JP6197684B2 - Colored composition, colored cured film, and display element - Google Patents

Description

  The present invention relates to a colored composition, a colored cured film, and a display element, and more specifically, a colored cured film used for a transmissive or reflective color liquid crystal display element, solid-state imaging element, organic EL display element, electronic paper, and the like. The present invention relates to a colored composition used for forming a colored cured film, a colored cured film formed using the colored composition, and a display element including the colored cured film.

  In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. A method of obtaining pixels of each color by irradiation (hereinafter referred to as “exposure”) and development is known (for example, see Patent Documents 1 and 2). In addition, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (see, for example, Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (for example, see Patent Document 4).

  In recent years, there has been a strong demand for higher contrast of liquid crystal display elements and higher definition of solid-state imaging elements, and in order to realize these, application of dyes as colorants is being studied. However, generally speaking, in comparison with the case where a pigment is applied as a colorant, there are many cases where problems arise in heat resistance and solvent resistance when a dye is applied.

  Under such a background, for example, Patent Document 5 proposes the use of a triarylmethane dye having an alkylsulfonylimide anion as a dye-containing coloring composition capable of forming a pixel having excellent heat resistance.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2012-83651 A

  However, the dye proposed in Patent Document 5 has been found to have a poor balance between pixel heat resistance and solvent resistance. In addition, the present inventors transfer the color of the dye in the pixel of the colored pattern to the adjacent other color pixel or a cured film that does not contain a colorant such as a protective film (hereinafter referred to as “transferability”). It has also been found that there is a problem that the display characteristics of the display element deteriorate, but this problem is not considered at all in Patent Document 5.

  Therefore, the subject of this invention is providing the coloring composition suitable for formation of the colored cured film which can make heat resistance and solvent resistance compatible, and the dye transfer property was suppressed. Furthermore, the subject of this invention is providing the colored cured film formed using the said coloring composition, and the display element which comprises the same.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by using a colorant having a specific structure.

  That is, the present invention is a colored composition containing (A) a colorant and (C) a polymerizable compound, wherein the colorant is a polymer having a structural unit represented by the following formula (1) (hereinafter, It is also referred to as “the present colorant”).

[In Formula (1),
R ⁰ represents a hydrogen atom or a methyl group,
X represents a group having a linking group containing a carbon atom, a hydrogen atom or an atom other than a halogen atom between the C-C bonds of a halo group, a halogenated hydrocarbon group, or a halogenated hydrocarbon group;
Y represents a single bond or a divalent organic group,
Z ⁺ represents a triarylmethane-based cationic chromophore represented by the following formula (2-1), a triarylmethane-based cationic chromophore represented by the following formula (2-2), and a methine-based cation Cationic chromophore, azo cationic chromophore, diarylmethane cationic chromophore, quinoneimine cationic chromophore, anthraquinone cationic chromophore, phthalocyanine cationic chromophore and xanthene cationic At least one cationic chromophore selected from the group consisting of chromophores; ]

[In Formula (2-1),
R ^{1 to} R ⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, or a substituted or unsubstituted group. Represents an aryl group,
R ^{7 to} R ⁹ each independently represent an alkyl group having 1 to 8 carbon atoms or a chlorine atom,
l and m each independently represent an integer of 0 to 4;
n shows the integer of 0-6.
However, l, m, and n are not 0 at the same time. ]

[In Formula (2-2),
R ^{11 to} R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, or a substituted or unsubstituted group. Represents an aryl group,
R ^{17 to} R ¹⁹ each independently represent an alkyl group having 1 to 8 carbon atoms or a chlorine atom,
s, t and u each independently represent an integer of 0 to 4. ]

  Moreover, this invention provides the display element which comprises the colored cured film formed using the said coloring composition, and this colored cured film. Here, the “colored cured film” means each color pixel, black matrix, black spacer, and the like used for a display element and a solid-state imaging element.

If the colored composition of the present invention is used, a colored cured film having both high heat resistance and solvent resistance at a high level and having suppressed dye transfer properties can be formed.
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 will be described in detail components of the colored composition of the present invention.

-(A) Colorant-
The coloring composition of this invention contains the polymer which has a structural unit represented by following formula (1) as a coloring agent.

[In Formula (1),
R ⁰ represents a hydrogen atom or a methyl group,
X represents a group having a linking group containing a carbon atom, a hydrogen atom or an atom other than a halogen atom between the C-C bonds of a halo group, a halogenated hydrocarbon group, or a halogenated hydrocarbon group;
Y represents a single bond or a divalent organic group,
Z ⁺ represents a triarylmethane-based cationic chromophore represented by the following formula (2-1), a triarylmethane-based cationic chromophore represented by the following formula (2-2), and a methine-based cation Cationic chromophore, azo cationic chromophore, diarylmethane cationic chromophore, quinoneimine cationic chromophore, anthraquinone cationic chromophore, phthalocyanine cationic chromophore and xanthene cationic At least one cationic chromophore selected from the group consisting of chromophores; ]

R ⁰ is preferably a methyl group among a hydrogen atom and a methyl group.
Examples of the halo group for X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group in X include (1) an aliphatic hydrocarbon group, (2) an alicyclic hydrocarbon group, and (3) an alicyclic hydrocarbon group as a substituent. An aliphatic hydrocarbon group (hereinafter referred to as “alicyclic hydrocarbon-substituted aliphatic hydrocarbon group”), (4) an aromatic hydrocarbon group, and (5) an aromatic having an aliphatic hydrocarbon group as a substituent. Aromatic hydrocarbon group (hereinafter referred to as “aliphatic hydrocarbon-substituted aromatic hydrocarbon group”), (6) aliphatic hydrocarbon group having an aromatic hydrocarbon group as a substituent (hereinafter referred to as “aromatic hydrocarbon-substituted”). And an aliphatic hydrocarbon group). The hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group is preferably the following characteristic group from the viewpoint of solubility in an organic solvent.

That is, the (1) aliphatic hydrocarbon group is preferably an alkyl group, and the alkyl group may be linear or branched. The alkyl group preferably has 1 to 20 carbon atoms, particularly preferably 1 to 8 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, neopentyl group , N-hexyl group, n-heptyl group, n-octyl and the like.
The (2) alicyclic hydrocarbon group may be a 2- to 4-ring bridged alicyclic hydrocarbon group. The alicyclic hydrocarbon group is preferably an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. Specifically, for example, a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecyl group, a norbornyl group, a bornyl group, an adamantyl group, a bicyclooctyl group, etc. Can be mentioned.
The (3) alicyclic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an alicyclic saturated hydrocarbon-substituted alkyl group, and preferably has 4 to 20 carbon atoms, particularly 6 to 14 carbon atoms. Preferably there is. Specific examples include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclohexylmethyl group, a cyclohexylpropyl group, an adamantylmethyl group, a 1- (1-adamantyl) ethyl group, and a cyclopentylethyl group.
The (4) aromatic hydrocarbon group is preferably an aryl group having 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. Specific examples include a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, an anthracenyl group, and the like, and among them, a phenyl group is preferable.
The (5) aliphatic hydrocarbon-substituted aromatic hydrocarbon group is preferably an alkyl-substituted phenyl group, and the carbon number thereof is preferably 7 to 30, and particularly preferably 7 to 20. Specifically, a tolyl group, a xylyl group, a mesityl etc. can be mentioned, for example.
The (6) aromatic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an aralkyl group, and preferably has 7 to 30 carbon atoms, particularly preferably 7 to 20 carbon atoms. Specific examples include a benzyl group and a phenethyl group.
In addition, the alkyl group in this specification may be linear or branched.

