WO2016121194A1

WO2016121194A1 - Coloring composition, color filter, pattern forming method, method for producing color filter, solid-state imagine element and image display device

Info

Publication number: WO2016121194A1
Application number: PCT/JP2015/081961
Authority: WO
Inventors: 陽祐村上; 貴規田口; 純一伊藤; 宏明出井
Original assignee: 富士フイルム株式会社
Priority date: 2015-01-29
Filing date: 2015-11-13
Publication date: 2016-08-04
Also published as: KR102018516B1; KR20170071574A; TW201627415A; JPWO2016121194A1; TWI712655B; JP6543275B2

Abstract

A coloring composition which contains a dye A having a triarylmethane skeleton, a dye B having a xanthene skeleton and a curable compound, and wherein at least one of the dye A and the dye B is a dye multimer; a color filter which uses this coloring composition; a pattern forming method; a method for producing a color filter; a solid-state imaging element; and an image display device.

Description

Coloring composition, color filter, pattern forming method, color filter manufacturing method, solid-state imaging device, and image display device

The present invention relates to a coloring composition. The present invention also relates to a color filter, a pattern forming method, a color filter manufacturing method, a solid-state imaging device, and an image display device.

Color filters are used as key devices for solid-state image sensors, liquid crystal display devices, and other optical elements equipped with image sensors such as CCD and CMOS. The color filter normally includes a coloring pattern of three primary colors of red (R), green (G), and blue (B), and plays a role of separating transmitted light into the three primary colors.

The color filter is manufactured by applying a colored composition onto a base material such as a glass substrate, prebaking at about 100 ° C., forming a pattern after exposure and development, and performing post baking at about 210 ° C. The

Conventionally, a blue coloring pattern (blue color filter) has a color index (CI) pigment blue 15: 6 and C.I. I. It is manufactured using a coloring composition containing CI Pigment Violet 23.
Patent Document 1 discloses a dye multimer having a xanthene skeleton, C.I. I. It is disclosed that a color filter is produced using a coloring composition containing CI Pigment Blue 15: 6.
Patent Document 2 discloses that a color filter is produced using a coloring composition containing a dye multimer having a triarylmethane skeleton.

JP 2012-32754 A US Patent Application Publication No. 2013/0141810

The color filter disclosed in Patent Document 1 is a conventional blue color filter, C.I. I. Pigment blue 15: 6 and C.I. I. Although it is superior in spectral characteristics to a color filter formed using a coloring composition containing a colorant composed of a combination with Pigment Violet 23, in recent years, further improvement in the spectral characteristics of the color filter has been demanded.
On the other hand, triarylmethane alone tends to have poor spectral characteristics, and the color filter disclosed in Patent Document 2 has been found to have poor spectral characteristics.

In recent years, organic electroluminescence (organic EL) of a light emission source of a liquid crystal display device and organic material of a photoelectric conversion film of an image sensor have been performed. Due to its characteristics, the color filter is required to be manufactured at a low temperature of about 100 ° C.
However, it was found that the color filter produced by curing at a low temperature tends to decrease the solvent resistance.

Therefore, an object of the present invention is to provide a colored composition capable of forming a cured film such as a color filter having good spectral characteristics and solvent resistance, a color filter, a pattern forming method, a color filter manufacturing method, a solid-state imaging device, and An object is to provide an image display device.

As a result of detailed studies, the present inventors have found that a cured film having good spectral characteristics can be formed by using a dye having a xanthene skeleton in combination with a dye having a triarylmethane skeleton. Then, at least one selected from a dye having a xanthene skeleton and a dye having a triarylmethane skeleton is a dye multimer, whereby the colored composition is cured at a low temperature to form a cured film. However, the present inventors have found that a cured film excellent in solvent resistance can be obtained, and have completed the present invention. The present invention provides the following.
<1> A coloring composition comprising a dye A having a triarylmethane skeleton, a dye B having a xanthene skeleton, and a curable compound, wherein at least one selected from the dye A and the dye B is a dye multimer. .
<2> The colored composition according to <1>, wherein the dye A and the dye B are dye multimers.
<3> The colored composition according to <1>, wherein the ratio of the number of moles of the triarylmethane skeleton of the dye A to the number of moles of the xanthene skeleton of the dye B is 40:60 to 75:25.
<4> At least one selected from Dye A and Dye B has at least one anion selected from a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion, and a tetraarylborate anion <1> to <3> The coloring composition in any one of.
<5> The colored composition according to any one of <1> to <4>, wherein the dye A has a cation moiety having a triarylmethane skeleton and an anion bonded to the cation moiety via a covalent bond.
<6> The coloring composition according to any one of <1> to <4>, wherein the dye B has a cation moiety having a xanthene skeleton and an anion bonded to the cation moiety via a covalent bond.
<7> The colored composition according to any one of <1> to <6>, wherein at least one selected from Dye A and Dye B has a group containing a polymerizable unsaturated double bond.
<8> A color filter using the colored composition according to any one of <1> to <7>.
-The color filter as described in <8> for organic electroluminescent elements.
<10> A step of forming a colored composition layer on a support using the colored composition according to any one of <1> to <7>, a step of exposing the colored composition layer in a pattern, A pattern forming method comprising: a step of developing and removing an exposed portion to form a colored pattern; and a step of heating the colored pattern at 50 to 120 ° C.
<11> A method for producing a color filter, comprising the pattern forming method according to <10>.
<12> A solid-state imaging device having the color filter according to <8>.
<13> An image display device having the color filter according to <8>.

According to the present invention, a colored composition capable of forming a cured film such as a color filter having good spectral characteristics and solvent resistance, a color filter, a pattern forming method, a color filter manufacturing method, a solid-state imaging device, and an image display It became possible to provide a device.

It is a figure which shows the evaluation criteria of reliability evaluation.

Hereinafter, the contents of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, light means actinic rays or radiation. “Actinic light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
In this specification, “exposure” means not only exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also drawing with electron beams, ion beams, etc. unless otherwise specified. Include in exposure.
In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored composition.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”. ") Allyl" represents both and / or allyl and methallyl, and "(meth) acryloyl" represents both and / or acryloyl and methacryloyl.
In the present specification, the polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by a gel permeation chromatograph (GPC) measurement.

<Coloring composition>
The coloring composition of the present invention includes a dye A having a triarylmethane skeleton, a dye B having a xanthene skeleton, and a curable compound, and at least one selected from the dye A and the dye B is a dye multimer. .
The colored composition of the present invention can form a cured film such as a color filter having good spectral characteristics and solvent resistance by adopting the above-described configuration. That is, a cured film having good spectral characteristics can be formed by using a pigment having a triarylmethane skeleton and a pigment having a xanthene skeleton in combination. Then, at least one selected from a dye having a triarylmethane skeleton and a dye having a xanthene skeleton is a dye multimer, whereby the colored composition is cured at low temperature to form a cured film. However, a cured film having excellent solvent resistance can be obtained. Furthermore, it is difficult for the pigment to escape from the film, and color mixing with other colors can be suppressed.
In the colored composition of the present invention, the dye A and the dye B are preferably dye multimers. A dye having a triarylmethane skeleton and a dye having a xanthene skeleton have good compatibility and hardly form an association state. For this reason, the phase separation of the pigments can be suppressed, soaking of the solvent can be suppressed, and excellent solvent resistance can be obtained. Furthermore, by making both into a dye multimer, the dye is more difficult to escape from the film, and color mixing with other colors can be effectively suppressed.
In the colored composition of the present invention, the ratio of the number of moles of the triarylmethane skeleton of the dye A to the number of moles of the xanthene skeleton of the dye B is preferably 40:60 to 75:25. If the ratio of both is the said range, the solvent resistance of a cured film can be improved more. In addition, color mixing with other colors can be more effectively suppressed. Furthermore, generation | occurrence | production of the bleedout of a film | membrane component etc. can be suppressed and it is excellent in the reliability of a film | membrane.
In the colored composition of the present invention, at least one selected from the dye A and the dye B has an anion selected from a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion, and a tetraarylborate anion. preferable. The anion is less susceptible to salt exchange than a chloroanion and can form a cured film having excellent heat resistance. Moreover, generation | occurrence | production of the bleed-out etc. of a film | membrane component can be suppressed and it is excellent in the reliability of a film | membrane.
Hereinafter, the present invention will be described in detail.

<< Colorant >>
The coloring composition of this invention contains the pigment | dye A which has a triarylmethane skeleton, and the pigment | dye B which has a xanthenemethane skeleton as a coloring agent. In the present invention, it is preferable that at least one selected from Dye A and Dye B is a dye multimer, and both Dye A and Dye B are dye multimers.
In the present invention, the dye multimer means a compound having two or more triarylmethane skeletons or xanthene skeletons in one molecule.

In the present invention, the dye A preferably has a cation portion having a triarylmethane skeleton and an anion. Moreover, it is preferable that the pigment | dye B has a cation part which has a xanthene skeleton, and an anion.
In the present invention, the anion may be present outside the cation moiety molecule, but is preferably bound to the cation moiety via a covalent bond. In addition, that an anion has outside the molecule | numerator of a cation part means the case where a cation part and an anion do not couple | bond together through a covalent bond, but exist as another compound. Hereinafter, the anion outside the molecule of the cation moiety is also referred to as a counter anion.
In the present invention, it is preferable that the dye A does not substantially contain a xanthene skeleton. Moreover, it is preferable that the pigment | dye B does not contain a triarylmethane skeleton substantially.

In the present invention, the content of the dye A in the colored composition is preferably 5 to 60% by mass based on the total solid content of the colored composition. The upper limit is more preferably 55% by mass or less, and further preferably 50% by mass or less. The lower limit is more preferably 10% by mass or more, and further preferably 15% by mass or more.
In the present invention, the content of the dye B in the coloring composition is preferably 5 to 60% by mass based on the total solid content of the coloring composition. The upper limit is more preferably 55% by mass or less, and further preferably 50% by mass or less. The lower limit is more preferably 7.5% by mass or more, and further preferably 10% by mass or more.
In the present invention, the total amount of the dye A and the dye B in the total amount of the colorant is preferably 50 to 100% by mass. The lower limit is more preferably 65% by mass or more, and further preferably 70% by mass or more.
In the present invention, the ratio of the number of moles of the triarylmethane skeleton of the dye A to the number of moles of the xanthene skeleton of the dye B is preferably 40:60 to 75:25, and more preferably 45:55 to 65:35. If the ratio of both is the said range, the solvent resistance of a cured film can be improved more. In addition, color mixing with other colors can be more effectively suppressed. Furthermore, generation | occurrence | production of the bleedout of a film | membrane component etc. can be suppressed and it is excellent in the reliability of a film | membrane.
In the present invention, the number of moles of the triarylmethane skeleton of the dye A means the number of moles of the dye A when the dye A is a monomer. Further, when the dye A is a dye multimer, a portion excluding a portion other than the triarylmethane skeleton (for example, DyeI of the general formula (A) described later, DyeIII of the general formula (C) described later, It means the number of moles of D) in the formula (D-1). The same applies to the number of moles of the xanthene skeleton of dye B.

In the present invention, it is preferable that at least one selected from Dye A and Dye B includes a group having a polymerizable unsaturated double bond (hereinafter, also simply referred to as “polymerizable group”). More preferably, it contains a group. By setting it as such a structure, it exists in the tendency for solvent resistance to improve more. In addition, color mixing with other colors is less likely to occur. Furthermore, generation | occurrence | production of the bleed-out etc. of a membrane component can be suppressed.
It is preferable that two or more polymerizable groups are contained in one molecule. Examples of the polymerizable group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.

<<< Dye A having a triarylmethane skeleton >>>
In the present invention, the dye A having a triarylmethane skeleton is exemplified by a structure represented by the following formula (TP).

Formula (TP)

In the formula (TP), Rtp ¹ to Rtp ⁴ each independently represents a hydrogen atom, an alkyl group or an aryl group. Rtp ⁵ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ⁹ Rtp ¹⁰ (Rtp ⁹ and Rtp ¹⁰ represent a hydrogen atom, an alkyl group or an aryl group). Rtp ⁶ , Rtp ⁷ and Rtp ⁸ represent a substituent. a, b and c each represents an integer of 0 to 4. When a, b and c are 2 or more, Rtp ⁶ , Rtp ⁷ and Rtp ⁸ may be linked to each other to form a ring. X ⁻ represents an anion structure. When X ⁻ is not present, at least one of Rtp ¹ to Rtp ⁷ contains an anion.

When the dye A is a dye multimer, in the formula (TP), through ^one of Rtp ¹ to Rtp ¹⁰ , another part of the dye multimer (preferably L in the general formula (A) described later) ¹ or R ² ) of the general formula (1) described later is preferably bonded, and more preferably bonded to another part of the dye multimer via Rtp ⁵ .

