TW201512315A - Colored composition, cured film, color filter, method for manufacturing color filter, solid-state image sensing device and image display device - Google Patents

Abstract

A colored composition having excellent heat resistance, solvent resistance and voltage holding ratio, a cured film, a color filter, a method for manufacturing color filter, a solid-state image sensing device and a liquid crystal display device are provided. The colored composition contains a coloring agent and a polymerizable compound. The coloring agent contains a triaryl methane structure and a counter anion. The triaryl methane structure has a crosslinking group and a cation, and a molecular weight thereof is 2000 or less.

Description

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

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

Previously, a color filter was produced by containing a pigment dispersion composition obtained by dispersing an organic pigment or an inorganic pigment with a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and optionally A coloring composition is prepared by using other components, and then a coloring pattern is formed by a photolithography method, an inkjet method, or the like using the coloring composition, thereby producing a color filter.

In recent years, color filters have been used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. As the use tends to expand, color filters are required to have high color characteristics in chromaticity, contrast, and the like. In addition, for color filters used for image sensors (solid-state imaging devices), color unevenness is similarly required. The color characteristics of the improvement of the color decomposition ability are further improved.

However, in the conventional pigment dispersion system, problems such as scattering due to coarse particles of the pigment and increase in viscosity due to poor dispersion stability are likely to occur, and it is often difficult to further improve contrast and brightness.

Therefore, as a coloring agent, it has been studied to use not only a pigment but also a dye (for example, refer to Patent Document 1). When a dye is used as a coloring agent, the hue or brightness of the display image at the time of image display can be improved by the color purity of the dye itself or the vividness of the hue, and since the coarse particles disappear, it is useful for improving the contrast.

Examples of dyes are known: phthalocyanine dyes, dipyrromethene dyes, pyrimidine azo dyes, pyrazole azo dyes, xanthene dyes. A compound having a plurality of dye precursors such as a triarylmethane dye (see, for example, Patent Document 2 to Patent Document 8).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-75375

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-292970

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-039478

[Patent Document 4] Japanese Patent Laid-Open No. Hei 9-157536

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2013-25194

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2012-201694

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2012-108469

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2000-095805

Here, the coloring composition used in a color filter or the like is required to be more excellent in heat resistance, solvent resistance, and voltage holding ratio.

An object of the present invention is to solve the above problems, and an object of the invention is to provide a coloring composition which is excellent in heat resistance, solvent resistance and voltage holding ratio. In particular, it is an object of the present invention to provide a coloring composition which is advantageous as a coloring composition for a blue filter.

Based on the above situation, the inventors of the present invention conducted active research and found that by disposing a coloring agent containing a triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2,000 or less and a relative anion, the composition can be solved. The subject.

Specifically, the above problem is solved by <2> to <14> by the following means <1>.

<1> A coloring composition comprising a colorant and a polymerizable compound, wherein the colorant comprises a triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2,000 or less and a counter anion.

<2> The coloring composition according to <1>, wherein the triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2,000 or less is represented by the general formula (TP1) and/or the general formula (TP2).

(In the general formula (TP1) and the formula (TP2), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group or an aryl group; and Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ and Rtp ₁₁ are each independently represented. a substituent; Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ₇₁ Rtp ₇₂ ; Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group or an aryl group; and Rtp ₁₀ represents a hydrogen atom, an alkyl group or an aryl group; a, b, and c each independently represent an integer of 0 to 4; when a, b, and c are 2 or more, two of Rtp ₆ , Rtp _{7 ,} and Rtp ₈ may be linked to each other to form a ring; Rtp ₁ ~ A crosslinkable group is present in any of Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ ).

<3> The coloring composition according to <1> or <2>, wherein the relative anion is selected from the group consisting of: selected from the group consisting of a fluoride anion, a chloride anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, and a borate At least one of an anion, PF ^6- and SbF ^6- ; and a structure selected from the group consisting of -SO ₃ ^- , -COO ^- , -PO ₄ ^- , the following formula (A1), and the following formula (A2) At least one of the structures indicated,

(In the formula (A1), R ¹ and R ² each independently represent -SO ₂ - or -CO-)

(In the formula (A2), R ³ represents -SO ₂ - or -CO-; and R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO- or -CN).

The colored composition according to any one of <1> to <3> wherein the relative anion is contained in the compound containing a crosslinkable group.

The colored composition according to any one of <1> to <3> wherein the relative anion is contained in the repeating unit.

<6> The coloring composition according to <1>, wherein the triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2,000 or less is represented by the formula (TP1A) or the formula (TP2A). 4]

(In the general formula (TP1) and the formula (TP2), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group or an aryl group; and Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ and Rtp ₁₁ are each independently represented. a substituent; Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ₇₁ Rtp ₇₂ ; Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group or an aryl group; and Rtp ₁₀ represents a hydrogen atom, an alkyl group or an aryl group; a, b, and c each independently represent an integer of 0 to 4; when a, b, and c are 2 or more, two of Rtp ₆ , Rtp _{7 ,} and Rtp ₈ may be linked to each other to form a ring; Rtp ₁ ~ Any one of Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ has a crosslinkable group; at least one of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ may be substituted by the general formula (P))

(In the formula (P), L represents a single bond or a divalent linking group; and X ^{1 is} selected from the group consisting of -SO ₃ ^- , -COO ^- , -PO ₄ ^- , and includes a structure represented by the following formula (A1) At least one of a group and a group containing a structure represented by the following formula (A2); formula (A1)

(In the formula (A1), R ¹ and R ² each independently represent -SO ₂ - or -CO-)

(In the formula (A2), R ³ represents -SO ₂ - or -CO-; and R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO- or -CN).

The colored composition according to any one of <1> to <6> which further comprises a photopolymerization initiator.

<8> The coloring composition according to any one of <1> to <7> which is used for forming a coloring 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 comprising the colored hardening film according to <9>.

<11> A method of producing a color filter, comprising the step of: applying a coloring composition according to any one of <1> to <8> to a support to form a color filter Coloring the composition layer; exposing the colored composition layer to a pattern; and developing and removing the unexposed portion to form a colored pattern.

<12> A method of producing a color filter, comprising the step of: applying a colored composition according to any one of <1> to <8> to a support to form a colored composition layer, and performing hardening Forming a coloring layer; forming a photoresist layer on the colored layer; patterning the photoresist layer by exposure and development to obtain a photoresist pattern; or dry etching the colored layer using the photoresist pattern as an etch mask.

<13> A color filter produced by the method for producing a color filter according to <11> or <12>.

<14> A solid-state imaging device or image display device comprising the color filter according to <10> or a color filter produced by the method of manufacturing the color filter according to <11> or <12> Light film.

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

Hereinafter, the contents of the present invention will be described in detail. In the present specification, the term "~" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit.

In the present specification, the term "all solid components" means all of the self-colored components. The total mass of the components from which the solvent is removed from the composition.

In the expression of the group (atomic group) in the present specification, the unsubstituted and unsubstituted expressions are not described as including not only a group having no substituent but also a group having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In addition, the term "radiation" in the present specification means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet light (EUV light), an X-ray, an electron beam, or the like. In addition, in the present invention, the term "light" means actinic rays or radiation. The term "exposure" as used in the present specification means not only exposure by far ultraviolet rays, X-rays, EUV light, etc. represented by mercury lamps or excimer lasers, but also electron beams, ion beams, and the like, unless otherwise specified. The drawing of the bundle is also included in the exposure.

In the present specification, "(meth)acrylate" means either or both of acrylate and methacrylate, and "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid. "(Meth)acrylonitrile" means either or both of an acryloyl group and a methacryloyl group.

In addition, in this specification, "single quantity" has the same meaning as "monomer". The monomer in the present specification is different from the oligomer and the polymer, and means 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 the present specification, the term "step" includes not only independent steps, but even if it is not clearly distinguishable from other steps, it is included in the term as long as the desired effect of the step is achieved.

The weight average molecular weight in the present invention means a value measured by Gel Permeation Chromatography (GPC) unless otherwise specified. GPC can be used to separate the obtained polymer by removing the solvent, and the obtained solid component is diluted to 0.1% by mass with tetrahydrofuran, using HLC-8020GPC (manufactured by Tosoh Corporation), and TSKgel Super Multipore HZ-H ( Manufactured by Tosoh Corporation (4.6 mm ID × 15 cm), three of them were connected in series as a column. As a condition, the sample concentration was 0.35% by mass, the flow rate was 0.35 mL/min, the sample injection amount was 10 μL, and the measurement temperature was 40° C., and the refractive index (Refractive Index, RI) detector was used.

<Coloring composition>

The colored composition of the present invention is characterized by comprising a coloring agent containing a triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2,000 or less, and a counter anion, and a polymerizable compound.

With such a configuration, it is possible to provide a coloring composition excellent in heat resistance, solvent resistance, and voltage holding ratio.

Hereinafter, the coloring agent will be described in the order of the first embodiment and the second embodiment.

The first embodiment is other than the second embodiment described below. For example, a case where a triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2,000 or less and a bonding moiety having a relative anion does not have a covalent bond may be mentioned.

In the second embodiment, a case where a triarylmethane skeleton having a triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2,000 or less is directly covalently bonded; or a relative anion and a triarylmethane skeleton Partial covalent bonding via a linking group.

First embodiment of coloring agent

Hereinafter, a triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2,000 or less and a relative anion will be described.

<<Triaryl methane structure>>

As the crosslinkable group which the triarylmethane structure has, a crosslinkable group which can be crosslinked by a radical, an acid, or a heat can be used. Specific examples thereof include a group having an ethylenically unsaturated double bond, a (meth)acryl group, a styryl group, a vinyl group, an allyl group, a cyclic ether group, etc., preferably selected from (methyl group). At least one of an acrylic group, a styryl group, a vinyl group and an allyl group, more preferably at least one selected from the group consisting of a (meth)acrylic group, a styryl group and a vinyl group, and more preferably a (methyl group) ) Acrylic and styryl groups.

The cyclic ether group is preferably, for example, an epoxy group or an oxetanyl group, and more preferably an epoxy group.

The triarylmethane structure having a crosslinkable group and a cation has a molecular weight of 2,000 or less, preferably 300 to 1,500, more preferably 300 to 900.

The triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2,000 or less is preferably represented by the following formula (TP1) and/or formula (TP2).

(In the general formula (TP1) and the formula (TP2), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group or an aryl group; and Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ and Rtp ₁₁ are each independently represented. a substituent; Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ₇₁ Rtp ₇₂ ; Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group or an aryl group; and Rtp ₁₀ represents a hydrogen atom, an alkyl group or an aryl group; a, b, and c each independently represent an integer of 0 to 4; when a, b, and c are 2 or more, two of Rtp ₆ , Rtp _{7 ,} and Rtp ₈ may be linked to each other to form a ring; Rtp ₁ ~ Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ have a crosslinkable group.) In the formula (TP1), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom. Or an alkyl group.

The carbon number of the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, still more preferably from 1 to 3. 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. The substituent which the alkyl group may have is a substituent listed in the item of the substituent group A mentioned later.

The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 12, and still more preferably 6. The substituent which the aryl group may have is a substituent listed in the item of the substituent group A mentioned later.

In the formula (TP1), Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ₇₁ Rtp ₇₂ , preferably a hydrogen atom or NRtp ₇₁ Rtp ₇₂ , more preferably NRtp ₇₁ Rtp ₇₂ .

The carbon number of the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, still more preferably from 1 to 3. The alkyl group may be any of a linear chain, a branched form, and a cyclic form, but is preferably linear. The substituent which the alkyl group may have is a substituent listed in the item of the substituent group A mentioned later. The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 12, and still more preferably 6.

Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom or an alkyl group.

The carbon number of the alkyl group is preferably from 1 to 10, more preferably from 1 to 8, and particularly preferably from 1 to 6. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. The alkyl group is preferably unsubstituted. The substituent which the alkyl group may have is a substituent listed in the item of the substituent group A mentioned later. The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 12, and still more preferably 6. The substituent which the aryl group may have is a substituent listed in the item of the substituent group A mentioned later.

In the formula (TP1), Rtp ₅ , Rtp ₆ and Rtp ₈ each independently represent a substituent. The substituents listed in the item of the substituent group A to be described later are exemplified. Particularly preferred are straight or branched alkyl groups having 1 to 5 carbon atoms, alkenyl groups having 1 to 5 carbon atoms, aryl groups having 6 to 15 carbon atoms, carboxyl groups or sulfo groups, and particularly preferably having a carbon number of 1 to 5 A chain or a branched alkyl group, a carbon number of 1 to 5 alkenyl group, a phenyl group or a carboxyl group. Particularly preferably, Rtp ₅ and Rtp ₆ each independently represent an alkyl group having 1 to 5 carbon atoms. Further, Rtp _{8 is} preferably such that two alkenyl groups may be 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, In particular, a and b preferably represent 0 or 1, more preferably 0. c preferably represents 0 to 2, more preferably 0 or 1.

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

In the formula (TP2), Rtp ₅ and Rtp ₆ each independently represent a substituent, and have the same meanings as Rtp ₅ and Rtp ₆ in the formula (TP1), and the preferred range is also the same.

In the general formula (TP2), Rtp ₉ and Rtp ₁₁ each independently represent a substituent, and the substituents listed in the item of the substituent group A to be described later can be used.

Rtp _{9 is} preferably an alkyl group, an alkoxy group and a halogen atom.

Rtp _{11 is} preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group is preferably linear or branched, and more preferably linear.

In the formula (TP2), Rtp ₁₀ represents a substituent, and the substituents listed in the item of the substituent group A to be described later can be used. In particular, Rtp _{10 is more} preferably an aryl group having 6 to 12 carbon atoms, more preferably a phenyl group.

