JP5482878B2 - Colorant, coloring composition, color filter and display element - Google Patents

Description

  The present invention relates to a colored composition, a color filter, and a display element. More specifically, the present invention is suitably used for a color filter such as a transmissive or reflective color liquid crystal display element, a solid-state imaging element, an organic EL display element, and electronic paper. The present invention relates to a colorant, a color composition containing the colorant, a color filter including a color layer containing the colorant, and a display element including the color filter.

  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. There is known a method (Patent Documents 1 and 2) for obtaining pixels of each color by irradiation (hereinafter referred to as “exposure”) and development. A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (Patent Document 3) is also known. Furthermore, a method of obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (Patent Document 4).

  By the way, it is known that it is effective to use a dye as a colorant in order to achieve high luminance and high color purity of a display element or high definition of a solid-state imaging element. For example, Patent Document 5 proposes the use of a xanthene dye having a specific structure.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2008-242311 A

However, the xanthene dye proposed in Patent Document 5 has a problem that the voltage holding ratio of the color filter is deteriorated. From the background as described above, development of a coloring composition suitable for producing a color filter having a good voltage holding ratio is strongly demanded.
Therefore, the subject of this invention is providing the coloring composition suitable for formation of the colored layer excellent in a voltage holding rate. Moreover, the subject of this invention is providing the display element which comprises the color filter provided with the colored layer formed from the said coloring composition, and the said color filter.

  In view of such a situation, the present inventors have conducted intensive studies and found that the above-mentioned problems can be solved by using a colorant having a specific structure, and the present invention has been completed.

That is, this invention provides the coloring composition containing the following component (A), (B) and (C).
(A) a xanthene-based colorant having a polymerizable unsaturated group in the color developing portion (hereinafter also referred to as “the present colorant”);
(B) a binder resin; and (C) a crosslinking agent.

  Moreover, this invention provides the display element which comprises the color filter provided with the colored layer formed using the said coloring composition, and the said color filter. Here, the “colored layer” means each color pixel, black matrix, black spacer, etc. used in the color filter.

  Furthermore, this invention provides the coloring agent which has a structure represented by following formula (1).

[In Formula (1),
R ^a represents a group having a polymerizable unsaturated group. ;
R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group (the alkyl group, cycloalkyl group, and phenyl group are substituted) Which may have a group). ;
R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a chlorine atom. ;
r represents an integer of 1 to 5, and when r is an integer of 2 or more, a plurality of ^Ra may be the same or different. ]

  If the colored composition of this invention is used, the colored layer which is excellent in a voltage retention can be formed. Therefore, the colored composition of the present invention is used for the production of various color filters including color filters for display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It can be used very suitably.

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 this coloring agent as (A) coloring agent.

The colorant is not particularly limited as long as it is a xanthene colorant having a polymerizable unsaturated group in the color developing portion. As said polymerizable unsaturated group, a (meth) acryloyl group, a vinylaryl group, a vinyloxy group, an allyl group etc. can be mentioned as a suitable example, for example. Of these, a (meth) acryloyl group is preferable.
In the present invention, since the coloring agent has a polymerizable unsaturated group, the polymerizable unsaturated group undergoes a crosslinking reaction during exposure or post-baking, and the elution of the dye into the liquid crystal is suppressed. The present inventors speculate that a good voltage holding ratio is exhibited.

  As the preferred colorant in the present invention, a xanthene colorant having a structure represented by the following formula (1) can be given.

[In Formula (1),
R ^a represents a group having a polymerizable unsaturated group. ;
R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group (the alkyl group, cycloalkyl group, and phenyl group are substituted) Which may have a group). ;
R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a chlorine atom. ;
r represents an integer of 1 to 5, and when r is an integer of 2 or more, a plurality of ^Ra may be the same or different. ]

Examples of the alkyl group having 1 to 8 carbon atoms in R ^{1 to} R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a tertiary butyl group, an isobutyl group, an amyl group, A tertiary amyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a tertiary octyl group, a 2-ethylhexyl group, and the like can be given. Especially, a C1-C6 alkyl group is preferable and a C1-C4 alkyl group is preferable.
The cycloalkyl group having 3 to 8 carbon atoms in R ¹ to R ^4, for example, a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like. Among these, a cycloalkyl group having 5 to 7 carbon atoms is preferable, and a cyclohexyl group is more preferable.

The alkyl group having 1 to 8 carbon atoms, the cycloalkyl group having 3 to 8 carbon atoms, and the phenyl group in R ^{1 to} R ⁴ may have a substituent. Examples of the substituent include a halogen atom, —R ⁷ , —OH, —OR ⁷ , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ⁷ , —SO ₃ R ⁷ , — Preferred examples include SO ₂ NHR ⁸ , —SO ₂ NR ⁸ R ⁹ , —SO ₃ ^{— and the} like.

Here, R < ⁷ > shows a C1-C10 saturated hydrocarbon group. 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 substituted with an oxygen atom, a carbonyl group or —NR ⁷ —. May be.
R ⁸ and R ⁹ each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms (preferably 3 to 8 carbon atoms), or -G. Or a heterocyclic group having 2 to 10 carbon atoms formed by bonding of R ⁸ and R ⁹ to each other. However, the hydrogen atom contained in the alkyl group and cycloalkyl group may be substituted with a hydroxyl group, a halogen atom, -G, -CH = CH ₂ or -CH = CHR ⁷ , 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 ⁷ —, and the hydrogen atom contained in the heterocyclic group is substituted with —R ⁷ , —OH or —G. May be.
M represents a sodium atom or a potassium atom.
G 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 ⁷ , —OR ⁷ , —NO ₂ , —CH═CH ₂ , —CH═CHR ⁷ or a halogen atom. May be substituted.

