside the molecule of the triarylmethane structure is also referred to as a counter anion.

Examples of the counter anion include fluorine anion, chlorine anion, bromine anion, iodine anion, cyanide ion, perchlorate anion, borate anion (BF ⁴⁻ etc.), PF ⁶⁻ and SbF ⁶⁻ .
The borate anion is a group represented by B (R ¹⁰ ) ⁴⁻ , and R ¹⁰ is exemplified by a fluorine atom, a cyano group, a fluorinated alkyl group, an alkoxy group, an aryloxy group, and the like.

The counter anion may be a compound having an anion portion. That is, the anion part may be included as part of the structure of the compound. In the case where the anion portion is included as a part of the structure of the compound, even if it is included in a part of the polymer having a repeating unit (polymer), it is included in a so-called low molecular compound having a molecular weight of 2000 or less. Also good. In the case of a low molecular weight compound, an embodiment in which at least one of an alkyl group, an aryl group and a crosslinkable group is included together with the anion portion is exemplified. In the present invention, an embodiment in which the counter anion is a compound containing a crosslinkable group and an embodiment in which the counter anion is a polymer containing a repeating unit having an anion moiety are preferred.

When the counter anion is a compound having an anion moiety, the anion moiety is represented by —SO ₃ ⁻ , —COO ⁻ , —PO ₃ ⁻ , a structure represented by the following general formula (A1), and the following general formula (A2). At least one selected from the structures represented is preferred.

General formula (A1)

(In general formula (A1), R ¹ and R ² each independently represents —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.

The general formula (A1) is more preferably represented by 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, the alkylene group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. When X ¹ represents an arylene group, the number of carbon atoms in the arylene group is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6. When X ¹ has a substituent, it is preferably substituted with a fluorine atom.
X ² represents an alkylene group or an arylene group, and an alkylene group is preferable. The alkylene group preferably has 1 to 8 carbon atoms, more preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1. When X ² has a substituent, it is preferably substituted with a fluorine atom.

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 ~ R ⁵ is -SO ₂ - - In formula (A2), at least one of R ³ ~ R ⁵ -SO ₂ more preferably represents.

Specific examples in the case where the counter anion is a compound having an anion moiety include R—SO ₃ ⁻ , R—COO ^— or R—PO ₄ ^— , wherein R is substituted with a halogen atom or a halogen atom. Examples of the alkyl group which may be substituted and an aryl group which may be substituted with a halogen atom are also exemplified.
Specific examples of the compound containing the group represented by the general formula (A1) include R ¹ as a halogen atom, an alkyl group which may be substituted with a halogen atom, and an aryl which may be substituted with a halogen atom. Examples are compounds bonded to a group.
As specific examples of the compound containing the group represented by the general formula (A2), R ⁴ and R ⁵ are each substituted with a halogen atom, an alkyl group which may be substituted with a halogen atom, or a halogen atom. The case where it is the aryl group which may be made is illustrated.

When the counter anion is a compound having an anion moiety, the counter anion is preferably a compound containing a bis (sulfonyl) imide anion, a compound containing a tris (sulfonyl) methide anion, or a compound containing a sulfonate anion.
The compound containing a bis (sulfonyl) imide anion may be a monomer or a polymer. The compound containing a bis (sulfonyl) imide anion is preferably represented by the following general formula (AN1).
General formula (AN1)

In general formula (AN1), R ¹ and R ² each independently represents an alkyl group or an aryl group. X ¹ and X ² may combine to form a ring.
R ¹ represents an alkyl group or an aryl group. The alkyl group may be linear, branched or cyclic. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. The alkyl group is preferably an alkyl group substituted with a fluorine atom. The number of carbon atoms of the alkyl group substituted with a fluorine atom is preferably 1 to 6, and more preferably 1 to 3. The alkyl group may have a substituent. In particular, a perfluoroalkyl group is preferable, and a perfluoromethyl group is more preferable.
The aryl group preferably has 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms. The aryl group is preferably an aryl group substituted with a fluorine atom.
R ² has the same meaning as R ¹ , and the preferred range is also the same.
As a specific example of the compound containing a bis (sulfonyl) imide anion, a bis (trifluoromethanesulfonyl) imide anion is preferable. By setting it as such a structure, heat resistance can be improved more.

The compound containing a tris (sulfonyl) methide anion is preferably a compound represented by the following general formula (AN2).
General formula (AN2)

In general formula (AN2), R ³ to R ⁵ each independently represents an alkyl group or an aryl group.
R ³ represents an alkyl group or an aryl group. The alkyl group may be linear, branched or cyclic. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. The alkyl group is preferably an alkyl group substituted with a fluorine atom. The number of carbon atoms of the alkyl group substituted with a fluorine atom is preferably 1 to 6, and more preferably 1 to 3. The alkyl group may have a substituent. In particular, a perfluoroalkyl group is preferable, and a perfluoromethyl group is more preferable.
The aryl group preferably has 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms. The aryl group is preferably an aryl group substituted with a fluorine atom.
R ⁴ has the same meaning as R ³ , and the preferred range is also the same.
R ⁵ has the same meaning as R ³ , and the preferred range is also the same.
As a specific example of the compound containing a tris (sulfonyl) methide anion, a tris (trifluoromethanesulfonyl) methide anion is preferable.

The compound containing a sulfonate anion is preferably represented by the following general formula (AN3).
General formula (AN3)
R-SO ₃ ^-
In General Formula (AN3), R represents an alkyl group or an aryl group. When R represents an alkyl group, an alkyl group substituted with a fluorine atom is preferred. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. In particular, a perfluoroalkyl group is preferable, and a perfluoromethyl group is more preferable.
When R represents an aryl group, an aryl group substituted with a fluorine atom is preferred. The aryl group preferably has 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms.
As a specific example of the compound containing a sulfonate anion, a trifluoromethanesulfonate anion is preferable.

Specific examples of other counter anions include the following, but the present invention is not limited thereto. In this specification, the following other specific examples of the counter anion are referred to as “counter anion A”.

Next, the case where the counter anion is a compound containing a crosslinkable group will be described.
Examples of the crosslinkable group include known polymerizable groups that can be cross-linked by radicals, acids, and heat. Specifically, a (meth) acryloyl group, a styryl group, a vinyl group, a cyclic ether group, and a group represented by —C—O—R (where R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). And at least one selected from a (meth) acryloyl group, a styryl group, a vinyl group and a cyclic ether group is preferable, and one selected from a (meth) acryloyl group, a styryl group and a vinyl group is more preferable A (meth) acryloyl group or a styryl group is more preferable.
The number of crosslinkable groups in the compound containing a crosslinkable group is preferably 1 to 3, and more preferably 1.

Further, the crosslinkable group and the counter anion may be directly bonded or may be bonded via a linking group, but are preferably bonded via a linking group.
A specific example in the case of a compound containing a counter anion crosslinkable group is preferably represented by the following general formula (B).

General formula (B)

(In general formula (B), P represents a crosslinkable group. L represents a single bond or a divalent linking group. Anion represents the counter anion.)
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, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, —CH═CH—, —O— , —S—, —C (═O) —, —CO—, —NR—, —CONR—, —OC—, —SO ₂ — and a combination of 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 preferably a linking group in which two or more alkylene groups having 1 to 10 carbon atoms, arylene groups having 6 to 12 carbon atoms, —NH—, —CO—, —O— and —SO ₂ — are combined.

In the case of a compound containing a counter anion crosslinkable group, it may have a functional group other than the crosslinkable group. Examples of other functional groups include acid groups. Examples of the acid group include a carboxy group, a sulfonic acid group, and a phosphoric acid group. When the counter anion further has an acid group, the number of acid groups in the compound is preferably 1 to 3, and more preferably 1.

Although the specific example in the case of a compound containing a counter anion crosslinkable group is shown below, this invention is not limited to these.

The molecular weight of the compound containing a crosslinkable group is preferably 200 to 2000, and more preferably 200 to 500.

Next, the case of a polymer containing a repeating unit having an anion moiety (hereinafter also referred to as an anion multimer) will be described.
The anion multimer may have an anion part in the side chain of the repeating unit, an anion part in the main chain of the repeating unit, or an anion part in both the main chain and the side chain. You may do it.
The anion multimer is preferably represented by the following general formula (C) and / or the following general formula (D).

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 the anion moiety.)

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, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, —CH═CH—, —O—, —S—, — COO—, —CO—, —NR—, —CONR—, —OCO—, —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.
L ¹ is a single bond or a combination of 2 or more of an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, —NH—, —CO ₂ —, —O—, and —SO ₂ —. A valent linking group is more preferred.

The anion multimer is preferably represented by the following general formula (AN4).
General formula (AN4)

In the general formula (AN4), X ¹ represents a main chain of repeating units. L ¹ represents a single bond or a divalent linking group. R ¹ represents an alkyl group or an aryl group.
X ¹ and L ¹ have the same meanings as X ¹ and L ¹ in the above the general formula (C), and preferred ranges are also the same.
R ¹ represents an alkyl group or an aryl group. The alkyl group may be linear, branched or cyclic. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. The alkyl group is preferably an alkyl group substituted with a fluorine atom. The number of carbon atoms of the alkyl group substituted with a fluorine atom is preferably 1 to 6, and more preferably 1 to 3. The alkyl group may have a substituent. In particular, a perfluoroalkyl group is preferable, and a perfluoromethyl group is more preferable. The aryl group preferably has 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms. The aryl group is preferably an aryl group substituted with a fluorine atom.

Formula (D)

(In General Formula (D), L ² and L ³ each independently represent a single bond or a divalent linking group. Anion represents an anion moiety.)

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—, —CO—, —COO—, —NR—, —CONR—, —OCO—, —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.
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.