Rtp ¹ to Rtp ⁶ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and a phenyl group. Rtp ⁵ is preferably a hydrogen atom or NRtp ⁹ Rtp ¹⁰ , particularly preferably NRtp ⁹ Rtp ¹⁰ . Rtp ⁹ and Rtp ¹⁰ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a phenyl group. Examples of the substituent represented by Rtp ⁶ , Rtp ⁷ and Rtp ⁸ include the substituent group A described in paragraph Nos. 0042 to 0053 of JP-A-2014-237809. A branched alkyl group, an alkenyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, a carboxyl group or a sulfo group is preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Of these, an alkenyl group, a phenyl group or a carboxyl group is more preferred. In particular, Rtp ⁶ and Rtp ⁸ are preferably alkyl groups having 1 to 5 carbon atoms, and Rtp ⁷ is preferably an alkenyl group (particularly a phenyl group in which two adjacent alkenyl groups are linked), a phenyl group or a carboxyl group. .
a, b or c each independently represents an integer of 0 to 4; In particular, a and c are each preferably 0 or 1, more preferably 0. b is preferably an integer of 0 to 2, more preferably 0 or 2.

When at least one of Rtp ¹ to Rtp ⁷ contains an anion, examples of the anion include —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , bis (sulfonyl) imide anion, tris (sulfonyl) methide anion and tetraarylborate anion. Preferably, bis (sulfonyl) imide anion, tris (sulfonyl) methide anion and tetraarylborate anion are more preferable, and bis (sulfonyl) imide anion and tris (sulfonyl) methide anion are still more preferable.
Specifically, a structure in which at least one of Rtp ¹ to Rtp ⁷ is substituted with the general formula (P) can be given.
General formula (P)

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

In general formula (P), L represents a single bond or a divalent linking group. Examples of the divalent linking group include —NR ¹⁰ —, —O—, —SO ₂ —, an alkylene group which may contain a substituent (for example, a halogen atom and a hydroxyl group, preferably a fluorine atom), and a substituent. It is preferable to represent an arylene group which may contain (for example, a halogen atom or a hydroxyl group, preferably a fluorine atom) or a group consisting of a combination thereof. In particular, a group consisting of a combination of —NR ¹⁰ —, —SO ₂ and an alkylene group containing a fluorine atom, a group consisting of a combination of —O— and an arylene group containing a fluorine atom, or —NR ¹⁰ — and —SO _A group consisting of a combination of ₂ and an alkylene group containing a fluorine atom is preferred.
In —NR ¹⁰ —, R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom.
The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms. The alkylene group containing a fluorine atom is more preferably a perfluoroalkylene group. Specific examples of the alkylene group containing a fluorine atom include a difluoromethylene group, a tetrafluoroethylene group, and a hexafluoropropylene group.
The carbon number of the arylene group is preferably 6 to 20, more preferably 6 to 14, and further preferably 6 to 10. Specific examples of the arylene group containing a fluorine atom include a tetrafluorophenylene group, a hexafluoro-1-naphthylene group, and a hexafluoro-2-naphthylene group.

In general formula (P), X ¹ represents an anion and is selected from —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion and a tetraarylborate anion. Species are preferred, one kind selected from bis (sulfonyl) imide anion, tris (sulfonyl) methide anion and tetraarylborate anion is more preferred, and bis (sulfonyl) imide anion or tris (sulfonyl) methide anion is still more preferred.

When at least one of Rtp ¹ to Rtp ⁷ contains an anion, a structure in which at least one of Rtp ¹ to Rtp ⁷ is substituted with the general formula (P-1) is also preferable.
Formula (P-1)

In general formula (P-1), L ¹ represents a single bond or a divalent linking group, and is preferably a single bond. Examples of the divalent linking group represented by L ¹ include an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —S—, or a group composed of a combination thereof.
L ² represents —SO ₂ — or —CO—.
G represents a carbon atom or a nitrogen atom.
n1 represents 2 when G is a carbon atom, and represents 1 when G is a nitrogen atom.
R ⁶ represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom. When n1 is 2, two R ⁶ may be the same or different.
The number of carbon atoms of the alkyl group containing a fluorine atom represented by R ⁶ is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3.
The number of carbon atoms of the aryl group containing a fluorine atom represented by R ⁶ is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10.

In the dye A, the cation is delocalized as follows.

<<< Dye B having xanthene skeleton >>>
In the present invention, examples of the dye B having a xanthene skeleton include a structure represented by the following formula (J).

In formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom or a monovalent substituent, R ⁸⁵ each independently represents a monovalent substituent, m Represents an integer of 0 to 5. X ⁻ represents a counter anion. When X ⁻ is not present, at least one of R ⁸¹ to R ⁸⁵ contains an anion.

When the dye B is a dye multimer, another part of the dye multimer (preferably L in the general formula (A) to be described later) is bonded via any one of R ⁸¹ to R ^{85 in} the formula (J). ¹ or R ² ) of the general formula (1) described later is preferably bonded, and more preferably bonded to another part of the dye multimer via R ⁸⁵ .

Examples of the substituent that can be taken by R ⁸¹ to R ⁸⁵ in formula (J) include substituent group A described in paragraph Nos. 0042 to 0053 of JP-A-2014-237809, the contents of which are incorporated herein. I will do it.
R ⁸¹ and R ^{82 in} formula (J), R ⁸³ and R ⁸⁴ , and R ^{85 in} the case where m is 2 or more are each independently bonded to each other to form a 5-membered, 6-membered or 7-membered saturated ring. Or a 5-membered, 6-membered or 7-membered unsaturated ring. As the ring to be formed, for example, pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine ring, A pyrazine ring and a pyridazine ring are mentioned, Preferably a benzene ring and a pyridine ring are mentioned.
When the ring formed is a further substitutable group, it may be substituted with the substituents described for R ⁸¹ to R ⁸⁵ , and when it is substituted with two or more substituents, These substituents may be the same or different.

In the formula (J), R ⁸² and R ⁸³ are preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and R ⁸¹ and R ⁸⁴ are preferably a substituted or unsubstituted alkyl group or a phenyl group. R ⁸⁵ is preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, a carboxyl group, or an amide group. The sulfo group, the sulfonamide group, the carboxyl group, More preferred is an amide group. R ⁸⁵ is preferably bonded to the adjacent part of carbon linked to the xanthene ring. The substituent that the phenyl group of R ⁸¹ and R ⁸⁴ has is particularly preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, or a carboxyl group.

When at least one of R ⁸¹ to R ⁸⁵ contains an anion, examples of the anion include the anions described above.

The compound having a xanthene skeleton represented by the formula (J) can be synthesized by a method described in the literature. Specifically, the methods described in Tetrahedron Letters, 2003, vol. 44, No. 23, pages 4355-4360, Tetrahedron, 2005, vol. 61, No. 12, pages 3097-3106, etc. Can be applied.

When X ⁻ represents an anion, the description in the case where the counter anion described later is a different molecule can be referred to.
In addition, when X ⁻ does not exist and at least one of R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ contains an anion, the description of the case where the counter anion is in the same structural unit can be referred to.

In the dye B, the cation is delocalized as follows.

<<< Counter anion >>>
In the present invention, when dye A and / or dye B is composed of a cation moiety and a counter anion, the counter anion is not particularly limited, but may be a non-nucleophilic anion from the viewpoint of heat resistance. preferable. As the non-nucleophilic anion, known non-nucleophilic anions described in JP-A-2007-310315, paragraph No. 0075 and the like are preferable. Here, the non-nucleophilic property means a property that does not nucleophilic attack the dye by heating.
As the counter anion, sulfonate anion, carboxylate anion, sulfonylimide anion, bis (sulfonyl) imide anion, tris (sulfonyl) methide anion, carboxylate anion, tetra aryl volley de ^{anion, -CON - CO -, - CON} - SO ₂ −, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , B ⁻ (CN) ₃ OCH ₃ is preferable. More preferably, it is at least one selected from a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion and a tetraarylborate anion, and more preferably at least one selected from a bis (sulfonyl) imide anion and a tris (sulfonyl) methide anion. It is.
The counter anion is more preferably a non-nucleophilic anion having a structure represented by the following (AN-1) to (AN-5).

In formula (AN-1), X ¹ and X ² each independently represent a fluorine atom or a C 1-10 alkyl group having a fluorine atom. X ¹ and X ² may be bonded to each other to form a ring.
X ¹ and X ² each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, More preferred is a perfluoroalkyl group of ˜10, more preferred is a perfluoroalkyl group having 1 to 4 carbon atoms, and a trifluoromethyl group is particularly preferred.

In formula (AN-2), X ³ , X ⁴ and X ⁵ each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms.
X ³ , X ⁴ and X ⁵ are each independently the same as X ¹ and X ² , and the preferred range is also the same.

In the formula (AN-3), X ⁶ represents an alkyl group having a fluorine atom having 1 to 10 carbon atoms.
X ⁶ is preferably a perfluoroalkyl group having 1 to 10 carbon atoms,
More preferably, it is a 4 perfluoroalkyl group.

In formula (AN-4), X ⁷ represents an alkylene group having 1 to 10 carbon atoms.
X ⁷ is preferably a perfluoroalkylene group having 1 to 10 carbon atoms, and more preferably a perfluoroalkylene group having 1 to 4 carbon atoms.

In formula (AN-5), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represents an aryl group.
Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further an aryl group having 6 to 10 carbon atoms preferable.
The aryl group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have a substituent. In the case of having a substituent, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamide group, a nitro group and the like can be mentioned, and a halogen atom and an alkyl group are preferable, A fluorine atom and an alkyl group are more preferable, and a fluorine atom and a perfluoroalkyl group having 1 to 4 carbon atoms are more preferable.
Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently more preferably a phenyl group having a halogen atom and / or an alkyl group having a halogen atom, and a phenyl group having a fluorine atom and / or an alkyl group having fluorine. Is more preferable.

The non-nucleophilic counter anion is also —B (CN) _n1 (OR ^a ) _4-n1 (R ^a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n1 represents It is preferably an integer of 1 to 4. ^Ra as the alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. R ^a as the aryl group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group.
n1 is preferably 1 to 3, and more preferably 1 to 2.

The non-nucleophilic counter anion is further —PF ₆ R ^P _(6-n2) ⁻ (R ^P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n2 represents an integer of 1 to 6) It is preferable that R ^P is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a perfluoroalkyl group having 1 to 3 carbon atoms.
n2 is preferably an integer of 1 to 4, and more preferably 1 or 2.

The mass per molecule of the non-nucleophilic counter anion is preferably 100 to 1,000, and more preferably 200 to 500.
Specific examples of the non-nucleophilic counter anion are shown below, but the present invention is not limited thereto.

(Dye multimer)
Next, a preferred embodiment of the dye multimer will be described. Hereinafter, the triarylmethane skeleton and the xanthene skeleton are collectively referred to as a dye skeleton.
Specific examples of the case where the dye having a triarylmethane skeleton (Dye A) is a multimer include compounds described in JP-A-2015-83652. This content is incorporated herein. The method for producing the dye multimer is not particularly limited, and an appropriate method may be selected as appropriate. For example, it can be produced by the method described in JP-A-2015-83652.
In the present invention, the dye multimer includes a dye multimer (also referred to as a dye multimer (A)) having a repeating unit represented by the general formula (A) described later, and a repeat represented by the general formula (B) described later. A dye multimer having a unit (also referred to as a dye multimer (B)), a dye multimer having a repeating unit represented by the following general formula (C) (also referred to as a dye multimer (C)), and a general formula The dye multimer represented by (D) (also referred to as dye multimer (D)) is preferred. The dye multimer (A), the dye multimer (C), and the dye multimer (D) are more preferable, and the dye multimer (A) and the dye multimer ( D) is particularly preferred. Hereinafter, the dye multimer will be described in detail.

<<< Dye Multimer (A) >>>
The dye multimer (A) includes a repeating unit represented by the following general formula (A). In the dye multimer (A), the ratio of the repeating unit represented by the following general formula (A) is preferably 10 to 100% by mass of the total repeating units constituting the dye multimer. The lower limit is more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 50% by mass or more. The upper limit is more preferably 95% by mass or less.

In general formula (A), X ¹ represents a linking group formed by polymerization, and L ¹ represents a single bond or a divalent linking group. DyeI represents a group having a triarylmethane skeleton or a xanthene skeleton.

