TW201536873A - Colored composition, cured film, color filter, method for manufacturing color filter, solid-state imaging device, and image display device - Google Patents

Abstract

The invention provides a colored composition, a cured film, a color filter, a manufacturing method for color filter, a solid-state imaging element and an image display device. The colored composition can form a colored layer with high luminance and excellent solvent resistance when forming a colored layer of color filter etc. The colored composition includes: a salt compound including a dye cation and a divalent or polyvalent anion, a solvent dissolving 1.0 mass% or more of the salt compound under 25 DEG C, and at least one purple colorant selected form xanthene pigment, pyrromethene pigment and tetraazaporphyrin. The dye cation further has 1 to 20 triarylmethane pigment structures in one molecule.

Description

Coloring composition, cured film, color filter, color filter Manufacturing method, solid-state imaging element, and image 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 device, and an image display device.

Coloring for the production of color filters that can be used in liquid crystal display devices or solid-state imaging devices (Charge Coupled Devices (CCD), Complementary Metal-Oxide Semiconductor (CMOS), etc.) One of the methods of the composition is known as a pigment dispersion method.

This pigment dispersion method is a method in which a color filter is produced by dispersing a pigment in various photosensitive compositions, and a color filter is produced by photolithography. Since it is patterned by the photolithography method, it is considered to be suitable for producing a color filter having high positional accuracy, large screen, and high definition. When a color filter is produced by a pigment dispersion method, a coloring composition is applied by a spin coater or a roll coater to form a coating film, and the coating film is exposed and developed to form a colored pattern. And This operation is repeated for each color, whereby a color filter can be obtained.

In recent years, color filters have a tendency to be used for liquid crystal display devices (Liquid Crystal Display (LCD)) as follows: not only for monitors but also for use in televisions (TVs). Along with the tendency to expand the use, color filters are required to have high color characteristics in terms of chromaticity, contrast, and the like. In addition, color filters for use in image sensors (solid-state imaging devices) are also required to further improve color characteristics such as reduction in color unevenness and improvement in color resolution.

In order to sufficiently satisfy the chromaticity requirements in recent years, a technique in which a dye is used in place of a pigment previously used as a coloring agent has been developed (for example, Patent Document 1 to Patent Document 3). In the color filter having a blue hue, a technique in which a triarylmethane dye is used as a color material has been proposed (for example, Patent Document 4 to Patent Document 6).

Further, a method of multimerizing a triarylmethane dye to insolubilize it has also been proposed (Patent Document 7).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent No. 3,875, 751 (Japanese Patent Laid-Open No. Hei 6-230210)

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

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-86375

[Patent Document 4] International Publication WO2011/162217 Manual

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2011-70171

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2011-116802

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2013-57053

When a dye is used as a coloring agent, since it is easily dissolved in a solvent compared with a pigment, solvent resistance tends to be unpreferable. Since the dye develops in a molecular state, the dye molecules can move freely in the film to some extent even after the coating film is hardened. Therefore, for example, when another color resist or a protective film is repeatedly applied onto the coating film, there is a tendency that the dye is easily eluted into other colored layers or protective layers applied thereafter, and as a result, sometimes formed Undesirable color layer.

In particular, in the liquid crystal display device, in addition to the elution of the dye by the reverse coating of the other color resist or the protective film, when the LCD panel is formed, there is a possibility that the dye component is eluted into the liquid crystal. In this case, the insulating property of the liquid crystal layer is liable to be lowered by the dye to be eluted.

In order to solve these problems, for example, in the technique described in Patent Document 7, it is difficult to obtain a good hue because the triarylmethane dye is insolubilized and the color of the dye in a molecular state is lost.

The present invention has been made in view of the above circumstances. In other words, an object of the present invention is to provide a coloring composition capable of forming a coloring layer having high luminance and excellent solvent resistance when forming a coloring layer such as a color filter. Further, an object of the present invention is to provide a cured film, a color filter, a method for producing the same, and a solid-state imaging device and an image display device including the color filter and capable of displaying good image quality.

As a result of intensive studies based on the above-described situation, the inventors of the present invention have found that a coloring composition having high brightness and excellent solvent resistance can be obtained by using the following coloring composition, and the present invention has been completed. The composition includes a salt compound containing a dye cation and a divalent or higher anion, a solvent which dissolves 1.0% by mass or more of the salt compound at 25 ° C, and a specific purple colorant.

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

<1> A coloring composition comprising: a salt compound containing a dye cation and a divalent or higher anion; a solvent for dissolving 1.0% by mass or more of the salt compound at 25 ° C; and a dye selected from the group consisting of xanthene pigment and pyrrole methylene a purple colorant of at least one of a pigment and a porphyrazine coloring matter; and the dye cation has one to 20 triarylmethane dye structures in one molecule.

<2> The coloring composition according to <1>, wherein the dye cation is represented by the general formula (A1) or the general formula (A2);

In the general formula (A1), Ar ⁺ each independently represents a triarylmethane dye structure, L ¹ represents a group in which two or more Ar ^{+ are} bonded, n1 represents an integer of 1 to 20, and m represents 0 or 1; when n1 represents At 1 o'clock, m represents 0;

In the general formula (A2), Ar ⁺ each independently represents a triarylmethane dye structure, L ² independently represents a divalent linking group, L ³ represents a divalent linking group, and q represents an integer of 1-18.

<3> The colored composition according to <1> or <2>, wherein the purple coloring agent contains the xanthene dye represented by the following general formula (I-1a) and is represented by the following general formula (II) At least one of a pyrrolethymethylene dye and a porphyrazine coloring matter represented by the following formula (III);

In the formula (I-1a), R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. The -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O-, -CO- or -NR ¹¹ -; and R ¹ and R ² may be bonded to each other to form a ring containing a nitrogen atom. R ³ and R ⁴ may be bonded to each other to form a ring containing a nitrogen atom; R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ ; R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 6 carbon atoms; and m 1 represents an integer of 0 to 5. When m1 is 2 or more, a plurality of R ^5A may be the same or different, and m2 and m3 each independently represent an integer of 0 to 3. When m2 and m3 are independently 2 or 3, respectively, a plurality of R ^5B and R ^5C are independent, different or different; a represents 0 or 1; when a represents 0, any one of xanthene pigment structures The base contains an anion; X ^- represents an anion; Z ⁺ represents N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ^{11 's} may be the same or different; R ⁸ represents a monovalent carbon number of 1-20 a saturated hydrocarbon group, wherein a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom; and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having a carbon number of 1 to 20, in the saturated aliphatic hydrocarbon group The -CH ₂ - contained may be substituted by -O-, -CO-, -NH- or -NR ⁸ -, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3-membered ring to a 10-membered ring containing a nitrogen atom. Ring; R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms;

In the formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent; and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, or an aromatic group. Base or heterocyclic group;

In the formula (III), all of Z ¹ , Z ² , Z ³ and Z ⁴ represent a nitrogen atom, or both of Z ¹ and Z ³ , Z ² and Z ⁴ represent a nitrogen atom, and the other group Represents CR, R independently represents a hydrogen atom, an alkyl group, or an aryl group; A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ each independently represent an alkyl group or an alkenyl group. , aryl, alkoxy, alkylthio, aryloxy, arylthio, halogen atom, hydroxy, alkoxycarbonyl, aryloxycarbonyl, amine, aminemethanyl, amine sulfonyl, fluorenyl a decyloxy group, a cyano group, a nitro group or a heterocyclic group; A ¹ and A ² , A ³ and A ⁴ , A ⁵ and A ⁶ , and A ⁷ and A ⁸ may be bonded to each other to form a ring structure, but At least one group does not form a ring structure; M represents a divalent metal atom, or a divalent atom or atom group as a substituted metal atom.

The colored composition according to any one of <1> to <3> wherein the dye cation contains a triarylmethane dye structure represented by the following formula (TP1), and is represented by the following formula ( At least one of the triarylmethane dye structures represented by TP2);

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

The colored composition according to any one of <1> to <4> wherein the dye cation has a crosslinkable group.

The colored composition according to any one of <1> to <5> wherein the divalent or higher anion has -SO ₃ ^- , -COO ^- , -PO ₄ ^- , and contains the following formula ( B2) a group of the structure represented by or a group containing a structure represented by the following formula (B3);

In the formula (B2), R ¹¹ and R ¹² each independently represent -SO ₂ - or -CO-;

In the formula (B3), R ¹³ represents -SO ₂ - or -CO-; and R ¹⁴ and R ¹⁵ each independently represent -SO ₂ -, -CO- or -CN.

<7> The coloring composition according to any one of <1> to <6> which further comprising selected from Pigment Blue 1, Pigment Blue 2, Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15: 2. Pigment blue 15:3, pigment blue 15:4, pigment blue 15:6, pigment blue 16, pigment blue 22, pigment blue 60, pigment blue 64, pigment blue 66, pigment blue 79, pigment blue 80 and pigment green At least one of Cl of 7 becomes OH.

The colored composition according to any one of <1> to <7> which further comprises a binder resin, a polymerizable compound, and a photopolymerization initiator.

<9> The coloring composition according to any one of <1> to <8> which is used for forming a coloring layer of a color filter.

<10> A cured film formed by curing the colored composition according to any one of <1> to <9>.

<11> A color filter using the coloring composition according to any one of <1> to <9>.

<12> A method of producing a color filter, comprising: a step of applying a coloring composition according to any one of <1> to <9> to a support to form a colored composition layer; a step of exposing the layer to a pattern; and developing the unexposed portion to form a colored pattern.

<13> A solid-state imaging element comprising the color filter according to <11> or a color filter obtained by the method of producing a color filter according to <12>.

<14> An image display device comprising the color filter according to <11> or a color filter obtained by the method for producing a color filter according to <12>.

According to the present invention, it is possible to provide a coloring composition which is excellent in brightness and excellent in solvent resistance. Further, a cured film using the colored composition, a color filter, a method of producing a color filter, a solid-state imaging device, and a liquid crystal display device can be provided.

Hereinafter, the contents of the present invention will be described in detail. In addition, in the specification of the present application, "~" is used in the meaning of including the numerical values described before and after the lower limit and the upper limit.

In the present specification, the total solid content refers to the total mass of the components after the solvent is removed from the total composition of the coloring composition.

In the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). 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 "radiation" in the present specification means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (Extreme Ultraviolet (EUV) light), an X-ray, an electron beam, or the like. Further, in the present invention, light means actinic rays or radiation.

The "exposure" in this specification refers to exposure by a mercury lamp, a far-ultraviolet light represented by a quasi-molecular laser, X-rays, EUV light, etc., using a beam of electron beams or ion beams, unless otherwise specified. The depiction made is also included in the exposure.

In the present specification, "(meth)acrylate" means either or both of acrylate and methacrylate, and "(meth)acrylic group" means both an acryl group and a methacryl group. One, "(meth)acryloyl" means acrylonitrile and A Either or both of the acryl groups.

In addition, in this specification, "single quantity" and "monomer" have the same meaning.

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 means a group which 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, Ph represents a phenyl group, and AC represents an ethyl group.

In the present specification, the term "step" means not only an independent step, but even if it cannot be clearly distinguished from other steps, it is included in the term as long as the intended effect of the step is achieved.

The weight average molecular weight in the present invention means any one measured by gel permeation chromatography (GPC) unless otherwise specified.

In the present specification, the total solid content refers to the total mass of the components after the solvent is removed from the total composition of the composition. The solid component in the present invention is a solid component at 25 °C.

[Coloring composition]

The colored composition of the present invention (hereinafter also referred to as a composition of the present invention) is characterized by comprising a salt compound containing a dye cation and a divalent or higher anion; and dissolving 1.0% by mass or more of the salt compound at 25 ° C Solvent; and selected from 呫 A purple colorant of at least one of a ton dye, a pyrrolemethylene pigment, and a porphyrazine coloring matter; and the dye cation has one to 20 triarylmethane dye structures in one molecule.

By adopting such a configuration, it is possible to provide a colored composition having high brightness and excellent solvent resistance. Although the mechanism is inferred, it is difficult to use a dye compound containing a dye cation having a triarylmethane dye structure and a divalent or higher anion as compared with a case where a dye compound in which a dye cation and an anion are monovalent to each other is used. The solvent is eluted in the liquid crystal when the other colored layer or the protective layer is formed in the LCD panel, so that the solvent resistance is improved. In particular, it is possible to effectively suppress elution of the dye into the liquid crystal when the LCD panel is formed. Therefore, it is possible to suppress a decrease in insulation of the liquid crystal layer and to improve electrical characteristics. Further, by dissolving the salt compound in a solvent, higher brightness can be obtained as compared with, for example, the case where the dye is subjected to lake formation.

Further, by using a purple coloring agent selected from at least one of a xanthene dye, a pyrrolemethylene dye, and a porphyrazine coloring matter in combination with the salt compound, light resistance can be improved. It can be considered that it absorbs the excitation energy of the excited triarylmethane dye cation in the form of fluorescence based on the purple colorant, while mitigating the excited triarylmethane dye cation.

<salt compound>

The salt compound contained in the composition of the present invention contains a dye cation and a divalent or higher anion.

<<Dye cation>>

The dye cation has 1 to 20 triarylmethane pigments in one molecule. Structure. The number of the triarylmethane dye structure in one molecule of the dye cation is preferably from 1 to 4, more preferably 2 or 3. With such a configuration, the solvent solubility of the salt compound used in the present invention can be further improved. Therefore, the salt compound used in the present invention can be suitably used, for example, as a color material for a color resist. The dye cation may also have a crosslinkable group. The crosslinkable group will be described later.

The dye cation preferably contains at least one of a triarylmethane dye structure represented by the following formula (TP1) and a triarylmethane dye structure represented by the following 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, an aryl group or a group having a crosslinkable group; Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ And Rtp ₁₁ each independently represents a substituent. Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group, a group having a crosslinkable group or NRtp ₇₁ Rtp ₇₂ . Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group, an aryl group or a group having a crosslinkable group. Rtp ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or a group having a crosslinkable group. a, b, and c each independently represent an integer of 0 to 4. When a, b, and c are 2 or more, Rtp ₅ and Rtp ₆ and Rtp ₈ and Rtp ₉ may be linked to each other to form a ring.

In the formula (TP1), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group or a group having a crosslinkable group.

In the formula (TP1), 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. Examples of the substituent which the alkyl group may have include the substituents listed in the substituent group A which will be described 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. Examples of the substituent which the aryl group may have include the substituents listed in the substituent group A which will be described later.

The group having a crosslinkable group may contain only a crosslinkable group, and may contain a linking group in addition to the crosslinkable group. In particular, the group having a crosslinkable group is preferably a group represented by -L ⁰ -P ⁰ . Here, L ⁰ represents a single bond or a divalent linking group, and P ¹ represents a crosslinkable group.

As the crosslinkable group, a crosslinkable group which can be crosslinked by a radical, an acid or 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 (meth)acrylic acid. At least one of a group, a styryl group, a vinyl group and an allyl group is more preferably at least one selected from the group consisting of a (meth)acryl group, a styryl group and a vinyl group, and more preferably a (meth)acryl group. And styrene. The cyclic ether group is preferably, for example, an epoxy group or an oxetanyl group, and more preferably an epoxy group.

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-. And -CONR-, -OC-, -SO-, -SO ₂ - and a combination of two or more of these. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

In particular, the divalent linking group is preferably an alkylene 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, still more preferably from 5 to 20, and particularly preferably from 5 to 10. Specifically, a methylene group, an ethylidene group, a propyl group, a butyl group, a hexyl group, a heptenyl group, a cyclopentenyl group, a cyclohexylene group or the like is preferable.

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

In the formula (TP1), Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group, a group having a crosslinkable 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 chain, and a cyclic chain, but is preferably linear. Examples of the substituent which the alkyl group may have include the substituents listed in the substituent group A which will be described 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, more preferably from 1 to 6. The alkyl group may be any of a linear chain, a branched chain, and a cyclic chain, but is preferably a linear chain or a branched chain. Branch shape. The alkyl group is preferably unsubstituted. Examples of the substituent which the alkyl group may have include the substituents listed in the substituent group A which will be described 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.

The group having a crosslinkable group has the same meaning as the group having a crosslinkable group in Rtp ₁ to Rtp ₄ in the above formula (TP1), and the preferred range is also the same.

In the formula (TP1), Rtp ₅ , Rtp ₆ and Rtp ₈ each independently represent a substituent. The substituent which is listed in the item of the substituent group A mentioned later is mentioned as a substituent. In particular, a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, a carboxyl group or a sulfo group is preferred, and a carbon number is more preferred. It is a linear or branched alkyl group of 1 to 5, an alkenyl group having 1 to 5 carbon atoms, a phenyl group, a group having a crosslinkable group or a carboxyl group. In particular, Rtp ₅ and Rtp _{6 are} preferably independently an alkyl group having 1 to 5 carbon atoms. Further, Rtp _{8 is} preferably such that two alkenyl groups are bonded to each other to form a ring. The ring is preferably a benzene ring.

The group having a crosslinkable group has the same meaning as the group having a crosslinkable group in Rtp ₁ to Rtp ₄ in the above formula (TP1), and the preferred range is also the same.

In the formula (TP1), a, b and c each independently represent an integer of 0 to 4, and 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 formula (TP2), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group or a group having a crosslinkable group, and have the same meanings as Rtp ₁ to Rtp ₄ in the formula (TP1). The preferred range is also the same. The group having a crosslinkable group has the same meaning as the group having a crosslinkable group in Rtp ₁ to Rtp ₄ in the above formula (TP1), and the preferred range is also the same.

In the formula (TP2), Rtp ₅ and Rtp ₆ each independently represent a substituent, and the meaning thereof is the same 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 substituent group A which will 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 still more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group is preferably linear or branched, and more preferably linear.

In the formula (TP2), Rtp ₁₀ represents a substituent, and a substituent exemplified in the group of the substituent group A described later or a group having a crosslinkable group can be used. In particular, Rtp _{10 is more} preferably an aryl group having 6 to 12 carbon atoms, and still more preferably a phenyl group. The group having a crosslinkable group has the same meaning as the group having a crosslinkable group in Rtp ₁ to Rtp ₄ in the above formula (TP1), and the preferred range is also the same.

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

In the triarylmethane dye structure, the cations are delocalized as follows, and the following structures have the same meanings, and are included in the present invention. Further, the cationic moiety may be located at any position in the molecule, but is preferably located on the nitrogen atom. If it is substituted on a nitrogen atom, there is a tendency that the color is further improved.

Substituent group A:

The substituent may, for example, be a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group or an aryloxy group. , decyloxy, heterocyclooxy, decyloxy, amine methoxycarbonyl, amine (including alkylamino, anilino), decylamino, aminocarbonylamino, alkoxycarbonylamine , aryloxycarbonylamino, amine sulfonylamino, alkylsulfonylamino or arylsulfonylamino, fluorenyl, alkylthio, arylthio, heterocyclic thio, amine sulfonium Alkyl, sulfo, alkylsulfinyl or arylsulfinyl, alkylsulfonyl or arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, amidyl, aryl Alkylazo or heterocyclic azo, oximine, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, decylalkyl and the like. The details will be described below.

