JP2019185034A - Coloring composition, cured coloring film, color filter, display element, photosensitive element, and light-emitting element - Google Patents

Abstract

Provided is a colored composition which is excellent in developability and can form a colored cured film in which migration is suppressed. SOLUTION: (A1) a dye multimer having a dye structure and having an alkali-soluble group represented by the formula (I) or (II) at a main chain terminal, and (B) coloring containing a polymerizable compound Composition. [In the formulas (I) and (II), Ra and Rb each independently represent a hydrogen atom or a monovalent substituent, and Za and Zb each independently represent a divalent linking group. , * Indicate the bonding position. ]. [Selection diagram] None

Description

  The present invention relates to a colored composition, a colored cured film, a color filter, a display element, a light receiving element, and a light emitting element, and more specifically, a transmissive or reflective color liquid crystal display element, a solid-state imaging element, an organic EL display element, Colored composition used for forming colored cured film used for electronic paper, etc., colored cured film that is a cured product of the colored composition, and color filter, display element, light receiving element and light emitting device comprising the colored cured film It relates to an element.

  One of the methods for producing a color filter used for a liquid crystal display device or a solid-state imaging device is a pigment dispersion method. In the pigment dispersion method, a colored photosensitive composition in which a pigment is dispersed in various photosensitive compositions is coated on a substrate using a spin coater, a roll coater, or the like, and dried to form a coated film. This is a method for producing a color filter by repeating the operation of obtaining a colored pixel by pattern exposure and development for a desired hue. As described above, the pigment dispersion method uses a pigment as a colorant and is stable to light and heat. Also, patterning is performed by a photolithography method, so that the positional accuracy is high, and the color filter for color display is manufactured. It has been widely used as a preferred method.

  However, in recent years, there has been a strong demand for higher contrast of liquid crystal display devices and higher definition of solid-state imaging devices, and the conventional pigment dispersion method has a limit in further improving the resolution. Therefore, the application of a dye as a colorant has been studied. However, when the dye concentration is increased, the colorant in the pixel of the color pattern is eluted, and the color shifts between adjacent pixels and the upper and lower layers stacked (hereinafter, referred to as “colorant”). "Transfer") is likely to occur. In addition, dyes may interact with other components in the colored composition, and it is difficult to control curability, so that pattern formability (developability) is likely to deteriorate.

  Under such a background, an azo dye having a polymerizable group introduced as a colorant is used, and before the heat treatment of the pattern formed by exposure / development, a process of irradiating ultraviolet rays with controlled exposure is provided. It has been reported that migration is suppressed and the light resistance of colored pixels can be improved (Patent Document 1).

JP-A-2-144502

  The subject of this invention is providing the coloring composition which is excellent in developability and can form the colored cured film by which dye transfer was suppressed. Furthermore, the subject of this invention is providing the color filter, display element, light receiving element, and light emitting element which comprise the colored cured film formed using the said coloring composition, and this colored cured film.

  As a result of detailed studies in view of such circumstances, the present inventors introduced a specific functional group at the end of the main chain of a dye multimer having a dye structure, and then added this with a polymerizable compound to develop the dye. It has been found that a colored composition is obtained that is capable of forming a colored cured film that is excellent in properties and in which migration is suppressed.

That is, the present invention provides a coloring composition containing (A ¹ ) a dye multimer having a dye structure and having an alkali-soluble group at the end of the main chain, and (B) a polymerizable compound.

The present invention also provides (A ² ) at least one dye multimer selected from the group consisting of the following (i) and (ii), and
(B) A colored composition containing a polymerizable compound is provided.
(I) a polymer obtained by polymerization of an unsaturated monomer in the presence of at least one compound selected from the group consisting of a polymerization initiator having an alkali-soluble group and a chain transfer agent having an alkali-soluble group, Dye multimer, which is a polymer of unsaturated monomers including an unsaturated monomer having a dye structure (ii) selected from the group consisting of a polymerization initiator having an alkali-soluble group and a chain transfer agent having an alkali-soluble group Unsaturated monomer comprising an unsaturated monomer having an ionic group and having no dye structure, which is a polymer obtained by polymerization of an unsaturated monomer in the presence of at least one compound A dye multimer which is a reaction product of a polymer of the above and a dye compound having an ionic group electrically different from the ionic group

The present invention further includes (A ³ ) at least one dye multimer selected from the group consisting of the following (iii) and (iv), and
(B) A colored composition containing a polymerizable compound is provided.
(Iii) a residue derived from at least one compound selected from the group consisting of a polymerization initiator having an alkali-soluble group and a chain transfer agent having an alkali-soluble group, and an unsaturated monomer having a dye structure A dye multimer having a structural unit (iv) a residue derived from at least one compound selected from the group consisting of a polymerization initiator having an alkali-soluble group and a chain transfer agent having an alkali-soluble group, and an ionic group It is a reaction product of a polymer having a structural unit derived from an unsaturated monomer having no dye structure and a dye compound having an ionic group electrically different from the ionic group Dye multimer

  The present invention further provides a colored cured film which is a cured product of the colored composition, and a color filter, a display element, a light receiving element and a light emitting element comprising the colored cured film. Here, in this specification, “colored cured film” refers to a bank (partition wall) that defines areas for forming each color pixel, interlayer insulating film, planarizing film, and light emitting layer used in display elements and solid-state imaging elements. , Black matrix, spacer, protective film and the like.

  The present invention still further provides a dye multimer having a dye structure and having an alkali-soluble group at the end of the main chain.

  ADVANTAGE OF THE INVENTION According to this invention, the coloring composition which is excellent in developability and can form the colored cured film with which transfer was suppressed can be provided. Therefore, the colored composition of the present invention can be used very suitably for the production of solid-state imaging devices such as color liquid crystal display devices, organic EL display devices, display devices such as electronic paper, and CMOS image sensors.

Hereinafter, the present invention will be described in detail.
Coloring composition The coloring composition of the present invention contains a specific dye multimer and a polymerizable compound, and the specific dye multimer is selected from the group consisting of the following (A ¹ ) and (A ³ ). It will be chosen.
(A ¹ ) a dye multimer having a dye structure and having an alkali-soluble group having a specific structure at the end of the main chain (A ³ ) a dye multimer having a dye structure and having an alkali-soluble group at the end of the main chain And at least one dye multimer selected from the group consisting of the following (iii) and (iv): (iii) selected from the group consisting of a polymerization initiator having an alkali-soluble group and a chain transfer agent having an alkali-soluble group A dye multimer having a residue derived from at least one kind of compound and a structural unit derived from an unsaturated monomer having a dye structure (iv) having a polymerization initiator having an alkali-soluble group and an alkali-soluble group Polymer having a residue derived from at least one compound selected from the group consisting of chain transfer agents, and a structural unit derived from an unsaturated monomer having an ionic group and not having a dye structure When ,
A dye multimer which is a reaction product with a dye compound having an ionic group electrically different from the ionic group

Hereinafter, “(A ¹ ) dye multimer” and “(A ³ ) dye multimer” will be described using “(A) dye multimer” as a generic term.

-(A) Dye multimer-

In the present specification, the “pigment multimer” refers to a polymer containing a structural unit having a dye structure. (A) The dye multimer can be contained alone or in combination of two or more.
The (A) dye multimer according to the present invention has a dye structure. Here, in the present specification, the “dye structure” is a partial structure derived from a dye and is a chromophore described later. The dye structure may have a charge, and in that case, any form of an intramolecular salt and an intermolecular salt may be used. A known dye structure can be adopted as the dye structure, and is not particularly limited. Specifically, for example, dipyrromethene dye, diarylmethane dye, triarylmethane dye, xanthene dye, acridine dye, anthraquinone dye, azo dye, quinoneimine dye, polymethine dye (oxonol dye, merocyanine dye, arylidene dye, styryl dye, cyanine dye) Dyes, squarylium dyes, croconium dyes, etc.), phthalocyanine dyes, subphthalocyanine dyes, and dye structures derived from those metal complex dyes. Among these, from the viewpoint of color characteristics, a dye structure derived from a dye selected from triarylmethane dyes, xanthene dyes, anthraquinone dyes, azo dyes, quinoneimine dyes, polymethine dyes, subphthalocyanine dyes, and phthalocyanine dyes is preferable. A dye structure derived from a dye selected from xanthene dyes, quinoneimine dyes and polymethine dyes is more preferred, and a dye structure derived from a dye selected from triarylmethane dyes, xanthene dyes, quinoneimine dyes and cyanine dyes is more preferred. When such a dye structure is employed, the developability can be improved and the dye transfer can be suppressed at a higher level.
For specific pigment compounds that can form the pigment structure, see "New Edition Dye Handbook" (Organic Synthetic Chemistry Association; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), "Dye Handbook" ( Okawara et al .; Kodansha, 1986).

  The dye structure may be composed of a cation moiety or an anion moiety, and may be, for example, a salt of a cationic chromophore and a counter anion, or a salt of an anionic chromophore and a counter cation. The counter ion may be an organic ion or an inorganic ion. As used herein, “cationic chromophore” refers to an atomic group having a positive charge. In addition, when the atomic group has a functional group having a positive charge and a functional group having a negative charge, and the total of these charges becomes a positive charge, it is included in the cationic chromophore. To do. The “anionic chromophore” refers to an atomic group having a negative charge. In addition, when the atomic group has a functional group having a positive charge and a functional group having a negative charge, and these charges are summed to become a negative charge as a whole, it is included in the anionic chromophore. To do. In the present specification, an atomic group that does not correspond to a cationic chromophore or an anionic chromophore, and does not have a positively charged functional group and a negatively charged functional group, or a positively charged functional group. Even if it has a functional group having a negative charge and a functional group having a negative charge, the total number of positive charges and the total number of negative charges are the same, and an atomic group that is electrically neutral as a whole is electrically "Neutral chromophore".

  The (A) dye multimer according to the present invention has a structure having an alkali-soluble group at the end of the main chain. Here, the “main chain” in the present specification refers to the longest chain structure portion in the molecular structure of the polymer, and it is allowed that the chain structure portion includes a ring structure. Examples of the main chain constituting the molecular structure of the polymer include a portion in which a single structural unit is repeatedly connected, a portion in which a plurality of structural units are regularly or randomly connected, and the like. Further, the “end of the main chain” means that in the structural unit constituting the main chain, a bond is formed with an adjacent structural unit in the first structural unit where the connection starts and the last structural unit where the connection stops. The unbonded bond becomes the end of the main chain, and the structure having an alkali-soluble group is bonded to the main chain end and is not included in the main chain.

The (A ¹ ) dye multimer has a group represented by the following formula (I) or a group represented by the following formula (II) as an alkali-soluble group. On the other hand, the alkali-soluble group of the (A ³ ) dye multimer is not particularly limited as long as it is a residue derived from a polymerization initiator or a chain transfer agent. For example, a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, etc. Can be mentioned. Especially, it is preferable to have a carboxyl group from a viewpoint of dye transfer suppression and the improvement of developability, and it is preferable to have a group represented by the following formula (I) or a group represented by the following formula (II). In addition, the alkali-soluble group may be present at both ends of the main chain or may be present at any one end.

[In Formula (I) and Formula (II),
R ^a and R ^b each independently represent a hydrogen atom or a monovalent substituent,
Z ^a and Z ^b each independently represent a divalent linking group,
* Indicates a binding position. ]

Although it does not specifically limit as a monovalent substituent which concerns on ^Ra and ^Rb , A halo group, a carboxyl group, a cyano group, a C1-C30 alkyl group, a C6-C30 monovalent aromatic hydrocarbon Group, monovalent heterocyclic group having 3 to 30 total atoms of carbon atom and hetero atom, -OR ^c , -SR ^c , -OC (= O) R ^c , -N (R ^c ) (R ^d ), - C (= O) OR c, -C (= O) N (R c) (R d), - P (= O) (OR c) 2, -P (= O) (R c) 2 A monovalent group having a polymer chain is preferable, and a cyano group, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 30 carbon atoms are more preferable. R ^c and R ^d each independently represent an alkyl group having 1 to 30 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

As the divalent linking group for Z ^a and Z ^b , a group having a linking group containing an atom other than a carbon atom and a hydrogen atom between CC bonds of a divalent hydrocarbon group and a divalent hydrocarbon group Can be mentioned.
Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. The divalent aliphatic hydrocarbon group may be either linear or branched, and the aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be saturated hydrocarbon groups or unsaturated hydrocarbon groups. It may be a hydrogen group. The position of the unsaturated bond of the unsaturated hydrocarbon group may be either in the molecular chain or at the end of the molecular chain, and can be at any position.

  Examples of the divalent aliphatic hydrocarbon group include an alkanediyl group and an alkenediyl group. Carbon number of a bivalent aliphatic hydrocarbon group becomes like this. Preferably it is 1-30, More preferably, it is 1-20, More preferably, it is 1-10, More preferably, it is 1-6. Specific examples of the alkanediyl group include, for example, a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, Propane-1,3-diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4 -Diyl group, pentane-1,5-diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, 2-methylpropane-1,2-diyl group, 2,2-dimethylpropane- Specific examples of the alkenediyl group include, for example, ethene-1,1-diyl group, ethene-1,2-diyl group, propene-1,2-diyl group, propene- 1,3-diyl group, propene-2, -Diyl group, 1-butene-1,2-diyl group, 1-butene-1,3-diyl group, 1-butene-1,4-diyl group, 2-pentene-1,5-diyl group, 3- Examples include hexene-1,6-diyl group.

Examples of the divalent alicyclic hydrocarbon group include a cycloalkylene group and a cycloalkenylene group. Carbon number of a bivalent alicyclic hydrocarbon group becomes like this. Preferably it is 3-20, More preferably, it is 3-12, More preferably, it is 3-6. Specific examples of the cycloalkylene group include, for example, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and the like. Specific examples of the cycloalkenylene group include, for example, a cyclobutenylene group and a cyclopentenylene. Group, cyclohexenylene group and the like. The divalent alicyclic hydrocarbon group is a bridge of norbornylene group such as 1,4-norbornylene group or 2,5-norbornylene group, 1,5-adamantylene group, 2,6-adamantylene group or the like. It may be a cyclic hydrocarbon group.
Examples of the divalent aromatic hydrocarbon group include an arylene group. Carbon number of a bivalent aromatic hydrocarbon group becomes like this. Preferably it is 6-20, More preferably, it is 6-14, More preferably, it is 6-10. Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, a phenanthrene group, and an anthrylene group.

Examples of the linking group containing an atom other than a carbon atom and a hydrogen atom at the C-C bond or at the terminal of a divalent hydrocarbon group include at least one selected from an alkanediyl group, a cycloalkylene group, and an arylene group. -O-, -S-, -NR'- (R 'represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), -CNR'- (R' is as defined above), And a group formed by combining at least one selected from —CO—, —COO—, —CONR′— (R ′ has the same meaning as described above), —NHCOO—, and —SO ₂ —. . Such linking groups may have two or more, and when two or more linking groups are present, they may be the same or different.
The divalent hydrocarbon group may have a substituent without departing from the gist of the present invention.
The position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different. Examples of the substituent include halo, carboxyl, hydroxyl, cyano, formyl, nitro, amino, dialkylamino, diarylamino, alkoxy, alkoxycarbonyl, alkylthio, arylthio, Examples thereof include an alkylsilyl group.