The saturated hydrocarbon group for R ⁷ may be linear, branched, or cyclic as long as it has 1 to 10 carbon atoms, and may have a bridged structure. Specific examples include nonyl group, decanyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecanyl group, in addition to the same alkyl group as R ^{1 to} R ⁴ . 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.
Specific examples of —CO ₂ R ⁷ which is a substituent of the alkyl group, cycloalkyl group and phenyl group in R ^{1 to} R ⁴ include methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, isopropyloxy Examples thereof include a carbonyl group, a butyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a methoxypropyloxycarbonyl group. Specific examples of —SO ₃ R ⁷ include a methanesulfonyl group, an ethanesulfonyl group, a hexanesulfonyl group, and a decanesulfonyl group.

Specific examples of the heterocyclic group formed by combining R ⁸ and R ⁹ with each other include pyrrole, pyridine, indole, isoindole, quinoline, isoquinoline, carbazole, phenanthridine, acridine, phenothiazine and the like. .

  Specific examples of the aromatic hydrocarbon group for G include a phenyl group, a naphthyl group, and an azulenyl group. Specific examples of the aromatic heterocyclic group 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. it can.

Examples of the alkyl group having 1 to 8 carbon atoms in R ⁵ and R ⁶ are the same as those described above.
r represents an integer of 1 to 5, and when r is an integer of 2 or more, a plurality of ^Ras may be the same or different, but r is preferably 1 or 2, and more preferably 1.

As the present colorant in the present invention, a colorant having a structure represented by the following formula (2) can be further preferably used. Incidentally, -COOR ^b group in the formula (2), it is preferably substituted in the o-position on the benzene ring.

[In Formula (2),
R ^b represents a group having a polymerizable unsaturated group. ;
R ¹ to R ⁶ have the same meanings as R ¹ to R ⁶ in formula (1). ]

Examples of the group having a polymerizable unsaturated group in R ^b include the same groups as described above. As the polymerizable unsaturated group in the present invention, a (meth) acryloyl group can be preferably used from the viewpoint of easy crosslinking reaction. Preferable specific examples of R ^b include a group represented by the following formula (2a) or (2b).

[In the formulas (2a) and (2b)
R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a methyl group.
Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a substituted or unsubstituted alkanediyl group having 1 to 12 carbon atoms.
Z represents a —CO— group or a —COO — (*) group (wherein, * represents a bond to Y ² ).
Q represents a divalent alicyclic hydrocarbon group.
p ¹ represents an integer of 0 to 12.
p ² and p ³ are independently of each other, an integer of 0 to 6. ]

R ¹⁰ and R ¹¹ are preferably a methyl group among a hydrogen atom and a methyl group.
Examples of the alkanediyl group having 1 to 12 carbon atoms in Y ^{1 to} Y ⁴ include a methylene group, an ethylene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, and a propane-1,2-diyl group. Propane-1,3-diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1, 2-diyl group, pentane-1,3-diyl group, pentane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, An octane-1,8-diyl group, a decane-1,10-diyl group, etc. can be mentioned, Among these, a C2-C8 alkanediyl group is preferable and a C2-C6 alkanediyl group is more preferable. .
Examples of the substituent of the alkanediyl group include a hydroxyl group, a halogen atom, a (meth) acryloyloxy group, and a phenoxy group. Of these, a hydroxyl group is preferred.
As a bivalent alicyclic hydrocarbon group in Q, a C3-C20 alicyclic hydrocarbon group is preferable, and a C3-C12 alicyclic hydrocarbon group is more preferable. The alicyclic hydrocarbon group may be a 2- to 4-ring bridged cyclic hydrocarbon group.
R ^b is preferably a (meth) acryloyloxyalkyl group. Moreover, 4-16 are preferable and, as for the total carbon number of the said (meth) acryloyloxyalkyl group, 4-10 are especially preferable.

p ¹ is preferably an integer of 0 to 3, and p ² and p ³ are independently preferably an integer of 0 to 3.

  The colorant having a structure represented by the above formula (2) can be obtained, for example, by an esterification reaction between a compound represented by the following formula (3) and a compound having a hydroxyl group and a (meth) acryloyl group. . A known method can be applied as the esterification reaction. Note that the —COOH group in the formula (3) is preferably substituted at the o-position on the benzene ring.

[In Formula (3),
R ¹ to R ⁶ have the same meanings as R ¹ to R ⁶ in formula (1).
X ⁻ represents an anion. ]

  The compound having a hydroxyl group and a (meth) acryloyl group only needs to have one or more hydroxyl groups and (meth) acryloyl groups in the compound. Is optional. Moreover, as a hydroxyl group, both an alcoholic hydroxyl group and a phenolic hydroxyl group can be used. Furthermore, when it has a substituent other than a hydroxyl group and a (meth) acryloyl group, its type, bonding position, and number of bonds are not limited.

  Examples of suitable compounds having a hydroxyl group and a (meth) acryloyl group include compounds represented by the following formula (3a) or (3b).

[In the formulas (3a) and (3b), R ¹⁰ , R ¹¹ , Y ¹ , Y ² , Y ³ , Y ⁴ , Z, Q, p ¹ , p ² and p ³ are as defined above. ]

  More preferable specific examples of the compound having a hydroxyl group and a (meth) acryloyl group include compounds represented by the following formulas (2-1) to (2-4).