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

It is preferred to have a crosslinkable group in any of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ , and particularly preferably a crosslinkable group in Rtp ₇₁ or Rtp ₇₂ .

The group having a crosslinkable group may contain only a crosslinkable group, and may further contain a linking group in addition to the crosslinkable group. The group having a crosslinkable group is particularly 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.

The crosslinkable group has the same meaning as the crosslinkable group, and the preferred range is also the same.

The divalent linking group is preferably an alkylene group, an extended aryl group, a heterocyclic linking group, -CH=CH-, -O-, -S-, -C(=O)-, -CO-, -NR-, -CONR-, -OC-, -SO-, -SO ₂ - and a group obtained by combining two or more of these groups. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

The divalent linkage is preferably an alkyl group.

The alkylene group may be any of a linear chain, a branched chain, and a cyclic chain. The carbon number of the alkylene group is preferably from 1 to 30, more preferably from 1 to 20, particularly preferably from 5 to 20, particularly preferably from 5 to 10. Specifically, a methylene group, an ethyl group, a propyl group, a butyl group, a hexyl group, a heptyl group, a cyclopentenyl group, a cyclohexyl group, and the like are preferable.

The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 18, and particularly preferably from 6 to 12. Specifically, the aryl group is preferably a phenyl group, a naphthyl group or the like.

The cation of the triarylmethane structure exists in the following manner instead of localization, and the following two structures have the same meanings and are all included in the present invention. Furthermore, the cationic moiety can be located anywhere in the molecule.

Substituent group A: the substituent may be exemplified by a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group. , aryloxy, decyloxy, heterocyclooxy, decyloxy, amine methyl methoxy, amine (including alkylamino, anilino), decylamino, aminocarbonylamino, Alkoxycarbonylamino, aryloxycarbonylamino, aminesulfonylamino, alkylsulfonylamino or arylsulfonylamino, fluorenyl, alkylthio, arylthio, hetero Cyclosulfanyl, sulfonyl, sulfo, alkylsulfinyl or arylsulfinyl, alkylsulfonyl or arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl , amine mercapto, aryl azo or heterocyclic azo, quinone imine, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, decyl and the like. The details will be described below.

The halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably a carbon number of 1) ~30 alkyl, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example The cyclohexyl group, the cyclopentyl group, and the polycycloalkyl group may, for example, be a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having a carbon number of 5 to 30, for example, a bicyclo[1,2,2 a polycyclic structure group such as heptan-2-yl, bicyclo[2,2,2]octane-3-yl) or tricycloalkyl; preferably a monocyclic cycloalkyl or bicycloalkyl group, Particularly preferred is a monocyclic cycloalkyl), straight or branched alkenyl group (linear or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, for example: vinyl , allyl, isoprenyl, geranyl, oleyl, cycloalkenyl (preferably substituted or unsubstituted cycloalkenyl having 3 to 30 carbon atoms, for example Listed: 2-cyclopenten-1-yl, 2-cyclohexen-1-yl; polycycloalkenyl, for example: bicycloalkenyl (preferably substituted or unsubstituted bicyclic ring having 5 to 30 carbon atoms) Alkenyl, for example, bicyclo[2,2,1]hept-2-en-1-yl, bicyclo[2,2,2]oct-2-en-4-yl) or tricycloalkenyl, particularly preferably Monocyclic cycloalkenyl), alkynyl (preferably substituted or unsubstituted alkynyl having 2 to 30 carbon atoms, for example: ethynyl, propargyl, trimethyldecyl ethynyl), aryl (preferably substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanylaminophenyl), heterocyclic ring a substituted (unsubstituted or unsubstituted saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group of 5 to 7 members, more preferably a ring constituent atom selected from carbon atoms a heterocyclic group having at least one of a nitrogen atom, an oxygen atom and a sulfur atom among the nitrogen atom and the sulfur atom, and more preferably a 5-membered or 6-membered aromatic heterocyclic ring having 3 to 30 carbon atoms. Base; for example: 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano, hydroxy, nitro, carboxy, alkoxy (preferably substituted or unsubstituted alkoxy with 1 to 30 carbon atoms) a group, for example, a methoxy group, an ethoxy group, an isopropoxy group, a third butoxy group, a n-octyloxy group, a 2-methoxyethoxy group, an aryloxy group (preferably having a carbon number of 6 to 30) Substituted or unsubstituted aryloxy group, for example: phenoxy, 2-methylphenoxy, 2,4-di-tripentylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecylaminophenoxy), decyloxy (preferably a decyloxy group having 3 to 20 carbon atoms, for example, trimethyldecyloxy group, a third butyl dimethyl fluorenyloxy group, a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, preferably a heterocyclic group) The heterocyclic moiety described in, for example, 1-phenyltetrazole-5-oxyl, 2-tetrahydropyranyloxy), decyloxy (preferably methyloxy), carbon 2 to 30 a substituted or unsubstituted alkylcarbonyloxy group, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, a methyl methoxy group, an ethoxy group, a trimethyl ethoxy group. Base, stearyloxy, benzhydryloxy, p-methoxyphenylcarbonyloxy), amine methyloxy (preferably substituted with 1 to 30 carbon atoms) Unsubstituted amine methyl methoxy group, for example: N,N-dimethylamine methyl methoxy, N,N-diethylamine methyl methoxy, morpholinylcarbonyloxy, N,N-di - n-octylaminocarbonyloxy, N-n-octylaminemethyloxy), alkoxycarbonyloxy (preferably substituted or unsubstituted alkoxycarbonyloxy having 2 to 30 carbon atoms) a group, for example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a third butoxycarbonyloxy group, an n-octylcarbonyloxy group, an aryloxycarbonyloxy group (preferably having a carbon number of 7 to 30) Substituted or unsubstituted aryloxycarbonyloxy group, for example: phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, p-hexadecyloxyphenoxycarbonyloxy) , an amine group (preferably an amine group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a carbon number of 0 ~30 heterocyclic amine groups, for example: amine group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group, N-1, 3, 5-three a pyridylamino group, a mercaptoamine group (preferably a mercaptoamine group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted carbon number of 6 to 30) Or an unsubstituted arylcarbonylamino group, for example, a decylamino group, an ethyl decylamino group, a trimethyl ethyl amide group, a lauryl amide group, a benzhydryl amide group, 3, 4 , 5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, for example, an aminomethyl sulfhydryl group Amine, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, morpholinylcarbonylamino), alkoxycarbonylamino (preferably carbon number 2) a substituted or unsubstituted alkoxycarbonylamino group of ~30, for example: methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, n-octadecyloxycarbonyl group Amine, N-methyl-methoxycarbonylamino), aryloxycarbonylamino (preferably substituted or not having a carbon number of 7 to 30) a substituted aryloxycarbonylamino group, for example, a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, a m-octyloxyphenoxycarbonylamino group, an aminesulfonylamino group (preferably A substituted or unsubstituted sulfonylamino group having a carbon number of 0 to 30, for example, an amine sulfonylamino group, an N,N-dimethylaminosulfonylamino group, and an N-n-octylamine group a sulfonylamino group, an alkylsulfonylamino group or an arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having a carbon number of 1 to 30, carbon number a substituted or unsubstituted arylsulfonylamino group of 6 to 30, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5 - trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), fluorenyl, Alkylthio group (preferably substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), arylsulfide a base (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), heterocyclic sulfur a base (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, preferably a heterocyclic ring described in the heterocyclic group, for example, a 2-benzothiazolyl group; Sulfhydryl, 1-phenyltetrazol-5-ylthio), aminsulfonyl (preferably substituted or unsubstituted sulfonamide having a carbon number of 0 to 30, for example, N-ethylamine Sulfonyl, N-(3-dodecyloxypropyl)amine sulfonyl, N,N-dimethylamine sulfonyl, N-acetyl sulfonyl, N-benzhydrazide Amidoxime, N-(N'-phenylaminecarbamimidino)sulfonyl), sulfo, alkylsulfinyl or arylsulfinyl (preferably from 1 to 30 carbon atoms) Substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted arylsulfinyl having 6 to 30 carbon atoms, for example, methylsulfinyl, ethylsulfinyl Phenylsulfinyl, p-methylphenylsulfinyl), alkylsulfonyl or arylsulfonyl (preferably substituted or unsubstituted alkylsulfonyl having 1 to 30 carbon atoms) a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl) a mercapto group (preferably a mercapto group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, for example, an ethyl fluorenyl group; , trimethylethenyl, 2-chloroethylidene, stearyl, benzhydryl, p-octyloxyphenylcarbonyl), aryloxycarbonyl (preferably having a carbon number of 7 to 30) a substituted or unsubstituted aryloxycarbonyl group, for example: phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butyl a phenoxycarbonyl group, an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a third butoxycarbonyl group) , n-octadecyloxycarbonyl), aminomethylindenyl (preferably a substituted or unsubstituted amine carbenyl group having a carbon number of 1 to 30, for example, an amine formazan group, an N-methylamine group) Sulfhydryl, N,N-dimethylaminecarbamyl, N,N-di-n-octylamine, fluorenyl, N-(methylsulfonyl)amine, arylazo or a heterocyclic 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 (heterocyclic moiety) Preferred are the heterocyclic moieties described in the heterocyclic group, for example: phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazole-2- Alkyl azo), a quinone imine group (preferably a substituted or unsubstituted quinone imine group having 2 to 30 carbon atoms, for example, N-butanediamine, N-phthalimide) a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino) a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group), a phosphinyl group An oxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy group, dioctyloxyphosphinyloxy group), phosphine oxide a base group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino group, dimethylaminophosphinylamino group), A decyl group (preferably a substituted or unsubstituted decyl group having a carbon number of 3 to 30, for example, a trimethyldecyl group, a tert-butyldimethylalkyl group, or a phenyldimethylalkyl group).

Specific examples of the triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2,000 or less include the following structures, but the present invention is not limited to these structures.

[化12]

<<relative anion>>

The relative anion is the relative anion of the cation possessed by the triarylmethane structure. The counter anion may comprise only the opposite anion or may be included as part of the structure of the compound.

When only the relative anion is contained, a fluorine anion, a chloride anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, a borate anion (BF ^4-, etc.), PF ^6- and SbF ^6- may be mentioned. And the like, preferably a borate anion and PF ^6- .

In the case where the relative anion is contained as a part of the structure of the compound, it may be a case where it is present as a counter anion unlike a triarylmethane having a crosslinkable group and a cation and having a molecular weight of 2,000 or less.

The borate anion is a group represented by B(R ¹⁰ ) ^4- , and R ¹⁰ may, for example, be a fluorine atom, a cyano group, a fluorinated alkyl group, an alkoxy group or an aryloxy group.

The case where the relative 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 2,000 or less. In the case of a low molecular weight compound, at least one of an alkyl group, an aryl group and a crosslinkable group is contained together with an anion site. In the present invention, a state in which the relative anion is contained in the compound having a crosslinkable group and a state in which the relative anion is contained in the repeating unit is more preferable, and a state in which the relative anion is contained in the repeating unit is more preferable.

When the relative anion is contained as a part of the structure of the compound, the anion portion is preferably selected from the group consisting of -SO ₃ ^- , -COO ^- , -PO ₄ ^- , a structure represented by the following formula (A1), and the following At least one of the structures represented by the formula (A2).

(In the formula (A1), R ¹ and R ² each independently represent -SO ₂ - or -CO-.)

In the general formula (A1), preferably at least R ¹ and R ² represents an -SO ₂ -, more preferably represents ² both R ¹ and R -SO ₂ -.

The above formula (A1) is more preferably represented by the following formula (A1-1).

(In the 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 extended aryl group.)

In the general formula (A1-1), the same as R ¹ and R ² in the general formula (A1) in the meaning of R ¹ and R ^2, preferred ranges are also the same.

In the case where X ¹ represents an alkylene group, the carbon number of the alkylene group is preferably from 1 to 8, more preferably from 1 to 6. In the case where X ¹ represents an aryl group, the carbon number of the extended aryl group is preferably from 6 to 18, more preferably from 6 to 12, and still more preferably 6. In the case where X ¹ has a substituent, it is preferably substituted with a fluorine atom.

X ² represents an alkyl group or an aryl group, preferably an alkyl group. The carbon number of the alkyl group is preferably from 1 to 8, more preferably from 1 to 6, particularly preferably from 1 to 3, particularly preferably 1. In the case where X ² has a substituent, it is preferably substituted with a fluorine atom.

General formula (A2) [Chemical 15]

(In the formula (A2), R ³ represents -SO ₂ - or -CO-; and R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO- or -CN.)

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

Specific examples of the case where the relative anion is contained as a part of the structure of the compound are R-SO ₃ ^- , R-COO ^- or R-PO ₄ ^- , and an alkyl group in which R is a halogen atom and can be substituted by a halogen atom is also exemplified. The case of an aryl group which may be substituted by a halogen atom.

Further, specific examples of the compound containing the group represented by the above formula (A1) include R ¹ and a halogen atom, an alkyl group which may be substituted by a halogen atom, and an aryl group which may be substituted by a halogen atom. The compound of the knot.

Further, specific examples of the compound containing the group represented by the above formula (A2) can be exemplified by the fact that R ⁴ and R ⁵ are each a halogen atom, an alkyl group which may be substituted by a halogen atom, or a halogen atom. The case of aryl.

The best is the following. Is a compound containing a group represented by the formula (A1-1), and R ¹ and R ² in the formula (A1-1) represent -SO ₂ -, at least one of X ¹ and X ² represents a stretched alkyl group. The basis of the base or the aryl group. It is a compound containing a group represented by the formula (A2), and a state in which R ⁴ and R ⁵ in the formula (A2) are bonded to an alkyl group substituted with a halogen atom. -PO ₄ ^- or ^- SO ₃ ^{- is} included as part of the structure of the compound. Chloride anion, cyanide ion, BF ^4- or PF ^6- .