  Among them, the divalent linking group includes a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a carbon atom other than a carbon atom and a hydrogen atom between the CC bonds of the divalent aliphatic hydrocarbon group. A group containing an atom is preferable, and a group having a linking group containing an atom other than a carbon atom and a hydrogen atom between CC bonds of an alkanediyl group, an arylene group, and an alkanediyl group is more preferable, and an alkane having 1 to 6 carbon atoms. A diyl group and an arylene group having 6 to 10 carbon atoms are more preferable.

  The (A) dye multimer according to the present invention is not particularly limited as long as it contains a structural unit having a dye structure, but the following aspects (a-1) to (a-3) are preferable as the dye multimer. Can be mentioned.

(A-1) The dye structure is a cationic chromophore, the dye multimer comprising the cationic chromophore and a structural unit having an anionic group (a-2) The dye structure is an anionic chromophore, and the anion Dye multimer comprising a structural unit having a cationic chromophore and a cationic group (a-3) The dye multimer comprising a structural unit having the chromophore, wherein the dye structure is an electrically neutral chromophore

First, the mode (a-1) will be described.
Examples of the cationic chromophore include C.I. in the Color Index (CI; published by The Society of Dyers and Colorists). It is also possible to use a cationic part of a dye classified as I. basic. Specifically, for example, triarylmethane chromophore, polymethine chromophore (cyanine chromophore, methine chromophore, squarylium chromophore), azo chromophore, diarylmethane chromophore, quinoneimine chromophore, anthraquinone chromophore, phthalocyanine chromophore. Xanthene chromophore, quinophthalone chromophore and the like. Among these, from the viewpoint of improving developability and suppressing dye transfer, the triarylmethane chromophore, cyanine chromophore, methine chromophore, azo chromophore, xanthene chromophore, and quinoneimine chromophore are preferable, and the triarylmethane chromophore and cyanine chromophore are preferable. More preferred are chromophores, xanthene chromophores, and quinoneimine chromophores.

  Examples of the triarylmethane chromophore include those represented by the following formula (1). In addition, although various resonance structures exist in the cation represented by the following formula (1), in this specification, the resonance structure is equivalent to the cation represented by the following formula (1). In the following description, when a resonance structure exists for a compound whose charge is described in the chemical formula, the same treatment is performed.

[In Formula (1),
Ar represents a divalent aromatic hydrocarbon group.
R < ¹ > -R < ⁴ > shows a hydrogen atom or a hydrocarbon group mutually independently.
R ^{5 to} R ¹² represent a hydrogen atom, a halo group, a hydrocarbon group, or —COOR ¹⁷ . However, R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
Y represents a hydrogen atom or a group represented by the following formula (2). ]

In [Equation (2), R ¹³ and R ¹⁴ are independently of each other, represent a hydrogen atom or a hydrocarbon group.
]

The aromatic hydrocarbon group according to Ar may be a monocyclic aromatic hydrocarbon group or a polycyclic aromatic hydrocarbon group, and preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. Specific examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group.
The divalent aromatic hydrocarbon group may have a substituent, and examples of the substituent include a halo group, a hydroxyl group, an amino group, a carboxyl group, an isocyanate group, an alkyl group having 1 to 6 carbon atoms, and a carbon number of 1 -6 alkoxy group etc. are mentioned. Specific examples of the halo group and the alkyl group having 1 to 6 carbon atoms are as described above. In addition, the position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different.
Among them, the aromatic hydrocarbon group related to Ar is preferably a phenylene group, a naphthylene group, a phenylene group substituted with an alkyl group having 1 to 6 carbon atoms, or a naphthylene group substituted with an alkyl group having 1 to 6 carbon atoms. .

Examples of the hydrocarbon group according to R ^{1 to} R ¹⁴ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be either linear or branched, and the aliphatic hydrocarbon group and alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The position of the unsaturated bond of the unsaturated hydrocarbon group may be either in the molecular chain or at the end of the molecular chain, and can be at any position. Here, in the present specification, the “alicyclic hydrocarbon group” is a concept excluding an aliphatic hydrocarbon group having no cyclic structure. In addition, in this specification, “alicyclic hydrocarbon group” and “aromatic hydrocarbon group” are not only a group consisting of only a ring structure, but also a divalent aliphatic hydrocarbon group substituted on the ring structure. In other words, the structure includes at least an alicyclic hydrocarbon or an aromatic hydrocarbon. Moreover, the hydrocarbon group may have a substituent within the range which does not deviate from the main point of this invention. The position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different. Examples of the substituent include a halo group, a hydroxyl group, an amino group, a carboxyl group, a cyano group, an isocyanate group, a formyl group, a nitro group, an alkoxy group, an aryloxy group, a trialkylsilyl group, and a heterocyclic group.

  Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. Carbon number of an aliphatic hydrocarbon group becomes like this. Preferably it is 1-30, More preferably, it is 1-20, More preferably, it is 1-12, More preferably, it is 1-6. Specific examples of the alkyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl group, Decyl, undecyl, 1-methyldecyl, dodecyl, 1-methylundecyl, 1-ethyldecyl, tridecyl, tetradecyl, tert-dodecyl, pentadecyl, 1-heptyloctyl, hexadecyl, octadecyl Groups and the like. Specific examples of the alkenyl group include, for example, ethenyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1,3-butadienyl group, 1-pentenyl group, 2-pentenyl group, A 1-hexenyl group, 2-ethyl-2-butenyl group, 2-octenyl group, (4-ethenyl) -5-hexenyl group, 2-decenyl group and the like can be mentioned. Specific examples of the alkynyl group include, for example, ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-ethyl-2-butynyl group, 2 -Octynyl group, (4-ethynyl) -5-hexynyl group, 2-decynyl group and the like can be mentioned.

Examples of the alicyclic hydrocarbon group include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged ring hydrocarbon group, a spiro hydrocarbon group, and a cyclic terpene hydrocarbon group. Carbon number of an alicyclic hydrocarbon group becomes like this. Preferably it is 3-30, More preferably, it is 3-20, More preferably, it is 3-12, More preferably, it is 3-6. Specific examples of the cycloalkyl group include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a t-butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. Specific examples of the cycloalkenyl group include Examples thereof include 1-cyclohexenyl group. Specific examples of the condensed polycyclic hydrocarbon group include tricyclodecanyl group, decahydro-2-naphthyl group, adamantyl group and the like. Specific examples of the bridged cyclic hydrocarbon group include, for example, Examples include tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, pentacyclopentadecanyl group, isobornyl group, dicyclopentenyl group, tricyclopentenyl group and the like. Furthermore, examples of the spiro hydrocarbon group include a spiro [3.4] heptane, a monovalent group obtained by removing one hydrogen atom from spiro [3.4] octane, and the cyclic terpene hydrocarbon group. Examples thereof include a monovalent group obtained by removing one hydrogen atom from p-menthane, tsujang, curan and the like.

The aromatic hydrocarbon group may be a monocyclic aromatic hydrocarbon group or a polycyclic aromatic hydrocarbon group, and examples thereof include an aryl group and an aralkyl group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10.
Specific examples of the aryl group include, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenylene group, an azulenyl group, a 9-fluorenyl group, and the like. A benzyl group, a phenethyl group, a trityl group, etc. are mentioned.

The hydrocarbon group according to R ^{1 to} R ¹⁴ may have a substituent, and examples of the substituent include a halo group, an alkoxy group, an aryloxy group, and a heterocyclic group. Examples of the halo group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkoxy group may be either a straight chain or branched chain, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a tert-butoxy group. Examples of the aryloxy group include a phenoxy group and a benzyloxy group. The heterocyclic group may be an alicyclic heterocyclic group or an aromatic heterocyclic group, for example, oxiranyl group, oxetanyl group, pyrrolidinyl group, imidazolidinyl group, pyrazolidinyl group, morpholinyl group, theomorpholinyl group, piperidyl group, piperidino group, Piperazinyl group, homopiperazinyl group, 1,3-dioxolan-2-yl group, furyl group, thienyl group, pyridyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, pyrazolyl group, pyrimidyl group, etc. Can be mentioned.

Among them, the hydrocarbon group according to R ^{1 to} R ¹⁴ is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, more preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 14 carbon atoms, More preferred are alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 10 carbon atoms.

  In the present invention, among the chromophores represented by the above formula (1), the color development represented by the following formula (1-1) or (1-2) from the viewpoint of improving storage stability and solvent resistance. A group is preferred.

[In the formulas (1-1) and (1-2),
R < ¹ > -R < ⁴ >, R < ¹³ > and R < ¹⁴ > show a hydrogen atom, a C1-C8 alkyl group, a C3-C8 cycloalkyl group, or a phenyl group mutually independently.
R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halo group or an alkyl group having 1 to 8 carbon atoms. ]

R ¹ , R ² , R ^13, and R ¹⁴ are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ³ is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 3 to 6 carbon atoms. A cycloalkyl group or a phenyl group is preferred. R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ¹⁵ and R ¹⁶ are preferably a hydrogen atom, a halo group or an alkyl group having 1 to 6 carbon atoms.

  Specific examples of the chromophore represented by the above formula (1) include the following chromophores.

  Examples of the polymethine chromophore include those represented by the following formula (3). As used herein, “polymethine chromophore” includes cyanine chromophore, methine chromophore, and squarylium chromophore.

[In Formula (3),
R ²¹ and R ²² each independently represent a hydrocarbon group.
R ^{23 to} R ²⁵ each independently represent a hydrogen atom, a halo group, or a hydrocarbon group. A plurality of R ²³ and R ²⁴ need not be the same.
Ring Z ¹ and ring Z ² each independently represent an aromatic hydrocarbon ring.
G ¹ and G ² each independently represent —O—, —S— or —CR ²⁶ R ²⁷ —. However, R ²⁶ and R ²⁷ each independently represent a hydrocarbon group.
s shows the integer of 1-3. ]

The hydrocarbon group according to R ^{21 to} R ²⁷ is the same as the hydrocarbon group according to R ^{1 to} R ¹⁴ , and the specific configuration thereof is as described above.
Specific examples of the halo group relating to R ^{23 to} R ²⁵ include the same ones as described above.
The aromatic hydrocarbon ring related to ring Z ¹ and ring Z ² may be a monocyclic aromatic hydrocarbon ring or a polycyclic aromatic hydrocarbon ring. 6-20 are preferable and, as for carbon number of an aromatic hydrocarbon ring, 6-10 are more preferable. Specific examples include benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, naphthacene ring, and triphenylene ring.
The aromatic hydrocarbon ring according to ring Z ¹ and ring Z ² may have a substituent, and examples of the substituent include a halo group and a halogenated hydrocarbon group. In addition, as a hydrocarbon group of a halogenated hydrocarbon group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C6 alkyl group is still more preferable. In addition, as a halogen atom in a halo group and a halogenated hydrocarbon group, the same thing as the above-mentioned can be mentioned.

Among them, as the hydrocarbon group of the R ²¹ and R ^22, preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
R ^{23 to} R ²⁵ are preferably hydrogen atoms.
As the ring Z ¹ and the ring Z ² , a benzene ring is preferable.
G ¹ and G ² are preferably —O— and —CR ²⁶ R ²⁷ —, and R ²⁶ and R ²⁷ are preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. A methyl group and an ethyl group are more preferable.
s is preferably 1 or 2, and more preferably 1.

  Specific examples of the cyanine chromophore represented by the above formula (3) include the following chromophores.

  Further, specific examples of the methine chromophore represented by the above formula (3) include the following chromophores.

  Examples of the azo chromophore include the following chromophores.

  Examples of the diarylmethane chromophore include the following chromophores.

  Examples of the quinoneimine chromophore include the following chromophores.

  Examples of the anthraquinone chromophore include the following chromophores.

  Examples of the phthalocyanine chromophore include the following chromophores. In the chemical formula below, CuPC represents a copper phthalocyanine residue.

  As a xanthene chromophore, what is represented by following formula (4) can be mentioned, for example.

[In Formula (4),
R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent a hydrogen atom or a hydrocarbon group. However, the hydrocarbon group is a halo group, —R ³⁸ , —OH, —OR ³⁸ , —SO ₃ H, —SO ₃ M ¹ , —CO ₂ H, —CO ₂ M ¹ , —CO ₂ R ³⁸ , It may be substituted with —SO ₃ R ³⁸ , —SO ₂ NHR ³⁹ or —SO ₂ NR ³⁹ R ⁴⁰ .
R ³⁵ and R ³⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ³⁷ represents an ^{_{-SO 3 H, -SO 3 M 1}} , -CO 2 H, -CO 2 R 38, -SO 3 R 38, -SO 2 NHR 39 or -SO ₂ NR ³⁹ R ^40.
u represents an integer of 0 to 5, and when u is an integer of 2 or more, the plurality of R ³⁷ need not be the same.
R ³⁸ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. However, the saturated hydrocarbon group may be substituted with a halo group, and the saturated hydrocarbon group may have —O—, —CO— or —NR ³⁸ — between C—C bonds. Good.
R ³⁹ and R ⁴⁰ each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or —X ^a , or R ³⁹ and R ⁴⁰ are bonded to each other. Represents a substituted or unsubstituted heterocyclic group having 2 to 10 carbon atoms. However, the alkyl group and cycloalkyl group may be substituted with ^a hydroxyl group, a halo group, —X ^a , —CH═CH ₂ or —CH═CHR ³⁸ , and the alkyl group and cycloalkyl group may be C It may have —O—, —CO— or —NR ³⁸ — between —C bonds, and this heterocyclic group may be substituted with —R ³⁸ , —OH or —X ^a .
M ¹ represents a sodium atom or a potassium atom.
X ^a represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms. However, the aromatic hydrocarbon group and the aromatic heterocyclic group are substituted with —OH, —R ³⁸ , —OR ³⁸ , —NO ₂ , —CH═CH ₂ , —CH═CHR ³⁸ or a halo group. Also good. ]

The hydrocarbon groups according to R ³¹ , R ³² , R ³³ and R ³⁴ are the same as the hydrocarbon groups according to R ^{1 to} R ¹⁴ , and the specific configuration thereof is as described above.
R ³¹ , R ³² , R ³³ and R ³⁴ are preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The specific configuration of the saturated hydrocarbon group having 1 to 10 carbon atoms is as described later.
The saturated hydrocarbon group according to R ³⁸ may be linear, branched or cyclic, and may have a bridge structure as long as it has 1 to 10 carbon atoms. Specific examples include saturated aliphatic hydrocarbon groups and saturated alicyclic hydrocarbon groups. Specific examples of the saturated aliphatic hydrocarbon group and saturated alicyclic hydrocarbon group are the same as those exemplified in the aforementioned alkyl group and cycloalkyl group.

The aromatic hydrocarbon group of the X ^a, preferably an aryl group having a carbon number of 6 to 10, and examples thereof include a phenyl group, a naphthyl group. The aromatic heterocyclic group having a carbon number of 5 to 10 according to X ^a, a furyl group, a thienyl group, a pyridyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, an imidazolyl group, a pyrazolyl group, A pyrimidyl group etc. can be mentioned.
Examples of the heterocyclic group having 2 to 10 carbon atoms formed by combining R ³⁹ and R ⁴⁰ with each other include pyrrolidinyl, pyrazolinyl, morpholinyl, theomorpholinyl, piperidyl, piperidino, piperazinyl, homopiperazinyl, tetrahydro Pyrimidine group, 1,3-dioxolan-2-yl group, pyridyl group, pyrazinyl group, pyrimidyl group, pyridazinyl group, quinolyl group, isoquinolyl group, phthalazinyl group, quinoxalinyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, A thiazolyl group, a benzothiazolyl group, an oxazolyl group, an indolyl group, an indazolyl group, a benzoimidazolyl group, a phthalimide group, and the like can be given. Examples of the substituent of the heterocyclic group, such as halo groups, hydroxy groups, other exemplified aromatic hydrocarbon group or an aromatic heterocyclic group in X ^a, can be exemplified such as an alkyl group having 1 to 6 carbon atoms. In addition, the position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different.