The anionic multimer may contain a repeating unit having a polymerizable group. When the repeating unit having a polymerizable group is contained, the amount thereof is preferably, for example, 10 to 50 mol, and more preferably 10 to 30 mol with respect to 100 mol of all repeating units.
The anionic multimer may contain a repeating unit having an acid group. When the repeating unit having an acid group is contained, the amount thereof is, for example, preferably 10 to 50 mol, more preferably 10 to 30 mol, relative to 100 mol of all repeating units.

The weight average molecular weight of the anionic multimer is preferably 1,000 to 30,000, more preferably 3,000 to 20,000.

When forming an anionic multimer, a chain transfer agent may be added. The chain transfer agent is preferably an alkyl mercaptan, preferably an alkyl mercaptan having 4 or more carbon atoms, an alkyl mercaptan substituted with a carboxy group, an ether group or an ester group.
The halogen ion content contained in the anionic multimer is preferably 10 to 3000 ppm, more preferably 10 to 2000 ppm, and even more preferably 10 to 1000 ppm.
Specific examples of the anion multimer include the structures described in paragraph numbers 0034 to 0035 of JP-A-2015-030742, the contents of which are incorporated herein.

In the triarylmethane structure represented by the general formula (TP1) and the triarylmethane structure represented by the general formula (TP2), the cation is present in a delocalized manner as follows, and the following structure Are synonymous and both are included in the present invention.

The triarylmethane structure is preferably represented by the following general formula (TP3).

In general formula (TP3), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Rtp ₂₂ each independently represents an aryl group having 6 to 10 carbon atoms, and Rtp ₇₁ represents an alkyl group. represents a group or an aryl group; X is either an anion, X is at least one contains an anion of Rtp _21, Rtp ₂₂ and Rtp ₇₁ to absent; repeated either Rtp _21, Rtp ₂₂ and Rtp ₇₁ is a unit The binding site to A is represented.

In general formula (TP3), Rtp ₂₁ is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably linear. The alkyl group preferably has 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms. Examples of the substituent that the alkyl group may have include the substituents mentioned in the section of Substituent Group A described later. By setting it as such a structure, light resistance can be improved more.
In General Formula (TP3), Rtp ₂₂ represents an aryl group having 6 to 10 carbon atoms. Rtp ₂₂ is preferably an aryl group having a substituent at least in the ortho position. Examples of the substituent that the aryl group may have include those described in the section of Substituent Group A described later, and an alkyl group having 1 to 3 carbon atoms is preferable. By setting it as such a structure, heat resistance can be improved more.
Rtp ₇₁ represents an alkyl group or an aryl group, and an alkyl group is preferable. The alkyl group may be linear, branched or cyclic, and is preferably cyclic. The alkyl group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms.
Any of Rtp ₂₁ , Rtp ₂₂ and Rtp ₇₁ represents a binding site with the repeating unit, and Rtp ₇₁ is preferably a binding site with the repeating unit.

The triarylmethane structure is preferably represented by the following general formula (TP3A).

In general formula (TP3A), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Rtp ₂₂ each independently represents an aryl group having 6 to 10 carbon atoms; X represents an anion Or X is absent and at least one of Rtp ₂₁ and Rtp ₂₂ contains an anion; * represents the binding site with repeat unit A.
For more information about rtp _21, rtp _22, the general formula (TP3) have the same meanings as rtp _21, rtp ₂₂ of, and preferred ranges are also the same.

Substituent group A:
Substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxy groups, nitro groups, alkoxy groups, aryloxy groups, silyloxy groups, heterocyclic oxy groups, acyloxy groups. Carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, Mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group A carbamoyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, and a silyl group. For details of the substituent group A, the description of paragraph numbers 0174 to 0185 in JP-A-2015-034966 can be referred to, and the contents thereof are incorporated in the present specification.

<<<<< Preferred Aspect of Repeating Unit A >>>>
The repeating unit A is preferably represented by the following general formula (TP3-1).

In general formula (TP3-1), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Rtp ₂₂ each independently represents an aryl group having 6 to 10 carbon atoms, and Rtp 21 _71a represents an alkylene group or an arylene group; L ₁ represents a divalent linking group having 2 to 30 carbon atoms, Rtp ₃₁ represents a hydrogen atom or a methyl group; X represents an anion, or X does not exist At least one of Rtp ₂₁ and Rtp ₂₂ contains an anion.

Rtp ₂₁ and Rtp ₂₂ are synonymous with Rtp ₂₁ and Rtp ₂₂ in the general formula (TP3) described above, and preferred ranges thereof are also the same.
Rtp _71a represents an alkylene group or an arylene group, and an alkylene group is preferable. The alkylene group may be linear, branched or cyclic, and is preferably cyclic. The alkylene group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. The arylene group preferably has 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms. The alkylene group and the arylene group may have a substituent or may be unsubstituted. Unsubstituted is preferred. Examples of the substituent include the substituents described in the substituent group A described above.
L ₁ represents a single bond or a divalent linking group. L ₁ has the same meaning as L ¹ in the general formula (A) described above, and the preferred range is also the same.
In the general formula (TP3-1), in the “—Rtp _71a -L ₁ —” portion, the atom constituting the chain connecting the main chain of the repeating unit A and the nitrogen atom to which Rtp _{71a of the} triarylmethane structure is bonded. The number is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and particularly preferably 5 or more. The upper limit is preferably 20 or less, for example. According to this aspect, in the synthesis of the polymer TP, it is possible to suppress a low-molecular triarylmethane compound that has not reacted or is insufficiently reacted. As a result, heat resistance and solvent resistance can be improved.

The repeating unit A is preferably represented by the following general formula (TP3-2).

In general formula (TP3-2), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Rtp ₂₄ each independently represents an alkyl group having 1 to 4 carbon atoms, and Rtp ₂₅ Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Rtp _71a represents an alkylene group or an arylene group; Rtp ₃₁ represents a hydrogen atom or a methyl group; L ₁ represents a single bond or X represents an anion, or X does not exist and at least one of Rtp ₂₁ and Rtp ₂₄ includes an anion.
Rtp ₂₁ is preferably each independently an alkyl group having 1 to 6 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably linear. The alkyl group preferably has 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms.
Rtp ₂₄ is preferably independently an alkyl group having 1 or 2 carbon atoms.
When Rtp ₂₅ represents an alkyl group having 1 to 3 carbon atoms, the alkyl group preferably has 1 or 2 carbon atoms.
Rtp _71a has the same meaning as rtp _71a in general formula (TP3-1), and preferred ranges are also the same.
L ₁ has the same meaning as L ₁ in formula (TP3-1) described above, and the preferred range is also the same.

Specific examples of the repeating unit A include the following structures, but the present invention is not limited to these. Specific examples of the repeating unit A include a repeating unit derived from a monomer having a triarylmethane structure, which will be described later.

<<< Repeating unit B >>>
The polymer TP includes a repeating unit B having a crosslinkable group. The repeating unit B is preferably contained in an amount of 1 to 99% by mass in all the repeating units of the polymer TP. The upper limit is more preferably 95% by mass or less, and still more preferably 90% by mass or less. The lower limit is more preferably 2% by mass or more, and further preferably 3% by mass or more. When the content of the repeating unit B is within the above range, the heat resistance and the solvent resistance are particularly excellent.

As the crosslinkable group, a known crosslinkable group that can be crosslinked by a radical, acid, or heat can be used. For example, a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetanyl group), an oxazoline group , A group represented by —C—O—R (wherein R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a carbonate group, and the like. Examples of the group containing an ethylenically unsaturated bond include a (meth) acryloyl group, a vinyl group, and a dicyclopentenyl group. As the carbonate group, a cyclocarbonate group is preferred.
The crosslinkable group includes an epoxy group, an oxetanyl group, an oxazoline group, a group represented by —C—O—R (where R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a carbonate group, ) At least one selected from an acryloyl group and a vinyl group is preferable, and an epoxy group or an oxetanyl group is more preferable.
The crosslinkable group possessed by the polymer TP reacts with the crosslinkable groups possessed by the polymer TP, or reacts with the crosslinkable groups possessed by an alkali-soluble binder or a crosslinking agent.

Examples of the repeating unit B include the following specific examples. However, the present invention is not limited to these.

<<< other repeating units >>>
The polymer TP may further have a repeating unit other than the above repeating units A and B. Examples of other repeating units include repeating units derived from at least one of (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylic acid amide.
Specific examples include a repeating unit having an acid group. Examples of the acid group include a carboxy group, a sulfonic acid group, and a phosphoric acid group, and a carboxy group is preferable. When the polymer TP further has a repeating unit having an acid group, the developing performance of the colored composition can be further improved. When the polymer TP further contains a repeating unit having an acid group, the ratio of the repeating unit containing the repeating unit having an acid group may be, for example, 10 to 80% by mass in all the repeating units of the polymer TP. Preferably, 10 to 60% by mass is more preferable.

Other repeating units include lactones, acid anhydrides, amides, —COCH ₂ CO—, development promoting groups such as cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups, hydroxy groups, maleimides It may have a functional group such as a hydrophilicity adjusting group such as a group or an amino group.

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

The polymer TP preferably has a structure containing a repeating unit derived from at least one of (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylic acid amide. For example, the above-described repeating unit A and / or repeating unit B is a repeating unit derived from at least one of (meth) acrylic acid, (meth) acrylic acid ester and (meth) acrylic amide, The aspect whose repeating unit is a repeating unit derived from at least 1 sort (s) of (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylic acid amide is mentioned.