Specific examples of the other relative anions include the following examples, but the present invention is not limited to the examples. In the present specification, a specific example of the following other relative anions is referred to as "relative anion A".

Hereinafter, the case where the relative anion is contained in the compound containing a crosslinkable group and the case where the relative anion is contained in the repeating unit will be described in detail.

The crosslinkable group may be a crosslinkable group which can be crosslinked by a radical, an acid or a heat, and has the same meaning as the crosslinkable group of the triarylmethane structure, and the preferred range is also the same.

The number of the crosslinkable groups in the compound having a crosslinkable group is preferably from 1 to 3, more preferably 1.

Further, the crosslinkable group and the counter anion may be directly bonded to each other or may be bonded via a linking group, but it is preferably bonded via a linking group.

The specific example in the case where the relative anion is contained in the compound containing a crosslinkable group is preferably represented by the following formula (B).

(In the formula (B), P represents a crosslinkable group; L represents a single bond or a divalent linking group; and an anion represents the relative anion.)

In the general formula (B), P represents a crosslinkable group, and the crosslinkable group is exemplified.

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 ethylidene group, a trimethylene group, a propyl group, or the like) is preferable. Butyl, etc.), a aryl group having 6 to 30 carbon atoms, a heterocyclic linkage group, -CH=CH-, -O-, -S-, -C(=O)-, -CO-, -NR- -CONR-, -OC-, -SO-, -SO ₂ - and a linking group in which two or more of these groups are combined. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

The linker is preferably an alkylene group having 1 to 10 carbon atoms (preferably -(CH ₂ )n- (n is an integer of 1 to 10) and an extended aryl group having 6 to 12 carbon atoms (preferably stretching) A linking group in which two or more of phenyl, naphthyl), -NH-, -CO-, -O-, and -SO ₂ - are combined.

<<Other functional groups>>

When the relative anion is contained as a part of the structure of the compound, it may have another functional group other than the crosslinkable group. Other functional groups include the other functional groups described in the repeating unit having a triarylmethane structure containing a cation, and preferred examples have the same meanings. In the case where the relative anion is contained as a part of the structure of the compound, the number of the polymerizable groups in the compound is preferably from 1 to 3, more preferably 1.

In the case where the relative anion is contained as a part of the structure of the compound, the number of the acid groups in the compound is preferably from 1 to 3, more preferably 1.

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

The molecular weight of the compound having a crosslinkable group is preferably from 200 to 2,000, more Good for 200~500.

In the case where the relative anion is contained in the repeating unit (hereinafter also referred to as an anionic polymer), it may have a relative anion in the side chain, or may have a relative anion in the main chain, or may be in the main chain as well as the side chain. Both have a relative anion.

The anionic polymer is preferably represented by the following formula (C) and/or the following formula (D).

(In the general formula (C), X ¹ represents a main chain of a repeating unit; L ¹ represents a single bond or a divalent linking group; and an anion represents the relative anion.)

In the general formula (C), X ¹ represents a main chain of a repeating unit, and usually represents a linking group formed by a polymerization reaction, and is preferably, for example, a (meth)acrylic acid, a styrene-based or a vinyl-based one. Further, the two parts indicated by * are the repeating units.

When L ¹ represents a divalent linking group, it is preferably an alkylene group having 1 to 30 carbon atoms (methylene group, ethylidene group, trimethylene group, propyl group, butyl group, etc.), carbon number 6~30 of aryl (phenyl, naphthyl, etc.), heterocyclic linkage, -CH=CH-, -O-, -S-, -C(=O)-, -CO-, - NR-, -CONR-, -OC-, -SO-, -SO ₂ - and a linking group obtained by combining two or more of these groups. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

L ^{1 is} particularly preferably a single bond or an alkylene group having a carbon number of 1 to 10 (preferably -(CH ₂ )n- (n is an integer of 5 to 10) and a aryl group having a carbon number of 6 to 12 (more) A divalent linking group in which two or more of a combination of a phenyl group and an anthranyl group, -NH-, -CO ₂ -, -O-, and -SO ₂ - are combined.

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 examples. Further, the anionic polymer is bonded to the relative anion at a portion indicated by * in (XX-1) to (X-30).

[Chem. 21]

Further, specific examples of the combination of X ¹ and L ¹ are also preferably the following examples. In the following specific examples, n represents an integer of 1 to 9. Further, it is shown that the relative anion is bonded to a portion indicated by *.

(In the general formula (D), L ² and L ³ each independently represent a single bond or a divalent linking group; and an anion represents the relative 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 extended aryl group having 6 to 30 carbon atoms, a heterocyclic linking group, and -CH=CH-, -O-, -S-, -C(=O)-, -CO ₂ -, -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ - and A linking group obtained by combining two or more of these groups. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

L ^{2 is} preferably a aryl group having 6 to 12 carbon atoms (particularly a phenyl group). The aryl group having 6 to 30 carbon atoms is preferably substituted by a fluorine atom.

L ^{3 is} preferably a group containing a combination of a aryl group (preferably a phenyl group) having a carbon number of 6 to 12 and -O-, and preferably at least one exoaryl group having a carbon number of 6 to 12 is fluorine. Replaced by atoms.

As the polymer forming the anionic polymer, a homopolymer (separate polymer) composed only of a dye compound component having a crosslinkable group can be preferably used, and a copolymer with other polymerizable compound can also be preferably used ( Copolymer), more preferably a homopolymer (separate polymer).

The molecular weight of the anionic polymer is preferably from 3,000 to 30,000 by weight average molecular weight and from 0.8 to 3.0 in terms of Mw/Mn, more preferably from 5,000 to 20,000 by weight average molecular weight and from 1 to Mw/Mn. 2.5.

In the case of forming an anionic multimer, a chain transfer agent may be added. The chain transfer agent is preferably an alkyl mercaptan, preferably an alkyl mercaptan having a carbon number of 10 or less or an ether group. An alkylthiol substituted with an ester group. More preferably, it is an alkylthiol having a logP value of 5 or less.

The raw material of the anionic polymer contained in the anionic polymer has a crosslinkable group The amount of the anionic monomer compound is preferably 5% or less, more preferably 1% or less.

The content of the halogen ion contained in the anionic polymer is preferably from 10 ppm to 3,000 ppm, more preferably from 10 ppm to 2,000 ppm, even more preferably from 10 ppm to 1,000 ppm.

Specific examples of the anionic polymer are shown below, but the present invention is not limited to these examples.

The following specific examples show a state in which the anion structure is not separated, and the state in which the anion structure is separated is of course within the scope of the present invention.

[化27]

[化28]

In the case where the relative anion is a polymer, it may have other repeating units.

In the case where the relative anion contains an anionic multimer, the amount of the anionic polymer is preferably from 1 mol to 50 mol, more preferably from 1 mol to 50 mol, based on all the repeating units of the coloring agent used in the present invention. 10 moles ~ 30 moles.

Further, in the case where the anionic polymer further contains a repeating unit having a polymerizable group, the repeating unit having a polymerizable group is preferably, for example, 10 mol to 50 mol, per 100 mol of all repeating units. More preferably 10 moles to 30 moles.

Specific examples of the repeating unit having a polymerizable group are as described below. However, the invention is not limited to the examples.

[化30]

[化32]

In the case where the anionic polymer further contains a repeating unit having an acid group, the proportion of the repeating unit having a repeating unit having an acid group is preferably, for example, 10 mol to 50 mol, relative to 100 mol of all repeating units. More preferably 10 moles to 30 moles.

In addition to this, a repeating unit having a functional group: a lactone, an acid anhydride, a decylamine, a -COCH ₂ CO-, a cyano group or the like, a development promoting group, a long chain and a cyclic alkyl group, an aralkyl group, an aryl group may be further included. A functional group such as a polyhydric alkyl group, a hydroxyl group, a maleimide group, or an amine group or the like.

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

[化33]

<<Specific example of coloring agent>>

Specific examples of the coloring agent of the first embodiment used in the present invention are shown below, but are not limited to these examples.

Among the following compounds, the triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2,000 or less in (D-21) has only a number equivalent to a repeating unit of a relative anion.

[化34]

[化35]

Second embodiment of coloring agent

In the second embodiment of the coloring agent, a triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2,000 or less is preferably represented by the formula (TP1A) or the formula (TP2A).

[化36]

(In the general formula (TP1) and the formula (TP2), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group or an aryl group; and Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ and Rtp ₁₁ are each independently represented. a substituent; Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ₇₁ Rtp ₇₂ ; Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group or an aryl group; and Rtp ₁₀ represents a hydrogen atom, an alkyl group or an aryl group; a, b, and c each independently represent an integer of 0 to 4; when a, b, and c are 2 or more, two of Rtp ₆ , Rtp _{7 ,} and Rtp ₈ may be linked to each other to form a ring; Rtp ₁ ~ Any one of Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ has a crosslinkable group; at least one of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ may be substituted by the general formula (P).

(In the formula (P), L represents a single bond or a divalent linking group, and X ^{1 is} selected from the group consisting of -SO ₃ ^- , -COO ^- , -PO ₄ ^- , and includes a structure represented by the following formula (A1) At least one of a group and a group containing a structure represented by the following formula (A2).

General formula (A1)

(In the formula (A1), R ¹ and R ² each independently represent -SO ₂ - or -CO-.)

(In the formula (A2), R ³ represents -SO ₂ - or -CO-; and R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO- or -CN.)

In the general formula (TP1A) and the general formula (TP2A), in addition to the fact that at least one of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ can be substituted by the general formula (P), The triarylmethane having a crosslinkable group and a cation and having a molecular weight of 2,000 or less has the same structural meaning, and the preferred range is also the same.

In the formula (P), L represents a single bond or a divalent linking group. When L represents a divalent linking group, a divalent linking group in which at least one hydrogen atom of the group exemplified below is substituted with X ¹ is preferred.

Alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heterocyclic, carboxy, alkoxy, aryloxy, decyloxy, heterocyclooxy, decyloxy, amine Oxyloxy, Amine (including alkylamino, anilino), mercaptoamine, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, aminesulfonylamino, alkylsulfonyl Amino or arylsulfonylamino, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfo, alkylsulfinyl or arylsulfinyl, alkyl Sulfonyl or arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, aminemethanyl, aryl or heterocyclic azo, quinone imine, phosphino, phosphinyl, oxygen Phosphonooxy, phosphinylamino, decyl, ether, thioether.

The alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and is preferably, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a t-butyl group, an n-octyl group, or 2 a divalent alkyl group obtained by removing one hydrogen from a chloroethyl group, a 2-cyanoethyl group or a 2-ethylhexyl group. In order to make the alkyl groups divalent, X ¹ can be introduced to any position.

The cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms. For example, a cyclohexyl group and a cyclopentyl group are mentioned. Further, a polycycloalkyl group such as a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, for example, bicyclo[1,2,2]heptane-2- is also exemplified. a group having a polycyclic structure such as a bicyclo[2,2,2]octane-3-yl) group or a tricycloalkyl group. Preferred is a monocyclic cycloalkyl group, a bicycloalkyl group, and particularly preferably a monocyclic cycloalkyl group. In order to make the cycloalkyl group divalent, X ¹ can be introduced to any position.

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, it is preferably a vinyl group, an allyl group, an isoprenyl group, a geranyl group or an oleyl group. In order to make the alkenyl groups divalent, X ¹ can be introduced to any position.

The cycloalkenyl group is preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms. For example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl; polycycloalkenyl, such as bicycloalkenyl, preferably a bicycloalkenyl group having 5 to 30 carbon atoms, for example, a bicyclo ring [ 2,2,1]hept-2-en-1-yl, bicyclo[2,2,2]oct-2-en-4-yl or tricycloalkenyl, particularly preferably a monocyclic cycloalkenyl group. In order to make these cycloalkenyl groups divalent, X ¹ can be introduced to any position.

The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and is preferably, for example, an ethynyl group, a propargyl group or a trimethyldecylalkylethynyl group. In order to make the alkynyl groups divalent, X ¹ can be introduced to any position.

The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. For example, a phenyl group, a p-tolyl group, a naphthyl group, a m-chlorophenyl group or an o-hexadecanylaminophenyl group is preferable. In order to make the aryl groups divalent, X ¹ can be introduced to any position.

The heterocyclic group is preferably a substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group of 5 to 7 members. More preferably, the ring constitutes a heterocyclic group in which the atom is selected from a carbon atom, a nitrogen atom and a sulfur atom, and has at least one of a nitrogen atom, an oxygen atom and a sulfur atom, and particularly preferably a carbon number of 3 to 30. 5 or 6 membered aromatic heterocyclic groups. For example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl is preferred. In order to make these heterocyclic groups divalent, X ¹ can be introduced to any position.

The alkoxy group is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, and is preferably, for example, a methoxy group, an ethoxy group, an isopropoxy group, a third butoxy group or a n-octyloxy group. 2-methoxyethoxy. In order to make the alkoxy groups divalent, X ¹ can be introduced to any position.

The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and is preferably, for example, a phenoxy group, a 2-methylphenoxy group, or a 2,4-di-p-pentylbenzene. Oxyl, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecylaminophenoxy. In order to make these aryloxy groups divalent, X ¹ can be introduced to any position.

The decyloxy group is preferably a substituted or unsubstituted decyloxy group having 3 to 20 carbon atoms, and is preferably, for example, a trimethyl decyloxy group or a tert-butyldimethyl decyloxy group. In order to make these decyloxy groups divalent, X ¹ can be introduced to any position.

