WO2017086245A1

WO2017086245A1 - Coloring composition, color filter, pattern forming method, solid-state imaging device, image display device and dye polymer

Info

Publication number: WO2017086245A1
Application number: PCT/JP2016/083490
Authority: WO
Inventors: 金子　祐士; 貴規田口; 祐継室
Original assignee: 富士フイルム株式会社
Priority date: 2015-11-16
Filing date: 2016-11-11
Publication date: 2017-05-26
Also published as: KR102152047B1; JPWO2017086245A1; JP6837988B2; TW201728695A; TWI707922B; KR20180064445A

Abstract

Provided is a coloring composition capable of manufacturing a cured film in which occurrence of color unevenness and defects is suppressed, a color filter, a pattern forming method, a solid-state imaging device, an image display device and a dye polymer. The coloring composition contains a dye polymer and a curable compound, wherein the dye polymer contains two or more hetero atoms, and one or more of the hetero atoms include a dye structure in which an azo group or aromatic ring group is bonded to a cationic hetero ring that is a nitrogen atom.

Description

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

The present invention relates to a coloring composition. In addition, the present invention relates to a color filter, a pattern forming method, a solid-state imaging device, an image display device, and a dye multimer using a colored composition.

In recent years, the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has greatly increased due to the spread of digital cameras and camera-equipped mobile phones. Color filters are used as key devices for displays and optical elements.

For example, Patent Documents 1 to 5 have yellow structures having a structure in which an azo group or an aromatic ring group is bonded to a cationic heterocycle containing two or more heteroatoms and one or more of the heteroatoms is a nitrogen atom. It describes that a color filter or the like is produced using a dye.
Patent Document 6 describes that a color filter is produced using a coloring composition containing a dye multimer.

JP 2011-145540 A JP 2011-184493 A JP 2011-144269 A JP2013-218186A JP 2012-158649 A Japanese Patent Laying-Open No. 2015-145439

Here, in the case of forming a cured film or a pattern using the colored composition as described in Patent Documents 1 to 6, the colored composition is applied to a support and dried, and after a while Then, a cured film may be produced by performing exposure or the like.
However, according to the study by the present inventors, a coloring composition using a yellow dye described in Patent Documents 1 to 5 is applied to a support and the like, and a dried film (uncured film) is long. It was found that when the cured film was manufactured by performing the curing process after leaving the time, color unevenness and defects were likely to occur in the obtained cured film. As the retention of the film was made longer, defects and color unevenness were more likely to occur in the resulting cured film. This is because the yellow dyes described in Patent Documents 1 to 5 have high polarity, so the compatibility with other components (curable compounds, resins, solvents, etc.) in the colored composition tends to decrease over time, For this reason, it is presumed that phase separation occurs between the yellow dye and the other components or aggregation of the yellow dye occurs during the leaving, and defects and color unevenness are likely to occur in the cured film.
Note that Patent Document 6 does not describe a study on defects and color unevenness associated with the holding.

Therefore, an object of the present invention is to provide a colored composition, a color filter, a pattern forming method, a solid-state imaging device, an image display device, and a dye multimer capable of producing a cured film in which the occurrence of color unevenness and defects is suppressed. It is in.

As a result of intensive studies, the present inventors have made the above object by making a dye compound having a cationic heterocycle containing two or more heteroatoms and at least one heteroatom being a nitrogen atom into a multimer. The inventors have found that this can be achieved and have completed the present invention. The present invention provides the following.
<1> A coloring composition comprising a dye multimer and a curable compound,
The dye multimer includes a dye structure having a structure in which an azo group or an aromatic ring group is bonded to a cationic heterocycle containing two or more heteroatoms and one or more of the heteroatoms being a nitrogen atom. Composition.
<2> The colored composition according to <1>, wherein the cationic heterocycle is represented by the following formula (I);
Formula (I)

Y ^a represents a sulfur atom or —NR ^Ya —, Y ^b represents a nitrogen atom or —CR ^Yb —, and R ^a , R ^b , R ^Ya and R ^Yb each independently represent a hydrogen atom, a substituent, a dye It represents the bonding site with the atomic group constituting the structure or the bonding site with the atomic group constituting the dye multimer, and R ^a and R ^Ya , R ^b and R ^Ya , and R ^b and R ^Yb are respectively They may combine to form a ring; any of the atoms that make up the ring, or the entire ring has a monovalent positive charge.
<3> The coloring composition according to <1> or <2>, wherein the dye structure is represented by the formula (Ia);

Ht represents a cationic heterocycle containing two or more heteroatoms, and one or more of the heteroatoms is a nitrogen atom;
L represents -N = N- or an arylene group,
B represents a substituent,
X represents an anion,
At least one of Ht, B, and X has a binding site with an atomic group constituting a dye multimer.
<4> The coloring composition according to <1> or <2>, wherein the dye multimer has a dye structure represented by formula (I-1);

In formula (I-1), R ¹ and R ⁸ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ² , R ⁷ , R ⁹ to R ¹² are each independently Represents a hydrogen atom or a substituent, Y ¹ represents a sulfur atom or —NR ^Y1 —, R ^Y1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, X represents an anion, R ¹ At least one of -R ² , R ⁷ -R ¹² , R ^Y1 and X has a bonding site with an atomic group constituting a dye multimer.
<5> The coloring composition according to <1> or <2>, wherein the dye multimer has a dye structure represented by formula (I-2);

In formula (I-2), R ¹⁰¹ , R ¹¹⁰ and R ¹¹¹ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ¹⁰² to R ¹⁰⁵ , R ¹⁰⁶ to R ¹⁰⁹ are Each independently represents a hydrogen atom or a substituent, R ¹¹⁰ and R ¹¹¹ may be bonded to form a ring, Y ² represents a sulfur atom or —NR ^Y2 —, and R ^Y2 represents a hydrogen atom; , X represents an anion, and at least one of R ¹⁰¹ to R ¹⁰⁹ , R ^Y2 and X has a bonding site with an atomic group constituting a dye multimer.
<6> The dye multimer includes at least one of a repeating unit represented by the following formula (A) and a repeating unit represented by the following formula (C), or represented by the following formula (D). The colored composition according to any one of <1> to <5>,

In formula (A), A ¹ represents the main chain of the repeating unit, L ¹ represents a single bond or a divalent linking group, DyeI contains two or more heteroatoms, and one or more of the heteroatoms are Represents a dye structure having a structure in which an azo group or an aromatic ring group is bonded to a cationic heterocycle which is a nitrogen atom;

In the formula (C), L ³ represents a single bond or a divalent linking group, and DyeIII is bonded to a cationic heterocyclic ring containing two or more heteroatoms and one or more of the heteroatoms is a nitrogen atom. Represents a dye structure having a structure in which a group or an aromatic ring group is bonded; m represents 0 or 1;

In the formula (D), L ⁴ represents an (n + k) -valent linking group, n represents an integer of 2 to 20, k represents an integer of 0 to 20, DyeIV contains 2 or more heteroatoms, And a dye structure having a structure in which an azo group or an aromatic ring group is bonded to a cationic heterocycle in which one or more heteroatoms are nitrogen atoms, P represents a substituent, and n is 2 or more The plurality of DyeIVs may be different from each other. When k is 2 or more, the plurality of Ps may be different from each other, and n + k represents an integer of 2 to 20.
<7> The colored composition according to any one of <1> to <6>, wherein the dye multimer has a bis (sulfonyl) imide anion or a tris (sulfonyl) methyl anion.
<8> The colored composition according to any one of <1> to <7>, further containing a pigment.
<9> The colored composition according to any one of <1> to <8>, wherein the curable compound contains a radical polymerizable compound and further contains a photopolymerization initiator.
<10> The colored composition according to any one of <1> to <9>, further comprising an alkali-soluble resin.
<11> A color filter using the colored composition according to any one of <1> to <10>.
<12> A step of forming a colored composition layer on a support using the colored composition according to any one of <1> to <10>, and a photolithography method or a dry etching method to form a colored composition layer. Forming a pattern with respect to the pattern.
<13> A solid-state imaging device having the color filter according to <11>.
<14> An image display device having the color filter according to <11>.
<15> A dye multimer having a dye structure represented by the following formula (I-1) or formula (I-2);

In formula (I-1), R ¹ and R ⁸ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ² , R ⁷ , R ⁹ to R ¹² are each independently Represents a hydrogen atom or a substituent, Y ¹ represents a sulfur atom or —NR ^Y1 —, R ^Y1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, X represents an anion, R ¹ At least one of -R ² , R ⁷ -R ¹² , R ^Y1 and X has a binding site with an atomic group constituting a dye multimer;

In formula (I-2), R ¹⁰¹ , R ¹¹⁰ and R ¹¹¹ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ¹⁰² to R ¹⁰⁵ , R ¹⁰⁶ to R ¹⁰⁹ are Each independently represents a hydrogen atom or a substituent, R ¹¹⁰ and R ¹¹¹ may be bonded to form a ring, Y ² represents a sulfur atom or —NR ^Y2 —, and R ^Y2 represents a hydrogen atom; , X represents an anion, and at least one of R ¹⁰¹ to R ¹⁰⁹ , R ^Y2 and X has a bonding site with an atomic group constituting a dye multimer.

According to the present invention, it is possible to provide a colored composition, a color filter, a pattern forming method, a solid-state imaging device, an image display device, and a dye multimer capable of producing a cured film in which occurrence of color unevenness and defects is suppressed. Became.

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 obtained by removing the solvent from all components 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 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 (Mw) and a number average molecular weight (Mn) are defined as a polystyrene conversion value by gel permeation chromatography (GPC) measurement.

<Coloring composition>
The colored composition of the present invention is a colored composition containing a dye multimer and a curable compound, wherein the dye multimer contains two or more heteroatoms, and one or more of the heteroatoms are nitrogen atoms. A dye structure having a structure in which an azo group or an aromatic ring group is bonded to a certain cationic heterocycle is included.
By adopting the above-described configuration, the coloring composition is applied to a support and the like, and after leaving a dried film (uncured film) for a long time, even after curing, there are few defects and color unevenness, A cured film can be produced. Furthermore, even if a pattern is formed after leaving the above-mentioned uncured film for a long time, it is possible to obtain a pattern in which color unevenness, defects and pattern surface roughness are small and pattern defects are suppressed.
The reason why such an effect is obtained is presumed to be as follows. First, a dye compound having a structure in which an azo group or an aromatic ring group is bonded to a cationic heterocycle containing two or more heteroatoms and one or more of the heteroatoms being a nitrogen atom is highly polar. Many. In particular, a dye compound having an asymmetric five-membered ring structure as a cationic heterocycle has a very high polarity as compared with xanthene, triarylmethane, cyanine and the like having high symmetry. On the other hand, many of the curable compounds used in the colored composition have a low polarity. For this reason, it is considered that such a highly polar dye compound is hardly compatible with other components in the coloring composition such as a curable compound. In addition, since a dye compound having one dye structure per molecule is likely to move in an uncured film, phase separation or the like occurs due to the interaction of dipoles, or the dye compound aggregates due to dipole interaction. It is presumed that defects, color unevenness, etc. were likely to occur. In contrast, in the present invention, a dye having a dye structure having the above-described cationic heterocycle is obtained by multimerizing a dye compound having a structure in which an azo group or an aromatic ring group is bonded to the above-described cationic heterocycle. It is presumed that the migration of the dye multimer in the film could be suppressed by using the multimer. Furthermore, since the molecular weight is increased by using the dye multimer, it is presumed that the polarity becomes smaller than that of a single-molecule dye compound, and the compatibility with other components in the film is less likely to be lowered. . Therefore, according to the present invention, the coloring composition is applied to a support or the like, and after the dried film (uncured film) is left for a long time and then cured, phase separation or Aggregation can be suppressed, and as a result, it is presumed that a cured film in which color unevenness and defects are suppressed can be produced. Furthermore, since phase separation and aggregation at the time of holding can be suppressed, the film can be uniformly cured even after holding. Therefore, even if a pattern is formed after leaving the above-mentioned uncured film for a long time, it is possible to obtain a pattern in which color unevenness, defects and pattern surface roughness are small and pattern defects are suppressed.
Hereinafter, the coloring composition of the present invention will be described in detail.

<< Dye Multimer >>
The coloring composition of the present invention has a dye structure having a structure in which an azo group or an aromatic ring group is bonded to a cationic heterocycle containing two or more heteroatoms and one or more of the heteroatoms being a nitrogen atom. Contains pigment multimers. In the present invention, the dye multimer includes structures such as a dimer, a trimer and a polymer. In addition, depending on the type of the dye structure (the type of substituent that the cationic heterocycle has, the type of the dye skeleton, etc.), the cation on the dye structure may be delocalized. The cationic heterocycle in the present invention includes a state where a cation is delocalized.

The dye multimer of the present invention has two or more of the above dye structures in one molecule, and preferably has three or more. The upper limit is not particularly limited, but can be 100 or less. The dye structures in one molecule may be the same dye structure or different dye structures. In the present invention, different dye structures include not only dye structures having different dye skeletons but also dye structures having the same dye skeleton and different types of substituents bonded to the dye skeleton.

The cationic heterocycle is preferably represented by the following formula (I).
Formula (I)

Y ^a represents a sulfur atom or —NR ^Ya —, Y ^b represents a nitrogen atom or —CR ^Yb —, and R ^a , R ^b , R ^Ya and R ^Yb each independently represent a hydrogen atom, a substituent, a dye It represents the bonding site with the atomic group constituting the structure or the bonding site with the atomic group constituting the dye multimer, and R ^a and R ^Ya , R ^b and R ^Ya , and R ^b and R ^Yb are respectively They may combine to form a ring; any of the atoms that make up the ring, or the entire ring has a monovalent positive charge.

Examples of the substituent include groups exemplified in Substituent group A described later. Examples thereof include a halogen atom, an alkyl group, an alkenyl group, an aryl group, and a heterocyclic group.
The ring formed by combining R ^a and R ^Ya , R ^b and R ^Ya , and R ^b and R ^Yb may be monocyclic or polycyclic. The ring is preferably an aromatic ring. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring. Examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Heteroaromatic rings include pyridine ring, pyrazine ring, pyrrole ring, quinoline ring, quinoxaline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, oxazole ring, thiazole ring, imidazole ring, pyrazole ring, indole ring, And a carbazole ring. The aromatic ring is preferably a hydrocarbon aromatic ring, and more preferably a benzene ring.

Specific examples of the cationic heterocycle include the following (1) to (6).

R ^a1 to R ^a23 each independently represent a bonding site with a hydrogen atom, a substituent, an atomic group constituting a dye structure, or a bonding site with an atomic group constituting a dye multimer. Examples of the substituent include groups exemplified in Substituent group A described later. Examples thereof include a halogen atom, an alkyl group, an alkenyl group, an aryl group, and a heterocyclic group.

Examples of the azo group bonded to the cationic heterocycle include a group represented by —N═N—R. R represents a substituent. Examples of the substituent include groups exemplified in Substituent group A described later. For example, an aryl group, a heterocyclic group and an amino group are preferable.