In general formula (A), X ¹ represents a linking group formed by polymerization. That is, X ¹ represents the main chain of the repeating unit. X ¹ is not limited as long as it is a linking group formed from a known polymerizable monomer. Linking groups represented by the following (XX-1) to (XX-30) are exemplified, and linking groups represented by the following (XX-1) to (XX-24) are preferred, and (XX-1), ( XX-2), (XX-10) to (XX-17), (XX-18), (XX-19) and (XX-24), more preferably selected from (XX-1), (XX More preferably selected from (XX-2), (XX-10) to (XX-17) and (XX-24), selected from (XX-1), (XX-2) and (XX-11) It is particularly preferred that
In the formula, it is linked to L ¹ at the site indicated by *. Me represents a methyl group. R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

L ¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, —CH═CH—, —O—, —S—, —C (═O )-, -CO _2- , -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ -and a linking group formed by linking two or more of these, (L- The group represented by 1) is mentioned. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

In formula (L-1), it is linked to X ¹ of formula (A) at the site indicated by * 1, and is linked to DyeI of formula (A) at the site indicated by * 2.

L ¹¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 18 carbon atoms, —O—, —CO—, —S—, —SO ₂ —, —NR ^A R ^B — or Examples include groups composed of these combinations. The alkylene group may be linear, branched or cyclic. The arylene group may be monocyclic or polycyclic. In —NR ^A R ^B —, R ^A and R ^B each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^A and R ^B are bonded to each other to form a ring. Also good.
L ¹² represents —SO ₂ — or —CO—.
L ¹³ represents a divalent linking group. Examples of the divalent linking group include the groups described for L ¹¹ , an arylene group having 6 to 18 carbon atoms (preferably a phenylene group), —O—, —CO—, —S—, —NR ^A R ^B -Or a group consisting of a combination thereof is preferred, and a group consisting of a combination of a phenylene group, -O- and -CO- is more preferred.
G represents a carbon atom or a nitrogen atom.
n2 represents 1 when G is a carbon atom, and represents 0 when G is a nitrogen atom.
R ^7A represents an alkylene group containing a fluorine atom or an arylene group containing a fluorine atom. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms. The carbon number of the arylene group is preferably 6 to 20, more preferably 6 to 14, and further preferably 6 to 10.
R ^7B represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms.

The dye multimer containing the repeating unit represented by the general formula (A) includes (1) a method of synthesizing a monomer having a dye skeleton by addition polymerization, and (2) an isocyanate group, an acid anhydride group, an epoxy group or the like It can be synthesized by a method in which a polymer having a reactive functional group is reacted with a dye having a functional group (hydroxyl group, primary or secondary amino group, carboxyl group, etc.) capable of reacting with a highly reactive group.
Known addition polymerizations (radical polymerization, anionic polymerization, and cationic polymerization) can be applied to the addition polymerization. Among these, synthesis by radical polymerization is particularly preferable because the reaction conditions can be moderated and the dye skeleton is not decomposed. Known reaction conditions can be applied to the radical polymerization.
The dye multimer having the repeating unit represented by the general formula (A) is a radical polymer obtained by radical polymerization using a dye monomer having an ethylenically unsaturated bond from the viewpoint of heat resistance. It is preferable.

(Other repeat units)
The dye multimer in the present invention may contain other repeating units in addition to the repeating unit represented by the general formula (A). Other repeating units may contain a functional group such as a polymerizable group or an acid group. It does not have to contain a functional group. The dye multimer preferably has at least one selected from a repeating unit having an acid group and a repeating unit having a polymerizable group, and more preferably includes a repeating unit having an acid group.

Examples of the polymerizable group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group and a (meth) acryloyloxy group, and a (meth) acryloyl group and a (meth) acryloyloxy group are preferable.
The ratio of the repeating unit having a polymerizable group is preferably 0 to 50% by mass of all repeating units constituting the dye multimer. The lower limit is more preferably 1% by mass or more, and still more preferably 3% by mass or more. The upper limit is more preferably 35% by mass or less, and still more preferably 30% by mass or less.

Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Only one type of acid group may be included, or two or more types of acid groups may be included.
The ratio of the repeating unit having an acid group is preferably 0 to 50% by mass of all repeating units constituting the dye multimer. The lower limit is more preferably 1% by mass or more, and still more preferably 3% by mass or more. The upper limit is more preferably 35% by mass or less, and still more preferably 30% by mass or less.

Other functional groups include groups consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains, development promoting groups such as lactones, acid anhydrides, amides, cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryls Groups, polyalkylene oxide groups, hydroxyl groups, maleimide groups, amino group and other hydrophilicity-adjusting groups, and the like, which can be appropriately introduced.
In the group consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains, the number of repeating alkyleneoxy chains is preferably 2 to 10, more preferably 2 to 15, and even more preferably 2 to 10. One alkyleneoxy chain is represented by — (CH ₂ ) _n O—, where n is an integer, n is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 or 3.

Although the specific example of another repeating unit is shown, this invention is not limited to this.

<<< Dye Multimer (B) >>>
The dye multimer (B) includes a cation having a triarylmethane skeleton or a xanthene skeleton and a repeating unit represented by the following general formula (B). In the dye multimer (B), the ratio of the repeating unit represented by the following general formula (B) is preferably 10 to 100% by mass of the total repeating units constituting the dye multimer. The lower limit is more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 50% by mass or more. The upper limit is more preferably 95% by mass or less.

In the general formula (B), X ² represents a linking group formed by polymerization, L ² represents a single bond or a divalent linking group, and Z represents an anion.

X ² has the same meaning as X ^{1 in} formula (A), and the preferred range is also the same.
L ² represents a single bond or a divalent linking group. Examples of the divalent linking group include a hydrocarbon group, —NH—, —CO—, —COO—, a divalent group containing a dye skeleton, etc., and an alkylene group having 1 to 20 carbon atoms, An arylene group having 20 carbon atoms, a heterocyclic group having 4 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, an alkylcarbonyl group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms. Arylcarbonyl groups having 1 to 20 carbon atoms, arylamino groups having 6 to 20 carbon atoms, alkylcarbonyloxy groups having 1 to 2 carbon atoms, arylcarbonyloxy groups having 6 to 20 carbon atoms, and the like. . These divalent linking groups are preferably substituted with an electron-withdrawing group. Examples of the electron-withdrawing group include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), nitro group, cyano group, Examples thereof include a halogenated alkyl group (for example, a trifluoromethyl group) and a halogenated aryl group.
Z represents an anion. The anion is not particularly limited, and examples thereof include —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , bis (sulfonyl) imide anion, tris (sulfonyl) methide anion, and tetraarylborate anion. An anion represented by the general formula (Z-1), an anion represented by the general formula (Z-2), and an anion represented by the following general formula (Z-3) are also preferable.
Z is preferably an anion represented by general formulas (Z-1) to (Z-3), a group represented by general formula (2-1), a fluorinated alkylsulfonimide group (general formula (2- 2), Y ² represents a nitrogen atom, A ² represents a fluorinated alkylsulfonyl group), or a fluorinated alkyl sulfonemethide group (in general formula (2-2), Y ² represents a carbon atom, and A ² represents a fluorine atom. Each of which represents an alkylsulfonyl group).

General formula (Z-1)
* -Y ¹ -A ¹
(In the general formula (Z-1), * represents a binding site with L ² in the general formula (B), Y ¹ represents a fluorinated alkylene group, A ¹ is SO ₃ ^- represents a.)

In general formula (Z-1), Y ¹ represents a fluorinated alkylene group. The fluorinated alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms. Moreover, it is more preferably a perfluoroalkylene group.

General formula (Z-2)
* -Y ^2- (A ² ) _n
In the general formula (Z-2), * represents a binding site with L ² in the general formula (B).
Y ² represents an anion composed of a boron atom, a carbon atom, a nitrogen atom, or a phosphorus atom.
When Y ² is a boron atom, n is 3, and A ² represents a halogen atom, a cyano group, an alkyl group containing at least one of a fluorine atom and a cyano group, or at least one of a fluorine atom and a cyano group. An aryl group is preferred.
When Y ² is a carbon atom, n is 2 and A ² is a halogen atom, a cyano group, an alkyl group containing at least one of a fluorine atom and a cyano group, an aryl containing at least one of a fluorine atom and a cyano group An alkylsulfonyl group which may contain at least one of a group, a fluorine atom and a cyano group, or an arylsulfonyl group which may contain at least one of a fluorine atom and a cyano group is preferred. Two A ² may be bonded to each other to form a ring.
When Y ² is a nitrogen atom, n is 1, and A ² is an alkyl group containing at least one of a fluorine atom and a cyano group, an aryl group containing at least one of a fluorine atom and a cyano group, a fluorine atom and a cyano group An alkylsulfonyl group which may contain at least one group or an arylsulfonyl group which may contain at least one of a fluorine atom and a cyano group is preferable.
When Y ² is a phosphorus atom, n is 1 or 3, and A ² is an alkyl group containing at least one of a fluorine atom and a cyano group, an aryl group containing at least one of a fluorine atom and a cyano group, a fluorine atom And an alkylsulfonyl group which may contain at least one of cyano groups, or an arylsulfonyl group which may contain at least one of a fluorine atom and a cyano group is preferable.
When n is 2 or more, the plurality of A ² may be the same or different.

When the general formula (Z-1) and the general formula (Z-2) contain a fluorine atom, the ratio of the fluorine atom contained in Z to the total number of atoms constituting Z is preferably 5 to 80%, preferably 10 to 70% is more preferable.

General formula (Z-3)

In the general formula (Z-3), * represents a binding site with L ² in the general formula (B).
R ¹ to R ⁴ are preferably each independently a cyano group or a fluorinated alkyl group.

Specific examples of the repeating unit represented by the general formula (B) include the structures described in paragraph numbers 0162 to 0166 in JP-A-2014-199436.

The dye multimer (B) may contain other repeating units described in the dye multimer (A) in addition to the repeating unit represented by the general formula (B). Moreover, the repeating unit represented by general formula (A) mentioned above and the repeating unit represented by general formula (C) mentioned later may further be included.

<<< Dye Multimer (C) >>>
The dye multimer (C) includes a repeating unit represented by the following general formula (C). In the dye multimer (C), the ratio of the repeating unit represented by the following general formula (C) is preferably 10 to 100% by mass of the total repeating units constituting the dye multimer. The lower limit is more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 50% by mass or more. The upper limit is more preferably 95% by mass or less.

In general formula (C), L ³ represents a single bond or a divalent linking group. DyeIII represents a group having a triarylmethane skeleton or a xanthene skeleton. m represents 0 or 1;

In general formula (C), L ³ represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L ³ include an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, —CH═CH—, —O—, and —S—. , —C (═O) —, —CO ₂ —, —NR—, —CONR—, —O ₂ C—, —SO—, —SO ₂ — and a linking group formed by linking two or more thereof. Are preferable.
m represents 0 or 1, but is preferably 1.

Details of the general formula (C) can be referred to the descriptions in paragraphs 0165 to 0167 of JP2013-29760A and paragraphs 0080 to 0088 of JP2015-57487A, the contents of which are described in this specification. Incorporated into.

Specific examples of the repeating unit represented by the general formula (C) include the following.

The dye multimer (C) may contain other repeating units described in the dye multimer (A) in addition to the repeating unit represented by the general formula (C).

The dye multimer (C) can be synthesized by sequential polymerization. Sequential polymerization means polyaddition (for example, reaction of diisocyanate compound and diol, reaction of diepoxy compound and dicarboxylic acid, reaction of tetracarboxylic dianhydride and diol, etc.) and polycondensation (for example, dicarboxylic acid). And a diol, a reaction of a dicarboxylic acid and a diamine, and the like. Among these, synthesis by polyaddition reaction is particularly preferable because the reaction conditions can be moderated and the dye skeleton is not decomposed. Known reaction conditions can be applied to the sequential polymerization.

<<< Dye Multimer (D) >>>
The dye multimer (D) is represented by the general formula (D).

In general formula (D), L ⁴ represents an n-valent linking group. n represents an integer of 2 to 20. DyeIV represents a polymer chain including a group having a triarylmethane skeleton or a xanthene skeleton, or a repeating unit having a triarylmethane skeleton or a xanthene skeleton.

In the general formula (D), n is preferably 2 to 15, more preferably 2 to 14, still more preferably 2 to 8, particularly preferably 2 to 7, and most preferably 2 to 6.
In addition, although n in one pigment | dye is an integer, the coloring composition of this invention may contain multiple things from which n differs as a pigment | dye multimer (D). Therefore, the average value of n in the colored composition of the present invention may not be an integer.
In the present invention, n in one dye preferably represents an integer of 2 to 20.
Further, when the dye multimer (D) is a mixture containing 50% by mass of the dye a1 in which n is 2 in the general formula (D) and 50% by mass of the dye a2 in which n is 1, the average value of n The dye a1 contained in this mixture corresponds to the dye multimer (D) because n satisfies an integer of 2 to 20.
Further, when the dye multimer (D) is a mixture of a plurality of dye multimers (D), the average value of n is preferably a number of 2 to 20.