The heterocyclic oxy group is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. The heterocyclic heterocyclic ring is preferably the heterocyclic ring described in the heterocyclic group, and is preferably, for example, 1-phenyltetrazole-5-oxy or 2-tetrahydropyranyloxy. In order to make these heterocyclic oxy groups divalent, X ¹ can be introduced to any position.

The decyloxy group is preferably a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms or a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, and is preferably, for example, formazan. Oxyl, ethoxylated, trimethylethenyloxy, stearyloxy, benzhydryloxy, p-methoxyphenylcarbonyloxy. In order to make these decyloxy groups divalent, X ¹ can be introduced to any position.

The amine methyl methoxy group is preferably a substituted or unsubstituted amine methyl methoxy group having 1 to 30 carbon atoms, and is preferably, for example, N,N-dimethylamine methyl methoxy group, N,N-diethyl group. Alkylmethyl methoxy, morpholinylcarbonyloxy, N,N-di-n-octylaminocarbonyloxy, N-n-octylamine methoxycarbonyl. In order to make these decyloxy groups divalent, X ¹ can be introduced to any position.

The alkoxycarbonyloxy group is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, and is preferably, for example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group or a third group. Oxycarbonyloxy, n-octylcarbonyloxy. In order to make these alkoxycarbonyloxy groups divalent, X ¹ may be introduced to any position.

The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, and is preferably, for example, a phenoxycarbonyloxy group or a p-methoxyphenoxycarbonyloxy group. , n-hexadecyloxyphenoxycarbonyloxy. In order to make the aryloxycarbonyloxy group divalent, X ¹ may be introduced to any position.

The amine group is preferably an amine group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a carbon number of 0 to 30. A heterocyclic amino group, for example, preferably an amine group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group, an N-1,3,5-triazine -2-ylamino group. In order to make these amine groups divalent, X ¹ can be introduced to any position.

The mercaptoamine group is preferably a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, preferably A. Mercaptoamine, etidylamino, trimethylethenylamine, laurylamine, benzhydrylamine, 3,4,5-tri-n-octyloxycarbonylcarbonyl . In order to make these mercaptoamine groups divalent, X ¹ can be introduced to any position.

The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, and is preferably, for example, an amine formazanyl group or an N,N-dimethylaminocarbonylamino group. , N,N-diethylaminocarbonylamino, morpholinylcarbonylamino. In order to make the aminocarbonylamino group divalent, X ¹ may be introduced to any position.

The alkoxycarbonylamino group is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, and is preferably, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group or a third group. Oxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group. In order to make these alkoxycarbonylamino groups divalent, X ¹ may be introduced to any position.

The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, and is preferably, for example, a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group or the like. N-octyloxyphenoxycarbonylamino group. In order to make the aryloxycarbonylamino group divalent, X ¹ may be introduced to any position.

The aminesulfonylamino group is preferably a substituted or unsubstituted sulfonylamino group having a carbon number of 0 to 30, and is preferably, for example, an aminesulfonylamino group or an N,N-dimethylaminosulfonyl group. Mercaptoamine, N-n-octylaminosulfonylamino. In order to make these aminesulfonylamino groups divalent, X ¹ can be introduced to any position.

The alkylsulfonylamino or arylsulfonylamino group is preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number of 6 to 30. Substituted arylsulfonylamino group. For example, preferred is methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonate. Mercaptoamine group. In order to make the alkylsulfonylamino group or the arylsulfonylamino group divalent, X ¹ may be introduced to any position.

The alkylthio group is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, and is preferably, for example, a methylthio group, an ethylthio group or a n-hexadecylthio group. In order to make the alkylthio groups divalent, X ¹ can be introduced to any position.

The arylthio group is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, and is preferably, for example, a phenylthio group, a p-chlorophenylthio group or a m-methoxyphenylthio group. In order to make the alkylthio groups divalent, X ¹ can be introduced to any position.

The heterocyclic thio group is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, and the heterocyclic ring portion is preferably a heterocyclic ring described in the heterocyclic group, and is preferably 2- Benzothiazolylthio, 1-phenyltetrazol-5-ylthio. In order to make the heterocyclic thio groups divalent, X ¹ may be introduced to any position.

The sulfonyl group is preferably a substituted or unsubstituted sulfonyl group having a carbon number of 0 to 30, and is preferably, for example, N-ethylaminesulfonyl, N-(3-dodecyloxypropane). Amine sulfonyl, N,N-dimethylamine sulfonyl, N-acetyl sulfonyl sulfonyl, N-benzamide sulfonyl, N-(N'-phenylamine A Amidoxime. In order to make these amine sulfonyl groups divalent, X ¹ can be introduced to any position.

The alkylsulfinyl or arylsulfinyl group is preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic having 6 to 30 carbon atoms. The sulfinyl group is, for example, preferably a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group or a p-methylphenylsulfinyl group. In order to make the alkylsulfinylene or arylsulfinylene group divalent, X ¹ may be introduced to any position.

The alkylsulfonyl 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. The group is preferably, for example, a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group or a p-methylphenylsulfonyl group. In order to make the alkylsulfonyl or arylsulfonyl group divalent, X ¹ may be introduced to any position.

The mercapto 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, and is preferably, for example, an ethyl fluorenyl group or a trimethyl group. Ethyl, 2-chloroethyl, stearyl, benzhydryl, p-octyloxyphenylcarbonyl. In order to make these thiol groups divalent, X ¹ can be introduced to any position.

The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, and is preferably, for example, a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, a m-nitrophenoxycarbonyl group, or a pair. Third butyl phenoxycarbonyl. In order to make the aryloxycarbonyl group divalent, X ¹ may be introduced to any position.

The alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, and is preferably, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a third butoxycarbonyl group, or n-octadecane. Alkoxycarbonyl group. In order to make the alkoxycarbonyl groups divalent, X ¹ may be introduced to any position.

The amine mercapto group is preferably a substituted or unsubstituted amine carbenyl group having 1 to 30 carbon atoms, such as an amine methyl sulfonyl group, an N-methyl amine methyl fluorenyl group, and an N,N-dimethylamine formazan group. Base, N,N-di-n-octylaminecarbamyl, N-(methylsulfonyl)aminecarbamyl. In order to make the amine mercapto group divalent, X ¹ can be introduced to any position.

The arylazo or heterocyclic azo group is preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms or a substituted or unsubstituted heterocyclic azo having 3 to 30 carbon atoms. The base (heterocyclic moiety is preferably the heterocyclic moiety described in the heterocyclic group). For example, phenylazo, p-chlorophenylazo, 5-ethylsulfanyl-1,3,4-thiadiazol-2-ylazo is preferred. In order to make the arylazo or heterocyclic azo groups divalent, X ¹ may be introduced to any position.

The quinone imine group is preferably a substituted or unsubstituted quinone imine group having 2 to 30 carbon atoms, and is preferably, for example, N-butylenedimine or N-phthalimido group. In order to make these quinone imine groups divalent, X ¹ can be introduced to any position.

The phosphino group is preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, and is preferably, for example, a dimethylphosphino group, a diphenylphosphino group or a methylphenoxyphosphino group. In order to make the phosphine groups divalent, X ¹ can be introduced to any position.

The phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, and is preferably, for example, a phosphinyl group, a dioctyloxyphosphinyl group or a diethoxyphosphinyl group. In order to make the phosphinyl group divalent, X ¹ can be introduced to any position.

The phosphinyloxy group is preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, and is preferably, for example, a diphenoxyphosphinyloxy group or a dioctyloxyphosphinyloxy group. . In order to make the phosphinyloxy group divalent, X ¹ can be introduced to any position.

The phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, and is preferably, for example, dimethoxyphosphinylamino group or dimethylaminophosphinylamine. base. In order to make the phosphinylamino group divalent, X ¹ can be introduced to any position.

The fluorenyl group is preferably a substituted or unsubstituted fluorenyl group having 3 to 30 carbon atoms, and examples thereof include a trimethyl decyl group, a tert-butyl dimethyl decyl group, and a phenyl dimethyl decyl group. In order to make these decyl groups bivalent, X ¹ can be introduced to any position.

Further, in the case where L represents a divalent linking group, preferably represents ^{-NR 10 -, - O -,} - SO 2 -, fluoro-substituted alkylene, fluoro-substituted phenylene or a combination comprising the plurality of groups Group. Particularly preferred are: a group comprising a combination of -NR ¹⁰ -, -SO ₂ and a fluorine-substituted alkylene group, a group comprising a combination of -O- and a fluorine-substituted phenylene group, or -NR ¹⁰ -, -SO ₂ and a combination of a fluorine-substituted alkylene group.

In -NR ¹⁰ -, R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom.

The carbon number of the fluorine-substituted alkylene group is preferably from 1 to 10, more preferably from 1 to 6, more preferably from 1 to 3. More preferably, the alkylene group is a perfluoroalkylene group. Specific examples of the fluorine-substituted alkylene group include a difluoromethylene group, a tetrafluoroextension ethyl group, and a hexafluoroextension propyl group.

The carbon number of the fluorine-substituted phenylene group is preferably from 6 to 20, more preferably from 6 to 14, more preferably from 6 to 10. Specific examples of the fluorine-substituted phenylene group include a tetrafluorophenylene group, a hexafluoro-1-naphthyl group, and a hexafluoro-2-naphthyl group.

In the formula (P), X ¹ is a relative anion, preferably selected from the group consisting of -SO ₃ ^- , -COO ^- , -PO ₄ ^- , a group comprising a structure represented by the formula (A1), and a general formula At least one of the groups of the structure represented by (A2). Here, the structure represented by the general formula (A1) and the structure represented by the general formula (A2) have the same meanings as those described in the first embodiment.

Including the general formula (A1) a group represented by the structure is preferably in the general formula (A1), wherein one end of the R ¹ and R ² having fluorine-substituted alkyl group, more preferably R ¹ and One of R ² is directly bonded to a fluorine-substituted alkyl group. The fluorine-substituted alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, still more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom. More preferably, the alkyl group is a perfluoroalkyl group. A specific example of the fluorine-substituted alkyl group is preferably a trifluoromethyl group.

The group containing the structure represented by the formula (A2) is preferably a fluorine-substituted alkyl group at the terminal of at least one of R ³ to R ⁵ in the formula (A2), more preferably R ^{3 .} At least two of ~R ⁵ are directly bonded to a fluorine-substituted alkyl group. It is particularly preferred that at least two of R ³ to R ⁵ have a fluorine-substituted alkyl group at the terminal, and more preferably at least two of R ³ to R ⁵ are directly bonded to a fluorine-substituted alkyl group. The fluorine-substituted alkyl group has the same meaning as that described in the group containing the structure represented by the general formula (A1), and the preferred range is also the same.

In addition to the above, specific examples of X ¹ include the above-mentioned relative anion A. In this case, any one of the hydrogen atoms or the halogen atom constituting the counter anion A is bonded to L in the formula (P).

The triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2,000 or less is in the formula (TP1A) and the formula (TP2A), and may have any of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ . A crosslinkable group, and any of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ having a crosslinkable group may be further substituted by the formula (P).

Further, in the general formula (TP1A) and the general formula (TP2A), the portion substituted by the general formula (P) may be present in only one place, or may be present in two or more places. In the case where there are two or more portions substituted by the general formula (P), in addition to the cations contained in the triarylmethane structure, the colorant has a number of cations corresponding to the amount of the relative anions.

Specific examples of the coloring agent of the second embodiment used in the present invention are shown below, but are not limited to these examples.

[化40]

[化41]

[化42]

[化43]

The triarylmethane dye used in the present invention may contain one type or group alone. It contains two or more types.

The content of the triarylmethane dye is preferably from 10% by mass to 60% by mass, and more preferably from 10% by mass to 40% by mass based on the total solid content of the colored composition of the present invention.

<<Other coloring compounds>>

The colored composition of the present invention may contain one or two or more kinds of coloring compounds other than the triarylmethane dye. Other coloring compounds may be exemplified by dye compounds, pigment compounds, and dispersions of the compounds.

The dye compound may be any compound as long as it does not affect the hue of the colored image, and examples thereof include an azo system (for example, Solvent Yellow 162) and a lanthanide system (for example, Japanese Patent Laid-Open Publication No. 2001-10881) The ruthenium compound described in the above), the phthalocyanine system (for example, the phthalocyanine compound described in US Pat. No. 2008/0076044 A1), the xanthene system (for example, CI Acid Red 289), and the triarylmethane system ( For example, CI Acid Blue 7 (CIAcid Blue 83), CI Acid Blue 83 (CIAcid Blue 83), CI Acid Blue 90 (CIAcid Blue 38), CI Solvent Blue 38 (CI Solvent Blue 38), CI Acid Violet 17 ( CIAcid Violet 17), CI Acid Violet 49, CI Acid Green 3, methine dye, and the like.