Examples of the aromatic ring group bonded to the cationic heterocycle include a hydrocarbon aromatic ring group and a heteroaromatic ring group. Examples of the hydrocarbon aromatic ring group include a benzene ring group, a naphthalene ring group, an anthracene ring group, and a phenanthrene ring group. Heteroaromatic ring groups include pyridine ring group, pyrazine ring group, pyrrole ring group, quinoline ring group, quinoxaline ring group, furan ring group, benzofuran ring group, thiophene ring group, benzothiophene ring group, oxazole ring group, thiazole Examples thereof include a ring group, an imidazole ring group, a pyrazole ring group, an indole ring group, and a carbazole ring group. The aromatic ring group is preferably a hydrocarbon aromatic ring group, and more preferably a benzene ring group.
The aromatic ring group may have a substituent or may be unsubstituted. Examples of the substituent include groups exemplified in Substituent group A described later. An electron donating group is preferred. Examples of the electron donating group include groups having a Hammett σp value of 0.2 or less. The σp value is preferably 0.1 or less, more preferably 0 or less. Specific examples of the electron donating group include an alkyl group, an alkoxy group, an amino group, a urea group, an allyl group, and a hydroxyl group, and an amino group is preferable. These groups are substituted with substituents such as alkyl groups, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, alkoxy groups, thiol groups, thioalkoxy groups, amino groups, halogen atoms and the like within a range not losing electron donating properties. It may be. Further, these substituents may be further substituted with these substituents, and if possible, may be bonded to each other to form a ring.

In the dye multimer of the present invention, the dye structure is preferably a dye structure represented by the formula (Ia).

Ht represents a cationic heterocycle containing two or more heteroatoms, and one or more of the heteroatoms is a nitrogen atom, L represents a single bond, —N═N—, or an arylene group; Represents a substituent, X represents an anion, and at least one of Ht, B and X has a bonding site with an atomic group constituting a dye multimer.

In the formula (Ia), examples of the cationic heterocycle represented by Ht include the cationic heterocycles represented by the above formula (I), and the cationic heterocycles represented by the above formulas (1) to (6) Is preferred.

In the formula (Ia), L represents —N═N— or an arylene group. The number of carbon atoms of the arylene group is preferably 6 to 30, more preferably 6 to 20, and particularly preferably 6 to 10. The arylene group may have a substituent or may be unsubstituted. Examples of the substituent include groups exemplified in Substituent group A described later.

In the formula (Ia), B represents a substituent. Examples of the substituent include those mentioned in Substituent Group A described later, and an aryl group, a heterocyclic group and an amino group are preferred.
When L represents an arylene group, B is preferably an electron donating group, and more preferably an amino group. The amino group is preferably a dialkylamino group or a cyclic amino group. Specific examples include a dimethylamino group, a diethylamino group, a piperidino group, and a morpholino group. Further, B is preferably substituted at the para position with respect to Ht.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 10 carbon atoms. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include groups exemplified in Substituent group A described later.
The heterocyclic group is preferably a 5- to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, and the ring-constituting atoms are a carbon atom, a nitrogen atom, A heterocyclic group having at least one hetero atom of either an oxygen atom or a sulfur atom is more preferable. Of these, a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms is most preferable. The heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include groups exemplified in Substituent group A described later. Examples of the heterocyclic group include 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl, 1-methyl-1H-indol-3-yl, 2-carbazoyl and the like. . Of these, 1-alkyl-1H-indol-3-yl is preferable.
Examples of the amino group include a group represented by —N (R ¹¹⁰ ) (R ¹¹¹ ). R ¹¹⁰ and R ¹¹¹ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. The group mentioned above is mentioned about a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group.
At least one of R ¹¹⁰ and R ¹¹¹ alkyl group is preferable, and more preferably both by R ¹¹⁰ and R ¹¹¹ is an alkyl group. That is, the amino group is more preferably a dialkylamino group. In particular, when L represents an arylene group, it is more preferable that both R ¹¹⁰ and R ¹¹¹ are alkyl groups.
R ¹¹⁰ and R ¹¹¹ are preferably bonded to form a ring. That is, the amino group is preferably a cyclic amino group. In particular, when both R ¹¹⁰ and R ¹¹¹ are alkyl groups, it is also preferred that they are bonded to form a ring. When R ¹¹⁰ and R ¹¹¹ are combined to form a ring, R ¹¹⁰ and R ¹¹¹ are divalent linking groups selected from the group consisting of —O—, —NH—, —CH ₂ —, and combinations thereof. It is preferable to connect to form a ring. The divalent linking group is preferably —O— or —CH ₂ —.

In the formula (Ia), X represents an anion. The anion will be described later.

In formula (Ia), at least one of Ht, B and X has a binding site with an atomic group constituting a dye multimer, and at least one of Ht and B is a binding site with an atomic group constituting a dye multimer. It is preferable that Ht has a binding site with an atomic group constituting a dye multimer. The dye multimer in which Ht is bonded to the atoms constituting the dye multimer has a particularly high effect of shielding cations, and the effect of the present invention is more remarkable.

In the dye multimer of the present invention, the dye structure is preferably a dye structure represented by the formula (Ia-1).

Y ^a represents a sulfur atom or —NR ^Ya —, Y ^b represents a nitrogen atom or —CR ^Yb —, R ^a , R ^Ya and R ^Yb each independently represents a hydrogen atom or a substituent, and R ^a R ^Ya , and R ^a and R ^Yb may be bonded to each other to form a ring, L represents —N═N— or an arylene group, B represents a substituent, and X represents an anion. Wherein at least one of R ^a , R ^Ya , R ^Yb , X and B has a bonding site with an atomic group constituting a dye multimer.

L and B in the formula (Ia-1) are synonymous with L and B in the formula (Ia) described above.
In the formula (Ia-1), Y ^a represents a sulfur atom or —NR ^Ya —, Y ^b represents a nitrogen atom or —CR ^Yb —, and R ^a , R ^Ya and R ^Yb each independently represent a hydrogen atom or Represents a substituent.
^Examples of the substituent represented by R ^a , R ^Ya and R ^Yb include the substituents ^exemplified in Substituent group A described later. Examples thereof include a halogen atom, an alkyl group, an alkenyl group, an aryl group, and a heterocyclic group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. Examples of the alkyl group include straight chain, branched, and cyclic, and straight chain or branched is preferable. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include groups exemplified in Substituent group A described later.
The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 10 carbon atoms. Examples of the alkenyl group include straight chain, branched, and cyclic, and straight chain or branched is preferable. The alkenyl group may have a substituent or may be unsubstituted. Examples of the substituent include groups exemplified in Substituent group A described later.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 10 carbon atoms. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include groups exemplified in Substituent group A described later.
The heterocyclic group is preferably a 5- to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, and the ring-constituting atoms are a carbon atom, a nitrogen atom, A heterocyclic group having at least one hetero atom of either an oxygen atom or a sulfur atom is more preferable.

In the formula (Ia-1), R ^a and R ^Ya , and R ^a and R ^Yb may be bonded to each other to form a ring. The ring may be monocyclic or polycyclic. The ring is preferably an aromatic ring. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring. Examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Heteroaromatic rings include pyridine ring, pyrazine ring, pyrrole ring, quinoline ring, quinoxaline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, oxazole ring, thiazole ring, imidazole ring, pyrazole ring, indole ring, And a carbazole ring. The aromatic ring is preferably a hydrocarbon aromatic aromatic ring, and more preferably a benzene ring.

In the formula ^{(Ia-1), R a} , R Ya, R Yb, at least one of X and B have the binding site of the atomic group forming a dye ^{^{multimer, R a, R Ya, R}} Yb and B It is preferable that at least one of the above has a binding site with an atomic group constituting the dye multimer, and at least one of R ^a , R ^Ya and R ^Yb has a binding site with the atomic group constituting the dye multimer. More preferred.

In the present invention, the dye multimer preferably has a dye structure represented by the formula (I-1) or a dye structure represented by the formula (I-2).

In formula (I-1), R ¹ and R ⁸ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ² , R ⁷ , R ⁹ to R ¹² are each independently Represents a hydrogen atom or a substituent, Y ¹ represents a sulfur atom or —NR ^Y1 —, R ^Y1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, X represents an anion, R ¹ At least one of -R ² , R ⁷ -R ¹² , R ^Y1 and X has a bonding site with an atomic group constituting a dye multimer.

In formula (I-1), R ¹ and R ⁸ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and preferably a hydrogen atom, an alkyl group or an aryl group.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. Examples of the alkyl group include straight chain, branched, and cyclic, and straight chain or branched is preferable. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include groups exemplified in Substituent group A described later.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 10 carbon atoms. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include groups exemplified in Substituent group A described later.
The heterocyclic group is preferably a 5- to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, and the ring-constituting atoms are a carbon atom, a nitrogen atom, A heterocyclic group having at least one hetero atom of either an oxygen atom or a sulfur atom is more preferable.

In the formula (I-1), Y ¹ represents a sulfur atom or —NR ^Y1 —. R ^Y1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom, an alkyl group or an aryl group. The alkyl group, aryl group and heterocyclic group represented by R ^Y1 have the same meanings as the alkyl group, aryl group and heterocyclic group described in R ¹ and R ⁸ , and the preferred ranges are also the same.

In the formula (I-1), R ² , R ⁷ and R ⁹ to R ¹² each independently represents a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified in Substituent group A described later. Examples thereof include a halogen atom, an alkyl group, an alkenyl group, an aryl group, and a heterocyclic group. Preferable ranges of the halogen atom, alkyl group, alkenyl group, aryl group and heterocyclic group are the same as those described for formula (Ia-1).

In formula (I-2), R ¹⁰¹ , R ¹¹⁰ and R ¹¹¹ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ¹¹⁰ and R ¹¹¹ may combine to form a ring.
R ¹⁰¹ is preferably a hydrogen atom, an alkyl group or an aryl group.
R ¹¹⁰ and R ¹¹¹ are each independently preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and even more preferably an alkyl group. When R ¹¹⁰ and R ¹¹¹ are combined to form a ring, R ¹¹⁰ and R ¹¹¹ are divalent linking groups selected from the group consisting of —O—, —NH—, —CH ₂ —, and combinations thereof. It is preferable to connect to form a ring. The divalent linking group is preferably —O— or —CH ₂ —.
The alkyl group, aryl group and heterocyclic group represented by R ¹⁰¹ , R ¹¹⁰ and R ¹¹¹ have the same meanings as the alkyl group, aryl group and heterocyclic group described for R ¹ and R ⁸ in formula (I-1), The preferable range is also the same.

In the formula (I-2), R ¹⁰² to R ¹⁰⁵ and R ¹⁰⁶ to R ¹⁰⁹ each independently represents a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified in Substituent group A described later. Examples thereof include a halogen atom, an alkyl group, an alkenyl group, an aryl group, and a heterocyclic group. Preferable ranges of the halogen atom, alkyl group, alkenyl group, aryl group and heterocyclic group are the same as those described for formula (Ia-1).

In the formula (I-2), Y ² represents a sulfur atom or —NR ^Y2 —. R ^Y2 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom, an alkyl group or an aryl group. The alkyl group, aryl group and heterocyclic group represented by R ^Y2 have the same meanings as the alkyl group, aryl group and heterocyclic group described for R ¹ and R ⁸ in formula (I-1), and the preferred ranges are also the same. .

In the formulas (I-1) and (I-2), X represents an anion. The anion may be an organic anion or an inorganic anion, and an organic anion is preferred. Examples of the anion include a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide anion, a perchlorate anion, and a non-nucleophilic anion. A non-nucleophilic anion is preferable from the viewpoint of heat resistance. Examples of the anion include known non-nucleophilic anions described in paragraph No. 0075 of JP-A-2007-310315, the contents of which are incorporated herein. Here, the non-nucleophilic property means a property that does not nucleophilic attack the dye by heating.

The anion is preferably an imide anion (for example, a bis (sulfonyl) imide anion), a tris (sulfonyl) methyl anion, or an anion having a boron atom, more preferably a bis (sulfonyl) imide anion or a tris (sulfonyl) methyl anion, ) Imide anion is more preferred. By using such anions, the effects of the present invention tend to be exhibited more effectively.

As the imide anion, a structure represented by the following general formula (AN-1) is preferable.

In formula (AN-1), X ¹ and X ² each independently represent a halogen atom, an alkyl group or an aryl group. X ¹ and X ² may be bonded to each other to form a ring. Y ¹ and Y ² each independently represent —SO ₂ — or —CO—.

X ¹ and X ² are each independently a fluorine atom or a fluorine atom-containing alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 10 carbon atoms. Further, a perfluoroalkyl group having 1 to 4 carbon atoms is more preferable, and a trifluoromethyl group is particularly preferable.
Y ¹ and Y ^2, at least one of -SO ₂ - preferably represents an, both -SO ₂ - and more preferably represents.

As the tris (sulfonyl) methyl anion, a structure represented by the following general formula (AN-2) is preferable.

In formula (AN-2), X ³ , X ⁴ and X ⁵ each independently represent a halogen atom or an alkyl group. The number of carbon atoms of the alkyl group represented by X ³ , X ⁴ and X ⁵ is preferably 1 to 10, and more preferably 1 to 4. The alkyl group may be an unsubstituted alkyl group or may have a substituent. As the substituent, a halogen atom is preferable, and a fluorine atom is more preferable.
X ³ , X ⁴ and X ⁵ are each independently preferably a fluorine atom or an alkyl group having a fluorine atom, more preferably an alkyl group having a fluorine atom. The alkyl group having a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and a perfluoroalkyl group having 1 to 4 carbon atoms. Is more preferable, and a trifluoromethyl group is particularly preferable.

Examples of the anion having a boron atom include a tetrafluoroborate anion, a tetraphenylborate anion, and a tetraperfluorophenylborate anion.

The non-nucleophilic anion may further have a crosslinkable group. Examples of the crosslinkable group include a group having an ethylenically unsaturated bond (for example, a vinyl group, an allyl group, a styryl group, a (meth) acryloyl group), a group having a cyclic ether structure such as an epoxy group or an oxetanyl group, or methylol. Groups and the like.

The molecular weight of the anion is preferably 100 to 1,000, and more preferably 200 to 500.

Specific examples of anions are shown below, but the present invention is not limited thereto. In addition, when the anion has a binding site with an atomic group constituting the dye multimer, a portion obtained by removing one or more atoms from the structural formulas shown in the following specific examples is the same as the atomic group constituting the dye multimer. It becomes a binding site.

In the formula (I-1), at least one of R ¹ , R ² , R ⁷ to R ¹² , R ^Y1 and X has a bonding site with an atomic group constituting a dye multimer, and R ¹ , R ² , Preferably, at least one of R ⁷ to R ¹² and R ^Y1 has a binding site with an atomic group constituting a dye multimer, and at least one of R ¹ , R ² and R ^Y1 is an atomic group constituting a dye multimer It is more preferable to have a binding site.
Yes.

In the formula (I-2), at least one of R ¹⁰¹ to R ¹⁰⁹ , R ^Y2 and X has a binding site with an atomic group constituting a dye multimer, and at least one of R ¹⁰¹ to R ¹⁰⁹ and R ^Y2 is It preferably has a binding site with an atomic group constituting the dye multimer, and more preferably at least one of R ¹⁰¹ to R ¹⁰⁵ and R ^Y2 has a binding site with the atomic group constituting the dye multimer.