  Among these, the hydrocarbon group forming the skeleton of the halogenated hydrocarbon group includes (1) an aliphatic hydrocarbon group, (3) an alicyclic hydrocarbon-substituted aliphatic hydrocarbon group, and (4) an aromatic hydrocarbon. Group, (5) aliphatic hydrocarbon-substituted aromatic hydrocarbon group or (6) aromatic hydrocarbon-substituted aliphatic hydrocarbon group, alkyl group, alicyclic saturated hydrocarbon-substituted alkyl group, phenyl group, alkyl-substituted group A phenyl group and an aralkyl group are more preferable, and an alkyl group is particularly preferable.

  In X, the halogen atom in the halogenated hydrocarbon group is preferably a fluorine atom from the viewpoint of the heat resistance of the colorant, and the fluorine atom substitutes part or all of the hydrogen atoms of the hydrocarbon group. Also good. By selecting a fluorine atom as a substituent, it is considered that a salt having a stronger ionic bond strength is formed and heat resistance is enhanced.

X 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. And the carbon number in paragraph [0024] means the total carbon number of the part except the carbon atom which comprises this coupling group.

  In the present invention, from the viewpoint of the heat resistance of the colorant, X is a halogenated hydrocarbon group or a linkage containing a carbon atom, a hydrogen atom or an atom other than a halogen atom between CC bonds of the halogenated hydrocarbon group. A group having a group is preferable, a group represented by the following formula (3) or (4) is more preferable, and a group represented by the following formula (3) that forms a conjugate base of an organic acid having a higher acidity is particularly preferable. preferable.

[In Formula (3),
R ²⁰ represents a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, an alicyclic hydrocarbon group, an alkoxy group, a fluorinated alkoxy group, R ²¹ COOR ²² — or R ²³ COOR ²⁴ CFH—,
R ²¹ and R ²³ each independently represent an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group, or a substituted or unsubstituted aryl group;
R ²² and R ²⁴ each independently represent an alkanediyl group,
q represents an integer of 1 or more,
“*” Indicates a bond. ]

[In Formula (4),
R ^{25 to} R ²⁹ each independently represent a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluorinated alkyl group or an alkoxy group,
“*” Indicates a bond.
However, at least one of R ^{25 to} R ²⁹ is a fluorine atom or a fluorinated alkyl group. ]

In Formula (3), the alkyl group for R ²⁰ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and further 1 to 4 carbon atoms. The alkyl group may be linear or branched. Specific examples include the same ones as described above.
The fluorinated alkyl group for R ²⁰ is preferably a fluorinated alkyl group having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and further 1 to 4 carbon atoms. The fluorinated alkyl group may be linear or branched. Specific examples include those obtained by substituting some or all of the hydrogen atoms of the aforementioned alkyl groups with fluorine atoms, and perfluoroalkyl groups are particularly preferred.
The alicyclic hydrocarbon group for R ²⁰ may be a 2- to 4-ring bridged alicyclic hydrocarbon group. The alicyclic hydrocarbon group is preferably an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. Specific examples include the same ones as described above.
As the alkoxy group for R ^20, an alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and further 1 to 4 carbon atoms is preferable. The alkoxy group may be linear or branched. Specific examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, iso-pentyloxy group, n-hexyl. Examples thereof include an oxy group, a methoxymethoxy group, an ethoxyethoxy group, and a 3- (iso-propyloxy) propyloxy group.
As the fluorinated alkoxy group for R ^20, 1 to 10 carbon atoms, further 1 to 6 carbon atoms, more preferably fluorinated alkoxy group having 1 to 4 carbon atoms. The fluorinated alkoxy group may be linear or branched. Specific examples include those in which part or all of the hydrogen atoms of the aforementioned alkoxy group are substituted with fluorine atoms, and perfluoroalkoxy groups are particularly preferred.

In R ²⁰ R ²¹ COOR ²² — and R ²³ COOR ²⁴ CFH— in R ²⁰ , R ²¹ and R ²³ are each independently an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group, or a substituted or unsubstituted aryl group. However, the alkyl group may be linear or branched, and the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. Specific examples include the same ones as described above. The alicyclic hydrocarbon group may be a 2-4 ring bridged alicyclic hydrocarbon group, and is preferably an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The heteroaryl group is preferably a group composed of a 5- to 10-membered aromatic heterocycle containing one or more heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom. Specific examples include a furyl group, a thienyl group, a pyrrolyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, and a carbazolyl group. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably a phenyl group. In addition, as a substituent of an aryl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a halogen atom, or a trifluoromethyl group is mentioned, for example, The position and number of a substituent are arbitrary. Yes, when having two or more substituents, the substituents may be the same or different.

R ²² and R ²⁴ independently represent an alkanediyl group, but an alkanediyl group having a linear or branched chain having 1 to 10 carbon atoms is preferable. Specific examples include methylene group, ethylene group, ethane-1,1-diyl group, propane-1,1-diyl group, 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, octane-1,8-diyl group, decane-1,10-diyl group and the like. Among these, an alkanediyl group having 2 to 6 carbon atoms is preferable, and an alkanediyl group having 2 to 4 carbon atoms is more preferable. Among these, an ethylene group is preferable from the viewpoint of ease of production.

In addition, 10 is preferable and the upper limit of q is more preferable.
R ²⁰ is preferably a fluorine atom, a fluorinated alkyl group, an alicyclic hydrocarbon group, a fluorinated alkoxy group, R ²¹ COOR ²² — or R ²³ COOR ²⁴ CFH—, and particularly a fluorine atom, an alicyclic hydrocarbon group. , A perfluoroalkoxy group, R ²¹ COOCH ₂ CH ₂ — or R ²³ COOCH ₂ CH ₂ CFH— is preferable.
In formula (4), the alkyl group, fluorinated alkyl group and alkoxy group in R ^{25 to} R ²⁹ are the same as the alkyl group, fluorinated alkyl group and alkoxy group in R ²⁰ of formula (3) described above. A configuration can be employed. However, at least one of R ^{25 to} R ²⁹ is a fluorine atom or a fluorinated alkyl group, but at least three of R ^{25 to} R ²⁹ are preferably a fluorine atom or a fluorinated alkyl group.

Examples of the divalent organic group in Y 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 hydrogen of these groups. A group in which a part of the atoms is substituted with a halogen atom can be exemplified. 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-, -COO-, -CONR'- (R 'represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. And a group formed by combining at least one selected from —SO ₂ — and the like.

Specific examples of the alkanediyl group include the same ones as described above. Among these, an alkanediyl group having 2 to 8 carbon atoms is preferable, and an alkanediyl group having 2 to 6 carbon atoms is more preferable.
Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, and an anthryl group. Among them, an arylene group having 6 to 10 carbon atoms is preferable, and a phenylene group is particularly preferable.
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.

And at least one selected from an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms, -O-, -S-, -COO-, -CONR'- (R 'is a hydrogen atom) Or an alkyl group having 1 to 8 carbon atoms) and a group formed by combining at least one selected from —SO ₂ — and an alkanediyl group having 1 to 10 carbon atoms and an arylene having 6 to 20 carbon atoms. A group formed by combining at least one selected from a group and at least one selected from —O—, —COO—, and —SO ₂ — is preferable, and is an alkanediyl group having 1 to 10 carbon atoms and 6 to 6 carbon atoms. A group formed by combining at least one selected from 20 arylene groups and at least one selected from —O— and —SO ₂ — is more preferable.