Examples of the pigment compound include perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone ( Benzimidazolone), disazo condensation, disazo, azo, indanthrone, Phthalocyanine, triaryl carbonium, dioxazine, amidoxime, diketopyrrolopyrrole, indigo, thioindigo, isoindoline ), isoindolinone, pyranthrone or isoviolanthrone. More specifically, for example, an anthraquinone compound pigment such as Pigment Red 190, Pigment Red 224 or Pigment Violet 29, a pigment purple orange 43 or a pigment red 194 such as a purple ketone compound pigment, Pigment Violet 19, Pigment Violet 42, Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 207, or quinacridone compound pigment of Pigment Red 209, Pigment Red 206, Pigment Orange 48, or quinacridone oxime compound pigment such as Pigment Orange 49, Pigment Yellow 147 Equivalent compound pigment, pigment red 168, etc. 蒽 蒽醌 compound pigment, pigment brown 25, pigment purple 32, pigment orange 36, pigment yellow 120, pigment yellow 180, pigment yellow 181, pigment orange 62, or pigment red 185, etc. Benzimidazolone compound pigment, pigment yellow 93, pigment yellow 94, pigment yellow 95, pigment yellow 128, pigment yellow 166, pigment orange 34, pigment orange 13, pigment orange 31, pigment red 144, pigment red 166, pigment red 220 Bismuth condensed compound pigment such as Pigment Red 221, Pigment Red 242, Pigment Red 248, Pigment Red 262, or Pigment Brown 23, bisazo compound pigment such as Pigment Yellow 13, Pigment Yellow 83, or Pigment Yellow 188, Pigment Red 187, Pigment Red 170 Pigment yellow 74, pigment yellow 150, pigment red 48, pigment red 53, pigment orange 64, or pigment red 247 and other azo compound pigments, pigment blue 60 and other indanthrone compound pigments, pigment green 7, pigment green 36, pigment green 37, pigment green 58, pigment blue 16, pigment blue 75, or pigment blue 15 and other phthalocyanine compound pigment, pigment blue 56, or pigment blue 61 and other triaryl carbon hydrazine compound pigment, pigment purple 23, or pigment purple 37-dioxazine compound pigment, pigment red 177 and other amine ruthenium compound pigment, pigment red 254, pigment red 255, pigment red 264, pigment red 272, pigment orange 71, or pigment orange 73 and other diketopyrrolopyrrole compounds Pigment, pigment red 88 thioindole compound pigment, pigment yellow 139, pigment orange 66 and other isoporphyrin compound pigment, pigment yellow 109, or pigment orange 61 and other isoindolinone compound pigment, pigment orange 40, or pigment red a pipione compound pigment such as 216 or an isopurinone pigment such as Pigment Violet 31.

In the present invention, a green to cyan colored material is preferable, and a phthalocyanine compound pigment such as Pigment Green 7, Pigment Green 36, Pigment Green 37, Pigment Green 58, Pigment Blue 16, Pigment Blue 75, or Pigment Blue 15 is preferable. , trifluorocarbon fluorene compound pigment such as pigment blue 56 or pigment blue 61, dioxazine compound pigment such as pigment violet 23 or pigment violet 37, amine hydrazine compound pigment such as pigment red 177, pigment red 254, pigment red 255 , pigment red 264, pigment red 272, pigment orange 71, or pigment orange 73 and other diketopyrrolopyrrole compound pigments, pigment red 88 and other sulfonium compound pigments, pigment yellow 139, pigment orange 66 and other isoporphyrin compound pigments, An isoindolinone compound pigment such as Pigment Yellow 109 or Pigment Orange 61, a Pipione compound pigment such as Pigment Orange 40 or Pigment Red 216, or an isopurinone pigment such as Pigment Violet 31.

In the case of blending the dye or the pigment as a dispersion, the adjustment can be carried out in accordance with the description of JP-A-H09-197118 and JP-A-2000-239544.

The content of the material or pigment can be used within the range not detracting from the effects of the present invention, and is preferably 0.5 with respect to the total solid content of the coloring composition of the present invention. Mass%~70% by mass. Moreover, it is preferable to add to the coloring composition so that the absorption intensity ratio (absorption of 450 nm / absorption of 650 nm) is in the range of 0.95 to 1.05.

<<Polymerized compound>>

The colored composition of the present invention contains a polymerizable compound. The polymerizable compound is, for example, an addition polymerizable compound having at least one ethylenically unsaturated double bond.

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

Examples of the monomer and the (co)polymer thereof include an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, etc.) or an ester thereof. The guanamines and their (co)polymers are preferably: esters of unsaturated carboxylic acids with aliphatic polyol compounds, and guanamines of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and their (co)polymer. In addition, it is also suitable to use an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, or an addition reaction of a monofunctional or polyfunctional isocyanate or an epoxy group, or a monofunctional group. Or a dehydration condensation reaction of a polyfunctional carboxylic acid or the like. Further, an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group or an addition reaction product of a decylamine with a monofunctional or polyfunctional alcohol, an amine or a thiol, and further having a halogen An unsaturated carboxylic acid ester of a detachable substituent such as a sulfonyloxy group or Substituted reactants of guanamines with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. Further, as another example, a compound group substituted with an unsaturated phosphonic acid, styrene, vinyl ether or the like may be used instead of the unsaturated carboxylic acid.

Specific examples of the monomer of the ester of the aliphatic polyol compound and the unsaturated carboxylic acid include, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butylene glycol diacrylate. Ester, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene methoxypropyl) ether, Trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate Ester, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(propylene oxyoxyethyl) An isocyanurate, a polyester acrylate oligomer, an ethylene oxide (EO) modified triacrylate, and the like.

Further, examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimethylolpropane trimethyl. Acrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethyl Acrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol Tetramethacrylate, bis[p-(3-methylpropenyloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p-(methacryloxyethoxy)benzene Base] dimethylmethane and the like.

Further, examples of the itaconate include, for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butylene glycol diitaconate, and 1,4-butanediol diitaconic acid. Ethyl ester, tetramethylene glycol bisitaconate, pentaerythritol diitaconate, sorbitol tetraconate, etc., and examples of the butenoate include ethylene glycol bisacrylate, Tetramethylene glycol methacrylate, pentaerythritol dibutenoate, sorbitol tetrabutyrate, etc., and methacrylates, for example, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate And sorbitol tetramethacrylate or the like, and examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, and pentaerythritol di-n-butene. Diacid ester, sorbitol tetramaleate, and the like.

For example, an aliphatic alcohol-based ester described in Japanese Patent Laid-Open Publication No. Sho 57-196231, Japanese Patent Laid-Open Publication No. SHO 57-196231, Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Further, the ester monomer can also be used as a mixture.

In addition, a urethane-based addition polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group is also suitable, and a specific example thereof is exemplified in one molecule described in Japanese Patent Publication No. Sho 48-41708. A vinyl urethane compound containing two or more polymerizable vinyl groups, which is represented by the following general formula (A), in a polyisocyanate compound having two or more isocyanate groups per molecule Made of a vinyl monomer containing a hydroxyl group.

CH ₂ =C(R)COOCH ₂ CH(R')OH...(A)

[In the general formula (A), R and R' each independently represent H or CH ₃ . ]

Further, the polymerizable compound is also preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercial product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercial product is KAYARAD D-310; Nippon Chemical Co., Ltd. Manufactured by the company), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and (meth)acryloyl group of these compounds via B The structure of the diol and propylene glycol residues. Oligomer types of these compounds can also be used.

Regarding the polymerizable compounds, the details of the structure, whether they are used singly or in combination, and the amount of addition can be arbitrarily set depending on the final performance design of the coloring composition. For example, from the viewpoint of sensitivity, a structure having a large content of unsaturated groups per molecule is preferable, and in many cases, it is preferably a bifunctional or higher. Further, from the viewpoint of improving the strength of the colored cured film, it is preferably a trifunctional or higher functional group, and further, by different functional numbers. Methods for adjusting both sensitivity and strength are also effective for different polymerizable groups (e.g., acrylates, methacrylates, styrene compounds, vinyl ether compounds). In addition, for other components contained in the colored composition (for example) Such as photopolymerization initiator, colorant (pigment), binder polymer, etc.) compatibility, dispersibility, choice of polymerizable compounds. The use method is also an important factor. For example, it may be used by low-purity compounds or two or more types to improve compatibility. Further, from the viewpoint of improving the adhesion to a hard surface such as a substrate, a specific structure can be selected.

From the viewpoint of obtaining the effect of the present invention more effectively, the content of the polymerizable compound in all the solid components of the colored composition is preferably from 10% by mass to 80% by mass, more preferably from 15% by mass to 75% by mass. , particularly preferably from 20% by mass to 60% by mass.

The composition of the present invention may contain only one type of polymerizable compound, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is the said 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 the polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

The photopolymerization initiator may, for example, be at least one active halogen compound selected from the group consisting of a halogenated methyl oxadiazole compound and a halogenated methyl-s-triazine compound, a 3-aryl-substituted coumarin compound, and a flavonoid. Dimer, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, hydrazine compound and the like. Specific examples of the photopolymerization initiator include the examples described in paragraphs [0070] to [0077] of JP-A-2004-295116. Among them, the party with rapid polymerization The surface or the like is preferably a ruthenium compound or a biimidazole compound.

The oxime-based compound (hereinafter also referred to as "an oxime-based photopolymerization initiator") is not particularly limited, and examples thereof include, for example, JP-A-2000-80068, WO02/100903A1, and JP-A-2001-233842. The lanthanide compound described in the above.

Specific examples of the lanthanoid compound can be referred to the description of paragraph 0053 of JP-A-2013-182215, which is incorporated herein by reference.

In the present invention, the ruthenium compound is more preferably a compound represented by the following formula (1) or (2) from the viewpoints of sensitivity, stability at the time of the run, and coloration at the time of post-heating.

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

In terms of high sensitivity, R is preferably a mercapto group, and specifically, is preferably an ethyl fluorenyl group, a propyl fluorenyl group, a benzamidine group or a tolylmethyl group.

In terms of improving the sensitivity and suppressing the coloring caused by heating over time, A is preferably an unsubstituted alkylene group, an alkyl group (e.g., methyl group, ethyl group, Tert-butyl substituted by tributyl, dodecyl), alkylene substituted by alkenyl (eg, vinyl, allyl), aryl (eg phenyl, p-tolyl, xylyl) An alkylene group substituted with cumenyl, naphthyl, anthracenyl, phenanthryl, styryl).

Ar is preferably a substituted or unsubstituted phenyl group in terms of improving the sensitivity and suppressing the coloring caused by heating over time. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In terms of improving solvent solubility and absorption efficiency in a long wavelength region, X is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, may have a substituent Alkynyl group, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylthio group which may have a substituent, aryl thiooxy which may have a substituent, amine which may have a substituent base. Further, n in the formula (1) is preferably an integer of 1 to 2.

In the formula (2), R ¹⁰¹ represents an alkyl group, an alkyl fluorenyl group, an olefin group, an aryl fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, a heteroaryloxycarbonyl group, an alkyl sulfide. Carbonyl, arylthiocarbonyl, heterocyclic thiocarbonyl, heteroarylthiocarbonyl or CO-CO-Rf. Rf represents a carbocyclic aromatic group or a heterocyclic aromatic group.

R ¹⁰² represents an alkyl group, an aryl group or a heterocyclic group, those which may be substituted.

R ¹⁰³ and R ¹⁰⁴ each independently represent an alkyl group, an aryl group or a heterocyclic group, and these groups may be further substituted with a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylcarbonyl group or the like.

R ¹⁰⁵ to R ¹¹¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryl fluorenyl group, a heteroaryl fluorenyl group, an alkylthio group, an arylsulfonyl group, or a hetero group. Aryl, alkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, heterocyclooxycarbonyl, nitro, amine, sulfonate, hydroxy, carboxylic acid, hydrazine Amino group, amine mercapto group or cyano group.

It is preferred that one or both of R ¹⁰⁵ to R ¹¹¹ be an electron-attractive substituent, that is, a nitro group, a cyano group, a halogen group, an alkylcarbonyl group or an arylcarbonyl group, because a higher hardenability is obtained. The coloring composition.

Specific examples of the compound having a fluorene structure represented by the above formula (2) are listed below. However, it is not limited to this compound.

[化47]

The compound having a fluorene structure represented by the above formula (2) can be synthesized, for example, according to the synthesis method described in the pamphlet of International Publication WO2014/050738.

Specific examples of the biimidazole-based compound can be referred to the description of paragraphs 0061 to 0070 of JP-A-2013-182213, which is incorporated herein by reference.

Further, in the coloring composition of the present invention, in addition to the photopolymerization initiator Other known photopolymerization initiators described in Paragraph No. 0079 of JP-A-2004-295116 may be used.

The content of the photopolymerization initiator in the total solid content of the coloring composition is preferably from 3% by mass to 20% by mass, more preferably from 4% by mass to 19%, from the viewpoint of obtaining the effect of the present invention more effectively. The mass% is particularly preferably from 5% by mass to 18% by mass.

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 contained, it is preferable that the total amount is the said range.

<<Organic solvent>>

The colored composition of the present invention preferably contains at least one organic solvent.

The organic solvent is not particularly limited as long as it satisfies the solubility of each component to be coherent or the coating property when the coloring composition is formed, and it is particularly preferable to consider the solubility, coatability, and safety of the binder. Come choose.

As the organic solvent, esters, ethers, ketones, and aromatic hydrocarbons can be used. Specifically, the solvent described in Paragraph No. 0161 to Paragraph No. 0162 of JP-A-2012-032754 can be exemplified.

The organic solvent is preferably mixed in two or more kinds from the viewpoints of the solubility of the components and the solubility of the coating layer in the case of containing an alkali-soluble polymer. In this case, it is particularly preferred to comprise a methyl ester selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethylene glycol dimethyl ether. , butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether Two or more mixed solutions of acetate.

The content of the organic solvent in the coloring composition is preferably such that the total solid content concentration in the composition is from 10% by mass to 80% by mass, more preferably from 15% by mass to 60% by mass.

The composition of the present invention may contain only one type of organic solvent, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is the said range.

<<Alkali Soluble Binder>>

The colored composition of the present invention preferably comprises an alkali-soluble binder. The alkali-soluble binder is not particularly limited as long as it has alkali solubility, and is preferably selected from the viewpoints of heat resistance, developability, and availability.

The alkali-soluble binder is preferably a linear organic high molecular polymer, and is soluble in an organic solvent and can be developed with a weakly alkaline aqueous solution. Such a linear organic high molecular polymer may be exemplified by a polymer having a carboxylic acid in a side chain, for example, Japanese Patent Laid-Open No. Sho 59-44615, Japanese Patent Publication No. Sho 54-34327, Japanese Patent No. Sho 58-12577 The methacrylic acid copolymer, acrylic acid copolymer, and itacon described in each of the publications of Japanese Patent Laid-Open Publication No. Sho 54-25957, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048 Acidic copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., similarly acidic cellulose derivatives having a carboxylic acid in a side chain .