a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably having a carbon number of 1 to 30) An alkyl group such as methyl, ethyl, n-propyl, isopropyl, a third butyl group, an n-octyl group, a 2-chloroethyl group, a 2-cyanoethyl group, a 2-ethylhexyl group, a cycloalkyl group (preferably a substituted or unsubstituted carbon number of 3 to 30) Examples of the cycloalkyl group include a cyclohexyl group, a cyclopentyl group, and a polycycloalkyl group. Examples thereof include a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having a carbon number of 5 to 30, for example, a bicyclo [ a polycyclic structure of 1,2,2]heptan-2-yl, bicyclo[2,2,2]oct-3-yl) or tricycloalkyl. Preferably, a monocyclic cycloalkyl group, a bicycloalkyl group, particularly preferably a monocyclic cycloalkyl group, a linear or branched alkenyl group (a linear or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms) , for example, vinyl, allyl, isoprenyl, geranyl, oleyl), cycloalkenyl (preferably substituted or unsubstituted cycloalkenyl having 3 to 30 carbon atoms, for example A 2-cyclopenten-1-yl group, a 2-cyclohexen-1-yl group, a polycycloalkenyl group, for example, a bicycloalkenyl group (preferably a substituted or unsubstituted bicyclic ring having a carbon number of 5 to 30) is preferable. Alkenyl group, for example, bicyclo[2,2,1]hept-2-en-1-yl, bicyclo[2,2,2]oct-2-en-4-yl) or tricycloalkenyl, especially preferably single Ring cycloolefin , alkynyl (preferably substituted or unsubstituted alkynyl having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethyldecyl ethynyl), aryl (preferably carbon number) a substituted or unsubstituted aryl group of 6 to 30, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanylaminophenyl, or a heterocyclic group (preferably 5) a substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group of a member to 7 members, more preferably a ring constituent atom selected from the group consisting of a carbon atom, a nitrogen atom and a sulfur atom. And a heterocyclic group having at least one hetero atom of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a 5-membered or 6-membered aromatic heterocyclic group having a carbon number of 3 to 30. For example, 2- Furanyl, 2-thienyl, 2- Pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano, hydroxy, nitro, carboxy, alkoxy (preferably substituted or unsubstituted with 1 to 30 carbon atoms) Substituted alkoxy groups, such as methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy, aryloxy (preferably carbon number) a substituted or unsubstituted aryloxy group of 6 to 30, such as phenoxy, 2-methylphenoxy, 2,4-di-p-pentylphenoxy, 4-tert-butylbenzene An oxy group, a 3-nitrophenoxy group, a 2-tetradecylaminophenoxy group, a decyloxy group (preferably a decyloxy group having a carbon number of 3 to 20, such as a trimethyldecyloxy group, a third butyl dimethyl decyloxy group, a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, preferably a heterocyclic group) The heterocyclic moiety described in, for example, 1-phenyltetrazole-5-oxyl, 2-tetrahydropyranyloxy), decyloxy (preferably methyloxy), having a carbon number of 2 to 30 Substituted or unsubstituted alkylcarbonyloxy group, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as methyl methoxy, ethoxylated , trimethylacetoxy, stearyloxy, benzhydryloxy, p-methoxyphenylcarbonyloxy), amine methoxycarbonyl (preferably substituted with 1 to 30 carbon atoms) Or unsubstituted amine methyl methoxy group, such as N,N-dimethylamine methyl methoxy, N,N-diethylamine methyl methoxy, morpholinylcarbonyloxy, N,N-di - n-octylaminocarbonyloxy, N-n-octylaminemethyloxy), alkoxycarbonyloxy (preferably substituted or unsubstituted alkoxycarbonyl having 2 to 30 carbon atoms) An oxy group such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a third butoxycarbonyloxy group, an n-octylcarbonyloxy group, or an aryloxycarbonyloxy group (preferably having a carbon number of 7~) 30 substituted or unsubstituted aryloxycarbonyloxy group, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, Orthogonal An oxyphenoxycarbonyloxy group, an amine group (preferably an amine group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number of 6 to 30) Substituted arylamino group, heterocyclic amine group having a carbon number of 0 to 30, such as an amine group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group , N-1,3,5-triazin-2-ylamino), mercaptoamine (preferably a mercaptoamine group, a substituted or unsubstituted alkylcarbonyl group having 1 to 30 carbon atoms) A substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, a decylamino group, an ethyl decylamino group, a trimethyl ethylamino group, a lauryl amide group , benzhydrylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted or unsubstituted having a carbon number of 1 to 30) Aminocarbonylamino group, such as amine carbylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, morpholinylcarbonylamino), alkoxy a carbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having a carbon number of 2 to 30, such as a methoxycarbonylamino group, an ethoxy group) a carbonylamino group, a third butoxycarbonylamino group, a n-octadecyloxycarbonylamino group, an N-methyl-methoxycarbonylamino group, an aryloxycarbonylamino group (preferably having a carbon number of 7~) a substituted or unsubstituted aryloxycarbonylamino group of 30, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m-octyloxyphenoxycarbonylamino), sulfonamide An amine group (preferably a substituted or unsubstituted sulfonylamino group having a carbon number of 0 to 30, such as an aminesulfonylamino group, an N,N-dimethylaminosulfonylamino group, N-n-octylaminosulfonylamino), alkylsulfonylamino or arylsulfonylamino (preferably substituted or unsubstituted alkylsulfon having a carbon number of 1 to 30) Mercaptoamine group, substituted or unsubstituted with 6 to 30 carbon atoms a substituted arylsulfonylamino group, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino , p-methylphenylsulfonylamino), fluorenyl, alkylthio (preferably substituted or unsubstituted alkylthio having a carbon number of 1 to 30, such as methylthio, ethylthio, positive Hexadecanethio), arylthio (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio) a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, and the heterocyclic ring is preferably a heterocyclic moiety described in the heterocyclic group, for example, 2 a benzothiazolylthio group, a 1-phenyltetrazol-5-ylthio group, an amine sulfonyl group (preferably a substituted or unsubstituted sulfonyl group having a carbon number of 0 to 30, such as N) -ethylamine sulfonyl, N-(3-dodecyloxypropyl)amine sulfonyl, N,N-dimethylamine sulfonyl, N-acetyl sulfonyl, N- Benzomethanesulfonyl, N-(N'-phenylaminecarbamimidino)sulfonyl), sulfo, alkylsulfinyl or arylsulfinyl (preferably carbon number) For the 1~30 Alken or unsubstituted alkylsulfinyl, 6 to 30 substituted or unsubstituted arylsulfinyl, such as methylsulfinyl, ethylsulfinyl, phenylsulfin Mercapto, p-methylphenylsulfinyl), alkylsulfonyl or arylsulfonyl (preferably substituted or unsubstituted alkylsulfonyl having a carbon number of 1 to 30, 6 ~30 substituted or unsubstituted arylsulfonyl, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), mercapto (preferably) a substituted or unsubstituted alkylcarbonyl group having a carbon number of 2 to 30, a substituted or unsubstituted arylcarbonyl group having a carbon number of 7 to 30, such as an ethylene group or a trimethyl group Sulfhydryl, 2-chloroethylidene, hard a sulfhydryl group, a benzhydryl group, a p-octyloxyphenylcarbonyl group, an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having a carbon number of 7 to 30, such as a phenoxy group) a carbonyl group, an o-chlorophenoxycarbonyl group, a m-nitrophenoxycarbonyl group, a p-tert-butylphenoxycarbonyl group, an alkoxycarbonyl group (preferably a substituted or unsubstituted carbon number of 2 to 30) Alkoxycarbonyl group, such as methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, n-octadecyloxycarbonyl group, amine mercapto group (preferably substituted or not having a carbon number of 1 to 30) Substituted amine mercapto group, for example, amine methyl sulfonyl, N-methylamine methyl fluorenyl, N,N-dimethylamine carbhydryl, N,N-di-n-octylamine fluorenyl, N -(methylsulfonyl)amine methyl hydrazide), arylazo or heterocyclic azo (preferably substituted or unsubstituted aryl azo, carbon having a carbon number of 6 to 30, carbon a substituted or unsubstituted heterocyclic azo group of 3 to 30 (the heterocyclic moiety is preferably a heterocyclic moiety illustrated in the heterocyclic group), for example, phenylazo, p-chlorophenyl Nitrogen, 5-ethylthio-1,3,4-thiadiazol-2-ylazo, quinone imine (preferably having a carbon number of 2 to 30) a substituted or unsubstituted quinone imine group, such as N-succinimide, N-phthalimine, a phosphino group (preferably a substituted or unsubstituted carbon number of 2 to 30) a phosphino group, such as a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group, a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having a carbon number of 2 to 30, For example, a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group, a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having a carbon number of 2 to 30) , for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino (preferably substituted or unsubstituted phosphinylamine having 2 to 30 carbon atoms) Base, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), A decyl group (preferably a substituted or unsubstituted decyl group having a carbon number of 3 to 30, such as a trimethyl decyl group, a tert-butyldimethyl decyl group, a phenyl dimethyl decyl group).

Specific examples of the triarylmethane dye structure are listed below, but the present invention is not limited to these specific examples.

The dye cation is preferably represented by the formula (A1) or the formula (A2).

In the general formula (A1), Ar ⁺ each independently represents a triarylmethane dye structure, L ¹ represents a group in which two or more Ar ^{+ are} bonded, n1 represents an integer of 1 to 20, and m represents 0 or 1; when n1 represents At 1 o'clock, m represents 0.

In the formula (A1), Ar ⁺ represents a triarylmethane dye structure, and its meaning is the same as that of the triarylmethane dye, and the preferred range is also the same.

When the triarylmethane dye structure is represented by the formula (TP1), the bonding position of the triarylmethane dye structure to L ¹ is any one of Rtp ₁ to Rtp ₈ , Rtp ₇₁ and Rtp ₇₂ , preferably Rtp ₇₁ or Rtp ₇₂ . Further, when the triarylmethane dye structure is represented by the formula (TP2), the bonding position of the triarylmethane dye structure to L ¹ is any one of Rtp ₁ to Rtp ₆ and Rtp ₉ to Rtp ₁₁ , preferably ( Rtp ₉ ~Rtp ₁₁ ).

In the formula (A1), L ¹ represents a group in which two or more Ar ^{+ are} bonded. L ¹ is a divalent or higher linking group, and preferably a divalent to hexavalent linking group.

L ^{1 is} preferably a hydrocarbon group, a heterocyclic group, -O-, -S-, -CO-, -NR-, -CONR-, -OC-, -SO-, or a combination of two or more of these. Base. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Further, the hydrocarbon group may be any of a linear chain, a branched chain or a cyclic chain. The carbon number of the hydrocarbon group is preferably from 1 to 30, more preferably from 1 to 18, and still more preferably from 1 to 12. The hydrogen atom contained in the hydrocarbon group may be substituted by a halogen atom. As the halogen atom, a fluorine atom is preferred.

When the hydrocarbon group is an aliphatic hydrocarbon group, the carbon number is preferably from 1 to 20, more preferably from 1 to 10. When the hydrocarbon group is an aromatic hydrocarbon group, the carbon number is preferably from 6 to 24, more preferably from 6 to 12.

The heterocyclic group preferably contains a nitrogen atom as a hetero atom. The heterocyclic group is preferably a 3-membered ring to an 8-membered ring, more preferably a 6-membered ring.

In particular, L ^{1 is} preferably an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 1 to 30 carbon atoms, or a group containing a combination of these.

For example, when L ¹ represents a divalent linking group, an alkylene group having a carbon number of 1 to 30 (methylene group, ethylidene group, trimethylene group, propyl group, butyl group, etc.), carbon The number of 6 to 30 exoaryl (phenyl, naphthyl, etc.), heterocyclic, -CH=CH-, -O-, -S-, -CO-, -NR-, -CONR-, - OC-, -SO-, or a combination of two or more of these. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

The carbon number of the alkylene group having 1 to 30 carbon atoms is preferably from 1 to 20, more preferably from 1 to 10. When the alkylene group having 1 to 30 carbon atoms has a substituent, a halogen atom may be mentioned as a substituent.

The heterocyclic group preferably contains a nitrogen atom as a hetero atom. The heterocyclic group is preferably a 3-membered ring to an 8-membered ring, more preferably a 6-membered ring.

The carbon number of the aryl group having a carbon number of 6 to 30 is preferably 6 to 24, more preferably 6 to 12.

Further, from the viewpoint of heat resistance, it is also preferred that L ¹ contains a cyclic aliphatic hydrocarbon group or an aromatic group. The carbon number of the cyclic aliphatic hydrocarbon group is preferably from 3 to 8, more preferably from 4 to 6. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. The carbon number of the aromatic group is preferably from 6 to 12, more preferably from 6 to 10.

It is preferred that the conjugated system is not contained in the bonding site of L ¹ and Ar ⁺ . By not including a conjugated system in the bonding sites of L ¹ and Ar ⁺ , formation of a conjugated system between Ar ⁺ and L ¹ can be suppressed, and the hue change of the triarylmethane dye can be effectively suppressed.

The formula of the L ¹ moiety in one molecule of the dye cation is preferably from 14 to 800, more preferably from 50 to 200.

Specific examples of L ¹ include the following structures, but the present invention is not limited to these structures. In the following structure, * represents a linking site with Ar ⁺ in the general formula (A1), and a represents an integer of 1 or more.

In the formula (A1), n1 represents an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 2 to 4, still more preferably 2 or 3. With such a configuration, the solvent solubility of the salt compound used in the present invention can be improved.

In the formula (A1), m represents 0 or 1. When n1 represents 1, m represents 0, that is, L ¹ does not exist.

In the general formula (A2), Ar ⁺ each independently represents a triarylmethane dye structure, L ² represents a divalent linking group, L ³ represents a divalent linking group, and q represents an integer of 1-18.

In the formula (A2), Ar ⁺ represents a triarylmethane dye structure, and its meaning is the same as Ar ⁺ in the formula (A1), and the preferred range is also the same.

In the formula (A2), L ² represents a divalent linking group, and the meaning thereof is the same as in the case where L ¹ in the formula (A1) represents a divalent linking group, and the preferred range is also the same.

In the formula (A2), L ³ represents a divalent linking group, and the meaning thereof is the same as in the case where L ¹ in the formula (A1) represents a divalent linking group, and the preferred range is also the same.

In the formula (A2), q represents an integer of 1 to 18, preferably an integer of 1 to 10, more preferably an integer of 1 to 3.

Specific examples of the dye cations are listed below, but are not limited to these specific examples. In the general formula (A1), a specific example of the structure of the triarylmethane dye is exemplified as a specific example in which n1 represents 1.

The molecular weight of the dye cation is preferably from 1,000 to 10,000, more preferably from 1,000 to 5,000.

<<Anion above two valence>>

The divalent or higher anion may be present as another molecule without being bonded to the dye cation via a covalent bond, or may be in the same molecule as the dye cation.

The divalent or higher anion constituting the salt compound of the present invention is not particularly limited, but preferably contains -SO ₃ ^- , -COO ^- , -PO ₄ ^- and contains a compound represented by the following formula (B2). The group of the structure or at least one of the groups having a structure represented by the following formula (B3) is more preferably -SO ₃ ^- and/or a group having a structure represented by the formula (B2). Further, the divalent or higher anion preferably has a fluorine atom.

The salt compound of the present invention may contain only one divalent or higher anion, or may contain two or more kinds.

General formula (B2)

In the formula (B2), R ¹¹ and R ¹² each independently represent -SO ₂ - or -CO-, and preferably at least one of R ¹¹ and R ¹² represents -SO ₂ -, more preferably R ¹¹ and R ¹² both represent -SO ₂ -.

The group having a structure represented by the formula (B2) is preferably a compound of the formula (B2), and one of R ¹¹ and R ¹² has a fluorine-substituted alkyl group at the terminal, more preferably one of R ¹¹ and R ¹² . Directly bonded to the fluorine-substituted alkyl group. The carbon number of the fluorine-substituted alkyl group is preferably from 1 to 10, more preferably from 1 to 6, more preferably from 1 to 3, still more preferably 1 or 2, particularly preferably 1. More preferably, the alkyl group is a perfluoroalkyl group. A specific example of the fluorine-substituted alkyl group is preferably a trifluoromethyl group.

In the formula (B3), R ¹³ represents -SO ₂ - or -CO-, and R ¹⁴ and R ¹⁵ each independently represent -SO ₂ -, -CO- or -CN.

In the general formula (B3), preferably at least one of R ¹³ ~ R ¹⁵ represents -SO ₂ -, more preferably represents at least two of R ¹³ ~ R ¹⁵ is -SO ₂ -.

The group having a structure represented by the formula (B3) is preferably a compound of the formula (B3), and at least one of R ¹³ to R ¹⁵ has a fluorine-substituted alkyl group at the terminal, more preferably R ¹³ to R ^{15 .} At least either of them is directly bonded to a fluorine-substituted alkyl group. In particular, it is preferred that at least two of R ¹³ to R ¹⁵ have a fluorine-substituted alkyl group at the terminal end. The meaning of the fluorine-substituted alkyl group is the same as that described for the group containing the structure represented by the general formula (B2), and the preferred range is also the same.

The divalent or higher anion is preferably an anion represented by the following formula (B1).

In the formula (B1), k represents an integer of 2 to 20; p represents 0 or 1; R represents a divalent to k-valent organic group; A represents a divalent linking group; and X ^- represents -SO ₃ ^- , -COO ^- , -PO ₄ ^- , a group containing a structure represented by the formula (B2) or a group containing a structure represented by the formula (B3).

In the general formula (B1), R is an organic group which represents a k-valent, and examples thereof include the following organic groups (a) to (e). Among these, an organic group of (a) or (c) is preferred.

(a) substituted or unsubstituted non-aromatic hydrocarbon groups

(b) a group in which a plurality of substituted or unsubstituted polyvalent aromatic hydrocarbon groups are bonded by a divalent linking group containing a hetero atom

(c) substituted or unsubstituted aromatic hydrocarbon group

(d) a group in which two substituted or unsubstituted aromatic hydrocarbon groups are bonded by a divalent linking group containing a hetero atom or a divalent non-aromatic hydrocarbon group.

(e) substituted or unsubstituted heterocyclic group

The non-aromatic hydrocarbon group in the organic group of the above (a) is preferably an aliphatic hydrocarbon group, and may be any of a linear chain, a branched chain or a cyclic chain. In particular, an alkylene group having a carbon number of 1 to 10 is preferred. When the non-aromatic hydrocarbon group has a substituent, the substituent is preferably a halogen atom (particularly a fluorine atom). Examples of the case where the non-aromatic hydrocarbon group has a substituent include an alkylene group having 1 to 10 carbon atoms which is substituted by a fluorine atom.

The number of atoms of the non-aromatic hydrocarbon group constituting (a) is preferably from 1 to 40, more preferably from 1 to 20.

Specific examples of the organic group (a) include the following specific examples, but the present invention is not limited to the specific examples. In the following structure, * represents a linking site with A or X ^- in the formula (B1).

The non-aromatic hydrocarbon group in the organic group of the above (b) is preferably an aliphatic hydrocarbon group, and may be any of a linear chain, a branched chain or a cyclic chain. When the non-aromatic hydrocarbon group has a substituent, examples of the substituent include a polymerizable group (for example, a (meth) acrylonitrile group or a vinyl group). Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfurogen. Son and so on.

The divalent linking group containing a hetero atom is preferably -O-, -N-, -S-, -CO-, or a group containing the combination with the alkylene group.

The number of atoms of the organic group constituting (b) is preferably from 6 to 100, more preferably from 8 to 60.

Specific examples of the (b) non-aromatic hydrocarbon group include the following specific examples, but the present invention is not limited to these specific examples. In the following structure, * represents a linking site with A or X ^- in the formula (B1).

The aromatic hydrocarbon group in the organic group of the above (c) is preferably an extended aryl group. The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 12. The aromatic hydrocarbon group may be a single ring or a polycyclic ring.

The number of atoms of the organic group constituting (c) is preferably from 6 to 60, more preferably from 6 to 30.

Specific examples of the organic group of (c) include the following specific examples, but the present invention is not limited to these specific examples. In the following structure, * represents a linking site with A or X ^- in the formula (B1).

The aromatic hydrocarbon group in the organic group of the above (d) has the same meaning as the aromatic hydrocarbon group of the above (c).

Examples of the hetero atom of the divalent linking group containing a hetero atom in the organic group of (d) include an oxygen atom, a nitrogen atom, and a sulfur atom. The divalent linking group containing a hetero atom has the same meaning as the divalent linking group containing a hetero atom in the organic group of the above (b). The divalent non-aromatic hydrocarbon group may, for example, be a non-aromatic hydrocarbon group in the organic group of the above (a).

The number of atoms of the organic group constituting (d) is preferably from 6 to 60, more preferably from 6 to 50.

Specific examples of the organic group of (d) include the following specific examples, but the present invention is not limited to these specific examples. In the following structure, * represents a linking site with A or X ^- in the formula (B1).

The heterocyclic group in the organic group of (e) may be an aromatic heterocyclic group or a non-aromatic heterocyclic group. The hetero atom contained in the heterocyclic group is preferably a nitrogen atom. The heterocyclic group is preferably a 3-membered ring to an 8-membered ring, and more preferably a 4-membered ring to a 6-membered ring. The number of carbon atoms constituting the heterocyclic group is preferably from 2 to 6.

The number of atoms of the organic group constituting (e) is preferably from 6 to 50, more preferably from 6 to 30.

Specific examples of the organic group of (e) include the following specific examples, but the present invention is not limited to these specific examples. In the following structure, * represents a linking site with A or X ^- in the formula (B1).

In the formula (B1), the divalent linking group represented by A is preferably an alkyl group, an aryl group, a heterocyclic group, -CH=CH-, -O-, -S-, -C(= O)-, -CO-, -NR-, -CONR-, -OC-, -SO-, -SO ₂ - and a combination of two or more of these.

Specific examples of the divalent or higher anion are listed below, but are not limited to these specific examples.

The weight average molecular weight (Mw) of the salt compound used in the present invention is preferably 1,000 or more and 10,000 or less, more preferably 1,000 or more and 7,500 or less, and particularly preferably 1,000 or more and 6,000 or less. Although the Mw is changed to 10,000 or less depending on the structure of the dye cation and the type of the anion, the solvent solubility of the salt compound can be further improved. Further, by setting Mw to 1,000 or more, electrical characteristics can be further improved.

The content of the salt compound in the composition of the present invention 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 composition of the present invention. These salt compounds may be used alone or in combination of two or more.

<Solvent for dissolving 1.0% by mass or more of the salt compound at 25 ° C>

The colored composition of the present invention contains a solvent which dissolves 1.0% by mass or more of the salt compound at 25 °C. By dissolving the salt compound in such a solvent When used as a color material of a color filter, the dye is easily dispersed in a molecular state, and a good hue and high brightness can be obtained.

The solubility of the salt compound in the solvent is preferably 3.0% by mass or more, and more preferably 5.0% by mass or more at 25 °C. Further, the upper limit of the solubility of the salt compound with respect to the solvent is usually 50% by mass or less at 25 °C. When the solubility of the salt compound with respect to the solvent satisfies the above range, the storage stability at the time of producing the colored composition and the precipitation of the dye in the color filter producing step can be more effectively suppressed.

The solvent is preferably an organic solvent such as an ester, an ether, a ketone or an aromatic hydrocarbon from the viewpoint of a resist for a color filter.

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyric acid. Ethyl ester, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (for example: methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically, Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate, 2 - alkyl oxypropionates, methyl 2-oxy-2-methylpropanoate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvic acid Propyl ester, ethyl acetate methyl acetate, ethyl acetate ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

Examples of the ethers include diethylene glycol dimethyl ether, cyclohexyl acetate, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve. Acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate Ester, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.

Examples of the ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.

Examples of the aromatic hydrocarbons include toluene, xylene, and the like.

As a solvent which satisfies the requirement of dissolving 1.0% by mass or more of the salt compound at 25 ° C and a coloring composition for a color filter, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, butyl acetate, 3-methoxy propyl Methyl ester, 2-heptanone, cyclohexanone, cyclohexyl acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

It is also preferable to mix two or more kinds of these organic solvents from the viewpoint of the solubility of each component in the coloring composition, the improvement of the coating surface, and the like. In this case, a mixed solvent containing two or more kinds of the above solvents is preferred, and diethylene glycol ethyl methyl ether and propylene glycol methyl ether acetate are more preferred.

The content of the solvent which dissolves 1.0% by mass or more of the salt compound at 25 ° C is preferably such that the total solid content concentration in the composition of the present invention becomes 10% by mass to 30% by mass, more preferably the composition of the present invention. The total solid content concentration in the product was changed to an amount of 10% by mass to 20% by mass. The solvent for dissolving 1.0% by mass or more of the salt compound at 25 ° C may be used alone or in combination of two or more. When two or more solvents which dissolve 1.0% by mass or more of the salt compound at 25 ° C are used in combination, it is preferred that the total is in the above range.

<purple colorant>

The composition of the present invention contains the salt compound and a purple coloring agent selected from at least one of a xanthene dye, a pyrrolemethylene dye, and a porphyrazine coloring matter. With such a configuration, the brightness and contrast of the formed colored cured film can be effectively improved. The purple colorant is preferably dissolved in a solvent which dissolves 1.0% by mass or more of the salt compound at 25 °C.