(Substituent group A)
Substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups, silyloxy groups, heterocyclic oxy groups. , Acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group , Alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, Group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, and a silyl group. Details are described below.
A halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom);
Alkyl group (straight-chain, branched or cyclic substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl) 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cyclohexyl and cyclopentyl. The cyclic alkyl group is a polycycloalkyl group such as a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms such as bicyclo [1,2,2] heptan-2-yl. And groups having a polycyclic structure such as bicyclo [2,2,2] octane-3-yl) and tricycloalkyl groups. The cyclic alkyl group is preferably a monocyclic cycloalkyl group or a bicycloalkyl group, and a monocyclic cycloalkyl group is particularly preferred);
Alkenyl groups (straight-chain, branched or cyclic substituted or unsubstituted alkenyl groups, preferably alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopentene-1- The cyclic alkenyl group is a polycycloalkenyl group such as a bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, such as Bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2-en-4-yl) and tricycloalkenyl groups are also preferred. A monocyclic cycloalkenyl group is particularly preferred).
An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group);
An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl);
Heterocyclic group (5- to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group is preferred, and the ring-constituting atoms are carbon, nitrogen, oxygen A heterocyclic group having at least one hetero atom of any one of an atom and a sulfur atom is more preferable, and a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms (heteroaryl group));
A cyano group;
A hydroxyl group;
A nitro group;
Carboxyl group (hydrogen atom may be dissociated (that is, carbonate group), salt state (metal salt (for example, sodium salt, potassium salt, magnesium salt, calcium salt, iron salt, aluminum salt, etc.), alkyl ammonium) Salts (eg, ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, stearylamine, quaternary alkylammonium salts such as palmityltrimethylammonium, dilauryldimethylammonium, distearyldimethylammonium salts, etc.) May be);
An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy);
Aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms such as phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy);
A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, tert-butyldimethylsilyloxy);
Heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, wherein the heterocyclic part is preferably the heterocyclic part described above for the heterocyclic group, for example, 1-phenyltetrazole -5-oxy, 2-tetrahydropyranyloxy);
An acyloxy group (preferably a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy, Stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy);
A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di -N-octylaminocarbonyloxy, Nn-octylcarbamoyloxy);
An alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octylcarbonyloxy);
Aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy );
Amino group (including alkylamino group, arylamino group and heteroarylamino group. Preferably, amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms. An arylamino group, a heteroarylamino group having 0 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazine-2- Ilamino);
An acylamino group (preferably a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, Lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino);
Aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino) ;
An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N— Methyl-methoxycarbonylamino);
Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) ;
Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonyl) amino);
An alkyl or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methylsulfonylamino, butyl Sulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino);
A mercapto group;
An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio);
An arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio);
Heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, and the heterocyclic portion is preferably the heterocyclic portion described above for the heterocyclic group, for example, 2-benzothiazolyl Luthio, 1-phenyltetrazol-5-ylthio);
Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl);
Sulfo group (hydrogen atom may be dissociated (that is, sulfonate group), salt state (metal salt (for example, sodium salt, potassium salt, magnesium salt, calcium salt, iron salt, aluminum salt, etc.), alkyl ammonium) Salts (eg, ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, stearylamine, quaternary alkylammonium salts such as palmityltrimethylammonium, dilauryldimethylammonium, distearyldimethylammonium salts, etc.) May be);
An alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl);
An alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl);
An acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl; , Stearoyl, benzoyl, pn-octyloxyphenylcarbonyl);
Aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl) ;
An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl);
A carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methyl Sulfonyl) carbamoyl)
An aryl or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocyclic portion is described in the above heterocyclic group) A heterocycle moiety thereof, for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo);
An imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms, such as N-succinimide, methylphthalimide);
A phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino);
A phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl);
A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy);
A phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino, dimethylaminophosphinylamino);
Examples thereof include a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, such as trimethylsilyl, tert-butyldimethylsilyl, phenyldimethylsilyl).
When these groups are further substitutable groups, they may further have a substituent. Examples of the further substituent include the groups described in the above-mentioned substituent group A.

<< Preferred Aspect of Dye Multimer >>
In the present invention, the dye multimer preferably has a structure in which two or more dye structures are bonded to a divalent or higher linking group. The dye multimer preferably has at least one selected from a repeating unit having a dye structure in the side chain and a repeating unit having a dye structure in the main chain.

Further, the dye multimer includes at least one of a repeating unit represented by the formula (A) described later and a repeating unit represented by the formula (C), or represented by the formula (D) described later. Is preferred. That is, the dye multimer includes a dye multimer having a repeating unit represented by the formula (A) (also referred to as a dye multimer (A)), and a dye multimer having a repeating unit represented by the formula (C) (dye Multimers (also referred to as multimers (C)) and multimers represented by formula (D) (also referred to as dye multimers (D)) are preferred.

<<< Dye Multimer (A) >>>
The dye multimer (A) preferably contains a repeating unit represented by the formula (A). In the dye multimer (A), the ratio of the repeating unit represented by the 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 formula (A), A ¹ represents the main chain of the repeating unit, L ¹ represents a single bond or a divalent linking group, DyeI contains two or more heteroatoms, and one or more of the heteroatoms are It represents a dye structure having a structure in which an azo group or an aromatic ring group is bonded to a cationic heterocycle which is a nitrogen atom.

In formula (A), A ¹ represents the main chain of the repeating unit. Examples of A ¹ include a linking group formed by a polymerization reaction, and a main chain derived from a compound having a (meth) acryl group, a styrene group, a vinyl group, or an ether group is preferable. Also preferred is an embodiment in which the main chain has a cyclic alkylene group. A ¹ is not particularly limited as long as it is a linking group formed from a known polymerizable monomer. A ¹ is preferably a linking group represented by the following (XX-1) to (XX-25), (XX-1), (XX-2), (XX-10) to (XX-17), More preferably selected from (XX-18), (XX-19), (XX-24) and (XX-25), and (XX-1), (XX-2), (XX-10) to More preferably, it is selected from (XX-17), (XX-24) and (XX-25).

In the following formulas, * is a binding site with L ^{1 in} formula (A). 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 )-, -COO-, -NR-, -CONR-, -OCO-, -SO-, -SO ₂ -and a linking group formed by linking two or more thereof. Here, each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

The alkylene group preferably has 1 to 30 carbon atoms. The upper limit is more preferably 25 or less, and still more preferably 20 or less. The lower limit is more preferably 2 or more, and still more preferably 3 or more. The alkylene group may be linear, branched or cyclic. The alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described in the substituent group A.
The carbon number of the arylene group is preferably 6 to 20, and more preferably 6 to 12. The arylene group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described in the substituent group A.
The heterocyclic linking group is preferably a 5-membered ring or a 6-membered ring. The hetero atom that the heterocyclic linking group has is preferably an oxygen atom, a nitrogen atom, or a sulfur atom. The number of heteroatoms contained in the heterocyclic linking group is preferably 1 to 3. The heterocyclic linking group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described in the substituent group A.

DyeI represents a dye structure having a structure in which an azo group or an aromatic ring group is bonded to a cationic heterocycle containing two or more heteroatoms and one or more of the heteroatoms being a nitrogen atom. The dye structure is preferably a structure in which one or more arbitrary atoms are removed from the cation or anion of the dye compound having a dye skeleton having a cationic heterocycle and an anion as described above. A structure in which one or more are removed is more preferable. That, combined in the present invention, in the dye structure represented by DyeI, may be the above-mentioned cations bound to A ¹ or L ¹ in formula (A), the anion is the A ¹ or L ¹ in formula (A) It is preferable that the cation is bonded to A ¹ or L ¹ of the formula (A). Specifically, examples of the repeating unit represented by the formula (A) include a repeating unit represented by the formula (A-1) and a repeating unit represented by the formula (A-2). The repeating unit represented by 1) is preferred. According to this aspect, the cation part of the dye structure is easily shielded by the polymer chain, aggregation of the dye multimer can be suppressed, and a more excellent effect can be easily obtained.

In the formula, A ¹ represents the main chain of the repeating unit, L ^1a and L ^1b each independently represent a single bond or a divalent linking group, and DyeI-1 and DyeI-2 each independently represent 2 A cation having a cationic heterocycle containing the above heteroatoms and one or more of the heteroatoms being a nitrogen atom is represented, and X1 and X2 each independently represent an anion.

In the formula (A-1), examples of the divalent linking group represented by L ^1a include the divalent linking group described for L ¹ in the formula (A). L ^1a is preferably a single bond or an alkylene group, an arylene group, —NH—, —CO—, —O—, —COO—, —OCO—, —S—, and a linking group in which two or more thereof are combined, A single bond or a divalent group formed by combining an alkylene group, an arylene group, and one or more selected from —O—, —COO—, and —OCO— is more preferable.

In formula (A-1), the cation represented by DyeI-1 is preferably a cation having the dye structure of formula (I-1) or formula (I-2) described above. Moreover, as an anion which X1 represents, the anion demonstrated by the pigment | dye structure mentioned above is preferable.

In the formula (A-2), examples of the divalent linking group represented by L ^1b include the divalent linking groups described for L ¹ in the formula (A). L ^1b is preferably a single bond, or an alkylene group, an arylene group, —NH—, —CO—, —O—, —COO—, —OCO—, —SO ₂ — and a combination group of two or more thereof. , An alkylene group, —O—, —SO ₂ — and a linking group obtained by combining two or more thereof are preferred. In addition, the alkylene group and the arylene group preferably have a substituent. As the substituent, an electron withdrawing group is preferable, and a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), nitro group, cyano group, halogenated alkyl group (for example, trifluoromethyl group), aryl halide Group and the like.

In formula (A-2), the cation represented by DyeI-2 is preferably a cation having the dye structure of formula (I-1) or formula (I-2) described above. Moreover, as an anion which X2 represents, the anion demonstrated by the pigment | dye structure mentioned above is preferable. Specific examples of the repeating unit represented by the formula (A-2) include structures described in paragraph numbers 0162 to 0166 in JP-A-2014-199436.

The dye multimer containing the repeating unit represented by the formula (A) is (1) a method of synthesizing a dye compound having a polymerizable group by addition polymerization, (2) an isocyanate group, an acid anhydride group, an epoxy group, or the like. The polymer having a highly reactive functional group can be synthesized by a method of reacting a dye compound having a functional group (hydroxyl group, primary or secondary amino group, carboxyl group, etc.) capable of reacting with the 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 a repeating unit represented by the formula (A) is preferably a radical polymer obtained by radical polymerization using a dye compound having an ethylenically unsaturated bond from the viewpoint of heat resistance. .

Specific examples of the repeating unit represented by the formula (A) include the following. In the following structural formulas, Me is a methyl group, and Et is an ethyl group.

Specific examples of the repeating unit represented by the formula (A-2) include the following.

(Other repeat units)
The dye multimer in the present invention may contain other repeating units in addition to the repeating unit represented by the formula (A). Other repeating units may contain a functional group such as a curable 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 curable group.

Examples of the curable group include a radical polymerizable group, a cyclic ether group (epoxy group, oxetanyl group), an oxazoline group, and a methylol group. Examples of the radically polymerizable group include groups containing an ethylenically unsaturated bond such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. The curable group is preferably a radical polymerizable group.
The ratio of the repeating unit having a curable group is preferably 0 to 50% by mass with respect to 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 can be appropriately introduced.
In the group consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains, the number of repeating alkyleneoxy chains is more preferably 2 to 15, and further 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 these.

<<< Dye Multimer (C) >>>
The dye multimer (C) preferably contains a repeating unit represented by the formula (C). In the dye multimer (C), the ratio of the repeating unit represented by the 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 formula (C), L ³ 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 )-, -COO-, -NR-, -CONR-, -OCO-, -SO-, -SO ₂ -and a linking group formed by linking two or more thereof. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.

The alkyl group and alkylene group preferably have 1 to 30 carbon atoms. The upper limit is more preferably 25 or less, and still more preferably 20 or less. The lower limit is more preferably 2 or more, and still more preferably 3 or more. The alkyl group and alkylene group may be linear, branched or cyclic.
The number of carbon atoms in the aryl group and arylene group is preferably 6-20, and more preferably 6-12.
The heterocyclic linking group and the heterocyclic group are preferably a 5-membered ring or a 6-membered ring. The hetero atom contained in the heterocyclic linking group and the heterocyclic group is preferably an oxygen atom, a nitrogen atom or a sulfur atom. The number of heteroatoms contained in the heterocyclic linking group and the heterocyclic group is preferably 1 to 3.
The alkylene group, arylene group, heterocyclic linking group, alkyl group, aryl group, and heterocyclic group may be unsubstituted or may have a substituent. Examples of the substituent include a curable group and an acid group. Examples of the curable group include a radical polymerizable group such as a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetanyl group), an oxazoline group, and a methylol group. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Further, a group consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains, a development promoting group such as lactone, acid anhydride, amide, cyano group, long chain and cyclic alkyl group, aralkyl group, aryl group, polyalkylene You may have a hydrophilic group, such as an oxide group, a hydroxyl group, a maleimide group, an amino group, etc. as a substituent.

L ³ is preferably an alkylene group, an arylene group, —NH—, —CO—, —O—, —COO—, —OCO—, —S—, or a linking group in which two or more thereof are combined.
DyeIII represents a dye structure having a structure in which an azo group or an aromatic ring group is bonded to a cationic heterocycle containing two or more heteroatoms and one or more of the heteroatoms being a nitrogen atom. The dye structure is preferably a structure in which one or more arbitrary atoms are removed from the cation or anion of the dye compound having a dye skeleton having a cationic heterocycle and an anion as described above. A structure in which one or more are removed is more preferable.
m represents 0 or 1, and 1 is preferable.

The dye multimer having the structural unit represented by the formula (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 structure is not decomposed. Known reaction conditions can be applied to the sequential polymerization.

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

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

In the formula (D), L ⁴ represents an (n + k) -valent linking group, n represents an integer of 2 to 20, k represents an integer of 0 to 20, DyeIV contains 2 or more heteroatoms, And a dye structure having a structure in which an azo group or an aromatic ring group is bonded to a cationic heterocycle in which one or more heteroatoms are nitrogen atoms, P represents a substituent, and n is 2 or more The plurality of DyeIVs may be different from each other. When k is 2 or more, the plurality of Ps may be different from each other, and n + k represents an integer of 2 to 20.

In the 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 further preferably 2 to 6.
The total of n and k is 2 to 20, 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.
Note that n and k in one dye multimer are integers, respectively, but in the present invention, a plurality of dye multimers in which n and k in formula (D) are different may be included. Therefore, the average value of n and k in the coloring composition of the present invention may not be an integer.

(N + k) -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 Groups consisting of 0 to 20 sulfur atoms are included.
Specific examples of the (n + k) -valent linking group include a group composed of a combination of two or more of the following structural units or the following structural units (which may form a ring structure). .

Specific examples of (n + k) -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.

