WO2015045622A1

WO2015045622A1 - Colored composition, cured film, color filter, method for producing color filter, solid state imaging element, and liquid crystal display device

Info

Publication number: WO2015045622A1
Application number: PCT/JP2014/070442
Authority: WO
Inventors: 樋口　聡; 加藤　隆志; 藤田　明徳
Original assignee: 富士フイルム株式会社
Priority date: 2013-09-30
Filing date: 2014-08-04
Publication date: 2015-04-02
Also published as: CN105593311A; TW201512315A; KR20160047561A; JP6147181B2; KR101855237B1; JP2015092217A; CN105593311B; TWI634162B

Abstract

Provided are: a colored composition having excellent heat resistance, excellent solvent resistance and an excellent voltage retention rate; a cured film; a color filter; a method for producing a color filter; a solid state imaging element; and a liquid crystal display device. The colored composition according to the present invention comprises: a coloring agent which contains a triarylmethane structure having a crosslinking group and a cation and having a molecular weight of 2000 or less and a counter anion; and a polymerizable compound.

Description

Coloring composition, cured film, color filter, method for producing color filter, solid-state imaging device, and liquid crystal display device

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

Conventionally, a color filter is made into a colored composition by containing a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components as necessary. This is used to form a colored pattern by a photolithography method, an ink jet method or the like.
In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. Along with this trend of expanding applications, color filters are required to have high color characteristics in terms of chromaticity and contrast. Similarly, color filters for image sensors (solid-state imaging devices) are required to further improve color characteristics such as reduction of color unevenness and improvement of color resolution.
However, in the conventional pigment dispersion system, problems such as the occurrence of scattering due to coarse particles of the pigment and the increase in viscosity due to poor dispersion stability are likely to occur, and it is often difficult to further improve the contrast and brightness.
Therefore, conventionally, as a colorant, it has been studied to use not only a pigment but also a dye (for example, see Patent Document 1). When a dye is used as a colorant, the hue and brightness of a display image when an image is displayed can be increased due to the color purity of the dye itself and the vividness of the hue, and contrast can be improved because coarse particles are eliminated. It is useful in terms.
As examples of dyes, compounds having a wide variety of chromophores such as phthalocyanine dyes, dipyrromethene dyes, pyrimidine azo dyes, pyrazole azo dyes, xanthene dyes, triarylmethane dyes are known (for example, Patent Documents 2 to 8). See).

JP-A-6-75375 JP 2008-292970 A JP 2007-039478 A JP-A-9-157536 JP 2013-25194 A JP 2012-201694 A JP 2012-108469 A JP 2000-095805 A

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

Under such circumstances, the inventor of the present application diligently studied, and as a result, by blending a colorant containing a triarylmethane structure having a molecular weight of 2000 or less having a crosslinkable group and a cation and a counter anion into the composition, I found that the problem could be solved.
Specifically, the above-mentioned problem has been solved by the following means <1>, preferably <2> to <14>.
<1> A colored composition comprising a triarylmethane structure having a crosslinkable group and a cation having a molecular weight of 2000 or less and a counter anion and a polymerizable compound.
<2> The colored composition according to <1>, wherein the triarylmethane structure having a molecular weight of 2000 or less having a crosslinkable group and a cation is represented by the general formula (TP1) and / or 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 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 and c each independently represent an integer of 0 to 4. When a, b and c are 2 or more, Rtp ₆ , Rtp Two of ₇ and Rtp ₈ may be linked to each other to form a ring, and any of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ has a crosslinkable group.)
<3> At least one selected from the group consisting of a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, a borate anion, PF ⁶⁻ and SbF ⁶⁻ , and
_{^{^{-SO 3 -, -COO -, -PO}}} 4 -, is selected from at least one selected from structures represented by the structure and the following general formula represented by the following general formula (A1) (A2), < The coloring composition as described in 1> or <2>.
General formula (A1)

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

(In the general formula (A2), R ³ represents —SO ₂ — or —CO—. R ⁴ and R ⁵ each independently represents —SO ₂ —, —CO— or —CN.)
<4> The colored composition according to any one of <1> to <3>, wherein the counter anion is contained in a compound containing a crosslinkable group.
<5> The colored composition according to any one of <1> to <3>, wherein a counter anion is contained in the repeating unit.
<6> The colored composition according to <1>, wherein the triarylmethane structure having a molecular weight of 2000 or less having a crosslinkable group and a cation is represented by the general formula (TP1A) or the general formula (TP2A).

(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 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 and c each independently represent an integer of 0 to 4. When a, b and c are 2 or more, Rtp ₆ , Rtp ₇ and two of Rtp ₈ is, .Rtp ₁ ~ Rtp ₁₁ with each other linked to the crosslinkable group in any of which may form a ring .Rtp ₁ ~ Rtp _11, Rtp ₇₁ and Rtp _72, Rt at least one p ₇₁ and Rtp _72, but the general formula (P) may be substituted.)
General formula (P)

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

(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.)
<7> The colored composition according to any one of <1> to <6>, further including a photopolymerization initiator.
<8> The colored composition according to any one of <1> to <7>, which is used for forming a colored layer of a color filter.
<9> A colored cured film obtained by curing the colored composition according to any one of <1> to <8>.
<10> A color filter having the colored cured film according to <9>.
<11> A step of applying the colored composition according to any one of <1> to <8> onto a support to form a colored composition layer, and a step of exposing the colored composition layer to a pattern. And a step of developing and removing the unexposed portion to form a colored pattern.
<12> A step of applying a colored composition according to any one of <1> to <8> onto a support to form a colored composition layer and curing to form a colored layer; A method for producing a color filter, comprising a step of forming a resist layer, a step of patterning a photoresist layer by exposure and development to obtain a resist pattern, or a step of dry etching a colored layer using the resist pattern as an etching mask.
<13> A color filter manufactured by the method for manufacturing a color filter according to <11> or <12>.
<14> A solid-state imaging device or an image display device having the color filter according to <10> or the color filter produced by the method for producing a color filter according to <11> or <12>.