The total amount of the purple colorant in the composition of the present invention is preferably from 1% by mass to 90% by mass, and more preferably from 5% by mass to 80% by mass based on the total amount of the salt compound. The purple coloring agent may be used alone or in combination of two or more.

Hereinafter, the xanthene dye, the pyrrolemethylene dye, and the porphyrazine coloring matter will be described.

<<呫 tons of pigment>>

The xanthene dye is a dye containing a compound having a xanthene skeleton in the molecule. The xanthene pigment is preferably dissolved in an organic solvent. The xanthene pigment is preferably, for example, a solubility of propylene glycol monomethyl ether acetate of 1% by mass or more, and more preferably 3% by mass or more.

The xanthene dye is preferably a dye containing a compound represented by the formula (I-1a) (hereinafter sometimes referred to as "compound (1a)"). Compound (1a) can also be a tautomer thereof. When the compound (1a) is used, the content of the compound (1a) in the xanthene dye is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. In particular, as the xanthene dye, it is preferred to use only the compound (1a).

General formula (I-1a)

In the formula (I-1a), R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. The -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O-, -CO- or -NR ¹¹ -; and R ¹ and R ² may be bonded to each other to form a ring containing a nitrogen atom. R ³ and R ⁴ may be bonded to each other to form a ring containing a nitrogen atom; R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ .

R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 6 carbon atoms; and m 1 represents an integer of 0 to 5. When m1 is 2 or more, a plurality of R ^{5 's} may be the same or different; m 2 and m 3 each independently represent an integer of 0 to 3. When m2 and m3 are independently 2 or 3, respectively, a plurality of R ⁶ and R ⁷ are independent, different or different; a represents 0 or 1; when a represents 0, any one of xanthene pigment structures The base contains an anion; X ^- represents an anion; Z ⁺ represents N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ^{11 's} may be the same or different; R ⁸ represents a monovalent carbon number of 1-20 a saturated hydrocarbon group, wherein a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom; and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having a carbon number of 1 to 20, in the saturated aliphatic hydrocarbon group The -CH ₂ - contained may be substituted by -O-, -CO-, -NH- or -NR ⁸ -, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3-membered ring to a 10-membered ring containing a nitrogen atom. Ring; R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ include a phenyl group, a tolylmethyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butyl group. Phenyl and the like. Among them, tolylene group, xylyl group, mesityl group, propylphenyl group, particularly tolylmethyl group and xylyl group are preferable, and among them, 2,6-dimethylphenyl group is preferable.

Examples of the substituent which the aromatic hydrocarbon group may have include a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ -, -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, - CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ . The Among these, as a substituent group, is preferably _{-SO 3 -, - SO 3 H} , -SO 3 - Z + and -SO ₂ NR ⁹ R ^10, more preferably -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ . As -SO ₃ ^- Z ^{+ in} this case, -SO ₃ ^- N ⁺ (R ¹¹ ) _{4 is} preferable. By using R ¹ to R ⁴ as such a group, it is possible to form a color filter having less generation of foreign matter and more excellent heat resistance from the coloring composition of the present invention containing the compound (1a).

Examples of the ring formed by bonding R ¹ and R ^{2 to} each other and the ring formed by bonding R ³ and R ^{4 to} each other include the following.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁸ to R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a decyl group. a linear alkyl group such as a fluorenyl group, a decyl group, a hexadecyl group or a hexyl group; a branched alkyl group such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group or a 2-ethylhexyl group; An alicyclic saturated hydrocarbon group having a carbon number of 3 to 20, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group.

Among them, preferred are methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, particularly preferably propyl, isopropyl, butyl. , hexyl, 2-ethylhexyl.

The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.

Examples of -OR ⁸ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and two. Decoxy and the like. Among them, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are preferred.

Examples of the -CO ² R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a third butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group. Among them, a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group are preferred.

Examples of -SR ⁸ include a methylthio group, an ethylthio group, a butylthio group, a hexylthio group, a mercaptothio group, and a decylthio group.

Examples of -SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and a decylsulfonyl group.

Examples of -SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a third butoxysulfonyl group, a hexyloxysulfonyl group, and Oxysulfonyl and the like.

Examples of -SO ₂ NR ⁹ R ¹⁰ include an aminesulfonyl group; N-methylaminesulfonyl group, N-ethylaminesulfonyl group, N-propylaminesulfonyl group, and N-isopropyl group; Aminesulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-tert-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentyl Aminesulfonyl, N-(1-ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl Aminesulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(2,2-dimethylpropyl)amine sulfonyl, N-(1-methylbutyl)amine sulfonate Mercapto, N-(2-methylbutyl)amine sulfonyl, N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl , N-(1,3-dimethylbutyl)amine sulfonyl, N-(3,3-dimethylbutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(1 -Methylhexyl)aminesulfonyl, N-(1,4-dimethylpentyl)aminesulfonyl, N-octylaminesulfonyl, N-(2-ethylhexyl)aminesulfonyl N-substituted aminesulfonyl group such as N-(1,5-dimethyl)hexylaminesulfonyl, N-(1,1,2,2-tetramethylbutyl)aminesulfonyl; N , N-dimethylamine sulfonyl, N,N-ethylmethylamine sulfonyl, N,N-Diethylamine sulfonyl, N,N-propylmethylamine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-tert-butylmethylamine sulfonate N,N-N-butylethylamine sulfonyl, N,N-bis(1-methylpropyl)amine sulfonyl, N,N-heptylmethylamine sulfonyl, etc. N,N- 2 substituted amine sulfonyl and the like.

Among them, preferred are N-methylamine sulfonyl, N-ethylamine sulfonyl, N-propylamine Sulfonyl, N-isopropylaminesulfonyl, N-butylaminesulfonyl, N-pentylaminesulfonyl, N-(2-ethylhexyl)aminesulfonyl, more preferably N - Methylamine sulfonyl, N-ethylamine sulfonyl, N-propylamine sulfonyl, N-butylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl.

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

R ^{5 is} preferably -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -CO ₂ NHR ⁹ , -SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H, -SO ₂ R ⁸ or -SO ₂ NHR ⁹ , more preferably -SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H or -SO ₂ NHR ⁹ .

M1 is preferably an integer of 1 to 4, more preferably 1 or 2.

R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 6 carbon atoms, and the alkyl group exemplified in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is 1 to 6 carbon atoms. alkyl.

M2 and m3 each independently represent an integer of 0 to 3, preferably 0.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

a represents 0 or 1, and when a represents 0, any one of the xanthene dye structures has an anion, and R ^5A preferably contains an anion.

Xanthene dye cation corresponding to the general formula (I-1a) represented by the valence contained contained X ^-, usually a monovalent or divalent, preferably a monovalent. The anion X ^- may, for example, be a fluorine anion, a chloride anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion or the like or a low nucleophilic anion, and is preferably a fluoride anion, a chloride anion, a bromine anion or an iodine anion. The low nucleophilic anion means an anion structure in which an organic acid having a pKa lower than the pKa of sulfuric acid is dissociated. Examples of the anion include the low nucleophilic anion described in paragraph 0075 of JP-A-2007-310315, and the anion described in paragraphs 0016 to 0025 of JP-A-2012-173399. An anion portion or the like described in paragraphs 0025 to 0033 of JP-A-2013-037316, the contents of which are incorporated herein by reference.

Z ⁺ is N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably N ⁺ (R ¹¹ ) ₄ .

N ⁺ (R ¹¹ ) _{4 is} preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms in at least two of the four R ¹¹ groups. Further, the total carbon number of the four R ¹¹ is preferably from 20 to 80, more preferably from 20 to 60. When N ⁺ (R ¹¹ ) ₄ is present in the compound (1a), by R ^{11 being such a} group, formation of foreign matter from the coloring composition of the present invention containing the compound (1a) produces less color filter sheet.

In the xanthene dye represented by the formula (I-1a), the cations are not delocalized as follows, and the following structures have the same meanings, and are included in the present invention. Further, the cationic moiety may be located at any position in the molecule, but is preferably located on the nitrogen atom.

The compound (1a) is preferably a compound represented by the formula (I-2a) (hereinafter sometimes referred to as "compound (2a)"). Compound (2a) may also be a tautomer thereof.

In the formula (I-2a), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may be bonded to each other to form a ring containing a nitrogen atom.

R ²⁵ represents -SO ₃ -, -SO ₃ H, -SO ₃ ^- Z ¹⁺ or -SO ₂ NHR ²⁶ .

M4 represents an integer from 0 to 5. When m4 is 2 or more, a plurality of R ^25s may be the same or different.

A1 represents an integer of 0 or 1. When a represents 0, any one of the xanthene dye structures contains an anion; X1 ^- represents an anion.

R ²⁶ represents a monovalent saturated hydrocarbon group having a carbon number of 1 to 20.

Z ¹⁺ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , and four R ^{27 's} may be the same or different.

R ²⁷ represents a monovalent saturated hydrocarbon group or a benzyl group having a carbon number of 1 to 20.

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ has the same meaning as those exemplified as the aromatic hydrocarbon group of R ¹ to R ⁴ in the formula (I-1a). The hydrogen atom contained in the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms may be replaced by -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ¹⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ .

R ²¹ and R ²³ are each a hydrogen atom, and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having a carbon number of 6 to 10, and the aromatic hydrocarbon group is contained in the combination of R ²¹ to R ²⁴ . The hydrogen atom is replaced by -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ¹⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ . More preferably, R ²¹ and R ²³ are a hydrogen atom, R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having a carbon number of 6 to 10, and a hydrogen atom contained in the aromatic hydrocarbon group is derived from -SO ₃ ^- Z ¹⁺ or -SO ₂ NHR ^{26 is} substituted. With such a configuration, R ²¹ to R ²⁴ can form a color filter which is more excellent in heat resistance from the colored composition of the present invention containing the compound (2a).

Examples of the nitrogen atom-containing ring formed by bonding R ²¹ and R ^{22 to} each other and the nitrogen atom-containing ring formed by bonding R ²³ and R ^{24 to} each other include R ¹ in the formula (I-1a). The same ring formed by bonding R ^{2 to} each other is preferably an aliphatic heterocyclic ring. Examples of the aliphatic heterocyclic ring include the following.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ has the same meaning as those exemplified as the saturated hydrocarbon group in R ⁸ to R ¹¹ .

When R ²¹ to R ²⁴ represent -R ²⁶ , -R ^{26 is} preferably independently methyl or ethyl, respectively. Further, -SO ₃ R ²⁶ and -SO ₂ NHR ²⁶ in R ^26, is preferably a branched chain alkyl group having a carbon number of 3 to 20, more preferably branched chain alkyl group having a carbon number 6 to 12 More preferably, it is 2-ethylhexyl. By R ²⁶ being such a group, a color filter which can form a foreign matter from the coloring composition of the present invention containing the compound (2a) can be produced less.

A1 represents 0 or 1, and when a1 represents 0, any one of the xanthene dye structures has an anion, and R ²⁵ preferably contains an anion.

X1 ^- is contained in the valence of the cation contained in the xanthene dye represented by the general formula (I-2a), and is usually monovalent or divalent, preferably monovalent. Examples of the anion X ^-, X with the meaning of general formula (I-1a) ^- the same as the preferred ranges are also the same.

Z ¹⁺ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ²⁷ ) ₄ . As ⁺ N(R ²⁷ ) ₄ , at least two of the four R ²⁷ are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ²⁷ is preferably from 20 to 80, more preferably from 20 to 60. When ⁺ N(R ²⁷ ) ₄ is present in the compound (2a), if R ^{27 is such a} group, the coloring composition of the present invention containing the compound (2a) can form a foreign matter to produce less color filter. sheet.

M4 is preferably from 1 to 4, more preferably 1 or 2.

In addition, as the compound (1a), a compound represented by the formula (I-3a) (hereinafter sometimes referred to as "compound (3a)") is also preferred. Compound (3a) can also be a tautomer thereof.

General formula (I-3a)

In the formula (I-3a), R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted by an alkoxy group having 1 to 3 carbon atoms, and the -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be -O-, -CO- or -NR ¹¹ - substituted.

R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms or an alkylsulfonyl group having 1 to 4 carbon atoms.

R ³¹ and R ³³ may be bonded to each other to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be bonded to each other to form a ring containing a nitrogen atom.

p and q each independently represent an integer of 0 to 5. When p is 2 or more, a plurality of R ³³ may be the same or different. When q is 2 or more, a plurality of R ³⁴ may be the same or different.

R is the same in (. 1A) R ¹¹ meaning as in formula ^11.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³¹ and R ³² include a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms as described in R ⁸ in the formula (1a). A monovalent saturated hydrocarbon group having a carbon number of 1 to 10. Among them, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a 2-ethylhexyl group are preferred. The aromatic hydrocarbon group having 6 to 10 carbon atoms which may be used as a substituent may be a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms as described for R ¹ in the formula (1a).

The alkoxy group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may, for example, be a methoxy group, an ethoxy group or a propoxy group.

R ³¹ and R ³² are each independently a monovalent saturated hydrocarbon group having a carbon number of 1 to 3.

Examples of the alkyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a second butyl group, and a third butyl group. Wait. Among them, a methyl group, an ethyl group, and a propyl group are preferred.

Examples of the alkylthio group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and an isopropylthio group.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropyl group. Kesulfonyl and the like.

p and q are preferably an integer of 0 to 2, preferably 0 or 1.

The compound (1a) is, for example, a compound represented by the compound (1-1) to the compound (1-43). Further, in the following structure, R represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, more preferably 2-ethylhexyl group.

Examples of the xanthene dye include CI acid red 51 (hereinafter, the description of CI acid red is omitted, only the number is described. Others are the same), 52, 87, 92, 94, 289, 388, CI acidity Acid violet 9, 30, 102, CI basic red 1 (rhodamine 6G), 2, 3, 4, 8, CI alkaline red 10 (rhodamine B), 11, CI alkaline Basic violet 10, 11, 25, CI solvent red 218, CI red (reddant red) 27, CI reactive red (reactive red) 36 (Bengal rose red B), sulforhodamine G, The xanthene dye described in Japanese Laid-Open Patent Publication No. 2010-32999, and the xanthene dye described in Japanese Patent No. 4492760.

As the xanthene dye, a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink R-H/C" manufactured by Sino-foreign Chemicals Co., Ltd., and "Rhodamin 6G" manufactured by Takooka Chemical Industry Co., Ltd.) can be used. In addition, a commercially available xanthene dye can also be used as a starting material, and it is also referred to Japanese Patent Laid-Open No. 2010-32999. The contents can be incorporated into the specification of the present application.

The xanthene pigment may be used alone or in combination of two or more. When two or more xanthene dyes are used in combination, it is preferred that the total amount satisfies the above range.

<<pyrromethene pigment>>

The pyrrolethymethylene dye is preferably a dipyrromethene-based metal-substituted compound in which a compound represented by the formula (I) is bonded to a metal atom or a metal compound.

In the formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group.

In the general formula (II), when R ¹ to R ⁶ represent a monovalent substituent, the substituent in the substituent group A may be exemplified as the monovalent substituent. When the monovalent substituent is a further substitutable group, it may be further substituted by any of the above groups. Further, when there are two or more substituents, the substituents may be the same or different.

In the formula (II), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ may be bonded to each other independently to form a ring of 5 members, 6 members or 7 members. . Examples of the ring to be formed include a saturated ring or an unsaturated ring. Examples of the saturated ring or the unsaturated ring of the five members, six members, or seven members include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, and a pyrrole. The pyridine ring, the piperidine ring, the cyclopentene ring, the cyclohexene ring, the benzene ring, the pyridine ring, the pyrazine ring, and the pyridazine ring are preferably a benzene ring or a pyridine ring.

Further, when the formed ring of 5 members, 6 members, and 7 members is a further substitutable group, it may be substituted by any of the substituent groups A, and when substituted by 2 or more substituents, These substituents may be the same or different.

The preferred range of the meaning of R ⁷ in the formula (II) is the same as the case where the R ¹ to R ⁶ are a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and the preferred range is also the same.

In the formula (II), R ¹ and R ^{6 are} preferably an alkylamino group, an arylamino group, a carboguanamine group, a ureido group, a guanidino group, an alkoxycarbonylamino group or a sulfonylamino group. More preferably, it is a carbenium group, a ureido group, an alkoxycarbonylamino group, a sulfonylamino group, and more preferably a carboguanamine group, a ureido group, an alkoxycarbonylamino group or a sulfonylamino group, particularly preferably Carboguanamine, urea group.

In the formula (II), R ² and R ^{5 are} preferably an alkoxycarbonyl group, an aryloxycarbonyl group, an aminecarbenyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group or a quinone imine group. An alkalyl sulfonyl group, more preferably an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, an alkyl sulfonyl group, a nitrile group, a quinone imine group, an amine carbaryl sulfonyl group, and the like Preferred is alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, nitrile, oxime imido, amine mercaptosulfonyl, particularly preferably alkoxycarbonyl, aryloxycarbonyl, aminecarboxamido .

In the formula (II), R ³ and R ^{4 are} preferably an alkyl group, an aryl group or a heterocyclic group, preferably an alkyl group or an aryl group.

In the general formula (II), when R ³ and R ⁴ represent an alkyl group, the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and examples thereof include: Base, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, and benzyl. Further, a branched or cyclic alkyl group having a carbon number of 1 to 12 is more preferable, and examples thereof include an isopropyl group, a cyclopropyl group, an isobutyl group, a tert-butyl group, a cyclobutyl group, and a cyclopentyl group. Cyclohexyl. Further, a secondary or tertiary alkyl group having 1 to 12 carbon atoms is preferred, and examples thereof include an isopropyl group, a cyclopropyl group, an isobutyl group, a tert-butyl group, a cyclobutyl group, and a cyclohexyl group.

In the formula (II), when R ³ and R ⁴ represent an aryl group, the aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

When R ³ and R ⁴ represent a heterocyclic group, as the heterocyclic group, a 2-thienyl group, a 4-pyridyl group, a 3-pyridyl group, a 2-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl or benzotriazol-1-yl, more preferably 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl or 1-pyridyl.

Next, a metal atom or a metal compound which forms a dipyrromethene-based metal-substituted compound will be described.

As the metal or metal compound, any metal atom or metal compound, including a divalent metal atom, a divalent metal oxide, or a divalent metal hydroxide, may be used as long as it is a metal atom or a metal compound capable of forming a complex. Or a divalent metal chloride. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., also includes AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ , metal chloride such as GeCl ₂ , metal oxide such as TiO or VO, metal hydroxide such as Si(OH) ₂ .

Among these, from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and manufacturing suitability of the complex, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, and preferably, Cu, Ni, Co, TiO, B, or VO, more preferably Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO, particularly preferably Fe, Zn, Cu, Co, B, or VO (V=O). Among them, Zn is particularly preferred.

In the dipyrromethene-based metal-substituted compound in which the compound represented by the formula (II) is bonded to a metal atom or a metal compound, a preferred embodiment is shown below. That is, the following formula: In the formula (II), R ¹ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a decyl group, a hydroxyl group, a cyano group, or an alkoxy group. Alkyl, aryloxy, heterocyclic oxy, fluorenyl, alkoxycarbonyl, aminemethanyl, amine, anilino, heterocyclic amine, carboguanyl, ureido, quinone, alkoxy Alkylcarbonylamino, aryloxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, arylsulfonyl, or phosphinium The amine group means that R ² and R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group or a heterocyclic ring. Oxyl, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, aminemethionyl, quinone imine, alkoxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or an amine sulfonyl group, wherein R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic ring. Base, fluorenyl, hydroxy, cyano, Oxyl, aryloxy, heterocyclic oxy, fluorenyl, alkoxycarbonyl, aminemethanyl, anilino, carboguanamine, ureido, oxime imido, alkoxycarbonylamino, sulfonium sulfonate Amino, azo, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, arylsulfonyl, sulfonyl, or phosphinylamino, R ⁷ is represented by a hydrogen atom A halogen atom, an alkyl group, an aryl group or a heterocyclic group is represented by a metal atom or a metal compound represented by Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO.

A more preferred form of the dipyrromethene-based metal-substituted compound is shown below. That is, the following formula: In the formula (II), R ¹ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a decyl group or an alkoxycarbonyl group. , amidyl, amine, heterocyclic amine, carboguanamine, ureido, oxime imido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, azo, Alkylsulfonyl, arylsulfonyl, or phosphinylamino, R ² and R ⁵ are each independently derived from alkyl, alkenyl, aryl, heterocyclyl, cyano, nitro, fluorenyl , alkoxycarbonyl, aryloxycarbonyl, aminemethantyl, quinone imine, alkylsulfonyl, arylsulfonyl, or aminesulfonyl, wherein R ³ and R ⁴ are independently hydrogen Atom, alkyl, alkenyl, aryl, heterocyclic, cyano, decyl, alkoxycarbonyl, amine carbaryl, carbamide, ureido, quinone, alkoxycarbonyl A sulfonylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or an aminesulfonyl group, wherein R ⁷ is a hydrogen atom, a halogen atom, an alkyl group, Aryl or heterocyclic group, metal atom or metallization The compound is represented by Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B or VO.

A preferred form of the dipyrromethene-based metal-substituted compound in which the compound represented by the formula (II) is bonded to a metal atom or a metal compound is The wrong compound represented by the formula (II-1), the formula (II-2) or the formula (II-3).

In the formula (II-1), R ¹ to R ⁶ each independently represent a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Ma represents a metal atom or a metal compound, X ¹ represents a group which can be bonded to Ma, and X ² represents a group required to neutralize the charge of Ma. Further, X ¹ and X ² may be bonded to each other to form a ring of 5 members, 6 members, or 7 members.

The same general formula R (II-1) ¹ ~ R in the meaning of general formula (II) ⁶ in R ¹ ~ R ^6, preferred forms are also the same.

In the formula (II-1), Ma represents a metal atom or a metal compound, and the meaning thereof is a metal atom in a complex of "the compound represented by the formula (II) is bonded to a metal atom or a metal compound". Or the metal compounds are the same, and the preferred range is also the same.

The same as the general formula (II-1) R in the meaning of general formula (II) ⁷ in R ^7, preferred forms are also the same.