Examples of —SO ₃ R ³⁸ include a methanesulfonyl group, an ethanesulfonyl group, a hexanesulfonyl group, and a decanesulfonyl group. Examples of —CO ₂ R ³⁸ include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, a butyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a methoxypropyloxycarbonyl group. Further, R ³⁹ and R ⁴⁰ related to —SO ₂ NHR ³⁹ , —SO ₂ NR ³⁹ R ⁴⁰ include a branched alkyl group having 6 to 8 carbon atoms, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, carbon An alkyl group having 2 to 8 carbon atoms and an aryl group substituted with an aralkyl group having 8 to 10 carbon atoms, a hydroxyl group or an alkoxy group are preferred.
The alkyl group of R ³⁵ and R ³⁶ according to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, a methyl group, an ethyl group are more preferable.

  Specific examples of the chromophore represented by the above formula (4) include the following chromophores.

In the embodiment of (a-1), the structural unit having an anionic group can be derived from an unsaturated monomer having an anionic group and not having a dye structure.
Examples of the anionic group include a sulfonate anion, an imide anion, and a carboxylate anion. Of these, an imide anion is preferable, and a sulfonylimide anion is more preferable.
Examples of the unsaturated group include (meth) acryloyloxy group, vinylaryl group, vinyloxy group, allyl group and the like. Among these, a (meth) acryloyloxy group and a vinylaryl group are preferable, and a vinylaryl group is more preferable.

  As an unsaturated monomer which has an anionic group and does not have a pigment structure, what is denoted by a following formula (5) is mentioned, for example.

[In Formula (5),
W ¹ represents a polymerizable unsaturated group,
X ¹ represents a halo group, a halogenated hydrocarbon group, or a group having a linking group containing a carbon atom, a hydrogen atom, or an atom other than a halogen atom between the CC bonds of the halogenated hydrocarbon group
Y ¹ represents a single bond or a divalent organic group. ]

As the polymerizable unsaturated group related to W ¹ , a (meth) acryloyloxy group and a vinylaryl group are preferable, and a vinylaryl group is more preferable.
Examples of the halo group related to X ¹ include the same ones as described above.
Examples of the hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group according to X ¹ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. These aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group are the same as the aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group according to R ^{1 to} R ¹⁴ . The specific configuration is as described above.
Among these, as the hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group, an alkyl group, an alicyclic saturated hydrocarbon-substituted alkyl group, a phenyl group, an alkyl-substituted phenyl group, and an aralkyl group are more preferable, and an alkyl group and an aralkyl group are preferable. Further preferred.

As the halogen atom of the halogenated hydrocarbon groups of the X ^1, from the viewpoint of improving the storage stability and solvent resistance, a fluorine atom is preferable. In addition, the fluorine atom may substitute a part or all of the hydrogen atoms of the hydrocarbon group.

X ¹ may be a group having a linking group containing an atom other than a carbon atom, a hydrogen atom or a halogen atom between the C—C bonds of the halogenated hydrocarbon group, but other than a carbon atom, a hydrogen atom or a halogen atom Examples of the linking group containing an atom include —O—, —S—, —CO—, —COO—, —CONH—, —SO ₂ — and the like.

X ¹ is a linkage containing a carbon atom, a hydrogen atom or an atom other than a halogen atom between the C—C bonds of a halogenated hydrocarbon group or a halogenated hydrocarbon group from the viewpoint of improving developability and suppressing migration. A group having a group is preferred.

Examples of the divalent organic group related to Y ¹ include a divalent hydrocarbon group, a divalent hydrocarbon group, and a group formed by combining a linking group containing atoms other than carbon atoms and hydrogen atoms, or these groups. And a group in which a part of the hydrogen atom is substituted with a halogen atom. Examples of such an organic group include an alkanediyl group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, an arylene alkanediyl group having 7 to 20 carbon atoms, or an alkanediyl group having 1 to 10 carbon atoms. At least one selected from a group and an arylene group having 6 to 20 carbon atoms, -O-, -S-, -NR'- (R 'represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), A group formed by combining at least one selected from —COO—, —CONR′— (R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), —NHCOO—, and —SO ₂ —; Can be mentioned.

Specific examples of the alkanediyl group and the arylene group are as described above.
An arylene alkanediyl group is a divalent group formed by combining an arylene group and an alkanediyl group. As the arylenealkanediyl group, an arylenealkanediyl group having 7 to 15 carbon atoms is preferable, and an arylenealkanediyl group having 7 to 13 carbon atoms is more preferable from the viewpoint of availability of raw materials and production. Specific examples include phenylene C _1-6 alkanediyl groups such as a phenylenemethylene group, a phenylenedimethylene group, a phenylenetrimethylene group, a phenylenetetramethylene group, a phenylenepentamethylene group, and a phenylenehexamethylene group. The arylenealkanediyl group includes ortho, meta, and para isomers, and is preferably a para isomer from the viewpoint of less steric hindrance.

Moreover, at least 1 sort (s) chosen from a C1-C10 alkanediyl group and a C6-C20 arylene group, and -O-, -S-, -NR'-, -CO-, -COO-,- The group formed by combining at least one selected from CONR′—, —NHCOO—, and —SO ₂ — is at least selected from an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms. A group formed by combining one kind and at least one selected from —O—, —COO—, and —SO ₂ — is preferable, and includes an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms. A group obtained by combining at least one selected from at least one selected from —O— and —SO ₂ — is more preferable.
Among them, Y ¹ is preferably a single bond or an alkanediyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom.

  Specific examples of the unsaturated monomer represented by the above formula (5) include the following.

  Examples of the unsaturated monomer having a sulfonate anion as an anionic group include p-styrene sulfonate and unsaturated monomers having a sulfonate anion described in International Publication No. 2006/121096. can do.

Next, the aspect of (a-2) is demonstrated.
As an anionic chromophore, C.I. An anion portion of a dye classified as I. Acid can be used. Specifically, for example, triarylmethane chromophore, polymethine chromophore, azo chromophore, diarylmethane chromophore, quinone imine chromophore, anthraquinone chromophore, phthalocyanine chromophore, xanthene chromophore, squarylium chromophore, quinophthalone chromophore, etc. Can be mentioned. Among them, a triarylmethane chromophore, an azo chromophore, a phthalocyanine chromophore, and a xanthene chromophore are preferable, and the triarylmethane chromophore having one or more substituents selected from —SO ₃ ^— and —CO ₂ ^— . Azo chromophore, phthalocyanine chromophore, or xanthene chromophore is more preferred.

  Specific examples of the anionic chromophore include a xanthene chromophore represented by the following formula (6).

[In Formula (6),
R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom or a hydrocarbon group. However, the hydrocarbon group is a halo group, —R ⁶⁸ , —OH, —OR ⁶⁸ , —SO ₃ H, —SO ₃ M ² , —SO ₃ ⁻ , —CO ₂ H, —CO ₂ M ² , — It may be substituted with COO ⁻ , —CO ₂ R ⁶⁸ , —SO ₃ R ⁶⁸ , —SO ₂ NHR ⁶⁹ or —SO ₂ NR ⁶⁹ R ⁷⁰ .
R ⁶⁵ and R ⁶⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ⁶⁷ is —SO ₃ H, —SO ₃ M ² , —SO ₃ ⁻ , —CO ₂ H, —CO ₂ M ² , —COO ⁻ , —CO ₂ R ⁶⁸ , —SO ₃ R ⁶⁸ , —SO _2. shows the NHR ⁶⁹ or -SO ₂ NR ⁶⁹ R ^70.
v represents an integer of 0 to 5, and when v is an integer of 2 or more, the plurality of R ⁶⁷ need not be the same.
R ⁶⁸ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. However, the saturated hydrocarbon group may be substituted with a halo group, and the saturated hydrocarbon group may have —O—, —CO— or —NR ⁶⁸ — between the C—C bonds. Good.
R ⁶⁹ and R ⁷⁰ each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or —X ^b , or R ⁶⁹ and R ⁷⁰ are bonded to each other. Represents a substituted or unsubstituted heterocyclic group having 2 to 10 carbon atoms. However, the alkyl group and the cycloalkyl group may be substituted with a hydroxyl group, a halo group, —X ^b , —CH═CH ₂ or —CH═CHR ⁶⁸ , and the alkyl group and cycloalkyl group may be C It may have —O—, —CO— or —NR ⁶⁸ — between —C bonds, and this heterocyclic group may be substituted with —R ⁶⁸ , —OH or —X ^b .
M ² represents a sodium atom or a potassium atom.
X ^b represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms, and the aromatic hydrocarbon group and the aromatic heterocyclic group are —OH, —R _{^{68, -OR 68, -NO 2,}} -CH = CH 2, may be substituted by -CH = CHR ⁶⁸ or halo groups.
However, any two or more of R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁷ have —SO ₃ ^— or —COO ⁻ . ]

The hydrocarbon groups according to R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are the same as the hydrocarbon groups according to R ^{1 to} R ¹⁴ , and the specific configuration thereof is as described above.
R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The saturated hydrocarbon group and aromatic hydrocarbon group, the alkyl group according to R ⁶⁵ and R ⁶⁶ , the saturated hydrocarbon group according to R ⁶⁸ , the alkyl group according to R ⁶⁹ and R ⁷⁰ , the cycloalkyl group and the heterocyclic group, And the aromatic hydrocarbon group and aromatic heterocyclic group relating to ^Xb are the aromatic hydrocarbon group, alkyl group, saturated hydrocarbon group, heterocyclic group and aromatic heterocyclic group described in the above formula (4). It is possible to employ the same configuration as that described above, and the preferred mode is also as described in the above formula (4).
The xanthene chromophore represented by the above formula (6) is one in which any two or more of R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁷ have —SO ₃ ^— or —COO ⁻ . However, as specific embodiments thereof, two or more of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are aromatic hydrocarbon groups substituted with —SO ₃ ^— or —COO ^— , or R ⁶⁷ is -SO ₃ ^- and -COO ^- 2 or more in either selected from or R ^61, R ^62, R ⁶³ and one or more of the R ⁶⁴ is -SO ₃ ^- or -COO ^- aromatic substituted with carbonized An embodiment in which it is a hydrogen group and one or more of R ⁶⁷ is —SO ₃ ^— or —COO ^— is exemplified.

  Representative examples of the xanthene chromophore represented by the above formula (6) include a chromophore represented by the following formula.

  Moreover, as a triarylmethane chromophore, the chromophore represented by following formula (7) or the chromophore represented by following formula (8) can be mentioned.

[In the formulas (7) and (8),
R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ and R ⁷⁶ each independently represent a hydrogen atom or a hydrocarbon group. However, hydrocarbon group, ^{halo, -R 79, -OH, -OR 79} , -SO 3 H, -SO 3 M 3, -SO 3 -, -CO 2 H, -CO 2 M 3, - It may be substituted with COO ⁻ , —CO ₂ R ⁷⁹ , —SO ₃ R ⁷⁹ , —SO ₂ NHR ⁷⁹ or —SO ₂ NR ⁷⁹ R ⁸⁰ .
R ⁷⁷ and R ⁷⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ⁷⁹ and R ⁸⁰ each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or —X ^c , or R ⁷⁹ and R ⁸⁰ are bonded to each other. Represents a substituted or unsubstituted heterocyclic group having 2 to 10 carbon atoms. However, the alkyl group and cycloalkyl group may be substituted with a hydroxyl group, a halo group, —X ^c , —CH═CH ₂ or —CH═CHR ⁷⁹ , and the alkyl group and cycloalkyl group may be C There may be —O—, —CO— or —NR ⁷⁹ — between the —C bonds, and the heterocyclic group may be substituted with —R ⁷⁹ , —OH or —X ^c .
M ³ represents a sodium atom or a potassium atom.
X ^c represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms, and the aromatic hydrocarbon group and the aromatic heterocyclic group are —OH, —R ⁷⁹ , —OR ⁷⁹ , —NO ₂ , —CH═CH ₂ , —CH═CHR ⁷⁹ or a halo group may be substituted.
However, one or more of R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ and R ⁷⁶ have —SO ₃ ^— or —COO ^— . ]

The hydrocarbon groups according to R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ and R ⁷⁶ are the same as the hydrocarbon groups according to R ^{1 to} R ¹⁴ , and the specific configuration thereof is as described above. It is.
R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ and R ⁷⁶ are preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. An aromatic hydrocarbon group having 6 to 10 carbon atoms is more preferable. In a more preferred embodiment, R ⁷¹ , R ⁷³ and R ⁷⁵ are hydrogen atoms, R ⁷² , R ⁷⁴ and R ⁷⁶ are aromatic hydrocarbon groups having 6 to 10 carbon atoms, and any one or more Is an aromatic hydrocarbon group having —SO ₃ ^— or —COO ^— as a substituent.
R ⁷⁷ and R ⁷⁸ are preferably a hydrogen atom.

  Specific examples of the chromophore represented by the above formula (7) or (8) include the following chromophores.

  As the anionic chromophore, an anion having an azo chromophore represented by the following formula (9) as a ligand can be used, and specific examples include an anion represented by the following formula (10).

[In Formula (9),
Ring Z ⁵ represents, independently of each other, a substituted or unsubstituted heterocyclic group,
Ring Z ⁶ represents, independently of each other, a substituted or unsubstituted aromatic hydrocarbon group,
t ¹ and t ² each independently represent 0 or 1. ]

[In Formula (10),
Ring Z ⁵ represents, independently of each other, a substituted or unsubstituted heterocyclic group,
Ring Z ⁶ represents, independently of each other, a substituted or unsubstituted aromatic hydrocarbon group,
M represents chromium, cobalt, iron, nickel, copper or aluminum;
t ¹ and t ² each independently represent 0 or 1. ]

The heterocyclic group according to ring Z ⁵ may be a monocyclic heterocyclic group or a polycyclic heterocyclic group. Specific examples of such a heterocyclic group include the heterocyclic groups having 2 to 10 carbon atoms exemplified in the formula (4). Among these, a nitrogen-containing aromatic heterocyclic group is preferable, and a pyridyl group and a pyrazolyl group are more preferable. Such a heterocyclic group may have a substituent, and examples of the substituent include a halo group, a hydroxyl group, an amino group, a carboxyl group, an isocyanate group, a cyano group, a formyl group, a nitro group, a dialkylamino group, and a diarylamino group. Group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylthio group, arylthio group, trialkylsilyl group, sulfanyl group, allyl group, alkylsulfonyl group, alkylsulfamoyl group, alkyl group, aromatic group having 6 to 20 carbon atoms Group hydrocarbon groups and the like. Especially, as a substituent of a heterocyclic group, a hydroxyl group, an amino group, a carboxyl group, an isocyanate group, a cyano group, a C1-C20 alkyl group, and a phenyl group are preferable. In addition, the alkyl group may have a linking group containing an atom other than a carbon atom, a hydrogen atom or a halogen atom between C—C bonds, and examples of the linking group include —O—, —S—, — CO—, —COO—, —CONH—, —SO ₂ — and the like can be mentioned. In addition, the position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different.