In addition to the compound, the alkali-soluble binder in the present invention may be used, such as an acid anhydride added to a polymer having a hydroxyl group, or a polyhydroxystyrene resin, a polyoxyalkylene resin, or a poly(( 2-hydroxyethyl methacrylate), polyvinylpyrrolidone or polyethylene oxide, polyvinyl alcohol, and the like. In addition, linear organic high scores The subpolymer may also be a polymer obtained by copolymerizing a monomer having hydrophilicity. Examples thereof include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, glycerol (meth) acrylate, (meth) acrylamide, and N-methylol propylene oxime. Amine, a 2-stage alkyl acrylamide or a 3-stage alkyl acrylamide, a dialkylaminoalkyl (meth) acrylate, a morpholine (meth) acrylate, an N-vinyl pyrrolidone, N -vinyl caprolactam, vinyl imidazole, vinyl triazole, methyl (meth)acrylate, ethyl (meth)acrylate, branched or linear propyl (meth) acrylate, branched or straight Chain butyl (meth) acrylate, or phenoxy hydroxypropyl (meth) acrylate or the like. In addition, the hydrophilic monomer may also include a tetrahydroindenyl group, a phosphoric acid group, a phosphate group, a 4- toluene group, an extended ethyloxy chain, a propyloxy chain, a sulfonic acid group, and A monomer derived from a salt group or a morpholinylethyl group.

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

(In the formula (b1), R ¹ represents a hydrogen atom, an aryl group or an alkyl group.)

Examples of the alkyl group in the case where R ¹ represents an alkyl group include a linear alkyl group having 1 to 10 carbon atoms, an alkyl group having a branched chain of 3 to 10 carbon atoms, a cyclic alkyl group having 5 to 20 carbon atoms, and the like. More specifically, a methyl group, an ethyl group, a tert-butyl group, a cyclohexyl group, etc. are mentioned.

The alkyl group may have a substituent, and examples of the substituent which may be introduced into the alkyl group include a phenyl group, a carbonyl group, an alkoxy group, a hydroxyl group, an amine group and the like.

Examples of the aryl group in the case where R ¹ represents an aryl group include an aryl group having a monocyclic structure, an aryl group having a polycyclic structure, an aryl group having a condensed ring structure, a heteroaryl group containing a hetero atom, and the like. More specifically, a phenyl group, a naphthyl group, a biphenyl group, a benzimidazolyl group, a pyridyl group, a furyl group, etc. are mentioned.

The aryl group may have a substituent, and the substituent which may be introduced into the aryl group may, for example, be an alkyl group such as a methyl group, an ethyl group, a tributyl group or a cyclohexyl group, an alkoxy group such as a methoxy group, a carboxyl group, a hydroxyl group or an amine group. , nitro, chloro, bromo and the like.

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

Examples of the alkyl group in the case where R ⁴ represents an alkyl group include a linear alkyl group having 1 to 20 carbon atoms, an alkyl group having a branched chain of 1 to 20 carbon atoms, a cyclic alkyl group having 5 to 20 carbon atoms, and the like. More specifically, a methyl group, an ethyl group, a tert-butyl group, a cyclohexyl group, a 2-ethylhexyl group, etc. are mentioned.

The alkyl group may have a substituent, and examples of the substituent which may be introduced into the alkyl group include a phenyl group, a carbonyl group, an alkoxy group and the like.

Examples of the aryl group in the case where R ⁴ represents an aryl group include an aryl group having a monocyclic structure, an aryl group having a polycyclic structure, an aryl group having a condensed ring structure, a heteroaryl group containing a hetero atom, and the like. More specifically, a phenyl group, a naphthyl group, a fluorenyl group, a biphenyl group, a benzimidazolyl group, a fluorenyl group, an imidazolyl group, an oxazolyl group, a carbazolyl group, a pyridyl group, a furyl group, etc. are mentioned.

The aryl group may have a substituent, and the substituent which may be introduced into the aryl group may, for example, be an alkyl group such as a mercapto group, a methyl group, an ethyl group, a t-butyl group or a cyclohexyl group, an alkoxy group such as a methoxy group, a carboxyl group or a hydroxyl group. , amine, nitro, chloro, bromo and the like.

Further, in order to improve the crosslinking efficiency, the alkali-soluble binder may have a polymerizable group in the side chain, and may be, for example, an allyl group, a (meth)acryl group, an allyloxyalkyl group or the like in the side chain. Polymers, etc. Examples of the polymerizable group-containing polymer include commercially available KS photoresist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and Cyclomer P series (Daicel Chemical). Industrial (stock) manufacturing) and so on. Further, in order to increase the strength of the hardened film, an alcohol-soluble nylon or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin may be used.

Among these various alkali-soluble binders, from the viewpoint of heat resistance, a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, and an acrylic acid/acrylamide are preferable. The polymer resin is preferably an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin from the viewpoint of developability control.

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

(In the formula (2), R ²⁰ represents a hydrogen atom or a methyl group, and R ²¹ to R ²⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an aryl group.)

(In the formula (3), R ¹¹ represents a hydrogen atom or a methyl group; and R ¹² and R ¹³ each independently represent a hydrogen atom or a carbonyl group having a carbon atom number of 3 to 20 which contains an unsaturated double bond as a partial structure, and R ¹² is absent. And both of R ¹³ are a hydrogen atom; and when at least one of R ¹² and R ¹³ represents a carbonyl group having 3 to 20 carbon atoms which contains an unsaturated double bond as a partial structure, it may further contain a carboxyl group. Part of the structure.)

The acrylic resin preferably contains benzyl (meth) acrylate, a copolymer of a monomer such as (meth)acrylic acid, hydroxyethyl (meth)acrylate, or (meth)acrylamide, or a commercially available KS photoresist-106 (Osaka Organic Chemical Industry Co., Ltd.) Manufacturing), Cyclomer P series (made by Daicel Chemical Industry Co., Ltd.).

Further, the alkali-soluble binder may further contain a structural unit derived from an ethylenically unsaturated monomer represented by the following formula (X).

(In the formula (X), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 10 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may include a benzene ring; Indicates an integer from 1 to 15.)

In the formula (X), the alkyl group of R ² preferably has 2 to 3 carbon atoms. Further, the alkyl group of R ³ has a carbon number of 1 to 20, more preferably 1 to 10, and the alkyl group of R ³ may contain a benzene ring. The alkyl group containing a benzene ring represented by R ³ may, for example, be a benzyl group or 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 a GPC method) of 1,000 to 200,000, more preferably 2,000 to 100,000, from the viewpoints of developability, liquid viscosity, and the like. A polymer, particularly preferably a polymer of 5,000 to 50,000.

The amount of the alkali-soluble binder is preferably from 10% by mass to 80% by mass, and more preferably from 20% by mass to 60% by mass based on the total solid content of the coloring composition.

Further, the acid value of the alkali-soluble binder is preferably from 10 mg/KOH to 1000 mg/KOH, more preferably from 50 mg/KOH to 300 mg/KOH, more preferably from 50 mg/KOH to 200 mg/KOH, and particularly preferably from 105 mg/KOH to 200 mg. /KOH.

The composition of the present invention may contain only one type of alkali-soluble binder, and may contain two or more types. When two or more types are contained, it is preferable that the total amount is the said range.

<<Crosslinker>>

The colored composition of the present invention may further comprise a crosslinking agent.

The crosslinking agent is not particularly limited as long as it is a crosslinking agent which can be cured by a crosslinking reaction, and examples thereof include (a) an epoxy resin; and (b) a selected from a methylol group and an alkoxy group. a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent of a methyl group and a decyloxymethyl group; (c) selected A phenol compound, a naphthol compound or a hydroxyquinone compound substituted with at least one substituent of a methylol group, an alkoxymethyl group, and a decyloxymethyl group. Among them, a polyfunctional epoxy resin is preferred.

For details of specific examples of the crosslinking agent, etc., refer to the description of paragraphs 0134 to 0147 of JP-A-2004-295116, which is incorporated herein by reference.

<<Interfacial active agent>>

The colored composition of the present invention may also comprise a surfactant. The surfactant may be any of a nonionic, cationic or anionic system, preferably having an epoxy B. A surfactant of alkane structure or a fluorine-based surfactant. Particularly preferred is a surfactant having an ethylene oxide structure having a Hydrophile-Lipophile Balance (HLB) value of 9.2 to 15.5 or a fluorine-based interface activity described in JP-A No. 2-54202. Agent.

When the coloring composition of the present invention contains a surfactant, the amount of the surfactant added is preferably 0.0001% by mass to 2.0% by mass, and more preferably 0.005% by mass based on the total solid content of the coloring composition. 1.0% by mass.

The composition of the present invention may contain only one type of surfactant, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is the said range.

The coloring composition of the present invention may further contain various additives such as a filler, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, a sensitizer, or a light stabilizer, as needed.

<<Dye Stabilizer>>

In the composition of the present invention, it is preferred to add a dye stabilizing agent in addition to the triarylmethane dye. As the stabilizer, for example, a surfactant such as a cationic system, an anionic system, a nonionic system, an amphoteric acid, an anthrone or a fluorine-based surfactant can be used. Among the surfactants, a polymer surfactant (polymer dispersant) is preferred in terms of uniform and fine dispersion.

Examples of the polymer dispersant include (co)polymers of unsaturated carboxylic acid esters such as polyacrylate; (partial) amine salts and (partial) ammonium salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid. Or a (partial) alkylamine salt; a (co)polymer of a hydroxyl group-containing unsaturated carboxylic acid ester such as a hydroxyl group-containing polyacrylate or a braid thereof a polymer of a sulfonic acid or a phosphoric acid having a crosslinkable group.

As the crosslinkable group, a crosslinkable group which can be crosslinked by a radical, an acid or a heat can be used. Specific examples thereof include a (meth)acrylic group, a styryl group, a vinyl group, a cyclic ether group, and a methylol group, preferably a (meth)acrylic group, a styryl group, a vinyl group, and more preferably (A). Acrylic group and styrene group.

Further, in addition to the surfactants, it is also effective to add a bistrifluoromethanesulfonimide sodium salt or a salt of the following anion (sodium salt, potassium salt or the like).

<antioxidant>

The composition of the present invention may comprise 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 a phenol-based antioxidant and a hindered amine-based antioxidant. Examples of the phenolic antioxidant include a hydroxyphenyl-propionate-based compound, a hydroxybenzyl-based compound, a thiobisphenol-based compound, a thiomethylphenol-based compound, and an alkanediylphenol-based compound. Among them, from the viewpoint of stability of color characteristics, A hydroxyphenyl propionate compound is preferred.

The peroxide decomposing agent is a compound which decomposes the peroxide generated by exposure to light to a harmless substance so as not to generate a new radical, and examples thereof include a phosphorus-based antioxidant and a sulfur-based antioxidant. Among them, a sulfur-based antioxidant is preferred from the viewpoint of stability of color characteristics.

Examples of the ultraviolet absorber include a salicylate-based antioxidant and a benzophenone-based antioxidant.

The singlet oxygen quencher is a compound which can inactivate singlet oxygen by energy transfer from oxygen in a singlet state, for example, an ethylene compound such as tetramethylethylene or cyclopentene, diethylamine, Amines such as triethylamine, 1,4-diazabicyclooctane (DABCO), N-ethylimidazole, substituted naphthalene, dimethylnaphthalene, dimethoxyanthracene, a condensed polycyclic aromatic compound such as hydrazine or diphenylhydrazine; 1,3-diphenylisobenzofuran, 1,2,3,4-tetraphenyl-1,3-cyclopentadiene, pentaphenyl In addition to the aromatic compound such as cyclopentadiene, a compound exemplified as a singlet oxygen agent in the following literature: "Hing H. Wasserman" "Singlet Oxygen" Chapter 5, Academic Press (1979); Nicholas J. Turro, "Modern Molecular Photochemistry", Chapter 14, Benjamin Publishing Company (The Benjamin) Cummings Publishing Co., Inc. (1978); and Chapter 7 (2002) of "High-Performance Chemicals for Color Photographic Materials" issued by CMC Corporation .

In addition to this, a metal having a compound having a sulfur atom as a ligand may be cited Complex compound. Examples of such a compound include a nickel complex, a cobalt complex, a copper complex, and manganese having a bisdithio-α-diketone, a bisphenyldithiol, and a thiobisphenol as a ligand. A transition metal chelate compound such as a complex compound or a platinum complex.

Examples of the sulfur-based antioxidant include a thiopropionate-based compound and a mercaptobenzimidazole-based compound. Among them, from the viewpoint of stability of color characteristics, a thiopropionate-based compound is preferred.

In the present invention, the antioxidant may be used singly or in combination of two or more. The content of the antioxidant is preferably from 0.01 part by mass to 20 parts by mass, particularly preferably from 0.1 part by mass to 10 parts by mass, per 100 parts by mass of the colorant.

<hardener>

The colored composition of the present invention may contain a compound that functions as a curing agent.

For example, at least one selected from the group consisting of an aromatic amine compound, a tertiary amine compound, an amine salt, a phosphonium salt, a phosphonium salt, a guanamine compound, a thiol compound, a blocked isocyanate compound, and an imidazole ring-containing compound can be used. 1 compound.

By including such a hardening agent in the colored composition, the low-temperature hardening of the colored pattern can be more effectively achieved. Further, the storage stability of the colored composition can be further improved.