According to the present invention, it is possible to provide a coloring composition having excellent heat resistance, solvent resistance and voltage holding ratio.

Hereinafter, the contents of the present invention will be described in detail. In this specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In this specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored composition.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acrylic” ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In the present specification, “monomer” and “monomer” are synonymous. The monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
The weight average molecular weight in the present invention refers to that measured by gel permeation chromatography (GPC) unless otherwise specified. GPC was isolated by removing the solvent from the obtained polymer, and the obtained solid content was diluted to 0.1% by mass with tetrahydrofuran, and HLC-8020 GPC (manufactured by Tosoh Corporation) was used. The column can be measured by connecting three TSKgel Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) in series. The conditions can be performed using a RI detector with a sample concentration of 0.35% by mass, a flow rate of 0.35 mL / min, a sample injection amount of 10 μL, and a measurement temperature of 40 ° C.

<Coloring composition>
The colored composition of the present invention is characterized by containing a colorant containing a triarylmethane structure having a crosslinkable group and a cation having a molecular weight of 2000 or less and a counter anion, and a polymerizable compound.
By setting it as such a structure, the coloring composition excellent in heat resistance, solvent resistance, and voltage holding ratio can be provided.
Hereinafter, the colorant will be described in the order of the first embodiment and the second embodiment.
The first embodiment is a case other than the second embodiment described below. For example, there may be mentioned a case where the bonding part between the counter aryl group and the triarylmethane structure having a molecular weight of 2000 or less having a crosslinkable group and a cation does not have a covalent bond.
In the second embodiment, the counter anion is directly covalently bonded to a triarylmethane skeleton portion of a triarylmethane structure having a molecular weight of 2000 or less having a crosslinkable group and a cation, or the counter anion is a triaryl. The case where it is covalently bonded to the methane skeleton portion via a linking group is mentioned.

First Embodiment of Colorant Hereinafter, a triarylmethane structure having a crosslinkable group and a cation having a molecular weight of 2000 or less and a counter anion will be described.
<< Triarylmethane Structure >>
As the crosslinkable group possessed by the triarylmethane structure, a crosslinkable group that can be crosslinked by a radical, an acid, or heat can be used. Specific examples include a group having an ethylenically unsaturated double bond, a (meth) acryl group, a styrene group, a vinyl group, an allyl group, and a cyclic ether group, and a (meth) acryl group, a styrene group, and a vinyl group. And at least one selected from allyl groups is preferred, at least one selected from (meth) acrylic groups, styrene groups and vinyl groups is more preferred, and (meth) acrylic groups and styrene groups are more preferred.
For example, the cyclic ether group is preferably an epoxy group or an oxetanyl group, and more preferably an epoxy group.

The molecular weight of the triarylmethane structure having a crosslinkable group and a cation is 2000 or less, preferably 300 to 1500, and more preferably 300 to 900.

The triarylmethane structure having a molecular weight of 2000 or less having a crosslinkable group and a cation is preferably represented by the following general formula (TP1) and / or 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 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 and c each independently represent an integer of 0 to 4. When a, b and c are 2 or more, Rtp ₆ , Rtp Two of ₇ and Rtp ₈ may be linked to each other to form a ring, and any of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ has a crosslinkable group.)

In general formula (TP1), Rtp ₁ to Rtp ₄ each independently represents a hydrogen atom, an alkyl group or an aryl group, and preferably a hydrogen atom or an alkyl 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 may have a substituent, but is preferably unsubstituted. 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 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, but is preferably linear or branched. The alkyl group is preferably unsubstituted. 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 carboxyl group, or a sulfo group is preferable, and a linear chain having 1 to 5 carbon atoms is preferable. Or a branched alkyl group, an alkenyl group having 1 to 5 carbon atoms, a phenyl group or a carboxyl group is more preferable. In particular, Rtp ₅ and Rtp ₆ are preferably each independently an alkyl group having 1 to 5 carbon atoms. Rtp ₈ preferably has two alkenyl groups bonded to each other to form a ring. The ring is preferably a benzene ring.

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

In general formula (TP2), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group or an aryl group, and 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 alkyl group, an alkoxy group, or a halogen atom.
Rtp ₁₁ is preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group is preferably linear or branched, and more preferably linear.

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 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 to 2, more preferably 0.

Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ each preferably have a crosslinkable group, and Rtp ₇₁ or Rtp ₇₂ preferably has a crosslinkable group.
The group having a crosslinkable group may comprise only a crosslinkable group, or may contain a linking group in addition to the crosslinkable group. In particular, the group having a crosslinkable group is preferably a group represented by -L ⁰ -P ⁰ . Here, L ⁰ represents a single bond or a divalent linking group, and P ¹ represents a crosslinkable group.
A crosslinkable group is synonymous with the crosslinkable group mentioned above, and its preferable range is also the same.
The divalent linking group includes an alkylene group, an arylene group, a heterocyclic linking group, —CH═CH—, —O—, —S—, —C (═O) —, —CO—, —NR—, —CONR. —, —OC—, —SO—, —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 divalent linking group is preferably an alkylene group.
The alkylene group may be linear, branched or cyclic. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, more preferably 5 to 20, and particularly preferably 5 to 10. Specifically, a methylene group, ethylene group, propylene group, butylene group, hexylene group, hepsylene group, cyclopentenylene group, cyclohexylene group and the like are preferable.
The number of carbon atoms of the arylene group is preferably 6 to 30, more preferably 6 to 18, and still more preferably 6 to 12. Specifically, the arylene group is preferably a phenylene group or a naphthalene group.

In the triarylmethane structure, cations are delocalized as follows, and the following two structures are synonymous, and both are included in the present invention. The cation moiety may be at any position in the molecule.