L ⁴ represents an n-valent linking group. n-valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 To 20 sulfur atoms are included, which may be unsubstituted or further substituted.
Specific examples of the n-valent linking group include the following structural unit or a group composed of a combination of two or more of the following structural units (which may form a ring structure).

Specific examples of n-valent linking groups are shown below. However, the present invention is not limited to these. In addition, a linking group described in paragraph Nos. 0071 to 0072 of JP-A-2008-222950 and a linking group described in paragraph No. 0176 of JP-A-2013-029760 are also included.

The dye multimer (D) is also preferably represented by the general formula (D1).

In general formula (D), L ⁴ represents an n-valent linking group. n represents an integer of 2 to 20. DyeIVa represents a polymer chain including a group having a triarylmethane skeleton or a xanthene skeleton, or a repeating unit having a triarylmethane skeleton or a xanthene skeleton. S represents a sulfur atom.

(Preferred embodiment 1 of the dye multimer (D))
One preferred embodiment of the dye multimer (D) is a structure represented by the following general formula (D-1).
(D-R ² ) _n -R ^1- (L ¹ -P) _m (D-1)
In general formula (D-1), R ¹ represents a (m + n) -valent linking group,
P represents a monovalent substituent having a repeating unit;
D represents a dye skeleton,
R ² and L ¹ each independently represents a single bond or a divalent linking group,
m represents an integer of 1 to 13,
when m is 1, P represents a monovalent substituent having two or more repeating units;
When m is 2 or more, the plurality of Ps may be different from each other, the average value of the number of repeating units constituting the plurality of Ps is 2 or more,
n represents an integer of 2 to 14,
when n is 2 or more, the plurality of D may be different from each other;
m + n represents an integer of 2 to 15.

In general formula (D-1), m represents an integer of 1 to 13. m is preferably 1 to 5, more preferably 1 to 4, and particularly preferably 1 to 3.
In general formula (D-1), n represents an integer of 2 to 14. n is preferably 2 to 8, more preferably 2 to 7, particularly preferably 2 to 6, and more preferably 2 to 5.
In general formula (D-1), m + n is preferably 2 to 15.
M and n in one dye are integers, but in the present invention, a plurality of dye multimers having different m and n in the general formula (D-1) may be included. Therefore, the average value of m and n in the coloring composition of the present invention may not be an integer. In the present invention, m in one dye preferably represents an integer of 1 to 13. When the dye multimer (D) is a mixture of a plurality of dye multimers (D), the average value of m is 1 to 13, and the average value of n is 2 to 14. preferable.

In general formula (D-1), R ¹ represents a (m + n) -valent linking group. m + n satisfies 2 to 15.
Examples of the (m + n) -valent linking group represented by R ¹ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200. Groups consisting of up to 20 hydrogen atoms and 0 to 20 sulfur atoms, which may be unsubstituted or further substituted. Specific examples of the (m + n) -valent linking group represented by R ¹ include the structure described above for L ⁴ .

In general formula (D-1), R ² and L ¹ each independently represents a single bond or a divalent linking group. When a plurality of R ² and L ¹ are present, they may be the same or different.
Divalent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 To 20 sulfur atoms are included, which may be unsubstituted or further substituted.

Specific examples of the divalent linking group include a group constituted by combining two or more of the following structural units or the following structural units. R ² and L ¹ are preferably a group containing —S—, more preferably —S—.

In general formula (D-1), P represents a substituent. As the substituent, a monovalent substituent having a repeating unit derived from a vinyl compound is preferable. When m is 2 or more, m Ps may be the same or different.
When m is 1, P is preferably a monovalent substituent having 2 to 20 (preferably 2 to 15, more preferably 2 to 10) repeating units derived from a vinyl compound. When m is 2 or more, the average number of repeating units derived from m P vinyl compounds is 2 to 20 (preferably 2 to 15, more preferably 2 to 10). It is preferable. According to this aspect, the flatness of the coating film is improved.
When m is 1, the number of repeating units of P, and when m is 2 or more, the average value of the number of repeating units of m P can be obtained by nuclear magnetic resonance (NMR). Specifically, for example, m can be calculated from the peak area ratio of the (m + n) -valent linking group represented by R ¹ and the dye skeleton D, and the peak area ratio of the repeating unit can be calculated by dividing by m. .

Examples of the repeating unit constituting P include the other repeating units described in the dye multimer (A) described above. The other repeating unit preferably has at least one selected from the above-described repeating unit having an acid group and the repeating unit having a polymerizable group, and more preferably includes a repeating unit having an acid group.
When P contains a repeating unit containing an acid group, the proportion of the repeating unit containing an acid group is preferably 10 to 80 mol%, more preferably 10 to 65 mol%, based on all the repeating units of P.
When P includes a repeating unit having a polymerizable group, the ratio of the repeating unit having a polymerizable group is preferably 10 to 80 mol%, more preferably 10 to 65 mol%, based on all the repeating units of P. . When P contains a repeating unit having a polymerizable group, the color transfer property can be further improved.

The dye multimer having the dye skeleton represented by the general formula (D-1) can be synthesized by the following method or the like.
(1) A polymer in which a functional group selected from a carboxyl group, a hydroxyl group, an amino group and the like is introduced at the end, an acid halide having a dye skeleton, an alkyl halide having a dye skeleton, or an isocyanate having a dye skeleton, and the like. Polymer reaction method.
(2) A method in which a polymer having a carbon-carbon double bond introduced at the terminal and a mercaptan having a dye skeleton are subjected to a Michael addition reaction.
(3) A method of reacting a polymer having a carbon-carbon double bond introduced at a terminal thereof with a mercaptan having a dye skeleton in the presence of a radical generator.
(4) A method in which a polymer having a plurality of mercaptans introduced at its terminal is reacted with a compound having a carbon-carbon double bond and a dye skeleton in the presence of a radical generator.
(5) A method in which a vinyl compound is radically polymerized in the presence of a thiol compound having a dye skeleton.
Of the above methods, the synthesis methods (2) to (5) are preferable and the synthesis methods (3) to (5) are more preferable because of ease of synthesis.

(Preferred embodiment 2 of dye multimer (D))
One preferred embodiment of the dye multimer (D) is a structure represented by the following general formula (D-2).
P- (Q) _n (D-2)
In general formula (D-2), P represents an n-valent linking group,
Q represents a polymer chain containing a repeating unit having a dye skeleton,
The average value of the number of repeating units of n Q having a dye skeleton is 2 or more,
n represents an integer of 3 to 10.

<<< Linking group P >>>
In general formula (D-2), P represents an n-valent linking group.
n-valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 To 20 sulfur atoms are included, which may be unsubstituted or further substituted.
The n-valent linking group represented by P includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and Groups consisting of 0 to 10 sulfur atoms are preferred. More preferably, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 atoms. It is a group consisting of the sulfur atom. More preferably, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 atoms. It is a group consisting of the sulfur atom.
The n-valent linking group represented by P is preferably a linking group derived from a polyhydric alcohol.

The dye multimer represented by the general formula (D-2) is preferably represented by the general formula (D-2a).

In general formula (D-2a), A ¹ represents an n-valent linking group,
B ¹ represents a single bond, —O—, —S—, —CO—, —NR—, —O ₂ C—, —CO ₂ —, —NROC—, or —CONR—,
R represents a hydrogen atom, an alkyl group or an aryl group,
C ¹ represents a single bond or a divalent linking group,
S represents a sulfur atom,
Q represents a polymer chain containing a repeating unit having a dye skeleton,
The average value of the number of repeating units of n Q having a dye skeleton is 2 or more,
n represents an integer of 3 to 10.

In the general formula (D-2a), A ¹ represents an n-valent linking group.
The n-valent linking group is preferably a group consisting of one or a combination of two or more selected from an aliphatic hydrocarbon group, an aromatic ring group and a heterocyclic group which may have an oxygen atom in the main chain.
Examples of the aliphatic hydrocarbon group include an alkylene group and an alkenylene group. The number of carbon atoms of the alkylene group is, for example, preferably 1-60, and more preferably 1-30. The number of carbon atoms of the alkenylene group is, for example, preferably 1-60, and more preferably 1-30.
Examples of the aliphatic hydrocarbon group having an oxygen atom in the main chain include groups represented by — (OR ^x1 ) _m — and — (R ^x1 O) _m —. The aliphatic hydrocarbon group having an oxygen atom in the main chain may be linear, branched or cyclic. The main chain refers to a skeleton portion of a linking group and does not include a substituent.
R ^x1 represents an alkylene group or an alkenylene group. m represents an integer of 1 or more. When m is 2 or more, m R ^{x1 s} may be the same or different.
The alkylene group represented by R ^x1 preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms. The alkylene group may be linear, branched or cyclic.
The carbon number of the alkenylene group represented by R ^x1 is preferably 2 to 20, more preferably 2 to 10, and still more preferably 2 to 5. The alkenylene group may be linear, branched or cyclic.
The aromatic ring group may be monocyclic or polycyclic.
The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be monocyclic or polycyclic. Examples of the hetero atom contained in the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. A nitrogen atom is preferred. The number of heteroatoms is preferably 1 to 3.

The n-valent linking group represented by A ¹ includes a hydrocarbon group that may have an oxygen atom in the main chain, an aromatic ring group, a heterocyclic group, and a hydrocarbon group that may have an oxygen atom in the main chain; Preferred examples include a combination with an aromatic ring group and a combination of a hydrocarbon group that may have an oxygen atom in the main chain and a heterocyclic group.

In the general formula (D-2a), B ¹ is a single bond, —O—, —S—, —CO—, —NR—,
Represents —O ₂ C—, —CO ₂ —, —NROC—, or —CONR—, and represents a single bond, —O—,
—CO—, —O ₂ C—, —CO ₂ —, —NROC—, or —CONR— is preferable.
R represents a hydrogen atom, an alkyl group or an aryl group.
The alkyl group represented by R preferably has 1 to 30 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic.
The number of carbon atoms of the aryl group represented by R is preferably 6-30, and more preferably 6-12.
R is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

In the general formula (D-2a), C ¹ represents a single bond or a divalent linking group.
The divalent linking group is preferably an alkylene group, an arylene group or an oxyalkylene group, more preferably an alkylene group or an oxyalkylene group.
The alkylene group and oxyalkylene group preferably have 1 to 30 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group and oxyalkylene group may be linear, branched or cyclic.
The number of carbon atoms in the arylene group is preferably 6 to 30, and more preferably 6 to 12.

Specific examples of the n-valent linking group represented by P are shown below. However, the present invention is not limited to these.

The polymer chain represented by Q represents a polymer chain containing a repeating unit having a dye skeleton, and the average value of the number of repeating units of n Q having a dye skeleton is 2 or more. The n Qs may be the same or different.
The polymer chain represented by Q preferably has an average value of 2 to 20 repeating units having a dye skeleton, more preferably 2 to 15 and even more preferably 2 to 10.
The average value of the number of repeating units having a dye skeleton can be determined by NMR (nuclear magnetic resonance). Specifically, for example, the number of repeating units in the general formula (D-2) is obtained from the peak area ratio between the n-valent linking group represented by P and the repeating unit of the polymer chain Q. Next, the number of repeating units in the polymer chain Q can be calculated by dividing the value by n.
The weight average molecular weight of the polymer chain Q is preferably 2000 to 40000.

The polymer chain represented by Q is not particularly defined as long as it contains a dye skeleton, but is a kind selected from (meth) acrylic resins, styrene resins, and (meth) acrylic / styrene resins. Preferably there is.
The skeleton structure of the repeating unit having a dye skeleton is not particularly defined, and examples thereof include the repeating unit represented by the general formula (A) described above and the repeating unit represented by the general formula (C) described above. . The total number of repeating units having a dye skeleton in all repeating units constituting the polymer chain Q is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and 20 to 40 mol%. Further preferred.

The polymer chain Q may contain other repeating units described in the dye multimer (A) in addition to the repeating unit having the dye skeleton described above. As another repeating unit, it is preferable to have one or more selected from a repeating unit having an acid group and a repeating unit having a polymerizable group.

When the polymer chain Q includes a repeating unit having a polymerizable group, the ratio of the repeating unit having a polymerizable group is preferably, for example, 5 to 50 mol with respect to 100 mol of all the repeating units of the polymer chain Q. Mole is more preferred.
When the polymer chain Q includes a repeating unit having an acid group, the ratio of the repeating unit having an acid group is preferably, for example, 5 to 50 moles relative to 100 moles of all the repeating units of the polymer chain Q, and 10 to 40 moles. More preferred.