In formula (D), P represents a substituent. Examples of the substituent include an acid group and a curable group. Examples of the curable group include a radical polymerizable group such as a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetanyl group), an oxazoline group, and a methylol group. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. Examples of the acid group include a carboxyl group, a sulfonic acid group and a phosphoric acid group.
The substituent represented by P may be a monovalent polymer chain having a repeating unit. The monovalent polymer chain having a repeating unit is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound. When k is 2 or more, the k Ps may be the same or different.
When P is a monovalent polymer chain having a repeating unit and k is 1, P has 2 to 20 repeating units derived from a vinyl compound (preferably 2 to 15, more preferably 2 to 10). Are preferable. In addition, when P is a monovalent polymer chain having repeating units and k is 2 or more, the average number of repeating units derived from k P vinyl compounds is 2 to 20 (preferably 2 to 15, more preferably 2 to 10).
When P is a monovalent polymer chain having repeating units, the number of repeating units of P when k is 1 and the average number of repeating units of P when k is 2 or more are expressed as It can be determined by resonance (NMR).

When P is a monovalent polymer chain having a repeating unit, examples of the repeating unit constituting P include other repeating units described in the dye multimer (A). It is preferable that another repeating unit has 1 or more types chosen from the repeating unit which has the acid group mentioned above, and the repeating unit which has a sclerosing | hardenable group. When the repeating unit having an acid group is contained, the developability can be improved. When the repeating unit having a curable group is included, the solvent resistance can be further improved.
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 curable group, the ratio of the repeating unit having a curable 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 curable group, color unevenness and the like can be further improved.

In the formula (D), DyeIV represents a dye structure. The dye structure represented by DyeIV is preferably a structure in which one or more arbitrary atoms have been removed from the cation or anion of the dye compound having a cation having a dye skeleton having a cationic heterocycle and an anion. A structure in which one or more atoms are removed is more preferable. That is, in the present invention, the dye structure represented by DyeIV preferably has the aforementioned cation bonded to L ^{4 of the} formula (D).

Further, the dye structure represented by DyeIV is a structure in which one or more arbitrary atoms of the dye compound are removed, and a part of the dye compound may be bonded to L ^4. The polymer chain may include a repeating unit having a dye structure (a structure in which one or more arbitrary atoms of the dye compound are removed) in the side chain. The polymer chain is not particularly defined as long as it contains a dye structure, but is one kind selected from (meth) acrylic resins, styrene resins, and (meth) acrylic / styrene resins. Is preferred. The repeating unit of the polymer chain is not particularly defined, and examples thereof include the repeating unit represented by the above formula (A) and the repeating unit represented by the above formula (C). The total number of repeating units having a dye structure in all repeating units constituting the polymer chain is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and further preferably 20 to 40 mol%. preferable.
The polymer chain may contain other repeating units described in the dye multimer (A) in addition to the repeating unit having a dye structure. As other repeating units, it is preferable to have one or more selected from repeating units having an acid group and repeating units having a curable group.
When the polymer chain includes a repeating unit having a curable group, the ratio of the repeating unit having a curable group is preferably, for example, 5 to 50 mol with respect to 100 mol of all repeating units of the polymer chain, and 10 to 40 mol. Is more preferable.
When the polymer chain 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 mol, more preferably 10 to 40 mol, relative to 100 mol of all repeating units of the polymer chain. preferable.

The dye multimer represented by the formula (D) can be synthesized by the following method.
(1) A compound 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 structure, an alkyl halide having a dye structure, an isocyanate having a dye structure, and the like. Polymer reaction method.
(2) A method of Michael addition reaction between a compound having a carbon-carbon double bond introduced at the terminal and a thiol compound having a dye structure.
(3) A method in which a compound in which a carbon-carbon double bond is introduced at a terminal and a thiol compound having a dye structure are reacted in the presence of a radical generator.
(4) A method in which a polyfunctional thiol compound having a plurality of thiol groups introduced at its terminal is reacted with a compound having a carbon-carbon double bond and a dye structure 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 structure.

The dye multimer (D) preferably has a structure represented by the formula (D-1).
^{^{_{(D 1 -L 42) n -L}}} 4 - (L 41 -P 1) k ··· (D-1)
In formula (D-1), L ⁴ represents an (n + k) -valent linking group. n represents an integer of 2 to 20, and k represents an integer of 0 to 20. D ¹ represents a dye structure, and P ¹ represents a substituent. When n is 2 or more, the plurality of D ¹ may be different from each other, and when k is 2 or more, the plurality of P ¹ may be different from each other. n + k represents an integer of 2 to 20.

Wherein ^{(D-1), L 4} , n and k are the same as L ^4, n and k of the formula (D), and preferred ranges are also the same.

In formula (D-1), L ⁴¹ and L ⁴² each independently represents a single bond or a divalent linking group. When a plurality of L ⁴¹ and L ⁴² 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 the following structural units or groups formed by combining two or more of the following structural units.

In formula (D-1), P ¹ represents a substituent. Examples of the substituent include an acid group and a curable group. Examples of the curable group include a radical polymerizable group such as a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetanyl group), an oxazoline group, and a methylol group. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. Examples of the acid group include a carboxyl group, a sulfonic acid group and a phosphoric acid group.
Further, the substituent represented by P ¹ may be a monovalent polymer chain having a repeating unit. The monovalent polymer chain having a repeating unit is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound. When k is 2 or more, k P ^{1 s} may be the same or different.
When P ¹ is a monovalent polymer chain having a repeating unit and k is 1, P ¹ has 2 to 20 repeating units derived from a vinyl compound (preferably 2 to 15, more preferably 2 Monovalent polymer chains having ˜10) are preferred. In addition, when P ¹ is a monovalent polymer chain having a repeating unit and k is 2 or more, the average number of repeating units derived from k P ¹ vinyl compounds is 2 to 20 ( The number is preferably 2 to 15, more preferably 2 to 10.

When P ¹ represents a monovalent polymer chain having a repeating unit, examples of the repeating unit constituting P ¹ include the other repeating units described in the dye multimer (A) described above. It is preferable that another repeating unit has 1 or more types chosen from the repeating unit which has the acid group mentioned above, and the repeating unit which has a sclerosing | hardenable group.
When P ¹ contains a repeating unit containing an acid group, the ratio of the repeating unit containing an acid group is preferably 10 to 80 mol%, more preferably 10 to 65 mol%, based on all repeating units of P ^1. .
When P ¹ includes a repeating unit having a curable group, the ratio of the repeating unit having a curable group is preferably 10 to 80 mol%, more preferably 10 to 65 mol%, based on all the repeating units of P. preferable.

In formula (D-1), D ¹ represents a dye structure. The dye structure represented by D ¹ may be ^{one in} which a part of the dye compound is bonded to L ⁴² , or may be a polymer chain containing a repeating unit having a dye structure in the main chain or side chain. The polymer chain is not particularly defined as long as it contains a dye structure, but is preferably one selected from (meth) acrylic resins, styrene resins, and (meth) acrylic / styrene resins. . The repeating unit of the polymer chain is not particularly defined, and examples thereof include the repeating unit represented by the above formula (A) and the repeating unit represented by the above formula (C). The total number of repeating units having a dye structure in all repeating units constituting the polymer chain is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and further preferably 20 to 40 mol%. preferable.
The polymer chain may contain other repeating units described in the dye multimer (A) in addition to the repeating unit having a dye structure. As other repeating units, it is preferable to have one or more selected from repeating units having an acid group and repeating units having a curable group.

The dye multimer (D) preferably has a structure represented by the formula (D-2).
^{^{(D 2 -S-C 1 -B}} 1) n -L 4 - (B 2 -C 2 -S-P 2) k ··· (D-2)
In formula (D-2), L ⁴ represents an (n + k) -valent linking group. n represents an integer of 2 to 20, and k represents an integer of 0 to 20. D ² represents a dye structure, and P ² represents a substituent. B ¹ and B ² are each independently a single bond, —O—, —S—, —CO—, —NR—, —O ₂ C—, —CO ₂ —, —NROC—, or —CONR—. Represents. R represents a hydrogen atom, an alkyl group or an aryl group. C ¹ and C ² each independently represents a single bond or a divalent linking group. S represents a sulfur atom. When n is 2 or more, the plurality of D ² may be different from each other, and when k is 2 or more, the plurality of P ² may be different from each other. n + k represents an integer of 2 to 20.

Wherein ^{(D-2), L 4} , n and k are the same as L ^4, n and k of the formula (D), and preferred ranges are also the same.

In the formula (D-2), B ¹ and B ² are each independently a single bond, —O—, —S—, —CO—, —NR—, —O ₂ C—, —CO ₂ —, — NROC-, or represents -CONR-, single bond, -O -, - CO -, - O 2 C -, - CO 2 -, - NROC-, or -CONR- is preferred.
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 formula (D-2), C ¹ and C ² each independently 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.

In formula (D-2), P ² represents a substituent. Examples of the substituent include an acid group and a curable group. Examples of the curable group include a radical polymerizable group such as a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetanyl group), an oxazoline group, and a methylol group. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. Examples of the acid group include a carboxyl group, a sulfonic acid group and a phosphoric acid group.
Further, the substituent represented by P ² may be a monovalent polymer chain having a repeating unit. The monovalent polymer chain having a repeating unit is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound. When k is 2 or more, k P ^{2 s} may be the same or different.
When P ² is a monovalent polymer chain having a repeating unit and k is 1, P ² contains 2 to 20 repeating units derived from a vinyl compound (preferably 2 to 15, more preferably 2 Monovalent polymer chains having ˜10) are preferred. In addition, when P ² is a monovalent polymer chain having a repeating unit and k is 2 or more, the average number of repeating units derived from k P ² vinyl compounds is 2 to 20 ( The number is preferably 2 to 15, more preferably 2 to 10.

When P ² represents a monovalent polymer chain having a repeating unit, examples of the repeating unit constituting P ² include the other repeating units described in the dye multimer (A) described above. It is preferable that another repeating unit has 1 or more types chosen from the repeating unit which has the acid group mentioned above, and the repeating unit which has a sclerosing | hardenable group. When P ² contains a repeating unit containing an acid group, the ratio 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 ² . When P ² contains a repeating unit having a curable group, the proportion of the repeating unit having a curable group is preferably 10 to 80 mol%, more preferably 10 to 65 mol%, based on all the repeating units of P ^2. preferable.

In the formula (D-2), D ² represents a dye structure. The dye structure represented by D ² may be one in which a part of the dye compound is bonded to —S—, or may be a polymer chain containing a repeating unit having a dye structure in the main chain or side chain. . The polymer chain is not particularly defined as long as it contains a dye structure, but is preferably one selected from (meth) acrylic resins, styrene resins, and (meth) acrylic / styrene resins. . The repeating unit of the polymer chain is not particularly defined, and examples thereof include the repeating unit represented by the above formula (A) and the repeating unit represented by the above formula (C). The total number of repeating units having a dye structure in all repeating units constituting the polymer chain is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and further preferably 20 to 40 mol%. preferable.
The polymer chain may contain other repeating units described in the dye multimer (A) in addition to the repeating unit having a dye structure. As other repeating units, it is preferable to have one or more selected from repeating units having an acid group and repeating units having a curable group.

Specific examples of the formula (D) include the following.

The weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and further preferably 6000 or more. The upper limit is more preferably 30000 or less, and still more preferably 20000 or less. By satisfying the above range, it is easy to produce a cured film in which color unevenness and defects are suppressed.
The ratio [(Mw) / (Mn)] of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dye multimer is preferably 1.0 to 2.0, and 1.1 to 1. 8 is more preferable, and 1.1 to 1.5 is particularly preferable.
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 chromatography (GPC) measurement, Specifically, the value measured by the method as described in the Example mentioned later. It is.

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 curable group value of the dye multimer is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, and still more preferably 0.3 mmol / g or more. When the curable group value is 0.1 mmol / g or more, a cured film excellent in light resistance and solvent resistance is easily obtained. Further, the color loss of the film due to the developer or the stripping solution can be more effectively suppressed. The upper limit of the curable group value is not particularly limited, but is preferably 2.0 mmol / g or less, and more preferably 1.5 mmol / g or less. The curable group value can be calculated by dividing the number of curable groups introduced into the dye multimer by the molecular weight of the dye multimer. It can also be actually measured by analysis means such as ¹ H-NMR (nuclear magnetic resonance).

The colored composition of the present invention preferably contains 0.01 to 50% by mass of the above-mentioned dye multimer in the total solid content of the colored composition of the present invention. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 15% by mass or less. When the coloring composition of this invention contains 2 or more types of pigment | dye multimers, it is preferable that the total amount is in the said range.

<< other colorants >>
The coloring composition of the present invention can further use a coloring agent (other coloring agent) other than the above-described dye multimer. The colored composition of the present invention preferably contains another colorant. The other colorant may be either a dye or a pigment, or a combination of both. Other colorants are preferably pigments. The other colorant may be a dye multimer.

Examples of the pigment include conventionally known various inorganic pigments or organic pigments. The primary particle size of the pigment is preferably 100 nm or less from the viewpoint of color unevenness and contrast. Moreover, it is preferable that it is 5 nm or more from a viewpoint of dispersion stability. The primary particle size of the pigment is more preferably 5 to 75 nm, further preferably 5 to 55 nm, and particularly preferably 5 to 35 nm. The primary particle size of the pigment can be measured by a known method such as an electron microscope.

Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, black pigments such as carbon black and titanium black, iron, cobalt, aluminum, cadmium, lead, copper, titanium, Mention may be made of metal oxides such as 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
Further, as the green pigment, a zinc halide phthalocyanine pigment having an average number of halogen atoms in the molecule of 10 to 14, bromine atoms on average 8 to 12, and chlorine atoms on average 2 to 5 should be used. Is also possible. Specific examples include the compounds described in WO2015 / 118720.
Further, as yellow pigments, quinophthalone pigments described in paragraphs 0011 to 0034 of JP2013-54339A, quinophthalone pigments described in paragraphs 0013 to 0058 of JP2014-26228A, and the like can also be used.
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, Japanese Patent No. 2592207, and US Pat. No. 4,808,501. No. 5,667,920, U.S. Pat. No. 505950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. Can be used. When classified as a 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, JP2013-041097A, JP2015-028144A, JP2015-030742A, and the like.

When the coloring composition of the present invention contains other coloring agent, the content of the other coloring agent is preferably 10 to 70% by mass with respect to the total solid content of the coloring composition. The upper limit is more preferably 60% by mass or less, and still more preferably 50% by mass or less. The lower limit is more preferably 20% by mass or more, and further preferably 25% by mass or more.
Moreover, the coloring composition of this invention can also be set as the aspect which does not contain other coloring agents substantially. Note that “substantially free of other colorants” means, for example, preferably 0.1% by mass or less with respect to the total amount of the colorants (total mass of the dye multimer of the present invention and other colorants). 0.05 mass% or less is more preferable, and it is still more preferable not to contain other colorants.

<< Resin >>
The colored composition of the present invention preferably contains a resin. The resin is blended, for example, for the purpose of dispersing a pigment or the like 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 an example, and the resin can be used for purposes other than such use.