[In Formula (2-1),
R ¹² represents a hydrogen atom or a methyl group.
a and b each independently represent an integer of 0 to 2,
c shows the integer of 1-6.
However, when at least one selected from a and b is an integer of 1 or more, the —CH (OH) — group, —CH (CH ₃ ) — group and —CH ₂ — group are bonded in any order. It may be. ]

[In Formula (2-2),
R ¹³ represents a hydrogen atom or a methyl group.
d and e show the integer of 1-12 independently of each other. ]

[In Formula (2-3),
R ¹⁴ represents a hydrogen atom or a methyl group.
f and g each independently represent an integer of 1 to 12. ]

[In Formula (2-4),
R ¹⁵ represents a hydrogen atom or a methyl group.
W represents a divalent group selected from the group of groups represented by the following formulas (I) to (IV).
h and i each independently represent an integer of 0 to 6. ]

  Examples of the compound represented by the formula (2-1) include (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 1-methyl-2-hydroxyethyl ester, and (meth) acrylic acid 2-methyl. 2-hydroxyethyl ester, (meth) acrylic acid 3-hydroxypropyl ester, (meth) acrylic acid 1-glycerol, (meth) acrylic acid 4-hydroxybutyl ester, (meth) acrylic acid 5-hydroxypentyl ester, ( (Meth) acrylic acid 6-hydroxyhexyl ester, (meth) acrylic acid 7-hydroxyheptyl ester, (meth) acrylic acid 8-hydroxyoctyl ester, (meth) acrylic acid 9-hydroxynonyl ester, (meth) acrylic acid 10- Hydroxydecyl ester, (meth) acrylic acid 1 - hydroxy undecyl ester, and (meth) acrylic acid 12-hydroxy-dodecyl ester.

  Examples of the compound represented by the formula (2-2) include (meth) acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester and (meth) acrylic acid 3- (6-hydroxyhexanoyloxy). ) Propyl ester, (meth) acrylic acid 4- (6-hydroxyhexanoyloxy) butyl ester, (meth) acrylic acid 5- (6-hydroxyhexanoyloxy) pentyl ester, (meth) acrylic acid 6- (6- (Meth) acrylic acid (6-hydroxyhexanoyloxy) alkyl esters such as (hydroxyhexanoyloxy) hexyl ester, and the like of (meth) acrylic acid (6-hydroxyhexanoyloxy) alkyl esters As a commercial item, it is a brand name and PLACEL FM1D and PLACEL F 2D (manufactured by Daicel Chemical Industries, Ltd.) and the like.

  Examples of the compound represented by the formula (2-3) include (meth) acrylic acid 2- (3-hydroxy-2,2-dimethylpropoxycarbonyloxy) ethyl ester, (meth) acrylic acid 3- ( 3-hydroxy-2,2-dimethylpropoxycarbonyloxy) propyl ester, (meth) acrylic acid 4- (3-hydroxy-2,2-dimethylpropoxycarbonyloxy) butyl ester, (meth) acrylic acid 5- (3- (Meth) acrylic acid (3-hydroxy-2) such as hydroxy-2,2-dimethylpropoxycarbonyloxy) pentyl ester, (meth) acrylic acid 6- (3-hydroxy-2,2-dimethylpropoxycarbonyloxy) hexyl ester , 2-dimethylpropoxycarbonyloxy) alkyl esters Examples of commercially available (meth) acrylic acid (3-hydroxy-2,2-dimethylpropoxycarbonyloxy) alkyl esters include HEMAC1 (manufactured by Daicel Chemical Industries, Ltd.) and the like under the trade name. Can do.

  Examples of the compound represented by the formula (2-4) include (meth) acrylic acid 4-hydroxycyclohexyl ester, (meth) acrylic acid (4-hydroxymethylcyclohexyl) methyl ester, (meth) acrylic acid 2 -[4- (2-hydroxyethyl) cyclohexyl] ethyl ester, (meth) acrylic acid 3-hydroxybicyclo [2.2.1] hept-5-en-2-yl ester, (meth) acrylic acid (3- Hydroxymethylbicyclo [2.2.1] hept-5-en-2-yl) methyl ester, (meth) acrylic acid 2- [3- (2-hydroxyethyl) bicyclo [2.2.1] hept-5 -En-2-yl] ethyl ester, (meth) acrylic acid 8-hydroxybicyclo [2.2.1] hept-5-en-2-yl ester, T) Acrylic acid 2-hydroxyoctahydro-4,7-methanoinden-5-yl ester, (meth) acrylic acid (2-hydroxymethyloctahydro-4,7-methanoinden-5-yl) methyl ester, (meth) Acrylic acid 2- [2- (2-hydroxyethyl) octahydro-4,7-methanoinden-5-yl] ethyl ester, (meth) acrylic acid 3-hydroxyadamantan-1-yl ester, (meth) acrylic acid (3 -Hydroxymethyladamantan-1-yl) methyl ester, (meth) acrylic acid 2- [3- (2-hydroxyethyl) adamantan-1-yl] ethyl ester, and the like.

Among the compounds having these hydroxyl groups and (meth) acryloyl groups, from the point of reactivity,
1) a compound in which a and b in formula (2-1) are 0 and c is 2 to 6,
2) a compound in which a in formula (2-1) is 1, b is 0, and c is 1 to 5,
3) A compound in which d in formula (2-2) is 2 or 3, and e is 1;
4) a compound in which f in formula (2-3) is 2 or 3, and g is 1;
5) A compound or the like in which h in formula (2-4) is 1 or 2, or i is 1 or 2, and W is a group represented by formula (I) or formula (IV) preferable.
Among them, (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 1-glycerol, (meth) acrylic acid 6-hydroxyhexyl ester, (meth) acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester (Meth) acrylic acid 2- (3-hydroxy-2,2-dimethylpropoxycarbonyloxy) ethyl ester, (meth) acrylic acid (4-hydroxymethylcyclohexyl) methyl ester, (meth) acrylic acid (3-hydroxymethyl) Adamantan-1-yl) methyl ester and the like are preferable.