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

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

Linear or branched alkenyl group (straight or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl A group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, and a polycycloalkenyl group such as bicyclo An alkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] Octo-2-en-4-yl) and tricycloalkenyl groups, with monocyclic cycloalkenyl groups being particularly preferred. Cycloalkenyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, e.g., ethynyl, propargyl, trimethylsilylethynyl group),

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

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

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

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

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

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

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

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

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

Specific examples of the triarylmethane structure having a molecular weight of 2000 or less having a crosslinkable group and a cation include the following structures, but the present invention is not limited thereto.

<< Counter anion >>
The counter anion is a cation counter anion of the triarylmethane structure. The counter anion may consist only of the counter anion or may be included as part of the structure of the compound.

In the case of consisting only of a counter anion, examples include a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, a borate anion (BF ⁴⁻ etc.), PF ⁶⁻ and SbF ^6−. Anions and PF ⁶⁻ are preferred.
As a case where the counter anion is included as a part of the structure of the compound, there is a case where it exists as a counter anion separately from the triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2000 or less.

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 case where the counter anion is contained as a part of the structure of the compound may be contained in a part of the polymer having a repeating unit or may be contained in a so-called low molecular compound having a molecular weight of 2000 or less. 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 moiety is exemplified. In the present invention, in particular, an embodiment in which the counter anion is contained in the compound containing a crosslinkable group and an embodiment in which the counter anion is contained in the repeating unit are preferred, and an embodiment in which the counter anion is contained in the repeating unit is more preferred. .

When a counter anion is included as part of the structure of the compound, the anion moiety is —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , a structure represented by the following general formula (A1), and a general formula (A2) At least one selected from the structure represented by

General formula (A1)

(In the 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 alkyl group or an aryl group, and an alkyl group is preferable. The alkyl 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 where the counter anion is included as part of the structure of the compound are R—SO ₃ ⁻ , R—COO ^— or R—PO ₄ ^— , wherein R is substituted with a halogen atom or halogen atom. Examples are an alkyl group which may be substituted and an aryl group which may be substituted with a halogen atom.
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.
In particular, the following embodiments are preferable. A compound containing a group represented by the general formula (A1-1), wherein R ¹ and R ² in the general formula (A1-1) represent —SO ₂ —, and at least one of X ¹ and X ² is An embodiment representing an alkylene group or an arylene group. A compound containing a group represented by the general formula (A2), wherein R ⁴ and R ⁵ in the general formula (A2) are bonded to an alkyl group substituted with a halogen atom. An embodiment in which —PO ₄ ^— or —SO ₃ ^— is included as part of the structure of the compound. Chlorine anion, cyanide ion, BF ⁴⁻ or PF ⁶⁻ .
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”.

Hereinafter, when the counter anion is contained in the compound containing a crosslinkable group, the case where the counter anion is contained in the repeating unit will be described in detail.
Examples of the crosslinkable group include a crosslinkable group that can be cross-linked by a radical, an acid, and heat.
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.
It is preferable that the specific example in case a counter anion is contained in the compound containing a crosslinkable group is 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 (for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group, etc.), a carbon number of 6 to 30 arylene groups, heterocyclic linking groups, —CH═CH—, —O—, —S—, —C (═O) —, —CO—, —NR—, —CONR—, —OC—, —SO —, —SO ₂ — and a linking group obtained by combining two or more thereof are preferred. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
In particular, the linking group is an alkylene group having 1 to 10 carbon atoms (preferably — (CH ₂ ) n— (n is an integer of 1 to 10), an arylene group having 6 to 12 carbon atoms (preferably a phenylene group or naphthalene). Group), —NH—, —CO—, —O— and —SO ₂ — are preferred.

<< other functional groups >>
When a counter anion is included as part of the structure of the compound, it may have a functional group other than the crosslinkable group. Other functional groups include other functional groups described in the above-described repeating unit having a triarylmethane structure containing a cation, and preferred examples are also synonymous. When the counter anion is included as part of the structure of the compound, the number of polymerizable groups in the compound is preferably 1 to 3, and more preferably 1.
When the counter anion is included as part of the structure of the compound, the number of acid groups in the compound is preferably 1 to 3, and more preferably 1.

Specific examples in the case where the counter anion is contained in a compound containing a crosslinkable group are shown below, but the present invention is not limited thereto.

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

When the counter anion is contained in the repeating unit (hereinafter also referred to as anion multimer), the side chain may have a counter anion, the main chain may have a counter anion, and the main chain and You may have a counter anion in both of the side chains.
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 counter anion.)

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

When L ¹ represents a divalent linking group, an alkylene group having 1 to 30 carbon atoms (methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.), an arylene group having 6 to 30 carbon atoms (phenylene group, Naphthalene group, etc.), heterocyclic linking group, —CH═CH—, —O—, —S—, —C (═O) —, —CO—, —NR—, —CONR—, —OC—, —SO —, —SO ₂ — and a linking group obtained by combining two or more thereof are preferred. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
In particular, L ¹ is a single bond, an alkylene group having 1 to 10 carbon atoms (preferably — (CH ₂ ) n— (n is an integer of 5 to 10), an arylene group having 6 to 12 carbon atoms (preferably phenylene group, naphthalene group) _{is, - NH -, - CO 2} -, - O- and -SO ₂ - is a divalent linking group formed by combining two or more preferred.

Specific examples of the combination of X ¹ and L ¹ include the following (XX-1) to (X-30), but the present invention is not limited to these. The anion multimer is linked to the counter anion at the site indicated by * in (XX-1) to (X-30).

Moreover, the following is also preferable as a specific example of the combination of X ¹ and L ¹ . In the following specific examples, n represents an integer of 1 to 9. Moreover, it represents connecting with the counter anion at the site indicated by *.

Formula (D)

(In general formula (D), L ² and L ³ each independently represent a single bond or a divalent linking group. Anion represents the counter anion.)

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

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

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

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

When the counter anion is a polymer, it may have other repeating units.