In the colorable composition of the present invention, the resin content is preferably 10 to 80% by mass with respect to the total solid content of the colorable composition. The lower limit is preferably 15% by mass or more, and more preferably 20% by mass or more. The upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less.

<<< Dispersant >>>
It is preferable that the coloring composition of this invention contains a dispersing agent as resin. The dispersant preferably includes at least an acidic dispersant, and more preferably only an acidic dispersant. When the dispersant includes at least an acidic dispersant, the dispersibility of the pigment is improved and luminance unevenness is less likely to occur. Furthermore, since excellent developability can be obtained, pattern formation can be suitably performed by photolithography. In addition, it is preferable that content of an acidic dispersing agent is 99 mass% or more in the total mass of a dispersing agent, for example that a dispersing agent is only an acidic dispersing agent, and shall be 99.9 mass% or more. You can also.

Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups occupies 70 mol% or more when the total amount of acid groups and basic groups is 100 mol%. A resin consisting only of groups is more preferred. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group.
The basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups accounts for 50 mol% or more when the total amount of acid groups and basic groups is 100 mol%. The basic group possessed by the basic dispersant is preferably an amine.
The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and still more preferably 60 to 105 mgKOH / g.

Examples of the dispersant include a polymer dispersant [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 copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine and the like.

Polymer dispersants can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures. The polymer dispersant acts to adsorb on the surface of the pigment and prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.

As the resin (dispersing agent), a graft copolymer containing a repeating unit represented by any of the following formulas (1) to (4) can also be used.

In formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH, and X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represents a hydrogen atom or a monovalent organic group, Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represents a monovalent organic group, R ³ represents an alkylene group, R ⁴ represents a hydrogen atom or a monovalent organic group, and n, m, p, and q each independently represents 1 to Represents an integer of 500, j and k each independently represent an integer of 2 to 8, and in formula (3), when p is 2 to 500, a plurality of R ³ may be the same or different from each other. may, in the formula (4), when q is 2 ~ 500, X ⁵ and R ⁴ existing in plural numbers may be different, even the same as each other

W ¹ , W ² , W ³ , and W ⁴ are preferably oxygen atoms. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably each independently a hydrogen atom or a methyl group, A methyl group is particularly preferred. Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly limited in structure. The structure of the monovalent organic group represented by Z ¹ , Z ² , Z ³ , and Z ⁴ is not particularly limited. Specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, Examples thereof include an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. Among these, as the organic group represented by Z ¹ , Z ² , Z ³ , and Z ⁴ , those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms. Of these, a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable. The alkyl group contained in the alkoxy group may be linear, branched or cyclic.

In the formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500. In the formulas (1) and (2), j and k each independently represent an integer of 2 to 8. J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoints of dispersion stability and developability.

In the formula (3), R ³ represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ³ may be the same or different.

In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited in terms of structure. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms is preferable, and 1 to 20 carbon atoms is preferable. Are more preferable, and linear alkyl groups having 1 to 6 carbon atoms are particularly preferable. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

Regarding the graft copolymer, the description of paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the above contents are incorporated in this specification. Specific examples of the graft copolymer include resins described in paragraph numbers 0072 to 0094 of JP2012-255128A, the contents of which are incorporated herein.

Also, as the resin (dispersant), an oligoimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain can be used. The oligoimine-based dispersant has a repeating unit having a partial structure X having a functional group of pKa14 or less and a side chain containing a side chain Y having 40 to 10,000 atoms, and has a main chain and a side chain. A resin having at least one basic nitrogen atom is preferred. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.

Regarding the oligoimine-based dispersant, the description in paragraphs 0102 to 0174 of JP 2012-255128 A can be referred to, and the above contents are incorporated in this specification. As specific examples of the oligoimine dispersant, for example, resins described in paragraph numbers 0168 to 0174 of JP 2012-255128 A can be used.

The dispersant is also available as a commercial product. Specific examples thereof include “DA-7301” manufactured by Enomoto Kasei Co., Ltd., “Disperbyk-101 (polyamidoamine phosphate)” manufactured by BYK Chemie, 107 (carboxylic acid). Ester), 110 (copolymer containing an acid group), 111 (phosphate dispersing agent), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), BYK -P104, P105 (high molecular weight unsaturated polycarboxylic acid) "," EFKA 4047, 4050-4165 (polyurethane type), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (manufactured by EFKA) Polyester amide), 5765 (high molecular weight polycarboxylate), 6220 Fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”,“ Ajispur PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fine Techno Co., Ltd.,“ Floren TG-710 (urethane oligomer), Polyflow No. manufactured by Kyoeisha Chemical Co., Ltd. .50E, No. 300 (acrylic copolymer), “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA- 703-50, DA-705, DA-725 ”,“ Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate), homogenol, manufactured by Kao Corporation L-18 (polymeric polycarboxylic acid), Emulgen 9 0, 930, 935, 985 (polyoxyethylene nonylphenyl ether), acetamine 86 (stearylamine acetate), “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester) manufactured by Nippon Lubrizol Co., Ltd. Amine), 3000, 12000, 17000, 20000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene) manufactured by Nikko Chemicals Sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), “Hinoact T-8000E” manufactured by Kawaken Fine Chemical Co., Ltd., “organosiloxane polymer K” manufactured by Shin-Etsu Chemical Co., Ltd. “P341”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450” manufactured by Morishita Sangyo Co., Ltd., “Disperse Aid 6, manufactured by San Nopco Co., Ltd. Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 and other polymer dispersants, ADEKA Co., Ltd. “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Kasei Co., Ltd., and the like. Also, Acrybase FFS-6752, Acrybase FFS-187, Acrycure RD-F8, and Cyclomer P can be used.
The resin described as the dispersant can be used for purposes other than the dispersant. For example, it can be used as a binder.

<<< 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 formation 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.

The alkali-soluble resin is preferably a polymer having a carboxyl group in the side chain, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified malein. Examples include acid copolymers, alkali-soluble phenol resins such as novolac 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, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene Macromonomer, polymethylmethacrylate macromonomer, and the like. As other monomers, N-substituted maleimide monomers described in JP-A-10-300922 can be used. Examples thereof include N-phenylmaleimide and N-cyclohexylmaleimide. 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.

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, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 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 A macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used. Further, as a commercially available product, for example, FF-426 (manufactured by Fujikura Kasei Co., Ltd.) can be used.

Further, as the alkali-soluble resin, 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 having a polymerizable group in the side chain is useful. Examples of the alkali-soluble resin having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co., Ltd.), Biscote R-264, KS resist 106 (any) Also manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (both manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel UCB Corporation), Acryl RD-F8 (Japan) Catalyst).

The alkali-soluble resin is a compound represented by the following general formula (ED1) and / or a compound represented by the general formula (1) of JP 2010-168539 A (hereinafter, these compounds are referred to as “ether dimers”). It is also preferable to include a polymer obtained by polymerizing a monomer component including

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

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 alkali-soluble resin may contain a repeating 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.

Specific examples of the alkali-soluble resin include the following resins. In the following formulae, Me is a methyl group.

For the alkali-soluble resin, description in 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, Incorporated herein. Further, the copolymer (B) described in paragraph Nos. 0029 to 0063 of JP 2012-32767 A and the alkali-soluble resin used in Examples, paragraphs 0088 to 0098 of JP 2012-208474 A The binder resin described in the description and the binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of JP2012-137531A and the binder resin used in the examples, JP2013-024934A Binder resin described in paragraph Nos. 0132 to 0143 of the gazette and the binder resin used in the examples, paragraph numbers 0092 to 0098 of the gazette of JP2011-242752 and the binder resin used in the examples, and JP2012 No. -032770, paragraph number 003 It is also possible to use 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 still more preferably 120 mgKOH / g or less.

The content of the alkali-soluble resin is preferably 0.1 to 20% by mass with respect to the total solid content of the coloring composition. The lower limit is preferably 1% by mass or more, and more preferably 2% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. The colored 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.

<< Solvent >>
The coloring composition of the present invention preferably contains a solvent. The solvent is preferably an organic solvent. The solvent is not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied.

Examples of organic solvents include the following. Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyloxyalkyl acetate (Eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-alkyloxypropionate Esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid) Til, ethyl 3-ethoxypropionate, etc.), alkyl esters of 2-alkyloxypropionic acid (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc.) Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and Ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, Methyl acetoacetate Ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as 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 monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as methyl ethyl ketone, Preferred examples of rhohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and aromatic hydrocarbons include toluene and xylene.

Organic solvents may be used alone or in combination of two or more. When two or more organic solvents are used in combination, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid It is a mixed solution composed of two or more selected from methyl, 2-heptanone, cyclohexanone, ethyl 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 solvent is preferably such that the total solid content of the colored composition is 5 to 80% by mass. The lower limit is preferably 10% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less.

<< 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. For example, a compound having a group having an ethylenically unsaturated bond, a cyclic ether (epoxy, oxetane) group, a methylol group and the like can be mentioned. 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 polymerizable compound, and more preferably a radical polymerizable compound.

The content of the curable compound is preferably 0.1 to 50% by mass with respect to the total solid content of the coloring 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 45% by mass or less, and still more preferably 40% 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.

(Polymerizable compound)
In the present invention, the polymerizable compound may be in a 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. When the polymerizable compound is a radical photopolymerizable compound, a monomer is preferable.
The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is preferably 2000 or less, and more preferably 1500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more.
The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound. Specific examples of these compounds include those described in paragraph Nos. 0095 to 0108 in JP-A-2009-288705, paragraph 0227 in JP-A-2013-29760, and paragraph numbers 0254 to 0257 in JP-A-2008-292970. Compounds can be taken into account, 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 (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, manufactured as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues (for example, SR454 commercially available from Sartomer, Inc. SR499) is preferred Yes. These oligomer types can also be used. KAYARAD RP-1040 and DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) can also be used. Also, the following compounds can be used.

The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Examples of commercially available products include M-305, M-510, and M-520 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.
Examples of the polymerizable compound having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.

As the polymerizable compound, a polymerizable compound having an alkyleneoxy group can also be used. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and 3 to 4 having 4 to 20 ethyleneoxy groups. A hexafunctional (meth) acrylate compound is more preferable.

Specific examples of the polymerizable compound having an alkyleneoxy group include the following compounds.

Examples of commercially available polymerizable compounds having an alkyleneoxy group include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy groups manufactured by Sartomer, and six pentyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy groups.

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. Is also preferable.
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 Chemical Co., Ltd.) and the like.

When a polymerizable compound is used as the curable compound, the content of the polymerizable compound is preferably 0.1 to 50% by mass with respect to the total solid content of the 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 45% by mass or less, and still more preferably 40% 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.
The content of the polymerizable compound is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, based on the total mass of the curable compound.

(Compound having an epoxy group)
In the present invention, a compound having an epoxy group can also be used as the curable compound. As the compound having an epoxy group, a compound having two or more epoxy groups in one molecule is preferable. It is preferable to have 2 to 100 epoxy groups in one molecule. For example, the upper limit may be 10 or less, and may be 5 or less.

In the present invention, the compound having an epoxy group preferably has a structure having an aromatic ring and / or an aliphatic ring, and more preferably has a structure having an aliphatic ring. The epoxy group is preferably bonded to the aromatic ring and / or the aliphatic ring via a single bond or a linking group. Examples of the linking group include an alkylene group, an arylene group, —O—, —NR ′ — (R ′ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. And a group containing at least one selected from —SO ₂ —, —CO—, —O—, and —S—.
In the case of a compound having an aliphatic ring, the epoxy group is preferably a compound formed by directly bonding (single bond) to the aliphatic ring. In the case of a compound having an aromatic ring, the epoxy group is preferably a compound formed by bonding to an aromatic ring via a linking group. The linking group is preferably an alkylene group or a group comprising a combination of an alkylene group and —O—.
Moreover, the compound which has an epoxy group can also use the compound which has a structure which two or more aromatic rings connected with the hydrocarbon group. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms. It is preferable that the epoxy group is connected via the connecting group.

The compound having an epoxy group preferably has an epoxy equivalent (= molecular weight of the compound having an epoxy group / number of epoxy groups) of 500 g / eq or less, more preferably 100 to 400 g / eq, more preferably 100 to 300 g. More preferably, it is / eq.

The compound having an epoxy group may be a low molecular weight compound (for example, a molecular weight of less than 2000, or even a molecular weight of less than 1000), or a macromolecule (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more). The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1500 or less.

Compounds having an epoxy group are described in paragraph numbers 0034 to 0036 of JP2013-011869A, paragraph numbers 0147 to 0156 of JP2014043556A, and paragraphs 0085 to 0092 of JP2014089408A. The prepared compounds can also be used. These contents are incorporated herein. As commercial products, for example, as bisphenol A type epoxy resin, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050 , EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc., and bisphenol F-type epoxy resins include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, Mitsubishi Chemical Corporation), EPICLON830, EPICLON835. (Above, DIC Corporation), LCE-21, RE-602S (above, Nippon Kayaku Co., Ltd.), etc. Yes, as phenol novolac type epoxy resin, jER152, jER154, jER157S70, jER157S65 (Mitsubishi Chemical Co., Ltd.), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC Corporation) Cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (or more DIC Co., Ltd.), EOCN-1020 (Nippon Kayaku Co., Ltd.), etc., and aliphatic epoxy resins are ADEKA RESIN EP-4080S, EP-4085. EP-4088S (above, manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEEAD PB 3600, PB 4700 (above, Daicel Corporation), Denacol EX-212L EX-214L, EX-216L, EX-321L, EX-850L (manufactured by Nagase ChemteX Corporation) and the like. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), jER1031S (manufactured by Mitsubishi Chemical Corporation), and the like.

When a compound having an epoxy group is used as the curable compound, the content of the compound having an epoxy group 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. The compound which has an epoxy group may be single 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount becomes the said range.
The content of the compound having an epoxy group is preferably 1 to 80% by mass and more preferably 1 to 50% by mass with respect to the total mass of the curable compound.
When the polymerizable compound and the compound having an epoxy group are used in combination, the mass ratio of the polymerizable compound and the compound having an epoxy group is such that the polymerizable compound: the compound having an epoxy group = 100: 1 to 100: 400. Is preferable, and 100: 1 to 100: 100 is more preferable.

<< Curing accelerator >>
In the colored composition of the present invention, a curing accelerator may be added for the purpose of promoting the reaction of the polymerizable compound or lowering the curing temperature. Examples of the curing accelerator include polyfunctional thiol compounds having two or more mercapto groups in the molecule. The polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like. 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 thiol compounds can be used alone or in combination.

Curing accelerators include methylol compounds (for example, compounds exemplified as a crosslinking agent in paragraph 0246 of JP-A-2015-34963), amines, phosphonium salts, amidine salts, amide compounds (above, for example, special No. 2013-41165, curing agent described in paragraph 0186), base generator (for example, ionic compound described in JP-A-2014-55114), cyanate compound (for example, JP-A-2012-150180) A compound described in paragraph 0071), an alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in JP2011-255304A), an onium salt compound (for example, paragraph 0216 in JP2015-34963A). Compounds exemplified as acid generators, JP2009 Compounds described in JP-180949) can also be used.