X ¹ in the general formula (II-1) may be any group which may be bonded to Ma, and examples thereof include water and an alcohol (for example, methanol, ethanol, or propanol), and the like. "Metal Chelate" [1] Sakaguchi Takeichi. The base of the compound described in Ueno Hiroshi (1995 Nanjiang Hall), "Metal Chelate" [2] (1996), "Metal Chelate" [3] (1997), etc. Among them, from the viewpoint of production, water, a carboxylic acid compound, an alcohol, an amine compound, and a guanamine compound are preferable, and water, a carboxylic acid compound, and a guanamine compound are more preferable.

X ² in the formula (II-1) represents a group required for neutralizing the charge of Ma, and represents, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxyl group, and an aliphatic quinone imine. (Examples include butylenediamine, maleimide, pentaneimine, diethylamine, etc., preferably, butadiene diimide and maleimide) a monovalent group, an aromatic quinone imine group or a heterocyclic quinone imide (for example, phthalimide, naphthyl imine, 4-bromophthalimide, 4 -methylphthalimide, 4-nitrophthalimide, naphthylcarboxyimine, tetrabromophthalimide, etc., preferably phthalic acid A monovalent group of an imine, 4-bromophthalimide, 4-methylphthalimide, derived from an aromatic carboxylic acid (for example, benzoic acid, 2-methoxy group) Benzoic acid, 3-methoxybenzoic acid, 4-methoxybenzoic acid, 4-chlorobenzoic acid, 2-naphthoic acid, salicylic acid, 3,4,5-trimethoxybenzoic acid, 4-heptyloxy Benzoic acid, 4-tert-butylbenzoic acid, etc., preferably benzoic acid, 4-methoxyl A monovalent group of formic acid, salicylic acid or the like is derived from an aliphatic carboxylic acid (for example, formic acid, acetic acid, acrylic acid, methacrylic acid, acetic acid, propionic acid, lactic acid, trimethylacetic acid, caproic acid, octanoic acid, 2-ethylhexanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid, 2-hexadecyl octadecanoic acid, 2-hexyl decanoic acid, ring Pentanecarboxylic acid, cyclohexanecarboxylic acid, 5-norbornene-2-carboxylic acid, 1-adamantanecarboxylic acid, etc., preferably, acetic acid, methacrylic acid, lactic acid, trimethylacetic acid, 2- A monovalent group of ethylhexanoic acid, stearyl acid, or the like, derived from dithiocarbamic acid (for example, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, and the like) The monovalent group of benzyldithiocarbamic acid is derived from a sulfonamide (for example, benzenesulfonamide, 4-chlorobenzenesulfonamide, 4-methoxybenzenesulfonamide, 4-methyl) The phenylsulfonamide, 2-methylbenzenesulfonamide, and methanesulfonamide are preferably a monovalent group derived from sulfonamide or methanesulfonamide, and are derived from hydroxamic acid (for example, Acetyl hydroxamic acid, octyl hydroxamic acid, benzylhydroxyl The monovalent group of the acid is derived from a nitrogen-containing cyclic compound (exemplified by carbendazim, 1-benzyl-5-ethoxyethyl carbazide, 1-allyl carbendazim, 5, 5 -diphenylethylene carbazide, 5,5-dimethyl-2,4-oxazolidinedione, barbituric acid, imidazole, pyrazole, 4,5-dicyanoimidazole, 4,5- Dimethylimidazole, benzimidazole, 1H-imidazole-4,5-dicarboxylic acid diethyl ester, etc., preferably 1-benzyl-5-ethoxyethyl carbazide, 5,5-di A monovalent group of methyl-2,4-oxazolidinedione, 4,5-dicyanoimidazole, 1H-imidazole-4,5-dicarboxylic acid diethyl ester.

Among them, from the viewpoint of production, a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic quinone imine group, an aromatic fluorenylene group, a sulfonic acid group, or a nitrogen-containing ring compound is preferable. More preferred are a hydroxyl group, an aliphatic carboxylic acid group, an aromatic quinone imine group, and a nitrogen-containing ring compound.

When X ¹ and X ² in the general formula (II-1) are bonded to each other and form a ring of 5 members, 6 members, or 7 members together with Ma, the formed ring of 5 members, 6 members, and 7 members It can be a saturated ring or an unsaturated ring. Further, the ring of 5 members, 6 members, and 7 members may contain only a carbon atom and a hydrogen atom, or may be a hetero ring having at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom.

In the formula (II-2), R ¹ to R ¹³ each independently represent a hydrogen atom or a substituent. R ⁷ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Ma represents a metal atom or a metal compound.

The same as the general formula (II-2) R ¹ ~ R in the meaning of general formula (II) ⁶ in R ¹ ~ R ^6, preferred forms are also the same.

The substituent represented by R ⁸ to R ¹³ in the formula (II-2) has the same meaning as the substituent represented by R ¹ to R ⁶ of the compound represented by the formula (II), and is preferably. The form is also the same. When the substituent represented by R ⁸ to R ¹³ of the compound represented by the general formula (I-2) is a further substitutable group, it may be substituted by any of the substituent group A, when by 2 When more than one substituent is substituted, the substituents may be the same or different.

The same as the general formula (II-2) the meaning of R in the general formula (I) ⁷ in R ^7, preferred forms are also the same.

R ¹⁴ in the formula (II-2) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and has the same meaning as R ⁷ in the formula (II), and the preferred range is also the same. When R ¹⁴ is a further substitutable group, it may be substituted by any of the substituents R, and when substituted by two or more substituents, the substituents may be the same or different.

In the formula (II-2), Ma represents a metal or a metal compound, and the meaning of the metal in the "compound compound in which the compound represented by the formula (II) is bonded to a metal atom or a metal compound" The atom or metal compound is the same, and the preferred range is also the same.

R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , R ¹² and R ¹³ in the formula (II-2) may be independently bonded to each other to form 5 members, 6 members, or 7 members. Saturated ring, or unsaturated ring. As the saturated or unsaturated ring formed, the meaning is the same as the saturated ring formed by R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ , or the unsaturated ring. The preferred examples are also the same.

In the formula (II-3), R ² to R ⁵ each independently represent a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. R ⁸ and R ⁹ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amino group. Ma represents a metal atom or a metal compound. X ³ and X ⁴ each independently represent NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or Sulfur atom. Y ¹ and Y ² each independently represent NRb (Rb represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, and sulfur. An atom, or a carbon atom. X ⁵ represents a group which can be bonded to Ma, and a represents 0, 1, or 2. R ⁸ and Y ¹ may be bonded to each other to form a ring of 5 members, 6 members, or 7 members, and R ⁹ and Y ² may be bonded to each other to form a ring of 5 members, 6 members, or 7 members.

Formula (II-3) R in the meaning of general formula (II) ² ~ R ⁵ and R ⁷ in the same group as R ² ~ R ⁵ and R ^7, preferred forms are also the same.

Ma in the general formula (II-3) represents a metal or a metal compound, and a metal atom or a metal compound in a complex compound in which a compound represented by the general formula (II) is bonded to a metal atom or a metal compound. In the same way, the preferred range is also the same.

In the formula (II-3), R ⁸ and R ⁹ each independently represent an alkyl group (preferably a linear, branched or cyclic alkyl group having a carbon number of 1 to 36, more preferably 1 to 12). , for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12, such as a vinyl group, an allyl group, a 3-buten-1-yl group) or an aryl group. (preferably, the aryl group having a carbon number of 6 to 36, more preferably 6 to 18, such as a phenyl group or a naphthyl group) or a heterocyclic group (preferably having a carbon number of 1 to 24, more preferably 1 to 12) Heterocyclic group, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzo Triazol-1-yl), alkoxy (preferably alkoxy having a carbon number of from 1 to 36, more preferably from 1 to 18, such as methoxy, ethoxy, propoxy, butoxy, Hexyloxy, 2-ethylhexyloxy, dodecyloxy, cyclohexyloxy), aryloxy (preferably an aryloxy group having a carbon number of 6 to 24, more preferably 1 to 18, for example Phenoxy, naphthyloxy), alkylamino group Preferred are alkylamino groups having a carbon number of from 1 to 36, more preferably from 1 to 18, such as methylamino, ethylamino, propylamino, butylamino, hexylamino, 2-ethyl Hexylamino, isopropylamino, tert-butylamino, trioctylamino, cyclohexylamino, N,N-diethylamino, N,N-dipropylamino, N , N-dibutylamino, N-methyl-N-ethylamino), arylamine (preferably an arylamine having a carbon number of 6 to 36, more preferably 6 to 18, for example Phenylamino, naphthylamino, N,N-diphenylamino, N-ethyl-N-phenylamino), or heterocyclic amine (preferably having a carbon number of 1 to 24, more Preferred are heterocyclic amino groups of 1 to 12, such as 2-aminopyrrolyl, 3-aminopyrazolyl, 2-aminopyridyl, 3-aminopyridyl.

In the formula (II-3), an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group or an arylamino group represented by R ⁸ and R ⁹ may be used. When the heterocyclic amino group is a further substitutable group, it may be substituted by any one of the substituent groups A, and when substituted by two or more substituents, the substituents may be the same or different.

In the formula (II-3), X ³ and X ⁴ each independently represent NRa, an oxygen atom or a sulfur atom. Ra represents a hydrogen atom, an alkyl group (preferably a linear, branched or cyclic alkyl group having a carbon number of 1 to 36, more preferably 1 to 12, such as a methyl group, an ethyl group, a propyl group or an isopropyl group). Base, butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl (preferably An alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12, such as a vinyl group, an allyl group, a 3-buten-1-yl group, or an aryl group (preferably having a carbon number of 6 to 36, more preferably An aryl group of 6 to 18, such as a phenyl group, a naphthyl group, or a heterocyclic group (preferably a heterocyclic group having a carbon number of 1 to 24, more preferably 1 to 12, such as 2-thienyl or 4-pyridine) , 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), decyl (preferably) a fluorenyl group having a carbon number of 1 to 24, more preferably 2 to 18, such as an ethyl fluorenyl group, a trimethyl ethane group, a 2-ethylhexyl group, a benzamidine group or a cyclohexyl group, or an alkyl sulfonate. Sulfhydryl (preferably an alkylsulfonyl group having a carbon number of 1 to 24, more preferably 1 to 18, such as methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclohexylsulfonyl) Base), arylsulfonyl (more) Having a carbon number of 6 to 24, more preferably an aryl sulfonic acyl group having 6 to 18, sulfonylureas such as phenyl, naphthyl sulfonic acyl). Further, when Ra may be substituted, it may be further substituted by a substituent, and when substituted by a plurality of substituents, the substituents may be the same or different.

X ³ and X ^{4 are} preferably each independently an oxygen atom or a sulfur atom, more preferably an oxygen atom.

In the general formula (II-3), Y ¹ and Y ² each independently represent NRb, a sulfur atom or a carbon atom, and Rb has the same meaning as Ra in X ³ .

Y ¹ and Y ² are each independently NRb (wherein Rb is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and particularly preferably both Y ¹ and Y ² are NH.

In the formula (II-3), R ⁸ and Y ¹ may be bonded to each other and form a 5-membered ring together with R ⁸ , Y ¹ and a carbon atom (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxane) Alkane, tetrahydrothiophene, pyrrole, furan, thiophene, anthracene, benzofuran, benzothiophene), 6-membered ring (eg cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane) , cyclopentane sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline), or 7-membered ring (eg, cycloheptane, hexamethyleneimine).

In the formula (II-3), R ⁹ and Y ² may be bonded to each other and form a ring of 5 members, 6 members, or 7 members together with R ⁹ , Y ² , and a carbon atom. The ring of the five members, the six members, and the seven members formed may be a ring in which one of the bonds formed by R ⁸ and Y ¹ and a carbon atom is changed into a double bond.

In the formula (II-3), when a ring of 5 members, 6 members, and 7 members formed by bonding R ⁸ and Y ¹ and R ⁹ and Y ^{2 is} a ring which may be further substituted, the substitution may be carried out. When the base substitution described in any one of the group A is substituted by two or more substituents, the substituents may be the same or different.

In the formula (II-3), X ⁵ represents a group which can be bonded to Ma, and the same group as X ² in the formula (II-1) can be mentioned. a represents 0, 1, or 2.

Preferred embodiments of the compound represented by the formula (II-3) are shown below. That is, R ² to R ⁵ , R ⁷ and Ma each contain a preferred form of a complex of a compound represented by the formula (II) and a metal atom or a metal compound, and are independently independent of X ³ and X ⁴ . The ground is NRa (Ra is a hydrogen atom, an alkyl group, a heterocyclic group), or an oxygen atom, and Y ¹ and Y ² are each independently NRb (Rb is a hydrogen atom or an alkyl group), a nitrogen atom, or a carbon atom, X ⁵ is a group bonded via an oxygen atom or a nitrogen atom, and R ⁸ and R ⁹ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, or R ⁸ and Y ¹ They are bonded to each other to form a 5-membered ring or a 6-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-membered ring and a 6-membered ring, and a is represented by 0 or 1.

A more preferred form of the compound represented by the formula (II-3) is shown below. That is, R ² to R ⁵ , R ⁷ and Ma each preferably comprise a preferred form of a complex of a compound represented by the formula (II) with a metal atom or a metal compound, and X ³ and X ⁴ are oxygen. An atom, Y ¹ is NH, Y ² is a nitrogen atom, X ⁵ is a group bonded via an oxygen atom or a nitrogen atom, and R ⁸ and R ⁹ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group. a group, or an alkylamine group, or R ⁸ and Y ¹ are bonded to each other to form a 5-membered ring or a 6-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-membered ring, a 6-membered ring, and a is 0 or 1 The form of representation.

A preferred form of the dipyrromethene-based metal-substituted compound in which the compound represented by the formula (II) is bonded to a metal atom or a metal compound is represented by the formula (II-1) and the formula (II). Among the wrong compounds represented by the formula (II-3), the compound represented by the formula (II-3) is particularly preferably a compound represented by the formula (II-3).

Specific examples of the dipyrromethene-based metal-based compound which is used in the present invention for the compound represented by the general formula (II) to be bonded to a metal atom or a metal compound can be referred to Japanese Patent Laid-Open No. 2012- The description of paragraphs 0179 to 0188 of the 237985 publication can be incorporated into the specification of the present application.

The pyrromethylene dye may be used alone or in combination of two or more. When two or more pyrromethene dyes are used in combination, it is preferred that the total amount satisfies the above range.

<<Tetraazaporphyrin pigment>>

The porphyrazine coloring matter is preferably a compound represented by the formula (III).

General formula (III)

In the formula (III), all of Z ¹ , Z ² , Z ³ and Z ⁴ represent a nitrogen atom, or both of Z ¹ and Z ³ , Z ² and Z ⁴ represent a nitrogen atom, and the other group Represents CR, R independently represents a hydrogen atom, an alkyl group, or an aryl group; A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ each independently represent an alkyl group or an alkenyl group. , aryl, alkoxy, alkylthio, aryloxy, arylthio, halogen atom, hydroxy, alkoxycarbonyl, aryloxycarbonyl, amine, aminemethanyl, amine sulfonyl, fluorenyl a decyloxy group, a cyano group, a nitro group or a heterocyclic group; A ¹ and A ² , A ³ and A ⁴ , A ⁵ and A ⁶ , and A ⁷ and A ⁸ may be bonded to each other to form a ring structure, but At least one group does not form a ring structure; M represents a divalent metal atom, or a divalent atom or atom group as a substituted metal atom.

In the formula (III), A ¹ and A ² , A ³ and A ⁴ , A ⁵ and A ⁶ , and A ⁷ and A ⁸ may be bonded to each other to form a ring structure, but at least one group does not form a ring structure. Shape.

Further, in the group in which the ring structure is formed, an alicyclic structure may be formed, but it is preferred that the aromatic ring structure is not formed, and more preferably A ¹ and A ² , A ³ and A ⁴ , A ⁵ and A ⁶ , and A ⁷ and A ⁸ do not form a ring structure.

The substituents represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ will be described.

The alkyl group is preferably a linear, branched or cyclic alkyl group having a carbon number of from 1 to 48, more preferably from 1 to 24, and specific examples thereof include a methyl group. Ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecanyl, cyclopropyl, cyclopentyl , cyclohexyl, 1-norbornyl, 1-adamantyl and the like. The alkenyl group is preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, and a 3-butene-1 group. - Base, etc. The aryl group is preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group. The alkoxy group is preferably an alkoxy group having a carbon number of from 1 to 48, more preferably from 1 to 24, and specific examples thereof include a methoxy group, an ethoxy group, and a 1-butoxy group. The group is a 2-butoxy group, an isopropoxy group, a tert-butoxy group, and a dodecyloxy group. Examples of the cycloalkyloxy group include a cyclopentyloxy group and a cyclohexyloxy group. The alkylthio group is preferably an alkylthio group having a carbon number of from 1 to 48, more preferably from 1 to 24, and specific examples thereof include a methylthio group, an ethylthio group, and an octylthio group. , cyclohexylthio group and the like. The aryloxy group is preferably an aryloxy group having a carbon number of from 6 to 48, more preferably from 6 to 24, and specific examples thereof include a phenoxy group and a 1-naphthyloxy group. The arylthio group is preferably an arylthio group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms. Specific examples thereof include a phenylthio group and the like. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and preferably a fluorine atom, a chlorine atom or a bromine atom. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having a carbon number of 2 to 48, more preferably a carbon number of 2 to 24. Specifically, for example, a An oxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group or the like.

The aryloxycarbonyl group is preferably an aryloxycarbonyl group having a carbon number of 7 to 32, more preferably 7 to 24 carbon atoms, and specific examples thereof include a phenoxycarbonyl group. The amine group is preferably an amine group having a carbon number of 32 or less, more preferably a carbon number of 24 or less. Specific examples thereof include an amine group, a methylamino group, and an N,N-dibutyl group. Amino group, tetradecylamino group, 2-ethylhexylamino group, cyclohexylamino group and the like. The amine carbenyl group is preferably an amine carbenyl group having a carbon number of from 1 to 48, more preferably from 1 to 24, and specific examples thereof include an amine carbenyl group and an N,N- group. Diethylamine, mercapto, N-ethyl-N-octylamine, mercapto, N,N-dibutylamine, mercapto, N-propylamine, mercapto, N-phenylamine A group, N-methyl-N-phenylaminecarbamyl, N,N-dicyclohexylamine, mercaptoalkyloxycarbonyl, and the like. The aminesulfonyl group is preferably an aminesulfonyl group having a carbon number of 32 or less, more preferably a carbon number of 24 or less. Specific examples thereof include an aminesulfonyl group and an N,N-dipropyl group. Amine sulfonyl group, N-ethyl-N-dodecylamine sulfonyl group, N-ethyl-N-phenylamine sulfonyl group, N-cyclohexylamine sulfonyl group, and the like. The mercapto group is preferably a mercapto group having a carbon number of from 1 to 48, more preferably from 1 to 24, and specific examples thereof include a mercapto group, an ethyl fluorenyl group, and a trimethyl acetamidine group. Base, benzamidine, tetradecyl, cyclohexyl, and the like. The decyloxy group is preferably a decyloxy group having a carbon number of from 1 to 32, more preferably a carbon number of from 1 to 18. Specific examples thereof include a trimethyldecyloxy group and a third butyl group. Dimethyl nonyloxy, diphenylmethyl nonyloxy, and the like. The heterocyclic group is preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, and specific examples thereof include a 2-thienyl group, a 4-pyridyl group, and 2 -furan A group, a 2-pyrimidinyl group, a 1-pyridyl group, a 2-benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group, a benzotriazol-1-yl group, and the like.