When the counter anion contains an anion multimer, the amount of the anion multimer is preferably from 1 to 50 mol, more preferably from 10 to 30 mol, based on 100 mol of all repeating units in the colorant used in the present invention.
Further, when the anionic multimer further contains a repeating unit having a polymerizable group, 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.

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

When the anionic multimer further contains a repeating unit having an acid group, the ratio of the repeating unit containing a repeating unit having an acid group is preferably, for example, 10 to 50 mol with respect to 100 mol of all repeating units. More preferred is 30 mol.

Other development accelerators such as lactones, acid anhydrides, amides, —COCH ₂ CO—, cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups, hydroxy groups, maleimide groups, amino groups It may contain a repeating unit having a functional group such as an affinity control group.

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

<< Specific examples of colorants >>
Although the specific example of the coloring agent of 1st Embodiment used for this invention below is shown, it is not limited to these.
In the following compound (D-21), a triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2000 or less exists in a number corresponding to the repeating unit of the counter anion.

Second Embodiment of Colorant In a second embodiment of the colorant, a triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2000 or less is represented by the general formula (TP1A) or the general formula (TP2A). It is preferred that

(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.)

In the general formulas (TP1A) and (TP2A), except that at least one of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ may be substituted with the general formula (P), the first implementation described above It is synonymous with a triarylmethane structure having a molecular weight of 2000 or less having a crosslinkable group and a cation in the form, and the preferred range is also the same.

In general formula (P), L represents a single bond or a divalent linking group. When L represents a divalent linking group, it is preferable that at least one hydrogen atom of the following groups is a divalent linking group substituted with X ¹ .
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino Groups (including alkylamino groups and anilino groups), acylamino groups, aminocarbonylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, sulfamoylamino groups, alkyl or arylsulfonylamino groups, alkylthio groups, arylthio groups, Heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl , Aryl or heterocyclic azo group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, a silyl group, ether group, thioether group.

The alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. For example, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl A divalent alkyl group obtained by removing one hydrogen from the group is preferred. X ¹ may be introduced at any position in order to make these alkyl groups be divalent.
The cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms. Examples thereof include cyclohexyl and cyclopentyl. In addition, a polycycloalkyl group such as a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms such as bicyclo [1,2,2] heptan-2-yl, bicyclo [ And 2,2,2] octane-3-yl) and tricyclic groups such as tricycloalkyl groups. A monocyclic cycloalkyl group and a bicycloalkyl group are preferable, and a monocyclic cycloalkyl group is particularly preferable. X ¹ may be introduced at any position in order to make these cycloalkyl groups be divalent.
The alkenyl group may be linear or branched. The alkenyl group is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms. For example, vinyl, allyl, prenyl, geranyl and oleyl are particularly preferred. X ¹ may be introduced at any position in order to make these alkenyl groups be divalent.
The cycloalkenyl group is preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms. Examples thereof include 2-cyclopenten-1-yl and 2-cyclohexen-1-yl. A polycycloalkenyl group such as a bicycloalkenyl group, preferably a bicycloalkenyl group having 5 to 30 carbon atoms, such as bicyclo [ 2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2-en-4-yl and tricycloalkenyl groups, with monocyclic cycloalkenyl groups being particularly preferred . X ¹ may be introduced at any position in order to make these cycloalkenyl groups be divalent.

The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, and trimethylsilylethynyl groups. X ¹ may be introduced at any position in order to make these alkynyl groups be divalent.
The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. For example, phenyl, p-tolyl, naphthyl, m-chlorophenyl and o-hexadecanoylaminophenyl are preferred. X ¹ may be introduced at any position in order to make these aryl groups be divalent.
The heterocyclic group is preferably a 5- to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group. More preferably, the ring-constituting atom is a heterocyclic group selected from a carbon atom, a nitrogen atom and a sulfur atom, and having at least one heteroatom of any of a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably a carbon atom A 5- or 6-membered aromatic heterocyclic group of 3 to 30. For example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl and 2-benzothiazolyl groups are preferred. X ¹ may be introduced at any position in order to make these heterocyclic groups divalent.
The alkoxy group is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, and for example, methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy and 2-methoxyethoxy are preferable. X ¹ may be introduced at any position in order to make these alkoxy groups be divalent.

The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. For example, phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 4-tert-butylphenoxy, 3 -Nitrophenoxy, 2-tetradecanoylaminophenoxy group is preferred. X ¹ may be introduced at any position in order to make these aryloxy groups be divalent.
The silyloxy group is preferably a substituted or unsubstituted silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy or tert-butyldimethylsilyloxy group. X ¹ may be introduced at any position in order to make these silyloxy groups be divalent.
The heterocyclic oxy group is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. As the heterocycle, the heterocycle moiety is preferably the heterocycle moiety described above for the heterocycle group, and for example, 1-phenyltetrazol-5-oxy and 2-tetrahydropyranyloxy groups are preferred. X ¹ may be introduced at any position in order to make these heterocyclic oxy groups be divalent.
The acyloxy group is preferably a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms and a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms. For example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy , Benzoyloxy and p-methoxyphenylcarbonyloxy groups are preferred. X ¹ may be introduced at any position in order to make these acyloxy groups be divalent.
The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. For example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di- n-octylaminocarbonyloxy and Nn-octylcarbamoyloxy groups are preferred. X ¹ may be introduced at any position in order to make these acyloxy groups be divalent.
The alkoxycarbonyloxy group is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, and n-octylcarbonyloxy group. X ¹ may be introduced at any position in order to make these alkoxycarbonyloxy groups be divalent.

The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy group. Is preferred. X ¹ may be introduced at any position in order to make these aryloxycarbonyloxy groups be divalent.
The amino group is preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 0 to 30 carbon atoms, For example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino groups are preferred. X ¹ may be introduced at any position in order to make these amino groups be divalent.
The acylamino group is preferably a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms or a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms. For example, formylamino, acetylamino, pivaloylamino, lauroylamino Benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino group is preferred. X ¹ may be introduced at any position in order to make these acylamino groups be divalent.
The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. For example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino group Is preferred. X ¹ may be introduced at any position in order to make these aminocarbonylamino groups be divalent.