Examples of the compound having a hydroxyl group and a (meth) acryloyl group other than the compounds represented by the formulas (2-1) to (2-4) include 4-hydroxyphenyl (meth) acrylate, pentaerythritol tri (meth) acrylate, di Examples thereof include pentaerythritol penta (meth) acrylate, glycerol dimethacrylate, and compounds shown in the following compound group a.
In this invention, the compound which has a hydroxyl group and a (meth) acryloyl group can be used individually or in mixture of 2 or more types.

Next, X ⁻ in the formula (3) will be described.
X ⁻ is not particularly limited, and examples thereof include a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, and a methide anion.

  Examples of the halogen ion include fluoride ion, chloride ion, bromide ion, and iodide ion.

As the boron anion, for example, BF ₄ ^-, etc. of the inorganic boron anion;
(CF ₃ ) ₄ B ⁻ , (CF ₃ ) ₃ BF ⁻ , (CF ₃ ) ₂ BF ₂ ⁻ , (CF ₃ ) BF ₃ ⁻ , (C ₂ F ₅ ) ₄ B ⁻ , (C ₂ F ₅ ) ₃ BF ⁻ , (C ₂ F ₅ ) BF ₃ ⁻ , (C ₂ F ₅ ) ₂ BF ₂ ⁻ , (CF ₃ ) (C ₂ F ₅ ) ₂ BF ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , [( CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ , (CF ₃ C ₆ H ₄ ) ₄ B ⁻ , (C ₆ F ₅ ) ₂ BF ₂ ⁻ , (C ₆ F ₅ ) BF ₃ ⁻ , (C ₆ H ₃ F ₂ ) ₄ B ⁻ , B (CN) ₄ ⁻ , B (CN) F ₃ ⁻ , B (CN) ₂ F ₂ ⁻ , B (CN) ₃ F ⁻ , (CF ₃ ) ₃ B (CN) ⁻ , (CF ₃ ) ₂ B (CN) ₂ ⁻ , (C ₂ F ₅ ) ₃ B (CN) ⁻ , (C ₂ F ₅ ) ₂ B (CN) ₂ ⁻ , (nC ₃ F ₇ ) ₃ B ^{(CN) -, (n-} C 4 F 9) 3 B (CN) -, (n-C 4 F 9) 2 B (CN) 2 -, (n-C 6 F 13) 3 B (CN) - , (CHF ₂ ) ₃ B (CN) ⁻ , (CHF ₂ ) ₂ B (CN) ₂ ⁻ , (CH ₂ CF ₃ ) ₃ B (CN) ⁻ , (CH ₂ CF ₃ ) ₂ B (CN) ₂ ⁻ , (CH ₂ C ₂ F ₅ ) ₃ B (CN) ⁻ , (CH ₂ C ₂ F ₅ ) ₂ B (CN) ₂ ⁻ , (CH ₂ CH ₂ C ₃ F ₇ ) ₂ B (CN) ₂ ⁻ , (n-C _{3 F 7 CH 2) 2 B (} CN) 2 -, (C 6 H 5) 3 B (CN) -, tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl ) Borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [ In addition to organic boron anions such as lith (pentafluorophenyl), phenyl] borate, tridecahydride-7,8-dicarboundeborate, JP-A-10-195119, JP-A-2010-094807, JP-A-2006 Examples include boron anions described in JP-A Nos. 243594, 2002-341533, and 08-015521.

Examples of phosphate anions include inorganic phosphate anions such as HPO ₄ ²⁻ , PO ₄ ³⁻ , and PF ₆ ⁻ ;
(C ₂ F ₅ ) ₂ PF ₄ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CF] ₃ PF ₃ , (n− C ₃ F ₇ ) ₂ PF ₄ ⁻ , (n-C ₃ F ₇ ) ₃ PF ₃ ⁻ , (n-C ₄ F ₉ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ⁻ , (n-C ₄ F ₉ ) ₂ PF ₄ ⁻ , (n-C ₄ F ₉ ) ₃ PF ₃ ⁻ , (C ₂ F ₄ H) (CF ₃ ) ₂ PF ₃ ⁻ , (C ₂ F ₃ H ₂ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ⁻ , octyl Examples thereof include organic phosphate anions such as phosphate anion, dodecyl phosphate anion, octadecyl phosphate anion, phenyl phosphate anion, and nonylphenyl phosphate anion.

Examples of the carboxylate anion include, for example, CH ₃ COO ⁻ , C ₂ H ₅ COO ⁻ , C ₆ H ₅ COO ^{− and the} like as described in JP-A-2009-265641 and JP-A-2008-096680. Mention may be made of acid anions.

Examples of sulfate anions include sulfate anions and sulfite anions.
Examples of the organic sulfonate anion include alkyl sulfonate anions such as methane sulfonic acid, ethane sulfonic acid, trifluoromethane sulfonic acid, and nonafluorobutane sulfonic acid;
In addition to arylsulfonic acid anions such as benzenesulfonic acid, benzenedisulfonic acid ion, p-toluenesulfonic acid, p-trifluoromethylsulfonic acid, pentafluorobenzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid ion, 2- (meta ) Acryloyloxy-1,1,2,2-tetrafluoroethanesulfonic acid, 2- (4-vinylphenyloxy) -1,1,2,2-tetrafluoroethanesulfonic acid, International Publication No. 2011/037195 And organic sulfonate anions described in Japanese Patent No. 3736221 and JP-A 2011-070172.