The aromatic hydrocarbon group of the ring Z ^6, preferably 6 to 20 carbon atoms, the number 6 to 10 and more preferably carbon. Specific examples of the aromatic hydrocarbon group are as described above. Of these, a phenyl group is preferred. Examples of the substituent of the aromatic hydrocarbon group include a sulfo group, a sulfamoyl group, and an alkylamide group in addition to those exemplified in the description of the heterocyclic group related to the ring Z ⁵ . Among these, a halo group, a hydroxyl group, an amino group, a carboxyl group, an isocyanate group, a cyano group, a nitro group, an alkoxy group, a sulfo group, an alkylsulfonyl group, a sulfamoyl group, an alkylsulfamoyl group, an alkylamide group, and an alkyl group are preferable. In addition, the position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different.

In the embodiment (a-2), the structural unit having a cationic group can be derived from an unsaturated monomer having a cationic group and not having a dye structure.
Examples of the cationic group include an ammonium cation, a phosphonium cation, a sulfonium cation, an iodonium cation, and a diazonium cation. Of these, an ammonium cation is preferred.
Examples of the unsaturated group include (meth) acryloyloxy group, vinylaryl group, vinyloxy group, allyl group and the like. Among these, a (meth) acryloyloxy group and an allyl group are preferable, and a (meth) acryloyloxy group is more preferable.

  Examples of the unsaturated monomer having a cationic group and not having a dye structure include those represented by the following formula (11).

[In Formula (11),
R ^{81 to} R ⁸³ each independently represent a hydrogen atom or a hydrocarbon group,
W ² represents an unsaturated group,
Y ² represents a single bond or a divalent organic group. ]

The hydrocarbon groups according to R ^{81 to} R ⁸³ are the same as the hydrocarbon groups according to R ^{1 to} R ¹⁴ , and the specific configuration thereof is as described above.
R ^{81 to} R ⁸³ are preferably a hydrocarbon group having 1 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a 7 to 10 carbon atom. Aromatic hydrocarbon-substituted aliphatic hydrocarbon groups are preferred. Among the aliphatic hydrocarbon groups having 1 to 6 carbon atoms, alkyl groups having 1 to 4 carbon atoms are preferable, and methyl groups and ethyl groups are more preferable. Among the aromatic hydrocarbon groups having 6 to 10 carbon atoms, a phenyl group and a naphthyl group are preferable, and among the aromatic hydrocarbon-substituted aliphatic hydrocarbon groups having 7 to 10 carbon atoms, a benzyl group is preferable.
The unsaturated groups of the W ^2, (meth) acryloyloxy group, an allyl group is preferable, (meth) acryloyloxy group is more preferable.
Examples of the divalent organic group related to Y ² include the same groups as those described above for Y ^1. Among them, an alkanediyl group having 1 to 6 carbon atoms, an alkanediyl group having 1 to 6 carbon atoms, and —O— A group formed by combining is preferred. Among the alkanediyl groups having 1 to 6 carbon atoms, alkanediyl groups having 1 to 4 carbon atoms are preferable, and ethane-1,2-diyl groups and propane-1,3-diyl groups are more preferable. Among the groups formed by combining an alkanediyl group having 1 to 6 carbon atoms and —O—, a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and —O— is preferable, and ethane-1,2 -A diyloxy group and a propane-1,3-diyloxy group are more preferable.

  Moreover, the structural unit having a cationic group can be derived from an unsaturated monomer having an ammonium cation. Specific examples include (meth) acryloyl such as (meth) acryloyloxyethyltrimethylammonium, (meth) acryloyloxyethyltriethylammonium, (meth) acryloyloxyethyldimethylbenzylammonium, (meth) acryloyloxyethylmethylmorpholinoammonium and the like. Quaternary ammonium having an oxy group; quaternary ammonium having a (meth) acryloylamino group such as (meth) acryloylaminopropyltrimethylammonium, (meth) acryloylaminoethyltriethylammonium, (meth) acryloylaminoethyldimethylbenzylammonium; dimethyl Examples include diallylammonium and trimethylvinylphenylammonium.

Next, the aspect of (a-3) is demonstrated.
The structural unit having an electrically neutral chromophore can be derived from an unsaturated monomer having an electrically neutral chromophore.
Examples of electrically neutral chromophores include triarylmethane chromophore, polymethine chromophore, azo chromophore, diarylmethane chromophore, quinoneimine chromophore, anthraquinone chromophore, phthalocyanine chromophore, subphthalocyanine chromophore, xanthene. Examples include chromophores, squarylium chromophores, and quinophthalone chromophores. These chromophores do not have a functional group having a positive charge and a functional group having a negative charge, or even if they have a functional group having a positive charge and a functional group having a negative charge. The total number of negative charges is the same. Among them, triarylmethane chromophore, anthraquinone chromophore, phthalocyanine chromophore, subphthalocyanine chromophore, xanthene chromophore, squarylium chromophore, and quinophthalone chromophore are preferable.

  Specific examples of the electrically neutral chromophore having the same number of positively charged functional groups and negatively charged functional groups include xanthene chromophore represented by the following formula (12). Can do.

[In Formula (12),
R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ each independently represent a hydrogen atom or a hydrocarbon group. However, the hydrocarbon group is a halo group, —R ⁹⁸ , —OH, —OR ⁹⁸ , —SO ₃ H, —SO ₃ M ⁴ , —SO ₃ ⁻ , —CO ₂ H, —CO ₂ M ⁴ , — It may be substituted with COO ⁻ , —CO ₂ R ⁹⁸ , —SO ₃ R ⁹⁸ , —SO ₂ NHR ⁹⁹ or —SO ₂ NR ⁹⁹ R ¹⁰⁰ .
R ⁹⁵ and R ⁹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ⁹⁷ is —SO ₃ H, —SO ₃ M ⁴ , —SO ₃ ⁻ , —CO ₂ H, —CO ₂ M ⁴ , —COO ⁻ , —CO ₂ R ⁹⁸ , —SO ₃ R ⁹⁸ , —SO ₂ NHR ⁹⁹ or an -SO ₂ NR ⁹⁹ R ^100.
w represents an integer of 0 to 5, and when w is an integer of 2 or more, the plurality of R ⁹⁷ need not be the same.
R ⁹⁸ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. However, the saturated hydrocarbon group may be substituted with a halo group, and the saturated hydrocarbon group may have —O—, —CO— or —NR ⁹⁸ — between the C—C bonds. Good.
R ⁹⁹ and R ¹⁰⁰ each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or —X ^d , or R ⁹⁹ and R ¹⁰⁰ are bonded to each other. Represents a substituted or unsubstituted heterocyclic group having 2 to 10 carbon atoms. However, the hydrogen atom contained in the alkyl group and cycloalkyl group may be substituted with a hydroxyl group, a halo group, —X ^d , —CH═CH ₂ or —CH═CHR ⁹⁸ , The alkyl group may have —O—, —CO— or —NR ⁹⁸ — between the C—C bonds, and the heterocyclic group is substituted with —R ⁹⁸ , —OH or —X ^d. May be.
M ⁴ represents a sodium atom or a potassium atom.
X ^d represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group and aromatic heterocyclic group is It may be substituted with —OH, —R ⁹⁸ , —OR ⁹⁸ , —NO ₂ , —CH═CH ₂ , —CH═CHR ⁹⁸ or a halo group.
However, any one of R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ and R ⁹⁷ has —SO ₃ ^— or —COO ^— . ]

The hydrocarbon groups according to R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ are the same as the hydrocarbon groups according to R ^{1 to} R ¹⁴ , and the specific configuration thereof is as described above.
R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ are preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The saturated hydrocarbon group and the aromatic hydrocarbon group, the alkyl group according to R ⁹⁵ and R ⁹⁶ , the saturated hydrocarbon group according to R ⁹⁸ , the alkyl group according to R ⁹⁹ and R ¹⁰⁰ , the cycloalkyl group and the heterocyclic group, And the aromatic hydrocarbon group and aromatic heterocyclic group relating to X ^d are the aromatic hydrocarbon group, alkyl group, saturated hydrocarbon group, heterocyclic group and aromatic heterocyclic group described in the above formula (4). It is possible to employ the same configuration as that described above, and the preferred mode is also as described in the above formula (4).
The xanthene chromophore represented by the above formula (12) is one in which any one of R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ and R ⁹⁷ has —SO ₃ ^— or —COO ^— . As specific embodiments thereof, any one of R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ is an aromatic hydrocarbon group substituted with —SO ₃ ^— or —COO ^— , or R ⁹⁷ is -SO ₃ ^- and -COO ^- include aspects is one selected from the.

  Moreover, the subphthalocyanine chromophore represented by following formula (13) can be mentioned.

[In Formula (13),
R ^{101 to} R ¹¹² each independently represent a hydrogen atom, a halo group, an alkyl group, an aryl group, a hydroxy group, a sulfanyl group, an amino group, an alkoxy group, an aryloxy group, or an alkylthio group.
^XP represents a coordinating anion. ]

R ^{101 to} R ¹¹² are preferably a halo group, an alkyl group, or an aryloxy group, more preferably a fluorine atom, a chlorine atom, an alkyl group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 30 carbon atoms, and a chlorine atom. Further, an alkyl group having 1 to 10 carbon atoms and an aryloxy group having 6 to 20 carbon atoms are more preferable. The alkyl group may have a substituent, and examples thereof include a halo group, a hydroxyl group, an amino group, a carboxyl group, an isocyanate group, a cyano group, and a nitro group. The aryloxy group may have a substituent, and examples thereof include a methyl group and a t-butyl group. In addition, the position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different.
The coordinating anions according to X ^P, for example, fluorine anion, chlorine anion, bromine anion, iodine anion, a perchlorate anion, thiocyanate anion, hexafluorophosphate anion, hexafluoroantimonate anion, tetrafluoroborate Inorganic anions such as anions; carboxylate anions such as acetate anions and benzoate anions; organic sulfonate anions such as benzenesulfonate anions, toluenesulfonate anions, trifluoromethanesulfonate anions; octyl phosphate anions, dodecyl phosphate anions, Organic phosphate anions such as octadecyl phosphate anion, phenyl phosphate anion, nonylphenyl phosphate anion; phenolate, 2,4-di-t-butylphenolate, 4-((meth) acryloyloxy) phenolate, 4-cal Examples include phenolate anions (phenol or a conjugate base of a phenol derivative) such as boxyphenolate and 1-methylpyridine-1-ium-3-olate. Among these, a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a perchlorate anion, a carboxylate anion, a phosphate anion, and a phenolate anion are preferable, and a perchlorate anion, a carboxylate anion, and a phenolate anion are more preferable.

  Specific examples of the subphthalocyanine chromophore represented by the above formula (13) include the following chromophores.

  On the other hand, specific examples of the electrically neutral chromophore that does not have a functional group having a positive charge and a functional group having a negative charge include, for example, a phthalocyanine chromophore represented by the following formula (14). Can do.

[In Formula (14),
R ^{121 to} R ¹³⁶ each independently represent a hydrogen atom, —SO ₂ NR ¹³⁷ R ¹³⁸ , —SR ¹³⁸ , or —OR ¹³⁸ . R ¹³⁷ represents a hydrogen atom or a hydrocarbon group, and R ¹³⁸ represents a hydrocarbon group.
M ^a represents Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Pb, Cu, Ni, a metal selected from Co and Fe. ]

The hydrocarbon groups according to R ¹³⁷ and R ¹³⁸ are the same as the hydrocarbon groups according to R ^{1 to} R ¹⁴ , and the specific configuration thereof is as described above.
R ¹³⁷ is preferably a hydrogen atom or an alkyl group having 3 to 20 carbon atoms, and R ¹³⁸ is preferably an alkyl group having 3 to 20 carbon atoms. Such an alkyl group may be either a straight chain or a branched chain, and may have a substituent. The position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different.

  Specific examples of the phthalocyanine chromophore represented by the above formula (14) include the following chromophores.

  Examples of the anthraquinone chromophore include C.I. I. Bat Blue 4, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. The coloring part of anthraquinone dyes such as Disperse Blue 60 can be mentioned.

  The squarylium chromophore is not particularly limited as long as it is electrically neutral, and examples thereof include a coloring portion of a compound described in paragraphs [0132] to [0135] of JP2012-013945A.

  The quinophthalone chromophore is not particularly limited as long as it is electrically neutral, and examples thereof include a coloring portion of a compound described in paragraphs [0084] to [0115] of JP2013-209614A.

Examples of the unsaturated group include (meth) acryloyloxy group, vinylaryl group, vinyloxy group, allyl group and the like. Of these, a (meth) acryloyloxy group is preferable.
The structural unit having an electrically neutral chromophore can be derived, for example, from an unsaturated monomer represented by the following formula (15).

[In Formula (15),
R ¹⁴⁰ represents a hydrogen atom or a methyl group.
X ⁵ represents a direct bond, a divalent hydrocarbon group, or a divalent group formed by combining the divalent hydrocarbon group and one or more linking groups containing atoms other than carbon atoms and hydrogen atoms. .
Q represents an electrically neutral chromophore. ]

  Q includes triarylmethane chromophore, polymethine chromophore, azo chromophore, diarylmethane chromophore, quinone imine chromophore, anthraquinone chromophore, phthalocyanine chromophore, subphthalocyanine chromophore, xanthene chromophore, squarylium chromophore, or quinophthalone chromophore. A group obtained by removing one hydrogen atom from the group can be mentioned. Among them, a group obtained by removing one hydrogen atom from a triarylmethane chromophore, anthraquinone chromophore, phthalocyanine chromophore, subphthalocyanine chromophore, xanthene chromophore, or quinophthalone chromophore is preferable.

Examples of the divalent hydrocarbon group related to X ⁵ include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. The divalent aliphatic hydrocarbon group may be either linear or branched, and the divalent aliphatic hydrocarbon group and the divalent alicyclic hydrocarbon group may be saturated hydrocarbons or unsaturated hydrocarbons. It may be a group.

As a bivalent aliphatic hydrocarbon group, an alkanediyl group and an alkenediyl group are mentioned, for example, 1-20 are preferable, 2-12 are more preferable, and 2-6 are especially preferable. Specific examples include the same ones as described above.
As a bivalent alicyclic hydrocarbon group, a cycloalkylene group and a cycloalkenylene group are mentioned, for example, 3-20 are preferable and 3-12 are more preferable. Specific examples include the same ones as described above.
The divalent aromatic hydrocarbon group may be a monocyclic aromatic hydrocarbon group or a polycyclic aromatic hydrocarbon group, and preferably has 6 to 14 carbon atoms. Specific examples include the same ones as described above.

In the divalent group formed by combining a divalent hydrocarbon group and one or more linking groups containing atoms other than carbon atoms and hydrogen atoms, examples of the linking group include -O- and -S-. , —SO ₂ —, —CO—, —COO—, —OCO—, —CONR ^X — (R ^X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —N═, —NR ^X —. (R ^X has the same meaning as described above), and one or more types can be included. The bonding position of the linking group is arbitrary, and for example, it can have a terminal of a divalent hydrocarbon group or between C-C bonds, but among them, it is preferable to have one terminal or between C-C bonds. In addition, a divalent hydrocarbon group and the linking group may be bonded to form a ring structure.