The substituents represented by the above A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ may be further substituted, and as the substitutable substituent, for example, a halogen atom (for example, fluorine) An atom, a chlorine atom, a bromine atom or the like, an alkyl group (it is preferably a linear, branched or cyclic alkyl group having a carbon number of 1 to 48, more preferably a carbon number of 1 to 24, specifically For example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecanyl, cyclic a propyl group, a cyclopentyl group, a cyclohexyl group, a 1-norbornyl group, a 1-adamantyl group or the like, an alkenyl group (e.g., preferably a carbon number of 2 to 48, more preferably a carbon number of 2 to 18) a base, specifically, for example, a vinyl group, an allyl group, a 3-buten-1-yl group, or the like, an aryl group (it is preferably a carbon number of 6 to 48, more preferably a carbon number of 6 to 24). The aryl group, specifically, for example, a phenyl group or a naphthyl group, or a heterocyclic group (preferably, a heterocyclic group having a carbon number of from 1 to 32, more preferably a carbon number of from 1 to 18), specifically, For example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1- An azole group, a 1-pyrazolyl group, a benzotriazol-1-yl group, or the like, and a decyl group (preferably, a decyl group having a carbon number of 3 to 38, more preferably a carbon number of 3 to 18), specifically For example, trimethyl decyl, triethyl decyl, tributyl decyl, tert-butyl dimethyl decyl, third hexyl dimethyl decyl, etc., hydroxyl, cyano, nitro, The alkoxy group is preferably an alkoxy group having a carbon number of from 1 to 48, more preferably a carbon number of from 1 to 24, and specifically, for example, a methoxy group, an ethoxy group or a 1-butoxy group. 2-butoxy group, isopropoxy group, tert-butoxy group, dodecyloxy group, and, if it is a cycloalkyloxy group, for example, a cyclopentyloxy group, a cyclohexyloxy group or the like), an aryloxy group (A preferred example is an aryloxy group having a carbon number of 6 to 48, more preferably a carbon number of 6 to 24, specifically, for example, a phenoxy group, a 1-naphthyloxy group, etc.) or a heterocyclic oxy group (may be mentioned). Preferred are a heterocyclic oxy group having a carbon number of from 1 to 32, more preferably a carbon number of from 1 to 18, specifically, for example, 1-phenyltetrazole-5-oxyl, 2-tetrahydropyranyloxy a decyloxy group (preferably, a decyloxy group having a carbon number of 1 to 32, more preferably a carbon number of 1 to 18, specifically, for example, three a methyl decyloxy group, a tributyl dimethyl decyloxy group, a diphenylmethyl decyloxy group, or the like, and a decyloxy group (it is preferably a carbon number of 2 to 48, more preferably a carbon number). 2 to 24 of an anthraceneoxy group, specifically, for example, an ethoxylated group, a trimethylethoxycarbonyl group, a benzamidineoxy group, a dodecyloxy group, etc.), an alkoxycarbonyloxy group (may be mentioned Preferably, the carbon number is from 2 to 48, more preferably an alkoxycarbonyloxy group having a carbon number of from 2 to 24, specifically, for example, an ethoxycarbonyloxy group or a third butoxycarbonyloxy group. In the case of a cycloalkoxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxy group or the like, an aryloxycarbonyloxy group (it is preferably a carbon number of 7 to 32, more preferably a carbon number of 7 to 5). An aryloxycarbonyloxy group of 24, specifically, for example, a phenoxycarbonyloxy group or the like, an amine methyl methoxy group (it is preferably a carbon number of from 1 to 48, more preferably a carbon number of from 1 to 24). Aminomethyl methoxy group, specifically, for example, N,N-dimethylamine methyl methoxy, N-butylamine methyl methoxy, N-phenylamine methyl methoxy, N-ethyl- N-phenylamine methyl methoxy group, etc., and amine sulfonyloxy group (exemplified by an amine sulfonyloxy group having a carbon number of 1 to 32, more preferably 1 to 24 carbon atoms) For example, N,N-diethylamine sulfonyloxy, N-propylamine sulfonyloxy, etc.), alkylsulfonyloxy (may be preferably a carbon number of 1 to 38, more preferably It is an alkylsulfonyloxy group having 1 to 24 carbon atoms, specifically, for example, methylsulfonyloxy group, hexylsulfonyloxy group, cyclohexylsulfonyloxy group, etc.), arylsulfonyloxy group (A preferred example is an arylsulfonyloxy group having a carbon number of 6 to 32, more preferably a carbon number of 6 to 24, specifically, for example, a phenylsulfonyloxy group) or a mercapto group (for example, Preferably, the carbon number is from 1 to 48, more preferably a fluorenyl group having a carbon number of from 1 to 24, specifically, for example, a fluorenyl group, an ethyl fluorenyl group, a trimethyl ethenyl group, a benzamidine group, and a fourteenth fluorene group. Alkoxycarbonyl group (e.g., preferably a carbon number of 2 to 48, more preferably an alkoxycarbonyl group having a carbon number of 2 to 24, specifically, for example, a methoxycarbonyl group , ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl, etc.), aryloxycarbonyl (may be listed Preferably, the carbon number is from 7 to 32, more preferably an aryloxycarbonyl group having a carbon number of from 7 to 24, specifically, for example, a phenoxycarbonyl group, etc., an amine formazan The base (it is preferably an alkylcarbenyl group having a carbon number of from 1 to 48, more preferably from 1 to 24 carbon atoms), specifically, for example, an aminomethyl group and an N,N-diethylamine methyl group. , N-ethyl-N-octylaminecarbamyl, N,N-dibutylaminecarbamyl, N-propylaminecarbamyl, N-phenylaminecarbamyl, N-methyl- An N-phenylamine methyl sulfonyl group, an N,N-dicyclohexylamine carbhydryl group, or the like, and an amine group (it is preferably an amine group having a carbon number of 32 or less, more preferably a carbon number of 24 or less). For example, an amine group, a methylamino group, an N,N-dibutylamino group, a tetradecylamino group, a 2-ethylhexylamino group, a cyclohexylamino group, etc.), an anilino group (it is preferable to mention The anilide group having a carbon number of 6 to 32, more preferably 6 to 24, specifically, for example, an anilino group or an N-methylanilino group, or a heterocyclic amino group (it is preferred that the carbon number is 1 to 2) 32, more preferably a heterocyclic amino group of 1 to 18, specifically, for example, a 4-pyridylamino group or the like, or a carboguanamine group (it is preferably a carbon number of 2 to 48, more preferably 2 to 2) a carboguanamine group of 24, specifically, for example, an acetamino group, a benzylamino group, a tetradecylguanidinium group, a trimethylethyl decylamino group, a cyclohexane guanidino group, etc.), urea Base Preferably, the number of carbon atoms is from 1 to 32, more preferably from 1 to 24, particularly, for example, urea group, N,N-dimethylureido group, N-phenylureido group, etc.) The quinone imine group (exemplified by a quinone imine group having a carbon number of 36 or less, more preferably a carbon number of 24 or less), specifically, for example, N-succinimide group, N-phthalic acid An alkoxycarbonylamino group, preferably an alkoxycarbonylamino group having a carbon number of 2 to 48, more preferably a carbon number of 2 to 24, specifically, for example, methoxy Alkylcarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group, etc.), aryloxycarbonylamino group (comparable Preferably, the carbon number is from 7 to 32, more preferably an aryloxycarbonylamino group having a carbon number of from 7 to 24, specifically, for example, a phenoxycarbonylamino group or the like, or a sulfonylamino group (it is preferred to mention The carbon number is from 1 to 48, more preferably a sulfonamide group having a carbon number of from 1 to 24, specifically, for example, a mesulfonylamino group, a sulfonamide group, a benzenesulfonylamino group, a hexadecanamide a base, a cyclohexylsulfonylamino group, or the like, an aminesulfonylamino group (it is preferably a carbon number of 1 to 48, more preferably carbon) The sulfonylamino group having a number of 1 to 24, specifically, for example, N,N-dipropylaminesulfonylamino group, N-ethyl-N-dodecylaminesulfonylamino group, etc.) An azo group (exemplified by an azo group having a carbon number of 1 to 32, more preferably a carbon number of 1 to 24, specifically, for example, a phenylazo group or a 3-pyrazolylazo group) And an alkylthio group (it is preferably an alkylthio group having a carbon number of 1 to 48, more preferably a carbon number of 1 to 24, specifically, for example, a methylthio group, an ethylthio group, an octylthio group, a cyclohexylthio group or the like, an arylthio group (preferably, an arylthio group having a carbon number of 6 to 48, more preferably a carbon number of 6 to 24, specifically, for example, a phenylthio group, etc.) or a heterocyclic ring A sulfur group (preferably, a heterocyclic thio group having a carbon number of 1 to 32, more preferably a carbon number of 1 to 18, specifically, for example, a 2-benzothiazolylthio group, a 2-pyridylthio group, or 1 - phenyltetrazoliumthiol or the like), alkylsulfinyl group (exemplified by an alkylsulfinyl group having a carbon number of 1 to 32, more preferably 1 to 24 carbon atoms), specifically, For example, dodecylsulfinyl group, etc., an arylsulfinyl group (exemplified by an arylsulfinyl group having a carbon number of 6 to 32, more preferably a carbon number of 6 to 24, specifically ,E.g Alkylsulfonyl, etc., preferably an alkylsulfonyl group having a carbon number of from 1 to 48, more preferably from 1 to 24, particularly, for example, methylsulfonate Sulfhydryl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecanosulfonyl, octylsulfonyl, a cyclohexylsulfonyl group or the like, an arylsulfonyl group (exemplified by an arylsulfonyl group having a carbon number of 6 to 48, more preferably a carbon number of 6 to 24, specifically, for example, phenylsulfonate A mercapto group, a 1-naphthylsulfonyl group, or the like, and an aminesulfonyl group (it is preferably an alkylsulfonyl group having a carbon number of 32 or less, more preferably a carbon number of 24 or less, specifically, for example, an amine sulfonate) Sulfhydryl, N,N-dipropylaminesulfonyl, N-ethyl-N-dodecylsulfonyl, N-ethyl-N-phenylaminesulfonyl, N-cyclohexylamine a mercapto group or the like, a sulfo group or a phosphinium group (preferably, a fluorenyl group having a carbon number of from 1 to 32, more preferably a carbon number of from 1 to 24, specifically, for example, a phenoxyphosphonium group, An octylphosphinyl group, a phenylphosphonium group, or the like, and a phosphinylamino group (preferably, a phosphinylamino group having a carbon number of 1 to 32, more preferably a carbon number of 1 to 24) Specifically, for example acyl diethoxy phosphino group, a phosphono group, acyl dioctyl amine and the like).

In the CR represented by Z ¹ , Z ² , Z ³ and Z ⁴ , the alkyl group and the aryl group represented by R have the meanings as A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ^{6 .} The alkyl group and the aryl group described by the substituent represented by A ⁷ and A ⁸ are the same.

In the general formula (III), the metal atom represented by M preferably represents Al, Si, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Mo, Ru, Rh, Pd, In, Sn, Pt, Pb, and Mg are more preferably Al, V, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Pt, Mg, and more preferably Al, V. Mn, Fe, Co, Ni, Cu, Zn, and Mg are particularly preferably V, Co, Ni, Cu, and Zn.

In the general formula (III), as a specific example of the substituted metal atom and a divalent atom or atom group represented by M, a halogenated metal atom (for example, Al-F, Al-Cl, Al-Br) may be mentioned. , Al-I, In-F , In-Cl, Fe-Cl, In-Br, In-I, SiF 2, SiCl 2, SiBr 2, SiI 2, TiF 2, TiCl 2, TiBr 2, TiI 2 , etc.) , MB (B is a substituent such as an alkyl group, an aryl group, a naphthyl group, an alkoxy group, or a hydroxyl group, and specifically, for example, Si(CH ₃ ) ₃ , Si(C ₂ H ₅ ) ₃ , Al-C ₆ H ₅ , In-C ₆ H ₅ , Al(OH), Mn(OH), Si(OH) ₂ , Zr(OH) ₂ , Al-OCH ₃ , Al-O(C ₆ H ₅ ), etc., oxidized metal atom (eg TiO, MnO, VO, etc.).

The porphyrazine coloring matter is preferably a tetraazaporphyrin compound in which all of Z ¹ , Z ² , Z ³ and Z ⁴ represent a nitrogen atom, and a compound represented by the formula (III-2) is preferred.

In the formula (III-2), the meanings of A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ and M are respectively related to A ¹ and A ² in the formula (III). A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ and M are the same.

The maximum value of the absorption spectrum of the compound represented by the general formula (III) is preferably 550 nm to 650 nm, more preferably 570 nm to 630 nm, and particularly preferably 570 nm, from the viewpoint of the transmittance of the color filter. ~610nm.

As a specific example of the compound represented by the above formula (III), the description of paragraphs 0124 to 0141 of JP-A-2013-210577 can be referred to, and the contents thereof can be incorporated into the specification of the present application.

The porphyrazine coloring matter may be used singly or in combination of two or more. When two or more kinds of porphyrazine coloring matter are used in combination, it is preferred that the total amount satisfies the above range.

<pigment>

The colored composition of the present invention may further contain a pigment. By containing a pigment, not only the hue can be adjusted, but also heat resistance, light resistance, patterning property, and the like can be further improved.

In the salt compound contained in the composition of the present invention, the triarylmethane dye has a blue hue. Therefore, as the pigment to be combined, a pigment having a hue of a purple to blue color is preferable, and a blue pigment is more preferable. More preferably, it is selected from the group consisting of Pigment Blue 1, Pigment Blue 2, Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment At least one of the pigments of Blue 16, Pigment Blue 22, Pigment Blue 60, Pigment Blue 64, Pigment Blue 66, Pigment Blue 79, Pigment Blue 80, and Pigment Green 7 Cl to OH. Among these pigments, pigment blue 1, pigment blue 15:3, pigment blue 15:6, pigment blue 66, and pigment blue are preferred. 79, more preferably pigment blue 15:3, pigment blue 15:6.

When a pigment having a hue of a purple to blue color is blended in the composition of the present invention, the total amount of the pigment having a hue of a purple to blue color is preferably 0.1% by mass to 20% based on the total amount of the salt compound. The mass% is more preferably from 1% by mass to 15% by mass.

The content of the pigment in the composition of the present invention is preferably 30% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less based on the total mass of the color material in the composition of the present invention. By setting it as such a range, the fall of a transmittance|permeability can be suppressed, and fall of brightness can be suppressed.

The composition of the present invention preferably contains a curable compound in addition to the above components. A polymerizable compound or an alkali-soluble binder (including an alkali-soluble binder containing a polymerizable group) can be exemplified as the curable compound, and is appropriately selected depending on the use or the production method. Further, the composition of the present invention preferably contains a photopolymerization initiator.

For example, when the coloring layer is formed by a photoresist, the composition of the present invention is preferably a solvent which dissolves 1.0% by mass or more of the salt compound at 25 ° C in addition to the salt compound, and the purple coloring. In addition to the agent, a pigment, a polymerizable compound as a curable compound, an alkali-soluble binder, and a photopolymerization initiator are contained. Further, a surfactant may be contained.

Further, when the coloring layer is formed by dry etching, the composition of the present invention is preferably a solvent which dissolves 1.0% by mass or more of the salt compound at 25 ° C in addition to the salt compound, and the purple coloring agent. Other than that, it contains a polymerizable compound as a curable compound, a solvent, and a photopolymerization initiator. Further, a surfactant may be contained.

Hereinafter, the details of these will be described.

<hardening compound>

The colored composition of the present invention preferably contains a curable compound. The curable compound preferably contains at least a polymerizable compound.

<<Polymerized compound>>

The colored composition of the present invention preferably contains at least one polymerizable compound.

The polymerizable compound is, for example, a polymerizable compound having at least one ethylenically unsaturated double bond, and can be selected from known components constituting the composition, and the paragraph number of JP-A-2006-23696 is exemplified. 0010]~ The components described in paragraph [0020], or the components described in paragraphs [0027] to [0053] of JP-A-2006-64921. The polymerizable compound is preferably a compound having a terminal ethylenically unsaturated bond, and more preferably a compound having 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 multimers thereof.

Further, a urethane-added polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group is also suitable, as disclosed in Japanese Patent Laid-Open No. Hei 51-37193, Japanese Patent Publication No. 2-32293, and Japan. The urethane amides described in Japanese Patent Publication No. 2-16765, or Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. SHO 56-17654, and Japanese Patent No. A urethane compound having an oxirane skeleton described in JP-A-62-39417 and JP-A-62-39418 is also suitable.

For example, the polyester acrylates described in each of the publications of the Japanese Patent Publication No. SHO-49-43191, the Japanese Patent Publication No. Sho. A polyfunctional acrylate or methacrylate such as an epoxy acrylate obtained by reacting an epoxy resin with (meth)acrylic acid. Further, it can also be used as a photocurable monomer and oligomer in Japanese Society of Science and Technology vol. 20, No. 7, 300 pages to 308 (1984).

Specific examples thereof include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris((methyl)). Acryloxyethyl)isocyanurate, pentaerythritol tetra(meth)acrylate EO modified body, dipentaerythritol hexa(meth)acrylate EO modified body, and the like, and commercially available products include NK ESTER A-TMMT, NK ESTER A-TMM-3, NK OLIGO UA-32P, NK OLIGO UA-7200 (above, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Aronix M-305, Arrow Aronix M-306, Aronix M-309, Aronix M-450, Aronix M-402, TO-1382, TO-2349 (above, East Asian synthesis) (share) manufacturing), V#802 (Manufactured by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD D-330, D-320, D-310, DPHA (above, manufactured by Nippon Kayaku Co., Ltd.) ) as a preferred example.

In addition, as the (C) polymerizable compound, from the viewpoint of low-temperature curability, a paragraph number [0031] of JP-A-2009-265630 can be cited. ~ The components described in paragraph [0061]. Among them, as the (C) polymerizable compound, (1) to (20) and (M-1) to (M-8) shown below are preferable. From the viewpoint of low-temperature curability, a coloring film formed using a polymerizable monomer having two ethylenically unsaturated bonds in the molecule is particularly excellent.

When the polymerizable compound is used for the coloring composition, the content of the polymerizable compound with respect to the total solid content of the composition is preferably from 10% by mass to 80% by mass, more preferably from 15% by mass to 75% by mass, particularly preferably It is 20% by mass to 60% by mass.

The polymerizable compound may be used alone or in combination of two or more. When two or more types of polymerizable compounds are used in combination, it is preferred that the total amount satisfies the above range.

<Photopolymerization initiator>

The colored composition of the present invention preferably contains at least one photopolymerization initiator.

The photopolymerization initiator may be any one that can polymerize the polymerizable compound. There is no particular limitation, and it is preferred to select from the viewpoints of characteristics, initial efficiency, absorption wavelength, availability, cost, and the like.

The photopolymerization initiator is a compound which is photosensitive by exposure light, and starts polymerization of a polymerizable compound and promotes it. It is preferably a compound which induces an actinic ray having a wavelength of 300 nm or more and starts polymerization of a polymerizable compound. Further, the photopolymerization initiator which does not directly induce actinic rays having a wavelength of 300 nm or more may be preferably used in combination with a sensitizer.

Specific examples thereof include an oxime ester compound, an organic halide, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxide, an azo compound, and a coumarin compound. Azido compound, metallocene compound, hexaarylbiimidazole compound, organoboric acid compound, disulfonic acid compound, phosphonium salt compound, mercaptophosphine (oxide) compound, benzophenone compound, acetophenone compound, benzene And imidazole compounds and derivatives thereof and the like.

Among these, from the viewpoint of sensitivity, an oxime ester compound or a hexaarylbiimidazole compound is preferred.

As the oxime ester compound, JP-A-2000-80068, JP-A-2001-233842, JP-A-2004-534797, International Publication No. 2005/080337, International Publication No. 2006 can be used. Japanese Patent Laid-Open No. 2007-210991, Japanese Patent Laid-Open No. 2007-231000, Japanese Patent Laid-Open No. Hei. No. 2007-269779, Japanese Patent Laid-Open No. 2009-191061, and International Publication No. 2009/ The compound described in the specification No. 131189.

Specific examples thereof include 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-butanedione and 2-(O-benzylidene fluorenyl).肟)-1-[4-(phenylthio)phenyl]-1,2-pentanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl] -1,2-hexanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-heptanedione, 2-(O-phenyl醯 肟)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 2-(O-benzylidene fluorenyl)-1-[4-(methylphenylthio) Phenyl]-1,2-butanedione, 2-(O-benzylidene fluorenyl)-1-[4-(ethylphenylthio)phenyl]-1,2-butanedione, 2 -(O-benzylidene fluorenyl)-1-[4-(butylphenylthio)phenyl]-1,2-butanedione, 1-(O-ethylindenyl)-1-[9 -ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-methyl-6- (2-Methylbenzylidene)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-propyl-6-(2-methylbenzene Mercapto)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-ethylbenzylidene)-9H -oxazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-butylbenzylidene)-9H-indazole-3- Ethyl ketone, 1-(O-ethylindenyl)-1-[9-ethyl-6-(thienylmethyl)- 9H-carbazol-3-yl]acetone and the like. However, it is not limited to these specific examples.

In the present invention, the oxime ester compound as a photopolymerization initiator is also suitable for the compound represented by the following formula (A) from the viewpoints of sensitivity, stability over time, and coloration upon post-heating. .

In the formula (A), X ¹ , X ² and X ³ each independently represent a hydrogen atom, a halogen atom or an alkyl group, and R ¹ represents -R, -OR, -COR, -SR, -CONRR', or -CN, R ² and R ³ each independently represent -R, -OR, -COR, -SR, or -NRR'. R and R' each independently represent an alkyl group, an aryl group, an arylalkyl group or a heterocyclic group, and the groups may be substituted by one or more selected from the group consisting of a halogen atom and a heterocyclic group. One or more carbon atoms of the alkyl chain in the alkyl group and the aralkyl group may be substituted by an unsaturated bond, an ether bond or an ester bond, and R and R' may be bonded to each other to form a ring.

In the general formula (A), examples of the halogen atom in the case where X ¹ , X ² and X ³ represent a halogen atom include fluorine, chlorine, bromine and iodine, and when X ¹ , X ² and X ³ represent an alkyl group, The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a third pentyl group or a hexyl group. , heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, Propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, A Oxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-(benzoxazole-2'-yl)vinyl, and the like.

Preferably, X ¹ , X ² and X ³ each represent a hydrogen atom, or X ¹ represents an alkyl group, and both X ² and X ³ represent a hydrogen atom.

In the general formula (A), examples of the alkyl group represented by R and R' include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, and a third group. Butyl, pentyl, isopentyl, third amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, fluorenyl, isoindole Base, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxy Ethoxyethyl, propoxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-(benzene And oxazole-2'-yl) vinyl and the like.

Examples of the aryl group represented by R and R' include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a chlorophenyl group, a naphthyl group, an anthracenyl group, and a phenanthryl group.

Examples of the aralkyl group represented by R and R' include a benzyl group, a chlorobenzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, and a phenylvinyl group. Wait.

Examples of the heterocyclic group represented by R and R' include a pyridyl group, a pyrimidinyl group, a furyl group, and a phenylthio group.

Further, examples of the ring formed by bonding R and R' to each other include a piperidine ring and a morpholine ring.

Particularly preferred forms of R ² and R ³ which are composed of R and R' are methyl, hexyl, cyclohexyl, -S-Ph, -S-Ph-Cl, and -S-, respectively. Ph-Br.

Among the photopolymerization initiators, in the general formula (A), X ¹ , X ² and X ³ are each a hydrogen atom; R ¹ is an alkyl group, especially a methyl group; and R ² is an alkyl group, especially It is a methyl group; R ³ is an alkyl group, especially an ethyl group, which is particularly suitable as a photopolymerization initiator.

Therefore, preferred examples of the photopolymerization initiator represented by the above formula (A) include the compounds A to G exemplified below. However, the present invention is not limited by any of the following compounds.

The photopolymerization initiator represented by the formula (A) can be synthesized, for example, by the method described in JP-A-2005-220097.

The compound represented by the general formula (A) used in the present invention has an absorption wavelength in a wavelength region of from 250 nm to 500 nm. More preferably, it is an absorption wavelength in the wavelength range of 300 nm - 380 nm. Particularly preferred are those with high absorbance at 308 nm and 355 nm.

In the present invention, the oxime ester compound as a polymerization initiator is also preferably a compound represented by the following formula (B) from the viewpoints of sensitivity, stability with time, and coloration at the time of post-heating.

In the formula (B), R ²² represents a monovalent substituent. A ²² represents a divalent linking group, and Ar represents an aryl group. n is an integer from 0 to 5. X ²² represents a monovalent substituent. When n is an integer of 2 to 4, a plurality of X ²² may be the same or different.

The monovalent substituent represented by R ²² is preferably a monovalent non-metal atom group shown below.

The monovalent non-metal atomic group represented by R ²² may, for example, be an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and an aromatic group which may have a substituent A sulfonyl group, a fluorenyl group which may have a substituent, a heterocyclic group which may have a substituent, and the like.