Next, Z ⁺ will be described.
Z ⁺ represents a triarylmethane-based cationic chromophore represented by the following formula (2-1), a triarylmethane-based cationic chromophore represented by the following formula (2-2), and a methine-based cation Cationic chromophore, azo cationic chromophore, diarylmethane cationic chromophore, quinoneimine cationic chromophore, anthraquinone cationic chromophore, phthalocyanine cationic chromophore and xanthene cationic At least one cationic chromophore selected from the group consisting of chromophores;
The triarylmethane-based cationic chromophore represented by the formula (2-1) and the triarylmethane-based cationic chromophore represented by the formula (2-2) have various resonance structures. However, in this specification, when the chromophore represented by each formula has a resonance structure, it is equivalent to the chromophore represented by the formula (2-1) and (2-2). .

[In the formulas (2-1) and (2-2),
R ^{1 to} R ⁶ and R ^{11 to} R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, Or a substituted or unsubstituted aryl group,
R ^{7 to} R ⁹ and R ^{17 to} R ¹⁹ are each independently an alkyl group having 1 to 8 carbon atoms or a chlorine atom,
l, m, s, t and u each independently represent an integer of 0 to 4;
n shows the integer of 0-6.
However, l, m, and n are not 0 at the same time. ]

Specific examples of the alkyl group having 1 to 8 carbon atoms in R ^{1 to} R ⁹ and R ^{11 to} R ¹⁹ include the same ones as described above. Among these, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is particularly preferable.
Specific examples of the cycloalkyl group having 3 to 8 carbon atoms in R ^{1 to} R ⁶ and R ^{11 to} R ¹⁶ include the same ones as described above. Among them, a cycloalkyl group having 4 to 6 carbon atoms is preferable, and a cyclohexyl group is particularly preferable.
The aryl group in R ^{1 to} R ⁶ and R ^{11 to} R ¹⁶ is preferably an aryl group having 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. Specific examples include those described above, and among them, a phenyl group is preferable.
Examples of the substituent of the alkyl group, cycloalkyl group and aryl group in R ^{1 to} R ⁶ and R ^{11 to} R ¹⁶ include an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a trifluoromethyl group, and a cyano group. The cycloalkyl group and the aryl group may be substituted with an alkyl group having 1 to 6 carbon atoms. Specific examples of these substituents can be the same as those 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.
R ^{7 to} R ⁹ and R ^{17 to} R ¹⁹ are preferably an alkyl group having 1 to 4 carbon atoms or a chlorine atom, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

In Formula (2-1), 1 and m are preferably integers of 0 to 2, and n is preferably 0 or 1. However, l, m, and n are not 0 at the same time. Among them, combinations of l, m, and n include l = 1, m = 0, n = 0, l = 0, m = 0, n = 1, l = 2, m = 0, n = 0 combination, l = 1, m = 1, n = 0 combination, l = 1, m = 1, n = 1 combination is preferred, l = 1, m = 0, n = 0 combination, l = A combination of 0, m = 0, n = 1, l = 1, m = 1, n = 0 is more preferable.
In formula (2-2), s is preferably an integer of 0 to 2, t and u are preferably 0 or 1, and one or more of s, t and u may be an integer of 1 to 4. preferable. Among them, combinations of s, t, and u include s = 0, t = 0, u = 0, s = 1, t = 0, u = 0, s = 2, t = 0, u = A combination of 0, a combination of s = 1, t = 1, u = 0, a combination of s = 1, t = 1, u = 1, and in particular a combination of s = 0, t = 0, u = 0, A combination of s = 1, t = 0, u = 0, and a combination of s = 1, t = 1, u = 0 are more preferable.

  Examples of the chromophore represented by the formula (2-1) or the chromophore represented by the formula (2-2) include chromophores shown in the following compound group a and compound group b. Among them, chromophores a1, a2, a3, a4, a5, a6, b1, b2, b3, b4, b6 are preferable, and a2, a3, a4, a5, a6, b3, b4 are more preferable.

  In addition to the above, examples of the triarylmethane-based cationic chromophore represented by the formula (2-1) include chromophores described in JP2012-17425A.

  As said methine type chromophore, what is represented by following formula (5-1)-(5-3) is preferable, and what is represented by following formula (5-1) is more preferable.

[In the formulas (5-1) to (5-3),
R ³¹ represents a hydrogen atom or a halo group,
R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent an alkyl group having 1 to 6 carbon atoms,
R ³⁶ represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
G represents —CH═CH—, —CH═CH—CH═, —CH═CH—NR ³⁷ — (R ³⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —CH═N—NR. ³⁷ — (R ³⁷ is as defined above) or —N═N—NR ³⁷ — (R ³⁷ is as defined above);
R ^a represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group. ]

The R ^a, preferred is a group represented by the following formula (5a) ~ (5h), and more preferably a group represented by the following formula (5b) or (5h).

[In Formula (5a)-(5h),
R ³⁸ and R ⁴⁵ each independently represent an alkyl group having 1 to 6 carbon atoms,
R ³⁹ represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
R ⁴⁰ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
R ⁴¹ , R ⁴⁶ and R ⁵⁰ are each independently a hydrogen atom, a halo group, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or cyano. Indicates a group.
]

The alkyl group in R ^{32 to} R ⁵⁰ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group. In addition, examples of the substituent for the alkyl group include a halo group, a cyano group, and a hydroxyl group. The halo group in R ³¹ , R ⁴¹ , R ⁴⁶ and R ⁵⁰ and the alkoxy group in R ⁴¹ , R ⁴⁶ and R ⁵⁰ are preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group. .

  Representative examples of the chromophore represented by the above formulas (5-1) to (5-3) include chromophores shown in the following compound group c.

  Examples of the azo chromophore include those represented by the following formulas (6-1) to (6-6), and those represented by the following formulas (6-1) to (6-5) are preferable. What is represented by Formula (6-1) is more preferable.

[In the formulas (6-1) to (6-6),
R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁷ each independently represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
R ⁵⁶ and R ⁶⁰ each independently represent a hydrogen atom, a halo group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group,
R ⁵⁸ represents an alkyl group having 1 to 6 carbon atoms,
R ⁵⁹ represents a group that forms a quaternary ammonium;
R ^b represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group. ]

The _{^{R 59, -NR 61 C ma H}} 2ma N + R 62 R 63 R 64 (ma is an integer from 1 to 5, R ⁶¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁶² , R ⁶³ and R ⁶⁴ each independently represent an alkyl group having 1 to 6 carbon atoms), _{—COC ma} H _2ma N ⁺ R ⁶² R ⁶³ R ⁶⁴ (ma, R ⁶² , R ⁶³ and R ⁶⁴ are as defined above. _{synonymous), - C ma H 2ma N} + ( a ^{_{NH 2) R 74 R 75 (}} ma synonymous with the, R ⁷⁴ and R ⁷⁵ represents an alkyl group having 1 to 6 carbon atoms independently of one another) Or a group represented by the following formula (6-i) or (6-ii).

[In the formulas (6-i) and (6-ii), R ⁶¹ and ma are as defined above. ]

R ^b is preferably a group represented by the following formulas (6a) to (6e) or a substituted or unsubstituted phenyl group, and more preferably a group represented by the following formula (6a). In addition, as a substituent of a phenyl group, a halo group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a hydroxyl group, a cyano group, and a nitro group are mentioned.