In the present invention, the weight average molecular weight of the polymer TP is preferably 3000 to 500,000. The lower limit is preferably 4000 or more, more preferably 5000 or more, still more preferably 7000 or more, and particularly preferably 10,000 or more. The upper limit is preferably 200000 or less, more preferably 100000 or less, and particularly preferably 50000 or less. That is, the weight average molecular weight of the polymer TP is particularly preferably 10,000 to 50,000. Heat resistance and solvent resistance are good by adjusting the weight average molecular weight of the polymer TP to the above-described range. Furthermore, the voltage characteristics can be improved.
The number average molecular weight of the polymer TP is preferably 2,000 to 500,000. The lower limit is preferably 2500 or more, more preferably 3000 or more, still more preferably 4000 or more, and particularly preferably 5000 or more. The upper limit is preferably 100,000 or less, more preferably 70000 or less, and particularly preferably 50000 or less.
The dispersity (weight average molecular weight / number average molecular weight) of the polymer TP is preferably 1.0 to 5.0. The upper limit is preferably 4.0 or less, more preferably 3.5 or less, and particularly preferably 2.0 or less.
The weight average molecular weight and number average molecular weight of the polymer TP are polystyrene-converted values in gel permeation chromatograph (GPC) measurement, and specifically are values measured by the method described in the examples described later.

In the present invention, in the polymer TP, the content of the compound A having a triarylmethane structure and a weight average molecular weight of 1500 or less is 20% by mass or less, preferably 10% by mass or less, preferably 5% by mass with respect to the mass of the polymer TP. % Or less is more preferable, 1% by mass or less is particularly preferable, and it can be substantially not contained. Note that substantially not containing means that, for example, the content of compound A is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and not more than 0.1% by mass with respect to the mass of the polymer TP. preferable.
By setting the content of Compound A to 20% by mass or less, it is possible to effectively suppress the elution of the polymer TP from the film, and as a result, it is possible to improve the solvent resistance and heat resistance of the film.
Compound A is a compound having a triarylmethane structure, and specifically means an unreacted material such as a raw material monomer having a triarylmethane structure, or a raw material monomer-containing impurity having no polymerizable group. To do.
The content of Compound A in the polymer TP can be measured by detecting with ultraviolet light in the GPC measurement of the polymer TP.
In the present invention, the content of Compound A in the polymer TP is 2 for TSKgel α-M (Tosoh Corp., 7.8 mm (inner diameter) × 30 cm) using HLC-8020GPC (Tosoh Corp.). The column is connected in series, and the measurement conditions are N-methyl-2-pyrrolidone (NMP) solution with a sample concentration of 0.35% by mass, a flow rate of 0.3 mL / min, and a sample injection amount of 10 μL. It is a value obtained by setting the temperature to 40 ° C. and using an ultraviolet detector.

The polymer TP is preferably a polymer containing a repeating unit represented by the general formula (TP-7).

In general formula (TP-7), each R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group preferably has 1 to 3 carbon atoms. The alkyl group is preferably linear.
R ² represents a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group may be linear, branched or cyclic, and is preferably linear or cyclic. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and is preferably an alkyl group. In particular, R ² is preferably a cyclic alkyl group having 5 to 10 carbon atoms, a linear alkyl group having 1 to 8 carbon atoms, or a branched alkyl group having 3 to 8 carbon atoms. The number of carbon atoms in the cyclic alkyl group is preferably 6 to 8, and more preferably 6. The linear alkyl group preferably has 1 or 2 carbon atoms, more preferably 1. The branched alkyl group preferably has 3 to 8 carbon atoms. The hydrocarbon group may have a substituent, and the substituent is preferably a hydroxy group. As an example of the case where the hydrocarbon group has a substituent, a hydroxyethyl group is preferable.
R ³ represents a crosslinkable group. The crosslinkable group includes an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, an oxazoline group, and a group represented by —C—O—R (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). And at least one selected from carbonate groups. Examples of the group containing an ethylenically unsaturated bond include a (meth) acryloyl group, a vinyl group, and a dicyclopentenyl group.
R ⁴ represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R ^1a represents an alkylene group or an arylene group, and an alkylene group is preferred. The alkylene group may be linear, branched or cyclic, and is preferably cyclic. The alkylene group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. The arylene group preferably has 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms. The alkylene group and the arylene group may have a substituent or may be unsubstituted. Unsubstituted is preferred. Examples of the substituent include the substituents described in the substituent group A described above.
L ¹¹ represents a single bond or a divalent linking group having 1 to 30 carbon atoms. The divalent linking group is selected from an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 12 carbon atoms, and —CO—, —OCO—, —O—, —NH— and —SO ₂ —. Group which combines 1 type is mentioned. The divalent linking group is preferably an alkylene group, an alkylene group, or a linking group in which the alkylene groups are linked via one or more selected from —O—, —COO—, and —OCO—.
L ¹² and L ^{13 each} represent a single bond or a divalent linking group having 1 to 30 carbon atoms. The divalent linking group is selected from an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 12 carbon atoms, and —CO—, —OCO—, —O—, —NH— and —SO ₂ —. Group which combines 1 type is mentioned. The alkylene group and the arylene group may have a substituent or may be unsubstituted. Examples of the substituent include the substituent group A described above. Of these, a hydroxy group is preferred.
In the general formula (TP-7), in the “—L ¹¹ —R ^1a —” moiety, the atoms constituting the chain connecting the main chain of the repeating unit A and the nitrogen atom to which R ^{1a of the} triarylmethane structure is bonded. The number is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and particularly preferably 5 or more. The upper limit is preferably 20 or less, for example.

In the general formula (TP-7), X represents a compound containing a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion or a sulfonate anion, and a compound containing a bis (sulfonyl) imide anion is preferred.
The compound containing a bis (sulfonyl) imide anion may be a monomer or a multimer. The compound containing a bis (sulfonyl) imide anion is preferably a compound represented by the general formula (AN1) described above.
The compound containing a tris (sulfonyl) methide anion is preferably a compound represented by the general formula (AN2) described above.
The compound containing a sulfonate anion is preferably a compound represented by the general formula (AN3) described above.

A to d are mass ratios of repeating units, a and d represent a number exceeding 0, and b and c each independently represent a number of 0 or more. When the sum of a to d is 1, a is preferably 0.01 to 0.99. b represents an integer of 0 or more, and preferably 0 to 90. c represents an integer of 0 or more, preferably 0 to 90. d is preferably from 0.01 to 0.99.

Although the specific example of polymer TP is shown to this invention below, it is not limited to these.

<Method for producing polymer TP>
The polymer TP of the present invention comprises a triarylmethane monomer having a triarylmethane structure represented by at least one selected from general formula (TP1a) and general formula (TP2a), and a monomer having a crosslinkable group. It can be produced by polymerizing at least raw material monomers. The raw material monomer may further include a monomer having an acid group and a monomer having a functional group described in the above-described other repeating unit.

In the general formulas (TP1a) and (TP2a), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group or an aryl group; Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ and Rtp ₁₁ are each Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ₇₁ Rtp ₇₂ ; Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group or an aryl group; Rtp ₁₀ represents a hydrogen atom, an alkyl group or an aryl group; a, b, c and d each independently represent an integer of 0 to 4; when a, b, c and d are 2 or more, Rtp _5, Rtp _6, two of Rtp ₈ and Rtp ₉ are each, linked may form a ring; or X is an anion, Rtp ₁ ~ Rtp ₁₁ without X is not present, R At least one of the p ₇₁ and Rtp ₇₂ including anion; having at least one polymerizable group Rtp ₁ ~ Rtp _11, Rtp ₇₁ and Rtp _72.

_{_{_{Rtp 1 ~ Rtp 11, Rtp 71}}} , Rtp 72 and X in general formula (TP1a), and, rtp ₁ ~ rtp ₁₁ of the general formula (TP2a), rtp _71, have the same meanings as rtp ₇₂ and X, the preferred range is also It is the same.
In the general formulas (TP1a) and (TP2a), at least one of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ has a polymerizable group. It is preferable that at least one of Rtp ₇₁ and Rtp ₇₂ has a polymerizable group. Examples of the polymerizable group include a vinyl group, a (meth) acryloyl group, and a styryl group, and a (meth) acryloyl group is preferable.

Specific examples of the triarylmethane monomer are shown below. Of the structures shown below, D-42 to D-44 are preferred from the viewpoint of polymerization.

The polymerization temperature is preferably 40 to 90 ° C, more preferably 50 to 70 ° C. By increasing the polymerization temperature within a range in which the crosslinkable group in the polymer does not react, the polymerization of the triarylmethane monomer can be facilitated. For example, by polymerizing in the above temperature range, the reaction between the epoxy group and the carboxy group in the polymer can be suppressed to suppress the increase in molecular weight, and as a result, a polymer excellent in luminance and heat resistance can be obtained. Further, the residual amount of triarylmethane monomer can be reduced, and the solvent resistance and voltage holding ratio can be improved.

The polymerization is preferably performed in a solution containing the above-mentioned raw material monomers in a total amount of 30 to 60% by mass. The content of the raw material monomer in the solution is more preferably 35 to 55% by mass, still more preferably 40 to 55% by mass. If content of a raw material monomer is the said range, it can make it easy to advance superposition | polymerization of a triarylmethane monomer. As a result, the content of compound A in the polymer TP can be reduced.
Examples of the solvent used in the preparation of the raw material monomer reaction solution include solvents that may be contained in the coloring composition described below.

A chain transfer agent may be added during the polymerization. As the chain transfer agent, an alkyl mercaptan is preferable, and an alkyl mercaptan having 4 or more carbon atoms or an alkyl mercaptan substituted with a carboxy group, an ether group or an ester group is preferable. In particular, dodecyl mercaptan and dipentaerythritol hexa-3-mercaptopropionate are preferable from the viewpoint of odor, and thiomalic acid and mercaptopropionic acid are preferable from the viewpoint of promoting developability.
After the polymerization is completed, a purification treatment may be performed. Thereby, content of the compound A can be reduced.