The alkoxycarbonylamino group is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. For example, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl- A methoxycarbonylamino group is preferred. X ¹ may be introduced at any position in order to make these alkoxycarbonylamino groups be divalent.
The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, and mn-octyloxyphenoxycarbonylamino group. preferable. X ¹ may be introduced at any position in order to make these aryloxycarbonylamino groups be divalent.
The sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino. Groups are preferred. X ¹ may be introduced at any position in order to make these sulfamoylamino groups be divalent.
The alkyl or arylsulfonylamino group is preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms. For example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, and p-methylphenylsulfonylamino groups are preferred. X ¹ may be introduced at any position in order to make these alkyl or arylsulfonylamino groups be divalent.
The alkylthio group is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, or n-hexadecylthio group. X ¹ may be introduced at any position in order to make these alkylthio groups be divalent.

The arylthio group is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, and m-methoxyphenylthio groups. X ¹ may be introduced at any position in order to make these alkylthio groups be divalent.
The heterocyclic thio group is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, and the heterocyclic moiety is preferably the heterocyclic moiety described above for the heterocyclic group, for example, 2-benzothiazolyl Ruthio and 1-phenyltetrazol-5-ylthio groups are preferred. X ¹ may be introduced at any position in order to make these heterocyclic thio groups be divalent.
The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. For example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N -Acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl groups are preferred. X ¹ may be introduced at any position in order to make these sulfamoyl groups be divalent.
The alkyl or arylsulfinyl group is preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms or a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms. For example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p- A methylphenylsulfinyl group is preferred. X ¹ may be introduced at any position in order to make these alkyl or arylsulfinyl groups be divalent.
The alkyl or arylsulfonyl group is preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms or a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms. For example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p- A methylphenylsulfonyl group is preferred. X ¹ may be introduced at any position in order to make these alkyl or arylsulfonyl groups be divalent.

The acyl group is preferably a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms or a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms. For example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl , Pn-octyloxyphenylcarbonyl group is preferred. X ¹ may be introduced at any position in order to make these acyl groups be divalent.
The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, and examples thereof include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, and p-tert-butylphenoxycarbonyl group. preferable. X ¹ may be introduced at any position in order to make these aryloxycarbonyl groups be divalent.
The alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, and n-octadecyloxycarbonyl. X ¹ may be introduced at any position in order to make these alkoxycarbonyl groups be divalent.
The carbamoyl group is a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) A carbamoyl group is preferred. X ¹ may be introduced at any position in order to make these carbamoyl groups be divalent.
The aryl or heterocyclic azo group includes a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocyclic portion is described in the above heterocyclic group). A heterocyclic portion is preferred. For example, phenylazo, p-chlorophenylazo, and 5-ethylthio-1,3,4-thiadiazol-2-ylazo are preferable. X ¹ may be introduced at any position in order to make these aryl or heterocyclic azo groups be divalent.

The imide group is preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms, such as N-succinimide and N-phthalimide groups. X ¹ may be introduced at any position in order to make these imide groups be divalent.
The phosphino group is preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, a dimethylphosphino, diphenylphosphino, or methylphenoxyphosphino group. X ¹ may be introduced at any position in order to make these phosphino groups be divalent.
The phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, and diethoxyphosphinyl groups. X ¹ may be introduced at any position in order to make these phosphinyl groups be divalent.
The phosphinyloxy group is preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy groups. X ¹ may be introduced at any position in order to make these phosphinyloxy groups be divalent.
The phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as a dimethoxyphosphinylamino or dimethylaminophosphinylamino group. X ¹ may be introduced at any position in order to make these phosphinylamino groups be divalent.
The silyl group is preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, and examples thereof include trimethylsilyl, tert-butyldimethylsilyl, and phenyldimethylsilyl groups. X ¹ may be introduced at any position in order to make these silyl groups be divalent.

When L represents a divalent linking group, it preferably represents a group consisting of —NR ¹⁰ —, —O—, —SO ₂ —, a fluorine-substituted alkylene group, a fluorine-substituted phenylene group, or a combination thereof. In particular, a group consisting of a combination of —NR ¹⁰ —, —SO ₂ and a fluorine-substituted alkylene group, a group consisting of a combination of —O— and a fluorine-substituted phenylene group, or —NR ¹⁰ —, —SO ₂ and a fluorine substitution A group consisting of a combination with an alkylene group 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 fluorine-substituted alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms. 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 fluorine-substituted phenylene group is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10. Specific examples of the fluorine-substituted phenylene group include a tetrafluorophenylene group, a hexafluoro-1-naphthylene group, and a hexafluoro-2-naphthylene group.

In the general formula (P), X ¹ is a counter anion, —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , a group containing a structure represented by the general formula (A1) and the general formula (A2) It is preferably selected from at least one selected from groups containing the structure represented. Here, the structure represented by the general formula (A1) and the structure represented by the general formula (A2) are synonymous with those described in the first embodiment.
The group including the structure represented by the general formula (A1) preferably has a fluorine-substituted alkyl group at one terminal of R ¹ and R ² in the general formula (A1) described above, and R ¹ and R ² More preferably, one of these 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.
Group containing a structure represented by the general formula (A2), in the above-mentioned general formula (A2), at least either end of R ³ ~ R ^5, preferably has a fluorine-substituted alkyl group, R ³ ~ More preferably, at least two of R ⁵ are directly bonded to a 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 melted directly fluorine-substituted alkyl group integration. 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 the counter anion A described above. In this case, any one hydrogen atom or halogen atom constituting the counter anion A is bonded to L in the general formula (P).