<Reduction inhibitor>

The coloring composition of the present invention may also be a compound which is more easily reduced than the dye to be used as a reduction inhibitor for the dye. Thereby, the dye reduction fading can be further suppressed during the sputtering of Indium Tin Oxide (ITO) after the formation of the pixels. Specifically, it is preferably a ruthenium compound, and preferably has a molecular weight of about 100 to 800. a ruthenium compound.

The colored composition of the present invention may further contain various additives such as a filler, an ultraviolet absorber, an anti-agglomerating agent, a sensitizer, or a light stabilizer, as needed.

[Preparation method of coloring composition]

The colored composition of the present invention is prepared by mixing the above components with any optional components as needed.

In addition, when preparing the colored composition, the components constituting the colored composition may be collectively formulated, and the components may be dissolved. Disperse in a solvent and then mix them one by one. In addition, the order of input or the working conditions at the time of preparation are not particularly restricted. For example, all ingredients can be dissolved at the same time. The composition is prepared by dispersing in a solvent, and if necessary, each component may be appropriately prepared into two or more kinds of solutions. The dispersions were mixed to prepare a composition when used (at the time of coating).

The colored composition prepared in the above manner can be used by filtration using a filter having a pore diameter of preferably 0.01 μm to 3.0 μm, more preferably a pore diameter of 0.05 μm to 0.5 μm, or the like.

The coloring composition of the present invention is suitable for forming a liquid crystal display device (LCD) or a solid-state imaging device (for example, a charge coupled device (CCD), a complementary metal oxide, because it can form a colored cured film having excellent hue and contrast. A coloring element such as a color filter used in a semiconductor (Complementary Metal-Oxide Semiconductor, CMOS) or the like, and can be suitably used for production of printing inks, inkjet inks, paints, and the like. It is particularly suitable for use in the formation of colored pixels for liquid crystal display devices.

[Color filter and method of manufacturing the same]

The color filter of the present invention is provided with a substrate, and is provided with a colored region containing the colored composition of the present invention on the substrate. The colored region on the substrate is composed of a colored film such as red (R), green (G), or blue (B) which forms each pixel of the color filter.

The color filter of the present invention can be formed by any method as long as it is a method capable of applying the colored composition of the present invention to a substrate to form a cured colored region (colored pattern). It is preferably produced by using the colored 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 JP-A-2011-252065 can also be used.

The method for producing a color filter of the present invention comprises: step (A), applying (preferably coating) the colored composition described above to a substrate to form a colored layer (also referred to as a colored composition layer); and a step (B), the colored composition layer formed in the step (A) is cured.

The step of hardening is preferably (preferably, via a mask) exposed to a pattern, and the uncured portion of the coating film is developed and removed by a developer to form a colored region (colored pattern). By performing these steps, a coloring pattern containing pixels of three colors or four colors can be formed, and a color filter can be obtained. Further, in the method for producing a color filter of the present invention, it is particularly preferable to provide the following steps: step (C), irradiating the colored pattern formed in the step (B) with ultraviolet rays; and step (D), Step The colored pattern irradiated with ultraviolet rays in the step (C) is subjected to heat treatment.

According to the method described above, the difficulty in the process is small, and the color filter used in the liquid crystal display element or the solid-state imaging element can be manufactured with high quality and low cost.

Hereinafter, a method of producing the color filter of the present invention will be described more specifically.

-Step (A)-

In the method for producing a color filter of the present invention, first, the colored composition of the present invention described above is applied onto a substrate directly or via another layer by a desired coating method to form a coating containing the colored composition. The film (coloring composition layer) is then pre-hardened (pre-bake) as needed to dry the colored composition layer.

Examples of the substrate include an alkali-free glass, a soda glass, a Pyrex (registered trademark) glass, a quartz glass, and a substrate on which a transparent conductive film is adhered to the liquid crystal display element or the like, or a solid. A photoelectric conversion element substrate used in a photographic element or the like, for example, an fluorenone substrate or a plastic substrate. Further, a black matrix in which each pixel is isolated may be formed on the substrates, or a transparent resin layer may be provided for the purpose of promoting adhesion or the like. Further, an undercoat layer may be provided on the substrate as needed in order to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the surface.

Further, the plastic substrate preferably has a gas barrier layer and/or a solvent resistant layer on its surface.

In addition, a substrate for driving a thin film transistor (hereinafter referred to as a "TFT-based liquid crystal driving substrate") in which a thin film transistor (TFT) type color liquid crystal display device is disposed as a substrate can be used. ,to A coloring pattern using the colored composition of the present invention is also formed on the driving substrate to form a color filter.

Examples of the substrate in the TFT liquid crystal driving substrate include glass, anthrone, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimine. For these substrates, an appropriate pretreatment such as chemical treatment such as a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction, or vacuum vapor deposition may be performed in advance. For example, a substrate in which a passivation film such as a tantalum nitride film is formed on the surface of the TFT liquid crystal driving substrate can be used.

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

In the coating step, the method of applying the colored composition of the present invention to a substrate is not particularly limited, and is preferably a slit-and-spin method or a spinless coating method. A method of using a slit nozzle (hereinafter referred to as a slit nozzle coating method).

In the slit nozzle coating method, the slit, the spin coating method, and the non-spin coating method differ depending on the size of the coated substrate, and for example, the fifth-generation glass substrate is applied by a non-rotation coating method ( In the case of 1100 mm × 1250 mm), the discharge amount of the colored composition from the slit nozzle is usually from 500 μL/sec to 2000 μl/sec, preferably from 800 μL/sec to 1500 μL/sec. The coating speed is usually from 50 mm/sec to 300 mm/sec, preferably from 100 mm/sec to 200 mm/sec.

In addition, the solid composition of the colored composition used in the coating step is usually 10%. ~20%, preferably 13%~18%.

When the coating film obtained from the coloring composition of the present invention is formed on a substrate, the thickness of the coating film (after the prebaking treatment) is usually 0.3 μm to 5.0 μm, preferably 0.5 μm to 4.0 μm. Most preferably, it is 0.5 μm to 3.0 μm.

Further, in the case of a color filter for a solid-state imaging device, the thickness of the coating film (after the prebaking treatment) is preferably in the range of 0.5 μm to 5.0 μm.

In the application step, the prebaking treatment is usually performed after the application. Vacuum treatment may also be carried out prior to prebaking, as needed. In the vacuum drying condition, the degree of vacuum is usually from 0.1 torr to 1.0 torr, preferably from about 0.2 to about 0.5 torr.

Further, the prebaking treatment may be carried out using a hot plate, an oven or the like in a temperature range of 50 ° C to 140 ° C, preferably about 70 ° C to 110 ° C, for 10 seconds to 300 seconds. Further, high frequency processing or the like can be used in combination in the prebaking treatment. High frequency processing can also be used alone.

The prebaking conditions include the following conditions: heating at 70 ° C to 130 ° C for 0.5 minutes to 15 minutes using a hot plate or an oven.

Further, the thickness of the colored composition layer formed of the colored composition can be appropriately selected depending on the purpose. The color filter for a liquid crystal display device preferably has a range of 0.2 μm to 5.0 μm, more preferably 1.0 μm to 4.0 μm, and most preferably 1.5 μm to 3.5 μm. Further, in the color filter for a solid-state imaging device, it is preferably in the range of 0.2 μm to 5.0 μm, more preferably in the range of 0.3 μm to 2.5 μm, and most preferably in the range of 0.3 μm to 1.5 μm.

Further, the thickness of the colored composition layer is the film thickness after prebaking.

-Step (B)-

Then, in the method for producing a color filter of the present invention, the film (coloring composition layer) containing the colored composition formed on the substrate as described above is exposed through, for example, a photomask. The light or radiation that can be applied during exposure is preferably g-ray, h-ray, i-ray, j-ray, KrF light, ArF light, and particularly preferably i-ray. When the i-ray is used for the irradiation of light, it is preferably irradiated with an exposure amount of 100 mJ/cm ² to 10000 mJ/cm ² .

In addition, other exposure light can also be used: ultra-high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, visible and ultraviolet laser light sources, fluorescent lamps, Tungsten lamps, sunlight, etc.

Exposure step using a laser source

In the exposure mode using a laser light source, an ultraviolet laser is used as a light source.

The irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, and is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm in terms of the wavelength of the photoresist. In particular, it is particularly suitable for the third harmonic (355 nm) of the neodymium doped yttrium aluminum garnet (Nd:YAG) laser with a high power and relatively inexpensive solid laser. Molecular laser XeCl (308 nm), XeF (353 nm).

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 . When the exposure amount is in this range, it is preferable in terms of productivity in pattern formation.

The exposure apparatus is not particularly limited, and a commercially available exposure apparatus can be used by Callisto (V-Technology Co., Ltd.) or Egis (made by V Technology Co., Ltd.). Or DF2200G (made by Dainippon Screen (share)). In addition, devices other than the above are also suitable for use.

When manufacturing a color filter for a liquid crystal display device, it is preferable to use exposure by a proximity exposure machine or a mirror projection exposure machine, and mainly using h-rays and i-rays. Further, in the case of producing a color filter for a solid-state imaging device, it is preferable to use a stepper exposure machine, and mainly use i-rays. Further, when a color filter is manufactured using a TFT liquid crystal driving substrate, the photomask used can be used to form a via hole or a horseshoe in addition to a pattern for forming a pixel (colored pattern). a mask of a pattern of pits.

The colored composition layer exposed in the manner described can be heated.

Further, in order to suppress oxidative fading of the colored material in the colored composition layer, exposure may be performed while flowing nitrogen gas in the chamber.

Then, the exposed coloring composition layer is developed by a developing solution. Thereby, a negative or positive coloring pattern (resist pattern) can be formed. In the developing step, the uncured portion of the applied coating film is dissolved in the developing solution, and only the hardened portion remains on the substrate.

The developer may be any one that dissolves the coating film (coloring composition layer) of the coloring composition in the uncured portion, but does not dissolve the hardened portion. For example, a combination of various organic solvents or an aqueous alkaline solution can be used.

The organic solvent used in the development may, for example, be a solvent which can be used in the preparation of the colored composition of the present invention.

Examples of the alkaline aqueous solution include tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, benzyltrimethylammonium hydroxide, and sodium hydroxide. , potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, gall a basic compound such as a base, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene at a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass An alkaline aqueous solution obtained by dissolving in a range of % to 1% by mass. When the developer is an alkaline aqueous solution, the alkali concentration may preferably be adjusted so that the pH is 11 to 13, and preferably the pH is 11.5 to 12.5.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may 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.

The development may be any one of an immersion method, a shower method, a spray method, and the like, and a swing method, a rotation method, an ultrasonic method, or the like may be combined therein. The developed surface may be previously wetted with water or the like before contact with the developer to prevent development unevenness. Alternatively, the substrate may be tilted to perform development.

Further, in the case of producing a color filter for a solid-state imaging element, puddle development is also used.

After the development treatment, the rinsing treatment for washing and removing the remaining developer is carried out, and after drying, heat treatment (post-baking) is performed in order to complete the curing.

The rinsing treatment is usually carried out in pure water. In order to save the liquid, the following method may be used: pure water is used in the final washing, and the used pure water is used in the initial stage of washing, and the substrate may be washed by tilting the substrate. Or use the method of ultrasonic irradiation.

After the rinsing treatment, after water removal and drying, heat treatment at about 200 ° C to 250 ° C is usually carried out. This heat treatment (post-baking) can use a heating plate, a convection oven (hot air circulation dryer), a high-frequency heating machine or the like in a continuous manner or in a continuous manner for the coating film after development. It is carried out in batches.

By performing the above steps in sequence for each color in accordance with the required number of hue, a color filter in which a cured film (colored pattern) of a plurality of colors is formed can be produced.

The color filter of the present invention can be suitably used for a solid-state imaging device or a liquid crystal display device because of high contrast, small color density unevenness, and good color characteristics.

-Step (C)-

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

-Step (D)-

It is preferable to carry out heat treatment for the colored pattern which has been subjected to post-exposure by ultraviolet irradiation as described above. The colored pattern can be further hardened by heat-treating the formed colored pattern (so-called post-baking treatment). This heat treatment can be performed using, for example, a hot plate, various heaters, an oven, or the like.

The temperature during the heat treatment is preferably from 100 ° C to 300 ° C, particularly preferably from 150 ° C to 250 ° C. Further, the heating time is preferably from about 10 minutes to about 120 minutes.

The colored pattern obtained in the manner described constitutes a pixel in the color filter. In the production of a color filter having pixels of a plurality of hue, the step (A), the step (B), and the optional step (C) or the step are repeated as long as the number of colors required is repeated. D) Yes.

Further, the step (C) and/or the step (D) may be performed at the end of formation, exposure, and development of each of the monochromatic coloring composition layers (each color), or may be in a desired color amount. After the formation, exposure, and development of all the coloring composition layers are completed, the steps (C) and/or the step (D) are collectively performed.

Further, the coloring composition of the present invention can also be applied to a method of producing a color filter including a dry etching step. An example of such a manufacturing method may include a manufacturing method comprising the steps of: forming a coloring layer using the coloring composition of the present invention; a step of forming a photoresist layer on the colored layer; and exposing and developing a step of patterning the photoresist layer to obtain a photoresist pattern; and a step of dry etching the colored layer using the photoresist pattern as an etch mask. In the case where 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, and the thermosetting agent is preferably a compound having two or more epoxy groups in one molecule.

The color filter (color filter of the present invention) obtained by the method for producing a color filter of the present invention is excellent in hue and contrast because the coloring 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 imaging element. Particularly suitable for the use of liquid crystal display devices. In the case of use in a liquid crystal display device, a triarylmethane dye is used as a colorant to achieve a good hue, and image display having excellent spectral characteristics and contrast can be obtained.