[In Formula (6a)-(6d),
R ⁶⁵ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group,
R ⁶⁶ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
R ⁶⁷ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group,
R ⁶⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
R ⁶⁹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
R ⁷⁰ to R ⁷³ represents independently of one another, a hydrogen atom, a halo group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group. ]

The alkyl group in R ^{51 to} R ⁵⁸ and R ^{60 to} R ⁷⁵ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group. In addition, examples of the substituent of the alkyl group include a halo group, a hydroxyl group, a cyano group, and a —CONH ₂ group.

  Representative examples of the chromophore represented by the above formulas (6-1) to (6-6) include chromophores shown in the following compound group d or compound group e.

  As the diaryl chromophore, those represented by the following formula (7-1) or (7-2) are preferred, and those represented by the following formula (7-2) are more preferred.

[In the formulas (7-1) and (7-2),
R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ and R ⁸⁹ each independently represent an alkyl group having 1 to 6 carbon atoms,
R ⁸⁵ , R ⁹⁰ and R ⁹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

The alkyl group for R ^{81 to} R ⁹¹ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

  Representative examples of the chromophore represented by the above formulas (7-1) to (7-2) include chromophores shown in the following compound group f.

  As said quinoneimine type chromophore, what is represented by following formula (8-1)-(8-3) is preferable, and what is represented by following formula (8-1) or (8-3) is more preferable.

[In the formulas (8-1) to (8-3),
^{R 101, R 102, R 103} , R 104, R 105, R 106, R 108, R 109, R 110, R 111, R 114, R 115, R 116, R 117 and R ¹¹⁸ are independently of one another , A hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a benzyl group;
R ¹⁰⁷ and R ¹¹³ each independently represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms,
R ¹¹² represents —NR ¹¹⁹ R ¹²⁰ (R ¹¹⁹ and R ¹²⁰ each independently represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms), a hydroxyl group, a nitro group, or a cyano group,
Q represents an oxygen atom or a sulfur atom. ]

Alkyl group in ^{R 101 ~R 111, R 113 ~R} 120 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. In addition, examples of the substituent of the alkyl group include a halo group, a hydroxyl group, and a cyano group. The aryl group having 6 to 20 carbon atoms in R ¹⁰⁷ and R ¹¹³ is preferably a phenyl group.

  Representative examples of the chromophores represented by the above formulas (8-1) to (8-3) include chromophores shown in the following compound group g.

  As said anthraquinone chromophore, what is represented by following formula (9-1) or (9-2) is preferable, and what is represented by following formula (9-1) is more preferable.

[In the formulas (9-1) and (9-2),
R ¹³¹ , R ¹³⁵ and R ¹³⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted phenyl group;
R ¹³² , R ¹³³ , R ¹³⁴ , R ¹³⁸ , R ¹³⁹ and R ¹⁴⁰ each independently represent an alkyl group having 1 to 6 carbon atoms, and R ¹³⁷ represents a methylene group or a substituted or unsubstituted alkylene group. . ]

The alkyl group in R ^{131 to} R ¹³⁶ and R ^{138 to} R ¹⁴⁰ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group. Examples of the substituent of the alkyl group include a halo group, a hydroxyl group, and a cyano group. Examples of the substituent of the phenyl group include an alkyl group having 1 to 6 carbon atoms, a halo group, a hydroxyl group, and a cyano group. It is done.
Moreover, as said alkylene group, C2-C4 alkylene groups, such as ethylene group, trimethylene group, propylene group, tetramethylene group, are preferable, As a substituent of an alkylene group, a hydroxyl group, a cyano group, a nitro group, etc. are mentioned. Can be mentioned.

  Representative examples of the chromophore represented by the above formula (9-1) or (9-2) include chromophores shown in the following compound group h.

As said phthalocyanine type chromophore, what is represented by following formula (10) is preferable.

[In Formula (10),
CuPc represents a copper phthalocyanine residue,
T represents a group represented by the following formula (10a) or (10b). ]

[In the formulas (10a) and (10b)
R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ , R ¹⁵⁶ , R ¹⁵⁷ and R ¹⁵⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group,
p ¹ independently represents an integer of 2 to 8,
mb represents an integer of 1 to 5 independently of each other. ]

Representative examples of the chromophore represented by the formula (10) include chromophores shown in the following compound group k.

  As said xanthene type chromophore, what is represented by following formula (11) is preferable.

[In Formula (11),
R ¹⁷¹ , R ¹⁷² , R ¹⁷³ and R ¹⁷⁴ are each independently a hydrogen atom, —R ¹⁷⁸ or an aromatic hydrocarbon group having 6 to 10 carbon atoms (provided that the hydrogen atom contained in the aromatic hydrocarbon group) Is a halogen atom, —R ¹⁷⁸ , —OH, —OR ¹⁷⁸ , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ¹⁷⁸ , —SO ₃ R ¹⁷⁸ , —SO ₂ NHR ¹⁷⁹ or — SO ₂ NR ¹⁷⁹ R ¹⁸⁰ may be substituted). ;
R ¹⁷⁵ and R ¹⁷⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ;
R ¹⁷⁷ represents —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ¹⁷⁸ , —SO ₃ R ¹⁷⁸ , —SO ₂ NHR ¹⁷⁹ or —SO ₂ NR ¹⁷⁹ R ¹⁸⁰ . ;
k represents an integer of 0 to 5, and when k is an integer of 2 or more, the plurality of R ¹⁷⁷ may be the same or different. ;
R ¹⁷⁸ represents a saturated hydrocarbon group having 1 to 10 carbon atoms (however, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and the methylene group contained in the saturated hydrocarbon group is , An oxygen atom, a carbonyl group, or —NR ¹⁷⁸ — may be substituted). ;
R ¹⁷⁹ and R ¹⁸⁰ independently represent a chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or —Z, or R ¹⁷⁹ and R ¹⁸⁰ are bonded to each other. Or a substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms formed. However, the hydrogen atom contained in the alkyl group and cycloalkyl group may be substituted with a hydroxyl group, a halogen atom, -Z, -CH = CH ₂ or -CH = CHR ¹⁷⁸ , and the alkyl group and cycloalkyl The methylene group contained in the group may be substituted with an oxygen atom, a carbonyl group or —NR ¹⁷⁸ —, and the hydrogen atom contained in the heterocyclic group is substituted with —R ¹⁷⁸ , —OH or —Z. May be. ;
M represents a sodium atom or a potassium atom. ;
Z represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms. However, the hydrogen atom contained in the aromatic hydrocarbon group and aromatic heterocyclic group is —OH, —R ¹⁷⁸ , —OR ¹⁷⁸ , —NO ₂ , —CH═CH ₂ , —CH═CHR ¹⁷⁸ or a halogen atom. May be substituted. ]

The saturated hydrocarbon group for R ¹⁷⁸ may be linear, branched or cyclic and may have a bridge structure as long as it has 1 to 10 carbon atoms. Specifically, in addition to the same alkyl group as R ⁴ in the above formula (2), nonyl group, decanyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecanyl group may be mentioned. it can. Examples of the group in which the methylene group contained in the saturated hydrocarbon group is substituted with an oxygen atom include a methoxypropyl group, an ethoxypropyl group, a 2-ethylhexyloxypropyl group, and a methoxyhexyl group.

Examples of the substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms formed by combining R ¹⁷⁹ and R ¹⁸⁰ with each other include pyrrole, pyridine, indole, isoindole, quinoline, isoquinoline, carbazole, phenanthridine, and acridine , Furan, pyran, isobenzofuran, isochromene, xanthene, thiophene, thianthrene, phenoxathiin, fanothiazine and the like. Examples of the substituent in the heterocyclic group include a halo group, a hydroxyl group, an alkoxy group, an amino group, and an alkyl group. Examples of the aromatic heterocyclic group having 5 to 10 carbon atoms in Z include a furyl group, a thienyl group, a pyridyl group, a pyrrolyl group, an oxazolyl group, an isoxazol group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a pyrazolyl group, and a pyrimidyl group. Can be mentioned.