The triarylmethane structure having a molecular weight of 2000 or less having a crosslinkable group and a cation has a crosslinkable group in any of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp _{72 in} the general formulas (TP1A) and (TP2A), In addition, any of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ having this crosslinkable group may be further substituted with the general formula (P).
Moreover, in general formula (TP1A) and (TP2A), the part substituted by general formula (P) may exist only in one place, and may exist in two or more places. When there are two or more moieties substituted with the general formula (P), there are a number of cations corresponding to the number of counter anions in addition to the cations contained in the triarylmethane structure in the colorant. To do.

Hereinafter, specific examples of the colorant of the second embodiment used in the present invention will be shown, but the present invention is not limited thereto.

The triarylmethane dye used in the present invention can be contained singly or in combination of two or more.
The content of the triarylmethane dye 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 coloring agent, that is, a triarylmethane dye. Examples of other coloring compounds include dye compounds, pigment compounds, and dispersions thereof.

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

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

When the dye or pigment is blended as a dispersion, it can be adjusted according to the descriptions in JP-A-9-197118 and JP-A-2000-239544.
The content of the above-mentioned material or pigment can be used as long as the effects of the present invention are not impaired, and is preferably 0.5% by mass to 70% by mass with respect to the total solid content of the colored composition of the present invention. 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 a compound group is widely known in the industrial field, and these can be used without any particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and their (co) polymers.

Examples of monomers and their (co) polymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, amides, and these (Co) polymers, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and these (co) polymers It is a polymer. 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.

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

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

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

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

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

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 interposed via ethylene glycol and propylene glycol residues. These oligomer types can also be used.

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

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

Examples of the photopolymerization initiator include at least one active halogen compound selected from 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, oxime compounds, and the like. Specific examples of the photopolymerization initiator include those described in paragraphs [0070] to [0077] of JP-A No. 2004-295116. Among these, an oxime compound or a biimidazole compound is preferable from the viewpoint of rapid polymerization reaction.

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

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

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

X is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl that may have a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. Group, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, a substituent An arylthioxy group which may have an amino group and an amino group which may have a substituent are 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 heteroaryloxycarbonyl group, an alkylthiocarbonyl group, an arylthiocarbonyl. Represents a group, a heterocyclic thiocarbonyl group, a heteroarylthiocarbonyl group or CO—CO—Rf. Rf represents a carbocyclic aromatic group or a heterocyclic aromatic group.

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

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

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

The compound having a fluorene structure represented by the general formula (2) can be synthesized according to the synthesis method described in, for example, International Publication WO 2014/05050738 Pamphlet.

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 herein.

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 for the colored composition of the present invention.

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

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

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.

These organic solvents are preferably mixed in two or more types from the viewpoints of the solubility of each of the above-mentioned components and, when an alkali-soluble polymer is included, the solubility of the components and the improvement of the coated surface. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol It is a mixed solution composed of two or more selected from acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

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

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

The alkali-soluble binder is preferably a linear organic 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 the following formulas (b1) and (b2) can also be preferably used.

Formula (b1)

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

Formula (b2)

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

Examples of the alkyl group when R ⁴ represents an alkyl group include a linear alkyl group having 1 to 20 carbon atoms, an alkyl group having a branched chain having 1 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. More specifically, a methyl group, an ethyl group, a t-butyl group, a cyclohexyl group, a 2-ethylhexyl group, and the like can be given.
The alkyl group may have a substituent, and examples of the substituent that can be introduced into the alkyl group include a phenyl group, a carbonyl group, and an alkoxy group.
Examples of the aryl group when R ⁴ represents an aryl group include a monocyclic aryl group, a polycyclic aryl group, a condensed ring aryl group, and a heteroaryl group containing a heteroatom. More specifically, a phenyl group, a naphthyl group, an anthranyl group, a biphenyl group, a benzimidazolyl group, an indolyl group, an imidazolyl group, an oxazolyl group, a carbazolyl group, a pyridyl group, a furyl group, and the like can be given.
The aryl group may have a substituent, and examples of the substituent that can be introduced into the aryl group include 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 in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. Examples of the 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 a structural unit derived from an ethylenically unsaturated monomer represented by the following formula (X).
Formula (X)

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

In the above 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 is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1,000 to 200,000 from the viewpoint of developability, liquid viscosity, etc., and 2,000 to 100,000. More preferred is a polymer of 5,000 to 50,000.

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

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

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

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

<< Dye stabilizer >>
In addition to the triarylmethane dye, a dye stabilizer is preferably added to the composition of the present invention. As the stabilizer, for example, cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants can be used. Among the surfactants, a polymer surfactant (polymer dispersant) is preferable because it can be uniformly and finely dispersed.
Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; (Partial) ammonium salt and (partial) alkylamine salt; (co) polymer of hydroxyl group-containing unsaturated carboxylic acid ester such as hydroxyl group-containing polyacrylic acid ester or knitted product thereof; sulfonic acid or phosphoric acid having a crosslinkable group And the like.
As the crosslinkable group, a crosslinkable group that can be crosslinked 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.
In addition to these surfactants, it is also effective to add bistrifluoromethanesulfonimide sodium salt and the following anion salts (sodium salt, potassium salt, etc.).