The dye multimer represented by the general formula (D-2) is not particularly limited, but has a polyfunctional thiol compound having 3 to 10 thiol groups in one molecule, a dye skeleton and a radical polymerizable group. It can be produced by a method of radical polymerization of a compound (radically polymerizable dye compound).
The radical polymerization of the polyfunctional thiol compound and the radical polymerizable dye compound is performed by, for example, dissolving the polyfunctional thiol compound and the radical polymerizable dye compound in an appropriate solvent, adding a radical generator to the solution, The addition can be carried out at a temperature of about 50 ° C. to 100 ° C. (thiol-ene reaction method).

<<< Properties of Dye Multimer >>>
The weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 40000. The lower limit is more preferably 3000 or more, and further preferably 4000 or more. The upper limit is more preferably 35,000 or less and even more preferably 30000 or less. By satisfy | filling the said range, solvent resistance and color transfer property become more favorable.
When the dye multimer includes a triarylmethane skeleton, that is, when the dye A is a dye multimer, the weight average molecular weight of the dye A is preferably 2000 to 40000. The lower limit is more preferably 3000 or more, and further preferably 4000 or more. The upper limit is more preferably 35,000 or less and even more preferably 30000 or less.
When the dye multimer includes a xanthene skeleton, that is, when the dye B is a dye multimer, the weight average molecular weight of the dye B is preferably 2000 to 40000. The lower limit is more preferably 3000 or more, and further preferably 4000 or more. The upper limit is more preferably 35,000 or less and even more preferably 30000 or less.
In addition, in this invention, the weight average molecular weight (Mw) of a pigment | dye multimer is a polystyrene conversion value by a gel permeation chromatograph (GPC) measurement, and specifically, it measured by the method as described in the Example mentioned later. Value.

The acid value of the dye multimer is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 27 mgKOH / g or more, and particularly preferably 30 mgKOH / g or more. The upper limit of the acid value is preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less, further preferably 180 mgKOH / g or less, still more preferably 130 mgKOH / g or less, and still more preferably 120 mgKOH / g or less. By satisfy | filling the said range, developability improves more and a development residue can be reduced more.

The ratio [(Mw) / (Mn)] of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the dye multimer is preferably 1.0 to 3.0, preferably 1.0 to 2. 5 is more preferable, and 1.0 to 2.0 is particularly preferable.

<< other colorants >>
The coloring composition of the present invention may contain a colorant other than the dye A and the dye B. The other colorant may be either a dye or a pigment.
The other colorant may be a dye multimer. The weight average molecular weight of the dye multimer is preferably 2,000 to 50,000, more preferably 3,000 to 30,000, and further preferably 6,000 to 20,000.
1 type may be sufficient as another colorant, and 2 or more types may be sufficient as it.

Examples of the pigment include conventionally known various inorganic pigments or organic pigments. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having an average particle size as small as possible, and considering the handling properties, the average particle size of the pigment is 0.01 to 0.1 μm is preferable, and 0.01 to 0.05 μm is more preferable.

Examples of inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, black pigments such as carbon black and titanium black, iron, cobalt, aluminum, cadmium, lead, copper, Mention may be made of metal oxides such as titanium, magnesium, chromium, zinc and antimony, and composite oxides of the above metals.

The following can be mentioned as an organic pigment. However, the present invention is not limited to these.
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175 176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc.,
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279
C. I. Pigment Green 7, 10, 36, 37, 58, 59
C. I. Pigment Violet 1,19,23,27,32,37,42
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80
C. I. Pigment Black 1
These organic pigments can be used alone or in various combinations in order to increase color purity.

Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, JP 2592207, and US Pat. No. 4,808,501. U.S. Pat. No. 5,667,920, U.S. Pat. No. 505950, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-51115. -The pigment | dye currently disclosed by 194828 gazette etc. can be used. When classified as chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.

As other colorants, the azo dyes described in paragraphs 0084 to 0134 of JP2013-41097A and paragraphs 0029 to 0136 of JP2011-162760A can also be used.

In the coloring composition of the present invention, the content of the other coloring agent is preferably 1 to 30% by mass with respect to the total amount of the coloring agent. The upper limit is more preferably 25% by mass or less, further preferably 20% by mass or less, and further preferably 15% by mass or less. The lower limit is more preferably 3% by mass or more, further preferably 5% by mass or more, and further preferably 7% by mass or more.
Moreover, it can also be set as the aspect which does not contain other coloring agents substantially. In addition, 0.1 mass% or less is preferable with respect to the whole quantity of a coloring agent, for example, and 0.05 mass% or less is more preferable, and it is still more preferable not to contain that other coloring agents are not contained substantially.

In the colored composition of the present invention, the content of the colorant with respect to the total solid content in the colored composition is preferably 10 to 60% by mass. The lower limit is more preferably 20% by mass or more, and further preferably 30% by mass or more. The upper limit is more preferably 55% by mass or less. If content of a colorant is the range mentioned above, content of components other than a colorant can be raised and developability can be improved more.

<< Curable compound >>
The coloring composition of the present invention contains a curable compound. As the curable compound, known compounds that can be cross-linked by radicals, acids, and heat can be used.
In the present invention, examples of the curable compound include a group having an ethylenically unsaturated bond, a cyclic ether (epoxy, oxetane) group, a methylol group, and the like, and a compound having an ethylenically unsaturated bond is preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
In the present invention, the curable compound is preferably a compound polymerizable by radicals, preferably a radical polymerizable compound, and more preferably a radical photopolymerizable compound (hereinafter, the radical polymerizable compound is also referred to as a polymerizable compound).

The polymerizable compound may be in any chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof. The polymerizable compound is preferably a monomer.
The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.
The molecular weight of the polymerizable compound is preferably 100 to 3000, and more preferably 200 to 2000.
Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters, amides, and multimers thereof. Preferred are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof. In addition, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, halogen groups and tosyloxy groups A reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as monofunctional or polyfunctional alcohols, amines or thiols is also suitable. Moreover, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like.
As these specific compounds, compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can be preferably used in the present invention.

In the present invention, the polymerizable compound is also preferably a compound having at least one group having an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure. As examples thereof, for example, compounds described in paragraph 0227 of JP 2013-29760 A and paragraphs 0254 to 0257 of JP 2008-292970 A can be referred to, the contents of which are incorporated herein.

The polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.). Dipentaerythritol penta (meth) acrylate (commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues (for example, commercially available from Sartomer, SR454, SR499) Is preferred . These oligomer types can also be used. KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.) can also be used.
Preferred embodiments of the polymerizable compound are shown below.

The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polymerizable compound having a group is more preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix M-510, Aronix M-520, Aronix TO-2349, and the like as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

The preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

The polymerizable compound is also preferably a compound having a caprolactone structure.
The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule.For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, Mention is made of an ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying (meth) acrylic acid and ε-caprolactone with a polyhydric alcohol such as tripentaerythritol, glycerin, diglycerol, trimethylolmelamine and the like. Can do. Of these, compounds having a caprolactone structure represented by the following general formula (Z-1) are preferred.

In the general formula (Z-1), all six R are groups represented by the following general formula (Z-2), or 1 to 5 of the six R are represented by the following general formula (Z -2), and the remainder is a group represented by the following general formula (Z-3).

In general formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2,
“*” Indicates a bond.

In general formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond. )

Polymerizable compounds having a caprolactone structure are commercially available, for example, from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (Z-1) to (Z-3), Number of groups represented by (Z-2) = 2, a compound in which R ¹ is all hydrogen atoms), DPCA-30 (formula, m = 1, number of groups represented by formula (Z-2)) = 3, a compound in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, a compound in which R ¹ is all hydrogen atoms) ), DPCA-120 (a compound in which m = 2 in the formula, the number of groups represented by formula (Z-2) = 6, and all R ¹ are hydrogen atoms).

As the polymerizable compound, a compound represented by the following general formula (Z-4) or (Z-5) can also be used.

In general formulas (Z-4) and (Z-5), each E independently represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O). —, Each independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
In the general formula (Z-4), the total of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40 .
In general formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60 .

In general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In the general formula (Z-4) or the general formula (Z-5), — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) — represents oxygen A form in which the end on the atom side is bonded to X is preferred.

The compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (Z-5), a form in which all six Xs are acryloyl groups is preferable.

The total content of the compound represented by the general formula (Z-4) or (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

The compound represented by the general formula (Z-4) or (Z-5) is a conventionally known process, which is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”). Among them, exemplary compounds (a), (f) b), (e) and (f) are preferred.

Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Thus, a colored composition having an extremely excellent photosensitive speed can be obtained.
Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

In the colored composition of the present invention, the content of the curable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the colored composition. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.
One curable compound may be used alone, or two or more curable compounds may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.

<< Polyfunctional thiol compound >>
The coloring composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound. The polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (T1).
General formula (T1)

(In the formula (T1), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.)

In the above general formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and a compound represented by the formula (T2) is particularly preferable. These polyfunctional thiols can be used alone or in combination.

When the coloring composition of the present invention contains a polyfunctional thiol, the content of the polyfunctional thiol is preferably 0.3 to 8.9% by mass with respect to the total solid content of the coloring composition, and preferably 0.8 to 6 More preferably, 4% by mass. Polyfunctional thiols may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.

<< photopolymerization initiator >>
The coloring composition of the present invention preferably contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones. Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compound described in JP-A-62-258241, compound described in JP-A-5-281728, compound described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

From the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums Compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

More preferred are trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound, trihalomethyltriazine compound, α-aminoketone Particularly preferred is at least one compound selected from the group consisting of compounds, oxime compounds, triallylimidazole dimer, and benzophenone compounds.

In particular, when the colored composition of the present invention is used for the production of a color filter for a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is important that it be developed. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Therefore, in view of these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device. Further, the use of an oxime compound can improve the color transfer.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm can also be used.
As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

More preferred examples of the photopolymerization initiator include oxime compounds.
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane Examples include -2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660),
J. et al. C. S. Perkin II (1979) pp. 156-162, Journal
of Photopolymer Science and Technology (1995) pp. Examples thereof include compounds described in 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166, and the like.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (made by ADEKA) can also be used.

Further, as oxime compounds other than those described above, compounds described in JP-T-2009-519904 in which oxime is linked to carbazole N position, and compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety And compounds described in JP 2010-15025 A and U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety, ketoxime compounds described in International Publication No. 2009-131189, triazine skeleton and oxime skeleton In the same molecule, a compound described in Japanese Patent Application Laid-Open No. 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, and the like. May be.
Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

In general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In General Formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
In the general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.

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

In the present invention, a compound represented by the following general formula (1) or (2) can also be used as a photopolymerization initiator.

In the formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or When an arylalkyl group having 7 to 30 carbon atoms is represented and R ¹ and R ² are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R ³ and R ⁴ are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, wherein X is a direct bond or carbonyl Indicates a group.

In the formula (2), R ^1, R ^2, R ³ and R ⁴ have the same meanings as R ^1, R ^2, R ³ and R ⁴ in Formula (1), R ⁵ is -R ^6, -OR ⁶ , —SR ⁶ , —COR ⁶ , —CONR ⁶ R ⁶ , —NR ⁶ COR ⁶ , —OCOR ⁶ , —COOR ⁶ , —SCOR ⁶ , —OCSR ⁶ , —COSR ⁶ , —CSOR ⁶ , —CN, halogen R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms; X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.

In the above formulas (1) and (2), R ¹ and R ² are preferably each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
Specific examples of the compounds represented by formula (1) and formula (2) include, for example, compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.

Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited thereto.

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 405 nm.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, more preferably from 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
For the molar extinction coefficient of the compound, a known method can be used. For example, in a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian), an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure.
You may use the photoinitiator used for this invention in combination of 2 or more type as needed.

The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1 to 20% by mass with respect to the total solid content of the coloring composition. is there. Within this range, better sensitivity and pattern formability can be obtained. The colored composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

In the present invention, the photopolymerization initiator is a photopolymerization initiator (hereinafter also referred to as a photopolymerization initiator (a)) having an extinction coefficient of 365 nm in methanol of 1.0 × 10 ³ mL / gcm or more. Photopolymerization initiator (hereinafter referred to as photopolymerization initiator) having an extinction coefficient of 365 nm in methanol of 1.0 × 10 ² mL / gcm or less and an extinction coefficient of 254 nm of 1.0 × 10 ³ mL / gcm or more. (B) is also preferably used in combination. According to this aspect, it is easy to form a cured film excellent in solvent resistance.
The content of the photopolymerization initiator (a) is preferably 1.5 to 10% by mass, more preferably 3 to 8% by mass, based on the total solid content of the colored composition of the present invention. A sensitivity is favorable if content of a photoinitiator (a) is 10 mass% or less. Moreover, if content of a photoinitiator (a) is 1.5 mass% or more, it will be easy to form the cured film excellent in solvent resistance.