Examples of the aromatic hydrocarbon group in R ¹⁷¹ , R ¹⁷² , R ¹⁷³ , R ¹⁷⁴ and Z include a phenyl group and a naphthyl group.
^Examples of —SO ₃ R ¹⁷⁸ in R ¹⁷¹ , R ¹⁷² , R ¹⁷³ , R ¹⁷⁴ and R ¹⁷⁷ include a methanesulfonyl group, an ethanesulfonyl group, a hexanesulfonyl group, and a decanesulfonyl group. Examples of —CO ₂ R ¹⁷⁸ include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, a butyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a methoxypropyloxycarbonyl group. Furthermore, -SO ₂ NHR ^179, as the R ^179, R ¹⁸⁰ in -SO ₂ NR ¹⁷⁹ R ^180, branched alkyl groups having 6 to 8 carbon atoms, alicyclic hydrocarbon group having 5 to 7 carbon atoms An allyl group, an aralkyl group having 8 to 10 carbon atoms, a hydroxyl group-containing alkyl group having 2 to 8 carbon atoms, an alkoxy group-containing alkyl group having 2 to 8 carbon atoms, and an aryl group are preferable.

R ¹⁷¹ , R ¹⁷² , R ¹⁷³ and R ¹⁷⁴ are preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or an ethyl group.
R ¹⁷⁵ and R ¹⁷⁶ are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably a methyl group or an ethyl group.
R ¹⁷⁷ is preferably —SO ₃ H, —SO ₃ M, —CO ₂ H, or —CO ₂ R ^178, more preferably —CO ₂ H or —CO ₂ R ¹⁷⁸ . R ¹⁷⁸ in -CO ₂ R ¹⁷⁸ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, more preferably methyl or ethyl.
k is preferably 1 or 2, and more preferably 1.

  Representative examples of the cation represented by the above formula (11) include a cation represented by the following formula.

Among these, from the viewpoint of heat resistance, Z ⁺ is a triarylmethane-based cationic chromophore represented by the formula (2-1), and a triarylmethane-based cationic chromophore represented by the formula (2-2). Preferred are methine-based cationic chromophores, azo-based cationic chromophores, diarylmethane-based cationic chromophores, quinoneimine-based cationic chromophores, and xanthene-based cationic chromophores. ), A triarylmethane cationic chromophore represented by formula (2-2), a triarylmethane cationic chromophore represented by formula (2-2), a methine cationic chromophore, and a xanthene cationic chromophore. Is more preferable.
The reason why the heat resistance varies depending on the type and structure of the chromophore is not clear. The present inventors consider that a chromophore having a resonance structure interacts with the structural unit represented by the formula (1), and thus is easily stabilized and heat resistance is increased.

  The present colorant may have a structural unit other than the structural unit represented by the formula (1) (hereinafter, also referred to as “other structural unit”). For example, structural units derived from ethylenically unsaturated monomers having one or more carboxyl groups, structural units derived from N-substituted maleimides, structural units derived from aromatic vinyl compounds, (meth) acrylic acid esters And a structural unit derived from a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain.

  The structural unit derived from the ethylenically unsaturated monomer having one or more carboxyl groups is, for example, (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxy Ethyl], ω-carboxypolycaprolactone mono (meth) acrylate, and ethylenically unsaturated monomers having a carboxyl group such as p-vinylbenzoic acid.

Moreover, the structural unit derived from N-position substituted maleimide can be obtained by N-position substituted maleimide such as N-phenylmaleimide and N-cyclohexylmaleimide.
The aromatic vinyl compound can be obtained by an aromatic vinyl compound such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene, and the like. .

Moreover, the structural unit derived from (meth) acrylic acid ester is, for example, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl ( (Meth) acrylate, benzyl (meth) acrylate, 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 glycol (degree of polymerization 2) -10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2-10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane -8-I (Meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4 -It can be obtained by (meth) acrylic acid ester such as epoxycyclohexylmethyl (meth) acrylate, 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane.

The structural unit derived from vinyl ether includes, for example, cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- ( It can be obtained with vinyl ethers such as vinyloxymethyl) -3-ethyloxetane.
The structural unit derived from the macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain is, for example, polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, or polysiloxane. It can be obtained by a macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain.

  Among these, from the viewpoint of dispersibility, the colorant preferably has a structural unit derived from (meth) acrylic acid ester as another structural unit, and has a structural unit derived from (meth) acrylic acid alkyl ester. Is more preferable.

When the present colorant has other structural units, the copolymerization ratio of the other structural units is preferably the following mode from the viewpoint of dispersibility.
That is, the ratio p of the structural unit represented by the formula (1) and the ratio r of the other structural units in all the structural units of the present colorant are molar ratios, and p / r = 1 / 0.5 to 1 / 19 is preferable, p / r = 1 / 1.5 to 1/9 is more preferable, and p / r = 1/2 to 1/7 is still more preferable.

  The colorant has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran), usually from 1,000 to 100,000, preferably 3,000 to 50,000. By setting it as such an aspect, heat resistance, a film characteristic, an electrical property, a pattern shape, and the resolution can be made favorable.

  Moreover, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the colorant in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to. 3.0. In addition, Mn here is the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).

  Although this coloring agent can be manufactured by a well-known method, it can be manufactured by the method similar to the Example of Unexamined-Japanese-Patent No. 2012-194466, for example. The colorant thus obtained is soluble in various organic solvents such as propylene glycol monomethyl ether acetate and has excellent solvent resistance.

  In the present invention, the colorant can be used alone or in admixture of two or more.

  The coloring composition of this invention can contain another coloring agent as (A) coloring agent. In this case, the content ratio of the present colorant is preferably 0.1 to 99% by mass, more preferably 1 to 80% by mass, still more preferably 10 to 70% by mass, and particularly preferably 20% in all colorants. -60 mass%.

  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 other than the present colorant can be used. However, organic pigments and organic dyes are preferable and organic pigments are more preferable in terms of obtaining pixels with high luminance and color purity.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), among which JP-A-2001-081348 and JP-A The rakes described in 2010-026334, 2010-191304, 2010-237384, 2010-237369, 2011-006602, 2011-145346, etc. Pigments, C.I. 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 green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 80, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211, C.I. I. Pigment orange 38, C.I. I. Organic pigments other than lake pigments such as CI Pigment Violet 23 are preferred. Among lake pigments, triarylmethane lake pigments, xanthene lake pigments, and azo lake pigments are preferable, and triarylmethane lake pigments and xanthene lake pigments are more preferable.

  In the present invention, when a pigment is used as another colorant, the pigment may be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Moreover, the pigment surface 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 Application Laid-Open No. 08-179111 can be employed.

  In the present invention, when a pigment is used as another colorant, a known dispersant and dispersion aid can be further contained. 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. A dispersant, a polyester-based dispersant, an acrylic-based dispersant and the like, and examples of the dispersion aid include a pigment derivative and the like.

  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)) ), And as a urethane-based dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2164 (manufactured by BYK Corporation (BYK) 76) Lubrizol Co., Ltd.), polyethyleneimine dispersant, Solsperse 24000 (Lubrisol Co., Ltd.), polyester dispersant And, Adisper PB821, Adisper PB822, Adisper PB880, Adisper PB881 (or more, Ajinomoto Fine-Techno Co., Ltd.), and the like.