Specific examples of the divalent hydrocarbon group having the linking group between C—C bonds include, for example, —CH ₂ —CH ₂ —CH ₂ —COO—CH ₂ —CH ₂ —, —CH ₂ —CH ( _{-CH 3) -CH 2 -COO-CH} 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -OCO-CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -CH 2 -COO _{-CH 2 -CH (CH 2 -CH 3} ) -CH 2 -CH 2 -CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -O-CH 2 -CH (CH 2 -CH 3) - _{CH 2 -CH 2 -CH 2 -CH 2} -, - (CH 2) 5 -COO- (CH 2) 11 -CH 2 -, - CH 2 -CH 2 -CH 2 -C (COO-CH 2 -CH _{3) 2 -, - CH 2} -CH 2 -O-CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -O-CH 2 -CH 2 -, - (CH 2 -CH 2 -O) _n -C ₂ - (n is an integer from 1 to _{8), - (CH 2 -CH 2} -CH 2 -O) m -CH 2 - (m is an integer of 1 to 5), - CH ₂ -CH ( _{CH 3) -O-CH 2 -CH} 2 -, - CH 2 -CH (OCH 3) -, - CH 2 -CH 2 -COO-CH 2 -CH 2 -O-CH 2 -CH (CH 2 -CH _{3) -CH 2 -CH 2 -CH 2} -CH 2 -, - CH 2 -CH 2 -CH 2 -O-CO-CH 2 -CH (CH 2 -CH 3) -CH 2 -CH 2 -CH 2 _{-CH 2 -, - CH 2 -CH} 2 -COO-CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH (CH 2 -CH 3) -CH 2 -CH 2 -CH 2 _{-CH 2 -, - CH 2 -CH} 2 -NH-COO-CH 2 -CH 2 -, - CH 2 -CH 2 -OCO-CH 2 - is and the like, are limited to Na Yes.

Specific examples of the group having a ring structure formed by bonding a divalent hydrocarbon group and the linking group include the following, but are not limited thereto. Note that * represents a bond to Q or O (oxygen atom) adjacent the X ^5.

  The divalent hydrocarbon group may have a substituent. Examples of the substituent include a halo group, a hydroxyl group, an amino group, a carboxyl group, an isocyanate group, a nitro group, an alkoxyl group, and an aryloxy group. Specific examples of the halo group and alkoxyl group include the same ones as described above. The aryloxy group is preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof include a phenoxy group and a benzyloxy group. The alkoxyl group and aryloxy group may have a substituent, and examples of the substituent include a halo group, a hydroxyl group, an amino group, a carboxyl group, an isocyanate group, a nitro group, and a sulfanyl group. In addition, the position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different.

  The dye multimer of the embodiments of (a-1) to (a-3) has a structural unit α having a dye structure. Examples of the structural unit α include the following formulas (16) to (18). The structural unit represented by each can be mentioned.

[In Formula (16)-(18),
X ¹ and Y ¹ are synonymous with X ¹ and Y ^{1 according} to the formula (5),
Dye ⁺ represents a cationic chromophore,
Dye ⁻ represents an anionic chromophore,
R ¹⁴⁰ represents a hydrogen atom or a methyl group,
R ⁸¹ to R ^83, and Y ^2, R ⁸¹ to R ⁸³ according to the equation (11), and Y ² in the above formula,
X ⁵ and Q are synonymous with X ⁵ and Q according to the formula (15). ]

The (A) dye multimer according to the present invention may have a structural unit β having no dye structure in addition to the structural unit α having a dye structure.
Examples of the unsaturated monomer that gives the structural unit β having no dye structure include (meth) acrylamide, (meth) acrylic acid ester, aromatic vinyl compound, polyhydric alcohol (meth) acrylic acid ester, N -Substituted maleimide, vinyl ether, ethylenically unsaturated monomer having an oxygen-containing saturated heterocyclic group, macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain, an unsaturated compound represented by the following formula (19) Examples thereof include saturated monomers and unsaturated monomers that generate isocyanate groups by heating represented by the following formula (20) (hereinafter also referred to as “unsaturated monomer (d1)”). In addition, 1 type (s) or 2 or more types can be used for an unsaturated monomer (d1).

  As the (meth) acrylamide, N-substituted (meth) acrylamide is preferable. For example, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N′-dimethyl (meth) acrylamide, N, N′— Examples include diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nt-octyl (meth) acrylamide.

Specific examples of (meth) acrylic acid esters include the following.
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, pentyl methacrylate, isoamyl acrylate, hexyl methacrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) ) Alkyl (meth) acrylates such as acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate;
Alkenyl (meth) acrylates such as vinyl (meth) acrylate and allyl (meth) acrylate;
Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Hydroxylalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate;
Dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, diethylaminobutyl (meth) acrylate, dimethylaminoethoxyethyl ( Aminoalkyl (meth) acrylates such as (meth) acrylate, dimethylaminoethoxypropyl (meth) acrylate, diethylaminobutoxybutyl (meth) acrylate;
Alicyclic hydrocarbon groups such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, etc. (Meth) acrylic acid ester having

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, acenaphthylene, and the like.
Examples of the (meth) acrylic acid ester of polyhydric alcohol include polyethylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene Examples include glycol (polymerization degree 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, glycerol mono (meth) acrylate, and the like.
Examples of the N-substituted maleimide include N-phenylmaleimide and N-cyclohexylmaleimide.
Examples of the vinyl ether include cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, and the like.

Examples of the ethylenically unsaturated monomer having an oxygen-containing saturated heterocyclic group include:
Glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, 2,3-bis Ethylene having an oxiranyl group such as (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl (meth) acrylate Unsaturated monomers;
(Vinyloxyalkyl) alkyloxetanes such as 3- (vinyloxymethyl) -2-methyloxetane, 2- (vinyloxyethyl) -2-methyloxetane;
(Meth) acryloyloxyalkyl oxetanes such as 3-[(meth) acryloyloxymethyl] oxetane, 2- [2- (meth) acryloyloxyethyl] oxetane;
3-[(meth) acryloyloxymethyl] -2-methyloxetane, 2- [2- (meth) acryloyloxyethyl] -2-ethyloxetane, 2-[(meth) acryloyloxymethyl] -2-phenyloxetane [(Meth) acryloyloxyalkyl] phenyloxetane, 4- [3- (3-ethyloxetane-3-ylmethoxy) propoxy] styrene, 4- [7- (3-ethyloxetane-3-ylmethoxy) heptyloxy] styrene An ethylenically unsaturated monomer having an oxetanyl group such as
(Meth) acrylic acid ester having a 3,4-epoxycyclohexyl group such as 3,4-epoxycyclohexylmethyl (meth) acrylate,
Examples thereof include (meth) acrylic acid esters having a tetrahydrofuranyl group such as tetrahydrofurfuryl methacrylate.

  Examples of the macromonomer include macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane. it can.

  Among them, as the unsaturated monomer (d1), at least one selected from (meth) acrylic acid esters and acrylamide is preferable, and (a) the glass transition temperature is 120 ° C. or less when a homopolymer is used. More preferred is at least one selected from (meth) acrylic acid esters and (b) acrylamide. Here, in the present specification, “the glass transition temperature is 120 ° C. or lower when a homopolymer is used” means that the glass transition temperature of a homopolymer obtained by homopolymerizing a (meth) acrylic acid ester is 120 ° C. or lower. The glass transition temperature is JIS- at a heating rate of 10 ° C./min under a nitrogen stream using DSC (differential scanning calorimetry, measuring instrument: Seiko DSC6200) for the solid content of the homopolymer. It is a midpoint glass transition temperature measured according to K7121. The glass transition temperature when used as a homopolymer is preferably -100 to 120 ° C, more preferably -70 to 0 ° C, and still more preferably -70 to -20 ° C. By setting the glass transition temperature in this way, improvement in developability can be realized at a higher level.

Specific examples of the unsaturated monomer that gives such a glass transition temperature include, for example, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) ) Acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, etc. C _8-18 alkyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) Examples thereof include alkoxy-containing (meth) acrylic acid esters such as acrylate and ethoxyethoxyethyl (meth) acrylate. Among these, C _10-18 alkyl (meth) acrylate and alkoxyalkyl (meth) acrylic acid ester are preferable from the viewpoint that the effects of the present invention can be easily enjoyed.

  Examples of the unsaturated monomer that gives the structural unit β having no dye structure include the unsaturated monomer represented by the following formula (19) and the unsaturated monomer represented by the following formula (20). It is preferable to have a structural unit derived from at least one unsaturated monomer selected. Such unsaturated monomers have the property of generating isocyanate groups upon heating and promptly causing an addition reaction or condensation reaction with a compound having an active hydrogen group, so that a crosslinked structure is formed between molecules or within a molecule. Can do. Thereby, the crosslinking density of the colored cured film is increased, and not only can the migration be further suppressed, but also the solvent resistance can be remarkably improved.

[In the formulas (19) and (20),
R ¹⁴¹ represents a hydrogen atom or a methyl group,
R ¹⁴² , R ¹⁴³ and R ¹⁴⁴ each independently represent a hydrocarbon group,
R ¹⁴⁵ is, -CO- or -COOR ¹⁴⁶ - indicates,
R ¹⁴⁶ represents an alkylene group having 1 to 10 carbon atoms which may contain at least one selected from an ether bond and a phenylene group.
x shows the integer of 0-3. However, when x is 2 or more, the plurality of R ¹⁴⁴ need not be the same. ]

The hydrocarbon groups according to R ¹⁴² , R ¹⁴³ and R ¹⁴⁴ are the same as the hydrocarbon groups according to R ^{1 to} R ¹⁴ , and the specific configuration thereof is as described above.
R ¹⁴² , R ¹⁴³ and R ¹⁴⁴ are preferably an aliphatic hydrocarbon group, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms.

R ¹⁴⁵ can be appropriately selected from —CO— and —COOR ¹⁴⁶ —.
The alkylene group for R ¹⁴⁶ may be either a straight chain or a branched chain. Specific examples of the alkylene group include the same ones as described above. Especially, a linear alkylene group is preferable, a C1-C5 alkylene group is more preferable, and a methylene group and ethylene group are still more preferable.

Contain an ether bond according to R ¹⁴⁶ is an alkylene group which may having 1 to 10 carbon atoms, any carbons constituting the alkylene group - and the oxygen atom that may be inserted between carbon bond. For _{example, -CH 2 -O- (CH 2)} 3 -, - (CH 2) 2 -O- (CH 2) 2 -, - (CH 2) 3 -O-CH 2 -, - CH 2 -O- (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —O—CH ₂ —, —CH ₂ —O—CH ₂ —, among others, —CH ₂ —O— (CH ₂ ) ₃ —, — ( CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —O—CH ₂ —, —CH ₂ —O— (CH ₂ ) ₂ — are preferred, — (CH ₂ ) ₂ —O. - _{(CH 2) 2} - is more preferable.

The alkylene group having 1 to 10 carbon atoms which may contain a phenylene group according to R ¹⁴⁶ means that a phenylene group may be inserted between any carbon-carbon bonds constituting the alkylene group. For _{example, -CH 2 -Ph- (CH 2)} 3 -, - (CH 2) 2 -Ph- (CH 2) 2 -, - (CH 2) 3 -Ph-CH 2 -, - CH 2 -Ph- (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —Ph—CH ₂ —, —CH ₂ —Ph—CH ₂ —, among others, —CH ₂ —Ph— (CH ₂ ) ₃ —, — ( _{CH 2) 2 -Ph- (CH 2} ) 2 -, - (CH 2) 3 -Ph-CH 2 -, - CH 2 -Ph- (CH 2) 2 - is preferably, _{- (CH} 2) 2 -Ph - _{(CH 2) 2} - is more preferable. In the present specification, “Ph” means an unsubstituted 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene group.

Further, in R ^146, _{e.g., -Ph-O -, - (} CH 2) 2 -Ph-O -, - Ph-O- (CH2) 2 -, - (CH 2) 2 -Ph-O- (CH ₂ ) Like the _2- , it may contain both the ether bond and the phenylene bond.

R ¹⁴¹ can be appropriately selected from a hydrogen atom and a methyl group.
x is an integer of 0 to 3, but 1 or 2 is preferable.

  Specific examples of the compound represented by the formula (19) include the following.

  Specific examples of the compound represented by the formula (20) include the following.

  The compound represented by the above formula (19) or (20) can be produced by a known method. Examples of the compound represented by the above formula (19) include Japanese Patent No. 58158871, JP It can be produced by the methods described in JP-A-2007-270216 and JP-A-2004-285272, and the compound represented by the above formula (20) is, for example, a method described in JP-A-2006-151967. Can be manufactured.

  The structural unit β that does not have a dye structure is a structural unit that does not contain an alkali-soluble group such as a carboxy group, and prevents the structural unit α that has a dye structure while ensuring alkali solubility and migration. Since more crosslinkable structural units can be introduced, it is preferable in terms of improving color development and suppressing dye transfer.

  When the dye multimer of the embodiments (a-1) to (a-3) is a copolymer containing a structural unit α having a dye structure and a structural unit β having no dye structure, an appropriate structure is adopted. For example, the unsaturated monomer that gives each structural unit may be block-bonded or randomly bonded.

(A) The proportion of the structural unit α having a dye structure in the dye multimer is preferably 10% by mass or more, more preferably 25% by mass or more, and still more preferably 50% in all structural units from the viewpoint of color characteristics. It is at least mass%. The upper limit of the ratio is not particularly limited, and may be 100% by mass, but is preferably 100% by mass or less, more preferably 75% by mass or less, from the viewpoint of improving developability and suppressing migration. Preferably it is 60 mass% or less.
In addition, when the (A) dye multimer has a structural unit β that does not have a dye structure, the proportion of the structural unit β can be selected as appropriate, but is preferably 5 to 90% by mass in all the structural units, More preferably, it is 10-75 mass%, More preferably, it is 25-50 mass%.

  (A) The dye multimer is weight average molecular weight (hereinafter abbreviated as “Mw”) measured by gel permeation chromatography (hereinafter abbreviated as “GPC”) from the viewpoint of improving storage stability and solvent resistance. ) Is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, and the Mw of the dye multimer and the number average molecular weight (hereinafter abbreviated as “Mn”). The ratio (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. In the present specification, “Mw” is a weight average molecular weight in terms of polystyrene measured by GPC (elution solvent: DMF, flow rate 2.0 mL / min: temperature: 23 ° C.), and “Mn” is GPC. It is a number average molecular weight in terms of polystyrene measured by (elution solvent: DMF, flow rate: 2.0 mL / min, temperature: 23 ° C.).

The (A) dye multimer according to the present invention comprises, for example, an unsaturated monomer that gives a structural unit α having a dye structure and, if necessary, another copolymerizable unsaturated monomer, an alkali-soluble group. It can be produced by subjecting it to a polymerization reaction in the presence of at least one compound selected from the group consisting of a polymerization initiator having a chain transfer agent having an alkali-soluble group. That is, (i) an unsaturated monomer containing an unsaturated monomer having a dye structure in the presence of at least one compound selected from the group consisting of a polymerization initiator having an alkali-soluble group and a chain transfer agent having an alkali-soluble group. It can be produced by polymerizing a saturated monomer. Such a dye multimer has the following characteristics.
(I) It has a dye structure and has an alkali-soluble group at the end of the main chain, and the alkali-soluble group is a residue derived from at least one selected from the group consisting of a polymerization initiator and a chain transfer agent. And a group represented by the formula (I) or (II).
(Iii) a residue derived from at least one compound selected from the group consisting of a polymerization initiator having an alkali-soluble group and a chain transfer agent having an alkali-soluble group, and an unsaturated monomer having a dye structure And a structural unit. The residue derived from the polymerization initiator and the chain transfer agent preferably has a group represented by the above formula (I) or (II) from the viewpoints of suppressing dye transfer and improving developability.