When the colored composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9% by mass, and preferably 0.8 to 6% based on the total solid content of the colored composition. More preferably, 4% by mass.

<< photopolymerization initiator >>
The colored composition of the present invention preferably further contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to light in the ultraviolet region to the visible 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 molecular 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 commercially available trihalomethyltriazine photopolymerization initiators include TAZ-107 (manufactured by Midori Chemical Co., Ltd.).

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, triarylimidazole compounds, benzimidazoles Compound selected from the group consisting of compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3-aryl substituted coumarin compounds Is preferred. Examples of the triarylimidazole compound, benzimidazole compound, and benzophenone compound include the following compounds.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators 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-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 whose absorption wavelength is matched with a long wave light source of 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.

In particular, when the colored composition of the present invention is used for the production of a color filter of 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, a stepper exposure machine 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.

More preferable examples of the photopolymerization initiator include oxime compounds. As specific examples of the oxime initiator, 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 can be used.

Examples of oxime compounds such as oxime derivatives that are suitably used as the photopolymerization initiator in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyimibutane. -2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluene) Sulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

Examples of oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995), pp. 156-162. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A Nos. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. Also, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Arcles 30 (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 an oxime is linked to the N-position of the carbazole ring, and those described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety Compounds, compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the dye site, ketoxime compounds described in International Publication No. WO2009 / 131189, and triazine skeleton and oxime skeleton are the same A compound described in US Pat. No. 7,556,910 contained in the 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-line light source, and the like may be used. . Preferably, for example, paragraphs 0274 to 0275 of JP 2013-29760 A can be referred to, the contents of which are incorporated herein. 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 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 fluorene ring can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A No. 2014-137466. This content is incorporated herein.

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, an oxime compound having a nitro group can be used as a photopolymerization initiator. Specific examples of oxime compounds having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, ADEKA Acruz NCI-831 (made by ADEKA) is mentioned.

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

The oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably a compound having an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably a compound having high absorbance at 365 nm and 405 nm.

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200,000 from the viewpoint of sensitivity. 000 is particularly preferred. For the measurement of the molar extinction coefficient of the compound, a known method can be used. Specifically, for example, an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) is used and an ethyl acetate solvent is used. It is preferable to measure at a concentration of 0.01 g / L.
You may use a photoinitiator in combination of 2 or more type as needed.

When the colored composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5%, based on the total solid content of the colored composition. -30% by mass, more preferably 1-20% by mass. 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.

<< Pigment derivative >>
The coloring composition of the present invention can contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group, or a phthalimidomethyl 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 quaternary ammonium base 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. As specific examples of the pigment derivative, the description in paragraphs 0162 to 0183 of JP2011-252065 A can be referred to, the contents of which are incorporated herein.

The content of the pigment derivative in the colored composition of the present invention is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, based on the total mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.

<< Surfactant >>
The colored composition of the present invention may contain various surfactants 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.

By including a fluorosurfactant in the colored composition of the present invention, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid-saving properties are further improved. can do. That is, when a film is formed using a coating liquid to which a coloring composition containing a fluorosurfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is reduced. Is improved, and the coating property to the coated surface is improved. For this reason, 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 the composition.

Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC -101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, K393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (above, the product made by OMNOVA) etc. are mentioned. As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of JP-A No. 2015-117327 can also be used. A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meta). ) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
As the fluorosurfactant, a fluoropolymer having an ethylenically unsaturated group in the side chain can also be used. 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 nonionic surfactants 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, Rusperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), etc. Also, NCW-101, NCW-1001, NCW-1002, manufactured by Wako Pure Chemical Industries, Ltd., Pionein D-6112- manufactured by Takemoto Yushi Co., Ltd. W, D-6315, etc. can also 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 the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Kasei Co., Ltd.), and the like.

Examples of silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.

Only one type of surfactant may be used, or two or more types may be combined.
The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the coloring composition.

<< Silane coupling agent >>
The coloring composition of the present invention can contain a silane coupling agent. As the silane coupling agent, silane compounds having at least two types of functional groups having different reactivity in one molecule are also preferable, and those having an amino group and an alkoxy group as functional groups are particularly preferable. Examples of such silane coupling agents include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ- Aminopropyl-trimethoxysilane (trade name KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (trade name KBE-602, manufactured by Shin-Etsu Chemical Co., Ltd.), γ -Aminopropyl-trimethoxysilane (trade name KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-triethoxysilane (trade name: KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxy Silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-503) and the like. For details of the silane coupling agent, the description of paragraph numbers 0155 to 0158 in JP2013-254047A can be referred to, the contents of which are incorporated herein.

When the coloring composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 0.001 to 20% by mass with respect to the total solid content of the coloring composition, 0.01 to 10% by mass is more preferable, and 0.1% by mass to 5% by mass is particularly preferable. The coloring composition of the present invention may contain only one type of silane coupling agent, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Polymerization inhibitor >>
The coloring composition of the present invention preferably contains a polymerization inhibitor. 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-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, primary cerium salt, etc.) and the like.
When the colored 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 total solid content of the colored 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.

<< 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. As the antioxidant, for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph No. 2011-90147 paragraph), a thioether compound, or the like can be used. Examples of commercially available products include ADEKA Corporation's ADK STAB series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO- 330). Two or more antioxidants may be mixed and used. 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 can be prepared by mixing the aforementioned components. There are no particular restrictions on the order of injection 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 is suitably used as two or more solutions or dispersions at the time of use (at the time of application). ) May be prepared by mixing them.

In preparation of the coloring composition, it is preferable to filter 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) And a filter using a material such as polyolefin resin). 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 within this range, it becomes possible to reliably remove fine foreign matters that hinder the preparation of a uniform composition and the formation of a smooth film in the subsequent steps. 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, selected from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nihon Microlith Co., Ltd.) can do.
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.

<Dye multimer>
Next, the dye multimer of the present invention will be described.
The dye multimer of the present invention is a dye multimer having a dye structure represented by the above formula (I-1) or formula (I-2). The details of the formula (I-1) and the formula (I-2) are the same as those described in the above-described coloring composition.

The curable group value of the dye multimer is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, and still more preferably 0.3 mmol / g or more. When the curable group value is 0.4 mmol / g or more, a cured film excellent in light resistance and solvent resistance is easily obtained. Further, the color loss of the film due to the developer or the stripping solution can be more effectively suppressed. The upper limit of the curable group value is not particularly limited, but for example, 2.0 mmol / g is preferable, and 1.5 mmol / g is more preferable. The curable group value can be calculated by dividing the number of curable groups introduced into the dye multimer by the molecular weight of the dye multimer. It can also be actually measured by analysis means such as ¹ H-NMR (nuclear magnetic resonance).

The dye multimer of the present invention can be used for applications such as color filters, inks (for inkjet, printing, etc.), paints, light-shielding films.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention is formed using the above-described colored composition of the present invention. The color filter of the present invention can be used for solid-state imaging devices such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor), image display devices, and the like.

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.

<Pattern formation method>
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, and a pattern is formed on the colored composition layer by a photolithography method or a dry etching method. And a step of performing.

Pattern formation by the photolithography method includes a step of forming a colored composition layer on a support using a colored composition, a step of exposing the colored composition layer in a pattern, and developing and removing an unexposed portion. Forming the step. If necessary, a step of baking the colored composition layer (pre-bake step) and a step of baking the developed pattern (post-bake step) may be provided.
In addition, pattern formation by the dry etching method includes forming a colored composition layer on a support using a colored composition and curing to form a cured product layer, and forming a photoresist layer on the cured product layer. It is preferable to include a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of forming a pattern by dry etching the cured product layer using the resist pattern as an etching mask. Hereinafter, each step will be described.

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

As the support, for example, a solid-state image sensor substrate in which a solid-state image sensor (light receiving element) such as a CCD or CMOS is provided on a substrate (for example, a silicon substrate) can be used.
The pattern in the present invention may be formed on the solid-state image sensor formation surface side (front surface) of the solid-state image sensor substrate, or may be formed on the solid-state image sensor non-formation surface side (back surface).
If necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.

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

The colored composition layer formed on the support may be dried (prebaked). When a pattern is formed by a low temperature process, pre-baking may not be performed.
When performing prebaking, the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower. For example, the lower limit may be 50 ° C. or higher, and may be 80 ° C. or higher. By performing the pre-baking temperature at 150 ° C. or lower, for example, when the photoelectric conversion film of the image sensor is made of an organic material, these characteristics can be more effectively maintained.
The prebake time is preferably 10 seconds to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Drying can be performed with a hot plate, oven, or the like.

(When forming a pattern by photolithography)
<< Exposure process >>
Next, the colored composition layer is exposed in a pattern (exposure process). For example, pattern exposure can be performed by exposing the coloring composition layer through 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.
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 (for example, 22% by volume, 30% by volume, 50% by volume) with an oxygen concentration exceeding 21% 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 (for example, 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 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. By setting the film thickness to 2.0 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 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. Moreover, in order to improve residue removability, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

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 dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene. As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water is preferably used. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass.
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 silicate, sodium metasilicate and the like are preferable.
Further, a surfactant may be used for the developer. Examples of the surfactant include the surfactant described in the above-described curable composition, and a nonionic surfactant is preferable.
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.

After the development, after drying, a heat treatment (post-bake) can be performed. Post-baking is a heat treatment after development for complete film curing. In the case of performing post-baking, the post-baking temperature is preferably 100 to 240 ° C., for example. From the viewpoint of film curing, 200 to 230 ° C. is more preferable. In addition, when an organic electroluminescence (organic EL) element is used as the light source, or when the photoelectric conversion film of the image sensor is made of an organic material, the post-bake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower. Preferably, 100 ° C. or lower is more preferable, and 90 ° C. or lower is particularly preferable. The lower limit can be, for example, 50 ° C. or higher.
Post-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, etc., so that the film after development is in the above-mentioned condition. . Further, when a pattern is formed by a low temperature process, post baking is not necessary.

(When pattern is formed by dry etching method)
In the pattern formation by the dry etching method, the colored composition layer formed on the support is cured to form a cured product layer, and then a patterned photoresist layer is formed on the obtained cured product layer. Etching with an etching gas using the photoresist layer as a mask can be used.
Specifically, it is preferable to form a photoresist layer by applying a positive or negative radiation sensitive composition on the cured product layer and drying it. In the formation of the photoresist layer, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming a photoresist, a mode in which heat treatment after exposure and heat treatment after development (post-bake treatment) are desirable.

As the photoresist layer, for example, a positive radiation sensitive composition sensitive to radiation such as ultraviolet rays (g-rays, h-rays, i-rays), excimer lasers, deep ultraviolet rays, electron beams, ion beams and X-rays. Is preferably used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable. Specifically, as the positive radiation sensitive composition, a composition containing a quinonediazide compound and an alkali-soluble resin is preferable. A positive radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin indicates that a quinonediazide group is decomposed by irradiation with light having a wavelength of 500 nm or less to produce a carboxyl group, resulting in alkali-solubility from an alkali-insoluble state. It is what you use. Since this positive photoresist has remarkably excellent resolving power, it is used for manufacturing integrated circuits such as IC (integrated circuit) and LSI (Large Scale Integration). Examples of the quinonediazide compound include a naphthoquinonediazide compound. As a commercial item, "FHi622BC" (made by FUJIFILM Electronics Materials) etc. are mentioned, for example.

The thickness of the photoresist layer is preferably from 0.1 to 3 μm, more preferably from 0.2 to 2.5 μm, still more preferably from 0.3 to 2 μm. In addition, the application method of a positive type radiation sensitive composition can be suitably performed using the application | coating method of the coloring composition mentioned above.

Next, the photoresist layer is exposed and developed to form a resist pattern (patterned photoresist layer) provided with resist through-hole groups. The formation of the resist pattern is not particularly limited, and can be performed by appropriately optimizing a conventionally known photolithography technique. By providing a resist through hole group in the photoresist layer by exposure and development, a resist pattern as an etching mask used in the next etching is provided on the cured product layer.

The exposure of the photoresist layer is performed by exposing the positive-type or negative-type radiation-sensitive composition with g-line, h-line, i-line, etc., preferably i-line, through a predetermined mask pattern. Can do. After the exposure, the photoresist is removed in accordance with a region where a colored pattern is to be formed by developing with a developer.

Any developer can be used as long as it does not affect the cured product layer and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist. For example, a combination of various solvents or an alkaline aqueous solution can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable. Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene. When an alkaline aqueous solution is used, a washing treatment with water is generally performed after development.

Next, using the resist pattern as an etching mask, patterning is performed by dry etching so that a through hole group is formed in the cured product layer.

The dry etching is preferably performed by the following method from the viewpoint of forming the pattern cross section closer to a rectangle and reducing damage to the support.
Using a mixed gas of fluorine-based gas and oxygen gas (O ₂ ), the first stage etching is performed up to a region (depth) where the support is not exposed, and after this first stage etching, nitrogen gas ( N ₂ ) and oxygen gas (O ₂ ), and a second stage etching is preferably performed to the vicinity of the region (depth) where the support is exposed, and over-etching is performed after the support is exposed. Is preferred. Hereinafter, a specific method of dry etching and the first stage etching, second stage etching, and over-etching will be described.

Dry etching is performed by obtaining etching conditions in advance by the following method.
(1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated respectively.
(2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated.
(3) The first-stage etching is performed according to the etching time calculated in (2) above.
(4) The second-stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time.
(5) The overetching time is calculated with respect to the total time of (3) and (4) described above, and overetching is performed.

The mixed gas used in the first-stage etching process preferably contains a fluorine-based gas and an oxygen gas (O ₂ ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape. Further, in the first stage etching process, damage to the support can be avoided by etching to a region where the support is not exposed. Further, in the second stage etching process and the over etching process, after the etching is performed up to the region where the support is not exposed by the mixed gas of fluorine-based gas and oxygen gas in the first stage etching process, damage to the support is avoided. From the viewpoint, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.

It is important to determine the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process so as not to impair the rectangularity due to the etching process in the first stage etching process. It is. The latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching process and the etching amount in the second-stage etching process) is preferably in the range of more than 0% and 50% or less, 10 to 20% is more preferable. The etching amount is an amount calculated from the difference between the remaining film thickness to be etched and the film thickness before etching.

Further, the etching preferably includes an over-etching process. The overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first. The over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and preferably 5 to 25% from the viewpoint of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.

Next, the resist pattern (that is, the etching mask) remaining after the etching is removed. The removal of the resist pattern preferably includes a step of applying a stripping solution or a solvent on the resist pattern so that the resist pattern can be removed, and a step of removing the resist pattern using cleaning water.

Examples of the step of applying a stripping solution or solvent on the resist pattern so that the resist pattern can be removed include, for example, a step of applying a stripping solution or solvent on at least the resist pattern and stagnating for a predetermined time to perform paddle development Can be mentioned. Although there is no restriction | limiting in particular as time to make stripping solution or a solvent stagnant, It is preferable that it is several dozen seconds to several minutes.