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

  In the present invention, other colorants can be used alone or in admixture of two or more.

  (A) The content ratio of the colorant is improved in heat resistance and solvent resistance, migratory suppression, and a pixel having high luminance and excellent color purity, or a black matrix having excellent light shielding properties, and a black spacer. Usually, it is 5-70 mass% in solid content of a coloring composition, Preferably it is 5-60 mass%. Here, solid content is components other than the solvent mentioned later.

-(B) Binder resin-
The colored composition of the present invention can contain a binder resin (excluding a polymer having a structural unit represented by the formula (1)). Thereby, the alkali solubility of a coloring composition, the binding property to a board | substrate, storage stability, etc. can be improved. The binder resin is not particularly limited as long as it does not correspond to the polymer containing the structural unit represented by the formula (1), but is a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Is preferred. Among them, a polymer having a carboxyl group (hereinafter 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”). (B1) ") and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as" unsaturated monomer (b2) ").

  Examples of the unsaturated monomer (b1) include those similar to the ethylenically unsaturated monomer having a carboxyl group. Moreover, an unsaturated monomer (b1) can be used individually or in mixture of 2 or more types.

  Further, as the unsaturated monomer (b2), for example, an N-position substituted maleimide, an aromatic vinyl compound, (meth) acrylic acid ester, vinyl ether, and a mono (meth) acryloyl group at the end of the polymer molecular chain. A macromonomer etc. can be mentioned, As a specific example, the same thing as the above-mentioned can be mentioned. Moreover, an unsaturated monomer (b2) can be used individually or in mixture of 2 or more types.

  In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

  Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300922, 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.

  The binder resin in the present invention has a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran), usually from 1,000 to 100,000. Preferably it is 3,000-50,000. By setting it as such an aspect, heat resistance, a film characteristic, an electrical property, a pattern shape, and the resolution can be made favorable.

  Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3. .0. In addition, Mn here is the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

  In this invention, binder resin can be used individually or in mixture of 2 or more types.

  In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts, More preferably, it is 50-350 mass parts, More preferably, it is 100-250 mass parts. By setting it as such an aspect, heat resistance, solvent resistance, alkali developability, the storage stability of a coloring composition, and chromaticity characteristic can be made favorable. Moreover, dye transfer property can be suppressed.

-(C) Polymerizable compound-
In the present invention, 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. In the present invention, the polymerizable compound is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a polyfunctional (meta) modified with caprolactone. ) Acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting hydroxyl-functional (meth) acrylate and polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group obtained by making a product react 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 dihydrate. A methacrylate etc. can be mentioned. 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 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. Modified with at least one selected from trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from modified isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide Pen modified with at least one selected from pentaerythritol 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 taerythritol tetra (meth) acrylate, ethylene oxide and propylene oxide Examples include hexa (meth) acrylate.

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril and the like.

Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethanes (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N ′ -Tetra (alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Among polyfunctional (meth) acrylates having a carboxyl group, erythritol hexaacrylate is obtained by reacting pentaerythritol triacrylate and succinic anhydride, and reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer. Moreover, heat resistance and solvent resistance can be improved and dye transfer property can be suppressed.
In this invention, (C) polymeric compound can be used individually or in mixture of 2 or more types.

  The content of the polymerizable compound (C) in the present invention is preferably 10 to 1,000 parts by weight, more preferably 20 to 700 parts by weight, and further 100 to 500 parts by weight with respect to 100 parts by weight of the (A) colorant. 200-400 mass parts is especially preferable. By setting it as such an aspect, heat resistance, solvent resistance, sclerosis | hardenability, and alkali developability can be made favorable. Moreover, dye transfer property can also be suppressed.

-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 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 the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

  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, Examples thereof include 4 ′, 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 the triazine compound 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 (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -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.

  In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) polymeric compounds, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. By setting it as such an aspect, heat resistance, solvent resistance, sclerosis | hardenability, and a film characteristic can be made favorable. Moreover, dye transfer property can also be suppressed.

-Solvent-
The coloring composition of the present invention contains the above components (A) and (C) and other components optionally added, but is usually prepared as a liquid composition by blending a solvent.
As the above-mentioned solvent, as long as the components (A) and (C) and other components constituting the colored composition are dispersed or dissolved and do not react with these components and have appropriate volatility, the above-mentioned solvent is appropriately used. You can choose to use.

Among such solvents, 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 these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, 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-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Pioneto acetate n- butyl acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
In this invention, a solvent can be used individually or in mixture of 2 or more types.

  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 the quantity used as 10-40 mass% 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 coating property and stability can be obtained.

-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 the like, and the like.

Colored cured film and method for forming the same The colored cured film of the present invention is formed using the colored composition of the present invention. Specifically, each color pixel used in a display device or a solid-state imaging device, a black matrix , Meaning black spacer.

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, a blue liquid composition of the radiation-sensitive colored composition of the present invention is applied on the substrate, and then pre-baked to evaporate the solvent to form 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 blue pixel patterns (colored cured films) are arranged in a predetermined arrangement.

  Subsequently, using each radiation sensitive coloring composition of green or red, application of each radiation sensitive coloring composition, pre-baking, exposure, development, and post-baking are performed in the same manner as described above to obtain a green pixel array and red color. Are sequentially formed on the same substrate. Thereby, a color filter in which a pixel array of the three primary colors of blue, green and red 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.

  The 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, the radiation sensitive material in which a black colorant is dispersed is used. It can also be formed in the same manner as in the case of forming the above-mentioned pixel by using the coloring composition.

Examples of the substrate used when forming the color filter 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 radiation-sensitive coloring composition to the substrate, an appropriate coating method such as spraying, roll coating, spin coating (spin coating), slit die coating (slit coating), bar coating, etc. In particular, it is preferable to employ a spin coating method or a slit die coating method.

  Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70-110 degreeC normally 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, 1,8-diazabicyclo- [5.4.0] -7-. An aqueous solution of undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene or the like 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 blue thermosetting coloring composition is discharged into the formed partition wall by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, the coating film is exposed as necessary, and then cured by post-baking to form a blue pixel pattern.

  Next, using the green or red thermosetting coloring composition, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate in the same manner as described above. As a result, a color filter in which the pixel patterns of the three primary colors of blue, green and red 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 colored composition of the present invention can also be suitably used for forming such a black spacer.

The radiation-sensitive 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 including the colored cured film of the present invention formed in this way has extremely high luminance and color purity, it can be used in color liquid crystal display elements, color imaging tube elements, color sensors, organic EL display elements, electronic paper, and the like. Very useful. In addition, the display element mentioned later should just have at least 1 or more of colored cured films formed using the radiation sensitive coloring composition of this invention.

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. Further, 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 acid value indium and zinc oxide) electrode It is also possible to adopt a structure in which the substrate on which the substrate is formed faces 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 color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence A white LED that obtains white light by color mixing by combining the body, 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 element 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.

  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.

<Synthesis of colorant>
Synthesis example 1
(Synthesis of polymer (1))
To a reaction vessel equipped with a condenser tube, 5.46 g of p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt, 4.51 g of methyl methacrylate, and 0.130 g of α-thioglycerol were added and dissolved in 20 g of cyclohexanone. The solution was heated to 100 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, a solution prepared by dissolving 98.0 mg of α, α'-azobisisobutyronitrile in 10.4 g of cyclohexanone was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours. Continued. Thereafter, the reaction solution was cooled to room temperature, and then 60 g of acetone was added to make a uniform solution, which was added dropwise to 1.1 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 8.14 g of a polymer represented by the following structural formula. The obtained polymer has Mw of 7,800 and Mn of 3,600, and ¹ H-NMR analysis confirmed that the ratio of p and r is 1 / 2.2 in molar ratio (p / r). did. This is referred to as a polymer (1).