Examples of the nitrogen anion include [(CN) ₂ N] ⁻ , [(FSO ₂ ) ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ SO ₂ )] ⁻ , and [(CF ₃ SO ₂ ). ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ CF ₂ SO ₂ )] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₂ CFSO ₂ }] ⁻ , [(FSO ₂ ) N (CF ₃ CF ^{_{2 CF 2 SO 2)] -}} , [(FSO 2) N (CF 3 CF 2 CF 2 CF 2 SO 2)] -, [(FSO 2) N {(CF 3) 2 CFCF 2 SO 2}] -, In addition to [(FSO ₂ ) N {CF ₃ CF ₂ (CF ₃ ) CFSO ₂ }] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₃ CSO ₂ }] ^{− and the} like, JP 2011-133844 A, Examples thereof include nitrogen anions described in JP 2011-116803 A and JP 2010-090341 A.

Examples of the methide anion include (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ CF ₂ SO ₂ ) ₃ C ⁻ , [(CF ₃ ) ₂ CFSO ₂ ] ₃ C ⁻ , and (CF ₃ CF ₂ CF ₂ SO ₂ ) ₃ C ⁻ , (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ ) ₃ C ⁻ , [(CF ₃ ) ₂ CFCF ₂ SO ₂ ] ₃ C ⁻ , [CF ₃ CF ₂ (CF ₃ ) CFSO ₂ ] ₃ C ⁻ , [(CF ₃ ) ₃ CSO ₂ ] ₃ C ⁻ , (FSO ₂ ) ₃ C ^{— and the} like, JP 2011-145540 A, US Pat. No. 5,554,664, JP 2005-309408 A Examples thereof include a methide anion described in JP-A-2004-085657, JP-A-2010-505787, and the like.

  The colorant can also be a xanthene-based lake pigment having a polymerizable unsaturated group in the color developing portion. Lake pigment refers to a soluble dye made into an insoluble pigment by a precipitating agent. Examples of the precipitating agent include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, and katanol. , Tamol, Complex heteropolyacids called complex acid (phosphotungstic acid, phosphomolybdic acid, phosphotungsten / molybdic acid, silicotungsten molybdic acid, silicotungstic acid, silicomolybdic acid, phosphotungsten molybdate, phosphotungsten Acid, phosphomolybdic acid) and the like. The coloring agent used as a lake pigment is prepared by, for example, rake-forming a compound obtained by an esterification reaction between a compound represented by the above formula (3) and a compound having a hydroxyl group and a (meth) acryloyl group with a precipitant. Can be manufactured.

The coloring composition of this invention can contain another coloring agent further as a coloring agent with this coloring agent. Other colorants are not particularly limited, and colors and materials can be appropriately selected according to the application.
As other colorants, pigments other than the present colorant, dyes other than the present colorant, and natural pigments can be used. In the sense of obtaining pixels with high brightness and color purity, organic pigments are used. Organic dyes are preferred.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyer's and Colorists), that is, the color index (CI) name as shown below. Can be mentioned.

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 48: 5, C.I. I. Pigment red 49, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 49: 3, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 52: 2, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 54, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 58, C.I. I. Pigment red 58: 1, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 3, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 63: 3, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 68, C.I. I. Pigment red 81, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 200, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 237, C.I. I. Pigment red 239, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 247, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Red pigments such as CI Pigment Red 272;

C. I. Pigment violet 1, C.I. I. Pigment violet 2, C.I. I. Pigment violet 3, C.I. I. Pigment violet 3: 1, C.I. I. Pigment violet 3: 3, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 27, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38, C.I. I. Purple pigments such as CI Pigment Violet 39;
C. I. Pigment blue 1, C.I. I. Pigment blue 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 9, C.I. I. Pigment blue 10, C.I. I. Pigment blue 14, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 17: 1, C.I. I. Pigment blue 24, C.I. I. Pigment blue 24: 1, C.I. I. Pigment blue 56, C.I. I. Pigment blue 60, C.I. I. Pigment blue 61, C.I. I. Pigment blue 62, C.I. I. Blue pigments such as CI Pigment Blue 80.

  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-2001-108817, and various commercially available resins for dispersing pigments. The organic pigment is preferably used by refining primary particles 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.

  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 the like as a urethane-based dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by Big Chemie (BYK)), Solsperse 76500 (Lubrisol) Etc.) as a polyethyleneimine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc. as a polyester-based dispersant. B821, Adisper PB822, Adisper PB880, Adisper PB881 (or more, Ajinomoto Fine-Techno Co., Ltd.), and the like, can be mentioned, respectively.

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

  As the organic dye, among the dyes having the color index (CI) name, the following organic dyes can be preferably used.

For example,
C. I. Solvent Red 45, C.I. I. Red dyes such as Solvent Red 49;
C. I. Solvent Blue 35, C.I. I. Solvent Blue 37, C.I. I. Solvent Blue 59, C.I. I. Blue dyes such as Solvent Blue 67;

C. I. Acid Red 91, C.I. I. Acid Red 92, C.I. I. Acid Red 97, C.I. I. Acid Red 114, C.I. I. Acid Red 138, C.I. I. Acid red dyes such as Acid Red 151;
C. I. Acid Blue 80, C.I. I. Acid Blue 83, C.I. I. Acid blue dyes such as Acid Blue 90.

  The colored composition of the present invention is preferably used for forming a red pixel or a blue pixel. When used for forming a red pixel, (A) the colorant preferably contains at least one selected from the group consisting of a red colorant and a purple colorant as the other colorant together with the present colorant. On the other hand, when used for forming a blue pixel, (A) the colorant may contain at least one selected from the group consisting of a blue colorant and a purple colorant as the other colorant, together with the present colorant. preferable. Examples of the red colorant include the above red pigments, red dyes, and acidic red dyes. I. Pigment red 177, C.I. I. Pigment red 242, C.I. I. Pigment Red 254 and the like are preferable. Examples of the purple colorant include the purple pigment described above. I. Pigment Violet 23 and the like are preferable. Examples of the blue colorant include the above-described blue pigments, blue dyes, and acidic blue dyes. I. Pigment blue 1, C.I. I. Pigment Blue 15: 6 and the like are preferable.