The (A) dye multimer according to the present invention is, for example, in the presence of at least one compound selected from the group consisting of (ii) a polymerization initiator having an alkali-soluble group and a chain transfer agent having an alkali-soluble group. To obtain a polymer of an unsaturated monomer having an ionic group and an unsaturated monomer having no dye structure, and then an ion that is electrically different from the ionic group of the polymer. It can be produced by subjecting a dye compound having a functional group and the polymer to a salt exchange reaction. The dye multimer obtained by the reaction has the following characteristics.
(I) It has a dye structure and has an alkali-soluble group at the end of the main chain, and the alkali-soluble group is a residue derived from at least one selected from the group consisting of a polymerization initiator and a chain transfer agent. And a group represented by the formula (I) or (II).
(Iv) a group derived from at least one compound selected from the group consisting of a polymerization initiator having an alkali-soluble group and a chain transfer agent having an alkali-soluble group, an ionic group, and a dye structure It is a reaction product of a polymer having a structural unit derived from an unsaturated monomer and a dye compound having an ionic group that is electrically different from the ionic group. The residue derived from the polymerization initiator and the chain transfer agent preferably has a group represented by the above formula (I) or (II) from the viewpoints of suppressing dye transfer and improving developability.

In addition, when using the polymerization initiator which has an alkali-soluble group, the chain transfer agent which has an alkali-soluble group may be used independently, or you may use together with another chain transfer agent. Moreover, when using the chain transfer agent which has an alkali-soluble group, you may use together with the polymerization initiator which has an alkali-soluble group, or may use together with the other conventionally known polymerization initiator. In addition, ¹ H-NMR, a pyrolysis gas chromatograph mass spectrometer (PyGC-MS) etc. were used for whether it has group represented by said Formula (I) or (II) in the principal chain terminal, for example. It can be confirmed by analysis. More specifically, for example, a pyrogram obtained by decomposing a predetermined amount of a dye multimer at 700 ° C. using an EGA / PY-3030D multi-shot pyrolyzer (manufactured by Agilent Technologies) and simultaneously analyzing by FID and FPD It is possible to confirm whether or not it has an alkali-soluble group (for example, a carboxylic acid structure) derived from a polymerization initiator or a chain transfer agent at the terminal.

The polymerization initiator having an alkali-soluble group and the chain transfer agent having an alkali-soluble group are decomposed during polymerization to generate radicals, and the group having an alkali-soluble group is introduced into the main chain terminal of the polymer.
Although it will not specifically limit if it has an alkali-soluble group as a polymerization initiator, For example, the compound represented by a following formula (Ia) can be mentioned.

[In Formula (Ia),
R ^a and R ^b each independently represent a hydrogen atom or a monovalent substituent,
Z ^a represents a divalent linking group independently of each other. ]

Specific structures of R ^a , R ^b and Z ^a are as described in formula (I). The compound represented by the formula (Ia) is decomposed during polymerization to generate a radical having a structure represented by the formula (I).

  Specific examples of the compound represented by the formula (Ia) include the following compounds.

  Moreover, the following compounds can also be used as a polymerization initiator.

  Although it will not specifically limit as long as it has an alkali-soluble group as a chain transfer agent, For example, the compound represented by a following formula (IIa) can be mentioned.

In [Formula (IIa), Z ^b represents a divalent linking group. ]

The specific configuration of Z ^b is as described in the formula (II). The compound represented by the formula (IIa) is decomposed during polymerization to generate a radical having a structure represented by the formula (II).

  Specific examples of the compound represented by the formula (IIa) include the following compounds.

  It can be analyzed by pyrolysis GC / MS method that a polymerization initiator having an alkali-soluble group and a chain transfer agent having an alkali-soluble group are contained in the dye multimer. That is, 0.1 mg of the dye multimer was decomposed at 700 ° C. using an EGA / PY-3030D multi-shot pyrolyzer (manufactured by Agilent Technologies), and a pyrogram obtained by simultaneous analysis by FID and FPD was obtained. It can be seen that both linking and thio-linking carboxylic acid structures are included.

The coloring composition of the present invention can further contain another colorant together with the (A) dye multimer. Other colorants are not particularly limited, and colors and materials can be appropriately selected according to the use, and any of pigments, dyes, and natural pigments can be used.
In terms of obtaining pixels with high luminance and high color purity, organic pigments and organic dyes are preferable, and organic pigments are more preferable. Another colorant can contain 1 type (s) or 2 or more types.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists). Among them, the following color index (C.I. .) Those numbered can be preferably used.

C. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment red 264, C.I. I. Pigment red 269, C.I. I. Pigment red 279, C.I. I. Red pigments such as CI Pigment Red 280;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment green 59, C.I. I. Pigment green 62, C.I. I. Green pigments such as CI Pigment Green 63;
C. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment blue 79, C.I. I. Blue pigments such as CI Pigment Blue 80;
C. I. Pigment yellow 83, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 179, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 211, C.I. I. Pigment yellow 215, C.I. I. Yellow pigments such as CI Pigment Yellow 231;
C. I. Orange pigments such as CI Pigment Orange 38;
C. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Purple pigment such as CI Pigment Violet 29.
In addition, brominated diketopyrrolopyrrole pigments represented by the formula (Ic) of JP-T-2011-523433 can also be preferably used.

  Examples of inorganic pigments include carbon black and titanium black. In addition, JP-A-2001-081348, JP-A-2010-026334, JP-A-2010-237384, JP-A-2010-237369, JP-A-2011-006602, JP-A-2011-145346, etc. Can be mentioned.

  In the present embodiment, the pigment can be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Further, these pigments may be used by modifying the particle surface with a resin, if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. As a resin coating method on the carbon black surface, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed. The organic pigment may be used after the primary particles are refined by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Laid-Open No. 8-179111 can be employed.

  The dye is not particularly limited. For example, a known dye may be used in addition to a compound classified as a dye in the color index (CI; issued by The Society of Dyers and Colorists). Can do. Examples of such dyes include triarylmethane dyes, cyanine dyes, xanthene dyes, xanthene dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, quinophthalone dyes, coumarin dyes, pyrazolone dyes, quinoline dyes, nitro dyes, from the structural aspect of chromophores. And dyes, quinoneimine dyes, phthalocyanine dyes, squarylium dyes, and the like. Among these, from the viewpoint of heat resistance, triarylmethane dyes, cyanine dyes, xanthene dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are preferable.

  Moreover, in this invention, a well-known dispersing agent and a dispersing aid can also be contained with the other coloring agent mixed arbitrarily. Known dispersants include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. Dispersants, polyester dispersants, acrylic dispersants and the like can be mentioned, and examples of the dispersion aid include pigment derivatives.

  Such dispersants are commercially available. For example, acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK Corporation (BYK) Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (Lubrizol) As a polyethyleneimine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc. AJISPER PB822, Ajisper PB880, Ajisper PB881 (or, Ajinomoto Fine manufactured Techno Co.), etc., can be exemplified respectively.

  Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivative of quinophthalone.

  The content of the (A) dye multimer in the colored composition of the present invention is preferably 5 to 70% by mass, more preferably in the solid content of the colored composition from the viewpoint of improving developability and suppressing dye transfer. Is 10-60 mass%, More preferably, it is 15-50 mass%. Here, “solid content” in the present specification means components other than the solvent described later. The content of other colorants can be appropriately selected within a range not departing from the gist of the present invention.

-(B) Polymerizable compound-
In the present specification, the “polymerizable compound” refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. Specific examples of the ethylenically unsaturated group are as described above. Among them, the polymerizable compound is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups from the viewpoint of dye transfer suppression and heat resistance improvement. More preferred are compounds having two or more (meth) acryloyl groups. (B) One or two or more polymerizable compounds can be contained.

  Specific examples of the compound having two or more (meth) acryloyl groups include polyfunctional (meth) acrylate, which is a reaction product of an aliphatic polyhydroxy compound and (meth) acrylic acid, and a polyfunctional (meta) modified with caprolactone. ) Acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate which is a reaction product of (meth) acrylate having hydroxyl group and polyfunctional isocyanate, (meth) acrylate having hydroxyl group and acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group which is a reaction material with a thing can be mentioned.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and 3 such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of aliphatic polyhydroxy compounds having a valence higher than that. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol dimethacrylate. Etc. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. The alkylene oxide-modified polyfunctional (meth) acrylate is modified with at least one selected from bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide. Penta modified with at least one selected from trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide Penta modified with at least one selected from erythritol tri (meth) acrylate, ethylene oxide and propylene oxide Dipentaerythritol modified with at least one selected from dipentaerythritol penta (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from thrisitol tetra (meth) acrylate, ethylene oxide and propylene oxide Examples include hexa (meth) acrylate.

As a compound having two or more oxiranyl groups, an epoxy resin, a (co) polymer of an ethylenically unsaturated monomer having an oxiranyl group, or a polyfunctional epoxy resin such as EHPE3150 (manufactured by Daicel Corporation) is used. be able to.
Moreover, as a compound which has 2 or more oxetanyl groups, in addition to the (co) polymer of the ethylenically unsaturated monomer which has an oxiranyl group, Aron oxetane OXT-121, OXT-221 (above, Toagosei Co., Ltd.) Manufactured).
Other aliphatic conjugated diene compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2,3-dimethyl-1,3-butadiene; divinylbenzene Non-conjugated divinyl compounds such as diisopropenylbenzene and trivinylbenzene can also be used.

  Among these polymerizable compounds, polyfunctional (meth) acrylate, which is a reaction product of trivalent or higher aliphatic polyhydroxy compound and (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylate, polyfunctional urethane (Meth) acrylates, polyfunctional (meth) acrylates having a carboxyl group, and (co) polymers of ethylenically unsaturated monomers having an oxiranyl group are preferred. Among these, from the viewpoint of improving developability, heat resistance and solvent resistance, and suppressing dye transfer, among polyfunctional (meth) acrylates, which are a reaction product of a trivalent or higher aliphatic polyhydroxy compound and (meth) acrylic acid Then, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferable. Among polyfunctional (meth) acrylates having a carboxyl group, pentaerythritol triacrylate, succinic anhydride, And a reaction product of dipentaerythritol pentaacrylate and succinic anhydride is preferable.

  (B) As for content of a polymeric compound, 10-1,000 mass parts is preferable with respect to 100 mass parts of (A) pigment | dye multimer, 20-800 mass parts is more preferable, 100-500 mass parts is further. preferable. By setting it as such an aspect, the developability improvement and dye transfer suppression can be realized at a higher level.

-(C) Solvent-
(C) As a solvent, (A) dye multimer and (B) polymerizable compound constituting the coloring composition, other components are dispersed or dissolved, and do not react with these components, and have appropriate volatility. As long as it has, it can select and use suitably. As the solvent, an organic solvent is usually used. (C) 1 type (s) or 2 or more types of solvents can be contained.

As an organic solvent, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate ;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Other esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

  Among them, as the solvent (C), from the viewpoint of solubility, storage stability, coating property, etc., propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxy Tilpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate, etc. preferable.

  (C) Although content of a solvent is not specifically limited, The quantity from which the total density | concentration of each component except the solvent of the coloring composition becomes 5-50 mass% is preferable, and it becomes 10-40 mass%. The amount is more preferred. By setting it as such an aspect, the coloring agent dispersion liquid with favorable dispersibility and stability and the coloring composition with favorable applicability | paintability can be obtained.

-(D) Binder resin-
The coloring composition of this invention can contain (D) binder resin.
(D) Although it does not specifically limit as binder resin, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). And a copolymer of the other copolymerizable ethylenically unsaturated monomer (also referred to as “body (d2)”). In addition, (D) binder resin can use 1 type (s) or 2 or more types.

Examples of the unsaturated monomer (d2) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth). Examples thereof include acrylate and p-vinylbenzoic acid.
The unsaturated monomer (d2) can be used alone or in combination of two or more.

  Examples of the ethylenically unsaturated monomer copolymerizable with the unsaturated monomer (d2) include the aforementioned unsaturated monomer (d1). The unsaturated monomer (d1) can be used alone or in combination of two or more.

  In the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2), the copolymerization ratio of the unsaturated monomer (d2) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (d2) in such a range, a colored composition that is excellent in alkali developability and storage stability and can form a colored cured film with suppressed migration is obtained. Can do.

  Specific examples of the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

  (D) The binder resin has a polystyrene-equivalent Mw measured by GPC (elution solvent: tetrahydrofuran) of usually 1,000 to 100,000, preferably 3,000 to 50,000. Moreover, (D) Ratio (Mw / Mn) of Mw of binder resin and Mn becomes like this. Preferably it is 1.0-5.0, More preferably, it is 1.0-3.0. By setting it as such an aspect, it can be set as the coloring composition excellent not only in dye transfer suppression and a heat resistant improvement but also in alkali developability and storage stability.

  (D) The binder resin can be produced by a known method. For example, the method disclosed in JP-A-2003-222717, JP-A-2006-259680, International Publication No. 2007/029871, etc. Thus, the structure, Mw, and Mw / Mn can be controlled.

  (D) Content of binder resin is 10-1000 mass parts normally with respect to 100 mass parts of (A) pigment | dye multimers, Preferably it is 20-500 mass parts. By setting it as such an aspect, the developability improvement and dye transfer suppression can be realized at a higher level.

-Photopolymerization initiator-
The coloring composition of the present invention can contain a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of the polymerizable compound (B) by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. .

  Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone type compound, a polynuclear quinone type compound, a diazo type compound, an imide sulfonate type compound etc. can be mentioned.

  In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

  Among preferred photopolymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

  Specific examples of acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- And morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′- Bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 Examples include '5,5'-tetraphenyl-1,2'-biimidazole.

  In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

  Specific examples of triazine compounds include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) ) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy) Triazine compounds having a halomethyl group such as styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like. As commercial products of O-acyloxime compounds, NCI-831, NCI-930 (manufactured by ADEKA Corporation) and the like can also be used.

  In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  0.01-120 mass parts is preferable with respect to 100 mass parts of (B) polymeric compound, and, as for content of a photoinitiator, 1-100 mass parts is still more preferable. Thereby, improvement in developability and suppression of dye transfer can be realized at a higher level.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanedio Residue improving agents such as succinic acid; development of succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. And a siloxane oligomer having a reactive functional group disclosed in Japanese Patent Application Laid-Open No. 2008-2242078 and the like.

  The coloring composition of the present invention can be prepared by an appropriate method. For example, (A) a dye multimer and (B) a polymerizable compound can be prepared by mixing and dispersing together with a solvent and other components optionally added using a bead mill, a roll mill or the like.

Colored cured film and method for forming the same The colored cured film of the present invention is a cured product formed using the colored composition of the present invention. Specifically, each color pixel used in a display element or a solid-state image sensor, black Means matrix, black spacer, infrared cut filter, etc.

Hereinafter, the colored cured film used for the color filter which comprises a display element and a solid-state image sensor, and its formation method are demonstrated.
As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, after applying a red liquid composition of the radiation-sensitive colored composition of the present invention on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns (colored cured films) are arranged in a predetermined arrangement.

  Next, each of the blue or green radiation-sensitive coloring compositions is used, and in the same manner as described above, each radiation-sensitive coloring composition is applied, pre-baked, exposed, developed, and post-baked to obtain a blue pixel array and green color. Are sequentially formed on the same substrate. Thereby, a color filter in which a pixel array of three primary colors of red, blue and green is arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithographic method. However, it is a radiation sensitive material in which a black colorant is dispersed. Using the coloring composition, it can be formed in the same manner as in the case of forming the pixel.

Examples of the substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  When applying the coloring composition to the substrate, an appropriate application method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method (slit coating method), a bar coating method, or the like is employed. In particular, it is preferable to employ a spin coating method or a slit die coating method.