The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl cyclopentyl group, a cyclohexyl group, and a trifluoromethyl group. Wait.

The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, and a 2-naphthyl group.

The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group and an ethylsulfonyl group.

The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group and a 1-naphthylsulfonyl group.

The fluorenyl group which may have a substituent is preferably a fluorenyl group having 2 to 20 carbon atoms, and examples thereof include an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, a trifluoromethylcarbonyl group, a amyl group, and a benzamidine group. , 1-naphthylmethyl, 2-naphthylmethyl, 4-methylthiobenzimidyl, 4-phenylthiobenzimidyl, 4-dimethylaminobenzimidyl, 4 -diethylaminobenzhydryl, 2-chlorobenzhydryl, 2-methylbenzhydryl, 2-methoxybenzimidyl, 2-butoxybenzhydryl, 3- Chlorobenzyl, 3-trifluoromethylbenzhydryl, 3-cyanobenzylidene, 3-nitrobenzhydryl, 4-fluorobenzhydryl, 4-cyanobenzamide Base, 4-methoxybenzimidyl and the like.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. For example, a thienyl group, a furyl group, a pyranyl group, etc. are mentioned.

As R ²² , an unsubstituted or substituted fluorenyl group is more preferable from the viewpoint of high sensitivity, and specifically, an unsubstituted or substituted ethyl fluorenyl group, a propyl fluorenyl group, Benzopyridinyl, toluylcarbenyl.

Examples of the substituent include a group represented by the following structural formula, and among them, any of (d-1), (d-4) and (d-5) is preferable.

Examples of the divalent linking group represented by A ²² include an alkylene group having 1 to 12 carbon atoms which may have a substituent, a cyclohexylene group which may have a substituent, and an alkynyl group which may have a substituent.

Examples of the substituent which can be introduced into the group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group or a third butoxy group, and benzene. An aryloxy group such as an oxy group or a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; and the like.

Among them, as the A ²² , an unsubstituted alkylene group and an alkyl group (for example, a methyl group, an ethyl group, and a third group) are preferred in terms of improving the sensitivity and suppressing the coloring caused by heating. Butyl, dodecyl) substituted alkylene, alkylene substituted by alkenyl (eg vinyl, allyl), aryl (eg phenyl, p-tolyl, xylyl, cumenyl) , naphthyl, anthracenyl, phenanthryl, styryl) substituted alkylene.

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent.

Specifically, Ar may be exemplified by phenyl, biphenyl, 1-naphthyl, 2-naphthyl, triphenyl, biphenyl, o-tolyl, m-tolyl, p-tolyl, xylene a base, an ortho-alkenyl group, a m-cumenyl group, and a p-cumenyl group, a mesityl group, and the like. Among them, a substituted or unsubstituted phenyl group is preferred from the viewpoint of improving sensitivity and suppressing coloration caused by heating.

When the phenyl group has a substituent, examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and an alkoxy group such as a methoxy group, an ethoxy group or a third butoxy group. An aryloxy group such as a phenoxy group or a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; an ethoxy group, a propenyloxy group or a benzamidine group; Is an alkyl group such as an oxo group, an ethyl fluorenyl group, an ethenyl group, a benzhydryl group, an isobutyl group, an acryl fluorenyl group, a methacryl fluorenyl group, a methoxyindenyl group, or an alkylamino group such as a methylamino group or a cyclohexylamino group. a dialkylamino group such as a dimethylamino group, a diethylamino group, a morpholinyl group or a piperidinyl group; a phenylamino group; an alkyl group such as a methyl group, an ethyl group, a t-butyl group or a dodecyl group; Hydroxy, carboxyl and the like.

In the general formula (B), the structure of "SAr" formed by the Ar and the adjacent S is preferably the following, and is preferable from the viewpoint of sensitivity.

The monovalent substituent represented by X ²² may, for example, be an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or may have The alkoxy group of the substituent, the aryloxy group which may have a substituent, the alkylthiooxy group which may have a substituent, the arylthiooxy group which may have a substituent, a halogen atom, etc.

The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, for example. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, a trifluoromethyl group, a 2-ethylhexyl group, and a benzamidinemethyl group.

The aryl group which may have a substituent is preferably an aryl group having a carbon number of 6 to 30, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a triphenylene group, and a biphenyl group. Base, o-tolyl, m-tolyl, p-tolyl, xylyl and the like.

The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.

The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a benzyl group. Oxyl and the like.

The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, and examples thereof include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a 2-chlorophenoxy group. , 2-methylphenoxy, 2-methoxyphenoxy, and the like.

The alkylthiooxy group which may have a substituent is preferably a thioalkoxy group having 1 to 30 carbon atoms, and examples thereof include a methylthiooxy group, an ethylthiooxy group, and a propylthiooxy group. Isopropylthiooxy, butylthiooxy, isobutylthiooxy, second butylthiooxy, tert-butylthiooxy, pentylthiooxy, isopentylthiooxy, hexyl Thiooxy, heptylthio, octylthiooxy, 2-ethylhexylthiooxy, sulfonyloxy, dodecyloxy, octadecyloxy, benzylthio Oxyl and the like.

As the arylthiooxy group which may have a substituent, it is preferably a aryl group having a carbon number of 6 to 30. Thiomethoxy group, for example, phenylthiooxy, 1-naphthylthiooxy, 2-naphthylthiooxy, 2-chlorophenylthiooxy, 2-methylphenylthiooxy, 2 -methoxyphenylthiooxy, 2-butoxyphenylthiooxy, 3-chlorophenylthiooxy, 3-trifluoromethylphenylthiooxy, 3-cyanophenylthiooxy 3-nitrophenylthiooxy, 4-fluorophenylthiooxy, 4-cyanophenylthiooxy, 4-methoxyphenylthiooxy, 4-dimethylaminobenzene Sulfuryloxy, 4-methylthiophenylthiooxy, 4-phenylthiophenylthiooxy, and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the halogenated alkyl group which may have a substituent include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a dichloromethyl group, a trichloromethyl group, a monobromomethyl group, a dibromomethyl group, and a tribromo group. Methyl and the like.

Examples of the guanamine group which may have a substituent on N include N,N-dimethylammonium group and N,N-diethylammonium group.

Among these, as X ²² , an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent may be preferable from the viewpoint of improving solvent solubility and absorption efficiency in a long wavelength region. Alkenyl group, alkynyl group which may have a substituent, alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthiooxy group which may have a substituent, an arylthiooxy group which may have a substituent A halogenated alkyl group which may have a substituent, an amine group which may have a substituent, or a guanamine group which may have a substituent on N, and more preferably an alkyl group which may have a substituent.

Further, n in the formula (B) represents an integer of 0 to 5, but from the viewpoint of easiness of synthesis, an integer of 0 to 3 is preferable, and an integer of 0 to 2 is more preferable.

In the general formula (B), when a plurality of X ²² are present, the plurality of X ²² may be the same or different.

Specific examples of the photopolymerization initiator represented by the above formula (B) are shown below.

The compound represented by the formula (B) used in the present invention has an absorption wavelength in a wavelength region of from 250 nm to 500 nm. More preferably listed as 300 Those having an absorption wavelength in the wavelength region of nm to 380 nm. Particularly preferred are those with high absorbance at 308 nm and 355 nm.

Specific examples of the organic halide include, for example, Lin, et al., "Bull Chem. Soc. Japan", 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. Sho 46- Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. SHO-62- 582 837, Japanese Patent Laid-Open Publication No. SHO-62-212401, Japanese Patent Laid-Open Publication No. SHO-63-70243 Japanese Laid-Open Patent Publication No. No. 3 (No. 3), (1970), and the like, in particular, an oxazole compound or a s-triazine compound substituted with a trihalomethyl group.

Examples of the hexaarylbiimidazole compound include various compounds described in each specification, such as Japanese Patent Publication No. Hei. 6-29285, U.S. Patent No. 3,479,185, U.S. Patent No. 4,311,783, and U.S. Patent No. 4,622,286. Specifically, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl)-4 , 4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2 '-Bis(o-chlorophenyl)-4,4',5,5'-tetrakis(m-methoxyphenyl)biimidazole, 2,2'-bis(o-,o-di-dichlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2' - bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-trifluorophenyl)-4,4',5,5'- Tetraphenyl Biimidazole and the like.

The photopolymerization initiator may be used alone or in combination of two or more. When two or more kinds are used, a plurality of compounds represented by the formula (A) can be used, and a plurality of compounds represented by the formula (B) can also be used. Further, at least one of the compounds represented by the general formula (A) and the formula (B) may be used. Further, at least one of the compounds represented by the general formula (A) and the general formula (B) and the ruthenium compound or ruthenium compound other than the compound represented by the general formula (A) and the general formula (B) may be used. A photopolymerization initiator other than the one. In addition, a sensitizer may also be used in combination.

The total content of the photopolymerization initiator is preferably from 0.1% by mass to 20% by mass, more preferably from 0.5% by mass to 10% by mass, most preferably from 1% by mass to 5% by mass based on the total solid content of the coloring composition. %. If it is in this range, the sensitivity at the time of exposure is high, and the color characteristic is also favorable.

<Binder resin>

In order to improve film formability, the coloring composition of the present invention may further contain a binder resin. As the binder resin, an alkali-soluble binder is preferably used from the viewpoint of pattern formability.

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.

As the alkali-soluble binder, a linear organic high molecular polymer which is soluble in an organic solvent and which can be developed by a weakly basic aqueous solution is preferred. Examples of such a linear organic high molecular polymer include a polymer having a carboxylic acid in a side chain, for example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Publication No. Sho 54-34327, and Japanese Patent. Methacrylic acid copolymer, acrylic acid copolymer described in each of the publications of Japanese Patent Publication No. Sho 59-53836, Japanese Patent Laid-Open Publication No. SHO 59-538 An acid, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, or the like, and an acidic cellulose derivative having a carboxylic acid in a side chain are also useful.

In addition to the above, as an alkali-soluble binder, an acid anhydride is added to a polymer having a hydroxyl group, or a polyhydroxystyrene resin, a polyoxyalkylene resin, or a poly((meth)acrylic acid 2-) Hydroxyethyl ester), polyvinylpyrrolidone or polyethylene oxide, polyvinyl alcohol and the like are also useful. Further, the linear organic high molecular polymer may be obtained by copolymerizing a monomer having hydrophilicity. Examples thereof include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, glycerol (meth)acrylate, (meth)acrylamide, and N-methylol. Acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinyl pyrrolidone, N-ethylene Amidoxime, vinylimidazole, vinyltriazole, methyl (meth)acrylate, ethyl (meth)acrylate, branched or linear propyl (meth)acrylate, branched or linear ( Butyl methacrylate, phenoxy hydroxypropyl (meth) acrylate, and the like. Further, as the hydrophilic monomer, it contains a tetrahydroindenyl group, a phosphoric acid group, a phosphate group, a quaternary ammonium salt group, an extended ethoxy chain, a propoxy chain, a sulfonic acid group, and a salt derived therefrom. A monomer such as a morpholinoethyl group or the like is also useful.

Further, in order to improve the crosslinking efficiency, the alkali-soluble binder may have a polymerizable group in the side chain, for example, a polymer having an allyl group, a (meth)acryl group, an allyloxyalkyl group or the like in a side chain. Etc. Also useful. As the polymerizable group-containing polymerization Examples of the materials include: Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), and Photomer 6173 (polyurethane acrylic oligomer containing COOH) , Diamond Shamrock Co., Ltd., Viscoat R-264, KS Resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series , Placcel CF200 series (all manufactured by Daicel Chemical Industry Co., Ltd.), Ebecryl 3800 (manufactured by Daicel-UCB Co., Ltd.). Further, in order to increase the strength of the hardened film, alcohol-soluble nylon or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin may also be useful.

Among these various alkali-soluble binders, polyhydroxystyrene resin, polyoxyalkylene resin, acrylic resin, acrylamide resin, acrylic acid/acrylamide are preferred from the viewpoint of heat resistance. The copolymer resin is preferably an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin from the viewpoint of controlling developability. Further, an allyl methacrylate/methacrylic acid copolymer is also preferred.

The acrylic resin preferably contains a copolymer of a monomer selected from the group consisting of benzyl (meth)acrylate, (meth)acrylic acid, hydroxyethyl (meth)acrylate, (meth)acrylamide, and the like. Object, or the described Photomer 6173, KS Resist-106, Cyclomer P series, and the like.

The alkali-soluble binder is preferably a weight average molecular weight (polystyrene-converted value measured by a GPC method) from the viewpoints of developability, liquid viscosity, and the like. The polymer of 1,000 to 200,000 is more preferably a polymer having a weight average molecular weight of 2,000 to 100,000, and particularly preferably a polymer having a weight average molecular weight of 5,000 to 50,000.

The alkali-soluble binder may be used singly or in combination of two or more.

<Other ingredients>

In the colored composition of the present invention, as long as the effects of the present invention are not impaired, a known additive may be further contained, for example, a polyfunctional thiol compound, a chain transfer agent, a polymerization inhibitor, an organic solvent, a surfactant, and an adhesion improvement. Agents, crosslinkers, development accelerators, and other additives.

Hereinafter, the components will be described.

<Multifunctional thiol compound>

The colored composition of the present invention may also contain a polyfunctional thiol compound.

The coloring composition of the present invention enhances sensitivity by containing a polyfunctional thiol compound, suppresses ion elution caused by a color material such as a dye, and the like, and uses the coloring composition of the present invention for color filter of a liquid crystal display device. When the light sheet is used, deterioration of image quality such as crosstalk can be prevented, and clear and high-quality display can be realized.

In the present invention, the "polyfunctional thiol compound" means a compound having two or more thiol groups in the molecule. The polyfunctional thiol compound is preferably a low molecular compound having a molecular weight of 100 or more. Specifically, the molecular weight is preferably from 100 to 1,500, more preferably from 150 to 1,000. The polyfunctional thiol compound preferably has 2 to 10 thiol groups in the molecule, more preferably 2 to 6 pieces, and particularly preferably 2 to 4 pieces. Further, it is preferred that the compounds are set to the radical polymerizable single A compound that is used in an auxiliary manner when the body is polymerized. Specifically, it is preferable that the amount of the polyfunctional thiol compound added is from 1% by mass to 20% by mass based on the total solid content of the composition, or that the radical polymerizable monomer is contained at the same time. The amount of addition is small.

Specific examples of the polyfunctional thiol compound which can be used in the present invention include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and tetraethylene glycol bis ( 3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetra(thioglycolate), pentaerythritol tetrakis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate) Acid ester), 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4 , 6(1H, 3H, 5H)-trione or the like as a suitable polyfunctional thiol compound. More preferably, it is a compound containing a secondary SH, and it is preferable to have a triazine skeleton from a viewpoint of liquid stability. Specifically, a Karenz MT series (manufactured by Showa Denko (share)) and the like can be cited.

The content of the polyfunctional thiol compound is preferably from 0.01% by mass to 20% by mass, and more preferably from 0.1% by mass to 10% by mass based on the total solid content of the coloring composition. When the content of the polyfunctional thiol compound is within this range, the coloring composition has good sensitivity, good storage stability, good adhesion of pixels in the obtained color filter, and no pattern defects, and is used for liquid crystal. When the device is displayed, a coloring composition having good electrical characteristics can be provided.

<sensitizer>

A sensitizer may also be added to the colored composition of the present invention. As a typical sensitizer used in the present invention, Crivello can be cited [J.V. Crivello, "Polymerization" As disclosed in Adv. in Polymer Sci, 62, 1 (1984), specifically, hydrazine, hydrazine, acridine, thioxanthone, 2-chlorothiazepine Ketone, benzoflavin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, benzophenone, coumarin, coumarinone, phenanthrene, camphorquinone, phenothiazine Things and so on. It is preferred to add a sensitizer in a ratio of 50% by mass to 200% by mass based on the photopolymerization initiator.

<chain transfer agent>

A chain transfer agent may also be added to the colored composition of the present invention. The chain transfer agent to be used in the present invention may, for example, be an N,N-dialkylaminobenzoic acid alkyl ester such as N,N-dimethylaminobenzoic acid ethyl ester or 2-mercaptobenzothiazole. a mercapto compound having a heterocyclic ring such as 2-mercaptobenzoxazole, 2-mercaptobenzimidazole or N-phenylmercaptobenzimidazole.

The chain transfer agent may be used alone or in combination of two or more.

From the viewpoint of reducing the sensitivity deviation, the amount of the chain transfer agent added is preferably in the range of 0.01% by mass to 15% by mass, more preferably 0.1% by mass to 10%, based on the total solid content of the colored composition of the present invention. The mass% is particularly preferably 0.5% by mass to 5% by mass.

<Polymerization inhibitor>

The coloring composition of the present invention may also contain a polymerization inhibitor.

The term "polymerization inhibitor" refers to a substance which supplies hydrogen (or imparts hydrogen), provides energy (or imparts energy), and provides electrons to a polymerization starting species such as a radical generated in a coloring composition by light or heat. (or electron-donating), etc., and function to inactivate the polymerization starting species and inhibit the polymerization from starting unintentionally. The polymerization described in paragraphs [0154] to [0173] of JP-A-2007-334322 can be used. Preparations, etc.

Among these, p-methoxyphenol is preferably used as the polymerization inhibitor.

The content of the polymerization inhibitor in the coloring composition of the present invention is preferably 0.0001% by mass to 5% by mass, more preferably 0.001% by mass to 5% by mass, particularly preferably 0.001% by mass, based on the total mass of the polymerizable compound. ~1% by mass.

<Surfactant>

The colored composition of the present invention may also contain a surfactant.

As the surfactant, any of an anionic, cationic, nonionic or amphoteric surfactant may be used, but a preferred surfactant is a nonionic surfactant. Specifically, the nonionic surfactant described in paragraph 0057 of JP-A-2009-098616 is preferred, and among them, a fluorine-based surfactant is preferred.

As other surfactants which can be used in the present invention, for example, Megafac F142D, Megafac F172, Megafac F173, Megafac F176, and Megafa (commercially available) are commercially available. Megafac) F177, Megafac F183, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781, Megafac ) F781-F, Megafac R30, Megafac R08, Megafac F-472SF, Megafac BL20, Megafac R-61, Megafac R -90 (made by DiCai (DIC)), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431, NOBEC FC-4430 (Sumitomo 3M) (Sumitomo 3M) (manufactured by the company), Asahi Guard AG 7105, Asahi Guard 7000, Asahi Guard 950, Asahi Guard 7600, Sha Fulong (Surflon) S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Shaflon (Surflon) S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Sha Fulong (Surflon) SC-105, Surflon SC-106 (made by Asahi Glass Co., Ltd.), Eftop EF351, Eftop EF352, Eftop EF801, Aifu Eftop EF802 (Mitsubishi Materials Electronics Co., Ltd.), Ftergent 250 (manufactured by Neos).

In addition, as a surfactant, a copolymer containing a structural unit A and a structural unit B represented by the following formula (W), and tetrahydrofuran as a solvent and permeating by a gel are mentioned as a preferable example. The polystyrene-equivalent weight average molecular weight (Mw) measured by the chromatography method is 1,000 or more and 10,000 or less.

(In the formula (W), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R ⁴ represents a hydrogen atom or a carbon number of 1 In the above alkyl group, 4 or less, L represents an alkylene group having 3 or more and 6 or less carbon atoms, p and q are mass percentages indicating a polymerization ratio, and p is a numerical value of 10% by mass or more and 80% by mass or less, and q is a value. a numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less.) L is preferably a branching extension represented by the following formula (W-2) alkyl. R ⁵ in the formula (W-2) represents an alkyl group having 1 or more and 4 or less carbon atoms, and the carbon number is preferably 1 or more from the viewpoint of compatibility and wettability to the surface to be coated. An alkyl group of 3 or less is more preferably an alkyl group having 2 or 3 carbon atoms.

The sum (p+q) of p and q in the formula (W) is preferably p + q = 100, that is, 100% by mass.

The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.

These surfactants may be used alone or in combination of two or more.

The amount of the surfactant added to the coloring composition of the present invention is preferably from 0.01% by mass to 2.0% by mass, particularly preferably from 0.02% by mass to 1.0% by mass, based on the total solid content of the coloring composition. If it is this range, the coatability and the uniformity of the cured film become good.

<Close Agent>

The coloring composition of the present invention may also contain a adhesion improving agent.

The adhesion improving agent is a compound which improves the adhesion between the inorganic substance to be a support and the cured film of the colored composition layer, and the inorganic substance is, for example, glass, an antimony compound such as cerium, cerium oxide or cerium nitride, gold, copper or aluminum. Specifically, a decane coupling agent etc. are mentioned. The decane coupling agent as the adhesion improving agent is not particularly limited as long as it is modified by the interface, and a known decane coupling agent can be used.

The decane coupling agent is preferably a decane coupling agent described in paragraph 0048 of JP-A-2009-98616, wherein γ-glycidoxypropyltrialkoxydecane or γ-甲 is more preferable. Alkyl acryloxypropyl trialkoxy decane. Further, 3-methacryloxypropyltrimethoxydecane can also be used.

The adhesion improving agent may be used alone or in combination of two or more.

The content of the adhesion improving agent in the coloring composition of the present invention is preferably from 0.1% by mass to 20% by mass, and more preferably from 0.2% by mass to 5% by mass, based on the total solid content of the coloring composition.

<crosslinker>

Further, the crosslinking agent may be used in the colored composition of the present invention to further increase the hardness of the colored layer obtained by curing the colored composition.

The crosslinking agent is not particularly limited as long as it can be cured by a crosslinking reaction, and examples thereof include (a) an epoxy resin and (b) an epoxy group selected from the group consisting of a methylol group and an alkoxy group. Melamine substituted with at least one substituent in the group and the methoxymethyl group a compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a phenol compound substituted with at least one substituent selected from the group consisting of a methylol group, an alkoxymethyl group, and a decyloxymethyl group, a naphthol compound or Hydroxyl hydrazine compound.

Among them, the epoxy resin is particularly preferable because it can form a stronger film by reacting with an acid (resin, monomer, etc.) or an SH compound which is present as a curing agent in the resist system. From the viewpoint of low viscosity, heat resistance and stability, an alicyclic epoxy group is preferred.

For details of specific examples of the crosslinking agent, etc., reference is made to paragraphs [0134] to [0147] of JP-A-2004-295116.