In the colored composition of the present invention, the content of the polymer TP is preferably 10 to 60% by mass and more preferably 10 to 40% by mass with respect to the total solid content of the colored composition of the present invention.

<< Other colored compounds >>
The coloring composition of the present invention may contain one or more coloring compounds other than the above-described polymer TP. Examples of other coloring compounds include dye compounds, pigment compounds, and dispersions thereof.
When the pigment compound is blended as a dispersion, it can be prepared according to the descriptions in JP-A-9-197118 and JP-A-2000-239544.

Examples of the dye compound include azo compounds (for example, Solvent Yellow 162), anthraquinone compounds (for example, anthraquinone compounds described in JP-A-2001-10881), and phthalocyanine compounds (for example, phthalocyanine described in US 2008 / 0076044A1). Compound), xanthene series (for example, C.I. Acid Red Red 289), triarylmethane series (for example, C.I. Acid Blue 7) C.I. Acid Blue 83 (CI Acid Blue 83), C.I. Acid Blue 90 (C.I. Acid Blue 90), C.I. Solvent Blue 38 (C.I. Solvent Blue 38), Sea I A Violet 17 (CI Acid Violet 17), CI Acid violet 49 (CI Acid violet 49), CI Acid Green 3), methine And dyes, xanthene dyes (for example, JP 2010-32999 A), dipyrromethene metal complex compounds (for example, JP 2012-237985 A), and the like.

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.
In particular, the other colored compound preferably includes at least one selected from a xanthene compound, a dipyrromethene metal complex compound, an oxazine compound, and a phthalocyanine compound, and includes at least one selected from a xanthene compound and a dipyrromethene metal complex compound. More preferably.

<Xanthene compound>
The xanthene compound is a compound having a xanthene skeleton in the molecule. As the xanthene compound, for example, Color Index (CI) Acid Red 51 (hereinafter, description of CI Acid Red is omitted, and only the number is described. Others are also the same), 52, 87. 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10 (Rhodamine B), 11, C.I. I. Basic violet 10, 11, 25, C.I. I. Solvent Red 218, C.I. I. Modern Tread 27, C.I. I. Reactive red 36 (rose bengal B), sulforhodamine G, xanthene compounds described in JP 2010-32999 A and xanthene compounds described in Japanese Patent No. 4492760.

The xanthene compound preferably contains a compound represented by the general formula (1a) (hereinafter sometimes referred to as “compound (1a)”). Compound (1a) may be a tautomer thereof. When using the compound (1a), the content of the compound (1a) in the xanthene compound is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (1a) as the xanthene compound.

General formula (1a)

In general formula (1a), R ¹ to R ⁴ each independently have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group is substituted with —O—, —CO— or —NR ¹¹ —. May be;
R ¹ and R ² may be bonded to each other to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be bonded to each other to form a ring containing a nitrogen atom;
R ⁵ _{^{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰ ;
R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms;
m1 represents an integer of 0 to 5. when m1 is 2 or more, the plurality of R ⁵ may be the same or different;
m2 and m3 each independently represents an integer of 0 to 3. when m2 and m3 are each independently 2 or 3, a plurality of R ⁶ and R ⁷ may be independently the same or different;
a represents 0 or 1; when a represents 0, any group of R ¹ to R ⁷ has an anion;
X ⁻ represents an anion;
Z ⁺ represents N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ¹¹ may be the same or different;
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom;
R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the saturated aliphatic hydrocarbon group is —O—, It may be substituted with —CO—, —NH— or —NR ⁸ —, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom ;
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group. Of these, a toluyl group, a xylyl group, a mesityl group, and a propylphenyl group are preferable, and a toluyl group and a xylyl group are particularly preferable, and among these, a 2,6-disubstituted xylyl group is preferable.

The aromatic hydrocarbon group substituent which may have a halogen ^{^{atom, -R 8, -OH, -OR 8}} , -SO 3 -, - SO 3 H, -SO 3 - Z +, -CO ₂ H, —CO ₂ R ⁸ , —SR ⁸ , —SO ₂ R ⁸ , —SO ₃ R ⁸ or —SO ₂ NR ⁹ R ¹⁰ may be mentioned. Among them, as the _{_{substituent, -SO 3 -, - SO 3}} H, -SO 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ is preferably, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ Is more preferable. The ^{^{_{^{Z +, -SO 3 - - -SO}}}} 3 in this case N ⁺ (R ¹¹⁾ ₄ are preferred.
When R ¹ to R ⁴ are these groups, a color filter having superior heat resistance can be formed.

Examples of the ring formed by combining R ¹ and R ² with each other and the ring formed by combining R ³ and R ⁴ with each other include the following.

Among these, the following structures are preferable from the viewpoint of compound stability.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁸ to R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Linear alkyl groups such as decyl group, dodecyl group, hexadecyl group, icosyl group; branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; cyclopropyl group, cyclopentyl group And alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.
Among them, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a 2-ethylhexyl group are preferable, and a propyl group, an isopropyl group, a butyl group, a hexyl group, A 2-ethylhexyl group is preferred.
The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.

Examples of —OR ⁸ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and an icosyloxy group. Of these, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are preferable.

Examples of —CO ² R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group. Of these, a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group are preferable.

Examples of —SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of —SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
Examples of —SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

—SO ₂ NR ⁹ R ¹⁰ includes, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2 -Methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentyl Rufamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1- Methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group An N-1 substituted sulfamoyl group such as an N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl group And N, N-2 substituted sulfamoyl groups such as a group.
Among them, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-pentylsulfamoyl group, N -(2-ethylhexyl) sulfamoyl group is preferred, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N- (2-ethylhexyl) A sulfamoyl group is more preferred.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁹ and R ¹⁰ may have a substituent, and examples of the substituent include a hydroxy group and a halogen atom.

R ⁵ _{_{^{is, -CO 2 H, -CO 2 -}}} Z +, -CO 2 R 8, -CO 2 NHR 9, -SO 3 -, -SO 3 - Z +, -SO 3 H, -SO 2 R 8 or -SO ₂ NHR ⁹ is _{^{_{preferably,, -SO 3 -, -SO 3}}} - Z +, -SO 3 H or -SO ₂ NHR ⁹ is more preferable.
m1 is preferably an integer of 1 to 4, and more preferably 1 or 2.
R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms.
m2 and m3 each independently represents an integer of 0 to 3, with 0 being preferred.
Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

a represents 0 or 1, and when a represents 0, any one of R ¹ to R ⁷ preferably has an anion, and R ⁵ preferably has an anion.
X ⁻ is included depending on the valence of the cation contained in the general formula (1a), and is usually monovalent or divalent, and monovalent is preferable. Examples of the anion X ⁻ include a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, and a low nucleophilic anion. A fluorine anion, a chlorine anion, a bromine anion or an iodine anion is preferable. . The low nucleophilic anion indicates an anion structure in which an organic acid having a pKa lower than that of sulfuric acid is dissociated. Examples of anions include low nucleophilic anions described in paragraph No. 0075 of JP2007-310315, anions described in paragraphs 0016 to 0025 of JP2012-173399, and JP2013-037316A. Examples include the anion moiety described in paragraphs 0025 to 0033, the contents of which are incorporated herein.
Z ⁺ is N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably N ⁺ (R ¹¹ ) ₄ .
N ⁺ (R ¹¹ ) ₄ is preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms, at least two of the four R ¹¹ . Further, the total carbon number of the four R ¹¹ is preferably 20 to 80, and more preferably 20 to 60.

The compound (1a) is preferably a compound represented by the general formula (3a) (hereinafter sometimes referred to as “compound (3a)”). Compound (3a) may be a tautomer thereof.

In the general formula (3a), R ³¹ and R ³² each independently represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. A hydrogen atom contained in an aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted with an alkoxy group having 1 to 3 carbon atoms, and is contained in a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. —CH ₂ — may be substituted with —O—, —CO— or —NR ¹¹ —.
R ³³ and R ³⁴ each independently represents an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
R ³¹ and R ³³ may be bonded to each other to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be bonded to each other to form a ring containing a nitrogen atom.
p and q each independently represents an integer of 0 to 5. When p is 2 or more, the plurality of R ³³ may be the same or different. When q is 2 or more, the plurality of R ³⁴ may be the same or different.
R ¹¹ has the same meaning as R ¹¹ in the general formula (1a).

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³¹ and R ³² include carbon among the monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms described for R ⁸ in the general formula (1a). Examples thereof include monovalent saturated hydrocarbon groups of several 1 to 10. Of these, methyl, ethyl, propyl, butyl, hexyl and 2-ethylhexyl are preferred. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be present as a substituent include the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms described for R ¹ in the general formula (1a). Can be mentioned.
Examples of the alkoxy group having 1 to 3 carbon atoms in which the hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted include a methoxy group, an ethoxy group, and a propoxy group.
R ³¹ and R ³² are preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Of these, a methyl group, an ethyl group, and a propyl group are preferable.
The alkylsulfanyl group R ³³ and carbon atoms in R ³⁴ 1 ~ 4, methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, a butyl sulfanyl group and an isopropyl sulfanyl group.
Examples of the alkylsulfonyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.

P and q are preferably integers of 0 to 2, preferably 0 or 1.

Specific examples of the compound (1a) include compounds represented by the formulas (1-1) to (1-43) described in paragraph numbers 0039 to 0046 of JP-A-2014-005451. Are incorporated herein.

As the xanthene compound, a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink RH / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industry Co., Ltd.) can be used. . Alternatively, a commercially available xanthene dye can be used as a starting material and synthesized with reference to Japanese Patent Application Laid-Open No. 2010-32999, the contents of which are incorporated herein.