The pre-baking is usually about 70 to 110 ° C. for about 1 to 10 minutes.
The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as the film thickness after drying.

Examples of the radiation light source used when forming at least one selected from the pixel and the black matrix include, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure. Examples thereof include a lamp light source such as a mercury lamp, and a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The wavelength is preferably radiation in the range of 190 to 450 nm.
Exposure of the radiation is generally preferred 10~10,000J / m ^2.

Examples of the alkali developer include sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, and 1,8-diazabicyclo- [5.4.0] -7-undecene. An aqueous solution of 1,5-diazabicyclo- [4.3.0] -5-nonene is preferable.
For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

  Further, as a second method for producing a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723 and JP-A-2000-310706 can be employed. . In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, a liquid composition of a red thermosetting coloring composition is discharged into the formed partition wall by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, this coating film is exposed as necessary and then cured by post-baking to form a red pixel pattern.

  Next, using each blue or green thermosetting coloring composition, a blue pixel pattern and a green pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of the three primary colors of red, blue and green are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

In addition, since the partition plays not only a light shielding function but also a function for preventing the color mixing of the thermosetting coloring compositions discharged in the respective sections, it is compared with the black matrix used in the first method described above. The film thickness is thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

  A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a radiation-sensitive colored composition in which a black colorant is dispersed is used, but the curable composition of the present invention can also be suitably used for forming such a black spacer.

The colored composition of the present invention can be suitably used in forming any colored cured film such as each color pixel, black matrix, and black spacer used in the color filter.
Since the color filter having the colored cured film of the present invention thus formed has extremely high luminance and color purity, it can be used in color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like. Very useful.

Color filter The color filter of the present invention comprises the colored cured film of the present invention. Specifically, what is necessary is just to comprise the colored cured film of this invention as members, such as each color pixel used for a color filter, a black matrix, a black spacer.

Display element The display element of the present invention comprises the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.
The color liquid crystal display element provided with the colored cured film of the present invention may be a transmissive type or a reflective type, and can take an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. Can be taken. Also, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (indium oxide doped with tin) electrode or an IZO (mixture of indium oxide and zinc oxide) electrode It is also possible to adopt a structure in which the formed substrate is opposed to the liquid crystal layer. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained. When the latter structure is adopted, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed, or on the substrate side on which the ITO electrode or IZO electrode is formed.

  The color liquid crystal display element including the colored cured film of the present invention can include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light by mixing red LED, green LED, and blue LED, a white LED that obtains white light by mixing blue LED, red LED, and green light emitting phosphor, blue A white LED that obtains white light by mixing colors, a white LED that obtains white light by mixing colors of a blue LED and YAG phosphor, a blue LED, an orange light emitting phosphor, and green light emission A white LED that obtains white light by color mixing by combining phosphors, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

  The color liquid crystal display device having the colored cured film of the present invention includes TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Plane Switching) type, VA (Vertical Alignment) type, OCB (Optical). An appropriate liquid crystal mode such as a Compensated Birefringence type is applicable.

Moreover, the organic EL display element provided with the colored cured film of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.
Moreover, the electronic paper provided with the colored cured film of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-2007-41169.

Light-receiving element The light-receiving element of the present invention comprises the colored cured film of the present invention.
The light receiving element of the present invention can take an appropriate structure. For example, the colored cured film of the present invention is used as a color filter constituting a solid-state image sensor, and combined with a photodiode, an image sensor such as a solid-state image sensor can be obtained. Can be configured. Further, by using the cured film of the present invention as an infrared light transmission filter and combining it with a photodiode, an infrared light detection pixel can be configured.

Light emitting element The light emitting element of the present invention comprises the colored cured film of the present invention.
The light emitting device of the present invention can take an appropriate structure. For example, in an organic EL light emitting device having a structure in which a transparent conductive layer of an anode made of a transparent electrode, a light emitting layer, and a cathode layer made of a metal electrode are laminated. The colored cured film of the present invention is used as a film, an insulating film, or a light emission wavelength selection member. The light emitting layer can be formed according to the above-described method for forming a colored cured film of the present invention using the colored composition of the present invention.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

The abbreviations of the raw materials used in the following “Synthesis Examples” are as follows.
MOI-BM: 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate (manufactured by Showa Denko KK, product name Karenz MOI-BM)
TBMA: t-butyl methacrylate (manufactured by Kyoeisha Chemical)
-MMA: Methyl methacrylate-HEMA: Hydroxyethyl methacrylate-EHMA: 2-ethylhexyl methacrylate (manufactured by Kyoeisha Chemical)
MTMA: 2-methoxyethyl methacrylate (Mitsubishi Chemical)
LMA: n-lauryl methacrylate (manufactured by Kyoeisha Chemical)
DMAA: Dimethylacrylamide (manufactured by KJ Chemicals)
・ DEAA: Diethylacrylamide (manufactured by KJ Chemicals)
・ HEAA: Hydroxyethylacrylamide (manufactured by KJ Chemicals)
ST: Styrene, PMI: N-Phenylmaleimide, CHMA: Cyclohexyl methacrylate, MA: Methacrylic acid, HOAMS: Succinic acid-2-acryloyloxyethyl (trade name HOA-MS (N), manufactured by Kyoeisha Chemical Co., Ltd.)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries)
V-501: 4,4′-azobis (4-cyanovaleric acid) (manufactured by Wako Pure Chemical Industries)
BMPA: β-mercaptopropionic acid (SC Organic Chemical)
EHMP: 2-ethylhexyl-3-mercaptopropionate (SC Organic Chemical)
・ PEMP: Pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd., trade name PEMP)
AIBN: 2,2′-azobisisobutyronitrile CHN: cyclohexanone PGMEA: propylene glycol ether monomethyl acetate

<Measurement of Mw and Mw / Mn>
Mw and Mn of the polymer obtained in each of the following synthesis examples and the binder resin were measured by GPC having the following specifications.
・ Apparatus: GPC-104 (made by Showa Denko)
Column: KD-G, KF-603, KF-602, KF-601 (manufactured by Showa Denko) were combined and used.
-Mobile phase: DMF
・ Standard: Polystyrene

<Confirmation of terminal alkali-soluble group>
About the dye multimer obtained in each of the following synthesis examples, 0.1 mg of the dye multimer was decomposed at 700 ° C. using an EGA / PY-3030D multi-shot pyrolyzer (manufactured by Agilent Technologies), and simultaneously with FID and FPD. By obtaining the analyzed pyrogram, it was confirmed whether or not it had a carboxylic acid structure derived from a polymerization initiator or a chain transfer agent at the terminal.

<Synthesis of a polymer having an anionic group>
Synthesis example 1
In a reaction vessel fitted with a condenser, 15.0 g p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt, 7.50 g MOI-BM, 3.00 g TBMA, 4.50 g MMA, 1.20 g BMPA was dissolved in 60.0 g CHN. This solution was heated to 75 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, 0.90 g of V-65 was added, and stirring was further continued for 4 hours. Subsequently, after cooling the reaction solution to room temperature, 60.0 g of acetone was added to make a uniform solution, which was added dropwise to 1.10 L of hexane. The produced precipitate was collected by filtration and washed with hexane. The obtained solid was dried at 50 ° C. under reduced pressure to obtain 27.9 g of a polymer represented by the following structural formula. It was confirmed by GPC that the obtained polymer had Mw of 6,800 and Mn of 3,500. This is referred to as a polymer (1). The polymer (1) was confirmed to contain a polymer having “—S (CH ₂ ) ₂ COOH” in at least one of the following chemical formulas.

Synthesis Examples 2-4
In the synthesis of the polymer (1) of Synthesis Example 1, 27.4 g of a polymer was obtained in the same manner as in Synthesis Example 1 except that the type and amount of the chain transfer agent were changed as shown in Table 1. Let this be a polymer (2)-(4). In addition, Table 1 shows Mw and Mn of the obtained polymer.

Synthesis example 5
In the synthesis of the polymer (1) of Synthesis Example 1, 27.6 g of a polymer was obtained in the same manner as in Synthesis Example 1 except that the types and amounts of the polymerization initiator and the chain transfer agent were changed as shown in Table 1. . This is designated as polymer (5). In addition, Table 1 shows Mw and Mn of the obtained polymer.

Synthesis Examples 6 to 11
In the synthesis of the polymer (5) of Synthesis Example 5, 26.4 g of a polymer was obtained in the same manner as in Synthesis Example 5 except that the type and amount of the unsaturated monomer were changed as shown in Table 1. Let this be a polymer (6)-(11). In addition, Table 1 shows Mw and Mn of the obtained polymer.

Synthesis Example 12
In the synthesis of the polymer (1) of Synthesis Example 1, 28.2 g of a polymer was obtained in the same manner as in Synthesis Example 1 except that the types and amounts of the polymerization initiator and the chain transfer agent were changed as shown in Table 1. . This is referred to as a polymer (12). In addition, Table 1 shows Mw and Mn of the obtained polymer.

Synthesis Examples 13 and 14
In the synthesis of the polymer (5) of Synthesis Example 5, 27.8 g of a polymer was obtained in the same manner as in Synthesis Example 5 except that the type and amount of the unsaturated monomer were changed as shown in Table 1. This is referred to as polymers (13) and (14). In addition, Table 1 shows Mw and Mn of the obtained polymer.

Synthesis Example 15
In the synthesis of the polymer (1) of Synthesis Example 1, 27.8 g of a polymer was obtained in the same manner as in Synthesis Example 1 except that the type and amount of the chain transfer agent were changed as shown in Table 1. This is designated as polymer (15). In addition, Table 1 shows Mw and Mn of the obtained polymer.

Synthesis Example 16
In the synthesis of the polymer (1) of Synthesis Example 1, 27.1 g of a polymer was obtained in the same manner as in Synthesis Example 1 except that the types and amounts of the polymerization initiator and the chain transfer agent were changed as shown in Table 1. . This is designated as polymer (16). In addition, Table 1 shows Mw and Mn of the obtained polymer.

<Synthesis of a polymer having a cationic group>
Synthesis Example 17
In a reaction vessel equipped with a condenser, 15.0 g of methacryloylpropyltrimethylammonium chloride, 10.5 g of MMA, 4.50 g of EHMA, and 1.70 g of thiomalic acid were dissolved in 60.0 g of CHN. This solution was heated to 75 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, 1.02 g of V-501 was added, and stirring was further continued for 4 hours. Subsequently, after cooling the reaction solution to room temperature, 60.0 g of acetone was added to make a uniform solution, which was added dropwise to 1.10 L of hexane. The produced precipitate was collected by filtration and washed with hexane. The obtained solid was dried at 50 ° C. under reduced pressure to obtain 27.8 g of a polymer represented by the following structural formula. This is designated as polymer (17). In addition, Table 1 shows Mw and Mn of the obtained polymer.

  In addition, it was confirmed that the polymer (17) includes a polymer having at least one alkali-soluble group shown below in the above chemical formula.

Synthesis Example 18
In a reaction vessel equipped with a condenser, 15.0 g of dimethylaminoethyl methacrylate, 10.5 g of MMA, 4.50 g of MTMA, 1.70 g of thiomalic acid was dissolved in 60.0 g of CHN. This solution was heated to 75 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, 1.02 g of V-501 was added, and stirring was further continued for 4 hours. Next, after the reaction solution was cooled to room temperature, 4.70 g of methyl chloride and 30.0 g of ethanol were added, the temperature was raised to 50 ° C. while stirring again, and stirring was continued for 2 hours. Subsequently, after cooling the reaction solution to room temperature, 60.0 g of acetone was added to make a uniform solution, which was added dropwise to 1.10 L of hexane. The produced precipitate was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50 ° C. to obtain 30.0 g of a polymer represented by the following structural formula. This is designated as polymer (18). In addition, Table 1 shows Mw and Mn of the obtained polymer.

  In addition, it was confirmed that the polymer (18) includes a polymer having at least one alkali-soluble group shown below in the above chemical formula.

Synthesis Example 19
15.0 g N, N-dimethylaminomethylstyrene, 10.5 g MMA, 4.50 g LMA, 1.70 g thiomalic acid were dissolved in 60.0 g CHN in a reaction vessel fitted with a condenser. . This solution was heated to 75 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, 1.02 g of V-501 was added, and stirring was further continued for 4 hours. Next, after the reaction solution was cooled to room temperature, 11.8 g of benzyl chloride and 30.0 g of ethanol were added, the temperature was raised to 50 ° C. while stirring again, and stirring was continued for 2 hours. Subsequently, after cooling the reaction solution to room temperature, 60.0 g of acetone was added to make a uniform solution, which was added dropwise to 1.10 L of hexane. The produced precipitate was collected by filtration and washed with hexane. The obtained solid was dried at 50 ° C. under reduced pressure to obtain 38.3 g of a polymer represented by the following structural formula. This is designated as polymer (19). In addition, Table 1 shows Mw and Mn of the obtained polymer.

  In addition, it was confirmed that the polymer (19) includes a polymer having at least one alkali-soluble group shown below in the above chemical formula.

Synthesis Example 20
In a reaction vessel equipped with a condenser tube, 15.0 g of N-vinylpyrrolidone, 10.5 g of MMA, 4.5 g of DMAA, 1.70 g of thiomalic acid were dissolved in 60.0 g of CHN. This solution was heated to 75 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, 1.02 g of V-501 was added, and stirring was further continued for 4 hours. Next, after the reaction solution was cooled to room temperature, 6.80 g of methyl chloride and 30.0 g of ethanol were added, the temperature was raised to 50 ° C. while stirring again, and stirring was continued for 2 hours. Subsequently, after cooling the reaction solution to room temperature, 60.0 g of acetone was added to make a uniform solution, which was added dropwise to 1.10 L of hexane.
The produced precipitate was collected by filtration and washed with hexane. The obtained solid was dried at 50 ° C. under reduced pressure to obtain 37.2 g of a polymer represented by the following structural formula. This is referred to as a polymer (20). In addition, Table 1 shows Mw and Mn of the obtained polymer.

  In addition, the polymer (20) confirmed that at least one E contained the polymer which has any one or more alkali-soluble group shown below in said chemical formula.

Synthesis Example 21
In the synthesis of the polymer (17) of Synthesis Example 17, the polymer was prepared in the same manner as in Synthesis Example 17 except that the types and amounts of unsaturated monomer, polymerization initiator and chain transfer agent were changed as shown in Table 1. 37.4 g was obtained. This is referred to as a polymer (21). In addition, Table 1 shows Mw and Mn of the obtained polymer.

<Synthesis of Dye Multimer 1>
Example 1
2.00 g of the polymer (1) of Synthesis Example 1 was dissolved in 40.0 mL of acetone. Next, as shown in the following scheme, it is equivalent to the number of moles of structural units derived from p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt calculated from the copolymerization ratio of the polymer (1). Amount of C.I. I. Basic Red 12 was added and stirred at room temperature for 1 hour. Thereafter, a precipitate obtained by adding 200 mL of ion-exchanged water to the residue obtained by concentrating the reaction solution under reduced pressure was collected by filtration and washed with water. The obtained solid was dried at 50 ° C. under reduced pressure to obtain 2.51 g of dye multimer 1 represented by the following structural formula. In addition, the compound obtained by HPLC, GPC, and ¹ H-NMR is the dye multimer 1, and in the following chemical formula, at least one E includes a polymer having “—S (CH ₂ ) ₂ COOH”. It was confirmed.