(Synthesis of polymer A)
2.0 g of the polymer (1) was dissolved in 40 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). A quantity of compound (1) 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 under reduced pressure at 50 ° C. to obtain 2.54 g of polymer A represented by the following structural formula. Polymer A corresponds to the present colorant.

Synthesis example 2
(Synthesis of polymer (2))
In the synthesis of the polymer (1), the following structure was obtained in the same manner as in Synthesis Example 1 except that p- (vinylphenyl) trifluoromethanesulfonylimide acid triethylamine salt was used instead of p-styrenesulfonic acid tetraethylammonium salt. 8.29 g of the polymer (2) represented by the formula was obtained. The obtained polymer (2) has an Mw of 8,800 and an Mn of 4,300, and the ¹ H-NMR analysis shows that the ratio of p and r is 1 / 2.8 in molar ratio (p / r). I confirmed that there was.

(Synthesis of polymer B)
In the synthesis of the polymer A, as shown in the following scheme, a polymer represented by the following structural formula is obtained in the same manner as in Synthesis Example 1 except that the polymer (2) is used instead of the polymer (1). 2.50 g of B was obtained. Polymer B is not the present colorant.

Synthesis example 3
(Synthesis of polymer (3))
To a reaction vessel equipped with a cooling tube, 4.55 g of p- (vinylphenyl) normalnonafluorobutanesulfonylimidic acid triethylamine salt, 5.41 g of methyl methacrylate and 0.130 g of α-thioglycerol were added and dissolved in 20 g of cyclohexanone. . The solution was heated to 100 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, a solution prepared by dissolving 98.0 mg of α, α'-azobisisobutyronitrile in 10.4 g of cyclohexanone was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours. Continued. Thereafter, the reaction solution was cooled to room temperature, and then 60 g of acetone was added to make a uniform solution, which was added dropwise to 1.1 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 8.02 g of a polymer represented by the following structural formula. The obtained polymer has Mw of 7,500, Mn of 3,300, and ¹ H-NMR analysis confirmed that the ratio of p and r is 1 / 2.6 in molar ratio (p / r). did. This is referred to as a polymer (3).

(Synthesis of polymer C)
In the synthesis of the polymer A, as shown in the following scheme, a polymer represented by the following structural formula is obtained in the same manner as in Synthesis Example 1 except that the polymer (3) is used instead of the polymer (1). 2.43 g of C was obtained. Polymer C corresponds to the present colorant.

Synthesis example 4
(Synthesis of polymer (4))
To a reaction vessel equipped with a condenser tube, 6.11 g of the following compound (2), 3.85 g of methyl methacrylate, and 0.130 g of α-thioglycerol were added and dissolved in 20 g of cyclohexanone. The solution was heated to 100 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, a solution prepared by dissolving 98.0 mg of α, α'-azobisisobutyronitrile in 10.4 g of cyclohexanone was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours. Continued. Thereafter, the reaction solution was cooled to room temperature, and then 60 g of acetone was added to make a uniform solution, which was added dropwise to 1.1 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 8.25 g of a polymer represented by the following structural formula. The obtained polymer has Mw of 8,000, Mn of 4,100, and ¹ H-NMR analysis confirmed that the ratio of p and r is 1 / 1.9 in molar ratio (p / r). did. This is referred to as a polymer (4).

(Synthesis of polymer D)
In the synthesis of the polymer A, as shown in the following scheme, a polymer represented by the following structural formula is obtained in the same manner as in Synthesis Example 1 except that the polymer (4) is used instead of the polymer (1). 2.65 g of D was obtained. Polymer D corresponds to the present colorant.

Synthesis Examples 5-15
(Synthesis of polymers E to O)
In the synthesis of Polymer A, Polymers E to O were obtained in the same manner as in Synthesis Example 1 except that the reaction was performed using combinations of raw materials shown in Table 1. Polymers E to O all correspond to the present colorant.

  In addition, C. used as a raw material. I. The structure of the numbered compound is as follows:

Synthesis Example 16
A 100 mL Erlenmeyer flask containing a stirrer was charged with 5.21 g of the compound (1) represented by the following formula and 4.31 g of bis (trifluoromethanesulfonyl) imide lithium, and 50 mL of chloroform and 25 mL of ion-exchanged water were added to room temperature. For about 2 hours. Thereafter, the aqueous layer was separated and removed, and the organic layer was washed twice with ion-exchanged water. The organic layer was concentrated under reduced pressure, and the residue was dried under reduced pressure at 50 ° C. for 12 hours to obtain 7.42 g of a compound represented by the following structural formula. The resulting compound is referred to as Dye A. Dye A is not the present colorant.

Preparation Examples 1-16
The obtained polymers A to O and the dye A and propylene glycol monomethyl ether acetate were mixed as shown in Table 2 to prepare a polymer solution or a dye solution. In Table 2, propylene glycol monomethyl ether acetate is abbreviated as PGMEA.

Preparation Example 17
As a coloring agent, C.I. I. 15 parts by mass of Pigment Green 58, 12.5 parts by mass of BYK-LPN21116 (produced by BYK) as a dispersant (solid content concentration 40% by mass), and 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent Then, a pigment dispersion (a-1) was prepared by treatment with a bead mill.

Preparation Example 18
As a coloring agent, C.I. I. 15 parts by weight of Pigment Yellow 138, 12.5 parts by weight of BYK-LPN21116 (manufactured by BYK) as a dispersant (solid content concentration 40% by weight), and 72.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent Then, a pigment dispersion (a-2) was prepared by treatment with a bead mill.

<Synthesis of binder resin>
Synthesis Example 17
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate 23 parts by mass, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) The solution was added dropwise over a period of time and polymerized for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The obtained binder resin had Mw of 12,200 and Mn of 6,500. This binder resin is referred to as “binder resin (B1)”.

Preparation of coloring composition for transferability evaluation Preparation Example 19
(A) 30.5 parts by weight of pigment dispersion (a-1) as a colorant, 25.0 parts by weight of pigment dispersion (a-2), (B) 26.3 parts by weight of a binder resin (B1) solution as a 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 Ciba Specialty Chemicals) and NCI-930 (manufactured by ADEKA Corporation) ) 0.1 parts by mass, 0.05 parts by mass of MegaFac F-554 (manufactured by DIC Corporation) as a fluorosurfactant, and Propylene glycol monomethyl ether acetate was mixed as a solvent to prepare a green coloring composition (G) having a solid content concentration of 20% by mass.

<Preparation and evaluation of coloring composition>
Example 1
(A) 7.2 parts by mass of the polymer solution (A-1) as the colorant, (B) 9.9 parts by mass of the binder resin (B1) solution as the binder resin, (C) dipentaerythritol hexaacrylate as the polymerizable compound Of dipentaerythritol pentaacrylate (Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) 15.4 parts by mass, 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 Ciba Specialty Chemicals) and 0.1 part by mass of NCI-930 (manufactured by ADEKA), mega as a fluorosurfactant Fax F-554 (manufactured by DIC Corporation) 0.05 parts by mass, and propylene glycol monomethyl as a solvent Ruether acetate was mixed to prepare a colored composition (S-1) having a solid concentration of 20% by mass.