<Dipyrromethene-based metal complex compound>
Examples of the dipyrromethene metal complex compound include compounds in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound.

Formula (I)

In general formula (I), R ¹ to R ⁶ each independently represents a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Examples of the substituent include the above-described substituent group A. When the substituent is a group that can be further substituted, it may be further substituted with any of the above-described substituents. In addition, when it has two or more substituents, those substituents may be the same or different.

In general formula (I), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are each independently bonded to each other to form 5-membered, 6-membered or 7-membered A ring may be formed. Examples of the ring formed include a saturated ring and an unsaturated ring. Examples of the 5-membered, 6-membered or 7-membered saturated ring or unsaturated ring include a pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, Examples include a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring and a pyridazine ring, and preferably a benzene ring and a pyridine ring.
In addition, when the formed 5-membered, 6-membered and 7-membered rings are further substitutable groups, they may be substituted with any of the above-mentioned substituent group A, and two or more substituents may be substituted. When substituted with a group, the substituents may be the same or different.

In general formula (I), R ¹ and R ⁶ are preferably an alkylamino group, an arylamino group, a carbonamido group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, a carbonamido group, a ureido group, An alkoxycarbonylamino group and a sulfonamide group are more preferable, a carbonamide group, a ureido group, an alkoxycarbonylamino group, and a sulfonamide group are more preferable, and a carbonamide group and a ureido group are particularly preferable.

In general formula (I), R ² and R ⁵ are preferably an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, a carbamoylsulfonyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, An alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group are particularly preferable.
In general formula (I), R ³ and R ⁴ are preferably an alkyl group, an aryl group or a heterocyclic group, and more preferably an alkyl group or an aryl group.

In the general formula (I), when R ³ and R ⁴ represent an alkyl group, the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, for example, methyl group, ethyl Group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, i-butyl group, tert-butyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and benzyl group. In addition, a branched or cyclic alkyl group having 1 to 12 carbon atoms is preferred, and examples thereof include isopropyl group, cyclopropyl group, i-butyl group, tert-butyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. A secondary or tertiary alkyl group having 1 to 12 carbon atoms is more preferable, and examples thereof include an isopropyl group, a cyclopropyl group, an i-butyl group, a tert-butyl group, a cyclobutyl group, and a cyclohexyl group.

In the general formula (I), when R ³ and R ⁴ represent an aryl group, the aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
When R ³ and R ⁴ represent a heterocyclic group, the heterocyclic group includes a 2-thienyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 2 A benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group or a benzotriazol-1-yl group, more preferably a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group or a 1-pyridyl group preferable.

Next, the metal atom or metal compound that forms the dipyrromethene-based metal complex compound will be described.
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or 2 Valent metal chlorides are included. For example, Zn, Mg, Si, Sn , Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, in addition to B, such as, AlCl, InCl, FeCl, TiCl 2, SnCl 2, SiCl 2 Further, metal chlorides such as GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are also included.
Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex Or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO (V = O) is more preferable. Particularly preferred. Among these, Zn is particularly preferable.

A preferred embodiment of the dipyrromethene-based metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound is described in paragraphs 0153 to 0176 of JP2012-237985A. The complex compounds represented by 1), (I-2) or (I-3) can be taken into account, the contents of which are incorporated herein.
As specific examples of the dipyrromethene-based metal complex compound, the description in paragraphs 0179 to 0186 of JP2012-237985A can be referred to, the contents of which are incorporated herein.

When the coloring composition of the present invention contains other coloring compounds, it is preferably 0.5 to 70% by mass with respect to the total solid content of the coloring composition of the present invention. Further, it is preferably added to the coloring composition so that the absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) is 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 compound groups are widely known in this industrial field, and in the present invention, these compounds can be used without any particular limitation. 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. Monomers are preferred.

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. In addition, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxy 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.

As specific examples of these compounds, paragraph numbers 0156 to 0159 of JP-A-2014-208808 can be referred to, and the contents thereof are incorporated in the present specification.

Further, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd.) Company-made) dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are bonded via an ethylene glycol or propylene glycol residue. These oligomer types can also be used.

About these polymerizable compounds, the structure, details of usage such as single use or combination, addition amount and the like can be arbitrarily set according to the final performance design of the coloring 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. Further, from the viewpoint of increasing the strength of the 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 coloring composition is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, and more preferably 20 to 60% 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 coloring composition of the present invention preferably contains a 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 halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl-substituted coumarin compounds, lophine dimers, benzophenone compounds, acetophenone compounds And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds. 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.

In the present invention, from the viewpoint of sensitivity, time stability, and coloring during post-heating, the oxime compound is more preferably a compound represented by the following general formula (1) or general formula (2).

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

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

A represents 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 with heating. An alkylene group substituted with an alkenyl group (eg, vinyl group, allyl group), an aryl group (eg, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with is preferred.

Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloration with 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, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkylthioxy group, an arylthioxy group or an amino group from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. preferable. In the general formula (1), n is preferably an integer of 1 to 2.

In the 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 heterocyclic oxycarbonyl group, an alkylthiocarbonyl group, an arylthiocarbonyl. Represents a group, a heterocyclic thiocarbonyl group, a heterocyclic thiocarbonyl 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, heterocyclic carbonyl 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.
A colored composition having much higher curability when one or two of R ¹⁰⁵ to R ¹¹¹ is an electron-withdrawing substituent, that is, a nitro group, a cyano group, an alkylcarbonyl group or an arylcarbonyl group. Is preferable.

Specific examples of the compound having a fluorene structure represented by the general formula (2) include compounds described in paragraph numbers 0087 to 0088 of JP 2014-177502 A, the contents of which are described in this specification. It will be incorporated.
The compound having a fluorene structure represented by the general formula (2) can be synthesized according to a synthesis method described in, for example, WO2014-050738.
Commercially available oxime photopolymerization initiators include IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831 (manufactured by ADEKA), Adeka Arcles NCI-930 (manufactured by ADEKA) and the like can be used.

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.
In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP-A 2013-164471 ( C-3). This content is incorporated herein.

The content of the photopolymerization initiator in the total solid content of the coloring composition is preferably 3 to 20% by mass, more preferably 4 to 19% by mass, from the viewpoint of more effectively obtaining the effects of the present invention. 18% by mass is particularly preferred.
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 colored composition of the present invention preferably contains an 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

Examples of the organic solvent include esters, ethers, ketones, and aromatic hydrocarbons, and specific examples include those described in paragraph numbers 0161 to 0162 of JP2012-032754A.

It is also preferable to mix two or more of these organic solvents from the viewpoint of the solubility of each component described above. 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 from 10 to 80% by mass, more preferably from 15 to 60% by mass.
The coloring 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 polymer, soluble in an organic solvent, and developable 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, 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 those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth)). 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 (b1) or formula (b2) can also be preferably used.

(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. 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.

(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. 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, 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 a nonyl group, a methyl group, an ethyl group, a t-butyl group, a cyclohexyl group and other alkyl groups, 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. For example, a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful. Examples of the above-mentioned polymer containing a 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, etc. 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.

(In the 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. )

(In General Formula (3), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² and R ¹³ each independently represents 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 carbonyl group having 3 to 20 carbon atoms containing an unsaturated double bond as a partial structure. When represented, it may further contain a carboxy group as a partial structure.)

Examples of acrylic resins 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.

Moreover, the alkali-soluble binder may contain the structural unit derived from a compound with the following general formula (X).
Formula (X)

In the general 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 1 to C carbon atoms that may contain a benzene ring. 20 alkyl groups are represented. n represents an integer of 1 to 15.

In general formula (X), the alkylene group of R ₂ preferably has 2 to 3 carbon atoms. The alkyl group of R ₃ has 1 to 20 carbon atoms, more preferably 1 to 10, and the alkyl group of R ₃ may contain 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 preferably has a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1,000 to 200,00 from the viewpoint of developability, liquid viscosity, etc., and 2,000 to 100,000. Is more preferable, and 5,000 to 50,000 is particularly preferable.
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 content 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 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 description in paragraphs 0134 to 0147 of JP-A No. 2004-295116, the contents of which are incorporated herein.
When the coloring composition of the present invention contains a crosslinking agent, the content of the crosslinking agent is preferably 0.01 to 50% by mass, more preferably 0.5 to 30%, based on the total solid content of the coloring composition. % By mass.

<< Surfactant >>
The coloring composition of the present invention may contain a surfactant. The surfactant may be nonionic, cationic, or anionic, but a surfactant having an ethylene oxide structure and a fluorosurfactant are preferred. In particular, a surfactant having an ethylene oxide structure having an HLB (Hydrophile-Lipophile Balance) 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 content of the surfactant is preferably 0.0001 to 2.0% by mass, more preferably 0, based on the total solid content of the coloring composition. 0.005 to 1.0 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.

<< Dye stabilizer >>
The coloring composition of the present invention may contain a dye stabilizer. As the dye stabilizer, a polymer surfactant (polymer dispersant) is preferable. 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.
It is also effective to add the following anion salts (lithium salt, sodium salt, potassium salt, etc.) as a dye stabilizer.
When the coloring composition of the present invention contains a dye stabilizer, the content of the dye stabilizer is preferably 0.01 to 50% by mass, more preferably 0, based on the total solid content of the coloring composition. .5 to 30% by mass.