<Antioxidant>
The composition of the present invention may contain an antioxidant. Examples of the antioxidant include a radical scavenger, a peroxide decomposer, an ultraviolet absorber, and a singlet oxygen quencher.
Examples of the radical scavenger include phenolic antioxidants and hindered amine antioxidants. Examples of phenolic antioxidants include hydroxyphenylpropionate compounds, hydroxybenzyl compounds, thiobisphenol compounds, thiomethylphenol compounds, alkanediylphenol compounds, and the like. Of these, hydroxyphenylpropionate compounds are preferred from the viewpoint of the stability of color characteristics.
A peroxide decomposer is a compound that decomposes peroxides generated by exposure to light into harmless substances and prevents the generation of new radicals. For example, phosphorus antioxidants, sulfur And system antioxidants. Among these, sulfur-based antioxidants are preferable from the viewpoint of the stability of color characteristics.
Examples of the ultraviolet absorber include salicylate-based antioxidants and benzophenone-based antioxidants.
A singlet oxygen quencher is a compound capable of deactivating singlet oxygen by energy transfer from oxygen in a singlet state. 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 agent>
The coloring composition of the present invention can contain a compound that functions as a curing agent.
For example, at least one compound selected from the group consisting of aromatic amine compounds, tertiary amine compounds, amine salts, phosphonium salts, amidine salts, amide compounds, thiol compounds, blocked isocyanate compounds, and imidazole ring-containing compounds can be used. .
When the coloring composition contains such a curing agent, the low-temperature curing of the coloring pattern can be more effectively realized. In addition, the storage stability of the colored composition can be further improved.

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

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

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

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

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

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

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

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

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

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

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

When forming a coating film of the colored composition of the present invention on a substrate, the thickness of the coating film (after pre-baking treatment) is generally 0.3 μm to 5.0 μm, preferably 0.5 μm to 4.0 μm. Most preferably, the thickness is 0.5 μm to 3.0 μm.
In the case of a color filter for a solid-state image sensor, the thickness of the coating film (after pre-baking) is preferably in the range of 0.5 μm to 5.0 μm.

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

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

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

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

Exposure process using a laser light source In an exposure method using a laser light source, an ultraviolet laser is used as the light source.
The irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm matches the photosensitive wavelength of the resist. Is preferable. Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
The exposure amount of the 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 has a through hole or a U-shaped depression in addition to a pattern for forming a pixel (colored pattern). The thing in which the pattern for forming is provided is used.

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

Subsequently, development is performed with a developer on the colored composition layer after exposure. Thereby, a negative type or positive type coloring pattern (resist pattern) can be formed. In the development step, the uncured portion of the coating film after exposure is eluted in the developer, and only the cured portion remains on the substrate.
Any developer can be used as long as it dissolves the coating film (colored composition layer) of the colored composition in the uncured part, but does not dissolve the cured part. For example, combinations of various organic solvents and alkaline aqueous solutions can be used.
Examples of the organic solvent used for development include the above-described solvents that can be used when preparing the colored composition of the present invention.
Examples of the alkaline aqueous solution include tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, benzyltrimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate Sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0 ] 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 a plurality of colors is formed.
Since the color filter of the present invention has high contrast, small color density unevenness, and good color characteristics, it can be suitably used for a solid-state imaging device or a liquid crystal display device.

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

-Process (D)-
It is preferable to further heat-treat the colored pattern that has been post-exposed by ultraviolet irradiation as described above. By heating the formed color pattern (so-called post-bake process), the color pattern can be further cured. 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 the production of a color filter having a plurality of hue pixels, the above steps (A), (B), and if necessary, the steps (C) and (D) are repeated according to the desired number of colors. Good.
It should be noted that the above step (C) and / or step (D) may be performed each time the formation, exposure, and development of the monochromatic coloring composition layer is completed (for each color) After all the colored composition layers have been formed, exposed, and developed, the step (C) and / or the step (D) may be performed collectively.

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

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

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

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

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

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

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

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

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

<Synthesis Example 1>
(Synthesis of Compound I-2)
Compound I-2 was synthesized according to the following route.

(Synthesis of Synthetic Intermediate (Compound 3))
17.0 g (118.8 mmol) of Compound 1 (1-naphthylamine) and 11.65 g (118.7 mmol) of 1,2-epoxycyclohexane were dissolved in 50 mL of hexafluoroisopropanol, and then heated to reflux for 5 hours. After confirming the completion of the reaction, the target compound was extracted into an organic layer with 50 mL of ethyl acetate, water and brine, and then concentrated. This crude product was dissolved in hexane, recrystallized, and then filtered to obtain 19.2 g of Compound 3 (yield 67%).

(Synthesis of Synthetic Intermediate (Compound 4))
Compound 3 (2.4 g (10 mmol)) and 1.5 g (15 mmol) of triethylamine were dissolved in 10 mL of THF. After the solution was cooled to 0 ° C., 1.15 g (11 mol) of methacrylic acid chloride was added dropwise. After confirming the completion of the reaction, the target product was extracted into an organic layer with 20 mL of ethyl acetate, water and brine, concentrated after washing. This crude product was purified by column chromatography to obtain 1.8 g of Compound 4 (yield 58%).

(Synthesis of Compound I-2)
Compound 4 (1.9 g (5.8 mmol)), compound 5 (1.8 g (5.8 mmol)), and phosphorus oxychloride 1.0 g (6.4 mmol) were dissolved in 6 mL of toluene and heated to 90 ° C. And stirred for 1 hour. After confirming the completion of the reaction, the operation of adding 10 mL of ethyl acetate to this solution and taking out the target product as a supernatant was repeated three times, and compound 6 was taken out as an ethyl acetate solution. A separately prepared bistrifluoromethanesulfonimide lithium salt 2.0 g (7.0 mmol) in methanol 20 mL was added to this solution. After confirming the completion of the salt exchange reaction, 50 mL of water was added, and the compound was extracted and concentrated in an ethyl acetate layer and purified by column chromatography to obtain the target compound I-2 (1.7 g (33%)). Got.
¹ H NMR (CHCl ₃ ): 1.25 (m, 16H), 1.8 (s, 3H), 3.6 (t, 8H), 3.75 (bs, 1H), 5.2 (dt, 1H), 5.55 (s, 1H), 6.1 (s, 1H), 6.2 (d, 1H), 6.75 (d, 4H), 7.2-7.5 (m, 9H) ), 7.8 (d, 1H)

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

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

Photopolymerizable compound (T-1): Kayalad DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
Alkali-soluble binder (U-1): benzyl methacrylate / methacrylic acid (85/15 [mass ratio] copolymer (weight average molecular weight: 12,000) in propylene glycol monomethyl ether acetate solution (solid content: 40.0 mass%) Acid value (100mgKOH / g)
Photopolymerization initiator (V-3): an oxime compound having the following structure

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

<Examples 2 to 27>
A colored composition was prepared in the same manner as in Example 1 except that the triarylmethane dye (I-1) was changed to the following (I-2) to (I-21) and (I-101) to (I-106). Prepared.