The photopolymerization initiator (a) preferably has an extinction coefficient at 365 nm in methanol of 1.0 × 10 ³ to 1.0 × 10 ⁴ mL / gcm, and 2.0 × 10 ³ to 9.0. It is more preferably × 10 ³ mL / gcm, and even more preferably 6.0 × 10 ³ to 8.0 × 10 ³ mL / gcm.
As the photopolymerization initiator (a), an oxime compound, an aminoacetophenone compound and an acylphosphine compound can be suitably used, and an oxime compound is preferable. As the oxime compound, a compound represented by the above general formula (OX-1) is preferable.
The content of the photopolymerization initiator (a) is preferably 1.5 to 10% by mass, more preferably 3 to 8% by mass, based on the total solid content of the colored composition of the present invention. If content of a photoinitiator (a) is the said range, it will be easy to form the cured film excellent in solvent resistance. A photoinitiator (a) may be used individually by 1 type, or may use 2 or more types together.

The photopolymerization initiator (b) preferably has an extinction coefficient at 365 nm in methanol of 10 to 1.0 × 10 ² mL / gcm, and 20 to 9.0 × 10 ² mL / gcm. Is more preferable.
The difference in the extinction coefficient at a wavelength of 365 nm between the photopolymerization initiator (a) and the photopolymerization initiator (b) is preferably 9.0 × 10 ² mL / gcm or more, and 9.0 × 10 ² to 1.0 × 10 ⁵ mL / gcm is more preferable, and 9.0 × 10 ² to 1.0 × 10 ⁴ mL / gcm is more preferable.
The photopolymerization initiator (b) preferably has an extinction coefficient at 254 nm in methanol of 1.0 × 10 ³ to 1.0 × 10 ⁶ mL / gcm, and preferably 5.0 × 10 ³ to 1.0. × 10 ⁵ mL / gcm is more preferable.
As the photopolymerization initiator (b), hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used.
The hydroxyacetophenone compound is preferably a compound represented by the following formula (V).

In the formula (V), Rv ¹ represents a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms), or a divalent organic compound. Represents a group. When Rv ¹ is a divalent organic group, two photoactive hydroxyacetophenone structures (that is, a structure in which the substituent Rv ¹ is excluded from the compound represented by the general formula (V)) are formed via Rv ¹ Represents a dimer formed by linking. Rv ² and Rv ³ each independently represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms). Rv ² and Rv ³ may combine to form a ring (preferably a ring having 4 to 8 carbon atoms). Alkyl and alkoxy groups as the Rv ^1, the alkyl group as Rv ² and Rv ^3, and, ring and Rv ² and Rv ³ is formed by bonding, it may further have a substituent.

The content of the photopolymerization initiator (b) is preferably 1.5 to 7.5% by mass and more preferably 2 to 6% by mass in the total solid content of the colored composition of the present invention. If content of a photoinitiator (b) is the said range, it will be easy to form the cured film excellent in solvent resistance. A photoinitiator (b) may be used individually by 1 type, or may use 2 or more types together.

<< Resin >>
The colored composition of the present invention preferably contains a resin. The resin is blended, for example, for the purpose of dispersing a colorant such as a pigment in the composition and the purpose of a binder. A resin used mainly for dispersing a colorant such as a pigment is also referred to as a dispersant. However, such use of the resin is merely an example, and the resin can be used for other purposes.
The weight average molecular weight (Mw) of the resin is preferably 5000 to 100,000. The number average molecular weight (Mn) is preferably 1000 to 20,000.

In the colored composition of the present invention, the resin content is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, based on the total solid content of the colored composition.

<<< Dispersant >>>
When the coloring composition of this invention contains a pigment, it is preferable to contain a dispersing agent.
Examples of the dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

Examples of the terminal-modified polymer include a polymer having a phosphate group at the terminal end described in JP-A-3-112992 and JP-T-2003-533455, and JP-A-2002-273191. Examples thereof include a polymer having a sulfonic acid group at the terminal and a polymer having a partial skeleton of organic dye or a heterocyclic ring described in JP-A-9-77994. In addition, polymers having two or more pigment surface anchor sites (acid groups, basic groups, organic dye partial skeletons, heterocycles, etc.) introduced at the polymer ends described in JP-A-2007-277514 are also available. It is preferable because of excellent dispersion stability.

Examples of the graft polymer include a polyester-based dispersant. Specifically, reaction products of poly (lower alkyleneimine) and polyester described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, etc. A reaction product of polyallylamine and polyester described in JP-A-169821 and the like, a copolymer of a macromonomer described in JP-A-10-339949, JP-A-2004-37986, and the like and a nitrogen atom monomer, JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, and the like, graft polymers having a partial skeleton or a heterocyclic ring of organic dyes, JP-A-2010-106268, etc. Copolymers of the described macromonomer and acid group-containing monomer, basic group and acid described in JP-A-2009-203462 Such amphoteric dispersion resin having the like.

As the macromonomer used when the graft polymer is produced by radical polymerization, a known macromonomer can be used. Macromonomer AA-6 manufactured by Toa Gosei Co., Ltd. Acid-6), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 (polyester whose terminal group is a methacryloyl group) Butyl acrylate), Placel FM5 manufactured by Daicel Chemical Industries, Ltd. (2-hydroxyethyl methacrylate with 5 molar equivalents of ε-caprolactone), FA10L (2-hydroxyethyl acrylate with 10 molar equivalents of ε-caprolactone) And polyesters described in JP-A-2-272009 System macromonomer and the like.

As the block polymer, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.

The pigment dispersant is also available as a commercial product, and as such a specific example,

“DA-7301” manufactured by Enomoto Kasei Co., Ltd., “Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), BY (Chemical acid ester)” manufactured by BYK Chemie, 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050-4010-4165 (polyurethane type) manufactured by EFKA Corporation ), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (Azo pigment derived ”,“ Ajispur PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fine Techno Co., Ltd.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd.,“ Polyflow No. 50E, No. 300 (acrylic copolymer) ” "Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725" manufactured by Enomoto Kasei Co., Ltd. "Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)", "Homogenol L-18 (polymer polycarboxylic acid)" ”,“ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl) ”,“ Acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (end part) manufactured by Nippon Lubrizol Co., Ltd. ” 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical Co., Ltd. ), Hinoact T-8000E manufactured by Kawaken Fine Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd., organosiloxane polymer KP341, Yusho Co., Ltd. “W001: Cationic surfactant”, polyoxyethylene lauryl Nonionic surfactants such as ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450” manufactured by Morishita Sangyo Co., Ltd., Polymer dispersants such as “Disperse Aid 6, Disperse Aid 8, Disperse Aid 15 and Disperse Aid 9100” manufactured by San Nopco Co., Ltd., ADEK Co., Ltd. “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123” manufactured by A, and Sanyo Chemical Co., Ltd. “Ionet (trade name) S-20” manufactured by the Company and the like can be mentioned.

When the coloring composition contains a dispersant, the content of the dispersant is preferably 1 to 80 parts by mass, more preferably 5 to 70 parts by mass with respect to 100 parts by mass of the pigment. More preferably, it is part by mass.

<<< Alkali-soluble resin >>>
The coloring composition of this invention can contain alkali-soluble resin as resin. By containing an alkali-soluble resin, developability and pattern formability are improved. The alkali-soluble resin can also be used as a dispersant or a binder.

The molecular weight of the alkali-soluble resin is not particularly defined, but the weight average molecular weight (Mw) is preferably 5000 to 100,000. The number average molecular weight (Mn) is preferably 1000 to 20,000.
The alkali-soluble resin may be a linear organic polymer, and has at least one alkali-soluble polymer in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having groups to promote.

The alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. What can be developed is preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.

For the production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

As the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification are used. Examples thereof include maleic acid copolymers, alkali-soluble phenol resins such as novolak resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers having a hydroxyl group added with an acid anhydride. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds.
As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc. Can be mentioned. Examples of the vinyl compound include styrene, α-methyl styrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer and the like. Examples of other monomers copolymerizable with (meth) acrylic acid include N-substituted maleimide monomers described in JP-A-10-300922, such as N-phenylmaleimide and N-cyclohexylmaleimide. Can do. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

Moreover, in order to improve the crosslinking efficiency of the coloring composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. Examples of the polymerizable group include a (meth) allyl group and a (meth) acryloyl group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing a polymerizable group in a side chain is useful.
Examples of the alkali-soluble resin containing a polymerizable group include: Dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (manufactured by COOH containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd.), Biscote R-264, KS resist 106 (All manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), Acryl-RD- And F8 (manufactured by Nippon Shokubai Co., Ltd.).

Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / Multi-component copolymers composed of (meth) acrylic acid / other monomers can be preferably used. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, described in JP-A-7-140654,
2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer,
2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and the like can also be preferably used.
As a commercial product, for example, Acrybase FF-426 (manufactured by Fujikura Kasei Co., Ltd.) can be used.

The alkali-soluble resin is a monomer containing a compound represented by the following general formula (ED1) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). It is also preferable to include a polymer (a) obtained by polymerizing the components.

In general formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description in JP 2010-168539 A can be referred to.

In the general formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include methyl, ethyl, n Linear or branched alkyl groups such as -propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, tert-butylcyclohexyl Alicyclic groups such as dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; benzyl An alkyl group substituted with an aryl group such as; Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

As a specific example of the ether dimer, for example, paragraph 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

The alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X).

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

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

As for the alkali-soluble resin, paragraphs 0558 to 0571 of JP2012-208494A (corresponding to <0685> to [0700] of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof can be referred to. It is incorporated herein.
Further, the copolymer (B) described in paragraph Nos. 0029 to 0063 described in JP 2012-32767 A and the alkali-soluble resin used in Examples, paragraph Nos. 0088 to 2020 of JP 2012-208474 A The binder resin described in 0098 and the binder resin used in Examples, the binder resin described in Paragraph Nos. 0022 to 0032 of JP 2012-137531 B, and the binder resin used in Examples, The binder resin described in paragraph Nos. 0132 to 0143 of No. 024934 and the binder resin used in Examples, the binder resin used in paragraph Nos. 0092 to 0098 and Examples of JP 2011-242752 A, Paragraph No. of Kokai 2012-032770 030 can also be used a binder resin according to ~ 0072. These contents are incorporated herein.

The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and even more preferably 120 mgKOH / g or less.

When the coloring composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, with respect to the total solid content of the coloring composition. 10 mass% is still more preferable. The coloring composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Pigment derivative >>
The colored composition of the present invention preferably contains a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group. As the pigment derivative, from the viewpoint of dispersibility and dispersion stability of the colorant A, a pigment derivative having an acidic group or a basic group is preferable. Particularly preferred are pigment derivatives having a basic group. Further, the combination of the resin (dispersant) and the pigment derivative described above is preferably a combination in which the dispersant is an acidic dispersant and the pigment derivative has a basic group.

Examples of the organic pigment for constituting the pigment derivative include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.
Moreover, as an acidic group which a pigment derivative has, a sulfonic acid group, a carboxylic acid group, and its salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is especially preferable. The basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.

When the coloring composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30% by mass, and more preferably 3 to 20% by mass with respect to the mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.

<< Organic solvent >>
The coloring composition of the present invention may contain an organic solvent.
The organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied, but in consideration of the solubility, coating property, and safety of the colorant and the curable compound. It is preferable to be selected.

Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. , Alkyl oxyacetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )) 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy- Methyl 2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2-oxobutanoic acid Ethyl etc., and ether As, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether Acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc., and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and aromatic hydrocarbons For example, toluene, xylene and the like are preferable.

It is also preferable to mix two or more of these organic solvents from the viewpoints of solubility of the dye (A), the curable compound, and the like, and improvement of the coating surface condition. In this case, particularly preferably, the above methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

The content of the organic solvent in the colored composition is preferably such that the total solid concentration of the colored composition is 5% to 80% by mass, and more preferably 5 to 60% by mass, from the viewpoint of applicability. 10 to 50% by mass is particularly preferable.
The coloring composition of the present invention may contain only one type of organic solvent or two or more types of organic solvents. When two or more types are included, the total amount is preferably within the above range.

<< Polymerization inhibitor >>
In the colored composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored composition.
Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
When the coloring composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the mass of the coloring composition.
The coloring composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Surfactant >>
Various surfactants may be added to the colored composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

For example, by containing a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved. That is, in the case of forming a film using a coloring composition containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid, The coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored composition.

Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox (registered trademark) PF-636, PF-656, PF-6320, PF-6520, PF-7002 (manufactured by OMNOVA), etc. It is done.
As the fluorosurfactant, a fluorosurfactant described in JP 2010-32698 A can also be used.
As the fluorosurfactant, a block polymer can be used. Specific examples thereof include compounds described in JP-A-2011-89090.
The fluorosurfactant has 2 or more (preferably 5 or more) repeating units derived from a (meth) acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group and / or a propyleneoxy group) ( A fluorine-containing polymer compound containing a repeating unit derived from a (meth) acrylate compound can also be preferably used.
Moreover, the fluoropolymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant. Specific examples thereof include compounds described in JP-A 2010-164965, paragraphs 0050 to 0090 and paragraphs 0289 to 0295, such as MegaFac RS-101, RS-102, and RS-718K manufactured by DIC.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1) Solsperse 20000 (Lubrizol Japan Co., Ltd.), and the like. Alternatively, Pionein D-6112-W manufactured by Takemoto Yushi Co., Ltd., NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. may be used.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

Specific examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.

When the coloring composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.001%, based on the total mass of the coloring composition. 005 to 1.0% by mass.
The coloring composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.

<< Other additives >>
Various additives, for example, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like can be blended with the colored composition of the present invention as necessary. Examples of these additives include those described in JP-A No. 2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein.
The coloring composition of the present invention may contain a sensitizer and a light stabilizer described in paragraph 0078 of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph 0081 of the same publication.

Depending on the raw materials used, the colored composition may contain a metal element, but from the viewpoint of suppressing the occurrence of defects, the content of Group 2 elements (calcium, magnesium, etc.) in the colored composition is 50 ppm or less. It is preferable to control to 0.01 to 10 ppm. The total amount of the inorganic metal salt in the coloring composition is preferably 100 ppm or less, and more preferably controlled to 0.5 to 50 ppm.

<Method for preparing colored composition>
The coloring composition of the present invention is prepared by mixing the aforementioned components.
In preparing the colored composition, the components constituting the colored composition may be blended together, or may be blended sequentially after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
The colored composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight) For example). Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, more preferably about 0.05 to 0.5 μm. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of the uniform and smooth coloring composition in a post process. Further, it is also preferable to use a fiber-shaped filter medium, and examples of the filter medium include polypropylene fiber, nylon fiber, glass fiber, and the like. , TPR005, etc.) and SHPX type series (SHPX003 etc.) filter cartridges can be used.

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

<Color filter, pattern formation method, color filter manufacturing method>
Next, the color filter, pattern forming method and color filter of the present invention will be described in detail through the manufacturing method. A method for producing a color filter using the pattern forming method of the present invention will also be described.

The color filter of the present invention is obtained by using the colored composition of the present invention.
The pattern forming method of the present invention includes a step of forming a colored composition layer on a support using the colored composition of the present invention, a step of exposing the colored composition layer in a pattern, and developing and removing unexposed portions. And a process of forming a colored pattern. Furthermore, you may provide the process (prebaking process) of baking a colored composition layer, and the process (post-baking process) of baking the developed coloring pattern as needed. Details of each step will be described below.

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

Examples of the support include transparent substrates such as glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. A thin film transistor for driving the organic EL element may be formed on these transparent substrates.
Further, a solid-state imaging device substrate in which a solid-state imaging device (light receiving element) such as a CCD or CMOS is provided on the substrate can be used.

As a method for applying the colored composition of the present invention on the support, various methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be used.

The colored composition layer formed on the support is preferably heated (pre-baked). The heating is preferably performed at 120 ° C. or less, more preferably 50 to 120 ° C., further preferably 80 to 110 ° C., and particularly preferably 90 to 105 ° C. By performing heating at 120 ° C. or lower, these characteristics are more effectively maintained when an organic EL element is used as the light source of the image display device or when the photoelectric conversion film of the image sensor is made of an organic material. can do.
The heating time is preferably 10 seconds to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. Heating can be performed with a hot plate, oven, or the like.

<< Exposure process >>
Next, the colored composition layer formed on the support is exposed in a pattern (exposure process). For example, pattern exposure can be performed by exposing the colored composition layer formed on the support using a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line). Irradiation dose (exposure dose), for example, preferably 0.03 ~ 2.5J / cm ^2, more preferably 0.05 ~ 1.0J / cm ^2, most preferably 0.08 ~ 0.5J / cm ² .
The oxygen concentration at the time of exposure can be appropriately selected. In addition to being performed in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially oxygen-free). ), Or in a high oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, 50% by volume). Further, the exposure illuminance can be set as appropriate, and can usually be selected from the range of 1000 W / m ² to 100,000 W / m ² (eg, 5000 W / m ² , 15000 W / m ² , 35000 W / m ² ). . Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m ² at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m ^2.

The thickness of the cured film is preferably 1.0 μm or less, more preferably 0.1 to 0.9 μm, and further preferably 0.2 to 0.8 μm. By setting the film thickness to 1.0 μm or less, high resolution and high adhesion can be easily obtained.

<< Development process >>
Next, the unexposed portion is developed and removed to form a colored pattern. The development removal of the unexposed portion can be performed using a developer. Thereby, the coloring composition layer of the unexposed part in an exposure process elutes in a developing solution, and only the photocured part remains.
As the developer, an organic alkali developer that does not damage the underlying solid-state imaging device or circuit is desirable.
The temperature of the developer is preferably 20 to 30 ° C., for example. The development time is preferably 20 to 180 seconds.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide. And organic alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene. An alkaline aqueous solution obtained by diluting these alkaline agents with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, is preferably used as the developer.
Moreover, you may use an inorganic alkali for a developing solution. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate and the like are preferable.
Further, a surfactant may be used for the developer. Examples of the surfactant include the above-described surfactants, and nonionic surfactants are preferable. When the developer contains a surfactant, the amount is preferably 0.001 to 2.0% by weight, more preferably 0.01 to 1.0% by weight, based on the total weight of the developer.
In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it is preferable to wash | clean (rinse) with a pure water after image development.

It is preferable to perform heat treatment (post-bake) after development and drying. If a multicolor coloring pattern is formed, a cured film can be produced by sequentially repeating the process for each color. Thereby, a color filter is obtained.
Post-baking is a heat treatment after development for accelerating curing, and the heating temperature is preferably 100 to 240 ° C., for example. Further, when an organic EL element is used as the light source of the image display device, or when the photoelectric conversion film of the image sensor is made of an organic material, it is 50 to 120 ° C. (more preferably 80 to 100 ° C., more preferably 80 ° C. It is preferable to perform heat treatment (post-bake) at a temperature of ~ 90 ° C.
The post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so that the film after development is in the above condition. it can.

In the present invention, when a polymerizable compound is used as the curable compound and a colored composition containing the above-described photopolymerization initiator (a) and photopolymerization initiator (b) is used, In the exposure step, exposure is performed with light having a wavelength of more than 350 nm and not more than 380 nm (preferably, light having a wavelength of 355 to 370 nm, particularly preferably i-line), and further to the colored composition layer after the development step, the wavelength 254 It is also preferable to perform exposure with light having a wavelength of ˜350 nm (preferably light having a wavelength of 254 nm).
Further, the difference between the wavelength of light used in the exposure before the development step and the wavelength of light used in the exposure after the development step is preferably 200 nm or less, and more preferably 100 to 150 nm or less. .
By exposing the colored composition layer in two stages before the development process and after the development process, the colored composition can be appropriately cured in the first exposure, and the entire colored composition is substantially cured in the next exposure. Can do. As a result, the curability of the colored composition can be improved even under a low temperature condition without post-baking at about 210 ° C., and the solvent resistance of the color filter can be improved. Moreover, color mixing with other colors can also be suppressed.

In the exposure prior to the development step, the irradiation amount of 380nm or less light than the wavelength 350 nm (exposure) is preferably ^{30mJ / cm 2 ~ 1500mJ / cm} 2, 50mJ / cm 2 ~ 100
0 mJ / cm ² is more preferable.
The reaction rate of the polymerizable compound in the exposure before the development step is preferably 30 to 60%. By setting such a reaction rate, the polymerizable compound can be appropriately cured. Here, the reaction rate of the compound having a polymerizable compound refers to the ratio of the reacted unsaturated double bond in all the unsaturated double bonds of the polymerizable compound.

In the exposure after the development step, the irradiation amount of light of wavelength 254 ~ 300 nm (exposure) is preferably ^{30mJ / cm 2 ~ 4000mJ / cm} 2, 50mJ / cm 2 ~ 3500mJ / cm 2 is more preferable.
Further, the reaction rate of the polymerizable compound in the exposure after the development step is preferably 60 to 90%. By setting it as such a reaction rate, the hardening state of the coloring composition layer after exposure can be made more favorable.

Also in this aspect, post-baking may be performed after exposure after the development step. However, when an organic EL element is used as a light source of an image display device, or a photoelectric conversion film of an image sensor is organic. In the case of a material, it is preferable to perform heat treatment (post-bake) at 50 to 120 ° C. (more preferably 80 to 100 ° C., more preferably 80 to 90 ° C.).

The color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

Moreover, the color filter of the present invention can be preferably used for an organic EL device. As the organic EL element, a white organic EL element is preferable. The organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, JP 2003-45676 A, supervised by Akiyoshi Mikami, “Frontier of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection”, Technical Information Association, 326-328 pages, 2008, etc. Examples of the tandem structure of the organic EL element include a structure in which an organic EL layer is provided between a lower electrode having light reflectivity and an upper electrode having light transmittance on one surface of a substrate. The lower electrode is preferably made of a material having a sufficient reflectance in the visible light wavelength region. The organic EL layer preferably includes a plurality of light emitting layers and has a stacked structure (tandem structure) in which the plurality of light emitting layers are stacked. For example, the organic EL layer may include a red light emitting layer, a green light emitting layer, and a blue light emitting layer in the plurality of light emitting layers. And it is preferable that they have a some light emission auxiliary layer for light-emitting a light emitting layer together with a some light emitting layer. The organic EL layer can have, for example, a stacked structure in which light emitting layers and light emitting auxiliary layers are alternately stacked. An organic EL element having an organic EL layer having such a structure can emit white light. In that case, the spectrum of white light emitted from the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm), and the yellow region (580 nm to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferable. By combining an organic EL element that emits white light (white organic EL element) and the color filter of the present invention, spectral characteristics excellent in color reproducibility can be obtained, and clearer images and images can be displayed. .

The film thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 2.0 μm or less, more preferably 1.0 μm or less, and even more preferably 0.7 μm or less. The lower limit can be, for example, 0.1 μm or more, and can also be 0.2 μm or more.
Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less. The lower limit can be, for example, 0.1 μm or more, and can also be 0.2 μm or more.

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

The support has a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.). It has a light-shielding film made of tungsten or the like that is open only in the light-receiving part, and has a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part. In addition, the solid-state image sensor color filter of the present invention is included.
Further, a configuration having a light condensing means (for example, a microlens, etc., the same applies hereinafter) on the device protection layer and under the color filter (on the side close to the support), a structure having the light condensing means on the color filter It may be.

<Image display device>
The color filter of the present invention can be used in an image display device such as a liquid crystal display device or an organic electroluminescence display device.

For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter of the present invention may be used in a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention relates to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), a STN (Super-Twist Nematic). ), TN (Twisted Nematic), VA (Vertical Alignment), OCS (On-chip spacer), FFS (Fringe field switching), and R-OCB (Reflective Optical Compensated).
In addition, the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system. In the case of a COA type liquid crystal display device, the required characteristics for the color filter layer require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the stripping solution, in addition to the normal required characteristics as described above. Sometimes. Since the color filter of the present invention is excellent in light resistance and the like, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends (issued in 2001 by Toray Research Center Research Division)".

In addition to the color filter of the present invention, the liquid crystal display device provided with the color filter of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. Regarding these components, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlighting, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Are listed.

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

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

<Measurement of weight average molecular weight>
The weight average molecular weight was measured by the following method.
Column type: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 linked column developing solvent: Tetrahydrofuran Column temperature: 40 ° C
Flow rate (sample injection amount): 1.0 μL (sample concentration: 0.1% by mass)
Device name: HLC-8220GPC manufactured by Tosoh Corporation
Detector: RI (refractive index) detector Calibration curve Base resin: Polystyrene

(Preparation of CI Pigment Blue 15: 6 (PB15: 6) Pigment Dispersion)
Pigment Blue 15: 6 15 parts as a pigment, Disperbyk-161 (manufactured by BYK Chemie) as a resin (dispersant) 50 parts, and a mixed liquid of propylene glycol monomethyl ether acetate (PGMEA) 35 parts as a solvent by a bead mill PB15: 6 pigment dispersion was prepared by mixing and dispersing for 15 hours.