<< Antioxidant >>
The coloring 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.
For example, compounds described in paragraphs 0013 to 0034 of JP2012-155243A and paragraphs 0030 to 0042 of JP2013-14748A can be preferably used.
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, an ethylenic compound such as tetramethylethylene and cyclopentene, diethylamine, triethylamine, 1,4- Amines such as diazabicyclooctane (DABCO) and N-ethylimidazole, condensed polycyclic aromatic compounds such as optionally substituted naphthalene, dimethylnaphthalene, dimethoxyanthracene, anthracene and diphenylanthracene; 1,3-diphenylisobenzofuran In addition to aromatic compounds such as 1,2,3,4-tetraphenyl-1,3-cyclopentadiene and 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 the present invention, the antioxidants can be used alone or in admixture of two or more. 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 accelerator >>
The coloring composition of the present invention can contain a compound that functions as a curing accelerator.
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 a curing accelerator, low-temperature curing of the coloring composition can be more effectively realized. In addition, the storage stability of the colored composition can be further improved.
Examples of commercially available curing accelerators include Karenz MT series such as Karenz MTBD-1 (manufactured by Showa Denko KK).
In this invention, a hardening accelerator can be used individually or in mixture of 2 or more types. The content of the curing accelerator 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 polymerizable compound.

<< Reduction inhibitor >>
The coloring composition of the present invention can also contain a reduction inhibitor. The reduction inhibitor is preferably a quinone compound, more preferably a quinone compound having a molecular weight of about 100 to 800 and having the following structure.

<< Acid generator >>
The coloring composition of the present invention can also contain an acid generator. The acid generator may be a photoacid generator or a thermal acid generator, but a thermal acid generator is preferred. When a thermal acid generator is used, the heat resistance of the cured film tends to be further improved.
The thermal acid generator refers to an acid generator that generates an acid when heated at 100 to 250 ° C. at 101.25 hPa. The acid generated is preferably an acid having a pKa of 5 or less. Specific examples of the acid generated include sulfonic acid, carboxylic acid, phosphoric acid and the like, and sulfonic acid is more preferable.
As the photoacid generator, the description in paragraphs 0103 to 0113 of JP-A-2006-259002 can be referred to, and the contents thereof are incorporated herein.
Thermal acid generators include ionic compounds (onium salts) and nonionic compounds.
As the ionic compound (onium salt), those containing no heavy metal or halogen ion are preferable, and onium salts of sulfonic acid are preferable.
Specific examples of the ionic thermal acid generator include triphenylsulfonium, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, 1-dimethylthio-4,7-dihydroxynaphthalene, 4-hydroxyphenyldimethyl. Sulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium, these Examples include methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, hexafluorophosphonate and the like.

<< Other ingredients >>
The coloring composition of the present invention may further contain a bis (trifluoromethanesulfonyl) imide salt. Heat resistance can be improved by including a bis (trifluoromethanesulfonyl) imide salt. Examples of the bis (trifluoromethanesulfonyl) imide salt include potassium bis (trifluoromethanesulfonyl) imide, sodium bis (trifluoromethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide and the like. The content of the bis (trifluoromethanesulfonyl) imide salt is preferably from 0.1 to 2 mol, more preferably from 0.3 to 0.8 mol, based on 1 mol of the triarylmethane repeating unit of the polymer TP.
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.

<Method for preparing colored composition>
The coloring composition of this invention can be adjusted by mixing each component mentioned above and arbitrary components as needed.
In preparing the colored composition, the components constituting the colored composition may be blended together, or may be blended sequentially 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 of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc. The filter using is mentioned. Among these materials, polypropylene (including high density polypropylene) is preferable.
The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, more preferably about 0.05 to 0.5 μm. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of the uniform and smooth coloring composition in a post process.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more.
Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
As the second filter, a filter formed of the same material as the first filter described above can be used.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

Since the colored composition of the present invention can form a cured film excellent in hue and contrast, for forming a colored layer (for forming colored pixels) such as a color filter used in an image display device or a solid-state imaging device, Moreover, it can use suitably as preparation uses, such as printing ink, inkjet ink, and a coating material.

<Method for producing cured film, color filter, color filter>
The cured film of the present invention is formed by curing the colored composition of the present invention. Such a cured film is preferably used for a 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.
In the case of producing a color filter for a solid-state imaging device using the colored composition of the present invention, the production method described in paragraphs 0359 to 0371 of JP2011-252065A can also be employed. .

The method for producing a color filter of the present invention includes a step of forming a colored composition layer using the colored composition of the present invention, a step of exposing the colored composition layer in a pattern-like manner, and an unexposed portion of the colored composition layer. And removing the film to form a colored pattern. Furthermore, you may provide the process (prebaking process) of baking a colored composition layer, and the process (post-baking process) of baking the developed coloring pattern as needed.

<< Step of Forming Colored Composition Layer >>
In the step of forming the colored composition layer, the colored composition layer is formed by applying the colored composition of the present invention on the substrate.

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 silicon 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, 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.

Application method of the coloring composition is preferably coating, and it is preferable to apply by a method such as spin coating, slit coating, cast coating, roll coating, bar coating, and ink jet.

The colored composition layer formed on the substrate is preferably dried (prebaked). Pre-baking 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, or the like, and can be performed under conditions of 10 seconds to 300 seconds. Note that pre-baking may be performed in combination with high-frequency processing. The high frequency treatment can be used alone. If necessary, vacuum treatment can be performed before pre-baking. As the conditions for vacuum drying, the degree of vacuum is preferably 13 to 133 Pa, and more preferably 26 to 66.5 Pa.

The thickness of the colored composition layer formed from the colored composition is appropriately selected according to the purpose. In the case of a color filter for an image display device, a range of 0.2 to 5.0 μm is preferable, a range of 1.0 to 4.0 μm is more preferable, and a range of 1.5 to 3.5 μm is most preferable. In the case of a color filter for a solid-state image sensor, a range of 0.2 to 5.0 μm is preferable, a range of 0.3 to 2.5 μm is more preferable, and a range of 0.3 to 1.5 μm is most preferable. In addition, the thickness of a coloring composition layer is a film thickness after prebaking.

<< Exposure Step >>
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 Step Using Laser Light Source In an exposure method using a laser light source, it is preferable to use an ultraviolet laser as the light source. The irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, and more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm. Specifically, the third harmonic (355 nm) of an Nd: YAG (yttrium, aluminum, garnet) laser, which is a relatively inexpensive solid laser with a large output, and the XeCl (308 nm), XeF (353 nm) of an excimer laser. Can be suitably used.
The exposure amount of the object to be exposed (pattern) is in the range of 1 mJ / cm ² to 100 mJ / cm ² , and more preferably in the range of 1 mJ / cm ² to 50 mJ / cm ² . 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 is for forming a depression such as a through hole in addition to a pattern for forming a pixel (colored pattern). Those provided with a pattern are 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.

<< Step of forming colored pattern >>
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 ] The concentration of an alkaline compound such as -7-undecene is 0.001 to 10% by mass, preferably 0.01 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 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 rinse treatment is usually performed with pure water, but 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. You may use the method of using ultrasonic irradiation together.

After the rinse treatment, after draining and drying, a heat treatment at 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 multiple colors is formed.

In the method for producing a color filter of the present invention, in particular, a colored pattern (pixel) formed using a colored composition can be post-exposed by irradiating with ultraviolet rays.

It is preferable to further heat-treat the colored pattern that has been post-exposed 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.
The temperature during the heat treatment is preferably 100 ° C. to 300 ° C., more preferably 150 ° C. to 250 ° C. The heating time is preferably about 10 minutes to 120 minutes.

The colored pattern thus obtained constitutes a pixel in the color filter. In manufacturing a color filter having pixels of a plurality of hues, the above steps may be repeated according to a desired number of colors.
It should be noted that the post-exposure and / or post-bake treatment may be performed each time the formation, exposure, and development of a single-color coloring composition layer is completed (for each color), or all colors having a desired number of colors may be used. After the formation, exposure, and development of the composition layer are completed, the post-exposure and / or post-bake treatment 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 production method, a step of forming a colored layer using the colored composition of the present invention,
Manufacturing comprising a step of forming a photoresist layer on a colored layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry etching the colored layer using the resist pattern as an etching mask A method is mentioned.

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 an image display device 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 having excellent spectral characteristics and contrast while achieving a good hue.

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.

<Image display device>
The image display device of the present invention comprises the color filter of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device. It is particularly suitable for liquid crystal display devices. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image with a good display image color and excellent display characteristics.

For the definition of the image display device and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Sangyo Tosho) Issued in 1989). The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 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 (Thin Film Transistor) type 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.)”. Further, the present invention relates to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), a STN (Super-Twist Nematic). ), TN (Twisted Nematic), VA (Vertical Alignment), OCS (On-chip spacer), FFS (Fringe field switching), and R-OCB (Reflective Optical Compensated).
The color filter of the present invention can also be used for a bright and high-definition COA (Color-filter On Array) system.

When the color filter of the present invention is used in an image display device, high contrast can be realized when combined with a conventionally known three-wavelength cold-cathode tube, but further, red, green, and blue light-emitting diode light sources (RGB-LED) ) As a backlight, an image display device having high luminance and high color purity and good color reproducibility can be provided.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes the above-described color filter of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it is a configuration that includes the color filter of the present invention and functions as a solid-state imaging device.

On a support, transfer electrodes made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) are provided. A nitride film formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part. The device has a device protective film made of silicone or the like, and has the color filter for a solid-state imaging device of the present invention on the device protective film.
Further, a configuration having light collecting means (for example, a microlens, etc., the same applies hereinafter) on the device protective film and below the color filter (on the side close to the support), or a structure having the light collecting 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.

<Method for measuring weight average molecular weight (Mw) (GPC measurement)>
The solvent was removed from the sample, and the obtained solid content was diluted to 0.1% by mass with tetrahydrofuran, and TSKgel α-M (manufactured by Tosoh Corporation), 7 by HLC-8020GPC (manufactured by Tosoh Corporation). .8 mm (inner diameter) × 30 cm) connected in series was measured as a column. The measurement conditions were N-methyl-2-pyrrolidone (NMP) with a sample concentration of 0.35 mass%, a flow rate of 0.3 mL / min, a sample injection volume of 10 μL, a measurement temperature of 40 ° C., and an ultraviolet detector. This is the value obtained.
<Content of Compound (Compound A) having Triarylmethane Structure and Weight Average Molecular Weight of 1500 or Less>
An amount having a weight average molecular weight of 1500 or less was estimated and calculated from data obtained by GPC measurement.