Further, examples of the step of removing the resist pattern using the cleaning water include a step of removing the resist pattern by spraying the cleaning water onto the resist pattern from a spray type or shower type spray nozzle. As the washing water, pure water can be preferably used. Further, examples of the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support. When the spray nozzle is movable, the resist pattern is more effectively removed by moving the support pattern from the center of the support to the end of the support more than twice during the process of removing the resist pattern and spraying the cleaning water. be able to.

The stripping solution generally contains an organic solvent, but may further contain an inorganic solvent. Examples of organic solvents include 1) hydrocarbon compounds, 2) halogenated hydrocarbon compounds, 3) alcohol compounds, 4) ether or acetal compounds, 5) ketones or aldehyde compounds, and 6) ester compounds. 7) polyhydric alcohol compounds, 8) carboxylic acids or acid anhydride compounds thereof, 9) phenol compounds, 10) nitrogen compounds, 11) sulfur compounds, and 12) fluorine compounds. The stripping solution preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specific examples include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, and triethanolamine. Preferred are monoethanolamine, diethanolamine and triethanolamine, and more preferred is monoethanolamine (H ₂ NCH ₂ CH ₂ OH). Examples of cyclic nitrogen-containing compounds include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, α-picoline, β-picoline, γ-picoline, 2- Preferred examples include pipecoline, 3-pipecoline, 4-pipecoline, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-lutidine, and 2,6-lutidine. Are N-methyl-2-pyrrolidone and N-ethylmorpholine, more preferably N-methyl-2-pyrrolidone (NMP).

The stripping solution preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound. Among these, as the acyclic nitrogen-containing compound, at least one selected from monoethanolamine, diethanolamine, and triethanolamine, and cyclic The nitrogen-containing compound preferably includes at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferably includes monoethanolamine and N-methyl-2-pyrrolidone.

When removing with a stripping solution, it is sufficient that the resist pattern formed on the pattern has been removed, and even if deposits that are etching products adhere to the side walls of the pattern, the deposits are completely removed. It does not have to be. A deposit means an etching product deposited and deposited on the side wall of a cured product layer.

As the stripping solution, the content of the non-cyclic nitrogen-containing compound is 9 parts by weight or more and 11 parts by weight or less with respect to 100 parts by weight of the stripping solution, and the content of the cyclic nitrogen-containing compound is 100 parts by weight of the stripping solution. On the other hand, what is 65 to 70 mass parts is desirable. Further, the stripping solution is preferably obtained by diluting a mixture of an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound with pure water.

<Solid-state imaging device>
The solid-state imaging device of the present invention has the color filter of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter in the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. .

A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on a support, and the photodiode and the transfer electrode are provided on the support. A light-shielding film made of tungsten or the like having an opening only in the light-receiving portion of the photodiode, and a device protection 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 portion. This is a configuration having the color filter of the present invention on the device protective film.
Further, a configuration having a light condensing means (for example, a microlens, etc., the same applies hereinafter) on the device protective film and under the color filter (on the side close to the support), or a structure having the light condensing means on the color filter Etc.

<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. The image display device provided with the color filter of the present invention can display a high-quality image having a good display color and excellent display characteristics. For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 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.)”. Furthermore, the present invention provides 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), and a STN (Super-Twist Nematic). ), TN (Twisted Nematic), VA (Vertical Alignment), OCS (On-chip spacer), FFS (Fringe field switching), and R-OCB (Reflexive Compensated). The color filter of the present invention can also be used for a COA (Color-filter On Array) system. These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market-(Toray Research Center Research Division, issued in 2001)".

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 compensation 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 backlights, SID meeting Digest 1380 (2005) (A. Konno et al.), Monthly Display December 2005, 18-24 pages (Yasuhiro Shima), 25-30 pages (Takaaki Yagi), etc. Are listed.

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. In the following structural formulas, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ts represents a tosyl group.

<Measurement of weight average molecular weight>
The weight average molecular weight was measured in terms of polystyrene by gel permeation chromatography (GPC) measurement.
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

<Synthesis example>
(Synthesis Example 1) Synthesis of Dye Monomer (X-1)

28.8 g of compound a was added to 200 mL of dehydrated tetrahydrofuran and cooled to −50 ° C. Next, 128 mL of 1.6 mol / L n-butyllithium (hexane solution) was added dropwise, and the temperature was raised to −5 to 0 ° C. Next, 45.4 g of ethyl iodide was slowly added and the temperature was raised to 30 ° C. Next, 100 mL of water was added and liquid-separated with 200 mL of ethyl acetate. The oil layer was washed twice with 100 mL of water, and the oil layer was concentrated to obtain 33.2 g of intermediate b. Next, 30.0 g of intermediate b, 16.0 g of p-chloromethylstyrene, 1.0 g of magnesium oxide, 80 mL of tetrahydrofuran, and 20 mL of ion-exchanged water were mixed and heated at 100 ° C. for 2 hours. After allowing to cool to room temperature, 31.1 g of sodium N, N bis (trifluoromethanesulfonyl) imide was added and stirred for 1 hour. 100 mL of ethyl acetate and 100 mL of 1 mol / L hydrochloric acid were added for liquid separation, and the oil layer was washed with 100 mL of water. The oil layer was concentrated and purified by column chromatography using silica gel to obtain 22.5 g of a dye monomer (X-1).

(Synthesis Example 2) Synthesis of Dye Monomer (X-2)

Intermediate d was obtained in the same manner as in Synthesis Example 1 except that p-chloromethylstyrene was changed to ethyl iodide.
Intermediate c was synthesized in the same manner as in the method described in paragraph 0372 of JP-A-2015-30742. 11.2 g of intermediate c and 10.0 g of intermediate d were stirred in 200 mL of methylene chloride at room temperature for 2 hours. Next, 100 mL of water was added for liquid separation. The oil layer was concentrated and purified by column chromatography using silica gel to obtain 15.5 g of a dye monomer (X-2).

Synthesis Example 3 Synthesis of Dye Monomer (X-3)

28.8 g of compound a was added to 200 mL of dehydrated tetrahydrofuran and cooled to −50 ° C. Next, 128 mL of 1.6 mol / L n-butyllithium (hexane solution) was added dropwise, and the temperature was raised to −5 to 0 ° C. Next, 70.0 g of compound e was slowly added and the temperature was raised to 30 ° C. Next, 100 mL of water was added and liquid-separated with 200 mL of ethyl acetate. The oil layer was washed twice with 100 mL of water, and the oil layer was concentrated to obtain 54,1 g of compound f. Next, 50.0 g of compound f, 30.0 g of dimethyl sulfate, and 1.0 g of magnesium oxide were heated at 80 ° C. for 2 hours in 80 mL of tetrahydrofuran and 20 mL of ion exchange water. After allowing to cool to room temperature, 31.1 g of sodium N, N bis (trifluoromethanesulfonyl) imide was added and stirred for 1 hour. After 100 mL of ethyl acetate and 100 mL of 1 mol / L hydrochloric acid were added for liquid separation, the oil layer was washed with 100 mL of water. The oil layer was concentrated and purified by column chromatography using silica gel to obtain 15.4 g of a dye monomer (X-3).

Synthesis Example 4 Synthesis of Dye Monomer (X-4)

30.4 g of Compound g was added to 200 mL of dehydrated tetrahydrofuran and cooled to −50 ° C. Next, 128 mL of 1.6 mol / L n-butyllithium (hexane solution) was added dropwise, and the temperature was raised to −5 to 0 ° C. Next, 22.7 g of ethyl iodide was slowly added and the temperature was raised to 30 ° C. Next, 100 mL of water was added and liquid-separated with 200 mL of ethyl acetate. The oil layer was washed twice with 100 mL of water, and the oil layer was concentrated to obtain 31.9 g of intermediate h. Next, 30.0 g of the intermediate h, 16.0 g of p-chloromethylstyrene, 1.0 g of magnesium oxide, 80 mL of tetrahydrofuran, and 20 mL of ion-exchanged water were mixed and heated at 100 ° C. for 2 hours. After allowing to cool to room temperature, 31.1 g of sodium N, N bis (trifluoromethanesulfonyl) imide was added and stirred for 1 hour. After 100 mL of ethyl acetate and 100 mL of 1 mol / L hydrochloric acid were added for liquid separation, the oil layer was washed with 100 mL of water. The oil layer was concentrated and purified by column chromatography using silica gel to obtain 16.2 g of a dye monomer (X-4).

(Synthesis Example 5) Synthesis of Dye Monomer (X-5)

26.8 g of compound i, 30.0 g of compound 1), 1.0 g of magnesium oxide, 80 mL of tetrahydrofuran, and 20 mL of ion-exchanged water were mixed and heated at 100 ° C. for 2 hours. After allowing to cool to room temperature, 31.1 g of sodium N, N bis (trifluoromethanesulfonyl) imide was added and stirred for 1 hour. After 100 mL of ethyl acetate and 100 mL of 1 mol / L hydrochloric acid were added for liquid separation, the oil layer was washed with 100 mL of water. The oil layer was concentrated and purified by column chromatography using silica gel to obtain 19.7 g of a dye monomer (X-5).

(Synthesis Example 6) Synthesis of Dye Monomer (X-6)

The same operation as in Synthesis Example 2 was performed except that the intermediate d in Synthesis Example 2 was changed to Basic Yellow 1, and 14.9 g of a dye monomer (X-6) was obtained.

(Synthesis Example 7) Synthesis of dye monomer (X-7)

The same procedure was performed except that the compound 1) of Synthesis Example 5 was changed to 2-bromoethanol to obtain 12.1 g of a dye monomer (X-7).

Synthesis Example 8 Synthesis of dye multimer (S-1)

Dye monomer (X-1) (16.4 g), methacrylic acid (3.00 g), dodecyl mercaptan (0.51 g), propylene glycol 1-monomethyl ether 2-acetate (hereinafter also referred to as “PGMEA”) (46.6 g) was mixed and half was added to a three neck flask and heated to 80 ° C. under a nitrogen atmosphere. To the remaining liquid, 2,2′-azobis (isobutyric acid) dimethyl (trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.) (0.58 g) was added and dissolved, and dropped into a three-necked flask over 2 hours. did. After stirring for 3 hours, the temperature was raised to 90 ° C., and the mixture was heated and stirred for 2 hours. Next, glycidyl methacrylate (1.60 g) and tetrabutylammonium bromide (0.10 g) were added and heated at 90 ° C. for 10 hours. After cooling to room temperature, the solution was added dropwise to a mixed solvent of methanol / ion exchange water = 100 mL / 10 mL to reprecipitate. The obtained solid was dispersed in hexane / ethyl acetate = 90 mL / 10 mL and filtered. The obtained solid was blown and dried at 40 ° C. for 2 days to obtain 14.2 g of a dye multimer (S-1).

(Synthesis Example 9) Dye multimer (S-2)
A dye multimer (S-2) was synthesized in the same manner as in Synthesis Example 8 except that the dye monomer (X-1) was changed to the dye multimer (X-2).

Synthesis Example 10 Dye Multimer (S-3)
The dye multimer (S-3) was synthesized in the same manner as in Synthesis Example 8 except that the dye monomer (X-1) was changed to the dye multimer (X-4).

(Synthesis Example 11) Dye multimer (S-4)
A dye multimer (S-4) was synthesized in the same manner as in Synthesis Example 8 except that the dye monomer (X-1) was changed to the dye multimer (X-5).

(Synthesis Example 12) Dye multimer (S-5)
A dye multimer (S-5) was synthesized in the same manner as in Synthesis Example 8 except that the dye monomer (X-1) was changed to the dye multimer (X-6).

(Synthesis Example 13) Synthesis of dye multimer (S-6)

Compound (X-3) 9.1 g (13.5 mmol), 1,1-bis (hydroxymethyl) propionic acid 2.2 g (16.5 mmol), methacrylic acid 2,3-dihydroxypropyl 6.3 g (39.1 mmol) ), 11.6 g (69.1 mmol) of 1,6-diisocyanatohexane and Neostan U-1000 (0.1 g) were added to 100 g of methyl ethyl ketone and heated at 80 ° C. for 10 hours under a nitrogen atmosphere. After cooling to room temperature, the gum-like substance added to 1000 mL of hexane was transferred to a petri dish and blown and dried at 40 ° C. for 2 days to obtain 20.4 g of a dye multimer (S-6).

Synthesis Example 14 Synthesis of dye multimer (S-7)

11.9 g (24.7 mmol) of compound (X-7) and 2.7 g (12.4 mmol) of pyromellitic anhydride were added to 50 g of PGMEA and heated to reflux for 10 hours under a nitrogen atmosphere. After cooling to room temperature, the solid obtained by adding to 1000 mL of hexane was filtered and air-dried at 40 ° C. for 2 days to obtain 17.5 g of a dye multimer (S-7).

Synthesis Example 15 Synthesis of dye multimer (S-8)

Dipentaerythritol hexakis (6-mercaptohexanolate) 3.0 g, dye monomer (X-1) 12.0 g and N-methylpyrrolidone 30 g were heated at 80 ° C. in a nitrogen atmosphere. Next, 2,2'-azobis (isobutyric acid) dimethyl) [trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.] (0.3 g) was added and heated for 7 hours. After allowing to cool, 2.0 g of methacrylic acid, 1.0 g of 2- (2-bromo-2-methylpropanoyl) ethyl methacrylate, 0.2 g of 2,2′-azobis (isobutyric acid) dimethyl) were added. This solution was added dropwise to 5 g of N-methylpyrrolidone heated at 80 ° C. in a nitrogen atmosphere over 1 hour, stirred for 3 hours, and then allowed to cool. To this, 2.0 g of diazabicycloundecene (DBU) was added, and after stirring for 12 hours, 2.0 g of methanesulfonic acid was added. The resulting solution was added dropwise to a solution of 250 mL methanol / 250 mL water. The obtained solid was filtered and dried to obtain 11.1 g of a dye multimer (S-8).

In the table, MMA represents methacrylic acid, GMA represents glycidyl methacrylate, HMP represents 1,1-bis (hydroxymethyl) propionic acid, and GLM represents 2,3-dihydroxypropyl methacrylate. PA represents pyromellitic anhydride, and MBMP represents 2- (2-bromo-2-methylpropanoyl) ethyl methacrylate.

<Test Example 1> Pattern formation using photolithography (preparation of resist solution for undercoat layer)
The following components were mixed and dissolved to prepare an undercoat layer resist solution.
-Composition of resist solution for undercoat layer-
Solvent (PGMEA): 19.20 parts Solvent (ethyl lactate): 36.67 parts Alkali-soluble resin (benzyl methacrylate / methacrylic acid-2-hydroxyethyl methacrylate copolymer (molar ratio = 60/22) / 18, 40% PGMEA solution having a weight average molecular weight of 15,000 and a number average molecular weight of 9,000)): 30.51 parts. Curable compound (dipentaerythritol hexaacrylate, KAYARAD DPHA (manufactured by Nippon Kayaku)): 12 20 parts-Polymerization inhibitor (p-methoxyphenol): 0.0061 parts-Fluorosurfactant (Megafac F475, manufactured by DIC): 0.83 parts-Photopolymerization initiator (trihalomethyltriazine-based photopolymerization) Initiator, TAZ-107, manufactured by Midori Chemical): 0.586 parts

(Preparation of silicon wafer substrate with undercoat layer)
A silicon wafer having a diameter of 6 inches (1 inch = 25.4 mm) was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the undercoat resist solution is applied onto the silicon wafer so as to have a dry film thickness of 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. A silicon wafer substrate was obtained.