The crosslinking agent may be used alone or in combination of two or more.

<Development accelerator>

When the alkali solubility in the non-exposed region when the colored composition layer is exposed is promoted, and the developability of the colored composition is further improved, a development accelerator may be added. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1,000 or less and a low molecular weight phenol compound having a molecular weight of 1,000 or less.

Specific examples thereof include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, diethylacetic acid, heptanoic acid, and caprylic acid; oxalic acid and malonic acid; , succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid, methylmalonic acid, ethylmalonic acid, dimethyl Aliphatic dicarboxylic acid such as malonic acid, methyl succinic acid, tetramethyl succinic acid, citraconic acid; aliphatic tricarboxylic acid such as 1,2,3-propane tricarboxylic acid, antacid, norbornene tricarboxylic acid Acid; benzoic acid, toluic acid, 4-isopropylbenzoic acid, 2,3-dimethylbenzoic acid, 3,5-dimethylbenzyl An aromatic monocarboxylic acid such as acid; phthalic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid, trimesic acid, 1,2,3,5-benzenetetracarboxylic acid, Aromatic polycarboxylic acid such as 1,2,4,5-benzenetetracarboxylic acid; phenylacetic acid, hydrogen atoic acid, hydrogen cinnamic acid, mandelic acid, phenyl succinic acid, atopic acid, cinnamic acid, cinnamic acid Methyl ester, benzyl cinnamate, benzylideneacetic acid, coumaric acid, umbrella acid, and the like.

The development accelerator may be used alone or in combination of two or more.

In the colored composition of the present invention, various additives such as a filler, a polymer compound other than the above, an ultraviolet absorber, an antioxidant, and the like may be further blended as needed. As such additives, those described in paragraphs 0155 to 0156 of JP-A-2004-295116 can be cited.

In the coloring composition of the present invention, the light stabilizer described in paragraph 0078 of JP-A-2004-295116, and the thermal polymerization inhibitor described in paragraph 0081 of the above-mentioned publication may be contained.

<Method for Preparing Colored Composition>

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

Furthermore, when preparing the colored composition, the components constituting the colored composition may be formulated at one time, and the components may be dissolved. Disperse in the solvent and then mix. In addition, the order of input or the working conditions at the time of preparation are not particularly limited. For example, all ingredients can be dissolved at the same time. The composition is prepared by dispersing in a solvent, and if necessary, the components may be suitably prepared into two or more kinds of solutions. Dispersion, these solutions are used (when applied). The dispersion was mixed to prepare as a coloring composition.

The colored composition prepared in the above manner can be used after being filtered by using a filter or the like which preferably has a pore diameter of about 0.01 μm to 3.0 μm.

Since the colored composition of the present invention can form a colored cured film having excellent brightness and contrast, it can be suitably used as a colored component for forming a colored pixel such as a color filter used in a liquid crystal display device, and is suitable for use. It is used as a printing ink, inkjet ink, paint, etc.

<Color filter and method of manufacturing the same>

The color filter of the present invention comprises a substrate and a colored pixel including a coloring film formed on the substrate by the colored composition of the present invention. The colored region on the substrate includes a coloring layer such as red (R), green (G), blue (B), or the like that forms each pixel of the color filter.

The method for producing a color filter of the present invention comprises a coloring layer forming step (A) of forming a coloring layer (colored composition layer) by applying the coloring composition described above to a support, and forming the same in the step (A) The coloring layer performs an exposure step (B) of pattern-like exposure, and a development step (C) of developing the exposed coloring layer to form a pattern.

Further, in the method for producing a color filter of the present invention, it is particularly preferable to further provide a form of post-baking (post-heating step) (D) of heat-treating the coloring pattern obtained in the step (C).

Further, a step of irradiating the colored pattern with ultraviolet rays (post exposure) may be provided between the developing step and the post-baking step.

The method for manufacturing a color filter of the present invention includes the following steps: preferably The step of applying the composition of the present invention to the support to form the colored composition layer, the step of exposing the colored composition layer to a pattern, and the step of developing and removing the unexposed portion to form a colored pattern.

Hereinafter, a method of producing the color filter of the present invention will be described more specifically. In addition to the manufacturing method mainly used in the past, a color filter on Array (COA) color filter manufacturing method effective for improving brightness and yield is also described.

<<Previous type color filter manufacturing method>>

-Step (A)-

In the method for producing a color filter of the present invention, first, the above-described present invention is applied by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, or inkjet. The colored composition is applied to the support to form a colored layer, and thereafter, the colored layer is dried by heating (prebaking), vacuum drying, or the like.

Examples of the support include sodium glass, alkali-free glass, borosilicate glass, quartz glass, a ruthenium substrate, and a resin substrate used in a liquid crystal display device.

Further, as the COA liquid crystal display device, a substrate for driving a liquid crystal display device of a thin film transistor (TFT) type can be used.

Further, in order to improve the adhesion to the upper layer, prevent the diffusion of the substance, or to flatten the surface of the substrate, an undercoat layer, an interlayer insulating film, or the like may be provided on the support as needed.

The conditions for prebaking include 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 coloring layer formed by the coloring composition is 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. Further, in the COA liquid crystal display device color filter, the thickness of the pixel film is preferably in the range of 0.3 μm to 5.0 μm, more preferably in the range of 0.5 μm to 3.5 μm. Further, the thickness of the colored layer is the film thickness after prebaking.

-Step (B)-

Then, in the method of producing a color filter of the present invention, the colored layer formed on the support is subjected to pattern exposure. As the light or radiation that can be applied to the exposure, g-rays, h-rays, i-rays, various kinds of laser light, and particularly preferably i-rays are preferable. When i-rays are used for the irradiation of light, it is preferably irradiated with an exposure amount of ⁵ mJ/cm ² to 500 mJ/cm ² .

In addition, as other exposure light, ultrahigh pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various laser sources, and the like can be used.

-Step (C)-

Then, the exposed coloring layer is developed with a developing solution. Thereby, a colored pattern can be formed. The developer may be a combination of various organic solvents or an alkaline aqueous solution as long as it dissolves the uncured portion of the colored layer and does not dissolve the hardened portion. When the developer is an alkaline aqueous solution, it is preferred to adjust the alkali concentration to preferably pH 10 to 13. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, and Ethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5,4,0]-7- An alkaline aqueous solution such as a monoene.

In the color filter used for the liquid crystal display device of the COA system, an organic alkaline developing solution is particularly preferable as the developing solution from the viewpoint of damage to the circuit or the like of the substrate.

The development time is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 120 seconds. The developing temperature is preferably from 20 ° C to 40 ° C, more preferably from 20 ° C to 30 ° C.

Development can be carried out by a puddle method, a shower method, a spray method, or the like.

Further, it is preferred to carry out washing with water after development using an alkaline aqueous solution.

In the method of producing a color filter of the present invention, it is also preferable to post-exposure a coloring pattern (pixel) formed using a coloring composition, particularly by ultraviolet irradiation.

-Step (D)-

It is preferable to further heat-treat the colored pattern after development or the colored pattern which is post-exposed by ultraviolet irradiation as described above. The colored pattern can be further hardened by subjecting the formed colored pattern to heat treatment (so-called post-baking treatment). This heat treatment can be performed, for example, by a heating plate, various heaters, an oven, or the like.

The temperature at the time of heat treatment is preferably from 100 ° C to 300 ° C, more 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 case of producing a color filter having a plurality of hues of pixels, the steps (A), (B), (C), and (D) may be repeated in combination with a desired number of colors.

Furthermore, the step (D) can be performed after the formation, exposure, and development of each of the monochromatic coloring layers (one color at a time), and the formation of the coloring layer of all the desired color numbers can be performed. After the exposure and development are completed, the step (D) is performed once.

Hereinafter, details of a color filter which is more suitable as a color filter using the coloring composition of the present invention, a method for producing the same, and a production of COA using the same will be described.

<<Method and method of manufacturing COA color filter>>

When the color filter of the present invention is produced by the COA method, it can be produced as follows. The composition of the present invention containing a coloring agent is applied onto a TFT substrate, and after forming a coating film of the composition, the coating film is subjected to pattern exposure, alkali development, post-baking treatment, or the like to form each painting. Prime. Then, a transparent electrode (Indium Tin Oxide (ITO)) film is sputtered on the respective pixels to form a positive photoresist coating film, and the photoresist film is subjected to pattern exposure. After development, the desired ITO is etched to form a pixel electrode pattern, and then the photoresist film remaining on the pixel electrode pattern is removed by a stripper to obtain a COA color filter.

When the composition of the present invention is applied to form a coating film, it may be directly or via a coating method such as spin coating (spin coating), slit coating, cast coating, or roll coating. The other layer may be applied to a substrate and dried (prebaked) or the like. The drying (prebaking) of the composition layer applied on the substrate can be carried out at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds by means of a hot plate, an oven or the like. Further, in recent years, since the substrate has been increased in size, slit coating has been effective as a method of forming a coating film, and this coating method is becoming widespread.

Further, the pattern exposure of the coating film can be performed by performing exposure by a predetermined mask pattern, partially curing only the light-irradiated coating film, and developing with a developing solution to form various colors. A pattern-like film of a pixel of three colors or four colors. As the radiation which can be used for exposure, ultraviolet rays such as g-rays and i-rays can be preferably used.

Then, the alkali development treatment is carried out, whereby the non-hardened portion where the exposure is not performed is eluted into the alkaline aqueous solution in the case of the negative type, and only the photocured portion remains. As the developer, an organic alkaline developer which does not cause damage to the circuit of the substrate or the like is preferable. The development temperature is usually 20 ° C to 30 ° C, and the development time is 20 seconds to 90 seconds.

As the base, for example, ammonia water, ethylamine, diethylamine, dimethylethanolamine, or the like can be used in a concentration of from 0.001% by mass to 10% by mass, preferably from 0.01% by mass to 1% by mass, based on pure water. Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-di An alkaline aqueous solution obtained by diluting an organic basic compound such as azabicyclo-[5,4,0]-7-undecene. Further, when a developer containing such an alkaline aqueous solution is used, it is usually washed (rinsed) with pure water after development.

Then, the remaining developer is washed and removed, and after drying, heat treatment (post-baking) is performed. The steps can be repeated sequentially for each color as described to produce a hardened film. Thereby, a color filter can be obtained.

The post-baking is a heat treatment after development for achieving complete hardening, and is usually subjected to a heat hardening treatment at 200 ° C to 240 ° C.

A heating plate or a convection oven (hot air circulation dryer), a high-frequency heating device or the like can be used to form the condition, and the developed coating film can be subjected to the continuous or batch type. Baking treatment.

Then, a transparent electrode (ITO) film is formed on the formed pixel by sputtering, and a positive photoresist film is formed thereon, and after pattern exposure and development, a chemical such as hydrofluoric acid is used. The required ITO is etched to form a pixel electrode. As the photoresist used at this time, a positive photoresist having etching resistance is required. Further, pattern exposure or development or etching can be carried out without any limitation using a generally known method.

Then, the positive resist remaining on the formed pixel electrode was quickly peeled off by the stripping solution. The peeling liquid is not particularly limited, and a conventionally known peeling liquid can be used. For example, Japanese Patent Laid-Open No. 51-72503, Japanese Patent Laid-Open No. Sho 57-84456, Japanese Patent Laid-Open No. Hei No. Hei 6-222573, and each of the specifications of the U.S. Patent No. 4,165,294 and European Patent No. 0,119,337 Various organic solvents disclosed in the above. Typical examples of the peeling liquid include a mixed solvent of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO). Further, by using an organic solvent heated to 60 ° C or higher as a peeling liquid, the time of the peeling step can be shortened, and further, It can eliminate the problem of development remnant. Since the composition of the present invention is particularly excellent in peeling resistance, even if an organic solvent heated to 60 ° C or higher is used, there is no peeling or swelling of the coating film such as a color filter. In the case of expansion, the resist film can be removed.

The color filter of the present invention is generally used for various display devices such as a TFT liquid crystal display device, as disclosed in Fig. 1 of Japanese Laid-Open Patent Publication No. Hei 9-311347.

The color filter obtained in the above manner is easy to align and can increase the aperture ratio, and thus is suitable for a COA type image display device. Further, since the composition of the present invention is used to form a pixel, the peeling resistance is high, so that the yield is high and the production efficiency is high. Further, the heat-resistant discoloration property, the low dielectric constant property, the film thickness uniformity, the resolution, the voltage holding ratio, the light resistance, and the like which are required for the color filter are generally good.

The configuration of the color filter is such that the pixel includes only one layer as described above, and a pixel film having a coating film containing a composition for a pixel between the substrate and the pixel electrode is formed on the surface of the color filter. The two layers of the pixel protective film containing the composition for the pixel protective film on the pixel film.

The film thickness of the pixel film is preferably from 0.3 μm to 5.0 μm, more preferably from 0.5 μm to 3.5 μm. Although the coating thickness is thick to achieve high chromaticity, if the coating thickness is thick, the resolution of the contact hole is deteriorated, so balance is required. Further, the film thickness of the pixel protective film is preferably 0.2 μm to 5.0 μm, more preferably 0.2 μm to 3.0 μm. Further, it is desirable to flatten the unevenness of the pixels of the substrate and to smooth the surface.

<display device>

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 brightness and contrast by using the coloring composition of the present invention.

The display device of the present invention is a color filter including the present invention.

Specific examples of the display device of the present invention include a liquid crystal display (liquid crystal display device; LCD), an organic electroluminescence (EL) display (organic EL display device), a liquid crystal projector, and a display device for a game machine. A display device such as a portable terminal display device, a digital camera display device, or a car navigation display device, such as a mobile phone, is particularly preferably a color display device.

When the color filter of the present invention is used in an organic EL display device, a liquid crystal display device, or the like, display of an image having high luminance, high spectral characteristics, and contrast can be realized.

<Liquid crystal display device>

A liquid crystal display device using the color filter of the present invention will be described. The definition of the organic EL display device or the liquid crystal display device or the details of each display device is, for example, "Electronic display device (Kogyo Chosakai Publishing (share) issued in 1990)", "Display element" (Ibuki Shun, "Sangyo Tosho" (shares issued in 1989)", etc. are described. In addition, the liquid crystal display device is described in, for example, "Next-generation liquid crystal display technology (edited by Uchida Natsuo, Industrial Research Association (share), 1994). The liquid crystal display device to which the present invention is applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "next generation liquid crystal display technology".

Among them, the color filter of the present invention is particularly effective for a liquid crystal display device of a color TFT type. A color TFT liquid crystal display device is described in, for example, "Color TFT Liquid Crystal Display (Kyoritsu Publishing Co., Ltd., 1996)". Further, the present invention can also be applied to a liquid crystal whose viewing angle is expanded, 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). Display device, or Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optically Compensated Splay (OCS), Fringe Field Switching ( Fringe Field Switching (FFS), and Reflective Optically Compensated Bend (R-OCB). Further, as described above, the color filter of the present invention is also available in a COA (Color-filter On Array) mode.

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a three-wavelength tube of a conventionally known cold cathode tube, and further, by using red, green, and blue light-emitting diodes A (Light Emitting Diode, LED) light source (RGB-LED) is used as a backlight to provide a liquid crystal display device having high luminance, high color purity, and good color reproducibility.

<Solid photographic element>

The composition of the present invention can also be preferably used as a solid photographic element. The solid-state imaging element of the present invention is a color filter provided with the present invention.

The configuration of the solid-state imaging device is a configuration in which a color filter manufactured using the composition of the present invention is provided, and functions as a solid-state imaging device. The configuration is not particularly limited, and examples thereof include the following configurations.

The configuration includes 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, and the light is The polarizer and the transfer electrode have a light-shielding film containing tungsten or the like which is opened only to the light-receiving portion of the photodiode, and the light-shielding film has a surface covering the entire surface of the light-shielding film and the photodiode light-receiving portion. The element protective film containing a tantalum nitride or the like has the color filter for solid-state imaging elements of the present invention on the element protective film.

Furthermore, it is also possible to have a configuration such as a light collecting means (for example, a microlens or the like, the same applies hereinafter) on the element protective layer and under the color filter (on the side close to the support), or The color filter has a configuration of a light collecting mechanism.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, 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 specified.

Dye 1A

Dye 4A

Dye 6A

Dye 8A

<Example 1>

- Production of coloring composition 1 -

The components described below were mixed and dissolved to prepare a colored composition.

. Organic solvent 1 (propylene glycol monomethyl ether acetate: PGMEA) 27.4 parts

. Organic solvent 2 (diethylene glycol ethyl methyl ether: MEDG) 12.6 parts

. Alkali-soluble binder (allyl methacrylate/methacrylic acid copolymer = molar ratio 70/30, weight average molecular weight 26800) 6.6 parts

. Polymeric compound (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 6.3 parts

. Polymerization inhibitor (p-methoxyphenol) 0.003 parts

. Photopolymerization initiator (1-(O-ethylindenyl)-1-[9-ethyl-6-(thiophenylamyl)-9H-indazol-3-yl]acetone) 0.3 parts

. Polyfunctional thiol compound 1 (1,4-bis(3-mercaptobutyloxy)butane)    0.2 parts

. Adhesion modifier (3-methacryloxypropyltrimethoxydecane) 0.2 parts

. Fluorine-based surfactant (Megafac F-554, 2% propylene glycol monomethyl ether acetate solution manufactured by Di Aisheng Co., Ltd.) 0.6 parts

. Dye A: (1A) 5% propylene glycol monomethyl ether acetate solution 41.6 parts

. Dye B: (1B) 5% propylene glycol monomethyl ether acetate solution 4.2 parts

<Example 2 to Example 21>

The colored composition 2 to the colored composition 21 were prepared in the same manner as in Example 1 except that the dye (1A) and the dye (1B) used in Example 1 were changed as described in the following Table.

<Example 22>

-Preparation of blue pigment dispersion -

- Preparation of pigments -

100 parts of CI Pigment Blue 15:6 (product name: Fastogen Blue EP-193), 400 parts of sodium chloride, and 140 parts of diethylene glycol were added to the table kneading machine (Jinjiang Chamber of Commerce (shares) )), and carry out 10 hours of mixing. Then, the kneaded material is stirred and mixed with water by a dissolver (manufactured by Nippon Seiki Co., Ltd.), and then filtered and washed with water to remove sodium chloride and a solvent to obtain a color material. Wet cake. Thereafter, the wet cake was dried in an oven at 80 ° C for 6 hours.

- coarse dispersion -

After the pigment was blended with the following composition, the mixture was dispersed using an Eiger mill (manufactured by Eiger Japan Co., Ltd.) and zirconia beads having a diameter of 0.8 mm.

. The blue pigment 100 parts

. 10 parts of the pigment derivative (I) described in paragraph 0388 of Japanese Patent Laid-Open Publication No. 2011-178865

. Polymer dispersant (exemplified compound A below) 120 parts

. Propylene glycol monomethyl ether acetate 220 parts

Further, the above-mentioned exemplified compound A is synthesized by the method described in JP-A-2011-178865.

<Precision dispersion>

The crude dispersion dispersion was taken out, and 30 parts of propylene glycol monomethyl ether acetate was added to 100 parts of the dispersion to carry out mixing. After that, use the EG grinder (Japan Iger (manufactured by the company) Disperse with zirconia beads having a diameter of 0.1 mm.

<concentration adjustment>

The finely dispersed pigment dispersion was taken out and diluted with propylene glycol monomethyl ether acetate so that the pigment concentration became 10% by mass to prepare a blue pigment dispersion.

- Preparation of coloring composition 22 -

The components described below were mixed and dissolved to prepare a colored composition.

. Organic solvent 1 (propylene glycol monomethyl ether acetate) 29.5 parts

. Organic solvent 2 (diethylene glycol ethyl methyl ether) 12.6 parts

. Alkali-soluble binder (allyl methacrylate/methacrylic acid copolymer = molar ratio 70/30, weight average molecular weight 26800) 6.6 parts

. Polymeric compound (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 6.3 parts

. Polymerization inhibitor (p-methoxyphenol) 0.003 parts

. Photopolymerization initiator (1-(O-ethylindenyl)-1-[9-ethyl-6-(thiophenylamyl)-9H-indazol-3-yl]acetone) 0.3 parts

. Polyfunctional thiol compound 1 (1,4-bis(3-mercaptobutyloxy)butane) 0.2 parts

. Adhesion modifier (3-methacryloxypropyltrimethoxydecane) 0.2 parts

. Fluorine-based surfactant (Megafac manufactured by Di Ai Sheng Company) F-554, 2% propylene glycol monomethyl ether acetate solution) 0.6 parts

. Dye A: (2A) 5% propylene glycol monomethyl ether acetate solution 37.4 parts

. Dye B: (1B) 5% propylene glycol monomethyl ether acetate solution 4.2 parts

. Pigment: the blue pigment dispersion 2.1 parts

<Example 23, Example 24>

A coloring composition 23 and a coloring composition 24 were prepared in the same manner as in Example 22 except that the dye (2A) and the dye (1B) were changed as in the following Table.

<Comparative Example 1>

- Production of coloring composition -

The colored components of Comparative Example 1 were prepared by mixing and dissolving the respective components described below.

. Organic solvent 1 (propylene glycol monomethyl ether acetate) 27.4 parts

. Organic solvent 2 (diethylene glycol ethyl methyl ether) 12.6 parts

. Alkali-soluble binder (allyl methacrylate/methacrylic acid copolymer = molar ratio 70/30, weight average molecular weight 26800) 6.6 parts

. Polymeric compound (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 6.3 parts

. Polymerization inhibitor (p-methoxyphenol) 0.003 parts

. Photopolymerization initiator (1-(O-ethylindenyl)-1-[9-ethyl-6-(thiophenylamyl)-9H-indazol-3-yl]acetone) 0.3 parts

. Polyfunctional thiol compound 1 (1,4-bis(3-mercaptobutyloxy)butane) 0.2 parts

. Adhesion modifier (3-methacryloxypropyltrimethoxydecane) 0.2 parts

. Fluorine-based surfactant (Megafac F-554, 2% propylene glycol monomethyl ether acetate solution manufactured by Di Aisheng Co., Ltd.) 0.6 parts

. Dye A: (The dye 7A) 5% propylene glycol monomethyl ether acetate solution 41.6 parts

. Dye B: (1B) 5% propylene glycol monomethyl ether acetate solution 4.2 parts

<Comparative Example 2, Comparative Example 3>

The coloring compositions of Comparative Example 2 and Comparative Example 3 were prepared in the same manner as in Comparative Example 1, except that the dye (7A) and the dye (1B) used in Comparative Example 1 were changed as described in the following Table.