<Synthesis Example 1>
(Synthesis of TAM1)
TAM1 was synthesized according to the following route.

(Synthesis of Synthetic Intermediate (Compound 2))
4,3′-Dichlorobenzophenone (Compound 1) 25.1 g, xylene 200 mL, sodium tert-butoxide 28.8 g and 1,3,5-mesitylamine were charged into a three-necked flask and subjected to nitrogen bubbling for 1 hour, and palladium acetate (II ) 22.5 mg and dicyclohexyl (1,1-diphenyl-1-propen-2-yl) phosphine 78.1 mg were added and stirred at 110 ° C. for 3 hours.
After cooling to room temperature, a mixed solution of 200 mL of ion-exchanged water and 40 mL of 2-propanol was added, filtered, and then washed in the order of a mixed solution of 160 mL of toluene and 20 mL of 2-propanol, 200 mL of ion-exchanged water, and 200 mL of 2-propanol. 39.3g (yield 87.6%) of compound 2 was obtained.

(Synthesis of Synthetic Intermediate (Compound 3))
After flowing into a three-necked flask with nitrogen, 150 mL of N-methylpyrrolidone and 8.0 g of sodium hydride were charged, and a solution prepared by dissolving 30.0 g of Compound 2 in 100 mL of N-methylpyrrolidone was added dropwise over 30 minutes and stirred for 3 hours. Then, 27.4 g of methyl p-toluenesulfonate was added dropwise over 30 minutes. Thereafter, the mixture was stirred for 2 hours, and a mixed solution of 220 mL of ion exchange water and 50 mL of 2-propanol was slowly added dropwise, and then 70 mL of 1 mol / L hydrochloric acid solution was added dropwise and filtered. Washing was carried out in the order of 200 mL of ion-exchanged water, 200 mL of methanol, 160 mL of hexane and 20 mL of 2-propanol to obtain 31.6 g (99.0%) of Compound 3.

(Synthesis of Synthetic Intermediate (Compound 5))
In a three-necked flask, 110 mL of acetonitrile, 24.5 g of 1-naphthylamine (compound 4) and 3.2 g of zinc perchlorate hexahydrate were added, the temperature was raised to 40 ° C., and 23.5 g of 1,2-epoxycyclohexane was added to 30 ml. After dropwise addition over a period of 5 minutes, the mixture was stirred for 5 hours. 110 mL of acetonitrile was added, 170 mL of ion exchange water was added dropwise, and the mixture was stirred for 20 minutes, then cooled to room temperature, stirred for 1 hour, and then filtered. The product was washed twice with 50 mL of ion-exchanged water to obtain 32.3 g (yield: 71.2%) of Compound 5.

(Synthesis of Synthesis Intermediate (R-2))
A three-necked flask was charged with 20 mL of acetonitrile, 4.8 g of 2-methacryloyloxyethyl succinic acid, 5.3 g of paratoluenesulfonyl chloride, and 4.8 g of compound 5, and 4.6 g of 1-methylimidazole was cooled to 10 ° C. or lower. After dropwise addition over 30 minutes, the mixture was stirred for 5 hours. After raising the temperature to room temperature, 30 mL of toluene and 30 mL of ion-exchanged water were added to separate the solution, washed twice with 30 mL of 5% NaHCO ₃ aqueous solution, and then concentrated under reduced pressure to obtain an oily compound.
A three-necked flask was charged with 8.9 g of the obtained oily compound, 20 mL of acetonitrile, 9.1 g of compound 3, and 6.4 g of phosphorus oxychloride, stirred at 90 ° C. for 3 hours, cooled to room temperature, Ion exchange water 60mL was added and liquid-separated. After washing with 5% NaHCO ₃ aqueous solution and adding 7.3 g of lithium bis (trifluoromethanesulfonyl) imide and stirring for 30 minutes, 60 mL of ion-exchanged water was added for liquid separation, followed by washing with 5% NaHCO ₃ aqueous solution.
After concentration under reduced pressure, the residue was purified by a silica gel column to obtain 8.9 g (yield 98.0%) of compound R-2.

<Synthesis of TAM1 (polymerization process)>
A three-necked flask was charged with 1.9 g of propylene glycol-1-monomethyl ether-2-acetate and heated to 60 ° C. while flowing nitrogen, and 4.5 g of propylene glycol-1-monomethyl ether-2-acetate and 0.24 g of dodecyl mercaptan. And a solution of 5.0 g of R-2, 0.56 g of cyclohexyl methacrylate, 0.67 g of glycidyl methacrylate, 0.43 g of methacrylic acid and 0.16 g of 2,2′-azobis (2,4-dimethylvaleronitrile) over 1 hour. After dropwise addition and stirring for 1 hour, 0.08 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and stirred for 5 hours. After cooling to room temperature, 35 mL of hexane was added, and the mixture was stirred for 1 hour, and then filtered to obtain 6.7 g (yield 96.6%) of TAM1.

<TAM2-6>
Synthesis was performed in the same manner as in Synthesis Example 1 except that the amount of dodecyl mercaptan in the polymerization step was changed.

<TAM7-15>
It synthesize | combined similarly to TAM3 except having changed the quantity of each monomer of a superposition | polymerization process.

<TAM16-22>
Synthesize | combined similarly to TAM3 except having changed each monomer of the superposition | polymerization process.

<TAM23>
This compound was synthesized in the same manner as TAM3 except that Compound 3 was changed to N, N, N ′, N′-tetraethyl-4,4′-diaminobenzophenone.

<TAM24>
Synthesis was performed in the same manner as TAM3 except that lithium bis (trifluoromethanesulfonyl) imide was changed to potassium tris (trifluoromethanesulfonyl) methide.

<TAM25>
Synthesis was performed in the same manner as TAM3 except that lithium bis (trifluoromethanesulfonyl) imide was changed to lithium trifluoromethanesulfonate.

<R-1>
Basic blue 7 (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

<R-3, 5>
Synthesis was performed in the same manner as in Synthesis Example 1 except that the amount of dodecyl mercaptan in the polymerization step was changed.

<R-4>
It synthesize | combined similarly to the synthesis example 1 except having changed the quantity of each monomer of a superposition | polymerization process.

[Test Example 1]
<Examples 1 to 25, Comparative Examples 1 to 5>
(Preparation of coloring composition)
The coloring composition was prepared by mixing raw materials having the following composition.
-composition-
Colorant: 5.1 parts by weight Polymerizable compound (T-1): 6.0 parts by weight Alkali-soluble binder (U-2): 5.3 parts by weight Photoinitiator (V-4) ... 0.3 parts by mass, curing accelerator (V-5) ... 0.2 parts by mass, solvent (X-1) ... 71 parts by mass, solvent (X-3) ... 13 parts by mass / Surfactant (Z-1) ... 0.01 parts by mass

Colorant: The following structure. In the following formula, the numerical value written in the repeating unit is the mass ratio of the charged raw materials.

Polymerizable compound (T-1): KAYARAD DPHA (Nippon Kayaku Co., Ltd., mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
Alkali-soluble binder (U-2): allyl methacrylate / methacrylic acid (77/23 “mass ratio” copolymer, weight average molecular weight 37,000, acid value 137 mg KOH / g)
Photopolymerization initiator (V-4): IRGACURE OXE-02 (BASF Japan)
Curing accelerator (V-5): Karenz MTBD-1 (Showa Denko KK)
Solvent (X-1): Propylene glycol monomethyl ether acetate Solvent (X-3): (Methyl ethyl diglycol (MEGD) manufactured by Nippon Emulsifier Co., Ltd.)
Surfactant (Z-1): The following mixture (Mw = 14000)

<Production of cured film>
The colored curable resin composition obtained above was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) by spin coating, and then dried at room temperature for 30 minutes to volatilize volatile components. To obtain a colored layer. This colored layer was irradiated with i-rays (wavelength 365 nm) exposed on the entire surface without using a photomask to form a latent image. An ultra-high pressure mercury lamp was used as the i-line light source, and it was irradiated as parallel light. At this time, the irradiation light quantity was 40 mJ / cm ² . Next, the colored layer on which the latent image was formed was developed with an aqueous solution of sodium carbonate / sodium bicarbonate (concentration 2.4%) at 26 ° C. for 45 seconds, and then rinsed with running water for 20 seconds. , Dried with spray. The dried film was baked at 230 ° C. for 20 minutes in a clean oven to obtain a cured film.
The following evaluation was performed about the cured film obtained above.