(Preparation of coloring composition)
<< Preparation of Pigment Dispersion Liquid 1 >>
Pigment dispersion 1 was prepared as follows.
C. I. A mixed solution comprising 13.0 parts of pigment green 36 (green pigment, average particle size 55 nm), 5.0 parts of pigment dispersant (Disperbyk-111, manufactured by BYK Chemie), and 82.0 parts of PGMEA was added to a bead mill (zirconia). A pigment dispersion was prepared by mixing and dispersing for 3 hours using beads having a diameter of 0.3 mm. Thereafter, dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain a pigment dispersion 1 (pigment concentration 13%).
With respect to the obtained pigment dispersion 1, the particle size of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) to be 24 nm.

<< Preparation of Pigment Dispersion 2 >>
In pigment dispersion 1, C.I. I. In place of Pigment Green 36, C.I. I. Pigment dispersion 2 was prepared in the same manner as pigment dispersion 1, except that Pigment Red 254 was used. The particle size of Pigment Dispersion Liquid 2 was 26 nm.

<< Preparation of pigment dispersion 3 >>
In pigment dispersion 1, C.I. I. In place of Pigment Green 36, C.I. I. Pigment dispersion 3 was prepared in the same manner as pigment dispersion 1, except that CI Pigment Green 58 was used. The particle size of Pigment Dispersion Liquid 3 was 29 nm.

<< Preparation of pigment dispersion 4 >>
In pigment dispersion 1, C.I. I. In place of Pigment Green 36, C.I. I. Pigment dispersion 4 was prepared in the same manner as pigment dispersion 1, except that CI Pigment Green 59 was used. The particle size of the pigment dispersion 4 was 24 nm.

<Preparation of coloring composition>
The following components were mixed, dispersed, dissolved, and filtered through a 0.45 μm nylon filter to obtain a colored composition.
-composition-
-Dye (compound described in the following table): 0.040 parts as a solid content-Pigment dispersion containing the pigment described in the following table (pigment concentration: 13.0%): 0.615 parts-Cyclohexanone: 100 parts-Alkali Soluble resin (the following J1 or J2: compounds described in the following table): 5 parts Solsperse 20000 (1% cyclohexane solution, manufactured by Nippon Lubrizol): 1 part Photopolymerization initiator (the following (I-1) to (I -8): Compounds described in the following table): 1 part curable compound (dipentaerythritol hexaacrylate, KAYARAD DPHA (manufactured by Nippon Kayaku)): 10 parts glycerol propoxylate (1% cyclohexane solution): 0. 1 copy

Photopolymerization initiator: structure shown below. The following (I-1) is IRGACURE (registered trademark) -OXE01, (I-2) is IRGACURE (registered trademark) -OXE02 (manufactured by BASF), (I-3) is IRGACURE (registered trademark) -379, (I- 4) is DAROCUR (registered trademark) -TPO (all of which are manufactured by BASF). In the following structural formulas, Ph represents a phenyl group.

Alkali-soluble resin: the following structure

Dye XH-1: Structure shown below

(Production of color filter)
Each colored composition prepared as described above was applied onto the undercoat layer of the silicon wafer substrate with the undercoat layer to form a composition layer (coating film). The coating amount of the coloring composition was set to a coating amount at which the dry film thickness was 0.6 μm. Next, this coating film was heat-treated (pre-baked) for 120 seconds using a hot plate at 100 ° C. The substrate after pre-baking was allowed to stand at room temperature for 24 hours (aging).

Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon), exposure was performed at various exposure doses of 50 to 1200 mJ / cm ² through an Island pattern mask having a pattern of 1.0 μm square at a wavelength of 365 nm. After that, the substrate on which the exposed film is formed is placed on a horizontal rotating table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (manufactured by Fuji Film Electronics Materials) is installed. Using this, paddle development was performed at 23 ° C. for 60 seconds to form a colored pattern.

The substrate on which the colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and pure water is showered from the spray nozzle from above the rotation center while rotating the silicon wafer substrate at a rotation speed of 50 rpm by a rotating device. The product was supplied in the form of a rinse, followed by spin drying. As described above, a color filter having a colored pattern was produced. The size of the colored pattern was measured using a measuring SEM (scanning electron microscope) “S-9260A” (manufactured by Hitachi High-Technologies). The exposure amount at which the pattern size was 1.0 μm was determined as the optimum exposure amount.

(Performance evaluation)
<Color unevenness>
The colored composition was applied to a glass substrate to form a coating film. The coating amount of the coloring composition was set to a coating amount at which the dry film thickness was 0.7 μm. Next, the coating film was subjected to heat treatment (pre-baking) for 120 seconds using a hot plate at 100 ° C. After leaving this at room temperature for 24 hours, a sample (a glass substrate with a colored layer) was produced by performing exposure in the same manner as the method for producing a color filter except that a mask was not used. The luminance distribution of the sample was measured by the following method, and the color unevenness was evaluated based on the ratio of the pixels whose deviation from the average is within ± 5% to the total number of pixels. The luminance distribution was measured using an image obtained by photographing the sample with a microscope MX-50 (Olympus). In the luminance distribution, the luminance with the largest number of pixels is defined as the average luminance. In the column of color unevenness in the table below, the ratio (%) of pixels whose deviation from the average is within ± 5% is described.

<Pattern shape>
The pattern shape of the obtained color filter was observed with SEM (scanning electron microscope).
A: No pattern distortion or surface roughness.
B: The pattern is distorted and the surface is rough.

<Pattern loss>
200 patterns were observed with an SEM to confirm the presence or absence of pattern defects. The more pattern defects, the worse the yield. The number of pattern defects is shown in the table below.

<Defect>
Each coloring composition was apply | coated on the undercoat layer of the silicon wafer substrate with an undercoat layer, and the coating film was formed. The coating amount of the coloring composition was set to a coating amount at which the dry film thickness was 0.6 μm. Next, this coating film was heat-treated (pre-baked) for 120 seconds using a hot plate at 100 ° C. After standing the substrate at room temperature for 24 hours (with time) was measured and the number of defects (number / cm ²⁾ at Applied Materials Inc. ComPlus. The smaller the number of defects, the better.

As is clear from the above table, in the colored compositions of the examples, the occurrence of color unevenness and defects was suppressed even after aging after pre-baking. Furthermore, the pattern shape was good and there were few pattern defects.
On the other hand, the comparative example was inferior in color unevenness and defects. Furthermore, the pattern shape was inferior and there were many pattern defects.

Note that PG36 in the above table is C.I. I. It is an abbreviation for Pigment Green 36. PG254 is a C.I. I. It is an abbreviation for Pigment Red 254. PG58 is C.I. I. It is an abbreviation for Pigment Green 58. PG59 is C.I. I. It is an abbreviation for Pigment Green 59.

In the coloring compositions of the examples, the same results were obtained even when dipentaerythritol hexaacrylate was changed to A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) with the same mass as the curable compound.

<Test Example 2> Pattern formation applying dry etching method (preparation of coloring composition)
The following components were mixed and dissolved to obtain a colored composition.
-composition-
Cyclohexanone: 1.133 parts Dye (compound described in the following table): 0.040 part as solid content Pigment dispersion containing pigment described in the following table (pigment concentration: 13.0%): 0.615 part Curable compound (EHPE-3150 (manufactured by Daicel Corporation, 2,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol)): 070 parts glycerol propoxylate (1% cyclohexane solution): 0.048 parts

(Production of color filter)
On the glass substrate, the said coloring composition was apply | coated using the spin coater so that the film thickness might be set to 0.6 micrometer, and the heat processing (prebaking) were performed for 120 second using a 100 degreeC hotplate. This was left at room temperature for 24 hours, and then heat-treated (post-baked) for 300 seconds using a 220 ° C. hot plate to prepare a cured film.
A positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials) was applied on the cured film and prebaked to form a photoresist layer having a thickness of 0.8 μm. Subsequently, the photoresist layer is subjected to pattern exposure using an i-line stepper (manufactured by Canon) at an exposure amount of 350 mJ / cm ² , and heat treatment is performed for 1 minute at a temperature at which the temperature of the photoresist layer or the atmospheric temperature becomes 90 ° C. Was done. Thereafter, a resist stripping process was performed for 120 seconds using a photoresist stripping solution “MS230C” (manufactured by Fuji Film Electronics Materials) to remove the resist pattern, and further cleaning with pure water and spin drying were performed. Thereafter, a dehydration baking process was performed at 100 ° C. for 2 minutes.
Next, dry etching was performed according to the following procedure.

RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, chamber internal pressure: 4.0 Pa, substrate temperature: 50 ° C., mixed gas using dry etching equipment (Hitachi High Technologies, U-621) Seed and flow rate were CF ₄ : 80 mL / min. , O ₂ : 40 mL / min. , Ar: 800 mL / min. As a result, the first stage etching process of 80 seconds was performed.

Next, in the same etching chamber, RF (radio frequency) power: 600 W, antenna bias: 100 W, wafer bias: 250 W, chamber internal pressure: 2.0 Pa, substrate temperature: 50 ° C., mixed gas type and flow rate N ₂ : 500 mL / min. , O ₂ : 50 mL / min. , Ar: 500 mL / min. (N ₂ / O ₂ / Ar = 10/1/10), and a second-stage etching process and an over-etching process were performed for 28 seconds.

After dry etching under the above conditions, the resist is removed by using a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials) for 120 seconds to remove the resist, followed by washing with pure water, spin Drying was performed. Thereafter, a dehydration baking process was performed at 100 ° C. for 2 minutes.

(Performance evaluation)
In the same manner as in Test Example 1, color unevenness, pattern shape, pattern defect and defect were evaluated. The results are shown in the table below.

Claims

A coloring composition comprising a dye multimer and a curable compound,
The dye multimer includes a dye structure having a structure in which an azo group or an aromatic ring group is bonded to a cationic heterocycle containing two or more heteroatoms and one or more of the heteroatoms being a nitrogen atom. , Coloring composition.
The colored composition according to claim 1, wherein the cationic heterocycle is represented by the following formula (I):
Formula (I)

Y a represents a sulfur atom or —NR Ya —, Y b represents a nitrogen atom or —CR Yb —, and R a , R b , R Ya and R Yb each independently represent a hydrogen atom, a substituent, a dye It represents the bonding site with the atomic group constituting the structure or the bonding site with the atomic group constituting the dye multimer, and R a and R Ya , R b and R Ya , and R b and R Yb are respectively They may combine to form a ring; any of the atoms that make up the ring, or the entire ring has a monovalent positive charge.
The coloring composition according to claim 1 or 2, wherein the dye structure is represented by the formula (Ia);

Ht represents a cationic heterocycle containing two or more heteroatoms, and one or more of the heteroatoms is a nitrogen atom;
L represents -N = N- or an arylene group,
B represents a substituent,
X represents an anion,
At least one of Ht, B, and X has a binding site with an atomic group constituting a dye multimer.
The coloring composition according to claim 1 or 2, wherein the dye multimer has a dye structure represented by the formula (I-1);

In formula (I-1), R 1 and R 8 each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R 2 , R 7 , R 9 to R 12 are each independently Represents a hydrogen atom or a substituent, Y 1 represents a sulfur atom or —NR Y1 —, R Y1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, X represents an anion, R 1 At least one of -R 2 , R 7 -R 12 , R Y1 and X has a bonding site with an atomic group constituting a dye multimer.
The coloring composition according to claim 1 or 2, wherein the dye multimer has a dye structure represented by the formula (I-2);

In formula (I-2), R 101 , R 110 and R 111 each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R 102 to R 105 , R 106 to R 109 are Each independently represents a hydrogen atom or a substituent, R 110 and R 111 may be bonded to form a ring, Y 2 represents a sulfur atom or —NR Y2 —, and R Y2 represents a hydrogen atom; , X represents an anion, and at least one of R 101 to R 109 , R Y2 and X has a bonding site with an atomic group constituting a dye multimer.
The dye multimer includes at least one of a repeating unit represented by the following formula (A) and a repeating unit represented by the following formula (C), or represented by the following formula (D). The coloring composition according to any one of claims 1 to 5;

In formula (A), A 1 represents the main chain of the repeating unit, L 1 represents a single bond or a divalent linking group, DyeI contains two or more heteroatoms, and one or more of the heteroatoms Represents a dye structure having a structure in which an azo group or an aromatic ring group is bonded to a cationic heterocycle in which is a nitrogen atom;

In the formula (C), L 3 represents a single bond or a divalent linking group, DyeIII includes two or more heteroatoms, and at least one of the heteroatoms is a nitrogen atom, Represents a dye structure having a structure in which an azo group or an aromatic ring group is bonded; m represents 0 or 1;

In the formula (D), L 4 represents an (n + k) -valent linking group, n represents an integer of 2 to 20, k represents an integer of 0 to 20, DyeIV contains 2 or more heteroatoms, And represents a dye structure having a structure in which an azo group or an aromatic ring group is bonded to a cationic heterocycle in which one or more of the heteroatoms are nitrogen atoms, P represents a substituent, and n represents 2 or more. In this case, the plurality of DyeIVs may be different from each other, and when k is 2 or more, the plurality of Ps may be different from each other, and n + k represents an integer of 2 to 20.
The colored composition according to any one of claims 1 to 6, wherein the dye multimer has a bis (sulfonyl) imide anion or a tris (sulfonyl) methyl anion.
The coloring composition according to any one of claims 1 to 7, further comprising a pigment.
The colored composition according to any one of claims 1 to 8, wherein the curable compound contains a radical polymerizable compound and further contains a photopolymerization initiator.
The colored composition according to any one of claims 1 to 9, further comprising an alkali-soluble resin.
A color filter using the colored composition according to any one of claims 1 to 10.
A step of forming a colored composition layer on a support using the colored composition according to any one of claims 1 to 10, and a pattern formed on the colored composition layer by a photolithography method or a dry etching method Forming a pattern.
A solid-state imaging device having the color filter according to claim 11.
An image display device having the color filter according to claim 11.
A dye multimer having a dye structure represented by the following formula (I-1) or formula (I-2);

In formula (I-1), R 1 and R 8 each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R 2 , R 7 , R 9 to R 12 are each independently Represents a hydrogen atom or a substituent, Y 1 represents a sulfur atom or —NR Y1 —, R Y1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, X represents an anion, R 1 At least one of -R 2 , R 7 -R 12 , R Y1 and X has a binding site with an atomic group constituting a dye multimer;

In formula (I-2), R 101 , R 110 and R 111 each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R 102 to R 105 , R 106 to R 109 are Each independently represents a hydrogen atom or a substituent, R 110 and R 111 may be bonded to form a ring, Y 2 represents a sulfur atom or —NR Y2 —, and R Y2 represents a hydrogen atom; , X represents an anion, and at least one of R 101 to R 109 , R Y2 and X has a bonding site with an atomic group constituting a dye multimer.