<Comparative Example 4>

- Production of coloring composition -

The colored components of Comparative Example 4 were prepared by mixing and dissolving the respective components described below. Further, since the dye 1A and the dye 1B are not completely dissolved in the PGME, they are used in a dispersed state.

. Organic solvent 1 (propylene glycol monomethyl ether: PGME) 27.4 parts

. Organic solvent 2 (diethylene glycol ethyl methyl ether: MEDG) 12.6 parts

. Alkali-soluble binder (allyl methacrylate/methacrylic acid copolymer = molar ratio 70/30, weight average molecular weight 26800) 6.6 parts

. Polymeric compound (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 6.3 parts

. Polymerization inhibitor (p-methoxyphenol) 0.003 parts

. Photopolymerization initiator (1-(O-ethylindenyl)-1-[9-ethyl-6-(thiophenylamyl)-9H-indazol-3-yl]acetone) 0.3 parts

. Polyfunctional thiol compound 1 (1,4-bis(3-mercaptobutyloxy)butane) 0.2 parts

. Adhesion modifier (3-methacryloxypropyltrimethoxydecane) 0.2 parts

. Fluorine-based surfactant (Megafac F-554, 2% propylene glycol monomethyl ether acetate solution manufactured by Di Aisheng Co., Ltd.) 0.6 parts

. Dye A: (1A) 5% propylene glycol monomethyl ether solution 41.6 parts

. Dye B: (1B) 5% propylene glycol monomethyl ether solution 4.2 parts

In the above table, 1A to 8A and 1B to 6B described in the dye A and the dye B represent the dye 1A to the dye 8A and the dye 1B to the dye 6B.

The properties of the colored composition prepared above were evaluated as follows.

- Formation of a colored composition layer (colored layer) -

The coloring composition prepared above was applied onto a glass (#1737; manufactured by Corning) substrate by a spin coating method, and then dried at room temperature for 30 minutes to volatilize volatile components. The colored layer was irradiated with a total exposure of i-rays (wavelength: 365 nm) without a mask to form a latent image. The light source of the i-ray is irradiated with an ultra-high pressure mercury lamp after becoming parallel light. At this time, the amount of irradiation light was set to 40 mJ/cm ² .

Then, the coloring layer on which the latent image was formed was spray-developed for 45 seconds using an aqueous solution of sodium carbonate/sodium hydrogencarbonate (concentration: 2.4% by mass, 26° C.), followed by rinsing with running water for 20 seconds, followed by air drying. . The dried film was calcined at 230 ° C for 20 minutes using a clean oven to obtain a colored layer. The thickness of the colored layer is adjusted so that the chromaticity (x, y) = (0.150, 0.06) in the CIE 1931 color system (C light source) corresponds to the hue of sRGB.

-Evaluation-

(1) Spectroscopic characteristics

The transmission spectrum of the coloring layer obtained above was measured using a photometric system (MCPD-3700 manufactured by Otsuka Electronics Co., Ltd.). The luminance in the chromaticity is obtained from the obtained transmission spectrum.

(2) Liquid crystal specific resistance (electrical characteristics)

The coloring layer obtained above was cut out from the substrate, and 9.0 mg of the cut material was added to 2.00 g of a liquid crystal material ZLI-4792 (manufactured by Merck), and heated at 120 ° C for 5 hours. Thereafter, filtration was carried out, and the specific resistance of the liquid crystal material was measured by a liquid crystal specific resistance measuring device (model: ADVANTEST R8340 ULTRA HIGHT RESISTANCE ME Advantest (manufactured by Philippine).

<Evaluation criteria>

A: When the specific resistance ≧1.0×10 ¹¹ MΩ was incorporated into a liquid crystal display device to form a panel, color unevenness, a decrease in response speed, and deterioration in display performance such as long-term afterimage were not observed.

B: The specific resistance ≧1.0×10 ¹⁰ MΩ, when assembled into a liquid crystal display device to form a panel, almost no color unevenness, a decrease in response speed, and a decrease in display performance such as long-term afterimage were observed, and there was no problem in performance.

C: Specific resistance <1.0×10 ¹⁰ MΩ, when assembled into a liquid crystal display device to form a panel, color unevenness, a decrease in response speed, and deterioration in display performance such as long-term afterimage are observed.

(3) Resistance to PGMEA

One drop of propylene glycol monomethyl ether acetate (PGMEA) was added dropwise to the colored film obtained above, and after standing at 25 ° C for 10 minutes, a clean cloth (Bemcot TR-7F, Asahi Kasei fiber) was used. Manufacture) blot the PGMEA dropped. Thereafter, it was rinsed with pure water and dried by blowing.

The color difference ΔE ^* ab before and after the dropping was evaluated by the same photometric system as (1). It can be said that the smaller the color difference, the less the dissolution caused by PGMEA, and the coating of the protective layer or other resist can withstand.

(4) Light resistance

The transmission spectrum of the coloring layer obtained above was calculated, and the colored layer was irradiated with an illuminance of 390 W/m ² using a Xenon Fade Meter (XL-75 manufactured by Suga Test Instruments Co., Ltd.). The color difference ΔE*ab of the transmission spectrum of the colored layer after an hour. When the color difference after 48 hours of irradiation is 3.0 or less, it can be said that it is suitable as a light-resistant property of a color material for a color filter.

From the results of the above table, it was found that the coloring composition used in the examples had high luminance and excellent PGMEA resistance (solvent resistance). In addition, the liquid crystal ratio is known. Excellent resistance and light resistance.

Further, it is understood that the liquid crystal specific resistance, the PGMEA resistance, and the light resistance can be further improved by further containing a blue pigment.

On the other hand, in Comparative Example 1 in which the anion in the salt compound was monovalent, the liquid crystal had lower specific resistance and PGMEA resistance, and was not satisfactory for the liquid crystal panel.

Further, in Comparative Example 2 in which the dye A was not completely dissolved and evaluated in a dispersed state, although there was no problem in liquid crystal specific resistance, PGMEA resistance, and light resistance, the dye used was insoluble and generally used for In the propylene glycol monomethyl ether acetate of the color resist, the brightness is greatly lowered.

In Comparative Example 3 in which a coloring composition containing no purple coloring agent selected from at least one of a xanthene dye, a pyrrolemethylene dye, and a porphyrazine coloring matter is used, light resistance and liquid crystal specific resistance are low, and It is difficult for the hue to conform to the general color like sRGB. Further, in Comparative Example 3, the purple tone was insufficient compared with the other dyes, and the chromaticity (x, y) = (0.150, 0.06) could not be matched, so that the luminance could not be obtained.

In Comparative Example 4 in which a solvent in which the dye was not dissolved was used, it was found that the luminance decreased greatly as in Comparative Example 2.

<Example 25>

-Production of liquid crystal display device -

A color filter was produced by the following method, and a liquid crystal display device using the same was produced, and the display characteristics were evaluated.

- Production of red coloring composition R -

The following red pigment dispersion composition was mixed and stirred at 3,000 rpm for 3 hours using a homogenizer. Further, the mixed solution obtained in the manner described above was subjected to dispersion treatment for 12 hours by using a bead disperser of 0.3 mm Φ zirconia beads (Dispermat (manufactured by GETZMANN)), and thereafter Further, a high-pressure disperser NANO-3000-10 (manufactured by BEE Co., Ltd.) equipped with a pressure reducing mechanism was used, and the dispersion treatment was carried out at a flow rate of 500 g/min under a pressure of 2000 kg/cm ³ . This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.

[Red pigment dispersion composition]

. C.I. Pigment Red 254 75 parts

. C.I. Pigment Red 177 50 parts

. Benzyl methacrylate/methacrylic acid copolymer 70 parts

(copolymerization composition ratio is 70/30, weight average molecular weight is 30,000, acid value is 40 mg/KOH)

. Propylene glycol monomethyl ether acetate 800 parts

Further, a component having the following composition was further added to the obtained pigment dispersion to prepare a red colored composition R.

[Red coloring composition R composition]

. The red pigment dispersion 100 parts

. Benzyl methacrylate/methacrylic acid (=70/30 [mole ratio]) copolymer (Mw: 30,000) propylene glycol monomethyl ether acetate solution (solid content 50%) 12 parts

. Polymeric Compound 1: Made by Nippon Chemical Co., Ltd., KAYARAD DPHA    12.1 servings

. Photopolymerization initiator: 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer 3.1 parts

. Sensitizing pigment: 4,4'-bis(diethylamino)benzophenone 4.2 parts

. Hydrogen-donating compound: 2-mercaptobenzothiazole 2.1 parts

. Polymerization inhibitor: p-methoxyphenol 0.001 parts

. Fluorine-based surfactant (trade name: Megafac R08 Di Aisheng (share) manufacturing) 0.5 parts

. Propylene glycol monomethyl ether acetate 60 parts

- Production of green coloring composition G -

In the preparation of the red coloring composition R, 103 parts of CI Pigment Green 58 was used instead of CI Pigment Red 254, and 19 parts of Pig Pigment Yellow 150 was used instead of CI Pigment Red 177, in addition to The green coloring composition G was produced in the same manner.

- Production of black coloring composition K -

The pigment dispersion composition having the following composition was changed, and dispersion treatment was carried out in the same manner as in the preparation of the red pigment dispersion to prepare a black pigment dispersion.

[Black pigment dispersion composition]

. Carbon black: trade name: Nipex 35, Japan Degussa Japan (shares) manufacturing 13.1 copies

. Polymer: benzyl methacrylate / methacrylic acid = 72/28 molar ratio of random copolymer (molecular weight of 37,000) 6.7 parts

. Propylene glycol monomethyl ether acetate 79.1 parts

. Dispersing agent (the following compound) 0.65 parts

The composition was dispersed using the obtained black pigment, and a black coloring composition K was prepared by the following composition.

[Black coloring composition K composition]

. The black pigment dispersion 25 parts

. Propylene glycol monomethyl ether acetate 8.5 parts

. Methyl ethyl ketone 53 parts

. Polymer: benzyl methacrylate/methacrylic acid = 78/22 molar ratio random copolymer (molecular weight: 38,000) mixture of 27 parts and propylene glycol monomethyl ether acetate 73 parts 9.1 parts

. Polymerization inhibitor: hydroquinone monomethyl ether 0.002 parts

. Polymeric compound: KAYARAD manufactured by Nippon Kayaku Co., Ltd. 12 copies of DPHA

. Polymerization initiator: 2,4-bis(trichloroethyl)-6-[4'(N,N-diethoxycarbonylmethyl)amino-3'-bromophenyl]-s-triazine 0.16 Share

. Methyl ethyl ketone 30% solution of surfactant (the following compound) 0.042 parts

(n=6, x=55, y=5, Mw=33940, Mw/Mn=2.55 PO: propylene oxide, EO: ethylene oxide)

-Color filter production -

- Formation of black matrix -

After cleaning the alkali-free glass substrate with an ultraviolet (Ultraviolet, UV) cleaning device, the brush is washed with a detergent, and ultrasonic cleaning is performed using ultrapure water. After the substrate was heat-treated at 120 ° C for 3 minutes to stabilize the surface state, the substrate was cooled and adjusted to 23 ° C.

The black coloring composition K is applied to the substrate by a coating machine for a glass substrate (manufactured by FAS Asia Co., Ltd., trade name: MH-1600) having a slit nozzle. on. Then, a part of the solvent was dried by vacuum drying (VCD) (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to lose the fluidity of the coating layer, and then pretreated at 120 ° C. The film was baked for 3 minutes to obtain a black photosensitive composition layer having a film thickness of 2.4 μm.

Using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the substrate and the mask (quartz exposure mask having an image pattern) are vertically arranged In the erected state, the distance between the exposure mask surface and the photosensitive resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ/cm ² .

Then, pure water is sprayed by a shower nozzle, and the surface of the black photosensitive composition layer is uniformly wetted, and then a potassium hydroxide (KOH)-based developing solution (KOH, containing a nonionic surfactant, trade name: CDK-1, manufactured by Fujifilm Electronic Materials Co., Ltd., was spray-developed at a flat nozzle pressure of 0.04 MPa for 80 seconds at 23 ° C to obtain a patterned image. Then, ultra-pure water was sprayed at a pressure of 9.8 MPa by an ultra-high pressure washing nozzle to carry out residue removal. Finally, heat treatment was performed at 220 ° C for 30 minutes to form a black matrix.

- Formation of RGB pixels -

On the glass substrate on which the black matrix was formed, the red coloring composition R, the green coloring composition G, and the blue photosensitive composition produced in Example 22 were sequentially laminated in the same manner as in the case of forming the black matrix. The object is patterned and a color filter of RGB 3 color pixels is obtained. At this time, the thickness of the coloring portion of each of the RGB colors was 1.6 μm.

- Formation of ITO electrodes -

The glass substrate on which the color filter was formed was placed in a sputtering apparatus, and ITO having a thickness of 1300 Å was subjected to full vacuum deposition at 100 ° C, and then annealed at 240 ° C for 90 minutes to crystallize the ITO. An ITO transparent electrode is formed.

- Formation of spacers -

A spacer was formed on the ITO transparent electrode produced above in the same manner as the spacer formation method described in [Example 1] of JP-A-2004-240335.

- Formation of protrusions for liquid crystal alignment control -

A liquid crystal alignment control projection is formed on the ITO transparent electrode on which the spacer is formed by using the coating liquid for a positive photosensitive resin layer described below.

However, the exposure, development, and baking steps use the following methods.

A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Co., Ltd.) was placed so as to have a predetermined distance from the surface of the photosensitive resin layer to a distance of 100 μm, and the ultra-high pressure mercury lamp was used to pass the mask at 150 mJ/cm ^{2 .} The exposure energy is for proximity exposure.

Then, development was carried out by spraying a 2.38% aqueous solution of tetramethylammonium hydroxide to the substrate at 33 ° C for 30 seconds while spraying the substrate. By developing and removing an unnecessary portion (exposure portion) of the photosensitive resin layer, a substrate for a liquid crystal display device in which a projection for liquid crystal alignment control is formed on the color filter side substrate is obtained, and the liquid crystal alignment control is performed. The protrusions include a photosensitive resin layer patterned into a desired shape.

Then, the substrate for a liquid crystal display device in which the liquid crystal alignment control projections were formed was baked at 230 ° C for 30 minutes to form a cured liquid crystal alignment control projection on the liquid crystal display device substrate.

[Formulation of Coating Solution for Positive Photosensitive Resin Layer]

. Positive type resist liquid (FH-2413F manufactured by Fujifilm Electronic Materials Co., Ltd.) 53.0 parts

. Methyl ethyl ketone 46.5 parts

. Megafac F-780F (made by Di Ai Sheng (share) company) 0.05 parts

-Production of liquid crystal display device -

On the substrate for a liquid crystal display device obtained above, an alignment film containing polyimine is further provided. Thereafter, the sealant of the epoxy resin is printed at a position corresponding to the pixel matrix surrounding the color filter so as to be disposed around the surrounding black matrix frame, and the liquid crystal for MVA mode is dropped and bonded to the opposite substrate. Thereafter, the bonded substrate is subjected to heat treatment to harden the sealant.

A polarizing plate HLC2-2518 manufactured by Sanritz Co., Ltd. was attached to both sides of the liquid crystal cell obtained in the manner described above. Then, an LED light source (a liquid crystal television manufactured by Sony Corporation, a backlight source of KDL-40ZX1) is disposed as a light source on the side of the back surface of the liquid crystal cell on which the polarizing plate is provided, thereby forming a liquid crystal display device ( LCD).

It is understood that the liquid crystal display device produced in the above manner has high contrast and brightness, and is suitable as a display device. Furthermore, in the embodiment, the MVA mode liquid crystal display is used. Although the display device was evaluated, it is considered that even if the coloring composition of the present invention is used for a liquid crystal display device of another mode or a color filter of an organic EL display, good image quality can be obtained in the same manner.

Claims (14)

A colored composition comprising: a salt compound containing a dye cation and a divalent or higher anion; a solvent for dissolving 1.0% by mass or more of the salt compound at 25 ° C; and a dye selected from the group consisting of xanthene pigment and pyrrole methylene pigment And a purple colorant of at least one of the porphyrazine coloring matter; and the dye cation has one to 20 triarylmethane dye structures in one molecule. The colored composition according to claim 1, wherein the dye cation is represented by the general formula (A1) or the general formula (A2); In the general formula (A1), Ar ⁺ each independently represents a triarylmethane dye structure, and L ¹ each independently represents a group in which two or more Ar ^{+ are} bonded, n1 represents an integer of 1 to 20, and m represents 0 or 1; When n1 represents 1, m represents 0; In the general formula (A2), Ar ⁺ each independently represents a triarylmethane dye structure, L ² represents a divalent linking group, L ³ represents a divalent linking group, and q represents an integer of 1-18. The coloring composition according to the first or second aspect of the invention, wherein the purple coloring agent comprises a xanthene dye represented by the following formula (I-1a), which is represented by the following formula (II) At least one of a pyrromethene dye represented by the above and a porphyrazine coloring matter represented by the following formula (III); In the formula (I-1a), R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O-, -CO- or -NR ¹¹ -; R ¹ and R ² may be bonded to each other to form a ring containing a nitrogen atom; and R ³ and R ⁴ may be bonded to each other; Forming a ring containing a nitrogen atom; R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ ; R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 6 carbon atoms; m1 represents an integer of 0 to 5; and when m1 is 2 or more, plural R ^5A may be the same or different; m2 and m3 respectively represent an integer of 0 to 3; when m2 and m3 are independently 2 or 3, respectively, a plurality of R ^5B and R ^5C are independent, may be the same, or may be Different; a represents 0 or 1; when a represents 0, any one of the xanthene dye structures contains an anion; X ^- represents an anion; Z ⁺ represents N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , 4 R ¹¹ may be the same or different; R ⁸ represents a saturated hydrocarbon group having a carbon number of 1 to 20 monovalent, saturated hydrocarbon group of the hydrogen atoms contained in the May be substituted with a halogen atom; R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a C monovalent saturated hydrocarbon group having 1 to 20, the saturated aliphatic hydrocarbon group contained -CH ₂ - may be -O -, - CO-, -NH- or -NR ⁸ - is substituted, and R ⁹ and R ¹⁰ may be bonded to each other to form a heterocyclic ring of a 3-membered ring to a 10-membered ring containing a nitrogen atom; R ¹¹ represents a hydrogen atom and has a carbon number of 1~ a monovalent saturated hydrocarbon group of 20 or an aralkyl group having a carbon number of 7 to 10; In the formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent; and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, or an aromatic group. Base or heterocyclic group; formula (III) In the formula (III), all of Z ¹ , Z ² , Z ³ and Z ⁴ represent a nitrogen atom, or both of Z ¹ and Z ³ , Z ² and Z ⁴ represent a nitrogen atom, and the other group Represents CR, R independently represents a hydrogen atom, an alkyl group, or an aryl group; A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ each independently represent an alkyl group or an alkenyl group. , aryl, alkoxy, alkylthio, aryloxy, arylthio, halogen atom, hydroxy, alkoxycarbonyl, aryloxycarbonyl, amine, aminemethanyl, amine sulfonyl, fluorenyl a decyloxy group, a cyano group, a nitro group or a heterocyclic group; A ¹ and A ² , A ³ and A ⁴ , A ⁵ and A ⁶ , and A ⁷ and A ⁸ may be bonded to each other to form a ring structure, but At least one group does not form a ring structure; M represents a divalent metal atom, or a divalent atom or atom group as a substituted metal atom. The coloring composition according to the first or second aspect of the invention, wherein the dye cation contains a triarylmethane dye structure represented by the following formula (TP1), and the following formula (TP2) At least one of the represented triarylmethane dye structures; In the general formula (TP1) and the formula (TP2), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group or a group having a crosslinkable group; Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ And Rtp ₁₁ each independently represents a substituent; Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group, a group having a crosslinkable group or NRtp ₇₁ Rtp ₇₂ ; and Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group, An aryl group or a group having a crosslinkable group; Rtp ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or a group having a crosslinkable group; a, b and c each independently represent an integer of 0 to 4; when a, b When c is 2 or more, Rtp ₅ and Rtp ₆ and Rtp ₈ and Rtp ₉ may be linked to each other to form a ring. The colored composition according to claim 1 or 2, wherein the dye cation has a crosslinkable group. The colored composition according to claim 1 or 2, wherein the divalent or higher anion has -SO ₃ ^- , -COO ^- , -PO ₄ ^- , and contains the following general formula (B2) a group of the structure represented or a group containing a structure represented by the following formula (B3); formula (B2) In the formula (B2), R ¹¹ and R ¹² each independently represent -SO ₂ - or -CO-; In the formula (B3), R ¹³ represents -SO ₂ - or -CO-; and R ¹⁴ and R ¹⁵ each independently represent -SO ₂ -, -CO- or -CN. The coloring composition according to claim 1 or 2, further comprising selected from the group consisting of pigment blue 1, pigment blue 2, pigment blue 15, pigment blue 15: 1, pigment blue 15: 2, pigment blue 15:3, pigment blue 15:4, pigment blue 15:6, pigment blue 16, pigment blue 22, pigment blue 60, pigment blue 64, pigment blue 66, pigment blue 79, pigment blue 80 and pigment green 7 Cl At least one of the OH founders. The coloring composition according to Item 1 or 2 of the patent application, further comprising a binder resin, a polymerizable compound, and a photopolymerization initiator. The colored composition according to claim 1 or 2, which is used for forming a coloring layer of a color filter. A cured film formed by curing the colored composition according to any one of items 1 to 9 of the patent application. A color filter used as in claims 1 to 9 The colored composition according to any one of the preceding claims. A method of producing a color filter, comprising: a step of applying a colored composition according to any one of claims 1 to 9 to a support to form a colored composition layer; a step of exposing the colored composition layer to a pattern; and developing a non-exposed portion to form a colored pattern. A solid-state photographic element comprising the color filter of claim 11 of the patent application. An image display device comprising the color filter of claim 11 of the patent application.