<Example 28>
A colored composition was prepared in the same manner as in Example 1 except that the alkali-soluble binder (U-1) used in Example 1 was changed to the following alkali-soluble binder (U-1-1).
Alkali-soluble binder (U-1-1): benzyl methacrylate / methacrylic acid / allyl methacrylate (20/60/20) [mass ratio] copolymer (weight average molecular weight: 20,000) in propylene glycol monomethyl ether acetate solution ( Solid content 40.0% by mass) Acid value (250 mgKOH / g)

<Example 29>
A colored composition was prepared in the same manner as in Example 1 except that the alkali-soluble binder (U-1) used in Example 1 was changed to the following alkali-soluble binder (U-2-1).
Alkali-soluble binder (U-2-1): GMA-MAA / methacrylic acid / cyclohexyl methacrylate (26/38/36) [mass ratio] copolymer (weight average molecular weight: 3,000) in propylene glycol monomethyl ether acetate solution (Solid content: 40.0% by mass) Acid value (125 mgKOH / g)
GMA-MAA has the following structure.

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

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

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

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

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

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

<Voltage holding ratio>
The colored composition was applied onto a glass substrate with an ITO electrode (trade name: 1737 manufactured by Corning) to a thickness of 2.0 μm after drying, and dried (prebaked) in an oven at 90 ° C. for 60 seconds. 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. It was developed at 25 ° C., washed with water and dried, and the coated film was heat-treated (post-baked) in an oven at 230 ° C. for 30 minutes to form a colored cured film. Next, the substrate on which this colored cured film is formed and the substrate on which ITO electrodes are simply deposited in a predetermined shape are bonded together with a sealant mixed with 5 μm glass beads, and then Merck liquid crystal MJ971118 (trade name) ) Was injected to prepare a liquid crystal cell.
Next, after putting the liquid crystal cell in a constant temperature layer at 70 ° C. for 48 hours, the voltage holding ratio of the liquid crystal cell was measured using the liquid crystal voltage holding ratio measuring system VHR-1A type (trade name) manufactured by Toyo Technica under the following measurement conditions. It measured and evaluated by the score shown to the following reference | standard. The higher the score, the better the voltage holding ratio.
Measurement conditions / Distance between electrodes: 5 μm to 15 μm
・ Applied voltage pulse amplitude: 5V
・ Applied voltage pulse frequency: 60 Hz
・ Applied voltage pulse width: 16.67 msec
* Voltage holding ratio: liquid crystal cell potential difference after 16.7 milliseconds / value of voltage applied in 0 milliseconds * judgment method 90% or more: 5
85% or more and less than 90%: 4
80% or more and less than 85%: 3
75% or more and less than 80%: 2
Less than 75%: 1

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

Claims

A coloring composition comprising a colorant comprising a triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2000 or less and a counter anion, and a polymerizable compound.
The coloring composition according to claim 1, wherein the triarylmethane structure having a molecular weight of 2000 or less and having a crosslinkable group and a cation is represented by the general formula (TP1) and / or the general formula (TP2);

In general formulas (TP1) and (TP2), 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 and c each independently represent an integer of 0 to 4; when a, b and c are 2 or more, Rtp 6 , Rtp 7 And Rtp 8 may be linked to each other to form a ring; any one of Rtp 1 to Rtp 11 , Rtp 71 and Rtp 72 has a crosslinkable group.
At least one selected from the group consisting of a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, a borate anion, PF 6− and SbF 6− , and
-SO 3 -, -COO -, -PO 4 -, is selected from at least one selected from structures represented by the structure and the following general formula represented by the following general formula (A1) (A2), wherein Item 3. The coloring composition according to Item 1 or 2;
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 3, wherein the counter anion is contained in a compound containing a crosslinkable group.
The colored composition according to any one of claims 1 to 3, wherein the counter anion is contained in a repeating unit.
The coloring composition according to claim 1, wherein the triarylmethane structure having a molecular weight of 2000 or less having a crosslinkable group and a cation is represented by the general formula (TP1A) or the general formula (TP2A);

In general formulas (TP1) and (TP2), 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 and c each independently represent an integer of 0 to 4; when a, b and c are 2 or more, Rtp 6 , Rtp 7 And two of Rtp 8 may be bonded to each other to form a ring; any of Rtp 1 to Rtp 11 , Rtp 71 and Rtp 72 has a crosslinkable group; Rtp 1 to Rtp 11 , Rtp At least one of 71 and Rtp 72 may be substituted with general formula (P);
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 6, further comprising a photopolymerization initiator.
The colored composition according to any one of claims 1 to 7, which is used for forming a colored layer of a color filter.
A colored cured film obtained by curing the colored composition according to any one of claims 1 to 8.
A color filter having the colored cured film according to claim 9.
A step of forming a colored composition layer by applying the colored composition according to any one of claims 1 to 8 on a support, a step of exposing the colored composition layer in a pattern, and an unexposed state And a step of developing and removing the portion to form a colored pattern.
A step of applying the colored composition according to any one of claims 1 to 8 on a support to form a colored composition layer and curing to form a colored layer, a photoresist layer on the colored layer A method for producing a color filter, comprising: a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, or a step of dry etching the colored layer using the resist pattern as an etching mask.
The color filter manufactured by the manufacturing method of the color filter of Claim 11 or 12.
The solid-state image sensor which has a color filter produced by the manufacturing method of the color filter of Claim 10, or the color filter of Claim 11 or 12.
An image display device comprising the color filter according to claim 10 or the color filter produced by the method for producing a color filter according to claim 11 or 12.