Examples 2 to 15 and Comparative Example 1
In the synthesis of the dye multimer 1 of Example 1, dye multimers 2 to 16 were obtained in the same manner as in Example 1 except that the type of polymer was changed as shown in Table 2. In addition, it was confirmed by HPLC, GPC and ¹ H-NMR that the obtained compound was a dye multimer 2-16.

Example 16
In the synthesis of the dye multimer 8 of Example 8, the dye multimer 17 was obtained in the same manner as in Example 8 except that the type of the dye was changed as shown in Table 2. In addition, it was confirmed by HPLC, GPC and ¹ H-NMR that the obtained compound was the dye multimer 17.

  In addition, it was confirmed that the dye multimer 17 includes a polymer having at least one alkali-soluble group shown below in the above chemical formula.

Examples 17-19
In the synthesis of the dye multimer 17 of Example 16, dye multimers 18 to 20 were obtained in the same manner as in Example 16 except that the type of the colorant was changed as shown in Table 2. In Table 2, C.I. used as the raw material 1 was used. I. The numbered compounds are as shown below. In addition, it confirmed that the obtained compound was the dye multimers 18-20 by HPLC, GPC, and < ¹ > H-NMR.

Example 20
2.00 g of the polymer (17) of Synthesis Example 17 was dissolved in 40.0 mL of acetone. Next, as shown in the following scheme, an equimolar amount of C.I. relative to the number of moles of the structural unit derived from the ammonium salt, calculated from the copolymerization ratio of the polymer (17). I. Acid Blue 93 was added and stirred at room temperature for 1 hour. Thereafter, a precipitate obtained by adding 200 mL of ion-exchanged water to the residue obtained by concentrating the reaction solution under reduced pressure was collected by filtration and washed with water. The obtained solid was dried at 50 ° C. under reduced pressure to obtain 2.62 g of dye multimer 21 represented by the following structural formula. In addition, it was confirmed by HPLC, GPC and ¹ H-NMR that the obtained compound was the dye multimer 21.

  In addition, it was confirmed that the dye multimer 21 in the above chemical formula includes at least one E containing a polymer having any one or more alkali-soluble groups shown below.

Example 21
In the synthesis of the dye multimer 21 of Example 20, a dye multimer 22 was obtained in the same manner as in Example 20 except that the type of the colorant was changed as shown in Table 2. In Table 2, the C.I. I. The numbered compounds are as shown below. In addition, it was confirmed by HPLC, GPC and ¹ H-NMR that the obtained compound was the dye multimer 22.

Examples 22 to 24 and Comparative Example 2
In the synthesis of the dye multimer 22 of Example 21, dye multimers 23 to 26 were obtained in the same manner as in Example 21 except that the type of polymer was changed as shown in Table 2. In addition, it confirmed that the obtained compound was the pigment | dye multimers 23-26 by HPLC, GPC, and < ¹ > H-NMR.

<Synthesis of dye multimers 2>
Example 25
In the synthesis of the polymer (5) of Synthesis Example 5, Synthesis Example 5 was used except that “Dye Monomer I” shown below was used instead of “p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt”. In the same manner as above, 41.8 g of dye multimer 27 was obtained. The obtained dye multimer 27 was confirmed by GPC that Mw was 8,100 and Mn was 4,200. Further, it was confirmed by HPLC, GPC and ¹ H-NMR that the obtained compound was the dye multimer 27.

  In addition, it was confirmed that the dye multimer 27 includes a polymer having at least one alkali-soluble group shown below in the above chemical formula.

Example 26
In the synthesis of the polymer (5) of Synthesis Example 5, “dye monomer II” shown below was used instead of “p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt”, and “MMA” was used instead. 40.3 g of dye multimer 28 was obtained in the same manner as in Synthesis Example 5 except that “EHMA” was used. It was confirmed by GPC that the obtained dye multimer 28 had Mw of 8,800 and Mn of 4,600. Further, it was confirmed by HPLC, GPC and ¹ H-NMR that the obtained compound was the dye multimer 28.

Example 27
In the synthesis of the polymer (5) of Synthesis Example 5, “dye monomer III” shown below was used instead of “p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt”, and “MMA” was used instead. 41.2 g of dye multimer 29 was obtained in the same manner as in Synthesis Example 5 except that “MTMA” was used. The obtained dye multimer 29 was confirmed by GPC that Mw was 7,900 and Mn was 4,000. Further, it was confirmed by HPLC, GPC and ¹ H-NMR that the obtained compound was the dye multimer 29.

Example 28
In the synthesis of the polymer (5) of Synthesis Example 5, “dye monomer IV” shown below was used instead of “p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt”, and “MMA” was used instead. Except that “LMA” was used, 42.8 g of dye multimer 30 was obtained in the same manner as in Synthesis Example 5. The obtained dye multimer 30 was confirmed by GPC that Mw was 7,700 and Mn was 4,000. Further, it was confirmed by HPLC, GPC and ¹ H-NMR that the obtained compound was the dye multimer 30. In addition, “OAc ⁻ ” in “Dye Monomer IV” is an acetate ion.

Example 29
In the synthesis of the polymer (5) of Synthesis Example 5, “dye monomer V” shown below was used instead of “p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt”, and “MMA” was used instead. Except that “DMAA” was used, 52.8 g of dye multimer 31 was obtained in the same manner as in Synthesis Example 5. The obtained dye multimer 31 was confirmed by GPC that Mw was 9,600 and Mn was 5,000. Further, it was confirmed by HPLC, GPC and ¹ H-NMR that the obtained compound was the dye multimer 31.

Example 30
In the synthesis of the polymer (5) of Synthesis Example 5, “dye monomer VI” shown below was used instead of “p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt”, and “MMA” was used instead. 58.2 g of dye multimer 32 was obtained in the same manner as in Synthesis Example 5 except that “DEAA” was used. It was confirmed by GPC that the obtained dye multimer 32 had Mw of 10,200 and Mn of 5,100. Further, it was confirmed by HPLC, GPC and ¹ H-NMR that the obtained compound was the dye multimer 32.

Example 31
In the synthesis of the polymer (5) of Synthesis Example 5, “dye monomer VII” shown below was used instead of “p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt”, and “MMA” was used instead. 57.7 g of dye multimer 33 was obtained in the same manner as in Synthesis Example 5 except that “HEAA” was used. It was confirmed by GPC that the obtained dye multimer 33 had Mw of 10,200 and Mn of 4,900. Further, it was confirmed by HPLC, GPC and ¹ H-NMR that the obtained compound was the dye multimer 33.

Comparative Example 3
In the synthesis of the dye multimer 27 of Example 1, “V-65” was used instead of “V-501”, and “EHMP” was used instead of “thiomalic acid”. Similarly, 40.7 g of dye multimer 34 was obtained. It was confirmed by GPC that the obtained dye multimer 34 had Mw of 7,800 and Mn of 4,000. Moreover, it confirmed that the obtained compound was the pigment | dye multimer 34 by HPLC, GPC, and < ¹ > H-NMR.

Preparation Example 1
10.0 parts by mass of dye multimer 1 and 90.0 parts by mass of PGMEA were mixed to prepare a dye multimer solution (A-1).

Preparation Examples 2-35
In Preparation Example 1, a dye multimer solution or a dye solution was prepared in the same manner as Preparation Example 1, except that the colorant shown in Table 4 was used instead of the dye multimer 1.

<Synthesis of binder resin>
Synthesis example 1
In a flask equipped with a condenser and a stirrer, ST10.00 g, PMI 12.00 g, HEMA 12.50 g, MMA 13.00 g, CHMA 25.00 g, MA 15.00 g, and HOAMS 12.50 g were dissolved in PGMEA 200 g, and AIBN 3.0 g and PEMP5 0.0 g was charged and then purged with nitrogen for 15 minutes. After the nitrogen purge, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubbling, and polymerized for 5 hours to obtain a solution containing 33% by mass of the binder resin (B1). This binder resin (B1) had Mw of 10,000 and Mw / Mn of 2.5.

<Preparation of coloring composition for transfer evaluation>
Preparation Example 36
As a coloring agent, C.I. I. Pigment Green 58 was treated by a bead mill using 15 parts by mass of BYK-LPN21116 (produced by BYK) as a dispersant and 72.5 parts by mass of PGMEA as a solvent. did. Subsequently, the pigment dispersion liquid (a-1) was prepared by centrifuging and refine | purifying using S type ultracentrifuge AT-8 (made by SCI techno Co., Ltd.).

Preparation Example 37
As a coloring agent, C.I. I. Treated with a bead mill using 15 parts by weight of Pigment Yellow 138, 12.5 parts by weight of BYK-LPN21116 (produced by BYK) as a dispersant (solid content concentration 40% by weight) and 72.5 parts by weight of PGMEA as a solvent did. Subsequently, the pigment dispersion liquid (a-2) was prepared by centrifuging and refine | purifying using S type ultracentrifuge AT-8 (made by SSC techno Co., Ltd.).

Preparation Example 38
(A) 30.5 parts by mass of the pigment dispersion (a-1) as the colorant, 25.0 parts by mass of the pigment dispersion (a-2), (B) 26.3 parts by mass of the binder resin (B1) solution as the binder resin 9.9 parts by weight of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a polymerizable compound, 2-benzyl as a photopolymerization initiator 1.8 parts by mass of 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by BASF) and 0.1 mass of NCI-930 (manufactured by ADEKA) Part, 0.05 part by mass of MegaFac F-554 (manufactured by DIC Corporation) as a fluorosurfactant, and PGMEA as a solvent To a solid content concentration of 20 mass% of a green coloring composition (G) was prepared.

<Preparation and evaluation of coloring composition>
Example 101
(A) 10.2 parts by mass of the dye multimer solution (A-1) as the colorant, 9.9 parts by mass of the binder resin (B1) solution as the (B) resin, (C) dipentaerythritol hexaacrylate as the polymerizable compound 15.4 parts by mass of a mixture of benzene and dipentaerythritol pentaacrylate (Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) as a photopolymerization initiator ) 1.8 parts by mass of butan-1-one (trade name Irgacure 369, manufactured by BASF) and 0.1 part by mass of NCI-930 (manufactured by ADEKA Co., Ltd.), Megafac F-554 (as fluorosurfactant) (Made by DIC Corporation) 0.05 parts by mass, lithium bis (trifluoromethanesulfonyl) imide 0.002 as an additive A colored composition (S-1) having a solid content concentration of 20% by mass was prepared by mixing PGMEA as an amount and a solvent.

<Development evaluation>
The coloring composition (S-1) is applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed using a spin coater, and then pre-baked on a hot plate at 100 ° C. for 2 minutes. To form a 2.5 μm-thick coating film. Next, after cooling the substrate to room temperature, a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was discharged at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm), whereby the coating film on the substrate was formed. The time required for complete disappearance (resolution time) was measured. “1” when the resolution time is less than 10 seconds, “2” when it is 10 seconds or more and less than 15 seconds, “3” when it is 15 seconds or more and less than 20 seconds, and “3” when it is 20 seconds or more and less than 25 seconds. The case of 4 ”, 25 seconds or more was designated as“ 5 ”.

<Evaluation of dye transfer>
The coloring composition (S-1) is applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed using a spin coater, and then pre-baked on a hot plate at 100 ° C. for 2 minutes. To form a 2.5 μm-thick coating film. Subsequently, after cooling this board | substrate to room temperature, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed to each coating film with the exposure amount of 400 J / m < ² > using the high pressure mercury lamp. At that time, a mask made of quartz of 5 inches in length and width and 0.9 inch in thickness was used as a pattern mask. Then, shower development was performed for 60 seconds by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Next, the substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 200 ° C. for 30 minutes, thereby forming dot patterns of 100 μm in size on the substrate.
About the obtained dot pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), a C light source, a chromaticity coordinate value (x, y) and a stimulus value (Y) in the CIE color system with a 2-degree visual field Was measured.

Next, after apply | coating the green coloring composition (G) on a dot pattern using a spin coater, it prebaked for 2 minutes with a 100 degreeC hotplate, and formed the coating film with a film thickness of 2.5 micrometers. Next, after cooling the substrate to room temperature, a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. is discharged to the substrate at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm). Then, the shower development was performed for 60 seconds. Thereafter, the substrate was washed with ultrapure water and air-dried.
A series of steps from application of the green coloring composition (G) to air drying is referred to as “(step-1)”. For the dot pattern after (Step-1), the chromaticity coordinate value (x, y) and the stimulus value (Y) were measured, and the color change before and after (Step-1), that is, ΔE ^* _ab was evaluated. As a result, the case where the value of ΔE ^* _ab was less than 5.0 was evaluated as “◯”, the case where it was 5.0 or more and less than 10.0 was evaluated as “Δ”, and the case where it was 10.0 or more was evaluated as “x”. The evaluation results are shown in Table 5. In addition, it can be said that transfer is suppressed, so that (DELTA ⁾ E ^* _ab value is small.

Examples 102-131 and Comparative Examples 101-104
In Example 101, colored compositions (S-2) to (S-35) were prepared in the same manner as in Example 101 except that the type of the colored composition was changed as shown in Table 5. Next, in place of the colored composition (S-1) in Example 101, the developability and transferability were the same as in Example 101 except that the colored compositions (S-2) to (S-35) were used. Evaluation was performed. The evaluation results are shown in Table 5.

Claims (10)

(A ¹ ) A dye multimer having a dye structure and having an alkali-soluble group represented by the following formula (I) or the following formula (II) at the main chain terminal, and (B) a coloring composition containing a polymerizable compound object.

[In Formula (I) and Formula (II),
R ^a and R ^b each independently represent a hydrogen atom or a monovalent substituent,
Z ^a and Z ^b each independently represent a divalent linking group,
* Indicates a binding position. ]. (A ³ ) a dye multimer having a dye structure and having an alkali-soluble group at the end of the main chain, wherein at least one dye multimer selected from the group consisting of the following (iii) and (iv): And
(B) A colored composition containing a polymerizable compound.
(Iii) a residue derived from at least one compound selected from the group consisting of a polymerization initiator having an alkali-soluble group and a chain transfer agent having an alkali-soluble group, and an unsaturated monomer having a dye structure A dye multimer having a structural unit (iv) a residue derived from at least one compound selected from the group consisting of a polymerization initiator having an alkali-soluble group and a chain transfer agent having an alkali-soluble group, and an ionic group And a polymer having a structural unit derived from an unsaturated monomer having no dye structure, and
A dye multimer which is a reaction product with a dye compound having an ionic group electrically different from the ionic group The coloring composition according to claim 1 or 2, wherein the (A ¹ ) dye multimer and the (A ³ ) dye multimer include a structural unit α having a dye structure and a structural unit β having no dye structure. The coloring composition according to claim 3, wherein the structural unit β having no dye structure contains at least one unsaturated monomer selected from the following (a) and (b).
(A) (meth) acrylic acid ester (b) (meth) acrylamide having a glass transition temperature of 120 ° C. or lower when it is a homopolymer   The colored cured film which is a hardened | cured material of the colored composition of any one of Claims 1-4.   A color filter comprising the colored cured film according to claim 5.   A display element comprising the colored cured film according to claim 5.   A light receiving element comprising the colored cured film according to claim 5.   A light emitting device comprising the colored cured film according to claim 5. A dye multimer having a dye structure and having an alkali-soluble group represented by the following formula (I) or the following formula (II) at the end of the main chain.

[In Formula (I) and Formula (II),
R ^a and R ^b each independently represent a hydrogen atom or a monovalent substituent,
Z ^a and Z ^b each independently represent a divalent linking group,
* Indicates a binding position. ]