(Preparation of CI Pigment Violet 23 (PV23) Pigment Dispersion)
A mixture of 15 parts of Pigment Violet 23, 50 parts of Disperbyk-161 (manufactured by BYK Chemie) as a resin (dispersant), and 35 parts of propylene glycol monomethyl ether acetate (PGMEA) as a solvent was mixed for 15 hours by a bead mill. Dispersed to prepare a PV23 pigment dispersion.

(Preparation of coloring composition)
The following components were mixed to obtain a colored composition.

The component symbols shown in the above table represent the following compounds, respectively.
(Dye A)
A-1: The following structure (pigment multimer, weight average molecular weight = 12000, the numerical value written in the repeating unit of the main chain is a mass ratio)

A-2: The following structure (pigment multimer, weight average molecular weight = 13200, the numerical value written in the repeating unit of the main chain is a mass ratio)

A-3: The following structure (pigment multimer, weight average molecular weight = 13200, the numerical value written in the repeating unit of the main chain is a mass ratio)

A-4: The following structure (pigment monomer)

A-5: The following structure (pigment multimer, weight average molecular weight = 10800, the numerical value written in the repeating unit of the main chain is a mass ratio)

A-6: The following structure (pigment multimer, weight average molecular weight = 9300, the numerical value written in the repeating unit of the main chain is mass ratio)

A-7: The following structure (pigment multimer (mass ratio of units having triarylmethane skeleton / methacrylic acid / polymerizable group = 43.15 / 13.2 / 25.93), weight average molecular weight = 8200)

A-8: The following structure (pigment multimer, weight average molecular weight = 11300)

A-9: The following structure (pigment multimer, weight average molecular weight = 10100, the numerical value written in the repeating unit of the main chain is a mass ratio)

(Dye B)
B-1: The following structure (pigment multimer, weight average molecular weight = 12000, the numerical value written together with the repeating unit of the main chain is a mass ratio)

B-2: The following structure (pigment multimer, weight average molecular weight = 13200, the numerical value written in the repeating unit of the main chain is a mass ratio)

B-3: The following structure (pigment multimer, weight average molecular weight = 13200, and the numerical value written in the repeating unit of the main chain is a mass ratio)

B-4: The following structure (pigment multimer (xanthene skeleton / methacrylic acid / methacrylic acid and glycidyl methacrylate adduct molar ratio = 5/6/6), repeating unit derived from methacrylic acid, methacrylic acid and glycidyl methacrylate The average number of repeating units derived from the adduct is 12), weight average molecular weight = 11600)

B-5: The following structure (pigment monomer)

B-6: The following structure (pigment multimer, weight average molecular weight = 11000, the numerical value written in the repeating unit of the main chain is a mass ratio)

B-7: The following structure (pigment multimer, weight average molecular weight = 9100, the numerical value written in the repeating unit of the main chain is a mass ratio)

B-8: The following structure (pigment multimer (xanthene skeleton / methacrylic acid / unit ratio having a polymerizable group = 46.42 / 12.44 / 24.44), weight average molecular weight = 8900)

B-9: The following structure (pigment multimer, weight average molecular weight = 13500)

B-10: The following structure (pigment multimer, weight average molecular weight = 14100)

B-11: The following structure (pigment multimer, weight average molecular weight = 8500, the numerical value written in the repeating unit of the main chain is a mass ratio)

(Other pigment multimers)
C-1: The following structure (weight average molecular weight = 13200, the numerical value written in the repeating unit of the main chain is a mass ratio)

(resin)
D-1: ACRYCURE-RD-F8 (manufactured by Nippon Shokubai Co., Ltd., weight average molecular weight = 11000)
D-2: Acrybase FF-426 (manufactured by Fujikura Kasei Co., Ltd., weight average molecular weight = 14000)
D-3: The following structure (weight average molecular weight = 11000, the numerical value written in the repeating unit of the main chain is a mass ratio)

D-4: The following structure (weight average molecular weight = 12000, the numerical value written in the repeating unit of the main chain is a mass ratio)

(Curable compound)
E-1: KARAYAD DPHA (manufactured by Nippon Kayaku Co., Ltd., monomer, molecular weight = 562)
E-2: Aronix TO-2349 (manufactured by Toagosei Co., Ltd., monomer, molecular weight = 625)
E-3: NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd., monomer, molecular weight = 1107)
E-4: NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd., monomer, molecular weight = 352) (photopolymerization initiator)
F-1: IRGACURE-OXE01 (BASF)
F-2: IRGACURE-OXE02 (BASF)
F-3: IRGACURE-369 (BASF)
F-4: The following compound

(Surfactant)
W-1: the following mixture (Mw = 14000)

W-2: PolyFox (registered trademark) PF-6320 (manufactured by OMNOVA)
(solvent)
PGMEA: Propylene glycol monomethyl ether acetate

(Spectral characteristic evaluation)
Each colored composition was spin-coated on a glass substrate so that the dry film thickness was 2 μm.
Then, this coating film was subjected to heat treatment (pre-baking) at 90 ° C. for 120 seconds.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at an exposure amount of 200 mJ / cm ² through an Island pattern mask having a pattern of 1.0 μm square at a wavelength of 365 nm.
Next, the exposed coating film was subjected to heat treatment (post-baking) at 100 ° C. for 300 seconds.
The color filter was manufactured by the above.
The transmission spectral characteristics of the obtained color filter were measured with a spectrophotometer MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.).
<Evaluation criteria>
5: The transmittance at a wavelength of 500 nm is less than 40%, the average transmittance at a wavelength of 550 to 650 nm is less than 3%, and the maximum transmittance at a wavelength of 400 to 460 nm is 85% or more.
4: The transmittance at a wavelength of 500 nm is less than 40%, the average transmittance at a wavelength of 550 to 650 nm is less than 3%, and the maximum transmittance at a wavelength of 400 to 460 nm is 80% or more and less than 85%.
3: The transmittance at a wavelength of 500 nm is less than 40%, the average transmittance at a wavelength of 550 to 650 nm is less than 3%, and the maximum transmittance at a wavelength of 400 to 460 nm is 75% or more and less than 80%.
2: The transmittance at a wavelength of 500 nm is less than 40%, the average transmittance at a wavelength of 550 to 650 nm is less than 3%, and the maximum transmittance at a wavelength of 400 to 460 nm is 70% or more and less than 75%.
1: The transmittance at a wavelength of 500 nm is less than 40%, the average transmittance at a wavelength of 550 to 650 nm is less than 3%, and the maximum transmittance at a wavelength of 400 to 460 nm is less than 70%.
0: The transmittance at a wavelength of 500 nm is 40% or more, or the average transmittance at a wavelength of 550 to 650 nm is 3% or more.

(Solvent resistance evaluation)
A color filter was produced by the same method as the spectral characteristic evaluation. After the obtained color filter was immersed in PGMEA for 10 minutes, the film thickness was measured and the remaining film ratio was calculated.
Residual film ratio = (film thickness of color filter after being immersed in PGMEA for 10 minutes / film thickness of color filter before being immersed in PGMEA) × 100
<Evaluation criteria>
5: The remaining film rate is 100%.
4: The remaining film ratio is 98% or more.
3: The remaining film ratio is 95% or more and less than 98%.
2: The remaining film ratio is 90% or more and less than 95%.
1: The remaining film rate is 80% or more and less than 90%.
0: Remaining film ratio is less than 80%.

(Color mixing evaluation)
A color filter was produced by the same method as the spectral characteristic evaluation. The maximum transmittance T0 in the wavelength range of 400 to 700 nm of the obtained color filter was measured using MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.).
Next, the following red coloring composition for color mixture evaluation is spin-coated on the obtained color filter so that the film thickness after drying becomes 2 μm, and heat treatment (prebaking) is performed at 100 ° C. for 120 seconds. It was. Next, shower development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) without performing exposure with an i-line stepper exposure apparatus. Thereafter, rinsing was performed in a spin shower using pure water, and the red coloring composition for color mixture evaluation was developed and removed.
The maximum transmittance T1 in the wavelength range of 400 to 700 nm of the color filter after the development and removal of the red coloring composition for color mixture evaluation was measured using MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.).
The maximum transmittance change (ΔT = T0−T1) was calculated and judged based on the following criteria. The smaller ΔT, the less color mixing, and more desirable.
<Evaluation criteria>
5: Maximum transmittance change is 0%.
4: Maximum transmittance change is greater than 0% and less than 1%.
3: The maximum transmittance change is 1% or more and less than 3%.
2: The maximum transmittance change is 3% or more and less than 5%.
1: The maximum transmittance change is 5% or more and less than 10%.
0: Maximum transmittance change is 10% or more.
<Red coloring composition for color mixture evaluation>
C. I. 9.9 parts of Pigment Red 254,
C. I. Pigment Yellow 139 4.4 parts,
1.4 parts of pigment derivative A,
A mixed solution composed of 15.6 parts of PGMEA solution containing 30% by mass of Dispersant A and 41.5 parts of PGMEA as a solvent was mixed and dispersed by a bead mill for 15 hours to prepare a Red pigment dispersion.
Then
37.7 parts of the above Red pigment dispersion,
5.6 parts of the above resin D-1;
17 parts of the curable compound E-17,
Photopolymerization initiator F-1 3.92 parts,
0.28 parts of the above surfactant W-1 and 51.47 parts of PGMEA as a solvent were uniformly mixed to prepare a red coloring composition for color mixing evaluation.
Pigment derivative A: structure shown below

Dispersant A: Structure shown below

(Reliability evaluation) High temperature and high humidity test A color filter was produced in the same manner as in the spectral evaluation. The obtained color filter was allowed to stand for 3 days under conditions of a temperature of 85 ° C. and a humidity of 85%, and the film surface was observed visually and with an optical microscope.
<Evaluation criteria>
6: As shown in FIG. 1A, no separation component is confirmed on the membrane surface. 5: One or two minute separation components as shown in FIG. 1B are seen on the membrane surface. 4: FIG. b) Several minute separation components as seen on the membrane surface can be seen 3: Dozens of minute separation components as seen in FIG. 1 (b) can be seen on the membrane surface 2: FIG. 1 (c) As shown, the separation component appears granular on the membrane surface 1: As shown in FIG. 1 (d), the separation component appears as spots on the membrane surface 0: Phase separation occurred and the membrane separated into two layers. 1 (a) shows the upper left frame of FIG. 1, FIG. 1 (b) shows the upper right frame of FIG. 1, FIG. 1 (c) shows the lower left frame of FIG. (D) shows the lower right frame of FIG.

As shown in the above table, the colored composition of the example was able to produce a color filter having good spectral characteristics and excellent solvent resistance. Further, the color filter of the example had a small color mixture with other colors. Furthermore, in the high-temperature and high-humidity test, separation of membrane components was small, and the reliability of the membrane was excellent.
On the other hand, the comparative example was unable to achieve both spectroscopic and solvent resistance.

Claims

A dye A having a triarylmethane skeleton, a dye B having a xanthene skeleton, and a curable compound;
A coloring composition, wherein at least one selected from the dye A and the dye B is a dye multimer.
The coloring composition according to claim 1, wherein the dye A and the dye B are dye multimers.
The colored composition according to claim 1, wherein the ratio of the number of moles of the triarylmethane skeleton of the dye A to the number of moles of the xanthene skeleton of the dye B is 40:60 to 75:25.
The at least one selected from the dye A and the dye B has at least one anion selected from a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion, and a tetraarylborate anion. 2. A coloring composition according to item 1.
The coloring composition according to any one of claims 1 to 4, wherein the dye A has a cation part having a triarylmethane skeleton and an anion bonded to the cation part through a covalent bond.
The coloring composition according to any one of claims 1 to 4, wherein the dye B has a cation moiety having a xanthene skeleton and an anion bonded to the cation moiety through a covalent bond.
The colored composition according to any one of claims 1 to 6, wherein at least one selected from the dye A and the dye B has a group containing a polymerizable unsaturated double bond.
A color filter using the colored composition according to any one of claims 1 to 7.
The color filter according to claim 8, which is used for an organic electroluminescence element.
Forming a colored composition layer on a support using the colored composition according to any one of claims 1 to 7,
Exposing the colored composition layer in a pattern;
A step of developing and removing an unexposed portion to form a colored pattern;
Heating the colored pattern at 50 to 120 ° C .;
A pattern forming method including:
A method for producing a color filter, comprising the pattern forming method according to claim 10.
A solid-state imaging device having the color filter according to claim 8.
An image display device having the color filter according to claim 8.