The use of the coloring composition of the present invention is mainly described above for the purpose of forming a coloring pattern of a color filter, but it can also be applied to forming a coloring pattern (pixel) constituting a color filter. Isolated black matrix.

The black matrix on the substrate can be formed by using a coloring composition of a processed pigment containing a black pigment such as carbon black or titanium black, passing through various steps of coating, exposure, and development, followed by post-baking as needed.

[Liquid Crystal Display Device]

The liquid crystal display element and solid-state imaging element of the present invention comprise the color filter of the present invention. More specifically, for example, an alignment film is formed on the inner surface side of the color filter so as to face the electrode substrate, and the liquid crystal is filled in the gap portion to be sealed, thereby obtaining a panel which is a liquid crystal display element of the present invention. Further, for example, the solid-state imaging element of the present invention is obtained by forming a color filter on the light-receiving element.

The definition of the liquid crystal display device or the details of each display device is described in, for example, "Electronic display device (sasaki Sasaki, Industrial Research Association (share) issued in 1990)", "Display device (Ibuki Shunzhang, Industrial Book) ) issued in 1989) and so on. In addition, the liquid crystal display device is described in, for example, "Next-Generation Liquid Crystal Display Technology (Editor Uchida Natsuo, Industrial Research Association, Ltd., 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited, and can be applied to, for example, a plurality of types of liquid crystal display devices described in the "next-generation liquid crystal display technology".

Among them, the color filter of the present invention is particularly effective for a color TFT liquid crystal display device. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT Liquid Crystal Display (Kyoritsu Publishing Co., Ltd., 1996)". Furthermore, the present invention can also be applied to a liquid crystal display device having a wide viewing angle such as a horizontal electric field driving method such as In Plane Switching (IPS) or a pixel division method such as Multi-domain Vertical Alignment (MVA). , or Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optically Compensated Splay (OCS), Fringe Field Switching, FFS) and Reflective Optically Compensated Bend (R-OCB).

In addition, the color filter of the present invention is also available in a bright and high-definition Color-filter On Array (COA) mode.

When the color filter of the present invention is used for a liquid crystal display element, high contrast can be achieved when combined with a conventional three-wavelength tube of a cold cathode tube, and further, an LED light source of red, green, and blue can be used ( RGB-LED is used as a backlight to provide a liquid crystal display device having high luminance and high color reproducibility.

[Solid photographic element]

The colored composition of the present invention can also be preferably used for solid-state imaging elements. The configuration of the solid-state imaging device is not particularly limited as long as it is a configuration that functions as a solid-state imaging device, and the configuration of the color filter described above is not particularly limited. For example, the following configuration can be cited.

a plurality of photodiodes constituting a light receiving region of a solid-state imaging device (a CCD image sensor, a CMOS image sensor, etc.) and a transfer electrode including a polysilicon or the like on the support, the photodiode and the transfer The electrode has a light-shielding film containing tungsten or the like which is open only in the light-receiving portion of the photodiode, and has a device protective layer containing tantalum 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. Further, the color filter for a solid-state imaging device of the present invention is provided on the protective layer of the device.

Furthermore, it may be configured on the device protective layer and under the color filter (the side close to the support) to have a condensing element (for example, a microlens or the like; the same applies hereinafter) or on the color filter. It has a configuration of a concentrating element, and the like.

[Examples]

The present invention will be further specifically described below by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "%" and "parts" are quality standards unless otherwise stated.

<Synthesis Example 1>

(Synthesis of Compound I-2)

Compound I-2 was synthesized according to the following route.

[54]

(Synthesis of synthetic intermediate (Compound 3))

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

(Synthesis of synthetic intermediate (Compound 4))

Compound 3 (2.4 g (10 mmol)), and triethylamine 1.5 g (15 mmol) Dissolved in 10 mL of tetrahydrofuran (THF). After the solution was cooled to 0 ° C, 1.15 g (11 mol) of methacrylonitrile chloride was added dropwise. After confirming the completion of the reaction, the target product was extracted into an organic layer with 20 mL of ethyl acetate and water and brine, and then concentrated. This crude product was purified by column chromatography, whereby 1.8 g of Compound 4 (yield: 58%) was obtained.

(Synthesis of Compound I-2)

Compound 4 (1.9 g (5.8 mmol)), Compound 5 (1.8 g (5.8 mmol)), and 1.0 g (6.4 mmol) of phosphorus oxychloride were dissolved in 6 mL of toluene, and the mixture was warmed to 90 ° C and stirred for 1 hour. After confirming the completion of the reaction, 10 mL of ethyl acetate was added to the solution, and the target product was taken out as a supernatant, and the operation was repeated three times, and the compound 6 was taken out as an ethyl acetate solution. To the solution was added a solution of 2.0 g (7.0 mmol) of a separately adjusted bistrifluoromethanesulfonimide lithium salt in 20 mL of methanol. After confirming the completion of the salt exchange reaction, 50 mL of water was added, and the compound was extracted into an ethyl acetate layer and concentrated, and then purified by column chromatography to obtain the object compound I-2 (1.7 g (33%)).

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 liquid))

<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 (solid content conversion value: 8.5 parts by mass)

. The following photopolymerization initiator (V-3)...1.0 parts by mass

. The following solvent (X-1) ... 7.2 parts by mass

. The following solvent (X-2)...0.4 parts by mass

. The following surfactant (Z-1)...0.006 parts by mass

Triarylmethane dye (I-1): a compound of the following structure

Photopolymerizable compound (T-1): KAYARAD 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) of propylene glycol Monomethyl ether acetate solution (solid content: 40.0% by mass) Acid value (100 mg KOH/g)

Photopolymerization initiator (V-3): a lanthanide compound of 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 Chemical Industry Co., Ltd.)

<Example 2 to Example 27>

Coloration 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). Composition.

[化57]

[化58]

<Example 28>

A coloring 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 ) propylene glycol monomethyl ether acetate solution (solid content: 40.0% by mass) acid value (250 mg KOH / g)

<Example 29>

The alkali-soluble binder (U-1) used in Example 1 was changed to the following. A coloring composition was prepared in the same manner as in Example 1 except for the 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) of propylene glycol single Methyl ether acetate solution (solid content: 40.0% by mass) Acid value (125mgKOH/g)

Further, GMA-MAA indicates the following structure.

<Example 30>

A coloring composition was prepared in the same manner as in Example 1 except that the alkali-soluble binder (U-I) 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-phenyl maleimide (15/20/30/35 [mass ratio] copolymer (weight average molecular weight: 20,000) of propylene glycol monomethyl ether acetate solution (solid content: 40.0% by mass) acid value (110 mg KOH / g)

<Comparative Example 1>

The coloring composition was adjusted 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 WO2010-123071.

Comparative compound 1

<Comparative Example 2>

The coloring composition was adjusted 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 is Alkaline Blue 7)

<Production of Colored Film Using Colored Composition>

The obtained coloring composition was applied to a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) in an oven at 100 ° C in such a manner that the maximum absorbance at 600 nm to 700 nm was 1.5 to 2.0. After drying for 180 seconds, a colored film was formed on the substrate.

The obtained coloring film was subjected to the following evaluation.

<heat resistance>

After the coloring film was heated at 230 ° C for 40 minutes, the change in chromaticity, that is, the ΔEab value was measured. The ΔEab value was calculated from the UV-Vis spectrum before and after heating. The ΔEab value is small, indicating that the light resistance is excellent.

<Solvent resistance (chromaticity difference)>

The colored film which was heated at 230 ° C for 20 minutes was immersed in N-methylpyrrolidone (NMP) at 25 ° C for 10 minutes, and the chromaticity before and after immersion was measured to calculate an index of color change. Eab. The ΔEab value was calculated from the UV-Vis spectrum before and after heating. Further, when the value of ΔEab is 3 or less, the hue change is small and the solvent resistance is excellent.

<voltage retention rate>

The colored composition was applied to a glass substrate (trade name: 1737, manufactured by Corning Incorporated) having an ITO electrode so that the film thickness after drying became 2.0 μm, and dried (prebaked) in an oven at 90 ° C. second. Then, exposure to 100 mJ/cm ² (illuminance: 20 mW/cm ² ) was carried out without using a mask, and a 1% aqueous solution of an alkali developer (trade name: CDK-1, manufactured by Fujifilm Electronic Materials Co., Ltd.) was used. The development was carried out at 25 ° C, and the coated film which was washed with water and dried was subjected to heat treatment (post-baking) in an oven at 230 ° C for 30 minutes to form a colored cured film. Then, the substrate on which the colored cured film was formed and the substrate on which the ITO electrode was deposited only in a predetermined shape were bonded together with a sealant in which 5 μm of glass beads were mixed, and then injected between Merck by the substrate. Liquid crystal MJ971189 (trade name), making a liquid crystal cell.

Then, the liquid crystal cell was placed in a constant temperature layer of 70 ° C for 48 hours, and a liquid crystal voltage retention ratio measurement system VHR-1A (trade name) manufactured by Toyo Technica was used, and the following measurement conditions were used. The voltage holding ratio of the liquid crystal cell was measured and evaluated based on the score shown by the following reference. The higher the score, the better the voltage retention.

Measuring condition

. Distance between electrodes: 5μm~15μm

. Applied voltage pulse amplitude: 5V

. Applied voltage pulse frequency: 60Hz

. Applied voltage pulse width: 16.67msec

* Voltage holding ratio: liquid crystal cell potential difference after 16.7 milliseconds / value of voltage applied in 0 milliseconds

*Judgement

More than 90%: 5

85% or more and less than 90%: 4

More than 80% and less than 85%: 3

75% or more and less than 80%: 2

Less than 75%: 1

According to the results, in the present invention, heat resistance and solvent resistance can be provided. A coloring composition excellent in properties and voltage retention.

On the other hand, in the colored composition of the comparative example, heat resistance, solvent resistance, and voltage holding ratio were not good.

Claims (15)

A colored composition comprising a colorant and a polymerizable compound, the colorant comprising a triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2,000 or less, and a counter anion. The colored composition according to claim 1, wherein the triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2,000 or less is represented by the general formula (TP1) and/or the general formula (TP2). Indicates: In the general formula (TP1) and the formula (TP2), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group or an aryl group; and Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ and Rtp ₁₁ each independently represent a substitution. Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ₇₁ Rtp ₇₂ ; Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group or an aryl group; Rtp ₁₀ represents a hydrogen atom, an alkyl group or an aryl group; , b and c each independently represent an integer of 0 to 4; when a, b, and c are 2 or more, two of Rtp ₆ , Rtp _{7 ,} and Rtp ₈ may be linked to each other to form a ring; Rtp ₁ to Rtp _11. A crosslinkable group in any of Rtp ₇₁ and Rtp ₇₂ . The colored composition according to claim 1 or 2, wherein the relative anion is selected from the group consisting of: selected from the group consisting of a fluoride anion, a chloride anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, and a borate At least one of an anion, PF ^6- and SbF ^6- ; and a structure selected from the group consisting of -SO ₃ ^- , -COO ^- , -PO ₄ ^- , the following formula (A1) and the following formula (A2) At least one of the structures indicated; In the formula (A1), R ¹ and R ² each independently represent -SO ₂ - or -CO-; formula (A2) In the formula (A2), R ³ represents -SO ₂ - or -CO-; and R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO- or -CN. The colored composition according to claim 1 or 2, wherein the relative anion is contained in a compound having a crosslinkable group. The colored composition as described in claim 1 or 2, wherein The opposite anion is included in the repeating unit. The colored composition according to claim 1, wherein the triarylmethane structure having a crosslinkable group and a cation and having a molecular weight of 2000 or less is represented by the formula (TP1A) or the formula (TP2A); In the general formula (TP1) and the formula (TP2), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group or an aryl group; and Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ and Rtp ₁₁ each independently represent a substitution. Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ₇₁ Rtp ₇₂ ; Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group or an aryl group; Rtp ₁₀ represents a hydrogen atom, an alkyl group or an aryl group; , b and c each independently represent an integer of 0 to 4; when a, b, and c are 2 or more, two of Rtp ₆ , Rtp _{7 ,} and Rtp ₈ may be linked to each other to form a ring; Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ have a crosslinkable group; at least one of Rtp ₁ to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ may be substituted by the general formula (P); 5] In the formula (P), L represents a single bond or a divalent linking group, and X ^{1 is} selected from a group selected from the group consisting of -SO ₃ ^- , -COO ^- , -PO ₄ ^- and a structure represented by the following formula (A1) And at least one of a group including a structure represented by the following formula (A2); In the formula (A1), R ¹ and R ² each independently represent -SO ₂ - or -CO-; In the formula (A2), R ³ represents -SO ₂ - or -CO-; and R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO- or -CN. The coloring composition as described in claim 1 or 2, further comprising a photopolymerization initiator. For the coloring composition as described in claim 1 or 2, Forming a colored layer of a color filter. A colored cured film obtained by curing the colored composition according to any one of the first to eighth aspects of the invention. A color filter comprising the colored hardening film according to claim 9 of the patent application. A method of producing a color filter, comprising: a step of applying a colored composition according to any one of claims 1 to 8 to a support to form a colored composition layer; 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. A method of producing a color filter, comprising: applying a colored composition according to any one of claims 1 to 8 to a support to form a colored composition layer, and curing is performed to form a colored composition layer a step of forming a photoresist layer; a step of forming a photoresist layer on the colored layer; a step of patterning the photoresist layer by exposure and development to obtain a photoresist pattern; or using the photoresist pattern as an etch mask a cover, the step of dry etching the colored layer. A color filter manufactured by the method of producing a color filter according to the eleventh or twelfth aspect of the patent application. A solid-state photographic element comprising the color filter of claim 10 of the patent application. An image display device comprising the color filter of claim 10 of the patent application.