Evaluation of heat resistance The colored composition (S-1) was applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed using a spin coater, and then a hot plate at 90 ° C. Was pre-baked for 2 minutes to form a coating film having a thickness of 2.5 μm.
Next, after cooling the substrate to room temperature, each coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 400 J / m ² through a photomask using a high-pressure mercury lamp. Then, shower development was performed for 90 seconds on these substrates 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). . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 200 ° C. for 30 minutes to form a dot pattern 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 field of view. Was measured.
Next, after the substrate was additionally baked at 230 ° C. for 90 minutes, the chromaticity coordinate values (x, y) and the stimulus value (Y) were measured, and the color change before and after the additional baking, that is, ΔE ^* ab was evaluated. . As a result, when the value of ΔE ^* ab is less than 2.0, “「 ”, when it is 2.0 or more and less than 4.0,“ ◯ ”, when it is 4.0 or more and less than 6.0,“ △ ”, The case of 6.0 or more was evaluated as “x”. The evaluation results are shown in Table 3. In addition, it can be said that heat resistance is so favorable that (DELTA ⁾ E ^* ab value is small.

Evaluation of solvent resistance The colored composition (S-1) was applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed using a spin coater, and then heated at 90 ° C. The plate was pre-baked for 2 minutes to form a coating film having a thickness of 2.5 μm.
Next, after cooling the substrate to room temperature, each coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 400 J / m ² through a photomask using a high-pressure mercury lamp. Then, shower development was performed for 90 seconds on these substrates 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). . Thereafter, this substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 30 minutes to form a dot pattern 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 field of view. Was measured.
Thereafter, the substrate was immersed in propylene glycol monomethyl ether acetate at 80 ° C. for 40 minutes. With respect to the dot pattern after immersion, chromaticity coordinate values (x, y) and stimulation values (Y) were measured, and color change before and after immersion, that is, ΔE ^* ab was evaluated. As a result, the case where the value of ΔE ^* ab was less than 3.0 was evaluated as “◯”, the case of 3.0 or more and less than 5.0 was evaluated as “Δ”, and the case of 5.0 or more was evaluated as “x”. The evaluation results are shown in Table 3. It can be said that the smaller the ΔE ^* ab value, the better the solvent resistance.

Evaluation of transferability After applying the green coloring composition (G) on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed using a spin coater, a hot plate at 90 ° C Was pre-baked for 2 minutes to form a coating film having a thickness of 2.4 μm.
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. Then, shower development was performed for 90 seconds on these substrates 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). . Thereafter, this substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 30 minutes to form a green cured film (T-1) on the substrate. About the obtained green cured film (T-1), using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), a chromaticity coordinate value (x, y) in the CIE color system with a C light source and a 2-degree field of view. And the stimulation value (Y) was measured.
Next, after apply | coating the coloring composition (S-1) on a green cured film (T-1) using a spin coater, it prebaked for 2 minutes with a 90 degreeC hotplate, and a film thickness of 2.5 micrometers is carried out. A coating film was formed. 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, shower development was performed for 90 seconds. Thereafter, the substrate was washed with ultrapure water and air-dried. A series of steps from application of the coloring composition (S-1) to air drying is referred to as “(step-1)”. For the green cured film (T-1) after (Step-1), the chromaticity coordinate value (x, y) and the stimulus value (Y) are measured, and the stimulus value change before and after (Step-1), that is, ΔY is measured. evaluated. As a result, the case where the value of ΔY was less than 0.2 was evaluated as “◯”, the case of 0.2 or more and less than 0.7 was evaluated as “Δ”, and the case of 0.7 or more was evaluated as “x”. The evaluation results are shown in Table 3. It can be said that the smaller the ΔY value, the more the dye transfer property is suppressed.

Examples 2-14 and Comparative Examples 1-2
In Example 1, coloring compositions (S-2) to (S-16) were prepared in the same manner as in Example 1, except that the types and amounts of the colorant and the binder resin solution were changed as shown in Table 1. did. The resulting colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Claims (10)

A coloring composition comprising (A) a colorant and (C) a polymerizable compound,
The coloring composition in which the colorant contains a polymer having a structural unit represented by the following formula (1).

[In Formula (1),
R ⁰ represents a hydrogen atom or a methyl group,
X represents a group having a linking group containing a carbon atom, a hydrogen atom or an atom other than a halogen atom between the C-C bonds of a halo group, a halogenated hydrocarbon group, or a halogenated hydrocarbon group;
Y represents a single bond or a divalent organic group,
Z ⁺ is lower following formula triarylmethane cationic chromophore represented by (2-2), a methine type cationic chromophores, cationic chromophores cationic coloring Dan及 beauty xanthene azo At least one cationic chromophore selected from the group consisting of: ]

[In Formula (2-2),
R ^{11 to} R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, or a substituted or unsubstituted group. Represents an aryl group,
R ^{17 to} R ¹⁹ each independently represent an alkyl group having 1 to 8 carbon atoms or a chlorine atom,
s, t and u each independently represent an integer of 0 to 4. ]   Y is a divalent hydrocarbon group, a group formed by combining a divalent hydrocarbon group and a linking group containing an atom other than a carbon atom and a hydrogen atom, or a part of hydrogen atoms of these groups is a halogen atom The coloring composition according to claim 1, which is a divalent group substituted with The polymer having the structural unit represented by the formula (1) further contains a structural unit other than the structural unit represented by the formula (1), and other than the structural unit represented by the formula (1). Structural units derived from ethylenically unsaturated monomers having one or more carboxyl groups, structural units derived from N-substituted maleimides, structural units derived from aromatic vinyl compounds, (meth) acrylic The coloring according to claim 1 or 2, which is a structural unit derived from an acid ester, a structural unit derived from vinyl ether, or a structural unit derived from a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain. Composition. The coloring composition according to any one of claims 1 to 3, wherein the methine-based cationic chromophore is represented by the following formula (5-1).

[In Formula (5-1),
R ³¹ Represents a hydrogen atom or a halo group,
R ³² , R ³³ And R ³⁴ Independently represent an alkyl group having 1 to 6 carbon atoms,
G represents -CH = CH-, -CH = CH-CH =, -CH = CH-NR ³⁷ -(R ³⁷ Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —CH═N—NR. ³⁷ -(R ³⁷ Is as defined above) or -N = N-NR ³⁷ -(R ³⁷ Is as defined above)
R ^a Represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group. ] R in the formula (5-1) ^a The coloring composition of Claim 4 which is group represented by following formula (5a)-(5h).

[In Formula (5a)-(5h),
R ³⁸ And R ⁴⁵ Independently represent an alkyl group having 1 to 6 carbon atoms,
R ³⁹ Represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
  R ⁴⁰ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁷ , R ⁴⁸ And R ⁴⁹ Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
R ⁴¹ , R ⁴⁶ And R ⁵⁰ Independently represent a hydrogen atom, a halo group, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group. ] The ratio p of the structural unit represented by the formula (1) and the ratio r of the structural unit other than the structural unit represented by the formula (1) are p / r = 1 / 0.5 to 1 in terms of molar ratio. The coloring composition of any one of Claims 3-5 which is / 19. (A) The coloring composition of any one of Claims 1-5 whose content rate of a coloring agent is 5-70 mass% in solid content of a coloring composition. Furthermore, the coloring composition of any one of Claims 1-7 containing (B) binder resin. The colored cured film formed using the coloring composition of any one of Claims 1-8 . A display device comprising the colored cured film according to claim 9 .