  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 usually 5 to 70% by mass in the solid content of the coloring composition, preferably from the point of forming a pixel having high luminance and excellent color purity, or a black matrix having excellent light shielding properties. 5 to 60% by mass. Solid content here is components other than the solvent mentioned later.

-(B) Binder resin-
Although it does not specifically limit as (B) binder resin in this invention, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). And a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as “unsaturated monomer (b2)”). .

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

Moreover, as said unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;

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 -10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) ) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (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-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (b2) can be used alone or in admixture of two or more.

  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. Copolymers disclosed in JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-3030212, JP-A-7-207211, JP-A-09-325494, 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. If Mw is too small, the remaining film rate of the resulting film may be reduced, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, resolution may be reduced. In addition, the pattern shape may be damaged, and dry foreign matter may be easily generated during application by the slit nozzle method.

  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 says 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 JP2003-222717A, JP2006-259680A, International Publication No. 2007/029871, 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. If the content of the binder resin is too small, for example, the alkali developability may be decreased, or the storage stability of the resulting colored composition may be decreased. On the other hand, if the content is too large, the colorant concentration is relatively high. Therefore, it may be difficult to achieve the target color density as a thin film.

-(C) Crosslinking agent-
In the present invention, (C) a crosslinking agent 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, (C) the crosslinking agent 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 caprolactone-modified polyfunctional ( (Meth) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, hydroxyl-functional (meth) acrylate and polyfunctional isocyanate obtained by reacting with polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid The polyfunctional (meth) acrylate which has a carboxyl group obtained by making an anhydride 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; glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of trivalent or higher aliphatic polyhydroxy compounds. 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-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 crosslinking agents, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, 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.
In the present invention, the crosslinking agent (C) can be used alone or in admixture of two or more.

  In the present invention, the content of the (C) crosslinking agent is preferably 10 to 1,000 parts by mass, and particularly preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. In this case, if the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, if the content of the crosslinking agent is too large, when the coloring composition of the present invention is imparted with alkali developability, the alkali developability is deteriorated, and the soil or film on the unexposed portion of the substrate or on the light shielding layer is deteriorated. There is a tendency for the rest to occur easily.

-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 (C) a crosslinking agent upon 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 compound, a polynuclear quinone compound, a diazo compound, an imide sulfonate compound, an onium salt 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 commercially available 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) crosslinking agents, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.

-Solvent-
The colored composition of the present invention contains the above components (A) to (C) and other components that are optionally added, but is usually prepared as a liquid composition by blending a solvent. As said solvent, (A)-(C) component which comprises a coloring composition, and another component are disperse | distributed or melt | dissolved, and it does not react with these components, but suitably has appropriate volatility. You can choose to use.

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

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

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

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

Among 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 applicability | paintability 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 a siloxane oligomer having a reactive functional group disclosed in Japanese Patent Application Laid-Open No. 2008-242078.

  The coloring composition of the present invention can be prepared by an appropriate method. When the coloring agent is a dye, it is disclosed in, for example, JP 2008-58642 A, JP 2010-132874 A, and the like. Can be prepared by any method. When using both the coloring agent and the pigment which are dyes as the coloring agent, as disclosed in JP 2010-132874 A, after passing the dye solution containing the coloring agent through the first filter, A method can be employed in which the dye solution that has passed through the first filter is mixed with a separately prepared pigment dispersion or the like, and the resulting colored composition is passed through a second filter. Moreover, after dissolving the dye containing this coloring agent, said (B)-(C) component, and the other component used as needed in a solvent, let the obtained solution pass a 1st filter, You may employ | adopt the method of preparing by mixing the solution which passed the 1st filter with the pigment dispersion liquid prepared separately, and passing the obtained coloring composition through a 2nd filter. Moreover, after passing the dye solution containing this coloring agent through a 1st filter, the dye solution which passed the 1st filter, said (B)-(C) component, and other components used as needed Is mixed and dissolved, the obtained solution is passed through the second filter, the solution that has passed through the second filter is further mixed with the separately prepared pigment dispersion, and the resulting colored composition is mixed with the third filter. It is also possible to adopt a method of preparing by passing through.

Color filter and method for producing the same The color filter of the present invention includes a colored layer formed using the colored composition of the present invention.

  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-sensitive composition of the radiation-sensitive composition of the present invention containing the coloring agent is applied on the substrate, and then prebaked 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 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 pixel arrays of the three primary colors of red, green and blue 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 the first method for producing a color filter, it is preferable that at least one of the red and blue pixel arrays is a colored layer formed using the colored composition of the present invention.

  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 photolithography method. Using the radiation coloring composition, it can be formed in the same manner as in the case of forming the pixel. The coloring composition of the present invention can also be suitably used for forming such a black matrix.

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 a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method may be employed. 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 radiation light sources used in forming pixels and / or black matrices include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, and low pressure mercury lamps. Examples thereof include a light source, 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 hydroxide, sodium bicarbonate, potassium hydroxide, tetramethylammonium hydroxide, choline, and 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.

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 120 to 280 ° C. for about 10 to 60 minutes, but from the viewpoint of heat resistance of the present colorant, the post-baking temperature is preferably 240 ° C. or less, particularly preferably 230 ° C. or less. is there.
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, JP-A-2000-310706, etc. 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 blue liquid composition of the thermosetting coloring composition of the present invention containing the coloring agent is ejected by an ink jet 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. Thereby, a color filter in which pixel patterns of the three primary colors of red, green and blue 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. Moreover, also in the 2nd method of manufacturing a color filter, it is preferable that any one or more of the said red and blue pixel array is a colored layer formed using the coloring composition of this invention.