<Heat resistance>
The color difference ΔEab between the transmission spectrum of the cured film obtained above and the transmission spectrum when the cured film obtained above was additionally baked at 230 ° C. for 80 minutes was calculated. A smaller ΔEab value indicates better heat resistance.
ΔEab is less than 2 ... 6
ΔEab is 2 or more and less than 3 ・・・ 5
ΔEab is 3 or more and less than 4 ・・・ 4
ΔEab is 4 or more and less than 5 ・・・ 3
ΔEab is 5 or more and less than 10 2
ΔEab is 10 or more ・・・ 1

<Solvent resistance (color difference)>
The cured film obtained above is heated at 230 ° C. for 30 minutes, and then immersed in propylene glycol monomethyl ether acetate (PGMEA) at 25 ° C. for 10 minutes, and the chromaticity before and after immersion is measured to change the color. The index ΔEab was calculated. The ΔEab value was calculated from the transmission spectrum of the cured film before and after being immersed in PGMEA. In addition, when the value of ΔEab was 3 or less, the hue change was small and the solvent resistance was excellent.
ΔEab is 1.5 or more and less than 2, 5
ΔEab is 2 or more and less than 3.5 4
ΔEab is 3.5 or more and less than 4, 3
ΔEab is 4 or more and less than 5, 2
ΔEab is 5 or more ・・・ 1

<Voltage holding ratio>
A colored composition is applied onto a glass substrate with ITO (Indium Tin Oxide) electrode (trade name: 1737 manufactured by Corning) to a thickness of 2.0 μm after drying, and dried in an oven at 100 ° C. for 60 seconds ( Pre-baked). Thereafter, exposure was performed at 100 mJ / cm ² without using a mask (illuminance was 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.) was used. The film was developed at 25 ° C., washed with water and dried, and then heat-treated (post-baked) in an oven at 230 ° C. for 20 minutes to form a cured film. Next, the substrate on which this cured film is formed and the substrate on which the ITO electrode is 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) between the substrates. Was injected to prepare a liquid crystal cell.
Next, after putting the liquid crystal cell in a constant temperature layer at 60 ° C. for 24 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 at 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, the example was able to form a cured film excellent in heat resistance and solvent resistance. Furthermore, the cured film was excellent in voltage holding ratio.
On the other hand, the comparative example could not achieve both heat resistance and solvent resistance.

[Test Example 2]
<Examples 26 to 48>
(Preparation of coloring composition)
The coloring composition was prepared by mixing raw materials having the following composition.
-composition-
Colorant: 5.1 parts by weight Polymerizable compound (T-1): 6.0 parts by weight Alkali-soluble binder (U-2): 5.3 parts by weight Photoinitiator (V-4) ... 0.3 parts by mass / curing accelerator (V-5) ... 0.2 parts by mass / additive (W-1) ... 0.5 parts by mass / solvent (X -1) ... 71 parts by mass, solvent (X-3) ... 13 parts by mass, surfactant (Z-1) ... 0.01 parts by mass

Colorant: Colorant described in the following table Polymerizable compound (T-1), alkali-soluble binder (U-2), photopolymerization initiator (V-4), curing accelerator (V-5), solvent (X -1), solvent (X-3), surfactant (Z-1): the above-described polymerizable compound (T-1), alkali-soluble binder (U-2), photopolymerization initiator (V-4), Curing accelerator (V-5), solvent (X-1), solvent (X-3), surfactant (Z-1)
Additive (W-1): Potassium bis (trifluoromethanesulfonyl) imide (Mitsubishi Materials Corporation)

The heat resistance, solvent resistance and voltage holding ratio were evaluated in the same manner as in Test Example 1. The results are shown in the table below.

From the above results, the example was able to form a cured film excellent in heat resistance and solvent resistance. Furthermore, the cured film was excellent in voltage holding ratio.

Claims

A polymer TP containing at least one repeating unit A having a triarylmethane structure selected from general formula (TP1) and general formula (TP2) and a repeating unit B having a crosslinkable group; and a polymerizable compound; Including,
The polymer TP has a weight average molecular weight of 3000 to 500,000, and the content of the compound A having a triarylmethane structure and a weight average molecular weight of 1500 or less is 20% by mass or less based on the mass of the polymer TP. Composition;

In the 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 each Rtp 7 represents a hydrogen atom, an alkyl group, an aryl group or NRtp 71 Rtp 72 ; Rtp 71 and Rtp 72 each independently represent a hydrogen atom, an alkyl group or an aryl group; Rtp 10 represents a hydrogen atom, an alkyl group or an aryl group; a, b, c and d each independently represent an integer of 0 to 4; when a, b, c and d are 2 or more, Rtp 5 , Rtp 6 , Rtp 8 and Rtp 9 may be linked to each other to form a ring; X represents an anion, or X is absent and Rtp 1 to Rtp 11 , Rtp At least one of 71 and Rtp 72 contains an anion; any of Rtp 1 to Rtp 11 , Rtp 71 and Rtp 72 represents a binding site to the repeating unit A.
The colored composition according to claim 1, wherein the content of the compound A in the polymer TP is 10% by mass or less based on the mass of the polymer TP.
The colored composition according to claim 1 or 2, wherein the polymer TP has a weight average molecular weight of 10,000 to 50,000.
The crosslinkable group of the repeating unit B is at least one selected from a group containing an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, an oxazoline group, a group represented by —C—O—R, and a carbonate group. The colored composition according to any one of claims 1 to 3, wherein R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
X is at least one anion selected from fluorine anion, chlorine anion, bromine anion, iodine anion, cyanide ion, perchlorate anion, borate anion, PF 6− and SbF 6− , and —SO 3 -, -COO -, -PO 4 - , is selected from compounds having at least one structure selected from structures represented by the following general formula represented by the structure and the following general formula (A1) (A2) The coloring composition according to any one of claims 1 to 4;
General formula (A1)

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

In general formula (A2), R 3 represents —SO 2 — or —CO—; R 4 and R 5 each independently represents —SO 2 —, —CO— or —CN.
The colored composition according to any one of claims 1 to 5, wherein X is a compound containing a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion, or a sulfonate anion.
The colored composition according to any one of claims 1 to 6, wherein X is a compound containing a crosslinkable group.
The colored composition according to any one of claims 1 to 7, wherein X is a polymer containing a repeating unit having an anion moiety.
The general formulas (TP1) and (TP2), wherein at least one of Rtp 1 to Rtp 11 , Rtp 71 and Rtp 72 is substituted with a group represented by the general formula (P) Or a coloring composition according to claim 1;
General formula (P)

In general formula (P), L represents a single bond or a divalent linking group, and X 1 includes —SO 3 − , —COO − , —PO 4 − , and a structure represented by the following general formula (A1). Selected from at least one selected from a group and a group containing a structure represented by the following general formula (A2);
General formula (A1)

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

In general formula (A2), R 3 represents —SO 2 — or —CO—; R 4 and R 5 each independently represents —SO 2 —, —CO— or —CN.
The colored composition according to any one of claims 1 to 9, wherein the triarylmethane structure of the repeating unit A is represented by the following general formula (TP3);

In the general formula (TP3), Rtp 21 each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6; Rtp 22 each independently represents an aryl group having 6 to 10 carbon atoms, Rtp 71 is It represents an alkyl group or an aryl group; X is either an anion, X is at least one of the anion of Rtp 21, Rtp 22 and Rtp 71 in the absence; Rtp 21, either above Rtp 22 and Rtp 71 The binding site with the repeating unit A is represented.
The coloring composition according to any one of claims 1 to 10, wherein the repeating unit A is represented by the following general formula (TP3-1);

In general formula (TP3-1), Rtp 21 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Rtp 22 each independently represents an aryl group having 6 to 10 carbon atoms, and Rtp 71a Represents an alkylene group or an arylene group; L 1 represents a single bond or a divalent linking group, Rtp 31 represents a hydrogen atom or a methyl group; X represents an anion, or X does not exist and Rtp At least one of 21 and Rtp 22 contains an anion.
The coloring composition according to any one of claims 1 to 11, wherein the repeating unit A is represented by the following general formula (TP3-2);

In general formula (TP3-2), Rtp 21 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Rtp 24 each independently represents an alkyl group having 1 to 4 carbon atoms, and Rtp 25 Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Rtp 71a represents an alkylene group or an arylene group; Rtp 31 represents a hydrogen atom or a methyl group; L 1 represents a single bond or X represents an anion, or X does not exist and at least one of Rtp 21 and Rtp 24 includes an anion.
The coloring according to any one of claims 1 to 12, wherein the polymer TP includes a repeating unit derived from at least one of (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylic acid amide. Composition.
The colored composition according to any one of claims 1 to 13, comprising at least one selected from a xanthene compound, a dipyrromethene metal complex compound, a dioxazine compound and a phthalocyanine compound.
The colored composition according to any one of claims 1 to 14, comprising a photopolymerization initiator.
The colored composition according to any one of claims 1 to 15, comprising a bis (trifluoromethanesulfonyl) imide salt.
The colored composition according to any one of claims 1 to 16, which is used for forming a colored layer of a color filter.
A cured film obtained by curing the colored composition according to any one of claims 1 to 17.
A color filter having the cured film according to claim 18.
Forming a colored composition layer using the colored composition according to any one of claims 1 to 17,
Exposing the colored composition layer in a pattern;
And a step of developing and removing an unexposed portion of the colored composition layer to form a colored pattern.
Forming a colored composition layer using the colored composition according to any one of claims 1 to 17 and curing to form a colored layer;
Forming a photoresist layer on the colored layer; patterning the photoresist layer by exposure and development to obtain a resist pattern;
And a step of dry etching the colored layer using the resist pattern as an etching mask.
A solid-state imaging device having the color filter according to claim 19.
An image display device having the color filter according to claim 19.
Content of compound A having a repeating unit represented by the following general formula (TP-7), the polymer having a weight average molecular weight of 3000 to 500,000 and having a triarylmethane structure and having a weight average molecular weight of 1500 or less Is 20% by mass or less based on the mass of the polymer;

In general formula (TP-7), each R 1 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 4 represents a hydrogen atom or a methyl group, and R 1a represents an alkylene group or an arylene group. L 11 represents a single bond or a divalent linking group having 1 to 30 carbon atoms; L 12 and L 13 represent a single bond or a divalent linking group having 1 to 30 carbon atoms. R 2 represents a hydrocarbon group having 1 to 10 carbon atoms; R 3 represents a crosslinkable group; X represents a compound containing a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion or a sulfonate anion A to d are mass ratios of repeating units, a and d each represent a number exceeding 0, and b and c each independently represent a number of 0 or more.