In addition, the partition has not only a light shielding function but also a function for preventing the color composition of each color discharged in the section from being mixed, so that the film is a film compared to the black matrix used in the first method described above. 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. Thus, the film thickness of the pixel formed by the inkjet method is about 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.
Since the color filter of the present invention thus obtained has extremely high luminance and color purity, it is extremely useful for color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like.

Display element The display element of the present invention comprises the color filter 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 color filter of the present invention may be a transmissive type or a reflective type, and can have 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. In addition, 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 a substrate in which an ITO (indium oxide doped with tin) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that faces each other via the 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.

  The color liquid crystal display device including the color filter of the present invention may 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 device having the color filter of the present invention includes a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, an IPS (In-Plane Switching) type, a VA (Vertical Alignment) type, and an OCB (Optical Optical). An appropriate liquid crystal mode such as a birefringence type can be applied.

  In addition, the organic EL display element including the color filter of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in Japanese Patent Application Laid-Open No. 11-307242.

  In addition, the electronic paper including the color filter of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in Japanese Patent Application Laid-Open No. 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 and Evaluation of the Colorant>
1. Synthesis synthesis example 1 of this colorant
Basic violet 10 (18 parts by mass), anhydrous chloroform (170 parts by mass), camphorsulfonic acid (1.0 parts by mass), 4- (N, N-dimethylamino) pyridine (1.4 parts by mass), 2-hydroxy Ethyl methacrylate (18 parts by mass) was added and stirred for about 30 minutes. Then, after slowly adding a solution prepared by adding anhydrous chloroform (47 parts by mass) to 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (10.5 parts by mass) and slowly adding it to room temperature. And stirred for about 2 hours. After performing the liquid separation operation twice with 1N hydrochloric acid aqueous solution (150 parts by mass), the organic layer was washed twice with 10% saline (150 parts by mass). Next, 43 parts by mass of anhydrous magnesium sulfate was added and stirred for about 30 minutes, and then the desiccant was filtered and the solvent was distilled off to obtain 20.6 parts by mass (yield 90%) of the compound represented by the following formula (A1). Obtained. Let the obtained compound be a coloring agent (A-1).

Synthesis example 2
A 500 mL Erlenmeyer flask containing a stirrer was charged with the above compound (A1) (20 parts by mass) and bis (trifluoromethanesulfonyl) imidolithium (14.5 parts by mass), chloroform (130 parts by mass), ion-exchanged water ( 100 parts by mass) was added and stirred at 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 (200 parts by mass). The organic layer was concentrated under reduced pressure, and the residue was dried under reduced pressure at 50 ° C. for 12 hours to obtain 26.6 parts by mass (yield 94%) of the compound represented by the following formula (A2). ^{By 1} H-NMR (solvent: deuterated chloroform) measurement, it was confirmed to be the target compound. Let the obtained compound be a coloring agent (A-2).

Synthesis example 3
A coloring agent was synthesized in the same manner as in Synthesis Example 2 except that potassium tetracyanoborate was used instead of bis (trifluoromethanesulfonyl) imide lithium in Synthesis Example 2, and ¹ H-NMR (solvent: deuterated chloroform) was used. By measurement, it was confirmed to be the target compound. Let the obtained compound be a coloring agent (A-3).

Synthesis example 4
A coloring agent was synthesized in the same manner as in Synthesis Example 2 except that potassium trifluoromethanesulfonate was used instead of bis (trifluoromethanesulfonyl) imide lithium in Synthesis Example 2, and ¹ H-NMR (solvent: deuterated chloroform) was synthesized. ) Measurement confirmed that the compound was the target compound. Let the obtained compound be a coloring agent (A-4).

Synthesis example 5
In the same manner as in Synthesis Example 2 except that potassium 2-acryloyloxy-1,1,2,2-tetrafluoroethanesulfonate was used in place of bis (trifluoromethanesulfonyl) imide lithium in Synthesis Example 2, the colorant was used. It was synthesized and confirmed to be the target compound by ¹ H-NMR (solvent: deuterated chloroform) measurement. Let the obtained compound be a coloring agent (A-5).

Synthesis Example 6
Similar to Synthesis Example 2 except that potassium 2- (4-vinylphenyloxy) -1,1,2,2-tetrafluoroethanesulfonate was used in place of bis (trifluoromethanesulfonyl) imide lithium in Synthesis Example 2. Then, a coloring agent was synthesized and confirmed to be the target compound by ¹ H-NMR (solvent: deuterated chloroform) measurement. Let the obtained compound be a coloring agent (A-6).

Synthesis example 7
A coloring agent was synthesized in the same manner as in Synthesis Example 2 except that tris (trifluoromethylsulfonyl) methidocesium was used in place of bis (trifluoromethanesulfonyl) imidolithium in Synthesis Example 2, and ¹ H-NMR (solvent: heavy Hydrogenated chloroform) was confirmed to be the target compound. Let the obtained compound be a coloring agent (A-7).

Synthesis example 8
In Synthesis Example 1, except that 2-hydroxyethyl acrylate was used instead of 2-hydroxyethyl methacrylate, a colorant was synthesized in the same manner as in Synthesis Example 1, and ¹ H-NMR (solvent: deuterated chloroform) was synthesized. ) Measurement confirmed that the compound was the target compound. Let the obtained compound be a coloring agent (A-8).

2. Evaluation of the present colorant The colorants (A-1) to (A-8) obtained in Synthesis Examples 1 to 8 were dissolved in cyclohexanone in an amount of 10% by mass or more, and these solutions exhibited a blue color.
Moreover, the 5% mass reduction | decrease temperature based on the thermogravimetric-differential-thermal simultaneous measurement analysis of the coloring agents (A-1)-(A-8) was 250 degreeC or more. On the other hand, C.I. I. The 5% mass loss temperature of Basic Violet 10 based on thermogravimetric-differential thermal simultaneous measurement analysis was less than 200 ° C. It can be said that the higher the 5% mass reduction temperature based on the thermogravimetric-differential heat simultaneous measurement analysis, the higher the heat resistance of the colorant.

<Preparation of dye solution>
Preparation Example 1
20 parts by weight of the colorant (A-1) and 80 parts by weight of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution (A-1).

Preparation Examples 2-8
In Preparation Example 1, dye solutions (A-2) to (A-2) to (A-2) were used in the same manner as Preparation Example 1, except that the colorants (A-2) to (A-8) were used instead of the colorant (A-1). (A-8) was prepared.

Preparation Example 9
A dye solution (A-9) was prepared in the same manner as in Preparation Example 1 except that Basic Violet 10 was used instead of Colorant (A-1) in Preparation Example 1.

<Synthesis of binder resin>
Synthesis Example 9
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 pigment dispersion>
Preparation Example 10
As a coloring agent, C.I. I. 15 parts by mass of Pigment Red 254, 12.5 parts by mass of BYK-LPN21116 (manufactured by BYK Corporation) 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 and evaluation of coloring composition>
Example 1
13.5 parts by weight of the pigment dispersion (a-1), 7.2 parts by weight of the dye solution (A-1), 21.6 parts by weight of the binder resin (B1) solution as the binder resin, and manufactured by Toagosei Co., Ltd. as the crosslinking agent M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 9.2 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1 as a photopolymerization initiator -ON (product name IRGACURE 369, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.2 parts by mass and NCI-930 (manufactured by ADEKA Co., Ltd.) 0.1 parts by mass, Megafac F-554 as a fluorosurfactant ( DIC Co., Ltd.) 0.2 parts by mass, and propylene glycol monomethyl ether as a solvent is mixed and solid Concentration of 20 wt% of the coloring composition (CR1) was prepared.

The coloring composition (CR1) was applied on a glass substrate using a spin coater, and then pre-baked on an 80 ° C. hot plate for 10 minutes to form a coating film. Three coating films having different film thicknesses were formed by the same operation while changing the rotation speed of the spin coater.
Next, after cooling these substrates to room temperature, a high-pressure mercury lamp is used, and a radiation containing each wavelength of 365 nm, 405 nm, and 436 nm is applied to each coating film without using a photomask at an exposure dose of 2,000 J / m ² . And exposed. Then, for these substrates, by a developer consisting of 0.04 wt% aqueous potassium hydroxide 23 ° C. for ejecting a developing pressure 1 kgf / cm ² (nozzle diameter 1 mm), it was 90 seconds shower development . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230 ° C. for 30 minutes to form a cured film for evaluation.

Evaluation of voltage holding ratio (%) A SiO ₂ film for preventing elution of sodium ions is formed on the surface, and an ITO (indium-tin oxide alloy) electrode is further deposited in a predetermined shape on the soda glass substrate. After spin-coating the composition, it was pre-baked for 1 minute on a hot plate at 100 ° C. to form a film having a thickness of 2.0 μm. Next, the film was exposed at an exposure amount of 700 J / m ² without using a photomask. Thereafter, the substrate is immersed in a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-treated at 230 ° C. for 30 minutes. Baking was performed to cure the coating, thereby forming a permanent cured film. Next, the substrate on which this pixel is formed and the substrate on which ITO electrodes are simply deposited in a predetermined shape are bonded together with a sealing agent mixed with 1.8 mm glass beads, and then liquid crystal made by Merck (MLC6608) is injected. A liquid crystal cell was produced. Next, the liquid crystal cell was placed in a constant temperature bath at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system (VHR-1A type, Toyo Corporation). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio is a value determined by (liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds). If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned. There is a risk of causing "burn-in".

Examples 2 to 8 and Comparative Example 1
A colored composition was prepared in the same manner as in Example 1, except that the types and amounts of the pigment dispersion and the dye solution were changed as shown in Table 1. The resulting colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Claims (6)

The following components (A), (B) and (C) :
(A) a xanthene-based colorant having a polymerizable unsaturated group in the color developing portion (B) a binder resin, and (C) a crosslinking agent
Containing
A colored composition , wherein the xanthene colorant has a structure represented by the following formula (2) .

[In Formula (2),
R ^b represents a group having a polymerizable unsaturated group. ;
R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group (the alkyl group, cycloalkyl group, and phenyl group are substituted) Which may have a group). ;
R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a chlorine atom. ] The polymerizable unsaturated group, (meth) acryloyl group, according to claim 1 Symbol placement colored composition. The coloring composition according to claim 1 , wherein the R ^b group is a group represented by the following formula (2a) or (2b).

[In the formulas (2a) and (2b)
R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a methyl group.
Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a substituted or unsubstituted alkanediyl group having 1 to 12 carbon atoms.
Z represents a —CO— group or a —COO — (*) group (wherein, * represents a bond to Y ² ).
Q represents a divalent alicyclic hydrocarbon group.
p ¹ represents an integer of 0 to 12.
p ² and p ³ are independently of each other, an integer of 0 to 6. ] The xanthene colorant, is obtained by an esterification reaction of the compound represented by the following formula (3), a compound having a hydroxyl group and (meth) acryloyl group, any of claims 1-3 1 The coloring composition according to item.

[In Formula (3),
R ¹ to R ⁶ have the same meanings as R ¹ to R ⁶ in Formula (2).
X ⁻ represents an anion. ] The color filter provided with the colored layer formed using the coloring composition of any one of Claims 1-4 . A display device comprising the color filter according to claim 5 .